Patentamt

J E u r o p European
a i s c h e sPatent Office Publication number: 0 1 2 2 6 4 6

Office europeen des brevets B1

EUROPEAN PATENT SPECIFICATION

Date of publication of patent specification: 10.08.88 Intel.4: C 01 F 11/44, C 01 B 2 5 / 2 2 ,

C 05 C 5 / 0 4
Application number: 84200310.5
Date of filing: 05.03.84

Process for separating off calcium nitrate tetrahydrate by crystallization.

(38) Priority: 07.03.83 NL 8300816 ® Proprietor: STAMICARBON B.V.

Mijnweg 1
NL-6167 AC Geleen (NL)
Date of publication of application:
24.10.84 Bulletin 84/43
Inventor: Calis, Gijsbertus Hendrikus M.
Burg. Kengenstraat 60
Publication of the grant of the patent: NL-6336 BK Hulsberg (NL)
Inventor: Jennekens, Matheus Hubertus G.
10.08.88 Bulletin 88/32
Velgraafweg 27
NL-6121 BH Born (NL)
Designated Contracting States:
ATBEDEFRGBITNLSE

References cited:
FR-A-1111495
GB-A-1 149 310
US-A-4 008 309
CHEMICAL ABSTRACTS, vol. 92, no. 23, June
1980, page 584, no. 197171k, Columbus, Ohio,
US

CO
CM
CM

Note: Within nine months from the publication of the mention of the grantof the European patent, any person may
give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall
Q. be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1 ) European patent convention).
LU
Courier Press, Leamington Spa, England.
 0 122 646
Description The comparative example 4, shows the addition
of seed crystals to the digestion liquor at a
The invention relates to a process for separ- temperature of 1°C lower than the saturation
ating calcium nitrate tetrahydrate by crystalliza- temperature, resulting in a much broader particle
tion from a liquor obtained by digesting phos- 5 size distribution than is obtained in the compar-
phate rock with nitric acid. able example 1 wherein seed crystals are added
Such a process is common knowledge and at a temperature of 5°C lower than the saturation
constitutes an essential part of the so-called Odda temperature, In the process of US—A—2,813,777
nitrophosphate process (see for instance patent relatively coarse crystals are obtained. This is
publication GB—A—339.340. In this known pro- 10 achieved by adding calcium nitrate-containing
cess the calcium nitrate formed in the digestion is seed material to a digestion liquor having a
continuously separated off by crystallization as temperature 2—10°C lower than the saturation
tetrahydrate by cooling the digestion liquor by temperature and by further cooling the liquor
means of a cold cooling liquid and separating the obtained. In this process the crystals obtained
crystallized salt from the mother liquor, which is is show a fairly wide particle size distribution.
processed, to form a mixed fertilizer. Depending Although the crystals can largely be separated off
on the final temperature of the cooled digestion through filtration, it has been found that, owing to
liquor, about 60—90% of the calcium nitrate the inhomogeneous particle size distribution,
present in the digestion liquor will crystallize out long filtration times are necessary. In this process,
in said process. 20 too, there will be a growth of fine calcium nitrate
A disadvantage of this known process is that tetrahydrate material on the cooling surfaces.
the crystals formed are very inhomogeneous in In US— A—4,008,309 a continuous two step
terms of particle size and, moreover, have a crystallization process is described without addi-
relatively small average particle diameter, so that tion of seed crystals. In this process, too, a large
it is very difficult indeed for the crystals to be 25 particle size distribution of the crystals is
separated off. In the separation of the crystals obtained.
from the mother liquor by, for instance, centrifu- The invention now provides a process in which
gation or filtration, this will, in many cases/lead to it is possible, without excessive cooling, for the
a substantial slip-through of crystals resulting, in calcium nitrate to be crystallized out in batches
the processing of the mother liquor into mixed 30 from a nitric acid digestion liquor substantially in
fertilizer products, in the formation of water- the form of very coarse and very uniform calcium
insoluble and sometimes also citrate-insoluble nitrate tetrahydrate crystals that can practically
phosphates and consequently in a loss of nutrient quantitatively be separated off from the liquor,
phosphate. and in which process there will no longer be any
. It is true that a larger quantity of calcium nitrate 35 growth of crystals on the cooling surfaces.
in the digestion liquor may be crystallized by This is obtained by adding a specific amount of
cooling the latter to very low temperatures as seed crystals at a temperature of the digestion
described in, for instance, Proces Techniek, dated liquor of 0.1 —2°C lower than the saturation
2.5.1969, pages 312—316. The disadvantage of temperature and subsequent controlled cooling
this process is that the cooling to very low 40 of the digestion liquor.
