WO2016189521A2 - Fertilized compositions based on a substituted calcium phosphate and/or calcium carbonate compound - Google Patents

Fertilized compositions based on a substituted calcium phosphate and/or calcium carbonate compound Download PDF

Info

Publication number
WO2016189521A2
WO2016189521A2 PCT/IB2016/053180 IB2016053180W WO2016189521A2 WO 2016189521 A2 WO2016189521 A2 WO 2016189521A2 IB 2016053180 W IB2016053180 W IB 2016053180W WO 2016189521 A2 WO2016189521 A2 WO 2016189521A2
Authority
WO
WIPO (PCT)
Prior art keywords
comprised
weight
particles
composition according
fertilizing composition
Prior art date
Application number
PCT/IB2016/053180
Other languages
French (fr)
Other versions
WO2016189521A3 (en
Inventor
Norberto Roveri
Alice CECCHINI
Silvana MORSELLI
Marco Lelli
Rocco MERCURI
Original Assignee
Bio Eco Active S.R.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bio Eco Active S.R.L. filed Critical Bio Eco Active S.R.L.
Priority to EP16738865.1A priority Critical patent/EP3303261A2/en
Publication of WO2016189521A2 publication Critical patent/WO2016189521A2/en
Publication of WO2016189521A3 publication Critical patent/WO2016189521A3/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05BPHOSPHATIC FERTILISERS
    • C05B17/00Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05DINORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00Other inorganic fertilisers

