Title of Invention

A PARTICULATE UREA-FORMALDEHYDE POLYMER MADE BY ACIDIFYING A AQUEOUS METHYLOL UREA SOLUTION

Abstract A slow release, particulate urea-formaldehyde polymer useful as a fertilizer for enhancing the extended delivery of nitrogen needed for plant development and growth and a granular fertilizer made with the particulate urea formaldehyde polymer.
Full Text A PARTICULATE UREA-FORMALDEHYDE POLYMER MADE BY ACIDIFYNG A
AQUEOUS METHYLOL UREA SOLUTION
This application claims the benefit of provisional application 60/367,278 filed
March 26,2002 and Provisional application 60/379,402 filed May 13, 2002.
FIELD OF THE INVENTION
[01] The present invention relates to a new source of slow release nitrogen for
enhancing the delivery of nitrogen needed for plant development and growth.
The invention specifically relates to a new particulate source of slow release
nitrogen, and to use of the particulate nitrogen source for enhancing plant
development and growth, by delivering nutrient nitrogen over an extended
period of time to growing plants. The present invention also is directed to the
use of the particulate source of slow release nitrogen in formulating a granular
fertilizer.
BACKGROUND OF THE INVENTION
[02] Fertilizer is often applied as a formulated (N-P-K) solid, granular or powder,
or sometimes as a liquid to an area to be fertilized. There are basically two
types of fertilizers, water soluble fertilizers and "slow release" fertilizers.
While water soluble fertilizers are generally less expensive than slow release
fertilizers, they have the disadvantage of leaching nutrients very quickly into
and through the soil. Some solid, water soluble fertilizers can be made slow
release by various coatings. Alternatively, a reduction in nitrogen availability
also can be obtained by using enzyme inhibitors. Slow release fertilizers are
designed to release nutrients to plants or soil over an extended period of time,
which is more efficient than multiple applications of water soluble fertilizers.
Therefore, slow release fertilizers (also referred to as controlled release or
extended release) minimize the frequency with which plants must be fertilized,
as well as reduce or minimize leaching.
[0,3] Urea-formaldehyde (UF) condensation products are widely used as slow
release nitrogen fertilizers in crops, ornamental plants and grasses. Urea-
formaldehyde fertilizer materials also can be supplied either as liquids or as
solids and are the reaction products of urea and formaldehyde. Such materials
generally contain at least 28% nitrogen, largely in an insoluble but slowly
available form.
[04] Extended release UF fertilizers (ureaform) can be prepared by reacting urea
and formaldehyde at an elevated temperature in an alkaline solution to
produce methylol ureas. The methylol ureas then are acidified to polymerize
the methylol ureas to methylene ureas, which increase in chain length as the
reaction is allowed to continue.
[05] The methylene urea polymers that the condensation products normally contain
have limited water solubility and thus release nitrogen throughout an extended
period. The mixture of methylene urea polymers generally have a range of
molecular weights and are understood to be degraded slowly by microbial
action into water soluble nitrogen. UF fertilizers are usually evaluated by the
amount and the release characteristics of their water insoluble nitrogen.
[06] U.S. 4,089,899 describes a solid, controlled release nitrogen fertilizer of the
ureaform type, which consists essentially of only two nitrogen fractions: water
soluble nitrogen and cold water insoluble nitrogen.
[07] U.S. 3,677,736 describes a urea-formaldehyde fertilizer suspension.
[08] Other disclosures of urea-formaldehyde fertilizer compositions, both liquid
and solid forms include U.S. 4,378,238, U.S. 4,554,005, U.S. 5,039,328, U.S.
5,266,097,U.S. 6,432,156, and U.S. 6,464,746.
[09] Granular nitrogen-containing fertilizers have been produced commercially by
a variety of techniques using water soluble nitrogen products, such as urea,
potassium nitrate, and ammonium phosphate. The practical advantages of
handling, blending, and storing such fertilizer granules are known and well
documented. The preparation of granular fertilizers using slow release UF
fertilizers also has been described in the prior art.
[10] The present invention proposes to provide a new source of a particulate slow-
release nitrogen (UF) as a plant fertilizer and to use such particles for forming
granular fertilizer compositions.

BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
[11] Figure 1 is a graph showing the lysimeter results (nitrogen release rate) over a
six (6) month time period for the UF polymer powder (particulate) of the
present invention as compared with several commercially available sources of
nitrogen fertilizers.
[12] Figure 2 is a photomicrograph of tall fescue seeds having an adherent coating
containing slow release nitrogen particles in accordance with the present
invention.
DETAILED DESCRIPTION OF THE INVENTION
[13] As noted above, the present invention is directed to a particulate source of
slow release nitrogen (urea-formaldehyde (UF or ureaform) polymer particles)
that is useful for enhancing the delivery of nitrogen needed for plant
development and growth. The invention specifically relates to slow release
nitrogen (UF) particles and to the use of the particles for enhancing plant
development and growth. The slow release nitrogen particles of the present
invention can be used in a variety of applications, for example they can be
adhered to the surface of a seed, or on the surface of an aggregate material,
such as sand, using an adhesive binder; they can used in preparing a granular
fertilizer; they can be used as a root dip or in a soil drench; or they can be used
as a soil additive. In yet another embodiment, the slow release nitrogen
particles of the invention may have use in animal nutrition and could be used
to coat urea, or another animal feed material.
[14] Because of the slow release character of the nitrogen particle of the present
invention, upwards of twenty times the amount of nitrogen fertilizer can be
supplied in many fertilizer applications than would be possible using common
quick release nitrogen fertilizers available in the prior art, such as urea or
methylol ureas, without damaging seeds or growing plants (phytotoxic effect).
[15] The slow release nitrogen UF polymer particles of the present invention are
prepared by reacting, in an aqueous environment, urea and formaldehyde at a
urea:formaldehyde mole ratio of about 1:1. Ammonia may be an optional
reactant, as will be understood by those skilled in the art, in an amount of up to
about 25% by weight of the formed UF polymer, usually in an amount below
about 10 % by weight, but in the preferred embodiment of the present
invention ammonia is not used at all.
[16] To prepare the UF polymer particles of the present invention, urea and
formaldehyde are reacted in admixture at a mole ratio of approximately 1:1,
for example at a UF mol ratio broadly in the range of 0.7:1 = U:F =1.25:1 and
more preferably in the range of 0.83:1 = U:F =1.1:1. The phase "at a mole
ratio of approximately 1:1" is intended to embrace these mole ratio ranges.
Particularly good results have been obtained at a U:F mole ratio between
0.95:1 and 1.05:1.
[17] In the initial step of preparing the UF polymer particles, reaction between urea
and formaldehyde is conducted in a manner to produce methylol ureas.
Methods of doing this are well known to those skilled in the art and any of
such known methods can be used. For example, reaction between the urea and
formaldehyde can be promoted by maintaining the aqueous mixture initially at
a moderate alkaline pH, with a pH in the range of about 7 to 9 being suitable
and with a pH more usually between about 7.5 and 8.5, to promote the
formation of methylol ureas. Given urea's inherent level of alkalinity, any
required pH adjustment may be accomplished using either an acid or a base.
The initial formation of methyol ureas generally can be conducted at a reaction
temperature broadly in the range of 70° F to 175° F (about 20° C to about 80°
C), with a reaction temperature in the range of 90° F to 160° F (about 30° C to
about 70° C) more usually employed. The pH may be adjusted using
commonly available acids and bases such as sodium hydroxide (caustic) and
sulfuric acid and any material that can alter the pH is suitable for this purpose.
The reaction pH also may be maintained (buffered) or adjusted by adding such
alkaline compounds as triethanolamine, sodium or potassium bicarbonate,
sodium or potassium carbonate, or other alkali metal hydroxides, such as
potassium hydroxide and lithium hydroxide. Alternatively (though not
generally preferred), the methylolation may also be done at a moderate acidic
pH, such as in the pH range of 5.0 to 6.0, as will be recognized by those
skilled in the art and the present invention is not limited by the way the initial
methylolation is conducted.
[18] Following the initial formation of methylol ureas, the nascent UF polymer then is condensed to the point where the polymer becomes insoluble in the
aqueous environment. This result is preferably accomplished by rapidly
acidifying the methylol ureas, to a pH below about 6, preferably below about 5
and usually to a pH below about 4, but above about 1. A pH in the range of
2.5 to 4.0 has proven to be suitable. Any organic or inorganic acid that will
lower the pH can be used. Particularly suitable is a strong acid, such as a
mineral acid and an organic acid such as the stronger carboxylic acids. Thus,
suitable acids include formic acid, acetic acid, nitric acid, phosphoric acid,
sulfuric acid and hydrochloric acid. However, in its broadest aspects the
present invention is not limited by the way the further polymerization of the
methylol ureas and ultimate insolubilization is conducted and obtained.
[19] In order to produce a useful range of UF polymer particle sizes, the aqueous
mixture of the methylol ureas is preferably mixed in the presence of a
dispersing agent during the step of rapid polymerization which leads to
insolubilization, such as the rapid acidification step, although it should be
possible to get a similar result by maintaining a sufficiently high level of
agitation (high shear) during the reaction in the absence of any dispersing
agent. The resulting dispersion of UF polymer particles formed from the
polymerization that occurs, for example, following acidification, can then be
used directly (possibly following some thickening, or concentration
enrichment), i.e., as a dispersion, to coat seed or sand, to treat roots, as a soil
drench or soil additive, or to form a granular fertilizer, or alternately (and
preferably) the dispersion of UF polymer particles can be recovered or isolated
from the dispersion to produce a UF polymer powder, which then is used in
any of the various applications noted above. The UF particulates formed in
this manner have approximately 36% by weight nitrogen.
[30] Particularly in the preferred embodiment, most of the nitrogen is chemically
bound in the UF polymer particulates and thus is agronomically unavailable
