EP4211096A1 - Oxidative method for preparing a fertilising composition - Google Patents
Oxidative method for preparing a fertilising compositionInfo
- Publication number
- EP4211096A1 EP4211096A1 EP21778186.3A EP21778186A EP4211096A1 EP 4211096 A1 EP4211096 A1 EP 4211096A1 EP 21778186 A EP21778186 A EP 21778186A EP 4211096 A1 EP4211096 A1 EP 4211096A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- humic substances
- mass
- average
- plant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 229
- 238000000034 method Methods 0.000 title claims abstract description 65
- 230000001590 oxidative effect Effects 0.000 title description 2
- 239000000126 substance Substances 0.000 claims abstract description 249
- 239000007788 liquid Substances 0.000 claims abstract description 73
- 238000002296 dynamic light scattering Methods 0.000 claims abstract description 65
- 239000002245 particle Substances 0.000 claims abstract description 41
- 238000011282 treatment Methods 0.000 claims abstract description 35
- 239000007800 oxidant agent Substances 0.000 claims abstract description 34
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 82
- 239000002689 soil Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 22
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 20
- 239000011707 mineral Substances 0.000 claims description 20
- 239000003415 peat Substances 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 239000003245 coal Substances 0.000 claims description 9
- 239000003337 fertilizer Substances 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 235000021466 carotenoid Nutrition 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 150000001747 carotenoids Chemical class 0.000 claims description 7
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003830 anthracite Substances 0.000 claims description 6
- 229930002868 chlorophyll a Natural products 0.000 claims description 6
- 229930002869 chlorophyll b Natural products 0.000 claims description 6
- 239000003077 lignite Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- NSMUHPMZFPKNMZ-VBYMZDBQSA-M chlorophyll b Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C=O)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 NSMUHPMZFPKNMZ-VBYMZDBQSA-M 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- -1 leonardite Substances 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 230000002786 root growth Effects 0.000 claims description 2
- 230000004936 stimulating effect Effects 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 52
- 241000196324 Embryophyta Species 0.000 description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000005259 measurement Methods 0.000 description 15
- 235000010755 mineral Nutrition 0.000 description 15
- 238000011993 High Performance Size Exclusion Chromatography Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 240000008042 Zea mays Species 0.000 description 12
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 12
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 12
- 235000009973 maize Nutrition 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 239000002609 medium Substances 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 238000006385 ozonation reaction Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 238000004108 freeze drying Methods 0.000 description 8
- 235000001055 magnesium Nutrition 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000003501 hydroponics Substances 0.000 description 6
- 239000011435 rock Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 101100108953 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) ANY1 gene Proteins 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002509 fulvic acid Substances 0.000 description 3
- 230000035784 germination Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004021 humic acid Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 230000008635 plant growth Effects 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000005653 Brownian motion process Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000003639 Student–Newman–Keuls (SNK) method Methods 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000000540 analysis of variance Methods 0.000 description 2
- 238000005842 biochemical reaction Methods 0.000 description 2
- 238000005537 brownian motion Methods 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229930002875 chlorophyll Natural products 0.000 description 2
- 235000019804 chlorophyll Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008241 heterogeneous mixture Substances 0.000 description 2
- 239000002663 humin Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010455 vermiculite Substances 0.000 description 2
- 229910052902 vermiculite Inorganic materials 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- GIMSJJHKKXRFGV-BYPJNBLXSA-N 4-amino-1-[(2r,3s,4r,5r)-3-fluoro-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-5-iodopyrimidin-2-one Chemical compound C1=C(I)C(N)=NC(=O)N1[C@H]1[C@@H](F)[C@H](O)[C@@H](CO)O1 GIMSJJHKKXRFGV-BYPJNBLXSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 244000241257 Cucumis melo Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 229920000832 Cutin Polymers 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- 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 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 235000003228 Lactuca sativa Nutrition 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 235000011430 Malus pumila Nutrition 0.000 description 1
- 235000015103 Malus silvestris Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 235000006029 Prunus persica var nucipersica Nutrition 0.000 description 1
- 244000017714 Prunus persica var. nucipersica Species 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 235000004789 Rosa xanthina Nutrition 0.000 description 1
- 241000109329 Rosa xanthina Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 244000300264 Spinacia oleracea Species 0.000 description 1
- 235000009337 Spinacia oleracea Nutrition 0.000 description 1
- 240000000359 Triticum dicoccon Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 230000036579 abiotic stress Effects 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 238000009362 arboriculture Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical group 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000005829 chemical entities Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000005446 dissolved organic matter Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 244000037666 field crops Species 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 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
- 235000016709 nutrition Nutrition 0.000 description 1
- 238000011369 optimal treatment Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- WURFKUQACINBSI-UHFFFAOYSA-M ozonide Chemical compound [O]O[O-] WURFKUQACINBSI-UHFFFAOYSA-M 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 230000001863 plant nutrition Effects 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
- C05F11/02—Other organic fertilisers from peat, brown coal, and similar vegetable deposits
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/40—Treatment of liquids or slurries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Definitions
- the invention relates to a method for preparing a fertilizer composition by oxidation of humic substances, the compositions thus obtained and their use as a fertilizer.
- the fertilizing compositions prepared can in particular be used in agriculture, in particular for stimulating the growth of plants.
- Humic substances are both macromolecular and supramolecular biomolecules [8]. Humic substances are largely responsible for the brown color of decomposed plant debris and also contribute to the black-brown color of soil surfaces. Humic substances are therefore very important components of the soil as they affect the physical and chemical properties of the soil and increase its fertility. In aquatic systems, such as rivers, humic substances make up about 50% of dissolved organic matter. Humic substances affect its pH and alkalinity.
- Humic substances are complex and heterogeneous mixtures of polydispersed materials formed by chemical and biochemical reactions during the decomposition and transformation of plants and microbial residues, resulting in a process known as humification.
- Plant lignin and its transformation products, as well as polysaccharides, melanin, cutin, proteins, lipids, nucleic acids, fine particles of carbonization residues, are important compounds participating in this humification process. .
- Humic substances are substances with very complex structures which are however considered as chemical entities in their own right. According to the definition given by the International Humic Substance Society (IHSS), humic substances are complex and heterogeneous mixtures of polydisperse materials formed in soils, sediments and natural waters by biochemical and chemical reactions during decomposition and the transformation of plant and microbial remains (a process called humification).
- IHSS International Humic Substance Society
- Humic substances include in particular humic acids (HA), fulvic acids (FA) and humin.
- HA humic acids
- FA fulvic acids
- humin humin
- humic substances In the field of agriculture, the use of humic substances has many advantages.
- an effective quantity of humic substances makes it possible to improve the state of health of the plants and the yield, with in particular a better use of water (reduced water consumption to make the same mass of dry matter), increased root length after germination, better rooting, increased biomass (leaves, stems, flowers and fruits) with better dry matter content, improved precocity of flowering and fruiting [1] .
- the oxidation, for example ozonation, of a composition of humic substances makes it possible to optimize its fertilizing properties, compared with a composition of non-oxidized humic substances.
- a composition of oxidized humic substances for example an ozonated composition of humic substances, significantly stimulated the absorption of minerals in the plant, compared to a composition of non-oxidized humic substances, for example a composition of non-ozonated humic substances.
- the present invention which finds application in the field of agriculture, aims to provide a new process for preparing a fertilizing composition by oxidation humic substances, the compositions thus obtained and their use as a fertilizer.
- the invention relates to a method for preparing a fertilizing composition, comprising a step of treating a liquid composition of humic substances whose mass-average hydrodynamic radius of the particles in solution, measured by Dynamic Light Scattering (DLS), is “Rh average before treatment” with an appropriate amount of oxidizing agent to obtain a liquid composition of oxidized humic substances whose mass average hydrodynamic radius of the particles in solution (Rh average after treatment), measured by DLS, CSt SUPERIOR TO AVERAGE Rh BEFORE TREATMENT-
- DLS Dynamic Light Scattering
- the invention relates to a fertilizing composition obtainable by the process according to the invention.
- the invention relates to the use of a composition according to the invention as a stimulant for the absorption of minerals in a plant, preferably the minerals are chosen from nitrogen, phosphorus, potassium, calcium, magnesium and/or sulfur.
- the invention relates to a method for fertilizing a plant, a soil or a growing medium comprising the application to said plant, said soil or said growing medium of a composition according to the invention.
- the invention relates to a process for fertilizing a plant, a soil or a growing medium consisting in preparing a fertilizing composition by implementing the process of the invention, and applying, for example directly after the preparation, said fertilizing composition to the plant, to the soil or to the growing medium.
- the present invention stems from the surprising advantages demonstrated by the inventors of the effect of oxidation, for example ozonation, on the fertilizing power of a liquid composition of humic substances.
- the invention relates to a method for preparing a fertilizing composition, comprising a step of treating a liquid composition of humic substances whose mass-average hydrodynamic radius of the particles in solution, measured by Dynamic Light Scattering (DLS) , is "Rh average before treatment” with an appropriate amount of oxidizing agent to obtain a liquid composition of oxidized humic substances whose the mass-average hydrodynamic radius of the particles in solution (average Rh after treatment), measured by DLS, is greater than the Rhmo y before treatment
- DLS Dynamic Light Scattering
- the description also relates to a method for improving the fertilizing properties of a composition of humic substances, comprising a step of treating a liquid composition of humic substances whose mass-average hydrodynamic radius of the particles in solution, measured by Dynamic Light Scattering (DLS), is "Rh avg before treatment” with an appropriate amount of oxidizing agent to obtain a liquid composition of oxidized humic substances whose mass-average hydrodynamic radius of the particles in solution (Rh avg after treatment), measured by DLS, is higher than the average Rh n before treatment-
- DLS Dynamic Light Scattering
- the method comprises the following steps: a) obtaining a liquid composition of humic substances whose mass-average hydrodynamic radius of the particles in solution, measured by Dynamic Light Scattering (DLS), is “Rh average before treatment * , b) treating the liquid composition of humic substances with an appropriate amount of oxidizing agent to obtain an oxidized liquid composition of humic substances whose mass-average hydrodynamic radius of the particles in solution (average Rh n after treatment), MEASUREMENT by DLS, is higher than the Rhaverage before treatment-
- DLS Dynamic Light Scattering
- fertilizer composition(s) are synonyms and designate a composition, a substance, or a mixture substances, of natural or synthetic origin, applied or intended to be applied to plants or their rhizosphere or to fungi or their mycosphere, alone or mixed with another material, with the aim of providing plants or to fungi of nutrients or to improve their nutritional efficiency or to stimulate plant nutrition processes independently of the nutrients it contains, for the sole purpose of improving one or more of the characteristics of plants or their rhizosphere such as nutrient use efficiency, abiotic stress tolerance, quality characteristics or availability of nutrients confined to the soil and rhizosphere.
- This definition is derived from the definition in European Union Regulation No. 2019 1009.
- the inventors have in fact shown that it is possible to improve the fertilizing properties of a liquid composition of humic substances by treating said composition with an appropriate amount of oxidizing agent, for example an appropriate amount of ozone.
- an appropriate amount of oxidizing agent for example an appropriate amount of ozone.
- the inventors have in fact noticed, quite unexpectedly, that mild oxidation of a liquid composition of humic substances increases the mass-average hydrodynamic radius of the particles in solution (average Rh), measured by DLS, and that this increase in the average Rh was associated with an increase in the fertilizing properties of said composition.
- the amount of oxidizing agent must be adapted to obtain a liquid composition of oxidized humic substances whose mass-average hydrodynamic radius of the particles in solution (Rh average after treatment), measured by DLS, is higher than the average Rh before treatment, measured by DLS.
- DLS Dynamic Light Scattering
- the principle of DLS is based on measurements of scattered light intensity fluctuation due to Brownian motion of the particles. The larger a particle the slower its movement will be. This phenomenon is described by the Stokes-Einstein law.
- the incident laser beam will pass through the analyzed liquid composition.
- the ray scattered at 90° (the most commonly used angle) will depend on the morphology of the particles.
- the intensity variation of the scattered ray gives information on the diffusion of the particles and therefore on their size [11].
- the values of Rh mean are calculated by weighting by the percentage by mass of each population.
- the measured scatter intensity range can be 1.36 x 106 to 3.14 x 106 counts per second (cps). All measurements can be taken at a detection angle of 90° and all reported sizes are averages of 15 sequences of 5 s each.
- a DLS protocol that can be implemented within the scope of the invention is described in the examples.
- the DLS analyzes make it possible to measure the mass-average hydrodynamic radius of the particles in solution, that is to say the mass-average hydrodynamic radius of the particles of the soluble fraction of the composition. liquid of humic substances.
- certain liquid compositions of humic substances may comprise a non-negligible amount of insoluble matter. This is the case, for example, when the liquid composition of humic substances is prepared from a raw material (eg peat) mixed with water.
- a raw material eg peat
- the person skilled in the art knows that he must carry out the measurements of the average Rh by DLS on the soluble fraction of the liquid composition of humic substances.
- the soluble fraction can be obtained very easily by separating it from the insoluble fraction, for example by decantation, filtration or by centrifugation.
- An example of separation of the soluble fraction and the insoluble fraction consists in centrifuging at 4800 rpm for 30 minutes.
- the liquid composition of humic substances to be oxidized can be obtained from natural humic substances. It may for example be a raw material containing humic substances, for example peat, leonardite, lignite, hard coal or anthracite. Thus, a liquid composition of humic substances can be a liquid composition of peat, leonardite, lignite, coal or anthracite.
- Peat is fossil organic matter formed by accumulation over long periods of time of dead organic matter, essentially plants, in an environment saturated with water. Peat forms most of the soils in peatlands. Peat can be more or less rich in humic substances depending on the degree of decomposition.
- the degree of decomposition of peat is classified according to the Von Post scale which goes from H1 (least decomposed peat) to H 10 (most decomposed peat) [9].
- Humus peat that is to say a peat classified from H6 to H 10 according to the Von Post scale, is the preferred peat for implementing the process according to the invention because it is richer in humic substances. than peat classified from H1 to H5 according to the Von Post scale.
- Leonardite is a rock which can contain more than 90% by weight of humic substances. This rock has undergone more extensive degradation than peat, but less extensive than coal.
- Lignite is a sedimentary rock composed of the fossil remains of plants. It is an intermediate rock between peat and coal.
- Coal is a sedimentary carbonaceous rock corresponding to a specific quality of coal, intermediate between lignite and anthracite. Blackish in color, it comes from the carbonization of plant organisms.
- Anthracite is a sedimentary rock of organic origin. It is a grey, blackish and shiny variety of coal extracted from the mines.
- the liquid composition of humic substances to be oxidized can also be obtained from synthetic humic substances.
- Synthetic humic substances can for example result from a process of synthesis [7] or from the transformation of natural humic substances, in particular by hemisynthesis.
- Humic substances can also be extracted from organic matter (peat, leonardite, lignite, hard coal, anthracite, soils rich in humic substances, composts of plant waste, etc.) using an alkaline agent such as sodium hydroxide (NaOH) or potassium hydroxide (KOH) and optionally subjected to purification [10].
- Humic substances can in particular be extracted and/or purified by methods well known to those skilled in the art [5] [10].
- the liquid composition of humic substances to be oxidized includes liquid compositions of a salt of humic substances.
- a salt of humic substances is used, such as potassium humates or potassium salt of humic substances.
- Salts of humic substances are sold commercially. Mention may be made, for example, of the potassium salt of humic substances marketed by the company Humatex under the brand name Dralig® (CAS 68514-28-3).
- Dralig® product is prepared from humic substances extracted from natural Czech oxyhumolite with a high content of humic substances.
- FIG. 5 shows the HPSEC profile of a liquid composition of humic substances which can be used in the method according to the invention (in dotted lines).
- concentration of humic substances in the liquid composition is not limited. It can for example be between 100 and 1000 mg/L, preferably between 400 and 500 mg/L, for example approximately 550 mg/L.
- the humic substance purity of the liquid composition of humic substances can also vary, for example depending on the source used. Of course, peat is generally less pure in humic substances than leonardite or a commercial powder of humic substances, such as the product Dralig® (CAS 68514-28-3).
- the liquid composition of humic substances to be treated comprises at least 50% by dry mass of humic substances, for example at least 60%, at least 70%, at least 80%, at least 85%, at least least 90%, at least 95%, or at least 99% by dry mass of humic substances.
- the appropriate amount of oxidizing agent necessary for the implementation of the method can depend on various parameters, such as the nature of the humic substances, the purity of the liquid composition of humic substances, the quantity of humic substances to be treated, the nature of the oxidizing agent, etc. Nevertheless, those skilled in the art will have no difficulty in determining the appropriate amount of oxidizing agent by simply measuring the average Rh by DLS , for example by following the evolution of the average Rh with increasing amounts of an agent. oxidant. These measurements can for example make it possible to define a quantity of oxidizing agent not to be exceeded so that the average Rh n after treatment, measured by DLS, is greater than the average Rh n before treatment, measured by DLS. Thus, it is easy to determine the appropriate amount of oxidizing agent for a given liquid composition of humic substances and a given oxidizing agent.
- Figure 8B shows the evolution of the average Rh, measured by DLS, with increasing amounts of ozone.
- the amount of oxidizing agent can be easily adapted so as to obtain, as far as possible, an average Rh, measured by DLS, the value of which is desired.
- the amount of oxidizing agent is chosen to obtain a maximum value of average Rh, measured by DLS.
- liquid compositions of humic substances may include a significant amount of insoluble matter. This is the case, for example, when treating a raw material (eg peat) mixed with water.
- a raw material eg peat
- DLS DLS measurements on the soluble fraction of the liquid composition comprising humic substances.
- the soluble fraction can be obtained very easily by separating it from the insoluble fraction, for example by filtration or by centrifugation, as detailed previously in the description.
- the average Rh after treatment is 3U minus 2 times higher than the average Rh before treatment, preferably at least 3 times, 4 times, 5 times, 6 times higher, for example at least
- the treatment time is not limiting as long as one obtains an average Rh after treatment higher than the average Rh before treatment.
- the duration of the treatment is between 5 minutes and 10 hours.
- the quantity of oxidizing agent, and possibly the duration of the treatment are adapted to the initial quantity of humic substances and to the oxidizing agent used. The duration of the optimal treatment can therefore be easily adapted by the person skilled in the art.
- the mass proportion of the particles in solution having a hydrodynamic radius of between 15 nm and 10,000 nm of the composition of oxidized humic substances, measured by DLS is at least 2 times greater than the mass proportion particles in solution having a hydrodynamic radius between 15 nm and 10000 nm of the composition of humic substances before oxidation, preferably at least 2.5 times, for example at least 3 times, at least 3.5 times, at least 4 times, at least 4.5 times, at least 5 times, at least 6 times.
- Figures 7 and 8A show the evolution of the mass proportion of particles in solution having a hydrodynamic radius between 15 nm and 10,000 nm, measured by DLS, with increasing amounts of ozone.
- the weight-average molar mass in solution (hereinafter "Mw") (expressed in Da) of the liquid composition of oxidized humic substances is greater than the Mw of the composition of humic substances before oxidation.
- Mi molar mass relative to the retention time obtained in HPLC (resulting from the column calibration carried out with standards).
- the calculation of Mw is generally done automatically by the HPLC device. To calculate Mw, it is possible to do it manually or to use software such as the Chromeleon software which is an HPLC data acquisition software.
- Figures 1 and 2 illustrate the increase in Mw with increasing amounts of ozone.
- the oxidizing agent is advantageously chosen from ozone, ultraviolet rays and/or hydrogen peroxide.
- the oxidizing agents can be used alone or combined with each other to obtain the desired composition.
- the oxidizing agent is ozone
- Ozone is a particularly advantageous oxidizing agent because it is easy to use, inexpensive and the quantity of which is easy to control for the implementation of the method of the invention. Since ozone is unstable, it is produced at the place of consumption. On an industrial scale, ozone is generally produced by electrical discharges in tubular generators. This production is due to an ozone generator, which is essentially composed of two conductive electrodes held facing each other. The air or oxygen is compressed, then dried, and passes between these two electrodes where it is subjected to an electric discharge in a high voltage alternating current field. Some of the oxygen turns into ozone. A cooling circuit absorbs the excess heat produced by the discharge.
- one of the electrodes or sometimes both are covered with a dielectric with high permittivity, of uniform thickness producing an equipotential surface.
- the dielectrics used are glasses whose permittivity varies, depending on the chemical composition, from 4 to 6.5. Ozone is therefore produced by causing an oxygenated fluid to slowly circulate in the remaining space and by creating in the gaseous space a sinusoidal alternating voltage of sufficiently high amplitude.
