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Presented at:

Third Joint China/USA Chemical Engineering Conference (CUChE-3)


Beijing, China, September 25 - 28, 2000

Modeling the Complex Chemical Reactions and Mass Transfer in a Phosphoric


Acid Reactor

Paul M. Mathias , Chau-Chyun Chen and Marten Walters

Aspen Technology, Inc.


KEMWorks Technology, Inc.
Ten Canal Park
5925 Imperial Parkway, Suite 105
Cambridge, MA 02141-2201
Mulberry FL 33860-7621
U.S.A.
U.S.A.

Introduction
The production of phosphoric acid by the wet process is a complex, large-scale industrial operation in
which phosphate rock is beneficiated, reacted with sulfuric acid and filtered to remove the by-product,
calcium sulfate. In this paper we demonstrate that valuable insight can be gained into this complex

chemical process through a fundamental model implemented in the Aspen Plus process simulator.
Phosphoric acid is primarily produced bywhat is known in the industry asthe wet process (Slack, 1968;
Becker, 1989). In the wet process, phosphate rock, which includescalcium, phosphate and a numberof
impurities, is mined, beneficiated (concentrated) and then sometimesground dry or wet through the use
of ball mills or rod mills. The rock is fed into an attack tankor reactor and reacted (digested) with sulfuric
acid (H2SO4). An extremely simple representation of the digestion is asfollows:
Ca 3(PO 4)

+ 3H2SO 4 + 6H2O

2H3PO4 + 3CaSO42H2O

(1)

The reaction producesphosphoric acid (H3 PO4 ) and calcium sulfate dihydrate or gypsum (CaSO
4 2H2O).
The gypsum precipitatesand is filtered, giving phosphoric acid asthe product. In a variation of the wet
process - the hemihydrate process - calcium sulfate hemihydrate (CaSO
4 H2O)is produced asthe
precipitate. The present phosphoric-acid discussion focuseson the production of phosphoric acid by the
dihydrate process.
The dihydrate process contains sections
Figure 1. Production of Phosphoric Acid by the Dihydrate Process
such as attack and digestion reactors, flash
Sulfuric
HO
Acid
coolers, filtration units, and phosphoric acid
Evap.
Water
concentration. The present
simulation
Phosphate
Rock
focuses mainly on the sulfuric-acid-attack
reactor, which is the heart of the process.
We have used a rigorous description of the
thermodynamic and rate-based chemistry
occurring in the attack reactors to develop a
Slurry
steady-state model of the sections of the
dihydrate process containing the attack and

digestion reactors, the flash or vacuum

Return

Acid
coolers and the filtration units. Figure 1
presents a simple representation of the
Product Acid
Gypsum
process flow diagram. In general, the return
acid is mixed with the sulfuric acid in order to
dilute the sulfuric acid, asshown in Figure 1. But this is, of course, not necessary in the model.
2

Further details on the model and its application are available in Mathiasand Mendez (1998) and Mathias
(1999).

Model Fundamentals Thermodynamics, Kinetics and Mass Transfer


Phosphate rock mineralogy can be highly variable depending primarily on the origin of the rock
(sedimentary origneous), formation and weathering. Most sedimentary deposits contain varietiesof
carbonate-fluorapatite collectively known asfrancolite, which containscalcium, phosphate, fluoride,
carbonate and other speciesheld togetherin a crystal lattice. When the rock is treated with a strong
mineral acid, such assulfuric acid, the phosphate constituent is solubilized asphosphoric acid. In the
simulation we treat the phosphate compound in the rock asa mixture of fluorapatite (Ca
10(PO4)6F 2)and
trical or calcium phosphate (Ca 3(PO 4) 2). In most cases we expect fluorapatite to be the dominant
constituent, but we mayalso need small amounts of trical to quantitatively describe the measured rock
composition. We treat the carbonate component ascalcium carbonate and use calcium fluoride to
describe anyfluoride component in excess of that contained in the apatite. In order to obtain a realistic
description of the phosphate rock, we include the following majorimpurities: SiO
2 , Al
2 O
3 , Fe
2 O
3 , MgO and
Na2O.
It is necessary to include the ionic speciesthat occurin the liquid phase of the attack tanks and much of
the process (Linkson, 1998; Liu and Watanasiri, 1999). Rigorousdescription of the chemical equilibrium
of the ionic and molecular species, and the nonideality of the resulting solution wasoften considered to
be extremely difficult, but this haschanged due to significant advancesin the theoretical framework
(Chen et al., 1982; Chen at al., 1984; Zemaitis et al., 1986; Chen, 1986) and the technological capability
of process simulators such asAspen Plus(for further information, see Aspen PlusGetting Started
Manual: Modeling Processes with Electrolytes). The Chen Electrolyte NRTL (ElecNRTL)model (Chen et
al., 1982; Chen at al., 1984; Chen, 1986) hasbeen used in this work.
Details of the electrolyte-based thermodynamic model are presented elsewhere (Mathiasand Mendez,
1998; Mathias, 1999). Here we only present some examplesthat demonstrate the concept.
+
H2SO 4 + H2O
H3O + HSO 4
+
2HSO 4 + H2O
H3O + SO4
2+
2Ca + SO4 + 2H2O
CaSO42H2O

