LU103449B1 - Additive for the production of stabilized urea particles and its use - Google Patents

Abstract

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-containing polymer; more preferably a polyvinylamine or a polyalkyleneimine; and (ii) optionally, a second polymer, preferably a polar polymer; more preferably a water-soluble polar polymer. The invention further relates to a process for preparing the particulate composition, an additive for a particulate composition, and the use of the particulate composition as a fertilizer. - Fig. 1 -

Description

240380P00LU 1

Additive for the production of stabilized urea particles and its use LU103449

[0001] The invention relates to a particulate composition (urea particles) which

urea, an inhibitor, preferably a urease inhibitor and/or a nitrification inhibitor, and an additive comprising or substantially consisting of, the additive comprising the components (i), (ii) and optionally (iii): (i) one or more polyhydric alcohols; preferably one or more

(ii) 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.

[0002] In conventional methods for producing urea particles such as granulation or

Prilling involves the addition of additives to the urea melt/solution before solidification.

Formaldehyde-based additives are added, such as urea-formaldehyde solutions. These additives are needed to improve granulation or pricking and thus the quality of the urea particles.

[0003] 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.

[0004] To produce stabilized urea, certain active substances must be added to the urea, in particular urease inhibitors, usually in the form of an inhibitor formulation. The most commonly used class of urease inhibitors are thiophosphoric acid retriamides. Examples of commercially available thiophosphoric acid triamides are N-(n-butyl)thiophosphoric acid retriamide (NBPT) and N-(n-propyl)thiophosphoric acid triamide (NPPT). Nitrification inhibitors are also frequently used as inhibitors.

[0005] Nowadays, urea particles are mainly treated with the inhibitor formulations by wholesalers, in small quantities in a separate treatment process in mixing stations/systems. In this process, the urea particles are coated with the inhibitor formulations. After application, inhibitors such as triamide thiophosphoric acids 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.

[0006] For the nitrogen utilization efficiency of the 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.

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[0007] 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.

[0008] However, at a storage temperature of 20°C, an unexpectedly strong degradation of the inhibitor was observed, particularly of thiophosphoric triamides, when the urea particles are treated directly with the inhibitor during granulation or prilling, as described above.

[0009] This observed rapid degradation means that the required minimum concentration of the inhibitor in the treated urea product cannot be achieved economically or practically with this method at the time of application in the field. The stabilized urea 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.

[0010] WO 2015 027244 A1 relates to a urea-nitrogen stabilizer composition as well as

Methods, systems, and equipment for their production. The composition is prepared in molten material.

Urea incorporated to obtain a composition containing less biuret, N-methyl-2-pyrrolidone (NMP), nitrogen stabilizer and/or impurities, and providing an effective solid

Fertilizer is supplied. These compositions are useful for odor control.

[0011] WO 2016 137815 A1 relates to a hygroscopic granulate with a nitrogen stabilizer and a

A carrier system that is essentially homogeneously distributed throughout the entire granule thickness. Various processes for the production of hemp granules 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).

[0012] WO 2019 197183 A1 relates to a process for producing a fertilizer composition comprising at least one urea-containing fertilizer and at least one (thio)phosphoric acid retriamide.

[0013] WO 2022 136360 A2 relates to a process for producing a homogeneous, solid, particulate, urea-based composition comprising urea and one or more additives in a urea production plant.

[0014] WO 2002 020471 A2 relates to a method for improving the compressive strength and impact strength of urea granules by adding an additive comprising a polyvinyl compound of the general formula (CHX-CHY), wherein n = 4-10,000 and X and Y are independently selected from

240380P00LU 3 of the group are selected, which 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 urea melt.

[0015] US 10,752,559 B2 relates to a particulate, urea-containing composition and use of an additive for the production of a particulate, urea-containing composition and process for the production of a particulate, urea-containing composition.

[0016] 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 intended to be used as a urea additive.

[0017] 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.

[0018] EP 3 157 889 B1 relates to a particulate, urea-containing composition, a method and an apparatus for its production, its use as a fertilizer, as a technical

Urea or feed additive, and the use of an additive for the manufacture of a particulate, urea-containing composition. The particulate composition contains (1) urea; and an additive comprising one or both of the following 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 (1) is > 60 wt.% and the weight fraction of the sum of components (1) and (iii) in the composition is < 1 wt.%. The additive may also comprise a component (iv): (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 (1) is > 60 wt.% and the weight fraction of the sum of components (ii), (iii) and (iv) in the composition is < 1 wt.%.

