Crystal Habit Modifiers for Enhanced Filtration of Phosphogypsum

H. El-Shall, E.A. Abdel-Aal and B. Moudgil

Engineering Research Center for Particle Science & Technology
Dept. of Materials Science and Engineering
University of Florida

Prepared for Presentation at

AIChE Clearwater Convention, 1998

Central Florida Section

 H. El-Shall, E.A. Abdel-Aal and B. Moudgil

April, 1998

AIChE shall not be responsible for statements or opinions contained in papers or printed in its
publications
ABSTRACT

Filtration of phosphogypsum is an important unit operation in wet-process phosphoric acid

production. Phosphate mining in Florida is moving towards the Southern region where the
rock is of less quality and higher MgO content. Filtration rates of Phosphogypsum obtained
from such rock are lower than that obtained from Central Florida region. Therefore, cost
effective improvement in filtration rate is desirable by all phosphoric acid producers in general,
and Florida’s phosphate industry in particular.

In this study, an anionic surfactant has been tested as crystal modifier for phosphogypsum
during production of phosphoric acid using phosphate concentrate from South Florida at
different sulfate contents. The improvement in filtration rate was up to 31%. In addition, the
reaction efficiency was higher by 2.1% to 3.9% and the overall P2O5 recovery was also higher
by 0.5% to 1.6% in the presence of surfactant.

Observed effects are correlated with crystal morphology and crystal size distribution. Best
results are obtained when the crystals from clusters and of narrow size distribution. Effect of
surfactant on filtration rate, P2O5 recovery, cake moisture content, and both digestion and
washing efficiencies are determined. Also, correlations between crystal size distribution and
filtration rate are presented in this paper.

2
INTRODUCTION

The purpose of filtration in wet-process phosphoric acid production is to separate the acid
from the phosphogypsum cake. Good crystallization quality of phosphogypsum leads to
higher filtration rate. The crystallization quality depends on crystal size, size distribution and
morphology of the crystals.

There is no published data about industrial crystallization of phosphogypsum using surfactants.

The available data in literature is about nucleation and crystal growth of gypsum from pure
chemicals (1-4). Also, the influence of different inhibitors on the growth rate of calcium sulfate
dihydrate crystals was reviewed (5-8). In addition, many papers are published explaining effect
of additives and impurities on crystallization of calcium sulfate (9-14). There are numerous
reports about improving the filtration rate using polymers(15-25). On the other hand, reports
dealing with effect of surfactants on filtration of phosphogypsum are limited (26-28). Even in
these studies, crystallization of calcium sulfate dihydrate from pure chemicals is reported. For
instance, Kopyleva et al.(28) tested addition of 1-2% aqueous surfactant solution to the slurry
before filtration and found that the specific cake resistance was decreased by 35-40% and the
filtration rate was increased by 1.5 - 2.3 times as well as decreasing of washing time by factor
of 1.2 - 1.7.

The main objective of this study is to test effect of a nonionic surfactant on the filtration rate
of phosphogypsum as well as the reaction efficiency and P2O5 recovery. To achieve this goal, a
high dolomitic phosphate concentrate is tested for phosphoric acid production with and
without surfactant at different (low, medium, high) sulfate contents. Due to high impurities
content in this concentrate, its filtration rate is relatively low. For testing the concentrate, the
conventional Dihydrate process conditions were simulated (24,25,29,30) and material balance
program was applied (30) for calculations of reactants feeding rates. The wash water was
calculated using this program and according to the water balance of the whole process. Size
distribution of the produced gypsum crystals was determined to know effect of surfactant on
the crystals growth at different sulfate levels and different time intervals.

EXPERIMENTAL

A. Materials Characterization

The phosphate concentrate sample is provided by IMC-Agrico Company. Chemical and sieve
analyses of this sample are given in Tables (1 and 2). Table (1) shows that the phosphate
concentrate contains high content of MgO (1.58%). MgO increases the acid viscosity and
consequently decreases the filtration rate. The accepted industrially limit of MgO in
commercial phosphate concentrates is less than 1.0%.

Table (2) shows the sieve analysis of the sample. It contains 51.8 % -100 mesh and 29.7 % -
200 mesh, which are required for the Dihydrate process. Most of the particle size of the
concentrate (80.5%) ranges between 44-295 Fm.

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The sulfuric acid used is pure 95.5% acid and has 1.835 g/ml specific gravity. The recycle
(return) acid is accumulated while carrying out the tests. It is adjusted to the required P2O5
content and recycled. The surfactant used is Crysmod (nonionic surfactant).

