CA1258189A - Triazone fertilizer and method of making - Google Patents
Triazone fertilizer and method of makingInfo
- Publication number
- CA1258189A CA1258189A CA000488768A CA488768A CA1258189A CA 1258189 A CA1258189 A CA 1258189A CA 000488768 A CA000488768 A CA 000488768A CA 488768 A CA488768 A CA 488768A CA 1258189 A CA1258189 A CA 1258189A
- Authority
- CA
- Canada
- Prior art keywords
- triazone
- urea
- ammonia
- compounds
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
- C05C9/02—Fertilisers containing urea or urea compounds containing urea-formaldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
- C05G5/23—Solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Fertilizers (AREA)
Abstract
TRIAZONE FERTILIZER AND METHOD OF MAKING
Inventor: Edwin F. Hawkins ABSTRACT OF THE DISCLOSURE
In a preferred embodiment, a triazone mixture contains triazone present in an amount of at least about 30% calculated on a dry weight basis of 100% solids, methylene diurea in an amount less than about 2.5%, monomethylolurea in an amount less than about 3%, and total methylene diurea and monomethylolurea taken together being less than about 5%, and hexamethylenetetramine in an amount less than about 1%, in water solution, of which on a dry weight basis the ratio of triazone to methylene diurea is at least about 6 and the ratio of triazone to urea is greater than about 1, of which typically about 80%
of the triazone present is of the empirical formula C3H7N3O in cyclic form, and a majority of remaining triazone present is of the empirical formula C5H10N4O3 in cyclic substituted-amine form, the triazone mixture being produced by a two-stage method in which urea and/or substituted urea is reacted with aldehyde(s) and ammonia and/or primary amine(s) with the urea to formaldehyde ratio ranging from preferably about 0.5 to 1.4, and with ammonia on a weight percentage of the batch being at preferably about 4% to about 6%, such that total nitrogen in solution ranges between about 16 and 31%
by weight, the first stage including heating reactants within a preferred range of about at least 87 degrees Centigrade up to about 92 degrees Centigrade while maintaining the pH at about pH 8.5 to about pH 9 by the continual addition of strong caustic such as sodium hydroxide over a heating period ranging preferably from about 20 to about 30 minutes, and the second stage proceeding at about the same temperature devoid of further addition of a caustic permitting the pH to drop during a continued heating over a period o-f preferably from about 10 minutes to about 30 minutes, the optimum mole ratio during the process of reactants urea, formaldehyde and ammonia, for example, being about 1.2/1.0/0.25.
Inventor: Edwin F. Hawkins ABSTRACT OF THE DISCLOSURE
In a preferred embodiment, a triazone mixture contains triazone present in an amount of at least about 30% calculated on a dry weight basis of 100% solids, methylene diurea in an amount less than about 2.5%, monomethylolurea in an amount less than about 3%, and total methylene diurea and monomethylolurea taken together being less than about 5%, and hexamethylenetetramine in an amount less than about 1%, in water solution, of which on a dry weight basis the ratio of triazone to methylene diurea is at least about 6 and the ratio of triazone to urea is greater than about 1, of which typically about 80%
of the triazone present is of the empirical formula C3H7N3O in cyclic form, and a majority of remaining triazone present is of the empirical formula C5H10N4O3 in cyclic substituted-amine form, the triazone mixture being produced by a two-stage method in which urea and/or substituted urea is reacted with aldehyde(s) and ammonia and/or primary amine(s) with the urea to formaldehyde ratio ranging from preferably about 0.5 to 1.4, and with ammonia on a weight percentage of the batch being at preferably about 4% to about 6%, such that total nitrogen in solution ranges between about 16 and 31%
by weight, the first stage including heating reactants within a preferred range of about at least 87 degrees Centigrade up to about 92 degrees Centigrade while maintaining the pH at about pH 8.5 to about pH 9 by the continual addition of strong caustic such as sodium hydroxide over a heating period ranging preferably from about 20 to about 30 minutes, and the second stage proceeding at about the same temperature devoid of further addition of a caustic permitting the pH to drop during a continued heating over a period o-f preferably from about 10 minutes to about 30 minutes, the optimum mole ratio during the process of reactants urea, formaldehyde and ammonia, for example, being about 1.2/1.0/0.25.
Description
12~
. .
TH~ SPECIFIC~TION
This invention relates to a novel liquid fertilizer ancl the novel method of ma]cing it.
BACI~GROUN~
Prior to the present inVentiOII there has been no method which w~len repeated continually will produce either triazones and/or a high concentration thereof reliabl~
and/or consistently. Also, by prior methods of making fertilizers by somewhat similar or related method(s), the resulting product or mixture of products exhibit low or poor stability, decomposing and/or converting to crystalline compounds or products that precipitate out thereby destroying their utility for use as liquid fertiiizer, solid fertilizer of the triazone or related types of insoluble (in water) nature not bein~ capable of releasing nitrogen to the roots suf-ficiently rapidLy as to be economically or commercially feasible or practica Moreover, it has been found that by current technology, it is impossible to separate individual triazone compounds from mixtures thereof in water-containing reaction product mixtures thereof, and until procedures utilized by the present inventor it has heretofore not been readily possible to ascertain exact structure(s) and formula(s) of aqueous reaction products of process(es) related to or somewhat similar to the present method. Likewise until research by the present inventor, it hereto-Eore had not been recoynized nor known what factors and/or yield of the final product(s) thereof such as in the present inventive process resultin~ in iligh concentration of hiyh solubility and stable products of principally triazone compound(s) of the ~resent invention presellt as a water-soluble mixture.
While there is no certainty that somewhat similar or related processes have resulted in the production of any triazone product~ as a part of the product-mixture in water solution, or that -- if any were present or so 12~8i8~
~f produced -- that amount of triazone therein was present in any appreciable nor significant amount, or for how long such would be present prior to decomposition thereof or prior to the overall-mixture (reaction product) beco~ing worthless insofar as utility for liquid fertilizer because of crystallization and precipitation of constituents thereof, the closest superficially related method or process to that of the present invention appears to be that of the Justice et al. United States Patent 3,462,256 issued on August 19, 1969, which is directed to and claimc a process utilizing different process parameters and different mole ratio-parameters for reactants, failing to recognize the presence (if any~ oE the triazone(s) of the present invention and the importance thereof as a liquid fertilizer and the importance of such parameters and resulting reaction product from the standpoint of each and both effectiveness as a fertilizer of liquid nature, lack of sensitivity thereto of human skin and long-term stability thereof of the present invention. The broad limits of the Justice patent include employing urea and formaldehyde reactants in urea/formaldehyde ratio of l/2, preferably 1.3/1.8, utilizing ammonia at a weight percentage of 0.3 to 6 broadly, preferably 0.7 to 3, at reaction temperatures ranging from 75 degrees Centigrade to boiling broadly, preferably from 85 to 95 degrees Centigrade, at a pE3 ranging broadly from 8.5 to lO, preferably 9 to 9.8, during a heating time of reaction broadly for 30 to 180 minutes, preferably froM 75 to 115 minutes. While some of the parameters overlap, there has been no recognition by Justice nor other prior art of the critical parameters of Applicant/inventor and of tihe combination thereof critically necessary for the obtaining of the present invention, as shall be evidenced by some of Applicant's experiments contained herein as Examples of methods that do not work.
~81t~
OBJEC`T~ ok-llrH~ INVENTION
An object of the present invention is to obtain a novel liquid fertilizer composition 4uitable for foliar application and sod application devoid of potential burning o~ foliage and/or sod.
Another object is to obtain a novel liquid fertilizer composition suitable for situations requiring slow-release nitrogen sources.
Another object is to obtain a novel composition havinc~ an elevated or high percentage of triazone composition suitable for use as a fertilizer for foliar and/or sod applications.
Another object is to obtain the above-noted compositions characterized by good stability and long-terl,l lS stability against crystallization(s) of components thereof and/or precipitation therefrom of components thereof immediately or during storage.
Another object is to obtain a novel triazone composition having a high triazone composition in aqueous form, that has a higll level of stability against decomposition of the triazone or against degradation thereof.
Another object is to obtain a novel triazone composition in aqueous solution having high concentration of particular triazone(s).
Another object is to obtain a novel method/process for producing said novel liquid fertilizer composition(s) and improved high stabilities and composition(s) having said slow-release and having the characteristics of non-burning of foliàge and/or sod when applied there~o.
Another object is to obtain a novel method of fertilizinc~ vegetation of varying types and includinc~ sod, utilizing novel compositions of this invention.
Other objects become apparent from the preceding and following disclosure.
12S8~39 6 ~
One or more objects of the invention are obtained by the invention as set forth herein, and as claimed in the appended claims.
SUMMARY OF THE INVENTION
Broadly the invention may be characterized as three inter-related inventions, namely a li~uid fertilizer of novel compositions(s), a novel method of producing those compositions, and a novel method of foliar fertilizer application.
More particularly, broadly stated the invention includes a liquid fertilizer composition having colnponents thereof present in particular amounts within stated ranges, including a triazone-type composition that is substantially solubl~ in water sufficiently to obtain stability to a practical commercial degree, a urea-type, compound, water sufficient in amount to obtain and retain a solution of the triazone(s), limited minor percentages of a monomethylol urea-type compound and a methylene diurea, and potentially minor amounts of a dimethylol urea-type compound and a hexamethylene tetramine-type compound. The triazone-type composition is present in an amount of at least about 30~, preferably about 35~ to about 50% and in an amount in ratio to urea by weight of at least 0.48, preferably at least about 1. The urea-type com!~ound on a dry-weigl~t basis i~ about 10% u~ to a~out 50%, preferably less than 35%, and the monomethylolurea-type compound is u~ to about 7~. On the dry-weight basis, the methylene diurea-type compound may be present up to about 3~, preferably less than about 2%, and the monomethylolurea Inay be present up to about 7%, ~referably less than about 3~, and provided the total weight of methylene diurea an~ monometllylolurea does not exceed about 10%, preferably less than about 6~ (u~ to 6%). The ratio of triazone(s) on a dry weight basis, to ~ethylene diurea is at least about 6, preferably at least about 11.
Dimethylol urea and hexamethylenetetramine may or May not lZ58189 be present, with dimethylolurea ranging up to a~out 2.75%
on a weight basis of total weight of the aqueous solution, and with hexamethylenetetramine u~ to about 2 percent, preferably up to about 1~ on a weight basis (dry weight), or less, normally th~re being no hexamethylene tetramine present. The above-stated amounts of triazone composition and its ratio to urea are critical to the utility of the total composition of fertilizer and water solution thereof as the liquid fertilizer for the above-stated objects.
The improved lower urea-content in the product achieves both lower phytotoxicity and higher triazone content, by this improved invention. When treating the aqueous solution of urea-type compound and aldehyde-type compound, with the ammonia, preferred results are obtained by maintaining the temperature below 65C, preferably below 60 de~rees Centigrade. Also, in order to have the high level of stability of the composition of this invention, the method must be limited critically to not more than the above-stated maximum amounts of compounds such as the monomethylol urea, dimethylol urea and methylene diurea because of their low and limited water-solubility and instability insofar as tending to crystallize and/or precipitate out. Substantially the same thiny is true for hexamethylenetetramine that is likewise limited in its maximum permissible amount of the inventive composition.
The present invention, then, in one aspect, resides in a liquid fertilizer composition comprisin~, as calculated on a dry weight basis of 100~ solids:
one or more substantially water soluble triazone compounds in an amount of at least 30~;
one or more urea compounds in an amount of from 10~ to 60%, and water, the composition containing not more than the indicated amounts (dry weight basis) of the following urea compounds 35 and of hexamethylenetetramine compounds:
methylene diurea compounds 7.9 125E31~39 monomethylol urea compounds 7.2 hexamethylenetetramine compounds 2%, all the above compounds beiny dissolved in the water and the triazone compound:methylene diurea compound weight ratio being 6:1 or more.
According to another embodiment of the invention there is provided a method for producin~ a water-solution fertilizer composition of substantially stable water-soluble components as a reaction product containiny one more more substantially water-soluble triazone-type compounds, comprising:
(a) reacting in aqueous solution a urea compound, an aldehyde and ammonia or a primary amine;
(b) thereafter further reacting in a first heating stage at a temperature between 80C and 95C for an additional reactiny period of from 15 minutes to 1 hour while adding as necessary during the additional reacting period a strony base to maintain the pl~ within the range of h to 9.5 and while addin~ as necessary during the additional reacting period the urea compound and the aldehyde to maintain a mole ratio of the urea compound to the aldehyde within the range of from 0.5 to 2, and while adding as necessary during the additional reactiny period ammonia or the amine to maintain a mole ratio of ammonia or amine to the aldehyde within a range of from 0.15 to 0.65, the ammonia or amine being reacted in an amount ranging from 2~ up to 6% on a total water-mixture weight basis of 100~ of reactants of the urea compound, the aldehyde and the ammonia or amine, and (c) thereafter as a second heatiny stage maintaining the reaction temperature between 80C and 95~` for a further period up to 1 hour, such that the final reaction product has a triazone compound:unreacted urea compound weight ratio of at least 0.5:1.
