U.S. patent application number 15/385290 was filed with the patent office on 2017-04-13 for chelated compositions and methods of making and using the same.
The applicant listed for this patent is Scott G. Williams, LLC. Invention is credited to Fernando Remigio Munoz, Sherman M. Ponder.
Application Number | 20170101351 15/385290 |
Document ID | / |
Family ID | 46314425 |
Filed Date | 2017-04-13 |
United States Patent
Application |
20170101351 |
Kind Code |
A1 |
Ponder; Sherman M. ; et
al. |
April 13, 2017 |
CHELATED COMPOSITIONS AND METHODS OF MAKING AND USING THE SAME
Abstract
A composition includes a first chelating agent, a second
chelating agent, and a plurality of metal ions. In one embodiment,
the second chelating agent includes citric acid and is different
than the first chelating agent. A method for forming a composition
includes mixing a first chelating agent, a second chelating agent,
and a metal salt together to form a mixture and processing the
mixture to form at least one of a granulated composition and a
powdered composition. In some embodiments, the second chelating
agent includes citric acid and is different than the first
chelating agent.
Inventors: |
Ponder; Sherman M.;
(Conyers, GA) ; Munoz; Fernando Remigio; (Atlanta,
GA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Scott G. Williams, LLC |
Conyers |
GA |
US |
|
|
Family ID: |
46314425 |
Appl. No.: |
15/385290 |
Filed: |
December 20, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14714983 |
May 18, 2015 |
9540289 |
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15385290 |
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14195560 |
Mar 3, 2014 |
9034071 |
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14714983 |
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12976627 |
Dec 22, 2010 |
8685133 |
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14195560 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07F 3/003 20130101;
C07F 3/06 20130101; A23L 29/015 20160801; C05G 5/38 20200201; C05D
9/02 20130101; C05G 5/12 20200201; C05D 9/02 20130101; C05G 5/37
20200201; C05G 5/30 20200201; C07F 15/025 20130101; C05D 9/02
20130101; C05G 5/23 20200201; C05D 3/00 20130101; C05G 5/23
20200201; C05G 5/23 20200201 |
International
Class: |
C05D 9/02 20060101
C05D009/02; C05G 3/00 20060101 C05G003/00; C07F 15/02 20060101
C07F015/02; C05D 3/00 20060101 C05D003/00; C07F 3/00 20060101
C07F003/00; C07F 3/06 20060101 C07F003/06 |
Claims
1. A method of providing nutrients to a plant, comprising: applying
a composition to at least one of a portion of the plant and foliage
proximate the plant, the composition including a first chelating
agent, a second chelating agent different than the first chelating
agent, wherein the first chelating agent includes at least one
selected from the group consisting of ethylenediamine tetraacetic
acid and tetrasodium ethylenediamine tetraacetate and the second
chelating agent includes citric acid, and wherein the composition
is in the form of at least one of the group consisting of a
plurality of granules and a water-soluble powder.
2. The composition of claim 1, wherein the composition is in the
form of a plurality of granules.
3. The composition of claim 1, wherein the composition is in the
form of a plurality of granules, one of the plurality of granules
includes at least one molecule of the first chelating agent, at
least one molecule of the second chelating agent, and at least one
of the plurality of metal ions.
4. The composition of claim 1, wherein the composition is in the
form of a water-soluble powder.
5. The composition of claim 1, wherein the composition is a
water-soluble powder, the powder having a plurality of particles,
one of the plurality of particles includes at least one molecule of
the first chelating agent, at least one molecule of the second
chelating agent, and at least one of the plurality of metal
ions.
6. The method of claim 1, wherein the composition is in the form of
a water-soluble powder, the method further comprising dissolving
the composition in an aqueous solution prior to the applying.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation application and claims
the benefit of U.S. application Ser. No. 14/714,983, filed on May
18, 2015 and titled "CHELATED COMPOSITIONS AND METHODS OF MAKING
AND USING THE SAME", which is a continuation application and claims
the benefit of U.S. application Ser. No. 14/195,560, filed on Mar.
3, 2014 and titled "CHELATED COMPOSITIONS AND METHODS OF MAKING AND
USING THE SAME", now U.S. Pat. No. 9,034,071, which is a
continuation application and claims the benefit of U.S. application
Ser. No. 12/976,627, filed on Dec. 22, 2010 and titled "CHELATED
COMPOSITIONS AND METHODS OF MAKING AND USING THE SAME", now U.S.
