Professional Documents
Culture Documents
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
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).
(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
70C
100
60C
50C
0
0
10
20
30
Wt% P2O 5
40
50
60
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
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.
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
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
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
Becker, P., Phosphatesand Phosphoric Acid. Raw Materials, Technology, and Economics of
the Wet Process, Marcel Dekker, Inc., Second Edition (1989).
Brown, E. H.; Carlton, D. W., VaporPressure of Phosphoric Acid, Ind. Eng. Chem., 44, 615,
(1952)
Chen, C.-C., Representation of Solid-Liquid Equilibrium of AqueousElectrolyte Systems with the
Electrolyte NRTL Model, Fluid Phase Equilibria, 27, 457, (1986)
Chen, C.-C.; Britt, H.I.; Boston, J.F., Process Simulation of Electrolyte Systems, Proceedings of
1984 Summer Computer Simulation Conference, Boston, pages552-557, 1984.
Chen, C.-C.; Britt, H.I.; Boston, J.F.; Evans, L.B., Local Composition Model for Excess Gibbs
Energyof Electrolyte Systems. Part I: Single Solvent, Single Completely Dissociated
Electrolyte Systems, AIChE J., 28, 588 (1982).
Chen, C.-C.; Evans, L.B., A Local Composition Model for the Excess GibbsEnergyof Aqueous
Electrolyte Systems, AIChE J., 32, 444 (1986).
Linke, W. F.; Solubilities Inorganic and Metallic-Organic Compounds, American Chemical
Society (1958).
Linkson, P.B., Can You Trust Your AqueousSystem Simulations? Chemical Engineering
Progress, page 63, May 1998.
Liu, Y., and Watanasiri, S., Successfully Simulate Electrolyte Systems, Chemical Engineering
Progress, page 25, October1999.
Mathias, P. M., Analysis and Comparison of the Dihydrate and Hemihydrate Processes Through
Process Modeling, presented at the SME/AIChE/AIPG/FIPR Fourteenth Annual Regional
Phosphate Conference, Lakeland, Florida, October 21-22, 1999
Mathias, P. M., and Mendez, M., Simulation of Phosphoric Acid Production bythe Dihydrate
nd
Process, presented at the 22 Clearwater Convention on Phosphate Fertilizer & Sulfuric Acid
Technology, Clearwater, Florida, 22-23 May, 1998.
Slack, A. V., Ed., Phosphoric Acid, Volume 1, Marcel Dekker, Inc. (1968).
Taperova, A. A., Shulgiva, N. M., Solubilitiesof CaSO 4Hydratesin Phosphoric Acid, Zh. Prikl.
Khim., 18, 521 (1945)
Taperova, A.A., Zh. Prikl.Khim., 13, 643 (1940).
Wagman, D. D.; Evans, W. H.; Parker, V. B.; Schumm, R. H.; Halow, I.; Bailey, S. M.; Churney,
K. L.; Nuttall, R. L., The NBSTablesof Chemical Thermodynamic Properties. Selected
Valuesfor Inorganic and C 1and C Organic
Substancesin SI Units, J. Phys. Chem. Ref.
2
Data, 11, 2-1, (1982)
Zemaitis, Jr., J. F., Clark, D. M., Rafal, M., Scrivner, N. C., Handbook of Aqueous Electrolyte
Thermodynamics Theory and Application, Design Institute of Physical Properties, American
Institute of Chemical Engineers (1986).