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Modeling the Complex Chemical Reactions and Mass Transfer in a Phosphoric

Acid Reactor

Article · January 2000

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 Presented at:
Third Joint China/USA C hemical 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 by what is known in the industry as the wet process (Slack, 1968;
Becker, 1989). In the wet process, phosphate rock, which includes calcium, phosphate and a number of
impurities, is mined, beneficiated (concentrated) and then sometimes ground dry or wet through the use
of ball mills or rod mills. The rock is fed into an attack tank or reactor and reacted (digested) with sulfuric
acid (H2SO4). An extremely simple representation of the digestion is as follows:

Ca 3(PO4)2 + 3H2SO4 + 6H2O > 2H3PO4 + 3CaSO4•2H2O (1)

The reaction produces phosphoric acid (H3PO4) and calcium sulfate dihydrate or gypsum (CaSO4• 2H2O).
The gypsum precipitates and is filtered, giving phosphoric acid as the product. In a variation of the wet
process - the hemihydrate process - calcium sulfate hemihydrate (CaSO4• ½H2O) is produced as the
precipitate. The present phosphoric-acid discussion focuses on 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 Sul furi c
HO
coolers, filtration units, and phosphoric acid Aci d 2
Evap.
Water
concentration. The present simulation Phosphate
focuses mainly on the sulfuric-acid-attack Rock

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 œ
digestion reactors, the flash or vacuum œœ œ
œœ œ
Return
coolers and the filtration units. Figure 1 Acid

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, as shown in Figure 1. But this is, of course, not necessary in the model.

Further details on the model and its application are available in Mathias and 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 or igneous), formation and weathering. Most sedimentary deposits contain varieties of
carbonate-fluorapatite collectively known as francolite, which contains calcium, phosphate, fluoride,
carbonate and other species held together in a crystal lattice. When the rock is treated with a strong
mineral acid, such as sulfuric acid, the phosphate constituent is solubilized as phosphoric acid. In the
simulation we treat the phosphate compound in the rock as a mixture of fluorapatite (Ca 10(PO4)6F2) and
trical or calcium phosphate (Ca3(PO4)2). In most cases we expect fluorapatite to be the dominant
constituent, but we may also need small amounts of trical to quantitatively describe the measured rock
composition. We treat the carbonate component as calcium carbonate and use calcium fluoride to
describe any fluoride component in excess of that contained in the apatite. In order to obtain a realistic
description of the phosphate rock, we include the following major impurities: SiO2, Al 2O3, Fe 2O3, MgO and
Na 2O.

It is necessary to include the ionic species that occur in the liquid phase of the attack tanks and much of
the process (Linkson, 1998; Liu and Watanasiri, 1999). Rigorous description of the chemical equilibrium
of the ionic and molecular species, and the nonideality of the resulting solution was often considered to
be extremely difficult, but this has changed due to significant advances in 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 as Aspen Plus (for further information, see Aspen Plus Getting Started
Manual: “Modeling Processe s with Electrolytes”). The Chen Electrolyte NRTL (ElecNRTL) model (Chen et
al., 1982; Chen at al., 1984; Chen, 1986) has been used in this work.

Details of the electrolyte-based thermodynamic model are presented elsewhere (Mathias and Mendez,
1998; Mathias, 1999). Here we only present some examples that demonstrate the concept.

H2SO4 + H2O <> H3O+ + HSO4- (2)

HSO4- + H2O <> H3O+ + SO42- (3)
Ca 2+ + SO42- + 2H2O <> CaSO4•2H2O (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 Plus databanks
provide many of the model parameters. Finally, the default values of the model parameters often provide
adequate accuracy. However, key model parameters must be obtained by fitting experimental data. The
Aspen Plus Data Regression System (DRS) has been used to obtain the optimum values of the model
parameters needed to accurately describe the important process conditions.

Figure 2 presents a comparison between model and Figure 2

Vapor Pr essure of Phosphoric Acid Solutions
data (Brown and Carlton, 1952) for the vapor 800

pressure of pure phosphoric acid solutions. These 700

data are important because accurate representation

of the vapor pressure is important for an accurate 600
Vapor Pressure (mmHg)

simulation of the flash coolers. The good agreement 500 100°C

between model and data also indicates that the
model provides an accurate description of the 400

90°C
nonideality of phosphoric acid-water mixtures, the 300

two major components in the product acid. 80°C

200

70°C
An excellent source for solubility data relevant to 100 60°C
the phosphoric-acid process is the compilation by 50°C