The present invention further provides a method of fertilizing vegetation and/or soil which comprises ~2sal~
applying to vegetation foliage and/or soil a li~uid fertilizer composition as described above.
In a preferred embodiment of the invention, on a weight percentage basis, a maJor amount of the triazone composition and/or mixture are triazones having the empirical formulas C3H7N30 (5-S-tetrahydrotriazone) and C5HloN403 ~N-hydroxymethylformamidetriazone), with cyclic formulas H~ H ~H~ H
H2 -~-CH2 and 2 ~ CH2 respectively, C=~NH-CH2-OH
of the total triazone the C3H7N30 on a weiyht basis amounts to preferably and normally at least about 80~
which is critical to obtaining preferred results as to the above-stated objects.
The method of the invention has a combination of :
critical temperature ranges, pH ranges, reactant ratios, essential reactants, and periods of reaction, as well as being a two-phase method insofar as periods of time of heating at different pH levels. In the absence of these critical limitations, it has been discovered by the present inventor to be impossible to obtain the high level of production of the triazone composition(s) of this invention, or to obtain a liquid fertilizer containing 5uch Witil a high level of stability, particularly in conjunction with the high level or weiyht percentage produced. Likewise, to obtain the non-burning triazones of this invention suitable for fertilizer Eoliar application as well as soil application, the critical limitations are necessary to obtain such product(s).
Naturally there are broad ranges for many of these limitations within which some degree of success may be 1258~8~3 obtained, but with the rnaximum and high quality production being limited to the method's preferred ranses.
More particularly, for the broader aspects of the invention, the process may be described as a method for producing a water-solution fertilizer composition of substantially stable water-soluble components, of ~hich the major novel component(s) thereof as reaction product(s) are substantially water-soluble triazone compounds, reaction components and steps being as follows.
rrhe urea-like component must be selected from urea and/or substituted urea. A second necessary reactant is an aldehyde. A third and ammonia-source reactant may be ammonia and/or a primary amine. Finally, there must ~e utilized a strong caustic during the initial first step or phase of period of heating an admixture of the above-noted reactants, which strong caustic is added gradually over the period of time of the first period of heating and reaction to the extent required in order to maintain the p~I within the critical broad or preferred ranges. During an initial first pnase of reaction, reaction of the above-noted reactants is achieved by heating the admixture thereof at a temperature within a range of from about 85 degrees Centigrade to about 93 degrees Centigra~e for a period of time ranging from about 15 minutes to about 60 minutes while maintaining pEI within a critical range of about 8 up to about 9.5 by adding the strong caustic as the pH tends to droy during that reaction ~eriod, during the initial first phase of reaction, the above-noted urea-like component relative to the aldehyde reactant must be maintained at least during the earlier and a dominant portion of the first phase at a reactant mole ratio of from about 0.5 to about 2.0, and likewise for ammonia on the basis of weight of ammonia, from the ammonia source above-noted, relative to the aldehyde within a ratio range of from about 0.20 to about 0.85. On a weight-basis of i2S~89 ammonia, relative to weight basis of 100% of reactants, the ammonia, relative to a weight basis of 100% of reactants, m~st be reacted in an amount within a ranye of from about 2.2% to about 6~, relative to the above-noted reactants on a weight basis of total water-solution weight. Following the first stage of heatiny and reacting, heating is continued within the same temperature range, for an additional period of about 0-60 minutes, preferably 10-30 minutes, while permitting the pll to decrease by reducing or terminating any further addition of the strong caustic, sufficiently to result in reaction product(s) of which triazone composition(s) thereby produced relative to unreacted amounts of the urea-like component on a weig~lt basis has a ratio of at least about l.
For the above-stated method, optimal results and production critically representing the heart of the present method are as follows. During the first phase above-noted, the reaction temperature is maintained at between about 91 deyrees Centigrade and about 93 degrees Centigrade, and the period of first-phase heating ranges between about 28 minutes to about 35 minutes, and the ratio of the urea-like component to aldehyde is maintained between about 0.5 and 1.2, and the ammonia to aldehyde above-noted ratio is about 0.55 to about 0.8, and the above-noted ammonia weight is maintained at from about 3%
to about 3.5%; and during the second, final phase of heating, the temperature of reaction is maintained at from about 90 degrees Centigrade to about 93 degrees Centigrade. In the method, for preferred reactants for optimal results critically representin~ the heart of the present invention, the aldehyde at least in a major proyortion thereof is formaldehyde, and the urea-like component at least in a major proportion thereof is urea, and the ammonia source in a Ina jor proportion thereof is ~L2S~89 ammonia. Good results are also obtained by use of methyl urea, in part or in w~lole as the urea-like component, and by use of methylamine as a substitute for ammonia, and likewise for ethylene diamine, and likewise for methylolamine and/or monoethanolamine. As the above-noted urea-like component, also good results are obtained by use of thiourea, in part or in whole as the urea-like component, and by use of acetaldehyde, in part or in whole as the aldehyde source, for example.
As a third aspect of the present invention, namely the method of fertilizing vegetation, the method may be broadly described as applying to vegetation foliage, a water solution of the fertilizer composition described above for each respectively of broad and narrow (preferred) statements of limitations, and including the method of applying each respectively or both of the triazones above-identified by the empirical formulas 3 7 3 nd/o C5HloN4O3 and having the cyclic formulas above stated respectively.
Urea-aldehyde mixture, as commercially available, is normally of pH range of about 7.5 to about 9; an old solution that might have a lower plI should be adjusted to pH 7.5-9 for preferred results.
DETAILED DESCRIPTION
For the method of this invention, and the product(s) thereof so produced, it has been determined that stable products cannot be made witn less than about
. .
TH~ SPECIFIC~TION
This invention relates to a novel liquid fertilizer ancl the novel method of ma]cing it.
BACI~GROUN~
Prior to the present inVentiOII there has been no method which w~len repeated continually will produce either triazones and/or a high concentration thereof reliabl~
and/or consistently. Also, by prior methods of making fertilizers by somewhat similar or related method(s), the resulting product or mixture of products exhibit low or poor stability, decomposing and/or converting to crystalline compounds or products that precipitate out thereby destroying their utility for use as liquid fertiiizer, solid fertilizer of the triazone or related types of insoluble (in water) nature not bein~ capable of releasing nitrogen to the roots suf-ficiently rapidLy as to be economically or commercially feasible or practica Moreover, it has been found that by current technology, it is impossible to separate individual triazone compounds from mixtures thereof in water-containing reaction product mixtures thereof, and until procedures utilized by the present inventor it has heretofore not been readily possible to ascertain exact structure(s) and formula(s) of aqueous reaction products of process(es) related to or somewhat similar to the present method. Likewise until research by the present inventor, it hereto-Eore had not been recoynized nor known what factors and/or yield of the final product(s) thereof such as in the present inventive process resultin~ in iligh concentration of hiyh solubility and stable products of principally triazone compound(s) of the ~resent invention presellt as a water-soluble mixture.
While there is no certainty that somewhat similar or related processes have resulted in the production of any triazone product~ as a part of the product-mixture in water solution, or that -- if any were present or so 12~8i8~
~f produced -- that amount of triazone therein was present in any appreciable nor significant amount, or for how long such would be present prior to decomposition thereof or prior to the overall-mixture (reaction product) beco~ing worthless insofar as utility for liquid fertilizer because of crystallization and precipitation of constituents thereof, the closest superficially related method or process to that of the present invention appears to be that of the Justice et al. United States Patent 3,462,256 issued on August 19, 1969, which is directed to and claimc a process utilizing different process parameters and different mole ratio-parameters for reactants, failing to recognize the presence (if any~ oE the triazone(s) of the present invention and the importance thereof as a liquid fertilizer and the importance of such parameters and resulting reaction product from the standpoint of each and both effectiveness as a fertilizer of liquid nature, lack of sensitivity thereto of human skin and long-term stability thereof of the present invention. The broad limits of the Justice patent include employing urea and formaldehyde reactants in urea/formaldehyde ratio of l/2, preferably 1.3/1.8, utilizing ammonia at a weight percentage of 0.3 to 6 broadly, preferably 0.7 to 3, at reaction temperatures ranging from 75 degrees Centigrade to boiling broadly, preferably from 85 to 95 degrees Centigrade, at a pE3 ranging broadly from 8.5 to lO, preferably 9 to 9.8, during a heating time of reaction broadly for 30 to 180 minutes, preferably froM 75 to 115 minutes. While some of the parameters overlap, there has been no recognition by Justice nor other prior art of the critical parameters of Applicant/inventor and of tihe combination thereof critically necessary for the obtaining of the present invention, as shall be evidenced by some of Applicant's experiments contained herein as Examples of methods that do not work.
~81t~
OBJEC`T~ ok-llrH~ INVENTION
An object of the present invention is to obtain a novel liquid fertilizer composition 4uitable for foliar application and sod application devoid of potential burning o~ foliage and/or sod.
Another object is to obtain a novel liquid fertilizer composition suitable for situations requiring slow-release nitrogen sources.
Another object is to obtain a novel composition havinc~ an elevated or high percentage of triazone composition suitable for use as a fertilizer for foliar and/or sod applications.
Another object is to obtain the above-noted compositions characterized by good stability and long-terl,l lS stability against crystallization(s) of components thereof and/or precipitation therefrom of components thereof immediately or during storage.
Another object is to obtain a novel triazone composition having a high triazone composition in aqueous form, that has a higll level of stability against decomposition of the triazone or against degradation thereof.
Another object is to obtain a novel triazone composition in aqueous solution having high concentration of particular triazone(s).
Another object is to obtain a novel method/process for producing said novel liquid fertilizer composition(s) and improved high stabilities and composition(s) having said slow-release and having the characteristics of non-burning of foliàge and/or sod when applied there~o.
Another object is to obtain a novel method of fertilizinc~ vegetation of varying types and includinc~ sod, utilizing novel compositions of this invention.
Other objects become apparent from the preceding and following disclosure.
12S8~39 6 ~
One or more objects of the invention are obtained by the invention as set forth herein, and as claimed in the appended claims.
SUMMARY OF THE INVENTION
Broadly the invention may be characterized as three inter-related inventions, namely a li~uid fertilizer of novel compositions(s), a novel method of producing those compositions, and a novel method of foliar fertilizer application.
More particularly, broadly stated the invention includes a liquid fertilizer composition having colnponents thereof present in particular amounts within stated ranges, including a triazone-type composition that is substantially solubl~ in water sufficiently to obtain stability to a practical commercial degree, a urea-type, compound, water sufficient in amount to obtain and retain a solution of the triazone(s), limited minor percentages of a monomethylol urea-type compound and a methylene diurea, and potentially minor amounts of a dimethylol urea-type compound and a hexamethylene tetramine-type compound. The triazone-type composition is present in an amount of at least about 30~, preferably about 35~ to about 50% and in an amount in ratio to urea by weight of at least 0.48, preferably at least about 1. The urea-type com!~ound on a dry-weigl~t basis i~ about 10% u~ to a~out 50%, preferably less than 35%, and the monomethylolurea-type compound is u~ to about 7~. On the dry-weight basis, the methylene diurea-type compound may be present up to about 3~, preferably less than about 2%, and the monomethylolurea Inay be present up to about 7%, ~referably less than about 3~, and provided the total weight of methylene diurea an~ monometllylolurea does not exceed about 10%, preferably less than about 6~ (u~ to 6%). The ratio of triazone(s) on a dry weight basis, to ~ethylene diurea is at least about 6, preferably at least about 11.
Dimethylol urea and hexamethylenetetramine may or May not lZ58189 be present, with dimethylolurea ranging up to a~out 2.75%
on a weight basis of total weight of the aqueous solution, and with hexamethylenetetramine u~ to about 2 percent, preferably up to about 1~ on a weight basis (dry weight), or less, normally th~re being no hexamethylene tetramine present. The above-stated amounts of triazone composition and its ratio to urea are critical to the utility of the total composition of fertilizer and water solution thereof as the liquid fertilizer for the above-stated objects.
The improved lower urea-content in the product achieves both lower phytotoxicity and higher triazone content, by this improved invention. When treating the aqueous solution of urea-type compound and aldehyde-type compound, with the ammonia, preferred results are obtained by maintaining the temperature below 65C, preferably below 60 de~rees Centigrade. Also, in order to have the high level of stability of the composition of this invention, the method must be limited critically to not more than the above-stated maximum amounts of compounds such as the monomethylol urea, dimethylol urea and methylene diurea because of their low and limited water-solubility and instability insofar as tending to crystallize and/or precipitate out. Substantially the same thiny is true for hexamethylenetetramine that is likewise limited in its maximum permissible amount of the inventive composition.
The present invention, then, in one aspect, resides in a liquid fertilizer composition comprisin~, as calculated on a dry weight basis of 100~ solids:
one or more substantially water soluble triazone compounds in an amount of at least 30~;
one or more urea compounds in an amount of from 10~ to 60%, and water, the composition containing not more than the indicated amounts (dry weight basis) of the following urea compounds 35 and of hexamethylenetetramine compounds:
methylene diurea compounds 7.9 125E31~39 monomethylol urea compounds 7.2 hexamethylenetetramine compounds 2%, all the above compounds beiny dissolved in the water and the triazone compound:methylene diurea compound weight ratio being 6:1 or more.