- the ozone can be gaseous ozone produced from oxygen, for example from air, from oxygen-enriched air or from pure oxygen.
- An ozone generator suitable for implementing the invention is Lab2b or CFS1 from the company Ozonia (Suez).
- the quantity of ozone is adapted to obtain an average Rh after treatment higher than the average Rh before treatment.
- the quantity of ozone will therefore essentially depend on the quantity of humic substances present in the composition.
- the mass of ozone/mass of humic substances ratio is less than 10.
- the mass of ozone corresponds to the mass of ozone applied to the liquid composition of humic substances.
- the mass of humic substances corresponds to the mass of humic substances present in the liquid composition of humic substances to be ozonated, that is to say the mass of humic substances before ozonation.
- the mass of humic substances can be determined by HPLC.
- the ratio mass of ozone/mass of humic substances can for example be less than 9, less than 8, less than 7, less than 6, less than 5, less than 4.5, less than 4, less than 3.5 , for example between 0.2 and 10, between 0.2 and 9, between 0.2 and 8, between 0.2 and 7, between 0.2 and 6, between 0.2 and 5 , between 0.2 and 3.5, between 0.5 and 3.5, between 1 and 10, between 1 and 9, between 1 and 8, between 1 and 7, between 1 and 6 , between 1 and 5, between 1 and 4, between 1 and 3, between 1 and 2, for example is equal to about 1.5.
- ozone generator Any type of ozone generator can be used in the implementation of the method according to the invention.
- air ozone generators dried air with a dew point of -50°C to - 70°C
- low frequency ozone generators 50 Hz
- medium frequency ozone generators 150 to 600 Hz
- the ozone is produced and injected into a reactor, where the composition to be treated is injected beforehand.
- Mention may be made, for example, of the CFS1 ozone generator from Ozonia, which is particularly suitable for implementing the method according to the invention. It is also possible to use excimers which are good generators of ozone.
- reactors equipped with porous diffusers reactors equipped with turbines, and U-tube piston flow reactors, equipped with a pump to overcome pressure drops.
- the gas containing ozone Before being injected into the liquid composition of humic substances, the gas containing ozone can be divided into "micro-bubbles", ie bubbling of the ozone, using various materials, for example using porous diffusers arranged in the lower part of the tanks or columns or a hydro-injector ensuring the spraying of the gas directly into the composition to be treated.
- the latter has the advantage of a better rate of dissolution of the ozone in the treated composition.
- the treatment is carried out by bubbling ozone into the liquid composition of humic substances, for example by bubbling 8 x W 4 at 0.5 grams of ozone per minute (g/min ), for example from 8 x W 4 g/min to 0.1 g/min, for example from 8.33 x W 4 g/min to 0.1 g/min of ozone, preferably from 1.5 x W 2 g/min at 1.9 x W 2 g/min ozone.
- the duration of bubbling depends on the quantity of ozone that one wishes to apply.
- the ozone concentration of the liquid composition is constant during the treatment, preferably the ozone concentration ranges from 1 g/m 3 to 120 g/m 3 , advantageously it is equal at approximately 20 g/m 3 .
- the method according to the invention may comprise one or more additional steps, for example one or more steps chosen from:
- liquid composition of oxidized humic substances for example freeze-drying, the liquid composition of oxidized humic substances; and granulating the liquid oxidized humic substance composition or a fertilizer composition comprising the liquid oxidized humic substance composition.
- a fertilizing composition comprising the liquid composition of oxidized humic substances can be prepared by adding, to the composition of oxidized humic substances, a mineral fertilizer, preferably containing one or more minerals chosen from nitrogen, phosphorus, potassium , calcium, magnesium and/or sulfur, to ozonated humic substances. The addition can be done before or after the additional steps mentioned above.
- the invention also relates to a fertilizing composition which can be obtained by the process according to the invention.
- the mass-average hydrodynamic radius of the particles in solution (Rh mO yen), measured by DLS is greater than 50 nm, preferably greater than 75 nm, for example greater than 100 nm, greater than 150 nm, greater than 200 nm, greater than 250 nm, greater than 500 nm, greater than 750 nm, greater than 1000 nm, greater than 1250 nm, greater than 1500 nm, greater than 1750 nm, greater than 2000 nm.
- the mass proportion of particles in solution having a hydrodynamic radius of between 15 nm and 10,000 nm, measured by DLS is greater than 15%, preferably greater than 20%, for example greater than 25%, greater than 30%, over 35%, over 40%, over 45%, over 50%, over 55%, over 60%, over 65%, over 70%, over 75%, over 80%.
- Mw of the fertilizing composition according to the invention is between 100 kDa and 300 kDa, for example between 100 kDa and 250 kDa, between 100 kDa and 200 kDa, between 100 kDa and 180 kDa, preferably between 150 kDa and 170 kDa, for example it is about 160 kDa.
- the diagram of degradation of humic substances by ozone is presented in Figure 3, taken from [6].
- the composition according to the invention further comprises one or more fertilizing substance(s) chosen from urea, ammonium sulphate, ammonium nitrate , phosphate, potassium chloride, ammonium sulfate, magnesium nitrate, manganese nitrate, zinc nitrate, copper nitrate, phosphoric acid, potassium nitrate and boric acid.
- fertilizing substance(s) chosen from urea, ammonium sulphate, ammonium nitrate , phosphate, potassium chloride, ammonium sulfate, magnesium nitrate, manganese nitrate, zinc nitrate, copper nitrate, phosphoric acid, potassium nitrate and boric acid.
- the composition according to the invention further comprises one or more mineral fertilizers.
- the mineral fertilizer preferably comprises one or more minerals chosen from nitrogen, phosphorus, potassium, calcium, magnesium and/or sulphur. It has in fact been shown that oxidized humic substances allow better absorption of minerals by the plant compared to non-ozonated humic substances.
- a composition according to the invention which also comprises one or more mineral fertilizers therefore has particularly advantageous properties.
- Figure 5 shows the HPSEC profile of a fertilizing composition according to the invention which was obtained by implementing the method according to the invention (solid line).
- Figure 7 shows a DLS profile of fertilizing compositions according to the invention which have been obtained by implementing the method according to the invention, with a mass ratio of ozone/mass of humic substances (R) equal to 0.1, equal to 0.5 or equal to 2.
- composition according to the invention can be in liquid form, for example in the form of a fertilizing solution, or in solid form, for example in the form of granules.
- the invention also relates to the use of a composition according to the invention as a stimulant for the absorption of minerals in a plant, preferably the minerals are chosen from nitrogen, phosphorus, potassium, calcium , magnesium and/or sulfur.
- the invention also relates to the use of a composition according to the invention as a stimulant for the production of pigments in a plant, preferably the production of carotenoids, chlorophyll A and/or chlorophyll B.
- the invention also relates to a method for fertilizing a plant, a soil or a growing medium comprising the application to said plant, said soil or said growing medium of a composition according to invention.
- the invention also relates to a process for fertilizing a plant, a soil or a growing medium consisting in (i) preparing a fertilizing composition by implementing the process of the invention, and ( ii) applying, for example directly after the preparation, said fertilizing composition to the plant, to the soil or to the growing medium.
- a culture support is intended to serve as a culture medium for a plant by making it possible both to anchor the absorbent organs of the plant and to bring them into contact with the solutions necessary for plant growth.
- the process according to the invention makes it possible to stimulate the absorption of minerals in the plant.
- the minerals are chosen from nitrogen, phosphorus, potassium, calcium, magnesium and/or sulphur.
- the method according to the invention makes it possible to stimulate the production of pigments in the plant, preferably the production of carotenoids, chlorophyll A and/or chlorophyll B.
- the use or the method according to the invention makes it possible to increase the photosynthetic activity of a plant and/or to stimulate the aerial and/or root growth of the plant.
- the fertilizing composition is applied to the plant, to the soil or to the growing medium, in liquid form, directly after the treatment with the oxidizing agent.
- the application can be done continuously, that is to say that the fertilizing composition in liquid form is applied to the soil or to the growing medium in a continuous flow as the treatment with the oxidizing agent.
- composition according to the invention can be applied to the plant via the leaf or root route.
- the soil is an acid soil.
- acidic soil is soil with a pH below pH 6.5.
- the inventors have in fact shown that under acidic conditions the ozonated humic substances precipitate less than the non-ozonated humic substances, and that they therefore retain their fertilizing properties.
- the present invention finds application in the treatment of a very wide variety of plants. Among these, we can mention in particular:
- cereals e.g. wheat, maize
- oilseeds e.g. soya, sunflower
- - grassland plants useful for animal feed specialized crops such as, in particular, market gardening (eg lettuce, spinach, tomato, melon), vines, arboriculture (pear, apple, nectarine), or horticulture (eg roses).
- market gardening eg lettuce, spinach, tomato, melon
- vines e.g., tomato, melon
- arboriculture pear, apple, nectarine
- horticulture eg roses
- Figure 1 is an HPSEC curve which shows the evolution of the weight average molar mass in solution (Mw) of the liquid composition of humic substances during the treatment with ozone. The figure also shows the evolution of the Number Average Molecular Mass (Mn) of the liquid composition of humic substances during treatment with ozone.
- FIG. 2 is an HPSEC curve which shows the evolution of the mean molar mass by weight in solution (Mw) of the liquid composition of humic substances as a function of the “mass of ozone/mass of humic substances” ratio.
- Mw mean molar mass by weight in solution
- Mn Number Average Molecular Mass
- Figure 3 represents the process of degradation of humic substances by oxidation with ozone.
- Figure 4 illustrates the assembly of a batch reactor used for the ozonation of a liquid composition of humic substances.
- Figure 5 is an HPSEC profile of an ozonated humic substance composition (parent composition of Example 1) and a non-ozonated humic substance composition (control composition of Example 1).
- the solid line shows the ozonated composition and the dotted line shows the non-ozonated control composition.
- Figure 6 is a histogram obtained from the HPSEC data of Figure 5 which represents the percentage of the different families of humic substances according to their molecular mass.
- FIG. 7 is a DLS (Dynamic light scattering) analysis which shows the evolution of the size of humic substances with increasing amounts of ozone.
- Figure 9 is a curve which compares the evolution of the length of the leaves of maize treated with a composition of ozonated humic substances (1.5.2+SN) and a composition of non-ozonated humic substances (T.2+SN ).
- Figure 10 represents the average leaf length of maize treated with an ozonated humic substance composition (1) and a non-ozonated humic substance composition (0).
- Figure 11 is a curve which compares the evolution of the length of the roots of maize treated with a composition of ozonated humic substances (1.5.2+SN) and a composition of non-ozonated humic substances (T.2+SN ).
- Figure 12 represents the average root length of maize treated with an ozonated humic substance composition (1) and a non-ozonated humic substance composition (0).
- FIG. 13 is a histogram which compares the length of the roots of maize treated with a composition of minerals, a composition of non-ozonated humic substances (T.2+SN), a composition of ozonated humic substances with a ratio “ mass of ozone/mass of humic substances” of 0.5 (0.5.2+SN), a composition of ozonated humic substances with a “mass of ozone/mass of humic substances” ratio of 1.5 (1.5.2 +SN) and a composition of ozonated humic substances with a “mass of ozone/mass of humic substances” ratio of 3.5 (3.5.2+SN).
- Figure 14 is a bar graph comparing the carotenoid content of maize leaves treated with an ozonated humic substance composition (left) and a non-ozonated humic substance composition (right).
- Figure 15 is a bar graph comparing the chlorophyll A content of maize leaves treated with an ozonated humic substance composition (left) and a non-ozonated humic substance composition (right).
- FIG. 16 Figure 16 is a bar graph comparing the chlorophyll B content of maize leaves treated with an ozonated humic substance composition (left) and a non-ozonated humic substance composition (right).
- Figure 17 is an HPSEC profile of a liquid composition of non-ozonated humic substances before and after lyophilization.
- Figure 18 is an HPSEC profile of a liquid composition of ozonated humic substances before and after lyophilization.
- Figure 19 is a curve showing the precipitation of humic substances as a function of pH in a liquid composition of ozonated humic substances (in solid lines) and in a liquid composition of non-ozonated humic substances (in dotted lines).
- a liquid composition of humic substances was obtained by diluting 11 grams of a potassium salt powder of humic substances (Dralig® product marketed by the company Humatex - CAS 68514-28-3) in 20 liters of water, to obtain 20 liters of a composition with a concentration of humic substances of 550 mg/L.
- This liquid composition of humic substances was used in the examples below as “control composition”.
- the ozonation reaction was carried out in a conventional batch reactor described in Figure 4.
- the reactor used was a simple glass bottle (1) containing IL of the composition of humic substances at 550 mg/L (2) . This solution was stirred with a magnetic stirrer (3).
- the ozone was produced with an ozone generator (CFS1 - Ozonia) powered by pure oxygen (4).
- the ozone concentration used was 20 g/m 3 in the gas flow entering the reactor (with a flow rate of 1.67x10'2 g/min of ozone) and was monitored using the ozone analyzer.
- ozone (5) The flow of gas entering the reactor was regulated at 50 L/h using a flow meter (6).
- the temperature of the incoming gas was measured with a thermometer (7) and was between 17 and 22°C.
- the gas was injected into the composition of humic substances with a glass inlet and a frit comprising pores of an average size of 200 ⁇ m (8).
- the excess ozone was then destroyed in a second reactor (9) containing a solution of potassium iodide (Kl) at 50 g/L (10).
- a valve was used to control the reaction (11). When the ozone was not used in the reactor, it was sent directly to the destroyer (9).
- the ozonation time was 50 minutes for IL of composition of humic substances at 550 mg/L.
- compositions of ozonated humic substances were diluted to a quarter with MilliQ water.
- the liquid composition of humic substances thus obtained was used in the examples below as “stock composition”.
- the measured scatter intensity range was 1.36 x 106 to 3.14 x 106 counts per second (cps). All measurements were taken at a 90° detection angle and all sizes reported are averages of 15 sequences of 5 seconds each. The reproducibility of the samples was analyzed 3 times. 20 ⁇ L of each solution was used and all solutions were adjusted to 25°C in the sample chamber of the instrument and allowed to equilibrate for 5 min.
- a disposable microcuvette (WYATT technology) was used to perform the DLS measurement.
- Dynamics software (WYATT technology) was used to control the acquisition of measurements and analyze the data.
- Example 2 characterization of the fertilizing composition
- control composition and the stock composition were also analyzed by DLS (Dynamic light scattering).
- DLS is an analytical technique based on the Brownian motion of particles, described by the Stokes-Einstein equation. It has been used to study the aggregation of humic substances.
- the DLS allowed to determine the hydrodynamic radius (Rh) and the polydispersity of humic substances in solution.
- the measured scattering intensity range was 1.36 x 10 6 - 3.14 x 10 6 counts per second (cps). All measurements were taken at a 90° detection angle and all sizes reported are averages of 15 sequential runs of 5 seconds each. Samples were analyzed 26 times for reproducibility. 20 ⁇ L of each composition was used and all solutions were adjusted to 25°C in the measuring chamber and allowed to equilibrate for 5 mins.
- a disposable microcuvette (WYATT technology) was used to perform the DLS analysis.
- Dynamics software (WYATT technology) was used to control the acquisition of measurements and analyze the data.
- HPSEC results with RI detector are shown in Figures 1 and 2 (Mw and Mn) and Figures 5 and 6.
- DLS results are shown in Figures 7 and 8.
- Figures 1 and 2 show the evolution of Mw and Mn during treatment with ozone.
- Figure 5 shows that ozonation leads to a structural modification of humic substances.
- the signal increases (around 5.2 minutes), which attests to the solubilization of certain molecules.
- the peak at 6 min is degraded in favor of several populations relating to smaller molar masses (at 6.6; 7.0; 7.7 and 8.9 minutes). It should be noted that the peak at 10 minutes corresponds to all the small molecules (size ⁇ 100 Da) in particular the salts contained in the mobile phase of the HPLC.
- Figure 6 represents the different percentages of the different families of humic substances according to the molecular mass.
- Figure 6 demonstrates an appearance of compounds with a molar mass greater than 170 kDa in the parent composition, whereas with the control composition, this family of molecules is not observed.
- Figure 6 also shows that ozonation leads to the formation of smaller humic substance molecules.
- FIG. 7 is a DLS (Dynamic light scattering) analysis which shows the evolution of the size of humic substances with increasing amounts of ozone.
- Rh hydrodynamic radius
- R mass ratio of ozone/mass of humic substances
- Figure 8A is a histogram obtained from the DLS data of Figure 7 which shows the mass distribution of humic substances as a function of their hydrodynamic radius (Rh) with increasing amounts of ozone.
- Composition "1.5.2+SN” (ozonated humic substances): 10 liters of stock composition (Example 1) were supplemented with hydroponic solutions, namely 2.5 mL of a solution of nitrogen, phosphorus and potassium (FloraGro® from General Hydroponics), 2.5 mL of a nitrogen and calcium solution (FloraMicro® from General Hydroponics) and 2.5 mL of a solution of phosphorus, potassium, magnesium and sulfur (FloraBloom® from General Hydroponics).
- hydroponic solutions namely 2.5 mL of a solution of nitrogen, phosphorus and potassium (FloraGro® from General Hydroponics), 2.5 mL of a nitrogen and calcium solution (FloraMicro® from General Hydroponics) and 2.5 mL of a solution of phosphorus, potassium, magnesium and sulfur (FloraBloom® from General Hydroponics).
- T.2+SN composition non-ozonated humic substances: 10 liters of control composition (Example 1) were supplemented with hydroponic solutions, namely 2.5 mL of a solution of nitrogen, phosphorus and potassium (FloraGro® from General Hydroponics), 2.5 mL of a nitrogen and calcium solution (FloraMicro® from General Hydroponics) and 2.5 mL of a solution of phosphorus, potassium, magnesium and sulfur (FloraBloom® from General Hydroponics).
- hydroponic solutions namely 2.5 mL of a solution of nitrogen, phosphorus and potassium (FloraGro® from General Hydroponics), 2.5 mL of a nitrogen and calcium solution (FloraMicro® from General Hydroponics) and 2.5 mL of a solution of phosphorus, potassium, magnesium and sulfur (FloraBloom® from General Hydroponics).
- Length of the leaves [0156] The length of the leaves was measured at each renewal of the compositions and at
- Table 5 Statistical analyzes / Tukey (HSD) / Analysis of the differences between the modalities with a confidence interval at 95% (leaf length).
- the length of the roots was measured at each renewal of the compositions and at D17. The results are shown in Figure 11. The average leaf length at D17 is shown in Figure 12.
- Table 7 Statistical analyzes / Tukey (HSD) / Analysis of the differences between the modalities with a 95% confidence interval (length of the roots).
- Table 8 Statistical analyzes / Newman-Keuls (SNK) / Analysis of the differences between the modalities with a confidence interval at 95% (length of the roots). The results show that the length of the roots is significantly greater with the composition comprising ozonated humic substances, compared with the composition comprising non-ozonated humic substances.
- Example 4 influence of the amount of ozone
- composition "0.5.2+SN” (ozonated humic substances ratio 0.5): corresponds to the composition "1.5.2+SN” except that the humic substances have been ozonated with a mass ratio of ozone/mass of humic substances of 0.5.
- composition “3.5.2+SN” (ozonated humic substances ratio 3.5): corresponds to the composition “1.5.2+SN” except that the humic substances have been ozonated with a mass ratio of ozone/mass of humic substances of 3.5.
- hydroponic cultures were maintained for 16 days, with a renewal of the compositions every 2-3 days.
- Example 3 The plants obtained in Example 3 were used to measure the chlorophyll and carotenoid content of the leaves by UV-Vis spectrophotometry.
- each tube was deposited on a 96-well plate in 6 replicas of 300 ⁇ L per well (that is to say 6 ⁇ 300 ⁇ L for tube 1 and 6 ⁇ 300 ⁇ L for tube 2).
- Chlorophyll B 34.09xA 645 - 15.28xA6 63
- freeze-drying is to determine whether the transition to the solid state of ozonated humic substances induces an intra and inter molecular rearrangement. If so, it can be deduced that the molecules should be used in solution and not in the form of solids.
- Figure 17 shows the curves obtained for the non-ozonated composition. The figure shows that the curves are similar, the two profiles being relatively close. Freeze-drying has little influence on non-ozonated humic substances (figure below).
- the ozonated humic substances according to the process of the invention are very stable and resist freeze-drying.
- the ozonated humic substances according to the invention can therefore be prepared both in liquid form and in solid form (freeze-dried form) without alteration.
- Example 1 The “control” and “mother” compositions of Example 1 were used. .
