HK1149542B - Mixture for the treatment of urea-containing fertilizers - Google Patents

Description

Mixture for treating urea-containing fertilizers

The invention relates to a mixture for treating urea-containing fertilizers and to the use thereof and to urea-containing fertilizers comprising the mixture, wherein the mixture has, in particular, an improved urease-inhibiting effect.

The major and increasing amount of nitrogen used for fertilization worldwide is used in the form of urea or urea-containing fertilizers. Urea itself is however in the form of nitrogen which is not or hardly absorbed, since it is relatively rapidly hydrolyzed to ammonia and carbon dioxide by enzymes which are ubiquitous in the soil, urease (Mobley, h.l.t., Island, m.d.hausinger, r.p. (1995) molecular biology of microbial ureas, microbiol.rev.59, 452-. In some cases the ammonia gas is released into the atmosphere and is no longer available to the plants in the soil, thereby reducing the efficiency of the fertilization.

A method is known for improving nitrogen utilization when using urea-containing fertilizers by broadcasting the urea-containing fertilizer with a substance that reduces or inhibits enzymatic urea decomposition (see Kiss, S for a general overview).(2002) Improving Efficiency of Urea Fertilizersby Inhibition of Soil Urease Activity, ISBN 1-4020-0493-1, Kluweracademic Publishers, Dordrecht, The Netherlands). N-alkyl thiophosphoric triamides and N-alkyl phosphoric triamides are among the most effective urease inhibitors known here, which are described, for example, in EP 0119487.

Mixtures of N-alkyl thiophosphoric triamides, such as N- (N-butyl) thiophosphoric triamide (NBPT) and N- (N-propyl) thiophosphoric triamide (NPPT), may also be used.

Such urease inhibitors are described, for example, in US 4,530,714. In order for such compounds to be useful as urease inhibitors, they are first converted to the corresponding oxygenated form (Oxoform). The oxygenated form then reacts with urease and produces an inhibitory effect.

It is advisable to add the urease inhibitor to the soil or to the soil together with the urea, since in this way it is ensured that the inhibitor comes into contact with the soil together with the fertilizer. The active substance can be introduced into the urea, for example, dissolved in the melt before the urea is granulated or pelletized. Such a process is described in US 5,352,265. Another possibility consists in applying the active substance, for example in the form of a solution, on urea granules or pellets.

Corresponding application methods and suitable solvents are described, for example, in EP-A-1820788.

The active substances have only a limited storage stability. The higher the temperature, the lower the storage stability. If the urea is stored under tropical conditions, the active substance is usually decomposed by more than 60% after about 4 weeks of storage. If the active substance is introduced into the urea melt, the decomposition is reduced. However, for the marketing of urea stabilized with this active substance, the application of the active substance on urea and the storage of the treated fertilizer on spreading are largely not allowed.

The object of the present invention is to provide a mixture for treating urea-containing fertilizers, in particular for inhibiting urease, which mixture is stable for a long time after application on a urea-containing fertilizer, which fertilizer can better withstand different dosing stages and protects the active substance applied on the urea from decomposition or loss. The mixture should be toxicologically uncritical and have no adverse effect on the active substance.

The object of the invention is achieved by a mixture for treating a urea-comprising fertilizer, the mixture comprising:

a) at least one (thio) phosphoric triamide of the formula (I) and/or (thio) phosphoric diamide of the formula (II) as component A,

R¹R²N-p(X)(NH₂)₂ (I)

R¹O-P(X)(NH₂)₂ (II)

wherein:

x is oxygen or sulfur

R¹And R²Each independently of the others being hydrogen, in each case substituted or unsubstituted C_1-10Alkyl radical, C_3-10-cycloalkyl, C_3-10-heterocycloalkyl radical, C_6-10-aryl, C_6-10-heteroaryl or diaminocarbonyl, wherein R¹And R²Can also form, together with the nitrogen atom to which they are bound, a 5-or 6-membered, saturated or unsaturated heterocyclic radical which can optionally also contain one or two further heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur,

b) as component B, at least one amino-containing compound having a boiling point of greater than 100 ℃, for example at least one amine.

The invention also relates to the use of said mixtures as additives and coating agents for urea-containing nitrogen fertilizers.

Furthermore, the invention relates to the use of the mixture for reducing nitrogen loss of organic fertilizer or during storage in manure pits and for reducing ammonia load in animal stalls.

Furthermore, the invention relates to a urea-comprising fertilizer, which comprises the mixture according to the invention in the following amounts: so that the total content of component A is from 0.001 to 0.5% by weight, based on the urea present.