temperatures requires a large amount of energy The invention therefore relates to a process for
and a very high cooling capacity. Moreover, it has separating calcium nitrate tetrahydrate by crys-
been found that, in this process, too, the calcium tallization from a liquor obtained by digesting
nitrate crystals formed have a rather small and phosphate rock with nitric acid, the crystallization
inhomogeneous particle size, so that in the 45 being effected by batchwise cooling of the liquor,
separation of these there will be a certain degree wherein in the beginning of the cooling process
of slip-through of these crystals. The two pro- calcium nitrate tetrahydrate seed material with a
cesses described above consequently require particle size smaller than 100 urn is added to the
substantial investments, either for effectively digestion liquor in a quantity of 50.000 to 200.000
separating off the crystals or for extra cooling 50 seed crystals per kg digestion liquor to be cooled
capacity, in order to obtain a mother liquor having at a temperature of the digestion liquor which is
a sufficiently low calcium nitrate concentration. 0.1 —2°C lower than the saturation temperature of
These known processes, moreoever, have the the digestion liquor, the digestion liquor is sub-
disadvantage that during the process the calcium sequently further cooled by means of a cooling
nitrate tetrahydrate formed on the cooling sur- 55 medium, whereby as long as the concentration of
faces must be removed. This involves an extra calcium nitrate tetrahydrate crystals in the diges-
increase in the amount of cooling energy tion liquor is less than about 20%, the cooling is
required. effected with a cooling medium having a
From patent publication US— A—2,813,777 a temperature higher than the nucleation tempera-
batchwise process is known for crystallizing out 60 ture of the digestion liquor to be cooled with the
calcium nitrate from nitric acid digestion liquors, cooling medium and, when the concentration of
in which process this calcium nitrate crystallizes crystals in the digestion liquor has increased to
out mainly in the form of relatively coarse crystals above 20%, the cooling is effected with, a cooling
(0.5 —1.0mm), after which these crystals can be medium having a temperature lower than the
separated off from the mother liquor by filtration. 65 nucleation temperature of the digestion liquor to
 0 122 646
be cooled with the cooling medium, and the having a very wide crystal size distribution. Pre-
calcium nitrate tetrahydrate crystallized out in this ference is given to adding the seed material to a
process is separated from the cooled digestion digestion liquor having a temperature 0.2 — 1.0°C
liquor. lower than the saturation temperature.
It has been found that — irrespective of the 5 In the preset process the seeded digestion
exact size of the seed material — seed crystals liquor is further cooled by means of a cooling
must be added, in a quantity of about 50,000 to medium. Preference is given to using, for this
200,000 per kg digestion liquor to be cooled in purpose, a liquid cooling medium, such as
order to achieve satisfactory crystallization during methanol, an aqueous ammoniacal solution or
cooling. If a smaller quantity of seed crystals is 10 aqueous solution of inorganic salts, e.g. calcium
used, it will be found that during cooling a nitrate, and the cooling is effected by indirect
substantial quantity of fine product crystals are contact between cooling medium and digestion
formed, in addition to relatively coarse product liquor to be cooled..
crystals, whereas, if a larger quantity of seed It has been found that the method of cooling is
crystals is used, the average diameter of the 15 important for obtaining product crystals having
product crystals will decrease strongly. The seed large and uniform particle dimensions.
material that can be used includes fine calcium According to one mode of realization, the cool-
nitrate tetrahydrate obtained by grinding coarser ing is effected in a plurality of cooling steps, while
calcium nitrate tetrahydrate particles, for instance using, in each step, a cooling medium having a
granules, grains, prills, crystals, and screening 20 constant temperature, which is lower than the
out a fraction having a particle size smaller than temperature of the cooling medium in the preced-
100 urn The grinding, however, requires rela- ing step.
tively much energy. According to a preferred mode of realization,
That is why preference is given in the present the temperature of the cooling medium in the
process to use seed material consisting of fine 25 crystallization system is lowered continuously. In
nuclei obtained by adding a calcium nitrate- principle such a continuous decrease in tempera-
containing material to a quantity of supercooled ture can be achieved in several ways. An advan-
calcium nitrate-containing digestion liquor. In this tageous method is to use cooling media from a
process there will momentarily be a spontaneous number of cooling systems each operating within
formation of very fine nuclei. The size of these 30 a different temperature range, and wherein the
nuclei is determined mainly by the degree to mixing ratio of said cooling media is carefully
which the liquor is supercooled. It has been found adjusted, e.g. with the aid of a microprocessor
that very fine and practically uniform nuclei based control system.