[0019] EP 3 484 601 BI relates to a process for the production of a NOx reducing agent AUS 32

Solution (Diesel Exhaust Fluid) comprising at least a mixture of water and a particulate composition containing (i) urea; and an additive comprising component (ii): (ii)

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 particle-shaped composition is > 60 wt.% and the weight fraction of component (ii) in the

240380P00LU 4 particulate composition < 1 wt.% and wherein a urea solution is obtained LU103449 and the weight fraction of component (i) in the obtained urea solution is between 31 wt.% and 34 wt.%.

[0020] EP 3 380 446 B1 relates to a particulate composition containing (i) urea; and an additive comprising one or both of the components (ii) and (iii): (ii) combination of at least one polymer or oligomer containing amino groups and at least one functionalized

(iii) a 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 (1) is > 10 wt.% and the weight fraction of the sum of components (ii) and (iii) in the composition is < 1 wt.%, which

Use of this additive for the production of the particulate, urea-containing composition, as well as the method and apparatus for producing the composition and its use as a fertilizer.

[0021] The known urea particles are not satisfactory in every respect and there is a need for improvements, especially with regard to storage stability.

[0022] It is an object of the invention to provide urea particles which contain additives other than formaldehyde-based additives and 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 urea particles should be easy and inexpensive to produce.

[0023] This problem is solved by the subject matter of the patent claims.

[0024] It was surprisingly found that the degradation of the inhibitor, in particular of thiophosphoric acid triamides, can be significantly reduced, i.e., the storage stability can be significantly improved, if an additive that has low reactivity towards the inhibitor is used as a replacement for a

A formaldehyde-based additive is used. Additives that are neither acidic nor acid-forming are particularly suitable.

[0025] Furthermore, it was surprisingly found that an additive with a combination of a polyhydric alcohol, in particular one or more carbohydrates such as corn syrup (high ethanol),

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. Such an additive is particularly suitable as an aqueous solution of

By adding urea melt and/or urea solution prior to granulation/prilling, 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,

240380P00LU and with an inhibitor, preferably a thiophosphoric triamide such as N-(n-butyl)thiophosphoric triamide (NBPT) or N-(n-propyl)thiophosphoric triamide (NPPT), or with inhibitor formulations containing these inhibitors, either during or after granulation/pricking, exhibited satisfactorily low degradation rates of the inhibitor. 5 [0026] A first aspect of the invention relates to a particulate composition comprising urea, an inhibitor, preferably a urease inhibitor and/or a nitrification inhibitor, and a

The additive comprises or essentially consists of the following components: (1), (11) and optionally (111): (1) one or more polyhydric alcohols; preferably one or more carbohydrates, preferably selected from monosaccharides, disaccharides, and oligosaccharides; (11) a first polymer, preferably an amine-containing polymer; more preferably a polyvinylamine or a polyalkyleneimine; and (3) optionally, a second polymer, preferably a polar polymer; more preferably a water-soluble polar polymer.

[0027] For the purposes of description, "essentially consisting of" means that the presence of other components in the mixture is not excluded, provided that they do not significantly alter essential characteristics of the mixture. Preferably, "essentially consisting of" means that the expressly listed components/ingredients of the mixture comprise a total of at least 95

constitute wt.% in relation to the total weight of the mixture, preferably at least 96 wt.%, more preferably at least 97 wt.%, most preferably at least 98 wt.%, and in particular at least 99 wt.%.

[0028] For the purposes of description, "particle-shaped" means a physical form which can also be described as granulated, prilled, crystalline, compacted, pulverized and the like, wherein the "particle-shaped" composition is a composition in a small uniform form (particles) as a multitude of small solid particles, i.e., particles whose

The dimensions are small compared to the scale of the particulate substance as a whole (i.e., as granules, prills, crystallites, pellets, powder, or pulver). Preferably, the particulate composition is in the form of granules, i.e., as a solid substance ("granular matter"). For the purpose of description, a "granule" consists of many individual, small, solid particles such as grains. Preferably, each grain comprises seed, e.g., recycled subcomponent, and material sprayed onto the seed.