Table (1)
Chemical Analysis of High Dolomitic
Phosphate Concentrate Sample

Constituent % Constituent %
P2O5 27.22 Al2O3 0.95
CaO 42.79 Na2O 0.73
MgO 1.58 K2O 0.12
Fe2O3 1.56 Insolubles 8.05

Table (2)
Sieve Analysis of High Dolomitic
Phosphate Concentrate Sample

Particle size Cumulative wt. %

Mesh* Inch Mm
-10 0.0650 1.651 100
-48 0.0116 0.295 87.5
-65 0.0082 0.208 68.1
-100 0.0058 0.147 51.8
-150 0.0041 0.104 40.1
-200 0.0029 0.074 29.7
-270 0.0021 0.053 18.6
-325 0.0017 0.044 7.0
* Tylor standard

B. Apparatus

The reaction was carried out in 1L reactor fitted with stirrer and placed in water bath adjusted
at 80 oC. The phosphate concentrate was added continuously using a vibrating rock feeder,
whereas the sulfuric acid was added continuously by using the peristaltic pump with Viton
tubing. The surfactant suspension was added continuously by using a small graduated
separating funnel. The filtration was performed by using the Buchner type filter of 4.6 inch
diameter. The filter cloth used was polypropylene which has 80 mesh opening size. The
vacuum pump was used to give the required vacuum (20 inch. Hg). A laser diffraction
analyzer was used to determine the size distribution of produced phosphogypsum crystals.

C. Procedure

For the first test (start-up), the required amount of recycle acid (about 18% P2O5) was
prepared by double-stage acidulation. The first stage with sulfuric acid and water and the
second stage with sulfuric acid and phosphoric acid solution (about 10 % P2O5 ) produced

4
from the previous run. For routine tests, add the required amount of the return (recycle) acid
to the reactor. After attaining the required temperature (80 oC), add continuously the
phosphate concentrate, the sulfuric acid and the surfactant suspension for 30 min. Continue
the reaction for another 2.5 hours. Then, filter and wash 3 times with wash liquors (10 and
5% P2O5) and wash water. The temperature of wash liquors is 60 oC.

In industry, the filtration rate is expressed in tons P2O5 produced per square meter per day. So
the same expression was used. The filtration rate was calculated applying the following
equation (24,25,29,30) :

F.R. = SW * SC * F Ton P2O5 /m2.day

T
where,
F.R. : Filtration rate, ton P2O5 /m2.day SW : Slurry weight, g
SC : Solid content, % F : Filtration factor
T : Total time of filtration, washing and drying, sec

During the experiment and after 0.5, 1, 2 and 3 hours from the start-up, take 3ml slurry and
disperse in 100ml methanol. Then sieve using 106Fm sieve and determine the size distribution
of obtained phosphogypsum crystals.

RESULTS AND DISCUSSION

High dolomitic phosphate concentrate is tested for phosphoric acid production with and
without surfactant at different sulfate contents (low, medium, and high). The results of
filtration rates, reaction efficiencies, P2O5 recoveries, washing efficiencies and size distribution
of formed phosphogypsum crystals are obtained at each sulfate level. These results are
considered exploratory data. These results are as follows:

A. Testing of the Concentrate at Low Sulfate Content (1.5-1.8%)

Tests have been carried out, with and without surfactant addition. The amount of applied
surfactant corresponds to 1.5 kg/ton P2O5. The results are given in Table (3&4) and Fig. (1).

The filtration data of the samples at relatively low sulfate contents of about 1.5% and 1.8%
with and without surfactant, respectively are given in Table (3). The obtained filtration rate is
4.24 ton P2O5 /m2.day without surfactant and improved to 5.54 ton P2O5 /m2.day with the
addition of surfactant. This corresponds to about 31% improvement. This is attributed to
modification and growth of produced crystals upon surfactant addition. The size distribution
of gypsum crystals which is given in Table (4) and Fig. (1) show that, the volume percentage
of fine produced gypsum crystals (<10Fm) is decreased to about 31% upon addition of
surfactant while it is about 64% without surfactant.

The obtained reaction efficiencies, P2O5 recoveries and washing efficiencies of the phosphate
concentrate with surfactant compared with the phosphate processed without surfactant
(baseline) are given in Table (3). It is important to note that the reaction efficiency is
increased with the addition of surfactant. This may be attributed to decrease of lattice (co-
crystallized) P2O5 which represents about 60% of the total P2O5 losses (31). Torocheshnikov et

5
al.(32) have stated that, presence of a surfactant led to reduction of P2O5 in the precipitated
calcium sulfate. They have concluded that (32), surfactants do have a definite effect in reducing
the capture of phosphate ions from solution by crystallizing crystals. Also, addition of
surfactant increases the phosphate concentrate solubility and consequently increases reaction
efficiency. Kopyleva (33) has stated that presence of surfactant increase the solubility of calcium
phosphate in thermal and wet-process phosphoric acid of 10-40% P2O5 concentration and at
temperature range of 40-75 oC.

