Note: Descriptions are shown in the official language in which they were submitted.
I
Use of aminocarboxylates in agriculture
The present invention relates to the use of formulations comprising
(A) one or more aminocarboxylates, selected from among methylglycine diacetate
(MGDA) and its alkali metal salts and glutamic diacetate (GLDA) and its alkali
metal salts,
(B) at least one inorganic compound selected from among inorganic phosphates,
inorganic phosphites, inorganic nitrates, ammonium salts and potassium salts
and
(C) optionally water
for the application to plants, the ground or growth substrates.
In some embodiments, the invention relates to the use of a formulation
comprising
(A) one or more aminocarboxylates selected from the group consisting of
methylglycine diacetate (MGDA) and its alkali metal salts and glutamic
diacetate
(GLDA) and its alkali metal salts,
(B) at least one inorganic compound selected from the group consisting of
inorganic
phosphates, inorganic phosphites, inorganic nitrates, ammonium salts and
potassium salts, and
(C) optionally water,
wherein the formulation has a pH value in the range from 6 to 8,
for the application to plants, the ground or growth substrates.
In some embodiments, the invention relates to a method of fertilizing plants,
wherein at least one
formulation comprising
(A) one or more aminocarboxylates selected from the group consisting of
methylglycine diacetate (MGDA) and its alkali metal salts and glutamic
diacetate
(GLDA) and its alkali metal salts,
(B) at least one inorganic compound selected from the group consisting of
inorganic
phosphates, inorganic phosphites, inorganic nitrates, ammonium salts and
potassium salts, and
(C) optionally water,
the formulation having a pH value in the range from 6 to 8,
is applied mechanically or manually to the ground and/or to plants.
The present invention furthermore relates to formulations comprising
(A) one or more aminocarboxylates, selected from among methylglycine diacetate
(MGDA) and its alkali metal salts and glutamic diacetate (GLDA) and its alkali
metal salts,
(B) at least one inorganic compound selected from among inorganic phosphates,
inorganic phosphites, inorganic nitrates, ammonium salts and potassium salts
and
(C) optionally water.
CA 2838329 2018-12-04
=
la
The present invention furthermore relates to a process for the preparation of
formulations
according to the invention. The present invention furthermore relates to the
use of aqueous
formulations comprising
(A) one or more aminocarboxylates, selected from among methylglycine diacetate
(MGDA)
and its alkali metal salts and glutamic diacetate (GLDA) and its alkali metal
salts,
to be applied to plants or the ground or growth substrates.
It has long been attempted to improve the yields of soils in terms of
fertility. By using fertilizers,
in particular what are known as NPK fertilizers, it is indeed possible to
improve the essential
mineral content. However, it is observed that, in many cases, only fractions
of the minerals
supplied to the soil are indeed taken up into plants. A considerable fraction
of the minerals
supplied, in contrast, is not taken up but enters the groundwater, where in
particular nitrates and
phosphates are undesired. Excess fertilizer application, therefore, is not
acceptable.
Regular fertilizing with low fertilizer concentrations is too time-consuming.
The bioavailability of phosphates is a problem. Phosphate minerals which, in
many cases,
include phosphate in a sparingly water-soluble form will in many cases not be
effective as
phosphate fertilizer in nature. The use of what are known as soluble
phosphates, which has
already been proposed as a solution, will, in soils which comprise significant
amounts of calcium
or iron ions in dissolved form, result in the precipitation of sparingly-
soluble phosphates, so that
the problem of the bioavailability of phosphate cannot be considered as
solved. What is know
CA 2838329 2018-12-04
PF 72853 EP CA 02838329 2013-12-05
2
as the mineralization of soluble phosphates can take place within a period of
less than two
weeks, depending on the soil composition.
An object was therefore to provide formulations whose mineral fertilizer
component can be
taken up readily by soils or plants. A further object was to provide uses of
formulations by
means of which mineral fertilizers, and in particular phosphate, can be taken
up readily by soils
or plants. A further object was to provide a method by means of which
phosphate can be
rendered readily bioavailable.
Accordingly, there have been found the uses and formulations defined at the
outset.
According to the invention, there is used at least one formulation comprising
(A) one or more aminocarboxylates, selected from among methylglycine diacetate
(MGDA)
and its alkali metal salts and glutamic diacetate (GLDA) and its alkali metal
salts, in each
case also called aminocarboxylate (A) or else, summarily, compound (A) for
short,
(B) at least one inorganic compound, also called inorganic compound (B) for
short, selected
from among inorganic phosphates, inorganic phosphites, inorganic nitrates,
ammonium
salts and potassium salts and
(C) optionally water
for the application to plants or the ground or growth substrate.
