Method for producing cellulose-coated NPK complex nutrients

Abstract

Fertilizer compositions comprising a nitrogen nutrient, a phosphorus nutrient, and a potassium nutrient and methods for making and using the fertilizer compositions are disclosed. The fertilizer composition may include a cellulose ammonium phosphate and an ammonium potassium phosphate encapsulated within the cellulose ammonium phosphate. The cellulose ammonium phosphate fertilizer may also include potassium ammonium phosphate adsorbed on the surface of the cellulose ammonium phosphate.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of European Application No. 22182600.1 filed on July 1, 2022, the entire contents of which are incorporated herein by reference. Background of the Invention

[0004] A. Technical field

[0005] The present invention belongs to the field of dual-release fertilizers. Generally, it relates to ammonium cellulose phosphate fertilizer compositions, which contain ammonium cellulose phosphate and potassium ammonium phosphate, wherein the potassium ammonium phosphate is encapsulated in the ammonium cellulose phosphate and in some cases adsorbed on the surface of the ammonium cellulose phosphate. Methods of production and use are also disclosed.

[0006] B. Related technical description

[0007] Fertilizers are chemical compositions added to plants and crops to provide nutrients that promote growth. Nitrogen, phosphorus, and potassium, or NPK, are found in many fertilizers, and these three main nutrients play a key role in plant nutrition and growth. Nitrogen is considered the most important nutrient, and plants absorb more nitrogen than any other element. Nitrogen is essential for the formation of proteins, which make up a significant portion of most living tissues. The second major nutrient, phosphorus, is related to the plant's ability to use energy and store energy, including the process of photosynthesis. Potassium is the third major nutrient in commercial fertilizers. It helps to increase resistance to disease and plays an important role in improving crop yields and overall quality. Potassium also protects plants when the weather is cold or dry, strengthening their root systems and preventing wilting.

[0008] Fertilizers provide different release curves, wherein the release rate of nitrogen nutrients, phosphorus nutrients and potassium nutrients is variable. Most commercial fertilizers are water-soluble quick-release fertilizers (QRFs), which release nutrients quickly when placed in soil. If unpredictable high leaching events such as floods occur, these quick-release fertilizers are impractical. Controlled-release fertilizers (CRFs) are fertilizers containing plant nutrients in a form that cannot be absorbed immediately by plants. Controlled-release fertilizers are usually coated or encapsulated with materials that control the rate, pattern and duration of plant nutrient release. Typically, encapsulated materials are not biodegradable and accumulate in soil and plants over time.

[0009] In many cases, it is desirable to provide a fertilizer that provides a combination of quick-release nutrients and delayed-release nutrients. Many fertilizer production technologies comprising polymer components have been developed in an attempt to slow the release of fertilizer nutrients. Mulyani et al., Characterisation of carboxymethylcellulose-based superabsorbent polymer hydrogel for slow-release of N-PK fertiliser, Journal of Chemical Technology and Metallurgy 2021, 56, 730-737, discloses graft polymerization of carboxymethylcellulose with acrylic acid to produce a superabsorbent polymer hydrogel. Subsequently, the polymer hydrogel is loaded with fertilizer nutrients to provide a slow-release fertilizer composition. Kudzin et al., Stability of cellulose phosphates in alkalic solutions, Phosphorus, Sulfur, and Silicon and the Related Elements 2022, discloses a suspension of cellulose phosphate in potassium hydroxide solution. CA2883269C discloses a composite fertilizer comprising a cellulosic material, an amino compound and optionally one or more nutrients. Belosinschi et al., Phosphorylation of cellulose in the presence of urea. Mechanism of reaction and reagent impact, Research Square 2021, discloses phosphorylation of cellulose in the presence of urea. CN103030129B discloses a method for generating a water-soluble potassium ammonium phosphate fertilizer. Rop et al., Formulation of slow release NPK fertilizer (cellulose-graft-poly(acrylamide) / nano-hydroxyapatite / soluble fertilizer) composite and evaluating its N mineralization potential, Annals of Agricultural Sciences 2018 63, 163-172, discloses a fertilizer composition comprising nanohydroxyapatite, urea, (NH4)2HPO4 and K2SO4 in a hyacinth cellulose-graft-poly(acrylamide) polymer gel. These fertilizers contain non-biodegradable components or do not contain slow-release components and delayed-release components.In the agricultural nutrient industry, there is a need for dual release fertilizer compositions that contain the primary N nutrient, the P nutrient, and the K nutrient, and can serve as a scaffold for additional nutrients. Summary of the invention

[0010] Disclosed herein is a composite fertilizer composition that uses a renewable and biodegradable polymer component and a salt component encapsulated in the polymer component. Both the polymer component and the salt component contain major fertilizer nutrients. When exposed to moisture, at least a portion of the salt component can dissolve rapidly, thereby providing quick-release fertilizer nutrients. In contrast, the polymer component has a lower solubility and is difficult to dissolve immediately. This allows the polymer component to release its fertilizer nutrients and / or fertilizer nutrients encapsulated by the polymer component over time. The resulting dual-phase nutrient release curve provides quick-release nutrients and slow-release nutrients, which is ideal for fertilizing crops.

[0011] In one aspect, a method for generating a dual-release cellulose fertilizer composition comprising nitrogen, phosphorus and potassium is disclosed. The method may include the following steps: i) reacting a cellulose material with phosphoric acid to generate a phosphorylated cellulose material, wherein at least a portion of the hydroxyl groups of the cellulose material are phosphorylated, ii) reacting the phosphorylated cellulose material with an ammonia source to generate cellulose ammonium phosphate, iii) reacting a potassium compound with phosphoric acid to form a potassium phosphate compound, iv) reacting the potassium phosphate compound with an ammonia source to generate potassium ammonium phosphate, and v) combining the cellulose ammonium phosphate and potassium ammonium phosphate to form a cellulose fertilizer composition, wherein the cellulose fertilizer composition comprises potassium ammonium phosphate encapsulated in the cellulose ammonium phosphate. In some aspects, the method includes step vi) drying the cellulose fertilizer composition. In some aspects, step i), step ii), step iii), and step iv) are performed in a single container. In some aspects, step i), step ii), step iii), step iv) and step v) are performed in a single container. In some aspects, step i) and step ii) are performed in a first container, and step iii) and step iv) are performed in a second container. In some aspects, a stoichiometric excess of phosphoric acid is used in step i), and at least a portion of the phosphoric acid reacted in step iii) comprises the stoichiometric excess of phosphoric acid used in step i). In some aspects, a stoichiometric excess of ammonia source is used in step ii), and at least a portion of the ammonia source reacted in step iv) comprises the stoichiometric excess of ammonia source used in step ii).

