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Patented Dec.

12, 1933
. .. . . .
1939,351
UNITED STAtes 1939,351.
ATENT OFFICE
PR O C Ess oF DIssolving. PHosPHATE
ROCK AND OF SEPARATING TSCONTEN."
OF LIME AND PHOSPHORC. ACD -
Erling Johnson, Odda, Norway, assignor to the
firm Odda Smelteverk A/S, Odda, Norway
No Drawing. Application September 24, 1930,
Serial No. 484,241, and in Norway September 28,
1929
2 Claims. (C. 23-165)
In my prior application Ser. No. 391,506, now phoric acid, namely, concentrating the phosphoric
Patent No. 1,816,285, I have disclosed a process acid mother liquor by removal of water in the
for treating rock phosphate with nitric acid and shape of water of crystallization in the calcium
separating the lime and phosphoric acid of the nitrate of the composition Ca (NO3)2.4H2O.
rock phosphate. According to said application It will be seen that by use of nitric acid of G).
the rock phosphate is dissolved in nitric acid of 63,7% in theoretically required quantities just the
medium grade and from the solution obtained entire water content of the acid is used up as
a very great part of the calcium nitrate is caused water of crystallization.
to crystallize so that after filtration of the CryS In Order to counteract the inconveniences which
O tals a mother liquor is obtained which contains Occur when the minimum of acid of said concen- 65.
the phosphoric acid of the rock phosphate. trations is used, mother liquor from prior opera
My present invention relates to some special tions may be introduced during the dissolving
measures for carrying out this process in a con and crystallization stage of the process. The
venient manner. The said measures are particul present invention relates to special. practical
larly important when it is desired to obtain the measures in connection with this use of mother
highest possible concentration of phosphoric acid liquor.
in the mother liquor and a possibly complete A certain quantity of mother liquor is con
separation of calcium nitrate. Said measures veniently added already to the fresh nitric acid,
have for their purpose to eliminate the incon or is; together with the later supplied to the
veniences which arise when relatively strong nitric phosphate rock to be dissolved. This mother liq- if:3
acid of say 60-75% is used in theoretically re uor is supplied cold or warm and is suitably con
quired quantities or in very slight excess, because Weyed in counter-current with the gases and acid
in this case the solution of rock phosphate in Vapors evolved in the dissolving apparatus. The
nitric acid, and also the mother liquor from the addition; of a suitable quantity of mother liquor
calcium nitrate, respectively the mixture of Solu already in this first stage of the process effects a
tion and crystals before filtration of the latter, regulation of the temperature of the reaction be
becomes so viscous and sticky that the operations tween phosphate rock and nitric acid and makes
of dissolving, crystallizing, and agitation as well it possible to maintain this temperature on a de
as the interchange of heat is greatly impeded. sired level f. i. at 75 C. Further the addition of
In this connection it may be mentioned that if mother liquor makes the reaction mass more fluid,
pure tri-calcium phosphate is treated with the and allows also an absorption and utilization of
theoretical quantity of nitric acid of exactly 63,7% the nitric acid of the escaping vapors.
just sufficient water is supplied to yield the entire In order to render the mixture of liquid and
amount of lime as crystallized solid calcium ni Solid Substances which results after crystalliza
35 trate Ca(NO3)2.4H2O and phosphoric acid of 100 tion of calcium nitrate more fluid further quan C
per cent according to the equation tities of cold mother liquor from prior opera
tions may be added before or during the crystal
lization of calcium nitrate. The mother liquor
40 If nitric acid of the said strength were used the which is to be supplied in this second stage of
product of reaction should theoretically be a mix Super-cooling,may
the process be subjected to pre-cooling, or
before it is supplied to the solu
ture of crystallized calcium nitrate and phosphoric tion, from which the calcium nitrate is to crys
acid of 100 per cent. tallize. This solution proper may previously
With such a product it is however very diffi have been subjected to a partial cooling down to
cult to obtain efficient separation of the thick
concentrated phosphoric acid and the calcium --5° C. or to about Zero. Upon addition of super
nitrate crystals. Already when nitric acid of little cooled mother liquor of say 20° C. below zero
more than 60 per cent is used a certain Surplus in Suitable quantities the entire mass may as
of acid, f. i. 15-100 per cent, is necessary in sume a temperature of f. i. 5° C. below zero. By
order to dilute the phosphoric acid so that a filter this previous separate cooling of the mother
able and easily moveable crystal mass is obtained. liquor, the advantage is obtained that the in
It is to be pointed out that in the process described terchange of heat with the cooling medium is
above a novel principle is used for separating the realized in absence of greater quantities of Solid
content of lime and phosphoric acid of the rock calcium nitrate which might easily impede the
55 phosphate, respectively for preparation of phos free circulation of the phosphoric acid solution O
