reaction products and methods for producing and using the same

专利摘要:
REACTION PRODUCTS AND METHODS TO PRODUCE AND USE THE SAMEReaction products and methods for producing and using them are provided.In at least one specific embodiment, the fertilizer may include a nitrogen source comprising urea, ammonia, ammonium nitrate, or any combination thereof and a formaldehyde reaction product, an ammonia source, and a nitrification inhibitor.
公开号:BR112012027904A2
申请号:R112012027904-1
申请日:2011-04-29
公开日:2020-08-25
发明作者:Kurt D. Gabrielson；Mary L. Epling
申请人:Koch Agronomic Services, Llc；
IPC主号:

专利说明:

“REACTION PRODUCTS AND METHODS TO PRODUCE AND USE THE SAME” Cross Reference to Related Orders This order claims priority to US Provisional Patent Applications having the serial number 61/329, 680, filed April 30, 2010, which is incorporated by reference here Background of the Invention Field Modalities described here generally refer to fertilizers. More particularly, such modalities refer to reaction products that provide an extended period of nitrication inhibitor and methods for producing and using the same.
Description of the Related Art Fertilizers typically include urea, ammonia, ammonium nitrate, or a mixture of them to provide a source of nitrogen. Nitrogen is a vital nutrient for plant growth. When urea is used as a nitrogen source in the fertilizer, aurea converts ammonia as a result of hydrolysis catalyzed by urease, which is an enzyme produced by numerous fungi and bacteria found in the soil. Ammonia rapidly undergoes ionization in the soil to form ammonium. In most soils, the resulting ammonium and ammonium nitrate, if present, are easily oxidized to nitrate (NO3), through a sequence of bacterial oxidation reactions, which is generally referred to as "nitrification". Ammonia nitrification, however, happens so fast that a large percentage of nitrogen in the fertilizer is lost before plants can use it.
Nitrogen is also lost from the soil through volatilization to the atmosphere. Nitrate, another source of nitrogen, is normally lost by leaching underground with rainwater and / or through denitrification, that is, the bacterial conversion of nitrate to elementary nitrogen.
Attempts to reduce such nitrogen losses have used urease inhibitors and / or nitrification inhibitors as additives to the fertilizer. Urease inhibitors are compounds capable of inhibiting the catalytic activity of the urease enzyme in urea in the soil. Nitrification inhibitors are compounds capable of inhibiting bacterial oxidation of ammonium to nitrate in the soil. Nitrification inhibitors, however, tend to leach into the soil, outside the plant, thereby becoming ineffective in inhibiting nitrification where it is needed, close to the plant.
There is a need, therefore, for improved fertilizers that provides an extended period of nitrification inhibition and methods for producing and using it. There is also a need for improved products that reduce nitrification in the soil and methods for producing and using it.
Summary of the Invention
In at least one specific embodiment, the fertilizer may include a nitrogen source comprising urea, ammonia, ammonium nitrate, or any combination of these and a formaldehyde reaction product, an ammonia source, and a nitrification inhibitor .
In at least one other specific embodiment, the fertilizer may include a nitrogen source comprising urea, ammonia, ammonium nitrate, or any combination of these and a product of the formaldehyde reaction, urea, an ammonia source, and an inhibitor nitrification pain.
In at least one specific embodiment, the method for producing the fertilizer may include reacting formaldehyde, a source of ammonia, and a nitrification inhibitor under conditions sufficient to produce a reaction product. The reaction product can be combined with a nitrogen source to produce the fertilizer. The nitrogen source may include, but is not limited to, urea, ammonia, ammonium nitrate, or any combination of these.
In at least one specific embodiment, the method for reducing nitrification in the soil may include reacting formaldehyde, a source of ammonia, and a nitrification inhibitor under conditions sufficient to produce a reaction product. The reaction product can be applied to a soil.
Detailed Description of the Invention The fertilizer can be or include a mixture of one or more nitrogen sources and a reaction product of any one of three or more of the following: formaldehyde, an ammonia source, a nitrification inhibitor, urea, and a urease inhibitor. For example, the fertilizer may be or include a mixture of one or more nitrogen sources and a formaldehyde reaction product, an ammonia source, and a nitrification inhibitor. The fertilizer may also be or include a mixture of one or more sources of nitrogen and a product of the formaldehyde reaction, a source of ammonia, a nitrification inhibitor and urea. The fertilizer can also be or include a mixture of one or more nitrogen sources and a formaldehyde reaction product, an ammonia source, a nitrification inhibitor, urea, and a urease inhibitor. The fertilizer can also be or include a mixture of one or more nitrogen sources and a formaldehyde reaction product, an ammonia source, a nitrification inhibitor, and a urease inhibitor. The fertilizer may also be or include a mixture of one or more sources of nitrogen and a product of the formaldehyde reaction, a source of ammonia, urea, and a urease inhibitor. The fertilizer may also be or include a mixture of one or more sources of nitrogen, one or more urease inhibitors, and one - a reaction product of any three or more of the following: formaldehyde, an ammonia source, an inhibitor of nitrification and urea.
The nitrogen source may include, but is not limited to, urea, ammonium nitrate,
anhydrous ammonia, aqueous ammonia, formaldehyde polymers, urea, or any combination of these. The nitrogen source can be a solid, liquid, gas, or any combination of these. Illustrative solid nitrogen sources can be in the form of pellets, granules, flakes, granules, and so on. Illustrative sources of liquid nitrogen can be aqueous and / or liquid solutions from one or more nitrogen sources. The nitrogen source can be rapid release nitrogen, controlled release nitrogen, or a combination of these. As used herein, the term "quick release nitrogen" refers to free urea, ammonium nitrate, anhydrous ammonia, aqueous ammonia, or any combination thereof. As used herein, the term "controlled release nitrogen" refers to substituted urea, reacted urea, for example, formaldehyde polymer, urea, or a combination thereof. The term "controlled nitrogen release" can also refer to a nitrogen containing material that shelters more slowly than urea in the soil for available plant nutrient ammonium and nitrate than a reference quick release nitrogen source. Another suitable source of nitrogen may be or include animal waste, such as urine and / or manure produced by one or more animals, for example, cows, sheep, chickens, turkeys, buffaloes, goats, pigs, horses, and the like.
As used herein, the term "nitrification inhibitor" refers to any compound (s) that reduces, inhibits, or otherwise slows the conversion of ammonium (NH, ”*) to nitrate in the soil when present in comparison with the conversion of ammonium (NH, ”*) to nitrate in soil when not present.
Illustrative nitrification inhibitors may include, but are not limited to, 2-chloro-6-trichloromethyl-pyridine, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, diciandiamide, 2-amino-4-chloro-6 -methyl-pyrimidine, 1,3-benzothiazol-2-thiol, 4-amino-N-1,3-thiazol-2-ylbenzenesulfonamide, thiourea, guanidine, 3,4-dimethylpyrazole phosphate, 2,4-diamino-6- trichloromethyl-o-triazine, polyetherionophores, 4-amino-1,2,4-triazole, 3-mercapto-1,2,4- (complete sentence on page 3 of the original) dithiocarbamate, 2,3, dihydro-2 , 2-dimethyl-7-benzofuranol methyl-carbamate, N- (2,6-dimethylphenyl) -N- (methoxyacetyl) -alanine methyl ester, ammonium thiosulfate, 1-hydroxypyrazole, 2-methylpyrazole-1-carboxamide, derivatives thereof, and any combination thereof. In at least one example, the nitrification inhibitor can be or include dicyandiamide (DCD). For example, 1-hydroxypyrazole can be considered as a 2-methylpyrazole-1-carboxamide derivative and ammonium dithiocarbamate can be considered a methyl carbamate derivative.
As used herein, the term "urease inhibitor" refers to any compound (s) that reduces, inhibits, or otherwise reduces the rate of conversion of urea to ammonia - (NHY) in the soil. Illustrative urease inhibitors may include, but are not limited to, N- (n-butiDthiophosphoric triamide, N- (n-butyl) phosphoric triamide, thiophosphoryl triamide, phenyl phosphorodiamidate, cyclohexyl phosphoric triamide, cyclohexyl triphosphoric triamide, phosphoric triamide, hydroxy phosphoramide triamide
na, p-benzoquinone, hexamidocyclotriphosphazene, thiopyridines, thiopyrimidines, thiopyridine-N-oxides, N, N-dihalo-2-imidazolidinone, N-halo-2-oxazolidinone, derivatives thereof, or any combination thereof. In at least one example, the urease inhibitor can be or include N- (n-butiNthiophosphoric triamide (NBPT).
Formaldehyde can be used in many ways. For example, parafform (solid, polymerized formaldehyde) and / or formalin solutions (aqueous formaldehyde solution, sometimes with methanol, in about 10% by weight, about 20% by weight, about 37% by weight , about 44% by weight, or about 50% by weight based on the weight of the formalin solution) forms are commonly used. For example, formaldehyde can be an aqueous solution having a concentration of formaldehyde ranging from about 10% by weight to about 50% by weight, based on the total weight of the aqueous solution. Formaldehyde gas can also be used. Formaldehyde substituted in part or in whole with substituted aldehydes such as acetaldehyde and / or propylaldehyde can be used as the source of formaldehyde. One or more other aldehydes, such as glyoxal, can be used in place of or in combination with formaldehyde. Any of these forms of formaldehyde sources can be used alone or in any combination to prepare the reaction product.
Urea can also be used in many ways. For example, urea can be a solid in the form of granules, flakes, granules, and the like, and / or a solution, such as an aqueous solution. In addition, urea can be combined with another portion, for example, formaldehyde and / or adducts of formaldehyde, urea, often in aqueous solution.
As noted above, (incomplete phrase on page 4 of the original) at least a portion of the urea, when present, may be in the form of animal waste. Any form of urea or urea in combination with formaldehyde can be used to make a urea-formaldehyde polymer. Both urea granules and combined urea-formaldehyde products can be used. Illustrative urea-formaldehyde products may include, but are not limited to, Urea-Formaldehyde Concentrate ("UFC"). These types of products can be as discussed and described in U.S. Patent Nos. 5,362,842 and 5,389,716, for example. Any of these sources of urea can be used alone or in - any combination to prepare the reaction product.
As used here, the term "ammonia source" refers to ammonia or any ammonium compound (s) that release ammonia when reacted with formaldehyde and nitrification inhibitor. Illustrative sources of ammonia may include, but are not limited to, ammonium salts such as ammonium chloride and ammonium nitrate, aqueous ammonia or ammonium hydroxide, anhydrous ammonia, or combinations thereof. Suitable aqueous ammonium solutions can have an ammonia concentration of about 28% by weight, about 30% by weight, about 32% by weight, or about 35% by weight, for example. Other suitable sources of ammonia may include, but are not limited to, primary amines or substituted primary amines, such as methyl amine, monomethanol amine, amino propanol, or any combination thereof.
Diffunctional amines, such as ethylene diamine, or any combination of organic amines, as long as a primary amine group is available to form a triazone ring can be used.
Another source of ammonia can be in the form of animal waste, such as urine and / or manure.
Any of these ammonia sources can be used alone or in any combination to prepare the reaction product.
And the ammonia source can be used in any form such as a solid, liquid and / or gas.
Preparation of the Reaction Product under Acid Conditions The reaction product can be produced under acid reaction conditions.