One of the most important factors affecting the filtration rate is gypsum morphology (size and
shape of the crystals). For best filtration and washing, crystals of uniform size are most
desirable. At low sulfate contents, the shape of the crystals is changed from tabular crystals to
clusters by addition of the surfactant.

Table (3)
Filtration and Reaction Data at Low Sulfate Content (1.5-1.8%)

Item Without Surfactant With Surfactant

Filtration rate, 4.24 5.54
ton P2O5 /m2.day
Moisture % 28.4 27.5
Change in filtration rate, % - + 31
Reaction efficiency, % 93.2 97.1
P2O5 recovery, % 92.5 94.1
Washing efficiency, % 99.3 97.0

Table (4)
Comparative Size Analyses of Gypsum Crystals
(At Low Sulfate Content and After 3 hr)

Size, Size, Cum. Volume % Passing Cum. Volume % Passing

µm mesh*
Without Surfactant With Surfactant
106 140 100.00 99.91
90 170 100.00 99.05
75 200 99.99 95.68
63 230 99.82 89.70
53 270 99.15 82.11
45 325 97.93 74.91
38 400 96.21 68.12
10 - 64.28 30.75
* ASTM standards

B. Testing of the Concentrate at Medium Sulfate Content (2.2-2.4%)

Experiments have been performed, in presence and absence of surfactant. The amount of
surfactant corresponds to 1.5 kg/ton P2O5. The data are given in Tables (5 & 6) and Fig. (2).

6
The filtration results of the samples at medium sulfate contents of about 2.2% and 2.4% with
and without surfactant, respectively, are given in Table (5). The obtained filtration rate is 5.13
ton P2O5 /m2.day without surfactant and improved to 6.42 ton P2O5 /m2.day with the addition
of surfactant. This corresponds to about 25% improvement. This is related to the growth of
produced crystals upon surfactant addition and formation of low volume % of fines (<10 Fm).
The size distribution of gypsum crystals which is given in Table (6) and Fig. (2) show that, the
volume percentage of fine produced gypsum crystals (<10 Fm) is decreased to about 10%
upon addition of surfactant while it is about 22% without surfactant.

The obtained reaction efficiencies, P2O5 recoveries and washing efficiencies of the phosphate
concentrate with surfactant compared with the phosphate processed without surfactant
(baseline) are given in Table (5). In this case also, that the reaction efficiency is increased with
the addition of surfactant. This may be attributed, as mentioned above, to decrease of lattice
(co-crystallized) P2O5 losses, which represent the majority of the total P2O5 losses.

Table (5)
Filtration and Reaction Data at Medium Sulfate Content (2.2-2.4%)

Item Without Surfactant With Surfactant

Filtration rate, 5.13 6.42
ton P2O5 /m2.day
Moisture % 28.3 27.8
Change in filtration rate, % - + 25
Reaction efficiency, % 95.8 98.6
P2O5 recovery, % 95.0 96.4
Washing efficiency, % 99.2 97.9

Table (6)
Comparative Size Analyses of Gypsum Crystals
(at medium sulfate content and after 3 hr)

Size, Size, Cum. Volume % Passing Cum. Volume % Passing

µm mesh*
Without Surfactant With Surfactant
125 120 100.00 99.85
106 140 99.88 99.18
90 170 98.95 98.06
75 200 95.63 95.65
63 230 89.86 90.55
53 270 82.47 80.54
45 325 74.98 66.31
38 400 67.09 49.95
10 - 22.06 10.38
* ASTM standards

C. Testing of the Concentrate at High Sulfate Content (3.2-3.5%)

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Tests have been conducted to study effect of surfactant addition at thses high levels of free
sulfate. As in previous tests, surfactant is added at alevel of 1.5 kg/ton P2O5.. The results
obtained are given in Tables (7 & 8) and Fig. (3).

The filtration data of the samples at relatively high sulfate contents of about 3.2% and 3.5%
with and without surfactant, respectively, are given in Table (7). The obtained filtration rate is
6.77 ton P2O5 /m2.day without surfactant and improved to 8.33 ton P2O5 /m2.day with the
addition of surfactant. This corresponds to about 23% improvement ton P2O5/m2.day). This
is related to the growth of produced crystals upon surfactant addition and formation of high
volume % of coarse crystals (>75 Fm). The size distribution of gypsum crystals which is
given in Table (8) and Fig. (3) shows that, the volume percentage of coarse produced gypsum
crystals (>75 Fm) is increased to about 15% upon addition of surfactant while it is about 10%
without surfactant.

The obtained reaction efficiencies, P2O5 recoveries and washing efficiencies of the phosphate
concentrate with surfactant compared with the phosphate processed without surfactant
(baseline) are given in Table (7). As in the previous tests, it is obvious that the reaction
efficiency is increased with the addition of surfactant. This may be attributed to decrease of
lattice (co-crystallized) P2O5 losses.