Urea.

[0029] 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.

240380P00LU 6

[0030] The particulate composition according to the invention comprises urea. LU103449

[0031] Preferably the urea content is at least 50 wt.%; preferably at least 60

wt.%, 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.

[0032] The particulate composition according to the invention further comprises an inhibitor, preferably a urease inhibitor and/or a nitrification inhibitor.

[0033] The urease inhibitor is preferably selected from the group consisting of N-(n-butyl)thiophosphoric triamide (NBPT), N-(n-propyl)thiophosphoric triamide (NPPT), hydroquinone, phosphotriamide, p-benzoquinone, cyclohexyl phosphate triamide, and hexaamidocyclotriphosphazene; preferably N-(n-butyl)thiophosphoric triamide and N-(n-propyl)thiophosphoric triamide.

[0034] The nitrification inhibitor is preferably selected from the group consisting of dicyandiamide, 1-methylpyrazole-1-hydroxyamide, 3-methylpyrazole, ethylene amide, chlorazole, 4-aminotriazole,

Thioham, acetylene, 2-ethinylpyridine, sulfathiazole, amidinothioham, 1-amino-2,4-dimethylpyrazole phosphate, thiosulfates, for example sodium thiosulfate, calcium carbide, 2,5-chloroaniline, 3-acetanilide, toluene, carbon disulfide, phenylacetylene, 2-propyn-1-ol and phenethylphosphonium diamide.

[0035] Preferably, the particle-shaped 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).

[0036] The composition can also include several urease inhibitors and/or several nitrification

Contains inhibitors. A composition containing at least one urease inhibitor (or several urease inhibitors) and additionally at least one nitrification inhibitor (or several nitrification inhibitors) is therefore preferred.

[0037] In preferred embodiments, the particle-shaped composition comprises two urease inhibitors; preferably two thiophosphoric triamides; preferably N-(n-butyl)thiophosphoric triamide (NBPT) and N-(n-propyl)thiophosphoric triamide (NPPT).

[0038] 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.

[0039] 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.

240380P00LU 7

[0040] Preferably, the particulate composition contains no solvent and no LU103449

Stabilizer for the inhibitor (or any unavoidable residual amounts thereof). Alternatively, the particulate composition according to the invention can also contain at least partially the solvent and/or the stabilizer for the inhibitor.

[0041] The particulate composition according to the invention comprises an additive, wherein the additive comprises the components (i), (ii) and optionally (iii): (1) one or more polyhydric alcohols; preferably one or more carbohydrates, preferably selected from monosaccharides, disaccharides, and oligosaccharides; (li) 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.

[0042] For the purposes of description, an "additive" is a composition that can advantageously be added to (conventional) fertilizers to improve their properties. In the

As a rule, a fertilizer additive is not a fertilizer as such. The primary function of the inventive-

Ben additives are preferably used 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.

[0043] The particle-shaped composition according to the invention comprises urea, the inhibitor, and components (i), (11), and optionally (iii) of the additive. For the purpose of description, the individual components (i), (11), and optionally (iii) of the additive can be distinguished during the preparation of the particle-shaped

The composition may be added together or separately. For example, one of the components (i), (ii) and optionally (iii) may be added separately to the urea or the inhibitor.

[0044] Preferably, the additive does not react with thiophosphoric triamides by decomposing or otherwise reducing the activity of the inhibitor. Preferably, the additive has a stabilizing effect on the inhibitor.

[0045] Preferably the additive is in the form of a solid, a liquid or a suspension; preferably as a solution.

[0046] 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 which (i)

Isoglucose, preferably corn syrup (High Fructose Com Syrup/HFCS), invert sugar syrup or honey, (11)

Polyvinylamine or polyethyleneimine and optionally (iii) polyvinyl alcohol.

[0047] In preferred embodiments, the additive additionally contains urea.

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[0048] The additive according to the invention comprises one or more polyhydric alcohols; preferably one or more carbohydrates.

[0049] For the purposes of description, “polyhydric alcohols” are organic compounds which contain two or more alcoholic hydroxyl groups (-OH). For the purposes of description, “polyhydric alcohols” include, for example, 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.

