DSM 15

CRO
KMO 5 april 1985

Development of a 'clean' phosphoric acid process

Author: K. Weterings, Central Laboratory DSM, Geleen, The Netherlands

Summary

The current 'wet' phosphoric acid processes are based on the digestion of
phosphate rock with sulphuric acid. Disadvantages of these processes are that
usually concentrated.phosporic acid can be obtained only by evaporation, and
that the phosphoric acid and the by-product, gypsum, are contaminated.with,Ra,
As, Cd and other heavy metals.
To avoid these drawbacks, a new process with a so-called pre-digestion route
has been proposed. In this process, the phosphate rock is first digested with
phosphoric acid, in this phase radium can be precipitated. Next, A s , Cd and
possibly other heavy metals are separated out, and only then Ca is removed
with sulphuric acid. During a gypsum colloquium in 1982, organized by the
14inistry for Physical Planning, and Environment of the Netherlands, DSM
pointed out that this is the only way to obtain both clean phosphoric acid and
clean gypsum. In September 1982, a government-sponsored-project for the deve-
lopment of this process on laboratory scale was started, with agreement from
the other producers of phosphate fertilizers.
The project is carried out by three doctoral candidates, under the respon-
sibility and supervision of UKF and DSM. The work on Cd-removal concentrates
on binding Cd to an immobilized organic complex, but other methods are also
.
invest igat ed
With regard to the removal of Ca, the final step in the production of
phosphoric acid, attention focusses on crystallization of a clean calcium-
sulphate-hemihydrate, that is, a hemihydrate containing the smallest possible
amount of co-crystallized phosphate. In this report, the several aspects of
the new phosphoric acid process will be discussed in detail, and particular
attention is paid to hemihydrate crystallization. The destiny of the clean -
hemihydrate can be further processing or, now that it is Cd-free, disposal as
a waste product.

Table of contents

1. Introduction

2. Reasons for a clean phosphoric acid process

3 . How to obtain clean gypsum

4 . Dissolution of phosphate in phosphoric acid: pre-digestion

5 . Purification

6 . Hemihydrate crystallization

7. Literature
,

1. Introductionl,
Phosphoric acid is an important chemical intermediate, which is used mainly in
the fertilizer industry.
Phosphate-containing fertilizers are produced from calcium phosphate rock.
The rock usually is converted first to phosphoric acid, because in this way
readily soluble fertilizers with a high nutrient content can be obtained. Glo-
bal phosphoric acid production i s directly related to the steadily growing
demand for phosphate fertilizers, to meet the food needs of increasing world
population. Phosphoric acid is produced either by the wet process or by the
electric furnace process. In the electric furnace process, phosphate rock is
reduced, with the aid of coke, in an electric furnace.
Si02 (gravel) is added to bind the CaO released to form CaSi03. The overall
reaction is given by

1500 OC
2 Ca3(P04)2 +6 Si02 + 10 C -
-) P4 + 6 (CaO, SiO2) + 10 CaO (OH = +730 kcal)

In this reaction scheme, the presence of other impurities (F, Cog) is ignored.
Since virtually all of the impurities in the rock remain behind in the by-
product (calcium silicate slags and a ferrophosphorus alloy), the electric
furnace process yields a very pure product acid, which is used in detergents
and as nutrient phosphate.
The energy demand of the electric furnace process however is enormous.
Therefore, the world demand for phosphoric acid for use in the fertilizer
industry is met by wet-process phosphoric acid plant; the impurities in the
phosphoric acid are usually not detrimental and may even be essential as
micronutrients and for granulating the fertilizers. Total wet-process
lo6 tonnes (World-1983),. In
phosphoric acid production is enormous: ca. 32
the Netherlands, the output is 0.6 .
106 tonnes. These quantities are
expressed as 100 X H3PO4. Conversion of phosphate rock to phosphoric acid
usually takes place by reaction of the rock with sulphuric acid; calcium pre-
cipitates as calcium-sulphate-hydrate, Cas04 2 H20 or Cas04 .
35. H20, which
is subsequently filtered off.