having a particle size of between 25 and 30 urn are The advantage of this mode of realization is that
obtained if a supercooled digestion liquor having 35 the maximum permissible difference in tempera-
a temperature of 18 to 22°C, particularly about ture between the cooling medium and the diges-
20°C, is started from. The calcium nitrate-contain- tion liquor to be cooled, given by the difference
ing material added to the supercooled digestion between the nucleation temperature (see below)
liquor may be, for instance, broken or unbroken and the saturation temperature of the digestion
calcium nitrate crystals. A small quantity of cal- 40 liquor to be cooled, is used throughout the cool-
cium nitrate-containing suspension having a ing process. This causes the crystallization pro-
temperature of, for instancce, 5°C or lower can be cess to proceed more rapidly so that a substantial
added also. Such a suspension is obtained in the capacity increase is effected.
present process at the end of the crystallization A further' advantage of the use of cooling
process. 45 medium from a number of cooling systems is that
It is in principle possible for the fine nuclei thus use can be made from the ultimately resulting
formed to be separated off from the spercooled cold mother liquor to lower by indirect heat
liquor and for these nuclei separated off to be exchange the temperature of the cooling medium
used as seed material. The separation of such used in the first traject of the crystallization.
very small nuclei is extremely laborious, how- so Furthermore in such a cooling system advan-
ever. Preference is therefore given to adding the tageously use can be made of cooling water to
nuclei-containing supercooled liquor as seed cool or precool by indirect heat exchange the
material. A quantity of about 0.05 to 0.2 ml of the cooling medium used in said first traject.
nuclei-containing supercooled liquor per kg It has further been found that the difference in
digestion liquor to be cooled will suffice to effect 55 temperature between the cooling medium and
satisfactory crystallization. the digestion liquor to be cooled is very important
An essential feature of the present process is for obtaining proper product crystals. If at any
the temperature of the digestion liquor at which moment the chosen difference in temperature
the seed material is added. In order to obtain an between cooling medium and digestion liquor to
optimum crystallization effect, the chosen so be cooled is too great, a drastic increase of small
temperature must be below and as close as product crystals will be found to occur. This is due
possible to the saturation temperature of the to the formation of new nuclei of calcium nitrate
digestion liquor to be cooled. If the seed material tetrahydrate — in addition to or instead of a
is added to a liquor having a lower temperature, it growth of calcium nitrate tetrahydrate crystalliz-
will be found that product crystals are obtained 65 ing out on the seed crystals present. As a result
 0 122 646
the average size of the product crystals decreases volume is realized. As long as the concentration
and, moreover, a great many product crystals of of crystals in the digestion liquor is lower than
very small size are formed. Consequently, the about 20%, preference is given to using a cooling
particle size distribution is considerable. It is medium having a temperature 2—6°C lower than
important, therefore, in the present process to 5 the saturation temperature of the digestion liquor
take care that throughout the whole cooling pro- to be cooled, and if the concentration of crystals
cess a cooling medium is used having a tempera- in the digestion liquor is higher than about 20%,
ture that does not permit of the spontaneous preference is given to using a cooling medium
formation of calcium nitrate tetrahydrate nuclei in having a temperature 5—15°C lower than the
the digestion liquor to be cooled, which, at the jo saturation temperature of the digestion liquor to
same time, prevents the growth of crystals on the be cooled.
cooling surfaces so that the transfer of heat is not In the present invention the calcium nitrate
adversely affected. tetrahydrate crystallizes out in the form of crystals
An extra advantage of this method of cooling is having a particularly great uniformity in terms of
that a substantial saving on the cooling energy 15 particle size, viz. a distribution of about 5— 10%.
requirements is achieved, because the tempera- In principle crystals of any desired size can be
ture to which large part of the cooling liquid to be made. In the process according to the invention
used has to be cooled may be less lowr which crystals will be produced having an average
allows the cooling equipment to function with particle size of between 1000 and 1500 urn. These
greater e f f i c i e n c y . . 20 crystals can be separated from the mother liquor
According to one mode of realization this can in a fairly simple manner and virtually quantita-
be achieved by using, throughout the cooling tively. Preference is given to separating by filtra-
process, a cooling medium having a temperature tion.
higher than the nucleation temperature of the The process described for crystallizing out cal-
digestion liquor to be cooled. 25 cium nitrate tetrahydrate can in principle be
Nucieation temperature is understood to mean applied to any liquor obtained by digesting phos-
in this connection the temperature at which in a phate rock with nitric acid. The highly erosive
crystalline calcium nitrate tetrahydrate-containing inert components present in such a digestion
saturated solution the supersaturation that occurs liquor can be removed partly if so desired prior to
during the cooling of this solution is removed 30 the crystallization of calcium nitrate, for instance
completely by the formation of nuclei and the by means of a hydrocyclone. Such a separation of
growth of crystals. This temperature can be deter- inert is necessary if the calcium nitrate crystallized
mined by fixing visually or through accurate out is separated off by means of a centrifuge. If,
temperature measurement the nucleation point however, the crystallization is effected according
as a function of the concentration of the sub- 35 to the present process, in which process the
stance to be crystallized out as described, for crystals may be separated off through filtration,
instance, in 'Crystal Growth' by B.R. Pamplin, the prior removal of inert is not necessary from an
Pergamon Press (1975) page 294. erosion point of view, because this method of
If the concentration of crystals in the digestion separation is hardly sensitive to erosion.