For example, the reaction product can be produced by reacting formaldehyde, the source of ammonia, for example, ammonium chloride, and the nitrification inhibitor, for example, dicyandiamide, under acidic reaction conditions at a pH lower than that 7. For example, acidic reaction conditions can be at a pH ranging from a minimum of about 2.5, about 3, about 3.5, about 4, or about 4 , 5 to a maximum of about 5.5, about 6, about 6.5, or about 6.9. The reaction product produced under the acid reaction conditions can be prepared by combining, mixing, or otherwise by contacting the reaction components (formaldehyde, the ammonium source, and the nitrification inhibitor, and optionally urea, the urease inhibitor, or (incomplete phrase on page 5 of the original) a mixture of formaldehyde, the source of ammonia, and the nitrification inhibitor produced under the acid reaction conditions may have a pH ranging from a minimum of about 3, about 3.5, about 4, or about 4.5 to a maximum of about 5.5, about 6, or about 6.5. Similarly, the reaction mixture formaldehyde, the source of ammonia, the nitrification inhibitor, and urea and / or the urease inhibitor produced under acid reaction conditions can also have a pH ranging from a minimum of about 3, to about 3, 5, about 4, or about 4.5 to a maximum of about 5.5, about 6, or about 6.5 The heat of the exothermic reaction it may be allowed to heat the reaction mixture to a temperature ranging from a minimum of about 50 ° C, about 60 ° C, or about 65 ° C and a maximum of about 75 ° C, about 80 ° C, about 90 ° C, or around 100ºC.
The reaction mixture can be maintained at an elevated temperature, for example, from about 50 ° C to about 95 ° C for a time ranging from about 1 minute to about 2 hours.
The resulting reaction mixture can then be cooled, for example, to room temperature, to provide the reaction product.
The reaction components (formaldehyde, the ammonia source, nitrification inhibitor, and the optional urea and / or urease inhibitor) can be combined with one another in any
either order or sequence.
For example, formaldehyde and nitrification inhibitor can first be combined to form a first mixture and the ammonia source can then be added to the first mixture to produce a second mixture.
In another example, formaldehyde and the ammonia source can be combined to produce a first mixture, and then the nitrification inhibitor can be added to the first mixture to produce the second mixture.
In yet another example, the ammonia source and nitrification inhibitor can be combined to produce a first mixture and formaldehyde can be added to the first mixture to produce the second mixture.
However in another example, formaldehyde, the source of ammonia, and nitrification inhibitor can be combined together at the same time, to produce a mixture.
The addition of urea and / or the urease inhibitor, if present, can similarly be combined in any order or sequence to produce the reaction mixture.
If the components of the reaction are combined such that greater than one mixture is formed, for example, a first mixture and a second mixture, the first mixture can be at least partially reacted before forming the second mixture.
Additional details for reacting formaldehyde, a source of ammonia, and dicyandiamide, under acidic conditions may be similar to those discussed and described in the U.S. Patent
Nos 3,015,649; 3,639,646 and 4,000,184. Before the reaction, during the reaction, and / or after the reaction between the reaction components (formaldehyde, ammonia source, and nitrification inhibitor, and optionally, urea and / or urease inhibitor), one or more acidic compounds can be added to lower the pH of the reaction mixture and / or the reaction product.
Illustrative acids can include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or any combination of these.
The reaction product produced under acidic reaction conditions may have a pH less than about 7. For example, the formaldehyde reaction product, the ammonia source, and the nitrification inhibitor produced under acidic reaction conditions can have a pH ranging from a minimum of about 3, to about 3.5, about 4, or about 4.5 to a maximum of about 5.5, about 6, or about 6.5. Similarly, the product of the formaldehyde reaction, the source of ammonia, the nitrification inhibitor, and urea and / or the urease inhibitor produced under the conditions of acid reactions may also have a pH ranging from a minimum of about 3 to about 3.5, about 4, or about 4.5 to a maximum of about 5.5, about 6, or about 6.5. Preparation of the Reaction Product under Basic Conditions The reaction product can be produced under basic or alkaline reaction conditions.
For example, the reaction product can be produced by reaction formaldehyde, the ammonia source, for example, ammonium hydroxide, the nitrification inhibitor, for example, dicyandiamide, and optionally urea and / or the urease inhibitor under basic reactions at a pH greater than 7. For example, basic reaction conditions can be at a pH ranging from a minimum of about 7, about 7.5, about 8, about 8 , 5, or about 9 to a maximum of about 9.5, about 10, about 10.5, or about 11.
The reaction product produced under the basic reaction conditions can be prepared by combining, mixing, or otherwise by contacting the reaction components (formaldehyde, the ammonium source, and the nitrification inhibitor, and optionally urea, the urease, or both) to produce a reaction mixture having a pH greater than about 7. For example, the formaldehyde reaction mixture, the ammonia source, and the —nitrification inhibitor under basic reaction conditions can have a pH ranging from a minimum of about 8, about 8.5, or about 9 to a maximum of about 9.5, about 10, about 10.5, or about 11. Similarly , the formaldehyde reaction mixture, the ammonia source, the nitrification inhibitor, and urea and / or the urease inhibitor under the basic reaction conditions can also have a pH ranging from a minimum of about 8 to about 38 , 5, or about 9 to a maximum of about 9.5, about 10, about 10.5, or about 11. The ca exothermic reaction can be allowed to heat the reaction mixture to a temperature ranging from a minimum of about 50 ° C, about 60 ° C, or about 65 ° C and a maximum of about 80 ° C, about 90 ° C, or around 100ºC. The reaction mixture can be kept at an elevated temperature, for example, from about 50 ° C to about 90 ° C for a time ranging from about 1 minute to about 3 hours. The resulting reaction mixture can then be resired, for example, at room temperature to provide the reaction product. The reaction components (formaldehyde, ammonia source, nitrification inhibitor, and optional urea and / or urease inhibitor) can be combined with one another in any order or sequence. For example, formaldehyde and a first portion of the ammonia source can be combined to produce a first mixture. The first mixture can be at least partially reacted. The nitrification inhibitor can then be added to the first mixture or at least partially reacted to the first mixture to produce a second mixture. The second mixture can be at least partially reacted. A second portion of the ammonia source can then be added to the second mixture or at least partially reacted to the second mixture to produce a third mixture. The third mixture can be at least partially reacted to produce the reaction product. The temperature of the first mixture and the second mixture can be maintained at a temperature ranging from about 25 ° C to about 70 ° C. The temperature of the third mixture can vary from about 60ºC to - about 90ºC and can be carried out at an elevated temperature, for example, from about 75ºC to about 90ºC, for a period of time ranging from about 5 minutes to about 3 hours.
In another example, formaldehyde and a first portion of the ammonia source can be combined to form a first mixture. The first mixture can be at least partially reacted. The nitrification inhibitor can then be added to the first mixture or at least partially reacted to the first mixture to produce a second mixture.
The second mixture can be at least partially reacted. Urea can then be added to the second mixture or at least partially reacted to the second mixture to produce a third mixture. The third mixture can be at least partially reacted. A second portion of the ammonia source can be added to the third mixture to produce a fourth mixture. The fourth mixture can be at least partially reacted to produce the reaction product of formaldehyde, urea, ammonia, and the nitrification inhibitor. The temperature of the first mixture, second mixture, and third mixture can be maintained at a temperature ranging from about 25 ° C to about 70 ° C. The temperature of the fourth mixture can vary from about 60 ° C to about 90 ° C and can be carried out at an increasing temperature, for a period of time ranging from about 5 minutes to about 3 am.
The addition of the urease inhibitor, if present, can similarly be combined in any order or sequence to produce another reaction mixture or can be combined with the first, second, third and / or fourth reaction mixture. In another example, the components of the reaction (formaldehyde, ammonia source, and nitrification inhibitor, and optional urea and / or urease inhibitor) can be simultaneously combined together with a single reaction mixture. However in another example, formaldehyde and nitrification inhibitor, and, if present, urea, and / or urease inhibitor can be combined to provide a first mixture and the ammonia source can then be added to the first mixture to produce a second mixture. The second mixture can then be reacted to produce the reaction product.
Exothermic heat generated from the first mixture, second mixture, third mixture, fourth mixture, or any number of mixtures, can be used, at least in part, as the heat source for heating any or more of the reaction mixtures .
In another example, heat can be introduced into any one or more of the reaction mixtures to provide a heated reaction mixture by means of a heating coil or other heat exchange device or system. The temperature of the reaction mixtures can be kept below a maximum desired temperature, for example, 100ºC, by means of a cooling coil or other heat exchange device or system.
One or more base or base compounds can be added before and / or during the reaction to any one or more of the reaction mixtures and / or the reaction product to maintain and / or adjust their pH. For example, the reaction product produced under basic reaction conditions can be maintained at a pH of about 8 to about 11 during the reaction and / or for the final reaction product. Illustrative basic compounds suitable for adjusting the pH of the reaction product may include, but are not limited to, ammonia, amines, for example, primary, secondary, and tertiary amines and polyamines, sodium hydroxide (NaOH), potassium hydroxide (KOH), or any combination thereof. An aqueous-based solution can have any concentration. For example, an aqueous solution of sodium hydroxide, potassium hydroxide, or a combination thereof, having a concentration ranging from a minimum of about 5% by weight to about 10% by weight, or about 15% by weight and a maximum of about 25% by weight, about 50% by weight, or about 75% by weight can be introduced into one or more of the reaction mixtures and / or the reaction product in order to adjust and / or maintain the pH of about 8 and about 11.
In another example, one or more pH buffering compounds, which can buffer the pH of the reaction mixture to a desired pH, can be added at the start of the reaction. (incomplete phrase on page 9 of the original) sodium borate, potassium bicarbonate, sodium carbonate, potassium carbonate, or any combination of these. In another example, one or more pH buffering compounds can be used in conjunction with one or more base compounds to adjust and / or maintain a desired pH of the reaction mixture.
The reaction product produced under the basic reaction conditions may have a pH greater than 7. For example, the formaldehyde reaction product, the ammonia source, and the nitrification inhibitor produced under the basic reaction conditions may have a pH ranging from a minimum of about 8, about 8.5, or about 9 to a maximum of about 9.5, about 10, about 10.5, or about 11. Similarly, the formaldehyde reaction product, the ammonia source, the nitrification inhibitor, and the urea and / or urease inhibitor produced under the basic reaction conditions may also have a pH ranging from a minimum of about 8, about 8.5, or about 9 to a maximum of about 9.5, about 10, about 10.5, or about 11.
Additional details for reaction of formaldehyde, urea, and a source of ammonia, under basic conditions are discussed and described in U.S. Patent Nos. 6,632,262 and 7,513,928 and U.S. Patent Application Publication No. 2006/0196241.