Figure 1: Schematic representation of the production of phosphoric acid and

gypsum (DH) from phosphate rock and sulphuric-acid according to the classical
dihydrate (DH) process.

H3P04
/* evapors- acid - 0.58
- / / t ion e
/
52 Z T205
b
+ DH/
. /
c

75-80 "C
[Ca3(P04)2]3.CaF2 + 10 H2SO4 ____* 6 H3PO4 -I- 10 Cas04 2 H20 J. + 2 HF 3.
water
 0

Most of the wet-process phosphoric acid produced in the world is obtained by

the classical DH-process. Drawbacks of this process are:
- the gypsum (DH) contains lattice P2O5, causing a low phosphate efficiency.
The gypsum is not suitable for the building industry and cannot be used as a
cement retarder.

- the gypsum as well a1 the phosphoric acid contain Ra, As, Cd and other heavy
metals.

- In the first instance, a dilute acid is obtained ( ca. 30 % P2O5). Con-

centrated acid (ca. 52 % PzO5) is obtained by evaporation. -

In the fertilizer industry, the concentration of phosphoric acid is usually

expressed in % P2O5. To obtaind the H3PO4 concentration, this figure should be
multiplied by 1.38. Thus, a P2O5 concentration of 30 % is equivalent to ca. 41
X H3PO4 and 52 % P2O5 to ca. 72 % H3PO4.
A separate gypsum purification step *in the current DH-processes (and in
HH-DH-processes) is perhaps technically feasible, but not economically.
Moreover, the phosphoric acid produced would stil contain Ra and Cd, and it
would still have to be concentrated by evaporation.
The so-called phosphogypsum can, in principle, be used instead of mineral gyp-
sum in the building industry, after urification. In spite of this ca. 90 % of
the phosphogypsum produced (115 %
10 tonnes, world, 1983) is disposed off
into rivers or seas or impounded on land, world gypsum consumption being
96 .
106 tonnes.
Phosphogypsum can hardly compete with mineral gypsum3), since it comes
available as a contaminated aqueous slurry, requiring extra purification and
drying operations.
Gypsum obtained in the DH-process contains too much co-crystallized P2O5, and
the slight radioactivity of phosphogypsum is a major reason for not using it
in the building,industry. No applications have been found for Dutch phospho-
gypsum. The quantity of phosphogypsum produced in the Netherlands (ca.
2,4 .
lo6 tonnes/yrb is much greater than the quantity of mineral gypsum con-
sumed (ca. 0.7 .
10 tonnesjyr).

phosphate-1 ~ sulphuric acid41 '+ water wash water

H3P04 /
/
evapo ra-
acid - 0.58
,HH -WDH . /
t ion *
-,+ HH 1 *
/
1 complex
5 2 27 P205

50 B 60 "C
10 Cas04 .f H20 I 10 Cas04 2 H20
H2S04/H3POq/water
 -4-

A higher phosphate efficiency, and a dihydrate suitable f o r building products

and as a cement retarder, is obtained by modifying the classical DH-process
into a HH-DH process (e.g. the Nissan I phosphoric acid plant of UKF in
Pernis, the Netherlands). In this process, the calcium sulphate lattice is
recrystallized from hemihydrate to dihydrate (DH) or the other way around; in
this way, co-crystallized phosphate is largely removed, but radium and other
heavy metals remain present in virtually the samen quantities.

-
2 . Reasons for a clean phosphoric acid process4)

In the production of phosphoric acid, the impurities originally present in the

phosphate rock will be distributed between the phosphoric acid and the gypsum
as indicated in Table 1. The distribution slightly varies with the process
used; Table I reflects the situation at the UKF plant in Pernis, the
Netherlands.