[0012] In some aspects, reacting the cellulosic material with phosphoric acid comprises combining a solution of the cellulosic material with a phosphoric acid solution. In other aspects, reacting the cellulosic material with phosphoric acid comprises adding the cellulosic material (pure, i.e., without additional solvent) to the phosphoric acid solution. In some aspects, the cellulosic material reacts with phosphoric acid in a weight ratio of 1:1 to 1:5. The weight ratio of the cellulosic material to the phosphoric acid can be any one of the following weight ratios, a ratio less than the following weight ratio, a ratio greater than the following weight ratio, or a ratio between the following weight ratios, or any range of weight ratios derivable therein: 1:1, 1:2, 1:3, 1:4, 1:5. In some aspects, reacting the cellulosic material with phosphoric acid comprises reacting at a temperature of about 100°C to about 200°C, preferably reacting at a temperature of about 125°C to about 175°C, and more preferably reacting at a temperature of about 150°C. Reacting the cellulosic material with phosphoric acid can be carried out at any of the following temperatures, below the following temperatures, above the following temperatures, between the following temperatures, or any range thereof: 100°C, 101°C, 102°C, 103°C, 104°C, 105°C, 106°C, 107°C, 108°C, 109°C, 110°C, 111°C, 112°C, 113°C, 114°C, 115°C , 116°C, 117°C, 118°C, 119°C, 120°C, 121°C, 122°C, 123°C, 124°C, 125°C, 126°C, 127°C, 128°C, 129°C, 130°C, 131°C, 132°C, 133°C, 134°C, 135°C, 136°C, 137°C, 138°C, 139°C, 140°C, 141°C, 142°C, 143°C, 144°C 44℃、145℃、146℃、147℃、148℃、149℃、150℃、151℃、152℃、153℃、154℃、155℃、156℃、157℃、158℃、159℃、160℃、161℃、162℃、163℃、164℃、165℃、166℃、167℃、168℃、169℃、170℃、171℃、172 ℃, 173 ℃, 174 ℃, 175 ℃, 176 ℃, 177 ℃, 178 ℃, 179 ℃, 180 ℃, 181 ℃, 182 ℃, 183 ℃, 184 ℃, 185 ℃, 186 ℃, 187 ℃, 188 ℃, 189 ℃, 190 ℃, 191 ℃, 192 ℃, 193 ℃, 194 ℃, 195 ℃, 196 ℃, 197 ℃, 198 ℃, 199 ℃ and 200 ℃. In some aspects, the cellulosic material is reacted with phosphoric acid to form a phosphorylated cellulosic material in the form of a gel.

[0013] In some aspects, the ammonia source comprises a solution of ammonium hydroxide, ammonium, ammonium carbonate, ammonia gas, succinimide and / or phthalimide. In some aspects, reacting the phosphorylated cellulosic material with the ammonia source comprises reacting at a temperature of about 70°C to about 170°C, preferably reacting at a temperature of about 100°C to about 140°C, and more preferably reacting at a temperature of about 120°C. Reacting the phosphorylated cellulosic material with the ammonia source can be carried out at any of the following temperatures, below, above, between, or any range thereof: 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C, 101°C, 102°C, 103°C, 104°C, 105°C, 106°C, 107°C, 108°C, 109°C, 110°C, 111°C, 112°C, 113°C, 114°C, 115°C, 116°C, 117°C, 118°C, 119°C, 6℃、117℃、118℃、119℃、120℃、121℃、122℃、123℃、124℃、125℃、126℃、127℃、128℃、129℃、130℃、131℃、132℃、133℃、134℃、135℃、136℃、137℃、138℃、139℃、140℃、141℃、142℃、143 , 144° C., 145° C., 146° C., 147° C., 148° C., 149° C., 150° C., 151° C., 152° C., 153° C., 154° C., 155° C., 156° C., 157° C., 158° C., 159° C., 160° C., 161° C., 162° C., 163° C., 164° C., 165° C., 166° C., 167° C., 168° C., 169° C., and 170° C. In some aspects, the phosphorylated cellulosic material is reacted with an ammonia source to form ammonium cellulose phosphate in the form of a gel.

[0014] In some aspects, the cellulosic fertilizer composition also includes ammonium phosphate adsorbed on the surface of the cellulosic fertilizer composition. In other aspects, the cellulosic fertilizer composition also includes ammonium potassium phosphate adsorbed on the surface of the cellulosic fertilizer composition. In some aspects, the cellulosic fertilizer composition also includes potassium phosphate adsorbed on the surface of the cellulosic fertilizer composition. In some aspects, the cellulosic fertilizer composition is in the form of powder, grain, granule and / or pellet. In some aspects, the cellulosic material does not contain lignin.

[0015] In some respects, the cellulosic material comprises cellulose, ethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose and / or carboxymethyl cellulose. In some respects, the potassium compound comprises one or more than one of potassium hydroxide, potassium carbonate, potassium nitrate, potassium chloride, potassium phosphate, potassium sulfate, potassium bicarbonate, potassium oxide, potassium permanganate, potassium bromide and / or potassium iodide. In some respects, the cellulosic fertilizer composition also comprises other nutrients, wherein before, during or after the formation of cellulose ammonium phosphate, other nutrients are added. In some respects, the cellulosic fertilizer composition does not contain urea.

[0016] Some aspects of the present disclosure relate to a dual-release cellulose fertilizer, which includes ammonium potassium phosphate encapsulated in ammonium cellulose phosphate. In some aspects, the dual-release cellulose fertilizer also includes ammonium phosphate on the surface of the cellulose fertilizer composition. In some aspects, the dual-release cellulose fertilizer also includes potassium phosphate on the surface of the cellulose fertilizer composition. In some aspects, the dual-release cellulose fertilizer also includes ammonium potassium phosphate on the surface of the cellulose fertilizer composition. In some aspects, the fertilizer is in the form of a powder, a grain, a granule or a pellet. In some aspects, the fertilizer also includes at least one other nutrient, and the other nutrient is selected from magnesium, chloride, sulfate, superphosphate (superphosphate), phosphate rock, potash, potassium sulfate (SOP), potassium chloride (MOP), kieserite, carnallite, magnesite, dolomite, boric acid, boron, copper, iron, manganese, molybdenum, zinc, selenium, silicon, free calcium, elemental sulfur, neem oil, seaweed extract, biological growth promoter, charcoal, ash from burning animal waste or burning animal tissue or any combination thereof. In some aspects, the fertilizer does not include urea.