Definitions

  • the present invention refers to fertilizing compositions comprising inorganic particles of a substituted and surface functionalised calcium phosphate compound; to fertilizing compositions comprising inorganic particles of a substituted and possibly surface functionalised calcium carbonate compound and to processes for preparing the aforementioned fertilizing compositions and inorganic particles.
  • the invention refers to fertilizing compositions that have preferred but not exclusive use in foliar fertilization for applications in farming and gardening.
  • the nutritional elements essential for the growth and development of plants are taken from the environment, meaning atmosphere-water- earth.
  • the atmosphere which is the main source of nutrition for plants since it provides carbon dioxide (CO2). CO2 is assimilated mainly during photosynthesis and carbon and oxygen together constitute about 90% of the dry matter of the upper plants.
  • the atmosphere also provides oxygen (O2), presiding aerobic respiration, a substantial amount of nitrogen (N2), traces of gaseous ammonia (NH3) and sulphur dioxide (SO2), also assimilable by some plants.
  • Water (H2O) is the second source of nutrition for plants. Although most of the water absorbed by the roots evaporates through transpiration from the leaves, a small fraction is used as reactant in metabolic transformations.
  • the earth constitutes the third source from which plants obtain the nutritional mineral elements, deriving from the breaking up and solubilisation of the bedrock and from the breaking down of animal and vegetable residues.
  • the chemical elements useful for the nutrition of plants are numerous : up to sixty have been found in the different plant tissues.
  • foliar fertilization being a technique of administering fertilizers that exploits the ability of plants to absorb water and the mineral salts dissolved in it through the epidermis and the stomata of the leaves, can be considered like a supplementing intervention that allows nutritional deficiencies to be solved for the main macro and micro elements, nutritional elements thus defined based on the fact that the former are absorbed in relatively higher amounts than the latter.
  • the macro elements can include nitrogen, potassium, phosphorus, calcium, magnesium and sulphur.
  • the micro elements can include iron, chlorine, sodium, zinc, copper, boron, manganese and molybdenum.
  • liquid foliar fertilizers on the market contain nitrogen, phosphorus and potassium (NPK) in high dosage, and since plants are unable to absorb phosphorus through the leaves, its use in foliar fertilizers risks actually damaging the foliage.
  • NPK nitrogen, phosphorus and potassium
  • the fertilizers used contain nutritional elements in a form not assimilable by the plant, and therefore such products actually are unable to make up for the nutritional deficiencies of the plants.
  • the main foliar fertilizers on the market are based on the presence of molecules that cannot be degraded by the soil (like for example EDTA, EDTHA and chelates in general) that are used to promote the entry thereof inside the plant, but at the expense of the health of the farmer/gardener, of the plant and of the earth since they are potentially toxic molecules.
  • molecules that cannot be degraded by the soil like for example EDTA, EDTHA and chelates in general
  • US 2011/0296885 describes a macronutrient sustained release composition for a plant locus containing a nanocomposite, wherein a nitrogen containing macronutrient compound adsorbed on the surface of nanoparticles of non-substituted hydroxyapatite is intercalated within the interlayer spacing of a nanoclay.
  • the nanocomposite containing adsorbed macronutrient compounds is slowly released in a sustained manner when contacted with an acidic soil.
  • US 2014/0165683 describes a solid fertilizer composition wherein a nitrogen-containing macronutrient is adsorbed on the surface of nanoparticles of non-substituted hydroxyapatite and wherein the ratio of the nitrogen-containing macronutrient to the hydroxyapatite phosphate is between 1 : 1 and 10: 1.
  • said solid fertilizer composition slowly releases the nitrogen-containing macronutrient to soil.
  • WO 2014/087202 describes a fertilizer composition wherein a nitrogen- containing macronutrient is adsorbed on the surface of nanoparticles of non-substituted hydroxyapatite . Said fertilizer composition slowly releases the nitrogen-containing macronutrient to the soil.
  • FR 3 013 184 describes the use of hydroxyapatite particles possibly substituted with Mg, Zn, Pb, Cd, Ba, K or Mn, for the prevention and/or treatment of esca grape disease.
  • These particles can be surface functionalised with at least one bioactive molecule selected from metallic ions and/or antibacterial molecules and/or antifungal molecules and/or antiparasite molecules and/or phytosanitary active ingredients.
  • the hydroxyapatite particles can also be surface functionalised with copper ion and/or sulphur ion and/or zinc ion and/or one or more essential oils of plant origin.
  • the Applicant has therefore faced the problem of providing a balanced fertilization, capable of supplying the correct nutrition to the plant without it being generated by an overdose of a fertilizer that indeed solves the pathology of the plant, but builds up in the soil, and in fruits.
  • the Applicant has surprisingly and experimentally found that it is possible to make a balanced fertilizer, which contains all of the nutritional elements of the plant, with high assimilability by the plant apparatus itself and with the characteristic of being able to be dosed prudently, so as not to have to be applied with overdoses, thus avoiding dangerous accumulations thereof both in the soil, and in the plant and root apparatus of the plant itself.
  • the present invention concerns fertilizing compositions comprising particles of a calcium phosphate compound having the following formula:
  • M is at least one metallic ion selected from the group comprising Zn, Cu, Mn, Mg, Mo, Fe, K, Se and mixtures thereof
  • y is a number comprised between 0 and 8
  • u is a number comprised between 0 and 2
  • v is a number comprised between 0 and 2
  • w is a number comprised between 0 and 0.5
  • z is a number comprised between 0 and 0,5; provided that at least one from y, w and z is different from zero;
  • the particles of the calcium phosphate compound are surface functionalised with at least one organic compound containing at least one hydroxyl group and at least one micro or macro nutritional element.
  • surface-functionalised particles is meant to indicate that on the surface of the particles of calcium phosphate or of calcium carbonate compound described here compounds or elements, for example organic compounds containing at least one hydroxyl group and/or micro and/or macro nutritional elements, are bonded through the formation of weak interactions like, for example, hydrogen bonds, van der Waals forces, hydrophobic and hydrophilic interactions.
  • the term “particles” is meant to indicate nanoparticles or microparticles.
  • the term “microparticle” is meant to indicate clusters of inorganic nanoparticles mentioned above.
  • macroelement is meant to indicate a chemical element useful for the nutrition of plants and absorbed in relatively high amounts terefrom.
  • Preferred macroelements for the purposes of the invention are selected from: nitrogen, potassium, phosphorus, calcium, magnesium and sulphur.
  • microelement is meant to indicate a chemical element useful for the nutrition of plants and absorbed in a smaller amount than those of the aforementioned macroelements.
  • Preferred microelements for the purposes of the invention are selected from : iron, chlorine, sodium, zinc, copper, boron, manganese, selenium and molybdenum.
  • the Applicant has also experimentally found an advantageous synergic effect between the calcium phosphate compound and the aforementioned at least one organic compound containing at least one hydroxyl group and the aforementioned at least one micro or macro nutritional element to the point that extremely small amounts of them are sufficient to be able to obtain the effect of the organic compound (for example antibacterial) and of the micro or macro nutritional element.
  • the particles of the aforementioned calcium phosphate compound have a surface having free positive and/or negative charges so as to have a deficiency of neutralization between the positive charges (cations) and the negative charges (anions) thus advantageously allowing weak interactions to be formed (for example hydrogen bonds and van der Waals forces) with the organic compounds containing at least one hydroxyl group and/or with the micro or macro nutritional element.
  • nutritional micro and macro nutritional elements can thus be present both internally in the particles of the inorganic carrier (whenever at least one metallic ion M selected from the group comprising Zn, Cu, Mn, Mg, Mo, Fe, K, Se is present in the structure of the particle), and externally.
  • this substitution/functionalization leads to a controlled release of the nutritional elements that will thus be released in sequence as well as in a form favoured and assimilable by the plant itself.
  • the fertilizing compositions in accordance with the invention advantageously have a double release kinetics of the micro and macro elements.
  • the particles of calcium phosphate compound initially release the micro and macro elements externally bonded to them, directly or possibly through the organic compounds containing at least one hydroxyl group, whereas, while they are present on the leaf surface they release the micro and macro elements contained inside the particles themselves more slowly.
  • the surface functionalization of the particles of calcium phosphate compound leads to a controlled release also of the at least one organic compound containing at least one hydroxyl group that will thus be released in a form favoured and assimilable by the plant itself, performing its action as well as it can.
  • the present invention concerns a fertilizing composition
  • a fertilizing composition comprising particles of a calcium carbonate compound of formula
  • x is a number comprised between 0,0001 and 2;
  • N is a metallic ion selected from the group comprising magnesium, manganese, copper, potassium, zinc and mixtures thereof,
  • yi is a number comprised between 0,01 and 2.
  • the present invention concerns the particles of calcium phosphate compound described in the present document.
  • the present invention concerns the particles of calcium carbonate compound described in the present document.
  • the present invention concerns a process for producing an aqueous suspension including particles of a calcium phosphate compound as described in the present document, comprising the steps of:
  • M preferably between 0,3 and 5 M
  • - ions M at a concentration comprised between 0,00001 M and 5 M, preferably between 0,0001 M and 3 M; and/or - ions BO3 " at a concentration comprised between 0.001 M and 0.6 M, preferably between 0.01 M and 0.2 M; and/or - ions S1O4 " at a concentration comprised between 0.001 M and 0.1 M, preferably between 0.01 M and 0.08 M;
  • step c2) possibly, acidifying said solution or aqueous suspension of step cl) up to a pH comprised between 0,5 and 3, preferably comprised between 0,7 and 2 and keeping under agitation for a time comprised between 1 hour and 5,5 hours, preferably between 2 hours and 5 hours;
  • the present invention concerns a process for preparing particles of a calcium phosphate compound as described in the present document, comprising the steps of:
  • the present invention concerns a process for producing an aqueous suspension including particles of a calcium carbonate compound as described in the present document, comprising the steps of:
  • a'l providing a solution or aqueous suspension comprising calcium ions at a concentration comprised between 0,0001 M and 15 M, preferably between 0,001 M and 10 M;
  • f'l possibly, adding at least one organic compound containing at least one hydroxyl group and/or at least one micro or macro nutritional element to the aqueous suspension thus obtained ; g'l) possibly, keeping the mixture obtained under agitation for a time of at least 30 minutes, preferably at least 45 minutes.
  • the present invention concerns a process for preparing particles of a calcium carbonate compound as described in the present document, comprising the steps of: I) preparing an aqueous suspension including said particles of calcium carbonate through a process according to any one of claims 38 or 39;
  • the present invention concerns a process for producing a liquid or gel fertilizing composition comprising the steps of:
  • the present invention concerns a process for producing a solid fertilizing composition comprising the steps of:
  • y is a number comprised between 0,0055 and 6 and/or u is a number comprised between 0,040 and 1,5 and/or v is a number comprised between 0,065 and 1,5 and/or w is a number comprised between 0,01 and 0,4 and/or z is a number comprised between 0,01 and 0,4.
  • M is Zn m Cumi Mn m 2 Mg m 3 Fe m 4 Moms Km6 Sem7 wherein m is a number comprised between 0 and 8, m i is a number comprised between 0 and 8, nri2 is a number comprised between 0 and 2, nri3 is a number comprised between 0 and 2, m 4 is a number comprised between 0 and 8, ms is a number comprised between 0 and 1, nri6 is a number comprised between 0 and 8, m 7 is a number comprised between 0 and 1, at least one from m-nri7 is different from zero and m + m i + nri2 + nri3 + m 4 + ms + nri6 + m 7 ⁇ 8.
  • the metallic ion M is present in an amount comprised between 0% by weight and 80% by weight, preferably between 2,0% by weight and 30% by weight, with respect to the total weight of calcium.
  • an inorganic carrier that contains the nutritional elements of the plant inside it.
  • the carrier itself is therefore a nutritional element for the plant, and not just a carrier of the active ingredients that externally functionalize the plant itself.
  • the zinc ion can be present in an amount comprised between 0,01% by weight and 80% by weight, preferably between 0,2% by weight and 20% by weight with respect to the total weight of calcium.
