Patented Nov.

19, 1935 2,021,699

UNITED STATES PATENT OFFICE

2,021,699
IYANUFACTURE OF PHOSPHATES
Louis Preisman, Wilmington, Del, assignor to
General Chemical Company, New York, N. Y.,
a corporation of New York
Application October 26, 1931, Serial No. 571275
9 Claims. (CI. 23-107)
This invention relates to the manufacture of furnacing, thus eliminating the furnacing opera
alkali metal phosphates and more particularly to tion. With its attendant difficulties, and effecting
a method for the recovery of phosphates and al a Saving Of the material quantities of Sulfuric
kali metals from alkali metal phosphate mother acid heretofore required in the preparation of
liquors, and the subsequent utilization of such the mother liquors for the furnacing operation. 5
recovered alkali metals in the production of al A further object of the invention lies in the pro
kali metal phosphates. In its more specific as Vision of a process in Which the alkali metal sul
pectS, the invention is directed to the recovery fate content of the mother liquors is eliminated
of phosphates and alkali metals from the al from the System by reaction of the liquor with a
kai metal phosphate mother liquors resulting Soluble alkaline earth phosphate such as mono- 10
from the production of alkali metal phosphates calcium phosphate or mono-barium phosphate
by furnacing phosphoric acid and alkali metal with resulting production of alkali metal phos
sulfate with reducing agents, for example as in phate and alkaline earth sulfate, whereby the
the processes of U. S. Patents Nos. 744,128 and Sulfate necessary for precipitation of the alkaline
1,037,837 to E. H. Strickler, and the improvements earth metal is obtained from the hitherto objec- 5
in Such processes as disclosed in U. S. Patents tionable alkali metal Sulfate of the mother liquor
Nos. 1,727,55i and 1,747,588 to W. H. Lohmann. and the alkali metal content of this alkali metal
The mother liquor from the above furnace Sulfate becomes available in the form of alkali
proceSS contains Substantial amounts of tri-al metal phosphate. Another object of the inven
kali metal phosphate contaminated with various tion is directed to the provision of a process for 20
impurities, including alkali metal sulfate. The making alkali metal phosphates in Which the al
latter impurity tends to contaminate the alkali kali metal content of the alkali phosphate nother
metal phosphate product With Sulfate and, if the liquors is utilized to partially neutralize phos
mother liquor is discarded to eliminate sulfate phoric acid, thus effecting a material reduction
25 impurities, a Substantial loSS of alkali metal phos in the quantity of alkali, for example, soda, ash 25
phate ensues. from Outside Sources, previously required for this
ReWorking of di- and tri-alkali metal phoS purpose.
phate mother liquors as constituents of the fur For convenience, the invention will be described
nace mix in the processes of the Strickler patents in connection. With the manufacture of sodium
30 has been proposed, for example, in Levermore phosphates, although the invention is obviously 30
U. S. Patent No. 1,866,657, July 12, 1932. In applicable to the production of other alkali metal
accordance therewith, it has been suggested to phosphates.
