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April 18, 1950 c. c. LEGAL, JR.

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Filed Jan. 28, 1947


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Patented Apr. 18, 1950



Casimer C. Legal, Jr., Pasadena, Thomasv 0.

Tongue, Curtis Bay, and Edward Il. Wight,`
Baltimore, Md., assignors to The Davison
Chemical Corporation, BaltimoraMd.
Application January 28, 1947, Serial No. 724,816
4 claims. l(c1. 23-165)
>Y"Ihis invention relates in the manufacture of a supply of sulphuric acid containing about 98%
phosphoric acid'by the so-called wet process in HzSO4 is continuously passed through a rotameter
which phosphate rock is treated with sulphuric and through aheater, and thence tothe pug
"acid, and more particularly has reference to such mill foradmixture with the ground phosphate
' a'process in which conditions are controlled to rock. It will be `noted that the phosphate rock
obtain _an acid'4 of high` concentration. with a which is ground and in finely divided form is
' minimum of uorine content. dry. In the heater,the 98% 'sulphurlc acid is
"In the manufacture of phosphoric acid. by the'
preferably heated to a temperature ranging be
action of sulphuric acid onphosphate rock as tween 100 C. and 300 C. although Ypreheatin'g
heretofore practiced, the resulting acid was of 10 of the acid is not absolutely necessary. When
low concentration andcontained a fairly high temperatures substantially. over 1009- C." 'are
percentage of'the original fluorine content of used, it is advisable to carry out the heating
the _phosphate rock. _ v , ` operation in a closed apparatus. ` ' '
One object of this invention is the direct pro 'I'he phosphate rock and sulphuric acld are
duction of strong phosphoric acid containing 15 introduced in a ratio of about 240 parts by
about 75% HaPO4 by means of a wet process weight of phosphate rock to about 205 parts by
without resorting to evaporation. weight of the 98% sulphuric acid. As indicated,
Another object of this invention is the pro the rock and acid are mixed, preferably, con
duction of phosphoric acid by a method where tinuously. . -' Y ' "

