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Патент USA US3091531

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United States Patent" 0 " lC€
3,091,522
Patented May 28, 1963
2
1
for such medium thus is characterized by being composed
3,091,522
of the ‘free chelating agent alone or admixed with the
METHOD AND COMPOSITION FOR
11VH’ROVING SOIL
John B. Hemwall, Long Beach, Calif., assignor to The
Dow Chemical Company, Midland, Mich., a corpora
tion of Delaware
No Drawing. Filed Apr. 2.7, 1959, Ser. No. 808,902
10 Claims. (Cl. 71--1)
iron complex of a compound corresponding to the fol
lowing drawing:
A
A
/A
A
A
wherein X is an alkylene hydrocarbon moiety which in
terposes 2-3 carbon atoms between the indicated nitrogen
This invention relates to a method for improving ara 10
atoms and is preferably -—CH2CH2——,
ble soil generally, any soils intended for cultivation, and
soils which are under cultivation, particularly alkaline
--CH(CH3)CHZ—
soils, with respect to improving their usefulness in the
1-2 cyclohexylene, —CH2CH2CH2-; A is selected from
growth of plant life and in making trace metals, such as
15 the group consisting of -—CH2COOH,
iron, available to plants growing in those soils.
—CH2OHOH
Many soils encountered in various parts of the world
are naturally de?cient with respect to certain trace ele
ments, resulting either from depletion of certain trace
metals in those soils or ?xation of the trace metals as
insoluble salts and organic complexes.
11280311
and their alkali metal, [alkaline earth metal, ammonium,
and ammonium base ‘salts, at least one and not more
Alkaline soils 20 than two of the A positions being occupied by a
induce the formation of iron oxide and insoluble iron
—CH2OHOH
compounds from ordinary iron salts which are added
thereto. Many soils in‘ fact which have an ample quan
tity of iron present in the soil will develop a condition 25 group; n is an integer having a value in‘ the range 0-4.
such that the iron is present in the soil only as highly
Polymers of the simple alkylene diamine used for the
insoluble inorganic compound, which, accordingly, is not
formation of the terminal hydroxy alkyl-sulfo alkyl
available to the plant. This also produces a condition of
groups may be used so that X may actually represent
iron chlorosis. A fundamental symptom of the iron
an Alkylene-N-Alkylene structure in polymer form so
chlorosis is pale green, yellowish foliage, poor growth, 30 that the ultimate compound is characterized ‘by repetition
and, sometimes, even a certain amount of die-back of
of this internal form through 1, 2, 3 or 4 units, e.g., as
the plant.
follows:
éHaSOsH
Various treatments are available for correcting the
iron de?ciency, but such treatments as direct application
of iron salts to the soil are ineffective, because the soluble 35
which typically becomes
iron salt in the soil quickly becomes insoluble iron hy
droxide or other insoluble iron salts. Application of che
lating agent, for example, as described in United States
/
l
\
Patent 2,828,182 is useful for the partial solubilization
Typical compounds corresponding to the drawing given
of mineral soil components, but is insuf?cient for quick 40
are the following:
correction if the situation involves iron chlorosis.
\N-Alkylene-lII-A lkylene-N<
\N—CHzCH2-—~N—~CH2CHn-N/
Fundamentally, therefore, it is an object of this inven
tion to provide a method and composition for controlled
solubilization of insoluble metal compounds in soil par
ticularly alkaline soil, and including such metals avail 45
able to plants in soil in the 'vicinity of plant roots.
Other objects and advantages of the invention will in
N-(carboxymethyl) -~N' - (Z-hydroxy - 3 - sulfopropyl)
N,N’-eth-ylenediglycine
CHzCOOH
C?zCOOH
part be obvious and in part appear hereinafter.