liquor is higher than about 20%, it will be found 40 The calcium nitrate tetrahydrate separated off
that there will be no perceptible spontaneous in the present process can be further treated as
formation of calcium nitrate tetrahydrate nuclei in known in the art, for instance be washed with cold
the liquor during cooling, not even when a cool- nitric acid to remove entrained mother liquor,
ing medium is used having a temperature lower which can be added to the mother liquor already
than the nulceation temperature of the liquor to 45 separated off, and subsequently be rewashed
be cooled. Apparently the total crystal surface with water. The nitric acid washing liquid can then
available has then become so large that the be returned advantageously to the digestion. The
supersaturation is eliminated completely by the water-containing calcium nitrate thus purified can
growth on crystals already present in the suspen- be converted in a manner also known in the art
sion. In the process of the present invention the 50 into calcium carbonate and ammonium nitrate.
cooling is therefore effected in such a manner The mother liquo.r of phosphoric acid and poss-
that, as long as the concentration of crystals in the ibly nitric acid remaining after separating off the
digestion liquor is lower than about 20%, a calcium nitrate tetrahydrate crystallized out still
cooling medium is used having a temperature contains a quantity of calcium, depending on the
higher than the nucleation temperature of the 55 final temperature of the cooling. It has been found
digestion liquor to be cooled with the cooling that, in applying the present process, cooling to
medium and, if the concentration of crystals in the for instance +5°C will produce a mother liquor
digestion liquor is higher than about 20%, a having a sufficiently low molar CaO:P2Os ratio for
cooling medium is used having a temperature the preparation of mixed fertilizers with at least
substantially lower than the nucleation tempera- so 80% water-soluble P2OS.
ture of the digestion liquor to be cooled with the The invention will be further elucidated in the
cooling medium. following examples without, however, being
The advantage of this is that the cooling limited thereto.
effected in the final phase of the cooling process
can be more rapid, so that a saving on crystallizer 65
 0 122 646 8
Example I Example V
Jordan phosphate with a CaO content of 50.8% The process of example III was repeated on
(wt) and a P2O5 content of 32.5% (wt) was the understanding that 0.05 ml nuclei-containing
digested at a temperature of 65°C with 60% (wt) suspension per kg digestion liquor was added.
HNO3 in a quantity of 2 parts by weight HNO3 s The resulting Ca(NO3)2.4 H2O crystals had a
solution per part by weight phosphate rock. The particle size between 1400 and 1500 urn.
resulting digestion liquor (CaO:P2Os molar ratio
of 3.95) was mixed with a quantity of cold diges- Comparative Example A
tion liquor with a lower CaO:P2O5 ratio obtained The process of example I was repeated, in
in a later stage of the process, which resulted in a 10 which process calcium nitrate tetrahydrate crys-
mixture having a temperature of about 40°C and a tals with an average diameter of 64 |im were
CaO:P2O5 molar ratio of 2.75. This mixture (sat- added to the digestion liquor (CaO:P2O5 molar
uration temperature 26.5°C) was fed into a 2.5- ratio 2.75) at a temperature of 26.1°C in a quantity
litre crystallizer provided with cooling coils and of 750 mg per kg of digestion liquor and the
cooled there in a first cooling step by means of is mixture was cooled in the first cooling step for 35
methanol (temperature 24°C) for about 30 minutes with methanol (23.7°C), in the second
minutes. During the cooling, at a temperature of step for 40 minutes with methanol (22.0°C), in the
26.1°C, calcium nitrate tetrahydrate seed crystals third step for 60 minutes with methanol (11.9°C)
with an average diameter of about 60 um were and in the fourth step for 60 minutes with
added to the mixture in a quantity of 25 mg per kg 20 methanol (-2.0°C).
digestion liquor (65,000 crystals/kg digestion The resulting suspension (0.5°C) was filtered,
liquor). These crystals had been obtained by producing as filtrate a mother liquor with a
grinding and screening coarse calcium nitrate CaO:P2O5 molar ratio of 0.68 and as filter cake
tetrahydrate crystals. Ca(NO3)2.4 H20 crystals having a particle size
In a second cooling step the resulting mixture 25 between 600 and 700 um.