[0017] One aspect of the present disclosure relates to a method for fertilizing crops, the method comprising applying the dual-release cellulosic fertilizer disclosed herein to soil, water, plants, or any combination thereof.

[0018] The following Aspect 1 to Aspect 31 of the present invention are also disclosed.

[0019] Aspect 1 is a method for preparing a dual-release cellulosic fertilizer composition comprising nitrogen, phosphorus and potassium, the method comprising the following steps: i) reacting a cellulosic material with phosphoric acid to produce a phosphorylated cellulosic material, wherein at least a portion of the hydroxyl groups of the cellulosic material are phosphorylated; ii) reacting the phosphorylated cellulosic material with an ammonia source to produce cellulose ammonium phosphate; iii) reacting a potassium compound with phosphoric acid to form a potassium phosphate compound; iv) reacting the potassium phosphate compound with an ammonia source to produce potassium ammonium phosphate; and v) combining the cellulose ammonium phosphate and the potassium ammonium phosphate to form a cellulosic fertilizer composition, wherein the cellulosic fertilizer composition comprises potassium ammonium phosphate encapsulated in the cellulose ammonium phosphate.

[0020] Aspect 2 is the method according to aspect 1, further comprising: vi) drying the cellulosic fertilizer composition.

[0021] Aspect 3 is a method according to any one of aspects 1 or 2, wherein reacting the cellulosic material with phosphoric acid comprises combining a cellulose solution with a phosphoric acid solution.

[0022] Aspect 4 is a method according to any one of aspects 1 to 3, wherein the cellulosic material and phosphoric acid are reacted in a weight ratio of 1:1 to 1:5.

[0023] Aspect 5 is a method according to any one of aspects 1 to 4, wherein reacting the cellulosic material with phosphoric acid comprises reacting at a temperature of about 100°C to about 200°C.

[0024] Aspect 6 is a method according to any one of aspects 1 to 5, wherein the cellulosic material is reacted with phosphoric acid to produce the phosphorylated cellulosic material in the form of a gel.

[0025] Aspect 7 is a method according to any one of aspects 1 to 6, wherein the ammonia source comprises a solution of ammonium hydroxide, ammonium, ammonium carbonate, ammonia gas, succinimide and / or phthalimide.

[0026] Aspect 8 is a method according to any one of aspects 1 to 7, wherein reacting the phosphorylated cellulosic material with an ammonia source comprises reacting at a temperature of about 70°C to about 170°C.

[0027] Aspect 9 is a method according to any one of aspects 1 to 8, wherein reacting the phosphorylated cellulosic material with an ammonia source produces ammonium cellulose phosphate in the form of a gel.

[0028] Aspect 10 is the method according to any one of aspects 1 to 9, wherein the cellulosic fertilizer composition further comprises ammonium phosphate adsorbed on the surface of the cellulosic fertilizer composition.

[0029] Aspect 11 is a method according to any one of aspects 1 to 10, wherein the cellulosic fertilizer composition further comprises ammonium potassium phosphate adsorbed on the surface of the cellulosic fertilizer composition.

[0030] Aspect 12 is the method according to any one of aspects 1 to 11, wherein the cellulosic fertilizer composition further comprises potassium phosphate adsorbed on the surface of the cellulosic fertilizer composition.

[0031] Aspect 13 is the method according to any one of aspects 1 to 12, wherein the cellulosic fertilizer composition is in the form of powder, granules, granules and / or pellets.

[0032] Aspect 14 is the method of any one of aspects 1 to 13, wherein the cellulosic material is free of lignin.

[0033] Aspect 15 is a method according to any one of aspects 1 to 14, wherein the cellulosic material comprises cellulose, ethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose and / or carboxymethyl cellulose.

[0034] Aspect 16 is a method according to any one of aspects 1 to 15, wherein the potassium compound comprises one or more than one of potassium hydroxide, potassium carbonate, potassium nitrate, potassium chloride, potassium phosphate, potassium sulfate, potassium bicarbonate, potassium oxide, potassium permanganate, potassium bromide and / or potassium iodide.

[0035] Aspect 17 is a method according to any one of aspects 1 to 16, wherein the cellulosic fertilizer composition further comprises additional nutrients, wherein the additional nutrients are added before, during or after the formation of the cellulose ammonium phosphate.

[0036] Aspect 18 is the method according to any one of aspects 1 to 17, wherein the cellulosic fertilizer composition does not contain urea.

[0037] Aspect 19 is a method according to any one of aspects 1 to 18, wherein step i), step ii), step iii) and step iv) are performed in a single container.

[0038] Aspect 20 is a method according to any one of aspects 1 to 19, wherein step i), step ii), step iii), step iv) and step v) are performed in a single container.

[0039] Aspect 21 is a method according to any one of aspects 1 to 18, wherein step i) and step ii) are performed in a first container, and step iii) and step iv) are performed in a second container.

[0040] Aspect 22 is the method according to any one of aspects 1 to 21, wherein a stoichiometric excess of phosphoric acid is used in step i), and at least a portion of the phosphoric acid reacted in step iii) comprises the stoichiometric excess of phosphoric acid used in step i).

[0041] Aspect 23 is a method according to any one of aspects 1 to 22, wherein a stoichiometric excess of ammonia source is used in step ii), and at least a portion of the ammonia source reacted in step iv) comprises the stoichiometric excess of ammonia source used in step ii).

[0042] Aspect 24 is a dual-release cellulosic fertilizer comprising ammonium potassium phosphate encapsulated within ammonium cellulose phosphate.

[0043] Aspect 25 is the dual-release cellulosic fertilizer according to aspect 24, further comprising ammonium phosphate on the surface of the cellulosic fertilizer composition.

[0044] Aspect 26 is the dual-release cellulosic fertilizer according to any one of aspects 24 or 25, further comprising potassium phosphate on the surface of the cellulosic fertilizer composition.

[0045] Aspect 27 is a dual-release cellulosic fertilizer according to any one of aspects 24 to 26, further comprising potassium ammonium phosphate on the surface of the cellulosic fertilizer composition.