_ I have found that iron may be ef?ciently added to soil
and made immediately available to plants growing in soil 50
in adequate amounts to satisfy the trace requirements of
plants growing in the soil by adding the iron to the soil
in the form of certain metal complexes. The advantage
CHnCOOH
N——CHzCHa—N
CHzCHOH
JlHaSOaH
N-(2-bis(carboxymethyl)aminoethyl) - N’ - (Z-hydroxy
3 -sulfopropyl ) -N,N'-ethylene di-glycine
CHIOOOH
CHZCOOH
N—CHqCHg-N—~CH2CH2N
of adding the iron in the complex form is that it enters
CHzCOOH
HzCOOH
CHaCHOH
the soil in the form of a complex organic amino sulfonic 55"
acid compound, which compound is very ef?cient for
11330311
holding the iron in solution over a very broad range of
3 - ((2 - bis -' (carboxymethyl)aminopropyl) (carboxy
pH and, to the extent that the compound decomposes in
methyl) amino) )—2-hydroxy-l-propanesulfonic acid
soil, it makes available to the plant certain other elements
OHiCOOH
of value to it, namely, nitrogen and sulfur. To the extent 60
CH3
CHzCOOH
the compound is not complexed with iron, the free or
game portion degrades the inorganic soil components in
which it is present to produce certain metal complexes
which are water soluble suf?ciently to render the metal
available to the plant growing in the medium in which 65
the exchange is occurring. Hence, the addition of the
iron complexes formulated in accordance with this in
vention' results in the production of conditions in the soil
around the plant roots which make available to the plant
N—(|JH—CH2N
CHQCOOH
OHzCHOH
GHaSOaH
N,-N’ - (carboxymethyliminodiethylene)bis(N - (2 - hy
dnoxy-S-sulfopropyl)glycine
traces of iron as well as other metal ions and elementary 70
components needed in plant nutrition. The composition
for use in or with a plant growth medium or fertilizer
CHQCHOH
OH2S03H
CHBOHOH
HaSOgH
3,091,522
4
The composition may be added directly to the soil as
be added to the soil may vary from about 0.0001 to
a dry powder, or as a water solution, or as the iron
chelate deposited on a carrier, such as vermiculite or
sand or other inert material, or as a component of a
about 0.1 percent by weight, or 0.1 to 1000 parts per
million of the soil in which the plant is growing. Obvi
ously, with a ?eld grown plant, quantitative ?gures of this
fertilizer. It may also include a free chelating agent, the
kind lose their meaning unless they are referred to a
de?nite depth of soil. It may be assumed that wherever
reference is made to ?eld soil, it means a layer of soil
amount of free chelating agent, depending upon condi
tions, being as much as 100 percent of the material added
to the carrier. The precise composition added to the soil
may be varied to suit conditions. That is, the composi
six inches deep. Accordingly, in the applicationof the
metal chelates under ?eld conditions initial application is
tion used may contain only a small amount of iron, or 10 best calculated and referred to an active soil volume
measured in such a ‘fashion.
it may be a 1:1 iron chelate.
In testing the chelating agents and iron chelate com
The addition to soil of small quantities of metal che
positions in accordance with this invention, the procedure
late-chelating mixture, results in development of unusual
was as follows:
effects manifested in an improved growth of the plants
The chelating agent X is formed and dissolved in
in the medium. ‘Plants, such as flax, corn, spinach, cot 15
water. In general, it is easiest in making iron chelate,
ton, tomatoes, soybean, curly dock, are all sharply re
to take the chelating agent solution and mix it with a
sponsive to the soil treated in accordance with this in~
vention.
The actual practice of the invention is like its testing;
ferric ammonium sulfate solution in a 1:1 molar ratio.
‘In quantitative experimental work in measuring the iron
small quantities of the iron chelate are added to soils 20 up-take ratios, it is our practice to label the iron with
Fe59. The iron .chelate solutions were then added to the
around plants, maintained in those soils at certain levels
alkaline soil in which seedlings of a certain size were
of concentration, and the e?fect on growth measured by
growing, in all cases maintaining plants in certain un
determining the amount of uptake of iron in terms of
treated soils as blanks for comparison. Various amounts
ratio of the iron uptake in said treated soil as compared
with the ratio of the uptake in such soil treated with an 25 of iron chelate were added. After two weeks’ growth
in a soil medium thus treated the aerial portion of the
iron salt such as ferric chloride or ferric sulfate.
The organic chelating agents of the class described
plant was harvested and assayed for Fe”. The .results
are expressed in the tabulation given hereinafter as the
above which are quite effective for purposes of this in
ratio in parts per million of iron in the plant to that ob
vention are, generally speaking, stable against metabolism
by the plant or by the bacteria occurring in the soil. 30 tained in plants with ‘the free iron salt added to soil.
They have a further advantage of forming stable water
Included in the data for comparison are tests conducted
with ethylenediaminetetraacetic acid as representative of
soluble metal complexes which are essential for adequate
a known chelating agent useful for soil addition.
plant growth, including the elements of calcium, mag
nesium, zinc, manganese, iron, copper, cobalt and others.