According to another embodiment of the invention there is provided a method for producin~ a water-solution fertilizer composition of substantially stable water-soluble components as a reaction product containiny one more more substantially water-soluble triazone-type compounds, comprising:
(a) reacting in aqueous solution a urea compound, an aldehyde and ammonia or a primary amine;
(b) thereafter further reacting in a first heating stage at a temperature between 80C and 95C for an additional reactiny period of from 15 minutes to 1 hour while adding as necessary during the additional reacting period a strony base to maintain the pl~ within the range of h to 9.5 and while addin~ as necessary during the additional reacting period the urea compound and the aldehyde to maintain a mole ratio of the urea compound to the aldehyde within the range of from 0.5 to 2, and while adding as necessary during the additional reactiny period ammonia or the amine to maintain a mole ratio of ammonia or amine to the aldehyde within a range of from 0.15 to 0.65, the ammonia or amine being reacted in an amount ranging from 2~ up to 6% on a total water-mixture weight basis of 100~ of reactants of the urea compound, the aldehyde and the ammonia or amine, and (c) thereafter as a second heatiny stage maintaining the reaction temperature between 80C and 95~` for a further period up to 1 hour, such that the final reaction product has a triazone compound:unreacted urea compound weight ratio of at least 0.5:1.
The present invention further provides a method of fertilizing vegetation and/or soil which comprises ~2sal~
applying to vegetation foliage and/or soil a li~uid fertilizer composition as described above.
In a preferred embodiment of the invention, on a weight percentage basis, a maJor amount of the triazone composition and/or mixture are triazones having the empirical formulas C3H7N30 (5-S-tetrahydrotriazone) and C5HloN403 ~N-hydroxymethylformamidetriazone), with cyclic formulas H~ H ~H~ H
H2 -~-CH2 and 2 ~ CH2 respectively, C=~NH-CH2-OH
of the total triazone the C3H7N30 on a weiyht basis amounts to preferably and normally at least about 80~
which is critical to obtaining preferred results as to the above-stated objects.
The method of the invention has a combination of :
critical temperature ranges, pH ranges, reactant ratios, essential reactants, and periods of reaction, as well as being a two-phase method insofar as periods of time of heating at different pH levels. In the absence of these critical limitations, it has been discovered by the present inventor to be impossible to obtain the high level of production of the triazone composition(s) of this invention, or to obtain a liquid fertilizer containing 5uch Witil a high level of stability, particularly in conjunction with the high level or weiyht percentage produced. Likewise, to obtain the non-burning triazones of this invention suitable for fertilizer Eoliar application as well as soil application, the critical limitations are necessary to obtain such product(s).
Naturally there are broad ranges for many of these limitations within which some degree of success may be 1258~8~3 obtained, but with the rnaximum and high quality production being limited to the method's preferred ranses.
More particularly, for the broader aspects of the invention, the process may be described as a method for producing a water-solution fertilizer composition of substantially stable water-soluble components, of ~hich the major novel component(s) thereof as reaction product(s) are substantially water-soluble triazone compounds, reaction components and steps being as follows.
rrhe urea-like component must be selected from urea and/or substituted urea. A second necessary reactant is an aldehyde. A third and ammonia-source reactant may be ammonia and/or a primary amine. Finally, there must ~e utilized a strong caustic during the initial first step or phase of period of heating an admixture of the above-noted reactants, which strong caustic is added gradually over the period of time of the first period of heating and reaction to the extent required in order to maintain the p~I within the critical broad or preferred ranges. During an initial first pnase of reaction, reaction of the above-noted reactants is achieved by heating the admixture thereof at a temperature within a range of from about 85 degrees Centigrade to about 93 degrees Centigra~e for a period of time ranging from about 15 minutes to about 60 minutes while maintaining pEI within a critical range of about 8 up to about 9.5 by adding the strong caustic as the pH tends to droy during that reaction ~eriod, during the initial first phase of reaction, the above-noted urea-like component relative to the aldehyde reactant must be maintained at least during the earlier and a dominant portion of the first phase at a reactant mole ratio of from about 0.5 to about 2.0, and likewise for ammonia on the basis of weight of ammonia, from the ammonia source above-noted, relative to the aldehyde within a ratio range of from about 0.20 to about 0.85. On a weight-basis of i2S~89 ammonia, relative to weight basis of 100% of reactants, the ammonia, relative to a weight basis of 100% of reactants, m~st be reacted in an amount within a ranye of from about 2.2% to about 6~, relative to the above-noted reactants on a weight basis of total water-solution weight. Following the first stage of heatiny and reacting, heating is continued within the same temperature range, for an additional period of about 0-60 minutes, preferably 10-30 minutes, while permitting the pll to decrease by reducing or terminating any further addition of the strong caustic, sufficiently to result in reaction product(s) of which triazone composition(s) thereby produced relative to unreacted amounts of the urea-like component on a weig~lt basis has a ratio of at least about l.
For the above-stated method, optimal results and production critically representing the heart of the present method are as follows. During the first phase above-noted, the reaction temperature is maintained at between about 91 deyrees Centigrade and about 93 degrees Centigrade, and the period of first-phase heating ranges between about 28 minutes to about 35 minutes, and the ratio of the urea-like component to aldehyde is maintained between about 0.5 and 1.2, and the ammonia to aldehyde above-noted ratio is about 0.55 to about 0.8, and the above-noted ammonia weight is maintained at from about 3%
to about 3.5%; and during the second, final phase of heating, the temperature of reaction is maintained at from about 90 degrees Centigrade to about 93 degrees Centigrade. In the method, for preferred reactants for optimal results critically representin~ the heart of the present invention, the aldehyde at least in a major proyortion thereof is formaldehyde, and the urea-like component at least in a major proportion thereof is urea, and the ammonia source in a Ina jor proportion thereof is ~L2S~89 ammonia. Good results are also obtained by use of methyl urea, in part or in w~lole as the urea-like component, and by use of methylamine as a substitute for ammonia, and likewise for ethylene diamine, and likewise for methylolamine and/or monoethanolamine. As the above-noted urea-like component, also good results are obtained by use of thiourea, in part or in whole as the urea-like component, and by use of acetaldehyde, in part or in whole as the aldehyde source, for example.
As a third aspect of the present invention, namely the method of fertilizing vegetation, the method may be broadly described as applying to vegetation foliage, a water solution of the fertilizer composition described above for each respectively of broad and narrow (preferred) statements of limitations, and including the method of applying each respectively or both of the triazones above-identified by the empirical formulas 3 7 3 nd/o C5HloN4O3 and having the cyclic formulas above stated respectively.
Urea-aldehyde mixture, as commercially available, is normally of pH range of about 7.5 to about 9; an old solution that might have a lower plI should be adjusted to pH 7.5-9 for preferred results.
DETAILED DESCRIPTION
For the method of this invention, and the product(s) thereof so produced, it has been determined that stable products cannot be made witn less than about
2~ (by weight of ammonia relative to about total weight of reactants) of ammonia up to about 6% ammonia, and that stable product(s) cannot be made at temperature(s) ~ligher than about 93 degrees Centigrade, and that it is difficult to make products at pEi values above about pE~ 9.5. During the developiny of the critical limitations of this invention, it was determined that the ~II of the reactant mix as above~described, the reaction temperature(s), and ~25~3189 the mole % of ammonia above-stated, each and all were much more critical to the reaction than had been initially believed. It is noted that the development of the procesC
of the present invention, and the eventual production of the novel composition(s) thereof, resu:Lted from finding and recognition that the currently heretofore available liquid fertilizer concentrates, such as obtained from the practice of the process of U.S. patent 3,462,256 to Justice et al., had unreliable shelf life as to period of time of stability prior to crystallization and/or precipitation rendering the products commercially useless and commercially impractical for foliar application, the shelf life having been observed to be variable from batch to batch produced. As a result, the process/method of the present invention was undertaken by the present inventor to produce the novel composition(s) thereof and the novel method of fertilizer application. Also, the present inventor discovered that monomethylolurea and dimethylolurea convert to methylenediurea on standing at ambient temperature and over a period of several weeks typically, causing solids to deposit. Moreover, it nas been found that methylol compounds when reacted with urea at low temperatures merely sufficiently high to dissolve the urea over a period of about 15 minutes results in an unstable mixture, due to slow reactions at ambient temperatures to form methylolureas, such product being typically produced by the Moore patent U.S. 4,304,588 issued 12/8/81 and U~S. patent 4,244,727 issued 1/13/81, in which patents the product(s) are identified as monomethylol urea. Moreover, it was discovered by the inventor, that concentration of methylene diurea is a major limiting factor to the storage stability of the product(s) of the present invention, and that the amoul~t of methylenediurea converted from urea, should not exceed about 3~ on a weight~basis as previousl~ set forth above, in order to insure adequate storaye life from a commercial practical viewpoint of utility of a liquid fertilizer product. Also, because each of monomethylol urea and dimethylolurea ilave been found to be unstable in solution and tend to convert to urea and methylene ureas, each and both should be kept to a minimum, as previously stated herein .
While the inventor is not to be bound by hypothesis of the exact reactions that occur, studies and research conducted by t~e present inventor indicates that the triazone(s) of the present invention are formed as a result of serially consecutive reactions as follows. Urea reacts with formaldehyde, for example, to produce monomethylol urea; the monomethylol urea reacts with formaldehyde, for example, to product dimethylol urea; and typically methyl amine reacts with the dimethylol urea to produce a methyltriazone, or an unsubstituted amine reacts with dimethylol urea to produce a hydrogen-triazone (S-tetrahydrotriazone), for example.
In experiment(s) using hexamethylenetetramine as the source of ammonia, it was found that the reaction proceeds very slowly and that an unsatisfactory product is formed which rapidly crystallized on standing. A large percentage of the ~lexamethylenetetramine remained unreacted. Also, in the method, too little ammonia and/or too much formaldehyde (or other aldehyde) results in too high a percentage of unreacted urea, for the above-described method of this invention. ~nen on a ~ry weiyht basis the ratio of triazone to methylene diurea of the final reaction product is less than 6%, yield of the triazone composition of this invention is unsatisfactorily low and poor; accordinyly, the method of the invention maintains the methylene diurea in the final product at a satisfactory minimum.
The product of this invention is prepared by mixiny together the required amount of urea, formaldehyde l'~S8~89 and ammonia in an aqueous solution, as a typical example.
The admixture and/or solution is heated thereafter to a carefully controlled temperature, maintained at about that temperature for a specific length of time while also carefully controlling the pEL during the initial first phase of heating and reacting by a slow addi-tion of strong alkali. Thereafter, the approximate same temperature is maintained for a second phase time period to bring about a completion of reaction. The batcil is then cooled and packaged.
The order of addition of the source(s) of urea, formaldehyde, ammonia and water are not considered to ~e very important provided there does not occur any prolonged periods of time of addin~ a final ingredient and/or provided imbalance of reactants in the required necessary amounts is not permitted for any significant period during reaction, and provided the one or more reactants are in admixture not permitted to sit in an unreacted state for any unreasonable or ~,rolonged period of time. The ammonia-type reactant sllould be slowly added to the above mix with controlled temperature of reaction.
The urea may be added either as pelleted or crystal urea, as urea solution or at least partially as an already partially condensed urea-formaldehyde reaction product. The formaldehyde may be added as commercially available formaldehyde solution or as ~araformaldehyde, or partially in the form of hexamethylene-tetramine or as an already partially condensed urea/formaldehyde reactant.
The ammonia may be added as anhydrous, aqua ammonia or partiall~ in the form of hexamethylenetetramine. The total nitroyen in the solution should be between at least 16% and 31~ or more on a weight basis of the total reaction product solution which may be later diluted.
Because, as noted-above, it had proven impossible to obtain stable liquid urea-formaldehyde fertilizer lZS818~
solutions when followiny the procedures and/or metnods of prior art patents and literature, due to the limited solubility of monomethylol urea, dimethylol urea and methylene diurea and also due to the inherent instability of these materials, it therefore became necessary for t~le present inventor to separate dnd to identify the components of the reaction product(s) of the present invention of liquid fertilizer solution.
High pressure liquid chromatography was used to separate the separate reaction products prepared by the method of this invention, and prepared by related methods. Most of its components were identified by the preparation of pure compounds and running them as standards on the liquid chromatography (HPLC).
One major component could not be identified by this procedure.
Paper chromatographic separation was used to concentrate this unknown component which was subsequently purified by recrystallization and identified as the ~ unknown by further HPLC analysis.
This invention-sample was then analyzed by mdss spectrophotometric, NMR, infrared and by an elemental analyzer, and determined to be an 80/20 mixture of S-tetrahydrotriazone above-identified herein as haviny the empirical formula C3H7N30 having the cyclic formula set forth above herein, and N-hydroxymethyl formamide triazone havin~ the empirical formula C5~10~4o3 having the cyclic formula set forth above.
A suitable caustic includes any one or Inore of sodium hydroxide, potassium hydroxide, lithiunn hydroxide, sodiurn carbonate or other strong caustic.
The triazones within the contemplation of this invention as liquid fertilizer suitable for application to foliage and/or sod, include the relatively few triazones that are cllaracterized by beiny substantially readily soluble in water, most triazones bein~ insoluble in water.