- the compositions were placed in vials and acidified with increasing volumes of 0.1 mol/L HCl.
- the flasks were weighed beforehand empty (m fiaC on) - All the acidified compositions were then stirred and then centrifuged. The pellets and the supernatants were separated, the pH of the supernatant was measured, the pellet was oven-dried.
- the vials were then weighed with the pellet (m C uiot+mfiacon) - The weighings were made once the samples had returned to ambient temperature.
- FIG 19 shows that the more the solution was acidified, the more the humic substances tended to precipitate. However, the non-ozonated humic substances were precipitated up to 60% while the ozonated humic substances were only precipitated at 30%. Ozonation therefore improved the solubility of humic substances in acidic pH.
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Abstract
The invention relates to a method for preparing a fertilising composition, comprising a step of treating a liquid composition having humic substances the mass-average hydrodynamic radius of the particles in solution of which, measured by dynamic light scattering (DLS), is the "average pre-treatment Rh", with an appropriate amount of oxidising agent to obtain a liquid composition having oxidised humic substances the mass-average hydrodynamic radius of the particles in solution (average post-treatment Rh) of which, measured by DLS, is greater than the average pre-treatment Rh; the invention also relates to a composition that can be obtained by the method and the use thereof.
Description
Procédé de préparation d'une composition fertilisante par oxydation Process for the preparation of a fertilizing composition by oxidation
Domaine Technique Technical area
[0001] L'invention concerne un procédé pour préparer une composition fertilisante par oxydation des substances humiques, les compositions ainsi obtenues et leur utilisation comme fertilisant. Les compositions fertilisantes préparées peuvent notamment être utilisées en agriculture, en particulier pour stimuler la croissance des plantes. The invention relates to a method for preparing a fertilizer composition by oxidation of humic substances, the compositions thus obtained and their use as a fertilizer. The fertilizing compositions prepared can in particular be used in agriculture, in particular for stimulating the growth of plants.
Technique antérieure Prior technique
[0002] Les substances humiques sont des biomolécules à caractère à la fois macromoléculaire et supramoléculaire [8]. Les substances humiques sont en grande partie responsables de la couleur brune des débris végétaux décomposés et contribuent également à la couleur brun noir de la surface des sols. Les substances humiques sont donc des composants très importants du sol car ils affectent les propriétés physiques et chimiques du sol et augmentent sa fertilité. Dans les systèmes aquatiques, tels que les rivières, les substances humiques représentent environ 50% de la matière organique dissoute. Les substances humiques en affectent le pH et l'alcalinité. [0002] Humic substances are both macromolecular and supramolecular biomolecules [8]. Humic substances are largely responsible for the brown color of decomposed plant debris and also contribute to the black-brown color of soil surfaces. Humic substances are therefore very important components of the soil as they affect the physical and chemical properties of the soil and increase its fertility. In aquatic systems, such as rivers, humic substances make up about 50% of dissolved organic matter. Humic substances affect its pH and alkalinity.
[0003] Les substances humiques sont des mélanges complexes et hétérogènes de matériaux polydispersés formés par des réactions chimiques et biochimiques lors de la décomposition et de la transformation des plantes et des résidus microbiens, résultant d'un processus connu sous le nom d'humification. La lignine des plantes et ses produits de transformation, ainsi que les polysaccharides, la mélanine, la cutine, les protéines, les lipides, les acides nucléiques, les fines particules de résidus de carbonisation, sont des composés importants participant à ce processus d'humification. [0003] Humic substances are complex and heterogeneous mixtures of polydispersed materials formed by chemical and biochemical reactions during the decomposition and transformation of plants and microbial residues, resulting in a process known as humification. Plant lignin and its transformation products, as well as polysaccharides, melanin, cutin, proteins, lipids, nucleic acids, fine particles of carbonization residues, are important compounds participating in this humification process. .
[0004] Les substances humiques sont des substances de structures très complexes qui sont toutefois considérées comme des entités chimiques à part entière. Selon la définition donnée par l'international Humic Substance Society (IHSS), les substances humiques sont des mélanges complexes et hétérogènes de matériaux polydispersés formés dans les sols, les sédiments et les eaux naturelles par des réactions biochimiques et chimiques lors de la décomposition et de la transformation de restes végétaux et microbiens (un processus appelé humification). [0004] Humic substances are substances with very complex structures which are however considered as chemical entities in their own right. According to the definition given by the International Humic Substance Society (IHSS), humic substances are complex and heterogeneous mixtures of polydisperse materials formed in soils, sediments and natural waters by biochemical and chemical reactions during decomposition and the transformation of plant and microbial remains (a process called humification).
[0005] Les substances humiques comprennent notamment les acides humiques (AH), les acides fulviques (AF) et l'humine.
[0006] Le tableau suivant est une représentation possible des propriétés physico-chimiques des acides humiques, fulviques et de l'humine selon [5]. [0005] Humic substances include in particular humic acids (HA), fulvic acids (FA) and humin. [0006] The following table is a possible representation of the physico-chemical properties of humic and fulvic acids and of humin according to [5].
[0007] [Table 1]
[0007] [Table 1]
[0008] Dans le domaine de l'agriculture, l'utilisation des substances humiques présente de nombreux avantages. En particulier, une quantité efficace de substances humiques permet d'améliorer l'état de santé des plantes et le rendement, avec notamment une meilleure utilisation de l'eau (consommation d'eau réduite pour faire la même masse de matière sèche), une augmentation de la longueur des racines après germination, un meilleur enracinement, une augmentation de la biomasse (feuilles, tiges, fleurs et fruits) avec une meilleur teneur en matières sèches, une amélioration de la précocité de la floraison et de la fructification [1]. [0008] In the field of agriculture, the use of humic substances has many advantages. In particular, an effective quantity of humic substances makes it possible to improve the state of health of the plants and the yield, with in particular a better use of water (reduced water consumption to make the same mass of dry matter), increased root length after germination, better rooting, increased biomass (leaves, stems, flowers and fruits) with better dry matter content, improved precocity of flowering and fruiting [1] .
[0009] Les déposants ont mis en évidence que l'oxydation, par exemple l'ozonation, d'une composition de substances humiques permettait d'en optimiser ses propriétés fertilisantes, par rapport à une composition de substances humiques non-oxydée. En particulier, les déposants ont mis en évidence qu'une composition de substances humiques oxydée, par exemple une composition de substances humiques ozonée, stimulait significativement l'absorption de minéraux chez la plante, par rapport à une composition de substances humiques non-oxydée, par exemple une composition de substances humiques non-ozonée. [0009] The applicants have demonstrated that the oxidation, for example ozonation, of a composition of humic substances makes it possible to optimize its fertilizing properties, compared with a composition of non-oxidized humic substances. In particular, the applicants have demonstrated that a composition of oxidized humic substances, for example an ozonated composition of humic substances, significantly stimulated the absorption of minerals in the plant, compared to a composition of non-oxidized humic substances, for example a composition of non-ozonated humic substances.
Résumé de l'invention Summary of the invention
[0010] La présente invention, qui trouve application dans le domaine de l'agriculture, vise à proposer un nouveau procédé de préparation d'une composition fertilisante par oxydation
des substances humiques, les compositions ainsi obtenues et leur utilisation comme fertilisant. The present invention, which finds application in the field of agriculture, aims to provide a new process for preparing a fertilizing composition by oxidation humic substances, the compositions thus obtained and their use as a fertilizer.
[0011] Selon un premier aspect, l'invention concerne un procédé de préparation d'une composition fertilisante, comprenant une étape de traitement d'une composition liquide de substances humiques dont le rayon hydrodynamique moyen en masse des particules en solution, mesuré par Dynamic Light Scattering (DLS), est « Rhmoyen avant traitement » avec une quantité appropriée d'agent oxydant pour obtenir une composition liquide de substances humiques oxydée dont le rayon hydrodynamique moyen en masse des particules en solution (Rhmoyen après traitement), meSUTe par DLS, CSt SUperîeUT aU Rhmoyen avant traitement-According to a first aspect, the invention relates to a method for preparing a fertilizing composition, comprising a step of treating a liquid composition of humic substances whose mass-average hydrodynamic radius of the particles in solution, measured by Dynamic Light Scattering (DLS), is “Rh average before treatment” with an appropriate amount of oxidizing agent to obtain a liquid composition of oxidized humic substances whose mass average hydrodynamic radius of the particles in solution (Rh average after treatment), measured by DLS, CSt SUPERIOR TO AVERAGE Rh BEFORE TREATMENT-
[0012] Selon un troisième aspect, l'invention concerne une composition fertilisante susceptible d'être obtenue par le procédé selon l'invention. According to a third aspect, the invention relates to a fertilizing composition obtainable by the process according to the invention.
[0013] Selon un quatrième aspect, l'invention concerne l'utilisation d'une composition selon l'invention comme stimulant de l'absorption de minéraux chez une plante, de préférence les minéraux sont choisis parmi l'azote, le phosphore, le potassium, le calcium, le magnésium et/ou le soufre. According to a fourth aspect, the invention relates to the use of a composition according to the invention as a stimulant for the absorption of minerals in a plant, preferably the minerals are chosen from nitrogen, phosphorus, potassium, calcium, magnesium and/or sulfur.
[0014] Selon un cinquième aspect, l'invention concerne un procédé de fertilisation d'une plante d'un sol ou d'un support de culture comprenant l'application à ladite plante, audit sol ou audit support de culture d'une composition selon l'invention. According to a fifth aspect, the invention relates to a method for fertilizing a plant, a soil or a growing medium comprising the application to said plant, said soil or said growing medium of a composition according to the invention.
[0015] Selon un sixième aspect, l'invention concerne un procédé de fertilisation d'une plante, d'un sol ou d'un support de culture consistant à préparer une composition fertilisante en mettant en œuvre le procédé de l'invention, et appliquer, par exemple directement après la préparation, ladite composition fertilisante à la plante, au sol ou au support de culture. [0015] According to a sixth aspect, the invention relates to a process for fertilizing a plant, a soil or a growing medium consisting in preparing a fertilizing composition by implementing the process of the invention, and applying, for example directly after the preparation, said fertilizing composition to the plant, to the soil or to the growing medium.
Description détaillée detailed description
[0016] La présente invention découle des avantages surprenants mis en évidence par les inventeurs de l'effet de l'oxydation, par exemple l'ozonation, sur le pouvoir fertilisant d'une composition liquide de substances humiques. The present invention stems from the surprising advantages demonstrated by the inventors of the effect of oxidation, for example ozonation, on the fertilizing power of a liquid composition of humic substances.
[0017] Procédé pour préparer une composition fertilisante [0017] Process for preparing a fertilizing composition
[0018] L'invention concerne un procédé de préparation d'une composition fertilisante, comprenant une étape de traitement d'une composition liquide de substances humiques dont le rayon hydrodynamique moyen en masse des particules en solution, mesuré par Dynamic Light Scattering (DLS), est « Rhmoyen avant traitement » avec une quantité appropriée d'agent oxydant pour obtenir une composition liquide de substances humiques oxydée dont
le rayon hydrodynamique moyen en masse des particules en solution (Rhmoyen après traitement), meSUre par DLS, est supérieur au Rhmoyen avant traitement’ The invention relates to a method for preparing a fertilizing composition, comprising a step of treating a liquid composition of humic substances whose mass-average hydrodynamic radius of the particles in solution, measured by Dynamic Light Scattering (DLS) , is "Rh average before treatment" with an appropriate amount of oxidizing agent to obtain a liquid composition of oxidized humic substances whose the mass-average hydrodynamic radius of the particles in solution ( average Rh after treatment), measured by DLS, is greater than the Rhmo y before treatment
[0019] La description concerne également un procédé pour améliorer les propriétés fertilisantes d'une composition de substances humiques, comprenant une étape de traitement d'une composition liquide de substances humiques dont le rayon hydrodynamique moyen en masse des particules en solution, mesuré par Dynamic Light Scattering (DLS), est « Rhmoyen avant traitement » avec une quantité appropriée d'agent oxydant pour obtenir une composition liquide de substances humiques oxydée dont le rayon hydrodynamique moyen en masse des particules en solution (Rhmoyen après traitement), mesuré par DLS, est supérieur au Rhmoyen avant traitement-[0019] The description also relates to a method for improving the fertilizing properties of a composition of humic substances, comprising a step of treating a liquid composition of humic substances whose mass-average hydrodynamic radius of the particles in solution, measured by Dynamic Light Scattering (DLS), is "Rh avg before treatment" with an appropriate amount of oxidizing agent to obtain a liquid composition of oxidized humic substances whose mass-average hydrodynamic radius of the particles in solution (Rh avg after treatment), measured by DLS, is higher than the average Rh n before treatment-
[0020] Dans un mode de réalisation particulier, le procédé comprend les étapes suivantes : a) obtenir une composition liquide de substances humiques dont le rayon hydrodynamique moyen en masse des particules en solution, mesuré par Dynamic Light Scattering (DLS), est « Rhmoyen avant traitement * , b) traiter la composition liquide de substances humiques avec une quantité appropriée d'agent oxydant pour obtenir une composition liquide de substances humiques oxydée dont le rayon hydrodynamique moyen en masse des particules en solution (Rhmoyen après traitement), meSUre par DLS, est supérieur au Rhmoyen avant traitement-In a particular embodiment, the method comprises the following steps: a) obtaining a liquid composition of humic substances whose mass-average hydrodynamic radius of the particles in solution, measured by Dynamic Light Scattering (DLS), is “Rh average before treatment * , b) treating the liquid composition of humic substances with an appropriate amount of oxidizing agent to obtain an oxidized liquid composition of humic substances whose mass-average hydrodynamic radius of the particles in solution (average Rh n after treatment), MEASUREMENT by DLS, is higher than the Rhaverage before treatment-
[0021] Les termes « composition(s) fertilisante(s) », « substance(s) fertilisante(s) » ou « produit(s) fertilisant(s) » sont synonymes et désignent une composition, une substance, ou un mélange de substances, d'origine naturelle ou d'origine synthétique, appliqués ou destinés à être appliqués sur des végétaux ou leur rhizosphère ou sur des champignons ou leur mycosphère, seuls ou mélangés avec une autre matière, dans le but d'apporter aux végétaux ou aux champignons des éléments nutritifs ou d'améliorer leur efficacité nutritionnelle ou de stimuler les processus de nutrition des végétaux indépendamment des éléments nutritifs qu'il contient, dans le seul but d'améliorer une ou plusieurs des caractéristiques des végétaux ou de leur rhizosphère comme l'efficacité d'utilisation des éléments nutritifs, la tolérance au stress abiotique, les caractéristiques qualitatives ou la disponibilité des éléments nutritifs confinés dans le sol et la rhizosphère. Cette définition est dérivée de la définition du Règlement de l'Union Européenne n° 2019 1009. The terms "fertilizing composition(s)", "fertilizing substance(s)" or "fertilizing product(s)" are synonyms and designate a composition, a substance, or a mixture substances, of natural or synthetic origin, applied or intended to be applied to plants or their rhizosphere or to fungi or their mycosphere, alone or mixed with another material, with the aim of providing plants or to fungi of nutrients or to improve their nutritional efficiency or to stimulate plant nutrition processes independently of the nutrients it contains, for the sole purpose of improving one or more of the characteristics of plants or their rhizosphere such as nutrient use efficiency, abiotic stress tolerance, quality characteristics or availability of nutrients confined to the soil and rhizosphere. This definition is derived from the definition in European Union Regulation No. 2019 1009.
[0022] L'art antérieur décrit déjà des procédés de traitement des substances humiques avec des agents oxydants tels que l'ozone [2-4]. Néanmoins, ces procédés ne concernent pas la préparation de compositions fertilisantes. Les procédés d'oxydation des substances humiques décrits dans l'art antérieur ont pour but de dégrader lesdites substances
notamment dans un but de nettoyage. Par conséquent, les substances humiques sont traitées avec des quantités d'agent oxydant très importantes qui dégradent fortement les substances humiques. A l'inverse de ce qui est mis en œuvre dans l'art antérieur, l'oxydation dans le cadre de l'invention est très douce. The prior art already describes methods for treating humic substances with oxidizing agents such as ozone [2-4]. However, these methods do not relate to the preparation of fertilizing compositions. The oxidation processes of humic substances described in the prior art are intended to degrade said substances especially for cleaning purposes. Consequently, the humic substances are treated with very large quantities of oxidizing agent which strongly degrade the humic substances. Contrary to what is implemented in the prior art, the oxidation in the context of the invention is very gentle.
[0023] De façon surprenante, les inventeurs se sont aperçus qu'une composition liquide de substances humiques traitées avec une quantité appropriée d'agent oxydant, par exemple une faible quantité d'ozone, avait des propriétés fertilisantes supérieures à celles d'une composition de substances humiques non traitée. [0023] Surprisingly, the inventors noticed that a liquid composition of humic substances treated with an appropriate quantity of oxidizing agent, for example a small quantity of ozone, had fertilizing properties superior to those of a composition of untreated humic substances.
[0024] Les inventeurs ont en effet montré qu'il était possible d'améliorer les propriétés fertilisantes d'une composition liquide de substances humiques en traitant ladite composition avec une quantité appropriée d'agent oxydant, par exemple une quantité appropriée d'ozone. Les inventeurs se sont en effet aperçus, de façon tout à fait inattendue, qu'une oxydation douce d'une composition liquide de substances humiques augmente le rayon hydrodynamique moyen en masse des particules en solution (Rhmoyen), mesuré par DLS, et que cette augmentation du Rhmoyen était associée à une augmentation des propriétés fertilisantes de ladite composition. The inventors have in fact shown that it is possible to improve the fertilizing properties of a liquid composition of humic substances by treating said composition with an appropriate amount of oxidizing agent, for example an appropriate amount of ozone. The inventors have in fact noticed, quite unexpectedly, that mild oxidation of a liquid composition of humic substances increases the mass-average hydrodynamic radius of the particles in solution ( average Rh), measured by DLS, and that this increase in the average Rh was associated with an increase in the fertilizing properties of said composition.
[0025] Ainsi, pour améliorer les propriétés fertilisantes d'une composition liquide de substances humiques, la quantité d'agent oxydant doit être adaptée pour obtenir une composition liquide de substances humiques oxydée dont le rayon hydrodynamique moyen en masse des particules en solution (Rhmoyen après traitement), mesuré par DLS, est supérieur au Rhmoyen avant traitement, mesure par DLS. Thus, to improve the fertilizing properties of a liquid composition of humic substances, the amount of oxidizing agent must be adapted to obtain a liquid composition of oxidized humic substances whose mass-average hydrodynamic radius of the particles in solution (Rh average after treatment), measured by DLS, is higher than the average Rh before treatment, measured by DLS.
[0026] Les procédés d'oxydation des substances humiques décrits dans l'art antérieur n'ont pas permis de mettre en évidence ce phénomène d'augmentation du Rhmoyen car, comme expliqué ci-dessus, les substances humiques sont traitée avec des quantités d'agent oxydant largement supérieures aux quantités utilisées pour la mise en œuvre du procédé selon l'invention. [0026] The processes for the oxidation of humic substances described in the prior art have not made it possible to highlight this phenomenon of increasing the average Rh because, as explained above, the humic substances are treated with quantities of oxidizing agent much greater than the quantities used for the implementation of the method according to the invention.
[0027] Mesure du rayon hydrodynamique moyen en masse des particules en solution (Rhmoyen) par DLS [0027] Measurement of the average hydrodynamic radius by mass of the particles in solution (average Rh n) by DLS
[0028] La DLS (Dynamic Light Scattering) est une technique permettant d'analyser la taille des particules présentes dans une composition liquide, en mesurant le Rhmoyen- Il s'agit de la technique de mesure la plus couramment utilisée pour analyser la taille des particules dans la gamme nanométrique. DLS (Dynamic Light Scattering) is a technique for analyzing the size of particles present in a liquid composition, by measuring the average Rh - This is the most commonly used measurement technique for analyzing the size particles in the nanometer range.
[0029] Brièvement, le principe de la DLS est basé sur les mesures de fluctuation d'intensité de lumière diffusées dues au mouvement Brownien des particules. Plus une particule est grosse
plus son déplacement va être lent. Ce phénomène est décrit par la loi de Stokes-Einstein. En pratique, le faisceau laser incident va traverser la composition liquide analysée. Le rayon diffusé à 90° (angle le plus communément utilisé) va être fonction de la morphologie des particules. La variation d'intensité du rayon diffusé donne des informations sur la diffusion des particules et donc sur leur taille [11]. Les valeurs de Rhmoyen se calculent en pondérant par le pourcentage en masse de chaque population. [0029] Briefly, the principle of DLS is based on measurements of scattered light intensity fluctuation due to Brownian motion of the particles. The larger a particle the slower its movement will be. This phenomenon is described by the Stokes-Einstein law. In practice, the incident laser beam will pass through the analyzed liquid composition. The ray scattered at 90° (the most commonly used angle) will depend on the morphology of the particles. The intensity variation of the scattered ray gives information on the diffusion of the particles and therefore on their size [11]. The values of Rh mean are calculated by weighting by the percentage by mass of each population.