until microorganisms, principally bacteria, enzymatically (e.g., using urease
and nitrogenase) degrade the polymer into a form useable by a growing plant.
It is this property that leads to labeling the UF polymer particle "slow release"
or "extended release." A small amount of the nitrogen, typically on the order
of 5% by weight of the particulate, may be of the fast or quick release variety
(e.g., principally unreacted urea) and thus may be immediately available to a
seed or plant. Because the UF polymer has only about 5% quick release
nitrogen, however, the chance of over fertilization using the particulate source
of nitrogen of the present invention is minimal. However, if desired, the
reaction conditions (including the mole ratio of reactants) and/or the extent of
the reaction also can be adjusted such that a higher amount of free urea is
present in/with the UF polymer particles, up to about 10% by weight, as a way
to deliver more immediately available nitrogen for a quicker initial
development or greening effect. Such adjustments are well within the skill of
the art in view of the present disclosure.
[21] Skilled practitioners recognize that the formaldehyde and urea reactants used
to make the UF polymer of this invention are commercially available in many
forms. Any form of these materials, which can react with the other reactant
and which does not introduce extraneous moieties deleterious to the desired
reaction and reaction product, can be used in the preparation of the slow
release nitrogen, urea-formaldehyde polymer particles of the invention.
[22] Formaldehyde is available in many forms. Paraform (solid, polymerized
formaldehyde) and formalin solutions (aqueous solutions of formaldehyde,
sometimes with methanol, in 37 percent, 44 percent, or 50 percent
formaldehyde concentrations) are commonly used sources of formaldehyde.
Formaldehyde also may be available as a gas. Each of these sources of
formaldehyde is suitable for use in the preparing the UF polymer of this
invention. Generally, for ease of use, formalin solutions are preferred as the
formaldehyde source. In addition, some of the formaldehyde may be replaced
with another aldehyde, such as acetaldehyde and/or propylaldehyde that can
react with urea. Glyoxal may also be used in place of formaldehyde, as may
other aldehydes not specifically enumerated.
[23] Urea also is available in many forms. Solid urea, such as prill, and urea solutions, typically aqueous solutions, are commercially available. Further,
urea often is chemically combined with formaldehyde in the form of a urea-
formaldehyde concentrate, such as UFC 85, or as a commercially-available
solution containing about 25 weight percent urea, about 60 weight percent
formaldehyde, and about 15 weight percent water, available under the
trademark STA-FORM 60.® Each of these sources of urea can be used in
preparing the UF polymer of this invention.
[24] The urea-formaldehyde condensation reaction that results in the UF polymer
particles of this invention is preferably conducted in an aqueous environment.
As noted above, the reaction is conducted until the growing urea-
formaldehyde polymer becomes insoluble in the aqueous reaction medium. A
dispersing agent is preferably included in the water to facilitate the production
of small polymer particles by the reaction. One suitable dispersant is the line
of DAXAD dispersants commercially available from Hampshire Chemicals, a
subsidiary of the Dow Chemical Company. One of the classes of these
dispersants is a condensed naphthalene sulfonate. Both the high and low
molecular weight species of this product line have been shown to be suitable,
such as DAXDAD 19. A variety of other dispersants, or surfactants also can
be used, including those that might be classified as anionic, such as
polyacrylates (also available under the DAXAD label - such as DAXAD 30
from Hampshire Chemicals). Nonionic and cationic dispersant compounds
also can be used. Suitable alternative materials can be identified using routine
experimentation. The nature of the specific dispersant/surfactant is not
critical. Another example would be a lignosulfonate salt or lignin. It is also
possible to dispense with the use of any dispersant, provided that the reaction
medium is sufficiently agitated (high shear) during the UF condensation
reaction to promote the formation of small polymer particles.
[15] The amount of dispersant to include in the aqueous solution of methylol urea
at the time of the insolubilization reaction can be readily determined by those
skilled in the art. The amount depends to some extent on the particular
dispersant chosen to use and the concentration of methylol urea in the aqueous
reaction medium. Generally, the urea and formaldehyde reactants and the
water vehicle are provided in amounts to yield a methylol urea concentration
that ultimately provides a dispersion of UF polymer particles at about a 20%
by weight solid concentration up to about 60% by weight solids. More
usually, the materials are provided so that the UF polymer dispersion is
between about 30% and 55% by weight solids. Preferably, the dispersion of
UF polymer particles is prepared at about a 40% by weight solids
concentration. Under these conditions, the dispersing agent is generally
supplied at a concentration of between about 0.1% and 5% by weight, and
usually in at least about 0.5% by weight up to about 2% by weight.
[26] The particle size of the UF polymer particulate material may vary fairly
widely. In general, a particular size is dictated by the specific application for
which the particle is too be used. In some applications, such as when used as a
soil additive, the particle size is less critical than when it may be used for
example in a seed coating where is likely would be desirable to have a particle
size smaller than the seed itself and usually substantially smaller than the seed.
Producing small UF particles helps one better obtain a necessary and desired
degree of adhesion of the UF particles in such applications. By using the
preferred method of making the UF polymer in the presence of a dispersant, it
is easy to produce most of the UF particles sufficiently small so as to pass
through a 100 mesh (U.S. or Tyler) screen, and generally at least a major
portion also pass through a 200 mesh screen. Thus, most of the UF polymer
particles will be smaller than about 150 microns and a large number of them
may be smaller than about 75 microns. While there is virtually no lower limit
to the UF polymer particle size for practicing the invention; as a practical
matter, most particles will be larger than one micron. Most of the particles,
prepared using the procedures and materials noted above, have a particle size
