Additive for producing stabilised urea particles, and use thereof

Abstract

The invention relates to a particulate composition which comprises, or substantially consists of, urea, an inhibitor, preferably a urease inhibitor and / or a nitrification inhibitor, and an additive, wherein the additive comprises components (i), (ii) and optionally (iii): (i) one or more polyhydric alcohols; preferably one or more carbohydrates, preferably selected from monosaccharides, disaccharides, and oligosaccharides; (ii) a first polymer, preferably a polymer containing amine groups, more preferably a polyvinylamine or a polyalkyleneimine; and (iii) optionally, a second polymer, preferably a polar polymer, more preferably a water-soluble polar polymer. The invention also relates to a method for producing the particulate composition, to an additive for a particulate composition, and to the use of the particulate composition as a fertiliser.

Description

Additive for the production of stabilized urea particles and its use

[0001] The priorities of German patent application no. 10 2024 210 784.0 of November 8, 2024; Luxembourg patent application no. LU103450 of November 8, 2024; German patent application no. 10 2024 210 783.2 of November 8, 2024; Luxembourg patent application no. LU103449 of November 8, 2024; German patent application no. 10 2025 105 782.6 of February 17, 2025; Belgian patent application no. BE 2025 / 5092 of February 17, 2025; and German patent application no. 10 2025 105 784.2 of February 17, 2025 are listed. claimed in Belgian patent application no. BE 2025 / 5093 of 17 February 2025; Belgian patent application no. BE 2025 / 5108 of 24 February 2025; German patent application no. 10 2025 106 835.6 of 24 February 2025; and German patent application no. 10 2025 137 495.3 of 17 September 2025.

[0002] The invention relates to a particulate composition (ham particles) comprising, or substantially consisting of, urea, an inhibitor, preferably a urease inhibitor and / or a nitrification inhibitor, and an additive, wherein the additive comprises components (i), (ii), and optionally (iii): (i) one or more polyhydric alcohols; preferably one or more carbohydrates, preferably selected from monosaccharides, disaccharides, and oligosaccharides; (ii) a first polymer, preferably an amine-containing polymer; more preferably a polyvinylamine or a polyalkyleneimine; and (iii) optionally, a second polymer, preferably a polar polymer; more preferably a water-soluble polar polymer. The invention further relates to a process for producing the particulate composition, an additive for a particulate composition, and the use of the particulate composition as a fertilizer.

[0003] In conventional methods for producing ham particles, such as granulation or prilling, formaldehyde-based additives, such as ham-formaldehyde solutions, are typically added to the ham melt solution before solidification. These additives are needed to improve granulation or prilling and thus the quality of the ham particles.

[0004] Due to new regulations requiring higher nitrogen use efficiency (NUE) and a reduction in ammonia and greenhouse gas emissions, the demand for stabilized urea is increasing and will be much higher in the future.

[0005] To produce stabilized urea, certain active ingredients must be added to the urea, particularly urease inhibitors, usually in the form of an inhibitor formulation. The most commonly used class of urease inhibitors are thiophosphoric triamides. Examples of commercially available thiophosphoric triamides are N-(n-butyl)thiophosphoric triamide (NBPT) and N-(n-propyl)thiophosphoric triamide (NPPT). Nitrification inhibitors are also frequently used.

[0006] Nowadays, ham particles are mainly treated with inhibitor formulations by wholesalers, in small quantities, in a separate treatment process in mixing stations / systems. The ham particles are coated with the inhibitor formulations. After application, inhibitors such as thiophosphoric triamides are relatively stable at a storage temperature of 20°C and show degradation rates of 10-50% of the initially present inhibitor after one year of storage.

[0007] For the nitrogen utilization efficiency of stabilized urea, a minimum concentration of the inhibitor in the urea particles must be ensured at the time of application in the field. In most regions, the potential to reduce nitrogen losses must be demonstrated / verified.

[0008] For the treatment of large quantities of urea with inhibitors, it is more economical to perform the treatment upstream in the value chain, directly during granulation or prilling. For example, the urea can be treated with an inhibitor formulation as a melt / solution before entering the granulator / prilling tower, during the granulation process, or during cooling.

[0009] However, at a storage temperature of 20°C, an unexpectedly strong degradation of the inhibitor was observed, particularly of thiophosphoric triamides, when the ham particles are treated directly with the inhibitor during granulation or prilling, as described above.

[0010] This observed rapid degradation means that the required minimum concentration of the inhibitor in the treated ham product cannot be achieved economically or practically with this method at the time of application in the field. The stabilized ham product would have to be applied immediately after its production, i.e., without intermediate storage, which is logistically impossible. Alternatively, the inhibitor would have to be added in a very high concentration, which is unacceptable from both an economic and environmental perspective.

[0011] WO 2015 001457 Al relates to a composition comprising: (A) a mixture comprising at least one (thio)phosphoric triamide according to the general formula (I) R'R 2 N- P(X)(NH2)2, where X is oxygen or sulfur; R 1 a Ci to C 20 -Alkyl-, C3- to C 20 -Cycloalkyl-, C6- to C 20-Aryl or dialkylaminocarbonyl group; R 2 H is or R 1 and R 2 together with the nitrogen atom connecting them, define a 5- or 6-membered saturated or unsaturated heterocyclic residue, optionally comprising 1 or 2 further heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, and (C) at least one amine selected from the group consisting of (CI) a polymeric polyamine and (C2) an amine having no more than one amino group and at least three alkoxy- or hydroxy-substituted C2 to Ci2 alkyl groups R 21 contains, wherein at least one of the groups R 21 distinguish themselves from the other groups R 21 differs, and (C3) an amine comprising no more than one amino group and at least two alkoxy- or hydroxy-substituted C2 to Ci2 alkyl groups R 22 contains, wherein at least one of the groups R 22the alkoxy or hydroxy substituent on a secondary or tertiary carbon atom and wherein at least one of the groups R 22 distinguishing themselves from the other group(s) R 22 differs, and (C4) an amine containing at least one saturated or unsaturated C8 to C 40 -Alkyl group R 23 contains, and (C5) a saturated or unsaturated heterocyclic amine containing at least one oxygen atom as a ring atom and no other alkoxy group.

[0012] WO 2015 027244 Al relates to a urea-nitrogen stabilizer composition and to processes, systems, and equipment for its production. The composition is incorporated into molten urea to obtain a composition containing less biuret, N-methyl-2-pyrrolidone (NMP), nitrogen stabilizer, and / or impurities, and providing an effective solid fertilizer. These compositions are useful for odor control.

[0013] WO 2016 137815 Al relates to a hemp granulate with a nitrogen stabilizer and a carrier system that is essentially homogeneously distributed over the entire granule thickness. Various methods for producing the hemp granulate are described, including pricking, fluidized bed, and drum granulation. The nitrogen stabilizer may contain a urease inhibitor such as NBPT, with the NBPT purity ranging from 90% to 99%. The nitrogen stabilizer may also contain a nitrification inhibitor such as dicyandiamide (DCD).

[0014] WO 2019 197183 Al relates to a process for the production of a fertilizer composition comprising at least one urea-containing fertilizer and at least one (thio)phosphoric acid retriamide.

[0015] WO 2022 136360 A2 relates to a process for the production of a homogeneous, solid, particulate, urea-based composition comprising urea and one or more additives in a urea production plant.

[0016] WO 2002 020471 A2 relates to a method for improving the compressive strength and impact strength of ham granules by adding an additive comprising a polyvinyl compound of the general formula (CHX-CHY) n includes, where n = 4-10,000 and X and Y are selected independently of each other. The group selected consists of a hydrogen atom, a hydroxyl group, a carboxylic acid group, an amine group, or an amide group. This process is characterized by the fact that it begins with a methane melt.