Compound (A) can be present as the free acid or, preferably, in partially or
fully neutralized
form, in other words as a salt. Examples of suitable counterions are inorganic
cations, for
example ammonium, alkali metal or alkaline-earth metal, preferably Mg2+, Ca2+,
Nat, K+, or
.. organic cations, preferably ammonium which is substituted by one or more
organic radicals, in
particular triethanolammonium, N,N-diethanolammonium, N-mono-Ci-C4-
alkyldiethanolammonium, for example N-methyldiethanolammonium or
N-n-butyldiethanolammonium, and N,N-di-C1-C4-alkylethanolammonium. Preferred
ions are
alkali-metal ions, especially preferably Nat and K.
In one embodiment of the present invention, compound (A) is selected from
among derivatives
of aminocarboxylates (A), for example from their methyl or ethyl esters.
Compound (A) is selected from among methylglycine diacetate (MGDA) and
glutamic diacetate
(GLDA) and their derivatives and preferably their salts, in particular their
sodium and potassium
salts. Very especially preferred are methylglycine diacetate and the trisodium
salt of MGDA.
In one embodiment of the present invention, the formulations used are those
which include at
least one aminocarboxylate (A), selected from among methylglycine diacetate
(MGDA) and its
.. alkali metal salts and glutamic diacetate (GLDA) and its alkali metal salts
and furthermore at
least one polyaminocarboxylate (A).
=
3
For the purposes of the present invention, polyaminocarboxylates (A) are
understood as
meaning those organic compounds which include at least two tertiary amino
groups which,
independently from one another, include in each case one or two CH2-COOH
groups which can
be partially or fully neutralized, as mentioned above.
In another embodiment of the present invention, polyaminocarboxylates (A) are
selected from
among those organic compounds which include at least two secondary amino
groups, each of
which includes one CH(COOH)CH2-COOH groups which can be partially or fully
neutralized, as
mentioned above.
Preferred polyaminocarboxylates (A) are selected from among 1,2-
diaminoethanetetraacetic
acid (EDTA), ethylenediaminedisuccinate (EDDS), diethylenetriaminepentaacetate
(DTPA),
hydroxyethylethylenediaminetriacetate (HEDTA) and their respective salts, in
particular alkali
metal salts, very especially preferred are the sodium salts and potassium
salts, and mixed
sodium potassium salts.
Inorganic compound (B) is selected from among inorganic phosphates, inorganic
phosphites,
inorganic nitrates, ammonium salts and potassium salts, it being possible for
inorganic
compound (B) to fall within one or more of the abovementioned categories.
Examples of inorganic nitrates are sodium nitrate, ammonium nitrate and
potassium nitrate,
potassium nitrate being an example of an inorganic compound (B) which falls
both within the
term potassium salts and within inorganic nitrates.
Potassium salts and ammonium salts may have inorganic or organic counterions,
inorganic
counterions being preferred.
Examples of potassium salts which may be selected as inorganic compound (B)
are potassium
chloride, potassium sulfate, potassium nitrate, potassium citrate, potassium
dihydrogenphosphate, dipotassium hydrogenphosphate, potassium metaphosphate,
potassium
orthophosphate and potassium salts of MGDA or GLDA, with potassium nitrate,
potassium
dihydrogenphosphate, dipotassium hydrogenphosphate, potassium metaphosphate,
potassium
orthophosphate and potassium salts of MGDA or GLDA being examples of compounds
which
fall within a plurality of terms within the scope of the present invention.
Examples of ammonium salts are ammonium sulfate, ammonium nitrate, ammonium
citrate,
ammonium chloride, ammonium dihydrogenphosphate, diammonium hydrogenphosphate,
ammonium metaphosphate, ammonium orthophosphate and ammonium salts of MGDA or
of
GLDA, with ammonium nitrate, ammonium dihydrogenphosphate, diammonium
hydrogenphosphate, ammonium metaphosphate, ammonium orthophosphate and
ammonium
salts of MGDA and of GLDA being examples of compounds which fall within a
plurality of terms
within the scope of the present invention.
11 CA 2838329 2018-12-04
PF 72853 EP CA 02838329 2013-12-05
4
Examples of inorganic phosphates are inorganic and organic salts of
metaphosphoric acid,
orthophosphoric acid, diphosphoric acid or higher polyphosphoric acids
including triphosphoric
acid. The term "salts of orthophosphoric acid" includes the corresponding mono-
and
dihydrogenphosphates.
Other examples of inorganic phosphates are natural phosphate-comprising
minerals, so-called
natural phosphates or crude phosphates, for example apatites such as
hydroxyapatite.
In one embodiment of the present invention, inorganic compound (B) is selected
from among
sodium dihydrogenphosphate, disodium hydrogenphosphate, ammonium
dihydrogenphosphate,
diammonium hydrogenphosphate, potassium dihydrogenphosphate, dipotassium
hydrogenphosphate, potassium nitrate, sodium nitrate, ammonium sulfate,
superphosphate and
alkali metal and alkaline-earth metal salts of tripolyphosphate, and natural
phosphate-
comprising minerals.
