FR2569685A1 - TRIAZONE CONTAINING FERTILIZER AND PROCESS FOR PRODUCING THE SAME - Google Patents

Abstract

THE INVENTION RELATES TO FERTILIZERS. IT CONCERNS A STABLE LIQUID FERTILIZER COMPRISING, ON A BASIS OF 100 SOLIDS, AT LEAST 30 WATER-SOLUBLE TRIAZONS, 10-50 OF A UREA-TYPE COMPOUND, THE TRIAZONESURE RATIO BEING AT LEAST 0.48, OF THE LIMITED QUANTITIES OF COMPOUNDS OF THE METHYLENEDIUREE TYPE, MONOMETHYLOLUREE, HEXAMETHYLENE-TETRAMINE, AND OF WATER, THE TRIAZONESCOMPOSED RATIO OF THE METHYLENEDIUREE TYPE BEING AT LEAST 6. USE IN PARTICULAR FOR FERTILIZING TURF.

Description

The invention relates to a new liquid fertilizer

  and a new process for its manufacture.

  Prior to the present invention, there was no method which, repeated continuously, can give triazones and / or high concentration thereof, reliably and / or consistently. On the other hand, in the more or less similar prior methods of manufacturing fertilizers, the product or mixture of products obtained has a reduced or poor stability,

  decomposing and / or converting to compounds or

  crystalline liquids which precipitate so that the utility as liquid fertilizers is lost, a solid fertilizer of the triazone type or of similar types, insoluble (in water), not being capable of supplying nitrogen

  roots quickly enough for it to be practically

  economically or commercially.

  In addition, it has been found that current technology makes it impossible to separate derivatives

  individual triazone starting from mixtures of these

  in aqueous reaction products and, therefore, prior to the present invention, it was not easy to

  determine the exact structure and formula of

  aqueous reaction products given by methods

  or somewhat similar to the present process.

  Also, prior to the invention, it was not understood which constituents of a reaction product contribute to the significant instability of its solubility in water, nor the factors which, in a manufacturing process, govern the stability and / or the yield of the end product (s) as in the process of the

  invention which results in a high concentration

  highly soluble and stable products, mainly

  triazone derivatives as a water-soluble mixture. Although it is not certain that

  somewhat similar or related processes

  triazones as part of a mixture of products in aqueous solution nor that such products

  are obtained - the amount of triazone they contain

  It is not clear how long they would be before decomposition or before the overall mixture (reaction product) became unusable as a liquid fertilizer because of crystallization and precipitation of constituents. it appears that the process most closely related, superficially, to that of the present invention is that of the patent

  US 3,462,256, in which various parameters are used.

  operating meters and different molar ratios of reagents, not recognizing the presence (if any) of the triazone (s) according to the present invention

  neither their importance as liquid fertilizer nor the importance

  such parameters as well as the reaction product

  In terms of both the effectiveness as a liquid fertilizer, the lack of sensitivity of human skin to this product and its long-term stability according to the present invention. The broad limits of the cited patent include the use of urea and formaldehyde as reagents, in a ratio urea / formaldehyde of 1/2, preferably 1.3 / 1.8, the use of ammonia at a rate of 0.3 to 6% and preferably from 0.7 to 3% by weight at temperatures

  75 C up to the boiling point

  preferably from 85 to 95 ° C at a pH of 8.5 to 10, preferably 9 to 9.8, for a reaction time of 30 to 180 minutes, preferably 75 to minutes. Although some of the parameters overlap, neither US Pat. No. 3,462,256 nor other prior art documents have recognized the critical parameters of the present invention nor their combination, absolutely necessary for carrying out the present invention, as well as will be demonstrated by some

  examples of processes that are unsatisfactory.

  An object of the present invention is to obtain

  a new liquid fertilizer composition suitable for application to foliage and grass and

not likely to burn them.

  Another goal is to obtain a new composition of liquid fertilizer suitable for situations

  which require slow release nitrogen sources.

  Another goal is to obtain a new composition containing a high percentage of triazone and

  suitable for use as fertilizer for

foliage and / or grass.

  Another object is to obtain compositions as above characterized by good stability

  and long-term stability against crystallization

  tion and / or precipitation of constituents, immediately

or during storage.