in the range of 10 to 80 microns, with a number average particle size between
about 25 and 35 microns. A number average particle size of about 30 microns
is quite common.
[27] In the broad practice of this invention, the aqueous dispersion of UF polymer
particles can be used directly for the wide variety of available applications,
such as coating seeds or coating sand, or the solid UF particles can be isolated
from the dispersion before use. In some cases, it may be easier and more cost
effective to use the dispersion directly. However, if there is a desire to isolate
the particles, and that may be preferred in some applications, then according to
the broadest aspects of the invention, any way for isolating the UF polymer
particles from the aqueous UF polymer dispersion can be used. For example,
the UF polymer particles in the dispersion may be isolated by filtration and
oven drying, or by thin film evaporation. When using these latter techniques,
it may then be necessary to reduce the particle size of the recovered solids, for
example by grinding, to obtain a desired particle size or size distribution for a
specific application.
[28] Another, often preferred, way of isolating or recovering the UF polymer
particles from the UF dispersion formed by the polymerization of urea and
formaldehyde as described above, is by spray-drying. As used herein, the
terms "spray dryer" and "spray drying" refer to the technically sophisticated
process of atomizing (in the form of finely divided droplets) the UF dispersion
or slurry into a gas stream (often a heated air stream) under controlled
temperature conditions and under specific gas/liquid contacting conditions to
effect evaporation of water from the atomized droplets and production of a dry
particulate solid product. Spray drying as used herein is typically carried out
with pressure nozzles (nozzle atomization) or centrifugal atomizers operating
at high speeds (e.g., a spinning disc). Despite the high velocity generation of
droplets, a spray dryer is designed so that the droplets do not contact the spray
dryer wall under proper operating procedures. This effect is achieved by a
precise balance of atomizer velocity, air flow, spray dryer dimensions of
height and diameter, and inlet and outlet means to produce a cyclonic flow of
gas, e.g., air in the chamber. A pulse atomizer also can be used to produce the
small droplets needed to facilitate evaporation of the water. In some cases, it
may be desirable to include a flow promoter, such as an aluminosilicate
material, in the aqueous dispersion that is processed in a spray dryer simply to
facilitate subsequent handling and transport of the spray dried UF powder
(e.g., to avoid clumping).
[29] In addition to the slow release nitrogen, UF polymer solid particles, a variety
of other additives, including other agriculturally acceptable particulate
materials, may also be combined with the UF polymer particles in the variety
of potential applications. Some materials may exhibit a high degree of water
solubility, and thus may be mixed with the UF polymer dispersion before its
use. In fact, in some cases one may be able to mix such materials, especially
the water soluble materials, with the UF polymer dispersion prior to spray-
drying.
[30] Included in materials that can be used in combination with the UF polymer
particles are materials commonly used in fertilizer applications that are not
toxic to seeds, or harmful to the soil environment in which seeds are planted,
or in which a plant is growing. Such materials may include calcium carbonate
(agricultural lime) in its various forms for adding weight and/or raising the pH
of acid soils; metal containing compounds and minerals such as gypsum, metal
silicates and chelates of various micronutrient metals such as iron, zinc and
manganese; talc; elemental sulfur; activated carbon, which may act as a
"safener" to protect against potentially harmful chemicals in the soil;
pesticides, herbicides and fungicides to combat or prevent undesired insects,
weeds and disease, super absorbent polymers, wicking agents, wetting agents,
plant stimulants to accelerate growth, an inorganic (N-P-K) type fertilizer,
sources of phosphorus, sources of potassium, and organic fertilizers, such as
urea as a way to deliver more immediately available nitrogen for a quicker
initial greening effect, surfactants, initiators, stabilizers, cross linkers,
antioxidants, UV stabilizers, reducing agents, colorants and plasticizers.
Mixtures of these different materials may of course also be employed. In a
preferred embodiment, described in more detail hereafter, one or more of these
materials is combined with the UF polymer particles of the invention to
produce granular fertilizer solids.
[31] Thus, in the broad practice of this invention, either the aqueous dispersion of
slow release nitrogen particles itself, or more preferably the isolated,
powdered UF polymer, slow release nitrogen, recovered from the aqueous
dispersion, preferably by spray-drying, then is used in the desired application.
[32] In one application, the UF polymer particles can be used to coat seeds or other
solid aggregates using an adhesive. In the broad practice of this embodiment,
the nature of the adhesive binder is not narrowly critical. Any non-toxic,
biocompatible adhesive material should be suitable.
[33] Based on these characteristics, adhesive classes which can potentially be used
as the adhesive binder in the various applications include, but are not limited
to, animal hide glues, celluloses including ethyl celluloses, methyl celluloses,
hydroxymethyl celluloses, hydroxypropyl celluloses, hydroxymethyl propyl
celluloses, carboxy methyl celluloses, polyvinyl alcohols and polyvinyl
alcohol copolymers, dextrins, malto-dextrins, alginates, sugars, molasses,
polyvinyl pyrrolidones, polyvinyl acetates and polyvinyl acetate copolymers,
polysaccharides, fats, oils, proteins, gum arabics, shellacs, vinylidene
chlorides, vinylidene chloride copolymers, lignosulfonates, starches, acrylate
polymers and copolymers, such as polyvinyl acrylates, zeins, gelatins,
chitosan, polyethylene oxide polymers, acrylamide polymers and copolymers,
polyhydroxyethyl acrylates, methylacrylamide polymers, polychloroprenes,
poly (methyl vinyl ether)-maleic anhydride copolymers,
vinylpyrrolidone/styrene copolymers, vinyl acetate/butyl acrylate copolymers,
styrene/acrylic ester copolymers, vinyl acetate/ethylene copolymers and
polyurethane polymers. Crosslinkable silicone materials as described in U.S.
4,753,035 also can be used. Still other materials, including natural inorganic
materials such as silica gel and clay may also be suitable in some applications