The reaction product produced through acidic conditions or basic conditions can include one or more other additives. For example, ethylene diamine can be added to the reaction product and / or to an intermediate mixture formed during the production of the same. Ethylene diamine can help adjust, control and / or maintain the water solubility of the reaction product. Other chelating agents include ethylenediaminetetraacetic acid (EDTA), diethylenetriaminopentacetic acid (DPTA),
Ní (hydroxyethyl) ethylenediaminetriacetico (HEDTA), nitrilotriacético acid (NTA), along with a wide range of conjugated bases for the previously listed acids. Suitable commercially available suspension additives may include, for example, K-Tionic, which is manufactured and distributed by GBS Biosciences, LLC. The reaction product of the formaldehyde reaction, the ammonia source, and the nitrification inhibitor under acidic conditions can include from about 30 mol% to about 70 mol% formaldehyde, from about 5% to about 25 mol% of ammonia, and about 15 mol% and about 45 mol% of nitrification inhibitor, based on the total weight of formaldehyde, ammonia, and nitrification inhibitor. Formaldehyde can be present in an amount ranging from a minimum of about 35 mol%, about 40 mol%, or about 45 mol% and a maximum of about 50 mol%, about 60 mol%, or about 65 mol%, based on the total weight of formaldehyde, ammonia, (incomplete phrase on page 10 of the original) to about 7 mol%, about 10 mol%, or about 12 mol% and a maximum of about 15 mol%, about 18 mol%, or about 20 mol%, based on the total weight of formaldehyde, ammonia, and nitrication inhibitor . The nitrification inhibitor can be present in an amount ranging from a minimum of about 20 mol%, from about 25 mol%, or from about 30 mol% to a maximum of about 35 mol%, from about 40 mol%, or about 43 mol%, based on the total weight of formaldehyde, ammonia, and nitrification inhibitor.
The reaction product of the formaldehyde reaction, the ammonia source, and the nitrification inhibitor under basic conditions, can include from about 30 mol% to about 80 mol% formaldehyde, from about 10 mol% to about 35 mol% of ammonia, and from about 10 mol% to about 35 mol% of nitrification inhibitor, based on the total weight of formaldehyde, ammonia, and nitrification inhibitor. Formaldehyde can be present in an amount ranging from a minimum of about 33 mol%, from about 37 mol%, or from about 40 mol% to a maximum of about 60 mol%, from about 70 mol%, or about 75 mol%, based on the total weight of formaldehyde, ammonia, and nitrification inhibitor. Ammonia can be present in an amount ranging from a minimum of about 12 mol%, about 15 mol%, or about 20 mol% to a maximum of about 25 mol%, about 30 mol%, or about 33 mol%, based on the total weight of formaldehyde, ammonia, and nitrification inhibitor. The nitrification inhibitor can be present in an amount ranging from a minimum of about 12 mol%, from about 15 mol%, or from about 20 mol% to a maximum of about 25 mol%, from about 30 mol%, or about 33 mol%, based on the total weight of formaldehyde, ammonia, and nitrification inhibitor.
The reaction product of the formaldehyde reaction, urea, the source of ammonia, and the nitrification inhibitor under acidic conditions can range from about 30 mol% to about
70 mol% of formaldehyde, from about 5% to about 25 mol% of urea, from about 5% to about 25 mol% of ammonia, and from about 5 mol% to about 45% in mol of nitrification inhibitor, based on the total weight of formaldehyde, urea, ammonia, and nitrification inhibitor.
Formaldehyde can be present in an amount ranging from a minimum of about 35 mol%, about 40 mol%, or about 45 mol% and a maximum of about 50 mol%, about 60 mol%, or about 65 mol%, based on the total weight of formaldehyde, urea, ammonia, and nitrification inhibitor.
Urea can be present in an amount ranging from a minimum of about 8 mol%, about 10 mol%, or about 12 mol% and a maximum of about 18 mol%, about 22 mol%, or about 24 mol%, based on the total weight of formaldehyde, urea, ammonia, and nitrification inhibitor.
Ammonia can be present in an amount ranging from a minimum of about 7 mol%, about 10 mol%, or about 12 mol% and a maximum of about 15 mol%, about 18 mol%, or about 20 mol%, based on the total weight of formaldehyde, urea, ammonia, and nitrification inhibitor.
The nitrification inhibitor can be present in an amount ranging from a minimum of about 10 mol%, about 15 mol%, or about 20 mol% and a maximum of about 35 mol%, of about 40 mol%, or about 45 mol%, based on the total weight of formaldehyde, urea, ammonia, and nitrification inhibitor.
The reaction product of the formaldehyde reaction, urea, the ammonia source, and the nitrification inhibitor under basic conditions, can include from about 25 mol% to about 65 mol% formaldehyde, from about 10 mol% to about 25% urea, from about 5% to about 25 mol% of ammonia, and from about 5 mol% to about 25 mol% of nitrification inhibitor, based on weight total formaldehyde, urea, ammonia, and nitrification inhibitor.
Formaldehyde can be present in an amount ranging from a minimum of about 25 mol%, about 30 mol%, or about 35 mol% and a maximum of about 50 mol%, about 55 mol%, or about 60 mol%, based on the total weight of formaldehyde, urea, ammonia, and nitrification inhibitor.
Urea can be present in an amount ranging from a minimum of about 12 mol% to about 14 mol%, or from about 16 mol% to a maximum of about 18 mol%, from about 22 mol%, or about 25 mol%, based on the total weight of formaldehyde, urea, ammonia, and nitrification inhibitor.
Ammonia can be present in an amount ranging from a minimum of about 7 mol%, about 9 mol%, or about 12 mol% and a maximum of about 18 mol%, about 22 mol%, —around about 25 mol%, based on the total weight of formaldehyde, urea, ammonia, and nitrification inhibitor.
The nitrification inhibitor can be present in an amount ranging from a minimum of about 7 mol%, about 9 mol%, or about 12%
in mol and a maximum of about 18 mol%, about 22 mol%, or about 25 mol%, based on the total weight of urea formaldehyde, ammonia, and nitrification inhibitor.
The reaction product of the formaldehyde reaction, the ammonia source, and the nitrification inhibitor under acidic conditions can have a molar ratio of formaldehyde to ammonia ranging from about 1: 1 to about 9: 1, from about 1: 1 to about 8: 1, about 3: 1 to about 9: 1, about 4: 1 to about 8: 1, about 5: 1 to about 9: 1, or about 6: 1 to about 8: 1. Similarly, the formaldehyde reaction product, urea, the ammonia source, and the nitrification inhibitor and / or the formaldehyde reaction product, the ammonia source, the nitrification inhibitor, and the urease inhibitor under acidic conditions can have a formaldehyde to ammonia molar ratio ranging from about 1: 1 to about 9: 1, from about 1: 1 to about 8: 1, from about 3: 1 to about 9: 1, about from 4: 1 to about 8: 1, from about 5: 1 to about 9: 1, or from about 6: 1 to about 8: 1. The formaldehyde reaction product, the ammonia source, and the nitrification inhibitor under acidic conditions can have a molar ratio of formaldehyde to nitrification inhibitor ranging from about 1: 1 to about 4: 1, from about 1: 1 to about 3: 1, from about 1: 1 to about 2: 1, from about 1.5: 1 to about 2.5: 1, from about 1: 1 to about 2 .5: 1, from about 1.7: 1 to about 2.3: 1, or from about 1.8: 1 to about 2.2: 1. The formaldehyde reaction product, the ammonia source, the nitrification inhibitor, and the urease inhibitor under acidic conditions can have a molar ratio of formaldehyde to nitrification inhibitor ranging from about 1: 1 to about 4: 1, from about 1: 1 to about 2: 1, from about 1.5: 1 to about 2.5: 1, from about 1: 1 to about 2.5: 1, about 1.7: 1 to about 2.3: 1, or about 1.8: 1 to about 2.2: 1. The molar ratio of formaldehyde to the urease inhibitor in the product of the formaldehyde reaction, the ammonia source, the nitrification inhibitor, and the deurease inhibitor under acidic conditions can be the same or similar to the molar ratio of formaldehyde to the nitrification inhibitor. .
The reaction product of formaldehyde, urea, the source of ammonia, and the nitrification inhibitor under acidic conditions can have a molar ratio of formaldehyde to urea ranging from about 1: 1 to about 2: 1, from about 1: 1 to about 1.9: 1, about 1.1: 1 to about 1.8: 1, about 1.2: 1a about 1.7: 1, or about 1 , 3: 1 to about 2: 1. The reaction product of formaldehyde, urea, the source of ammonia, the nitrification inhibitor, and the urease inhibitor under acidic conditions can have a molar ratio of formaldehyde to urea ranging from about 1: 1 to about 2: 1, from about 1: 1 to about 1.9: 1, from about 1.1: 1 to about 1.8: 1, from about 1.2: 1 to about 1.7: 1, or from about 1.3: 1 to about
21.
The formaldehyde reaction product, the ammonia source, and the nitrification inhibitor under basic conditions, can have a molar ratio of formaldehyde to ammonia ranging from about 1: 1 to about 8: 1, from about 2: 1 about 6: 1, about 2.5: 1 to about 5: 1, about 3: 1 to about 4: 1, or about 2: 1 to about 4: 1. The reaction product of formaldehyde, urea, the source of ammonia, and the nitrification inhibitor under basic conditions, can have a molar ratio of formaldehyde to ammonia ranging from about 1: 1 to about 8: 1, about 2: 1 about 6: 1, from about 3: 1 to about 5: 1, or from about 3.5: 1 to about 4.5: 1. The reaction product of formaldehyde, urea, the ammonia source, the nitrification inhibitor, and the urease inhibitor under basic conditions, can have a molar ratio of formaldehyde to ammonia ranging from about 1: 1 to about 8: 1 from about 2: 1 to about 6: 1, from about 3: 1 to about 5: 1 or from about 3.5: 1 to about 4.5: 1.
The formaldehyde reaction product, the ammonia source, and the nitrification inhibitor, under basic conditions can have a molar ratio of formaldehyde to nitrification inhibitor ranging from about 1: 1 to about 7: 1, from about from 1.5: 1 to about 6.5: 1, from about 2: 1 to about 6: 1, from about 2.5: 1 to about 5: 1, from about 2: 1 to about 4: 1, or about 2.5: 1 to about 3.5: 1. The reaction product of formaldehyde, urea, the source of ammonia, and the nitrification inhibitor under basic conditions can have a molar ratio of formaldehyde to nitrification inhibitor ranging from about 1: 1 to about 8: 1, from about 1: 1 to about 7: 1, about 2: 1 to about 8: 1, about 3: 1 to about 7.5: 1, or about 3.5: 1 to about 7: 1.
The product of the formaldehyde reaction, the ammonia source, the nitrification inhibitor, and the urease inhibitor under basic conditions can have a molar ratio of formaldehyde to nitrification inhibitor ranging from about 1: 1 to about 7: 1, about from 1: 1 to about 5: 1, from about 1.5: 1 to about 4: 1, from about 2: 1 to about 4: 1, from about 2.5: 1 to about 3.5: 1, or from about 2.7: 1 to about 3.5: 1. The molar ratio of formaldehyde to the urease inhibitor in the product of the formaldehyde reaction, the ammonia source, the nitrication inhibitor, and the urease inhibitor under basic conditions can be the same or similar to the molar relationship of formaldehyde to the nitrification inhibitor.
The reaction product of formaldehyde, urea, the source of ammonia, and the nitrification inhibitor under basic conditions can have a molar ratio of formaldehyde to urea ranging from about 1: 1 to about 4: 1, from about 1.1: 1 to about 3.9: 1, from about 1: 1 to about 2: 1, about 1: 1 to about 1.5: 1, or about 1: 1 to about 1.3: 1. The reaction product of formaldehyde, urea, the source of ammonia, the nitrification inhibitor, and the urease inhibitor under basic conditions can have a molar ratio of formaldehyde to urea ranging from 1: 1 to about 4: 1 , from about 1.1: 1 to about 3.9: 1, from about 1: 1 to about 2: 1, from about 1: 1 to about 1.5: 1, or about 1: 1 to about 1.3: 1.
The reaction product can be produced by reacting formaldehyde, a source of ammonia, and a nitrification inhibitor. In another example, the reaction product can be produced by reacting formaldehyde, urea, an ammonia source, and a nitrification inhibitor.
In yet another example, the reaction product can be produced by reacting formaldehyde, an ammonia source, a nitrification inhibitor, and a urease inhibitor. In another example, the reaction product can be produced by reacting formaldehyde, urea, an ammonia source, a nitrification inhibitor, and a urease inhibitor. In another example, the reaction product can be produced by reacting formaldehyde, a source of ammonia, and a nitrification inhibitor mixed with a urea inhibitor. In yet another example, the reaction product can be produced by reacting formaldehyde, urea, an ammonia source, and a nitrification inhibitor mixed with a urease inhibitor. In other words, the urease inhibitor can be reacted in the formaldehyde reaction product, the ammonia source, the nitrification inhibitor, and optionally urea, mixed with the reaction product, or both.