[0046] Aspect 28 is the dual release cellulosic fertilizer according to any one of aspects 24 to 27, wherein the fertilizer is in the form of powder, granules, granules or pellets.

[0047] Aspect 29 is a dual-release cellulosic fertilizer according to any one of aspects 24 to 28, wherein the fertilizer further comprises at least one additional nutrient, the additional nutrient comprising magnesium, chloride, sulfate, superphosphate / salt, phosphate rock, potash, sulfate of potash (SOP), chloride of potash (MOP), kieserite, carnallite, magnesite, dolomite, boric acid, boron, copper, iron, manganese, molybdenum, zinc, selenium, silicon, free calcium, elemental sulfur, neem oil, seaweed extract, biostimulant, charcoal, ash from incinerated animal waste or incinerated animal tissue, or any combination thereof.

[0048] Aspect 30 is a dual release cellulosic fertilizer according to any one of aspects 24 to 29, wherein the fertilizer does not contain urea.

[0049] Aspect 31 is a method for fertilizing crops, comprising applying the dual-release cellulose fertilizer of any one of aspects 24 to 30 to soil, water, plants, or any combination thereof.

[0050] Included below are definitions of various terms and phrases used throughout this specification.

[0051] The term "fertilizer" is defined as a substance applied to soil or plant tissue to provide one or more than one plant nutrient essential or beneficial to plant growth and / or a growth promoter or enhancer that promotes or enhances plant growth. Non-limiting examples of fertilizers include materials having one or more than one of urea, ammonium nitrate, calcium ammonium nitrate, urea calcium sulfate adducts, one or more than one superphosphate / salt, binary NP fertilizer, binary NK fertilizer, binary PK fertilizer, NPK fertilizer, molybdenum, zinc, copper, boron, cobalt and / or iron. In some aspects, fertilizers include agents that enhance plant growth and / or enhance the ability of plants to benefit from fertilizers, such as, but not limited to, biopromoters, urease inhibitors, and nitrification inhibitors.

[0052] The term "nutrient" is defined as a chemical element or chemical substance used for normal growth and development of a plant. Non-limiting examples of nutrients include N, P, K, Ca, Mg, S, B, Cu, Fe, Mn, Mo, Zn, Se and Si or compounds thereof.

[0053] The term "granule" may include solid materials. The granules may have a variety of shapes, non-limiting examples of which include spheres, spherical shapes, ovoid shapes, rod-shaped shapes, ellipsoidal shapes, or random shapes. The term "grain" refers to a solid sphere of a substance formed by condensation of a liquid. The term "pellet" refers to a round compressed mass of fertilizer. The term "powder" refers to dry particles produced by grinding, crushing, or breaking of a fertilizer composition.

[0054] The term "about" or "approximately" is defined as close to what one of ordinary skill in the art understands. In a non-limiting embodiment, the term is defined as within 10% deviation, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0055] The terms "wt %, "volume %" or "mole %" refer to the weight percent of a component, the volume percent of a component or the mole percent of a component, respectively, based on the total weight of the material including the component, the total volume of the material or the total moles. In a non-limiting example, 10 grams of a component in 100 grams of a material is 10 wt % of the component.

[0056] The term "substantially" and variations thereof are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.

[0057] When used in the claims and / or specification, the terms "inhibit" or "reduce" or "prevent" or "avoid" or any variation of these terms include any measurable reduction or complete inhibition to achieve the desired result.

[0058] When the term "effective" is used in the specification and / or claims, the term means suitable for achieving a desired, expected, or intended result.

[0059] When used in conjunction with any of the terms "comprising," "including," "containing," or "having" in the claims or description, the indefinite quantifier preceding the term may mean "a," but is also consistent with the meaning of "one or more," "at least one," and "one or more than one."

[0060] The words "comprising," "having," "including," or "having" are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0061] The dual-release cellulosic fertilizer compositions and methods of producing dual-release cellulosic fertilizer compositions of the present invention may "comprise / include," "consist essentially of," or "consist of" specific ingredients, components, compositions, steps, etc. disclosed throughout the specification. In one non-limiting aspect, with respect to the transitional phrase "consist essentially of," the basic and novel feature of the dual-release cellulosic fertilizer compositions of the present invention is the presence of potassium ammonium phosphate encapsulated within the cellulose ammonium phosphate of the dual-release cellulosic fertilizer composition and adsorbed on the surface of the cellulose ammonium phosphate. DETAILED DESCRIPTION

[0062] A method for generating a dual-release fertilizer composition is disclosed, the composition comprising a combination of cellulose ammonium phosphate and potassium ammonium phosphate encapsulated in the cellulose ammonium phosphate. The dual-release fertilizer composition comprises a cellulose ammonium phosphate component and a potassium ammonium phosphate component, the potassium ammonium phosphate component being encapsulated in the cellulose ammonium phosphate component and / or being dispersed throughout the cellulose ammonium phosphate component. The potassium ammonium phosphate can be encapsulated in the cellulose ammonium phosphate and can also be provided on the surface of the cellulose ammonium phosphate. The encapsulated potassium ammonium phosphate component can be easily dissolved in water and constitutes the quick-release component of the dual-release fertilizer. The cellulose ammonium phosphate component can have a plurality of ammonium phosphate groups, wherein the phosphate groups are covalently bonded to the polymer cellulose backbone. The covalent bond between the cellulose and the phosphate is relatively durable and can be broken over time, and imparts the functionality of delayed release of phosphate and nitrogen. Additional advantages of this fertilizer composition include the ability to provide non-urea-based nitrogen, since urea may reduce the storage stability, biodegradability of the fertilizer, and provide a sustainable source of components of the fertilizer.

[0063] Cellulosic fertilizers contain cellulose or cellulose derivatives, such as ammonium cellulose phosphate. Cellulose is a substance having the formula (C6H 10 O5) n A linear polymeric organic compound, wherein n is typically several hundred to several thousand. The D-glucose units are interconnected by β(1→4) glycosidic bonds, wherein the β(1→4) glycosidic bonds can be hydrolyzed in the presence of water to provide smaller cellulose chains and free glucose monosaccharides. Cellulose can also be biodegraded by microorganisms. Cellulase enzymes in microorganisms in the soil can break down cellulose into smaller cellulose chains and free glucose monosaccharides. Importantly, cellulose is primarily obtained from natural sources such as wood pulp and other plant sources, and constitutes a renewable scaffold for the fertilizer compositions disclosed herein.