[0050] Preferably, the one polyhydric alcohol or the several polyhydric alcohols are selected independently of one another from monosaccharides, disaccharides and oligosaccharides; preferably monosaccharides; particularly preferably glucose and fructose or mixtures of the aforementioned, in particular mixtures of glucose and fructose.

[0051] Preferably, the component (i) comprises two or more polyhydric alcohols; preferably glucose and fructose; more preferably isoglucose or invert sugar; even more preferably high fructose corn syrup (HFCS) or invert sugar syrup.

[0052] For the purpose of description, “corn syrup” (high fructose corn syrup/HFCS) is a glucose-

Fructose syrup (isoglucose syrup), which is an aqueous solution of isoglucose (isomeric sugar), a mixture of fructose and glucose. In corn syrup, 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, corn syrup contains, in addition to fructose and glucose, small amounts of other polyhydric alcohols, especially disaccharides such as maltose and sucrose. Furthermore, for the purpose of description, Invert Sugar Syrup® is also glucose-fructose syrup, but it is an aqueous solution of invert sugar (invertose), a

A mixture of fructose and glucose, which can be obtained in particular by hydrolysis (typically catalytic, especially enzymatic) of table sugar (sucrose).

[0053] It was surprisingly found that different polyhydric alcohols have a different effect on granulation/pricking, with corn syrup and invert sugar syrup being particularly advantageous.

[0054] 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.

[0055] Preferably, the one polyhydric alcohol or the several polyhydric alcohols are water-soluble.

240380P00LU 9

[0056] For the purpose of describing polyhydric alcohols, "water-soluble" means that in LU103449

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.

[0057] Preferably, the one polyhydric alcohol or the several 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.

[0058] 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.

[0059] The additive according to the invention comprises a first polymer, preferably an amine group-containing polymer.

[0060] 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.

[0061] 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 can contain primary, secondary or tertid amino groups which independently contain alkyl or aryl-alkyl groups, for example C;5-alkyl or aryl-C;5-alkyl, wherein aryl is particularly suitable for

Phenyl or pyridyl may be unsubstituted or may be substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of F, CI, Br, CF;, Ci,6-alkyl, C,_s-alk-oxy, NH,, Ci,4-alkylamino and Di(C,,4-alkyl)amino.

[0062] Preferably the first polymer is a polyethyleneimine and/or a polyvinylamine.

[0063] 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.

[0064] 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.

[0065] 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.

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[0066] Preferably, the first polymer is water-soluble. LU103449

[0067] Preferably the first polymer is polar.

[0068] 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.

[0069] For the purposes of description, "polar polymer" means a polymer with a polar

The polar group refers to a functional group that includes a dipole with an uneven center of positive and negative charges due to a distorted distribution of

Electron clouds result from a difference in the electronegativity of the atoms, which determine the functional

Polar groups are formed by the formation of a group. Examples of polar groups include ether groups, carboxyl groups, sulfone groups, phosphate groups, formyl groups, amino groups, amide groups, hydroxyl groups, cyano groups, epoxy groups, ester groups, carbonate groups, and lactone groups. Examples of polar polymers include polyethers, polyacrylonitrile, polyvinyl carbonate, polycarbonate, polyesters, and polymethyl methacrylate, 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.

[0070] 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.%, still more preferred 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 particle-shaped composition.

[0071] The additive according to the invention optionally comprises a second polymer, preferably a polar one.

Polymer.

[0072] The additive according to the invention comprises (li) 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.

[0073] Preferably the second polymer is an organic polymer.

[0074] Preferably the second polymer is a vinyl polymer, a polyester, a polyether, or a polyacrylate; preferably a vinyl polymer, a polyester, or a polyether.

[0075] For the purposes of description, "vinyl polymer" also includes functionalized polyvinyl compounds. According to the invention, functionalized polyvinyl compounds are in particular compounds based on the repeating unit (CHX-CHY), wherein X is selected from the

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The group consisting of H, OH, COOH, COR, CH,OH and CH,OR and Y is selected from the group LU103449 consisting of OH, COOH, COR, CH,OH and CH,OR and wherein R can each independently stand for alkyl, in particular C,5-alkyl, or aryl, in particular 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, CF;, CI,6-alkyl, C,5-alkoxy.