The reaction product produced under acidic reaction conditions or basic reaction conditions can be mixed or otherwise combined with one or more nitrogen sources to provide a fertilizer product. If the reaction product includes urea reacted as formaldehyde, the ammonia source, and nitrification inhibitor, and optionally the urease inhibitor, the reaction product can be used alone as a nitrogen fertilizer product. In other words, reaction products that include reacted urea and formaldehyde or urea formaldehyde polymers can be used alone as a nitrogen-containing fertilizer.
The reaction product can be mixed, mixed, or otherwise combined with one or more nitrogen sources to form the fertilizer. For example, the reaction product can be mixed with one or more nitrogen sources, a pot or container to supply the fertilizer. Similarly, one or more sources of nitrogen can be mixed, mixed, or combined with the reaction product to form the fertilizer. For example, the nitrogen source can be mixed with the reaction product in a pot or container to supply the fertilizer. The amount of the reaction product and one or more nitrogen sources can vary, and the amount of the reaction product can be measured in terms of the amount of nitrogen contained in the nitrogen source. For example, the amount of reaction product in the fertilizer can vary from about 0.1% by weight to about 25% by weight, based on the total amount of nitrogen with one or more nitrogen sources in the fertilizer. In another example, the amount of reaction product in the fertilizer can vary from a minimum of about 0.5% by weight, from about 1% by weight, from about 2% by weight, from about 3% by weight, from about 4% by weight, or from about 5% by weight to a maximum of about 10% by weight, from about 12% by weight, from about - 15% by weight, from about 18 % by weight, about 20% by weight, or about 25% by weight, based on the total amount of nitrogen with one or more sources of nitrogen in the fertilizer. In another example, the amount of reaction product in the fertilizer can vary from about 0.5% by weight to about 3% by weight, from about 5% by weight to about 15% by weight, from about 8 % by weight to about 12% by weight, or from about 10% by weight to about 20% by weight, based on the total amount of nitrogen with one or more nitrogen sources in the fertilizer.
In a specific example, a fertilizer product containing 907 kg (2,000 pounds) of a solution of urea ammonium nitrate containing 32% by weight of nitrogen (32% UAN) may contain 2.9 kg (incomplete sentence on page 16 of the original ) of solution. In another specific example, a fertilizer product containing 1,000 kg (2,200 pounds) of a 32% UAN solution could contain approximately 32 kg (70.5 Ibs), or 10% by weight of the reaction product, based on the quantity total nitrogen in the UAN solution. However in another specific example, a fertilizer product containing about 1,000 kg (2,200 pounds) of anhydrous ammonia, which has a nitrogen content of 82% by weight, can contain about 82 kg (181 pounds) or about 10% by weight of the reaction product, based on the total amount of nitrogen in the anhydrous ammonia.
In another example, the nitrogen source can be mixed with the reaction product inside the soil, on or over the soil surface, or a combination of these. For example, the nitrogen source can be or include animal waste, such as urine and / or manure deposited on and / or in the soil. In another example, the nitrogen source may be or include a fertilizer product previously applied to the soil. Likewise, the reaction product can be applied to the soil and mixed with animal waste and / or the fertilizer previously applied on the surface of and / or inside the soil. The reaction product can be applied to the soil before, during and / or after animal waste and / or fertilizer (s) are deposited on / in the soil. In another example, the nitrogen source may be or include animal waste, such as urine and / or manure that can be collected and placed in a maintenance tank, pond, or the like, and the reaction product - tion can be added to animal waste to provide a mixture. The mixture can then be deposited on the soil to act as a fertilizer here.
If the nitrogen source includes animal waste, such as urine and / or manure, the amount of reaction product mixed or otherwise combined with the nitrogen source that includes animal waste can vary from about 0.1% by weight to about 25% by weight, based on the total amount of nitrogen with one or more nitrogen sources. In another example, the amount of reaction product mixed or otherwise combined with the nitrogen source that includes animal waste may vary from a minimum of about 0.5% by weight, from about 1% by weight, about 2% by weight, about 3% by weight, about 4% by weight, or about 5% by weight and a maximum of about 10% by weight, about 12% by weight , about 15% by weight, about 18% by weight, about 20% by weight, or about 25% by weight, based on the total amount of nitrogen in one or more nitrogen sources in the fertilizer . In another example, the amount of reaction product mixed or otherwise combined with the nitrogen source that includes animal waste can vary from about 0.5% by weight to about 3% by weight, from about 5% by weight to about 15% by weight, from about 8% by weight to about 12% by weight, or from about 10% by weight to about 20% by weight, based on the total amount of nitrogen, with one or more nitrogen sources in the fertilizer. In another example, in addition to or instead of animal waste as supplying the nitrogen source, the nitrogen source can be supplied from one or more previous applications for a fertilizer containing urea, ammonia, ammonium nitrate , or any combination of them, for example. In other words, the reaction product can be applied to a soil that contains a fertilizer containing urea, ammonia, ammonium nitrate, animal waste, or any combination thereof previously applied or a soil to which a fertilizer containing urea , ammonia, ammonium nitrate, animal residues, or any combination thereof, can be expected to be applied to it.
In another example, the reaction product can be mixed or combined with one or more sources of rapid release nitrogen and one or more sources of controlled release nitrogen to provide the fertilizer. For example, a fertilizer product may include a mixture of the reaction product, a urea-formaldehyde (UF) polymer, and an aqueous urea solution (U), an aqueous ammonium nitrate solution (AN), a solution aqueous solution of urea-ammonium nitrate (UAN), or any combination thereof. For example, the fertilizer product containing both rapid release and controlled release nitrogen sources may include the controlled release nitrogen source in an amount ranging from a minimum of about 10% by weight, to about 20 wt%, about 30 wt%, or about 40 wt% and a maximum of about 60 wt%, about 70 wt%, about 80 wt%, about 90 wt % by weight, or about 95% by weight, based on the total weight of nitrogen in both the controlled release nitrogen source and the quick release nitrogen source. The fertilising product containing both rapid release and controlled release nitrogen sources may have a concentration of the reaction product ranging from about 0.5% by weight to about 25% by weight, from about 1% by weight to about from 15% by weight, from about 5% by weight to about 20% by weight, or from about 1% by weight to about 20% by weight, based on the total nitrogen in the quick release nitrogen source. In another example, the fertilizer product may include an aqueous solution of urea-formaldehyde (UF) mixed with a source of fast-release nitrogen in a weight ratio of about 90:10 to about 10:90, about 80:20 to about 20:80, from about 75:25 to about 25:75, or from about 30:70 to about 70:30 and the reaction product can be present in an amount ranging from about from 1% by weight to about 20% by weight based on the total amount of nitrogen in the quick release nitrogen source. One or more fertilizer nutrient additives can be mixed or combined with the reaction product and / or a reaction and mixture product from the nitrogen source. Illustrative fertilizer nutritional additives may include, but are not limited to, nutrient based phosphorus and / or potassium. A commercially available fertilizer nutrient may include, for example, K-Fol 0-40-53, which is a solution containing 40% by weight of potassium phosphate and 53% by weight, which is manufactured and distributed by GBS Bios - sciences. LLC.
One or more pesticides, herbicides, fungicides, or any combination of the same, can also be mixed or combined with the reaction product and / or a reaction and mixture product from the nitrogen source. Suitable pesticides, herbicides and fungicides are well known.
Depending on the particular composition of the reaction product and / or the particular composition of the fertilizer product containing the reaction product and one or more rates of application of nitrogen sources to the soil can vary widely. For example, a fertilizer product containing the reaction product and one or more sources of nitrogen and having a concentration of the reaction product ranging from about 0.5% by weight to about 25% by weight, based on the total amount of nitrogen with one or more nitrogen sources, can be applied to a soil in an amount ranging from a minimum of about 5 kg / hectare (kg / ha), to about 10 kg / ha, of about 20 kg / ha, about 30 kg / ha, about 40 kg / ha, or about 50 kg / ha and a maximum of about 100 kg / ha, about 150 kg / ha, about 200 kg / ha, about 250 kg / ha, about 300 kg / ha, about 350 kg / ha, or about 400 kg / ha. In another example, the reaction product alone can be applied to a soil in an amount ranging from a minimum of about 1 kg / ha, about 3 kg / ha, about 5 kg / ha, about 7 kg / ha, or about 10 kg / ha and a maximum of about 30 kg / ha, about 35 kg / ha, about 40 kg / ha, about 45 kg / ha, about 50 kg / ha, about 60 kg / ha, about 70 kg / ha, or about 80 kg / ha.
The particular amount of the reaction product, when applied to the soil alone, - can be based, at least in part, on the amount of nitrogen inside and / or on the soil and / or the amount of nitrogen must be deposited on and / or inside the soil. Examples In order to provide a better understanding of the previous description, the following non-limiting examples are offered. Although the examples may be aimed at fashion-specific specificities, they are not to be seen as limiting the invention in any specific aspect. All parts, proportions and percentages are by weight unless otherwise indicated.
Incubation tests Three reaction products (Ex. 1-3) mixed with a urea solution to produce a liquid fertilizer solution were prepared and incubation tests were performed. A comparative example of a urea solution alone, that is, a solution of urea in a reaction product (CI), and a comparative example of a solution of urea mixed with dicyandiamide (DCD) (C2) were also prepared and evaluated. For example comparative C2, the urea solution mixed with DCD was not reacted. In other words, the DCD was mixed with the urea solution to provide the fertilizer. A control was also prepared that consisted of soil, that is, any source of nitrogen or reaction product was added.
For example 1, the reaction product was prepared according to the following procedure. In a reaction vessel, about 1640 g of a 50% by weight solution of formaldehyde was added at room temperature and the temperature was increased to 50ºC with a heating coil. Over a period of about 15 minutes, the temperature was reduced to 25 ° C (about 1.7 per minute) with a cooling coil, and 1150 grams of DCD was added. The temperature was raised to 60ºC and then about 208 g of ammonium chloride was added slowly in small amounts over a period of about 30 minutes. The addition of ammonium chloride caused an exothermic reaction and produced a reaction product, that is, the reaction product. During the addition of ammonium chloride, the temperature of the reaction product was allowed to rise to 80 ° C and was maintained for about 10 minutes at 80 ° C and then cooled at room temperature. The final fertilization additive had a pH of 5.1.