as will be readily apparent to those skilled in the art.
[34] In a preferred embodiment of the invention, the UF polymer particles are used to prepare a composite fertilizer as granular particles. Granular particles can
be prepared by commingling the UF polymer particles with one or more
fertilizer enhancing solids. The fertilizer enhancing solids preferably contain a
source of phosphorus and a source of potassium. The source of potassium may
be potash (potassium chloride) or its sulfates, which are available
commercially, such as the sulfate of potash ("SOP") or the sulfate of potash-
magnesia ("SPM"). The source of phosphorus may be mbnoammonium
phosphate ("MAP"), diammonium phosphate ("DAP"), or triple super
phosphate ("TSP"), all of which are generally available from commercial
sources. The amounts of nitrogen, phosphorus, and potassium included in the
final fertilizer granules is not critical and typically will range from 0% to
about 60% for each component. Most preferably, between about 1-100%
slow-release nitrogen, 0-60% of a potassium source, and 0-60% of a
phosphorus source are included in the final fertilizer granules.
[35] In addition to phosphorus, and potassium, the fertilizer enhancing solids also
preferably include other fertilizer components and/or nutrients (including
materials previously identified) such as iron, manganese, calcium,
micronutrients, and the like. The forms and sources of these additional
components are known to persons skilled in the art, and the appropriate
amounts may be selected to include in the fertilizer granules without undue
experimentation. In this regard, the disclosure of U.S. 5,797,976, which
provides an extensive list of fertilizer enhancing solids for enhancing the
growth and development of plants, is herein incorporated by reference in its
entirety for its disclosure.
[36] To prepare the fertilizer granules, the UF polymer particles are combined with
one or more of the fertilizer enhancing solids and a binder and then mixed to
granulate the ingredients into more or less homogeneous granules. In many
applications, as is well understood by those skilled in the art of granulation,
plain water can be used as the binder simply by moistening the dry
components to accomplish granulation. The water may be provided at
ambient temperature, or it may be heated to provide additional energy for the
granulation process. In some cases it may be preferred to provide the water as
steam.
[37] According to one process, the dry fertilizer ingredients, including the UF polymer particles, are combined and are mixed until a well-mixed blend of the
ingredients is obtained. Fertilizer enhancing solids of an appropriate size for
granulation, as is well-known to those skilled in the art of granulation, may be
purchased from commercial sources, or they may be obtained by crushing or
milling larger sized particles and screening for size. The dry ingredients can
be blended by tumbling in a rotary mixer, although other methods of mixing
may be used. For example, mixing in a paddle mixer or in a ribbon or other
type of batch mixer may be preferred in certain cases.
[38] After blending the ingredients to obtain a fairly uniform mixture, a binder is
added to the mixture of particles, for example as noted above, the particles can
simply be moistened, and then are further mixed to begin the granulation
process. To obtain the granular fertilizer, one normally would employ a
granulator that subjects the particles to a rolling action during the granulation.
Such rolling-type granulators include dish-type granulators, drum-type
granulators, or stirring-type (agitation-type) granulators in which stirring
vanes or paddles rotate in a vessel. As recognized by those skilled in
granulating solids, the blended particles can be moistened by spraying them
with steam to heat the particles simultaneously during the moistening.
Alternatively, the blended particles may be moistened with plain water, which
may be sprayed onto the blend of particles. In yet another embodiment, a
solution of an adhesive, such as a methylol urea solution, or a solution of one
of the earlier identified agriculturally acceptable adhesives, is used as the
binder (moisturizer). Any of these binders may be used alone, or in
combination with others. Regardless of whether steam, water, or another
binder is used, the moistening with the binder and the mixing preferably takes
place in a tumbler or other mixer granulator so that the particles are evenly
moistened.
[39] As understood by skilled workers, the amount of binder/moisture added to the
granules should be controlled; too little or too much binder being detrimental
to final granule integrity. The temperature during granulation in not narrowly
critical. The dry ingredients are mixed with binder until homogeneous
particles of fertilizer granules, i.e., granules that contain most, if not all, of the
fertilizer components, are obtained. In most cases, the fertilizer granules
contain, in addition to the UF polymer particles of the present invention, a
source of phosphorus, and a source of potassium. Those skilled in the art
recognize that not all of the granules will contain the same ratio of all
components, but it is preferred that the majority of the granules include each
ingredient.
[40] The desired particle size of the granules is generally dictated by the particular
application of the resulting fertilizer. Granule particle sizes in the range of 20
mils to 250 mils (about 0.5 to about 6.0 mm) are typical. To obtain granules
having a smaller particle size, one would typically initiate the granulation
process using powder ingredients having a finer particle size. Particle size is
controlled by properly adjusting the amount of binder and the rate of binder
addition, the operating conditions of the gramilator and the granulation time.
[41] After granulation, the granules may be fed into a dryer to facilitate final
production and recovery of the granulated fertilizer. For example, one might
employ a rotating drum dryer with a drying zone temperature between 100°
and 250° F (about 40° to about 120° C), usually between about 185° F and 200°
F (between 85° C and about 95° C). After drying, the material is cooled to
ambient temperature, and then is passed to a screening apparatus to separate
granules meeting desired size specifications. Oversize granules and fines can
be recycled to the granulation step, with oversize granules first being milled or
crushed. Appropriately sized granules are recovered as the granulated
fertilizer product.
[42] According to this process a granular, slow-acting nitrogen fertilizer can be
obtained, which is excellent in the physical properties for use as a fertilizer,
having an acceptable hardness with minimal breakage.