was cooled in the crystallizer for about 50 minutes
with methanol (temperature 21.6°C), sub- Example VI
sequently in a third cooling step for about 50 In the same way as in example I Jordan phos-
minutes with methanol (temperature 11.8°C) and phate was digested with 60% (wt) HNO3 and the
finally in • a fourth cooling step for about 50 30 resulting digestion liquor mixed with a cold diges-
minutes with methanol (temperature -0.3°C). tion liquor with a lower CaO:P2O5 molar ratio,
The resulting suspension (temperature 2.1 °C) producing a mixture having a temperature of
was filtered, producing as filtrate a mother liquor about 42°C and a CaO:P2O5 molar ratio of 3.25.
with a CaO:P2O5 molar ratio of 0.75 and as filter This mixture (saturation temperature 28.5°C)
cake calcium nitrate tetrahydrate crystals having a 35 was cooled in a first step for 30 minutes with
particle size between 1300 en 1400 um. methanol (26.2°C) a quantity of 30 mg seed
crystals with an average diameter of 64 (am being
Example II added per kg liquor at a temperature of 28.0°C.
The process of example I was repeated on the The mixture was cooled in a second step for
understanding that the seed material added was a 40 about 60 minutes with methanol (23.2°C), sub-
nuclei-containing suspension in a quantity of 0.1 sequently in a third step for about 50 minutes with
ml per kg digestion liquor. This suspension had methanol (12.5°C), and in a fourth step for about
been obtained by cooling part of the digestion 40 minutes with methanol (-2.0°C).
liquor obtained in example I to 20°C and adding to The resulting suspension (temperature 0.0°C)
this a few calcium nitrate tetrahydrate crystals. 45 was filtered, producing a mother liquor having a
The results were the same as those of example CaO:P2O5 molar ratio of 0.72 and Ca(NO3)2.4 H2O
crystals having a particle size between 1200 and
1300 urn.
Example III
The process of example II was repeated on the so Comparative Example B
understanding that the nuclei-containing suspen- The process of example VI was repeated on the
sion had been obtained by adding to the digestion understanding that the liquor was cooled in the
liquor cooled to 20°C a small quantity of cold second cooling step (nucleation temperature
calcium nitrate suspension obtained in the fourth about 23°C) for about 70 minutes with methanol
cooling step of example I. 55 of 22.5°C. In this process nucleation occurred in
The results were the same as those of this second step.
examples I and II. The resulting Ca(NO3)2.4 H2O crystals con-
sequently had a particle size between 700 and
Example IV 1100 urn.
The process of example III was repeated on so
the understanding that 0.2 ml nuclei-containing
suspension per kg digestion liquor was added. Example VII
The resulting Ca(NO3)2.4 H2O crystals had a In the same way as in example I Kola phosphate
particle size between 1050 and 1150 um. (CaO content 52.0% (wt); P2O5 content 38.4%
S5 (wt)) was digested with 60% (wt) HNO3, resulting
 0 122 646 10
in a digeston liquor with a CaO:P2Os molar ratio crystals having a particle size between 100 and
of 3.36 (saturation temperature 29.3°C). 200 urn.
This liquor was cooled in a first step for about This shows that in consequence of the forced
45 minutes with methanol (27°C), in which pro- cooling in the third step Ca(NO3)2.4 H2O nuclei
cess 25 mg Ca(NO3)2.4 H2O seed crystals (dso: 64 were formed.
u) per kg digestion liquor was added to the liquor
at a temperature of 28.9°C. Example X
The mixture was cooled in a second step for 80 In the same way as in example I Jordan phos-
minutes with methanol (22°C), subsequently in a phate was digested wih HNO3 and the resulting
third step for 80 minutes with methanol (12°)and 10 digestion liquor mixed with a quantity of cold
finally in a fourth step for 60 minutes with digestion liquor with a lower CaO:P2O5 molar
methanol (-1.0°C). ratio, producing a mixture with a temperature of
The resulting suspension (temperature 2.2°C) about 40°C and a CaO:P2O5 molar ratio of 2.75.
was filtered, producing on the one side a mother This mixture was cooled in a crystallizer for 15
liquor with a CaO:P2O5 molar ratio of 0.40 and on 15 minutes, using methanol with a temperature of
the other Ca(NO3)2.4 H2O crystals with a particle 24.0°C, a quantity of 25 mg seed crystals (dS0:64
size of 1300—1400 urn. urn) per kg mixture being added during the
cooling at a temperature of 26.1°C.