For example 2, the reaction product was prepared according to the following procedure. In a reaction vessel, about 1290 g of a 50% by weight solution of added formaldehyde, at room temperature and the temperature was increased and maintained between 30ºC and 50ºC. The first portion of ammonium hydroxide (60 g) was then added to the reaction vessel and the temperature of the mixture was kept below 60ºC. About 260 g of DCD was then added to the reaction vessel and the temperature of the mixture was adjusted to between 35 ° C and 50 ° C. About 1.388 g of urea was then added to the reaction vessel. A second portion of ammonium hydroxide (250 g) was then added to the reaction vessel. At the temperature of the reaction mixture it was allowed to rise exothermically to about 90 ° C for less than 30 minutes and the temperature was reduced to 85 ° C and maintained for 120 minutes. After heating the reaction mixture to 85ºC, distillation was started and carried out at 416.1 g of distillate was removed from the reaction mixture. A 25 wt% sodium hydroxide solution was added throughout the reaction and distilled as necessary to adjust the pH. The pH of the reaction mixture was maintained above 8.4 during the reaction. After distillation the reaction mixture was cooled to provide the reaction product eg
2. The reaction product for example 2 had a final pH of 9.12.
For example 3, the reaction product was prepared according to the following procedure. In a reaction vessel, about 555 g of a 50% by weight solution of formaldehyde was added at room temperature. About 260g of ammonium hydroxide was slowly added to the reaction vessel and the temperature was allowed to rise exothermically to 80ºC. About 186 g of DCD was then added to the reaction vessel and the temperature of the reaction mixture was maintained at 75 ° C for about 20 minutes.
The reaction mixture was then cooled to produce the reaction product For example 3. A 25 wt% sodium hydroxide solution was added throughout the reaction as needed to adjust the pH. The pH of the reaction mixture was maintained above 8.4 during the reaction. The reaction product For Example 3 had a final pH of 7.81.
Incubation tests were performed using each Example 1-3 to evaluate the nitrogen transformations for each sample. The effect of each reaction product (Ex. 1-3) on the nitrogen concentration in the soil as well as ammonium-nitrogen and nitrate-nitrogen were evaluated at three different concentrations of the reaction products. More particularly, the DCD concentration for a first set of samples was 0.75% by weight (Table 1), a second set of samples was 1.5% by weight (Table 2), and a third set of samples was 3% by weight (Table 3), where the weight percentages of the DCD concentration are based on the total weight of nitrogen in the urea solution. The soil used in the incubation tests was Greenville clay soil (clay-clay, silica , Plinthic Kandiudults thermal). The soil has a pH of 6.76, an ammonium-nitrogen concentration of 1.3 ppm, and a nitrate-nitrogen concentration of 2.4 ppm. The soil had a total nitrogen concentration of 0.062% by weight, before adding any of the fertilizer solutions, a concentration of organic matter of 1.14% by weight, a CEC of 16.2 cmol / kg, concentration phosphorus of 3.55 ppm, a sulfur concentration of 3.5 pom, and a zinc concentration of 0.11 ppm. The concentration of phosphorus and sulfur were determined according to the Bray-1 test. The zinc concentration was determined according to the DTPA soil test (diethylenetriamineapentaacetic acid).
Before the introduction of the fertilizer solutions, each soil sample was incubated for 1 week at 24ºC and had an initial humidity in the field capacity. As used here, the term "field capacity" refers to the upper drain limit or moisture content below which there is no free drain flow. During an incubation period of one week, the humidity has been reduced to about 80% For each 50 g soil test it was placed in a cup and each cup was covered with a lid having four holes to allow aeration and to minimize water loss.
The raw material solutions containing each example were prepared by adding 2.15 g of urea and the corresponding amount of DCD (C2), or the reaction product (Ex. 1-3) to a 500 mL (incomplete phrase) on page 20 of the original) 3) DCD based on the total nitrogen concentration in the urea solution. After the addition of urea (CI), more DCD urea (C2), and more urea the reaction products (Ex. 1-3), for beakers, the content of each beaker was diluted to 500 mL with distilled water for provide a raw material solution. For the examples shown in Tables 1-3 below, 5 mL of the corresponding raw material solution was introduced using a pipette for each 50g soil sample and the coating was placed over it. The amount of nitrogen contained in each example (Ex. 1-3, Cl and C2) was 10 mg and the nitrogen was in the form of urea. The soil has at least an 80% field moisture capacity for each sample and if necessary additional distilled water was used in order to reach the 80% field moisture capacity.
Soil extractions were carried out at 1-week intervals, in order to determine the amount of ammonium-nitrogen and nitrate-nitrogen in each example. A total of 10 extractions were performed, that is, in time = O and after 1st week, 2nd weeks, 3rd weeks, 4th weeks, 5th weeks, 6th week, 7th weeks, 8th week, and 10th week. Extracting nitrogen from each sample was performed by adding 100 mL of a 2 M potassium chloride solution (KCl) for each soil sample to be tested. The amount of nitrogen in the form of ammonium (NH, *) and nitrate (NOz) was then determined.
The amount of ammonium was determined using the well-known Berthelot reaction in which ammonia is chlorinated to monochloroamine, which then reacts with salicylate to form 5-aminosalicylate. After oxidative coupling and oxidation, a green colored complex was formed which was measured at 660 nm using a spectrophotometer.
The determination of nitrate was determined based on the reduction of nitrate (NO; z) of nitrogen dioxide (NO) by hydrazinium sulfate or meta cadmium. Then, the nitrite was determined by diazotization with sulfanilamide and coupling with a-naphthylethylenediamine dihydrochloride to form a color azo dye that was measured at 540 nm with a spectrophotometer.
Table 1 shows the results for samples that had 0.75% by weight DCD (C2eEx 1-3) based on a total weight of nitrogen in the urea solution. Table 2 shows the results for samples that had 1.5% by weight of DCD (C2 and Ex. 1-3) based on a total weight of nitrogen in the urea solution.
Finally, Table 3 shows the results for samples that had 3% by weight of DCD (C2 and Ex 1 - 3.) based on a total weight of nitrogen in the urea solution. Table 1 urea (CI DCD (C2 '
mg N Ammonium mg N Ammonium Ammonium mg N Ammonium Ammonium Ammonium 6 Nitrate (NO) | 1.48 10.66 10.50 - | 10.69 | 10.98 | 10.77 Ammonium 7 Nitrate (NOs): | 131 10.85 10.46 | 10.66 | 10.67 | 10.72 Ammonium 8 Nitrate (NOs), 10.97 10.76 10.88 | 10.98 | 10.73 Ammonium 1st Nitrate (NO): 10.98 10.86 | 10.84 | 11.22 | 10,82 As shown in Table 1, urea and reaction product solutions (Ex. 1-3) having a nitrification inhibitor (DCD) concentration of 0.75% by weight based on the amount of nitrogen in the urea performed substantially better than urea only solution (IC), and similarly to urea + DCD solution (C2).
For all Examples 1-3 the amount of nitrogen in the form of ammonium (NH4 ') was substantially increased compared to the urea solution only (C1) for weeks 3 to 5. At about the 6th week the concentration of ammonium ( NH4 *) for all examples fell. Similarly, for all Examples 1-3 the amount of nitrogen in the form of nitrate (NO;) was substantially less than the urea solution only (CI) for weeks 3 to 5. At about the 6th week, nitrate (NO) level concentration. The displayed nitrification inhibition For example 1-3 performed similarly to urea + DCD solution (C2) in inhibiting the nitrification process.
Table 2: 1.5% by weight of DCD based on the weight of nitrogen in the fertilizer Only Urea + Ammonium mg N Ammonium mg N Ammonium Ammonium mg N Ammonium Ammonium Ammonium Ammonium 7 Nitrate (NOs): 10.85 10.02 | 10.54 | 10.94 | 10.25 Ammonium 8 Nitrate (NOs): 10.97 1068 - | 10.92 | 11.01 | 10.50 Ammonium Week | pear | oo [am | om 00 one [om] 19 | Nitrate (NO), 10.98 1063 | 10.74 10.85 | 10,61 As shown in Table 2, urea and reaction product solutions (Ex. 1-3) having a nitrification inhibitor (DCD) concentration of 1.5% by weight based on the total amount of nitrogen similarly urea + DCD solution (C2). For all examples 1-3, the amount of nitrogen in the form of ammonium (NH4 *) was substantially greater than that of the urea solution only (CI) for weeks 3 to 5. Ex. 2 and Ex. 3 showed a substantial increase in amount of nitrogen present in the form of ammonium (NH4 *) through the 6th week.
Similarly, for all Examples 1-3 the amount of nitrogen in the form of nitrate (NOz) was substantially less than the urea solution only (CI)
for weeks 3 to 5. Ex. 2 and Ex. 3 continued to show a substantial reduction in the concentration of nitrogen in the form of nitrate (NO; z)) through the 6th week.
The inhibition of nitrification displayed For example 1-3 (especially Ex. 2 and 3), performed similarly to urea + DCD solution (C2) in inhibiting the nitrification process.
Table 3: 3% by weight of DCD based on the weight of nitrogen in the fertilizer Only Urea + Ammonium mg N Ammonium Week | tteenium | 018 8714 | 806 sos mg N Ammonium mg N Ammonium Ammonium Ammonium Ammonium mg N Ammonium 7 Nitrate (NO: 1: 10.85 10.48 | 10.74 | 10.55 Ammonium 8 Nitrate (NOs): 10.97 10385 - | 10, 78 | 10.91 | 10.74 Ammonium 10 Nitrate (NOs), 10.98 10.66 | 10.85 11.35 | 10.88 As shown in Table 3, urea and reaction product solutions (Ex. 1-3) having a nitrification inhibitor (DCD) at a concentration of 3% by weight based on the total amount of nitrogen in the urea solution performed substantially better than the urea solution only (IC), and similarly to urea + DCD solution (C2) .For all examples
examples 1-3 the amount of nitrogen in the form of ammonium (NH4) was substantially greater than the urea only (CI) solution for the weeks | to 6. Ex. 2 showed a substantial increase in the amount of nitrogen present in the form of ammonium (NH4 '), through the 8th week. Similarly, for all Examples 1-3 the amount of nitrogen in the form of nitrate (NO3) was substantially less than the urea solution only (CI) for weeks 1 to 6. The inhibition of nitrification displayed For example 1 -3 (especially Ex. 2 and 3), performed similarly to urea + DCD solution (C2) in inhibiting the inhibition process.
It was surprisingly and unexpectedly discovered that a reaction product (incomplete phrase on page 26 of the original) nitration inhibitor reaction product with formaldehyde, urea, and a source of ammonia (Ex. 2) reduces the rate at which nitrification of nitrogen in the fertilizer occurs. As shown in Tables 1-3, the reaction products of Examples 1-3 showed a decrease in substance! at the rate at which nitrification occurred in the urea solution only (CI) and performed similarly to the urea + DCD solution (C2).
The leaching tests A reaction product (Ex. 4) mixed with a urea solution to produce a liquid fertilizer solution was prepared and leaching tests were performed.
In addition to Ex. 4, two comparative examples (C3 and C4) were also prepared.
Comparative example C3 was a mixture of urea and DCD. Comparative example C4 was a mixture of urea ammonium nitrate (UAN), DCD, and a urea-formaldehyde polymer (UFP).
The reaction product used to produce the liquid fertilizer solution from Ex. 4 was the same reaction product used in Ex. 2. For example 4 and C3, a urea solution of the raw material was prepared by dissolving 152.6 g of urea in distilled water and diluting to 1 L. 50 mL of the urea solution of the raw material was then added to each — 500 ml volumetric flasks. To prepare the Ex. 4 fertilizer solution, about 1.008.9 mg of the Ex. 4 reaction product was added from the first volumetric flask and distilled water was added to bring the volume to 500 mL. To prepare the fertilizer solution of comparative example C3, about 106.2 mg of DCD was added to the second volumetric flask and distilled water was added to bring the volume to 500 ml.
The urea-formaldehyde polymer (UFP) of comparative example C4 was prepared according to the following procedure. In a reaction vessel, about 1.884 g of a 50% formaldehyde solution was added at room temperature and the temperature was raised and maintained at about 30 ° C and about 50 ° C. The first portion of ammonium hydroxide (about 70 g) was then added to the reaction vessel and the temperature of the mixture was kept below about 60 ° C. About 942 grams of urea was then added to the reaction vessel and the temperature of the mixture was adjusted to around 35ºC and about 50ºC. A second portion of ammonium hydroxide (about 403 g) was then added to the reaction vessel. The temperature of the reaction mixture was allowed to rise exothermically at about 90 ° C for less than 30 minutes and the temperature was reduced to about 85 ° C and maintained for about 120 minutes during which the distillation was started and carried out about 921 g of distillate was removed from the reaction mixture. A 25% by weight solution (incomplete phrase on page 27 of the original) will keep the pH of the reaction mixture above about 8.4 throughout the reaction. After distillation, the reaction mixture was cooled to provide a urea-formaldehyde polymer (UFP) reaction product, which had a final pH of about 10.2 and a nitrogen concentration of about 22% in weight based on the weight of the reaction product.