Pat. No. 8,685,133, each of which is incorporated herein by
reference in entirety.
TECHNICAL FIELD
[0002] This disclosure relates generally to the manufacture and
composition of chelated micronutrients for use in agriculture and
animal husbandry. More particularly, this disclosure relates to a
group of micronutrient metals bound in a network of chelator or
chelating agent molecules.
BACKGROUND
[0003] Small amounts of iron, copper, manganese, cobalt, magnesium,
calcium, and zinc have been determined to be helpful, if not
necessary, for plant and animal life. In the course of agriculture,
the soil or other growing medium can become depleted of these
elements due to plant uptake, and other factors such as erosion,
insolubility from combination with other materials in the soil,
and/or weathering. Thus, there is a need to replenish these
micronutrients so that the growing medium can be reused for new
crops. A lack of or a depletion of these micronutrients can create
a multitude of problems, including, but not limited to, stunted
growth and crop loss. Additionally, livestock animals that feed on
grasses and other vegetation that are low in micronutrients do not
obtain their full requirement of micronutrients and thereby may
suffer poor health and/or slow growth.
[0004] Micronutrient replenishment has been handled by the direct
bulk addition of metal sulfates to the soil. This method had some
drawbacks. First, the majority of the metal sulfate would either
run off in the first water application, leach into lower levels of
the soil, or the metal would oxidize and have limited
bioavailability. Second, in neutral or alkaline soils, for example
chalcareous soils, the metal ions would react and precipitate as
insoluble, and non-bioavailable, oxides and hydroxides.
[0005] Chelates have been developed and provide a means to maintain
bioavailability of the micronutrient metals by binding with the
coordination sites of the metal ions to maintain their mobility and
bioavailability. For example, ethylenediamine tetraacetic acid
("EDTA") can recruit up to six coordination sites in the form of
four carboxylic acid moieties and two amine moieties, thereby
forming a cage-like structure that resists any reactivity with
oxide or hydroxide ions present in the metal ion's environment.
Accordingly, the metal ion can retain its bioavailable state even
in the presence of reactive caustic anions until it can contact a
root hair and be taken up by the plant.
[0006] The manufacture of known metal chelates has traditionally
included a process of dissolving a metal salt in a large amount of
water, then adding the chelator, and then drying the reaction
product until it crystallizes. This process is energy-, water-, and
time-intensive.
[0007] Accordingly, it is desirable to provide a metal chelated
product that creates a metal-chelator network and that may be
manufactured by a process that minimizes the amount of water and
subsequent drying needed. This manufacturing process can be adapted
to produce either granulated chelated micronutrients, which are
typically intended to remain in semi-solid form for a period of
time in the soil, or micronutrient powders, which typically are
intended to dissolve into water quickly and completely.
SUMMARY
[0008] A composition includes a first chelating agent, a second
chelating agent, and a plurality of metal ions. In one embodiment,
the second chelating agent includes citric acid and is different
than the first chelating agent.
[0009] In some embodiments, the first chelating agent includes
ethylenediamine tetraacetic acid. In other embodiments, the first
chelating agent includes tetrasodium ethylenediamine
tetraacetate.
[0010] In some embodiments, the first chelating agent includes a
chelating molecule that has a moiety and the second chelating agent
includes a chelating molecule that has a moiety. One of the
plurality of metal ions has at least a first coordination site and
a second coordination site. The first coordination site is occupied
by the first moiety of the chelating molecule of the first
chelating agent and the second coordination site is occupied by the
first moiety of the chelating molecule of the second chelating
agent.
[0011] In some embodiments, the first chelating agent includes a
chelating molecule and the second chelating agent includes a
chelating molecule. One of the plurality of metal ions is bound to
the chelating molecule of the first chelating agent and to the
chelating molecule of the second chelating agent.
[0012] In some embodiments, the first chelating agent includes a
chelating molecule, and the second chelating agent includes a
chelating molecule. The chelating molecule of the first chelating
agent is bound to the chelating molecule of the second chelating
agent.
[0013] In some embodiments, the composition includes a plurality of
granules. In some embodiments, one of the plurality of granules
includes at least one molecule of the first chelating agent, at
least one molecule of the second chelating agent, and at least one
of the plurality of metal ions.