Table I
Thus, when the chelating agent is added to the soil in 35 Compound:
Uptake ratio
the form of an iron complex, together with a certain
amount of free chelating agent, the other inorganic metals
are thereby rendered available to the plants.
(1) ¢Fe(NH4)(SO4)2 ______________ _,_____
.41
(2) EDTA ___________________________ __ 1.00
(3 ) Carboxymethylimino-bis (ethylenenlitrilo)
In the preparation of fertilizers and compositions for
tetracetic acid _______________________ __ 1.09
addition to soils having the advantages of this invention 40
(4) N~(carboxymethyl)-N’-(2-hydroxy-3-sulfo
it should be recognized that the properties of the chelat
propyl)-N,N'-ethylenediglycine _________ __ 3.55
ing agent’iron chelate mixture, or of the ‘free chelating
In
a
different series of experiments, iron chelates of the
agents, or the iron chelating agent alone, may be obtained
compounds identi?ed were tested as described using the
by adding the compounds as such to the soil. Techniques
for application of the materials as a dry dust or a solu 45 indicated six species of plants.
tion are well understood by those skilled in the art and
need no elaboration. It is also possible to obtain the
Table II
bene?ts of the composition by application to soil in a
carrier which carrier may be .sand or vermiculite as a
diluent or it may be a fertilizer. Any commercial fer 50
Uptake Ratio
Chemical
tilizer of conventional type, characterized by its content
Curly
Flax
Dock
Spin-
Cot-
ach
ton
To-
Soy
mato been
of nitrogen, phosphorus, and potassium compounds may
beusedand bene?ted by the incorporation of a small pro
1. .Fe(NH4)(SO4)z ________ __
. 07
.09
.16
. 12
.19
.15
2. EDTA ________________ __
1.00 1.00
1.00 1.00 1.00
1.00
portion of the chelating composition in accordance with
3. carboxymethylimindbis
this invention. It is particularly valuable for incorpora 55 (ethylenenltrilo) tetra
aeetic acid _________________________________________ __ 1. 00 ____ __
tion into organic fertilizers such as those derived from
4. N-(carboxymethyl)-N’
sewage sludges. A typical one of this is the commercial
(2-hydroxy-3-su1fo-pro
pyl)7N,N’-ethy1enedi1 37
Milorganite, which is an ‘activated, dried sewage sludge.
glycine _________________ __
1.65 2. 44
1.29 3.22 {4-35 }1.18
Urea formaldehyde resins are a ‘favored class of syn
thetic- lorganic fertilizers and it is, of course, apparent that 60
the chelating agents may be blended therewith in accord
ance with this invention.
To a fertilizer of whatever character is used, there is
added chelating agent corresponding to this invention to
5. H-EDTA ______________ __
6. DTPA _________________ __
.76
.85
1.43
1.22
.91
.93
1.02
2.12
1.15
.93
.69
.64
ED'1‘A—ethylenediaminetetraacetic acid.
H-EDTA-hydr0xyethylethylenediarninetriacetic acid.
DTPA-diethylcnetriaminepentraacetic acid.
It will be apparent from the tabulation that theiron salt
react with some or all of the trace metals present in such 65
directly applied, typi?ed by 'FeNH4(SO4)2 is essentially
fertilizer. In general, this will be a minor quantity but
ineffective in inducing iron uptake of the plants. Ethyl
nevertheless the effect of the addition of the chelating
enediaminetetraacetic acid is valued at unity in the table.
agent is to solubilize the metals. The basic formula to be
On this scale, therefore, the compounds carrying the
followed in addition of chelating agent to the fertilizer,
whatever its composition, is to incorporate it in amounts 70 hydroxy alkyl-sulfonic acid group as de?ned herein are
such that when the fertilizer is applied to soil at recom~
mended levels, the accompanying amount of chelating
about two times more effective than EDTA and about
twenty-thirty times more effective than ferric ammoni
um sulfate. Despite the fact that the data indicate in
dividual differences among the effectiveness of the free
agent or iron chelate-chelating agent mixture in accord
ance with this invention will be applied.