in_ up to 98% of the fluorine originally present 20 During the mixing operation, approximately
in the .phosphate rock is eliminated. 65% of the total fluorine present inthe phos
Yet another object of this invention is the phate rock is volatilized. Afterfmixing. the mix
manufacture of phosphoric acid of such purity ture is passed into an indirectly fired rotary
.that it can be used without any treatment, di heater in which it is heated to a temperature
rectly in the manufacture of phosphatic animal 25 ranging from 200 C. to 300 C. for a period'of
feed supplements or for use as silage preserva about l0 to 30 minutes. A direct fired 'heater
tive. may also be used, but when> maximum fluorine
Still *another object of this invention is the recovery is desired, the indirect method is pre
manufacture of a wet phosphoric acid with a ferred. During the 'heat treatment, approxi
fluorine content low enough to allow low cost _ mately 25% additional fluorine is driven off
treatment to bring it down to a point where so that altogether about' 90% of the fluorine
the phosphoric acid may be used for food pur present in the phosphate rock is eliminated in
poses as for instance the manufacture of mono an easily recoverable form. As indicated on
calcium phosphate for baking powder or self the drawing, the fluorine evolved in the pug
rising flour. mill and, also, the fluorine evolved in the ro
Other objects will appear more fully herein tary heater, are passed to a fluorine recovery
after. system.
In order to facilitate an understanding of this The calcined product is transported directly,
invention, reference is `made to the accompany preferably, without substantial cooling, >into a
ing drawing in which the single figure is a dia 40 system of counter-current leaching tanks.. The
grammatic representation of a flow sheet show heat treated product is dropped directly into
ing the several steps of the process in-sequence. lthe strong phosphoric acid. In the counter
In carrying out the present invention, a dry, Vcurrent leaching operation which may utilize
`finely divided phosphate rock was used which a series voi? 6 or 8 units, the liquid flow is always
had a composition as follows: 45 downward and thus actually the leaching opera
` f " ' " Per cent
tion is a step counter-current procedure.
Moisture __________ ___ _______________ __ 0.70
In the leaching system, the leaching liquid.
Total P205; __________________________ __ 33.00
which is water, will be brought first into con
Total CaO ____ _Q_______ __' ____________ __ 45.79
tact with the nearly spent clinker, whereas the
Fluorine ..... ___ ____________ __ _______ __ 3.66 50 leaching medium, after it has taken up a con
sider'able portion of the P205 from the clinker,
Y As diagrammatically illustrated in the accom is brought into contact with the freshly heated
panying drawing. ground phosphate rock of the mixture, and the overflow from this last con
above composition is continuously fed through tacting step is the production acid.
a weighometer intola pug mill. Simultaneously, 56 The residue from the leaching operation,
4 ,
which 'is substantially calcium sulphate. may ' lism, the ratio in question should closely approach
be disposed of in any desired manner. the latter gure. Additional calcium can of
Enough sulphuric acid should be used in the course be furnished in the form of CaCO: as
original mix to take care of all reactible com ground limestone~ which is fully assimilable.
pounds present in the phosphate rock. This ci Taking this into account, it is an advantage tc
means not only the tricalcium phosphate but supply the phosphatic material in as concentrated
also the calcium carbonate and calcium fluoride form as practical tothe feed manufacturer, who
as well as iron and alumina compounds present then corrects the Cao/P205 ratio to the proper
in the rock. It there is a deficiency of sulphuric figure when he makes the nnal feed mixture.
acid in the original mix, then the resulting prod A material having a higher P205 concentration
uct after heat treatment does not perform satis is produced by mixing 60 parts of the acid with
factorily in the leaching system because it has a 22 parts of hydrated lime. A dry product re
tendency to disintegrate and choke up the system. sults, with the following analysis:
Therefore, it is better to have a slight excess of Per cent
sulphuric acid rather than a slight deficiency in 15 P205 45.00
the original mix. A. ' - CaO _ 22.62
Phosphoric acid produced in the countercurrent
leaching system can easily be taken out as 75% The moisture content of the above product is
H3PO4 or even higher concentration. The ex
traction in the leaching system is so thorough v about.18%, mostly present as water of crystal
that it shows a. recovery of up to 99% of the P205
lization because the product is dry and friable.
present inthe phosphate rock. By eliminating 10% moisture, the P205 content
can be easily brought up to 50%.
An example of the analysis of the phosphoric It should be noted that the fluorine content is
acid produced in this manner is as follows: far below the permissible limit which is 0.3% F.
Per cent 25 for a product containing 30% P2Os-on a. basis
Total P20: 53.70 of 30% P205 the product of this invention con
S03 1.72 tains 0.07% F. or less than V4 of the permissible
F 0.12 amount.
A total P205 content of 53.70% would corre 30 The uorine content of the strong phosphoric
spond to 74.1% HsPOl. There is, however, a small acid made by the process of this invention is so
amount of iron and alumina present in the acid. low that a simple additional treatment with hy
so that all the P205 cannot be counted as free drous silicates, as for instance silica gel. will
HaPOr. 'I'he Fe20a and A1203 content of the acid easily accomplish the removal of the fluorine to
a point low enough to make the phosphoric acid .
is around 2.5%.