[0014] In some embodiments, the composition is a water-soluble
powder. In some embodiments, the powder has a plurality of
particles. One of the plurality of particles includes at least one
molecule of the first chelating agent, at least one molecule of the
second chelating agent, and at least one of the plurality of metal
ions.
[0015] In some embodiments the first chelating agent, the second
chelating agent, and the plurality of metal ions form a network of
chelated metal ions.
[0016] A method for forming a composition includes mixing a first
chelating agent, a second chelating agent, and a metal salt
together to form a mixture and processing the mixture to form at
least one of a granulated composition and a powdered composition.
In some embodiments, the second chelating agent includes citric
acid and is different than the first chelating agent.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] The Fig. is a flow chart illustrating a method of forming a
chelated metal composition according to an embodiment of the
invention.
DETAILED DESCRIPTION
[0018] This disclosure relates generally to the manufacture and
composition of chelated micronutrients for use in agriculture and
animal husbandry. More particularly, the disclosure relates to
group of micronutrient metals bound in a network of chelator
molecules. In some embodiments, the network of chelator molecules
provides superior agronomic and metabolic efficacy as compared to
traditional chelated micronutrient metals. In some embodiments,
these micronutrients-in-network materials can be designed, for
example, for longer term soil stability as solid-phase granules, or
as powders for immediate and complete solubility and use as foliar
applications or for ingestion by livestock. In some embodiments,
the processes of making these micronutrients-in-network materials
not only create the novel network structure, but also allow
chelated micronutrients to be manufactured at significantly lower
cost and effort than traditional chelated micronutrients.
[0019] Some chelates have a one-to-one ratio of chelated metal ion
to chelator. For example, the EDTA is considered to bind to a
single metal ion using the usual six coordination sites present in
an octahedral structure available to period 4 transition metals.
However, in some cases, one of the amine moieties does not become
ionized until pH reaches above about 10. So, in some cases it is
not necessary for all six coordination sites on a metal ion to be
bound to a chelator for the metal to be considered chelated. Other
chelators, such as citric acid and nitrilotriacetic acid ("NTA"),
only have three or four chelation sites and so, they can never by
themselves bind all six coordination sites of a single metal
ion.
[0020] In some cases, metal ions are held in chelation and
protected from precipitation when three or two coordination sites
are occupied by chelator moieties. In some embodiments, it was
found that metal ions can be maintained in chelation when two or
three of the ion coordination sites are occupied by chelator
moieties that do not necessarily belong to the same chelator
molecule. The arrangement of chelator molecules joining across
metal ion coordination sites creates a network of chelated metal
that in some cases helps resist alkali disruption better than
traditional chelates, is cheaper to manufacture, and/or still
maintains the metal ion in the liquid and bioavailable state in
high pH environments. For example, in some embodiments, the
arrangement of chelator molecules maintains the metal ion in the
liquid and bioavailable state in environments that are above a pH
of 9 or above a pH of 10.
[0021] In some embodiments, the use of multiple chelators or
chelating agents, such as citric acid and EDTA (or its conjugate
base) (each of which contain multiple moieties for bonding or
association to coordination sites of a metal ion), can be induced
to bond not only across a single metal ion, but also to bind to
other chelator molecules, thereby creating a shared network of
chelated metal ions in a random distribution of linked chelators.
In some embodiments, the distribution of linked chelators is an
ordered distribution.
[0022] In some embodiments, the manufacturing process that creates
the metal-chelator network discussed above minimizes the amount of
water and subsequent drying required by pre-existing methods.
Furthermore, in some embodiments, the manufacturing process can be
adapted to produce either granulated chelated micronutrients, which
are typically intended to remain in semi-solid form for a period of
time in the soil, or micronutrient powders, which typically are
intended to dissolve into water quickly and completely. For
example, in some embodiments, the powder dissolves into water
within a few minutes (or even less than 30 seconds).
[0023] In some embodiments, a composition or a chelated
micronutrient includes a network of chelators and metal ions which
is capable of maintaining its micronutrient metal in solution above
the pH where the oxide or hydroxide of the micronutrient metal
would normally precipitate, and the means to manufacture such. The
chelation network is formed by reacting a mixture of organic
chelators concurrently with a metal salt, while simultaneously
controlling the water content of the mixture to promote network
formation. In some embodiments, the manufacturing process helps
prevent the formation of separate metal-EDTA chelates and
metal-citrate chelates in the end product.