The component B contains at least one amino group, such as a primary, secondary or tertiary amino group, wherein any further functional groups and residues such as hydroxyl, halogen, carboxyl, carbamoyl, carbonyl, Oxyalkyl (Oxyalkenyl), mercapto, M-thio (M-sulfo), sulfinyl (Sulfoxy), sulfo, Phospho (Phospho), siloxy, amino, amido, imino, imido, oxyamido, etc., may be present in the compound. Component B is described in detail below with an exemplary amine. The statements also apply generally to component B.

It was found in accordance with the invention that the active substance of component A applied on urea has a significantly longer storage stability (at least 2-3 months) if it is used in combination with at least one amine with a boiling point of greater than 100 ℃ as component B. The boiling point of the amines of component B is preferably greater than 150 ℃ and particularly preferably greater than 200 ℃ at ambient pressure (1 bar). The amine may be a primary, secondary or tertiary amine or polyamine with multiple amino groups. Preference is given to using secondary and/or tertiary amines as amines. Particular preference is given to using tertiary amines, which may also be present in the form of polymers. Preference is given to using amines which are unreactive with the active substances of component A or with the component C solvents optionally used together. For example, the amine of component B is selected from methyldiethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N, N, N ', N ' -tetramethyl-1, 6-hexanediamine, N, N ', N ' -tris (dimethylaminopropyl) hexahydrotriazine, 2 ' -dimorpholinodiethylether or mixtures thereof.

The component B is used in an amount sufficient to increase the storage stability of the active substance of component A in the urea-comprising fertilizer. The amount of component B used is preferably at least 0.2 times, particularly preferably 0.5 to 3 times, in particular 1 to 2 times, the molar amount of component A.

Amines with high boiling points are advantageous in applications based on odor and explosion protection.

Surprisingly, amides such as N-methylpyrrolidone (NMP) have no stabilizing effect.

This stabilizing effect is independent of the use of a solvent. The amine additive shows a stabilizing effect when NMP is used and an alkylene glycol such as 1, 2-propanediol is used as a solvent.

In addition, the stabilization can be further increased by adding polymer auxiliaries.

As component A, at least one (thio) phosphoric triamide of the formula (I) and/or (thio) phosphoric diamide of the formula (II) is used. It is also possible to use a single compound and a mixture of two or more such compounds. It may be, for example, ｃA mixture as described in EP-A-1820788.

The residue R¹And R²Each of which may be unsubstituted or substituted, such as by halogen and/or nitro.

Examples of alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl and isodecyl. Cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl, aryl is, for example, phenyl or naphthyl or substituted 2-nitrophenyl. Heterocyclic radical R₁R₂Examples of N are piperazinyl, morpholinyl, pyrrolyl, pyrazolyl, triazolyl,Oxazolyl, thiazolyl, or imidazolyl.

Such compounds are known, for example, from EP 0119487, WO 00/58317 and EP 1183220 as urease inhibitors.

Examples of compounds of the general formula (II) are, for example, phenylphosphimide (phenylphosphonodiamide).

Preference is given to formulations containing N-N-butyl thiophosphoric triamide (NBPT) as one of the active substances. The at least one further active substance is preferably a derivative selected from the group consisting of N-cyclohexyl phosphoric triamide, N-pentyl phosphoric triamide, N-isobutyl phosphoric triamide and N-propyl phosphoric triamide and the corresponding thiophosphoric triamides. Particularly preferred are formulations which contain NBPT in an amount of from 40 to 95% by weight, very particularly preferably from 60 to 80% by weight, based in each case on the total amount of active substance of component A.

Thiophosphoric triamides are known to be relatively susceptible to hydrolysis to the corresponding phosphoric triamides. Since moisture is usually not completely excluded, thiophosphoric triamides and the corresponding phosphoric triamides are often present in a mixture with one another. The term "(thio) phosphoric triamide" in this context therefore refers both to the pure thiophosphoric triamide or to the phosphoric triamide and to mixtures thereof.

Particular preference is given to N-alkylthiophosphoric triamides (where X ═ S and R²H) and N-alkylphosphoric triamides (wherein X ═ O and R²＝H)。

The preparation of such urease inhibitors can be carried out, for example, in a known manner starting from thiophosphoryl chloride, primary or secondary amines and ammonia, as described in U.S. Pat. No. 4,5,770,771. Wherein thiophosphoryl chloride is reacted with an equivalent of a primary or secondary amine in the presence of a base in a first step, followed by reaction of the product with an excess of ammonia to the final product.