[0017] US 10,752,559 B2 relates to a particulate urea-containing composition and the use of an additive for the manufacture of a particulate urea-containing composition and a process for the manufacture of a particulate urea-containing composition.

[0018] US 7,816,561 B2 relates to a method for improving compressive strength and reducing dust formation and the tendency of urea particles to clump together by adding an organic compound to the molten urea, wherein at least one carbohydrate and optionally a polyvinyl compound is added to the urea, and a composition to be used as a urea additive.

[0019] US 8,084,642 B2 relates to a method for improving the compressive strength, impact strength and compressibility of urea granules by adding a compound to the molten urea, wherein the compound comprises both a polyvinyl compound and an organic molecule consisting of 1 to 10 carbon atoms and 1 to 10 polar organic groups.

[0020] US 2022 / 242803 relates to increasing and / or maintaining the nitrogen content in soil by adding nitrogen source particles coated with urease inhibitors. In one embodiment, urease inhibitors are dispersed in an improved organic liquid transport system at concentrations of 60 to 95%. In another embodiment, urease inhibitors are applied to nitrogen source particles in a non-aqueous organic liquid transport system, using simple mixing devices at temperatures of 20 to 70 °C. A further embodiment discloses dry, free-flowing nitrogen sources coated with a urease inhibitor that can be applied directly to the soil, to a dry natural and / or artificial fertilizer, or to a liquid fertilizer, thereby reducing nitrogen loss from the soil.In another embodiment, a composition of urea and < 0.2% dimethyl sulfoxide improves the compressive strength of the urea particles.

[0021] EP 3 157 889 Bl relates to a particulate urea-containing composition, a process and apparatus for its production, its use as a fertilizer, as technical urea or feed additive, and the use of an additive for the production of a particulate urea-containing composition. The particulate composition contains (i) urea; and an additive comprising one or both of the components (ii) and (iii): (ii) a combination of at least one polymer or oligomer containing amino groups and at least one functionalized polyvinyl compound; (iii) at least one aliphatic C2-C8 dialdehyde; wherein the weight fraction of component (i) is > 60 wt.% and the weight fraction of the sum of components (ii) and (iii) in the composition is < 1 wt.%. The additive may also include a component (iv) comprise: (iv) at least one compound selected from the group consisting of aliphatic dicarboxylic acids, their salts and anhydrides, aliphatic tricarboxylic acids, their salts and anhydrides, aromatic dicarboxylic acids, their salts and anhydrides, and aldehydic acids, their salts and anhydrides, wherein the weight fraction of component (i) is > 60 wt.% and the weight fraction of the sum of components (ii), (iii) and (iv) in the composition is < 1 wt.%.

[0022] EP 3 484 601 Bl relates to a process for the production of a NOx reducing agent AUS 32 solution (Diesel Exhaust Fluid) comprising at least the mixing of water and a particulate composition containing (i) urea; and an additive comprising component (ii): (ii) a combination of at least one polymer or oligomer containing amino groups and at least one functionalized polyvinyl compound; wherein the weight fraction of component (i) in the particulate composition is > 60 wt.% and the weight fraction of component (ii) in the particulate composition is < 1 wt.% and wherein a urea solution is obtained and the weight fraction of component (i) in the obtained urea solution is between 31 wt.% and 34 wt.%.

[0023] EP 3 380 446 Bl relates to a particulate composition containing (i) urea; and an additive comprising one or both of the components (ii) and (iii): (ii) a combination of at least one polymer or oligomer containing amino groups and at least one functionalized polyvinyl compound; (iii) at least one aliphatic C2-C8 dialdehyde; and an additive comprising one or more of the components (iv) to (vi): (iv) sulfur; (v) ammonium sulfate; (vi) at least one trace element; wherein the weight fraction of component (i) is > 10 wt.% and the weight fraction of the sum of components (ii) and (iii) in the composition is < 1 wt.%, the use of this additive for the production of the particulate, urea-containing composition, the process and apparatus for producing the composition, and its use as a fertilizer.

[0024] The known ham particles are not satisfactory in every respect and there is a need for improvements, especially with regard to storage stability.

[0025] It is an object of the invention to provide ham particles containing additives other than formaldehyde-based additives, as well as urease inhibitors, in particular thiophosphoric triamides, and / or nitrification inhibitors, and which are characterized by improved storage stability, particularly with regard to the inhibitor content. The ham particles should be easy and inexpensive to produce.

[0026] This problem is solved by the subject matter of the patent claims.

[0027] It was surprisingly found that additives containing no formaldehyde can be used as granulation aids. Furthermore, it was surprisingly found that the degradation of the inhibitor, particularly thiophosphoric triamides, is significantly reduced, thus improving storage stability. The results can be significantly improved by using an additive with low reactivity towards the inhibitor as a replacement for a formaldehyde-based additive. Additives that are neither acidic nor acid-forming are particularly suitable.

[0028] Furthermore, it was surprisingly found that an additive combining a polyhydric alcohol, in particular one or more carbohydrates such as high fructose corn syrup (HFCS), invert sugar syrup, or even honey, with a first polymer, preferably an amine-containing polymer, in particular polyethyleneimine or polyvinylamine, and optionally a second polymer, preferably a polar polymer, in particular polyvinyl alcohol, is particularly suitable as an additive. If such an additive is added as an aqueous solution to a urea melt and / or urea solution prior to granulation / pricking, urea particles can be obtained that meet the usual quality criteria and exhibit improved storage stability (inhibitor degradation rate). Urea particles containing such an additive and an inhibitor, preferably a thiophosphoric triamide such as...Samples treated with N-(n-butyl)thiophosphoric acid retriamide (NBPT) or N-(n-propyl)thiophosphoric acid triamide (NPPT), or with inhibitor formulations containing these inhibitors, either during or after granulation / pricking, showed satisfactorily low degradation rates of the inhibitor.

[0029] A first aspect of the invention relates to a particulate composition comprising or substantially consisting of urea, an inhibitor, preferably a urease inhibitor and / or a nitrification inhibitor, and an additive, wherein the additive comprises components (i), (ii) and optionally (iii): (i) one or more polyhydric alcohols; preferably one or more carbohydrates, preferably selected from monosaccharides, disaccharides, and oligosaccharides; (ii) a first polymer, preferably an amine-group-containing polymer; more preferably a polyvinylamine or a polyalkylenemine; and (iii) optionally, a second polymer, preferably a polar polymer; more preferably a water-soluble polar polymer.

[0030] For descriptive purposes, "essentially consisting of" means that the presence of other components in the mixture is not excluded, provided they do not significantly alter essential characteristics of the mixture. Preferably, "essentially consisting of" means that the expressly listed components / ingredients of the mixture constitute at least 95% by weight of the mixture, more preferably at least 96% by weight, more preferably at least 97% by weight, most preferably at least 98% by weight, and particularly at least 99% by weight.

[0031] For descriptive purposes, "particulate" means a physical form which can also be described as granulated, prilled, crystalline, compacted, pulverized and the like, wherein The "particulate" composition is defined as a composition in a small, uniform form (particles) as a multitude of small, solid particles, i.e., particles whose dimensions are small compared to the scale of the particulate substance as a whole (e.g., as granules, prills, crystallites, pellets, powder, or pulverized powder). Preferably, the particulate composition is in the form of granules, i.e., as a granular substance ("granular matter"). For the purposes of description, a "granule" consists of many individual, small, solid particles, such as grains. Preferably, each grain comprises seed, e.g., recycled subsoil, and urea sprayed onto the seed.