[0024] In some embodiments, the intermixed network of chelated
micronutrient allows the metal to be chelated in the most
bioavailable valence state of the metal. For example, in one
embodiment, iron is chelated as Fe(II), instead of the more usual
Fe(III). This allows uptake and use by the target organism (such as
a plant) without having to reduce the Fe(III), by metabolites or
other biochemical means, to a valence state available to the
metabolism of the organism. Additionally, in some embodiments, the
composition, without any insoluble fillers, is 100% soluble, which
is equal to the solubility of traditional metal-EDTA chelates.
[0025] In some embodiments, the intermixed network of chelated
metal provides superior buffering against alkaline soil particles.
For example, the chelated metal might come into contact with
alkaline soil particles such as carbonates and/or hydroxides.
Because the alkali in natural soils is not homogeneously
distributed, but is in fact unevenly micro-distributed among the
faces and interiors of assorted soil particles, metals, including
non-buffered chelated metals, come into contact with
micro-environments that can be significantly higher or lower in pH
than the overall average pH of the bulk soil. Metal ions, including
non-buffered metal chelates, that traverse the soil and come into
contact with micro-pockets of alkaline pH higher than their
precipitation point are precipitated within that micro-pocket of
alkaline pH and are thereby rendered unavailable as a plant
nutrient. In some embodiments, the composition provides a buffering
action that resists contact with up to eight times the amount of
alkaline materials before precipitating out of solution, as
compared to traditional non-buffered chelates. For example, in some
embodiments, a standard EDTA chelate might absorb one portion or
mole of alkali before the pH rises and a precipitate forms while
the buffering action of the composition of the present invention
absorbs 8 portions or moles before its pH rises and a precipitate
is formed.
[0026] In some embodiments, the method of production of the
composition ensures that the complexation reactions are
substantially completed, while at the same time the total water
used is minimized or reduced.
[0027] Composition
[0028] In some embodiments, the composition includes a first
chelating agent, a second chelating agent, and a plurality of metal
ions. The first chelating agent is different than the second
chelating agent. In other words, the first chelating agent has a
different chemical make-up (i.e., has a different chemical formula)
than the second chelating agent.
[0029] The first and the second chelating agents can be any type of
chelating agent. For example, the first chelating agent and the
second chelating agent can be any one of the following: disuccinic
acid, nitrilo triacetic acid, glucoheptonate,
monoethanolethylenediamine triacetic acid,
diethanolethylenediaminediacetic acid, diethylenatriamine
pentacetic acid, monoethanoldiethylenetriaminetetraacetic and
(i.e., N-hydroxyethyl or N'-hydroxyethyl),
diethanoldiethylenetriamine-triacetic acid (i.e.,
N,N'-dihydroxyethyl or N',N''-dihydroxethyl), and the corresponding
compounds based upon propylene, isopropylene, methylethylene and
cyclohexylene. In some embodiments, the first chelating agent is
EDTA (or its conjugate base) and the second chelating agent is
citric acid.
[0030] The metal ion can be an ion of any metal, including but not
limited to iron, copper, manganese, cobalt, magnesium, calcium, and
zinc. In some embodiments, the source of the metal ion is a metal
salt. For example, in some embodiments, a metal salt such as a
sulfate hydrate, a chlorine, or a nitrate, can be the source of the
metal ion.
[0031] In some embodiments, the composition forms a network of
chelated metal ions. Specifically, in some embodiments, a single
metal ion is bound to a molecule of the first chelating agent and
to a molecule of the second chelating agent. More specifically, in
some embodiments, a single metal ion is directly bound to a
molecule of the first chelating agent and is directly bound to a
molecule of the second chelating agent. For example, a single metal
ion may be bound at a first coordination site of the metal ion to a
moiety of a molecule of the first chelating agent and may be bound
at a second coordination site of the metal ion to a moiety of a
molecule of the second chelating agent. In other embodiments, a
single metal ion may be directly bound to a molecule of the first
chelating agent and indirectly bound to a molecule of the second
chelating agent. In other words, the metal ion is removed from
direct bonding to the molecule of the second chelating agent but is
indirectly bound to the molecule of the second chelating agent
because both the metal ion and the molecule of the second chelating
agent are bound in the same network.
[0032] Additionally, in some embodiments, the composition includes
molecules of the first chelating agent that are directly bound to
molecules of the second chelating agent.