Further suitable urease inhibitors are described, for example, in WO 00/61522, WO 00/58317, WO 02/083697, WO 01/87898, WO 2006/010389. The compounds mentioned therein are, for example, thiophosphoric triamides, heterocyclic-substituted (thio) phosphoric triamides, N- (2-pyrimidinyl) (thio) phosphoric triamides and N-phenyl phosphoric triamides.

A mixture of N- (N-butyl) thiophosphoric triamide and N- (N-propyl) thiophosphoric triamide is described in particular in EP-A-1820788.

According to the invention, it is particularly preferred to use these mixtures in addition to the individual substances.

The (thio) phosphoric acid triamides of the formula (I) or (thio) phosphoric acid diamides of the formula (II) used as component A can be pure substances or mixtures of two or more pure substances. Depending on the synthesis conditions, it may also contain by-products from the synthesis of the active substances. Typically, this component a is present in at least 70% purity.

The mixtures according to the invention may contain only components A and B. For example, optionally component B can be used as a solvent for component A, so that a liquid or readily meltable composition is formed. Solid mixtures of components A and B as well as mixtures in the form of emulsions or dispersions can also be used according to the invention.

According to one embodiment of the invention, the mixture may also contain a solvent for the (thio) phosphoric triamide as component C. In this case, all suitable solvents can be used. As solvents, compounds which are polar and thus have sufficient dissolving power for component A are generally used. These compounds should preferably have a sufficiently high boiling point so that no significant evaporation of the solvent is taken into account when applying them. Suitable solvents are, for example, alcohols, amines, carboxylic acid derivatives such as esters, amides, urea derivatives, halogenated compounds, substituted aromatic compounds and mixtures thereof. Suitable solvents are described, for example, in EP-A-1820788. Suitable solvents are water, alcohols, glycols and NMP or dimethyl phthalate. Examples of suitable liquid formulations are listed in WO 07/22568. Solvents based on glycols or glycol derivatives are described. Examples of suitable diols are propylene glycol and dipropylene glycol. The diol can be generally described as a terminal C_2-10-an alkylene glycol. Examples of further diols are neopentyl glycol, pinacol, 2-diethyl-1, 3-propanediol, 2-ethyl-1, 3-hexanediol, hexane,2-ethyl-2-butyl-1, 3-propanediol, iso-butylene glycol, 2, 3-dimethyl-1, 3-propanediol, 1, 3-diphenyl-1, 3-propanediol, 3-methyl-1, 3-butanediol. Examples of cyclic diols are 1, 4-cyclohexanedimethanol and p-xylylene glycol. Examples of polyglycols are polyethylene glycol and polypropylene glycol. Suitable derivatives may be esters such as stearates or octanoates. For example, glycerol or glycerol esters may also be used. Other suitable additional solvents may be liquid amides, 2-pyrrolidones and N-alkyl-2-pyrrolidones such as NMP.

Dimethyl phthalate is particularly preferably used as solvent.

Alternatively, solid formulations can also be used which, in addition to the mixture, can contain additives such as fillers, binders or granulation auxiliaries such as lime, gypsum, silica or kaolin. The mixtures according to the invention can contain, in addition to components A and B, both solvents or solvent mixtures and additives and can be present as suspensions.

According to the invention, the polymer can be contained in the mixture in dissolved or dispersed form as an additional component D. Such polymers are preferably polymers which do not react chemically with components A and B. The polymer may be present in solution, emulsion or dispersion form. Preferably, a dissolved polymer is used, preferably having a number average molecular weight of at least 5000. Suitable polymers may be derived from vinylic monomers, such as from styrene or (meth) acrylates or acrylonitrile. For example, dissolved polystyrene-acrylonitrile polymers or such polymers containing grafted rubber may be used. In addition, for example, polyesters or polyalkylene glycols can be used. The stabilization of the urease inhibitors of component A can be improved again by adding the polymer. The polymer may also be used to delay the release of the mixture in a "controlled release" manner. The components are preferably contained in the mixture in the following amounts.

The content of component A urease inhibitors is preferably 5 to 90% by weight, particularly preferably 10 to 40% by weight, in particular 15 to 30% by weight. The amine content of component B is preferably from 1 to 50% by weight, particularly preferably from 2 to 25% by weight, in particular from 3 to 15% by weight. If a solvent is also used as component C, the content of the solvent in the mixture is preferably from 10 to 94% by weight, particularly preferably from 20 to 88% by weight, in particular from 30 to 82% by weight. The amount of optional polymer component D is preferably from 0 to 70% by weight, particularly preferably from 0 to 50% by weight, in particular from 0 to 25% by weight. When component D is present, this amount is preferably from 0.5 to 70% by weight, particularly preferably from 1 to 50% by weight, in particular from 2 to 25% by weight. Wherein the total amount of component A, B, C and optional D is 100% by weight.