Tabel 1. Average composition of sedimentary phosphate, phosphori'c acid and

phosphogypsum

Sedimentary Phosphoric Phosphogypsum

phosphate -
acid
__
~ 2 0 5 ' wt. % 32 52 (HH-DH) : 0.4;l.O (DH)
F wt. % 4 1.2 1 .o
si02 wt. % 3 .O 0.6 1.1
org. C. wt. % 0.30 0.12 0.15
V-PPm 240 290 ca. 20
Cr-ppm 170 310 5
U-PPm 120 170 5
Ra-10'6 ppm 38 2 - 3 22
As PPm 20 18 3
Cu ppm 33 47 4
Pb PPm 10 2 4
Cd PPm 8-100 (28)* 12-130 (36)* 1-15 (2 - 3 ) *
Mg PPm 0.1-0.5 0.1-0.3 4;0.1-0.3

* UKF-Pernis

The table shows that phosphogypsum is slightly contaminated with heavy metals
(ppm-level). In Western Europe there are international skeletal agreements __
aiming at progressive reduction of gypsum dumping.
Since 1975, the Dutch National Working Party on Phosphogypsum, in which the
. governement and the phosphate fertilizer industry are represented, has been ~

working on the problem. It has become clear that, in terms of environmental

hygiene and economics, fill utilization of the available phosphate gypsum is
hardly feasible.
This holds especially for the current, Ra- and Cd-containing, gypsum.
Recentiy, severai phosphoric acid plants have been built which involve a
direct route to strong acid by modified conditions (no sulphuric-acid
,

dilution; higher temperature). These are the so-called HH-processes (e.g.

Fisons) and the HH-DH-process with intermediate filtration of HH followed by
HH- td DH-recrystallization (Nissan 11). These processes are more
energy-efficient. The drawbacks that remain are a low phosphate efficiency
because of incorporation of P2O5 in the HH (Fisons) and the presence of
impurities in the HH or DH and in the phosphoric acid (Fisons, Nissan 11).

Figure 3. Schematic representation of the HH-process (Fisons-process)

phosphate-1 96 Z sulphuric acid-1 wash water

I J I. hemihydrate 1.3
1 T;: lattice P205
/
4

H3P0 /
- 0

HH 1, /
/

product acid
-
'
. return acid -c
ca. 42 ,"d P205

Figure 4. Schematic representation of the HH-DH-process (Nissan 11)

96 Z sulphu- 0.25 X lattice P205

phosphate-] riC acid-1
wash water

- H3P04
+ HH /
-
0
/
/
0
HH - DH
-
- ,
/
/
/
/

L A /

ca. 100 "C

[Ca3(P04)2]3 e CaF2 + 10 H2SO46- H3PO4 + 10 Cas04 e f H20 + + 2 HF .t
less water -
than with DH
and Nissan I
 -b-

The newly proposed, clean phosphoric acid process, which is yet to be

developed, aims at producing clean phosphoric acid and gypsum free from heavy
metals and P2O5, so that disposal and/or further processing of the gypsum is
less of a problem.

3 . How to obtain clean gypsum4)

In principle, there are three ways to obiain clean gypsum, possibly in com-
bination with clean'phosphoric acid:
- using clean phosphate rock;
- gypsum purification
- a clean phosphoric acid process.

Almost all phosphate rocks are sedimentary deposits. Igneous rocks are much
purer, especially with regard to heavy metals (Cd 8 ppm; Ra 1-2.10'6 ppm).
However, their lead content is the same or higher. The world reserves of
igneous rock are very limited, so that the use of igneous phosphate as raw
material is no solution of the purity problem.

As pointed out in Chapter 2 , much research has been done, on an international

scale, on methods torpurify phosphogypsum by re-crystallization during the
manufacture of phosphoric acid, to obtain a grade suitable for use as a
building material and as a cement retarder. However, this does not solve the
problem of gypsum contaminated with Ra, As and heavy metals. A separate gypsum
purification is not economically feasible, while in addition the phosphoric
acid produced still contains Cd.