[0033] In some embodiments, the composition includes a ratio of
chelated metal ions to total chelator molecules that is greater
than 1 to 1. For example, in some embodiments, the composition
includes more chelated metal ions than total chelator
molecules.
[0034] In some embodiments, additional materials are also added to
the mixture. For example, in some embodiments, a filler such as
ammonium sulfate or iron oxide fines are added to the mixture. In
some embodiments, a granulation aid is added to the mixture. For
example, in some embodiments, a granulation aid such as water,
lignin sulfonate, or ethyl alcohol is added to the mixture.
[0035] In some embodiments, the composition is in the form of a
plurality of granules. For example, in some embodiments, the
granules of the composition have a diameter of about 0.25 inches
(6.35 mm). In other embodiments, the granules have a diameter of
less than 0.25 inches (6.35 mm). In yet further embodiments, the
granules have a diameter of greater than 0.25 inches (6.35 mm). In
some embodiments, one or each of the granules of the composition
includes at least one molecule of the first chelating agent, at
least one molecule of the second chelating agent, and at least one
metal ion. For example, in some embodiments, one or each of the
plurality of granules includes a network of chelated metal
ions.
[0036] In some embodiments, the granules are solid and
partially-soluble. In some embodiments, the granules are configured
to retain the chelated metal in ionic form within the soil for a
period of up to one year.
[0037] In other embodiments, the composition is in the form of a
powder. Specifically, in some embodiments the composition is a
powder that includes a plurality of particles. In some embodiments,
the particles are between 1.18 mm and 0.6 mm in diameter. In some
embodiments, the particles are greater than 1.18 mm in diameter. In
yet further embodiments, the particles are less than 0.6 mm in
diameter. In some embodiments, one or each of the particles of the
powder of the composition includes at least one molecule of the
first chelating agent, at least one molecule of the second
chelating agent, and at least one metal ion. For example, in some
embodiments, one or each of the particles includes a network of
chelated metal ions. In some embodiments, the powder of the
composition is partially-soluble. In other embodiments, the powder
of the composition is completely soluble.
[0038] In some embodiments, the composition includes a coating. For
example, in some embodiments, the composition includes a coating
that is configured to control the release of the metal ions from
the chelated network. In some embodiments, the coating is a polymer
coating. In other embodiments, the coating is a wax coating. In
some embodiments, the coating is formed of a biodegradable
material.
[0039] For example, in some embodiments, the granules of the
composition are covered or substantially covered with a
coating.
[0040] Manufacture
[0041] The FIG. is a flow chart that illustrates a method 100 of
making the metal chelated composition. In some embodiments, an
amount of a first chelating agent, an amount of a second chelating
agent, and an amount of a metal salt are mixed together 110. In
some embodiments, water is added to the mixture 120. Finally, in
some embodiments, the mixture is converted or processed into a
plurality of granules or a powder 130.
[0042] In some embodiments, an amount of a metal salt is added to
the container for mixture. For example, in some embodiments, 200 to
1500 pounds (lbs.) of metal salt is used per ton of product
desired. More specifically, in some embodiments, 480 to 1000 lbs.
of metal salt is used per ton of product desired. In other
embodiments, more or less of the metal salt is added to the
container for mixture.
[0043] In some embodiments, the metal may be any transition metal,
including iron, nickel, cobalt, zinc, copper, or manganese, or an
alkaline earth metal, including magnesium or calcium. In one
embodiment, the transition metal is iron, cobalt, zinc, copper, or
manganese. In one embodiment, the metal is either magnesium or
calcium. In one embodiment, the metal is a mixture of two or more
transition metal salts or alkaline earth metal salts. In one
embodiment the metal salt is a sulfate, a chloride, or a
nitrate.
[0044] In some embodiments, a first chelating agent is added to the
container for mixture. In some embodiments, the first chelating
agent is either EDTA or Na4EDTA. In some embodiments, 1 to 150 lbs.
of EDTA solid or its conjugate base ("tetrasodium ethylenediamine
tetraacetate" or "Na4EDTA") in 39% aqueous solution per ton of
product desired is added to the container for mixture. In one
embodiment, the weight of the EDTA solid or Na.sub.4EDTA that is
added is between 1% and 75% of the weight of the metal salt that is
added.