rework tri-alkali metal phosphate mother liquors Briefly, the invention comprises the prepara
by returning the same to the digest tanks in tion of a phosphoric acid Solution, containing
35 which the furnace mix is made up. In this Way soluble calcium as in the form of mono-calcium
it has been possible to utilize relatively largephosphate, preferably by the digestion of phos
quantities of mother liquor and form a Satis phate rock With phosphoric acid containing a
factory furnace mix. However, in order to de Small amount of Sulphuric acid. The acid solu
velop an operating procedure having accurate tion, after the separation therefrom of calcium
40 control of the ratio of alkali metal Sulfate to Sulfate and other undissolved solids, is treated 40
phosphoric anhydride in the furnace mix, it has with Sodium phosphate mother liquor containing
been desirable to convert all the alkali metal Sodium compounds including sodium sulfate,
present in the mother liquors to alkali metal preferably obtained from the processes of the
sulfate by the addition of sulfuric acid. In this aforementioned patents, in quantities such that
45 manner, considerable quantities of Sulfuric acid the Sodium sulfate of the mother liquor reacts 45
were consumed in converting the alkali metal in With the mono-calcium phosphate content of the
the mother liquors to alkali metal sulfate, the acid Solution to precipitate Substantially all of
use of such amounts of acid being, of course, an the sulfate as calcium sulfate, and also such that
additional item of expenSe. the mixed Solution of mother liquor and phos
50 It is the principal object of the present inven phoric acid will contain more than 50% of its 50
tion to provide a method for recovering the phos P2O5 content as phosphoric acid. The reaction
phate and alkali metal content of alkali phos of the sodium sulfate of the mother liquor and
phate mother liquors, and utilizing the Same in the monocalcium phosphate of the acid solution
the subsequent production of alkali metal phoS produces principally mono-sodium phosphate
55 phates without subjecting the mother liquors to and calcium sulfate, and at the same time, the 55
 2 2,021,699
tri-Sodium phosphate and the Sodium of the tation, at this stage, of the so-called “white
other sodium compounds in the mother liquor mud', containing phosphates of iron, Calcium,
react With the phosphoric acid to form mono aluminum and Sodium fluosilicate, which precip
Sodium phosphate. After settling and Separa itation interferes with the settling or filtering out
tion of the mud containing chiefly calcium Sul of the calcium sulfate. Although not likely to 5
fate, the resulting clear Solution containing occur in practice, should a situation arise in
mono-sodium phosphate and phosphoric acid is which the quantity of the sodium sulfate in the
further neutralized by the addition of Suitable mother liquor is insufficient to provide in the
quantities of Soda ash to produce the desired di mixed solution of mother liquor and phosphoric
O alkali phosphates. acid reacting proportions of Sodium sulfate and O
Referring to the accompanying drawing show mono-calcium phosphate, but the remaining al
ing a flow sheet of the improved process, the kaline sodium compounds of the mother liquor
phosphoric acid solution employed for treat are present in quantities great enough to neu
ment of the mother liquor is made up, prefer tralize the acid Solution to Such an extent that
5 ably, by digesting in tank phosphate rock With the mixed solution of mother liquor and phos- lis
phosphoric acid (H3PO4) containing, for exam phoric acid will contain less than 50% of its
ple about 15-17% P2O5 and a Small amount of P2O5 content as phosphoric acid, the proper bal
sulfuric acid, so as to produce a phosphoric acid ance in the mixed solution of mother liquor and
solution containing about 18 to 20% P2O5 and phosphoric acid may be obtained by the addi
20 preferably more than about 3.3% mono-calcium tion thereto of a suitable amount of phosphoric 20
phosphate. A suitable phosphoric acid Solution acid containing no mono-calcium phosphate.
containing the proper amount of mono-calcium For the reason noted above in connection with
phosphate may also be prepared directly by di the prevention of precipitation of the “white
gesting phosphate rock with a deficiency of sul muds', the mixed solution of mother liquor and
25 furic acid. However the acid solution is made phosphoric acid should contain more than 50% 2 s
up, the calcium sulfate, formed by the reaction of its P2O5 content as phosphoric acid. On com
of the phosphate rock and phosphoric or Sul pletion of the reactions resulting from the addi
furic acid, together with other insoluble impuri tion of the mother liquor to the phosphoric acid
ties are separated from the Solution after the solution, the liquor containing, for example,
30 digestion by settling and decantation, or by other about 0.9 to 1.0% Soluble SO3 and about 0.3 to 30
suitable means in a separator . While the 0.5% CaO is filtered or settled in a separator 4
acid solution collecting in tank 2 should, as to effect removal of the calcium sulfate and other
noted, contain preferably more than 3.3% mono insoluble impurities. There is no interference
calcium phosphate, acid Solutions containing less with the settling or filtering of calcium sulfate
35 than 3.3% may be utilized. and other insoluble impurities in the absence of 3 5
The tri-sodium phosphate mother liquors ob “White muds'.
tained in the practice of the processes of the Indications are that the reactions between the
above noted patents contain in addition to tri phosphoric acid Solution and the mother liquor
sodium phosphate various quantities of other seem to take place as follows:
40 sodium compounds such as sodium sulfate
(Na2SO4), sodium carbonate (Na2CO3), Sodium
aluminate (NaAlO2), sodium hydroxide (NaOH),
together with Small amounts of organic matter,
arsenic and other soluble impurities.