  • the zinc performs an important action in certain enzyme reactions.
  • the potassium ion can be present in an amount comprised between 0,001% by weight and 80% by weight, preferably between 0,1% and 60% with respect to the total weight of calcium.
  • the potassium is of fundamental importance for cell expansion, protein synthesis, activation of enzymes, photosynthesis and also acts as transporter of other elements and carbohydrates through the cellular membrane. It also assumes an important role in keeping the osmotic potential of the cell in equilibrium and of adjusting the stomatic opening.
  • the iron ion can be present in an amount comprised between 0,001% by weight and 80% by weight, preferably between 0,1% by weight and 40% by weight with respect to the total weight of calcium.
  • the iron is among the most important nutritional elements since it is involved in many biological processes like for example photosynthesis.
  • the copper ion can be present in an amount comprised between 0,01% by weight and 80% by weight, preferably between 0,1% by weight and 60% by weight with respect to the total weight of calcium.
  • copper is involved in the respiratory and photosynthesis processes.
  • the manganese ion can be present in an amount comprised between 0,01% by weight and 20% by weight, preferably between 0,1% by weight and 3% by weight with respect to the total weight of calcium.
  • manganese forms part of many coenzymes and is involved in the elongation of the root cells and their resistance to pathogens.
  • the magnesium ion can be present in an amount comprised between 0,01% by weight and 20% by weight, preferably between 0,1% by weight and 1,5% by weight with respect to the total weight of calcium.
  • magnesium is of particular importance since it is part of the make-up of chlorophyll molecules.
  • the molybdenum ion can be present in an amount comprised between 0,001% by weight and 2% by weight, preferably between 0,01% by weight and 1% by weight with respect to the total weight of calcium.
  • molybdenum is essential in the synthesis of proteins and in the metabolism of nitrogen.
  • the selenium ion can be present in an amount comprised between 0,01% by weight and 5% by weight, preferably between 0,01% by weight and 3% by weight with respect to the total weight of calcium.
  • selenium is a natural antioxidant having direct benefits on the plant.
  • the calcium ion can be present in an amount comprised between 10% by weight and 90% by weight, preferably between 30% by weight and 50% by weight with respect to the total weight of the particles.
  • calcium is involved in the formation of the cell wall, in the permeability of the membrane and in the division and extension of the cells.
  • a good availability gives the plant greater resistance to fungal attacks and to bacterial infections.
  • the ion H can be present in an amount comprised between 0,01% by weight and 5% by weight, preferably between 0,01% by weight and 3% by weight with respect to the total calcium content.
  • the carbonate ion can be present in an amount comprised between 0,01% by weight and 10% by weight, preferably between 3% by weight and 7% by weight with respect to the total phosphate content.
  • the boron ion can be present in an amount comprised between 0,01% by weight and 2% by weight, preferably between 0,02% by weight and 0,7% by weight with respect to the total phosphate content.
  • boron is essential for fecundation, fruit setting and the development of seeds.
  • the silicon ion can be present in an amount comprised between 0,01% by weight and 4% by weight, preferably between 0,02% by weight and 2% by weight with respect to the total phosphate content.
  • silicon is important for the defences of the plant, but is not very assimilable in the forms present in the soil.
  • the particles of substituted calcium phosphate compound with micro and macro elements and externally functionalized with at least one organic compound containing at least one hydroxyl group and at least one micro or macro nutritional element have micrometric dimensions, indeed they have a length and/or a width of variable size, but comprised between 0,1 micron and 10 micron, preferably comprised between 0,2 micron and 2 micron.
  • the surface area of the particles of calcium phosphate compound, possibly aggregated to give "clusters" or phosphate microaggregates is comprised between 60 and 150 m 2 /g, preferably between 90 and 120 m 2 /g-
  • the microaggregates formed by the particles of calcium phosphate compound, having a large surface area are superficially nano-structured and have high reactivity.
  • the carrier based on calcium phosphate can be in crystalline form with pseudoapatitic structure, in semiamorphous form, in crystalline form with pseudobrushitic structure or a mixture thereof.
  • all of the aforementioned steps are capable of constituting micrometric aggregates, superficially nano-structured, with large area and surface reactivity.
  • the organic compound containing at least one hydroxyl group is selected from the group comprising : resorcinol, phloroglucinol, polyethylene glycol (PEG), cyclodextrin, proteins (like for example lactoferrin), gluconic acid and its salts (gluconates).
  • phloroglucinol is a natural element present in some plants as secondary metabolite for which reason it contributes to making the fertilizing composition particularly suitable for stimulating the growth of the plant itself.
  • lactoferrin and resorcinol have antibacterial properties and, as such, increase the antibacterial power of the fertilizing composition.
  • cyclodextrins have chelating properties useful for conveying to the plant and, in particular to its leaf surface, useful compounds or elements like for example one or more of the micro/macronutritional elements described in the present document.
  • gluconic acid and its salts can be capable of performing various useful functions in the fertilizing composition, like for example that of regulating acidity, dissolving mineral deposits, particularly in the presence of basic pH, and chelating, in the case of a clear negative charge (anion), Ca 2+ , Fe 2+ , Al 3+ , and other heavy metals.
  • the total amount of organic compound containing at least one hydroxyl group in the particles of substituted calcium phosphate compound with micro and macro elements is comprised between 5 and 40% by weight with respect to the total weight of the particles.
  • the total amount of organic compound containing at least one hydroxyl group in the particles of substituted calcium phosphate compound is comprised between 0.0003 mg/mL and 3 mg/mL of inorganic compound .
  • the aforementioned at least one micro or macro nutritional element that surface functionalizes the particles of calcium phosphate compound is selected from the group comprising : K, P, Ca, Mg, Fe, Zn, Cu, B, Mn, Mo, Se.
  • the total amount of the aforementioned at least one micro or macro nutritional element in the particles of calcium phosphate compound is comprised between 1 and 30% by weight with respect to the total weight of the particles.
  • the particles of substituted calcium phosphate compound with micro and macro elements have a crystallinity degree (CD) comprised between 40% and 80%, more preferably comprised between 50% and 75%.
  • CD crystallinity degree
  • the crystallinity degree can be calculated using methods well known to those skilled in the art, like for example through the analysis of X-ray diffraction data.
  • the crystallinity degree (CD) can be calculated using the method described in: Landi, E., Tampieri, A., Celotti, G., Sprio, S., "Densification behaviour and mechanisms of synthetic hydroxyapatites", J. Eur. Ceram. Soc, 2000, 20, 2377-2387 (here in brief: Landi method).
  • the metallic ion N of the aforementioned calcium carbonate compound is present in an amount comprised between 0.01% by weight and 70% by weight with respect to the total weight of calcium.
  • the calcium carbonate compound has a micrometric size, but is nanostructured.
  • the calcium carbonate compound can be in crystalline form or in semiamorphous form.
  • the zinc ion can be present in the calcium carbonate compound in an amount comprised between 0,01% and 90%, preferably between 0,2% and 40% with respect to the calcium content.
  • the calcium ion can be present in the calcium carbonate compound in an amount comprised between 0,001% and 80%, preferably between 0,1% and 40%.
  • the manganese ion can be present in the calcium carbonate compound in an amount comprised between 0,01% and 35%, preferably between 0,1% and 5% with respect to the calcium content.
  • the potassium ion can be present in the calcium carbonate compound in an amount comprised between 0,01% and 35%, preferably between 0,1% and 5% with respect to the calcium content.
  • the magnesium ion can be present in the calcium carbonate compound in an amount comprised between 0,01% and 35%, preferably between 0,1% and 5% with respect to the calcium content.
  • the copper ion can be present in the calcium carbonate compound in an amount comprised between 0,01% and 65%, preferably between 0,1% and 15% with respect to the calcium content.
  • the carbonate ion can be present in the calcium carbonate compound in an amount comprised between 0,01% and 40%, preferably between 3% and 10% with respect to the total weight of the particles.
  • the particles of the calcium carbonate compound have a crystallinity degree (CD) comprised between 40% and 80%, more preferably comprised between 50% and 75%.
  • the crystallinity degree can be calculated using methods well known to those skilled in the art, like for example through the analysis of X-ray diffraction data.
  • the crystallinity degree (CD) can be calculated using the Landi method described in Landi, E., Tampieri, A., Celotti, G., Sprio, S., "Densification behaviour and mechanisms of synthetic hydroxy apatites” , J. Eur. Ceram. Soc, 2000, 20, 2377-2387.
  • the surface area of the calcium carbonate compound is comprised between 20 and 100 m 2 /g, preferably between 30 and 80 m 2 /g-
  • the calcium carbonate compound has micrometric size, and indeed having indeed a length and a width of variable size, comprised between 0,1 micron and 10 micron, more preferably between 0,2 micron and 4 micron.
  • the calcium carbonate compound is surface functionalized with at least one organic compound containing at least one hydroxyl group and/or with at least one micro or macro nutritional element as described above.
  • the total amount of organic compound containing at least one hydroxyl group in the particles of calcium carbonate compound is comprised between 5 and 40% by weight with respect to the total weight of the particles.
  • the total amount of organic compound containing at least one hyd roxyl g rou p in the particles of calcium carbonate compound is comprised between 0.0003 mg/mL and 3 mg/mL of inorganic compound .
  • the fertilizing composition comprising the aforementioned calcium carbonate compou nd described above further comprises particles of a calcium phosphate compou nd not su rface functionalized having the following formu la :
  • MY is a metallic ion selected from the g rou p comprising Zn, Cu, M n, Mg, Mo, Fe, K, Se and mixtu res thereof, wherein y is a number comprised between 0 and 8;
  • u is a number comprised between 0 and 2
  • v is a number comprised between 0 and 2
  • w is a number comprised between 0 and 0,5
  • z is a number comprised between 0 and 0,5.
  • At least one from y, w and z is d ifferent from zero.
  • y is a number comprised between 0,0055 and 6 and/or u is a number comprised between 0,040 and 1,5 and/or v is a number comprised between 0,065 and 1 ,5 and/or w is a number comprised between 0,01 and 0,4 and/or z is a number comprised between 0,01 and 0,4.
  • the fu rther preferred characteristics of the aforementioned non-su rface fu nctionalized calcium phosphate compound a re the same preferred characteristics described above with reference to the particles of calcium phosphate su rface functionalised with at least one organic compound containing at least one hydroxyl g rou p and at least one micro or macro nutritional element, for which reason they will not be repeated here for the sake of keeping the description brief.
  • the aforementioned pa rticles of a non-surface functionalized calcium phosphate compou nd having the following formu la :
  • Ca(io-y) My H u (P0 4 ) (6-v-w-z) (C0 3 )v (B0 3 )w (Si0 4 )z(O H) 2 wherein M, y, u, v, w and z are as ind icated above, can be prepared throug h a process as described above for the production of a suspension of particles or for the production of particles of ca lcium phosphate compound, except for the fact that the surface functionalizing steps fl) and g l) are not present.
  • the particles of a calcium phosphate compou nd described above of the fertilizing composition comprising the aforementioned calcium carbonate compound described above, can be su rface fu nctionalised with at least one organic compound containing at least one hyd roxyl g rou p a nd/or with at least one micro or macro nutritional element.
  • the particles of calcium phosphate compound used in the fertilizing composition in combination with the particles of calcium carbonate compound can be (if su rface functionalised with at least one organic compou nd conta ining at least one hyd roxyl g rou p and with at least one micro or macro nutritional element) the particles described above in relation to the first aspect of the invention and can be prepared with the relative production processes described above.
  • the aforementioned at least one organic compou nd containing at least one hyd roxyl g roup a nd the aforementioned at least one micro or macro nutritional element have preferred characteristics that are the same as those described above with reference to the particles of su rface functionalized calcium phosphate, for which reason they will not be repeated here in order to keep the description brief.
  • the particles of calcium phosphate are present in the fertilizing composition in an amount by weight comprised between 10% and 90%.
  • the particles of calcium carbonate compound are present in the fertilizing composition in an amount by weight comprised between 10% and 50%.
