Optimum

Recirculation Rates
in Phosphoric Acid
Production

Prepared by:

Paul S. Waters, P.E.

James Byrd

Clearwater AIChE
June 2013
 INTRODUCTION

Integral to modern phosphoric acid reaction circuits is the concept of recirculation

rates. Recirculation of reactor slurry is critical in optimizing regular crystal growth and
controlling sulfates. Filtration rates and P2O5 losses are correlated to both crystal growth
and sulfate control. In most plants, at least part of the reactor recirculation is passed
through a vacuum cooler to maintain optimum slurry temperature. The balance between
circulation through the cooler and through the reactor outside the cooler is critical for
proper crystal growth. Optimum excess sulfates, the primary parameter governing reactor
operation, and regular crystal growth are a function of source ore and the physical
reaction circuit. Therefore, the optimum recirculation rate is not equal for all phosphate
ores or reactors. This paper discusses parameters affected by reactor recirculation,
consequences of deviation and means to optimize a given reaction circuit.

DESCRIPTION

Quite simply put, reactor recirculation is the quantity of reactor slurry circulated
rather than passed on to the filter feed. More typically, a recirculation ratio or rate is
referenced, which is the quantity circulated divided by the filter feed rate. Ratios
reported in industry vary from 20 to 100. Measurement of the circulated acid is not
always straight forward and will be dependent< on the reaction system.

The simplest to measure is the external circulation. In a usual configuration, this

will be the flash cooler feed minus the filter feed. There are some systems in industry
that employ circulation pumps outside of the flash cooler circuit. Still other circuits, such
as the Rhone-Poulenc and Isothermal, do not have external circulation.

More difficult to measure is internal circulation. In some circuits, such as the

Jacobs and Rhone-Poulenc, additional circulation is achieved through agitation. With an
open annular circuit, a flywheel effect can take place if the agitators and reactor geometry
are properly sized. This effect can result in significant circulation benefits and has been
reported to equal the external circulation in some systems. Other forms of internal
circulation can result from Couch pumps and geometric configuration of the reaction
circuit.

External and internal recirculation is additive. Total measure is possible through

testing and review of equipment data. There are different approaches, but the change in
concentration of a traceable additive with respect to time can provide data that can be
analyzed to this end. The effort is not trivial in deriving the internal rate both in practice
and in data analysis. Even so, there are qualitative results from such testing that can
provide insight to this parameter.

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 OPERATING CONSIDERATIONS

Reactor recirculation is one of the more critical operating parameters in the

phosphoric acid reaction circuit. The parameter has direct effects on sulfate control and
filtration rates. Process Engineers in industry need to understand this effect by
correlating data in optimizing operations. Not all recirculation rates will be ideal between
facilities. Dependencies include rock source, reaction technology, specific reactor
volume and operating philosophy.

Arguably, the single most important tool an operator has during the course of
running a phosphoric acid plant is a measure of excess sulfates. Usually, there is a target
the operator attempts to achieve. Controlling the excess sulfates in achieving this target
then becomes the Operator’s challenge. But understanding the reasons why sulfate
control determines the course of an Operator’s success merits discussion.

Sulfate ions from sulfuric acid dissociation react with calcium in the rock to form
gypsum in the reactor slurry. The kinetics of this reaction is relatively fast, but not
instantaneous, and is somewhat different depending on the rock source and dissolution
rates. During the course of this reaction, the P2O5 in the rock slurry becomes soluble and
forms phosphoric acid, the liquid phase of the reactor slurry containing gypsum solids.
Concerns herein are losses of P2O5, or overall yield.