[0030] Les mesures de DLS peuvent être réalisées avec un Dynapro Nanostar (WYATT technology) équipé d'un laser ( = 662 nm). La plage d'intensité de diffusion mesurée peut être de 1,36.106 à 3,14.106 coups par seconde (cps). Toutes les mesures peuvent être prises à un angle de détection de 90° et toutes les tailles rapportées sont des moyennes de 15 séquences de 5 s chacune. Un protocole de DLS qui peut être mis en œuvre dans le cadre de l'invention est décrit dans les exemples. The DLS measurements can be carried out with a Dynapro Nanostar (WYATT technology) equipped with a laser (=662 nm). The measured scatter intensity range can be 1.36 x 106 to 3.14 x 106 counts per second (cps). All measurements can be taken at a detection angle of 90° and all reported sizes are averages of 15 sequences of 5 s each. A DLS protocol that can be implemented within the scope of the invention is described in the examples.
[0031] Dans le cadre de l'invention, les analyses DLS permettent de mesurer le rayon hydrodynamique moyen en masse des particules en solution, c'est-à-dire le rayon hydrodynamique moyen en masse des particules de la fraction soluble de la composition liquide de substances humiques. In the context of the invention, the DLS analyzes make it possible to measure the mass-average hydrodynamic radius of the particles in solution, that is to say the mass-average hydrodynamic radius of the particles of the soluble fraction of the composition. liquid of humic substances.
[0032] Comme expliqué ci-après, certaines compositions liquides de substances humiques peuvent comprendre une quantité non négligeable de matières insolubles. C'est le cas, par exemple, lorsque la composition liquide de substances humiques est préparée à partir d'une matière brute (ex. de la tourbe) mélangée à de l'eau. Dans ce cas particulier, l'Homme du métier sait qu'il doit effectuer les mesures du Rhmoyen par DLS sur la fraction soluble de la composition liquide de substances humiques. La fraction soluble peut être obtenue très facilement en la séparant de la fraction insoluble, par exemple par décantation, filtration ou par centrifugation. Un exemple de séparation de la fraction soluble et de la fraction insoluble consiste à centrifuger à 4800 rpm pendant 30 minutes. Ces paramètres permettent de précipiter la matière insoluble sans toutefois précipiter les particules solubles, notamment les substances humiques solubles de grande taille. [0032] As explained below, certain liquid compositions of humic substances may comprise a non-negligible amount of insoluble matter. This is the case, for example, when the liquid composition of humic substances is prepared from a raw material (eg peat) mixed with water. In this particular case, the person skilled in the art knows that he must carry out the measurements of the average Rh by DLS on the soluble fraction of the liquid composition of humic substances. The soluble fraction can be obtained very easily by separating it from the insoluble fraction, for example by decantation, filtration or by centrifugation. An example of separation of the soluble fraction and the insoluble fraction consists in centrifuging at 4800 rpm for 30 minutes. These parameters make it possible to precipitate the insoluble matter without however precipitating the soluble particles, in particular the large soluble humic substances.
[0033] Composition liquide de substances humiques [0033] Liquid composition of humic substances
[0034] La composition liquide de substances humiques à oxyder peut être obtenue à partir de substances humiques naturelles. Il peut par exemple s'agir d'une matière brute contenant des substances humiques, par exemple de la tourbe, de la léonardite, du lignite, de la houille ou de l'anthracite. Ainsi, une composition liquide de substances humiques peut être une composition liquide de tourbe, de léonardite, de lignite, de houille ou d'anthracite.
[0035] La tourbe est une matière organique fossile formée par accumulation sur de longues périodes de temps de matière organique morte, essentiellement des végétaux, dans un milieu saturé en eau. La tourbe forme la majeure partie des sols des tourbières. La tourbe peut être plus ou moins riche en substances humiques selon le degré de décomposition. Le degré de décomposition de la tourbe est classé selon l'échelle de Von Post qui va de H1 (Tourbe la moins décomposée) H 10 (tourbe la plus décomposée) [9]. La tourbe humus, c'est-à-dire une tourbe classée de H6 à H 10 selon l'échelle de Von Post, est la tourbe préférée pour la mise en œuvre du procédé selon l'invention car elle est plus riche en substances humique que la tourbe classée de H1 à H5 selon l'échelle de Von Post. The liquid composition of humic substances to be oxidized can be obtained from natural humic substances. It may for example be a raw material containing humic substances, for example peat, leonardite, lignite, hard coal or anthracite. Thus, a liquid composition of humic substances can be a liquid composition of peat, leonardite, lignite, coal or anthracite. [0035] Peat is fossil organic matter formed by accumulation over long periods of time of dead organic matter, essentially plants, in an environment saturated with water. Peat forms most of the soils in peatlands. Peat can be more or less rich in humic substances depending on the degree of decomposition. The degree of decomposition of peat is classified according to the Von Post scale which goes from H1 (least decomposed peat) to H 10 (most decomposed peat) [9]. Humus peat, that is to say a peat classified from H6 to H 10 according to the Von Post scale, is the preferred peat for implementing the process according to the invention because it is richer in humic substances. than peat classified from H1 to H5 according to the Von Post scale.
[0036] La léonardite est une roche qui peut contenir plus de 90% en poids de substances humiques. Cette roche a subi une dégradation plus poussée que la tourbe, mais moins poussée que la houille. [0036] Leonardite is a rock which can contain more than 90% by weight of humic substances. This rock has undergone more extensive degradation than peat, but less extensive than coal.
[0037] Le lignite est une roche sédimentaire composée de restes fossiles de plantes. C'est une roche intermédiaire entre la tourbe et la houille. Lignite is a sedimentary rock composed of the fossil remains of plants. It is an intermediate rock between peat and coal.
[0038] La houille est une roche carbonée sédimentaire correspondant à une qualité spécifique de charbon, intermédiaire entre le lignite et l'anthracite. De couleur noirâtre, elle provient de la carbonisation d'organismes végétaux. Coal is a sedimentary carbonaceous rock corresponding to a specific quality of coal, intermediate between lignite and anthracite. Blackish in color, it comes from the carbonization of plant organisms.
[0039] L'anthracite est une roche sédimentaire d'origine organique. C'est une variété de charbon grise, noirâtre et brillante extraite des mines. Anthracite is a sedimentary rock of organic origin. It is a grey, blackish and shiny variety of coal extracted from the mines.
[0040] La composition liquide de substances humiques à oxyder peut également être obtenue à partir de substances humiques synthétiques. Les substances humiques synthétiques peuvent par exemple résulter d'un processus de synthèse [7] ou de la transformation de substances humiques naturelles, notamment par hémisynthèse. The liquid composition of humic substances to be oxidized can also be obtained from synthetic humic substances. Synthetic humic substances can for example result from a process of synthesis [7] or from the transformation of natural humic substances, in particular by hemisynthesis.
[0041] Les substances humiques peuvent également être extraites de matières organiques (tourbe, léonardite, lignite, houille, anthracite, sols riches en substances humiques, composts de déchets végétaux, etc.) à l'aide d'un agent alcalin tel que l'hydroxyde de sodium (NaOH) ou l'hydroxyde de potassium (KOH) et éventuellement soumises à une purification [10]. Les substances humiques peuvent notamment être extraites et/ou purifiées par des procédés bien connus de l'Homme du métier [5] [10]. [0041] Humic substances can also be extracted from organic matter (peat, leonardite, lignite, hard coal, anthracite, soils rich in humic substances, composts of plant waste, etc.) using an alkaline agent such as sodium hydroxide (NaOH) or potassium hydroxide (KOH) and optionally subjected to purification [10]. Humic substances can in particular be extracted and/or purified by methods well known to those skilled in the art [5] [10].
[0042] La composition liquide de substances humiques à oxyder englobe les compositions liquides d'un sel de substances humiques. Parmi les sels préférés, on peut notamment citer les sels d'ammonium, les sels sodiques, les sels potassiques. De préférence, on utilise un sel potassique de substances humiques, tel que les humâtes de potassium ou le sel potassique de substances humiques. Des sels de substances humiques sont vendus dans le commerce.
On peut par exemple citer le sel potassique de substances humiques commercialisé par la société Humatex sous la marque Dralig® (CAS 68514-28-3). Le produit Dralig® est préparé à partir de substances humiques extraites de l'oxyhumolite naturel tchèque à grand contenu de substances humiques. The liquid composition of humic substances to be oxidized includes liquid compositions of a salt of humic substances. Among the preferred salts, mention may in particular be made of ammonium salts, sodium salts, potassium salts. Preferably, a potassium salt of humic substances is used, such as potassium humates or potassium salt of humic substances. Salts of humic substances are sold commercially. Mention may be made, for example, of the potassium salt of humic substances marketed by the company Humatex under the brand name Dralig® (CAS 68514-28-3). The Dralig® product is prepared from humic substances extracted from natural Czech oxyhumolite with a high content of humic substances.
[0043] L'homme du métier n'aura aucune difficulté à préparer une composition liquide de substances humiques à partir de substances humiques ou d'un sel de substances humiques. Il suffit par exemple de mélanger des substances humiques ou un sel de substances humiques avec un solvant tel que de l'eau. La Figure 5 montre le profil HPSEC d'une composition liquide de substances humiques qui peut être utilisée dans le procédé selon l'invention (en pointillés). [0043] A person skilled in the art will have no difficulty in preparing a liquid composition of humic substances from humic substances or from a salt of humic substances. It suffices, for example, to mix humic substances or a salt of humic substances with a solvent such as water. Figure 5 shows the HPSEC profile of a liquid composition of humic substances which can be used in the method according to the invention (in dotted lines).
[0044] L'Homme du métier peut facilement adapter la concentration en substances humiques de la composition liquide selon les besoins, par exemple en adaptant la quantité de solvant. La concentration en substances humiques de la composition liquide n'est pas limitée. Elle peut par exemple être comprise entre 100 et 1000 mg/L, de préférence entre 400 et 500 mg/L, par exemple environ 550 mg/L. [0044] A person skilled in the art can easily adapt the concentration of humic substances in the liquid composition as required, for example by adapting the amount of solvent. The concentration of humic substances in the liquid composition is not limited. It can for example be between 100 and 1000 mg/L, preferably between 400 and 500 mg/L, for example approximately 550 mg/L.
[0045] La pureté en substances humiques de la composition liquide de substances humiques peut également varier, par exemple en fonction de la source utilisée. Bien entendu, la tourbe est généralement moins pure en substances humiques que la léonardite ou qu'une poudre commerciale de substances humiques, tel que le produit Dralig® (CAS 68514-28-3). Dans un mode de réalisation particulier, la composition liquide de substances humiques à traiter comprend au moins 50% en masse sèche de substances humiques, par exemple au moins 60%, au moins 70%, au moins 80%, au moins 85%, au moins 90%, au moins 95%, ou au moins 99% en masse sèche de substances humiques. The humic substance purity of the liquid composition of humic substances can also vary, for example depending on the source used. Of course, peat is generally less pure in humic substances than leonardite or a commercial powder of humic substances, such as the product Dralig® (CAS 68514-28-3). In a particular embodiment, the liquid composition of humic substances to be treated comprises at least 50% by dry mass of humic substances, for example at least 60%, at least 70%, at least 80%, at least 85%, at least least 90%, at least 95%, or at least 99% by dry mass of humic substances.
[0046] Traitement avec /'agent oxydant [0046] Treatment with the oxidizing agent
[0047] La quantité appropriée d'agent oxydant nécessaire à la mise en œuvre du procédé peut dépendre de différents paramètres, tel que la nature des substances humiques, la pureté de la composition liquide de substances humiques, la quantité de substances humiques à traiter, la nature de l'agent oxydant, etc. Néanmoins, l'Homme du métier n'aura aucune difficulté à déterminer la quantité appropriée d'agent oxydant en mesurant simplement le Rhmoyen par DLS, par exemple en suivant l'évolution du Rhmoyen avec des quantités croissantes d'un agent oxydant. Ces mesures peuvent par exemple permettre de définir une quantité d'agent oxydant à ne pas dépasser pour que le Rhmoyen après traitement, mesuré par DLS, soit supérieur au Rhmoyen avant traitement, mesuré par DLS. Ainsi, il est facile de déterminer la
quantité appropriée d'agent oxydant pour une composition liquide de substances humiques donnée et un agent oxydant donné. The appropriate amount of oxidizing agent necessary for the implementation of the method can depend on various parameters, such as the nature of the humic substances, the purity of the liquid composition of humic substances, the quantity of humic substances to be treated, the nature of the oxidizing agent, etc. Nevertheless, those skilled in the art will have no difficulty in determining the appropriate amount of oxidizing agent by simply measuring the average Rh by DLS , for example by following the evolution of the average Rh with increasing amounts of an agent. oxidant. These measurements can for example make it possible to define a quantity of oxidizing agent not to be exceeded so that the average Rh n after treatment, measured by DLS, is greater than the average Rh n before treatment, measured by DLS. Thus, it is easy to determine the appropriate amount of oxidizing agent for a given liquid composition of humic substances and a given oxidizing agent.
[0048] La Figure 8B montre l'évolution du Rhmoyen, mesuré par DLS, avec des quantités croissantes d'ozone. [0048] Figure 8B shows the evolution of the average Rh, measured by DLS, with increasing amounts of ozone.
[0049] La quantité d'agent oxydant peut être facilement adaptée de manière à obtenir, dans la mesure du possible, un Rhmoyen, mesuré par DLS, dont la valeur est souhaitée. Par exemple, la quantité d'agent oxydant est choisie pour obtenir une valeur maximale de Rhmoyen, mesuré par DLS. The amount of oxidizing agent can be easily adapted so as to obtain, as far as possible, an average Rh, measured by DLS, the value of which is desired. For example, the amount of oxidizing agent is chosen to obtain a maximum value of average Rh, measured by DLS.
[0050] La détermination d'une quantité appropriée d'agent oxydant pour la mise en œuvre du procédé de l'invention est donc à la portée de l'Homme du métier et ne présente aucune difficulté particulière. Toutefois, certaines compositions liquides de substances humiques peuvent comprendre une quantité non négligeable la matière insoluble. C'est le cas, par exemple, lorsqu'on traite une matière brute (ex. de la tourbe) mélangée à de l'eau. Dans ce cas particulier, l'Homme du métier sait que pour analyser les particules en solution par DLS, il est nécessaire d'effectuer les mesures de DLS sur la fraction soluble de la composition liquide comprenant des substances humiques. La fraction soluble peut être obtenue très facilement en la séparant de la fraction insoluble, par exemple par filtration ou par centrifugation, comme détaillé auparavant dans description. The determination of an appropriate quantity of oxidizing agent for the implementation of the method of the invention is therefore within the reach of those skilled in the art and does not present any particular difficulty. However, some liquid compositions of humic substances may include a significant amount of insoluble matter. This is the case, for example, when treating a raw material (eg peat) mixed with water. In this particular case, those skilled in the art know that in order to analyze the particles in solution by DLS, it is necessary to carry out the DLS measurements on the soluble fraction of the liquid composition comprising humic substances. The soluble fraction can be obtained very easily by separating it from the insoluble fraction, for example by filtration or by centrifugation, as detailed previously in the description.
[0051] Bien évidemment, une fois que la quantité d'agent oxydant appropriée a été déterminée, il n'est plus nécessaire de suivre le ou les paramètres de DLS susmentionnés pour mettre en œuvre le procédé de l'invention. Il suffit simplement de traiter la composition liquide de substances humiques avec une quantité d'agent oxydant appropriée. Of course, once the appropriate amount of oxidizing agent has been determined, it is no longer necessary to follow the aforementioned DLS parameter(s) to implement the method of the invention. It is enough simply to treat the liquid composition of humic substances with an appropriate amount of oxidizing agent.
[0052] Avantageusement, le Rhmoyen après traitement eSt 3U mOÏnS 2 fOÏS Supérieur aU Rhmoyen avant traitement, de préférence au moins 3 fois, 4 fois, 5 fois, 6 fois supérieur, par exemple au moinsAdvantageously, the average Rh after treatment is 3U minus 2 times higher than the average Rh before treatment, preferably at least 3 times, 4 times, 5 times, 6 times higher, for example at least
7 fois supérieur, 8 fois supérieur, 9 fois supérieur, 10 fois supérieur, 15 fois supérieur, 20 fois supérieur, 25 fois supérieur, 30 fois supérieur, 35 fois supérieur, 40 fois supérieur, 45 fois supérieur, 50 fois supérieur, 55 fois supérieur, 60 fois supérieur, 65 fois supérieur, 70 fois supérieur. 7 times, 8 times, 9 times, 10 times, 15 times, 20 times, 25 times, 30 times, 35 times, 40 times, 45 times, 50 times, 55 times higher, 60 times higher, 65 times higher, 70 times higher.
[0053] Le temps de traitement n'est pas limitatif tant que l'on obtient un Rhmoyen après traitement supérieur au Rhmoyen avant traitement- En général, la durée du traitement est comprise entre 5 minute et 10 heures. En fait, la quantité d'agent oxydant, et éventuellement la durée du traitement, sont adaptées à la quantité initiale de substances humiques et à l'agent oxydant utilisé. La durée du traitement optimale pourra donc être facilement adaptée par l'Homme du métier
[0054] Dans un mode de réalisation particulier, la proportion massique des particules en solution ayant un rayon hydrodynamique compris entre 15 nm et 10000 nm de la composition de substances humiques oxydée, mesurée par DLS, est au moins 2 fois supérieure à la proportion massique des particules en solution ayant un rayon hydrodynamique compris entre 15 nm et 10000 nm de la composition de substances humiques avant oxydation, de préférence au moins 2,5 fois, par exemple au moins 3 fois, au moins 3,5 fois, au moins 4 fois, au moins 4,5 fois, au moins 5 fois, au moins 6 fois supérieure. The treatment time is not limiting as long as one obtains an average Rh after treatment higher than the average Rh before treatment. In general, the duration of the treatment is between 5 minutes and 10 hours. In fact, the quantity of oxidizing agent, and possibly the duration of the treatment, are adapted to the initial quantity of humic substances and to the oxidizing agent used. The duration of the optimal treatment can therefore be easily adapted by the person skilled in the art. In a particular embodiment, the mass proportion of the particles in solution having a hydrodynamic radius of between 15 nm and 10,000 nm of the composition of oxidized humic substances, measured by DLS, is at least 2 times greater than the mass proportion particles in solution having a hydrodynamic radius between 15 nm and 10000 nm of the composition of humic substances before oxidation, preferably at least 2.5 times, for example at least 3 times, at least 3.5 times, at least 4 times, at least 4.5 times, at least 5 times, at least 6 times.
[0055] Les Figures 7 et 8A montrent l'évolution de la proportion massique des particules en solution ayant un rayon hydrodynamique compris entre 15 nm et 10000 nm, mesurée par DLS, avec des quantités croissantes d'ozone. Figures 7 and 8A show the evolution of the mass proportion of particles in solution having a hydrodynamic radius between 15 nm and 10,000 nm, measured by DLS, with increasing amounts of ozone.
[0056] Dans un autre mode de réalisation particulier, la masse molaire moyenne en poids en solution (ci-après « Mw ») (exprimée en Da) de la composition liquide de substances humiques oxydée, est supérieure à la Mw de la composition de substances humiques avant oxydation. In another particular embodiment, the weight-average molar mass in solution (hereinafter "Mw") (expressed in Da) of the liquid composition of oxidized humic substances is greater than the Mw of the composition of humic substances before oxidation.
[0057] Mw peut être calculé selon la formule suivante :
avec hi = intensité du signal HPLC, et [0057] Mw can be calculated according to the following formula: with hi = HPLC signal intensity, and
Mi = masse molaire relative au temps de rétention obtenu en HPLC (issue de la calibration de colonne réalisée avec des standards). Mi = molar mass relative to the retention time obtained in HPLC (resulting from the column calibration carried out with standards).
[0058] Le calcul de Mw est généralement fait automatiquement par l'appareil HPLC. Pour calculer Mw, il est possible de le faire manuellement ou d'utiliser un logiciel tel que le logiciel Chroméléon qui est un logiciel d'acquisition de donnée HPLC. The calculation of Mw is generally done automatically by the HPLC device. To calculate Mw, it is possible to do it manually or to use software such as the Chromeleon software which is an HPLC data acquisition software.