In current phosphoric acid processes, phosphate rock is directly digested with

H2SO4. In the first reactor, the gypsum or HH will precipitate, and many
impurities will co-crystallize. Up to now a considerable reduction of these
impurities by re-crystallization during the process has been found t o be
impossible, except for P20.j.
This problem can be solved by a process with a pre-digestion step in which
Cas04 precipitation is preceded by digestion of the phosphate rock with
phosphoric acid.
Figure 5. Schematic representation of the pre-digestion route

phosphate rock-l sulphuric acid- 1 wash water

7

product acid -
pre-
diges-
purif i-
cation
HH-
precipi- L /
- 9.64
L-
/
t ion tation / 47 % P*05
I ,/ / -

I
impurities
I I I 11

After the pre-digestion step, during which special measures are taken to pre-
cipitate radium, first As, Cd and possibly other heavy metals are removed;
after this Ca is removed by HH-precipitation with H2SO4:
- Pre-digestion:
[Ca3(P04)2]3 .
CaF2 + excessive amount of phosphoric acid + Ca(H2P04)~ in
phosphoric acid.
- Purification: measures for removal of undes€rable elements. Possibly,
measures are taken to prevent incorporation of Cd in HH. In that case, only
the product acid still needs to be purified.
- Calcium sulphate precipitation:
2 Ca(H~P04)2 + 2 H2SO4 + H20 -+ 2 Cas04 . +
f H20 + 4 H3PO4.
Since the current phosphoric acid processes (e.&, UKF Pernis) involve a high
energy cost for evaporation of product acid (30 X P2O5) to concentrated
phosphoric acid (52 % P2O5>, the variable production costst of phosphoric acid
production according to the pre-digestion route, in which concentrated acid is
obtained directly, may well be lower than the variable costs of current
-
processes, so that production of clean phosphoric acid and gypsum according td
the pre-digestion route may be possible at not too high additional costs.
In cooperation with DSM and UKF, the Delft Institute of Technology has been
doing exploratory work on pre-digestion and on removal of Ra and heavy metals.
In particular, the precipitation of Cd as a Cd complex has been studied.
During a gypsum colloquium in March 1982, which was organized by the then
Mihistry of Health and Environment of the Netherlands, DSM pointed out that
production of clean phosphoric acid and clean gypsum required new technology,
and in September 1982 a government-sponsored development project was started
at the Delft Institute of Technology, with agreement from the Dutch Phosphate
Fertilizer Industry and under the responsibility and supervision of UKF and
DSM, Since late 1983 early 1984 and early 1985 three doctoral candidates are
working on the project.

4. Dissolution of phosphate in phosphoric acid: pre-digestion

When phosphate rock is digested with phosphoric acid, unwanted impurities in
the phosphate rock, such as Fe, A I and Si, dissolve to a lesser extent than
with digestion by sulphuric acid. undissolved impurities can be removed as
inerts after digestion.
.
Phosphate rock contains about 5 0 % CaO, whereas only 3 - 5 . 5 % CaO dissolves in
phosphoric acid, depending on temperature ( 8 0 - 1 2 0 " C ) and phosphoric-acid con-
centration ( 4 2 - 4 7 % PzO5). Therefore, very large recycle streams are
necessary, compared with the current processes (see Figure 5 ) . This disadvan-
tage is offset by the fact that the dissolution of phosphate, in the presence
of free H2SO4, can be a fast reaction and also because the evaporation step is
largely or totally dispensed with.
-
At a high phosphoric acid concentration ( 4 7 % P 2 O 5 ) , the maximum percentage of
CaO (5.6 %) dissolves only at high temperatures ( 1 2 0 "C), as indicated in
Figure 6 .
At low temperatures, a high percentage of CaO can dissolve ( 5 . 7 X), but then -
the phosphoric acid concentration should be much lower. In order to have
favourable laboratory operating conditions, it was decided to use a digestion
temperature of ca. 90 "C, at which temperature about 3 . 5 % CaO dissolves.
The phosphoric acid concentration being 47 % P2O5.

