WO2025007201A1 - Engrais à base de bois - Google Patents
Engrais à base de bois Download PDFInfo
- Publication number
- WO2025007201A1 WO2025007201A1 PCT/BR2024/050284 BR2024050284W WO2025007201A1 WO 2025007201 A1 WO2025007201 A1 WO 2025007201A1 BR 2024050284 W BR2024050284 W BR 2024050284W WO 2025007201 A1 WO2025007201 A1 WO 2025007201A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fertilizer
- soil
- hemicellulose
- cellulose
- primary
- Prior art date
Links
- 239000002023 wood Substances 0.000 title claims abstract description 16
- 239000003337 fertilizer Substances 0.000 title claims description 89
- 239000002689 soil Substances 0.000 claims abstract description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229920002678 cellulose Polymers 0.000 claims abstract description 46
- 239000001913 cellulose Substances 0.000 claims abstract description 46
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 13
- 230000008635 plant growth Effects 0.000 claims abstract description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 241000209504 Poaceae Species 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 57
- 150000003335 secondary amines Chemical class 0.000 claims description 40
- 150000003141 primary amines Chemical class 0.000 claims description 31
- 241000196324 Embryophyta Species 0.000 claims description 29
- 239000000835 fiber Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 239000012048 reactive intermediate Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 230000004720 fertilization Effects 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 4
- 238000004382 potting Methods 0.000 claims description 3
- 125000001302 tertiary amino group Chemical group 0.000 claims description 3
- 241000609240 Ambelania acida Species 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- 239000011236 particulate material Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000004576 sand Substances 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000618 nitrogen fertilizer Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000012010 growth Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 238000010951 particle size reduction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241001057636 Dracaena deremensis Species 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 240000007154 Coffea arabica Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000021185 dessert Nutrition 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000011890 leaf development Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000021749 root development Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C11/00—Other nitrogenous fertilisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
Definitions
- Nitrogenous fertilizers provide nitrogen to the soil, which is an important element to sustain plant growth. By enhancing nitrogen presence in a soil, plant growth can be stimulated.
- nitrogen fertilizers (urea, ammonium nitrate, ammonium sulphate, and the like] have the drawback of a high solubility. Although high solubility facilitates distribution of the fertilizer through soil, and also facilitates uptake of (nitrogenous substances derived from] the fertilizer by the plant, it also results in leakage: nitrogenous substances may wash out of the soil by unavoidable processes such as watering (by hand or by rain], or by diffusion. This results in nitrogen loss, which hampers efficiency of use. Also, nitrogen leakage may be detrimental to the environment, for example in cases where agriculture is practiced in areas close to natural areas which naturally thrive in low nitrogen conditions. In such cases, the natural area may become enriched in nitrogen (nitrification], altering the natural state of the area.
- the present invention provides a fertilizer which overcomes the above drawbacks.
- FIG. 1 Scanning electron microscopy (SEM) picture of the wood used in example 1 for preparing the fertilizer (A), and of the fertilizer of the invention (B).
- FIG. 1 The fertilizer of the invention after preparation and drying to equilibrium moisture content
- Figure 3 (A): corn seeds seeded in pots containing washed sand enriched with the fertilizer of the invention in different proportions. (B) the same pots having germinated seeds after 7 days.
- Figure 4 Leaf development of an exemplary corn plant grown in a soil mixture comprising washed sand and the fertilizer of the invention.
- Figure 5 Corn plants grown in a soil mixture comprising washed sand and the fertilizer of the invention after 28 days.
- Figure 6 schematic procedure for preparing the fertilizer of the invention by reacting a material comprising fibers from cellulose and/or hemicellulose with an aqueous hydroxide base to provide a material comprising activated cellulose and/or activated hemicellulose, and separately reacting a primary or secondary amine with a carbonyl compound to provide a reactive intermediate, and subsequently combining the material comprising activated cellulose and/or activated hemicellulose with the reactive intermediate to provide the fertilizer, which is thereafter isolated by filtration, dried and ground.
- the invention provides a fertilizer comprising fibers from cellulose and/or hemicellulose, wherein said fibers comprise covalently bonded nitrogen-containing side groups.
- the present fertilizer can be used for (nitrogen] fertilization for most common plants. It is an advantage of the present invention that the fertilizer provides high efficiency of nitrogen fertilization, essentially without leakage to the environment. The present fertilizer provides for increased duration of nitrogen presence in the soil where it was admixed to,
- the fertilizer can be made using readily accessible materials, in an easy to use process.