~Z581t~
The liquid fertilizer product(s) of this invention were compared to certain other chemical and commercial products with regard to phytotoxicity, as follows. ~en averaged over all ~our species of turf, grasses, for St. ~ugustine, Hybri~ Bermuda, Fescue and Perennial Ryegrass, for a series of tests eml~loying different numbers of pounds per square ft. as the i~ rate, the urea-triazone mixture of this invention was less phytotoxic than "Formolene"(~) or urea by 37.5% and 44.4 percent, respectively, at the most commonly used rate of N
on turf (1 lb./1,000 sq. ft.). When averaged over all species and rates, the urea-triazone mixture of this invention was 6.6~ and 30~ less phytotoxic than "Formolene"(~) and urea, respectively.
The urea-triazone of this invention is substantially safer than Formolene(~) when applied at 2.65 lbs. N/1000 sq. ft. (an undiluted application).
Accordingly, the triazone(s) (urea-triazones) above-identified for this invention, are a safer turf nitrogen than the other items above-tested for comparable uses.
Likewise, for the DOT skin corrosion tests, the triazone products were found to be not corrosive.
Following are typical runs, some by the method of this invention, and others outside of the limitations of the inventive method, serving in part to illustrate some of the critical limitations of the method of this invention.
EXA~PLE I
(samples 1-2, 2-2, 3-2, ~-~, tested at one point in time) (Based on water soln. wt.) lZ5818~
- 1~3 -ComporIellts of / Percentage pre~sent reaction product / by weiqht 1-2 2-2 3-~ 4-2 -Urea 28.7 27.3 30.0 3~.9 MonometIIylol urea1.8 1.8 6.1 0.9 Methylene diurea 0.8 1.3 1.1 1.1 Dimethylol urea 0-7 1.1 0.7 1.2 Triazone 18.8 19.6 12.9 8.2 IIexamethylene tetramine ~ 2.5 The Sample 3-2 having am monomethylol urea (MM~) percentage of 6.1~ had poor stability, the methylene diurea crystallizing-out as the monomethylol decomposed when stored for a short period on the shelf. Likewise, the sample, 4-2 was unsatisfactory in its yield of triazone, at 8.2%, as a result of the final product having a high concentration of unreacted urea at 36.9% and as well there being present an unsatisfactorily large percentage of hexamethylene tetramine at ~.~%, causing also instability resulting in crystallization and precipitation of components, rendering the products totally unsatisfactory for use as a liquid foliant. From the above table of which the balance of percentage for each sample is water, the percentages present on a basis of total solids are:
1_2 2-2 3-2 4-2 Urea 56.50 53.33 5g.04 72~00 Monomethylol urea (M~IU) 3.54 3.52 12.01 1.76 Methylene diurea (MDU) 1.57 2.54 2.17 2.15 Dimethylol urea (DMU) 1.37 2.15 1.41 2.34 30 Triazone 37.01 3~.28 25.89 16.0 Hexamethylenetetramine -- -- -~ 6-36 Wt. ratio of Triazone/urea 0.65 0.72 0.43 0.22 Wt. ratio of Triazone/MDu 23.5 15.1 11.7 2.6 i~S8~89 -- 19 ~
Four days later, again the components percentages after that ad~itional shelf-life, were tested, giving the following results for the above-noted samples.
(% Oll basis of total water solution~
Com~onents of reaction pdt. 1-2 2-2 3-2 4-2 5-2 __ _ (prior run) Urea 29.4 27.9 30.0 35.5 28.7 MMU (less than) 0.1 0.8 5.3 0.4 2.3 YDU 0-9 1.2 1.2 1.2 1.2 DMU 0.5 0.5 0.8 1.0 0.6 Triazone 20.0 20.4 13.7 9.5 18.3 Hexamethylene tetramine -- -- -- 6.36 --The solids percentages by weight for this preceding table 15 are:
1_2 2-2 3-2 4-2 5-Urea 57.7 54.9 59.5 69.9 56.2 MMU 0.2 1.6 10.5 0.~3 4~5 MDU 1.~ 2.4 2.4 2.4 2.4 DMU 0.98 0.98 0.4 1.2 1.. 2 Triazone 39.3 40.2 26.9 1~.7 35.8 Hexamethylene tetramine -- -- ~~ 5-7 ~~
As can be seen, the amount of hexamethylenetetramine is high and the triazone is low for experiment 4-2.
Some of the preferred triazones of this invention include S-tetrahydrotriazone, and methyl-triazone, and beta-ethanol-triazone.
~'or the several above-noted reaction products of the preceding Example I above discussed and disclosed, the formulations utilized and the common (same) method applied to each were as fo.llows:
i2S8~8~
Formulation (wt.%) 1-2 2-2 3-2 4-2 Urea: 52.3 52.353.2 48.5 25% urea-60g6 formal-dehyde: 31.3 31.331.3 29.0 KOH Soln. (25%): 3.0 3.0 0.3 0.
Aqua Ammonia (28%~I!)3 10.710.7 10.7 19.7 Water 2.7 2.7 5.4 2.5 Mole ratio (1.6/1/.28 1.6/1/.28 (urea/HCHO/NH3): ( 1.6/1/.28 1.6/1/.56 10 The procedures followed for the above-noted formulations, were as follows:
1-2: ~ater, urea-formaldehyde and the urea were mixed together in a reaction kettle and slowly the aqua ammonia was added while mixing. That mixture was heated to &3 15 degrees Centigrade and maintained at a temperature below 90 degrees Centiyrade and at a pH between about pH 8.7 and pH 9 for 45 minutes, the pEI being maintained by the addition of the KOH. Thereafter, further heating and reaction were accomplished by maintaining tha temperature 20 of reactants at between 83 degrees Centigrade and about 9 degrees Centiyrade for an additional 15 minute~.
Thereafter, the reaction product was permitted to cool and was packaged.
2-2: The water, urea-formaldehyde and the urea were 25 mixed together in a reaction kettle and the pH was adjusted to p~l 9.0 by addition of ~OH. That mixture was then heated to 81 degrees Centigrade and the pH durin;~ th~
heating was maintained at between 8.7 to 9.0 by continual additions of KOH~ 13 mixture while heatirlg to 90 degrees 30 Centigrade. The temuerature was thereafter maintained at between 8~ to 90 degrees Centigrade at a pEI ranging from 8.7 to 9.0 until all of the KOH-NE13 mixture had been added. Thereafter heating and reactants' temperature was maintained at between ~38 and 90 degrees Centigrade for an 35 additional 15 minutes, followed by ~ermittin~ the reaction ~roduct to cool, after which it was packaged.
;~s~9
of the present invention, and the eventual production of the novel composition(s) thereof, resu:Lted from finding and recognition that the currently heretofore available liquid fertilizer concentrates, such as obtained from the practice of the process of U.S. patent 3,462,256 to Justice et al., had unreliable shelf life as to period of time of stability prior to crystallization and/or precipitation rendering the products commercially useless and commercially impractical for foliar application, the shelf life having been observed to be variable from batch to batch produced. As a result, the process/method of the present invention was undertaken by the present inventor to produce the novel composition(s) thereof and the novel method of fertilizer application. Also, the present inventor discovered that monomethylolurea and dimethylolurea convert to methylenediurea on standing at ambient temperature and over a period of several weeks typically, causing solids to deposit. Moreover, it nas been found that methylol compounds when reacted with urea at low temperatures merely sufficiently high to dissolve the urea over a period of about 15 minutes results in an unstable mixture, due to slow reactions at ambient temperatures to form methylolureas, such product being typically produced by the Moore patent U.S. 4,304,588 issued 12/8/81 and U~S. patent 4,244,727 issued 1/13/81, in which patents the product(s) are identified as monomethylol urea. Moreover, it was discovered by the inventor, that concentration of methylene diurea is a major limiting factor to the storage stability of the product(s) of the present invention, and that the amoul~t of methylenediurea converted from urea, should not exceed about 3~ on a weight~basis as previousl~ set forth above, in order to insure adequate storaye life from a commercial practical viewpoint of utility of a liquid fertilizer product. Also, because each of monomethylol urea and dimethylolurea ilave been found to be unstable in solution and tend to convert to urea and methylene ureas, each and both should be kept to a minimum, as previously stated herein .
While the inventor is not to be bound by hypothesis of the exact reactions that occur, studies and research conducted by t~e present inventor indicates that the triazone(s) of the present invention are formed as a result of serially consecutive reactions as follows. Urea reacts with formaldehyde, for example, to produce monomethylol urea; the monomethylol urea reacts with formaldehyde, for example, to product dimethylol urea; and typically methyl amine reacts with the dimethylol urea to produce a methyltriazone, or an unsubstituted amine reacts with dimethylol urea to produce a hydrogen-triazone (S-tetrahydrotriazone), for example.
In experiment(s) using hexamethylenetetramine as the source of ammonia, it was found that the reaction proceeds very slowly and that an unsatisfactory product is formed which rapidly crystallized on standing. A large percentage of the ~lexamethylenetetramine remained unreacted. Also, in the method, too little ammonia and/or too much formaldehyde (or other aldehyde) results in too high a percentage of unreacted urea, for the above-described method of this invention. ~nen on a ~ry weiyht basis the ratio of triazone to methylene diurea of the final reaction product is less than 6%, yield of the triazone composition of this invention is unsatisfactorily low and poor; accordinyly, the method of the invention maintains the methylene diurea in the final product at a satisfactory minimum.
The product of this invention is prepared by mixiny together the required amount of urea, formaldehyde l'~S8~89 and ammonia in an aqueous solution, as a typical example.
The admixture and/or solution is heated thereafter to a carefully controlled temperature, maintained at about that temperature for a specific length of time while also carefully controlling the pEL during the initial first phase of heating and reacting by a slow addi-tion of strong alkali. Thereafter, the approximate same temperature is maintained for a second phase time period to bring about a completion of reaction. The batcil is then cooled and packaged.
The order of addition of the source(s) of urea, formaldehyde, ammonia and water are not considered to ~e very important provided there does not occur any prolonged periods of time of addin~ a final ingredient and/or provided imbalance of reactants in the required necessary amounts is not permitted for any significant period during reaction, and provided the one or more reactants are in admixture not permitted to sit in an unreacted state for any unreasonable or ~,rolonged period of time. The ammonia-type reactant sllould be slowly added to the above mix with controlled temperature of reaction.
The urea may be added either as pelleted or crystal urea, as urea solution or at least partially as an already partially condensed urea-formaldehyde reaction product. The formaldehyde may be added as commercially available formaldehyde solution or as ~araformaldehyde, or partially in the form of hexamethylene-tetramine or as an already partially condensed urea/formaldehyde reactant.
The ammonia may be added as anhydrous, aqua ammonia or partiall~ in the form of hexamethylenetetramine. The total nitroyen in the solution should be between at least 16% and 31~ or more on a weight basis of the total reaction product solution which may be later diluted.
Because, as noted-above, it had proven impossible to obtain stable liquid urea-formaldehyde fertilizer lZS818~
solutions when followiny the procedures and/or metnods of prior art patents and literature, due to the limited solubility of monomethylol urea, dimethylol urea and methylene diurea and also due to the inherent instability of these materials, it therefore became necessary for t~le present inventor to separate dnd to identify the components of the reaction product(s) of the present invention of liquid fertilizer solution.
High pressure liquid chromatography was used to separate the separate reaction products prepared by the method of this invention, and prepared by related methods. Most of its components were identified by the preparation of pure compounds and running them as standards on the liquid chromatography (HPLC).
One major component could not be identified by this procedure.
Paper chromatographic separation was used to concentrate this unknown component which was subsequently purified by recrystallization and identified as the ~ unknown by further HPLC analysis.
This invention-sample was then analyzed by mdss spectrophotometric, NMR, infrared and by an elemental analyzer, and determined to be an 80/20 mixture of S-tetrahydrotriazone above-identified herein as haviny the empirical formula C3H7N30 having the cyclic formula set forth above herein, and N-hydroxymethyl formamide triazone havin~ the empirical formula C5~10~4o3 having the cyclic formula set forth above.
A suitable caustic includes any one or Inore of sodium hydroxide, potassium hydroxide, lithiunn hydroxide, sodiurn carbonate or other strong caustic.
The triazones within the contemplation of this invention as liquid fertilizer suitable for application to foliage and/or sod, include the relatively few triazones that are cllaracterized by beiny substantially readily soluble in water, most triazones bein~ insoluble in water.
~Z581t~
The liquid fertilizer product(s) of this invention were compared to certain other chemical and commercial products with regard to phytotoxicity, as follows. ~en averaged over all ~our species of turf, grasses, for St. ~ugustine, Hybri~ Bermuda, Fescue and Perennial Ryegrass, for a series of tests eml~loying different numbers of pounds per square ft. as the i~ rate, the urea-triazone mixture of this invention was less phytotoxic than "Formolene"(~) or urea by 37.5% and 44.4 percent, respectively, at the most commonly used rate of N
on turf (1 lb./1,000 sq. ft.). When averaged over all species and rates, the urea-triazone mixture of this invention was 6.6~ and 30~ less phytotoxic than "Formolene"(~) and urea, respectively.