Linke (1958). The solubility of gypsum in solutions 0

0 10 20 30 40 50 60

of phosphoric acid and sulfuric is extremely Wt% P 2O5

 Fi gure 3
important to the process. Figure 3 presents a Solubi li ty of Calcium Sul fate in P hosphori c Acid Sol uti ons
1.6 Comparison of ASPE N PLUS Model to Data of Taperova (1940) and Taperova
comparison between model and data for the and Shul gina (1945)

solubility of gypsum in phosphoric acid solutions. 1.4

The model provides an accurate correlation over a 1.2

80 °C

Wt% CaSO 4 in Saturated Solution

wide range of conditions. 6 0°C

1.0

4 0°C
The present thermodynamic model provides a 0.8

comprehensive description of the thermodynamic 0.6

2 5°C

properties of this system. Further details are

provided in Mathias and Mendez (1998). 0.4

0.2

The key reaction kinetics and mass transfer

0.0
phenomena in the reactor are rock dissolution and 0 10 20 30 40 50 60

its tendency to coat, precipitation of gypsum (both Wt% P O in Solution 2 5

normal and nucleated) and co-precipitation of phosphate compounds in the gypsum (Slack, 1968; Becker,
1989). The plant losses are the undissolved or coated rock (known as citrate-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:

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 for the stirred-tank reactor (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. Aspen Plus Simulation of the D ihydrate Process
S ulfuric Acid Phosphate Rock
and the RCSTR model. Each tank of the reactor 0.0 1 0.01
is an RCSTR block and the other pieces of 0.01
0.98 Water
equipment in the plant are represented by 0.01
blocks such as HEATER, FLASH2 (2-phase Rx 1 Rx 2 0.01
flash), SEP2 (two-outlet component splitter) etc. 0 .01 Gases P roduct
The filtration system is treated as a series of H 2O Acid
Evap.
SEP2 blocks. A schematic representation of a Rx 9
0.98
Rx 3 0.98
Filter
particular Aspen Plus flowsheet is presented in Gypsum
Figure 4. It is assumed that most of the rock is Ret urn
Rx 8 Rx 4
fed to Rx2, and that most of the sulfuric acid Acid
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 configurations can easily be modeled.
The Aspen Plus model has many uses, including gaining insight into the process, trouble-shooting plant
problems and anticipating the effect of design changes. Here we only briefly describe three studies of 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 studies presented below, the acid strength was held constant at 26% P 2O5.

A. Plant throughput. The model predicts that the effect of increased production with the same equipment
is to increase CI losse s, while keeping the CS losses approximately constant. This effect results
because the reactors have less residence time to dissolve the rock, and the result is in agreement
with plant experience.
Figur e 5. Lo sses as a F un ctio n 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
sulfate level of the product acid. The CS losses CSL+CI L

Weight % CS and CI Losses

go through a weak maximum at a sulfate level of 4

about 2.5%. This is a complicated effect CSL

resulting from the direct beneficial effects of 3

increasing the sulfate level (lower CS losse s) 2

and the negative secondary effect where
increased sulfate level shifts more of the 1 CIL

gypsum precipitation to Compartment #2 where

the sulfate levels are lower (higher CS loss). 0
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 versions of the
model we plan to include the description of the particle-size distribution of the gypsum crystals.
F ig ure 6. Effect of Su lfu ric Acid Sp lit o n Los ses
C. Sulfuric acid split. Figure 6 predicts the effect of
feeding the sulfuric acid to the rock compartment 6

(Rx 2 in Figure 4) rather than Compartment #3. 5 CSL+CIL

The CS losse s come down because sulfate level
WQeight % CS and CI Losses

in the rock compartment rises, but unfortunately 4 CSL

the CI losse s rise faster because the higher

sulfate level significantly increases the rate of 3

rock coating. 2

CIL
The above examples indicate the value that can be 1

gained from a fundamentally based process model

incorporated into a process simulator. 0
0 5 10 15 20
% of Sul furi c Acid Fed to Com partment 2

Conclusions

Phosphoric acid reactors have been considered to be too complex to be modeled on a fundamental
basis. This work demonstrates that these kinds of chemical processe s can indeed be modeled and that
the benefits in terms of process understanding and rational process improvement are considerable.
 References
Becker, P., “Phosphates and Phosphoric Acid. Raw Materials, Technology, and Economics of
the Wet Process,” Marcel Dekker, Inc., Second Edition (1989).
Brown, E. H.; Carlton, D. W., “Vapor Pressure of Phosphoric Acid,” Ind. Eng. Chem., 44, 615,
(1952)
Chen, C.-C., “Representation of Solid-Liquid Equilibrium of Aqueous Electrolyte 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, pages 552-557, 1984.
Chen, C.-C.; Britt, H.I.; Boston, J.F.; Evans, L.B., “Local Composition Model for Excess Gibbs
Energy of 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 Gibbs Energy of 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 Aqueous System Simulations?” Chemical Engineering
Progress, page 63, May 1998.
Liu, Y., and Watanasiri, S., “Successfully Simulate Electrolyte Systems,” Chemical Engineering
Progress, page 25, October 1999.
Mathias, P. M., “Analysis and Comparison of the Dihydrate and Hemihydrate Processe s 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 by the Dihydrate
Process,” presented at the 22 nd 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., “Solubilities of CaSO4 Hydrates in 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 NBS Tables of Chemical Thermodynamic Properties. Selected
Values for Inorganic and C1 and C2 Organic Substances in SI Units,” J. Phys. Chem. Ref.
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).

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