  Another aim is to obtain a new composition with a high triazone content in aqueous form, which has a high stability against decomposition or

degradation of triazone.

  Another aim is to obtain a new composition of triazone in aqueous solution having a strong

  concentration of one or more particular triazones.

  Another object is to obtain a novel process for the manufacture of this novel composition of liquid fertilizer of improved stability with slow release, not

  not burning foliage and / or grass when applying

  cation. Another aim is to obtain a new method of stimulating vegetation of various types, including turf, using new compositions.

of the invention.

  Other goals will appear in the description

below.

  Broadly, it can be said that the invention comprises three related inventions, namely a liquid fertilizer of novel composition, a process

  new production of these compositions and a

  yielded new fertilizer application to foliage.

  More particularly, the invention broadly comprises a liquid fertilizer composition of which

  the constituents are present in particular amounts

  in ranges indicated, comprising a composition

  which is significantly soluble in water, sufficient to obtain stability to a commercially acceptable degree, urea, water in sufficient quantity to obtain and maintain a

  solution of the triazone or triazones, minor percentages

  limited quantities of monomethylolurea and methylene-

  diurea and minor amounts of dimethylolurea and hexamethylenetetramine. The composition of triazone

  is present at least about 30%, preferably

  from about 35 to about 40 percent and a weight ratio of at least about 1 relative to urea. Urea, based on the dry weight, represents about 20 to 50%, preferably less than 35% and monomethylolurea to about 7%. On the dry weight basis, the methylenediurea may be present up to about 3%, preferably less than about 2%, and the monomethylolurea may be present up to about 7%, preferably less than about 4%. approximately, with the proviso that the total weight of methylenediurea and monomethylolurea

  not exceed approximately 10% and preferably

  about 6%. The ratio triazone (s) / methylene

  diurea, based on the dry weight, is at least about 6, preferably at least about 11. Dimethylolurea and hexamethylenetetramine may or may not be present, the proportion of dimethylolurea being up to about 2.75 % of the total weight of the

  aqueous solution and the proportion of hexamethylenetetra-

  to about 2%, preferably up to about 1% by weight (dry), or less, hexamethylenetetramine not being present normally. The quantities of

  composition of triazone indicated above and the report

  urea are critical to the use of

  the overall composition of the fertilizer and its solu-

  as a liquid fertilizer for the purposes indicated

  above. The lower urea product content provides both lower phytotoxicity and higher triazone content. When the aqueous solution of the urea compound and the compound is reacted

  of the aldehyde type on ammonia, results are obtained

  preferred states by maintaining a temperature below 65 C, preferably below 60 C. In addition, to obtain the high stability of the fertilizer composition of the invention, it is necessary that the process is limited critically to the maximum amounts indicated ci above, such as monomethylolurea, dimethylolurea and methylenediurea because of their limited solubility in water and their instability, since they tend to crystallize and / or precipitate. The same can be said of hexamethylenetetramine, which is also limited to the maximum amount allowed in the composition of the invention.

  In a preferred embodiment of the invention,

  on the basis of the percentage by weight, a quantity

  The majority of the triazone composition and / or the mixture is formed of triazones having the empirical formulas C3H7N30 and C5H10N403, with respective cyclic formulas:

O O

NH-C-NH NH-C-NH

and, 1 and NIIHC-N-H

H2C-N-CH2 H2C-N-CH2

H O = C-NH-CH 2 -OH

  the compound C3H7N30 representing, by weight, preferably

  and at least about 80% of the triazo-

  total, which is critical to achieving

  preferred results, as to the goals indicated above.

  The method of the invention comprises a combination

  the critical temperature ranges, critical pH ranges, reagent critical ratios, essential reagents and reaction times, while being a two-step process with respect to heating times at different pH levels. In the absence of these critical limitations, it has been found that it is impossible to obtain the high rate of formation of triazone composition (s) of the invention and also to obtain a liquid fertilizer containing them and having such great stability, especially

  together with the high percentage by weight obtained.

  Similarly, to obtain the non-burning triazones of the invention suitable for application as fertilizer on the foliage as well as on the grass, the limitations

  critics are needed to obtain such

  ucts. Naturally, for many of these

  wide ranges in which it is possible to obtain

  a certain success, but the maximum production and high quality is limited by the preferred ranges

indicated.