[0076] Preferably the second polymer does not contain any amine groups.

[0077] 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; preferred polyvinyl alcohol (PVOH).

[0078] 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.

[0079] Preferably the second polymer is water-soluble.

[0080] 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.

[0081] Preferably the second polymer is biodegradable.

[0082] 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 according to OECD 301 A or B, preferably within 28 days and at a concentration of 10 to 40 mg DOC/L (DOC = "dissolved organic carbon").

[0083] Preferably, the second polymer is not harmful to the environment.

[0084] 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) is

Polymers) with a particulate composition content of 10 wt% immediately after dissolution at a pH of at least 8.0; preferably in the range of 8.0 to 10. Preferably, the particulate composition does not include acidic components.

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[0085] Preferably, the second polymer is non-acidic. LU103449

[0086] Preferably, an aqueous solution of the second polymer with a second polymer content of 5.0 wt% has a pH value of at least 5.0 immediately after dissolution, more preferably in the range of 5.0 to 6.5.

[0087] Preferably, the second polymer has a pKa value of at least 7.0, preferably at least 10.0, particularly preferably at least 12.

[0088] 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 preferred 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.

[0089] 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 urea resin.

[0090] 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.

[0091] In preferred embodiments, the total additive content, i.e., components (i), (i1) and optionally (iii), is at least 0.02 wt.%; preferably at least 0.04 wt.%, more preferably at least 0.06 wt.%, 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.

[0092] In preferred embodiments, the total additive content, i.e., components (i), (11) and optionally (iii), is at most 1.5 wt.%, preferably at most 1.0 wt.%; preferably at most 0.8

wt.%, preferably not more than 0.6 wt.%, even more preferably not more than 0.4 wt.%, and most preferably not more than 0.2 wt.%; in each case relative to the urea content in the particulate matter

Composition.

[0093] 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.%;

Each relative to the urea content in the particulate composition.

[0094] In preferred embodiments, the total content of additive, i.e. components (i), (i1) and optionally (iii), is at least 0.02 wt.%; preferably at least 0.04 wt.%, more preferably at least 0.06 wt.%, 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.

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[0095] In preferred embodiments, the total additive content, i.e., components (i), LU103449 (11) and optionally (iii), is at most 1.5 wt.%, preferably at most 1.0 wt.%; preferably at most 0.8

wt.%, preferably not more than 0.6 wt.%, even more preferably not more than 0.4 wt.%, and most preferably not more than 0.2 wt.%; in each case relative to the total weight of the particulate composition.

[0096] 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.%;

Each relative to the total weight of the particle-shaped composition.

[0097] 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.

[0098] 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.

[0099] In preferred embodiments, the relative weight ratio of component (1i) 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.

[0100] In preferred embodiments, the total content of additive, i.e. components (i), (Gi) and (iii), and inhibitor 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.%, more preferably at most 0.4 wt.%, and most preferably at most 0.2 wt.%; in each case relative to the content of urea in the particulate composition.

[0101] 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.

[0102] The additive can comprise either (elemental) sulfur or ammonium sulfate or at least one trace element. Likewise, the additive can comprise all possible combinations of the aforementioned components or may also include further components. 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. The following are preferred as trace elements:

240380P00LU 14 refers to such elements which are necessary for a living organism and are usually present in mass fractions of less than 50 mg/kg in an organism. Trace elements can, for example,

These include aluminum, boron, chlorine, iron, copper, manganese, molybdenum, and/or zinc. A person skilled in the art recognizes that the term trace element encompasses both a single element and any possible mixture of two or more elements.

[0103] In preferred embodiments, the particulate composition according to the invention comprises ammonium sulfate.

[0104] Preferably the content of ammonium sulfate 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.

[0105] The particulate composition according to the invention can contain further components in addition to those mentioned. For example, the particulate composition according to the invention can

Contains water, e.g. in an amount of 0.05 to 0.5 wt.%, in particular 0.1 to 0.3 wt.% and

Byproducts of urea synthesis, such as biuret or NH₄; or antifoaming agents, such as...