[0032] Preferably the mean particle size (D50 (mass-averaged)) of the particulate composition is in the range of 0.5 mm to 5.0 cm; preferably 1.0 mm to 1.0 cm, more preferably 1.0 mm to 6.0 mm, even more preferably 2.0 mm to 5.0 mm, and most preferably 2.0 mm to 4.0 mm; preferably determined by sieve analysis according to DIN EN 1235:2003-08.

[0033] The particulate composition according to the invention includes urea.

[0034] Preferably the urea content is at least 50 wt.%; preferably at least 60 wt.%, more preferably at least 70 wt.%, even more preferably at least 80 wt.%, most preferably at least 90 wt.%, and in particular at least 95 wt.%; in each case relative to the total weight of the particulate composition.

[0035] The particulate composition according to the invention further comprises an inhibitor, preferably a urease inhibitor and / or a nitrification inhibitor.

[0036] The urease inhibitor is preferably selected from the group consisting of N-(n-butyl)thiophosphoric triamide (NBPT), N-(n-propyl)thiophosphoric triamide (NPPT), hydroquinone, phosphorus triamide, p-benzoquinone, cyclohexyl phosphate triamide, and hexaamidocyclotriphosphazene; preferably N-(n-butyl)thiophosphoric triamide and N-(n-propyl)thiophosphoric triamide.

[0037] The nitrification inhibitor is preferably selected from the group consisting of dicyandiamide, 1-methylpyrazole-l-hydroxyamide, 3-methylpyrazole, ethyleneham, chlorazole, 4-aminotriazole, thioham, acetylene, 2-ethinylpyridine, sulfathiazole, amidinothioham, l-amino-2,4-dimethylpyrazole phosphate, thiosulfates, for example sodium thiosulfate, calcium carbide, 2,5-chloroaniline, 3-acetanilide, toluene, carbon disulfide, phenylacetylene, 2-propyn-l-ol and phenethylphosphoniumdiamide.

[0038] Preferably, the particulate composition according to the invention comprises a urease inhibitor; preferably a thiophosphoric triamide; preferably N-(n-butyl)thiophosphoric triamide (NBPT) and / or N-(n-propyl)thiophosphoric triamide (NPPT).

[0039] The composition may also contain several urease inhibitors and / or several nitrification inhibitors. A composition with at least one urease inhibitor is therefore preferred. tor (or with several urease inhibitors) and additionally at least one nitrification inhibitor (or with several nitrification inhibitors).

[0040] In preferred embodiments, the particulate composition comprises two urease inhibitors; preferably two thiophosphoric triamides; preferably N-(n-butyl)thiophosphoric triamide (NB PT) and N-(n-propyl)thiophosphoric triamide (NPPT).

[0041] In preferred embodiments, the inhibitor content is at most 1.0 wt.%; preferably at most 0.5 wt.%, more preferably at most 0.1 wt.%, and even more preferably at most 0.05 wt.%; in each case based on the sum of all inhibitors contained in the particulate composition and relative to the total weight of the particulate composition.

[0042] In preferred embodiments, the inhibitor content is in the range of 0.005 to 0.5 wt.%; preferably 0.01 to 0.1 wt.%, more preferably 0.02 to 0.08 wt.%, and even more preferably 0.04 to 0.06 wt.%; in each case based on the sum of all inhibitors contained in the particulate composition and relative to the total weight of the particulate composition.

[0043] Preferably, the particulate composition contains no solvent and no stabilizer for the inhibitor (or at most unavoidable residual amounts thereof). Alternatively, the particulate composition according to the invention may also contain at least some of the solvent and / or the stabilizer for the inhibitor.

[0044] The inventive particulate composition comprises an additive, wherein the additive comprises components (i), (ii) and optionally (iii): (i) one or more polyhydric alcohols; preferably one or more carbohydrates, preferably selected from monosaccharides, disaccharides, and oligosaccharides; (ii) a first polymer, preferably an amine-group-containing polymer; more preferably a polyvinylamine or a polyalkylenemine; and (iii) optionally, a second polymer, preferably a polar polymer; more preferably a water-soluble polar polymer.

[0045] For descriptive purposes, an "additive" is a composition that can advantageously be added to (conventional) fertilizers to improve their properties. A fertilizer additive is generally not a fertilizer itself. The primary function of the additive according to the invention is preferably to improve the production, storage, and application of the inhibitor-treated fertilizer or fertilizer granules, in particular the granulation behavior and product quality (crushing strength, caking, and bulk density) of the granules.

[0046] The particulate composition according to the invention comprises urea, the inhibitor, and components (i), (ii), and optionally (iii) of the additive. For the purpose of description, the The individual components (i), (ii) and optionally (iii) of the additive may be added together or separately during the preparation of the particulate composition. For example, one of the components (i), (ii) and optionally (iii) may be added separately to the urea or the inhibitor.

[0047] Preferably, the additive does not react with thiophosphoric triamides, thereby degrading or otherwise reducing the activity of the inhibitor. Preferably, the additive has a stabilizing effect on the inhibitor.

[0048] Preferably, the additive is in the form of a solid, a liquid or a suspension; preferably as a solution.

[0049] Preferably, the additive is a mixture of water-soluble substances; more preferably, an aqueous solution. In particularly preferred embodiments, the additive is an aqueous solution comprising (i) isoglucose, preferably high fructose corn syrup (HFCS), invert sugar syrup, or honey, (ii) polyvinylamine or polyethyleneimine, and optionally (iii) polyvinyl alcohol.

[0050] In preferred formulations, the additive also contains urea.

[0051] The additive according to the invention comprises one or more polyhydric alcohols; preferably one or more carbohydrates.

[0052] For descriptive purposes, "polyhydric alcohols" are organic compounds containing two or more alcoholic hydroxyl groups (-OH). Examples of "polyhydric alcohols" include polyols, carbohydrates such as monosaccharides, disaccharides, and oligosaccharides, as well as diols and triols, for example, ethanediol, propanediol, butanediol, pentanediol, hexanediol, decanediol, benzyldimethanol, or propanetriol.

[0053] Preferably, the one or more polyhydric alcohols are selected independently from monosaccharides, disaccharides and oligosaccharides; preferably monosaccharides; particularly preferably glucose and fmctose or mixtures of the aforementioned, in particular mixtures of glucose and fmctose.

[0054] The component (i) preferably comprises two or more polyhydric alcohols; preferably glucose and Fmctose; preferably isoglucose or invert sugar; more preferably high Fmctose corn syrup (HFCS) or invert sugar syrup.

[0055] For the purposes of description, "high-fructose corn syrup" (HFCS) is a glucose-fructose simulant (isoglucose simulant), which is an aqueous solution of isoglucose (isomeric sugar), a mixture of fructose and glucose. In the case of the corn simulant, the isoglucose can be obtained enzymatically from glucose by converting a portion of the glucose into fructose (typically by glucose isomerase), the glucose having previously been obtained from cornstarch by (enzymatic) hydrolysis. Preferably, in addition to fructose and glucose, the corn simulant contains small amounts of other polyhydric alcohols, especially disaccharides such as maltose and sucrose. Furthermore, for the purpose of description, "invert sugar syrup" is also a glucose-fructose syrup, although it is an aqueous solution of invert sugar (invertose), a mixture of fructose and glucose, which can be obtained in particular by hydrolysis (typically catalytic, especially enzymatic) of table sugar (sucrose).