[43] The amount of UF polymer particles of the invention used in any particular
application may vary fairly widely, but will usually depend on the particular
application and its need for nitrogen fertilization, as well as the optional
presence of other particulates and solids besides the essential UF polymer
particles of the present invention.
[44] The UF polymer particles of present invention, and the related fertilizer
granules are useful for fertilizing a wide variety of seeds and plants, including
seeds used to grow crops for human consumption, for silage, or for other
agricultural uses. Indeed, virtually any seed or plant can be treated in
accordance with the present invention using UF polymer particles of the
present invention, such as cereals, vegetables, ornamentals, conifers, coffee,
turf grasses, forages and fruits, including citrus. Plants that can be treated
include grains such as barley, oats and corn, sunflower, sugar beets, rape,
safflower, flax, canary grass, tomatoes, cotton seed, peanuts, soybean, wheat,
rice, alfalfa, sorghum, bean, sugar cane, broccoli, cabbage and carrot.
[45] It will be understood that while the invention has been described in
conjunction with specific embodiments thereof, the foregoing description and
examples are intended to illustrate, but not limit the scope of the invention.
Other aspects, advantages and modifications will be apparent to those skilled
in the art to which the invention pertains, and these aspects and modifications
are within the scope of the invention, which is limited only by the appended
claims.
EXAMPLE 1
[46] A urea-formaldehyde (UF) dispersion, suitable for producing UF polymer
particles of the present invention, is prepared as follows. Water (32.3 parts by
weight) and a 50% aqueous solution of formaldehyde (31.8 parts by weight)
are added to a reaction vessel equipped with vacuum reflux, a heater and a
mixer. While adjusting the temperature of the agitated aqueous mixture to
100° F, its pH is also adjusted to about 7.0 (6.8 to 7.2) using either 50%
caustic (NaOH), or 35% sulfuric acid, as needed. Once the aqueous mixture
has been heated to 100° F (about 38° C), 31.8 parts by weight of prilled urea
also is added and mixing is continued. The temperature of the agitated
aqueous mixture then is increased to 120° F (about 50° C) and held for a time
(usually about 15 minutes) sufficient to dissolve the urea. While maintaining
the temperature of the agitated mixture at 120° F (about 50° C), the pH is
adjusted to within the range of 8.0 to 8.4, again using either 50% caustic
(NaOH), or 35% sulfuric acid as needed. Using, as appropriate, a combination
of the reaction exotherm and external heating, the reaction mixture is heated to
a temperature of 158° F and the temperature is controlled using vacuum reflux.
The pH of the mixture is adjusted, as needed, to about 7.8 to 8.2, using either
50% caustic (NaOH), or 35% sulfuric acid. The agitated mixture is held at a
temperature of about 158° F (70° C) for about 30 minutes and the pH continues
to be adjusted, as needed, to about 7.8 to 8.2, using either 50% caustic
(NaOH), or 35% sulfuric acid so that the reactants form methylol ureas.
While continuing agitation, the aqueous mixture is cooled to about 105° F
(about 40° C) and a dispersant (one part by weight of DAXAD 19) is added
while the batch is cooled. Upon reaching 105° F (about 40° C), the batch is
placed under full vacuum. While maintaining full vacuum and applying
cooling to the agitated batch, the pH of the aqueous mixture is adjusted, as
quickly as possible, to a pH of about 3.3 to 3.5, using 35% sulfuric acid, at
which point the batch may exotherm to a temperature of above 175° F (about
80° C) before the exotherm subsides. This procedure causes rapid
condensation of the methylol ureas to a solid network polymer. After
completing the pH adjustment, the temperature of the aqueous mixture is
cooled to 105° F (about 40° C) as quickly as possible while it is held for 20
minutes. Following the 20 minute holding period, the pH of the aqueous
mixture is adjusted to 6.5 to 7.5, using either 50% caustic (NaOH), or 35%
sulfuric acid, as needed, and then is discharged to storage. The UF polymer
dispersion at about 38 weight percent solids should be agitated during its
storage.
EXAMPLE 2
[47] The dispersion made in accordance with Example 1 can then be spray dried to produce UF polymer particles. A Niro P6 spray dryer can be fed with 15
pounds per hour of the dispersion of Example 1. The spray dryer receives an
inlet gas stream at a flow rate of about 415 standard cubic feet per minute and
a temperature of 330- 340° F (165-170° C). The outlet temperature of the
spray dryer was measured as 75-95° F (25-35° C). The recovered UF polymer
particle product (at about 1 wt. % moisture) had particle sizes distributed from
10 to 80 microns, with a number average size of 30 microns.
EXAMPLE 3
[48] Using a Niro industrial-sized spray dryer (ON 030-5051), a UF polymer
dispersion made in accordance with Example 1 having about a 38 wt. % solids
content, at a temperature of 28° C and at a feed rate of 100 lbs/minute was
spray-dried with the atomizer wheel operating at 13,000 RPMs. Air, at a flow
rate of 49,400 standard cubic feet per minute and at a temperature of 186° C
was delivered to the spray dryer. The outlet air temperature was measured as
88° C. Spray-dried UF polymer particles were recovered from the spray dryer.
EXAMPLE 4
[49] In order to assess the release performance of the UF powder of the present
invention, the sprayed dried UF powder product of Example 3 was tested in an
incubation lysimeter, a procedure developed by Dr. Jerry Sartain of the
University of Florida. An individual lysimeter is simply a 12 inch long piece
of 3" diameter PVC piping. The pipe has a permanent cap on the bottom and a
removable cap on the top. The bottom cap has an opening where water can
drain and vacuum can be applied to remove excess water. A sand-soil mixture
is prepared by mixing ninety-five (95) parts sand and five (5) parts topsoil.
An amount of the sand-topsoil mixture sufficient to fill the column then is
mixed thoroughly with an amount of each of the fertilizers to be tested
sufficient to provide 450 mg of nitrogen in the column. After filling the
lysimeter column, enough water is added to moisten the column contents. The
column then is ready for the start of the testing. Once a month, 500 milliliters
of 0.01 M citric acid is added to the column, allowed to flow downwardly
through the column, and is collected from the bottom drain. Any excess water
(citric acid) is removed from the column using a vacuum and combined with
the amount collected from the drain. The collected liquid is analyzed for