Mono- and diglycerides of fatty acids and dimethylpolysiloxane. The proportion of by-products is usually not more than 1.5% by weight, and in particular not more than 1.25% by weight.

[0106] Another aspect of the invention relates to an additive as described above comprising the components (1), (11) and optionally (iii) for producing a particulate composition as described above.

[0107] 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.

[0108] Another aspect of the invention relates to a method for producing a particulate

Composition as described above, wherein the process comprises the steps of: (a) providing an inhibitor composition containing 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) optionally pre-cooling the particulate composition; (c) optionally classifying the particulate composition to obtain particle fractions;

240380P00LU 15 (f) optionally separating a particle fraction obtained in step (e); and recycling this separated particle fraction to a granulation or prilling device used in step (c) (optionally after comminution of the particles of this particle fraction); and (g) optionally post-cooling the particulate composition; wherein component (i), component (ii), and optionally component (iii) of an additive as described above are added independently of one another; preferably to the provided inhibitor composition or to the urea-containing solution and/or melt; wherein the inhibitor composition is added to the urea-containing solution and/or melt or brought into contact with the particulate composition.

[0109] Preferably, the inhibitor composition is brought into contact with the particulate composition (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).

[0110] In preferred embodiments, the inhibitor composition of the urea-containing

Solution and/or melt added before or during step (c) of the process according to the invention.

[0111] In preferred embodiments, the inhibitor composition of the urea-containing

Solution and/or melt added as a liquid or suspension, preferably as a solution.

[0112] Particularly pronounced advantages arise when granulation is carried out as fluidized bed granulation.

[0113] 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.

[0114] Preferably the inhibitor composition is liquid, preferably a solution.

240380P00LU 16

[0115] Typically, the inhibitor composition contains a solvent and a stabilizer LU103449 for the inhibitor. However, the inhibitor composition can also contain the components in undissolved form. The particulate composition according to the invention can contain at least some of the solvent and/or the stabilizer for the inhibitor.

[0116] In preferred embodiments, the additive, i.e., components (i), (11), 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.

[0117] Preferably, the additive, i.e., components (i), (ii), and optionally (iii), is added in

Section (c) of the method according to the invention.

[0118] Preferably, the additive is added in step (c) to the urea-containing solution and/or

Melt; preferably before the solidification of the ammonium-containing solution and/or melt.

[0119] Preferably, the additive is added, preferably before or during step (c), as a solid, liquid or suspension; preferably as a solution; more preferably as an aqueous solution.

[0120] In preferred embodiments, the additive additionally contains urea.

[0121] Preferably, the additive is added, preferably before or during step (c), as an aqueous solution or aqueous suspension; more preferably as a urea-containing aqueous solution.

[0122] Alternatively, the additive can also be added to a urea melt or urea solution as a solid.

[0123] In embodiments, the addition of the second polymer is carried out as a reactive monomer of the

Polymers, wherein the reactive monomer preferably polymerizes in situ, thereby forming the second polymer. Preferably, the monomer does not react with the inhibitor.

[0124] In preferred embodiments, the addition of component (i), component (ii) and/or optional component (111) to the urea-containing solution and/or melt is carried out together in one step; preferably in a solution.

[0125] In other preferred embodiments, the component (i), the component (i1) and the optional component (iii) are added to the urea-containing solution and/or melt sequentially. Preferably, the component (i), the component (ii) and the optional component (iii) are added sequentially.

Component (iii) is added to the urea-containing solution and/or melt in separate solutions. Preferably, the addition of component (i), component (11), and optional component (iii) to the urea-containing solution and/or melt is carried out sequentially. In preferred embodiments, the addition of components (i) and (ii), or of components (i) and (iii), or of components (11) and (iii) is carried out in a common solution. In preferred embodiments, the addition of component (1) is carried out before the addition of components (ii) and (iii). In other preferred embodiments,

240380P00LU 17 In the following flow methods, component (11) is added before components (1) and (iii). LU103449

In further preferred embodiments, component (iii) is added before components (i) and (ii).

[0126] 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.

[0127] Another aspect of the invention relates to the use of a particle-shaped composition as described above as a fertilizer.

[0128] The following examples serve to illustrate the invention, but are not to be interpreted as limiting.