[0045] In one embodiment, EDTA solid or acid is used to eventually
create a granular final product. In another embodiment,
Na.sub.4EDTA in 39% aqueous solution is used to create a powder
final product. In other embodiments, a sodium or potassium salt of
EDTA is used in dry powdered form to create either a granular or a
powder final product. For example, in some embodiments, tetrasodium
ethylenediamine tetraacetate in a powder form is used in the
composition.
[0046] In some embodiments, a second chelating agent is added to
the container for mixture. For example, in some embodiments, 400 to
900 lbs. of citric acid per ton of product desired is added to the
container for mixture. In some embodiments, the weight of the
citric acid that is added is between 25% and 450% of the weight of
the metal salt that is added. In some embodiments, trisodium
citrate is used in place of citric acid.
[0047] In some embodiments, the metal salt, the first chelating
agent, and the second chelating agent are mixed together. For
example, they may be mixed in a mixing container using a known
mixing method. In some embodiments, water is then added to the
mixture to create a material with the consistency of wet sand (in
other words, the mixture is not entirely saturated). In some
embodiments, the weight of the water added is between 100 and 300
lbs. In some embodiments, the weight of the water added to the
mixture (i.e., the mixture of the metal salt, the first chelating
agent, and the second chelating agent) is less than 60% of the
weight of the mixture. In some embodiments, the weight of the water
added to the mixture is less than 30% of the weight of the mixture.
In some embodiments, the weight of the water added to the mixture
is less than 15% of the weight of the mixture.
[0048] In some embodiments, the citric acid is between 35% and 55%
of the total weight of the mixture (citric acid, EDTA, and the
metal salt), the EDTA is between 3% and 20% of the total weight of
the mixture, and the metal salt is between 35% and 55% of the total
weight of the mixture. For example in some embodiments, the citric
acid is about 45% of the total weight, the EDTA is about 10% of the
total weight, and the metal salt is about 45% of the total
weight.
[0049] The wetted material is mixed for a period of time sufficient
for the substitution reactions to begin with the metal ion
coordination sphere, thereby creating the networked metal chelate.
For example, in some embodiments, the wetted material is mixed by
turning the material in a container or mixer.
[0050] The material is then processed to form the final product. In
some embodiments, the final product is a granulated product. In
other embodiments, the final product is a powdered product.
[0051] In some embodiments, the processing includes granulation,
drying, and screening. Specifically, in some embodiments, the
material is passed through a rotating granulation drum and
additional water is added as needed to substantially complete the
chelation reactions and to agglomerate the granules. In other
embodiments, another granulation processed is used to agglomerate
or form the granules.
[0052] Once the granules have been formed, the granules are dried.
For example, in some one embodiment, the granules are passed
through a gas-fired rotary drum dryer. In other embodiments, the
granules are exposed to another drying process.
[0053] Once the granules have been dried, the granules are cooled.
For example, in some embodiments, the granules are passed through a
rotating drum cooler. In other embodiments, the granules are
exposed to another cooling process.
[0054] The resulting material is then screened and collected. In
some embodiments, the material is screened to a specific size, such
as a +12/-4 screen size. In other embodiments, the material is
screened to a larger or smaller size. In some embodiments, the
particle size may range from -50 mesh for powders, and up to 0.25
inches in diameter for granules. In some embodiments, the oversized
or larger materials are collected, ground, and screened again.
[0055] In some embodiments, 100 to 300 lb. of granulation aids are
added to the existing mixture. Granulation aids include, but are
not necessarily limited to: water, lignin sulfonate, and/or ethyl
alcohol. All of these ingredients are then mixed to create the
network of chelated metals and a sodium ionic salt. In one
embodiment, this sodium ionic salt is sodium sulfate. In another
embodiment, the sodium ionic salt is either sodium nitrate or
sodium chloride.
[0056] In some embodiments, 1 to 1800 lbs. of filler material is
added to the mixture to create a solid, partially-soluble, granule
with a lower overall percentage (0.15 to 15%) of chelated metal
that will continue to maintain ionic metal in the soil for up to
one year. For example, in some embodiments, 1 to 400 lbs. of
ammonium sulfate and/or 1 to 850 lbs. of iron oxide fines are added
as filler. In some embodiments, to maximize the percentage of
chelated metal, a filler is not added to the mixture.