nitrogen (nitrate and ammonia) content. The amount of nitrogen (nitrate and
ammonia) eluted from the column each month is determined. In addition to
the UF powder of Example 6, sulfur coated urea (SCU), a polymer coated urea
(Poly-On), a low molecular weight methylene urea (Nitroform) and an even
lower molecular weight methylene urea (Nutralene) also were tested. Each
material was tested in triplicate and the results of the testing are illustrated in
the Figure 1. The graph of Figure 1 plots the total nitrate released each month
(average of three replicates) over a six month period of time. As shown, the
UF powder had the lowest level released in the first month and then sustained
the highest levels of release in the fourth, fifth and sixth months. Furthermore,
as shown by the release curve in Figure 1, the release rate of nitrogen (as
nitrate) from the UF polymer particles of the present invention is substantially
uniform (constant) over a period of six months.
[50] The present invention has been described with reference to specific
embodiments. However, this application is intended to cover those changes
and substitutions that may be made by those skilled in the art without
departing from the spirit and the scope of the invention. Unless otherwise
specifically indicated, all percentages are by weight. Throughout the
specification and in the claims the term "about" is intended to encompass + or
- 5%.
WE CLAIM;
1. A particulate urea-formaldehyde polymer made by acidifying a aqueous methylol urea
solution, wherein the aqueous methylol urea solution is made by reacting urea and formaldehyde
at a urea: formaldehyde mole ratio of from 0.7:1 to 1.25:1 and wherein the aqueous methylol
urea solution either contains a dispersing agent or is subjected to a high shear condition during
the acidifying, to form an aqueous dispersion of insoluble urea-formaldehyde polymer particles
and drying the dispersion to recover the urea-formaldehyde polymer particles.
2. The particulate urea-formaldehyde polymer as claimed in claim 1 wherein the aqueous
methylol urea solution is made by reacting urea and formaldehyde at a urea:formaldehyde mole
ratio of approximately 1:1.
3. The particulate urea-formaldehyde polymer as claimed in claim 1 wherein the aqueous
methylol urea solution is made by reacting urea and formaldehyde at a urea:formaldehyde mole
ratio of approximately 1:1 and wherein the methylol urea solution contains a dispersing agent
during the acidifying.
4. The particulate urea-formaldehyde polymer as claimed in claim 2 wherein the aqueous
methylol urea solution is made by reacting urea and formaldehyde at a urea:formaldehyde mole
ratio of from 0.83:1 to 1.1:1.
5. The particulate urea-formaldehyde polymer as claimed in claim 3 wherein the aqueous
methylol urea solution is made by reacting urea and formaldehyde at a urea:formaldehyde mole
ratio of from 0.83:1 to 1.1:1,
6. The particulate urea-formaldehyde polymer as claimed in claim 1 wherein the aqueous
methylol urea solution is made by reacting urea and formaldehyde at a urea:formaldehyde mole
ratio of from 0.95:1 to 1.05:1 and wherein the methylol urea solution contains a dispersing agent
during the acidifying.
7. The particulate urea-formaldehyde polymer as claimed in claim 1 wherein the aqueous
methylol urea solution is made by reacting urea and formaldehyde at a urea:formaldehyde mole
ratio of from 0.95:1 to 1.05:1.
8. The particulate urea-formaldehyde polymer as claimed in claim 1, 2, 3, 4, 5, 6, or 7
wherein the aqueous dispersion of urea-formaldehyde polymer particles is dried by spray drying.
9. A granular fertilizer made by granulating the particulate urea-formaldehyde polymer as
claimed in claim 8 with a fertilizer-enhancing solid and a binder.
10. The granular fertilizer as claimed in claim 9 wherein said fertilizer-enhancing solid is
selected from the group consisting of calcium carbonate; gypsum; metal silicates; metal chelates
of a metal selected from iron, zinc and manganese; talc; elemental sulfur; activated carbon;
pesticides; herbicides; fungicides; super absorbent polymers; wicking agents; wetting agents;
plant stimulants; urea; a potassium source and a phosphorus source.
11. A method of producing a particulate urea-formaldehyde polymer comprising forming an
aqueous solution of methylol urea by reacting urea and formaldehyde at a urea: formaldehyde
mole ratio of 0.95:1 to 1.05:1; acidifying the aqueous methylol urea solution, wherein the aqueous
methylol urea solution either contains a dispersing agent or is subjected to a high shear condition
during the acidifying, to form an aqueous dispersion of insoluble urea-formaldehyde polymer
particles and drying the dispersion to recover the urea-formaldehyde polymer particles.
12. The method as claimed in claim 11 wherein the methylol urea solution contains a
dispersing agent during the acidifying and the aqueous dispersion of urea-formaldehyde polymer
particles is dried by spray drying.
13. The particulate urea-formaldehyde polymer as claimed in claim 1 wherein the urea-
formaldehyde polymer particles have a number average particle size between 25 and 35 microns.
14. A particulate urea-formaldehyde polymer made by acidifying an aqueous methylol urea
solution, wherein the aqueous methylol urea solution is made by reacting urea and formaldehyde
at a urea:formaldehyde mole ratio of from 0.7:1 to 1.25:1 and wherein the aqueous methylol urea
solution either contains a dispersing agent or is subjected to a high shear condition during the
acidifying, to form an aqueous dispersion of insoluble urea-formaldehyde polymer particles,
wherein most of the urea-formaldehyde particles have a size between 1 and 150 microns.
15. The particulate urea-formaldehyde polymer as claimed in claim 14 wherein most of the
urea-formaldehyde particles have a size between 10 and 80 microns.
16. The particulate urea-formaldehyde polymer as claimed in claim 15 wherein the urea-
formaldehyde particles have a number average particle size between 25 and 35 microns.
17. The particulate urea-formaldehyde polymer as claimed in claim 14 wherein the
dispersing agent is selected from the group consisting of a condensed naphthalene sulfonate, a
polyacrylate, a lignosulfonate salt and lignin.
18. The particulate urea-formaldehyde polymer as claimed in claim 6 wherein the dispersing
agent is selected from the group consisting of a condensed naphthalene sulfonate, a polyacrylate,
a lignosulfonate salt and lignin.
19. The particulate urea-formaldehyde polymer as claimed in claim 12 wherein the
dispersing agent is selected from the group consisting of a condensed naphthalene sulfonate, a polyacrylate, a lignosulfonate salt and lignin.