  More particularly, for the broad aspects of the invention, it can be said that it is a method of manufacturing a fertilizer composition in solution.

  aqueous composition of water-soluble constituents

  which the major new constituent or constituents, as reaction products, are substantially water-soluble triazone

  reagents and the steps being as below.

  The urea component should be urea and / or substituted urea. A second necessary reagent is an aldehyde. A third reagent, serving as an ammonia source, must be ammonia and a primary amine. Finally, a strong caustic must be used during the initial step of heating a mixture of the reagents above, gradually adding

  strong caustic during the first heating period

  and reaction, to the extent necessary to

  maintain the pH in the wide range or the preferred range.

  During an initial reaction step, the aforesaid reactants are reacted by heating the mixture at a temperature of about 85 to 93 ° C for a period of about 60 minutes while maintaining the pH in a critical range of about 8 to about 9.5. adding caustic as the pH tends to drop during Ce

  reaction time; during the initial phase of reac-

  the ratio indicated above between the constituent of the urea type and the reagent of the type

  aldehyde, at least during an initial part and

  dominant of the first stage, at a molar ratio

  from about 0.5 to 2.0 and, similarly, the ratio of ammo

  niac with aldehyde, in a range of about 0.15 to 0.65. For 100% by weight of the reagents, it is necessary to

  react with ammonia at about 2.2 to 6% relative

  to the above reagents, on the basis of the total weight

  of the aqueous solution. After the first stage of heating

  and reaction, heating is continued in the

  same temperature range for an additional time

  from about 0 to 60, preferably 10 to 30 minutes

  while allowing the pH to decrease by decreasing or stopping the addition of the strong caustic, sufficiently to obtain one or more reaction products in which the ratio by weight of the triazone derivative (s) formed to the unaltered amounts of the constituent of the urea type is

at least about 1.

  In order to achieve optimum results in the process described above, the following conditions will be used. During the first step indicated above, the reaction temperature is maintained between about 91 and 93 ° C. and the heating time of the first step

  is approximately 28 to 35 minutes, and the report is

  the component of the urea to aldehyde type between 0.5 and 1.2 and the above mentioned ammonia / aldehyde ratio is about 0.55 to 0.65 and the weight of ammonia mentioned above is maintained between 3 and 3.5%, and during the second and last heating step, the reaction temperature is maintained between 90 and 93 C approximately. In the process, in view of an optimum result essential to the invention, at least a major proportion of the aldehyde is formed of formaldehyde, at least a majority proportion of the

  urea component is formed of urea and a

  majority portion of the ammonia source is formed

  ammonia. Good results are also obtained by using

  methylamine as a replacement for ammonia, and

  also methylolamine and / or monoethanolamine

  mine. As a constituent of the urea type, good results are obtained by using, partially or totally, thiourea. Similarly, good results are obtained using methylurea, partially or totally, as a constituent of the urea type. Good results are also obtained using acetaldehyde, partly

  or totally, as a source of aldehyde.

  According to a third aspect of the invention, which is the method of fertilizing vegetation, the process can be described broadly as being

  apply to the foliage of the vegetation a solution

  aqueous composition of fertilizer composition described above falling within the broad or narrow (preferential) limitations, and including the application of a major amount of substantially water-soluble triazone as a fertilizer composition, to the turf, and methods of apply each of the triazones

  empirical formulas C3R7N30 and / or C5H10N403,

  sensing the respective cyclic formulas indicated

upper.

  The urea-aldehyde mixture, as commercially available, normally has a pH of about 7.5 to about 9; an old solution, which may have a lower pH, should be adjusted to pH 7.5 to 9 for

preferential results.

  For the process of the invention and the products

  obtained, it has been determined that it can not be

  stable products with less than about 2.2 to about 6% ammonia (on the total weight of reagents) and that stable products can not be obtained at temperatures above about 93 C and that It is difficult to prepare stable products at pH greater than about 9.5. During the determination of the critical limitations of the invention, it has been determined that the pH of the reagent mixture described above, the reaction temperature (s) and the mole percentage of ammonia indicated above are all much more critical. than we originally thought. It should be noted that the development of the process of the invention and the final production of the corresponding products result from the idea that previously available liquid fertilizer concentrates, such as those obtained by the process of US Pat. 462 256, have an unreliable shelf life with respect to the stability time before crystallization and / or precipitation makes the

  commercially unusable products for the application

  foliage and it has been observed that the duration of

  storage is variable from one batch of product to another.