[0059] Les Figures 1 et 2 illustrent l'augmentation de Mw avec des quantités croissantes d'ozone. [0059] Figures 1 and 2 illustrate the increase in Mw with increasing amounts of ozone.
[0060] L'agent oxydant est avantageusement choisi parmi l'ozone, les ultra-violets et/ou le peroxyde d'hydrogène. Les agents oxydants peuvent être utilisés seuls ou combinés entre eux pour obtenir la composition souhaitée. The oxidizing agent is advantageously chosen from ozone, ultraviolet rays and/or hydrogen peroxide. The oxidizing agents can be used alone or combined with each other to obtain the desired composition.
[0061] L 'agent oxydant est l'ozone [0061] The oxidizing agent is ozone
[0062] L'ozone est un agent oxydant particulièrement intéressant car facile à utiliser, peu cher et dont la quantité est facile à contrôler pour la mise en œuvre du procédé de l'invention.
[0063] L'ozone étant instable, il est produit sur le lieu de consommation. A l'échelle industrielle, l'ozone est généralement produit par décharges électriques dans des générateurs tubulaires. Cette production est due à un générateur d'ozone, qui est essentiellement composé de deux électrodes conductrices maintenues en regard l'une de l'autre. L'air ou l'oxygène est comprimé, puis séché, et passe entre ces deux électrodes où il est soumis à un effluve électrique dans un champ de courant alternatif à haute tension. Une partie de l'oxygène se transforme en ozone. Un circuit de refroidissement absorbe l'excès de chaleur produite par la décharge. Pour homogénéiser la décharge, l'une des électrodes ou parfois les deux, sont recouvertes d'un diélectrique à permittivité élevé, d'épaisseur uniforme réalisant une surface équipotentielle. Généralement, les diélectriques mis en œuvre sont des verres dont la permittivité varie, selon la composition chimique, de 4 à 6,5. L'ozone est donc produit en faisant circuler lentement dans l'espace restant un fluide oxygéné et en créant dans l'espace gazeux une tension alternative sinusoïdale d'amplitude suffisamment élevée. [0062] Ozone is a particularly advantageous oxidizing agent because it is easy to use, inexpensive and the quantity of which is easy to control for the implementation of the method of the invention. Since ozone is unstable, it is produced at the place of consumption. On an industrial scale, ozone is generally produced by electrical discharges in tubular generators. This production is due to an ozone generator, which is essentially composed of two conductive electrodes held facing each other. The air or oxygen is compressed, then dried, and passes between these two electrodes where it is subjected to an electric discharge in a high voltage alternating current field. Some of the oxygen turns into ozone. A cooling circuit absorbs the excess heat produced by the discharge. To homogenize the discharge, one of the electrodes or sometimes both, are covered with a dielectric with high permittivity, of uniform thickness producing an equipotential surface. Generally, the dielectrics used are glasses whose permittivity varies, depending on the chemical composition, from 4 to 6.5. Ozone is therefore produced by causing an oxygenated fluid to slowly circulate in the remaining space and by creating in the gaseous space a sinusoidal alternating voltage of sufficiently high amplitude.
[0064] L'ozone peut être de l'ozone gazeux produit à partir d'oxygène, par exemple à partir d'air, à partir d'air enrichi en oxygène ou à partir d'oxygène pur. Un ozoneur adapté à la mise en œuvre de l'invention est le Lab2b ou CFS1 de la société Ozonia (Suez). The ozone can be gaseous ozone produced from oxygen, for example from air, from oxygen-enriched air or from pure oxygen. An ozone generator suitable for implementing the invention is Lab2b or CFS1 from the company Ozonia (Suez).
[0065] Comme détaillé ci-dessus, la quantité d'ozone est adaptée pour obtenir un Rhmoyen après traitement supérieur au Rhmoyen avant traitement- La quantité d'ozone va donc essentiellement dépendre de la quantité de substances humiques présentes dans la composition. Dans un mode de réalisation particulier, le ratio masse d'ozone/masse de substances humiques est inférieur à 10. La masse d'ozone correspond à la masse d'ozone appliquée à la composition liquide de substances humiques. La masse de substances humiques correspond à la masse de substances humiques présente dans la composition liquide de substances humiques à ozoner, c'est-à-dire la masse de substances humiques avant l'ozonation. La masse de substances humiques peut être déterminée par HPLC. Le ratio masse d'ozone/masse de substances humiques peut par exemple être inférieur à 9, inférieur à 8, inférieur à 7, inférieur à 6, inférieur à 5, inférieur à 4,5, inférieur à 4, inférieur à 3,5, par exemple compris entre 0,2 et 10, compris entre 0,2 et 9, compris entre 0,2 et 8, compris entre 0,2 et 7, compris entre 0,2 et 6, compris entre 0,2 et 5, compris entre 0,2 et 3,5, compris entre 0,5 et 3,5, compris entre 1 et 10, compris entre 1 et 9, compris entre 1 et 8, compris entre 1 et 7, compris entre 1 et 6, compris entre 1 et 5, compris entre 1 et 4, compris entre 1 et 3, compris entre 1 et 2, par exemple est égal à environ 1,5. As detailed above, the quantity of ozone is adapted to obtain an average Rh after treatment higher than the average Rh before treatment. The quantity of ozone will therefore essentially depend on the quantity of humic substances present in the composition. In a particular embodiment, the mass of ozone/mass of humic substances ratio is less than 10. The mass of ozone corresponds to the mass of ozone applied to the liquid composition of humic substances. The mass of humic substances corresponds to the mass of humic substances present in the liquid composition of humic substances to be ozonated, that is to say the mass of humic substances before ozonation. The mass of humic substances can be determined by HPLC. The ratio mass of ozone/mass of humic substances can for example be less than 9, less than 8, less than 7, less than 6, less than 5, less than 4.5, less than 4, less than 3.5 , for example between 0.2 and 10, between 0.2 and 9, between 0.2 and 8, between 0.2 and 7, between 0.2 and 6, between 0.2 and 5 , between 0.2 and 3.5, between 0.5 and 3.5, between 1 and 10, between 1 and 9, between 1 and 8, between 1 and 7, between 1 and 6 , between 1 and 5, between 1 and 4, between 1 and 3, between 1 and 2, for example is equal to about 1.5.
[0066] Tout type d'ozoneur peut être utilisé dans la mise en œuvre du procédé selon l'invention. Par exemple, des ozoneurs à air (air séché avec un point de rosée de -50°C à - 70°C), les ozoneurs à basse fréquence (50 Hz) dont la production unitaire par heure est
environ de 1 à 3 kg d'ozone et les ozoneurs à moyenne fréquence (150 à 600 Hz) dont la production unitaire peut atteindre 60 kg par heure. C'est dans ces derniers que l'ozone est produit et injecté dans un réacteur, où est préalablement injectée la composition à traiter. On peut par exemple citer l'ozoneur CFS1 de chez Ozonia qui est particulièrement adapté à la mise en œuvre du procédé selon l'invention. On peut également utiliser les excimères qui sont de bons générateurs d'ozone. Any type of ozone generator can be used in the implementation of the method according to the invention. For example, air ozone generators (dried air with a dew point of -50°C to - 70°C), low frequency ozone generators (50 Hz) whose unit production per hour is approximately 1 to 3 kg of ozone and medium frequency ozone generators (150 to 600 Hz) whose unit production can reach 60 kg per hour. It is in the latter that the ozone is produced and injected into a reactor, where the composition to be treated is injected beforehand. Mention may be made, for example, of the CFS1 ozone generator from Ozonia, which is particularly suitable for implementing the method according to the invention. It is also possible to use excimers which are good generators of ozone.
[0067] Il existe plusieurs sortes de réacteurs. Par exemple, des réacteurs équipés de diffuseurs poreux, des réacteurs équipés de turbines, et des réacteurs à flux piston tube en U, équipé d'une pompe pour vaincre les pertes de charge. There are several kinds of reactors. For example, reactors equipped with porous diffusers, reactors equipped with turbines, and U-tube piston flow reactors, equipped with a pump to overcome pressure drops.
[0068] Avant d'être injecté dans la composition liquide de substances humiques, le gaz contenant l'ozone peut être divisé en "micro-bulles", i.e. bullage de l'ozone, à l'aide de divers matériels, par exemple à l'aide de diffuseurs poreux disposés en partie basse des cuves ou colonnes ou d'un hydro-injecteur assurant la pulvérisation du gaz directement dans la composition à traiter. Ce dernier présente l'avantage d'un meilleur taux de dissolution de l'ozone dans la composition traitée. Ainsi, dans un mode de réalisation préféré, le traitement est réalisé par bullage de l'ozone dans la composition liquide de substances humiques, par exemple par bullage de 8 x W4 à 0,5 gramme d'ozone par minute (g/min), par exemple de 8 x W4 g/min à 0,1 g/min, par exemple de 8,33 x W4 g/min à 0,1 g/min d'ozone, de préférence de 1,5 x W2 g/min à 1,9 x W2 g/min d'ozone. La durée de bullage dépend de la quantité d'ozone que l'on souhaite appliquer. [0068] Before being injected into the liquid composition of humic substances, the gas containing ozone can be divided into "micro-bubbles", ie bubbling of the ozone, using various materials, for example using porous diffusers arranged in the lower part of the tanks or columns or a hydro-injector ensuring the spraying of the gas directly into the composition to be treated. The latter has the advantage of a better rate of dissolution of the ozone in the treated composition. Thus, in a preferred embodiment, the treatment is carried out by bubbling ozone into the liquid composition of humic substances, for example by bubbling 8 x W 4 at 0.5 grams of ozone per minute (g/min ), for example from 8 x W 4 g/min to 0.1 g/min, for example from 8.33 x W 4 g/min to 0.1 g/min of ozone, preferably from 1.5 x W 2 g/min at 1.9 x W 2 g/min ozone. The duration of bubbling depends on the quantity of ozone that one wishes to apply.
[0069] Dans un mode de réalisation particulier, la concentration en ozone de la composition liquide est constante au cours du traitement, de préférence la concentration d'ozone va de 1 g/m3 à 120 g/m3, avantageusement elle est égale à environ 20 g/m3. In a particular embodiment, the ozone concentration of the liquid composition is constant during the treatment, preferably the ozone concentration ranges from 1 g/m 3 to 120 g/m 3 , advantageously it is equal at approximately 20 g/m 3 .
[0070] Autres étapes [0070] Other steps
[0071] Le procédé selon l'invention peut comprendre une ou plusieurs étapes additionnelles, par exemple une ou plusieurs étapes choisies parmi : The method according to the invention may comprise one or more additional steps, for example one or more steps chosen from:
- préparer une composition fertilisante comprenant la composition liquide de substances humiques oxydée ou utiliser directement la composition liquide de substances humiques oxydée comme composition fertilisante ; - preparing a fertilizing composition comprising the liquid composition of oxidized humic substances or directly using the liquid composition of oxidized humic substances as a fertilizing composition;
- sécher, par exemple lyophiliser, la composition liquide de substances humiques oxydée ; et
granuler la composition liquide de substances humiques oxydée ou une composition fertilisante comprenant la composition liquide de substances humiques oxydée. - drying, for example freeze-drying, the liquid composition of oxidized humic substances; and granulating the liquid oxidized humic substance composition or a fertilizer composition comprising the liquid oxidized humic substance composition.
[0072] Une composition fertilisante comprenant la composition liquide de substances humiques oxydée peut être préparée en ajoutant, à la composition de substances humiques oxydée, un engrais minéraux, de préférence contenant un ou plusieurs minéraux choisis parmi l'azote, le phosphore, le potassium, le calcium, le magnésium et/ou le soufre, aux substances humiques ozonées. L'ajout peut se faire avant ou après les étapes additionnelles susmentionnées. A fertilizing composition comprising the liquid composition of oxidized humic substances can be prepared by adding, to the composition of oxidized humic substances, a mineral fertilizer, preferably containing one or more minerals chosen from nitrogen, phosphorus, potassium , calcium, magnesium and/or sulfur, to ozonated humic substances. The addition can be done before or after the additional steps mentioned above.
[0073] Composition fertilisante [0073] Fertilizing composition
[0074] L'invention concerne également une composition fertilisante susceptible d'être obtenue par le procédé selon l'invention. The invention also relates to a fertilizing composition which can be obtained by the process according to the invention.
[0075] Avantageusement, le rayon hydrodynamique moyen en masse des particules en solution (RhmOyen), mesuré par DLS, est supérieur à 50 nm, de préférence supérieur à 75 nm, par exemple supérieur à 100 nm, supérieur à 150 nm, supérieur à 200 nm, supérieur à 250 nm, supérieur à 500 nm, supérieur à 750 nm, supérieur à 1000 nm, supérieur à 1250 nm, supérieur à 1500 nm, supérieur à 1750 nm, supérieur à 2000 nm. Advantageously, the mass-average hydrodynamic radius of the particles in solution (Rh mO yen), measured by DLS, is greater than 50 nm, preferably greater than 75 nm, for example greater than 100 nm, greater than 150 nm, greater than 200 nm, greater than 250 nm, greater than 500 nm, greater than 750 nm, greater than 1000 nm, greater than 1250 nm, greater than 1500 nm, greater than 1750 nm, greater than 2000 nm.
[0076] Avantageusement, la proportion massique des particules en solution ayant un rayon hydrodynamique compris entre 15 nm et 10000 nm, mesurée par DLS, est supérieure à 15%, de préférence supérieure à 20%, par exemple supérieure à 25%, supérieure à 30%, supérieure à 35%, supérieure à 40%, supérieure à 45%, supérieure à 50%, supérieure à 55%, supérieure à 60%, supérieure à 65%, supérieure à 70%, supérieure à 75%, supérieure à 80%. Advantageously, the mass proportion of particles in solution having a hydrodynamic radius of between 15 nm and 10,000 nm, measured by DLS, is greater than 15%, preferably greater than 20%, for example greater than 25%, greater than 30%, over 35%, over 40%, over 45%, over 50%, over 55%, over 60%, over 65%, over 70%, over 75%, over 80%.
[0077] Avantageusement, Mw de la composition fertilisante selon l'invention est comprise entre 100 kDa et 300 kDa, par exemple entre 100 kDa et 250 kDa, entre 100 KDa et 200 kDa, entre 100 kDa et 180 kDa, de préférence comprise entre 150 kDa et 170 kDa, par exemple elle est d'environ 160 kDa. La réaction d'oxydation majoritaire des substances humiques permet la création d'un ozonure primaire sur une double liaison C=C puis la formation de fonctions cétones, aldéhydes ou acides carboxyliques, comme illustré ci-après :
[0078] Au sens de l'invention, l'oxydation permet donc de dégrader les substances humiques en plus petites molécules. Le schéma de dégradation des substances humiques par l'ozone est présenté dans la Figure 3, tirée de [6]. Advantageously, Mw of the fertilizing composition according to the invention is between 100 kDa and 300 kDa, for example between 100 kDa and 250 kDa, between 100 kDa and 200 kDa, between 100 kDa and 180 kDa, preferably between 150 kDa and 170 kDa, for example it is about 160 kDa. The majority oxidation reaction of humic substances allows the creation of a primary ozonide on a C=C double bond and then the formation of ketone, aldehyde or carboxylic acid functions, as illustrated below: Within the meaning of the invention, oxidation therefore makes it possible to degrade humic substances into smaller molecules. The diagram of degradation of humic substances by ozone is presented in Figure 3, taken from [6].
[0079] Dans un mode de réalisation particulier, la composition selon l'invention comprend en outre une ou plusieurs substance(s) fertilisante(s) choisie(s) parmi l'urée, le sulfate d'ammonium, le nitrate d'ammonium, le phosphate, le chlorure de potassium, du sulfate d'ammonium, le nitrate de magnésium, le nitrate de manganèse, le nitrate de zinc, le nitrate de cuivre, l'acide phosphorique, le nitrate de potassium et l'acide borique. In a particular embodiment, the composition according to the invention further comprises one or more fertilizing substance(s) chosen from urea, ammonium sulphate, ammonium nitrate , phosphate, potassium chloride, ammonium sulfate, magnesium nitrate, manganese nitrate, zinc nitrate, copper nitrate, phosphoric acid, potassium nitrate and boric acid.
[0080] De préférence, la composition selon l'invention comprend en outre un ou plusieurs engrais minéraux. L'engrais minéraux comprend de préférence un ou plusieurs minéraux choisis parmi l'azote, le phosphore, le potassium, le calcium, le magnésium et/ou le soufre. Il a en effet été montré que les substances humiques oxydées permettaient une meilleure absorption des minéraux par la plante par rapport à des substances humiques non ozonées. Une composition selon l'invention qui comprend en outre un ou plusieurs engrais minéraux présente donc des propriétés particulièrement avantageuses. Preferably, the composition according to the invention further comprises one or more mineral fertilizers. The mineral fertilizer preferably comprises one or more minerals chosen from nitrogen, phosphorus, potassium, calcium, magnesium and/or sulphur. It has in fact been shown that oxidized humic substances allow better absorption of minerals by the plant compared to non-ozonated humic substances. A composition according to the invention which also comprises one or more mineral fertilizers therefore has particularly advantageous properties.
[0081] La Figure 5 montre le profil HPSEC d'une composition fertilisante selon l'invention qui a été obtenue par la mise en œuvre du procédé selon l'invention (trait plein). [0081] Figure 5 shows the HPSEC profile of a fertilizing composition according to the invention which was obtained by implementing the method according to the invention (solid line).
[0082] La Figure 7 montre un profil DLS de compositions fertilisantes selon l'invention qui ont été obtenue par la mise en œuvre du procédé selon l'invention, avec un ratio masse d'ozone/masse de substances humiques (R) égal à 0,1, égal à 0,5 ou égal à 2. [0082] Figure 7 shows a DLS profile of fertilizing compositions according to the invention which have been obtained by implementing the method according to the invention, with a mass ratio of ozone/mass of humic substances (R) equal to 0.1, equal to 0.5 or equal to 2.
[0083] La composition selon l'invention peut être sous forme liquide, par exemple sous forme de solution fertilisante, ou sous forme solide, par exemple sous forme de granulés. The composition according to the invention can be in liquid form, for example in the form of a fertilizing solution, or in solid form, for example in the form of granules.
[0084] Utilisation de la composition fertilisante et procédé de fertilisation [0084] Use of the fertilizing composition and method of fertilizing
[0085] L'invention concerne également l'utilisation d'une composition selon l'invention comme stimulant de l'absorption de minéraux chez une plante, de préférence les minéraux sont choisis parmi l'azote, le phosphore, le potassium, le calcium, le magnésium et/ou le soufre. The invention also relates to the use of a composition according to the invention as a stimulant for the absorption of minerals in a plant, preferably the minerals are chosen from nitrogen, phosphorus, potassium, calcium , magnesium and/or sulfur.
[0086] L'invention concerne également l'utilisation d'une composition selon l'invention comme stimulant de la production de pigments chez une plante, de préférence la production de caroténoïdes, de chlorophylle A et/ou de chlorophylle B. The invention also relates to the use of a composition according to the invention as a stimulant for the production of pigments in a plant, preferably the production of carotenoids, chlorophyll A and/or chlorophyll B.
[0087] L'invention concerne également un procédé de fertilisation d'une plante, d'un sol ou d'un support de culture comprenant l'application à ladite plante, audit sol ou audit support de culture d'une composition selon l'invention.
[0088] L'invention concerne également un procédé de fertilisation d'une plante, d'un sol ou d'un support de culture consistant à (i) préparer une composition fertilisante en mettant en oeuvre le procédé de l'invention, et (ii) appliquer, par exemple directement après la préparation, ladite composition fertilisante à la plante, au sol ou au support de culture. The invention also relates to a method for fertilizing a plant, a soil or a growing medium comprising the application to said plant, said soil or said growing medium of a composition according to invention. The invention also relates to a process for fertilizing a plant, a soil or a growing medium consisting in (i) preparing a fertilizing composition by implementing the process of the invention, and ( ii) applying, for example directly after the preparation, said fertilizing composition to the plant, to the soil or to the growing medium.
[0089] Au sens de l'invention, un support de culture est destiné à servir de milieu de culture à une plante en permettant à la fois d'ancrer les organes absorbants de la plante et de les mettre en contact avec les solutions nécessaires à la croissance de la plante. [0089] Within the meaning of the invention, a culture support is intended to serve as a culture medium for a plant by making it possible both to anchor the absorbent organs of the plant and to bring them into contact with the solutions necessary for plant growth.