[0064] A. Method for Producing Potassium Ammonium Phosphate / Cellulose Ammonium Phosphate Fertilizer

[0065] Disclosed is a method for producing a dual-release fertilizer composition comprising ammonium potassium phosphate encapsulated in cellulose ammonium phosphate. In some aspects, the method can be produced by the following reaction steps:

[0066] a)Cel-OH+PO4H3→Cel-O-PO3H2+H2O

[0067] In the above-mentioned step a), a cellulosic material (Cel-OH) is first provided. In some aspects, the cellulosic material is cellulose. In some aspects, the cellulosic material is ethyl cellulose. In some aspects, the cellulosic material is methyl cellulose. In some aspects, the cellulosic material is hydroxypropyl cellulose. In some aspects, the cellulosic material is hydroxyethyl cellulose. In some aspects, the cellulosic material is carboxymethyl cellulose. The "Cel-OH" nomenclature used herein describes a non-limiting example of a polymeric cellulose backbone "Cel-" consisting of a plurality of glucose units and the hydroxyl "-OH" of the glucose units. For clarity, a single "-OH" group is used above, however, a typical cellulose molecule contains hundreds to thousands of hydroxyl groups. The cellulosic material can be combined with phosphoric acid, for example, cellulose is dissolved in phosphoric acid. As a non-limiting example, phosphoric acid can be 85% by weight H3PO4 in H2O. When a mixture of the cellulosic material and phosphoric acid is heated, a dehydration coupling reaction may occur between the cellulose hydroxyl and the phosphoric acid molecules to provide a cellulose phosphate, such as "Cel-O-PO3H2". On average, less than one, one or more than one (e.g., two) cellulose hydroxyl groups in each glucose unit can react with a phosphoric acid molecule. Each internal glucose monomer within the cellulose polymer chain can have up to three phosphate groups, such as Cel-O-PO3H2, Cel-(O-PO3H2)2, and Cel-(O-PO3H2)3. The terminal glucose monomer at the end of the cellulose polymer chain can have up to four phosphate groups, such as Cel-O-PO3H2, Cel-(O-PO3H2)2, Cel-(O-PO3H2)3, and Cel-(O-PO3H2)4. For simplicity, glucose monomers with a single phosphate group are described herein. The mixture can be heated at a temperature of about 100°C to about 200°C, preferably at a temperature of about 125°C to about 175°C, and more preferably at a temperature of about 150°C. The reaction can be carried out in a sealed container to prevent the loss of water. Each dehydration coupling reaction between cellulose and phosphoric acid generates a water molecule "H2O". In some aspects, the cellulose phosphate is in the form of a gel.

[0068] b) Cel-O-PO3H2+H3PO4→Cel-O-PO3H2(+free H3PO4)

[0069] In addition to the dehydration coupling between cellulose and phosphoric acid, some free phosphoric acid may remain unreacted and present in the colloidal cellulose phosphate (as described in step b above).

[0070] c)Cel-O-PO3H2+2NH3→Cel-O-PO3(NH4)2

[0071] Substitution c) Cel-O-PO3H2+2NH4OH→Cel-O-PO3(NH4)2+2H2O

[0072] After, during or before the formation of cellulose phosphate, an ammonia source is added to the mixture. In some aspects, the ammonia source is an ammonium hydroxide solution. In some aspects, the ammonia source is ammonia gas or liquid ammonia obtained by cooling ammonia gas to below its boiling point (-33°C). In some aspects, the ammonia source is an ammonium hydroxide solution. In some aspects, the ammonia source is ammonium carbonate. In some aspects, the ammonia source is succinimide. In some aspects, the ammonia source is phthalimide. The mixture of cellulose phosphate and ammonia source can be heated at a temperature of about 70°C to about 170°C, preferably at a temperature of about 100°C to about 140°C, more preferably at a temperature of about 120°C. Since the alkalinity of ammonia is stronger than that of phosphate, ammonia will take protons from cellulose phosphate "Cel-O-PO3H2" to provide cellulose ammonium phosphate "Cel-O-PO3(NH4)2", as described in step c above. When ammonium hydroxide is used as the ammonia source (alternative step c above), the hydroxide will abstract a proton from the cellulose phosphate to provide water and ammonium cellulose phosphate.

[0073] d) KOH + H3PO4 → KH2PO4 + H2O

[0074] d2)2KOH+H3PO4→HK2PO4+2H2O

[0075] d3)3KOH+H3PO4→K3PO4+3H2O

[0076] Potassium compound reacts with phosphoric acid to generate potassium phosphate compound. In some aspects, potassium source is potassium hydroxide. In some aspects, potassium source is potassium carbonate. In some aspects, potassium source is potassium nitrate. In some aspects, potassium source is potassium chloride. In some aspects, potassium source is potassium phosphate. In some aspects, potassium source is potassium sulfate. In some aspects, potassium source is potassium bicarbonate. In some aspects, potassium source is potassium oxide. In some aspects, potassium source is potassium permanganate. In some aspects, potassium source is potassium bromide. In some aspects, potassium source is potassium iodide. Step d, step d2 and step d3 above describe non-limiting exemplary reactions using different relative amounts of potassium hydroxide and phosphoric acid and generating different potassium phosphate compounds. Typical reactions between potassium hydroxide and phosphoric acid can generate a mixture of the above three potassium phosphate compounds, and the relative concentration of the potassium phosphate compound will depend on the relative amounts of potassium hydroxide and phosphoric acid used.

[0077] e)KH2PO4+2NH3→K(NH4)2PO4

[0078] e2)HK2PO4+NH3→K2(NH4)PO4

[0079] Substitution e) KH2PO4 + 2NH4OH → K(NH4)2PO4 + 2H2O

[0080] Substitution e2) HK2PO4 + NH4OH → K2(NH4)PO4 + H2O

[0081] After the potassium phosphate compound is formed, during the formation, or before the formation, an ammonia source is added to the mixture. The ammonia source may be the remaining unreacted ammonia source exemplified in the above step c) and the alternative step c). The ammonia source may be another ammonia source added after the potassium phosphate compound is formed, during the formation, or before the formation. The ammonia source may be a source of ammonia different from the ammonia source used in the above step c) and the alternative step c). In the reaction described in the above non-limiting example step e, the reaction between potassium dihydrogen phosphate and the ammonia source may provide potassium diammonium phosphate. In step e2, the reaction between potassium hydrogen phosphate and ammonia may provide dipotassium ammonium phosphate. When ammonium hydroxide is used as an ammonia source (the above alternative step e and the alternative step e2), the same potassium ammonium phosphate compound is generated, and water is generated as a byproduct. In some aspects, the ammonia source is an ammonium hydroxide solution. In some aspects, the ammonia source is ammonia gas or liquid ammonia obtained by cooling ammonia gas to below its boiling point (-33°C). In some aspects, the ammonia source is an ammonium hydroxide solution. In some aspects, the ammonia source is ammonium carbonate. In some aspects, the ammonia source is succinimide. In some aspects, the source of ammonia is phthalimide.