  As a result, the method of the present invention has been created.

  for obtaining the new compositions and the

  yielded new fertilizer application. We also discovered

  green that monomethylolurea and dimethylolurea

  convert to methylenediurea at rest at

  ambient and typically within a few weeks, causing solids deposition. Furthermore, it has been found that methylol compounds, when reacted on urea at low temperatures, only sufficient to dissolve the urea in about 15 minutes, result in an unstable mixture as a result of slow reactions at ambient temperatures for the formation of methylolureas, this product being typically obtained by the process of US Pat. No. 4,304,588 and

  4,274,727 in which the product or products are identi-

  as monomethylolurea. In addition, it has been found that the concentration of methylenediurea is an important factor which limits the stability of the products of the invention to storage and that the amount of methylenediurea formed by urea conversion should not exceed about 3% by weight, so to ensure a sufficiently long shelf life from the practical commercial point of view of utility as a liquid fertilizer. On the other hand, since it has been found that monomethylolurea and dimethylolurea are unstable in solution and tend to convert to urea and methyleneurea, each of these compounds must be kept to a minimum,

as indicated above.

  The invention is not related to the hypothesis

  according to which such or such particular reactions

  However, research shows that the triazones of the invention are formed as a result of consecutive reactions which are as follows. Urea reacts on formaldehyde for example to form monomethylolurea; monomethylolurea reacts with formaldehyde for example to form dimethylolurea, and typically methylamine reacts with dimethylolurea.

  to form a methyltriazone, or a non-substituted amine

  killed reacts on dimethylolurea to form a

  hydrogenated triazone (S-tetrahydrotriazone), for example.

  In experiments using hexamethylene

  tetramine as the source of ammonia, it has been found that the reaction progresses very slowly and that an unsatisfactory product is formed which crystallizes rapidly at rest. A large percentage of hexamethylenetetramine remains unchanged. On the other hand, in the process, too small a quantity of ammonia and / or too much formaldehyde (or other aldehyde) results in a too high percentage of unaltered urea in the process.

  method of the invention, described above. When the report

  triazone / methylenediurea port, in dry weight, in the final reaction product, is less than about 6,

  the yield of triazone composition according to the invention

  This is why the process of the invention maintains the methylenediurea in the

  final product to a satisfactory minimum.

  The product of the invention is prepared by mixing the desired amounts of urea, formaldehyde and ammonia in an aqueous solution, according to a typical example. The mixture and / or the solution is then heated to a carefully adjusted temperature, held at about this temperature for a specified period of time while carefully adjusting the pH during the initial heating phase as well.

  of reaction, by slow addition of strong alkali.

  Then, maintain the same approximate temperature during a second phase to complete the completion

  of the reaction. Then, we cool and pack the lot.

  The order of addition of the sources of urea, formaldehyde, ammonia and water is not considered very important, provided that the addition time of a final ingredient is not prolonged and that an imbalance of reagents in the desired quantities is not allowed during a significant time during the reaction, and that the mixture is not allowed to stand

  reagents without reaction for an excessive time.

  Urea can be added in the form of

  or crystals, in solution form or at least partially in the form of a partially condensed urea-formaldehyde reaction product. We can

  add formaldehyde as a commercial solution

  cial or paraformaldehyde or partially in the form of hexamethylenetetramine or urea reagent /

  formaldehyde already partially condensed. We can add

  ammonia in anhydrous or aqueous or partial form

  as hexamethylenetetramine. The total nitrogen in the solution must represent at least 16% and at most 31% of the total weight of the product solution

  reaction that can be diluted later.

  Since, as noted above, it has been found impossible to obtain stable liquid solutions of urea-formaldehyde fertilizer when following the prior methods, due to the limited solubility of the monomethylolurea, dimethylolurea and methylenediurea and also as a result of instability

  inherent in this matter, it has therefore become necessary

  to separate and identify the constituents of the reaction products of the invention, constituting a

liquid fertilizer solution.