Example VIII The mixture was subsequently cooled with
The process of example VII was repeated on the 20 methanol, in which process the temperature of
understanding that a nuclei-containing suspen- the methanol was lowered continuously, and that
sion was added to the digestion liquor at 28.9CC in for 20 minutes by 4°C per hour, subsequently for
a quantity of 0.09 ml per kg digestion liquor. This 20 minutes by 8°C per hour and finally for 90
suspension had been obtained by cooling part of minutes by 20°C per hour.
the digestion liquor to 19.5°C and adding to it a 25 The eventually resulting suspension (2.2°C) was
small quantity of cold crystallizer slurry obtained filtered, producing a mother liquor with a
in the fourth cooling step of example VII. CaO:P2O5 molar ratio of 0.73 and Ca(NO3)2.4 H2O
The results were the same as those of example crystals with a particle size between 1300 and
VII. 1400 urn.
30
Example IX Claims
In the same way as in example I Youssouffia
phosphate (50.8% (wt) CaO and 31.2% (wt) P2O5) 1. Process for separating calcium nitrate tetra-
was digested with HNO3, resulting in a digestion hydrate by crystallization from a liquor obtained
liquor with a CaO:P2O5 molar ratio of 3.95 and a 35 by digesting phosphate rock with nitric acid, the
saturation temperature of 30.4 °C. crystallization being effected by batchwise cool-
This digestion liquor was cooled with methanol ing of the liquor, wherein in the beginning of the
in four steps with a cooling time of 60 minutes per cooling process calcium nitrate tetrahydrate seed
step, using in the first step methanol with a material with a particle size smaller than 100 urn
temperature of 25.4CC, in the second step 17.8°C, 40 is added to the digestion liquor at a temperature
in the third step 10.4°C and in the fourth step of the digestion liquor which is 0.1 —2°C lower
0.0°C. In the first step 25 mg Ca(NO3)2.4 H2O seed than the saturation temperature of the digestion
crystals (d50: 64 urn) per kg liquor was added to liquor, which process is characterized in that the
the liquor at a temperature of 29.9 °C. calcium nitrate tetrahydrate seed material is
The suspension (temperature about 5°C) result- 45 added in a quantity of 50,000 to 200,000 seed
ing after the fourth step was filtered, producing a crystals per kg digestion liquor to be cooled and
mother liquor with a CaO:P2O5 molar ratio of 0.73 that the digestion liquor is subsequently further
and Ca(NO3)2.4 H20 crystals with a particle size cooled by means of a cooling medium whereby
between 1300 and 1400 urn. as long as the concentration of calcium nitrate
so tetrahydrate crystals in the digestion liquor is less
Comparative example C than about 20%, the cooling is effected with a
The process of example IX was repeated on the cooling medium having a temperature higher
understanding that the digestion liquor was than the nucleation temperature of the digestion
cooled with methanol in three steps, and that in liquor to be cooled with the cooling medium and,
the first step for about 90 minutes with methanol 55 when the concentration of crystals in the diges-
with a temperature of 25.4°C, in the second step tion liquor has increased to above about 20%, the
for about 100 minutes with methanol of 17.8°C cooling is effected with a cooling medium having
and in the third step for about 70 minutes with a temperature lower than the nucleation tempera-
methanol of 0°C. ture of the digestion liquor to be cooled with the
After filtration of the resulting suspension 60 cooling medium, and the calcium nitrate tetrahy-
(5.0°C), again a mother liquor with a CaO:P205 drate crystallized out in this process is separated
molar ratio of 0.73 was obtained. The resulting from the cooled digestion liquor.
filter cake consisted of Ca(NO3)2.4 H2O crystals 2. Process according to claim 1, characterized in
having substantially a particle size between 1100 that the seed material used consists of fine nuclei
and 1200 urn, in addition to a small fraction of 65 obtained by adding a solid calcium nitrate-con-
 11 0 122 646 12
taining material to a supercooled calcium nitrate- sung, und die KCihlung, wenn die Konzentration
containing digestion liquor. der Kristalle in der AufschlufSlosung auf oberhalb
3. Process according to claim 2, characterized in etwa 20% angestiegen ist, mit einem Kuhlme-
that the solid calcium nitrate-containing material dium durchgefiihrt wird, dessen Temperatur
is added to a digestion liquor supercooled to a 5 niedriger ist als die Kernbildungstemperatur der
temperature of 18— 22°C and the resulting liquor, mit dem Kiihlmedium zu kuhlenden AufschlulSo-
containing nuclei having a particle size of 25—30 sung, und daft das bei diesem Verfahren auskri-
um, is used as seed material. stallisierte Calciumnitrat-Tetrahydrat von der
4. Process according to claim 2 or 3, charac- gekiihlten AufschluKlosung abgetrennt wird.
terized in that 0.05 —0.2 ml of the nuclei-contain- 10 2. Verfahren nach Anspruch 1, dadurch gekenn-
ing digestion liquor is used per kg digestion liquor zeichnet, daft das verwendete Keimmaterial aus
to be cooled. feinen Kemen besteht, die durch Zusatz eines
5. Process according to any one of claims 1—4, festen, Calciumnitrat enthaltenden Materials zu
characterized in that the seed material is added to einer Ciberkiihlten Calciumnitrat enthaltenden
the digestion liquor to be cooled at a temperature 15 Aufschluftlosung erhalten wurden.