- the present fertilizer is essentially a natural fertilizer, capable of providing sustained nitrogen presence for prolonged periods of time.
- the present fertilizer may be used to enhance water retention, and/or to enhance soil aeration, and the character anionic of the material, what easy the permutation of cations.
- a plant can be any plant, such as a wild plant (defined as a plant which grows naturally in its location], an ornamental plant, an agricultural plant, or a horticultural plant. Plants suitable for use in food are preferred, such as human food or animal feed. Further preferred are plants which require high quantities of nitrogen for optimal growth. The skilled person knows which plants require high quantities of nitrogen, in order to achieve optimal growth.
- the present fertilizer comprises fibers from cellulose and/or hemicellulose. In one embodiment, the present fertilizer comprises fibers from cellulose. In another embodiment, the present fertilizer comprises fibers from hemicellulose. In much preferred embodiments, the present fertilizer comprises fibers from cellulose and from hemicellulose.
- the fibers from cellulose and/or hemicellulose are preferably present in the form of a material comprising cellulose and/or hemicellulose and/or lignin.
- the material is rich in cellulose and/or hemicellulose.
- the material comprises 50 wt.% - 99 wt.%, more preferably 55 wt.% - 90 wt.%, even more preferably 60 wt.% - 85 wt.% of cellulose and/or hemicellulose.
- the material comprises 35 - 85 wt.% cellulose, preferably 40 - 70 wt.% cellulose.
- the material comprises 10 - 50 wt.
- the material additionally comprises lignin, such as in a quantity of 10 - 35 wt.%, preferably 15 - 30 wt.%.
- the material is plant material.
- Plant material in this context, refers to any material obtained from plants which comprises cellulose and/or hemicellulose and/or lignin.
- the material is plant material processed by physical and/or chemical.
- Preferred material is plant material from trees, shrubs or grasses. In much preferred embodiments, the material is wood. In other preferred embodiments, the material is and waste of the crops (corn, rice, wheat and coffee).
- the material which provides the fibers from cellulose and/or hemicellulose of the present fertilizer is a particulated material.
- Particulated in this regard, means that the particle size of the material is 0.05 - 6.0 cm, preferably 0.1 - 4.0 cm, more preferably 0.5 - 2.0 cm.
- Particle size is herein defined as the longest straight-line distance between opposing sides of a particle.
- the fibers from cellulose and/or hemicellulose in the present fertilizer comprise covalently bonded nitrogen-containing side groups. That is, the fibers have been modified to incorporate (nitrogen-containing) side groups on the cellulose and/or hemicellulose molecules.
- the nitrogen-containing side groups comprise at least one nitrogen atom.
- the nitrogen-containing side group comprises multiple nitrogen atoms.
- the nitrogen-containing side groups are derived from a primary or secondary amine, preferably a primary or secondary amine which is rich in nitrogen.
- Nitrogen rich is defined as at least 30 wt.%, relative to molecular weight of the amine, of nitrogen atoms, preferably at least 40 wt.%, more preferably at least 45 wt.%, even more preferably at least 50 wt.% nitrogen, even more preferably at least 60 wt.%. nitrogen (“N”).
- the nitrogen-containing side groups are derived from a primary amine.
- the nitrogen-containing side groups are preferably derived from melamine (a primary amine having 66 wt.% N), urea (a primary amine having 46 wt.% N), ethylene diamine (a primary amine having 46 wt.% N)
- SUBSTITUTE SHEET (RULE 26) or diethylene triamine (a primary and secondary amine having 42 wt.% N), preferably melamine.
- the nitrogen-containing side group is attached to the cellulose and/or hemicellulose backbone through a secondary or tertiary amine bond.
- Side groups derived from a primary amine provide side groups attached to the cellulose and/or hemicellulose backbone through a secondary amine group.
- Side groups derived from a secondary amine provide side groups attached to the cellulose and/or hemicellulose fiber through a tertiary amine group.
- the attachment of the primary or secondary amine is through a covalent bond.
- the cellulose and/or hemicellulose fiber is substituted with nitrogen-rich moieties as defined above through secondary or tertiary amine groups.
- the quantity of nitrogen which can be present in the present fertilizer may vary within wide ranges.
- the present fertilizer may have a nitrogen (NJ content of 10 - 500 mg N per gram fertilizer, preferably 20 - 250 mg N per gram fertilizer, more preferably 30 - 150 mg N per gram fertilizer.