The urea-triazone of this invention is substantially safer than Formolene(~) when applied at 2.65 lbs. N/1000 sq. ft. (an undiluted application).
Accordingly, the triazone(s) (urea-triazones) above-identified for this invention, are a safer turf nitrogen than the other items above-tested for comparable uses.
Likewise, for the DOT skin corrosion tests, the triazone products were found to be not corrosive.
Following are typical runs, some by the method of this invention, and others outside of the limitations of the inventive method, serving in part to illustrate some of the critical limitations of the method of this invention.
EXA~PLE I
(samples 1-2, 2-2, 3-2, ~-~, tested at one point in time) (Based on water soln. wt.) lZ5818~
- 1~3 -ComporIellts of / Percentage pre~sent reaction product / by weiqht 1-2 2-2 3-~ 4-2 -Urea 28.7 27.3 30.0 3~.9 MonometIIylol urea1.8 1.8 6.1 0.9 Methylene diurea 0.8 1.3 1.1 1.1 Dimethylol urea 0-7 1.1 0.7 1.2 Triazone 18.8 19.6 12.9 8.2 IIexamethylene tetramine ~ 2.5 The Sample 3-2 having am monomethylol urea (MM~) percentage of 6.1~ had poor stability, the methylene diurea crystallizing-out as the monomethylol decomposed when stored for a short period on the shelf. Likewise, the sample, 4-2 was unsatisfactory in its yield of triazone, at 8.2%, as a result of the final product having a high concentration of unreacted urea at 36.9% and as well there being present an unsatisfactorily large percentage of hexamethylene tetramine at ~.~%, causing also instability resulting in crystallization and precipitation of components, rendering the products totally unsatisfactory for use as a liquid foliant. From the above table of which the balance of percentage for each sample is water, the percentages present on a basis of total solids are:
1_2 2-2 3-2 4-2 Urea 56.50 53.33 5g.04 72~00 Monomethylol urea (M~IU) 3.54 3.52 12.01 1.76 Methylene diurea (MDU) 1.57 2.54 2.17 2.15 Dimethylol urea (DMU) 1.37 2.15 1.41 2.34 30 Triazone 37.01 3~.28 25.89 16.0 Hexamethylenetetramine -- -- -~ 6-36 Wt. ratio of Triazone/urea 0.65 0.72 0.43 0.22 Wt. ratio of Triazone/MDu 23.5 15.1 11.7 2.6 i~S8~89 -- 19 ~
Four days later, again the components percentages after that ad~itional shelf-life, were tested, giving the following results for the above-noted samples.
(% Oll basis of total water solution~
Com~onents of reaction pdt. 1-2 2-2 3-2 4-2 5-2 __ _ (prior run) Urea 29.4 27.9 30.0 35.5 28.7 MMU (less than) 0.1 0.8 5.3 0.4 2.3 YDU 0-9 1.2 1.2 1.2 1.2 DMU 0.5 0.5 0.8 1.0 0.6 Triazone 20.0 20.4 13.7 9.5 18.3 Hexamethylene tetramine -- -- -- 6.36 --The solids percentages by weight for this preceding table 15 are:
1_2 2-2 3-2 4-2 5-Urea 57.7 54.9 59.5 69.9 56.2 MMU 0.2 1.6 10.5 0.~3 4~5 MDU 1.~ 2.4 2.4 2.4 2.4 DMU 0.98 0.98 0.4 1.2 1.. 2 Triazone 39.3 40.2 26.9 1~.7 35.8 Hexamethylene tetramine -- -- ~~ 5-7 ~~
As can be seen, the amount of hexamethylenetetramine is high and the triazone is low for experiment 4-2.
Some of the preferred triazones of this invention include S-tetrahydrotriazone, and methyl-triazone, and beta-ethanol-triazone.
~'or the several above-noted reaction products of the preceding Example I above discussed and disclosed, the formulations utilized and the common (same) method applied to each were as fo.llows:
i2S8~8~
Formulation (wt.%) 1-2 2-2 3-2 4-2 Urea: 52.3 52.353.2 48.5 25% urea-60g6 formal-dehyde: 31.3 31.331.3 29.0 KOH Soln. (25%): 3.0 3.0 0.3 0.
Aqua Ammonia (28%~I!)3 10.710.7 10.7 19.7 Water 2.7 2.7 5.4 2.5 Mole ratio (1.6/1/.28 1.6/1/.28 (urea/HCHO/NH3): ( 1.6/1/.28 1.6/1/.56 10 The procedures followed for the above-noted formulations, were as follows:
1-2: ~ater, urea-formaldehyde and the urea were mixed together in a reaction kettle and slowly the aqua ammonia was added while mixing. That mixture was heated to &3 15 degrees Centigrade and maintained at a temperature below 90 degrees Centiyrade and at a pH between about pH 8.7 and pH 9 for 45 minutes, the pEI being maintained by the addition of the KOH. Thereafter, further heating and reaction were accomplished by maintaining tha temperature 20 of reactants at between 83 degrees Centigrade and about 9 degrees Centiyrade for an additional 15 minute~.
Thereafter, the reaction product was permitted to cool and was packaged.
2-2: The water, urea-formaldehyde and the urea were 25 mixed together in a reaction kettle and the pH was adjusted to p~l 9.0 by addition of ~OH. That mixture was then heated to 81 degrees Centigrade and the pH durin;~ th~
heating was maintained at between 8.7 to 9.0 by continual additions of KOH~ 13 mixture while heatirlg to 90 degrees 30 Centigrade. The temuerature was thereafter maintained at between 8~ to 90 degrees Centigrade at a pEI ranging from 8.7 to 9.0 until all of the KOH-NE13 mixture had been added. Thereafter heating and reactants' temperature was maintained at between ~38 and 90 degrees Centigrade for an 35 additional 15 minutes, followed by ~ermittin~ the reaction ~roduct to cool, after which it was packaged.
;~s~9
3-2: The water, urea-formaldehyde and urea were admixed in the reaction kettle and the pH was adjusted to 9.5 with addition of the KOH solution. The admixture/solution of reactants was then heated to about 73 degrees Centigrade at which point the urea was completely dissolved, and thereafter the reactant mixture/solution was maintained at a p~ of 8.5 to 9.~ witn a slow addition of aqua ammonia for approximately 10 minutes while heatiny to 90 degrees Centigrade.
Thereafter heating and maintaining reactants at 88 to 90 degrees Centigrade were continued for an additional 30 minut s, followed by permitting the reaction ~roduct to cool and then by packaging the reaction product.
_ : The same steps were followed as for 3-2 above, except as follows. The addition of aqua ammonia was started at about 75 degrees Centigrade and pH was maintained between 8.5 and 9.0 by a slow addition of the KOH while heating the reactants to 90 degrees Centigrade for approximately 1~ minutes. Thereafter the reactants' temperature was maintained by heating, at between 88 and 90 degrees Centigrade for an additional 3 minutes.
From the above procedures, ~hich resulted in the reaction products already discussed, it will be seen tilat the limitations of the method of this invention are in fact critical. It is also noted that in the above 3-2 procedure, the first-phase above-noted addition of aqua ammonia for the ten minutes, was not the equivalent of use of a strong caustic such as KOH and proved to be unsatisfactory and unacceptable for the method of the present invention. It is also noted that the pH 9.5 of procedure 3-2, was slightly above the broad range of the method of this invention, and that tlle yield of it was relatively poor, as compared (for example) to the much higher yields of 1-2 and 2-2. The reaction product of 4-2 crystallized when permitted to stand (shelf-life) for 72 hour s .
lZ~81~9 EXAMPLE II
Another series of experiments were designed in order to determine and illustrate the effects of v~rious reaction conditions on the quality of the ~roduct. The first of the conditions investigated was the percentaye of ammonia in the cook. This was varied from 0~ to 3.C% (on the basis of weight of the water solution) with the followin~ results.
Run #: 1 2 3_ 4 5 6 10 ~eactant or product 96 NH3 0 1.0 1.5 2.0 2.5 3.0 Unreacted urea 31. 8 30 . 6 34 . 8 37 . 7 34. 7 35. 8 MMU* 20.2 4.3 7.1 1.~ 1.7 Tr. (trace) MDU* 27.7 14.2 15.8 7.9 5.9 7.7 DMU* 18.2 7.1 Tr. Tr. Tr. Tr.
Triazones (the water soln) 1. 3 43. 8 42.3 52.7 57.7 56.5 Tr.=Trace The runs nos. 4, 5 and 6 represent limitations within the method of the present invention.
For the above-noted runs, ratios of triazone(s) to MDU and of NH3 to formaldehyde, and of triazones to unreacted formaldehyde, were as follows:
2 5 Reactant - Pdt triazone(s)/MDU 0.08 5.9 5.0 12.5 18.2 13.7 NH3/HC~lo 0- 05 0.14 0.18 0.23 0.28 triazones/unreacted urea 0.013 0.46 0.39 0.45 0.54 0.51 30 It is noted particularly that triazone(s)/MD~l ratios of runs 1, 2 and 3 were all below 6, and that the resultant yields were poor for the triazone(s), the ~ NH3 reactant for those runs being far below the required limitations of the method of this invention.
35 (NOTE*: MMU=monomethylol urea; MDU=methylene diurea DMU=dimethylol urea) J:
iZ5~189 It is noted that the #4 run has insufficient ammonia reactant which results in excessive unreacted urea and also in a ~roduct of poor stability, i.e., crystallization and ~uick precipitation, i.e., poor shelf life resulted and can be expected, even thouyh yield of the triazone(s) was reasonably acceptable. Also these tests (runs) show that ammonia is necessary for production of a storaye stable composition that includes t~le triazone products in a acceptable yields, within the range of the method of this invention, and the importance of the ratio limitation.
It is within the scope and contemplation of this invention to make such variations and modifications and substitution of equivalents as would be apparent to a person having ordinary skill in this particular art.
In a preferred method of the invention, improved content is obtained by cooling the reaction product immediately (i.e., promptly) after the final second-stage final heating period, down to a lower temperature within a ran~e of about 33 degrees Centigrade to about 37 degrees Centigrade.
Urea type compounds include substituted ureas typically such as thiourea, and monourea and diethylurea and the like, there being many well known conventional such substituted ureas.
Typical aldehydes utilizable, are HCHO
(formaldehyde), para-formaldehyde, acetaldehyde, propionaldehyde, HI~T (commercial designation), and the like.
Typical ammonia sources include ammonia, aqua and anhydrous ammonia, ~T, and primary amines sucn as monoethanolamine, methyl amine, ethylene diamine, and the like.
With regard to use of substituted and/or alternative compounds utilized as reactants in the lZ5~1~39 ~ 24 -above-disclose~ process(es), and to the therefore substituted and/or alternative intermediate and final products and/or compounds, the suffix "-type compound" is utilized herein, and in the accompanying claims to generically encompass such substituted and/or alternative compound~s) of the same root or common structure(s), such as for example terms urea-type compound, triazone-type compound, methylene diurea-type compound, monomethylol urea-type compound, hexamethylene-tetramine-type compound, for example. Likewise, "ammonia source" is intended to generically encompass alternative ammonia-type compounds that either produce or provide ammonia as a reactant and/or that react similarly such as above-noted ammonia sources discussed above.
For the followiny two examples of products produced within the preceding preferred parameters (ranges of temperature, l~ercentages, etc.), the content based on analysis, on a wet (solution) basis, was as follows, where the processes employed a urea/formaldehyde ratio of 1.2, as contrasted to prior examples herein having had a ratio of 1.6.
Batch #: #l _#2 _~
% urea 19.5 20.2 % MMV (monomethylolurea) 3.8 4.3 25 ~ MDU (methylene diurea) 1.8 1.8 % Triazone 30.8 28.8 Triazone/urea ratio1.58 1.43 (by weight/dry) Triazone/MDU
(by dry weight) 17.1 16.0 For the above data, expressed on à dry basis, the analysis i s :
% urea 32.5 33.7 ~ MMU 6.3 7.2 35 % MDU 3.0 3.0 % Triazone 51.3 4&
izs~s SUPPLEMENTARY DISCLOSURE
The present in~ention, in one aspect, as described hereinbefore in the Principal Disclosure, resides in a liquid fertilizer composition consisting essentially of: as calculated on a dry weight basis of 1~0% sol;ds, a triazone composition that is substantïally soluble in water, present at at least about 30% tdry weight~, a urea-type compound present in an amount of from at least about 10~ up to about 50% (dry weight) such that the ratio of amount of trïazone-type compound present ~elati~e to the amount of said urea-type compound present is at least about 0.48, a methylene diurea-type compound up to about 3% (.dry weight), a monomethylol urea type compound up to about 7~ (.dry weight) with total weight ~dry weight) of methylene diurea-type compound and monomethylolurea-type compound up to about 10%, a hexamethylenetetramine type compound up to 2% (.dry weight2, and water in an amount at least sufficient for solution of said triazone composition, said urea-type compound, said methylene diurea-type compound, said monomethylolurea-type compound and said hexamethylenetetramine-type compound being dissolved therein, and said triazonecomposition on a dry weight basis, relative to said methylene diurea type compound being in a ratio of at least about 6.