The mixture of the present invention can be prepared by simply mixing component A, B and optionally C and D. The mixing may also be carried out at elevated temperatures, for example 30-60 ℃. The order of addition of the components is arbitrary. When a solvent is used in combination, it is common to first dissolve components A and B in the solvent and then introduce component D polymer. Component A is preferably added last, as long as it is necessary to heat the mixture during preparation.

The mixtures according to the invention are used as additives or coating agents for urea-containing nitrogen fertilizers.

As an additive, it can be broadcast before, after or together with the urea-containing nitrogen fertilizer. The mixture according to the invention can be metered separately from the urea-containing nitrogen fertilizer. The mixtures according to the invention are often introduced into urea-containing nitrogen fertilizers, for example applied to the urea-containing nitrogen fertilizers in the melt or as coating agents. When used together as an additive for urea-containing fertilizers, the amount of the mixture according to the invention is preferably from 0.1 to 30% by weight, based on the weight of the nitrogen fertilizer.

In parallel with improving the nitrogen utilization of urea-containing inorganic and organic fertilizers, sometimes significantly increased yield of crop plants or biomass production is achieved by using the formulation.

At the same time, the mixture of the invention can be added to organic fertilizers, such as manure pits, during storage to avoid nitrogen-nutrient losses by preventing the conversion of the respective nitrogen forms into gaseous and thus volatile nitrogen compounds and thereby simultaneously reduce the ammonia burden in the animal stalls.

The mixtures of the invention have surprising biological effectiveness. In particular, very high yield growth rates.

It does not matter whether the formulation of the invention is, for example, fused into the fertilizer or applied to the fertilizer surface, or applied separately from the fertilizer broadcast, for example as a (suspension) concentrate, solution or formulation.

It is particularly preferred according to the invention that the mixture according to the invention is used as a coating agent for urea-containing nitrogen fertilizers.

The invention also relates to a urea-comprising fertilizer which comprises a mixture as described above in such an amount that the total content of component A is 0.001 to 0.5% by weight, based on the urea present. The content of component A is particularly preferably from 0.01 to 0.3% by weight, in particular from 0.02 to 0.2% by weight, based on the urea present. In urea containing fertilizers, the mixture is preferably applied to the surface of a urea containing fertilizer.

Urea-comprising fertilizers first mean urea itself. Depending on the usual quality of the fertilizer on the market, the purity is at least 90%, and may be present, for example, in the form of crystals, granules, compacts, pellets or ground. In addition, mixtures of urea with one or more other nitrogen fertilizers, such as ammonium sulfate, ammonium nitrate, ammonium chloride, cyanamide, dicyanamide (DCD) or calcium nitrate, and with slow-release fertilizers, such as urea-formaldehyde condensates, urea-acetaldehyde condensates or urea-glyoxal condensates, should also be included. Also included are urea-containing multi-nutrient fertilizers which, in addition to containing nitrogen, contain at least one other nutrient such as phosphorus, potassium, magnesium, calcium or sulfur. In addition, trace elements such as boron, iron, copper, zinc, manganese or molybdenum can be contained. Such urea-containing multi-nutrient fertilizers may also be granulated, compacted, pelletized, ground or present as a mixture of crystals. Also included are liquid urea-containing fertilizers, such as ammonium nitrate-urea solutions or manure liquors. The urea-containing fertilizer may also contain 0.01-20% by weight of one or more other substances such as nitrification inhibitors, herbicides, bactericides, insecticides, growth regulators, hormones, pheromones or other plant protection agents as soil aids.

The fertilizer of the invention can be prepared by the following steps: the liquid or solid mixtures according to the invention are mixed with or granulated, compacted or pelletized into urea-containing fertilizers, wherein they are added to the respective fertilizer mixture or to the slurry or melt. It is particularly preferred to apply the mixture according to the invention to the surface of the ready-made urea-comprising granules, compacts or pellets, for example by spraying, dusting or dipping. This can also be achieved with the use of other auxiliary agents, such as adhesion agents or coating materials. Suitable devices for applying the application are, for example, trays, drums, mixers or fluidized bed devices, which can also be applied on a conveyor belt or at the discharge point thereof or by means of a pneumatic solids conveyor. It may also be treated last with an anti-caking agent (Antipermit) and/or a dust-proofing agent. The fertilizer or mixture of the invention can be used when fertilizing with a urea-containing fertilizer. Preferably on agricultural or horticultural land.