A solution of urea ammonium nitrate / urea-formaldehyde polymer (UFP / UAN) was prepared by mixing about 73.3 g of urea ammonium nitrate (UAN) having a nitrogen concentration of about 32% by weight , with about 26.7 g of the urea-formaldehyde (UFP) polymer to produce an 80:20 mixture, where about 80% of the nitrogen was in the UAN and about 20% of the nitrogen was from the UFP .
A final solution containing DCD and the UFP / UAN solution was then prepared. About 12.2 g of the UAN / UFP solution (about 29.1% N) was then added to a 500 ml volumetric flask together with about 106.2 mg of DCD. The flask was loaded with 500 mL using distilled water. This UAN / UFP / DCD solution was used as the fertilizer for comparative example C4.
Table 4 below summarizes the amount of each nitrification inhibitor included in Ex. 4, C3, and C4.
mem EIA SS maaçã SER Example | or (% by weight of added inhibitor | each per total column of DCD inipidated% by weight to the 500 ml flask | in 50 ml (mg of (mg) l and nitrogen: ml (mg inhibitor) Cc3 The leaching tests were conducted in two soil types and each example (Ex. 4, C3, and C4) were replicated 3 times, as well as the total number of leaching columns was equal to 3 nitrogen sources x 2 soil types x 3 repetitions for a total of 18 leaching columns.
The first type of soil used in the leaching tests was Greenville clayey clay (a fine, kaolinitic, thermal Rhodic Kandiudults), having the following properties: a soil pH of about 6.82, a concentration of ammonium -N of about 6.3 pom, a nitrate-N concentration of about 3.1 ppm, 0.060% by weight of total nitrogen, 1.14% by weight of organic matter, a cation exchange capacity (CEC ) of about 16.2 cmol kg, a phosphorus concentration (Bray-1 P) of 3.55 ppm, a sulfur concentration of 3.5 ppm, and a zinc concentration of extractable acid diethylenetriamine-
pentaacetic (DTPA-Zn) of 0.11 pom. Greenville soil has an optimum pH for nitrification, moderate texture and a low N content enough to show the added effect of fertilizer N. The second type of soil used in the leaching tests was sandy Tifton clay soil (a fin- clay, siliceous, thermal Plinthic Kandiudults), having the following properties: a soil pH of about 4.90, of about 1.15% by weight of organic matter, an ammonium-N concentration of about 4 , 1 pom, a nitrate-N concentration of about 9.0 ppm, about 0.038% by weight of total nitrogen, a CEC of about 1.8 emol kg, and about 79% by weight of sand.
The leaching columns had an internal diameter of 15 cm, a height of 30 cm, and were kept at room temperature, that is, around 20ºC and 24ºC. Each leaching column has the bottom 5 cm loaded with about 800 g of acid-washed sand and the rest of the column was uniformly loaded with about 6 kg of suitable soil. The sand was washed with 1 M HCl, washed with deionized water, and dispersed to dry before being placed in the leaching columns.
The duration of the experiment was 10 weeks (2 weeks before the application of the fertilizer, in addition to a period of 7 weeks of water addition, plus the final week of the drying cycle). The soil used in the leaching columns had a moisture content of the soil at 50% of the field capacity for three weeks before the start of the experiment, that is, before loading into the leaching columns. The two types of soil differed in moisture content from field capacity - Greenville soil had a moisture content from field capacity of 24.5% and Tifton soil had moisture content from field capacity of 11.52%.
The total amount of nitrogen (N) applied as urea or UAN + UFP to the soil in the leaching columns was equal to about 200 kg N / ha, or about 354 mg N / leaching column. In other words, the total amount of nitrogen (N) applied to each leach column was equal to about 354 mg.
After application of the fertilizer / inhibitor (Ex. 4, C3, and C4), the leaching columns were maintained at about 80-90% moisture content of the field capacity for the first four days. On the farm until the seventh day (day 5-7), each leach column received 14 millimeters of water per day (250 ml per day) released evenly over the soil surface. The three days of water addition were followed by two dry days (days 8-9) to ensure the soil moisture in none of the leaching columns exceeded the field capacity for an extended period of time. The three-day watering, followed by two dry day cycles was repeated until the 20th. Thereafter, the three-day watering, followed by —quadrodias dryas was followed until the application of water on the 50th. continued to end the experiment (on day 57).
Leached from the clayey Greenville clay soil was analyzed for DCD every two days. Table 5 shows the average daily DCD concentration (ppm), the amount leachate (DCD mg per day), DCD recovery (percentage of DCD added to the soil that was recovered in the leachate) and DCD in the soil (percentage of DCD that did not was leached from the soil) into the clayey Greenville clay soil. Mild darkness | - - Greenville - As shown in Table 5, the Ex. 4 fertilizer, that is, the urea mixture and the surprising and unexpected reaction product performed better than substantially both the urea / DCD (C3) solution and the UAN / UFP / DCD (C4) solution for leaching to inhibit DCD. The total loss of DCD leaching for urea and reaction product solution (Ex. 4) was 42 times less than the urea / DCD solution (C3) and 41 times lower than the UAN / UFP / solution. DCD (C4). In other words, the urea and reaction product solution (Ex. 4) maintained 84.6% of the DCD applied to the soil inside the soil, thus only 15.4% of the DCD leached out of the soil. In contrast, comparative examples C3 and C4 maintained only about 38.6% and about 40.2% of the DCD applied to the soil inside the soil. Thus, Table 5 clearly shows that the Ex. 4 performed substantially superior to both comparative examples (C3 and C4) which had about 61.4% and about 59.8% of the DCD applied to the soil, respectively, leach - do here.
Leachate from the sandy clay soil Tifton was also analyzed by DCD every two days. Table 6 shows the average daily DCD concentration (ppm), the amount leachate (DCD mg per day), DCD recovery (percentage of DCD added to the soil that was recovered in the leachate) and DCD in the soil (percentage of DCD that did not was leached from the soil) Tifton sandy loam.
Table 6: Results of the analysis of DCD - sandy clay soil Tifton Ex. 4 As shown in Table 6, the fertilizer of Ex. 4, that is, the mixture of urea and the product of the surprising and unexpected reaction substantially both urea / DCD solution (C3) and UAN / UFP / DCD solution (C4), for the leaching of DCD inhibition. The total loss of DCD leaching for urea and reaction product solution (Ex. 4) was about 37 times less than the urea / DCD solution (C3) and about 41 times less than the UAN / UFP / DCD (C4). Otherwise, the urea and reaction product solution (Ex. 4) maintained about 82.9% of the DCD applied to the soil inside the soil, while only about 17.1% of the leached DCD out of the ground.
In contrast, comparative examples C3 and C4 maintained only about 40.3% and about 32.9% of the DCD applied to the soil inside the soil.
In this way, Table 6 clearly shows that Ex. 4 performed substantially superior to both comparative examples (C3 and C4) which had about 59.7% and about 67.1% of the DCD applied to the soil, respectively, leach - do here.
Not wishing to be limited by theory, it is believed that the reaction products produced by the reaction of the nitrification inhibitor with formaldehyde and an ammonia source (Ex. 1 and Ex. 3) or with formaldehyde, urea, and an ammonia source ( Ex. 2) and (Ex. 4) will present superior nitrification inhibition in real applications compared to the nitrification inhibitor applied alone or simply mixed with urea (U), ammonium nitrate (AN), and / or nitrate urea ammonium (UAN) because the leaching of the nitrification inhibitor in the surrounding soil and away from the nitrogen source contained in the fertilizer must be reduced or avoided.
In other words, the reaction of the nitrification inhibitor in a polymer must retain or maintain the presence of the nitrification inhibitor at the point of application, ie the roots of the plant, where the fertilizer, for example, urea, ammonium nitrate , or a mixture of ammonium nitrate and urea, is present, thereby providing a better nitrification inhibitor.
Likewise, the nitrification inhibitor can more effectively inhibit nitrogen loss from a nitrogen source through the nitrification process, because the tendency for the nitrification inhibitor to leach into the soil and elsewhere the fertilizer is reduced or inhibited.
In addition, as shown in comparative example C4, simply mixing nitrification inhibitor (DCD) with a urea-formaldehyde polymer instead of reacting the nitrification inhibitor in the urea formaldehyde polymer (Ex. 1- 4) the amount of nitrification inhibitor leached from the soil did not decrease.
In fact, there is no statistically significant difference between the two comparisons C3 and C4. Consequently, the incorporation of the nitrification inhibitor in the reaction product can more effectively inhibit the loss of nitrogen from a nitrogen source through the nitrification process, because the tendency for the nitrification inhibitor to leach into the soil and to away from fertilizer it is reduced or inhibited.
Furthermore, it is not intended to be limited by theory, it is believed that the application of a reaction product produced by the reaction of formaldehyde, a source of ammonia, and a nitrification inhibitor and, optionally, urea and / or an inhibitor of urease to the soil or other substrates it already contains or can be expected to contain one or more sources of nitrogen can reduce or prevent the loss of at least one of the one or more sources of nitrogen through the nitrification process, because the tendency to the nitrification inhibitor to leach into the soil and away the fertilizer is reduced or inhibited. Likewise, the reaction product can be applied to a soil that contains or can be expected to contain sources of nitrogen such as those introduced into the soil of one or more animals, through manure and / or urine and / or applications of previous fertilizers and the loss of the nitrogen source (s) through nitrification can be reduced or avoided.
Modalities described here still concern any one or more of the following paragraphs:
1. A fertilizer, comprising: a nitrogen source comprising urea, ammonia, ammonium nitrate, or any combination thereof, and a product of the formaldehyde reaction, a source of ammonia, and a nitrification inhibitor.
2. The fertilizer according to paragraph 1, where the reaction product additionally comprises urea reacted with formaldehyde, the source of ammonia, and nitrification inhibitor.
3. The fertilizer according to paragraph 1 or 2, where the molar ratio of formaldehyde to ammonia in the reaction product ranges from about 3: 1 to about 9: 1 and a molar ratio of formaldehyde to the inhibitor of nitrification in reaction products ranges from about 1: 1 to about 3: 1.
4. Fertilizer according to any of paragraphs 1 to 3, where the crop product is produced under acidic reaction conditions and has a pH ranging from about 4 to (incomplete phrase on page 33 of the original)
5. Fertilizer according to any of paragraphs 1 to 4, where the reaction of formaldehyde, ammonia source, and nitrification inhibitor comprises: combining formaldehyde and nitrification inhibitor in a molar ratio of about 1: 1 to about 3: 1 to produce a first mixture; heating the first mixture to a temperature ranging from about 50ºC to about 80ºC; introduction of ammonium chloride into the first mixture to produce a second mixture, where the total amount of ammonium chloride introduced into the first mixture provides a formaldehyde to ammonia molar ratio ranging from about 3: 1 to about 9: 1 ; heating the second mixture to a temperature ranging from about 70ºC to about 90ºC, and cooling the second mixture to produce the reaction product.
6. The fertilizer according to any of paragraphs 1 to 5, where the reaction product comprises from about 30 mol% to about 70 mol% of formaldehyde, from about 5 mol% to about 25% in mol of ammonia, and from about 15 mol to about 45% in a nitrification inhibitor mold, based on the total weight of formaldehyde, ammonia, and nitrification inhibitor.