[0057] Use
[0058] In some embodiments, the composition may be used in
agriculture and/or livestock. For example, in some embodiments, the
composition in the form of granules may be placed or disposed in or
on soil that is proximate to a plant. For example, in some
embodiments, the granules may be placed on or delivered to soil
that a plant uses for nutrients. In some embodiments, such
solid-phase granules can be designed for longer term soil
stability.
[0059] In some embodiments, the composition in the form of a powder
may be disposed in or on soil that is proximate to a plant. For
example, the powder may be dissolved in a liquid such as water and
then applied to the soil. In other embodiments, the powder may be
dissolved in water and applied to the foliage of a plant or used
for ingestion by livestock.
EXAMPLE 1
[0060] Composition
[0061] 850 lbs. of iron sulfate monohydrate was placed in a mixer
with 750 lbs. of citric acid, 200 lbs. of ethylenediamine
tetracetic acid and 100 lbs. of ammonium sulfate. These were
thoroughly mixed and 200 lbs. of water was added. Although 200 lbs.
of water was added in this embodiment, in other embodiments, more
or less water was added. For example, in some embodiments, an
amount of water equal to about 50% of the other materials is added.
In other embodiments, an amount of water equal to about 30% of the
weight of the other materials is added. The material was mixed for
15 minutes until it assumed the consistency of wet sand, then the
material was conveyed to a rotating granulation drum. The material
was rolled in the granulation drum with water added as necessary to
agglomerate the material into granules or balls with an average
diameter of 3 to 5 mm. The material was passed to a gas-fired
rotary drier, then to a rotary cooler, and then screened to a
+12/-4 mesh size.
[0062] Analysis
[0063] The finished material was tested by diluting it into
fertilizer, then extracting it into an acetate/acetic acid buffer,
then oxidizing all the available iron, then raising the pH above
the precipitation point of aqueous Fe (III). The resulting liquid
was then tested for iron content.
[0064] First, the material was ground in an analytical laboratory
grinder. Additionally, standard 10-10-10 fertilizer (Vigoro) was
ground by the same method. The iron chelate was diluted 20:1 by
mixing 0.2556 g of chelate with 4.7827 g of 10-10-10 fertilizer.
1.2537 g of this mixture was weighed out and put into a 250 mL
volumetric flask with 125 mL of an extraction buffer composed of: 1
g of sodium acetate and 25 mL of glacial acetic acid in a 1 L
volumetric flask that was then filled with deionized water. 10 mL
of household bleach (6% NaOCl) was added to the 250 mL volumetric
flask to oxidize all the iron. Then 20 mL of a solution composed of
10 g of diammonium phosphate in 1 L deionized water was added to
the 250 mL volumetric flask to raise the pH. The volumetric was
then filled to volume with deionized water and 3 1.00 mL aliquot
were removed. The aliquots were each diluted to a dilution factor
of 16 and the samples were tested by atomic absorption
spectroscopy. The aliquots were found to contain 14.4% chelated
iron.
EXAMPLE 2
[0065] Composition
[0066] 480 lbs. of iron sulfate monohydrate were mixed with 300
lbs. of citric acid, 180 lbs. of ethylenediamine tetracetic acid,
100 lbs. of ammonium sulfate, and 820 lbs. of iron oxide fines. 200
lbs. of water were added while mixing to create a wet sand. The
material was mixed for 15 minutes until it assumed the consistency
of wet sand, then the material was conveyed to a rotating
granulation drum. The material was rolled in the granulation drum
with water added as necessary to agglomerate the material into
granules or balls with an average diameter of 3 to 5 mm. The
material was passed to a gas-fired rotary drier, then to a rotary
cooler, and then screened to a +12/-4 mesh size.
[0067] Analysis
[0068] The finished material was tested by diluting it into
fertilizer, then extracting it into an acetate/acetic acid buffer,
then oxidizing all the available iron, then raising the pH above
the precipitation point of aqueous Fe(III). The resulting liquid
was then tested for iron content.
[0069] First, the material was ground in an analytical laboratory
grinder. Additionally, standard 10-10-10 fertilizer (Vigoro) was
ground by the same method. The iron chelate was diluted 20:1 by
mixing 0.2549 g of chelate with 4.7646 g of 10-10-10 fertilizer.