  A high pressure liquid chromatography apparatus was used to separate the reaction products formed by the process of the invention and related methods. Many of their constituents have been identified by the preparation of pure compounds

  and the use of these as stallions on the chro-

  liquid matograph (HPLC). An important constituent could not be

identified by this method.

  The chromatographic separation on paper was used to concentrate this unknown component which was then purified by recrystallization from a

new analysis by HPLC.

  This sample according to the invention was then analyzed by mass spectrophotometry, by NMR, by infrared and by means of an elemental analyzer and it was determined that it was an 80/20 mixture of Stetahydrotriazone mentioned above as having the empirical formula C3H7N30 and the cyclic formula

  above, and N-hydroxymethylformamide-

  triazone having the empirical formula C5H10N403 and the

  cyclic formula indicated above.

  Appropriate caustics include hy-

  sodium hydroxyl, potassium hydroxide, hydroxide

  of lithium, sodium carbonate or other caustic

strengths.

  The triazones contemplated according to the invention as a liquid fertilizer suitable for application to foliage and / or grass comprise the relatively few triazones which are characterized by a notable solubility in water, most of which is

insoluble.

  We compared the liquid fertilizers obtained

  according to the invention to certain other commercial products

  phytotoxicity, as follows.

  When we averaged four species of grass and grass that are St. Augustine grass, hybrid Bermuda grass, fescue and perennial ryegrass, in a series of trials using different numbers of grams per square meter, as a nitrogen level, the

  urea-triazone mixture of the invention was less

  that Formolene (registered trademark) or urea, respectively at 37.5% and 44.4%, at the nitrogen dose most commonly used on turf (4.88 g / m2). When averaging all species and all doses, the urea-triazone mixture of the invention was 6.6% and 30% less phytotoxic than Formolene (brand

deposited) and urea.

  The urea-triazone mixture of the invention is significantly safer than Formolene (registered trademark)

  when applied at a rate of 12.93 g N / m2 (

  undiluted cation). As a result, the triazones (urea-triazone mixtures) according to the invention, identified above, are a safer nitrogen fertilizer for turf.

  that the other products tested for comparative purposes

  ble. Similarly, for DOT skin corrosion tests, it has been found that the products of the invention

were not corrosive.

  The following are typical operations, some according to the invention and others coming out

  limitations of the invention, serving in part to illustrate

  some of the critical limitations of the process

of the invention.

  Example I (samples 1-2, 2-2, 3-2, 4-2 tested at the same time)

Constituents of the

  Reaction Duty (Based on Weight of Percent by Weight Present Aqueous Solution) 1-2 2-2 3-2 4-2 Urea 28.7 27.3 30.0 36.9 Monomethylolurea 1.8 1.8 6.1 0.9 Methylenediurea 0.8 1.3 1.1 1.1 Dimethylolurea 0.7 1.1 0.7 1.2 Triazone 18.8 19.6 12.9 8.2 Hexamethylenetetramine --- - 2.9 Sample 3-2, containing 6.1% percent monomethylolurea (MMU), was poor in stability with methylenediurea crystallizing as the monomethylolurea decomposed during short storage. Similarly, sample 4-2 was not satisfied with its triazone yield of 8.2% because the final product had a high concentration of urea.

  remained unchanged at 36.9% and that there was also a

  excess of hexamethylenetetramine, 2.9%,

  causing instability which led to

  and precipitation of constituents so that the product was not satisfactory for foliar application. According to the table above,

  in which the remaining percentage for each sample

  Where water is concerned, the percentages present, on the basis of total solids, are:

1-2 2-2 3-2 4-2

  Urea 56.50 53.33 59.04 72.00 Monomethylolurea (MMU) 3.54 3.52 12.01 1.76 Methylenediuride (MDU) 1.57 2.54 2.17 2.15 Dimethylolurea (DMU) 1 , 37 2.15 1.41 2.34 Triazone 37.01 38.28 25.89 16.02 Hexamethylenetetramine - - 6, 36 Triazone / urea molar ratio 0.65 0.72 0.43 0.22 Ratio triazone / MDU 23.5 15.1 11.7 2.6

  Four days later, the percentages of constituents were checked again after additional storage time, which

gave the following results

for the above samples.