(2)
(3)
(4)

Eqns. (2) and (3)present the dissociation of sulfuric acid and Eqn. (4) shows the precipitation of gypsum.
Many of the parameters in the thermodynamic model can be estimated or derived from published values
of chemical thermodynamic properties, for example Wagman et al. (1982). The Aspen Plusdatabanks
provide manyof the model parameters. Finally, the default valuesof the model parameters often provide
adequate accuracy. However, key model parameters must be obtained byfitting experimental data.The
Aspen PlusData Regression System (DRS) hasbeen used to obtain the optimum valuesof the model
parameters needed to accurately describe the important process conditions.
Figure 2 presents a comparison between model and
data (Brown and Carlton, 1952) for the vapor
pressure of pure phosphoric acid solutions. These
data are important because accurate representation
of the vapor pressure is important for an accurate g)
H
simulation of the flash coolers. The good agreement mm
between model and data also indicates that the
e(
ressu
model provides an accurate description of
the
r
nonideality of phosphoric acid-water mixtures, the
P
r
o
p
a
two major components in the product acid.
V

Figure 2
Vapor Pressure of Phosphoric Acid Solutions

800

700

600

500

100C

400

90C

300

80C

200

An excellent source for solubility data relevant to


the phosphoric-acid process is the compilation by
Linke (1958). The solubility of gypsum in solutions
of phosphoric acid and sulfuric
is extremely

70C
100

60C
50C

0
0

10

20

30

Wt% P2O 5

40

50

60

important to the process. Figure 3 presents a


comparison between model and data for the
solubility of gypsum in phosphoric acid solutions.
The model providesan accurate correlation over a
wide range of conditions.
The present thermodynamic model provides a
comprehensive description of the thermodynamic
properties of this system.
Further details are
provided in Mathiasand Mendez(1998).

Figure 3
Solubility of Calcium Sulfate in Phosphoric Acid Solutions
Comparison of ASPEN PLUS Model to Data of Taperova (1940) and Taperova
and Shulgina (1945)

1.6

1.4

80 C
1.2

n
o
it
lu
o
S
d
e
t
a
r
u
t
a
S
in4
O
S
a
C
%
Wt

6 0C
1.0

4 0C
0.8

2 5C
0.6

0.4

0.2

The key reaction kinetics and mass transfer


phenomena in the reactor are rock dissolution and
its tendency to coat, precipitation of gypsum (both
normal and nucleated) and co-precipitation of phosphate compoundsin the gypsum (Slack, 1968; Becker,
1989). The plant lossesare the undissolved or coated rock (known ascitrate-insoluble or CI loss) and the
phosphate co-precipitation (known as the citrate-soluble or CS loss). These rate phenomena have been
captured with the following assumptions:
0.0

10

20

30

40

50

60

Wt% P 2O inSolution
5

1. Rock dissolution, assumed to be proportional to the concentration of undissolved rock and inversely
proportional to the sulfate concentration.
2. Rock coating, assumed to be proportional to the concentration of undissolved rock, the gypsum
precipitation rate and the sulfate concentration.
3. Normal gypsum precipitation, assumed to be proportional to the calcium and sulfate concentrations
and the distance from equilibrium.
4. Nucleated gypsum precipitation, assumed to be negligible up to the supersaturated limit, and
extremely fast once this limit is reached.
5. Co-precipitation losses, assumed to be proportional to the total gypsum precipitation rate and ratio of
the phosphate and sulfate concentrations.
All these effects have been incorporated into a user subroutine forthe stirred-tankreactor (RCSTR)in
Aspen Plus.