[0090] Avantageusement, le procédé selon l'invention permet de stimuler l'absorption de minéraux chez la plante. De préférence les minéraux sont choisis parmi l'azote, le phosphore, le potassium, le calcium, le magnésium et/ou le soufre. Advantageously, the process according to the invention makes it possible to stimulate the absorption of minerals in the plant. Preferably the minerals are chosen from nitrogen, phosphorus, potassium, calcium, magnesium and/or sulphur.
[0091] Avantageusement, le procédé selon l'invention permet de stimuler la production de pigments chez la plante, de préférence la production de caroténoïdes, de chlorophylle A et/ou de chlorophylle B. Advantageously, the method according to the invention makes it possible to stimulate the production of pigments in the plant, preferably the production of carotenoids, chlorophyll A and/or chlorophyll B.
[0092] Avantageusement, l'utilisation ou le procédé selon l'invention permet d'augmenter l'activité photosynthétique d'une plante et/ou de stimuler la croissance aérienne et/ou racinaire de la plante. Advantageously, the use or the method according to the invention makes it possible to increase the photosynthetic activity of a plant and/or to stimulate the aerial and/or root growth of the plant.
[0093] Dans un mode de réalisation particulier, la composition fertilisante est appliquée à la plante, au sol ou au support de culture, sous forme liquide, directement après le traitement avec l'agent oxydant. Dans ce mode de réalisation, l'application peut se faire en continue, c'est-à-dire que la composition fertilisante sous forme liquide est appliquée au sol ou au support de culture en flux continu au fur et à mesure du traitement avec l'agent oxydant. In a particular embodiment, the fertilizing composition is applied to the plant, to the soil or to the growing medium, in liquid form, directly after the treatment with the oxidizing agent. In this embodiment, the application can be done continuously, that is to say that the fertilizing composition in liquid form is applied to the soil or to the growing medium in a continuous flow as the treatment with the oxidizing agent.
[0094] La composition selon l'invention peut être appliquée à la plante par voie foliaire ou racinaire. The composition according to the invention can be applied to the plant via the leaf or root route.
[0095] Dans un mode de réalisation particulier, le sol est un sol acide. En agriculture, un sol acide est un sol ayant un pH inférieur à pH 6,5. Les inventeurs ont en effet montré qu'en conditions acides les substances humiques ozonées précipitaient moins que les substances humiques non-ozonées, et qu'elles conservaient donc leurs propriétés fertilisantes. [0095] In a particular embodiment, the soil is an acid soil. In agriculture, acidic soil is soil with a pH below pH 6.5. The inventors have in fact shown that under acidic conditions the ozonated humic substances precipitate less than the non-ozonated humic substances, and that they therefore retain their fertilizing properties.
[0096] La présente invention trouve application dans le traitement d'une très grande variété de plantes. Parmi celles-ci, on citera en particulier : The present invention finds application in the treatment of a very wide variety of plants. Among these, we can mention in particular:
- les plantes de grande culture telles que les céréales (ex. blé, maïs), - field crops such as cereals (e.g. wheat, maize),
- les protéagineux (ex. pois), - protein crops (eg peas),
- les oléagineux (ex. soja, tournesol), - oilseeds (e.g. soya, sunflower),
- les plantes prairiales utiles pour l'alimentation animale,
les cultures spécialisées telles qu'en particulier le maraîchage (ex. laitue, épinards, tomate, melon), la vigne, l'arboriculture (poire, pomme, nectarine), ou l'horticulture (ex. rosiers). - grassland plants useful for animal feed, specialized crops such as, in particular, market gardening (eg lettuce, spinach, tomato, melon), vines, arboriculture (pear, apple, nectarine), or horticulture (eg roses).
Description des figures Description of figures
[0097] [Fig. 1] La Figure 1 est une courbe HPSEC qui montre l'évolution de la masse molaire moyenne en poids en solution (Mw) de la composition liquide de substances humiques au cours du traitement à l'ozone. La figure montre également l'évolution de la Masse Moléculaire Moyenne en Nombre (Mn) de la composition liquide de substances humiques au cours du traitement à l'ozone. [0097] [Fig. 1] Figure 1 is an HPSEC curve which shows the evolution of the weight average molar mass in solution (Mw) of the liquid composition of humic substances during the treatment with ozone. The figure also shows the evolution of the Number Average Molecular Mass (Mn) of the liquid composition of humic substances during treatment with ozone.
[0098] [Fig. 2] La Figure 2 est une courbe HPSEC qui montre l'évolution de la masse molaire moyenne en poids en solution (Mw) de la composition liquide de substances humiques en fonction du ratio « masse d'ozone/masse de substances humiques ». La figure montre également l'évolution de la Masse Moléculaire Moyenne en Nombre (Mn) de la composition liquide de substances humiques en fonction du ratio « masse d'ozone/masse de substances humiques ». [0098] [Fig. 2] Figure 2 is an HPSEC curve which shows the evolution of the mean molar mass by weight in solution (Mw) of the liquid composition of humic substances as a function of the “mass of ozone/mass of humic substances” ratio. The figure also shows the evolution of the Number Average Molecular Mass (Mn) of the liquid composition of humic substances as a function of the “mass of ozone/mass of humic substances” ratio.
[0099] [Fig. 3] La Figure 3 représente le processus de dégradation des substances humiques par oxydation à l'ozone. [0099] [Fig. 3] Figure 3 represents the process of degradation of humic substances by oxidation with ozone.
[0100] [Fig. 4] La Figure 4 illustre le montage d'un réacteur batch utilisé pour l'ozonation d'une composition liquide de substances humiques. [0100] [Fig. 4] Figure 4 illustrates the assembly of a batch reactor used for the ozonation of a liquid composition of humic substances.
[0101] [Fig. 5] La Figure 5 est un profil HPSEC d'une composition de substances humiques ozonée (composition mère de l'Exemple 1) et d'une composition de substances humiques non-ozonée (composition témoin de l'Exemple 1). En trait plein la composition ozonée et en pointillés la composition témoin non-ozonée. [0101] [Fig. 5] Figure 5 is an HPSEC profile of an ozonated humic substance composition (parent composition of Example 1) and a non-ozonated humic substance composition (control composition of Example 1). The solid line shows the ozonated composition and the dotted line shows the non-ozonated control composition.
[0102] [Fig. 6] La Figure 6 est un histogramme obtenu à partir des données HPSEC de la Figure 5 qui représente le pourcentage des différentes familles de substances humiques en fonction de leur masse moléculaire. [0102] [Fig. 6] Figure 6 is a histogram obtained from the HPSEC data of Figure 5 which represents the percentage of the different families of humic substances according to their molecular mass.
[0103] [Fig. 7] La Figure 7 est une analyse DLS (Dynamic light scattering) qui montre l'évolution de la taille des substances humiques avec des quantités croissantes d'ozoneen. La figure montre l'apparition de molécules de substances humiques avec un rayon hydrodynamique (Rh) plus grand (familles de particules 2 et 3) avec un ratio masse d'ozone/masse de substances humiques (R) égal à 0,1, R=0,5 et R=2. Avec R=8, on
observe une dégradation des substances humiques de grande taille (famille 3) en de plus petites molécules (familles 1 & 2). [0103] [Fig. 7] Figure 7 is a DLS (Dynamic light scattering) analysis which shows the evolution of the size of humic substances with increasing amounts of ozone. The figure shows the appearance of molecules of humic substances with a larger hydrodynamic radius (Rh) (particle families 2 and 3) with a mass ratio of ozone/mass of humic substances (R) equal to 0.1, R =0.5 and R=2. With R=8, we observes a degradation of large humic substances (family 3) into smaller molecules (families 1 & 2).
[0104] [Fig. 8A] La Figure 8A est un histogramme obtenu à partir des données DLS de la Figure 7 qui montre la distribution massique des substances humiques en fonction de leur rayon hydrodynamique (Rh) avec des quantités croissantes d'ozone. La figure montre que la proportion massique des particules en solution de taille comprise entre 15 nm et 10000 nm augmente lorsque le ratio masse d'ozone/masse de substances humiques (R) est égal à 0,1, R=0,5 et R=2. [0104] [Fig. 8A] Figure 8A is a histogram obtained from the DLS data in Figure 7 that shows the mass distribution of humic substances as a function of their hydrodynamic radius (Rh) with increasing amounts of ozone. The figure shows that the mass proportion of particles in solution with a size between 15 nm and 10,000 nm increases when the mass ratio of ozone/mass of humic substances (R) is equal to 0.1, R=0.5 and R =2.
[0105] [Fig. 8B] La Figure 8B est un histogramme obtenu à partir des données DLS de la Figure 7 qui montre le rayon hydrodynamique moyen en masse des particules en solution (Rhmoyen) avec des quantités croissantes d'ozone. La figure montre que le Rhmoyen augmente lorsque le ratio masse d'ozone/masse de substances humiques (R) est égal à 0,1, R=0,5 et R=2. [0105] [Fig. 8B] Figure 8B is a histogram obtained from the DLS data of Figure 7 that shows the mass average hydrodynamic radius of particles in solution ( avg Rh) with increasing amounts of ozone. The figure shows that the average Rh increases when the ratio mass of ozone/mass of humic substances (R) is equal to 0.1, R=0.5 and R=2.
[0106] [Fig. 9] La Figure 9 est une courbe qui compare l'évolution de la longueur des feuilles de maïs traité avec une composition de substances humiques ozonée (1,5.2+SN) et une composition de substances humiques non-ozonée (T.2+SN). [0106] [Fig. 9] Figure 9 is a curve which compares the evolution of the length of the leaves of maize treated with a composition of ozonated humic substances (1.5.2+SN) and a composition of non-ozonated humic substances (T.2+SN ).
[0107] [Fig. 10] La Figure 10 représente la longueur moyenne des feuilles de maïs traité avec une composition de substances humiques ozonée (1) et une composition de substances humiques non-ozonée (0). [0107] [Fig. 10] Figure 10 represents the average leaf length of maize treated with an ozonated humic substance composition (1) and a non-ozonated humic substance composition (0).
[0108] [Fig. 11] La Figure 11 est une courbe qui compare l'évolution de la longueur des racines de maïs traité avec une composition de substances humiques ozonée (1,5.2+SN) et une composition de substances humiques non-ozonée (T.2+SN). [0108] [Fig. 11] Figure 11 is a curve which compares the evolution of the length of the roots of maize treated with a composition of ozonated humic substances (1.5.2+SN) and a composition of non-ozonated humic substances (T.2+SN ).
[0109] [Fig. 12] La Figure 12 représente la longueur moyenne des racines de maïs traité avec une composition de substances humiques ozonée (1) et une composition de substances humiques non-ozonée (0). [0109] [Fig. 12] Figure 12 represents the average root length of maize treated with an ozonated humic substance composition (1) and a non-ozonated humic substance composition (0).
[0110] [Fig. 13] La Figure 13 est un histogramme qui qui compare la longueur des racines de maïs traité avec une composition de minéraux, une composition de substances humiques non-ozonée (T.2+SN), une composition de substances humiques ozonée avec un ratio « masse d'ozone/masse de substances humiques » de 0,5 (0,5.2+SN), une composition de substances humiques ozonée avec un ratio « masse d'ozone/masse de substances humiques » de 1,5 (1,5.2+SN) et une composition de substances humiques ozonée avec un ratio « masse d'ozone/masse de substances humiques » de 3,5 (3,5.2+SN).
[0111] [Fig. 14] La Figure 14 est un histogramme qui compare la teneur en caroténoïdes des feuilles de maïs traité avec une composition de substances humiques ozonée (à gauche) et une composition de substances humiques non-ozonée (à droite). [0110] [Fig. 13] Figure 13 is a histogram which compares the length of the roots of maize treated with a composition of minerals, a composition of non-ozonated humic substances (T.2+SN), a composition of ozonated humic substances with a ratio “ mass of ozone/mass of humic substances” of 0.5 (0.5.2+SN), a composition of ozonated humic substances with a “mass of ozone/mass of humic substances” ratio of 1.5 (1.5.2 +SN) and a composition of ozonated humic substances with a “mass of ozone/mass of humic substances” ratio of 3.5 (3.5.2+SN). [0111] [Fig. 14] Figure 14 is a bar graph comparing the carotenoid content of maize leaves treated with an ozonated humic substance composition (left) and a non-ozonated humic substance composition (right).
[0112] [Fig. 15] La Figure 15 est un histogramme qui compare la teneur en chlorophylle A des feuilles de maïs traité avec une composition de substances humiques ozonée (à gauche) et une composition de substances humiques non-ozonée (à droite). [0112] [Fig. 15] Figure 15 is a bar graph comparing the chlorophyll A content of maize leaves treated with an ozonated humic substance composition (left) and a non-ozonated humic substance composition (right).
[0113] [Fig. 16] La Figure 16 est un histogramme qui compare la teneur en chlorophylle B des feuilles de maïs traité avec une composition de substances humiques ozonée (à gauche) et une composition de substances humiques non-ozonée (à droite). [0114] [Fig. 17] La Figure 17 est un profil HPSEC d'une composition liquide de substances humiques non-ozonée avant et après lyophilisation. [0113] [Fig. 16] Figure 16 is a bar graph comparing the chlorophyll B content of maize leaves treated with an ozonated humic substance composition (left) and a non-ozonated humic substance composition (right). [0114] [Fig. 17] Figure 17 is an HPSEC profile of a liquid composition of non-ozonated humic substances before and after lyophilization.
[0115] [Fig. 18] La Figure 18 est un profil HPSEC d'une composition liquide de substances humiques ozonée avant et après lyophilisation. [0115] [Fig. 18] Figure 18 is an HPSEC profile of a liquid composition of ozonated humic substances before and after lyophilization.
[0116] [Fig. 19] La Figure 19 est une courbe qui montre la précipitation des substances humiques en fonction du pH dans une composition liquide de substances humiques ozonée (en trait pleins) et dans une composition liquide de substances humiques non-ozonée (en pointillés).
[0116] [Fig. 19] Figure 19 is a curve showing the precipitation of humic substances as a function of pH in a liquid composition of ozonated humic substances (in solid lines) and in a liquid composition of non-ozonated humic substances (in dotted lines).
EXEMPLES EXAMPLES
[0118] Exemple 1 : Matériels et méthodes [0118] Example 1: Materials and Methods
[0119] Procédé de préparation d'une composition fertilisante [0119] Process for the preparation of a fertilizing composition
[0120] Une composition liquide de substances humiques a été obtenue en diluant 11 grammes d'une poudre de sel potassique de substances humiques (Produit Dralig® commercialisé par la société Humatex - CAS 68514-28-3) dans 20 litres d'eau, pour obtenir 20 litres d'une composition de concentration en substances humiques de 550 mg/L. Cette composition liquide de substances humiques a été utilisée dans les exemples ci-après comme « composition témoin ». A liquid composition of humic substances was obtained by diluting 11 grams of a potassium salt powder of humic substances (Dralig® product marketed by the company Humatex - CAS 68514-28-3) in 20 liters of water, to obtain 20 liters of a composition with a concentration of humic substances of 550 mg/L. This liquid composition of humic substances was used in the examples below as “control composition”.
[0121] La réaction d'ozonation a été réalisée dans un réacteur batch classique décrit dans la Figure 4. Le réacteur utilisé était une simple bouteille en verre (1) contenant IL de la composition de substances humiques à 550 mg/L (2). Cette solution a été agitée avec un agitateur magnétique (3). L'ozone a été produit avec un ozoneur (CFS1 - Ozonia) alimenté par de l'oxygène pur (4). La concentration d'ozone utilisée était de 20 g/m3 dans le flux de gaz entrant dans le réacteur (avec un débit de l,67xl0’2 g/min d'ozone) et a été suivie grâce à l'analyseur d'ozone (5). Le débit de gaz entrant dans le réacteur a été régulé à 50 L/h grâce à un débitmètre (6). La température du gaz entrant a été mesurée avec un thermomètre (7) et était comprise entre 17 et 22°C. Le gaz a été injecté dans la composition de substances humiques avec une arrivée en verre et un fritté comportant des pores de taille 200 pm en moyenne (8). L'ozone en excès a ensuite été détruit dans un second réacteur (9) contenant une solution d'iodure de potassium (Kl) à 50 g/L (10). Une vanne a été utilisée afin de maîtriser la réaction (11). Lorsque l'ozone n'était pas utilisé dans le réacteur, il était directement dirigé vers le destructeur (9). The ozonation reaction was carried out in a conventional batch reactor described in Figure 4. The reactor used was a simple glass bottle (1) containing IL of the composition of humic substances at 550 mg/L (2) . This solution was stirred with a magnetic stirrer (3). The ozone was produced with an ozone generator (CFS1 - Ozonia) powered by pure oxygen (4). The ozone concentration used was 20 g/m 3 in the gas flow entering the reactor (with a flow rate of 1.67x10'2 g/min of ozone) and was monitored using the ozone analyzer. ozone (5). The flow of gas entering the reactor was regulated at 50 L/h using a flow meter (6). The temperature of the incoming gas was measured with a thermometer (7) and was between 17 and 22°C. The gas was injected into the composition of humic substances with a glass inlet and a frit comprising pores of an average size of 200 μm (8). The excess ozone was then destroyed in a second reactor (9) containing a solution of potassium iodide (Kl) at 50 g/L (10). A valve was used to control the reaction (11). When the ozone was not used in the reactor, it was sent directly to the destroyer (9).
[0122] Le temps d'ozonation a été de 50 minutes pour IL de composition de substances humiques à 550 mg/L. The ozonation time was 50 minutes for IL of composition of humic substances at 550 mg/L.
[0123] Le pH de la composition de substances humiques ainsi traitées avec l'ozone a ensuite été ajusté à pH = 7,0 avec une solution d'acide chlorhydrique 0,1 mol/L et le cas échéant avec une solution d'hydroxyde de sodium à 0,1 mol/L. The pH of the composition of humic substances thus treated with ozone was then adjusted to pH=7.0 with a 0.1 mol/L hydrochloric acid solution and, where appropriate, with a hydroxide solution. of sodium at 0.1 mol/L.
[0124] Les compositions de substances humiques ozonées ont été diluées au quart avec de l'eau MilliQ. La composition liquide de substances humiques ainsi obtenue a été utilisée dans les exemples ci-après comme « composition mère ». The compositions of ozonated humic substances were diluted to a quarter with MilliQ water. The liquid composition of humic substances thus obtained was used in the examples below as “stock composition”.
[0125] Mesures DLS
[0126] Les mesures de DLS ont été réalisées avec un Dynapro Nanostar (WYATT technology) équipé d'un laser ( = 662 nm). La plage d'intensité de diffusion mesurée était de 1,36.106 à 3,14.106 coups par seconde (cps). Toutes les mesures ont été prises à un angle de détection de 90° et toutes les tailles rapportées sont des moyennes de 15 séquences de 5 secondes chacune. La reproductibilité des échantillons a été analysée 3 fois. 20 pL de chaque solution ont été utilisés et toutes les solutions ont été ajustées à 25°C dans la chambre d'échantillon de l'instrument et laissées à l'équilibre pendant 5 min. Une microcuvette jetable (technologie WYATT) a été utilisée pour effectuer la mesure DLS. Le logiciel Dynamics (technologie WYATT) a été utilisé pour piloter les acquisitions de mesures et analyser les données. [0125] DLS measurements The DLS measurements were carried out with a Dynapro Nanostar (WYATT technology) equipped with a laser (=662 nm). The measured scatter intensity range was 1.36 x 106 to 3.14 x 106 counts per second (cps). All measurements were taken at a 90° detection angle and all sizes reported are averages of 15 sequences of 5 seconds each. The reproducibility of the samples was analyzed 3 times. 20 µL of each solution was used and all solutions were adjusted to 25°C in the sample chamber of the instrument and allowed to equilibrate for 5 min. A disposable microcuvette (WYATT technology) was used to perform the DLS measurement. Dynamics software (WYATT technology) was used to control the acquisition of measurements and analyze the data.