Figure 6 . The relation between the phosphoric acid concentration and the tem-
perature at which the maximum percentage of CaO dissolves

% P O 2./
5.5

2t5 47 % P,O,

/-120 I o (y boiling
point)

dissolved CaO
/
constant at about 5 . 7 0

lo 1I
0
I

20
1

40
I

60
I

80 100
I I

120
I

140
I

160
-t
__
Temp. in OC

The dissolution of phosphate in phosphoric acid and the precipitation of hemi-

hydrate from the solution constitute an essential element of the new ~

phosphoric acid technology which is being developed. If too many sulphate ions
are present in the recycled acid, precipitation of calcium sulphate on the
surface of the phosphate rock particles may present a major problem, because
the resultant impermeable coating around the particles blocks further
digestion. This problem may also arise in current processes with also a large
amount of HH already being produced in the predigestion step. When the con-
 -7-

centration of sulphate ions increases, the calcium sulphate nucleation front

moves through the liquid film towards the particle surface. When the
sulphuric acid concentration is sufficiently high, the fron will reach the
particle surface, completely blocking the digestion reaction.
Obviously, this should be prevented by keeping the excess amount of
H2SO4 sufficiently low (< 2 %).

5. Purification

---------------
5.1. Ra-removal

In one version of the process (DSM), the pre-digestion of the phosphate with
phosphoric acid (return acid) is combined with simultaneous precipitation of
ca. 10 % of the calcium ions by addition of a suitable quantity of sulphuric
acid to the return acid. By, for example, flocculation, followed by
f.iltration, the fine RaS04 particles are removed together with the hemihydrate*
obtained. Next, after removal of Cd etc., the actual hemihydrate precipiation
step takes place. In another process (Giulini),.BaC03 is added to precipitate
RaS04 *together with Bas04 and hemihydrate:
Ca3(P04)2 + excessive amount of phosphoric acide + very deficient amount of
sulphuric acid + (possibly) BaC03 +
Ca(H2P04)2 in phosphoric acid + Cas04 .
f H20 J. f Ba(Ra)SOq + .
Other methods of removing Ra are being studied by the DelEt Institute of
Technology.

---------------
5.2. Cd-removal

The problem of Cd storage and disposal is least when cadmium and other unde-
sirable elements are removed after the contaminated HH and inerts formed
during digestion have been separated from the monocalcium-sulphate-in-
phosphoric-acid-solution.
In principle, there are many ways to remove Cd, for example precipitation, ion
exchange, absorption, adsorption, electrodialysis etc. Some methods are not
economically feasible, e.g. extraction. Others are chemically or technically
impossible (zeolites cannot be used for example, because of the pH of the
solution and the presence of Ca in the digestion liquor). In practice, the
choice of Cd-removal method is restricted to (co)-precipitation, adsorption
(whether or not preceded by precipitation) and ion exchange. The most obvious
technique, precipitation as CdS (with Na2S or H2S), will result in the for-
mation of colloidally dispersed CdS due to the small quantities involved,
while H2S will inevitably also be formed, which is undesirable. H2S formation
is also a drawback of co-precipitation of CdS with, for example, CuS or MCP.
A possibility which has been researched extensively, is precipitation of Cd as
a Cd-complex. For this purpose a selection was made out of. organic
S-compounds. A problem is the stability demands under the prevailing con-
ditions (95 "C, 47 % P2O5).
The indicated stability demands are important as well in the method of
ion-exchange. -
Next to the above-mentioned methods, studies are in progress to prevent Cd-
incorporation in HH. In that case, only the product acid still needs to be
purified, which, because-of the smaller quantity to be treated and the
possibly l e a s stringent c o n d i t i o n s , could offer an attractive alternative.
 -1u-

6 . Hemihydrate crystallization5)