[0056] Surprisingly, it was found that different polyhydric alcohols have different effects on granulation / pricking, with corn syrup and invert sugar syrup being particularly beneficial.

[0057] Preferably, the one polyhydric alcohol or the several polyhydric alcohols have a molecular weight of at most 3000 g / mol; preferably at most 2600 g / mol, more preferably at most 2200 g / mol, even more preferably at most 1800 g / mol, most preferably at most 1400 g / mol, and in particular at most 1000 g / mol.

[0058] Preferably, one or more polyhydric alcohols are water-soluble.

[0059] For the purpose of describing polyhydric alcohols, "water-soluble" means that at room temperature (20°C) an aqueous solution of the polyhydric alcohol is present which contains at least 1 g / L of the polyhydric alcohol.

[0060] Preferably, one or more polyhydric alcohols have a pK A -value of at least 7.5; preferably at least 8.0, more preferably at least 9.0, even more preferably at least 10, most preferably at least 11, and in particular at least 12.

[0061] In preferred embodiments, the total content of the one polyhydric alcohol or the several polyhydric alcohols is in the range of 0.001 to 1.5 wt.%, preferably 0.002 to 1.0 wt.%; preferably 0.004 to 0.8 wt.%, more preferably 0.006 to 0.6 wt.%, even more preferably 0.008 to 0.4 wt.%, and most preferably 0.01 to 0.2 wt.%; in each case relative to the total weight of the particulate composition.

[0062] The additive according to the invention comprises a first polymer, preferably an amine group-containing polymer.

[0063] Preferably, the first polymer is selected from polyamines, polyalkylenemines, preferably polyethyleneimines and polypropyleneimines, polyvinylamines, polyalkoxylated polyamines, ethoxylated polyamines, propoxylated polyamines, and alkylated and / or benzylated polyamines; preferably polyamines, polyalkylenemines, preferably polyethyleneimines and polypropyleneimines, and polyvinylamines; preferably polyalkylenemines, preferably polyethyleneimines and polypropyleneimines, and polyvinylamines.

[0064] Preferably, the first polymer, preferably the polymers containing amino groups, can have a nitrogen content of 10 to 50 wt.%, based on the weight of the polymer and primary, secondary or tertiary amino groups containing independent alkyl or aryl alkyl groups, for example Ci.6-alkyl or aryl-Ci.3-alkyl, where aryl can in particular stand for phenyl or pyridyl, which can be unsubstituted or optionally substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of F, CI, Br, CF3, Ci.6-alkyl, Ci.6-alk-oxy, NH2, Ci.6-alkylamino and Di(Ci.6-alkyl)amino

[0065] Preferably, the first polymer is a polyethyleneimine and / or a polyvinylamine.

[0066] Preferably, the first polymer has a molecular weight in the range of 200 to 2,000,000 g / mol; preferably 400 to 1,000,000 g / mol, more preferably 600 to 500,000 g / mol, even more preferably 800 to 250,000 g / mol, most preferably 1000 to 100,000 g / mol, and particularly 1200 to 10,000 g / mol.

[0067] In preferred embodiments, the first polymer is a polyethyleneimine and has a molecular weight in the range of 500 to 2,000,000 g / mol.

[0068] In other preferred embodiments, the first polymer is a polyvinylamine and has a molecular weight in the range of 500 to 1,000,000 g / mol.

[0069] Preferably, the first polymer is water-soluble.

[0070] The first polymer is preferably polar.

[0071] For the purpose of describing the first polymer, "water-soluble" means that at room temperature (20°C) an aqueous solution of the first polymer is present which contains at least 1 g / L of the first polymer.

[0072] For descriptive purposes, "polar polymer" means a polymer with a polar group. The polar group refers to a functional group that forms a dipole with an uneven center of positive and negative charge due to a distorted distribution of electron clouds resulting from a difference in the electronegativity of the atoms that make up the functional group. Examples of polar groups include an ether group, a carboxyl group, a sulfone group, a phosphate group, a formyl group, an amino group, an amide group, a hydroxyl group, a cyano group, an epoxy group, an ester group, a carbonate group, and a lactone group.Examples of polar polymers include polyethers, polyacrylonitrile, polyvinyl carbonate, polycarbonate, polyesters, and polymethyl ethacrylate, each containing an ether bond in a repeating unit, or polyvinyl alcohols, each containing a hydroxyl group in a repeating unit. A polar polymer typically has a dipole moment greater than 0 D at 25°C.

[0073] In preferred embodiments, the total content of the first polymer is in the range of 0.002 to 2.0 wt.%; preferably 0.004 to 1.5 wt.%, more preferably 0.006 to 1.0 wt.%, even more preferably 0.008 to 0.75 wt.%, and most preferably 0.01 to 0.5 wt.%; in each case relative to the total weight of the particulate composition.

[0074] The additive according to the invention optionally comprises a second polymer, preferably a polar polymer.

[0075] The additive according to the invention comprises (ii) the first polymer, which is preferably an amine-group-containing polymer; and (iii) optionally, the second polymer, which is preferably a polar polymer; wherein the first polymer is different from the second polymer.

[0076] Preferably, the second polymer is an organic polymer.

[0077] Preferably the second polymer is a vinyl polymer, a polyester, a polyether, or a polyacrylate; preferably a vinyl polymer, a polyester, or a polyether.

[0078] Preferably, the second polymer is an alcohol; preferably a polyol (polyalcohol). For the purposes of description, a "polyol" contains at least two hydroxyl groups.

[0079] For the purposes of description, "vinyl polymer" also includes functionalized polyvinyl compounds. According to the invention, functionalized polyvinyl compounds include, in particular, compounds based on the repeating unit (CHX-CHY). nConsidering, wherein X is selected from the group consisting of H, OH, COOH, COR, CH2OH and CH2OR and Y is selected from the group consisting of OH, COOH, COR, CH2OH and CH2OR and wherein R can each independently represent alkyl, in particular Ci.6-alkyl, or aryl, in particular phenyl or pyridyl, which can be unsubstituted or optionally substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of F, CI, Br, CF3, Ci.6-alkyl, Ci.6-alkoxy.

[0080] Preferably, the second polymer does not contain any amine groups.

[0081] Preferably the second polymer is selected from the group consisting of polyvinyl alcohol (PVOH), polyethylene glycol (PEG), polylactic acid (PLA), polyethylene glycol esters, butenediol-vinyl alcohol copolymer (BVOH), polyvinylpyrrolidone (PVP), and polyacrylamide (PAM); preferably polyvinyl alcohol (PVOH), polyethylene glycol (PEG), polylactic acid (PLA), and polyethylene glycol esters; preferably polyvinyl alcohol (PVOH).

[0082] Preferably, the second polymer has a molecular weight in the range of 200 to 2,000,000 g / mol; preferably 400 to 1,000,000 g / mol, more preferably 600 to 500,000 g / mol, even more preferably 800 to 250,000 g / mol, most preferably 1000 to 100,000 g / mol, and particularly 1200 to 10,000 g / mol.

[0083] Preferably, the second polymer is water-soluble.

[0084] For the purpose of describing the second polymer, "water-soluble" means that at room temperature (20°C) an aqueous solution of the second polymer is present which contains at least 1 g / L of the second polymer.

[0085] Preferably, the second polymer is biodegradable.

[0086] For the purpose of describing the second polymer, "biodegradable" means that at least 60 wt% of the second polymer is biodegradable, in particular by a process in accordance with OECD 301 A or B, preferably within 28 days and at a concentration of 10 to 40 mg DOC / L (DOC = "dissolved organic carbon").