45 The clear phosphoric acid solution of tank 2 On the addition of the mother liquor to the acid 45
containing mono-calcium phosphate obtained by solution, from which the calcium sulfate and
the digestion of phosphate rock and phosphoric other insolubles have been separated, the reac
acid is now treated in a vat or tank 3 with tri tions between the tri-sodium phosphate, sodium
sodium phosphate mother liquor in quantities hydroxide and Sodium carbonate appear to be as
50 sufficient so that in the resulting solution, the indicated producing respectively mono-sodium 50
sulfate of the sodium sulfate of the mother liq phosphate. According to (2), it will be seen that
uor reacts with the calcium of the calcium mono the sodium sulfate of the mother liquor precipi
phosphate of the acid solution and so that the tates the calcium of the mono-calcium phosphate
remaining total alkaline sodium compounds in as calcium sulfate, the sodium sulfate thus act
55 the mother liquor will neutralize the acid solu ing to replace the sulfuric acid formerly used in 55
tion to such an extent that the mixed Solution the precipitation of the calcium of the calcium
of mother liquor and phosphoric acid will con phosphate. Considering the reaction of the
tain more than 50% of its P2O5 content as phos mother liquor as a whole with the phosphoric
phoric acid. The sulfate of the sodium sulfate acid solution, it will be seen primarily that the
60 of the mother liquor and the calcium of the sodium contained in the mother liquor acts to 60
mono-calcium phosphate react to produce cal produce mono-Sodium phosphate, and the Sul
cium sulfate, and the phosphoric acid of the acid fate of the Sodium Sulfate operates to precipitate
Solution reacts with the tri-sodium phosphate the calcium of the mono-calcium phosphate as
and other sodium compounds such as Sodium car Calcium Sulfate. The important features of the
bonate and Sodium hydroxide to form mono-so reaction are that the sodium content of the 65
dium phosphate. The purpose of regulating the mother liquor is utilized directly to partially neu
amount of mother liquor added to the phosphoric tralize phosphoric acid with the twofold advan
acid solution so that the total alkaline sodium tage that no Sulfuric acid is necessary to first con
compounds in the nother liquor, aside from the vert the Sodium compounds to the sulfate, as
70 neutral Sodium Sulfate, Will neutralize the phos When furnacing the mother liquor, and that be- 70
phoric acid solution to such an extent that the cause of the use of the sodium content to par
mixed Solution of mother liquor and phosphoric tially neutralize phosphoric acid, the quantities
acid will contain more than 50% of its P2O5 con of Soda ash necessary for subsequent neutraliza
tent as phosphoric acid, the remainder being tion to obtain the desired ultimate di-alkali prod
75 mono-sodium phosphate, is to prevent precipi uct are greatly reduced. Additionally, since the is
 2,021,699
Sulfate of the sodium sulfate of the mother liquor
effects precipitation of the calcium of the
calcium mono-phosphate, this eliminates the ne
cessity of employing sulfuric acid to bring about
the precipitation of the calcium as has been prac
ticed.
On completion of the reaction between the
Several constituents in the mother liquor and the
phosphoric acid solution containing calcium
0 phosphate, the liquor is allowed to settle or is
filtered to effect separation of the calcium sulfate
and other insoluble impurities from the solution
now containing a mixture of phosphates. The
clear Solution is then further neutralized in tank
15 5 With soda, ash in the usual manner to produce
the desired di-alkali phosphate. The neutraliza
tion of the clear solution with soda ash precipi
tates as white mud not only the remaining in
purities present in the phosphoric acid, but also
20 the impurities originally present in the trisodium
phosphate mother liquor, Such as sodium alu
iminate and other Soluble metals. The White mud
may be separated by filter 6 from the disodium
phosphate liquor. The process thus purifies the
25 trisodium phosphate mother liquor, and utilizes
the sodium content of the mother liquor as a sub
stitute for a part of the Soda ash required to neu
tralize the phosphoric acid.