- Nitrogen content can be determined by Kjeldahl determination, as is known in the art.
- the fertilizer of the invention preferably has a particle size, defined as above, of 0.05 - 6.0 cm, preferably 0.1 - 4.0 cm, more preferably 0.5 - 2.0 cm.
- the fertilizer preferably has a pH of from 3.0 - 10.0, such as 3.5 - 9.0.
- the fertilizer has a pH of 4.5 - 7.0, preferably 5.0 - 7.0.
- the fertilizer has a pH of from 6.5 - 10.0, preferably 7.0 - 9.5.
- the fertilizer is a free flowing powder.
- the free-flowing powder preferably has a moisture content of from 1.0 - 15 wt.%, preferably 3 - 12 wt.%.
- the moisture content is preferably the equilibrium moisture content, as dictated by the humidity of the surroundings.
- the invention further provides a method for preparing the fertilizer described above, comprising:
- SUBSTITUTE SHEET (RULE 26) a) providing a material comprising fibers from cellulose and/or hemicellulose; b) reacting said material with an aqueous hydroxide base, preferably sodium hydroxide, to provide a material comprising activated cellulose and/or activated hemicellulose; c) providing a primary or a secondary amine; d) reacting said primary or secondary amine with a carbonyl compound to provide a reactive intermediate; e) reacting the material comprising activated cellulose and/or activated hemicellulose obtained under b) with the reactive intermediate obtained under d) to provide the fertilizer.
- an aqueous hydroxide base preferably sodium hydroxide
- the material comprising fibers from cellulose and/or hemicellulose has been defined above, and is preferably plant material, such as for example wood or bagasse, most preferably wood.
- the material is reacted with an aqueous hydroxide base, preferably sodium hydroxide, to provide a material comprising activated cellulose and/or activated hemicellulose.
- the aqueous hydroxide base preferably has a concentration of hydroxide salt (e.g. NaOH) in water of 1 - 30 wt.%, more preferably 5 - 25 wt.%, more preferably 10 - 20 wt.%, optimally about 15 - 20 wt.%.
- hydroxide salt e.g. NaOH
- the reaction can be carried out by combining the material with the aqueous hydroxide base in any appropriate vessel, preferably while providing some form of mixing (e.g. stirring) and allowing the reaction to occur.
- the temperature is maintained between 20 - 100 °C, in which case the reaction may be allowed to proceed for a period of 1 - 30 hours.
- Higher temperatures allow for a considerable shortening of the reaction time: in the preferred embodiment where the material is heated in the aqueous hydroxide solution (to 70 - 100 °C), the reaction could provide sufficient quantities of activated cellulose and/or activated hemicellulose in as little as 0.5 - 5 hours, preferably 0.5 - 2.5 hours.
- the material comprising activated cellulose and/or activated hemicellulose is separated from the aqueous hydroxide solution.
- SUBSTITUTE SHEET (RULE 26) This may be achieved in any conceivable way, such as by decanting, filtering, centrifuging or cycloning. This provides a solid particulate material comprising activated cellulose and/or activated hemicellulose.
- the material is subsequently washed, preferably to a pH of 7.0 - 9.0, more preferably 7.0 - 8.0. Said washing is preferably performed with an aqueous medium having a temperature of 20 - 90 °C, said aqueous medium preferably being water.
- the method further comprises a step of providing a primary or secondary amine.
- Said primary or secondary amine will become the nitrogen-containing side group, to be coupled through the nitrogen atom of the primary or secondary amine.
- the primary or secondary amine has been defined above: it is preferably a nitrogen-rich primary or secondary amine, most preferably a nitrogen-rich primary amine.
- the primary or secondary amine is melamine, urea, ethylene diamine or diethylene triamine, most preferably melamine.
- the primary or secondary amine is reacted with a carbonyl compound to provide a reactive intermediate.
- the carbonyl compound is preferably a small molecular compound.
- a small molecular compound in this context, is a compound which has a molecular weight of from 30 to 100, preferably from 30 - 80, more preferably from 30 to 60.
- the carbonyl compound is preferably formaldehyde, acetaldehyde or acetone, most preferably formaldehyde.
- the reaction of the primary or secondary amine with the carbonyl compound is preferably performed by heating the primary or secondary amine in the presence of the carbonyl compound.