  Product constituents 1-2 2-2 3-2 4-2 5-1 reaction (% on previous (total aqueous solution operation)) Urea 29.4 27.9 30.0 35.5 28.7 MMU less 0.1 0.8 5.3 0.3 2.3

MDU 0.9 1.2 1.2 1.2 1.2 1.2

  DBlU 0.5 0.5 0.8 1.0 0.6 Triazone 20.0 20.4 13.7 9.5 18.3

  Hexamethylenetetramine -. . 6.36 -

  The percent solids by weight for the previous table are:

(1-2) (2-2) (3-2) (4-2) (5-1)

Urea 57.7 54.9 59.5 69.9 56.2

MMU 0.2 1.6 10.5 0.8 4.5

MDU 1,8 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 18.7 35.8

  Hexamethylenetetramine - - - 5.7 -

  As can be seen, the amount of hexamethylenetetramine

  is large and the triazone is small for the experiment.

experience 4-2.

Some of the preferred triazones of the invention are Stetahydrotriazone, methyltriazone and C-hydroxyethyltriazone. For the different reaction products of Example I, the compositions used, with each time the same process, were as follows: Composition (% by weight) 1-2 2-2 3-2 4-2 Urea: 52.3 52.3 52.3 48.5% urea60% formaldehyde: 31.3 31.3 31.3 29.0 KOH solution (25%): 3.0 3.0 0, 3 0.3 Ammonia water ( 28% NH3): 10.7 10.7 10.7 19.7 Water: 2.7 2.7 5.4 2.5 Molar ratio 1.6 / 1 / 0.28 116 // 0.28 urea / HCHO / NH 3): 1.6 / 6, 1.6 / 1 / 0.56

  The procedures followed for the composi-

  The above statements were as follows: 1-2: Water, urea-formaldehyde and urea were mixed together in a reactor and the ammonia water was slowly added while mixing. This mixture was heated to 83 C and maintained at a temperature of

  less than 90 C and a pH of about 8.7 to 9 during

  minutes, the pH being maintained by the addition of KOH.

  Then, heating and additional reaction was carried out by maintaining the temperature of the reagents

  between 83 and 90 C for another 15 minutes.

  Then the product was allowed to cool and packed.

  2-2: Water, urea-formaldehyde and urea were mixed together in a reactor and the pH adjusted to 9.0 by addition of KOH. This mixture was then heated to 810 C and the pH was maintained during heating between 8.7 and 9.0 by continuous additions of KOH-NH3 mixture while heating at 90 C. The temperature was then maintained between 88 and 90 ° C. at a pH of 8.7 to 9.0

  until all the KOH-NH3 mixture has been added.

  Then, the temperature of the reagents was maintained between 88 and 90 C for another 15 minutes, then

  cool the product and pack it.

  3-2: The water, urea-formaldehyde and urea were mixed in the reactor and the pH was adjusted to 9.5 by addition of the KOH solution. The mixture was then heated to about 73 ° C, where the urea was completely dissolved, and then the mixture was maintained at a pH of 8.5 to 9.0 with slow addition of ammonia water.

  for about 10 minutes while heating at 90 C.

  Then, the reagents were maintained between 88 and 90 C for another 30 minutes, after which

  allowed the product to cool, then wrapped.

  4-2: The same steps were followed as for 3-2 above, except for the following points. The addition of ammonia water was begun at about 75 ° C and the pH was maintained between 8.5 and 9.0 by slow addition of KOH while heating at 90 ° C for about 18 minutes. Then, the temperature was maintained by heating between 88 and 90 C for 3 minutes more. According to the above procedures, which resulted in the reaction products already described, it will be seen that the limitations of the process of the invention are in fact critical. It will also be noted that in process 3-2 above, the first addition step

  ammonia water for 10 minutes was not the equi-

  are worth the use of a strong caustic such as KOH and appeared unsatisfactory for the process of the invention. It is also noted that the pH 9.5 of process 3-2 was slightly higher than the broad range of the process of the invention and that the yield was rather poor in comparison, for example, 1-2 and 2-2 which give much higher yields. The product of 4-2 crystallized when left to rest

for 72 hours.