2 1,989,851
When this had to be cooled by direct interchange of the finished mixed product is supplied with
of heat, this acid.
A part of the cold mother liquor which leaves In the manner described a mother liquor may
the system is very conveniently utilized for cool be obtained with a content of 30 per cent P2O5,
ing of the reaction product of rock phosphate 1.5 per cent nitrate nitrogen, 6.5 per cent nitric 80
and nitric acid, acid nitrogen and 3,0 per cent lime as calcium
After the calcium nitrate crystals have been nitrate. This solution is so concentrated that
separated from the mother liquor on a filter or when it in the finely divided state is neutralized
in a centrifugal machine the crystals may be with ammonia dry spreadable, two-componential
10 washed with suitable liquids such as cooled con fertilizers are immediately obtained with little or 85
centrated nitric acid, a cooled saturated Solution even without any Supply of heat.
If potassium salts are admixed to or dissolved
of calcium nitrate or of ammonium, nitrate, and
such like. If nitric acid or a calcium nitrate in the mother liquor prior to neutralization three
solution is used for this purpose the wash-liquid componential fertilizers are obtained.
5 is conveniently returned to the operation of dis The quantity of mother liquor which is re- 90
turned to prior stages of the process may vary
solving phosphate rock with nitric acid, to which greatly according to the conditions under which
as already mentioned mother-liquor may also be these prior stages are carried out. Conveniently
added. Instead of nitric acid alone, even nitric
acid which is cooled and saturated with calcium the quantity of mother liquor returned may cor
20 nitrate at a temperature of between zero and 10 respond to the weight of phosphate rock and/or 95
below zero may be used for Washing. . . . r nitric acid entering the primary operation.
When the measures mentioned above are mad Further it proves convenient to add 20-40 per
use of, nitric acid of the said concentration may cent of this quantity of mother liquor already
be used only in a minimum of excess, or even in the first stage of the process, i. e. during the
25 only in the theoretically required quantity, With dissolution of phosphate rock with nitric acid, 100
out offending against the two principal condi while 60-80 per cent are added immediately be
tions for carrying out the new proceSS SucceSS fore or during the crystallization of calcium ni
fully: First to have at least so much water pres trate. This crystallization may in known man
ent, eventually a suitable Smaller Surplus, aS is iner be carried out continuously in apparatus
30 consumed as water of crystallization by the cal
equipped with devices for stirring and cooling. 105
cium nitrate in the shape of Ca (NO3)2.4H2O and 1. I claim: .
simultaneously to obtain a mass of crystals and In a process of dissolving phosphate rock
mother liquor which is sufficiently fluid to avoid in nitric acid and of separating the content of
difficulties in the interchange of heat, transport, calcium nitrate and phosphoric acid from the
solution so obtained by crystallization of the cal- 110
35 filtering, centrifuging and Washing of the cium nitrate, the steps which comprise adding
Crystals,
. When f.i. nitric acid of 60-65 per cent is used one portion of the solution of phosphoric acid
the manner of working described above makes saturated with calcium nitrate which is ob
it possible to obtain a quantity of calcium nitrate tained as mother liquor from a prior crystalliza
40 Ca(NO3)2.4H2O corresponding to as much as 95 tion of calcium nitrate in the operation of dis- 115
per cent of the lime content of the solution, and Solving phosphate rock With nitric acid and in
after filtration of the crystals a mother liquor supplying a second portion of such mother liquor
results, which f. i. may contain 35 per cent to the reaction product of phosphate rock and
P2O5, some 1,5 per cent nitrogen in the form of acid during crystallization of calcium nitrate
45 nitric acid, some 1,5 per cent nitrogen as calcium therefrom, 120
nitrate and some 3 per cent calcium calculated 2. In a process of dissolving phosphate rock
as CaO. in nitric acid and of separating its content of
The relative ratio of components may Of course calcium nitrate and phosphoric acid from the so
vary within wide limits according to the quantity lution so obtained by crystallization of the cal
cium nitrate, the steps which comprise adding 125
50 of nitric acid used, the concentration and the during the dissolving operation a portion of
degree of cooling. A product of the above named mother liquor from a prior crystallization of cal
composition may easily be worked upon ferti
lizers of two or three components or upon va cium nitrate after said mother liquor has been
rious phosphate products free from nitric acid used for Washing and cooling of the vapors and
and line. - gases escaping from the dissolving of phosphate 130
If it is desired to make compound fertilizers rock and in supplying a second portion of mother
with a considerably higher content of nitric acid liquor to the reaction product of the phosphate
nitrogen, the primary dissolution of phosphate rock and acid during crystallization of calcium
rock may be carried out with such a surplus of nitrate therefrom.
60 nitric acid, that the desired quantity of nitrogen . ERLING JOHNSON. 135

65 140

45
70

150