[0082] f) Cel-O-PO3(NH4)2+K(NH4)2PO4→cellulose fertilizer composition

[0083] f2) Cel-O-PO3(NH4)2+K2(NH4)PO4→cellulose fertilizer composition

[0084] The cellulose ammonium phosphate from step c or alternative step c can be combined with the potassium ammonium phosphate compound from step e and step e2 or alternative step e and alternative step e2. In some aspects, the cellulose ammonium phosphate and potassium ammonium phosphate are generated in the same reaction vessel, and the generated mixture comprises a cellulose fertilizer composition. In other aspects, the cellulose ammonium phosphate and potassium ammonium phosphate are prepared separately and then combined to provide a cellulose fertilizer composition. The cellulose fertilizer composition can then be dried.

[0085] The above reaction provides the fertilizer comprising N nutrient, P nutrient and K nutrient (in the form of ammonium, phosphate and potassium), and these nutrients can be chemically bonded to the cellulose carrier material and be encapsulated therein. The potassium ammonium phosphate through physical adsorption can be present on the surface of the cellulose material and in the pore cavity. In some aspects, the above reaction provides the mixture of potassium ammonium phosphate and cellulose ammonium phosphate in gel form. From this gel-like mixture, remove water subsequently, to provide the cellulose ammonium phosphate in solid form, wherein the potassium ammonium phosphate is encapsulated in the solid cellulose ammonium phosphate. Can adopt different technologies to provide the solid cellulose fertilizer composition in the form of powder, grain, particle or pellet before drying, during drying or after drying.

[0086] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.

[0087] B. Solid Forms of Fertilizer Compositions

[0088] In some cases, the dry solid fertilizer composition generated can contain a small amount of moisture. The free moisture content of the dry solid fertilizer composition can be less than 0.6 weight %, less than 0.5 weight % water or 0.25 weight % to less than 0.6 weight % water. In some cases, the free moisture content is the content of the following weight %, less than the content of the following weight %, greater than the content of the following weight % or between the following weight % or any range thereof: 0.5 weight %, 0.4 weight %, 0.3 weight %, 0.2 weight %, 0.1 weight % or 0 weight %.

[0089] The solid fertilizer composition of drying can generate with the form of powder, grain, particle or pellet.In some non-limiting aspects, powder can comprise the particle with following particle size, be less than following particle size, be greater than following particle size or between following particle size or the particle of the mean particle size of its any scope: 1 micron, 2 microns, 3 microns, 4 microns, 5 microns, 6 microns, 7 microns, 8 microns, 9 microns, 10 microns, 11 microns, 12 microns, 13 microns, 14 microns, 15 microns, 20 microns, 30 microns, 40 microns, 50 microns, 60 microns, 70 microns, 80 microns, 90 microns, 100 microns, 200 microns, 300 microns, 400 microns, 500 microns, 600 microns, 700 microns, 800 microns or 900 microns.In some embodiments, particle can be elongated particle, or can be the combination of spherical particle or other shapes or these shapes substantially.The limiting examples of shape comprises spherical, spherical, ovoid, rod-shaped, elliptical or random shape.

[0090] In some cases, the dry solid fertilizer composition can contain a coating on the surface of the fertilizer composition. In some cases, the coating can include a nutrient for plant, an inhibitor of urea hydrolysis and / or nitrification, a reagent that slows down or increases particle and / or fertilizer degradation rate, a reagent that repels moisture and / or provides a hydrophobic layer, a reagent that reduces or increases particle and / or fertilizer reactivity, a reagent that provides other benefits for plant, a reagent that increases particle and / or fertilizer stability and / or crushing strength, a pH buffer, a desiccant, a biological growth promoter, a microorganism, etc., or any combination thereof. The coating can be a commercially available coating, oil, fertilizer, micronutrient, talcum, seaweed and / or seaweed extract, bacterium, wax, etc. In some cases, the coating can contain a surfactant. In some cases, the coating contains wax, a surfactant and / or a compound based on an amine.

[0091] In some aspects, the fertilizer composition comprises a coating on a cellulosic fertilizer composition, e.g., a core comprising ammonium potassium phosphate encapsulated in cellulose ammonium phosphate, and a shell coating provided around the core. In some aspects, the fertilizer composition comprises ammonium cellulose phosphate and ammonium potassium phosphate encapsulated in cellulose ammonium phosphate within a matrix of the coating, e.g., uniformly distributed therein, e.g., extruded fertilizer particles.

[0092] In some aspects, the fertilizer composition contains cellulose ammonium phosphate as a matrix, the matrix comprising potassium ammonium phosphate and optional other ingredients, such as one or more additional nutrients, one or more inhibitors, alkaline substances, acidic substances, one or more biological growth promoters, one or more microorganisms, etc. In some aspects, the fertilizer composition contains a core with a cellulose ammonium phosphate coating and potassium ammonium phosphate encapsulated in the coating. The core may contain nutrients for plants, inhibitors of urea hydrolysis and / or nitrification, agents that slow down or increase the degradation rate of particles, agents that repel moisture and / or provide a hydrophobic layer, agents that reduce or increase the reactivity of particles, agents that provide additional benefits to plants, agents that increase particle stability and / or crushing strength, pH buffers, desiccants, microorganisms, etc., or any combination thereof.

[0093] C. Mixed fertilizer composition or compound fertilizer composition

[0094] The fertilizer composition disclosed herein may also be included in a mixed fertilizer composition or a composite fertilizer composition comprising other fertilizers such as other fertilizer particles. Additional fertilizers may be selected according to the special needs of certain types of soil, climate or other growth conditions to maximize the effectiveness of the fertilizer composition in promoting plant growth and crop yield. Other fertilizer particles may be particles of urea, superphosphate (SSP), triple superphosphate (TSP), ammonium sulfate, monoammonium phosphate (MAP), diammonium phosphate (DAP), potassium chloride (MOP) and / or potassium sulfate (SOP) etc.