The present invention, in another aspect, as described hereinabove in the Principal Disclosure, resides in a method for producing a water-solution fertilizer composition of substantially stable water-soluble components as a reaction product containing substantially water-soluble triazine type compounds, comprising: reacting an aqueous solution of a urea-type compound and an aldehyde-type compound, with an ammonia -SD~-lZ58~89 source selected from the group consisting of ammonia and primary amines; ~nd therea~ter further reacting at a temperature heated to and maintained between about 85 degrees Centigrade and 93 degrees Centigrade for an additional reacting period of from about 15 minutes to about 60 minutes while adding as necessary during said additional reacting period a strong caustic sufficient in amount(.s) to maintain the pH within a range of about 8 to about 9.5 and while adding as necessary during said additional reacting period sufficient amounts of any of said urea-type compound and said aldehyde-type compound to maintain a mole ratio of said urea-type compound relative to said aldehyde-type co~pound within a range of from about 0.5 to about 2, and while adding as necessary during said addit~onal reacting period a sufficient amount of said ammonia source to maintain a mole ratio of ammonia-type compound f~om said ammonia source relative to said aldehyde-type compound within a range of fr~m about 0.2 to about 0.85, said ammonia-type compound from said ammonia source being reacted in an amount ranging from about 2% up to about 6~ of ammonia-type compound on a total water-mixture/solution weight basis of lO0~ of reactants of said urea-type compound, said aldehyde-type compound, and said ammonia source; and thereafter as a second stage of reaction, maintaining reaction temperature at said temperature for a further period up to about sixty minutes, such that for a final reaction product including the triazone-type compound, said triazone type compound relative to unreacted amounts of said urea-type compound on a weight basis has a ratio of at l~ast about 0.48.
In an embodiment deemed most preferred and optimal, the composition of the invention has about 20% by weight, of unreacted urea, and has about 50% by weight, of the triazone , . , -SD~2-~ZS818~
(.soluble trïazonel, and a triazone~urea weïght ratio of about 2.5, and has methylenediureas up to a maximum of 3~, and has monomethylolurea up to a maximum of 4%, and has hexamethylene-tetramine up to a maximum of 0.5%, all percentageslbeing by weight on a dry basis.
Specific triazones which.may consti.tute a major amount of the trïazone composition, as prevïously described in the Principal Disclosure, are triazones having the empirical formula C3H7N30 (5-S-tetrahydrotriazone) and th.e empirical formula C5HlON~03~N-hydroxymethyl-formamide triazone), which are designated by the respectïve cyclic ~ormulas:
o HN-~-NH HN-C-NH
~ I andl l t H2C-N_ CH2 H O=CNH-CH2-OH
(5-S tetrahydrotriazonel (N-hydroxymethylformamide triazone~
- Another triazone which. may constitute a major amount of the triazone composition is the triazone having the empirical formula C5HllN302 (5-B-hydroxyethyltriazone) and ha~ing the cyclic formula O
H~N-C-NH
2 ~C 2 (5-~-hydroxyethyltri.aæone~
The 5-B-hydroxyethyltriazone may be present in the triazone composition, by weight, in an amount ~preferably and normallyl of at least about 80%; this is critical to obtaining preferred re~ults ïn accordance ~ith this invention. All of the above-mentïoned three triazones are characterized by high solutility in water.
~ 7 -SD~-lZS8~39 The above-noted compound o~ empirical formula C5HllN3O2(5-~-hydroxyethyltriazone) is the more preferred product typi.cally obtained by the most preferred optimal process of this invention in greatest purity and highest weight percent. It i.s particularly preferred because of its high solubility, its good stabilïty and virtual absence of phytotoxicity. Th.is particular trïazone has a multiple utility, namely being the better foliar fertili~er of this invention, as well as having good fungïcidal properties. The 5-~-hydroxyethyltriazone is produced by using ethanolamine as a substitute for ammonia, as the ammoni.a source, the method being other~ise the same as described for the generic and preferred methods of producing the triazones of this invention.
The most preferred and optimal method of making the composition of this invention, is as previously described for the broad and preferred processes, e~cept that during the previously identifi.ed ini.ti.al first phase of reaction, reaction of the noted reactants is achieved by heating the admixture thereof at a temperature withi.n a range of from about 88 to about 90 degrees Centi.grade, and while maintaining the pH at between 8.5-9, the first phase reaction period being heated for a period of from about 20 to 30 minutes, and the second phase of heating being from about 10 minutes to about 30 minutes; the urea/aldehyde ratio during the initial first phase is maintained at between.a~out 0.~ to about 1.2, and the ammonia/aldehyde ratio as previously described, is maintained at between about 1.5 to about 3, and th.e trïazone/urea wt.ratio is about 2.5 and the nitrogen content is from a~out 24 to about 31 on a ~eight basis of the total reaction product solution, which may be later diluted.
-SD`2~-~258~89 For the abo~e-stated method, the broad range of reactants is as follows.
~ he mole ratio of the urea-like component to aldehyde is maintained between about 0.5 and 1.6, and the ammonia to aldeh~de mole ratio is between about 0.2 to about 0.65 and the abo~e-noted ammonia ~eight is maintained at from about 2% to about 11%. ~he reaction condit;ons are as follows: During the first phase above-noted, the reaction temperature is maintained between about 80 degrees C. and about 93 degrees C, and the period of first phase heating ranges between about lS minutes to about 60 minutes, and while maintaining the p~ at between 8.0 to 9.5 and during the second phase of heating, the temperature of reaction is maintained at from about 80 degrees C, to abollt 83 degrees C.
For the abo~e-stated method, optimal results and production critically representing the heart of the present method are as follows. During the first phase above-noted, the reaction temperature is maintained at between about 90 degrees C.
and about 92 degrees C., and the period of first phase heating ranges between about 20 minutes to about 30 minutes while maintaining the pH between about 8.5 and about 9, and the mole ratio of the urea-like component to aldehyde is maintained between about 0.25 and 0.40 and above-noted ammonia weight is maintained between about 3% and about 6~; and during the second, final phase of heating, reaction temperature is maintained betweenabout 90 degrees C. and about 92 degrees C. In the method, for preferred reactants for optimal results critically rep-resenting the heart of the present invention, the aldehyde at least in a predominant proportion thereof is formaldehyde, and the urea-like component at least in a predominant proportion thereof is urea, and the ammonia source in a predominant --S D~5--iZ5~
proportion thereof is a~nonia. Good results are also obtained by use of methylurea, in part or in whole as the urea-like component, and by use of methylamine as a substitute for ammonia, and likewise for sthylene dïamine, and likewise for monoethanolamine. As the above-noted urea-like component, also good results are obtained ~y use oE thiourea, in part or in whole as the urea-like component, and E~y use of acetaldehyde, in part or in whole as the aldehyde source, for example.
The following is a further example of the present 10 invention:
Example III
Example of Triazone Production on a Co~nercial Basis Twenty-three batches of triazone product were prepa^ed in a 2800 gallon capacity vessel equipped with good agitation and cooling coils and containing a sparger tube for the introduction of the anhydrous ammonia. The first three batches were approximately eleven tons while all subsequent batches were twelve ton batches.
Formulation (Wt.g6) Tons/12 Tons UF-85 (25% Urea, 6096HCHOJ 25.07 4.208 Urea (100%~ 41.70 5.004 Anhydrous Ammonia 3.00 0.360 50% Sodium HydroxideSolution 1.40 0.168 Water 18.83 2.260 Mole Ratio Urea/Formaldehyde/Ammonia-1.2/1/0.25 P_edure Followed:
A) Add the water, UF-85 and urea to reactor.
B) Slowly add the anhydrous ammonia to the reactor at a rate to prevent localized overheating and such that the temperature does not go above 65 degrees Centigrade (approximately 18 lbs. per minutel.
C) Initial Reaction -- Heat the ~atch to 89 degrees Centi-grade + 1 degree Centigrade and maintain this temperature ~ ~, --SD~
lZ58~8~
for forty-five minutes while simultaneously maintaining the p~ between 8.5 and 8.8 by the slow addition of 50%
sodium hydro~ide solution.
D) Secondary Reaction - Continue to maintain temperature at 89 degrees Centigxade ~ 1 degree Centigrade for an additional twenty minutes but end pH control. (pH will slowly drop.~
E) Turn off steam and cool the batch as rapïdly as possible to no more than 40 degrees Centigrade (preferably 30 degrees Centigrade~ and pump to storage.
Composition of Commercial Production Of the twenty-three batches, the retained samples of twenty of them have remained clear on storage. Composition of these batches is as follows:
% Unreacted % Methalol- %Methylene %
Urea Ureas Ureas Triazones Min. 21 1.9 2.7 29.1 Ma~. 23.3 5.3 3.5 38.1 Avg. 22 3.0 3.0 36.9 The composition of the three batches which became cloudy on storage is as ~ollows:
Avg. 21.1 4.2 4.3 30.3 The three bad ~atches were due to failure of the pH or temperature c~ntrollers resulting in pH above 9.0 or temperature above 92 degrees Centigrade.
The variation in the triazone content of the products is due primarily to variations in the ammonia addition.
The composition of these triazone products has been determined by the use of a Hewlett/Packard Model 1084B high pressure liquid chromatograph (HPLCi after first preparing pure s~ples of the constituents and determining their retention times and sensitivity factors under our test conditions.
~/
' --SD~--
Thereafter heating and maintaining reactants at 88 to 90 degrees Centigrade were continued for an additional 30 minut s, followed by permitting the reaction ~roduct to cool and then by packaging the reaction product.
_ : The same steps were followed as for 3-2 above, except as follows. The addition of aqua ammonia was started at about 75 degrees Centigrade and pH was maintained between 8.5 and 9.0 by a slow addition of the KOH while heating the reactants to 90 degrees Centigrade for approximately 1~ minutes. Thereafter the reactants' temperature was maintained by heating, at between 88 and 90 degrees Centigrade for an additional 3 minutes.
From the above procedures, ~hich resulted in the reaction products already discussed, it will be seen tilat the limitations of the method of this invention are in fact critical. It is also noted that in the above 3-2 procedure, the first-phase above-noted addition of aqua ammonia for the ten minutes, was not the equivalent of use of a strong caustic such as KOH and proved to be unsatisfactory and unacceptable for the method of the present invention. It is also noted that the pH 9.5 of procedure 3-2, was slightly above the broad range of the method of this invention, and that tlle yield of it was relatively poor, as compared (for example) to the much higher yields of 1-2 and 2-2. The reaction product of 4-2 crystallized when permitted to stand (shelf-life) for 72 hour s .
lZ~81~9 EXAMPLE II
Another series of experiments were designed in order to determine and illustrate the effects of v~rious reaction conditions on the quality of the ~roduct. The first of the conditions investigated was the percentaye of ammonia in the cook. This was varied from 0~ to 3.C% (on the basis of weight of the water solution) with the followin~ results.
Run #: 1 2 3_ 4 5 6 10 ~eactant or product 96 NH3 0 1.0 1.5 2.0 2.5 3.0 Unreacted urea 31. 8 30 . 6 34 . 8 37 . 7 34. 7 35. 8 MMU* 20.2 4.3 7.1 1.~ 1.7 Tr. (trace) MDU* 27.7 14.2 15.8 7.9 5.9 7.7 DMU* 18.2 7.1 Tr. Tr. Tr. Tr.
Triazones (the water soln) 1. 3 43. 8 42.3 52.7 57.7 56.5 Tr.=Trace The runs nos. 4, 5 and 6 represent limitations within the method of the present invention.
For the above-noted runs, ratios of triazone(s) to MDU and of NH3 to formaldehyde, and of triazones to unreacted formaldehyde, were as follows:
2 5 Reactant - Pdt triazone(s)/MDU 0.08 5.9 5.0 12.5 18.2 13.7 NH3/HC~lo 0- 05 0.14 0.18 0.23 0.28 triazones/unreacted urea 0.013 0.46 0.39 0.45 0.54 0.51 30 It is noted particularly that triazone(s)/MD~l ratios of runs 1, 2 and 3 were all below 6, and that the resultant yields were poor for the triazone(s), the ~ NH3 reactant for those runs being far below the required limitations of the method of this invention.
35 (NOTE*: MMU=monomethylol urea; MDU=methylene diurea DMU=dimethylol urea) J:
iZ5~189 It is noted that the #4 run has insufficient ammonia reactant which results in excessive unreacted urea and also in a ~roduct of poor stability, i.e., crystallization and ~uick precipitation, i.e., poor shelf life resulted and can be expected, even thouyh yield of the triazone(s) was reasonably acceptable. Also these tests (runs) show that ammonia is necessary for production of a storaye stable composition that includes t~le triazone products in a acceptable yields, within the range of the method of this invention, and the importance of the ratio limitation.
It is within the scope and contemplation of this invention to make such variations and modifications and substitution of equivalents as would be apparent to a person having ordinary skill in this particular art.
In a preferred method of the invention, improved content is obtained by cooling the reaction product immediately (i.e., promptly) after the final second-stage final heating period, down to a lower temperature within a ran~e of about 33 degrees Centigrade to about 37 degrees Centigrade.
Urea type compounds include substituted ureas typically such as thiourea, and monourea and diethylurea and the like, there being many well known conventional such substituted ureas.