  • the fertilizing composition comprises particles (the carrier) based on calcium phosphate (substituted with macro and micro elements and surface functionalized or not) and the calcium carbonate compound
  • such a composition has two different solubilities in an acid environment (acid rain, humidity) : one due to the solubilisation of the phosphate component and the other due to the solubilisation of the carbonate component, for which reason a very advantageously modulated and controlled release of the nutritional ingredients is obtained by the complex fertilizing composition thus formulated.
  • the plants can absorb the nutritional elements necessary for their development through the leaves and the stems, and therefore it is possible to administer, particularly through the foliage surfaces, both the main elements (macroelements) and the microelements and the organic compounds containing at least one hydroxyl group, where present.
  • This treatment can be very important when there is a momentary impossibility of the plants absorbing nutrition from the soil : this can occur in the case of parasite attacks to the roots, when there is a lack of nutritional elements in the soil or furthermore in the case of frosts.
  • the absorption of the conventional foliar fertilizer takes variable amounts of time and can, in general, by comprised between 3 and 24 hours; therefore, the foliage fertilized plants are neither sprayed nor wetted for at least 24 hours from the moment of treatment.
  • the fertilizing composition according to the invention it is possible to obtain a homogeneous distribution of product on the leaf and an optimal foliar adhesion in 3-4 hours, thus avoiding overdoses of the macro and micro elements that could become harmful for the plant.
  • the present invention concerns a fertilizing composition in the form of a suspension, gel, solution or solid .
  • the fertilizing compositions according to the invention can advantageously be used directly as such or diluted with water.
  • the concentration of the micro/macro elements present inside the fertilizing solution is comprised between 0.1% by weight and 20% by weight.
  • Such a percentage can vary from metal to metal based on the solubility thereof.
  • step dl) of adding by dripping a solution or aqueous suspension containing phosphate ions of the process for producing the aforementioned aqueous suspension including particles of a surface functionalized calcium phosphate compound is carried out through simultaneous stirring of the solution so as to capture the CO2 present in the atmosphere or through the addition of carbonate ions to the solution or aqueous suspension containing phosphate ions.
  • step fl) or step f'l) of the aforementioned processes for producing an aqueous suspension of the particles of a calcium phosphate or calcium carbonate compound comprises adding an aqueous solution comprising at least one organic compound containing at least one hydroxyl group to a concentration comprised between 0.0003 mg/mL and 300 mg/mL, preferably between 0.001 mg/mL and 100 mg/mL and adding an aqueous solution comprising at least one micro or macro nutritional element at a concentration comprised between 0.001 M and 10 M, preferably between 0.01 M and 8 M or adding an aqueous solution comprising said at least one organic compound containing at least one hydroxyl group and said at least one micro or macro nutritional element at said concentrations.
  • the separation step ii) of the process for preparing the particles of a surface functionalized calcium phosphate compound or the separation step II) of the process for preparing the particles of a calcium carbonate compound is carried out by decanting, centrifuging or filtration.
  • the drying step iii) of the process for preparing the particles of a surface functionalized calcium phosphate compound or the drying step III) of the process for preparing the particles of a calcium carbonate compound is carried out through lyophilization at a temperature of less than 0°C until a constant weight is obtained.
  • the fertilizing products of the invention can comprise further ingredients commonly used and known in the field to formulate such products, like for example: natural or artificial rubbers, used as suspending agents (xanthan gum, carrageenan), clay (bentonite, montmorillonite).
  • natural or artificial rubbers used as suspending agents (xanthan gum, carrageenan), clay (bentonite, montmorillonite).
  • aqueous suspension including the particles of a calcium phosphate compound, both surface functionalized and not, and/or the particles of a calcium carbonate compound, both surface functionalized and not, as described above, it is possible to use solid particles as such.
  • the aforementioned solid particles can preferably be obtained from the aqueous suspension by separation through decanting, centrifuging or filtration using apparatuses and techniques well known to those skilled in the art.
  • the wet solid particles thus obtained are then preferably dried through lyophilization at a temperature of less than 0°C until a constant weight is obtained.
  • the drying step is preferably carried out through lyophilization of the wet solid particles at a temperature comprised between -20 ° and -50 ° C, more preferably at about -40 ° C.
  • the mixing step b) is obtained through a mixer kept under vacuum, easily selected by those skilled in the art in order to obtain an even mixture of ingredients.
  • said heating step bi) or b'i) is obtained by heating on a heating plate or in a water or silicone bath.
  • said dripping step ci) is obtained with a speed comprised between 0,03 and 10 L/min, preferably comprised between 0,1 L/min and 6 L/min and with a flow comprised between 0,001 and 4 L/min, preferably comprised between 0,1 L/min and 2 L/min.
  • said acidification step C2) is obtained with phosphoric acid, sulphuric acid, hydrochloric acid, acetic acid, lactic acid, nitric acid, citric acid or a mixture thereof.
  • said dripping step di) is obtained with a speed comprised between 0,03 and 10 L/min, preferably comprised between 0,1 L/min and 6 L/min.
  • said step of keeping under stirring ei) takes place at a stirringspeed of the solution comprised between 100 rpm and 5000 rpm, preferably comprised between 500 rpm and 1500 rpm.
  • the final pH of the solution or suspension of particles of calcium phosphate or calcium carbonate described above obtained is comprised between 2 and 12, preferably between 2 and 7 or between 9 and 12.
  • the pH is modified with the addition of a base, preferably, NaOH, KOH, NH 3 or a mixture thereof.
  • the product obtained has a dry residue comprised between 10% and 40% (w/w), preferably comprised between 15% and 30% (w/w).
  • source of calcium ions it is possible to use: Ca(OH)2, CaCOs, CaO, Ca(CH 3 COO) 2 , Ca(N0 3 )2*4H 2 0, Ca(N0 3 ) 2 *2H 2 0 or a mixture thereof.
  • source of phosphate ions and hydrogen ions it is possible to use: H 3 P04, H 2 P0 4 , H 2 KP0 4 , HK 2 P0 4 , K 3 P04, NH 4 H 2 P0 4 or a mixture thereof.
  • the ions M are selected from the group comprising zinc, potassium, iron, copper, manganese, magnesium, molybdenum and selenium.
  • source of zinc ions it is possible to use: ZnO, ZnN0 3 , ZnC0 3 , ZnS0 4 , ZnCI 2 , Zn(OH) 2 , Zn(CH 3 COO) 2 , or a mixture thereof.
  • source of potassium ions it is possible to use: K 3 P0 4 , H 2 KP0 4 , HK 2 P0 4 , K 2 C0 3 , KCI, K(OH) or a mixture thereof.
  • iron ions it is possible to use: FeC0 3 , FeS0 4 , FeO, FeN0 3 , Fe(OH) 2 or a mixture thereof.
  • source of copper ions it is possible to use: CuS0 4 , CuO, Cu(OH) 2 , Copper Gluconate, CuC0 3 , CuN0 3 or a mixture thereof.
  • source of manganese ions it is possible to use: MnS0 4 , MnC0 3 , MnO, Mn(OH) 2 or a mixture thereof.
  • magnesium ions As source of magnesium ions it is possible to use MgS0 4 , MgO, MgC03, Mg(OH)2 or a mixture thereof.
  • selenium ions As source of selenium ions it is possible to use SeO, SeC03, SeCI, Se(OH)2, or a mixture thereof.
  • boron ethanolamine H3BO3 or a mixture thereof.
  • source of silicon ions it is possible to use potassium silicate, sodium silicate, or a mixture thereof.
  • step di) or step d'i) is carried out through simultaneous agitation of the solution, preferably through a mechanical stirrer, so as to capture the CO2 present in the atmosphere, or through the add ition of carbonate ions to the solution or aqueous suspension containing phosphate ions.
  • source of carbonate ions it is possible to use CaC03,
  • the ions N are selected from the group comprising magnesium, manganese, copper, potassium, zinc.
  • said dripping step c'i) is obtained with a speed comprised between 0,03 and 10 L/min, preferably comprised between 0,1 L/min and 6 L/min and with a flow comprised between 0,001 and 4 L/min, preferably comprised between 0,1 L/min and 2 L/min.
  • said dripping step d'i) is obtained with a speed comprised between 0,03 and 10 L/min, preferably comprised between 0,1 L/min and 6 L/min.
  • said step of keeping under stirring e'i) takes place at astirring speed of the solution comprised between 100 rpm and 5000 rpm, preferably comprised between 500 rpm and 1500 rpm.
  • the fina l pH of the solution or suspension obtained is comprised between 3 and 12, preferably between 4 and 10.
  • the product obtained has a d ry residue comprised between 10% and 40% (w/w), preferably comprised between 15 % and 30% (w/w) .
  • step fl) is carried out so that the aqueous suspension obtained from step gl) is used in an amount by weight comprised between 10% and 90%.
  • step f'l) is carried out so that the aqueous suspension obtained from step e'l) is used in an amount by weight comprised between 10% and 50%.
  • the mixture comprising the aqueous suspension obtained from step gl) and the aqueous suspension obtained from step e'l) or g'l) constitutes between 3% and 50%, more preferably between 5% and 30% of the final fertilizing composition.
  • figure 1 is an X-ray diffraction spectrum of an example of particles of a calcium phosphate compound (Example 1) used for producing fertilizing compositions according to an aspect of the invention
  • figure 2 is a Scanning Electron Microscope image (SEM) of an example of particles of a calcium phosphate compound (Example 1) used for producing fertilizing compositions according to an aspect of the invention;
  • FIG. 3 is an X-ray diffraction spectrum of an example of a carbonate compound (Example 2) used for producing fertilizing compositions according to an aspect of the invention
  • figure 4 is a Scanning Electron Microscope image (SEM) of an example of a carbonate compound (Example 2) used for producing fertilizing compositions according to an aspect of the invention
  • figure 5 is a Scanning Electron Microscope image (SEM) of the foliar distribution of a conventional reference fertilizing product
  • FIG. 6 is a Scanning Electron Microscope image (SEM) of the foliar distribution of a fertilizing product (Example 1) according to an aspect of the invention.
  • the X-ray diffraction spectrum highlights a crystalline material that has the diffraction maximums characteristic of a calcium phosphate (Example 1).
  • the diffraction maximum of the calcium phosphate obtained in this example are as follows: 2 Theta 26 - 32 - 33 - 34.
  • the morphological analysis by Scanning Electron Microscope shows that the particles of calcium phosphate have crystalline formations of micrometric dimensions, comprised between 0,2 micron and 2 micron.
  • the X-ray diffraction spectrum highlights a crystalline material that has the diffraction maximums characteristic of a zinc and calcium carbonate (Example 2).
  • the diffraction maximum of the carbonate obtained in this example are as follows: 2 Theta 23 - 29 - 39 - 39 - 43.
  • the morphological analysis by Scanning Electron Microscope shows that the particles of carbonate have crystalline formations of micrometric dimensions, comprised between 0,2 micron and 1 micron.
  • Solution 2 was then added to solution 1, by dripping, at a flow equal to 0,2 L/min.
  • the synthesis product was aged inside the reaction environment, keeping it under stirring, in thermostated environment, for a total time equal to 10 hours.
  • the pH is brought to a value comprised between 6 and 13, preferably between 9 and 12, with suitable addition of base like for example NaOH, KOH, N H3 or a mixture thereof.
  • suitable addition of base like for example NaOH, KOH, N H3 or a mixture thereof.
  • the resulting suspension was then kept under agitation for 45 minutes.
  • the suspension of particles of calcium phosphate surface functionalised with micro and macro elements obtained was then used to produce fertilizing compositions according to the invention.
  • Solution 2 was then added to solution 1, by dripping, at a flow equal to 0,125 L/min.
  • a fertilizing composition according to the invention was made by mixing 70 g of the aqueous suspension of Example 1 with 30 g of the aqueous suspension of Example 2. In this way 100 g of fertilizing composition are obtained .
  • the SEM image of figure 5 shows how the foliar distribution of a conventional copper-based product is not very capillary on the foliar wall itself and how the rough dimensions of a conventional product (a sing le particle is visible in the high part of the SEM image) do not allow homogeneous coverage of the leaf.
  • the plants treated did not show attacks from the disease (peronospora), but with respect to the conventional treatment defined above, one third of the copper was used, which however conveyed through the formulation described in example 3, allowed it to be much more functional (despite the low dose) actually obtaining comparable results to a conventional treatment, containing a greater amount of copper.
  • the SEM image of figure 6 shows how the foliar distribution of a product made according to example 3 is much more capillary and the product is much better distributed over the entire foliar wall examined as highlighted by the numerous particles visible on the leaf and distributed evenly on its surface.
  • the use of a fertilizing product according to the invention gives the plant the nutritional elements that it needs, avoiding overdoses and obtaining homogeneous distribution of the product on the foliage and optimal foliar adhesion.