- the carbonyl compound is preferably a liquid at the reaction temperature, so that the carbonyl
- SUBSTITUTE SHEET (RULE 26) compound may function as solvent as well as reactant.
- the carbonyl compound and primary or secondary amine are dissolved in an appropriate solvent.
- Appropriate solvents for this type of reaction are well-known in the art of organic chemistry.
- Formaldehyde for example, is preferably used in the form of an aqueous solution, such as a 37 % formaldehyde solution (formalin).
- the primary or secondary amine is combined in a 1 : 2 or 1 : 1, respectively, mass ratio with formaldehyde, and subsequently heated, preferably while stirring, as defined elsewhere.
- the primary or secondary amine is dissolved in an alkaline medium, preferably having a pH of 7.1 - 11.0, preferably 8 - 11, more preferably 8.5 - 10.0, in a concentration of 0.5 - 5 wt.%, preferably 1.0 - 3.0 wt.%, relative to the total mass of the alkaline medium.
- the alkaline medium may optionally comprise a base; suitable bases are known in the art.
- the primary or secondary amine is dissolved in formalin, at the indicated concentration or mass ratio.
- the heating can be to any suitable temperature, as is known in the art.
- the temperature can be from 30 - 90 °C, more preferably 50 - 70 °C, more preferably about 60 °C.
- the duration of heating can be 5 - 300 minutes, preferably 10 - 120 minutes, more preferably about 40 minutes.
- the reaction between the primary or secondary amine and the carbonyl compound is performed by heating the amine (preferably melamine) in an aqueous formaldehyde solution to a temperature of 40 - 80 °C for a period of 20 - 120 minutes. This provides a solution of a reactive intermediate.
- the reactive intermediate may for example be an amine alcohol, depending on the chosen reactants and reaction conditions.
- the material comprising activated cellulose and/or activated hemicellulose is subsequently reacted with the reactive intermediate to provide the fertilizer.
- the reaction may be referred to as a coupling reaction, which effects the coupling of the primary or secondary amine to the
- SUBSTITUTE SHEET (RULE 26) (activated) cellulose and/or hemicellulose, to provide a material which comprises cellulose and/or hemicellulose bearing (covalently bounded) nitrogen-containing side groups.
- the reaction can be achieved by combining the solution of the reactive intermediate as obtained in step d) with the material comprising activated cellulose and/or activated hemicellulose as obtained under b), preferably in a mass ratio of 1 : 1 - 1 : 10, preferably 1 : 1 - 1 : 5.
- the reaction is preferably performed by heating the material comprising activated cellulose and/or activated hemicellulose in the presence of the reactive intermediate at a temperature of 30 - 95 °C, preferably 50 - 90 °C, more preferably about 85 °C.
- the reaction time is preferably a period of 5 - 300 minutes, more preferably 10 - 120 minutes.
- the reaction mixture is subsequently neutralized, such as by using an acid, for example acetic acid.
- the pH of the fertilizer can be adjusted as needed, such as by addition of an acid or base, to a pH of from 3.0 - 10.0, such as 3.5 - 9.0.
- the pH can be adjusted to 4.5 - 7.0, preferably 5.0 - 7.0.
- the pH can be adjusted to 6.5 - 10.0, preferably 7.0 - 9.5.
- Suitable acids or bases to achieve pH adjustment are known in the art, and include any acid or base which does not hamper plant growth, and which does not degrade the fertilizer of the invention. Examples include dilute hydroxide solutions, or weak acids or bases such as ammonia /ammonium solutions, acetic acid/acetate solutions, or citric acid/citrate solutions.
- the product of the reaction is subsequently separated from the reaction mixture, such as by filtration, decanting, sieving or cycloning. In further preferred embodiments, the product is subsequently dried to provide a powder.
- the reaction (e) to provide the fertilizer from the material comprising cellulose and/or hemicellulose and the primary or secondary amine is preferably performed so that the quantity of primary or secondary amine (under c) of the method) is 2 - 50 wt.%, preferably 10 - 35 wt.%, more
- SUBSTITUTE SHEET (RULE 26) preferably about 25 wt.%, of the quantity of material under a) of the method.
- the reactions are performed batch- wise, so that the quantity of material under a) and the quantity of primary or secondary amine under c) are adapted to provide a single batch of material comprising activated cellulose and/or hemicellulose under b) and a single batch of reactive intermediate under d), said single batches being appropriate to be combined so as to provide the fertilizer with the abovespecified ratio of primary or secondary amine to material comprising cellulose and/or hemicellulose.
