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Патент USA US3024109

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Patent ?tice
H ited
.,
3,@Z4,l®
,
1
Patented Mar. 6, 1962
2
fertilizer composition which can be employed in alumi
3,024,100
CORROSION-INHIBITED LIQUID FERTILIZER
num equipment.
The preferred suitable ?uosilicates are sodium ?uosili
COMPOSITIONS
Robert Parks Langguth and Eli Seifter, Dayton, Ohio, as
signors to Monsanto Chemical Company, St. Louis,
cate, ammonium ?uosilicate, and potassium ?uosilicate.
The preferred suitable molybdates are ammonium molyb
Mo., a corporation of Delaware
date, potassium molybdate and sodium molybdate. The
N0 Drawing. Filed May 20, 1957, Ser. No. 660,039
7 Claims. (Cl. 71-—34)
ratio of the ?uorine from the ?uosilicate to the molybdate
compound can vary from about 2.5 to l to about 10 to l
with the ratio of about 5 to 1 being generally preferred.
This invention relates to improved liquid fertilizer com
It was found that ratios of less‘ than about 2.5 to l tended
to give a yellow phosphomolybdate color to the fertilizer
solution with the subsequent possibility of eventual pre—
cipitation of the complex. On the other hand ratios
greater than about 10 to 1 generally do ‘not provide the
positions which are characterized by a material reduction
in the corrosion of storage containers and application
equipment.
More speci?cally this invention relates to
corrosion-inhibited liquid fertilizer compositions which
are suitable for use with aluminum equipment.
necessary inibition of pitting of the aluminum equipment.
An early source of nitrogen in agricultural application 15 The substantially neutral liquid fertilizer compositions
was the use of ammonium nitrate solutions.
The ammo
are generally formulated by various mixtures of mono
nium nitrate solutions were generally held in aluminum
storage tanks and dispensed in the ?eld with aluminum
ammonium phosphate, diammonium phosphate, ammo
nium nitrate, ammonium sulfate, urea, potassium chlo
equipment. Accordingly, the industry has a considerable 20 ride, potassium nitrate, monopotassium phosphate, dipo
present investment in aluminum storage vessels and ap—
plication equipment. In recent years there has been a
tassium phosphate, and the like, or by the use of anhy
ever it was found that the presence of liquid fertilizer
phate or ammonium phosphate to which has been added
drous ammonia, aqua ammonia, phosphoric acid, potas
growing demand for liquid fertilizers generally, i.e. ferti
sium hydroxide, and the like to directly produce a sub
lizer compositions which also contain P205 with or with?
stantially neutral salt solution. Thus the neutral liquid
out K20 to provide a complete liquid formulation. How 25 fertilizer solutions can be a solution of ammonium phos
compositions containing P205 caused excessive corrosion
ammonium nitrate, urea, potassium chloride, and the like
to the aluminum equipment which was then in wide use.
It was subsequently found that the presence of from about
to form a variety of N~—P or N-—P—K liquid fertilizers.
The pH of a 1-10 dilution of the liquid fertilizer compo
200 up to about 500 p.p.m. of ?uorine as a ?uosilicate, 30 position preferably ranges from about 6 to about 8.
e.g. sodium ?uosilicate, potassium ?uosilicate and ammo
As is well known, fertilizer compositions are conven
nium ?uosilicate, effected a material reduction in the cor
tionally labeled in terms of the principal nutrient com
rosion rate of neutral liquid fertilizer compositions con
ponents therein, i.e. nitrogen, phosphorus, and potassium,
taining P205. However it was subsequently found that
the ?uosilicate-modi?ed liquid fertilizer composition was
not a complete solution to the problem as the formula
tion caused pitting of the aluminum.
It is the principal object of this invention to provide a
substantially neutral liquid fertilizer composition contain
35
wherein phosphorus and potassium are given in terms of
P205 and K20, respectively, and the N——P—-K designa
tion hereinabove and hereinafter employed will be under
stood in these terms.
Various illustrative neutral liquid fertilizer composi
tions are shown in the following table wherein the var
ing P205 which can be stored and dispensed with alumi 40 ious components are indicated in parts by weight.
Ammonia
num equipment.
Another object of this invention is to
Urea
Phosphoric
acid
Monoam- Diammom'um monium
phos~
phos-
Potas-
Potas~
sium
chloride
sium
nitrate
Water
The pH of the above formulations as a l to 10 dilution
provide a substantially neutral liquid fertilizer composi
with water will vary between about 6 to about 8 and most
tion containing P205 which is characterized by a low rate
will vary between about 6.5 to about 7.5.
of corrosion and is substantially free from causing pitting
The subject liquid fertilizer compositions can also con
when employed with aluminum equipment. Other ob 65
tain minor amounts of surfactants to facilitate the as
jects will be apparent from the following disclosure.