Typical aldehydes utilizable, are HCHO
(formaldehyde), para-formaldehyde, acetaldehyde, propionaldehyde, HI~T (commercial designation), and the like.
Typical ammonia sources include ammonia, aqua and anhydrous ammonia, ~T, and primary amines sucn as monoethanolamine, methyl amine, ethylene diamine, and the like.
With regard to use of substituted and/or alternative compounds utilized as reactants in the lZ5~1~39 ~ 24 -above-disclose~ process(es), and to the therefore substituted and/or alternative intermediate and final products and/or compounds, the suffix "-type compound" is utilized herein, and in the accompanying claims to generically encompass such substituted and/or alternative compound~s) of the same root or common structure(s), such as for example terms urea-type compound, triazone-type compound, methylene diurea-type compound, monomethylol urea-type compound, hexamethylene-tetramine-type compound, for example. Likewise, "ammonia source" is intended to generically encompass alternative ammonia-type compounds that either produce or provide ammonia as a reactant and/or that react similarly such as above-noted ammonia sources discussed above.
For the followiny two examples of products produced within the preceding preferred parameters (ranges of temperature, l~ercentages, etc.), the content based on analysis, on a wet (solution) basis, was as follows, where the processes employed a urea/formaldehyde ratio of 1.2, as contrasted to prior examples herein having had a ratio of 1.6.
Batch #: #l _#2 _~
% urea 19.5 20.2 % MMV (monomethylolurea) 3.8 4.3 25 ~ MDU (methylene diurea) 1.8 1.8 % Triazone 30.8 28.8 Triazone/urea ratio1.58 1.43 (by weight/dry) Triazone/MDU
(by dry weight) 17.1 16.0 For the above data, expressed on à dry basis, the analysis i s :
% urea 32.5 33.7 ~ MMU 6.3 7.2 35 % MDU 3.0 3.0 % Triazone 51.3 4&
izs~s SUPPLEMENTARY DISCLOSURE
The present in~ention, in one aspect, as described hereinbefore in the Principal Disclosure, resides in a liquid fertilizer composition consisting essentially of: as calculated on a dry weight basis of 1~0% sol;ds, a triazone composition that is substantïally soluble in water, present at at least about 30% tdry weight~, a urea-type compound present in an amount of from at least about 10~ up to about 50% (dry weight) such that the ratio of amount of trïazone-type compound present ~elati~e to the amount of said urea-type compound present is at least about 0.48, a methylene diurea-type compound up to about 3% (.dry weight), a monomethylol urea type compound up to about 7~ (.dry weight) with total weight ~dry weight) of methylene diurea-type compound and monomethylolurea-type compound up to about 10%, a hexamethylenetetramine type compound up to 2% (.dry weight2, and water in an amount at least sufficient for solution of said triazone composition, said urea-type compound, said methylene diurea-type compound, said monomethylolurea-type compound and said hexamethylenetetramine-type compound being dissolved therein, and said triazonecomposition on a dry weight basis, relative to said methylene diurea type compound being in a ratio of at least about 6.
The present invention, in another aspect, as described hereinabove in the Principal Disclosure, resides in a method for producing a water-solution fertilizer composition of substantially stable water-soluble components as a reaction product containing substantially water-soluble triazine type compounds, comprising: reacting an aqueous solution of a urea-type compound and an aldehyde-type compound, with an ammonia -SD~-lZ58~89 source selected from the group consisting of ammonia and primary amines; ~nd therea~ter further reacting at a temperature heated to and maintained between about 85 degrees Centigrade and 93 degrees Centigrade for an additional reacting period of from about 15 minutes to about 60 minutes while adding as necessary during said additional reacting period a strong caustic sufficient in amount(.s) to maintain the pH within a range of about 8 to about 9.5 and while adding as necessary during said additional reacting period sufficient amounts of any of said urea-type compound and said aldehyde-type compound to maintain a mole ratio of said urea-type compound relative to said aldehyde-type co~pound within a range of from about 0.5 to about 2, and while adding as necessary during said addit~onal reacting period a sufficient amount of said ammonia source to maintain a mole ratio of ammonia-type compound f~om said ammonia source relative to said aldehyde-type compound within a range of fr~m about 0.2 to about 0.85, said ammonia-type compound from said ammonia source being reacted in an amount ranging from about 2% up to about 6~ of ammonia-type compound on a total water-mixture/solution weight basis of lO0~ of reactants of said urea-type compound, said aldehyde-type compound, and said ammonia source; and thereafter as a second stage of reaction, maintaining reaction temperature at said temperature for a further period up to about sixty minutes, such that for a final reaction product including the triazone-type compound, said triazone type compound relative to unreacted amounts of said urea-type compound on a weight basis has a ratio of at l~ast about 0.48.
In an embodiment deemed most preferred and optimal, the composition of the invention has about 20% by weight, of unreacted urea, and has about 50% by weight, of the triazone , . , -SD~2-~ZS818~
(.soluble trïazonel, and a triazone~urea weïght ratio of about 2.5, and has methylenediureas up to a maximum of 3~, and has monomethylolurea up to a maximum of 4%, and has hexamethylene-tetramine up to a maximum of 0.5%, all percentageslbeing by weight on a dry basis.
Specific triazones which.may consti.tute a major amount of the trïazone composition, as prevïously described in the Principal Disclosure, are triazones having the empirical formula C3H7N30 (5-S-tetrahydrotriazone) and th.e empirical formula C5HlON~03~N-hydroxymethyl-formamide triazone), which are designated by the respectïve cyclic ~ormulas:
o HN-~-NH HN-C-NH
~ I andl l t H2C-N_ CH2 H O=CNH-CH2-OH
(5-S tetrahydrotriazonel (N-hydroxymethylformamide triazone~
- Another triazone which. may constitute a major amount of the triazone composition is the triazone having the empirical formula C5HllN302 (5-B-hydroxyethyltriazone) and ha~ing the cyclic formula O
H~N-C-NH
2 ~C 2 (5-~-hydroxyethyltri.aæone~
The 5-B-hydroxyethyltriazone may be present in the triazone composition, by weight, in an amount ~preferably and normallyl of at least about 80%; this is critical to obtaining preferred re~ults ïn accordance ~ith this invention. All of the above-mentïoned three triazones are characterized by high solutility in water.
~ 7 -SD~-lZS8~39 The above-noted compound o~ empirical formula C5HllN3O2(5-~-hydroxyethyltriazone) is the more preferred product typi.cally obtained by the most preferred optimal process of this invention in greatest purity and highest weight percent. It i.s particularly preferred because of its high solubility, its good stabilïty and virtual absence of phytotoxicity. Th.is particular trïazone has a multiple utility, namely being the better foliar fertili~er of this invention, as well as having good fungïcidal properties. The 5-~-hydroxyethyltriazone is produced by using ethanolamine as a substitute for ammonia, as the ammoni.a source, the method being other~ise the same as described for the generic and preferred methods of producing the triazones of this invention.
The most preferred and optimal method of making the composition of this invention, is as previously described for the broad and preferred processes, e~cept that during the previously identifi.ed ini.ti.al first phase of reaction, reaction of the noted reactants is achieved by heating the admixture thereof at a temperature withi.n a range of from about 88 to about 90 degrees Centi.grade, and while maintaining the pH at between 8.5-9, the first phase reaction period being heated for a period of from about 20 to 30 minutes, and the second phase of heating being from about 10 minutes to about 30 minutes; the urea/aldehyde ratio during the initial first phase is maintained at between.a~out 0.~ to about 1.2, and the ammonia/aldehyde ratio as previously described, is maintained at between about 1.5 to about 3, and th.e trïazone/urea wt.ratio is about 2.5 and the nitrogen content is from a~out 24 to about 31 on a ~eight basis of the total reaction product solution, which may be later diluted.
-SD`2~-~258~89 For the abo~e-stated method, the broad range of reactants is as follows.
~ he mole ratio of the urea-like component to aldehyde is maintained between about 0.5 and 1.6, and the ammonia to aldeh~de mole ratio is between about 0.2 to about 0.65 and the abo~e-noted ammonia ~eight is maintained at from about 2% to about 11%. ~he reaction condit;ons are as follows: During the first phase above-noted, the reaction temperature is maintained between about 80 degrees C. and about 93 degrees C, and the period of first phase heating ranges between about lS minutes to about 60 minutes, and while maintaining the p~ at between 8.0 to 9.5 and during the second phase of heating, the temperature of reaction is maintained at from about 80 degrees C, to abollt 83 degrees C.
For the abo~e-stated method, optimal results and production critically representing the heart of the present method are as follows. During the first phase above-noted, the reaction temperature is maintained at between about 90 degrees C.
and about 92 degrees C., and the period of first phase heating ranges between about 20 minutes to about 30 minutes while maintaining the pH between about 8.5 and about 9, and the mole ratio of the urea-like component to aldehyde is maintained between about 0.25 and 0.40 and above-noted ammonia weight is maintained between about 3% and about 6~; and during the second, final phase of heating, reaction temperature is maintained betweenabout 90 degrees C. and about 92 degrees C. In the method, for preferred reactants for optimal results critically rep-resenting the heart of the present invention, the aldehyde at least in a predominant proportion thereof is formaldehyde, and the urea-like component at least in a predominant proportion thereof is urea, and the ammonia source in a predominant --S D~5--iZ5~
proportion thereof is a~nonia. Good results are also obtained by use of methylurea, in part or in whole as the urea-like component, and by use of methylamine as a substitute for ammonia, and likewise for sthylene dïamine, and likewise for monoethanolamine. As the above-noted urea-like component, also good results are obtained ~y use oE thiourea, in part or in whole as the urea-like component, and E~y use of acetaldehyde, in part or in whole as the aldehyde source, for example.
The following is a further example of the present 10 invention:
Example III
Example of Triazone Production on a Co~nercial Basis Twenty-three batches of triazone product were prepa^ed in a 2800 gallon capacity vessel equipped with good agitation and cooling coils and containing a sparger tube for the introduction of the anhydrous ammonia. The first three batches were approximately eleven tons while all subsequent batches were twelve ton batches.
Formulation (Wt.g6) Tons/12 Tons UF-85 (25% Urea, 6096HCHOJ 25.07 4.208 Urea (100%~ 41.70 5.004 Anhydrous Ammonia 3.00 0.360 50% Sodium HydroxideSolution 1.40 0.168 Water 18.83 2.260 Mole Ratio Urea/Formaldehyde/Ammonia-1.2/1/0.25 P_edure Followed:
A) Add the water, UF-85 and urea to reactor.
B) Slowly add the anhydrous ammonia to the reactor at a rate to prevent localized overheating and such that the temperature does not go above 65 degrees Centigrade (approximately 18 lbs. per minutel.
C) Initial Reaction -- Heat the ~atch to 89 degrees Centi-grade + 1 degree Centigrade and maintain this temperature ~ ~, --SD~
lZ58~8~
for forty-five minutes while simultaneously maintaining the p~ between 8.5 and 8.8 by the slow addition of 50%
sodium hydro~ide solution.
D) Secondary Reaction - Continue to maintain temperature at 89 degrees Centigxade ~ 1 degree Centigrade for an additional twenty minutes but end pH control. (pH will slowly drop.~
E) Turn off steam and cool the batch as rapïdly as possible to no more than 40 degrees Centigrade (preferably 30 degrees Centigrade~ and pump to storage.
Composition of Commercial Production Of the twenty-three batches, the retained samples of twenty of them have remained clear on storage. Composition of these batches is as follows:
% Unreacted % Methalol- %Methylene %
Urea Ureas Ureas Triazones Min. 21 1.9 2.7 29.1 Ma~. 23.3 5.3 3.5 38.1 Avg. 22 3.0 3.0 36.9 The composition of the three batches which became cloudy on storage is as ~ollows:
Avg. 21.1 4.2 4.3 30.3 The three bad ~atches were due to failure of the pH or temperature c~ntrollers resulting in pH above 9.0 or temperature above 92 degrees Centigrade.
The variation in the triazone content of the products is due primarily to variations in the ammonia addition.
The composition of these triazone products has been determined by the use of a Hewlett/Packard Model 1084B high pressure liquid chromatograph (HPLCi after first preparing pure s~ples of the constituents and determining their retention times and sensitivity factors under our test conditions.
~/
' --SD~--
Claims (34)
1. A liquid fertilizer composition comprising, as calculated on a dry weight basis of 100% solids:
one or more substantially water soluble triazone compounds in an amount of at least 30%;
one or more urea compounds in an amount of from 10% to 60; and water, the composition containing not more than the indicated amounts (dry weight basis) of the following urea compounds and of hexamethylenetetramine compounds:
methylene diurea compounds 7.9 monomethylol urea compounds 7.2%
hexamethylenetetramine compounds 2%, all the above compounds being dissolved in the water and the triazone compound methylene diurea compound weight ratio being 6:1 or more.
one or more substantially water soluble triazone compounds in an amount of at least 30%;
one or more urea compounds in an amount of from 10% to 60; and water, the composition containing not more than the indicated amounts (dry weight basis) of the following urea compounds and of hexamethylenetetramine compounds:
methylene diurea compounds 7.9 monomethylol urea compounds 7.2%
hexamethylenetetramine compounds 2%, all the above compounds being dissolved in the water and the triazone compound methylene diurea compound weight ratio being 6:1 or more.