The amount of the iron chelate or chelating agent to 75 acid, its salts and variants in number of hydroxy alkyl
3,091,522
6
sulfonic acid groups, it should ‘be noted that it is better
to consider the eilectiveness of the compounds as being
of the same order of magnitude. That is, consistently,
with a variety of plants such as the representative ones
listed, the effectiveness of the compounds at least im
the growth of plants which comprises, a carrier selected
from the group consisting of inert inorganic carriers,
inorganic chemical fertilizers, urea formaldehyde poly
mers fertilizers, and organic fertilizers made from fer
mented composted organic materials, and an iron chelate
of a chelating agent having a formula corresponding to
proved on that of EDTA and, generally, considerably
exceeded this level.
Though the invention has been described with reference
the following:
to only a limited number of examples, it is to be under
stood that variants thereof may be adopted without de 10
parting from its spirit or scope.
What is claimed is:
wherein, X represents a central spacer moiety selected
1. The method of enhancing the growth of plants in
‘from the group consisting of alkylene and cycloalkylene
soil which comprises, adding to the soil in which the
radicals which interpose 2—3 carbon atoms between the
plant is growing a small amount of an iron chelate of a 15 indicated nitrogen atoms; A represents a moiety selected
chelating agent having a formula corresponding to the
from the group consisting of ——CH2COOH,
following:
—OH2OHOH
A
A
A
A
HzSOaH
20 as the free acid, alkali metal and ammonium base salts;
at least one and not more than two of the A positions
being occupied by a
wherein, X represents a central spacer moiety selected
from the group consisting of alkylene and cycloalkylene
——OH2CHOH
radicals which interpose 2—3 carbon atoms between the
H2SO3H
indicated nitrogen atoms; A represents a moiety selected 25 group; n is an integer in the range 0-4, and maintaining
from the group consisting of —CH2COOH,
the amount of said composition at a level of about 0.01
to 100 paits per million of chelated iron in the carrier.
7. A composition in accordance with claim 6, in which
as the free acid, alkali metal and ammonium base salts; 30 the chelating agent is N-‘(carboXymethyD-N’-(2-hydroxy
3-sulfopropyl)-N,N'-ethylenediglycine.
at least one and not more than two of the A positions
8. A composition in accordance with claim 3, in which
‘being occupied by a
—GH2CHOH
CHgSOgH
the chelating agent is N-(2-'bis(carboxymethyl)amino
ethyl)-N’-(2-hydroxy - 3 - sulfopropyl)-N,N’~ethylenedi~
35
glycine.
9. A composition in accordance with claim 4 in which
group; n is an integer in the range 04, and maintaining
the chelating agent is 3-(1(2-bis (carboxy)methylaminopro
the amount of said composition at a level of about 0.01
pyl)(carboxymethyhamino))-2-hydroxy - 1 - propane
to 100 parts per million of chelated iron thus added in
sulfonic acid.
the soil.
10. A composition in accordance with claim 5 in
2. The method in accordance with claim 1 in which 40
which the chelating agent is N,N'-(carboxymethylimino
diethylene ) bis ( N~( 2-hydroxy-3-sulfopropyl) glycine) .
3. The method in accordance with claim 1 in which
References Cited in the ?le of this patent
the chelating agent is N-(2-bis(carboxymethyl)amino
UNITED STATES PATENTS
ethyl) -N ' (Z-hydroxy-B ~sulfopropy‘1) -N,N'-ethyldi-glycine. 45
the chelating agent is N-(carboxymethyl)-N'-(2=hydroxy
3 -sulfopropyl) -N,N'-ethylenediglycine.
4. The method in accordance with claim 1 in which
the chelating agent is 3-(bis((carboxymethyDaminopro
pyl) (carboxymethyl) amino) ) - Z-hydroxy-l-propanesul
fonic acid.
5. The method in accordance with claim 1 in which 50
the chelating agent is N,N'-(carboxymethylimino-diethyl
ene) bis(2-hydroxy-3 -sulfopropyl) -glycine) .
6. A composition for application to soils to enhance
2,673,213
2,673,214
2,808,435
2,816,060
2,828,182
2,859,104
2,961,311
2,967,196
Bersworth et a1 _______ __ Mar. 23,
Bersworth et al. ______ __ Mar. 23,
Young ______________ __ Oct. 1,
Carter ______________ __ Dec. 10,
Cheronis ____________ __ Mar. 25,
Kroll et a1. __________ __ Nov. 4,
Bersworth et al. ______ __ Nov. 22,
Kroll et al. __________ __ Jan, 3,
1954
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