It has now been found that the combination of from
about 200 up to about 500 p.p.m. of ?uorine as a soluble
?uosilicate and from about 20 to about 200 p.p.m. of a
similation of the nutrient composition by the plant, minor '
amounts of soluble compounds containing essential trace
elements in available form, and the like. The desired
soluble molybdate when present in substantially neutral 70 liquid fertilizer composition can be formulated batchwise
liquid fertilizer compositions containing the phosphate
or by a continuous process as will be readily understood
nutrient, i.e. the orthophosphate ion, provides a liquid
by those skilled in the art.
_ 3,024,100
4i
were again fertilized at the same rate and the yields ob
The following examples are illustrative of the instant
invention.
tained after an additional 13-day growth period. The
following table summarizes the data obtained in this
Example 1
evaluation study.
Since the high phosphate content liquid fertilizer com
position was found to cause the most severe corrosion
rate of the various formulations, the 8-24-0 composition
was selected such that the following evaluation results
would generally exemplify the most drastic corrosive ef
fects which might be met in the ?eld.
Parts by weight of grass
Time in days
Control
8-24-0
Inhibited
8-24-0
A liquid fertilizer composition (8-24—0) was prepared.
by dissolving 107 parts by weight of monoammonium
phosphate and 3281 parts by weight of diammonium
phosphate in 564.9 parts by weight of water. Similar
compositions were prepared which contained 500 p.p.m.
13
15
23. 5
27.6
81.0
70. 5
29. 4
81. 0
86. 5
151.6
1179. 1
1196. 9
of ?uorine as sodium ?uosilicate and 500 p.p.m. of ?uo- '
1 Total.
rine as sodium ?uosilicate in combination with 100 p.p.m.
of ammonium molybdate. It was found that the cor
These evaluation results clearly demonstrate that the
rosion rate for the uninhibited liquid fertilizer composi
combined inhibitors do not exhibit any phytotoxic effect
tion on 3S0 aluminum at 140° F. was 31050 m.p.y. Un
20 on plant growth.
'
der similar conditions it was found that the presence of
We claim:
1. A corrosion inhibited aqueous composition useful
in the protection of aluminum storage and handling
500 p.p.m. of ?uorine as sodium ?uosilicate in the liquid
fertilizer composition reduced the corrosion rate to 25
m.p.y., but caused pitting. The addition of 100 p.p.m.
of ammonium molybdate to the latter liquid fertilizer
equipment from corrosion by orthophosphate ions, which
composition has a pH between about 6 and about 8 and
contains an inorganic orthophosphate salt selected from
composition was found to reduce the corrosion rate to 31
m.p.y. and the aluminum was free from pitting. It was
further found that the corrosion rate was generally re
duced to less than about 10 m.p.y. for the corrosion-in
diammonium orthophosphate, monopotassium orthophos
Example 2
sodium ?uosilicate, potassium ?uosilicate, and ammonium
the group consisting of monoammonium orthophosphate
hibited composition when the system was not subjected 303 phate, and dipotassium orthophosphate, and from about
200 to about 500 p.p.m. of ?uorine as a soluble ?uosili
to temperatures greater than about 100° F.
cate compound selected from the group consisting of
?uosilicate and an amount of a soluble molybdate com~
In order to determine whether the presence of the
pound selected from the group consisting of sodium
combined corrosion inhibitors was deleterious to the
35 molybdate, potassium molybdate, and ammonium molyb
germination of seed, qualitative tests were run in green
date, such that the weight ratio of said ?uorine to said
house ?ats. Radish, cucumber, tomato, and rye grass
seeds were selected for this evaluation as these plants do
soluble molybdate compound is between about 25:1 and
not have particularly hardy seedlings.
about 10:1.
Quadruplicate
2. A corrosion inhibiting composition according to
greenhouse ?ats containing the aforesaid seeds were pre 40
claim 1 containing about 500 p.p.m. of ?uorine as sodi
pared and two sets of ?ats were fertilized with the un
um ?uosilicate and about 100 p.p.m. of ammonium
inhibited liquid fertilizer composition of Example 1 and
molybdate.
the other two sets of ?ats were fertilized with the liquid
3. A corrosion inhibited aqueous composition useful
fertilizer composition of Example 1 which contained the
combined corrosion inhibitor composition of 500 p.p.m.