Abstract

The present invention refers to fertilizing compositions comprising inorganic particles of a calcium phosphate compound substituted with micro and macro elements and surface functionalised with at least one organic compound containing at least one hydroxyl group and at least one micro or macro nutritional element and/or comprising a substituted and possibly surface functionalised calcium carbonate compound. Other aspects of the invention include a process for preparing fertilizing compositions and processes for preparing particles of calcium phosphate compound and calcium carbonate compound.

Description

FERTILIZING COMPOSITIONS BASED ON A SUBSTITUTED CALCIUM PHOSPHATE AND/OR CALCIUM CARBONATE
COMPOUND
DESCRIPTION
Background of the invention
The present invention refers to fertilizing compositions comprising inorganic particles of a substituted and surface functionalised calcium phosphate compound; to fertilizing compositions comprising inorganic particles of a substituted and possibly surface functionalised calcium carbonate compound and to processes for preparing the aforementioned fertilizing compositions and inorganic particles.
More specifically, the invention refers to fertilizing compositions that have preferred but not exclusive use in foliar fertilization for applications in farming and gardening.
Related art
The nutritional elements essential for the growth and development of plants are taken from the environment, meaning atmosphere-water- earth.
The atmosphere which is the main source of nutrition for plants since it provides carbon dioxide (CO2). CO2 is assimilated mainly during photosynthesis and carbon and oxygen together constitute about 90% of the dry matter of the upper plants. The atmosphere also provides oxygen (O2), presiding aerobic respiration, a substantial amount of nitrogen (N2), traces of gaseous ammonia (NH3) and sulphur dioxide (SO2), also assimilable by some plants.
Water (H2O) is the second source of nutrition for plants. Although most of the water absorbed by the roots evaporates through transpiration from the leaves, a small fraction is used as reactant in metabolic transformations.
The earth constitutes the third source from which plants obtain the nutritional mineral elements, deriving from the breaking up and solubilisation of the bedrock and from the breaking down of animal and vegetable residues.
The chemical elements useful for the nutrition of plants are numerous : up to sixty have been found in the different plant tissues.
The nutrition of plants, as known, is regulated by the Sprengel and Von Liebig's law of the minimum (1840). According to such a law, the absence or limited availability of a nutritional element is sufficient to compromise the development and growth of the vegetable organism. In the absence of only one of the essential elements, plants display symptoms of deficiency, characteristic of the element of which there is not enough, and reduce production capacity or die prematurely.
In particular, foliar fertilization, being a technique of administering fertilizers that exploits the ability of plants to absorb water and the mineral salts dissolved in it through the epidermis and the stomata of the leaves, can be considered like a supplementing intervention that allows nutritional deficiencies to be solved for the main macro and micro elements, nutritional elements thus defined based on the fact that the former are absorbed in relatively higher amounts than the latter.
This does not mean that the micro elements are less important, and indeed in the case of absence or scarcity of these, the plant can display more or less serious diseases, generically called deficiency physiopathies.
The macro elements can include nitrogen, potassium, phosphorus, calcium, magnesium and sulphur. The micro elements, on the other hand, can include iron, chlorine, sodium, zinc, copper, boron, manganese and molybdenum.
Often liquid foliar fertilizers on the market contain nitrogen, phosphorus and potassium (NPK) in high dosage, and since plants are unable to absorb phosphorus through the leaves, its use in foliar fertilizers risks actually damaging the foliage.
In other formulations currently present on the market, the fertilizers used contain nutritional elements in a form not assimilable by the plant, and therefore such products actually are unable to make up for the nutritional deficiencies of the plants.
Moreover, the main foliar fertilizers on the market are based on the presence of molecules that cannot be degraded by the soil (like for example EDTA, EDTHA and chelates in general) that are used to promote the entry thereof inside the plant, but at the expense of the health of the farmer/gardener, of the plant and of the earth since they are potentially toxic molecules.
It is also known how some foliar fertilizers, despite solving the deficiency of the plant, cause a modification of the pH of the earth and of the plant itself with consequent negative effects.
Sutter et a I., "Mineralogical and Chemical Characterization of Iron-, Manganese-, and Copper-Containing Synthethis Hydroxyapatites", Soil Sci. Soc. Am. J., 67: 1935-1942 (2003), describe hydroxyapatites comprising Fe, Mn and Cu in the crystalline structure (substituted hydroxyapatites) for use as potential slow-release sources of fertilizing micronutrients.
Golden D.C. et al, " Nutrient-Substituted Hydroxyapatites: Synthesis and Characterization", Soil Sci. Soc. Am. J., 63 :657-664 (1999), describe materials for hydroponic farming on zeolites of plants, consisting of hydroxyapatite substituted with Mg, S, Fe, Cu, Mn, Zn, Mo, B and CI for use as a slow-release source of fertilizing micronutrients.
Liu Ruiqiang at al, "Synthetic apatite nanoparticles as a phosphorous fertilizer for soybean (Glycine max)", Scientific Reports, 4: 5686, 14 July 2014, article No. 5686, shows that non-substituted hydroxyapatite nanoparticles can be used as an effective source of P in the fertilization of plants.
US 2011/0296885 describes a macronutrient sustained release composition for a plant locus containing a nanocomposite, wherein a nitrogen containing macronutrient compound adsorbed on the surface of nanoparticles of non-substituted hydroxyapatite is intercalated within the interlayer spacing of a nanoclay. The nanocomposite containing adsorbed macronutrient compounds is slowly released in a sustained manner when contacted with an acidic soil.
US 2014/0165683 describes a solid fertilizer composition wherein a nitrogen-containing macronutrient is adsorbed on the surface of nanoparticles of non-substituted hydroxyapatite and wherein the ratio of the nitrogen-containing macronutrient to the hydroxyapatite phosphate is between 1 : 1 and 10: 1. In some embodiments, said solid fertilizer composition slowly releases the nitrogen-containing macronutrient to soil.
WO 2014/087202 describes a fertilizer composition wherein a nitrogen- containing macronutrient is adsorbed on the surface of nanoparticles of non-substituted hydroxyapatite . Said fertilizer composition slowly releases the nitrogen-containing macronutrient to the soil.
FR 3 013 184 describes the use of hydroxyapatite particles possibly substituted with Mg, Zn, Pb, Cd, Ba, K or Mn, for the prevention and/or treatment of esca grape disease. These particles can be surface functionalised with at least one bioactive molecule selected from metallic ions and/or antibacterial molecules and/or antifungal molecules and/or antiparasite molecules and/or phytosanitary active ingredients. The hydroxyapatite particles can also be surface functionalised with copper ion and/or sulphur ion and/or zinc ion and/or one or more essential oils of plant origin.
Summary of the invention
One of the problems linked to the use of fertilizers concerns the pollution of water and the soil. In particular, a big problem derives from the use of fertilizers and from the consequent accumulation thereof in the soil and in the groundwater. This problem impacts not only on the soil, but also on the food that comes from it and therefore on people who eat it.
The Applicant has therefore faced the problem of providing a balanced fertilization, capable of supplying the correct nutrition to the plant without it being generated by an overdose of a fertilizer that indeed solves the pathology of the plant, but builds up in the soil, and in fruits. The Applicant has surprisingly and experimentally found that it is possible to make a balanced fertilizer, which contains all of the nutritional elements of the plant, with high assimilability by the plant apparatus itself and with the characteristic of being able to be dosed prudently, so as not to have to be applied with overdoses, thus avoiding dangerous accumulations thereof both in the soil, and in the plant and root apparatus of the plant itself.
The Applicant has also surprisingly and experimentally found that it is possible to make a balanced fertilizer that is capable of effectively conveying to the plant, and in particular to its foliage, both nutritional elements and element with different functionality, for example to support the metabolic functions of the plant or of the antibacterial type. More specifically according to a first aspect, the present invention concerns fertilizing compositions comprising particles of a calcium phosphate compound having the following formula:
Ca(io-y) My Hu (P04)(6-v-w-z) (C03)v (B03)w (Si04)z(OH)2 wherein M is at least one metallic ion selected from the group comprising Zn, Cu, Mn, Mg, Mo, Fe, K, Se and mixtures thereof, y is a number comprised between 0 and 8; u is a number comprised between 0 and 2, v is a number comprised between 0 and 2, w is a number comprised between 0 and 0.5 and z is a number comprised between 0 and 0,5; provided that at least one from y, w and z is different from zero;
and wherein the particles of the calcium phosphate compound are surface functionalised with at least one organic compound containing at least one hydroxyl group and at least one micro or macro nutritional element.
Definitions
In the present description and in the subsequent claims, the expression "surface-functionalised particles" is meant to indicate that on the surface of the particles of calcium phosphate or of calcium carbonate compound described here compounds or elements, for example organic compounds containing at least one hydroxyl group and/or micro and/or macro nutritional elements, are bonded through the formation of weak interactions like, for example, hydrogen bonds, van der Waals forces, hydrophobic and hydrophilic interactions.
In the present description and in the subsequent claims, the term "particles" is meant to indicate nanoparticles or microparticles. In the present description and in the subsequent claims, the term "microparticle" is meant to indicate clusters of inorganic nanoparticles mentioned above.
In the present description and in the subsequent claims, the term "macroelement" is meant to indicate a chemical element useful for the nutrition of plants and absorbed in relatively high amounts terefrom. Preferred macroelements for the purposes of the invention are selected from: nitrogen, potassium, phosphorus, calcium, magnesium and sulphur.
In the present description and in the subsequent claims, the term "microelement" is meant to indicate a chemical element useful for the nutrition of plants and absorbed in a smaller amount than those of the aforementioned macroelements. Preferred microelements for the purposes of the invention are selected from : iron, chlorine, sodium, zinc, copper, boron, manganese, selenium and molybdenum.
In the present description and in the subsequent claims, all of the numerical magnitudes indicating quantities, parameter, percentages, and so on should in all circumstances be considered to be preceded by the term "about" unless indicated otherwise. Moreover, all of the ranges of numerical magnitudes include all of the possible combinations of maximum and minimum numerical values and all of the possible intermediate ranges, as well as those specifically indicated hereinafter.
The Applicant has experimentally found that thanks to the aforementioned specific characteristics of the substituted calcium phosphate compound with micro and macro elements, which will be described further hereinafter, this manages to act as phosphate carrier for balanced fertilization. Advantageously, it is thus possible to provide fertilizers that obtain a series of very advantageous technical effects with respect to conventional ones, including giving the plant the nutritional elements that it needs, avoiding overdoses, obtaining a homogeneous distribution of the product on the foliage and optimal foliage adhesion. The Applicant has also experimentally found an advantageous synergic effect between the calcium phosphate compound and the aforementioned at least one organic compound containing at least one hydroxyl group and the aforementioned at least one micro or macro nutritional element to the point that extremely small amounts of them are sufficient to be able to obtain the effect of the organic compound (for example antibacterial) and of the micro or macro nutritional element.
Although the Applicant does not wish to be limited by any interpretative theory, it is thought that the particles of the aforementioned calcium phosphate compound have a surface having free positive and/or negative charges so as to have a deficiency of neutralization between the positive charges (cations) and the negative charges (anions) thus advantageously allowing weak interactions to be formed (for example hydrogen bonds and van der Waals forces) with the organic compounds containing at least one hydroxyl group and/or with the micro or macro nutritional element.
Advantageously, nutritional micro and macro nutritional elements can thus be present both internally in the particles of the inorganic carrier (whenever at least one metallic ion M selected from the group comprising Zn, Cu, Mn, Mg, Mo, Fe, K, Se is present in the structure of the particle), and externally.
Advantageously, this substitution/functionalization leads to a controlled release of the nutritional elements that will thus be released in sequence as well as in a form favoured and assimilable by the plant itself.
In particular, the fertilizing compositions in accordance with the invention advantageously have a double release kinetics of the micro and macro elements. Indeed, the particles of calcium phosphate compound initially release the micro and macro elements externally bonded to them, directly or possibly through the organic compounds containing at least one hydroxyl group, whereas, while they are present on the leaf surface they release the micro and macro elements contained inside the particles themselves more slowly.
As well as this, the surface functionalization of the particles of calcium phosphate compound leads to a controlled release also of the at least one organic compound containing at least one hydroxyl group that will thus be released in a form favoured and assimilable by the plant itself, performing its action as well as it can.
In accordance with a second aspect thereof, the present invention concerns a fertilizing composition comprising particles of a calcium carbonate compound of formula
Figure imgf000010_0001
wherein x is a number comprised between 0,0001 and 2; N is a metallic ion selected from the group comprising magnesium, manganese, copper, potassium, zinc and mixtures thereof, yi is a number comprised between 0,01 and 2.
The Applicant has experimentally found that thanks to the aforementioned specific characteristics of the substituted calcium carbonate compound with micro and macro elements, which will be described further hereinafter, this manages to act as carbonate carrier for balanced fertilization.
Advantageously, it is thus possible to provide fertilizers that obtain a series of very advantageous technical effects with respect to conventional ones, including giving the plant the nutritional elements that it needs, avoiding overdoses, obtaining a homogeneous distribution of the product on the foliage and optimal foliage adhesion. In accordance with a third aspect thereof, the present invention concerns the particles of calcium phosphate compound described in the present document.
In accordance with a fourth aspect thereof, the present invention concerns the particles of calcium carbonate compound described in the present document.
In accordance with a fifth aspect thereof, the present invention concerns a process for producing an aqueous suspension including particles of a calcium phosphate compound as described in the present document, comprising the steps of:
al) providing a solution or aqueous suspension comprising calcium ions at a concentration comprised between 0,1 M and 10
M, preferably between 0,3 and 5 M;
bl) heating said solution or aqueous suspension to a temperature comprised between 10°C and 90°C, preferably between 20°C and 40°C;
cl) adding by dripping at least one solution or aqueous suspension containing at least one from :
- ions M at a concentration comprised between 0,00001 M and 5 M, preferably between 0,0001 M and 3 M; and/or - ions BO3" at a concentration comprised between 0.001 M and 0.6 M, preferably between 0.01 M and 0.2 M; and/or - ions S1O4" at a concentration comprised between 0.001 M and 0.1 M, preferably between 0.01 M and 0.08 M;
c2) possibly, acidifying said solution or aqueous suspension of step cl) up to a pH comprised between 0,5 and 3, preferably comprised between 0,7 and 2 and keeping under agitation for a time comprised between 1 hour and 5,5 hours, preferably between 2 hours and 5 hours;
dl) adding by dripping a solution or aqueous suspension containing phosphate ions at a concentration comprised between 0,1 M and 10 M, preferably between 0,2 M and 5 M ;
el) keeping under stirring the mixture obtained for a time comprised between 30 minutes and 24 hours, preferably between 2 and 15 hours;
fl) adding at least one organic compound containing at least one hydroxyl group and at least one micro or macro nutritional element to the aqueous suspension thus obtained ;
gl) keeping under agitation the mixture obtained for a time of at least 30 minutes, preferably at least 45 minutes.
In accordance with a sixth aspect thereof, the present invention concerns a process for preparing particles of a calcium phosphate compound as described in the present document, comprising the steps of:
i) preparing an aqueous suspension including said particles of calcium phosphate through a process according to any one of claims 32-34;
ii) separating solid particles from the suspension obtained from step i);
iii) drying the wet solid particles thus obtained. In accordance with a seventh aspect thereof, the present invention concerns a process for producing an aqueous suspension including particles of a calcium carbonate compound as described in the present document, comprising the steps of:
a'l) providing a solution or aqueous suspension comprising calcium ions at a concentration comprised between 0,0001 M and 15 M, preferably between 0,001 M and 10 M;
b'l) heating said solution or aqueous suspension to a temperature comprised between 2°C and 30°C, preferably between 3°C and 15°C;
c'l) adding by dripping a solution or aqueous suspension containing ions N at a concentration comprised between 0,001 M and 10 M, preferably between 0,001 M and 5 M;
d'l) adding a solution or aqueous suspension containing carbonate ions at a concentration comprised between 0,001 M and 10 M, preferably between 0,01 M and 5 M;
e'l) keeping under stirring the mixture obtained for a time comprised between 30 minutes and 24 hours, preferably between 2 and 15 hours;