. Practically all wet process phosphoric acid pro available for the production of monocalcium
duced industrially up to the present time has used phosphate for leavening purposes.
the well known Dorr process or modifications Although the use of 98% acid has been featured 1
thereof. This phosphoric acid from the filters in the foregoing description, a weaker acid can,
contains around 32.0% P205 and about 2.0% 40 of course, be used, i. e. a'60 or 66 B. sulphuric
fluorine. The corresponding figures for the acid acid. This would not be as economical as 98%
produced by the process of this invention are acid because it would require substantial moisture
53.7% P205 and 0.12% fluorine. On an equiva elimination from the mixing during the heat
lent P2Os basis the Dorr acid contains over 25
treating operation.
times more fluorine than the acid from this proc From the foregoing, it will be realized that the
ess. This is a startling dierence. present invention provides a process of producing
In addition to the advantage of the product of strong phosphoric acid directly by an aqueous
this invention being a very strong phosphoric leaching of phosphate rock after mixing with
acid which requires no evaporation prior to its sulphuric acid and with a very low iluorine, even
use in the manufacture of triple superphosphate, though the phosphate rock has a usual fluorine
the fluorine content of this strong acid of 75% 60 content.
We claim: .
H3P04 is only a small fraction of that of prior
wet phosphoric acid. The actual uorine content 1. A process for the manufacture of concen
is from 0.1 to 0.2%. This means that on the basis trated phosphoric acid in concentrations up to
of P205 content, the fluorine in the acid is only 55 75% H3PO4 having a low iluorine content com
prising mixing finely divided phosphate rock
from 2 to 5% of that originally present in the
rock. with about 98% sulphuric acid in an acid to rock
Actually the iluorine content is so low that the ratio ranging from a value at least high enough
phosphoric acid can be used directly as silage to a value slightly in excess of that necessary to
preservative. Moreover, it can be neutralized react with all sulphuric acid reactible compounds
with hydrated lime so that a solid product results 60 in the rock and form phosphoric acid from the
which is eminently satisfactory as a phosphatic calcium phosphate in the rock, heating the mix
animal feed supplement. i ture of rock and acid to a temperature ranging
A phosphatic animal feed supplement made by from about 200 C. to 300 C. to form a clinker,
mixing 63 parts by weight of the phosphoric acid said mixing and heating steps volatilizing about
of the above given analysis with 50 parts by 65 90% of the uorine in the phosphate rock to
weight of hydrated lime produced a dry material form a clinker substantially free of tluorine, and
with the following analysis: leaching the clinker with water to form phos
phoric acid.
- Per cent
2. A process for the manufacture of concen
P205 -_ 34.30 70 trated phosphoric acid in concentrations up to
Cao` ____ __ 38.13
75% HsP04 characterized by a low fluorine con
F--- .08 centration comprising heating about 98% -sul
The ratio of CaO to P205 is 1.12. The same phuric acid to about 100 C. to 200? C.. mixing
ratio in pure tricalcium phosphate is 1.18. To finely divided phosphate rock with the 98% sul
be properly assimilated during animal metabo 75 phuric acid in an acid to rock ratio ranging~ from
5 6
a value at least high enough to a value slightly acterized by a low uorine concentration com
in excess of that necessary to react with all sul prising mixing about 240 parts by weight of dry
phuric acid reactible compounds in the rock and finely divided phosphate rock with about 205
form phosphoric acid from the calcium phos parts by Weight of about 98% sulphuric acid at
phate in the rock, maintaining the mixture of a temperature ranging from about 100 C. to 300
rock and acid at a temperature ranging from C., maintaining the mixture at a temperature
about 200 C. to 300 C. to form a clinker, about ranging from about 200 C. to 300 C. for a period
90% of the fluorine in the phosphate rock vola of about ten to thirty minutes to form a clinker,-
tilizing during the mixing and clinker formingr about 90% of the uorine being volatilized from
periods to form a clinker substantially free of the rock during the mixing and clinker forming
iluorine, and leaching the clinker with water to steps, and leaching phosphoric acid from the
form phosphoric acid. clinker with water.
3. A process for the manufacture of concen CASIMER C. LEGAL. Ja.
trated phosphoric acid in concentrations up to THOMAS O. TONGUE.
75% HaPO4 characterized by a low fluorine con EDWARD H. WIGHT.
centration comprising mixing nely divided phos
phate rock with about 98% sulphuric acid in an REFERENCES CITED
acid to rock ratio ranging from a value at least
high enough to a value slightly in excess of that The following references are of record in the
le of this patent:
necessary to react with all sulphuric acid reacti~
ble compounds in the rock and form phosphoric UNITED STATES PATENTS
acid from the calcium phosphate in the rock, Number Name Date
heating the mixture of rock and acid to a tem 1,712,404 Rupp ____________ _.. Mar. 7, 1929
perature ranging from aboutv200 C. to 300 C. to 1,851,179 Hechenbleikner ____ Mar. 29, 1932
form a clinker, said mixing and heating steps 1,929,442 Milligan _________ __ Oct. 10, 1933
volatilizing about 90% of the fluorine in the phos 2,338,407 Coleman _________ __ Jan. 4, 1944
phate rock to form a clinker substantially free of
iluorine, and passing water substantially counter
currently in contact with the clinker to leach Number Country Date
phosphoric acid from the rock. 165,759 Great Britain ____ __ Nov. 211, 1921
4. A process for the manufacture of phosphoric 295,848 Great Britain ____ __ Aug. 23, 1928
acid in concentrations of up to 75% H3PO4 char