An excess of sulfate is targeted in the reactor to drive the reaction through

completion. Thus, unreacted rock losses, or citrate insoluble losses, are typically small.
Phosphate, or P2O5, can also penetrate the gypsum lattice resulting in co-crystallized
losses, or citrate soluble losses. These types of losses can be more significant, but can be
minimized by targeting a higher excess sulfate, see Figure 1. The danger with high
sulfate targets is that the sulfate ions can surround, or coat the rock and not react with
available calcium. This results in a runaway effect with excess sulfates climbing at high
rates which lowers yields and reduces filtration rates. Low filtration rates further lowers
yields as water soluble losses increase. This is liquid in the gypsum cake post filtration
which contains P2O5. Thus, loss of sulfate control adversely affects both production and
overall yield.

Each ore source will have an ideal sulfate target which maximizes recovery.
Operators tend to run their targets somewhat lower than this ideal in order to mitigate
variations in calcium feed against the potential of the runaway coating effect. The better
control the operator has over the reactor and excess sulfates, the closer the Operator can
safely operate to the ideal target. The Process Engineer should be evaluating the target
on a routine basis to determine the optimum for the given circuit.

3
Figure 1.

10

AVERAGE ALL TESTS DORR-

OLIVER PILOT PLANT

1
1 10
TOTAL SULFATE AS % H2SO4 IN 30
30-32% P2O5 ACID

In addition to recovery, the sulfate target should maximize regular crystal growth.
Control over crystal growth is how the operator
perator will maximize throughput on the filter, or
filtration rates. Regular crystal growth is determined by a myriad of factors including
temperature, time, viscosity,
ity, concentration, particle size distribution, available surface
area for growth versus nucleation and importantly, impurities in the acid. However, as
referenced, the most important ddetermining
etermining factor for gypsum crystal growth in a
phosphoric acid reactor is excess sulfate management.

Recirculation rates are a powerful tool for the Operator. The higher the rate, the
more forgiving the system against sulfate upsets. This occurs for a variety of reasons.
From a theoretical perspective, addition of a stoichiometric quantity of sulfuric acid to
provide the excess sulfates for a given target should move the solution past the
supersaturation point. This causes spontaneous nucleation. Too much spontaneous
nucleation will skew the gypsum particle size distribution too low for adequate filtration,
regardless of the crystal shape. By increasing the circulation for an equal addition of
sulfuric acid, the solution will move across the saturati
saturation
on curve to some lesser degree of
the supersaturation point as the overall excess sulfate concentration is somewhat less. It
is control of supersaturation in the reactor that results in the optimal amount of
spontaneous nucleation such that the overall gy
gypsum
psum particle size distribution maximizes
both filtration rates and yields.

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 REACTOR TECHNOLOGIES

A generic gypsum crystallization curve is shown in Figure 2. This crystallization

curve plots fixed gypsum crystallization rates against percent weight concentrations of
free Ca and SO4 ions in 30% P2O5 wet process phosphoric acid. The lower bolded line is
the saturation line below which no crystallization occurs. The upper bolded line is the
supersaturated line above which spontaneous nucleation occurs. Crystallization growth
occurs between the bolded lines as a function of available surface area rather than
nucleation. The optimum operating point for a phosphoric acid reactor is between the
bolded lines. However, in the course of rock dissolution and sulfuric acid introduction,
the operating point will move. This movement is dictated by reactor type, agitation and
feed location.

Figure 2.

Figure (2)(5)– -CaSO4

Figure Crystallisation
C aSO 4 Crystallisation
1.0
0.9
0.8
0.7
Weight % CaO

0.6
0.5
0.4
0.3
0.2
0.1
0.0
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0

W eight % SO4

Figure 3 follows rock dissolution and reaction for a Jacobs Reactor. For the
system analyzed in Figure 3, dye tests indicated the internal recirculation was half the
external recirculation. In other circuits, internal recirculation in a Jacobs Reactor has
been measured at equal rates to the external recirculation. The internal recirculation in a
Jacobs Reactor is a function of power input to unit volume, impeller type, reactor
modifications and internals design. Point A represents the return from the cooler seal
tank. At this point it is mixed with incoming rock slurry. The theoretical mixture should
go to point B, but rock dissolution takes a couple of minutes giving the slurry time to
reach the sulfuric and return acid introduction and the gypsum formation reaction
competes for Ca ions stunting the breach into the supersaturation zone as shown to point
B1. Dissolution continues to point C. The introduction of sulfuric and return acid mixes
rapidly and returns the acid to point D. As the sulfuric acid and calcium ions continue to
react through the remainder of the reactor, the slurry moves back to point A. Point F

5
represents desaturation in the maturation circuit. Desaturation is an important
consideration in scale prevention downstream of the reaction circuit.