As a rule, natural phosphates comprise a certain amount of impurities. In this
context, impurities
are considered to be compounds of those elements which are not part of the
general formula
under which the natural phosphate in question usually comes. Thus,
hydroxyapatite has, as a
rule, the formula Ca5(PO4)3(OH) assigned to it. In addition, it is possible
for example for MgO,
A1203, Fe2O3, F-, C032-, S042-, SiO2 (or silicate) or Cl- contents to be
present.
As a rule, natural phosphates are sparingly soluble in water. If it is desired
to use them in
accordance with the invention, for example in formulation according to the
invention, it is
preferred to employ them in comminuted form, for example with a mean particle
diameter in the
range of from 0.5 to 500 pm, preferably 2 to 100 pm. Comminuting can be
effected for example
by grinding.
In accordance with the invention, one uses formulations which may comprise
water (C).
Formulations according to the invention may comprise water (C). Water may be
present for
example in amounts of from 0.1 to 10% by weight, based on the total
formulation according to
the invention, or the total formulation used in accordance with the invention.
In another
embodiment, formulation according to the invention, or formulation used in
accordance with the
invention, comprises more than 10 up to 95% by weight, of water. In another
embodiment of the
present invention, formulation according to the invention, or formulation used
in accordance with
the invention, comprises water (C) in the range of from 95.01 to 99.9% by
weight.
Formulations according to the invention may be present as a powder, a moist
powder, a
suspension, a powder slurry or a solution.
To employ formulations according to the invention, they can be applied to
plants or to ground or
to growth substrate, for example as a fertilizer. To this end, formulation
according to the
= PF 72853 EP CA 02838329 2013-12-05
invention can be applied manually or mechanically to bare soil or growth
substrate or to soil or
growth substrate which is not vegetated, or else formulation according to the
invention may be
applied manually or mechanically to plants.
5 For the purposes of the present invention, growth substrate is understood
as meaning soil-
comprising substrates and industrial soils which are employed for example in
hydroponic
cultures or greenhouses.
Examples of suitable plants are vegetables, cereals, trees, root crops,
bushes, shrubs and
flowers. Especially preferred are oilseed rape, wheat, millet/sorghum, rye,
barley, avocado,
citrus fruits, mango, coffee, deciduous tree crops, grapes and other soft
fruit plants, beans, in
particular soybeans, furthermore maize, tomatoes, cucumbers, in particular
zucchini and salad
cucumbers, pumpkins, furthermore stone fruit, lettuce, potatoes, field beet,
sugar beet, paprika,
sugarcane, hops, tobacco, pineapple, palms, in particular coconut palms,
furthermore rubber
trees, including Brazilian rubber trees (Hevea brasiliensis), and ornamental
plants, in particular
roses, dahlias, hydrangeas, tulips, narcissus, daffodils, carnations and
chrysanthemums.
For application purposes, formulation according to the invention can be
applied above an area
to be treated, for example by aircraft or vehicle, or it can be applied with
the aid of an irrigation
system. Types of application are spraying and root dosage, liquid or solid.
In one embodiment of the present invention, at least one formulation
comprising at least one
cation selected from among Ca2+, Mg2+, Cu2+, Mn2+, Zn2+, Fe2+, Fe3+, Al3+,
Cr3+ and Co2+ in
chelated form is used. In this context, the cation in question is preferably
chelated by
compound (A).
In one embodiment of the present invention, the formulation used according to
the invention
comprises chelated cation(s) selected from among Ca2+, Mg2+, Cu2+, Mn2+, Zn2+,
Fe2+, Fe3+, Al3+,
Cr3+ and Co2+ in the range of in total 0.001 to 10% by weight, preferably 0.01
to 5% by weight,
based on the total amount of compound(s) (A).
In one embodiment of the present invention, the formulation used according to
the invention
may comprise further trace elements, for example boron (as borate) or
molybdenum.
In one embodiment of the present invention, the formulation used according to
the invention
may comprise in the range of in total 0.001 to 10% by weight, preferably 0.01
to 5% by weight,
based on the total amount of compound(s) (A), further trace elements, for
example boron (as
borate) or molybdenum in the range of in total 0.001 to 10% by weight,
preferably 0.01 to 5% by
weight, based on the total amount of compound(s) (A).
In one embodiment of the present invention, at least one formulation is used
in accordance with
the invention, which formulation comprises at least one organic compound (D)
selected from
= PF 72853 EP CA 02838329 2013-12-05
6
among urea and citric acid and its alkali metal salts. Preferred alkali metal
salts of citric acid are
tripotassium citrate ("potassium citrate") and the trisodium salt of citric
acid ("sodium citrate").
In one embodiment of the present invention, at least one formulation is used
in accordance with
the invention, which formulation comprises at least one active substance (E)
selected from
among fungicides, herbicides and insecticides.