EXAMPLE II

  Another series of experiments was designed to determine and illustrate the effects of different reaction conditions on the quality of the product. The

  The first condition studied was the percentage of ammo-

  niac. It was varied from 0 to 3.0% (based on the weight of the aqueous solution) with the following results: Operation n 1 2 3 4 5 6 Reagent or product

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 1.8 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.

  Triazone (solution 1,3 43,8 42,3 52,6 57,7 56,5 aqueous) Operations 4, 5 and 6 represent limitations

  in the context of the process of the invention.

  For the operations indicated above, the ratios of triazone (s) / MDU and NH3 / formaldehyde and triazone (s) / unaltered formaldehyde were as follows:

1 2 3 4 5 6

  Triazone (s) / MDU 0.08 5.9 5.0 12.5 18.2 13.7 (by weight) NH3 / HCHO 0.0 0.09 0.14 0.18 0.23 0.28 ( mol ratio Triazone (s) / urea 0.013 0.46 0.39 0.45 0.54 0.51 (by weight) unaltered It is particularly noted that the triazone (s) / MDU ratios of operations 1, 2 and 3 were all less than 6 and the yields obtained were poor for the triazones, the percentage of NH3 for these operations

  being much lower than the limitations required by the

transferred from the invention.

  It is noted that in operation 4, there is insufficient

  ammonia, which results in a

  excessive urea and also to a stabi-

  mediocre quality, that is, rapid crystallization and precipitation; that is, poor storage time was obtained, even though the yield of triazone (s) was reasonably acceptable. These tests also show that ammonia is necessary for the preparation of a storage-stable composition comprising the triazones as products, with acceptable yields, in the context of the process of the invention, and show

  also the importance of the limitations of proportions.

  It is also part of the invention

  to make the modifications and substitutions of equiva-

  slow that would appear to a person with a

  ordinary skill in this particular technique.

  In a preferred process of the invention, an improved product content is obtained by cooling the reaction product immediately after the final second stage heating period to a lower temperature of between about 33 and 37 ° C. Urea compounds include substituted ureas such as, typically, thiourea, monourea and diethylurea, etc., and exist

  many well-known substituted ureas.

  Typical useful aldehydes are HCHO (formaldehyde), paraformaldehyde, acetaldehyde, propionaldehyde, HMT (commercial designation), and the like. Typical sources of ammonia include

  aqueous and anhydrous ammonia, HMT and primary amines

  mayors such as monoethanolamine, methylamine, ethylenediamine, etc. With regard to the use of substituted and / or substitute compounds as reagents in the processes described above and thus the intermediates and final products substituted and / or replacement, the indication "of the type ..." is used here. to encompass

  generically such structural replacement compounds

  a similar compound, for example composed of the urea type, triazone compound, methylenediurea compound, monomethylolurea type compound, hexamethylenetetramine type compound. Similarly, "ammonia source" generically encompasses ammonia-type replacement compounds that provide ammonia as a reagent and / or react in a similar manner, such as

  the sources of ammonia mentioned above.

  For the following two examples of products obtained in the context of the preferred parameters indicated above (temperature ranges, percentages, etc.), the content, according to the analysis, on a wet basis (solution) was as follows: processes using a urea / formaldehyde ratio of 1.2, in contrast to

  previous examples where the ratio is 1.6.

  Batch n: 1 2 Urea% 19.5 20.2 MMU (monomethylolurea)% 3.8 4.3 MDU (methylenediurea)% 1.8 1.8 Triazone% 30.8 28.8 Triazone / urea ratio 1, 58 1.43 (dry weight) Triazone / MDU -17.1 16.0 (dry weight) Based on the above data, expressed on a dry basis, the analysis is: Urea%: 32.5 33 7

MMU% 6.3 7.2

MDU% 3.0 3.0

Triazone% 51.3 48

Claims (10)