[0087] Preferably, the second polymer is not harmful to the environment.

[0088] Preferably, the particulate composition according to the invention is not acidic with respect to its pH value. Preferably, the pH value of an aqueous solution of the particulate composition (including the second polymer) with a particulate composition content of 10 wt% does not fall below a pH value of 7.0 immediately after dissolution. Preferably, the pH value of an aqueous solution of the particulate composition (including the second polymer) with a particulate composition content of 10 wt% immediately after dissolution is at least 8.0; more preferably in the range of 8.0 to 10. Preferably, the particulate composition does not comprise any acidic components.

[0089] Preferably, the second polymer is non-acidic.

[0090] Preferably, an aqueous solution of the second polymer with a content of 5.0 wt% of the second polymer has a pH value of at least 5.0 immediately after dissolution, more preferably in the range of 5.0 to 6.5.

[0091] Preferably, the second polymer has a pKa value of at least 7.0, preferably at least 10.0, and particularly preferably at least 12.

[0092] In preferred embodiments, the total content of the second polymer is in the range of 0.002 to 1.0 wt.%; preferably 0.004 to 0.8 wt.%, more preferably 0.006 to 0.6 wt.%, even more preferably 0.008 to 0.4 wt.%, and most preferably 0.01 to 0.2 wt.%; in each case relative to the total weight of the particulate composition.

[0093] Preferably the second polymer is not a polyamide, i.e. preferably not a linear polymer with regularly repeating amide bonds along the main chain; more preferably not a ham resin.

[0094] Preferably, the one or more polyhydric alcohols, the first polymer and the optional second polymer are different from each other, i.e., the additive according to the invention preferably comprises at least two different compounds and optionally a further third compound.

[0095] In preferred embodiments, the total additive content, i.e., components (i), (ii) and optionally (iii), is at least 0.02 wt.%; preferably at least 0.04 wt.%, more preferably at least 0.06 wt.%, even more preferably at least 0.08 wt.%, and most preferably at least 0.1 wt.%; in each case relative to the urea content in the particulate composition.

[0096] In preferred embodiments, the total additive content, i.e., components (i), (ii) and optionally (iii), is at most 1.5 wt.%, preferably at most 1.0 wt.%; preferably at most 0.8 wt.%, more preferably at most 0.6 wt.%, still more preferably at most 0.4 wt.%, and most preferably at most 0.2 wt.%; in each case relative to the urea content in the particulate composition.

[0097] In preferred embodiments, the total additive content, i.e., components (i), (ii) and optionally (iii), is in the range of 0.12 ± 0.1 wt.%; preferably 0.12 ± 0.08 wt.%, more preferably 0.12 ± 0.06 wt.%, even more preferably 0.12 ± 0.04 wt.%, and most preferably 0.12 ± 0.02 wt.%; in each case relative to the urea content in the particulate composition.

[0098] In preferred embodiments, the total additive content, i.e., components (i), (ii) and optionally (iii), is at least 0.02 wt.%; preferably at least 0.04 wt.%, more preferably at least 0.06 wt.%, even more preferably at least 0.08 wt.%, and most preferably at least 0.1 wt.%; in each case relative to the total weight of the particulate composition.

[0099] In preferred embodiments, the total content of additive, i.e. components (i), (ii) and optionally (iii), is at most 1.5 wt.%, preferably at most 1.0 wt.%; preferably at most 0.8 wt.%, more preferably at most 0.6 wt.%, still more preferably at most 0.4 wt.%, and most preferably at most 0.2 wt.%; in each case relative to the total weight of the particulate composition.

[0100] In preferred embodiments, the total additive content, i.e., components (i), (ii) and optionally (iii), is in the range of 0.12 ± 0.1 wt.%; preferably 0.12 ± 0.08 wt.%, more preferably 0.12 ± 0.06 wt.%, even more preferably 0.12 ± 0.04 wt.%, and most preferably 0.12 ± 0.02 wt.%; in each case relative to the total weight of the particulate composition.

[0101] In preferred embodiments, the relative weight ratio of component (i) to component (ii) is in the ratio of 10:1 to 1:10, preferably 8:1 to 1:8, more preferably 6:1 to 1:6, even more preferably 4:1 to 1:4, most preferably 3:1 to 1:3 and in particular 2:1 to 1:2.

[0102] In preferred embodiments, the relative weight ratio of component (i) to optional component (iii) is in the ratio of 10:1 to 1:10, preferably 8:1 to 1:8, more preferably 6:1 to 1:6, even more preferably 4:1 to 1:4, most preferably 3:1 to 1:3 and in particular 2:1 to 1:2.

[0103] In preferred embodiments, the relative weight ratio of component (ii) to optional component (iii) is in the ratio of 10:1 to 1:10, preferably 8:1 to 1:8, more preferably 6:1 to 1:6, even more preferably 4:1 to 1:4, most preferably 3:1 to 1:3 and in particular 2:1 to 1:2.

[0104] In preferred embodiments, the total additive content, i.e., components (i), is (ii) and (iii), and inhibitor at most 1.5 wt.%, preferably at most 1.0 wt.%; preferably at most 0.8 wt.%, more preferably at most 0.6 wt.%, more preferably at most 0.4 wt.%, and most preferably at most 0.2 wt.%; in each case relative to the urea content in the particulate composition.

[0105] In particularly preferred embodiments, the particulate composition contains no formaldehyde and / or ham-formaldehyde.

[0106] In preferred embodiments, the particulate composition contains no additional dye. In such embodiments, the particulate composition is preferably colored by the additive.

[0107] Preferably the particulate composition is granulated or prilled.

[0108] Preferably, at least the urea is contained within the granules.

[0109] Particularly preferred are at least the urea and components (i), (ii) and optionally (iii) of the additive contained within the granules.

[0110] Preferably, the urea, components (i), (ii), and optionally (iii) of the additive, and optionally the inhibitor are granulated or prilled and contained within the granules. More preferably, the urea, components (i), (ii), and optionally (iii) of the additive, and optionally the inhibitor are mixed and homogeneously distributed within the particulate composition, preferably within the granules. The particulate composition thus preferably does not exist in the form of core-shell particles, wherein the particle core comprises the inhibitor and the particle shell the urea. In other preferred embodiments, the urea and components (i), (ii), and optionally (iii) of the additive are granulated or prilled together and subsequently brought into contact with the inhibitor composition.

[0111] In preferred embodiments, the particulate composition is not in the form of core-shell particles, i.e., not in the form of coated cores. Instead, the particulate composition preferably consists of a homogeneous mixture of all ingredients and components (monoliths).

[0112] In other preferred embodiments, the particulate composition is in the form of core-shell particles, i.e., in the form of coated cores. In this case, preferably at least a subset, more preferably the entire set of components (i), (ii) and optionally (iii) of the Additives are contained in the cores. If the coating contains components (i), (ii) and optionally (iii) of the additive at all, it is therefore preferably at most a subset thereof.

[0113] For the purposes of description, core-shell particles according to the invention have an inner core and a coating (shell) surrounding this inner core, the coating preferably completely surrounding the inner core. The chemical composition of the core differs from the chemical composition of the coating in at least one property, preferably in its chemical nature and / or in the weight fraction of at least one ingredient. Preferably, the core and the coating are each formed from chemical compositions that independently contain all of their respective ingredients in a homogeneous distribution. If the core and the coating have the same chemical composition, they are therefore not core-shell particles within the meaning of the invention.