Aspen Plus Implementation and Results


The key building blocks for the Aspen Plus

simulation model are the thermodynamic model Figure 4. AspenPlus Simulation of the Dihydrate Process
Sulfuric Acid Phosphate Rock
0.0 1
and the RCSTR model. Each tankof the reactor
0.01
0.01
is an RCSTR block and the other pieces of
0.98
Water
equipment in the plant are represented by
0.01
blocks such as HEATER, FLASH2 (2-phase
0.01
Rx 1
Rx 2
0 .01
flash), SEP2 (two-outlet component splitter) etc.
Gases
Product
Ac id
The filtration system is treated as a series of
HO
Evap.
0.98
Rx
9
Rx
3
SEP2 blocks. A schematic representation of a
Filter
0.98
particular Aspen Plus flowsheet is presented in
Gypsum
Figure 4. It is assumed that most of the rock is
Return
Rx 8
Rx 4
fed to Rx2, and that most of the sulfuric acid
Ac id
and return acid are fed to Rx3. The sulfuric acid
and return acid are assumed to be piped
Rx 6/7
Rx 5
independently, but, as noted earlier, in current
Slurry
practice recycle acid and sulfuric
acid are
generally mixed prior to addition to the reactor. Other plant configurationscan easily be modeled.
2

The Aspen Plus model hasmany uses, including gaining insight into the process, trouble-shooting plant
problems and anticipating the effect of design changes. Here we only briefly describe three studiesof the
effect of plant operation on CI and CS losses.
A. Plant throughput
B. Sulfate level
C. Sulfuric acid split between Reactors 2 and 3 (see Figure 4)
In all the studiespresented below, the acid strength washeld constant at 26% 2P O
5 .
A. Plant throughput. The model predicts that the effect of increased production with the same equipment
is to increase CI losses, while keeping the CS lossesapproximately constant. This effect results
because the reactors have less residence time to dissolve the rock, and the result is in agreement
with plant experience.
Figure 5. Losses as a Function of SO4

B. Sulfate level. Figure 5 shows the effect of


6
increasing the sulfuric acid flow to the plant,
which will result in an increase in the residual
5
CSL+CIL
sulfate level of the product acid. The CS losses sses
go through a weakmaximum at a sulfate level of o 4
L
I
C
about 2.5%. This is a complicated effect
CSL
d
an 3
resulting from the direct beneficial effects of
S
C
%
increasing the sulfate level (lower CS losses)
t 2
h
g
i
and the negative secondary effect where
e
W
CIL
increased sulfate level shifts more of the
1
gypsum precipitation to Compartment #2 where
0
the sulfate levels are lower (higher CS loss).
1. 5
2. 0
2. 5
3.0
3.5
This kind of insight into the interaction of effects
Weight % SO4 in Product Acid
can only be gained through a complete plant
model like the present one. It should be noted that the present model suggests operating at the
lowest possible sulfate levels in order to minimize the total phosphate loss. However, it is well known
that the gypsum crystals that form at low sulfate levels are difficult to filter. In future versionsof the
model we plan to include the description of the particle-size distribution of the gypsum crystals.
C. Sulfuric acid split. Figure 6 predicts the effect of
feeding the sulfuric acid to the rock compartment
(Rx 2 in Figure 4) rather than Compartment #3.
The CS losses come down because sulfate level
in the rock compartment rises, but unfortunately
the CI losses rise faster because the higher
sulfate level significantlyincreases the rate of
rock coating.
The above examplesindicate the value that can be
gained from a fundamentally based process model
incorporated into a process simulator.

Figure 6. Effect of Sulfuric Acid Spliton Losses


6

CSL+CIL

5
sses

CSL

o 4
L
I
C
d
an 3
S
C
%
t 2
h
g
ei
Q
W
1

CIL

0
0

10

15

% of Sulfuric Acid Fed to Compartment 2

Conclusions
Phosphoric acid reactors have been considered to be too complex to be modeled on a fundamental
basis. This work demonstratesthat these kindsof chemical processes can indeed be modeled and that
the benefits in terms of process understanding and rational process improvement are considerable.

20

References
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nd
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2
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