The Jacobs reactor is well suited to use the Jacobs high yield mode to reduce co-
crystallized, citrate soluble, losses below 2% of rock fed. Because the sulfuric acid is
well mixed with recycled acid and the addition point can be well separated from the rock
addition point avoiding high local concentration. The Jacobs reactor can achieve 97.5%
recovery of P2O5 fed. These results were achieved in a commercial plant on western rock
finely ground for overland pipe transport. The Jacobs reactor allows the addition of a
small amount of rock to desulfate the acid if required for downstream products.

Figure 3.

Figure (3)(6)
Figure – Jacobs Crystallisation
- Jacobs Crystallisation
0.60
B Recirculation - External - 40:1
- Internal - 20:1
Total - 60:1
Rock Dissolution - 1.8 mins
0.50
B1 Sulfuric Reaction - 2 mins
Weight % CaO

Filter Feed - 26 mins

C D
0.40

A
0.30
F

0.20
2.00 2.50 3.00 3.50 4.00

Weight % SO4

6
Figure 3a.
Figure (3a) – Jacobs Reactor

VACUUM
REACTOR COOLER
6

5
COOLER FILTER
COOLER SEAL FEED
FEED
4
Slurry to Filter

1
ADJUSTMENT
3

Sulfuric Acid/ 2
Recycle Acid
ADJUST-
MENT
Rock Slurry

Figure 4 represents a similar profile for a multi-compartment reactor. Jacobs experience

and data analysis has shown the inherently reduced recirculation rate necessitates this
type of reactor to run at lower relative sulfate targets. The reason is due to rock particle
occlusion resulting in sulfate control instability. Lower recirculation affects the ability of
the system to mitigate feed variations because supersaturation is amplified. Note that the
curve in Figure 4 is the same curve in Figure 3, but the operating points are different
because of the necessity to target lower sulfates. Because of this, sulfuric acid addition
will push the system into supersaturation. Higher recirculation rates run the risk of
pushing the reactor into plug flow, which could result in a more exaggerated swing into
supersaturation zones in addition to creating hypersaturation zones in the reactor. Use of
an Advisory Control System is strongly recommended for multi-compartment reactors for
these reasons.

These types of reactors typically report “fish eyes”, or large rock particles coated with
calcium sulfate which build up in the reactor, particularly in the overflow compartments.
These buildups often require cleanups more frequently than once per year.

7
Figure 4.

Figure (4)
Figure (7)–-Prayon
PrayonCrystallisation
Crystallisation
1.0 Recirculation - External - 40:1
B
- Internal - 0:1
0.9 B1 Total - 40:1
Rock Dissolution - 2.1 mins
Sulfuric Reaction - 2.3 mins
Weight % CaO

0.8 Filter Feed - 62 mins

C
D
0.7

0.6

A
0.5

F
0.4
1.00 1.50 2.00 2.50 3.00

Weight % SO4

Figure (3)(4a)
Figure Prayon
PrayonReactor System
Reactor System

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Figure 5 represents the rock dissolution plot for a single tank reactor. The central agitator
creates pumping power equal to about a recirculation ratio of around 330:1. As a result,
the rock, sulfuric and return acid are mixed very quickly resulting in very small changes
in concentrations. The obvious advantage herein is avoidance of the system to move to
the supersaturation zone. However, the high recirculation prevents regular crystal growth
from approaching the crystal size distributions seen in both the Jacobs and multi-
compartment reaction systems.

Figure 5.