The invention will be illustrated by the following examples.

Examples

In the following examples, abbreviations have the following meanings:

NBPT N- (N-butyl) -thiophosphoric triamide

NPPT N- (N-propyl) -thiophosphoric triamide

NMP N-methyl-pyrrolidone

MDEA methyldiethanolamine

KAS ammonium calcium nitrate

Examples 1 and 2 relate to the storage stability of the active substance on the fertilizer treated according to the invention, and example 3 relates to the plant compatibility of the mixture according to the invention.

Example 1:

the following NBPT-loss (analyzed by HPLC) was determined in a 60-day storage experiment at 30 ℃ and 60% air humidity. At the start of the storage experiment, the NBPT was applied in a concentration of 0.12 wt% in solution, calculated as fertilizer, as follows. Granulated urea was used as a carrier fertilizer.

Example 2:

the following NBPT-loss (analyzed by HPLC) was determined in another storage experiment at 30 ℃ and 60% air humidity for 30 days. At the start of the storage experiment, the NBPT was applied in a concentration of 0.12 wt% in solution, calculated as fertilizer, as follows. Granulated urea was used as a carrier fertilizer.

Example 3:

plant cultivation experiments in a greenhouse in 12 plastic pots showed the plant compatibility of methyldiethanolamine, dimethyl phthalate with urea or, as a comparison, ammonium calcium nitrate. Limburgerhof soil (slightly fertile sand, pH 6.8) was used as a test crop. The soil has the following characteristics, measured according to the CAL method:

P₂O₅35mg/100g soil

K₂O18 mg/100g soil

Mg 5Mg/100g soil

Pulpable component: clay is less than 2 mu m 7%

＜20μm 17％

76 percent of sand

Total nitrogen: 0.08 percent

Humus: 1.2 percent of

The fertilizer is mixed into the soil one day before planting. Similar results occur in the case of fertilizer applied to the soil (not shown). In both cases the container is watered from above with tap water at horticulture.

MDEA ═ methyldiethanolamine

Claims (8)

1. A mixture for treating a urea-comprising fertilizer, the mixture comprising:

a) at least one (thio) phosphoric triamide of the formula (I) and/or (thio) phosphoric diamide of the formula (II) as component A,

R¹R²N-P(X)(NH₂)₂ (I)

R¹O-P(X)(NH₂)₂ (II)

has the following meanings:

x is oxygen or sulfur

R¹And R²Each independently of the others being hydrogen, in each case substituted or unsubstituted 2-nitrophenyl, C_1-10Alkyl radical, C_3-10-cycloalkyl, C_3-10-heterocycloalkyl radical, C_6-10-aryl, C_6-10-heteroaryl or diaminocarbonyl, wherein R¹And R²Can also form, together with the nitrogen atom to which they are bound, a 5-or 6-membered, saturated or unsaturated heterocyclic radical which can optionally also contain one or two further heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur,

b) as component B at least one amine selected from the group consisting of methyldiethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N, N, N ', N ' -tetramethyl-1, 6-hexanediamine, N, N ', N ' -tris (dimethylaminopropyl) hexahydrotriazine, 2 ' -dimorpholinyldiethylether or mixtures thereof,

component B is used in an amount of at least 0.2 times the molar amount of component A.

2. The mixture according to claim 1, wherein X is S and R is²H and/or wherein X is O and R²N-alkyl phosphoric triamides of ═ H as (thio) phosphoric triamides of general formula (I).

3. The mixture according to any one of claims 1 to 2, comprising:

5 to 90 wt.% of component A,

1 to 50 wt.% of component B,

0% or 10 to 94% by weight of a solvent for the (thio) phosphoric triamide as component C,

0 to 70% by weight of a polymer in dissolved or dispersed form as component D,

the total amount of components A to D is 100% by weight

4. Use of the mixture according to any of claims 1 to 3 as an additive or coating agent for urea-containing nitrogen fertilizers.

5. Use according to claim 4, characterized in that the mixture is sown separately from or simultaneously with the fertilizer in the form of a formulation, solution or dispersion, or is mixed into the fertilizer, or is applied to the fertilizer.

6. Use of the mixture according to any of claims 1 to 3 for reducing nitrogen loss in organic fertilizers or during storage in manure pits and for reducing ammonia load in animal stalls.

7. A urea-comprising fertilizer comprising the mixture of one of claims 1 to 3 in the following amounts: so that the total content of component A is from 0.001 to 0.5% by weight, based on the urea present.

8. Urea-containing fertilizer according to claim 7, characterized in that the mixture is applied to the surface of the urea-containing fertilizer.