In one embodiment of the present invention, at least one formulation is used
in accordance with
the invention, which formulation comprises at least one additive (F) selected
from among
wetters, antifoams, surfactants and spreaders (spreading agents). Particularly
suitable additives
(F) are inorganic surfactants, for example C8-C20ralkylsulfates, C3-C20-
alkylsulfonates and C8-
C20-alkyl ether sulfates having one to 6 ethylene oxide units per molecule. In
this context, it is
possible for example that the same surfactant acts as wetter and as antifoam
or as wetter and
antifoam.
In one embodiment of the present invention, at least one formulation is used
according to the
invention which comprises at least one further inorganic compound, for example
sodium
hydroxide or an inorganic sulfate.
A further subject matter of the present invention are formulations comprising
(A) one or more aminocarboxylates, selected from among methylglycine diacetate
(MGDA)
and its alkali metal salts and glutamic diacetate (GLDA) and its alkali metal
salts,
(B) at least one inorganic compound (B), and
(C) optionally water.
In one embodiment of the present invention, formulation according to the
invention comprises at
least one aminocarboxylate (A) and at least one polyaminocarboxylate (A).
Aminocarboxylates (A), polyaminocarboxylates (A) and compounds (B) are
described
hereinabove.
In one embodiment of the present invention, inorganic compound (B) is selected
from among
sodium dihydrogenphosphate, disodium hydrogenphosphate, ammonium
dihydrogenphosphate,
diammonium hydrogenphosphate, potassium dihydrogenphosphate, dipotassium
hydrogenphosphate, potassium nitrate, sodium nitrate, ammonium sulfate,
superphosphate and
alkali metal and alkaline-earth metal salts of tripolyphosphate, and natural
phosphate-
comprising minerals.
In one embodiment of the present invention, formulation according to the
invention comprises:
in total in the range of from 1 to 90% by weight, preferably 10 to 50% by
weight, of
aminocarboxylate (A), selected from among methylglycine diacetate (MGDA) and
its alkali metal
salts and glutamic diacetate (GLDA) and its alkali metal salts, and optionally
PF 72853 EP CA 02838329 2013-12-05
7
polyaminocarboxylate (A), where the context of polyaminocarboxylate (A) may be
zero, and in
total in the range of from 10 to 99% by weight, preferably 50 to 90% by
weight, of inorganic
compound (B).
In this context, % by weight refers in each case to the solids content of
formulation according to
the invention.
Formulation according to the invention may furthermore comprise water (C).
In one embodiment of the present invention, the formulation according to the
invention
comprises at least one cation selected from among Ca2+, Mg2+, Cu2+, Mn2+,
Zn2+, Fe2+, Fe3+,
Al3+, Cr3+ and Co2+ in chelated form. In this context, the cation in question
is preferably chelated
by compound (A).
In one embodiment of the present invention, the formulation according to the
invention
comprises chelated cation(s) selected from among Ca2+, Mg2+, Cu2+, Mn2+, Zn2+,
Fe2+, Fe3+, Al3+,
Cr3+ and Co2+ in the range of in total 0.001 to 10% by weight, preferably 0.01
to 5% by weight,
based on the total amount of compound(s) (A).
In one embodiment of the present invention, the formulation according to the
invention
comprises in total in the range of from 0.01 to 2% by weight. preferably from
0.02 to 1% by
weight, of cation(s) selected from among Ca2+, Mg2+, Cu2+, Mn2+, Zn2+, Fe2+,
Fe3+, Al3+, Cr3+ and
Co2+ in chelated form, the percentage by weight being based on the total
amount of inorganic
compound (B).
In one embodiment of the present invention, the formulation according to the
invention may
comprise further trace elements, for example boron (as borate) or molybdenum.
In one embodiment of the present invention the formulation according to the
invention may
comprise further trace elements in the range of in total 0.001 to 10% by
weight, preferably 0.01
to 5% by weight, based on the total amount of compound(s) (A), for example
boron (as borate)
or molybdenum in the range of in total 0.001 to 10% by weight, preferably 0.01
to 5% by weight,
based on the total amount of compound(s) (A).
In one embodiment of the present invention, formulation according to the
invention comprises at
least one further substance selected from among
(D) organic compounds which are selected from among urea and citric acid and
its alkali
metal salts,
(E) active substances selected from among herbicides, fungicides and
insecticides,
(F) additives selected from among wetters, antifoams, surfactants and
spreaders.
8
Organic compounds (D), active substances (E) and additives (F) are described
hereinabove.
In one embodiment of the present invention, formulation according to the
invention comprises
in total in the range of from zero to 15% by weight, preferably 1 to 10% by
weight, of organic
compound(s) (D),
in total in the range of from zero to 5% by weight, preferably 0.1 to 2.5% by
weight, of active
substance(s) (E),
in total in the range of from zero to 5% by weight, preferably 0.1 to 2% by
weight, of additive(s)
(F).