- reaction sequence may be executed continuously so as to provide the fertilizer with the abovespecified ratio of primary or secondary amine to material comprising cellulose and/or hemicellulose.
- the skilled person is able to convert a batch process as shown herein to a continuous process using common general knowledge and some routine experiments.
- the fertilizer can be subjected to particle size reduction to obtain a preferred particle size.
- a preferred particle size is 0.01 - 6.0 cm, preferably 0.05 - 4.0 cm, more preferably 0.1 - 2.0 cm, even more preferably 0.1 - 1.0 cm, even more preferably 0.2 - 0.5 cm.
- Particle size reduction can be achieved by any means known in the art, such as for example grinding, milling, cutting or crushing. Grinding is preferred. Techniques for particle size reduction, including grinding, are conventionally known in the art, and any technique can be used. An example is a ball mill.
- the invention furthermore provides a soil mixture comprising the fertilizer as herein defined.
- Soil in this context, is to be understood broadly as any type of medium suitable to sustain at least some plant growth. Plain sand is encompassed in the definition of soil, such as for example dessert sand or river sand.
- soil comprising a mixture of inorganic particles and organic matter. Said inorganic particles may be selected from clay, sand and the like.
- soil is to be understood as the
- SUBSTITUTE SHEET (RULE 26) total of inorganic particles and all further organic matter which may be present in a soil used for plant growth, except for the fertilizer.
- the soil may be combined with the fertilizer in any usable ratio.
- the soil mixture comprises soil in a quantity of 25 - 99 wt.%, more preferably 40 - 95 wt.%, even more preferably 50 - 90 wt.%, most preferably 60 - 80 wt.%.
- the soil mixture comprises the fertilizer in a quantity of 1 - 75 wt.%, preferably 5 - 60 wt.%, more preferably 10 - 50 wt.%, most preferably 20 - 40 wt.%.
- the soil mixture may comprise, in addition to the soil as herein defined and the fertilizer, up to 10 wt.% of other components.
- Such components may include, for example, a source of potassium, sulphur and/or phosphorous.
- the soil furthermore comprises minerals, such as nitrogen, potassium, sulphur and/or phosphorous, in quantities sufficient to sustain at least some plant growth.
- a soil of the invention comprising the fertilizer of the invention has the advantage that it provides a steady nitrogen supply for prolonged periods, without leakage of nitrogen into the environment.
- a soil of the invention has the further advantage that it provides for improved water holding (relative to the soil without the present fertilizer), and improved aeration: the soil is more "loose” by enriching it with the present fertilizer.
- the soil mixture of the invention is preferably a soil for growing plants.
- the soil can be present in an agricultural field, in a greenhouse, a garden, or a in container for growing plants, such as a pot.
- the soil is preferably potting soil, garden soil, agricultural soil or horticultural soil.
- the soil mixture of the invention preferably has any pH which is convention for the type of soil in question.
- the pH may be of from 3.0 - 10.0, such as 3.5 - 9.0.
- the soil mixture has a pH of 4.5 - 7.0, preferably 5.0 - 7.0.
- the soil mixture has a pH of from 6.5 - 10.0, preferably 7.0 - 9.5.
- the invention also provides a method for fertilization, comprising a step of providing soil with the fertilizer of the invention.
- the soil may be provided with the present fertilizer in any conceivable means.
- the soil can be provided with the fertilizer by combining the fertilizer with the soil, and optional subsequent mixing.
- the fertilizer may be distributed on top of the soil, or it may be mixed into the soil.
- the fertilizer is mixed into the soil, such as by (pre)mixing (in the case of potting soil or gardening soil), or by distribution of the fertilizer on the soil and subsequent mixing, such as by ploughing, scratching or raking (in the case of larger patches of soil, such as agricultural soil).
- the mass ratio of fertilizer to soil is preferably 100 : 1 - 1 : 100, more preferably 50 : 1 - 1 : 50, more preferably 1 : 1 - 1 : 50.
- the fertilizer is used in a quantity of 1 - 75 wt.%, preferably 5 - 60 wt.%, more preferably 10 - 50 wt.%, most preferably 20 - 40 wt.%, relative to the mass of the soil after enrichment with the fertilizer.
- the invention furthermore provides use of the present fertilizer for promoting plant growth.