0.2 —1.0°C lower than the saturation temperature 3. Verfahren nach Anspruch 2, dadurch gekenn-
of the digestion liquor. zeichnet, daft dasfeste, Calciumnitrat enthaltende
6. Process according to any one of claims 1—5, Material zu einer auf eine Temperatur von
characterized in that the cooling is effected in a 18—22°C uberkiihlten Aufschluftlosung hinzuge-
plurality of cooling steps and in each step a 20 fugt und die resultierende Losung, die Kerne mit
cooling medium is used having a constant einer Teilchengrofte von 25—30 urn enthalt, als
temperature, which is lower than the temperature Keimmaterial verwendet wird.
of the cooling medium in the preceding step. 4. Verfahren nach Anspruch 2 oder 3, dadurch
7. Process according to any one of claims 1—5, gekennzeichnet, daft 0,0—0,2 ml der die Kerne
characterized in that the temperature of the cool- 25 enthaltenden Aufschluftldsung pro kg der zu kuh-
ing medium used is lowered continuously. lenden Aufschluftlosung verwendet werden.
8. Process according to any one of claims 1—7, 5. Verfahren nach einem der Ansprilche 1—4,
characterized in that, as long as the concentration dadurch gekennzeichnet, daft das Keimmaterial
of calcium nitrate tetrahydrate crystals in the derzu kuhlenden Aufschluftlosung bei einer Tem-
digestion liquor does not amount to about 20%, 30 peratur, die 0,2 — 1,0°C niedriger ist als die Satti-
the cooling is effected with a cooling medium the gungstemperatur der Aufschluftiosung, zugesetzt
temperature of which is 2—6°C lower than the wird.
saturation temperature of the digestion liquor to 6. Verfahren nach einem der Anspruche 1—5,
be cooled and, when the concentration of crystals dadurch gekennzeichnet, daft die Kiihlung in
in the digestion liquor is more than about 20%, 35 einer Vielzahl von Kuhlstufen durchgefuhrt und in
the cooling is effected with a cooling medium the jeder Kuhlstufe ein Kiihlmedium mit einer kon-
temperature of which is 5— 15°C lower than the stanten Temperatur verwendet wird, die niedriger
saturation temperature of the digestion liquor to ist als die Temperatur des in der vorhergehenden
be cooled. Kuhlstufe verwendeten Kuhlmediums.
40 7. Verfahren nach einem der Anspruche 1—5,
Patentanspriiche dadurch gekennzeichnet, daft die Temperatur des
verwendeten Kuhlmediums kontinuierlich
1. Verfahren zur Abtrennung von Calciumnitrat- gesenkt wird.
Tetrahydrat durch Kristallisation aus einer beim 8. Verfahren nach einem der Anspruche 1—7,
Aufschluft von Phosphatgestein mit Salpeter- 45 dadurch gekennzeichnet, daft die Kuhlung,
saure erhaltenen Losung, wobei die Kristallisation solange die Konzentration der Calciumnitrat-
durch absatzweises Kiihlen der Losung erfolgt Tetrahydratkristalle in der Aufschluftlosung nicht
und am Beginn des Kiihvorganges Calcium nitrat- etwa 20% betragt, mit einem Kuhlmedium durch-
Tetrahydrat-Keimmaterial mit einer Teilchen- gefuhrt wird, dessen Temperatur um 2—6°C nied-
grofte von weniger als 100 um zur Aufschluftlo- 50 riger ist als die Sattigungstemperatur der zu
sung bei einer Temperatur der Aufschluftlosung, kuhlenden Aufschluftlosung, und die Kuhlung,
die 0,1 —2°C niedriger ist als die Sattigungs- wenn die Konzentration der Kristalle in der Auf-
temperatur der AufschluBlosung, zugesetzt wird, schluftlosung hoher ist als etwa 20%, mit einem
dadurch gekennzeichnet, daft das Calciumnitrat- Kuhlmedium durchgefuhrt wird, dessen Tempe-
Tetrahydrat-Keimmaterial in einer Menge von 55 ratur um 5— 15°C niedriger ist als die Sattigungs-
50.000 bis 200.000 Keimkristallen pro kg der zu temperatur der zu kuhlenden Aufschluftlosung.