  A liquid fertilizer composition characterized in that it comprises essentially, on a dry weight basis of 100% solids, a substantially water-soluble triazone composition present at least about 30% by weight. % (dry weight), a compound of the urea type present in an amount of at least about 10 to about% (dry weight) so that the triazone / urea compound type compound ratio is at least 0.48%; about a maximum of about 3% methylenediurea compound (dry weight), a monomethylolurea type compound of about 7% maximum (dry weight), the total (dry) weight of composed of the methylenediurea type and of monomethylolurea type compound being about 10% maximum, a hexamethylenetetramine type compound at a maximum of 2% (dry weight) and water in an amount at least sufficient to dissolve the composition triazone, the urea compound, the methyl compound imediurea, the monomethylolurea type compound and the hexamethylenetetramine type compound being   and the ratio, in dry weight, of the composition   triazone to the methylenediurea compound being at least about 6.   2. Composition according to claim 1, characterized   in that, on the basis of the dry weight, the composition   triazone is present at least 35%   at about 50%, the urea-type compound at about   At most 35%, the weight ratio of triazone to the urea compound is at least about 1; the methylenediurea compound is present   about 2.5% maximum, and the mono-type compound   The total dry weight of the methylenediurea compound and the monomethylolurea type compound is about 5% maximum and the hexamethylenetetramine compound is about 1% maximum, the ratio. u   composed of the triazone type to the i.ethylene-   diurea being at least about 11.   3. The composition as claimed in claim 2, characterized in that the triazol composition comprises, in a major amount relative to the total triazone composition, a compound of the following type:   triazone having the empirical formula C3H7N30 and the cyclic mule: o I HN-C-NH t I H C-N-CH 2, 2   H 4. Composition according to claim 3, characterized in that the triazone composition comprises a triazone-type compound having the empirical formula C5H10N403 and the cyclic formula: NH-C-NH H2C-N -CH 2 3 2 O = C-NH-CH2-OH   5. Process for the preparation of a composition   fertilizer in aqueous solution of substantially stable water-soluble products as a reaction product containing compounds of the type   triazone substantially soluble in water,   characterized in that an aqueous solution of a urea compound and an aldehyde compound is reacted with an ammonia source selected from the group consisting of ammonia and primary amines; and   then we still react by heating and maintaining   between 85 and 93 C during a reaction time   additional 15 to 60 minutes, while adding, if necessary, during this additional reaction time, a strong caustic in sufficient quantity to maintain the pH between about 8 and 9.5 and while adding, if necessary, during additional reaction time, sufficient amounts of urea-type compound and aldehyde-type compound to maintain a compound molar ratio of the urea / aldehyde-type compound of between about 0.5 and 2, and while adding if necessary, during this additional reaction time, a sufficient amount of the ammonia source to maintain an ammonia / aldehyde type compound molar ratio of between about 0.15 and 0.65, the ammonia compound being reacted with a quantity ranging from   About 2.2 to 6% on a total water-weight basis   mixture / solution of 100% urea compound reagents, aldehyde compound and ammonia source, and then, as a second reaction step, the reaction temperature is maintained at this level during a new up to about 60 minutes, so that for a final reaction product comprising a triazone compound, the weight ratio of this triazone compound to   the urea compound is at least about 0.48.   6. Process according to claim 5,   in that during the further reaction the temperature is about 91 to 93 ° C for about 28 to 35 minutes, the molar ratio of the urea / aldehyde compound type varies from about 0.5 to about 1.2. , and the ammonia / aldehyde compound molar ratio is about 0.55 to 0.65, and the ammonia compound is reacted with   approximately 3 to 3,5%, and during the second and   In the reaction stage, the reaction temperature is maintained at about 90 to 93 ° C for about 10 minutes, so that the total nitrogen content, based on the total solution weight, is about 16 to 31%. 7. A method of fertilizing vegetation, characterized in that a fertilizer composition comprising a fertilizer composition is applied to the foliage of the vegetation.   quantity of the triazone-type compound   soluble in water, in aqueous solution, according to   any of claims I to 4.   8. Process according to claim 7, characterized   in that the water-soluble compound of the triazone type   is selected from the group consisting of triazone hydro-   gene, methyltriazone, and e-hydroxyethyltriazone.   9. Method of fertilizing the grass,   characterized in that a fertilizer composition is applied to the turf comprising a major amount of triazone-type compound substantially soluble in water, in particular   aqueous solution, according to any one of the claims 1 to 4.   10. Process according to claim 6, characterized   in that immediately after the completion of the overtime, the reaction product is cooled to   a temperature of 33 to 37 C approximately.