7. Fertilizer according to paragraph 1 or 2, where a molar ratio of
maldehyde to ammonia in the reaction product ranges from about 1: 1 to about 8: 1 and a molar ratio of formaldehyde to nitrification inhibitor in the reaction products ranges from about 1: 1 to about 7: 1 .
8. The method according to any of paragraphs 1, 2, or 7, where the reaction product comprises from about 30 mol% to about 80 mol% of formaldehyde, from about 5 mol% to about 25 mol% of ammonia, and from about 10 mol% to about 35 mol% of nitrification inhibitor, based on the total weight of formaldehyde, the ammonia source, and the nitrification inhibitor.
9. Fertilizer according to any of paragraphs 1, 2, 7 or 8, where the reaction product is produced under alkaline reaction conditions and has a pH ranging from about 8 to about 11.
10. Fertilizer according to any of paragraphs 1 or 7 to 9, where the reaction product is produced by reacting formaldehyde, the ammonia source, and nitrification inhibitor in water under alkaline reaction conditions, to obtain an aqueous reaction product.
11. The fertiizer according to any of paragraphs 1 or 7 to 10, where the reaction product is produced by reacting the formaldehyde, the ammonia source, and nitrification inhibitor, at a temperature ranging from about 70ºC to about 95ºC and with a pH ranging from about 7.5 to about 10.5 for a time ranging from about 10 minutes to about 120 minutes.
12. The fertilizer according to paragraph 2, where the reaction product is produced by reacting formaldehyde, urea, the source of ammonia, and nitrification inhibitor in water under alkaline reaction conditions, to obtain a product of alkaline reaction. aqueous reaction.
13. The fertilizer according to paragraph 2 or 12, where the reaction product is produced by reaction of formaldehyde, urea, the source of ammonia, and nitrification inhibitor at a temperature ranging from about 70ºC to about 95ºC and a pH ranging from about 7.5 to about 10.5 for a time ranging from about 10 minutes to about 120 minutes.
14. A method for making a fertilizer, comprising: the reaction of formaldehyde, a source of ammonia, and a nitrification inhibitor in conditions sufficient to produce a reaction product, and the combination of the reaction product with a source of nitrogen for the production of a fertilizer, where the nitrogen source comprises urea, ammonia, ammonium nitrate, or any combination of these.
15. A method for reducing nitrification in the soil, comprising: the reaction of formaldehyde, a source of ammonia, and a nitrification inhibitor under conditions sufficient to produce a reaction product; applying the reaction product to a soil.
16. The method of paragraph 15, where one or more nitrogen sources is available inside the soil and the reaction product is combined with one or more nitrogen sources.
inside the soil.
17. The method of paragraph 16, where the amount of reaction product for application to the soil varies from about 1 kg / ha to about 50 kg / ha.
18. The method according to paragraph 16 or 17, where the amount of the reagent product for application to the soil varies from about 1% by weight to about 25% by weight, based on a total amount of nitrogen, with a or more sources of nitrogen.
19. The method according to paragraph 14 or 15 additionally comprises urea which reacts with formaldehyde, the source of ammonia, and nitrification inhibitor to produce the reaction product.
20. The method according to paragraph 14, where the amount of reaction product in the fertilizer varies from about 0.1% by weight to about 20% by weight, based on a total amount of nitrogen at the source nitrogen.
21. The method according to any of paragraphs 14 to 20, where a mole ratio of formaldehyde to ammonia in the reaction products ranges from about 3: 1 to about 9: 1 and a mole ratio of formaldehyde to the inhibitor of nitrification in the reaction product ranges from about 1: 1 to about 3: 1.
22. The method according to any of paragraphs 14 to 21, where the reaction product has a pH ranging from about 4 to about 6.
23. The method according to any of paragraphs 14 to 22, where the reaction of the formaldehyde source of ammonia, and a nitrification inhibitor comprises: combining the formaldehyde and the nitrification inhibitor at a molar ratio of about 1: 1 to about 3: 1 to produce a first mixture; heating the first mixture to a temperature ranging from about 50 ° C to about 80 ° C; introduction of ammonium chloride into the first mixture to produce a second mixture, where the total amount of ammonium chloride introduced into the first mixture provides a formaldehyde to ammonia molar ratio ranging from about 3: 1 to about 9: 1; heating the second mixture to a temperature ranging from about 70ºC to about 90ºC, and resirring the second mixture to produce the reaction product.
24. The method according to any of paragraphs 14 to 23, where the product - reaction comprises from about 30 mol% to about 70 mol% of formaldehyde, from about 5 mol% to about 25% in mol of ammonia, and from about 15 mol to about 45 mol% of nitrification inhibitor, based on the total weight of formaldehyde, the source of ammonia, and the nitrification inhibitor.
25. The method according to any of paragraphs 14 to 20, where the reaction product comprises from about 30 mol% to about 80 mol% of formaldehyde, from about 5 mol% to about 25 mol% of ammonia, and from about 10 mol% to about 35 mol% of nitrification inhibitor, based on the total weight of formaldehyde, the source of ammonia, and the nitrification inhibitor.
26. The method according to any of paragraphs 14 to 20 or 25, where the molar ratio of formaldehyde to ammonia in the reaction product ranges from about 1: 1 to about 8: 1 and a molar ratio of formaldehyde for the nitrification inhibitor in the reaction products ranges from about 1: 1 to about 7: 1.
27. The method according to any of paragraphs 14 to 20, 25, or 26, where the reaction product comprises a reaction product produced under alkaline reaction conditions.
28. The method according to any of paragraphs 14 to 20 or 25 to 27, where the reaction product is produced by reacting formaldehyde, the source of ammonia, and nitrification inhibitor in water under alkaline reaction conditions, to obtain an aqueous reaction product.
29. The method according to any of paragraphs 14 to 20 or 25 to 28, where the reaction product is produced by reacting the formaldehyde, the ammonia source, and "nitrification inhibitor", at a temperature ranging from about 70ºC at about 95ºC and at a pH ranging from about 7.5 to about 10.5 for a time ranging from about 10 minutes to about 120 minutes.
30. The fertilizer or method according to any of paragraphs 1 to 29, where the nitrogen source comprises urea, ammonia, ammonium nitrate, animal manure, animal urine, or any combination thereof.
31. The fertilizer or method according to any of paragraphs 1 to 37, where the nitrogen source comprises anhydrous ammonia.
32. The fertilizer or method according to any of paragraphs 1 to 31, where the nitrification inhibitor comprises 2-chloro-6-trichloromethyl-pyridine, 5-ethoxy-3-trichloromethyl-1,2,4- thiadiazole, diciandiamide, 2-amino-4-chloro-6-methyl-pyrimidine, 1,3-benzothiazole-2-thiol, 4-amino-N-1,3-thiazol-2-ylbenzenesulfonamide, thiourea; guanidine, 3,4-dimethylpyrazole phosphate, 2,4-diamino-6-trichloromethyl-5-triazine, polyetherionophores, 4-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, azide potassium, carbon disulfide, sodium trithiocarbonate, ammonium dithiocarbamate, 2,3, dihydro-2,2-dimethyl-7-benzofuranol methyl-carbamate, N- (2,6-dimethylphenyl) -N- (methoxyacetyl) - Alanine methyl ester, ammonium thiosultate, 1-hydroxypyrazole, 2-methylpyrazole-1-carboxamides, derivatives thereof, and any combination thereof.
33. The fertilizer or method according to any of paragraphs 1 to 32, where the nitrification inhibitor is dicyandiamide.
34. The fertilizer or method according to any of paragraphs 1 to 33, where the ammonia source comprises one or more ammonium salts, aqueous ammonia, anhydrous ammonia, or any combination thereof.
35. The fertilizer or method according to any of paragraphs 1 to 34, where formaldehyde comprises an aqueous solution, and where the concentration of formaldehyde in the aqueous solution varies from about 10% by weight to about 50% in weight, based on the total weight of the aqueous solution.
36. The fertilizer or method according to any one of paragraphs 1 to 35, where formaldehyde comprises an aqueous solution, and where the concentration of formaldehyde in the aqueous solution varies from about 37% by weight to about 50% in weight, based on the total weight of the aqueous solution.
37. The fertilizer or method according to any of paragraphs 1 to 14 or 19a36, where the concentration of the fertilizer reaction product ranges from about 0.5% by weight to about 20% by weight, based on a total amount of nitrogen in the source nitrogen.
38. The fertilizer or method according to any of paragraphs 1 to 14 or 19 to 37, where the concentration of the reaction product of the fertilizer varies from about 1% by weight to about 15% by weight, based on an amount total nitrogen in the source nitrogen.
39. The fertilizer or method according to any of paragraphs 1 to 38, where the nitrogen source is a solid, a liquid, or a combination thereof.
40. The fertilizer or method according to any one of paragraphs 1, 3 to 18, or 20 to 3 39, where the reaction product additionally comprises a urease inhibitor reacted with formaldehyde, the ammonia source, and nitrification inhibitor.
41. The fertilizer or method according to paragraph 2, or 19, where the reaction product additionally comprises a urease inhibitor reacted with formaldehyde, urea, ammonia source, and nitrification inhibitor.
42. The fertilizer or method according to any of paragraphs 1 to 41, additionally comprising one or more urease inhibitors, combined with the reaction product.
43. The fertilizer or method according to any of paragraphs 40 to 4, where the urease inhibitor comprises thiophosphoric N- (n-butyl) triamide, N- (n-butly) phosphoric triamide, thiophosphoryl triamide, phenyl phosphorodiamidate, cyclohexyl phosphoric triamide, thiophosphoric cyclohexyl triamide, triamide, phosphoric triamide, hydroquinone, p-benzoquinone, hexamidocyclophosphatene, thiopyridines, thiopyrimidines, thiopyridine-N-oxides, N-oxides, N-oxides, N halo-2-oxazolidinone, derivatives thereof, or any combination thereof.
44. The fertilizer or method according to any of paragraphs 1 to 14 or 19a43, where the fertilizer is applied to a soil in an amount ranging from about 30 kg / ha to about 350 kg / ha.
45. The method according to any of paragraphs 16 to 18, where one or more nitrogen sources comprises urea, ammonia, ammonium nitrate, or any combination thereof.
46. The method according to either of paragraphs 16 to 18 or 45, additionally comprising the elimination of one or more nitrogen sources in the soil, inside the soil, or both, where one or more nitrogen sources comprise manure animal, animal urine, or a combination thereof.
47. The method according to any of paragraphs 16 to 18, 45, or 46, where the reaction product is applied to the soil after one or more sources of nitrogen.
48. The method according to any of paragraphs 16 to 18 or 45 to 47, where the reaction product is applied to the soil before one or more nitrogen sources. Certain modalities and characteristics have already been described using a set of | upper numerical limits and a set of lower numerical limits. It should be noted that ranges from any lower limit to any upper limit are contemplated, unless otherwise indicated. Certain lower, upper and lower limits appear in one or more claims below. All numerical values are "about" or "approximately" the indicated value, and take into account experimental error and the variations that would be expected from a person having knowledge of the technique. Several terms have been defined above. Insofar as the term used in a claim is not defined above, the broadest definition should be given to persons in the relevant art having given that term as reflected in at least one print publication or issued patents. In addition, all patents, testing procedures and other documents cited in this application are fully incorporated by reference to the disclosure to such an extent, it is not inconsistent with this application and in all jurisdictions in which incorporation is permitted. While the foregoing is concerned with modalities of the present invention, another and additional modalities of the invention can be designed without departing from the basic scope of the same, and the scope of the same is determined by the claims that follow.