[0127] Exemple 2 : caractérisation de la composition fertilisante [0127] Example 2: characterization of the fertilizing composition
[0128] Les compositions de substances humiques témoins (i.e. avant ozonation) et ozonées selon l'Exemple 1 (composition mère) ont été analysées par HPSEC. Cette analyse a été faite à l'aide d'une chaîne Dionex Ultimate 3000 équipée d'une colonne TSK G2000SWXL (Phenomenex, USA - 7,5 x 300 mm). La chaîne disposait d'un échantillonneur automatique ainsi que d'une pompe isocratique. Deux détecteurs ont été utilisés : un détecteur UV- Visible avec une longueur d'onde de détection fixée à 254 nm (analyse des doubles liaisons C=C) et un détecteur Ri Optilab T-rEX (WYATT Technology). L'éluant utilisé était un mélange acide acétique / acétate de sodium à lOmM avec le pH fixé à 7. L'éluant a été filtré à 0,45 pm et 0,1 pm. Le débit utilisé était de 1 mL/min. Le volume d'injection des échantillons était de 20 pL. The compositions of control humic substances (ie before ozonation) and ozonated according to Example 1 (parent composition) were analyzed by HPSEC. This analysis was carried out using a Dionex Ultimate 3000 chain equipped with a TSK G2000SW XL column (Phenomenex, USA - 7.5 x 300 mm). The line had an automatic sampler as well as an isocratic pump. Two detectors were used: a UV-Visible detector with a detection wavelength fixed at 254 nm (analysis of the C=C double bonds) and a Ri Optilab T-rEX detector (WYATT Technology). The eluent used was a 10 mM acetic acid/sodium acetate mixture with the pH set at 7. The eluent was filtered at 0.45 μm and 0.1 μm. The flow rate used was 1 mL/min. The sample injection volume was 20 µL.
[0129] La composition témoin et la composition mère ont également été analysées par DLS (Dynamic light scattering). La DLS est une technique analytique basée sur le mouvement brownien des particules, décrit par l'équation de Stokes-Einstein. Elle a été utilisée pour étudier l'agrégation des substances humiques. De plus, la DLS a permis de déterminer le rayon hydrodynamique (Rh) et la polydispersité des substances humiques en solution. The control composition and the stock composition were also analyzed by DLS (Dynamic light scattering). DLS is an analytical technique based on the Brownian motion of particles, described by the Stokes-Einstein equation. It has been used to study the aggregation of humic substances. In addition, the DLS allowed to determine the hydrodynamic radius (Rh) and the polydispersity of humic substances in solution.
[0130] Les expériences de DLS ont été réalisées avec un Dynapro Nanostar 22 (technologie WYATT) équipé d'un laser ( = 662 nm). La plage d'intensité de diffusion mesurée était de 1,36 x 106 - 3,14 x 106 comptes par seconde (cps). Toutes les mesures ont été prises à un angle de détection de 90° et toutes les tailles rapportées sont des moyennes de 15 exécutions séquentielles de 5 secondes chacune. Les échantillons ont été analysés 26 fois pour la reproductibilité. 20 pL de chaque composition ont été utilisés et toutes les solutions ont été ajustées à 25°C dans la chambre de mesure et elles ont été laissées s'équilibrer
pendant 5 min. Une microcuvette jetable (technologie WYATT) a été utilisée pour effectuer l'analyse DLS. Le logiciel Dynamics (technologie WYATT) a été utilisé pour piloter les acquisitions de mesures et analyser les données. The DLS experiments were carried out with a Dynapro Nanostar 22 (WYATT technology) equipped with a laser (=662 nm). The measured scattering intensity range was 1.36 x 10 6 - 3.14 x 10 6 counts per second (cps). All measurements were taken at a 90° detection angle and all sizes reported are averages of 15 sequential runs of 5 seconds each. Samples were analyzed 26 times for reproducibility. 20 µL of each composition was used and all solutions were adjusted to 25°C in the measuring chamber and allowed to equilibrate for 5 mins. A disposable microcuvette (WYATT technology) was used to perform the DLS analysis. Dynamics software (WYATT technology) was used to control the acquisition of measurements and analyze the data.
[0131] Les résultats HPSEC avec détecteur RI sont présentés aux Figures 1 et 2 (Mw et Mn) et aux Figures 5 et 6. Les résultats DLS sont présentés aux Figures 7 et 8. HPSEC results with RI detector are shown in Figures 1 and 2 (Mw and Mn) and Figures 5 and 6. DLS results are shown in Figures 7 and 8.
[0132] Mw et Mn [0132] Mw and Mn
[0133] Les Figures 1 et 2 montrent l'évolution de Mw et Mn au cours du traitement avec l'ozone. Figures 1 and 2 show the evolution of Mw and Mn during treatment with ozone.
[0134] HPSEC avec détecteur Ri [0134] HPSEC with Ri detector
[0135] La Figure 5 montre que l'ozonation conduit à une modification structurale des substances humiques. En ce qui concerne les agrégats, on s'aperçoit que le signal augmente (vers 5,2 minutes) ce qui atteste la solubilisation de certaines molécules. Le pic à 6min quant à lui se dégrade au profit de plusieurs populations relatives à des masses molaires plus petites (à 6,6 ; 7,0 ; 7,7 et 8,9 minutes). A noter que le pic à 10 minutes correspond à toutes les petites molécules (taille < 100 Da) notamment les sels contenus dans la phase mobile de l'HPLC. Figure 5 shows that ozonation leads to a structural modification of humic substances. With regard to the aggregates, it is seen that the signal increases (around 5.2 minutes), which attests to the solubilization of certain molecules. The peak at 6 min is degraded in favor of several populations relating to smaller molar masses (at 6.6; 7.0; 7.7 and 8.9 minutes). It should be noted that the peak at 10 minutes corresponds to all the small molecules (size <100 Da) in particular the salts contained in the mobile phase of the HPLC.
[0136] La Figure 6 représente les différents pourcentages des différentes familles de substances humiques en fonction de la masse moléculaire. La Figure 6 met en évidence une apparition de composés de masse molaire supérieure à 170kDa dans la composition mère alors qu'avec la composition témoin on n'observe pas cette famille de molécule. La Figure 6 montre également que l'ozonation conduit à la formation de plus petites molécules de substance humique. [0136] Figure 6 represents the different percentages of the different families of humic substances according to the molecular mass. Figure 6 demonstrates an appearance of compounds with a molar mass greater than 170 kDa in the parent composition, whereas with the control composition, this family of molecules is not observed. Figure 6 also shows that ozonation leads to the formation of smaller humic substance molecules.
[0137] DLS [0137] DLS
[0138] La Figure 7 est une analyse DLS (Dynamic light scattering) qui montre l'évolution de la taille des substances humiques avec des quantités croissantes d'ozoneen. La figure montre l'apparition de molécules de substances humiques avec un rayon hydrodynamique (Rh) plus grand (familles de particules 2 et 3) avec un ratio masse d'ozone/masse de substances humiques (R) égal à 0,1, R=0,5 et R=2. Avec R=8, on observe une dégradation des substances humiques de grande taille (famille 3) en de plus petites molécules (familles 1 & 2). FIG. 7 is a DLS (Dynamic light scattering) analysis which shows the evolution of the size of humic substances with increasing amounts of ozone. The figure shows the appearance of molecules of humic substances with a larger hydrodynamic radius (Rh) (particle families 2 and 3) with a mass ratio of ozone/mass of humic substances (R) equal to 0.1, R =0.5 and R=2. With R=8, a degradation of large humic substances (family 3) into smaller molecules (families 1 & 2) is observed.
[0139] La Figure 8A est un histogramme obtenu à partir des données DLS de la Figure 7 qui montre la distribution massique des substances humiques en fonction de leur rayon hydrodynamique (Rh) avec des quantités croissantes d'ozone. La figure montre que la
proportion massique des particules en solution de taille comprise entre 15 nm et 10000 nm augmente lorsque le ratio masse d'ozone/masse de substances humiques (R) est égal à 0,1, R=0,5 et R=2. Figure 8A is a histogram obtained from the DLS data of Figure 7 which shows the mass distribution of humic substances as a function of their hydrodynamic radius (Rh) with increasing amounts of ozone. The figure shows that the mass proportion of particles in solution with a size between 15 nm and 10,000 nm increases when the ratio mass of ozone/mass of humic substances (R) is equal to 0.1, R=0.5 and R=2.
[0140] La Figure 8B est un histogramme obtenu à partir des données DLS de la Figure 7 qui montre le rayon hydrodynamique moyen en masse des particules en solution (Rhmoyen) avec des quantités croissantes d'ozone. La figure montre que le hmoyen augmente lorsque le ratio masse d'ozone/masse de substances humiques (R) est égal à 0,1, R=0,5 et R=2. Figure 8B is a histogram obtained from the DLS data of Figure 7 which shows the mass average hydrodynamic radius of particles in solution ( avg Rh) with increasing amounts of ozone. The figure shows that the average h increases when the ratio mass of ozone/mass of humic substances (R) is equal to 0.1, R=0.5 and R=2.
[0141] On déduit des Figures 7, 8A et 8B, notamment de la Figure 8B, que la quantité d'ozone nécessaire pour avoir un R=0,l, un R=0,5 et un R=2 correspond à une quantité appropriée d'ozone au sens de l'invention. Par contre, la quantité d'ozone nécessaire pour avoir un R=8 ne correspond pas à une quantité appropriée d'ozone au sens de l'invention. It is deduced from Figures 7, 8A and 8B, in particular from Figure 8B, that the quantity of ozone necessary to have an R=0.1, an R=0.5 and an R=2 corresponds to a quantity appropriate ozone within the meaning of the invention. On the other hand, the quantity of ozone necessary to have an R=8 does not correspond to an appropriate quantity of ozone within the meaning of the invention.
[0142] Exemple 3 : effets sur la croissance végétale Example 3: effects on plant growth
[0143] Matériels et méthodes [0143] Materials and methods
[0144] Plusieurs compositions ont été préparées : Several compositions were prepared:
[0145] Composition « 1,5.2+SN » (substances humiques ozonées) : 10 litres de composition mère (Exemple 1) ont été supplémentés avec des solutions hydroponiques, à savoir 2,5 mL d'une solution d'azote, phosphore et potassium (FloraGro® de la société Général hydroponics), 2,5 mL d'une solution d'azote et calcium (FloraMicro® de la société Général hydroponics) et 2,5 mL d'une solution de phosphore, potassium, magnésium et soufre (FloraBloom® de la société Général hydroponics). Composition "1.5.2+SN" (ozonated humic substances): 10 liters of stock composition (Example 1) were supplemented with hydroponic solutions, namely 2.5 mL of a solution of nitrogen, phosphorus and potassium (FloraGro® from General Hydroponics), 2.5 mL of a nitrogen and calcium solution (FloraMicro® from General Hydroponics) and 2.5 mL of a solution of phosphorus, potassium, magnesium and sulfur (FloraBloom® from General Hydroponics).
[0146] Composition « T.2+SN » (substances humiques non ozonées) : 10 litres de composition témoin (Exemple 1) ont été supplémentés avec des solutions hydroponiques, à savoir 2,5 mL d'une solution d'azote, phosphore et potassium (FloraGro® de la société Général hydroponics), 2,5 mL d'une solution d'azote et calcium (FloraMicro® de la société Général hydroponics) et 2,5 mL d'une solution de phosphore, potassium, magnésium et soufre (FloraBloom® de la société Général hydroponics). “T.2+SN” composition (non-ozonated humic substances): 10 liters of control composition (Example 1) were supplemented with hydroponic solutions, namely 2.5 mL of a solution of nitrogen, phosphorus and potassium (FloraGro® from General Hydroponics), 2.5 mL of a nitrogen and calcium solution (FloraMicro® from General Hydroponics) and 2.5 mL of a solution of phosphorus, potassium, magnesium and sulfur (FloraBloom® from General Hydroponics).
[0147] La composition des solutions FloraMicro, FloraGro et FloraBloom ajoutées dans les compositions de substances humiques est présentée dans les tableaux 2 à 4 ci-après respectivement.
[0148] [Table 2]
The composition of the FloraMicro, FloraGro and FloraBloom solutions added to the compositions of humic substances is presented in Tables 2 to 4 below respectively. [0148] [Table 2]
Tab eau 2 : Composition de la solution FloraMicro (NPK : 5-0-1). Tab eau 2: Composition of the FloraMicro solution (NPK: 5-0-1).
[0149] [Table 3]
[0149] [Table 3]
Tableau 3 : Composition de la solution FloraGro (NPK : 3-1-6). [0150] [Table 4]
Table 3: Composition of FloraGro solution (NPK: 3-1-6). [0150] [Table 4]
Tableau 4 : Composition de la solution FloraBloom (NPK : 0-5-4). Table 4: Composition of FloraBloom solution (NPK: 0-5-4).
[0151] A JO, 400 graines de maïs de la variété Amaretto ont été placées sur de la vermiculite imbibée d'eau dans l'obscurité pendant 48 heures à 30°C, afin d'initier la germination. On D0, 400 maize seeds of the Amaretto variety were placed on vermiculite soaked in water in the dark for 48 hours at 30° C., in order to initiate germination.
[0152] A J2, les graines germées ont été placées en culture hydroponique selon 2 modalités (200 graines par modalité) : On D2, the germinated seeds were placed in hydroponic culture according to 2 modalities (200 seeds per modality):
- Modalité 1 : 35 mL de composition « 1,5.2+SN » - Modality 1: 35 mL of composition "1.5.2+SN"
- Modalité 0 : 35 mL de composition « T.2+SN »
[0153] Les cultures hydroponiques ont été maintenues pendant 16 jours, avec un renouvèlement des compositions tous les 2-3 jours. - Modality 0: 35 mL of “T.2+SN” composition The hydroponic cultures were maintained for 16 days, with a renewal of the compositions every 2-3 days.
[0154] Résultats [0154] Results
[0155] Longueur des feuilles [0156] La longueur des feuilles a été mesurée à chaque renouvellement des compositions et à[0155] Length of the leaves [0156] The length of the leaves was measured at each renewal of the compositions and at
J16. Les résultats sont présentés à la Figure 9. La longueur moyenne des feuilles à J17 est présentée à la Figure 10. D16. The results are shown in Figure 9. The average leaf length at D17 is shown in Figure 10.
[0157] Les résultats ont été analysés statistiquement (Analyse des différences entre les modalités avec un intervalle de confiance à 95%) selon le test ANOVA. Les calculs sont présentés dans les Tableaux 5 et 6. The results were analyzed statistically (Analysis of the differences between the methods with a confidence interval at 95%) according to the ANOVA test. The calculations are presented in Tables 5 and 6.
[0158] [Table 5]
[0158] [Table 5]
Tableau 5 : Analyses statistiques / Tukey (HSD) / Analyse des différences entre es modalités avec un intervalle de confiance à 95% (longueur des feuilles). Table 5: Statistical analyzes / Tukey (HSD) / Analysis of the differences between the modalities with a confidence interval at 95% (leaf length).
[0159] [Table 6]
modalités avec un intervalle de confiance à 95% (longueur des feuilles).
[0160] Les résultats montrent que la longueur des feuilles est significativement plus importante avec la composition comprenant des substances humiques ozonées, par rapport à la composition comprenant des substances humiques non-ozonées. [0159] [Table 6] modalities with a 95% confidence interval (leaf length). The results show that the length of the leaves is significantly greater with the composition comprising ozonated humic substances, compared with the composition comprising non-ozonated humic substances.
[0161] Il a également été montré que l'aire des feuilles augmentait significativement avec la composition comprenant des substances humiques ozonées, par rapport à la composition comprenant des substances humiques non-ozonées (résultats non-présentés). [0161] It was also shown that the area of the leaves increased significantly with the composition comprising ozonated humic substances, compared to the composition comprising non-ozonated humic substances (results not shown).
[0162] Longueur des racines [0162] Root length
[0163] La longueur des racines a été mesurée à chaque renouvellement des compositions et à J17. Les résultats sont présentés à la Figure 11. La longueur moyenne des feuilles à J17 est présentée à la Figure 12. The length of the roots was measured at each renewal of the compositions and at D17. The results are shown in Figure 11. The average leaf length at D17 is shown in Figure 12.
[0164] Les résultats ont été analysés statistiquement (Analyse des différences entre les modalités avec un intervalle de confiance à 95%) selon le test ANOVA. Les calculs sont présentés dans les Tableaux 7 et 8. The results were analyzed statistically (Analysis of the differences between the methods with a confidence interval at 95%) according to the ANOVA test. The calculations are presented in Tables 7 and 8.
[0165] [Table 7]
Tableau 7 : Analyses statistiques / Tukey (HSD) / Analyse des différences entre es modalités avec un intervalle de confiance à 95% (longueur des racines). [0165] [Table 7] Table 7: Statistical analyzes / Tukey (HSD) / Analysis of the differences between the modalities with a 95% confidence interval (length of the roots).
[0166] [Table 8]
[0166] [Table 8]
Tableau 8 : Analyses statistiques / Newman-Keuls (SNK) / Analyse des différences entre les modalités avec un intervalle de confiance à 95% (longueur des racines).
[0167] Les résultats montrent que la longueur des racines est significativement plus importante avec la composition comprenant des substances humiques ozonées, par rapport à la composition comprenant des substances humiques non-ozonées. Table 8: Statistical analyzes / Newman-Keuls (SNK) / Analysis of the differences between the modalities with a confidence interval at 95% (length of the roots). The results show that the length of the roots is significantly greater with the composition comprising ozonated humic substances, compared with the composition comprising non-ozonated humic substances.
[0168] Exemple 4 : influence de la quantité d'ozone [0168] Example 4: influence of the amount of ozone
[0169] Plusieurs compositions ont été préparées : Several compositions were prepared:
- Composition « 1,5.2+SN » (substances humiques ozonées ratio 1,5) : cf. Exemple 3.- Composition “1.5.2+SN” (ozonated humic substances ratio 1.5): cf. Example 3.
- Composition « 0,5.2+SN » (substances humiques ozonées ratio 0,5) : correspond à la composition « 1,5.2+SN » sauf que les substances humiques ont été ozonées avec un ratio masse d'ozone/masse de substances humiques de 0,5. - Composition "0.5.2+SN" (ozonated humic substances ratio 0.5): corresponds to the composition "1.5.2+SN" except that the humic substances have been ozonated with a mass ratio of ozone/mass of humic substances of 0.5.
- Composition « 3,5.2+SN » (substances humiques ozonées ratio 3,5) : correspond à la composition « 1,5.2+SN » sauf que les substances humiques ont été ozonées avec un ratio masse d'ozone/masse de substances humiques de 3,5. - Composition “3.5.2+SN” (ozonated humic substances ratio 3.5): corresponds to the composition “1.5.2+SN” except that the humic substances have been ozonated with a mass ratio of ozone/mass of humic substances of 3.5.
- Composition « T.2+SN » (substances humiques non ozonées) : cf. Exemple 3 - “T.2+SN” composition (non-ozonated humic substances): cf. Example 3
[0170] A J0, 80 graines de maïs de la variété Amaretto ont été placées sur de la vermiculite imbibée d'eau dans l'obscurité pendant 48 heures à 30°C, afin d'initier la germination. On D0, 80 maize seeds of the Amaretto variety were placed on vermiculite soaked in water in the dark for 48 hours at 30° C., in order to initiate germination.
[0171] A J2, les graines germées ont été placées en culture hydroponique selon 4 modalités (20 graines par modalité) : On D2, the germinated seeds were placed in hydroponic culture according to 4 modalities (20 seeds per modality):
- 35 mL de composition « 0,5.2+SN » - 35 mL of “0.5.2+SN” composition
- 35 mL de composition « 1,5.2+SN » - 35 mL of composition "1.5.2+SN"
- 35 mL de composition « 3,5.2+SN » - 35 mL of composition “3.5.2+SN”
- 35 mL de composition « T.2+SN ». - 35 mL of “T.2+SN” composition.
[0172] Les cultures hydroponiques ont été maintenues pendant 16 jours, avec un renouvèlement des compositions tous les 2-3 jours. The hydroponic cultures were maintained for 16 days, with a renewal of the compositions every 2-3 days.
[0173] Résultats [0173] Results
[0174] La longueur des racines a été mesurée à J14. Les résultats sont présentés à la Figure 13. The length of the roots was measured on D14. The results are shown in Figure 13.
[0175] Les résultats montrent que la longueur des racines augmente avec l'augmentation du ratio masse d'ozone/masse de substances humiques.
[0176] Exemple 5 : effets sur l'activité Dhotosvnthétiaue The results show that the length of the roots increases with the increase in the ratio mass of ozone/mass of humic substances. [0176] Example 5: effects on Dhotosvnthétiaue activity
[0177] Les plantes obtenues à l'Exemple 3 ont été utilisées pour mesurer la teneur des feuilles en chlorophylles et en caroténoïdes par spectrophotométrie UV-Visible. The plants obtained in Example 3 were used to measure the chlorophyll and carotenoid content of the leaves by UV-Vis spectrophotometry.