A slow release, particulate urea-formaldehyde polymer useful as a fertilizer for enhancing the extended delivery of
nitrogen needed for plant development and growth and a granular fertilizer made with the particulate urea formaldehyde polymer.

Documents:

1373-KOLNP-2004-(18-05-2012)-FORM-27.pdf

1373-kolnp-2004-abstract.pdf

1373-kolnp-2004-assignment.pdf

1373-kolnp-2004-claims.pdf

1373-kolnp-2004-correspondence.pdf

1373-kolnp-2004-description (complete).pdf

1373-kolnp-2004-drawings.pdf

1373-kolnp-2004-examination report.pdf

1373-kolnp-2004-form 1.pdf

1373-kolnp-2004-form 13.pdf

1373-kolnp-2004-form 18.pdf

1373-kolnp-2004-form 3.pdf

1373-kolnp-2004-form 5.pdf

1373-KOLNP-2004-FORM-27.pdf

1373-kolnp-2004-gpa.pdf

1373-kolnp-2004-reply to examination report.pdf

1373-kolnp-2004-specification.pdf


Patent Number 239803
Indian Patent Application Number 1373/KOLNP/2004
PG Journal Number 14/2010
Publication Date 02-Apr-2010
Grant Date 31-Mar-2010
Date of Filing 16-Sep-2004
Name of Patentee GEORGIA-PACIFIC RESINS, INC.
Applicant Address 133 PEACTREE STREET, N.E., ATLANTA, GA
Inventors:
# Inventor's Name Inventor's Address
1 DAVIS C. R. 180 LANELLA PARKWAY, CONYERS, GA 30013
2 WERTZ STACEY 2671 WELLINGTON WAY, CONYERS, GA 30013
3 WRIGHT JAMES 5178 WINDING GLEN DRIVE, LITHONIA, GA 30038
4 BAXTER PAUL 1701 OLD DOVER WAY, CONYERS, GA 30094
5 KNIGHT JAMES 1604 SUGARPLUM DRIVE, SW, CONYERS, GA 30094
6 GABRIELSON KURT 1710 LAKE LUCERNE ROAD, LILBURN, GA 30047
PCT International Classification Number C05C 9/02
PCT International Application Number PCT/US2003/08454
PCT International Filing date 2003-03-26
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/367,278 2002-03-26 U.S.A.
2 60/379,402 2002-05-13 U.S.A.