f'l) possibly, adding at least one organic compound containing at least one hydroxyl group and/or at least one micro or macro nutritional element to the aqueous suspension thus obtained ; g'l) possibly, keeping the mixture obtained under agitation for a time of at least 30 minutes, preferably at least 45 minutes.
In accordance with an eighth aspect thereof, the present invention concerns a process for preparing particles of a calcium carbonate compound as described in the present document, comprising the steps of: I) preparing an aqueous suspension including said particles of calcium carbonate through a process according to any one of claims 38 or 39;
II) separating solid particles from the suspension obtained from step I);
III) drying the wet solid particles thus obtained.
In accordance with a ninth aspect thereof, the present invention concerns a process for producing a liquid or gel fertilizing composition comprising the steps of:
a) providing an aqueous suspension including particles of a calcium phosphate compound as described in the present document or particles of a calcium carbonate compound as described in the present document, possibly in combination with particles of a calcium phosphate compound as described hereinafter; and
b) mixing said aqueous suspension with the other ingredients of the fertilizing composition.
In accordance with a tenth aspect thereof, the present invention concerns a process for producing a solid fertilizing composition comprising the steps of:
a') providing particles of a calcium phosphate compound as described in the present document or particles of a calcium carbonate compound as described in the present document possibly in combination with particles of a calcium phosphate compound as described hereinafter; and
b') mixing said particles with the other ingredients of the fertilizing composition.
The present invention in one or more of the aforementioned aspects can have one or more of the preferred characteristics given hereinafter. In a preferred embodiment, y is a number comprised between 0,0055 and 6 and/or u is a number comprised between 0,040 and 1,5 and/or v is a number comprised between 0,065 and 1,5 and/or w is a number comprised between 0,01 and 0,4 and/or z is a number comprised between 0,01 and 0,4.
In this way, it is advantageously possible to have an optimisation of the effect of the substituents present in the particles of calcium phosphate.
In a preferred embodiment, M is Znm Cumi Mnm2 Mgm3 Fem4 Moms Km6 Sem7 wherein m is a number comprised between 0 and 8, m i is a number comprised between 0 and 8, nri2 is a number comprised between 0 and 2, nri3 is a number comprised between 0 and 2, m4 is a number comprised between 0 and 8, ms is a number comprised between 0 and 1, nri6 is a number comprised between 0 and 8, m7 is a number comprised between 0 and 1, at least one from m-nri7 is different from zero and m + m i + nri2 + nri3 + m4 + ms + nri6 + m7≤ 8.
Preferably, in the carrier based on calcium phosphate the metallic ion M is present in an amount comprised between 0% by weight and 80% by weight, preferably between 2,0% by weight and 30% by weight, with respect to the total weight of calcium.
In this way, an inorganic carrier is obtained that contains the nutritional elements of the plant inside it. The carrier itself is therefore a nutritional element for the plant, and not just a carrier of the active ingredients that externally functionalize the plant itself.
Preferably, the zinc ion can be present in an amount comprised between 0,01% by weight and 80% by weight, preferably between 0,2% by weight and 20% by weight with respect to the total weight of calcium.
Advantageously, the zinc performs an important action in certain enzyme reactions.
Preferably, the potassium ion can be present in an amount comprised between 0,001% by weight and 80% by weight, preferably between 0,1% and 60% with respect to the total weight of calcium.
Advantageously, the potassium is of fundamental importance for cell expansion, protein synthesis, activation of enzymes, photosynthesis and also acts as transporter of other elements and carbohydrates through the cellular membrane. It also assumes an important role in keeping the osmotic potential of the cell in equilibrium and of adjusting the stomatic opening.
The iron ion can be present in an amount comprised between 0,001% by weight and 80% by weight, preferably between 0,1% by weight and 40% by weight with respect to the total weight of calcium.
Advantageously, the iron is among the most important nutritional elements since it is involved in many biological processes like for example photosynthesis.
The copper ion can be present in an amount comprised between 0,01% by weight and 80% by weight, preferably between 0,1% by weight and 60% by weight with respect to the total weight of calcium.
Advantageously, copper is involved in the respiratory and photosynthesis processes.
The manganese ion can be present in an amount comprised between 0,01% by weight and 20% by weight, preferably between 0,1% by weight and 3% by weight with respect to the total weight of calcium. Advantageously, manganese forms part of many coenzymes and is involved in the elongation of the root cells and their resistance to pathogens.
The magnesium ion can be present in an amount comprised between 0,01% by weight and 20% by weight, preferably between 0,1% by weight and 1,5% by weight with respect to the total weight of calcium. Advantageously, magnesium is of particular importance since it is part of the make-up of chlorophyll molecules.
The molybdenum ion can be present in an amount comprised between 0,001% by weight and 2% by weight, preferably between 0,01% by weight and 1% by weight with respect to the total weight of calcium. Advantageously, molybdenum is essential in the synthesis of proteins and in the metabolism of nitrogen.
The selenium ion can be present in an amount comprised between 0,01% by weight and 5% by weight, preferably between 0,01% by weight and 3% by weight with respect to the total weight of calcium. Advantageously, selenium is a natural antioxidant having direct benefits on the plant.
Preferably, the calcium ion can be present in an amount comprised between 10% by weight and 90% by weight, preferably between 30% by weight and 50% by weight with respect to the total weight of the particles.
Advantageously, calcium is involved in the formation of the cell wall, in the permeability of the membrane and in the division and extension of the cells. A good availability gives the plant greater resistance to fungal attacks and to bacterial infections.
Preferably, the ion H can be present in an amount comprised between 0,01% by weight and 5% by weight, preferably between 0,01% by weight and 3% by weight with respect to the total calcium content. The carbonate ion can be present in an amount comprised between 0,01% by weight and 10% by weight, preferably between 3% by weight and 7% by weight with respect to the total phosphate content. The boron ion can be present in an amount comprised between 0,01% by weight and 2% by weight, preferably between 0,02% by weight and 0,7% by weight with respect to the total phosphate content.
Advantageously, boron is essential for fecundation, fruit setting and the development of seeds.
The silicon ion can be present in an amount comprised between 0,01% by weight and 4% by weight, preferably between 0,02% by weight and 2% by weight with respect to the total phosphate content.
Advantageously, silicon is important for the defences of the plant, but is not very assimilable in the forms present in the soil.
In a preferred embodiment of the invention, the particles of substituted calcium phosphate compound with micro and macro elements and externally functionalized with at least one organic compound containing at least one hydroxyl group and at least one micro or macro nutritional element, have micrometric dimensions, indeed they have a length and/or a width of variable size, but comprised between 0,1 micron and 10 micron, preferably comprised between 0,2 micron and 2 micron.
In a preferred embodiment of the invention, the surface area of the particles of calcium phosphate compound, possibly aggregated to give "clusters" or phosphate microaggregates, is comprised between 60 and 150 m2/g, preferably between 90 and 120 m2/g- Advantageously, the microaggregates formed by the particles of calcium phosphate compound, having a large surface area, are superficially nano-structured and have high reactivity.
The carrier based on calcium phosphate can be in crystalline form with pseudoapatitic structure, in semiamorphous form, in crystalline form with pseudobrushitic structure or a mixture thereof.
Advantageously, all of the aforementioned steps are capable of constituting micrometric aggregates, superficially nano-structured, with large area and surface reactivity.
In a preferred embodiment, the organic compound containing at least one hydroxyl group is selected from the group comprising : resorcinol, phloroglucinol, polyethylene glycol (PEG), cyclodextrin, proteins (like for example lactoferrin), gluconic acid and its salts (gluconates).
Advantageously, phloroglucinol is a natural element present in some plants as secondary metabolite for which reason it contributes to making the fertilizing composition particularly suitable for stimulating the growth of the plant itself.
Advantageously, lactoferrin and resorcinol have antibacterial properties and, as such, increase the antibacterial power of the fertilizing composition.
Advantageously, cyclodextrins have chelating properties useful for conveying to the plant and, in particular to its leaf surface, useful compounds or elements like for example one or more of the micro/macronutritional elements described in the present document. Advantageously, gluconic acid and its salts (gluconates) can be capable of performing various useful functions in the fertilizing composition, like for example that of regulating acidity, dissolving mineral deposits, particularly in the presence of basic pH, and chelating, in the case of a clear negative charge (anion), Ca2+, Fe2+, Al3+, and other heavy metals.
Preferably, the total amount of organic compound containing at least one hydroxyl group in the particles of substituted calcium phosphate compound with micro and macro elements is comprised between 5 and 40% by weight with respect to the total weight of the particles.
Preferably, the total amount of organic compound containing at least one hydroxyl group in the particles of substituted calcium phosphate compound is comprised between 0.0003 mg/mL and 3 mg/mL of inorganic compound .
In a preferred embodiment, the aforementioned at least one micro or macro nutritional element that surface functionalizes the particles of calcium phosphate compound is selected from the group comprising : K, P, Ca, Mg, Fe, Zn, Cu, B, Mn, Mo, Se.
Preferably, the total amount of the aforementioned at least one micro or macro nutritional element in the particles of calcium phosphate compound is comprised between 1 and 30% by weight with respect to the total weight of the particles.
In a preferred embodiment of the invention, the particles of substituted calcium phosphate compound with micro and macro elements have a crystallinity degree (CD) comprised between 40% and 80%, more preferably comprised between 50% and 75%.
For the purposes of the invention, the crystallinity degree (CD) can be calculated using methods well known to those skilled in the art, like for example through the analysis of X-ray diffraction data.
In particular, in the present invention the crystallinity degree (CD) can be calculated using the method described in: Landi, E., Tampieri, A., Celotti, G., Sprio, S., "Densification behaviour and mechanisms of synthetic hydroxyapatites", J. Eur. Ceram. Soc, 2000, 20, 2377-2387 (here in brief: Landi method).
In a preferred embodiment, the metallic ion N of the aforementioned calcium carbonate compound is present in an amount comprised between 0.01% by weight and 70% by weight with respect to the total weight of calcium.
In a preferred embodiment of the invention, the calcium carbonate compound has a micrometric size, but is nanostructured.
The calcium carbonate compound can be in crystalline form or in semiamorphous form.
Preferably, the zinc ion can be present in the calcium carbonate compound in an amount comprised between 0,01% and 90%, preferably between 0,2% and 40% with respect to the calcium content. Preferably, the calcium ion can be present in the calcium carbonate compound in an amount comprised between 0,001% and 80%, preferably between 0,1% and 40%.
Preferably, the manganese ion can be present in the calcium carbonate compound in an amount comprised between 0,01% and 35%, preferably between 0,1% and 5% with respect to the calcium content. Preferably, the potassium ion can be present in the calcium carbonate compound in an amount comprised between 0,01% and 35%, preferably between 0,1% and 5% with respect to the calcium content. Preferably, the magnesium ion can be present in the calcium carbonate compound in an amount comprised between 0,01% and 35%, preferably between 0,1% and 5% with respect to the calcium content. Preferably, the copper ion can be present in the calcium carbonate compound in an amount comprised between 0,01% and 65%, preferably between 0,1% and 15% with respect to the calcium content. Preferably, the carbonate ion can be present in the calcium carbonate compound in an amount comprised between 0,01% and 40%, preferably between 3% and 10% with respect to the total weight of the particles. In a preferred embodiment of the invention, the particles of the calcium carbonate compound have a crystallinity degree (CD) comprised between 40% and 80%, more preferably comprised between 50% and 75%.
For the purposes of the invention, the crystallinity degree (CD) can be calculated using methods well known to those skilled in the art, like for example through the analysis of X-ray diffraction data.
Also in this case and as outlined above, the crystallinity degree (CD) can be calculated using the Landi method described in Landi, E., Tampieri, A., Celotti, G., Sprio, S., "Densification behaviour and mechanisms of synthetic hydroxy apatites" , J. Eur. Ceram. Soc, 2000, 20, 2377-2387.
In a preferred embodiment of the invention, the surface area of the calcium carbonate compound is comprised between 20 and 100 m2/g, preferably between 30 and 80 m2/g-
Preferably, the calcium carbonate compound has micrometric size, and indeed having indeed a length and a width of variable size, comprised between 0,1 micron and 10 micron, more preferably between 0,2 micron and 4 micron.
In a further preferred embodiment, the calcium carbonate compound is surface functionalized with at least one organic compound containing at least one hydroxyl group and/or with at least one micro or macro nutritional element as described above.
Preferably, the total amount of organic compound containing at least one hydroxyl group in the particles of calcium carbonate compound is comprised between 5 and 40% by weight with respect to the total weight of the particles.
Preferably, the total amount of organic compound containing at least one hyd roxyl g rou p in the particles of calcium carbonate compound is comprised between 0.0003 mg/mL and 3 mg/mL of inorganic compound .
In a preferred embod iment, the fertilizing composition comprising the aforementioned calcium carbonate compou nd described above further comprises particles of a calcium phosphate compou nd not su rface functionalized having the following formu la :
Ca(io-y) My H u (P04) (6-v-w-z) (C03)v (B03)w (Si04)z(O H)2 wherein MY is a metallic ion selected from the g rou p comprising Zn, Cu, M n, Mg, Mo, Fe, K, Se and mixtu res thereof, wherein y is a number comprised between 0 and 8;
u is a number comprised between 0 and 2, v is a number comprised between 0 and 2, w is a number comprised between 0 and 0,5 and z is a number comprised between 0 and 0,5.
Preferably, at least one from y, w and z is d ifferent from zero.
Preferably, y is a number comprised between 0,0055 and 6 and/or u is a number comprised between 0,040 and 1,5 and/or v is a number comprised between 0,065 and 1 ,5 and/or w is a number comprised between 0,01 and 0,4 and/or z is a number comprised between 0,01 and 0,4.
Preferably, the fu rther preferred characteristics of the aforementioned non-su rface fu nctionalized calcium phosphate compound a re the same preferred characteristics described above with reference to the particles of calcium phosphate su rface functionalised with at least one organic compound containing at least one hydroxyl g rou p and at least one micro or macro nutritional element, for which reason they will not be repeated here for the sake of keeping the description brief.
Preferably, the aforementioned pa rticles of a non-surface functionalized calcium phosphate compou nd having the following formu la :
Ca(io-y) My H u (P04) (6-v-w-z) (C03)v (B03)w (Si04)z(O H)2 wherein M, y, u, v, w and z are as ind icated above, can be prepared throug h a process as described above for the production of a suspension of particles or for the production of particles of ca lcium phosphate compound, except for the fact that the surface functionalizing steps fl) and g l) are not present.
In a further preferred embod iment, the particles of a calcium phosphate compou nd described above of the fertilizing composition comprising the aforementioned calcium carbonate compound described above, can be su rface fu nctionalised with at least one organic compound containing at least one hyd roxyl g rou p a nd/or with at least one micro or macro nutritional element.
In this preferred embod iment, therefore, the particles of calcium phosphate compound used in the fertilizing composition in combination with the particles of calcium carbonate compound can be (if su rface functionalised with at least one organic compou nd conta ining at least one hyd roxyl g rou p and with at least one micro or macro nutritional element) the particles described above in relation to the first aspect of the invention and can be prepared with the relative production processes described above.
As a consequence the aforementioned at least one organic compou nd containing at least one hyd roxyl g roup a nd the aforementioned at least one micro or macro nutritional element have preferred characteristics that are the same as those described above with reference to the particles of su rface functionalized calcium phosphate, for which reason they will not be repeated here in order to keep the description brief. Preferably, the particles of calcium phosphate are present in the fertilizing composition in an amount by weight comprised between 10% and 90%.
Preferably, the particles of calcium carbonate compound are present in the fertilizing composition in an amount by weight comprised between 10% and 50%.
Advantageously, in the preferred embodiment of the invention in which the fertilizing composition comprises particles (the carrier) based on calcium phosphate (substituted with macro and micro elements and surface functionalized or not) and the calcium carbonate compound, such a composition has two different solubilities in an acid environment (acid rain, humidity) : one due to the solubilisation of the phosphate component and the other due to the solubilisation of the carbonate component, for which reason a very advantageously modulated and controlled release of the nutritional ingredients is obtained by the complex fertilizing composition thus formulated.
Advantageously, through foliar fertilization the plants can absorb the nutritional elements necessary for their development through the leaves and the stems, and therefore it is possible to administer, particularly through the foliage surfaces, both the main elements (macroelements) and the microelements and the organic compounds containing at least one hydroxyl group, where present.