kuhlenden Aufschluftlosung zugesetzt und die
Aufschluftldsung sodann mittels eines Kuhlme- Revendications
diums weiter abgekuhlt wird, wobei die Kuhlung,
solange die Konzentration der Calciumnitrat- 60 1. Procede pour separer le nitrate de calcium
Tetrahydratkristalle in der AufschluBlosung tetrahydrate par cristallisation a partir d'une
wenigter als etwa 20% betragt, mit einem Kuhl- liqueur obtenue en digerant de la roche phospha-
medium durchgefuhrt wird, dessen Temperatur tee avec de I'acide nitrique, la cristallisation etant
hoher ist als die Kernbildungstemperatur der mit @ effectuee au pours d'un refroidissement discon-
dem Kuhlmedium zu kuhlenden AufschlulSlo- 65 tinu de la liqueur, dans lequel, au deut du proces-
 13 0 122 646 14
sus de refroidissement, on ajoute de la matiere qu'on utilise la liqueur obtenue, contenant des
d'ensemencement de nitrate de calcium tetrahy- noyaux ayant une taille particulaire de 25—30 um,
drate ayant une taille particulaire inferieure a 100 comme matiere d'ensemencement.
|im a cette liqueur de digestion a une temperature 4. Procede selon I'une des revendications 2 ou
de la liqueur de digestion qui est inferieure de 0,1 3, caracterise en ce qu'on utilise de 0,05 a 0,2 ml
a 2°C a la temperature de saturation de la liqueur de la liqueur de digestion contenant des noyaux
de digestion, procede caracterise en ce que I'on par kg de liqueur de digestion a refroidir.
ajoute le materiau d'ensemencement de nitrate 5. Procede selon I'une quelconque des revendi-
de calcium tetrahydrate en une quantite de 50.000 cations 1—4, caracterise en ce qu'on ajoute la
a 200.000 cristaux d'ensemencement par kg de 10 matiere d'ensemencement a la liqueur de diges-
liqueur de digestion a refroidir, la liqueur de tion a refroidir a une temperature inferieure de 0,2
digestion etant ulterieurement encore refroidie au a 1,0°C a la temperature de saturation de la
moyen d'un milieu de refroidissement ettant que liqueur de digestion.
la concentration de cristaux de nitrate de calcium 6. Procede selon I'une quelconque des revendi-
tetrahydrate dans la liqueur de digestion ne 15 cations 1—5, caracterise en ce qu'on conduit le
s'eleve pas a environ 20%, on conduit le refroidis- refroidissement en plusieurs etapes de refroidis-
sement avec un milieu de refroidissement ayant sement et que, dans chaque etape, on utilise un
une temperature superieure a la temperature de milieu de refroidissement ayant une temperature
nucleation de la liqueur de digestion a refroidir constante, qui est inferieure a la temperature du
avec le milieu de refroidissement et en ce que, 20 milieu de refroidissement dans I'etape prece-
lorsque la concentration de cristaux dans la dente.
liqueur de digestion est superieure a environ 7. Procede selon I'une quelconque des revendi-
20%, le refroidissement s'effectue avec un milieu cations 1—6, caracterise en ce qu'on abaisse
de refroidissement ayant une temperautre infe- continuellement la temperature du milieu de
rieure a la temperature de nucleation de la liqueur 25 refroidissement utilise.
de digestion a refroidir avec le milieu de refroidis- 8. Procede selon I'une quelconque des revendi-
sement e le nitrate de calcium tetrahydrate se cations 1—7, caracterise en ce que, tant que la
separant par cristailisation dans ce procede etant concentration de cristaux de nitrate de calcium
separe de la liqueur de digestion refroidie. tetrahydrate dans la liqueur de digestion ne
2. Procede selon la revendication 1, caracterise 30 s'eleve pas a environ 20%, le refroidissement
en ce que la matiere d'ensemencement utilisee se s'effectue avec un milieu de refroidissement dont
compose de fins noyaux obtenus en ajoutant une la temperature est inferieure de 2 a 6°C a la
matiere solide contenant du nitrate de calcium a temperature de saturation de la liqueur de diges-
une liqueur de digestion surfondue contenant du tion a refroidir et en ce que, lorsque la concentra-
nitrate de calcium. 35 tion de cristaux dans la liqueur de digestion est
3. Procede selon la revendication 2, caracterise superieure a environ 20%, le refroidissement
en ce qu'on ajoute la matiere solide contenant du dont la temperature est inferieure de 5 a 15°C a la
nitrate de calcium a une liqueur de digestion temperature de saturation de la liqueur de diges-
surfondue a une temperature de 18—22°Cetence tion a refroidir.
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