In this context, % by weight refers in each case to the solids content of
formulation according to
the invention.
In one embodiment of the present invention, the formulation according to the
invention has a pH
value in the range from 5 to 9, preferably from 6 to 8.
In one embodiment of the present invention, the formulation according to the
invention may
comprise at least one further inorganic compound, for example sodium hydroxide
or an
inorganic sulfate.
Formulations according to the invention can be used in a particularly suitable
manner for
efficiently improving the mineral supply of plants without large amounts of
undesired salts
reaching the groundwater or leading to the eutrophication of inland river
courses.
In embodiments in which the formulation according to the invention comprises
chelated cation(s)
selected from among Ca2+, Mg2+, Cu2*, Mn2+, Zn2+, Fe2+, Fe3+, Al3+, Cr 3+ and
Co2+, the
formulation according to the invention may furthermore be used as a
micronutrient fertilizer.
A further subject matter of the present invention is a process for the
preparation of formulations
according to the invention, also referred to in the context of the present
invention as preparation
process according to the invention.
In one embodiment of the preparation process according to the invention, a
procedure is
followed in which
(A) one or more aminocarboxylate(s) (A), selected from among methylglycine
diacetate
(MGDA) and its alkali metal salts and glutamic diacetate (GLDA) and its alkali
metal
salts,
(B) at least one inorganic compound selected from among inorganic phosphates,
inorganic phosphites, ammonium salts and potassium salts
are mixed with each other in the presence of water (C) and
all or some of the water (C) is optionally removed.
T CA 2838329 2018-12-04
PF 72853 EP CA 02838329 2013-12-05
9
In one embodiment of the present invention, at least one compound (A) and at
least one
inorganic compound (B) are dissolved in water (C), for example in 10% by
volume up to the 10-
fold (volume-based), based on the total of compound (A) and inorganic compound
(B).
Thereafter, all or some of the water (C) may be removed.
In another embodiment of the present invention, at least one inorganic
compound (B) is
suspended in a solution of at least one compound (A) in water (C), for example
in 10% by
volume up to the 10-fold (volume-based), based on the total of compound (A)
and inorganic
compound (B). Thereafter, all or some of the water (C) may be removed. This
embodiment is
preferred when inorganic compound (B) takes the form of a natural phosphate.
In another embodiment of the present invention, at least one inorganic
compound (B) is ground
in a solution of at least one compound (A) in water (C), for example in 10% by
volume up to the
10-fold (volume-based), based on the total of compound (A) and inorganic
compound (B).
Thereafter, all or some of the water (C) may be removed. This embodiment is
preferred when
inorganic compound (B) takes the form of a natural phosphate.
In another embodiment of the preparation process according to the invention, a
procedure is
followed in which, in the presence of water (C) and
(A) one or more aminocarboxylate(s), selected from among methylglycine
diacetate (MGDA)
and its alkali metal salts and glutamic diacetate (GLDA) and its alkali metal
salts,
(B) at least one inorganic compound, preferably at least two inorganic
compounds, in each
case selected from among inorganic phosphates, inorganic phosphites, ammonium
salts
and potassium salts
is prepared and
all or some of the water (C) is optionally removed.
Thus, it is possible, for example, to select potassium hydroxide and
phosphoric acid as
inorganic compounds (B) and thereby to prepare potassium phosphate, potassium
dihydrogenphosphate and/or dipotassium hydrogenphosphate in situ.
In another variant, potassium hydroxide is employed as the inorganic compound
(B), and a
mixture with aminocarboxylate(s) (A) or polyaminocarboxylate(s) as free
acid(s) is prepared in
the presence of water (C), in which manner potassium salts of
aminocarboxylate(s) (A) or
polyaminocarboxylate(s), respectively, are prepared.
In one embodiment of the present invention, in particular if it is desired to
prepare formulations
according to the invention to be employed for the micronutrient fertilization,
at least one
compound which includes at least one cation selected from among Ca2+, Mg2+,
Cu2+, Mn2+, Zn2+,
Fe2+, Fe3+, A13 , Cr3+ and Co2+ is additionally also employed. Examples of
suitable compounds
are sulfates, nitrates, phosphates, halides, in particular chlorides, and
especially preferably
nitrates and sulfates. Suitable compounds may comprise water of hydration or
else be
PF 72853 EP CA 02838329 2013-12-05
anhydrous. In one variant, complex compounds are employed, for example aquo
complexes or
amino complexes of Cu2+, Mn2+, Zn2+, Fe2+, Fe3+, Al3+, Cr3+ or Co2+. In one
variant, a plurality of
compounds, each of which includes at least one cation selected from among
Ca2+, Mg2+, Cu2+,
Mn2+, Zn2+, Fe2+, Fe3+, Al3+, Cr3+ and Co2+, are employed.