[0114] In particularly preferred embodiments, the particulate composition does not exist in the form of core-shell particles.

[0115] In other particularly preferred embodiments, the particulate composition is in the form of core-shell particles, wherein the chemical composition of the core and the coating (shell) differs only in the weight fraction of the nitrification inhibitor and / or the urease inhibitor and / or their formulation.

[0116] Preferably, the components (i), (ii) and optionally (iii) of the additive are not applied as a coating.

[0117] Preferably, the particulate composition is not extruded.

[0118] In preferred embodiments, the particulate composition according to the invention comprises one or more additives; preferably the additives contain one or more of the following components: - Sulfur; - Ammonium sulfate; - at least one trace element.

[0119] The additive can comprise either (elemental) sulfur or ammonium sulfate, or at least one trace element. Likewise, the additive can comprise any possible combination of the aforementioned components or may also contain other constituents. The sulfur can be used in its elemental form or as a component of a compound. For example, the additive can comprise sulfur in the form of sulfates. Trace elements are preferably those elements that are necessary for a living organism and are typically present in organisms in mass fractions of less than 50 mg / kg. Trace elements can include, for example, aluminum, boron, chlorine, iron, copper, manganese, molybdenum, and / or zinc. recognizes that the term trace element encompasses both a single element and any possible mixture of two or more elements.

[0120] In preferred embodiments, the particulate composition according to the invention comprises ammonium sulfate.

[0121] Preferably, the ammonium sulfate content is at most 1.0 wt.%; preferably at most 0.75 wt.%, more preferably at most 0.5 wt.%, and even more preferably at most 0.3 wt.%; in each case relative to the total weight of the particulate composition.

[0122] The particulate composition according to the invention may contain additional components besides those already mentioned. For example, the particulate composition according to the invention may contain water, e.g., in an amount of 0.05 to 0.5 wt.%, particularly 0.1 to 0.3 wt.%, and byproducts of methane synthesis such as biuret or NH3, or antifoaming agents such as mono- and diglycerides of fatty acids and dimethylpolysiloxane. The proportion of byproducts is usually not more than 1.5 wt.%, and in particular not more than 1.25 wt.%.

[0123] Another aspect of the invention relates to an additive as described above comprising components (i), (ii) and optionally (iii) for producing a particulate composition as described above.

[0124] Another aspect of the invention relates to the use of an additive as described above for the production of a particulate composition as described above.

[0125] Another aspect of the invention relates to a method for producing a particulate composition as described above, wherein the method comprises the steps: (a) Providing an inhibitor composition which includes an inhibitor, preferably a urease inhibitor and / or a nitrification inhibitor; (b) Providing a urea-containing solution and / or melt; (c) Granulating or pricking the urea-containing solution and / or melt to obtain a particulate composition; (d) optional pre-cooling of the particulate composition; (e) optionally classifying the particulate composition to obtain particle fractions; (f) optionally separating a particle fraction obtained in step (e); and returning this separated particle fraction to a granulation or pricking unit used in step (c) (optionally after comminution of the particles of this particle fraction); and (g) optional post-cooling of the particulate composition; wherein component (i), component (ii), and optionally component (iii) of an additive as described above are added independently of each other; preferably to the provided inhibitor composition or to the urea-containing solution and / or melt.

[0126] In preferred embodiments, component (i), component (ii), and optionally component (iii) of the additive are added to the urea-containing solution and / or melt. In these preferred embodiments, the inhibitor composition is preferably added to the urea-containing solution and / or melt or brought into contact with the particulate composition.

[0127] In other preferred embodiments, component (i), component (ii), and optionally component (iii) of the additive are added to the provided inhibitor composition. In these preferred embodiments, the inhibitor composition is preferably added to the urea-containing solution and / or melt. Preferably, in these preferred embodiments, the inhibitor composition is not brought into contact with the particulate composition.

[0128] The additive is therefore preferably added to the urea-containing solution and / or melt. In contrast, the inhibitor composition is preferably added either together with the additive to the urea-containing solution and / or melt, or brought into contact with the particulate composition without the additive.

[0129] The inhibitor composition is preferred, (i) after step (c) and before step (d); (ii) during step (d); (iii) after step (d) and before step (e); (iv) during step (e); (v) after step (e) and before step (f); (vi) during step (f); (vii) after step (f) and before step (g); (viii) during step (g); and / or (ix) after step (g); brought into contact with the particulate composition.

[0130] In preferred embodiments, the inhibitor composition is added to the urea-containing solution and / or melt before or during step (c) of the inventive process.

[0131] In preferred embodiments, the inhibitor composition is added to the urea-containing solution and / or melt as a liquid or suspension, preferably as a solution.

[0132] Particularly pronounced advantages arise when granulation is carried out as fluidized bed granulation.

[0133] Preferably, the temperature of the urea-containing solution and / or melt is at least 120°C; preferably at least 125°C, and more preferably at least 130°C.

[0134] The inhibitor composition is preferably liquid, preferably a solution.

[0135] Solvents according to the invention are preferably liquid in pure form at room temperature and atmospheric pressure.

[0136] Typically, the inhibitor composition contains a solvent and a stabilizer for the inhibitor. However, the inhibitor composition can also contain the components in undissolved form. The particulate composition according to the invention may contain at least some of the solvent and / or the stabilizer for the inhibitor.

[0137] In preferred embodiments, the additive, i.e., components (i), (ii), and optionally (iii), is added to the urea-containing solution and / or melt before or during step (c) of the process according to the invention.

[0138] Preferably, the additive, i.e., components (i), (ii), and optionally (iii), is added in step (c) of the method according to the invention.

[0139] Preferably, the additive is added in step (c) to the urea-containing solution and / or melt; preferably before the urea-containing solution and / or melt solidifies.

[0140] The additive is preferably added as a solid, liquid or suspension, preferably before or during step (c); preferably as a solution; more preferably as an aqueous solution.

[0141] In preferred embodiments, the additive additionally contains urea.

[0142] The additive is preferably added as an aqueous solution or aqueous suspension, preferably before or during step (c); more preferably as a urea-containing aqueous solution.

[0143] Alternatively, the additive can also be added to a hygrotherm melt or hygrotherm solution as a solid.

[0144] In embodiments, the second polymer is added as a reactive monomer of the polymer, wherein the reactive monomer preferably polymerizes in situ, thereby forming the second polymer. Preferably, the monomer does not react with the inhibitor.

[0145] In preferred embodiments, the addition of component (i), component (ii) and / or optional component (iii) to the urea-containing solution and / or melt is carried out together in one step; preferably in a solution.

[0146] In other preferred embodiments, component (i), component (ii), and optional component (iii) are added sequentially to the urea-containing solution and / or melt. Preferably, component (i), component (ii), and optional component (iii) are added to the urea-containing solution and / or melt in separate solutions. Preferably, component (i), component (ii), and optional component (iii) are added to the urea-containing solution and / or melt sequentially. In preferred embodiments, components (i) and (ii), or components (i) and (iii), or components (ii) and (iii) are added in a common solution. In preferred embodiments, component (i) is added before components (ii) and (iii). In other preferred embodiments, component (ii) is added before components (i) and (iii).In other preferred embodiments, component (iii) is added before components (i) and (ii).

[0147] Preferably, the additive is added to the urea-containing solution and / or melt separately from the addition of the inhibitor composition to the urea-containing solution and / or melt.

[0148] Preferably, solid starting materials, i.e., any solids to be introduced, such as solid additives, solid excipients, solid active ingredients, solid inhibitor compositions, solid components (i), solid components (ii), solid component (iii), etc., are introduced or added, preferably independently of one another, separately or as a mixture, using a solid-liquid mixture. The solid starting material is then preferably contained within the particulate composition, preferably homogeneously distributed.