This treatment can be very important when there is a momentary impossibility of the plants absorbing nutrition from the soil : this can occur in the case of parasite attacks to the roots, when there is a lack of nutritional elements in the soil or furthermore in the case of frosts. The absorption of the conventional foliar fertilizer takes variable amounts of time and can, in general, by comprised between 3 and 24 hours; therefore, the foliage fertilized plants are neither sprayed nor wetted for at least 24 hours from the moment of treatment.
Advantageously, with the fertilizing composition according to the invention it is possible to obtain a homogeneous distribution of product on the leaf and an optimal foliar adhesion in 3-4 hours, thus avoiding overdoses of the macro and micro elements that could become harmful for the plant.
In a preferred embodiment, the present invention concerns a fertilizing composition in the form of a suspension, gel, solution or solid .
The fertilizing compositions according to the invention can advantageously be used directly as such or diluted with water.
Preferably, the concentration of the micro/macro elements present inside the fertilizing solution is comprised between 0.1% by weight and 20% by weight.
Such a percentage can vary from metal to metal based on the solubility thereof.
In a preferred embodiment, step dl) of adding by dripping a solution or aqueous suspension containing phosphate ions of the process for producing the aforementioned aqueous suspension including particles of a surface functionalized calcium phosphate compound, is carried out through simultaneous stirring of the solution so as to capture the CO2 present in the atmosphere or through the addition of carbonate ions to the solution or aqueous suspension containing phosphate ions.
In a preferred embodiment, step fl) or step f'l) of the aforementioned processes for producing an aqueous suspension of the particles of a calcium phosphate or calcium carbonate compound comprises adding an aqueous solution comprising at least one organic compound containing at least one hydroxyl group to a concentration comprised between 0.0003 mg/mL and 300 mg/mL, preferably between 0.001 mg/mL and 100 mg/mL and adding an aqueous solution comprising at least one micro or macro nutritional element at a concentration comprised between 0.001 M and 10 M, preferably between 0.01 M and 8 M or adding an aqueous solution comprising said at least one organic compound containing at least one hydroxyl group and said at least one micro or macro nutritional element at said concentrations.
In a preferred embodiment, the separation step ii) of the process for preparing the particles of a surface functionalized calcium phosphate compound or the separation step II) of the process for preparing the particles of a calcium carbonate compound, is carried out by decanting, centrifuging or filtration.
Preferably, the drying step iii) of the process for preparing the particles of a surface functionalized calcium phosphate compound or the drying step III) of the process for preparing the particles of a calcium carbonate compound, is carried out through lyophilization at a temperature of less than 0°C until a constant weight is obtained.
The fertilizing products of the invention can comprise further ingredients commonly used and known in the field to formulate such products, like for example: natural or artificial rubbers, used as suspending agents (xanthan gum, carrageenan), clay (bentonite, montmorillonite).
As an alternative to the aqueous suspension including the particles of a calcium phosphate compound, both surface functionalized and not, and/or the particles of a calcium carbonate compound, both surface functionalized and not, as described above, it is possible to use solid particles as such.
As outlined above, the aforementioned solid particles can preferably be obtained from the aqueous suspension by separation through decanting, centrifuging or filtration using apparatuses and techniques well known to those skilled in the art. The wet solid particles thus obtained are then preferably dried through lyophilization at a temperature of less than 0°C until a constant weight is obtained.
The drying step is preferably carried out through lyophilization of the wet solid particles at a temperature comprised between -20 ° and -50 ° C, more preferably at about -40 ° C.
In a preferred embodiment of the processes according to the invention for producing a fertilizing composition, the mixing step b) is obtained through a mixer kept under vacuum, easily selected by those skilled in the art in order to obtain an even mixture of ingredients.
Preferably, said heating step bi) or b'i) is obtained by heating on a heating plate or in a water or silicone bath.
Preferably, said dripping step ci) is obtained with a speed comprised between 0,03 and 10 L/min, preferably comprised between 0,1 L/min and 6 L/min and with a flow comprised between 0,001 and 4 L/min, preferably comprised between 0,1 L/min and 2 L/min.
Preferably, said acidification step C2) is obtained with phosphoric acid, sulphuric acid, hydrochloric acid, acetic acid, lactic acid, nitric acid, citric acid or a mixture thereof.
Preferably, said dripping step di) is obtained with a speed comprised between 0,03 and 10 L/min, preferably comprised between 0,1 L/min and 6 L/min.
Preferably, said step of keeping under stirring ei) takes place at a stirringspeed of the solution comprised between 100 rpm and 5000 rpm, preferably comprised between 500 rpm and 1500 rpm.
Preferably, the final pH of the solution or suspension of particles of calcium phosphate or calcium carbonate described above obtained is comprised between 2 and 12, preferably between 2 and 7 or between 9 and 12.
If necessary, the pH is modified with the addition of a base, preferably, NaOH, KOH, NH3 or a mixture thereof.
In a preferred embodiment, the product obtained has a dry residue comprised between 10% and 40% (w/w), preferably comprised between 15% and 30% (w/w).
Preferably, as source of calcium ions it is possible to use: Ca(OH)2, CaCOs, CaO, Ca(CH3COO)2, Ca(N03)2*4H20, Ca(N03)2*2H20 or a mixture thereof.
Preferably, as source of phosphate ions and hydrogen ions it is possible to use: H3P04, H2P04, H2KP04, HK2P04, K3P04, NH4H2P04 or a mixture thereof.
As outlined above, the ions M are selected from the group comprising zinc, potassium, iron, copper, manganese, magnesium, molybdenum and selenium.
Preferably, as source of zinc ions it is possible to use: ZnO, ZnN03, ZnC03, ZnS04, ZnCI2, Zn(OH)2, Zn(CH3COO)2, or a mixture thereof. Preferably, as source of potassium ions it is possible to use: K3P04, H2KP04, HK2P04, K2C03, KCI, K(OH) or a mixture thereof.
Preferably, as source of iron ions it is possible to use: FeC03, FeS04, FeO, FeN03, Fe(OH)2 or a mixture thereof.
Preferably, as source of copper ions it is possible to use: CuS04, CuO, Cu(OH)2, Copper Gluconate, CuC03, CuN03 or a mixture thereof.
Preferably, as source of manganese ions it is possible to use: MnS04, MnC03, MnO, Mn(OH)2 or a mixture thereof.
Preferably, as source of magnesium ions it is possible to use MgS04, MgO, MgC03, Mg(OH)2 or a mixture thereof.
Preferably, as source of molybdenum ions it is possible to use M0S2, CaMo04, M0O3, M0O4 or a mixture thereof
Preferably, as source of selenium ions it is possible to use SeO, SeC03, SeCI, Se(OH)2, or a mixture thereof.
Preferably, as source of boron ions it is possible to use boron ethanolamine, H3BO3 or a mixture thereof.
Preferably, as source of silicon ions it is possible to use potassium silicate, sodium silicate, or a mixture thereof.
In a preferred embodiment, step di) or step d'i) is carried out through simultaneous agitation of the solution, preferably through a mechanical stirrer, so as to capture the CO2 present in the atmosphere, or through the add ition of carbonate ions to the solution or aqueous suspension containing phosphate ions.
Preferably, as source of carbonate ions it is possible to use CaC03,
CuC03, MnC03, MgC03 or a mixture thereof.
As outlined above, the ions N are selected from the group comprising magnesium, manganese, copper, potassium, zinc.
Preferably, said dripping step c'i) is obtained with a speed comprised between 0,03 and 10 L/min, preferably comprised between 0,1 L/min and 6 L/min and with a flow comprised between 0,001 and 4 L/min, preferably comprised between 0,1 L/min and 2 L/min.
Preferably, said dripping step d'i) is obtained with a speed comprised between 0,03 and 10 L/min, preferably comprised between 0,1 L/min and 6 L/min.
Preferably, said step of keeping under stirring e'i) takes place at astirring speed of the solution comprised between 100 rpm and 5000 rpm, preferably comprised between 500 rpm and 1500 rpm. Preferably, the fina l pH of the solution or suspension obtained is comprised between 3 and 12, preferably between 4 and 10.
In a preferred embod iment, the product obtained has a d ry residue comprised between 10% and 40% (w/w), preferably comprised between 15 % and 30% (w/w) .
In the process for producing a suspension of particles of calcium carbonate as sou rce of calcium ions it is preferable to use : Ca(OH)2, CaCOs, CaO, Ca(CH3COO)2, Ca (N03)2*4H20, Ca(N03)2*2H20 or a mixture thereof.
In the process for producing a suspension of particles of calcium carbonate, as sou rce of zinc ions it is preferable to use : ZnO, ZnN03, ZnC03, ZnS04, ZnC , Zn(OH)2, Zn(CH3COO)2, or a mixture thereof. In the process for producing a suspension of particles of calcium carbonate, as source of mag nesium ions it is preferable to use MgS04, MgO, MgC03, Mg (OH)2 or a mixture thereof.
In the process for producing a suspension of particles of calcium carbonate, as sou rce of copper ions it is preferable to use : CuS04, CuO, Cu (OH)2, copper g luconate, CuC03, CuN03 or a mixtu re thereof.
In the process for producing a suspension of particles of calcium carbonate, as sou rce of manganese ions it is preferable to use : M nS04, M nC03, M nO, M n(OH)2 or a mixture thereof.
In the process for producing a suspension of particles of calcium carbonate, as sou rce of potassium ions it is preferable to use : K3P04, H2KP04, HK2PO4, K2C03, KCI, K(OH) or a mixtu re thereof.
In the process for producing a suspension of particles of calcium carbonate, as source of carbonate ions it is preferable to use : NaHC03, Na2C03, CO2 (in gaseous phase blown inside the solution), KHC03 calcium carbonate, mag nesium carbonate, potassium carbonate, zinc carbonate or a mixture thereof.
In a preferred embodiment, step fl) is carried out so that the aqueous suspension obtained from step gl) is used in an amount by weight comprised between 10% and 90%.
In a preferred embodiment, step f'l) is carried out so that the aqueous suspension obtained from step e'l) is used in an amount by weight comprised between 10% and 50%.
Preferably, the mixture comprising the aqueous suspension obtained from step gl) and the aqueous suspension obtained from step e'l) or g'l) constitutes between 3% and 50%, more preferably between 5% and 30% of the final fertilizing composition.
Brief description of the figures
Further characteristics and advantages of the invention will become clearer from the following description of some preferred embodiments thereof, made hereafter, for indicating and not limiting purposes, with reference to the attached drawings. In such drawings:
figure 1 is an X-ray diffraction spectrum of an example of particles of a calcium phosphate compound (Example 1) used for producing fertilizing compositions according to an aspect of the invention;
figure 2 is a Scanning Electron Microscope image (SEM) of an example of particles of a calcium phosphate compound (Example 1) used for producing fertilizing compositions according to an aspect of the invention;
- figure 3 is an X-ray diffraction spectrum of an example of a carbonate compound (Example 2) used for producing fertilizing compositions according to an aspect of the invention;
figure 4 is a Scanning Electron Microscope image (SEM) of an example of a carbonate compound (Example 2) used for producing fertilizing compositions according to an aspect of the invention;
figure 5 is a Scanning Electron Microscope image (SEM) of the foliar distribution of a conventional reference fertilizing product;
- figure 6 is a Scanning Electron Microscope image (SEM) of the foliar distribution of a fertilizing product (Example 1) according to an aspect of the invention.
Detailed description of the currently preferred embodiments
With reference to figure 1, the X-ray diffraction spectrum highlights a crystalline material that has the diffraction maximums characteristic of a calcium phosphate (Example 1).
The diffraction maximum of the calcium phosphate obtained in this example are as follows: 2 Theta 26 - 32 - 33 - 34.
More specifically and as illustrated in figure 2, the morphological analysis by Scanning Electron Microscope (SEM) shows that the particles of calcium phosphate have crystalline formations of micrometric dimensions, comprised between 0,2 micron and 2 micron.
With reference to figure 3, the X-ray diffraction spectrum highlights a crystalline material that has the diffraction maximums characteristic of a zinc and calcium carbonate (Example 2).
The diffraction maximum of the carbonate obtained in this example are as follows: 2 Theta 23 - 29 - 39 - 39 - 43.
More specifically and as illustrated in figure 4, the morphological analysis by Scanning Electron Microscope (SEM) shows that the particles of carbonate have crystalline formations of micrometric dimensions, comprised between 0,2 micron and 1 micron.
In the following examples, given purely for indicative and not limiting purposes, the results of a series of experimental tests carried out by the Applicant on the fertilizing compositions in accordance with the present invention are provided .
EXAMPLE 1
Preparation solution 1
In a reaction flask in thermostated environment, at a constant temperature of 35°C, 2,0 kg of water was introduced, to which 160 g of Ca(OH)2 and 5 g of CaC03 were added.
The whole thing was left under vigorous stirring for 10 minutes.
Preparation solution 2
Separately, a solution comprising 1 kg of water to which 6,0 g of ZnO,
12,5 g of CuS04, 1,0 g of MgO, 32,1 g of K2CO3, 1,0 g of FeS04, 2,5 g of Mn02, 1,0 g of H3BO3 and 2 g of SeO were added.
The whole thing was left under vigorous stirring for 60 minutes.
Preparation solution 3
Separately, 2 kg of water was prepared to which 130 g of H3PO4 and
0,50 g of H2KP04 were added.
Solution 2 was then added to solution 1, by dripping, at a flow equal to 0,2 L/min.
Once the addition was finished, the two solutions were made to interact for 2 hours under stirring, at the end of which solution 3 was added by dripping at a flow equal to 0,4 L/min.
Once this step has ended, the synthesis product was aged inside the reaction environment, keeping it under stirring, in thermostated environment, for a total time equal to 10 hours.
At the end of the addition of solution 3, the pH is brought to a value comprised between 6 and 13, preferably between 9 and 12, with suitable addition of base like for example NaOH, KOH, N H3 or a mixture thereof. The X-ray diffraction spectrum is given in Figure 1.
Thereafter, 100 ml_ of a suspension of particles thus obtained were added to with 900 g of a solution containing 200g of CuSO4*5H2O and 4g of resorcinol.
The resulting suspension was then kept under agitation for 45 minutes. The suspension of particles of calcium phosphate surface functionalised with micro and macro elements obtained was then used to produce fertilizing compositions according to the invention.
EXAMPLE 2
Preparation solution 1'
In a reaction flask in thermostated environment, at a constant temperature of 6°C, 0,5 kg of water was introduced, to which 52,4 g of Ca(CH3COO)2 was added .
Preparation solution 2'
Thereafter 0,98 g of Zn(CH3COO)2 was prepared, it was dissolved in
200 g of water and then it was dripped into the solution with calcium ions.
The whole thing was left under vigorous stirring for 10 minutes.
Preparation solution 3'
Separately, a solution was made comprising 0,5 kg of water to which 17,8 g of NaHCO3 and 2,6 g of Na2CO3 were added.
The whole thing was left under vigorous stirring for 30 minutes at controlled temperature of 25°C.
Solution 2 was then added to solution 1, by dripping, at a flow equal to 0,125 L/min.
Once this step ended, the synthesis product obtained was kept under stirring, in thermostated environment, for a total time equal to 8 hours. The X-ray diffraction spectrum is given in Figure 3. The suspension of particles of the calcium zinc carbonate compound obtained was then used to produce fertilizing compositions accord ing to the invention.
EXAMPLE 3
A fertilizing composition according to the invention was made by mixing 70 g of the aqueous suspension of Example 1 with 30 g of the aqueous suspension of Example 2. In this way 100 g of fertilizing composition are obtained .
EXAMPLE 4
("Evaluation of the fertilizing activity of a sample of example 3 vs a reference sample1)
The tests carried out to evaluate the fertilizing activity were performed on land of about 0,5 HA.
5 successive treatments were carried out, 7 days apart from one another, with copper oxychloride (conventional reference treatment based on ossiclor35) for a total of 1000 g of product corresponding to 600 g of elementary copper (i.e. 120 grams of treatment copper) . The treatment allows the plant to remain protected from attacks of peronospora, a disease typical of many cultures that are commonly fought with copper-based treatments.
The SEM image of figure 5 shows how the foliar distribution of a conventional copper-based product is not very capillary on the foliar wall itself and how the rough dimensions of a conventional product (a sing le particle is visible in the high part of the SEM image) do not allow homogeneous coverage of the leaf.
On the other hand, by carrying out 5 treatments with a fertilizing composition according to the invention (Example 3) using a total of 5000 g of product (i.e. 1000 grams of treatment product), a total of 250 g of copper (metal) were used, corresponding to 50 g of copper metal per treatment.
Also in this case, the plants treated did not show attacks from the disease (peronospora), but with respect to the conventional treatment defined above, one third of the copper was used, which however conveyed through the formulation described in example 3, allowed it to be much more functional (despite the low dose) actually obtaining comparable results to a conventional treatment, containing a greater amount of copper.
An excessive presence of copper interferes with the absorption of Fe, Mn, Mo, causing deficiencies that become apparent with internerval chlorosis that lead to the collapse of the tissues of the lamina that seem dried.
The SEM image of figure 6 shows how the foliar distribution of a product made according to example 3 is much more capillary and the product is much better distributed over the entire foliar wall examined as highlighted by the numerous particles visible on the leaf and distributed evenly on its surface.
Advantageously, the use of a fertilizing product according to the invention gives the plant the nutritional elements that it needs, avoiding overdoses and obtaining homogeneous distribution of the product on the foliage and optimal foliar adhesion.
Of course, those skilled in the art can bring modifications and variants to the finding described above in order to satisfy specific and contingent application requirements, said variants and modifications in any case being covered by the scope of protection as defined by the following claims.