5
In one embodiment of the present invention, further compounds may be added,
for example
boric acid, sodium borate, molybdenum oxide, ammonium molybdate,
heteropolyacids of
molybdenum or their salts, for example molybdatophosphoric acid or the sodium
or ammonium
salt of molybdatophosphoric acid.
In one variant, at least one inorganic compound (B) is added which is
contaminated with traces
of at least one compound which includes at least one cation selected from
among Ca2+, Mg2+,
Cu2+, Mn2+, Zn2+, Fe2+, Fe3+, Al3+, Cr3+ and Co2+.
Optionally, it is possible in each case before or after removal of the water
(C), additionally to
prepare a mixture with at least one further substance selected from among
(D) organic compounds which are selected from among urea and citric acid and
its alkali
metal salts,
(E) active substances selected from among herbicides, fungicides and
insecticides and
(F) additives selected from among wetters, antifoams, surfactants and
spreaders.
In another embodiment, it is possible additionally to prepare a mixture with
at least one further
substance selected from among
(D) organic compounds which are selected from among urea and citric acid and
its alkali
metal salts,
(E) active substances selected from among herbicides, fungicides and
insecticides and
(F) additives selected from among wetters, antifoams, surfactants and
spreaders
without removing the water (C).
In one embodiment of the preparation process according to the invention, a
procedure is
followed in which all or some of the water (C) is removed by evaporation,
distillation,
lyophilization, in particular by spray-drying or spray-granulating.
A further subject matter of the present invention is a method of fertilizing
plants, wherein at least
one formulation according to the invention is applied mechanically or manually
to the ground
and/or to plants.
A further subject matter of the present invention is the use of aqueous
formulations comprising
(A) one or more aminocarboxylates, selected from among methylglycine diacetate
(MGDA)
and its alkali metal salts and glutamic diacetate (GLDA) and its alkali metal
salts,
for the application to plants or to the ground.
' PF 72853 EP CA 02838329 2013-12-05
11
A further subject matter of the present invention is the use of aqueous
formulations comprising
(A) one or more aminocarboxylates, selected from among methylglycine diacetate
(MGDA)
and its alkali metal salts and glutamic diacetate (GLDA) and its alkali metal
salts,
for the application to growth substrates for plants.
Aqueous formulations for the two last-mentioned uses may comprise at least one
further
substance selected from among
(D)organic compounds which are selected from among urea and citric acid and
its alkali
metal salts,
(E) active substances selected from among herbicides, fungicides and
insecticides and
(F) additives selected from among wetters, antifoams, surfactants and
spreaders.
However, they are free from inorganic compound (B).
Especially preferred compounds (A) in the two last-mentioned uses are the
sodium salts and in
particular the potassium salts of GLDA and MGDA.
In one variant, one or more compounds which include in each case at least one
cation selected
from among Ca2+, gm 2+, cu2+, mn2+, zn2+, F-2+,
e Fe3+, Al3+, Cr3+ and Co2+ are additionally
employed in such uses according to the invention.
In one embodiment of the present invention, further compounds may be added,
for example
boric acid, sodium borate, molybdenum oxide, ammonium molybdate,
heteropolyacids of
molybdenum or their salts, for example molybdatophosphoric acid or the sodium
or ammonium
salt of molybdatophosphoric acid.
The invention is illustrated by working examples.
Unless expressly specified otherwise, all % are % by weight.
I. Preparation of formulations according to the invention and of
comparative formulations:
1.1 Preparation of formulation F.1
300 g of the tripotassium salt of methylglycinediacetate (Al) were dissolved
in 600 g of water.
A pH of 7 was adjusted with semiconcentrated sulfuric acid, and the mixture
was diluted with
water to a total weight of 1000 g.
This gave formulation F.1 as a stable solution which, due to the K20 content
of 12.5%,
comprised a fertilizer with the classification 0-0-12.5.
1.2 Preparation of formulation F.2
PF 72853 EP CA 02838329 2013-12-05
12
260 g of the trisodium salt of methylglycinediacetate (A.2) were dissolved in
600 g of water. A
pH of 7 was adjusted with semiconcentrated sulfuric acid, and the mixture was
diluted with
water to a total weight of 1000g.
This gave formulation F.2 as a stable solution.
1.3 Preparation of formulation EF.3 according to the invention
240 g of the tripotassium salt of methylglycinediacetate (A.1) and 150 g of
diammonium
orthophosphate (B.2) were dissolved in 560 g of water. A pH of 7.5 was
adjusted using 60 g of
phosphoric acid (B.3). This gave formulation EF.3 according to the invention
as a stable
solution, which comprised a fertilizer with the classification 2.7-10.7-8.1.