[0178] Matériel et méthodes [0178] Materials and methods
[0179] 0.5 g de feuilles broyées (broyage au mortier) ont été mis dans deux tubes flacon de lmL chacun. 4,5 mL de solution MeOH 100% ont été ajoutés au premier tube. 4,5mL de solution MeOH/3%KOH (0,3g de KOH dilué dans lOmL de MeOH 100%) ont été ajoutés au deuxième tube. Les deux tubes ont ensuite été vortexés puis ils ont été laissés 15min dans de la glace. Les tubes ont ensuite été centrifugés à 10000 RPM pendant 10min à 4°C. 0.5 g of ground leaves (grinding with a mortar) were placed in two vial tubes of 1 mL each. 4.5 mL of 100% MeOH solution was added to the first tube. 4.5mL of MeOH/3%KOH solution (0.3g of KOH diluted in 10mL of 100% MeOH) was added to the second tube. The two tubes were then vortexed and then left in ice for 15 minutes. The tubes were then centrifuged at 10,000 RPM for 10 min at 4°C.
[0180] Le contenu de chaque tube a été déposé sur une plaque 96 puits en 6 réplicas de 300pL par puit (c'est-à-dire 6 x 300pL pour le tube 1 et 6 x 300pL pour le tube 2). The content of each tube was deposited on a 96-well plate in 6 replicas of 300 μL per well (that is to say 6×300 μL for tube 1 and 6×300 μL for tube 2).
[0181] L'absorbance de chaque puit a été mesurée par TECAN et analysée sur le logiciel « Tecan control » selon les conditions suivantes : The absorbance of each well was measured by TECAN and analyzed on the "Tecan control" software according to the following conditions:
- Tube avec MeOH 100% : lecture à 663nm, 645nm et 470nm - Tube with 100% MeOH: reading at 663nm, 645nm and 470nm
- Tube avec MeOH/3%KOH : lecture à 472nm et 508nm. - Tube with MeOH/3%KOH: reading at 472nm and 508nm.
[0182] Les teneurs en caroténoïdes et en chlorophylles A et B ont été mesurées selon les équations suivantes : The carotenoid and chlorophyll A and B contents were measured according to the following equations:
- Caroténoïdes (en pg/mL) = (A472X 1724,3 - A508x2450,l) / 270,9 - Carotenoids (in pg/mL) = (A472X 1724.3 - A 508 x2450.l) / 270.9
- Chlorophylle A (en pg/mL) = 16,72xA663 - 9,16xA645 - Chlorophyll A (in pg/mL) = 16.72xA 663 - 9.16xA 645
- Chlorophylle B (en pg/mL) = 34,09xA645 - 15,28xA663 - Chlorophyll B (in pg/mL) = 34.09xA 645 - 15.28xA6 63
[0183] Résultats [0183] Results
[0184] Les résultats sont présentés aux Figures 14 à 16 et dans le Tableau 9 ci-après. The results are presented in Figures 14 to 16 and in Table 9 below.
[0185] [Table 9]
[0185] [Table 9]
[0186] Les résultats montrent que les teneurs en caroténoïdes et en chlorophylles augmentent lorsque le maïs est traité avec la composition comprenant des substances humiques ozonées, par rapport à la composition comprenant des substances humiques non-ozonées.
[0187] Exemple 6 : Analyses phvsico-chimiaue des substances humiaues témoins et ozonées The results show that the carotenoid and chlorophyll contents increase when the maize is treated with the composition comprising ozonated humic substances, compared with the composition comprising non-ozonated humic substances. Example 6: Phvsico-chemical analyzes of control and ozonated humic substances
[0188] Effet de la lyophilisation [0188] Effect of lyophilization
[0189] Le but de la lyophilisation est de déterminer si le passage à l'état solide des substances humiques ozonés, induit un réarrangement intra et inter moléculaire. Dans l'affirmative, on peut en déduire que les molécules devront être utilisées en solution et non sous forme de solides. The purpose of freeze-drying is to determine whether the transition to the solid state of ozonated humic substances induces an intra and inter molecular rearrangement. If so, it can be deduced that the molecules should be used in solution and not in the form of solids.
[0190] Protocole [0190] Protocol
[0191] 15 mL de des compositions « témoin » et « mère » de l'Exemple 1 ont été lyophilisées. Les compositions lyophilisées ont ensuite été dissoutes dans 15 mL d'eau MilliQ. Les solutions ainsi obtenues ont ensuite été analysées par HPSEC. [0191] 15 mL of the “control” and “stock” compositions of Example 1 were freeze-dried. The lyophilized compositions were then dissolved in 15 mL of MilliQ water. The solutions thus obtained were then analyzed by HPSEC.
[0192] Résultats HPSEC [0192] HPSEC Results
[0193] La Figure 17 montre que les courbes obtenues pour la composition non ozonée. La figure montre que les courbes sont similaires, les deux profils étant relativement proches. La lyophilisation n'influe que peu sur les substances humiques non ozonées (figure ci-dessous). Figure 17 shows the curves obtained for the non-ozonated composition. The figure shows that the curves are similar, the two profiles being relatively close. Freeze-drying has little influence on non-ozonated humic substances (figure below).
[0194] Dans le cas des substances humiques ozonées (Figure 18), on a obtenu des différences similaires à celles obtenues avec les substances humiques non ozonés. Il y avait un décalage de 8 secondes entre les deux courbes. De plus l'intensité du pic à 8 min était plus importante après la lyophilisation pour les substances humiques ozonées. Mis à part ces différences, les courbes sont similaires. In the case of ozonated humic substances (FIG. 18), differences similar to those obtained with non-ozonated humic substances were obtained. There was an 8 second lag between the two curves. In addition, the intensity of the peak at 8 min was greater after freeze-drying for ozonated humic substances. Apart from these differences, the curves are similar.
[0195] Les substances humiques ozonés selon le procédé de l'invention sont très stables et résistent à la lyophilisation. Les substances humiques ozonées selon l'invention peuvent donc être préparées à la fois sous forme liquide et sous forme solide (forme lyophilisée) sans altération. The ozonated humic substances according to the process of the invention are very stable and resist freeze-drying. The ozonated humic substances according to the invention can therefore be prepared both in liquid form and in solid form (freeze-dried form) without alteration.
[0196] Solubilité des substances humiaues en fonction du DH [0196] Solubility of humic substances as a function of DH
[0197] Protocole [0197] Protocol
[0198] Les compositions « témoin » et « mère » de l'Exemple 1 ont été utilisées. . Les compositions ont été placées dans des flacons et acidifiées avec des volumes croissants d'HCI à 0,1 mol/L. Les flacons ont été préalablement pesés vides (mfiaCon)- Toutes les compositions acidifiées ont ensuite été agitées puis centrifugées. Les culots et les surnageants ont été séparés, le pH du surnageant a été mesuré, le culot a quant à lui été
séché à l'étuve. Les flacons ont ensuite été pesés avec le culot (mCuiot+mfiacon)- Les pesées se sont faites une fois que les échantillons sont revenus à température ambiante. The “control” and “mother” compositions of Example 1 were used. . The compositions were placed in vials and acidified with increasing volumes of 0.1 mol/L HCl. The flasks were weighed beforehand empty (m fiaC on) - All the acidified compositions were then stirred and then centrifuged. The pellets and the supernatants were separated, the pH of the supernatant was measured, the pellet was oven-dried. The vials were then weighed with the pellet (m C uiot+mfiacon) - The weighings were made once the samples had returned to ambient temperature.
[0199] Pour chaque échantillon le pourcentage massique des substances humiques a été calculé selon la formule suivante : For each sample, the mass percentage of humic substances was calculated according to the following formula:
% SH massique — ((mcu|ot + mf|aCon) mf|aCon) X 100 / I ISH initial avec : % SH mass — ((m cu |ot + mf| aC on) mf| aC on) X 100 / I initial ISH with:
%SHmassique = % de substances humiques insolubles mcuiot = masse du culot mfiacon = masse du flacon vide mSH initiai = masse de substances humiques mises dans le flacon avant acidification. %SHmass = % of insoluble humic substances mcuiot = mass of the pellet mfiacon = mass of the empty bottle m SH initial = mass of humic substances put in the bottle before acidification.
[0200] Résultats [0200] Results
[0201] Le pH a été mesuré pour tous les échantillons. Mis à part pour l'échantillon sans ajout d'HCI pour lequel la différence est importante (3 unités pH), les autres valeurs de pH étaient relativement proches les unes des autres pour un même volume d'HCI ajouté. [0201] The pH was measured for all the samples. Apart from the sample without addition of HCl for which the difference is significant (3 pH units), the other pH values were relatively close to each other for the same volume of HCl added.
[0202] La Figure 19 montre que plus on a acidifié la solution plus on a eu tendance à faire précipiter les substances humiques. Cependant les substances humiques non ozonées ont été précipitées à hauteur de 60% tandis que les substances humiques ozonées ont été précipitées à 30% seulement. L'ozonation a donc amélioré la solubilité des substances humiques dans les pH acides.
[0202] Figure 19 shows that the more the solution was acidified, the more the humic substances tended to precipitate. However, the non-ozonated humic substances were precipitated up to 60% while the ozonated humic substances were only precipitated at 30%. Ozonation therefore improved the solubility of humic substances in acidic pH.
BIBLIOGRAPHIE BIBLIOGRAPHY
[1] Y. Karakurt, H. Unlu, H. Unlu, H. Padem, The influence of foliar and soil fertilization of humic acid on yield and quality of pepper, Acta Agric. Scand. Sect. B Soil Plant Sci. 59 (2009) 233-237. [1] Y. Karakurt, H. Unlu, H. Unlu, H. Padem, The influence of foliar and soil fertilization of humic acid on yield and quality of pepper, Acta Agric. scand. sect. B Soil Plant Sci. 59 (2009) 233-237.
[2] B.L. Loeb, C.M. Thompson, J. Drago, H. Takahara, S. Baig, Worldwide Ozone Capacity for Treatment of Drinking Water and Wastewater: A Review, Ozone Sci. Eng. 34 (2012) 64- 77. [2] B.L. Loeb, C.M. Thompson, J. Drago, H. Takahara, S. Baig, Worldwide Ozone Capacity for Treatment of Drinking Water and Wastewater: A Review, Ozone Sci. Eng. 34 (2012) 64-77.
[3] A.A.-P. Pascual A. A4 - Llorca, I. A4 - Canut, A., Use of ozone in food industries for reducing the environmental impact of cleaning and disinfection activities, Trends Food Sci. Technol. v. 18 (2007) S29-S35-2007 v.18. [3] A.A.-P. Pascual A. A4 - Llorca, I. A4 - Canut, A., Use of ozone in food industries for reducing the environmental impact of cleaning and disinfection activities, Trends Food Sci. Technology. v. 18 (2007) S29-S35-2007 v.18.
[4] M. Bataller, E. Veliz, R. Pérez-Rey, L.A. Fernandez, M. Gutierrez, A. Marquez, Ozone swimming pool water treatment under tropical conditions, Ozone Sci. Eng. 22 (2000) 677- 682. [4] M. Bataller, E. Veliz, R. Pérez-Rey, L.A. Fernandez, M. Gutierrez, A. Marquez, Ozone swimming pool water treatment under tropical conditions, Ozone Sci. Eng. 22 (2000) 677-682.
[5] Stevenson, 1994, Humus Chemistry, Deuxième édition, Wiley, New York (https: //books. google.fr/books/about/Humus_Chemist ry.html?id=7kCQch_YKoMC&redir_esc =y ). [5] Stevenson, 1994, Humus Chemistry, Second Edition, Wiley, New York (https://books.google.fr/books/about/Humus_Chemistry.html?id=7kCQch_YKoMC&redir_esc=y).
[6] X. Zhong et al. Formation of Aldehydes and Carboxylic acids in humic acid ozonation. Water Air Soil Pollut. (2017) p228. [6] X. Zhong et al. Formation of Aldehydes and Carboxylic acids in humic acid ozonation. Water Air Soil Pollut. (2017) p228.
[7] Hanninen et al., 1987, La science de l'environnement total, 62, 201-210 [7] Hanninen et al., 1987, The Science of the Total Environment, 62, 201-210
[8] Fuentes M., Simultaneous Presence of Diverse Molecular Patterns in Humic Substances in Solution, J. Phys. Chem. B (2007) 111, 35, 10577-10582. [8] Fuentes M., Simultaneous Presence of Diverse Molecular Patterns in Humic Substances in Solution, J. Phys. Chem. B (2007) 111, 35, 10577-10582.
[9] Les amendements organiques, Utilisation des matières organiques en construction (http://www.alaindehaye.com/Amendements%20organi.%205.PDF). [9] Organic amendments, Use of organic materials in construction (http://www.alaindehaye.com/Amendements%20organi.%205.PDF).
[10] Saito et al., Alkaline Extraction of Humic Substances, Brazilian Journal of Chemical Engineering, Vol. 31, No. 03, pp. 675 - 682, July - September, 2014. [10] Saito et al., Alkaline Extraction of Humic Substances, Brazilian Journal of Chemical Engineering, Vol. 31, No. 03, p. 675 - 682, July - September, 2014.
[11] Bhattacharjee S. DLS and zeta potential - What they are and what they are not? Journal of Controlled Release (2016) 235, 337-351.
[11] Bhattacharjee S. DLS and zeta potential - What they are and what they are not? Journal of Controlled Release (2016) 235, 337-351.
Claims
REVENDICATIONS
Procédé de préparation d'une composition fertilisante, comprenant une étape de traitement d une composition liquide de substances humiques dont le rayon hydrodynamique moyen en masse des particules en solution, mesuré par Dynamic Light Scattering (DLS), est « Rhmoyen avant traitement » avec une quantité appropriée d'agent oxydant pour obtenir une composition liquide de substances humiques oxydée dont le rayon hydrodynamique moyen en masse des particules en Solution (Rhmoyen après traitement), meSUre par DLS, eSt Supérieur au Rhmoyen avant traitement- Process for the preparation of a fertilizing composition, comprising a step of treating a liquid composition of humic substances, the mass-average hydrodynamic radius of the particles in solution of which, measured by Dynamic Light Scattering (DLS), is " average Rh before treatment" with an appropriate amount of oxidizing agent to obtain a liquid composition of oxidized humic substances whose mass-average hydrodynamic radius of the particles in solution (Rhaverage after treatment), measured by DLS, is greater than the Rhaverage before treatment-
2. Procédé selon la revendication 1, ladite composition liquide de substances humiques est obtenue à partir de la tourbe, de la léonardite, du lignite, de la houille ou de l'anthracite. 2. Method according to claim 1, said liquid composition of humic substances is obtained from peat, leonardite, lignite, coal or anthracite.
3. Procédé selon l'une quelconque des revendications 1 à 2, ladite composition liquide de substances humiques comprend au moins 50% en masse sèche de substances humiques. 3. Method according to any one of claims 1 to 2, said liquid composition of humic substances comprises at least 50% by dry mass of humic substances.
4. Procédé selon l'une quelconque des revendications 1 à 3, ledit agent oxydant est choisi parmi l'ozone, les ultra-violets et/ou le peroxyde d'hydrogène. 4. Method according to any one of claims 1 to 3, said oxidizing agent is chosen from ozone, ultraviolet rays and/or hydrogen peroxide.
5. Procédé selon l'une quelconque des revendications 1 à 4, ledit le Rhmoyen après traitement est aU moins 5 fois supérieur au Rhmoyen avant traitement- 5. Method according to any one of claims 1 to 4, said average Rh after treatment is at least 5 times greater than average Rh before treatment-
6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisée en ce que la proportion massique des particules en solution ayant un rayon hydrodynamique compris entre 15 nm et 10000 nm de la composition de substances humiques oxydée, mesurée par DLS, est au moins 2 fois supérieure à la proportion massique des particules en solution ayant un rayon hydrodynamique compris entre 15 nm et 10000 nm de la composition de substances humiques avant oxydation. 6. Method according to any one of claims 1 to 5, characterized in that the mass proportion of the particles in solution having a hydrodynamic radius of between 15 nm and 10,000 nm of the composition of oxidized humic substances, measured by DLS, is at least 2 times greater than the mass proportion of particles in solution having a hydrodynamic radius between 15 nm and 10000 nm of the composition of humic substances before oxidation.
7. Composition fertilisante susceptible d'être obtenue par le procédé selon les revendications 1 à 6. 7. Fertilizing composition obtainable by the process according to claims 1 to 6.
8. Composition fertilisante selon la revendication 7, caractérisée en ce que le rayon hydrodynamique moyen en masse des particules en solution (Rhmoyen), mesuré par DLS, est supérieur à 50 nm.
8. Fertilizing composition according to claim 7, characterized in that the mass-average hydrodynamic radius of the particles in solution ( average Rh), measured by DLS, is greater than 50 nm.
9. Composition selon la revendication 7 ou 8, caractérisée en ce que la proportion massique des particules en solution ayant un rayon hydrodynamique compris entre 15 nm et 10000 nm, mesurée par DLS, est supérieure à 15%. 9. Composition according to claim 7 or 8, characterized in that the mass proportion of the particles in solution having a hydrodynamic radius of between 15 nm and 10,000 nm, measured by DLS, is greater than 15%.
10. Composition selon l'une quelconque des revendications 7 à 9, comprenant en outre un ou plusieurs engrais minéraux, de préférence contenant un ou plusieurs minéraux choisis parmi l'azote, le phosphore, le potassium, le calcium, le magnésium et le soufre. 10. Composition according to any one of claims 7 to 9, further comprising one or more mineral fertilizers, preferably containing one or more minerals chosen from nitrogen, phosphorus, potassium, calcium, magnesium and sulfur .
11. Utilisation d'une composition selon l'une quelconque des revendications 7 à 10 comme stimulant de l'absorption de minéraux chez une plante, de préférence les minéraux sont choisis parmi l'azote, le phosphore, le potassium, le calcium, le magnésium et/ou le soufre. 11. Use of a composition according to any one of claims 7 to 10 as a stimulant for the absorption of minerals in a plant, preferably the minerals are chosen from nitrogen, phosphorus, potassium, calcium, magnesium and/or sulfur.
12. Utilisation d'une composition selon l'une quelconque des revendications 7 à 10 comme stimulant de la production de pigments chez une plante, de préférence la production de caroténoïdes, de chlorophylle A et/ou de chlorophylle B. 12. Use of a composition according to any one of claims 7 to 10 as a stimulant for the production of pigments in a plant, preferably the production of carotenoids, chlorophyll A and/or chlorophyll B.
13. Utilisation selon l'une quelconque des revendications 11 et 12, pour stimuler la croissance aérienne et/ou racinaire de la plante. 13. Use according to any one of claims 11 and 12, for stimulating aerial and/or root growth of the plant.
14. Procédé de fertilisation d'une plante, d'un sol ou d'un support de culture comprenant l'application à la plante, audit sol ou audit support de culture d'une composition selon l'une des revendications 7 à 10. 14. A method of fertilizing a plant, a soil or a growing medium comprising the application to the plant, to said soil or to said growing medium of a composition according to one of claims 7 to 10.
15. Procédé de fertilisation d'une plante, d'un sol ou d'un support de culture consistant à : 15. Process for fertilizing a plant, soil or growing medium consisting of:
- préparer une composition fertilisante en mettant en œuvre un procédé selon l'une quelconque des revendications 1 à 6, et - preparing a fertilizing composition by implementing a method according to any one of claims 1 to 6, and
- appliquer ladite composition fertilisante à la plante, au sol ou au support de culture. - Applying said fertilizing composition to the plant, to the soil or to the growing medium.
16. Procédé selon l'une quelconque des revendications 14 à 15, caractérisé en ce que l'application à la plante, au sol ou audit support de culture permet de stimuler l'absorption de minéraux chez une plante et/ou de stimuler la production de pigments chez la plante. 16. Method according to any one of claims 14 to 15, characterized in that the application to the plant, to the soil or to the said growing medium makes it possible to stimulate the absorption of minerals in a plant and/or to stimulate the production pigments in the plant.
17. Procédé selon l'une quelconque des revendications 14 à 16, caractérisé en ce que la composition est appliquée à un sol acide.
17. Method according to any one of claims 14 to 16, characterized in that the composition is applied to an acid soil.
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|---|---|---|---|
| FR2009050A FR3113903B1 (en) | 2020-09-07 | 2020-09-07 | Process for preparing a fertilizing composition by oxidation |
| PCT/FR2021/051524 WO2022049355A1 (en) | 2020-09-07 | 2021-09-06 | Oxidative method for preparing a fertilising composition |
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| EP (1) | EP4211096A1 (en) |
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| JOP20190195A1 (en) * | 2017-02-14 | 2019-08-15 | Univ Navarra | Humic substance-encapsulated particles, compositions and method of making the same. |
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