After pre-digestion, inerts filtration and specific procedures for either

removal of undesirable elements or for prevention of incorporation of such
elements in HH, actual phosphoric-acid production takes place by Ca-
precipitation as hemihydrate, the Cas04 modification stable at the prevailing
temperature and phosphoric acid concentration. The current status of the work
on continuous HH-crystallization is represented by the schematic diagram of
the continuous laboratory set-up below (Figure 7 ) .
-
Figure 7. Continuous HH-precipitation by combination of the digestion liquor
and the H2SOq/H3P04 mixture

a
digestion liquor
this s t e p may be
3.2 % CaO; 45 X P 3 0 5
4.”
left 01 It I

H3P0 (45-47 %>

P,O,

1
I d

with 17 2 H2S04
7 - 7 b

. O X -H b
-1 % H, 0

1 product a$d lhemihydrate

The amount of free H2SO4 to be applied is arbitrary, except in the final

. crystallizer.
In order to achieve a high P2O5 efficiency, but also to make the gypsum
suitable for building applications or to facilitate disposal of the gypsum, it
is essential that the phosphate content of the gypsum is as low as possible.
Phosphate is mainly present in the gypsum as lattice P2O5, which- is phosphate
incorporated in the Cas04 crystal lattice by replacement of SO4- ions by
HPO4= ions. This can hardly be prevented: Cas04 and CaHP04 have the same
crystal structure, with the same unit cell dimensions.
.
The substitution results in a solid solution of Cas04 nH20 and CaHP04 nH20. .
The undesirable substitution is promoted by a high phosphate concentration,
and by an increased viscosity, which slows down the reaction to CaSOq-hydrate
by diffusi‘on inhibition. The substitution is reduced by a temperature
increase, which results in a lower viscosity, and by an excess of free H2SO4,
so-that more protons are available to desolvate the phosphate-ligand of
__
Ca2+ and more Cas04 and hence less Ca-phosphate is present.
Note: by free H2SO4 is meant the amount of sulphuric acid which is con-
tinuously present in excess of the stoichiometric amount of Ca* and SO4= ions
required for precipitation of CaSOq-hydrate. There are limits to the amount of __
free H2SO4 that can be applied, in connection with undesirable secondary
nucleation (see below).
The calcium sulphate precipitate should meet the following requirements:
- it should be easy to filter, i.e. the crystals should be large and not t o o
reguiar (no dendrites!);
- it should be easy to wash, i.e. the crystals should be firm and smooth;
 --

- the crystals should be maximally pure.

A compromise must be struck between the first two requirements.

Also in HH-crystallization, the sulphate-ion concentration plays a dominant

role.
When this concentration is-high, the rate of secondary nucleation is also
high, resulting in a very large amount of small crystals and in defects and
dislocations, because of the high degree of supersaturation.
The extent to which the sulphate-ion concentration deviates Erom the
stoichiometric concentration greatly influences the shape and dimensions of
the CaSOq-hydrate crystals formed, especially in industrial crystallizers (in
a medium of pure monocalciumphosphate and H2SO4 this influence is much
smaller) :
1) a large excess of free sulphuric acid:
long thin needles; readily filterable but less readily washable.

2) a moderate excess of sulphuric acid:

larger crystals, in the shape of short, thick needles, which are readily
filterable and washable.

3) a small excess or even a deficiency of sulphuric acid:

relatively small crystals.

Besides S0q'-ions, impurities also have a large influence. In view of the poor
solubility of a salt like hemihydrate, there should be sufficient crystal sur-
face area (more than 10 wt % crystals present).
In order for the crystals to be maximally pure, they should not grow too East;
otherwise, co-precipitation and inclusion of impurities are likely to occur.
Phosphate losses, by imperfect digestion do not occur in the pre-digestion
route. Phosphate losses by inclusion of phosphoric acid and lattice P2O5, can
be prevented by quick levelling of-local high calcium sulphate supersaturation
in the medium and a well-controlled, slow crystallization of the HH, that i s ,
an optimum concentration of free SOq2' at a constant Ca-supply. At a par-
ticular percentage of free acid, high supply rat-es of monocalcium phosphate
solution and, hence, of H2SOq/phosphoric acid mixture, which are both factors
determ-ining the degree of supersaturation, always yield higher amounts of lat-
tice P2O5 than low supply rates'). Further, at a particular supply rate the
amount of lattice P2O5 first decreases, as the concentration of free acid
increases from 1 X to about 2.2 % but then increases. The minimum is about
0.35 % lattice P2O5 (relative to DH) at a phosphate rock throughput of 100
kg/hr.m3.