权利要求:
Claims (40)
[1]
1. Fertilizer, CHARACTERIZED by the fact that it comprises: a nitrogen source comprising urea, ammonia, ammonium nitrate, or any combination thereof, and a formaldehyde reaction product, an ammonia source, and a nitrifi inhibitor - cation.
[2]
2. Fertilizer, according to claim 1, CHARACTERIZED by the fact that the nitrification inhibitor comprises 2-chloro-6-trichloromethyl-pyridine; 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole; diciandiamide; 2-amino-4-chloro-6-methyl-pyrimidine; 1,3-benzothiazole-2-thiol; 4-amino-N-1,3-thiazol-2-ylbenzenesulftonamide; thiourea; guanidine; 3,4-dimethylpyrazole phosphate; 2,4-diamino-6-trichloromethyl-5-triazine; ionophore polyether; 4-amino-1,2,4-triazole; 3-mercapto-1,2,4-triazole; potassium azide; carbon disulfide; sodium trithiocarbonate; ammonium dithiocarbamate; 2,3-dihydro-2,2-dimethyl-7-benzofuranol methyl carbamate; N- (2,6-dimethylphenyl) - N- (methoxyacetyl) -alanine = methyl ester; ammonium thiosultate, 1-hydroxypyrazole; 2-methylpyrazole-1-carboxamide; derivatives thereof; and any combination thereof.
[3]
3. Fertilizer according to claim 1, CHARACTERIZED by the fact that a molar ratio of formaldehyde to ammonia in the reaction products varies from about 3: 1 to about 9: 1 and a molar ratio of formaldehyde to the inhibitor of nitrification in the reaction products ranges from about 1: 1 to about 3: 1.
[4]
4. Fertilizer, according to claim 1, CHARACTERIZED by the fact that the reaction of formaldehyde, source of ammonia, and nitrification inhibitor comprises: combining formaldehyde and nitrification inhibitor in a molar ratio of about 1: 1 to about 3: 1 to produce a first mixture; heating the first mixture to a temperature ranging from about 50ºC to about 80ºC; introducing ammonium chloride into the first mixture to produce a second mixture, where the total amount of ammonium chloride introduced into the first mixture provides a formaldehyde to ammonia molar ratio ranging from about 3: 1 to about 9: 1; heat the second mixture to a temperature ranging from about 70 ° C to about 90 ° C, and cool the second mixture to produce the reaction product.
[5]
5. Fertilizer, according to claim 1, CHARACTERIZED by the fact that the reaction product comprises from about 30 mol% to about 70 mol% of - formaldehyde, from about 5 mol% to about 25 mol mol% of ammonia, and about 15 mol% to about 45 mol% of nitrification inhibitor, based on the total weight of formaldehyde, ammonia, and nitrification inhibitor.
[6]
6. Fertilizer, according to claim 1, CHARACTERIZED by the fact that the molar ratio of formaldehyde to ammonia in the reaction product ranges from about 1: 1 to about 8: 1 and a molar ratio of formaldehyde to the inhibitor of nitrification in reaction products ranges from about 1: 1 to about 7: 1.
[7]
7. Fertilizer, according to claim 1, CHARACTERIZED by the fact that the reaction product is produced by reaction of formaldehyde, ammonia source, and nitrification inhibitor in water under alkaline reaction conditions, to obtain a reaction product - aqueous tion.
[8]
8. Fertilizer, according to claim 1, CHARACTERIZED by the fact that ammonia source comprises one or more ammonium salts, aqueous ammonia, anhydrous ammonia, or any combination thereof.
[9]
9. Fertilizer, according to claim 1, CHARACTERIZED by the fact that the concentration of the reaction product in the fertilizer varies from about 0.1% by weight to about 20% by weight, based on a total amount of nitrogen in the nitrogen source.
[10]
10. Fertilizer, according to claim 1, CHARACTERIZED by the fact that the concentration of the reaction product of the fertilizer varies from about 1% by weight to about 15% by weight, based on a total amount of nitrogen at the source of nitrogen.
[11]
11. Fertilizer, according to claim 1, CHARACTERIZED by the fact that the reaction product additionally comprises a urease inhibitor reacted with formaldehyde, ammonia source, and nitrification inhibitor, and where the urease inhibitor comprises N - (n-butyl) thiophosphoric triamide, N- (n-butyl) thiophosphoric triamide, thiophosphoryl triamide, phenyl phosphorodiamidate, cyclohexyl phosphoric triamide, cyclohexyl thiophosphoric triamide, —hydroquinone, p-benzoin, tyridine, tyridine, tyridine, tyridine, tyridine - dine-N-oxides, N, N-dihalo-2-imidazolidinone, N-halo-2-oxazolidinone, derivatives thereof, or any combination thereof.
[12]
12. Fertilizer, according to claim 1, CHARACTERIZED by the fact that it additionally comprises one or more urease inhibitors.
[13]
13. Fertilizer, according to claim 1, CHARACTERIZED by the fact that the urea reaction product additionally comprises urea reacted with formaldehyde, ammonia source, and nitrification inhibitor.
[14]
14. Fertilizer, according to claim 1, CHARACTERIZED by the fact that the nitrogen source comprises anhydrous ammonia.
[15]
15. Method for making a fertilizer, CHARACTERIZED by the fact that it comprises: Reacting formaldehyde, a source of ammonia, and a nitrification inhibitor under conditions
sufficient tions to produce a reaction product; and combining the reaction product with a nitrogen source for the production of a fertilizer, where the nitrogen source comprises urea, ammonia, ammonium nitrate, or any combination of these.
[16]
16. Method according to claim 15, CHARACTERIZED by the fact that it additionally comprises the reaction of at least one urea and a urease inhibitor with formaldehyde, ammonia source, and nitrification inhibitor to produce the reaction product.
[17]
17. Method according to claim 15, CHARACTERIZED by the fact that the nitrification inhibitor comprises 2-chloro-6-trichloromethyl-pyridine acid: 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, diciandiamide, 2-amino-4-chloro-6-methyl-pyrimidine; 1,3-benzothiazol-2-thiol, 4-amino-N-1,3-thiazol-2-ylbenzenesulfonamide; thiourea; guanidine; 3,4-dimethylpyrazole phosphate; 2,4-diamino-6-trichloromethyl-5-triazine; ionophore polyether, 4-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole; potassium azide; carbon disulfide; sodium trithiocarbonate; ammonium dithiocarbamate; 2,3, dihydro-2,2-dimethyl-7-benzofuranol methyl-carbamate, N- (2,6-dimethylphenyl) -N- (methoxyacetyl) -alanine methyl ester; ammonium thiosulfate, 1-hydroxypyrazo |, 2-methylpyrazole-1-carboxamide; derivatives thereof, or any combination thereof.
[18]
18. Method, according to claim 15, CHARACTERIZED by the fact that an amount of the reaction product in the fertilizer varies from about 0.5% by weight to about 20% by weight, based on a total amount of nitrogen in the nitrogen source.
[19]
19. Method, according to claim 15, CHARACTERIZED by the fact that the nitrogen source is disposed within a soil and the reaction product is combined with the nitrogen source in the soil.
[20]
20. Method according to claim 15, CHARACTERIZED by the fact that a molar ratio of formaldehyde to ammonia in the reaction products ranges from about 3: 1 to about 9: and a molar ratio of formaldehyde to the nitrification inhibitor in reaction products it varies from about 1: 1 to about 3: 1.
[21]
21. Method according to claim 15, CHARACTERIZED by the fact that formaldehyde sandblasting, ammonia source, and nitrification inhibitor comprises: combining formaldehyde and nitrification inhibitor in a molar ratio of about 1: 1 to about 3: 1 to produce a first mixture; heating the first mixture to a temperature ranging from about 50ºC to about 80ºC; introduce ammonium chloride into the first mixture to produce a second mixture, where the total amount of ammonium chloride introduced into a first mixture provides a formaldehyde to ammonia molar ratio ranging from about 3: 1 to about 9: 1 ;
o heat the second mixture at a temperature ranging from about 70ºC to about 90ºC, and cool the second mixture to produce the reaction product.
[22]
22. Method according to claim 15, CHARACTERIZED by the fact that the reaction product comprises from about 30 mol% to about 70 mol% formaldehyde, from about 5 mol% to about 25 mol% of ammonia, and from about 15 mol% to about 45 mol% of nitrification inhibitor, based on total weight of formaldehyde, ammonia, and nitrification inhibitor.
[23]
23. Method according to claim 15, CHARACTERIZED by the fact that a molar ratio of formaldehyde to ammonia in the reaction products ranges from about 1: 1 to about 8: 1 and a molar ratio of formaldehyde to the inhibitor of nitrification in the reaction products ranges from about 1: 1 to about 7: 1.
[24]
24. Method, according to claim 15, CHARACTERIZED by the fact that the reaction product is produced by reacting the formaldehyde, ammonia source, and water-nitrification inhibitor under alkaline reaction conditions, to obtain a aqueous reaction.
[25]
25. Method according to claim 15, CHARACTERIZED by the fact that the ammonia source comprises one or more ammonium salts, aqueous ammonia, anhydrous ammonia, or any combination thereof.
[26]
26. Method, according to claim 15, CHARACTERIZED by the fact that the concentration of the reaction product in the fertilizer varies from about 0.1% by weight to about 20% by weight, based on a total amount of nitrogen in the nitrogen source.
[27]
27. Method, according to claim 15, CHARACTERIZED by the fact that a concentration of the reaction product in the fertilizer varies from about 1% by weight to about 15% by weight, based on a total amount of nitrogen at the source of nitrogen.
[28]
28. Method according to claim 15, CHARACTERIZED by the fact that the reaction product additionally comprises a urease inhibitor reacted with the formaldehyde, the ammonia source, and nitrification inhibitor, and where the urease inhibitor buys - end N- (n-butylthiophosphoric triamide, N- (n-butyl) phosphoric triamide, thiophosphoryl triamide, phenyl phosphorodiamidate, cyclohexyl phosphoric triamphoric triamide, phosphoric triamide, hydroquinone, p-benzoquinone, t-benzoyl-trioxide, thyridine, tyramidine - N-oxides, N, N-dihalo-2-imidazolidinone, N-halo-2-oxazolidinone, derivatives thereof, or any combination thereof.
[29]
29. Method according to claim 15, CHARACTERIZED by the fact that it additionally comprises one or more urease inhibitors with the reaction product and the nitrogen source.
[30]
30. Method, according to claim 15, CHARACTERIZED by the fact that the nitrogen source comprises anhydrous ammonia.
[31]
31. Method for reducing nitrification in the soil, CHARACTERIZED by the fact that it comprises: reacting formaldehyde, a source of ammonia, and a nitrification inhibitor in sufficient conditions to produce a reaction product; apply the reaction product to a soil.
[32]
32. Method, according to claim 31, CHARACTERIZED by the fact that one or more nitrogen sources are disposed inside the soil and the reaction product is combined with one or more nitrogen sources inside the soil.
[33]
33. Method, according to claim 32, CHARACTERIZED by the fact that one or more sources of nitrogen comprise urea, ammonia, ammonium nitrate, or any combination thereof.
[34]
34. Method according to claim 31, CHARACTERIZED by the fact that it additionally comprises the elimination of one or more nitrogen sources in the soil, inside the soil, or both, where one or more nitrogen sources comprises animal manure, urine animals, or a combination of these.
[35]
35. Method, according to claim 34, CHARACTERIZED by the fact that the reaction product is applied to the soil after one or more nitrogen sources, before one or more nitrogen sources, or both.
[36]
36. Method, according to claim 31, CHARACTERIZED by the fact that the amount of reaction product applied to the soil varies from about 1 kg / ha to about 50 kg / ha.
[37]
37. Method, according to claim 32, CHARACTERIZED by the fact that an amount of the reaction product applied to the soil varies from about 1% by weight to about 25% by weight, based on a total amount of nitrogen, with one or more nitrogen sources.
[38]
38. Method according to claim 31, CHARACTERIZED by the fact that it additionally comprises urea reacted with formaldehyde, the source of ammonia, and nitrification inhibitor to produce the reaction product.
[39]
39. Method according to claim 31, CHARACTERIZED by the fact that it additionally comprises the reaction of a urease inhibitor with formaldehyde, the ammonia source, and nitrification inhibitor, and where the urease inhibitor comprises N- (n - butyl) thiophosphoric triamide, N- (n-butyl) phosphoric triamide, triamidatiophosphoryl, phenyl phosphorodiamidate, cyclohexyl phosphoric triamide, cyclohexyl phosphoric triamide, phosphoric triamide, hydroquinoline, p-benzoquinone, hexamidine-thyridine-thyridines, thyridine-trioxide, thyridine-tyrosine N-oxides, N, N-dihalo-2-imidazolidinone, N-halo-2-oxazolidinone, derivatives thereof,
or any combination of these.
[40]
40. Method according to claim 31, CHARACTERIZED by the fact that it additionally comprises the combination of a urease inhibitor with the reaction product.

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同族专利:

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公开号 | 公开日

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WO2011137393A1|2011-11-03|

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EP2563745A4|2016-11-02|

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EP2563745B1|2019-12-11|

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US20190047918A1|2019-02-14|

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CL2012003049A1|2013-05-17|

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CN102939275B|2015-08-26|

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US20110296886A1|2011-12-08|

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EP2563745A1|2013-03-06|

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WO2011137393A9|2016-11-10|

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MX2012012692A|2013-04-03|

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EA021642B1|2015-07-30|

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AR084383A1|2013-05-15|

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NZ603307A|2014-12-24|

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US20160052833A1|2016-02-25|

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EA201291139A1|2013-06-28|

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US11148982B2|2021-10-19|

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AU2011245115B2|2015-05-14|

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CN102939275A|2013-02-20|

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CA2798039C|2018-12-04|

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法律状态:
2020-09-08| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-09-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-01-05| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|

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2021-11-23| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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US32968010P| true| 2010-04-30|2010-04-30|

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US61/329,680|2010-04-30|

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