Table (7)
Filtration and Reaction Data at High Sulfate Content (3.2-3.5%)

Item Without Surfactant With Surfactant

Filtration rate, 6.77 8.33
ton P2O5 /m2.day
Moisture % 27.9 28.4
Change in filtration rate, % - + 23
Reaction efficiency, % 96.9 99.0
P2O5 recovery, % 96.4 96.9
Washing efficiency, % 99.5 97.8

Table (8)
Comparative Size Analyses of Gypsum Crystals
(At High Sulfate Content and After 3hr)

Size, Size, Cum. Volume % Passing Cum. Volume % Passing

µm mesh*
Without Surfactant With Surfactant
125 120 99.91 99.70
106 140 99.01 97.75
90 170 96.15 92.97
75 200 89.76 84.77
63 230 81.11 76.14
53 270 71.31 68.25
45 325 62.10 61.57
38 400 53.26 55.06

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 10 - 64.28 30.75
* ASTM standards

D. Correlation between Crystal Size Distribution and the Filtration Rate

The correlation between the crystal size distribution and the filtration rate are given in Table
(9). These results show that, with decreasing the % volume fraction of fine crystals and/or
increasing the volume % of the coarse crystals, the filtration rate is increased at each sulfate
level.

Table (9): Relation between Crystal Size Distribution and Filtration Rate

Item Phosphogypsum Phosphogypsum Filtration

Fines (-10 F m), Coarse (+75 F m), rate, ton
vol. % vol. % P2O5/m2.day
Low sulfate content:
Without surfactant 64.3 0.0 4.24
With surfactant 30.8 4.3 5.54
Medium sulfate content:
Without surfactant 22.1 4.4 5.13
With surfactant 10.4 4.4 6.42
High sulfate content:
Without surfactant 18.0 10.2 6.77
With surfactant 20.1 15.2 8.33

E. Mechanism of Improvement in Filtration Rate

The data and observations obtained in this study suggest possible mechanism for the effect of
surfactant on phosphogypsum filtration as given below:

1. The used anioinc surfactant modifies the shape of the produced calcium sulfate dihydrate
crystals e.g. at low sulfate content the crystals change from tabular to small clusters and at
medium and high sulfate contents, the crystals change from small clusters to large clusters.
2. The surfactant decreases the nucleation at the same sulfate or calcium contents (27).
Consequently, this leads to growth of the crystals (both fine and coarse). It is obvious
that, the volume % of fine crystals (<10 µm) is decreased and/or the volume % of coarse
crystals (>75 µm) is increased with addition of surfactant.

9
3. Narrow size distribution is obtained upon addition of the surfactant. This could be
attributed to the reported observation that the surfactant decreases the hydration of Ca2+
ions and consequently increases the growth rate of crystals (26).

CONCLUDING REMARKS

High dolomitic phosphate concentrate from the South Florida area was tested for phosphoric
acid production. The obtained filtration rate at high sulfate content was 6.77 ton P2O5/m2.day,
which was improved to 8.33 ton P2O5/m2.day by addition of 1.5kg surfactant/ton P2O5. The
% improvement in filtration rate is about 23%. Also the size of produced gypsum crystals was
increased. The experimental results show that 10.2% and 15.2% of the produced gypsum
crystals were more than 75 µm without and with surfactant, respectively.

The reaction (digestion) efficiencies, P2O5 recoveries (overall efficiencies) and washing
(filtration) efficiencies achieved were 96.9%, 96.4% and 99.5% without surfactant and were
99.0%, 96.9% and 97.8% with surfactant, respectively. The P2O5 in the filter (product) acids
are 27.9% and 28.4% without and with addition of the surfactant, respectively.

Similar results are obtained at low sulfate (1.5-1.8%) and medium sulfate (2.2-2.5) contents.
The data show that the filtration rate, size of the gypsum crystals, reaction efficiency and P2O5
recovery are increased with addition of the surfactant.

ACKNOWLEDGEMENT

Financial support from the following institutions is acknowledged and greatly appreciated: the
Florida Institute of Phosphate Research; the Engineering Research Center (ERC) for Particle
Science and Technology at the University of Florida; the National Science foundation (NSF),
under grant EEC-94-02989; and the Industrial Partners of the ERC.

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 Fig. (1)
Comparative Size Analyses of Gypsum Crystals
(at low sulfate content and after 3 hr)

Fig. (2)
Comparative Size Analyses of Gypsum Crystals
(at medium sulfate content and after 3 hr)

14
 Fig. (3)
Comparative Size Analyses of Gypsum Crystals
(at high sulfate content and after 3 hr)

15