In the event that the arSenic and organic
30 impurities in the mother liquor rise above per
missible limits, as indicated by the final products,
a portion of the mother liquor may be reworked
by subjecting the same to the furnacing opera
tion of the Strickler patents. Such furnacing
35 operation eliminates arsenic and organic matter,
and thus reduces the quantity of these impuri
ties in the mother liquor circuit to below the per
missible amounts.
It will thus be seen that the invention provides
40 a process for the treatment of mother liquors
containing tri-Sodium phosphate and Sodium.
compounds by Which the phosphates and Sodium
of the liquors may be recovered and the Sodium
utilized for the neutralization of phosphoric acid
45 Without the necessity of Subjecting the entire
bulk of the mother liquor to a furnacing opera
tion. As to the major portion of the mother
liquor, the furnacing operation is eliminated.
The invention makes provision for the economic
utilization of large quantities of alkali metal
phosphate mother liquor Without furnacing. The
comparatively large amounts of Sulfuric acid
heretofore employed in making up the furnace
mix to utilize the mother liquors are Saved. The
Sodium content of the mother liquor is employed
to partially neutralize the phosphoric acid, thus
reducing to a large degree the amount of Soda,
ash Subsequently required to effect the ultimate
neutralization of the acid to the desired extent.
60 Further, the sulfate of the sodium sulfate of the
mother liquor is utilized to effect precipitation
of the calcium of the calcium phosphate of the
acid solution in this way replacing the Sulfuric
acid heretofore used for this purpose.
65 The process is not limited to the treatment
of trisodium phosphate in other liquors produced
in the processes of the Strickler patents. The
invention is applicable to the treatment of
mother iiquors resulting from the manufacture
70 of alkali metal phosphates where such liquors
contain sodium in combinations. Such for exam
ple as tri-sodium or di-Sodium phosphate from
which the sodium may be utilized for the neu
tralization of phosphoric acid.
75 In the appended claims, the term "neutra
3
lized', unless otherwise modified, is intended to
define any degree of neutralization of a phos
phoric acid Solution, and is not limited to indi
cate complete neutralization.
I claim: 5
1. In the manufacture of alkali metal phos
phates involving the furnacing of a mix contain
ing a phosphate radical and an alkali metal Sul
fate in the presence of a reducing agent with the
production from the furnaced product of alkali, 10
metal phosphate and mother liquor containing
alkali metal compounds including an alkali metal
Sulfate, the method of recovering the alkali metal
content of the mother liquor which comprises
treating the mother liquor with a phosphoric 15
acid Solution containing soluble calcium phos
phate whereby the Sulfate of the alkali sulfate
is removed from Solution and phosphoric acid is
neutralized.
2. In the manufacture of alkali metal phos- 20
phates involving the furnacing of a mix contain
ing a phosphate radical and an alkali metal Sull
fate in the presence of a reducing agent With
the production fron the furnaced product of al
kali metal phosphate and nother liquor Con- 25
taining alkali metal compounds including an al
kali metal Sulfate, the method of recovering the
alkali metal content of the nother liquor which
comprises treating the nother liquor With a
phosphoric acid solution containing mono-cal- 30
cium phosphate whereby the sulfate of the al
kali metal Sulfate is precipitated and phosphoric
acid is partially neutralized, Separating Solid res
idues from the solution and further neutralizing
the solution by the addition of an alkali metal 35
thereto.