Fig. (8)(5)
Figure - Raytheon Crystallisation
– Isothermal Crystallisation

1.0
Recirculation - External - 0:1
- Internal - 330:1
0.9
Total - 330:1
Weight % CaO

0.8

0.7

B
0.6
C

0.5 A

0.4
1.00 1.50 2.00 2.50 3.00

Weight % SO4

9
 Figure (5a)
Figure Isothermal Reactor
(1) Raytheon Reactor System
System

OTHER FACTORS

Integral to this point is adequate agitation in the reaction system. If the reactor
geometry or low agitation power per unit volume allows for inadequate dissolution of the
rock, there will be hypersaturation zones and desaturated zones resulting in losses for
competing reasons. This also minimizes the available reaction volume affecting crystal
growth which in turn affects filtration rates and overall yields.

Each ore and reaction circuit will also have a specific reaction volume for which
adequate time is allowed for regular crystal growth. The required volume is often
determined in pilot plants prior to design and construction. Volume is diminishing over
time as scale forms in the reactor. As the volume decreases, sulfate control will become
more difficult. Smaller crystals will pass through the recirculation circuit resulting in less
available surface area for crystals to grow which shifts equilibrium to more spontaneous
nucleation and a smaller overall particle distribution. Over time, the problem will
compound resulting in lower production and higher losses. This phenomenon is a
primary reason some designers have moved to larger specific reaction volumes such that
at the end of the turnaround cycle the required volume is still available.

It is important for the Process Engineer to be apprised and react according during
the course of a turnaround cycle. Small changes will result in small results, but over the
course of time these small results can have significant economic impacts. Addressed thus

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far are but a few of the variables to be considered, but at point is an understanding of
gypsum crystal properties at any given time against yields and production.

CONCLUSION

So the argument can be made that the higher the recirculation rates the better
control is available. So why not increase rates for all plants at every site? It is important
is note that a plant is designed for a given rate, a nameplate production. This production
rate should take into consideration the required specific reaction volume, heat removal,
adequate agitation, and maturation. The designer will provide the required recirculation
rates in accordance with a combination of calculations and experience. Given all the
interdependencies, any modification of recirculation rates will have consequences.
Simply increasing recirculation rates can have unintended consequences if not studied in
depth.

In some reaction circuits, an increase to power input to unit volume in agitation

can increase internal recirculation. The primary concern herein is which agitators are
targets such that high shear agitators do not impede in the high efficiency zone. Other
considerations are the flow dynamics, which should increase performance but could
impact existing recirculation depending on the age of the design or modifications post
installation.

Many multicompartment reactors will have significant restrictions at overflows

and underflows which must be modified requiring expensive concrete and brick work.

If an external pump is used, care must be taken that thermal impacts are
considered. If the flash coolers are bypassed and the hot slurry is returned to the front
end, the supersaturation curve is impacted impacting crystallization kinetics.

Often when production rate is increased significantly without increasing

recirculation the cooler, the ∆T across the cooler increases to point scaling in the
downleg causes frequent shut downs for cleaning.

With any increase in recirculation, stresses and flow dynamics must be addressed.
In a multicompartment vessel, horizontal stresses on agitator shafts must be accounted so
catastrophic failures do not occur. Of particular concern in a mulicompartment reactor
are plug flow limitations. Once plug flow is attained, hypersaturation zones will
effectively de-rate the entire circuit. As rock or sulfuric acid flows are changed, large
unintended swings in sulfate concentration can move around the reactor in plug flow are
very difficult to correct.

Despite these concerns, the benefits of additional recirculation are such that each
facility should consider its merit if any optimizations are attempted. After careful
consideration of the consequences, further study is warranted.
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 In conclusion, recirculation rates are one of the most powerful tools available to
the operator. During plant design, current practice is to have a very high ratio relative to
industry practice. This gives the plant superior control relative to older plants and will
allow flexibility for future growth. Older plants should consider increasing recirculation
ratios, but must take into consideration all elements such that the best intentions do not
result in unintended consequences.

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