Example 1:

[0129] A particulate composition comprising urea, an inhibitor, and an additive was prepared. To this end, 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 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 resulting combined mixture of concentrated

The urea solution and additive were then fed into a fluidized bed granulator and granulated, forming the particulate composition. Upon subsequent storage of the particulate composition, only a slight degradation of the inhibitor was observed after three months.

Example 2:

[0130] A particulate composition comprising urea, an inhibitor, and an additive was prepared. High fructose corn syrup (HFCS) and an aqueous solution of

Polyvinylamine was added to a 97% urea solution either manually or at a constant rate via a dosing 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 particle-shaped composition, only a slight degradation of the inhibitor was observed after three months.

Example 3:

[0131] A particulate composition comprising urea, an inhibitor, and an additive was prepared. High fructose corn syrup (HFCS), an aqueous solution of phosphate-

240380P00LU 18 Lyvinylamine and an aqueous solution of polyvinyl alcohol were added either manually or at a constant rate via a dosing pump to a 97% ham solution.

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.

[0132] Figure 1 shows the degradation of the inhibitor when using an additive according to Examples 1, 2 and 3, and when using urea-formaldehyde as the additive. It illustrates the decrease over time in the percentage inhibitor content of the product, based on the amount present immediately after production, during storage. A decrease to approximately 20% was observed.

Storage of urea diene granules over several months for granules with conventional

An additive from a pilot plant was observed. A decrease to approximately 40% was seen during storage of

A decrease of less than 10% was observed in the storage of urea fertilizer granules over several months for granules with a conventional additive from a commercial plant. This decrease was observed for granules with three different additives according to the invention, as shown in Examples 1, 2, and 3, from a pilot plant.

Claims (20)

240380P00LU 1 Patent claims: LU103449 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), (11) and optionally (111): (i) one or more polyhydric alcohols; preferably one or more carbohydrates, preferably selected from monosaccharides, disaccharides, and oligosaccharides; (li) 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. 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 particle-shaped composition according to one of the preceding claims, wherein the one polyhydric alcohol or the several polyhydric alcohols is/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 the component (i) comprises two or more polyhydric alcohols; preferably glucose and fructose; preferably isoglucose or invert sugar; more preferably corn syrup or invert sugar syrup. 6. The particulate composition according to any one 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.%, and even more preferably 0.008 to 0.4 wt.%, and 240380P00LU 2 preferably 0.01 to 0.2 wt.%; each relative to the total weight of the particulate LU103449 composition. 7. The particulate composition according to any one of the preceding claims, wherein the first polymer, preferably the amine-group-containing 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; 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 any of the preceding claims, wherein the second polymer is water-soluble and/or biodegradable. 11. The particle-shaped 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 particle-shaped composition. 240380P00LU 3 12. The particulate composition according to one of the preceding claims, comprising one or more additives; preferably the additives contain one or more of the following components: - sulfur; - ammonium sulfate; - at least one trace element. 13. 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. 14. Use of an additive according to claim 13 for the production of a particulate composition according to any one of claims 1 to 12. 15. A method for producing a particulate composition according to any one of claims 1 to 12, comprising the steps of: (a) providing an inhibitor composition containing an inhibitor; (b) providing a urea-containing solution and/or melt; (c) granulating or prilling the urea-containing solution and/or melt to obtain a particulate composition; (d) optionally cooling the particulate composition; (e) optionally classifying the particulate composition to obtain particle fractions; (f) optionally separating a particle fraction obtained in step (e) and recycling this separated particle fraction to the granulation or prilling apparatus 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 13 are added independently of one another; preferably to the provided inhibitor composition or to the urea-containing solution and/or melt; wherein the inhibitor composition is added to the urea-containing solution or brought into contact with the particulate composition. 240380P00LU 4 16. The method according to claim 15, 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. 17. The method according to claim 15 or 16, 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); preferably before the solidification of the urea-containing solution and/or melt. 18. The method according to any one of claims 15 to 17, wherein - the additive is added, preferably before or during step (c), as a solid, 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. 19. The method according to any one of claims 15 to 18, wherein the addition of component (i), component (ii) and/or optional component (111) to the ammonium-containing solution and/or melt is carried out together in one step or successively. 20. Use of a particulate composition according to any one of claims 1 to 12 as a fertilizer.