[0095] In one aspect, the fertilizer composition may include one or more than one inhibitor. The inhibitor may be a urease inhibitor or a nitrification inhibitor or a combination thereof. In one aspect, a urease inhibitor and a nitrification inhibitor are included. In one aspect, the inhibitor may be a urease inhibitor. Suitable urease inhibitors include, but are not limited to, N-(n-butyl)thiophosphoric triamide (NBTPT) and phenylphosphoric diamide (PPDA). In one aspect, the fertilizer composition may include NBTPT or PPDA or a combination thereof. In another aspect, the inhibitor may be a nitrification inhibitor. Suitable nitrification inhibitors include, but are not limited to, 3,4-dimethylpyrazole phosphate (DMPP), dicyandiamide (DCD), thiourea (TU), 2-chloro-6-(trichloromethyl)-pyridine (Nitrapyrin), manufactured by OHP Inc., USA under the trade name In one aspect, the nitrification inhibitor may include DMPP, DCD, TU, nitrapyrin, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, AM, MBT, or ST, or a combination thereof. In one aspect, the fertilizer composition may include NBTPT, DMPP, TU, DCD, PPDA, nitrapyrin, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, AM, MBT, ST, or a combination thereof.

[0096] D. Methods of using the fertilizer compositions

[0097] The fertilizer composition disclosed herein can be used in a method for increasing the amount of nitrogen, phosphorus and potassium in the soil and promoting plant growth. Such a method may include applying an effective amount of a composition comprising the fertilizer composition disclosed herein to the soil. The method may include increasing the growth and yield of crops, trees, ornamental plants, etc., such as palm, coconut, rice, wheat, corn, barley, oats and soybeans. The method may include applying the fertilizer composition disclosed herein to at least one of soil, an organism, a liquid carrier, a liquid solvent, etc.

[0098] The non-limiting examples of plants that can benefit from fertilizer disclosed herein include lianas, trees, shrubs, stem plants, ferns, etc. The plant can include orchard crops, lianas, ornamental plants, food crops, timber and the plants harvested. The plant can include gymnosperms, angiosperms and / or ferns. Gymnosperms can include plants from Araucariaceae, Cupressaceae, Pinaceae, Podocarpaceae, Sciadopitaceae, Taxaceae, Cycadaceae and Ginkgoaceae. Angiosperms can include plants from the following families: Aceraceae, Agavaceae, Anacardiaceae, Annonaceae, Apocynaceae, Aquifoliaceae, Araliaceae, Arecaceae, Asphodelaceae, Asteraceae, Berberidaceae, Betulaceae, Bignoniaceae, Bombacaceae, Boraginaceae, Burseraceae, Buxaceae, Canellaceae, Cannabaceae, Cistanche Apparidaceae), Caprifoliaceae, Caricaceae, Casuarinaceae, Celastraceae, Cercidiphyllaceae, Chrysobalanaceae, Clusiaceae, Combretaceae, Cornaceae, Cyrillaceae, Davidsoniaceae, Ebenaceae, Elaeagnaceae, Ericaceae, Euphorbiaceae, Fabaceae, Fagaceae, Grossulariaceae,Hamamelidaceae, Hippocastanaceae, Illiciaceae, Juglandaceae, Lauraceae, Lecythidaceae, Lythraceae, Magnoliaceae, Malpighiaceae, Malvaceae, Melastomataceae, Meliaceae, Moraceae, Moringa ceae), Muntingiaceae, Myoporaceae, Myricaceae, Myrsinaceae, Myrtaceae, Nothofagaceae, Nyctaginaceae, Nyssaceae, Olacaceae, Oleaceae, Oxalidaceae, Pandanaceae, Papaveraceae, Phyllanthaceae aceae), Pittosporaceae, Platanaceae, Poaceae, Polygonaceae, Proteaceae, Punicaceae, Rhamnaceae, Rhizophoraceae, Rosaceae, Rubiaceae, Rutaceae, Salicaceae, Sapindaceae, Sapotaceae, Sisaceae maroubaceae), Solanaceae, Staphyleaceae, Sterculiaceae, Strelitziaceae, Styracaceae, Surianaceae, Symplococeae, Tamaricaceae, Theaceae, Theophrastaceae, Thymelaeaceae, Tiliaceae, Ulmaceae,Verbenaceae and / or Vitaceae.

[0099] The effectiveness of a composition comprising the fertilizer composition disclosed herein can be determined by measuring the amount of nitrogen, phosphorus, potassium, or by measuring the amount of nitrogen, phosphorus and potassium in the soil at different times after the fertilizer composition is applied to the soil. It is understood that different soils have different properties, which may affect the stability of nitrogen in the soil. The effectiveness of a fertilizer composition can also be directly compared to other fertilizer compositions by making a side-by-side comparison in the same soil under the same conditions.

[0100] In one aspect, the fertilizer composition disclosed herein can have a density greater than water. This can make particles and / or fertilizers sink into the water instead of floating. This is particularly useful when intended to be applied to crops that are at least partially or completely submerged in water. A non-limiting example of such a crop is rice, because the land of a paddy field is usually submerged in water. Therefore, the fertilizer composition can be applied to such a crop so that the particles and / or fertilizers are evenly distributed on the ground submerged in water. In contrast, particles and / or fertilizers having a density less than that of water will tend to remain in or on the water surface, which may cause the particles and / or fertilizers to be washed away and / or agglomerated, both of which cannot achieve uniform distribution of particles and / or fertilizers on the ground submerged in water.

[0101] Example

[0102] The present invention will be described in more detail by specific examples. The following examples are provided only for illustrative purposes and are not intended to limit the present invention in any way. Those skilled in the art will easily recognize various non-critical parameters that can be changed or altered to produce substantially the same results.

[0103] A. Example 1 - Production of Cellulosic Fertilizer from Cellulose

[0104] 1. Phosphorylation of cellulose. In an exemplary reaction, 100 g of cellulose can be combined with 181.5 g of H3PO4 (85 wt % in water), and the reaction mixture can be heated to 150°C. This combination of the amounts of cellulose and phosphoric acid provides cellulose phosphate, in which about two hydroxyl groups of each glucose monomer are converted to phosphate groups. The reaction can consume about 60.5 g of phosphoric acid and provide a gel-like mixture. About 121 g of unreacted phosphoric acid will remain in the gel-like mixture.