2. A liquid fertilizer composition as claimed in claim 1, in which the triazone compound content is between 35% and 50%, the urea compound content is not more than 35%, the methylene diurea compound content is not more than 2.5%, the monomethylol urea compound content is not more than 3%, with the total dry weight of methylene diurea compounds and monomethylol urea compounds being not more than 5%, and the hexamethylenetetramine compound content is not more than 1%.
3. A liquid fertilizer composition as claimed in claim 1 in which a major portion on a dry weight basis of the triazone compounds are of the formula:
(I)
(I)
4. A liquid fertilizer composition as claimed in claim 3, in which a minor portion of the of the triazone compounds are of the formula:
5. A liquid fertilizer composition as claimed in claim 3 or claim 4 in which the triazone compound of formula (I) constitutes at least 80% of all triazones present, on a dry weight basis.
6. A liquid fertilizer composition as claimed in claim 1 or claim 2 which includes triazone compounds having empirical formulae C3H7N3O and C5H10N4O3.
7. A method for producing a water-solution fertilizer composition of substantially stable water-soluble components as a reaction product containing one or more substantially water-soluble triazone-type compounds, comprising:
(a) reacting in aqueous solution a urea compound, an aldehyde and ammonia or a primary amine;
(b) thereafter further reacting in a first heating stage at a temperature between 80°C and 95°C for an additional reacting period of from 15 minutes to 1 hour while adding as necessary during the additional reacting period a strong base to maintain the pH within the range of 8 to 9.5 and while adding as necessary during the additional reacting period the urea compound and the aldehyde to maintain a mole ratio of the urea compound to the aldehyde within the range of from 0.5 to 2, and while adding as necessary during the additional reacting period ammonia or the amine to maintain a mole ratio of ammonia or amine to the aldehyde within a range of from 0.15 to 0.65, the ammonia or amine being reacted in an amount ranging from 2% up to 6% on a total water-mixture weight basis of 100% of reactants of the urea compound, the aldehyde and the ammonia or amine; and (c) thereafter as a second heating stage maintaining the reaction temperature between 80°C and 95°C for a further period up to 1 hour, such that the final reaction product has a triazone compound unreacted urea compound weight ratio of at least 0.5:1.
(a) reacting in aqueous solution a urea compound, an aldehyde and ammonia or a primary amine;
(b) thereafter further reacting in a first heating stage at a temperature between 80°C and 95°C for an additional reacting period of from 15 minutes to 1 hour while adding as necessary during the additional reacting period a strong base to maintain the pH within the range of 8 to 9.5 and while adding as necessary during the additional reacting period the urea compound and the aldehyde to maintain a mole ratio of the urea compound to the aldehyde within the range of from 0.5 to 2, and while adding as necessary during the additional reacting period ammonia or the amine to maintain a mole ratio of ammonia or amine to the aldehyde within a range of from 0.15 to 0.65, the ammonia or amine being reacted in an amount ranging from 2% up to 6% on a total water-mixture weight basis of 100% of reactants of the urea compound, the aldehyde and the ammonia or amine; and (c) thereafter as a second heating stage maintaining the reaction temperature between 80°C and 95°C for a further period up to 1 hour, such that the final reaction product has a triazone compound unreacted urea compound weight ratio of at least 0.5:1.
8. A method as claimed in claim 7 wherein the temperature in stages (b) and (c) is between 85°C and 93°C.
9. A method as claimed in claim 7 in which during step (b) the temperature is between 87°C and 92°C for from 20 minutes to 30 minutes, the urea compound: aldehyde molar ratio is from 0.9:1 to 1.2:1, the ammonia or amine:
aldehyde mole ratio is from 0.25 to 0.65, and the ammonia or amine is in an amount from 4% to 6% such that total nitrogen on a basis of total weight of solution is between 16% and 31%; and in which step (c) lasts from 10 minutes to 30 minutes.
aldehyde mole ratio is from 0.25 to 0.65, and the ammonia or amine is in an amount from 4% to 6% such that total nitrogen on a basis of total weight of solution is between 16% and 31%; and in which step (c) lasts from 10 minutes to 30 minutes.
10. A method as claimed in any one of claim 7 to 9 in which as the aldehyde there is used formaldehyde or a mixture of aldehydes a major portion of which is formaldehyde.
11. A method as claimed in any one of claims 7 to 9 in which as the aldehyde there is used acetaldehyde or a mixture of aldehydes a major portion of which is acetaldehyde.
12. A method as claimed in any one of claims 7 to 9, in which as the urea compound there is used urea or a mixture of urea compounds of which a major portion is urea.
13. A method as claimed in any one of claims 7 to 9 in which as the urea compound there is used thiourea or a mixture of urea compounds a major portion of which is thiourea.
14. A method as claimed in any one of claims 7 to 9 in which as the urea compound there is used methyl urea or a mixture of urea compounds a major portion of which is methyl urea.
15. A method as claimed in any one of claims 7 to 9 in which as the ammonia or amine there is used ammonia or a mixture of ammonia and one or more amines of which a major portion is ammonia.
16. A method as claimed in any one of claims 7 to 9 in which as the ammonia or amine there is used methylamine or a mixture of amines or of one or more amines and ammonia, a major portion of which is methylamine.
17. A method as claimed in any one of claims 7 to 9 in which as the ammonia or amine there is used monoethanolamine or a mixture of amines or of one or more amines and ammonia, a major portion of which is monoethanolamine.
18. A method as claimed in any one of claims 7 to 9 in which as the ammonia or amine there is used ethylenediamine or a mixture of amines or of one or more amines and ammonia, a major portion of which is ethylenediamine.
19. A method as claimed in claim 9 in which the aldehyde comprises formaldehyde, the urea compound comprises urea, and the ammonia or amine reactant comprises ammonia.
20. A method as claimed in claim 19 in which the aldehyde is formaldehyde, the urea compound is urea, and the ammonia or amine reactant is ammonia.
21. A method as claimed in claim 7 in which the temperature is maintained below 65°C during step (a) of claim 7.
22. A method as claimed in claim 21, in which the temperature is maintained below 60°C during step (a) of claim 7.
23. A method as claimed in any one of claims 7 to 9 in which a strong base is added as necessary to the aqueous solution to adjust the pH thereof to within a range of from 7.5 to 9 prior to the step (a) reaction.
24. A method as claimed in any one of claims 7 to 9 including, immediately subsequent to completion of step (c), cooling the reation product thereof to a temperature of from 33 to 37°C.
25. A method of fertilizing vegetation and/or soil which comprises applying to vegetation foliage and/or soil a liquid fertilizer composition as claimed in claim 1.
26. A method as claimed in claim 25, in which the triazone compound is hydrogen-triazone (S-tetrahydrotriazone).
27. A method as claimed in claim 25, in which the triazone compound is methyl-triazone.
28. A method as claimed in claim 25, in which the triazone compound is beta-ethanol-triazone.
29. A method of fertilizing vegetation comprising applying to vegetation foliage, a water solution of fertilizer consisting essentially of, as calculated on a dry weight basis of 100% solids:
one or more triazone compounds that are substantially soluble in water in an amount of at least 30%;
one or more urea compounds in an amount of from 20% to 60%;
the composition containing not more than the indicated amounts (dry weight basis) of the following compounds:
methylene diurea compounds 7.9%
monomethylol urea compounds 7.2%
(methylene diurea compounds +
monomethylol urea compounds) 10.2%
hexamethylenetetramine compounds 2%
and the composition containing water in an amount at least sufficient for solution of all the above compounds, and the triazone compound methylene diurea compound ratio being at least 6:1 on a dry weight basis.
one or more triazone compounds that are substantially soluble in water in an amount of at least 30%;
one or more urea compounds in an amount of from 20% to 60%;
the composition containing not more than the indicated amounts (dry weight basis) of the following compounds:
methylene diurea compounds 7.9%
monomethylol urea compounds 7.2%
(methylene diurea compounds +
monomethylol urea compounds) 10.2%
hexamethylenetetramine compounds 2%
and the composition containing water in an amount at least sufficient for solution of all the above compounds, and the triazone compound methylene diurea compound ratio being at least 6:1 on a dry weight basis.
30. A method of fertilizing vegetation as claimed in claim 29, in which the triazone compound content is from 35% to 40%, the urea compound content is up to 35%, the triazone compound urea compound ratio being at least 1:1, the methylene diurea compound content being not more than 2.5%, the monomethylol urea compound content being not more than 3%, with the total (methylene diurea compound plus monomethylol urea compound) content being not more than 5%, and the hexamethylenetetramine compound content being not more than 1%, the trizaone compound methylene diurea compound ratio being at least 11:1.
31. A method of fertilizing vegetation as claimed in claim 29 wherein a major portion, on a dry weight basis, of the triazone compounds is S-tetrahydrotriazone.
32. A method of fertilizing vegetation as claimed in claim 31 wherein the triazone compounds further include N-hydroxymethylformanide triazone.
33. A liquid fertilizer composition in accordance with claim 1 in which said triazone composition comprises a major amount, relative to the total triazone composition, of the triazone having the empirical formula C5H11N3O2 and the cyclic formula:
34. A method of fertilizing vegetation in accordance with claim 29 wherein said triazone composition of said fertilizer comprises a major amount, relative to the total triazone composition, of the triazone having the empirical formula C5H11N3O2, and the cyclic formula
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/644,975 US4554005A (en) | 1984-08-28 | 1984-08-28 | Triazone fertilizer and method of making |
| US644,975 | 1984-08-28 | ||
| US75780785A | 1985-07-22 | 1985-07-22 | |
| US757,807 | 1985-07-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1258189A true CA1258189A (en) | 1989-08-08 |
Family
ID=27094599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000488768A Expired CA1258189A (en) | 1984-08-28 | 1985-08-15 | Triazone fertilizer and method of making |
Country Status (7)
| Country | Link |
|---|---|
| AU (1) | AU588824B2 (en) |
| CA (1) | CA1258189A (en) |
| DE (1) | DE3530329A1 (en) |
| FR (1) | FR2569685B1 (en) |
| GB (1) | GB2164929B (en) |
| IT (1) | IT1201351B (en) |
| NL (1) | NL8502239A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017156464A1 (en) * | 2016-03-11 | 2017-09-14 | Oms Investments, Inc. | Iron-supplemented fertilizer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6632262B2 (en) | 2000-08-22 | 2003-10-14 | Georgia-Pacific Resins, Inc. | Controlled release urea-formaldehyde liquid fertilizer resins |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2826500A (en) * | 1954-12-30 | 1958-03-11 | Hercules Powder Co Ltd | Use of cationic-modified urea-formaldehyde resins in the manufacture of wet strengthpaper |
| GB976713A (en) * | 1961-08-18 | 1964-12-02 | Swift & Co | Improvements in or relating to stable urea-formaldehyde suspensions |
| US3462256A (en) * | 1966-10-31 | 1969-08-19 | Allied Chem | Process for producing urea-formaledhyde aqueous concentrates |
| DD115566A1 (en) * | 1974-02-04 | 1975-10-12 | ||
| US4244727A (en) * | 1979-02-07 | 1981-01-13 | Ashland Oil, Inc. | Urea-formaldehyde solution for foliar fertilization |
| US4304588A (en) * | 1980-05-05 | 1981-12-08 | Moore Jr William P | Foliar feed compositions |
| JPS58501858A (en) * | 1981-11-09 | 1983-11-04 | リクイ−ボツクス．コ−ポレ−シヨン | Coupling and valve assembly for beverage vending machines |
-
1985
- 1985-08-13 NL NL8502239A patent/NL8502239A/en not_active Application Discontinuation
- 1985-08-15 CA CA000488768A patent/CA1258189A/en not_active Expired
- 1985-08-24 DE DE19853530329 patent/DE3530329A1/en active Granted
- 1985-08-27 GB GB08521313A patent/GB2164929B/en not_active Expired
- 1985-08-27 FR FR858512761A patent/FR2569685B1/en not_active Expired - Lifetime
- 1985-08-27 IT IT09486/85A patent/IT1201351B/en active
- 1985-08-28 AU AU46897/85A patent/AU588824B2/en not_active Ceased
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017156464A1 (en) * | 2016-03-11 | 2017-09-14 | Oms Investments, Inc. | Iron-supplemented fertilizer |
| US11208360B2 (en) | 2016-03-11 | 2021-12-28 | Oms Investments, Inc. | Iron-supplemented fertilizer |
| US11905225B2 (en) | 2016-03-11 | 2024-02-20 | Oms Investments, Inc. | Iron-supplemented fertilizer |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3530329A1 (en) | 1986-05-15 |
| AU588824B2 (en) | 1989-09-28 |
| FR2569685B1 (en) | 1991-03-29 |
| IT8509486A0 (en) | 1985-08-27 |
| DE3530329C2 (en) | 1991-12-19 |
| FR2569685A1 (en) | 1986-03-07 |
| IT1201351B (en) | 1989-01-27 |
| AU4689785A (en) | 1986-03-06 |
| GB2164929B (en) | 1988-05-11 |
| NL8502239A (en) | 1986-03-17 |
| GB2164929A (en) | 1986-04-03 |
| GB8521313D0 (en) | 1985-10-02 |
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