in protecting aluminum equipment from corrosion by
of ?uorine as sodium ?uosilicate and 100 p.p.m. of am 45 orthophosphate ions, which composition has a pH be
tween about 6 and about 8 and contains a mixture of an
monium molybdate. The liquid fertilizer compositions
ammonium orthophosphate and at least one of the com
were applied at the rate of 400 pounds per acre and 1000
pounds selected from the group consisting of ammonium
pounds per acre to the duplicate ?ats. The former rate
nitrate, ammonium sulfate, urea, potassium chloride,
of application is typical of ’ actual ?eld practice while the
latter rate of application would be higher than would be 50 monopotassium phosphate, dipotassium phosphate and
potassium nitrate, and also contains from about 200 p.p.m.
used in fertilizer practice, but was employed to ascertain
to about 500 p.p.m. of ?uorine as a soluble ?uosilicate
whether there was any observable deleterious effects to
the seeds at substantially higher than normal application
compound selected from the group consisting of sodium
rates. ‘It was found that the inhibited fertilizer composi
tion produced no phytotoxic eifect on the germination or
?uosilicate, potassium ?uosilicate, and ammonium ?uosili
cate, and an amount of a soluble molybdate compound
growth of the test plants.
Example 3
selected from the group consisting of sodium molybdate,
potassium molybdate, and ammonium molybdate such
To demonstrate whether there was any observable
quantitative effect of the combined inhibitors on the
molybdate compound in said composition is between
that the weight ratio of said ?uorine to said soluble
about 2.5:1 and about 10:1.
growth of plants triplicate greenhouse ?ats were seeded
4. A corrosion inhibiting composition according to
with perennial rye grass at the rate of 400 pounds of seed
claim 3 which contains about 500 p.p.m. of ?uorine as
sodium ?uosilicate and about 100 p.p.m. of ammonium
per acre. This high rate of planting was selected to ob
molybdate.
tain large amounts of plant growth and to make such
growth more dependent on the added nutrients. The un
inhibited and inhibited liquid fertilizer ‘Compositions of
Example 2 were applied to separate experimental ?ats at
planting time at the optimum rate of 400 pounds per
acre and the third control ?at was not fertilized.
The
65
5. A corrosion inhibited aqueous composition useful
in protecting aluminum equipment from corrosion by
orthophosphate ions, which composition has a pH between
about 6 and about 8 and comprises an ammonium ortho
phosphate, from about 200 to about 500 p.p.m. of ?uorine
experimental plots were cut 21 days after planting and 70 as a soluble ?uosilicate compound selected from the group
fertilizing to determine the yield of grass obtained by the
consisting of sodium ?uosilicate, potassium ?uosilicate,
and ammonium ?uosilicate, and an amount of a soluble
various treatments. After these cuttings were made, the
molybdate compound selected from the group consisting
plots were again fertilized at the rate of 400 pounds per
of sodium molybdate, potassium molybdate, and am
acre of liquid fertilizer and yields again determined after
a growth period of 12 days. After this cutting, the ?ats 75 monlum molybdate such that the weight ratio of said ?uo
3,024,100
rine to said soluble molybdate compound is between about
2.5:1 and about 10:1.
6. A method of inhibiting the corrosion of aluminum
equipment by an aqueous, liquid fertilizer composition hav
ing a pH between about 6 and about 8 and containing
an inorganic orthophosphate salt selected from the group
consisting of monoammouium orthophosphate, diam
monium orthophosphate, monopotassium orthophosphate,
and dispotassium orthophosphate, said method comprising
the incorporation in said composition of from about 200 10
to about 500 p.p.m. of ?uorine as a soluble ?uosilicate
compound selected from the group consisting of sodium
?uosilicate, potassium ?uosilicate, and ammonium ?uosili
cate, and an amount of a soluble molybdate compound
selected from the group consisting of sodium molybdate, 15
potassium molybdate and ammonium molybdate such that
the ratio of said ?uorine to said soluble molybdate com
pound in said composition is between about 2.5 :1 and
about 10:1.
6
7. A method according to claim 6 wherein about 500
p.p.m. of ?uorine as sodium ?uosilicate and about 100
ppm. of ammonium molybdate are employed.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,147,395
2,238,651
2,586,709
2,719,781
2,739,886
2,770,538
Bayes ______________ __ Feb. 14,
Keenen _______________ __ Apr. 15,
Phillips _______________ __ Feb. 19,
Hesch ________________ __ Oct. 4,
Facer _______________ .._ Mar. 27,
Vierling ____________ __ Nov. 13,
1939
1941
1952
1955
1956
1956
2,778,712
Caldwell _____________ __ Ian. 22, 1957
2,755,170
Stubble?eld ____________ __ July 17, 1957
736,215
Great Britain ___________ __ Sept. 7, 1955
FOREIGN PATENTS
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