1.4 Preparation of formulation EF.4 according to the invention
250 g of the tripotassium salt of methylglycinediacetate (A.1) together with
250 g of Moroccan
crude phosphate 0-30-0 (particle size 20-100 p.m) (B.4) were made into a
slurry with 300 g of
water and stirred for six hours at 80 C. Thereafter, 60 g of concentrated
phosphoric acid (B.3)
were added and the suspension was stirred at 40 C over a period of 5 minutes.
Thereafter, the
mixture was diluted with water to a total weight of 1000 g. The formulation
had a pH of 7.5.
This gave formulation EF.4 according to the invention as a suspension with the
classification
0-11-10.8.
The Moroccan crude phosphate employed had the following composition, as
determined by
elemental analysis:
P205 30%
CaO 48.0 to 49.5%
MgO 0.3 to 0.4%
A1203 0.3 to 0.5%
Fe2O3 1.9 to 2.2%
K2O 0.04-0.06%
S102 5.0 to 6.5%
3.0 to 3.1%
Na2O 0.4 to 0.6%
CaCO3 10.2 to 11.8%
(CO2 4.5 to 5.2%)
S042- 1.5 to 2.0, determined as SO3
H20 4% MAX
Cl 0.05 to 0.09%
1.5 Preparation of comparative formulation V-F.5
. PF 72853 EP CA 02838329 2013-12-05
13
300 g of diammonium monohydrogenphosphate (B.2) and 90 g of potassium
hydroxide were
dissolved in 510 ml of water, and 100 g of concentrated phosphoric acid (B.3)
were added, with
cooling. This gave a fertilizer formulation (pH 7-8) of the composition 5.4-
20.1-6.3.
Pure water was employed as comparative formulation V-F.6.
II. Uses according to the invention and comparative uses of
formulations
For testing, the formulations according to the invention and the formulations
not according to the
invention were in each case diluted with water in the ratio 1/200, this gave
fertilizer solutions
according to the invention and fertilizer solutions not according to the
invention.
11.1 Treatment of tomatoes
The primary fertilization of the soil was carried out using in each case 10 ml
of fertilizer solution
per pot. To fertilize the tomato plants after 35 days (see hereinbelow), in
each case 5 ml of the
same fertilizer solution were sprayed onto the tomato plant.
Plastics pots 5 inches in diameter were filled with medium-heavy loose-
sediment brown earth
from the Bavarian foothills of the Alps. The loose-sediment brown earth
employed had a
phosphate content (determined as P205) of 22 mg P205/100 g soil.
To test a fertilizer solution, in each case 10 pots were planted; the data
listed in tables 1 and 2
are in each case means of in each case 5 pots/fertilizer solution.
Tomato seeds "Berner Rose" (Solanum lycopersicum) were planted at a depth of
2.5 cm at a
rate of 3 seeds per pot. The primary fertilization with in each case 10 ml of
fertilizer solution (see
above) was applied at a depth of 2 cm, immediately after planting. The tomato
plants were first
grown for 35 days in the greenhouse under standard conditions until the
beginning of anthesis.
Analysis after 35 days:
The tomato plants of in each case 5 of the 10 pots in question were cut off
above the roots,
washed with water and dried at 75 C over a period of 24 hours. Thereafter,
they were analyzed
for potassium and phosphate. The result is compiled in table 1.
Table 1: Analysis of the tomato plants after 35 days
K2O [% by wt.] P205 [/0 by wt.]
F.1 1.73 0.53
F.2 1.26 0.50
EF.3 1.56 0.71
EF.4 1.64 0.61
V-F.5 1.53 0.55
V-F.6 1.30 0.34
i
14
The tomato plants of the remaining in each case 5 of the in each case 10 pots
were sprayed
with in each case 5 ml of the diluted fertilizer formulations and grown for a
further 45 days in the
greenhouse under standard conditions. After 70 days, the plants were cut off,
the still unripe
fruits were removed, and the plants were analyzed as described above. The
results are
compiled accordingly in table 2.
Table 2: Analysis of the tomato plants after 70 days
K20 [%] P205 Ecim
F.1 1.69 0.48
F.2 1.26 0.51
EF.3 1.56 0.66
EF.4 1.64 0.61
V-F.5 1.53 0.51
V-F.6 1.21 0.29
11.2 Treatment of potatoes
A waxy table potato cv. Annabelle was planted on 1.5 hectares. Planting was as
recommended
by the Amt fOr Landwirtschaft und Forsten [Department of Agriculture and
Forestry] Augsburg,
ALE A ¨ 2.1P- Stadtbergen, 18.02.2009 (Hinweise zum Kartoffelanbau [Notes on
potato
planting] 2009). The planting distance was in each case 33 cm and the rows
were spaced
75 cm apart, corresponding to a plant number of 41 000 plants per ha.
The soil of the field had a phosphate content (determined as P205) of 21
mg/100 g soil.