3. In the manufacture of Sodium phosphates
involving the furnacing of a mix containing a
phosphate radical aid sodium sulfate in the
presence of a reducing agent with the production 40
from the furnaced product of a sodium phos
phate and mother liquor containing Sodium com
pounds including Sodium. Sulfate, the method of
recovering the Sodium content of the mother
liquor which comprises treating the mother 45
liquor with a phosphoric acid Solution contain
ing mono-calcium phosphate whereby the Sulfate
of the Sodium. Sulfate is renoved from Solution,
and the Sodium content of the liquor is utilized
to neutralize phosphoric acid. 50
4. In the manufacture of Sodium phosphates
involving the furnacing of a mix containing a
phosphate radical and Sodium sulfate in the
presence of a reducing agent with the produc
tion from the furnaced product of a SodiumphOS- 55
phate and mother liquor containing Sodium com
pounds including Sodium Sulfate, the method of
recovering the Sodium content of the mother
liquor which comprises treating the mother liq
uor with a phosphoric acid solution containing 60
more than about 3.3% mono-calcium phosphate
Whereby the sulfate of the Sodium sulfate is
precipitated as calcium Sulfate and the phos
phoric acid partially neutralized, separating solid
residues from the resulting solution, and further 65
neutralizing the solution by the addition of
Sodium carbonate thereto.
5. The method of producing Sodium phosphate
which comprises forming a phosphoric acid solu
tion containing monocalcium phosphate, treat- 70
ing the solution with such quantities of sodium
phosphate mother liquor containing sodium com
pounds including sodium sulfate that the total
alkaline sodium compounds in the mother liquor
Will neutralize the acid solution to Such an ex-75
 4 2,021,699
tent that the mixed solution of mother liquor phoric acid partially neutralized, separating solid
and phosphoric acid. Will contain more than 50%
of its P2O5 content as phosphoric acid, whereby
calcium sulfate is precipitated and sodium phos
phate is produced.
6. The method of producing Sodium phos
phate which comprises forming a phosphoric acid
Solution containing monocalcium phosphate,
treating the solution. With such quantities of
O Sodium phosphate mother liquor containing sodi
lum compounds including Sodium Sulfate that the
Sodium Sulfate of the mother liquor and the
mono-calcium phosphate content of the acid so
lution are present in reacting proportions and
5 that the total alkaline Sodium compounds in the
mother liquor will neutralize the acid solution to
Such an extent that the mixed Solution of mother
liquor and phosphoric acid will contain more
than 50% of its P2O5 content as phosphoric acid,
20 Whereby calcium sulfate is precipitated and sodi
um phosphate is produced.
7. The method of producing sodium phos
phates which comprises forming a phosphoric
acid Solution containing more than about 3.3%
25 mono-calcium phosphate, treating the solution
With Such quantities of tri-sodium phosphate
mother liquor containing Sodium compounds in
cluding sodium sulfate that the Sodium sulfate
of the mother liquor and the mono-calcium phoS
30 phate are present in reacting proportions and
that the total alkaline sodium compounds in the
mother liquor will neutralize the acid solution to
such an extent that the mixed solution of mother
liquor and phosphoric acid will contain more
35 than 50% of its P2O5 content as phosphoric acid,
whereby the sulfate of the Sodium sulfate is
precipitated as calcium sulfate and the phoS
residues from the resulting solution, and further
neutralizing the solution by the addition of Sodi
um carbonate thereto,
8. The method for producing alkali metal
phosphate which comprises forming a phoS
phoric acid Solution containing mono-calcium
phosphate, treating the Solution with such quan
tities of alkali metal phosphate mother liquor
containing alkali metal compounds including al 0.
kali metal Sulfate that the total alkaline metal
compounds in the mother liquor will neutralize
the acid Solution to Such an extent that the
mixed solution of mother liquor and phosphoric
acid. Will contain more than 50% of its P2O5 con 5
tent as phosphoric acid, whereby calcium sul
fate is precipitated and alkali metal phosphate
is produced.
9. The method for producing alkali metal
phosphate which comprises forming a phosphoric 20
acid solution containing mono-calcium phos
phate, treating the solution with such quantities
of alkali metal phosphate mother liquor contain
ing the alkali metal compounds including alkali
metal sulfate that the alkali metal sulfate of the 25
mother liquor and the mono-calcium phosphate
content of the acid solution are present in react
ing proportions and that the total alkaline al
kali metal compounds in the mother liquor will 30
neutralize the acid Solution to such an extent
that the mixed solution of mother liquor and
phosphoric acid will contain more than 50% of
its P2O5 content as phosphoric acid, whereby cal
cium sulfate is precipitated and alkali metal 35
phosphate is produced.
LOUIS PREISMAN.