[0105] 2. Amination of cellulose phosphate. 55.4 g of ammonia can be added to the above reaction mixture, and the resulting combination can be heated at 120° C. The amount of ammonia is sufficient to react with the cellulose phosphate groups and with unreacted phosphoric acid. The result can be a gel-like mixture of cellulose ammonium phosphate and ammonium phosphate.

[0106] 3. Generation of potassium ammonium phosphate. 86 g of H3PO4 (85 wt% in water) can be combined with 41.7 g of KOH, and the reaction mixture can be stirred. 12.5 g of ammonia can then be added to the reaction mixture to provide potassium ammonium phosphate.

[0107] 4. Combination of cellulose ammonium phosphate and potassium ammonium phosphate. The mixture of cellulose ammonium phosphate and ammonium phosphate from step 2 can be combined with the potassium ammonium phosphate from step 3. The resulting fertilizer composition combination can be stirred to provide a uniform mixture. The fertilizer composition mixture can then be dried to provide a fertilizer composition comprising cellulose ammonium phosphate and potassium ammonium phosphate encapsulated in polymeric cellulose ammonium phosphate and adsorbed on the surface of the polymeric cellulose ammonium phosphate.

Claims

1. A method for preparing a dual-release cellulosic fertilizer composition comprising nitrogen, phosphorus and potassium, the method comprising the following steps: i) reacting a cellulosic material with phosphoric acid, preferably in a weight ratio of 1:1 to 1:5, and preferably at a temperature of about 100° C. to about 200° C., to produce a phosphorylated cellulosic material, wherein at least a portion of the hydroxyl groups of the cellulosic material are phosphorylated; ii) reacting the phosphorylated cellulosic material with an ammonia source, preferably at a temperature of about 70° C. to about 170° C., to produce ammonium cellulose phosphate; iii) reacting the potassium compound with phosphoric acid to form a potassium phosphate compound; iv) reacting the potassium phosphate compound with an ammonia source to form ammonium potassium phosphate; v) combining the ammonium cellulose phosphate and the ammonium potassium phosphate to form a cellulosic fertilizer composition; and vi) optionally, drying the cellulosic fertilizer composition, wherein the cellulosic fertilizer composition comprises potassium ammonium phosphate encapsulated in cellulose ammonium phosphate.

2. The method of claim 2, wherein reacting the cellulosic material with phosphoric acid comprises combining a cellulose solution with a phosphoric acid solution.

3. The method according to any one of claims 1 to 2, wherein: reacting the cellulosic material with phosphoric acid to produce a phosphorylated cellulosic material in the form of a gel; and / or The phosphorylated cellulosic material is reacted with an ammonia source to produce ammonium cellulose phosphate in the form of a gel.

4. The method according to any one of claims 1 to 3, wherein: The ammonia source includes a solution of: ammonium hydroxide, ammonium, ammonium carbonate, ammonia gas, succinimide and / or phthalimide; The cellulosic material comprises cellulose, ethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose and / or carboxymethyl cellulose; and / or The potassium compound includes one or more than one of potassium hydroxide, potassium carbonate, potassium nitrate, potassium chloride, potassium phosphate, potassium sulfate, potassium bicarbonate, potassium oxide, potassium permanganate, potassium bromide and / or potassium iodide.

5. The method according to any one of claims 1 to 4, wherein: The cellulosic fertilizer composition further comprises ammonium phosphate adsorbed on a surface of the cellulosic fertilizer composition; The cellulosic fertilizer composition further comprises potassium ammonium phosphate adsorbed on the surface of the cellulosic fertilizer composition; and / or The cellulosic fertilizer composition also includes potassium phosphate adsorbed on the surface of the cellulosic fertilizer composition.

6. The method according to any one of claims 1 to 5, wherein: The cellulosic fertilizer composition is in the form of powder, grains, granules and / or pellets; The cellulosic material is free of lignin; and / or the cellulosic fertilizer composition is free of urea.

7. The method of any one of claims 1 to 6, wherein the cellulosic fertilizer composition further comprises additional nutrients, wherein the additional nutrients are added before, during or after the formation of the cellulose ammonium phosphate.

8. The method according to any one of claims 1 to 7, wherein: Step i), step ii), step iii) and step iv) are carried out in a single container; Step i), step ii), step iii), step iv) and step v) are carried out in a single container; or Step i) and step ii) are performed in a first container, and step iii) and step iv) are performed in a second container.

9. The method according to any one of claims 1 to 8, wherein: A stoichiometric excess of phosphoric acid is used in step i), and at least part of the phosphoric acid reacted in step iii) comprises the stoichiometric excess of phosphoric acid used in step i); and / or In step ii) a stoichiometric excess of the ammonia source is used, and at least part of the ammonia source reacted in step iv) comprises the stoichiometric excess of the ammonia source used in step ii).

10. A dual release cellulosic fertilizer comprising ammonium potassium phosphate encapsulated within ammonium cellulose phosphate.

11. The dual-release cellulose fertilizer according to claim 10, further comprising: ammonium phosphate on the surface of the cellulosic fertilizer composition; potassium phosphate on the surface of the cellulosic fertilizer composition; and / or Ammonium potassium phosphate on the surface of the cellulosic fertilizer composition.

12. A dual release cellulose fertilizer according to any one of claims 10 to 11, wherein the fertilizer is in the form of powder, grains, granules or pellets.

13. The dual release cellulosic fertilizer according to any one of claims 10 to 12, wherein the fertilizer further comprises at least one additional nutrient, the additional nutrient comprising magnesium, chloride, sulfate, superphosphate, phosphate rock, potash, sulfate of potash (SOP), chloride of potash (MOP), kieserite, carnallite, magnesite, dolomite, boric acid, boron, copper, iron, manganese, molybdenum, zinc, selenium, silicon, free calcium, elemental sulfur, neem oil, seaweed extract, biostimulant, charcoal, ash from incinerated animal waste or incinerated animal tissue, or any combination thereof.

14. A dual release cellulose fertilizer according to any one of claims 10 to 13, wherein the fertilizer does not contain urea and / or lignin.

15. A method for fertilizing crops, comprising applying the dual-release cellulose fertilizer of any one of claims 10 to 14 to soil, water, plants or any combination thereof.