Plants were grown traditionally on field plot 1 using comparative formulation
V-F.5. Food plot 2
was treated with formulation EF.3 according to the invention. Food plot 3 was
treated with
formulation F.1 according to the invention, in other words without the
addition of phosphate.
V-F.6 was employed in field plot 4.
The fertilization was carried out in the form of a two-step basal dressing by
applying in each
case in accordance with the invention and by comparison 250 kg/ha in the
spring, and a further
200 kg/ha at the beginning of tuber formation (buffing up). 60 days after
planting, a top dressing
of in each case 250 kg/ha was applied by foliar application. Fertilization
with magnesium in the
form of kieserite (27% MgO) was always carried out with 45 kg of MgO/ha (basal
dressing). By
replenishing potassium salt, a calculated total amount of K20 of (converted)
140 kg K20 /ha was
applied in total. Nitrogen fertilization is carried out with an amount of (in
total) 160 kg/ha.
In addition, the plots were managed identically (planting density, chitting,
pest control, disease
prevention and the like, see ALF A ¨ 2.1P-).
After 160 days, the plants were harvested. The results are compiled in table
3.
r CA 2838329 2018-12-04
PF 72853 EP CA 02838329 2013-12-05
Phosphorus was determined using dried, powdered potatoes, the P content being
back
converted to the weight of the freshly harvested potatoes. To this end, 25 kg
of potatoes
(randomly chosen) were first shredded, dried and then powdered. The P content
was
determined by elemental analysis.
5
Table 3: Results of P content of potatoes and yield
Formulation Yield in P content potatoes [mg/kg]
tonnes/ha
Field plot 1 V-F.5 41 500
Field plot 2 EF.3 45 512
Field plot 3 F.1 39 494
Field plot 4 V-F.6 32 461
Therefore, good results were obtained on field plot 3 although no separate P
fertilization was
carried out.
Ill. Use as micronutrient fertilizer
The following formulations are prepared for use as micronutrient fertilizer:
111.1 Preparation of a formulation according to the invention EF.7
300 g of the tripotassium salt of methylglycine diacetate (A.1) are dissolved
in 600 g of water.
The following are also added:
171 mg of boric acid (corresponds to 0.01% by weight of boron),
47 mg of CuSO4=5H20 (corresponds to 0.004% by weight of copper),
111 mg of MnSO4.H20 (corresponds to 0.012% by weight of manganese),
55 mg of Zn(NO3)2.6H20 (corresponds to 0.004% by weight of zinc),
73 mg of molybdatophosphoric acid (12 Mo03.1-13Pa4x H20, water content 22% by
weight,
corresponds to 0.001% by weight of molybdenum.
The mixture is brought to pH 7 using semi-concentrated sulfuric acid and
diluted with water to a
total weight of 1000 g.
This gives the formulation according to the invention EF.7. It is suitable for
use for example as a
hydrangea fertilizer.
111.2 Preparation of a formulation according to the invention EF.8
240 g of the tripotassium salt of methylglycine diacetate (A.1) and 150 g of
diammonium
orthophosphate (B.2) are dissolved in 560 g of water.
265 mg of boric acid (corresponds to 0.01% by weight of boron),
122 mg of CuSO4=5H20 (corresponds to 0.007% by weight of copper),
142 mg of MnSO4=H20 (corresponds to 0.013% by weight of manganese),
= PF 72853 EP CA 02838329 2013-12-05
16
119 mg of Zn(NO3)2.6H20 (corresponds to 0.006% by weight of zinc),
3.0 g of FeSO4=7H20 (corresponds to 0.2% by weight of iron)
109 mg of molybdatophosphoric acid (12 Mo03.1-13P0.4.x H20, water content 22%
by weight,
corresponds to 0.001% by weight of molybdenum)
60 g of phosphoric acid (B.3) are added. This gives the formulation according
to the invention
EF.8. It is suitable for use for example as a rose fertilizer.
111.3 Preparation of a formulation according to the invention EF.9
240 g of the tripotassium salt of methylglycine diacetate (A.1), 75 g of
ammonium sulfate and
75 g of potassium nitrate (B.2) are dissolved in 560 g of water.
265 mg of boric acid (corresponds to 0.01% by weight of boron),
70 mg of CuSO4-5H20 (corresponds to 0.007% by weight of copper),
131 mg of MnSO4=H20 (corresponds to 0.013% by weight of manganese),
4.0 g of Zn(NO3)2.6H20 (corresponds to 0.2% by weight of zinc),
3.0 g of FeSO4.7H20 (corresponds to 0.2% by weight of iron)
109 mg of molybdatophosphoric acid (12 Mo03.H3PO4.x H20, water content 22% by
weight,
corresponds to 0.001% by weight of molybdenum)
60 g of phosphoric acid (B.3) are added. This gives formulation according to
the invention EF.9.
It is suitable for use for example as a citrus fruit fertilizer.