Claims

1. A fertilizing composition comprising particles of a calcium phosphate compound having the following formula :
Ca(io-y) My H u (P04)(6-v-w-z) (C03)v (B03)w (Si04)z(O H)2 wherein M is at least one metallic ion selected from the group comprising Zn, Cu, Mn, Mg, Mo, Fe, K, Se and mixtures thereof, y is a number comprised between 0 and 8; u is a number comprised between 0 and 2, v is a number comprised between 0 and 2, w is a number comprised between 0 and 0,5 and z is a number comprised between 0 and 0,5; provided that at least one from y, w and z is different from zero;
and wherein the particles of the calcium phosphate compound are surface functionalised with at least one organic compound containing at least one hydroxyl group and at least one micro or macro nutritional element.
2. A fertilizing composition according to claim 1, y is a number comprised between 0,0055 and 6 and/or u is a number comprised between 0,040 and 1,5 and/or v is a number comprised between 0,065 and 1,5 and/or w is a number comprised between 0,01 and 0,4 and/or z is a number comprised between 0,01 and 0,4.
3. A fertilizing composition according to claim 1, wherein M is Znm Cumi Mnm2 Mgm3 Fem4 Moms Km6 Sem7 wherein m is a number comprised between 0 and 8, m i is a number comprised between 0 and 8, nri2 is a number comprised between 0 and 2, nri3 is a number comprised between 0 and 2, nri4 is a number comprised between 0 and 8, ms is a number comprised between 0 and 1, nri6 is a number comprised between 0 and 8, m7 is a number comprised between 0 and 1, wherein at least one from m-nri7 is different from zero and m + m i + nri2 + nri3 + nri4 + nri5 + nri6 + nri7≤ 8.
4. A fertilizing composition according to any one of claims 1-3, wherein the metal ion M is present in a quantity comprised 0% by weight and 80% by weight, preferably between 2,0% by weight and 30% by weight, with respect to the total weight of calcium.
5. A fertilizing composition according to any one of claims 1-4, wherein the carbonate ion is present in a quantity comprised between 0,01% by weight and 10% by weight, preferably between 3% by weight and 7% by weight and/or the boron ion is present in a quantity comprised between 0,01% by weight and 2% by weight, preferably between 0,02% by weight and 0,7% by weight and/or the silicon ion is present in a quantity comprised between 0,01% by weight and 4% by weight, preferably between 0,02% by weight and 2% by weight with respect to the total weight of phosphate.
6. A fertilizing composition according to any one of claims 1-5, wherein the particles of the calcium phosphate compound have length and/or width comprised between 0,1 micron and 10 micron, preferably between 0,2 micron and 2 micron.
7. A fertilizing composition according to any one of claims 1-6, wherein the particles of the calcium phosphate compound have a superficial area comprised between 60 and 150 m2/g, preferably between 90 and 120 m2/g.
8. A fertilizing composition according to any one of claims 1-7, wherein said at least one organic compound containing at least one hydroxyl group is selected from the group: resorcinol, phloroglucinol, polyethylene glycol (PEG), cyclodextrin, proteins, gluconic acid and its salts.
9. A fertilizing composition according to any one of claims 1-8, wherein said at least one micro or macro nutritional element is selected from the group comprising : K, P, Ca, Mg, Fe, Zn, Cu, B, Mn, Mo, Se.
10. A fertilizing composition comprising particles of a calcium carbonate compound of formula
Figure imgf000040_0001
wherein x is a number comprised between 0,0001 and 2; N is a metal ion selected from the group comprising magnesium, manganese, copper, potassium, zinc and mixtures thereof, yi is a number comprised between 0,01 e 2.
11. A fertilizing composition according to claim 10, wherein the metal ion N is present in a quantity comprised between 0.01% by weight and 70% by weight with respect to the total weight of calcium.
12. A fertilizing composition according to any one of claims 10-11, wherein magnesium ion is present in a quantity comprised between 0,01% by weight and 35% by weight, preferably between 0,1% by weight and 5% by weight and/or manganese ion is present in a quantity comprised between 0,01% by weight and 35% by weight, preferably between 0,1% by weight and 5% by weight and/or copper ion is present in a quantity comprised between 0,01% by weight and 65% by weight, preferably between 0,1% by weight and 15% by weight and/or potassium ion present in a quantity comprised between 0,01% by weight and 35% by weight, preferably between 0,1% by weight and 5% by weight and/or zinc ion is present in a quantity comprised between 0,01% by weight and 90% by weight, preferably between 0,2% by weight and 40% by weight with respect to the total weight of calcium.
13. A fertilizing composition according to any one of claims 10-12, wherein the particles of the calcium carbonate compound have length and/or width comprised between 0,1 micron and 10 micron, preferably between 0,2 micron and 4 micron.
14. A fertilizing composition according to any one of claims 10-13, wherein the particles of the calcium carbonate compound have superficial area comprised between 20 and 100 m2/g, preferably between 30 and 80 m2/g-
15. A fertilizing composition according to any one of claims 10-14, wherein the particles of the calcium carbonate compound are surface functionalised with at least one organic compound containing at least one hydroxyl group and/or at least one micro or macro nutritional element.
16. A fertilizing composition according to claim 15, wherein said at least one organic compound is selected from the group comprising: resorcinol, phloroglucinol, polyethylene glycol (PEG), cyclodextrin, proteins, gluconates.
17. A fertilizing composition according to claim 15, wherein said at least one micro or macro nutritional element is selected from the group comprising: K, P, Ca, Mg, Fe, Zn, Cu, B, Mn, Mo, Se.
18. A fertilizing composition according to any one of claims 10-17, further comprising particles of a calcium phosphate compound having the following formula:
Ca(io-y) My Hu (P04)(6-v-w-z) (C03)v (B03)w (Si04)z(OH)2 wherein MY is a metallic ion selected from the group comprising Zn, Cu, Mn, Mg, Mo, Fe, K, Se and mixtures thereof, wherein y is a number comprised between 0 e 8;
u is a number comprised between 0 and 2, v is a number comprised between 0 and 2, w is a number comprised between 0 and 0,5 and z is a number comprised between 0 and 0,5.
19 A fertilizing composition according to claim 18, wherein at least one from y, w and z is different from zero.
20. A fertilizing composition according to any one of claims 18-19, wherein y is a number comprised between 0,0055 and 6 and/or u is a number comprised between 0,040 and 1,5 and/or v is a number comprised between 0,065 and 1,5 and/or w is a number comprised between 0,01 and 0,4 and/or z is a number comprised between 0,01 and 0,4.
21. A fertilizing composition according to any one of claims 18-20, wherein M is Znm Cumi Mnm2 Mgm3 Fem4 Moms Km6 Sem7 wherein m is a number comprised between 0 and 8, mi is a number comprised between 0 and 8, nri2 is a number comprised between 0 and 2, nri3 is a number comprised between 0 and 2, nri4 is a number comprised between 0 and 8, ms is a number comprised between 0 and 1, nri6 is a number comprised between 0 and 8, nri7 is a number comprised between 0 and 1, wherein at least one from m-nri7 is different from zero and m + mi + ΠΊ2 + ΙΤΠ3 + m4 + ms + me + m7 < 8.
22. A fertilizing composition according to any one of claims 18-21, wherein the metal ion M of said calcium phosphate compound is present in a quantity comprised between 0% by weight and 80% by weight, , preferably between 2,0% by weight and 30% by weight, with respect to the total weight of calcium.
23. A fertilizing composition according to any one of claims 18-22, wherein the carbonate ion is present in a quantity comprised between 0,01% by weight and 10% by weight, preferably between 3% by weight and 7% by weight and/or the boron ion is present in a quantity comprised between 0,01% by weight and 2% by weight, preferably between 0,02% by weight and 0,7% by weight and/or the silicon ion is present in a quantity comprised between 0,01% by weight and 4% by weight, preferably between 0,02% by weight and 2% by weight with respect to the total weight of phosphate of said calcium phosphate compound.
24. A fertilizing composition according to any one of claims 18-23, wherein the particles of the calcium phosphate compound have length and/or width comprised between 0,1 micron and 10 micron, preferably between 0,2 micron and 2 micron.
25. A fertilizing composition according to any one of claims 18-24, wherein the particles of the calcium phosphate compound have superficial area comprised between 60 and 150 m2/g, preferably between 90 and 120 m2/g-
26. A fertilizing composition according to any one of claims 18-25, wherein the particles of the calcium phosphate compound are surface functionalised with at least one organic compound containing at least one hydroxyl group and/or at least one micro or macro nutritional element.
27. A fertilizing composition according to claim 26, wherein said at least one organic compound is selected from the group comprising : resorcinol, phloroglucinol, polyethylene glycol (PEG), cyclodextrin, proteins, gluconates.
28. A fertilizing composition according to claim 26, wherein said at least one micro or macro nutritional element is selected from the group comprising : K, P, Ca, Mg, Fe, Zn, Cu, B, Mn, Mo, Se.
29. A fertilizing composition according to any one of the preceding claims, in suspension, gel, solution, or solid form.
30. Particles of a calcium phosphate compound according to any one of claims 1-9.
31. Particles of a carbonate compound according to any one of claims 10-17.
32. A process for producing an aqueous suspension including particles of a calcium phosphate compound according to claim 30, comprising the steps of:
al) providing a solution or aqueous suspension comprising calcium ions at a concentration comprised between 0,1 M and 10 M, preferably between 0,3 and 5 M;
bl) heating said solution or aqueous suspension to a temperature comprised between 10°C and 90°C, preferably between 20°C and 40°C;
cl) adding by dripping at least one solution or aqueous suspension containing at least one from :
- ions M at a concentration comprised between 0,00001 M and 5 M, preferably between 0,0001 M and 3 M; and/or
- ions BO3" at a concentration comprised between 0.001 M and 0.6 M, preferably between 0.01 M and 0.2 M; and/or
- ions S1O4" at a concentration comprised between 0.001 M and 0.1 M, preferably between 0.01 M and 0.08 M;
c2) possibly, acidifying said solution or aqueous suspension of step cl) up to a pH comprised between 0,5 and 3, preferably comprised between 0,7 and 2 and keeping under agitation for a time comprised between 1 hour and 5,5 hours, preferably between 2 hours and 5 hours;
dl) adding by dripping a solution or aqueous suspension containing phosphate ions at a concentration comprised between 0,1 M and 10 M, preferably between 0,2 M and 5 M ;
el) keeping under stirring the mixture obtained for a time comprised between 30 minutes and 24 hours, preferably between 2 and 15 hours;
fl) adding at least one organic compound containing at least one hydroxyl group and at least one micro or macro nutritional element to the aqueous suspension thus obtained ;
gl) keeping under stirring the mixture obtained for a time of at least 30 minutes, preferably at least 45 minutes.
33. A process according to claim 32, wherein step dl) is carried through simultaneous stirring of the solution so as to capture the CO2 present in the atmosphere or through the addition of carbonate ions to the solution or aqueous suspension containing phosphate ions.
34. A process according to claims 32 or 33, wherein step fl) comprises adding an aqueous solution comprising at least one organic compound containing at least one hydroxyl at a concentration comprised between 0.0003 mg/mL and 300 mg/mL, preferably between 0.001 mg/mL and 100 mg/mL and adding an aqueous solution comprising at least one micro or macro nutritional element at a concentration comprised between 0.001 M and 10 M, preferably between 0.01 M and 8 M or adding an aqueous solution comprising said at least one organic compound containing at least one hydroxyl group and said at least one micro or macro nutritional element at said concentrations.
35. A process for preparing particles of a calcium phosphate compound according to claim 30, comprising the steps of:
i) preparing an aqueous suspension including said particles of calcium phosphate through a process according to any one of claims 32-34;
ii) separating solid particles from the suspension obtained from step i); iii) drying the wet solid particles thus obtained.
36. Process according to claim 35, wherein said separation step ii) is carried out by decanting, centrifuging or filtration.
37. Process according to claim 35, wherein said drying step iii) is carried out through lyophilisation at a temperature of less than 0°C until a constant weight is obtained.
38. A process for producing an aqueous suspension including particles of a calcium carbonate compound according to claim 31, comprising the steps of:
a'l) providing a solution or aqueous suspension comprising calcium ions at a concentration comprised between 0,0001 M and 15 M, preferably between 0,001 M and 10 M;
b'l) heating said solution or aqueous suspension to a temperature comprised between 2°C and 30°C, preferably between 3°C and 15°C;
c'l) adding by dripping a solution or aqueous suspension containing ions N at a concentration comprised between 0,001 M and 10 M, preferably between 0,001 M and 5 M;
d'l) adding a solution or aqueous suspension containing carbonate ions at a concentration comprised between 0,001 M and 10 M, preferably between 0,01 M and 5 M ;
e'l) keeping under stirring the mixture obtained for a time comprised between 30 minutes and 24 hours, preferably between 2 and 15 hours;
f'l) possibly, adding at least one organic compound containing at least one hydroxyl group and/or at least one micro or macro nutritional element to the aqueous suspension thus obtained; g'l) possibly, keeping the mixture obtained under agitation for a time of at least 30 minutes, preferably at least 45 minutes.
39. A process according to claim 38, wherein step f'l) comprises adding an aqueous solution comprising at least one organic compound containing at least one hydroxyl at a concentration comprised between 0.0003 mg/mL and 300 mg/mL, preferably between 0.001 mg/mL and 100 mg/mL and adding an aqueous solution comprising at least one micro or macro nutritional element at a concentration comprised between 0.001 M and 10 M, preferably between 0.01 M and 8 M or adding an aqueous solution comprising said at least one organic compound containing at least one hydroxyl group and said at least one micro or macro nutritional element at said concentrations.
40. A process for preparing particles of a calcium carbonate compound according to claim 31, comprising the steps of:
I) preparing an aqueous suspension including said particles of calcium carbonate through a process according to any one of claims 38 or 39;
II) separating solid particles from the suspension obtained from step I);
III) drying the wet solid particles thus obtained.
41. Process according to claim 40, wherein said separation step II) is carried out by decanting, centrifuging or filtration.
42. Process according to claim 40, wherein said drying step III) is carried out through lyophilisation at a temperature of less than 0°C until a constant weight is obtained .
43. A process for producing a liquid or gel-type fertilizing composition comprising the steps of:
a) providing an aqueous suspension including particles of a calcium phosphate compound according to claim 30 or particles of a calcium carbonate compound according to claim 31, possibly in combination with particles of a calcium phosphate compound according to any one of claims 18-28; and
b) mixing said aqueous suspension with the other ingredients of the fertilizing composition.
44. A process for producing a solid fertilizing composition comprising the steps of:
a') providing particles of a calcium phosphate compound according to claim 30 or particles of a calcium carbonate compound according to claim 31 possibly in combination with particles of a calcium phosphate compound according to any one of claims 18-28; and
b') mixing said particles with the other ingredients of the fertilizing composition.
PCT/IB2016/053180 2015-05-28 2016-05-30 Fertilized compositions based on a substituted calcium phosphate and/or calcium carbonate compound WO2016189521A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP16738865.1A EP3303261A2 (en) 2015-05-28 2016-05-30 Fertilized compositions based on a substituted calcium phosphate and/or calcium carbonate compound

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITUB2015A000913A ITUB20150913A1 (en) 2015-05-28 2015-05-28 Fertilizer compositions based on an inorganic compound substituted with micro and macro elements
ITUB2015A000913 2015-05-28

Publications (2)

Publication Number Publication Date
WO2016189521A2 true WO2016189521A2 (en) 2016-12-01
WO2016189521A3 WO2016189521A3 (en) 2017-03-16

Family

ID=54064442

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2016/053180 WO2016189521A2 (en) 2015-05-28 2016-05-30 Fertilized compositions based on a substituted calcium phosphate and/or calcium carbonate compound

Country Status (3)

Country Link
EP (1) EP3303261A2 (en)
IT (1) ITUB20150913A1 (en)
WO (1) WO2016189521A2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111606760A (en) * 2020-06-03 2020-09-01 江西省农业科学院土壤肥料与资源环境研究所 Fertilizer composite film material and special slow/controlled release fertilizer for ratoon rice in southern red soil region
WO2023203253A1 (en) * 2022-04-22 2023-10-26 Nanointec, S.L. Calcium phosphate nanoparticles and uses thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2032035A5 (en) * 1969-02-17 1970-11-20 Letargat Michel Novel fertiliser for aquatic uses
WO1981000711A1 (en) * 1979-09-07 1981-03-19 Nat Res Dev Fertilizer material from apatite
FR2723085B1 (en) * 1994-07-29 1996-08-30 Meac Sa DUST AMENDMENTS, THEIR PROCESS FOR OBTAINING AND THEIR USE
DE102005031397A1 (en) * 2005-07-05 2007-01-11 Klose, Siegfried, Dipl.-Agr.-Ing. Combined, granulated composition, useful as fertilizer for grass, comprises a basic calcium or magnesium compound mixed with microorganisms, biocatalysts, metal salts and biopolymers
US20140165683A1 (en) * 2010-06-05 2014-06-19 Sri Lanka Institute of Nanotechnology (Pvt) Ltd. Compositions and methods for sustained release of agricultural macronutrients
US8361185B2 (en) * 2010-06-05 2013-01-29 Sri Lanka Istitute of Nanatechnology (PVT) Ltd. Compositions for sustained release of agricultural macronutrients and process thereof
ES2651092T3 (en) * 2011-05-26 2018-01-24 Coswell S.P.A. Dental care products comprising carbonate substituted fluorohydroxyapatite particles
WO2014087202A1 (en) * 2012-12-07 2014-06-12 Sri Lanka Institute Of Nanotechnology (Pvt) Ltd Composition and method for sustained release of agricultural macronutrients
FR3013182B1 (en) * 2013-11-19 2016-12-30 Nbvd Sa HYDROXYAPATITE PARTICLE, COMPOSITIONS BASED ON THIS PARTICLE, USE AS VECTOR OF BIOACTIVE MOLECULES

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111606760A (en) * 2020-06-03 2020-09-01 江西省农业科学院土壤肥料与资源环境研究所 Fertilizer composite film material and special slow/controlled release fertilizer for ratoon rice in southern red soil region
CN111606760B (en) * 2020-06-03 2021-11-05 江西省农业科学院土壤肥料与资源环境研究所 Fertilizer composite film material and special slow/controlled release fertilizer for ratoon rice in southern red soil region
WO2023203253A1 (en) * 2022-04-22 2023-10-26 Nanointec, S.L. Calcium phosphate nanoparticles and uses thereof

Also Published As

Publication number Publication date
WO2016189521A3 (en) 2017-03-16
EP3303261A2 (en) 2018-04-11
ITUB20150913A1 (en) 2016-11-28

Similar Documents

Publication Publication Date Title
US11807587B2 (en) Acid treatment for fertilizers to increase zinc solubility and availability
US20110269627A1 (en) Formulation based on micronized natural calcite mineral as a plant booster and mineral fertilizer
AU2012356769B2 (en) Nutrient composition for biological systems
US20140165683A1 (en) Compositions and methods for sustained release of agricultural macronutrients
AU2003281667B2 (en) Agrochemical composition containing phosphite and process for the preparation thereof
Madanayake et al. The effect of hydroxyapatite nanoparticles on Raphanus sativus with respect to seedling growth and two plant metabolites
ES2714998T3 (en) Foliar fertilizer
WO2016189521A2 (en) Fertilized compositions based on a substituted calcium phosphate and/or calcium carbonate compound
TWI787397B (en) Npk-si fertilizer, method for production and use thereof
CA3001156C (en) Stable, flowable aqueous dispersions of potassium calcium polyphosphate including methods for preparing and methods for using as liquid fertilizer
Bhavani et al. Performance of slow release hydroxyapatite coated urea nanofertilizer on aerobic paddy
Thathsarani Nanofertilizer for precision and sustainable agriculture
WO2022180504A1 (en) Method of making a nano-fertilizer composition for sustained release of macronutrients
Bhuvaneshwari Nanophosphorous fertilizer: promoting sustainable agriculture practices
Vishwakarma et al. MINERAL NUTRITION OF P IN PLANT
CN114455991A (en) Phosphorus potassium iron ternary composite nano fertilizer for promoting rice growth and preparation method thereof
Carmona Fernández Nanosized Calcium Phosphates as Novel Macronutrient Nano-Fertilizers
Carmona et al. Nanosized Calcium Phosphates as Novel Macronutrient Nano-Fertilizers. Nanomaterials 2022, 12, 2709
Irshad et al. The synthesis of nanofertilizers: biological approaches
WO2023046851A1 (en) Nano-chelated complexes
Madanayake et al. INVESTIGATION OF HYDROXYAPATITE NANOPARTICLES TOXICITY ON Raphanus sativus
WO2023126895A1 (en) Nano bio-carrier with plant additives coated on chemical fertilizers
BR102017000646A2 (en) production process of homogeneous suspension fluid organomineral fertilizer and product obtained
RO129081B1 (en) Process for preparing complex organomineral foliar fertilizers comprising mineral nutrients and polyhumates
RO127894B1 (en) Npk type extraradicular fertilizer with humic substances, process for obtaining and method for applying the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16738865

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2016738865

Country of ref document: EP