[0149] The solid starting material is preferably first introduced into a fluid. Preferably, the fluid is aqueous. Preferably, the fluid contains urea. Preferred fluids include water, aqueous urea solutions, and urea melts. Preferably, the fluid differs from the urea-containing solution and / or melt described above. Preferably, the fluid has a higher water content than the urea-containing solution and / or melt described above. Compared to using an aqueous solution of the solid starting material, directly introducing the solid starting material into the fluid reduces the amount of additional water that needs to be evaporated.Preferably, the fluid is generated in a plant for the production of the particulate composition, for example as process condensate, during the evaporation of fresh urea synthesis, during separate evaporation, in a tank, as a scrubbing solution for an exhaust gas scrubber, or in a pipeline. Optionally, the fluid is conveyed to the solid-liquid mixer by a feed pump, the feed pump preferably being arranged upstream of the solid-liquid mixer in the direction of fluid flow.

[0150] The solid starting material to be introduced into the fluid is preferably stored as a supply in a reservoir (e.g., silo, big bag, hopper). Preferably, a device for solid material handling is used. Dosing involves feeding a defined quantity of the solid feed material into the solid-liquid mixer. Dosing can be performed, for example, gravimetrically or volumetrically. Examples of suitable devices for solid feed include metering screws or rotary valves. Preferably, the solid feed material has a particle size of < 1 mm.

[0151] In a solid-liquid mixer, the solid feedstock is mixed with the fluid. An example of a suitable solid-liquid mixer is the MHD2000 from IKA Werke GmbH. The resulting mixture can be a solution and / or a suspension. It can also be an emulsion, for example, if the melting point of the solid feedstock is below the temperature of the fluid or if a complex mixing ratio is present. The solid feedstock and the fluid are mixed in a defined ratio, which can be controlled and regulated using the optional feed pump and / or the solid dosing device. The ratio can be set manually or automatically controlled.

[0152] Optionally, the resulting mixture is then passed through a degassing unit, which may remove any gas that was previously introduced by the solid starting material or the solid-liquid mixer.

[0153] Optionally, the pressure of the generated mixture is subsequently increased using a pressure boosting device, preferably a pump. Such a pressure increase may be necessary if the back pressure downstream is higher than the outlet pressure of the solid-liquid mixer or the optional degassing unit. Since the generated mixture can be viscous, the pump is preferably suitable for pumping liquids of varying viscosities (e.g., a progressive cavity pump or a screw pump). The pump is also preferably suitable for pumping suspensions. The pump's delivery rate is preferably in a defined ratio to the outlet of the solid-liquid mixer. This ratio can be set manually or automatically controlled by means of a circuit.

[0154] The degassing unit and pressure boosting device can be separate or combined. Depending on the type of pressure boosting device, degassing and pressure boosting can be combined.

[0155] In preferred embodiments, the generated mixture is subsequently introduced into the urea-containing solution and / or melt, preferably at a feed point. The urea-containing solution and / or melt is preferably the main stream fed to the granulation or pricking unit. Preferably, the flow rate of the urea-containing solution and / or melt is greater than the flow rate of the generated mixture. The generated mixture is introduced into the urea-containing solution and / or melt in a defined ratio. This ratio can be set manually or automated by means of a circuit. Preferably, the distance between the solid-liquid mixer and the feed point is as short as possible. Preferably, the residence time of the mixture between the solid-liquid mixer and the feed point is as short as possible. Possible. The feed point is preferably located upstream of the granulation or pricking unit (e.g., fluidized bed granulation, pricking, drum granulator). Optionally, intensified mixing of the generated mixture and the urea-containing solution and / or melt can take place downstream of the feed point and upstream of the granulation or pricking unit. A pump can be used for this mixing, particularly if the feed point is located upstream of a pump for the granulation or pricking unit. Alternatively, a static mixer, such as a filter, can be located downstream of the feed point and upstream of the granulation or pricking unit.

[0156] In other preferred embodiments, the generated mixture is subsequently introduced into a liquid composition obtained during evaporation or in a recycling system (e.g., exhaust gas scrubber). This liquid composition is preferably aqueous. The liquid composition preferably contains urea.

[0157] Preferably, liquid starting materials, i.e., any liquids to be introduced, such as liquid additives, liquid excipients, liquid active ingredients, etc., are introduced, preferably independently of one another, either separately or as a mixture, preferably with the aid of liquid-liquid mixtures. The liquid starting material is then preferably contained within the particulate composition, preferably homogeneously distributed.

[0158] For liquid starting material, an additional dosing device can optionally be provided.

[0159] In preferred embodiments, the liquid starting material is introduced upstream or downstream of the optional feed pump, downstream of the solid-liquid mixer, into or downstream of the degassing unit, upstream or downstream of the pressure boosting device, upstream or downstream of the feed point, or directly upstream of the granulation or pricking device used.

[0160] Another aspect of the invention relates to the use of a particulate composition as described above as a fertilizer.

[0161] The following examples serve to illustrate the invention, but are not to be interpreted restrictively. Example 1:

[0162] A particulate composition comprising urea, an inhibitor, and an additive was prepared. To this end, corn syrup (high fructose corn syrup / HFCS), an aqueous solution of polyethyleneimine, and an aqueous solution of polyvinyl alcohol were first added to a 97% urea solution, either manually or at a constant rate using a metering pump. An inhibitor composition (Limus®Direct from BASF, containing a combination of NPPT and NBPT) was then added to the urea-containing melt, either manually or using a constant-rate metering pump. The inhibitor was added at a rate of ten via a dosing pump. The resulting combined mixture of concentrated ham solution and additive was then fed into a fluidized bed granulator and granulated, forming the particulate composition. Upon subsequent storage of the particulate composition, only minimal degradation of the inhibitor was observed after three months. Example 2:

[0163] A particulate composition comprising urea, an inhibitor, and an additive was prepared. High-fructose corn syrup (HFCS) and an aqueous solution of polyvinylamine were added to a 97% urea solution, either manually or at a constant rate via a metering pump. An inhibitor composition (Limus®Direct from BASF, containing a combination of NPPT and NBPT) was added to the urea-containing melt, either manually or at a constant rate via a metering pump. The combined mixture was then fed into a granulator and granulated. Upon subsequent storage of the particulate composition, only minimal degradation of the inhibitor was observed after three months. Example 3:

[0164] A particulate composition comprising urea, an inhibitor, and an additive was prepared. Maize succinate (high-fructose corn syrup / HFCS), an aqueous solution of polyvinylamine, and an aqueous solution of polyvinyl alcohol were added to a 97% urea solution, either manually or at a constant rate via a metering pump. An inhibitor composition (Limus®Direct from BASF, containing a combination of NPPT and NBPT) was added to the urea-containing melt, either manually or at a constant rate via a metering pump. The combined mixture was then fed into a granulator and granulated. Upon subsequent storage of the particulate composition, only minimal degradation of the inhibitor was observed after two months.

[0165] Figure 1 shows the degradation of the inhibitor when using an additive according to Examples 1, 2, and 3, and when using ham-formaldehyde as the additive. It depicts the decrease over time in the percentage of inhibitor content of the product, relative to the amount present immediately after production, during storage. A decrease to approximately 20% was observed over several months for ham-formaldehyde fertilizer granules with a conventional additive from a pilot plant. A decrease to approximately 40% was observed over several months for ham-formaldehyde fertilizer granules with a conventional additive from a commercial plant. A decrease of less than 10% was observed over several months for ham-formaldehyde fertilizer granules with three different additives according to Examples 1, 2, and 3 from a pilot plant.