1.2493 g of this mixture was weighed out and put into a 250 mL
volumetric flask with 125 mL of an extraction buffer composed of: 1
g of sodium acetate and 25 mL of glacial acetic acid in a 1 L
volumetric flask that was then filled with deionized water. 10 mL
of household bleach (6% NaOCl) was added to the 250 mL volumetric
flask to oxidize all the iron. Then 20 mL of a solution composed of
10 g of diammonium phosphate in 1 L deionized water was added to
the 250 mL volumetric flask to raise the pH. The volumetric was
then filled to volume with deionized water and 3 1.00 mL aliquot
were removed. The aliquots were each diluted to a dilution factor
of 16 and the samples were tested by atomic absorption
spectroscopy. The aliquots were found to contain 5.02% chelated
iron.
EXAMPLE 3
[0070] Composition
[0071] 1000 lbs. of zinc sulfate was mixed with 700 lbs. of citric
acid and 300. lbs. of 39% aqueous tetrasodium ethylenediamine
tetraacetate. The material was mixed until it reached the
consistency of wet sand, then the material was conveyed to a
rotating granulation drum. The material was rolled in the
granulation drum for about 20 minutes to allow the chelation
reactions to complete. The material was passed to a gas-fired
rotary drier, then to a rotary cooler, and then screened to a -30
mesh size.
[0072] Analysis
[0073] The finished material was tested by titration with 0.5 M
NaOH. A 1% w/w solution was made of the material by placing 1.0042
g in a 100 mL of deionized water. 0.5 M NaOH was then titrated into
this solution. The material absorbed 23.8 mL of the 0.5 M NaOH
while the solution pH rose from about 2 to about 10.2, whereupon a
precipitate formed. In contrast, pure zinc EDTA chelate was found
to absorb 5.8 mL of the NaOH solution until its pH went above 10.2
and a precipitate formed.
[0074] EXAMPLE 4
[0075] Composition
[0076] 1100 lbs. of calcium chloride was mixed with 900 lbs. of
citric acid and 2.2 lbs. of powdered tetrasodium ethylenediamine
tetraacetate. This dry material was passed to a rotating
granulation drum wherein water was added to bring the material to
the consistency of damp powder. After 40 minutes, the material was
passed to a gas-fired rotary drier, then to a rotary cooler, and
then screened to a -30 mesh size.
[0077] Analysis
[0078] Samples were dissolved in water and tested by atomic
absorption spectroscopy, which showed a 17.8% calcium content.
[0079] EXAMPLE 5
[0080] Analysis
[0081] 20.0090 g of iron sulfate monohydrate was placed in a 1.000
volumetric flask with about 800 mL of deionized water. The mixture
was shaken for 20 minutes, then 9.0034 g of citric acid and 1.0012
g of tetrasodium ethylenediamine tetraacetate were added and the
flask was filled to volume with deionized water. The flask was
shaken for 25 minutes, during which time the solution turned a
clear yellow color.
[0082] 1.00 mL of the yellow solution was added to a 250.00 mL
volumetric flask with 125 mL of an extraction buffer composed of:
1.00 g of sodium acetate and 25.0 mL of glacial acetic acid in a
1.000 L volumetric flask that was then filled with deionized water.
10.00 mL of household bleach (6% NaOCl) was added to the 250.00 mL
volumetric flask to oxidize all the iron. Then 25.00 mL of a
solution composed of 10.00 g of diammonium phosphate in 1.000 L
deionized water was added to the 250.00 mL volumetric flask to
raise the pH. The 250.00 mL volumetric was then filled to volume
with deionized water and shaken. The resulting solution was
filtered, then tested for iron content on by an atomic absorption
spectrophotometer (Buck Scientific 200A) at 248.3 nm.
[0083] Total theoretical iron present in the aliquot was 6.58 ppm
and total iron found was 5.26 ppm. This was 79.95% of the total
theoretical iron and corresponds to a molar ratio of chelators per
iron of 0.52. Differently stated, the atomic absorption
spectrophotometer revealed a molar ratio of 1.92 iron(III) ions per
chelator molecule (a ratio greater than one chelated metal ion per
chelator molecule) being maintained in its liquid state at a pH
above the normal precipitation point of non-chelated iron
(III).
[0084] While certain features of the described implementations have
been illustrated as described herein, many modifications,
substitutions, changes and equivalents will now occur to those
skilled in the art. It is, therefore, to be understood that the
appended claims are intended to cover all such modifications and
changes as fall within the scope of the embodiments.
* * * * *