- Use of the invention can be in any context, such as promoting plant growth in areas where plants only grow with difficulty, or promoting plant growth so as to stimulate said growth beyond the capacity of the soil itself.
- Use of the invention thus may provide enhanced flowering, or increase a harvest.
- Ground wood with particles having particle sizes (the longest straight-line distance between opposing sides of a particle) between 0.5 and 2.0 cm was activated in a 20 wt.% aqueous NaOH solution at 100 °C for 2 hours under stirring.
- the wood particles were isolated by filtration and washed with water to a pH in the range of 7.0 - 8.0.
- SUBSTITUTE SHEET (RULE 26) Melamine was dissolved in a 37 % aqueous formaldehyde solution ("formalin”) at a concentration of 2.0 wt.%. The pH of the solution was around 9.0. The solution was heated to 60 °C for a period of 40 minutes, thereby providing a reactive intermediate suitable for reaction with the activated wood.
- formalin aqueous formaldehyde solution
- the isolated activated wood was combined with the melamine-formaldehyde solution and heated to a temperature of 85 °C for 30 minutes under stirring.
- the product was subsequently filtered, washed with water and dried, and then ground using a ball mill to a particle size of 0.2 - 0.5 cm.
- the quantity of nitrogen in the wood was 21,4 g N/100 g fertilizer, as determined by Kjeldahl.
- Example 2 application of the fertilizer to stimulate plant growth River sand was thoroughly washed with fresh (tap) water to pH 7.5 to remove all nutrients.
- the washed sand was combined with the fertilizer of the invention in four different proportions, providing sand/fertilizer (soil) mixtures having 100.0, 200.0, 300.0 and 400.0 mg N/kg of washed sand (0.470, 0.935, 1.405 and 1,870 g fertilizer per kg of sand).
- Pots were filled with the sand/fertilizer mixture, and corn was seeded in the soil mixture.
- Table 1 growth parameters for plants grown in plain sand using various quantities of the fertilizer of the invention.
- the plant is able to dedicate its energy to growth, which can be seen from the increase in leaf and stem mass, and in particular leaf area. Plants without the fertilizer of the invention direct their energy to the search for more nutrients, as can be seen from higher attention given to root development in control 1.
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Abstract
La présente invention concerne un procédé de production et un produit à utiliser comme engrais azoté dans des plantations agricoles. Le procédé comprend : des étapes de traitement du bois (arbres et/ou arbustes et/ou graminées) suivies de deux autres étapes, la préparation de la substance azotée (mélamine, méthylol-mélamine et tous les dérivés de mélamine) qui se lient au bois (cellulose et/ou hémicellulose) et la réaction de fixation du composé dans le bois. Le produit (composite de bois azoté (cellulose/hémicellulose)) a été appliqué dans des expériences agricoles : dans du sable lavé pour tester la libération d'azote et dans le sol pour surveiller la croissance des plantes.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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BR1020230134513 | 2023-07-04 | ||
BR102023013451-3A BR102023013451A2 (pt) | 2023-07-04 | Processo de produção e produto nitrogenado para adubação |
Publications (1)
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WO2025007201A1 true WO2025007201A1 (fr) | 2025-01-09 |
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Family Applications (1)
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PCT/BR2024/050284 WO2025007201A1 (fr) | 2023-07-04 | 2024-07-02 | Engrais à base de bois |
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WO (1) | WO2025007201A1 (fr) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000047628A2 (fr) * | 1999-02-10 | 2000-08-17 | Hercules Incorporated | Polysaccharide microfibrillaire transforme en derive |
WO2001066600A1 (fr) * | 2000-03-09 | 2001-09-13 | Hercules Incorporated | Cellulose microfibrillaire stabilisee |
CN112469775A (zh) * | 2018-07-11 | 2021-03-09 | 纳米及先进材料研发院有限公司 | 交联纳米多孔糖类基材料及其制造方法 |
-
2024
- 2024-07-02 WO PCT/BR2024/050284 patent/WO2025007201A1/fr unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000047628A2 (fr) * | 1999-02-10 | 2000-08-17 | Hercules Incorporated | Polysaccharide microfibrillaire transforme en derive |
WO2001066600A1 (fr) * | 2000-03-09 | 2001-09-13 | Hercules Incorporated | Cellulose microfibrillaire stabilisee |
CN112469775A (zh) * | 2018-07-11 | 2021-03-09 | 纳米及先进材料研发院有限公司 | 交联纳米多孔糖类基材料及其制造方法 |
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