Claims

Patent claims:

1. Particle-shaped composition comprising or substantially consisting of urea, an inhibitor, preferably a urease inhibitor and / or a nitrification inhibitor, and an additive, wherein the additive comprises components (i), (ii) and optionally (iii): (i) one or more polyhydric alcohols; preferably one or more carbohydrates, preferably selected from monosaccharides, disaccharides, and oligosaccharides; (ii) a first polymer, preferably an amine-group-containing polymer; more preferably a polyvinylamine or a polyalkylenemine; and (iii) optionally, a second polymer, preferably a polar polymer; more preferably a water-soluble polar polymer.

2. The particulate composition according to claim 1, wherein the urea content is at least 50 wt.%; preferably at least 60 wt.%, more preferably at least 70 wt.%, more preferably at least 80 wt.%, most preferably at least 90 wt.%, and in particular at least 95 wt.%; in each case relative to the total weight of the particulate composition.

3. The particulate composition according to claim 1 or 2, comprising a urease inhibitor; preferably a thiophosphoric triamide; preferably N-(n-butyl)thiophosphoric triamide (NBPT) and / or N-(n-propyl)thiophosphoric triamide (NPPT).

4. The particulate composition according to any of the preceding claims, wherein the one polyhydric alcohol or the several polyhydric alcohols are / are selected independently of one another from monosaccharides, disaccharides and oligosaccharides; preferably monosaccharides; particularly preferably glucose and / or fructose.

5. The particulate composition according to any one of the preceding claims, wherein component (i) comprises two or more polyhydric alcohols; preferably glucose and fructose; more preferably isoglucose or invert sugar; more preferably corn syrup or invert sugar syrup.

6. The particulate composition according to any of the preceding claims, wherein the total content of the one polyhydric alcohol or the several polyhydric alcohols is in the range of 0.001 to 1.5 wt.%, preferably 0.002 to 1.0 wt.%; preferably 0.004 to 0.8 wt.%, more preferably 0.006 to 0.6 wt.%, more preferably 0.008 to 0.4 wt.%, and most preferably 0.01 to 0.2 wt.%; in each case relative to the total weight of the particulate composition.

7. The particulate composition according to any one of the preceding claims, wherein the first polymer, preferably the amine-containing polymer, is selected from polyamines, polyalkylenemines, preferably polyethyleneimines and polypropyleneimines, polyvinylamines, poly-alkoxylated polyamines, ethoxylated polyamines, propoxylated polyamines, and alkylated and / or benzylated polyamines; preferably polyamines, polyalkylenemines, preferably polyethyleneimines and polypropyleneimines, and polyvinylamines; more preferably wherein the first polymer is a polyethyleneimine and / or a polyvinylamine.

8. The particulate composition according to any of the preceding claims, wherein the total content of first polymer is in the range of 0.002 to 2.0 wt.%; preferably 0.004 to 1.5 wt.%, more preferably 0.006 to 1.0 wt.%, even more preferably 0.008 to 0.75 wt.%, and most preferably 0.01 to 0.5 wt.%; in each case relative to the total weight of the particulate composition.

9. The particulate composition according to any one of the preceding claims, wherein the second polymer, preferably the polar polymer, is a vinyl polymer, a polyester, a polyether, or a polyacrylate; preferably a vinyl polymer, a polyester, or a polyether; more preferably the second polymer is selected from the group consisting of polyvinyl alcohol (PVOH), polyethylene glycol (PEG), polylactic acid (PLA), polyethylene glycol esters, butenediol-vinyl alcohol copolymer (BVOH), polyvinylpyrrolidone (PVP), and polyacrylamide (PAM); more preferably polyvinyl alcohol (PVOH), polyethylene glycol (PEG), polylactic acid (PLA), and polyethylene glycol esters; even more preferably polyvinyl alcohol (PVOH).

10. The particulate composition according to one of the preceding claims, wherein the second polymer is an alcohol; preferably a polyol.

11. The particulate composition according to any of the preceding claims, wherein the second polymer is water-soluble and / or biodegradable.

12. The particulate composition according to any of the preceding claims, wherein the total polymer content is in the range of 0.002 to 1.0 wt.%; preferably 0.004 to 0.8 wt.%, more preferably 0.006 to 0.6 wt.%, even more preferably 0.008 to 0.4 wt.%, and most preferably 0.01 to 0.2 wt.%; in each case relative to the total weight of the particulate composition.

13. The particulate composition according to any of the preceding claims, comprising one or more additives; preferably the additives comprise one or more of the following components: - Sulfur; - Ammonium sulfate; - at least one trace element.

14. The particulate composition according to any of the preceding claims, which does not contain formaldehyde and / or ham-formaldehyde.

15. The particulate composition according to any of the preceding claims, which is granulated or prilled.

16. The particulate composition according to one of the preceding claims, wherein at least the urea is contained within the granules.

17. The particulate composition according to any of the preceding claims, wherein at least the urea and the components (i), (ii) and optionally (iii) of the additive are contained within the granules.

18. The particulate composition according to any of the preceding claims, wherein the urea, the components (i), (ii) and optionally (iii) of the additive, and optionally the inhibitor are mixed and homogeneously distributed within the particulate composition, preferably within the granules.

19. An additive as defined in any of the preceding claims comprising the components (i), (ii) and optionally (iii) for producing a particulate composition as described above.

20. Use of an additive according to claim 19 for the production of a particulate composition according to any one of claims 1 to 18.

21. A method for producing a particulate composition according to any one of claims 1 to 18, wherein the method comprises the steps: (a) Providing an inhibitor composition which contains an inhibitor; (b) Providing a urea-containing solution and / or melt; (c) Granulating or pricking the urea-containing solution and / or melt to obtain a particulate composition; (d) optional cooling of the particulate composition; (e) optionally classifying the particulate composition to obtain particle fractions; (f) optionally separating a particle fraction obtained in step (e); and returning this separated particle fraction to the granulation or pricking device used in step (c); and (g) optionally cooling the particulate composition; wherein component (i), component (ii), and optionally component (iii) of an additive according to claim 19 are added independently of one another; preferably to the provided inhibitor composition or to the urea-containing solution and / or melt.

22. The method according to claim 21, wherein the temperature of the urea-containing solution is at least 120°C; preferably at least 125°C, and more preferably at least 130°C.

23. The method according to claim 21 or 22, wherein the additive is added to the urea-containing solution and / or melt.

24. The method according to any one of claims 21 to 23, wherein the addition of the additive to the urea-containing solution and / or melt takes place before or during step (c); preferably in step (c); more preferably before the solidification of the urea-containing solution and / or melt.

25. The method according to any one of claims 21 to 24, wherein - the additive is added, preferably before or during step (c), as a pesticide, liquid or suspension; preferably as a solution; more preferably as an aqueous solution; even more preferably as a urea-containing aqueous solution; and / or - the inhibitor composition is added, preferably before or during step (c), as a liquid or suspension to the urea-containing solution and / or melt, preferably as a solution.

26. The method according to any one of claims 21 to 25, wherein the addition of component (i), component (ii) and / or optional component (iii) to the urea-containing solution and / or melt is carried out together in one step or successively.

27. The method according to any one of claims 21 to 26, wherein the inhibitor composition is brought into contact with the particulate composition.

28. Use of a particulate composition according to any one of claims 1 to 18 as a fertilizer.

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