In the classical DH-process and its process variations (e.g. HH .+ DH and HH),

the percentage of lattice P2O5 keeps decreasing as the concentration of free

sulphuric acid increases (see Fig. 8). In the pre-digestion route, however,
there is an optimum in the concentration of free acid. The initial decrease in
the inclusion of lattice P2O5 with increasing sulphuric-acid concentration has
the same explanation as in the classical DH process: more protons are
available to desolve phosphate ligand, and more Cas04 is present than
Ca-phosphate.
9

Figure 8. Lattice P2O5 in DH (classical route) and HH (pre-digestion) as a

function of the concentration of free sulphuric acid

Z lattice P 0 I
2 5
(calculated re- I
lative to DH) I

1 e is present

k 250 pre-digestion
* 100
(47 2 '205)

classical DH-proces
(30 Z P205)
1 I I I a
-1 0 1 2 3 4

Z free H2S04

3
Phosphate-rock throughput in kg/m .hr

The'increase in the concentration of lattice P2O5 in the predigestion route ~

which occurs at free sulphuric acid concentrations of more than about 2.2 % is
probably due to the fact that HH is instantaneously formed from Ca2+ and
S042', whereas in the classical phosphate digestion with H2S04, HH and DH are
formed from S042' and phosphate rock. Furthermore if the concentration of
free sulphuric acid becomes too high, the increased degree of.secondary
nucleation that may result from this will cause the amount of phosphate
' included in crystals to increase.
As indicated in Figure 7 , first HH is precipitated to yield a free-sulphuric-
acid concentration of 2 %.The excess sulphuric acid is compensated in the
second crystallizer. Fig. 9 below shows that at 0 % H2SO4 much HH i s dissolved
in the phosphoric acid. If this phosphoric acid is used for dissolving __
(digesting) the phosphate rock, a large amount of Ca-ions will be returned
together with the phosphoric acid, so that during pre-digestion the dissolved
HH will crystallize (again see Fig. 9). This can be prevented by adding mono-
calciumphosphate to the return acid in a third crystallizer, for example until -
the free-sulphuric-acid conentration is -1 %, so that most of the HH will
crystallize there.
Figure 9. The solubility of hemihydrate, as % CaS04, as a function of the
percentage of free S042', at 90 "C and 45 % P2O5

1 .o
0.94.
7, CaS04 \

-3 -2 -1 1 2 3

.
? * 0

7. Literature
1. Fertilizer Science and Technology series
Volume I, part I and 11, Phosphoric acid
edited by A.V. Slack; Marcel Delcker inc., New York-1968

2. Fertilizer Science and Technology series

Volume 111, Phosphates and phosphoric acid
Pierre Becker, Marcel Dekker inc., New York and Basel-1983

3. K. Weterings
Verwerking van afvalgips uit de fosforzuurbereiding (phosphogypsum processing)
PT-procestechniek -
35, 1980, no. 2, pp. 79 - 86
Chemisch Magazine, April 1980, M 233 and 234.

4. K. Weterings
The Utilisation of phosphogypsum
The Fertilizer Society, Londen 21110182, Proceedings no. 208

5. M. Jansen, A. Waller, J. Verbiest, R.C. van Landschoot, G.M. v. Rosmalen

Incorporation of phosphoric acid in calciumsulphate-hemihydrate crystallized
from a monocalciumphosphate solution.
9th symposium om Industrial Crystallization, 25-28 Sept. 1984
Process Technology, Proceedings 2, Elsevier, dated by S.J. Jancic and E.J. de
Jong, pg. 171-176. .

6 . S . E . Dahlgren
Physico-chemical aspects of phosphoric acid by-produced calciumsulphate as a
raw material.
Chemie-1ng.-Techn. MS 104174.

7. A . B . Amin and M.A. Larson

i & EC, Process Design and Development 7, 1968, 135.