ACID DEFLUORINATION
FOR ANIMAL FEEDS
By
Andrea C, Perkins
Senior Process Engineer
IMC Fertilizer, Inc.
New Wales Operations
Mulberry, Florida
Presented at the
American Institute of Chemical Engineers
Central Florida Section
Annual Clearwater Meeting
May 28, 1988ACID DEFLUORINATION FOR ANIMAL FEEDS
INTRODUCTION
IMC Fertilizer, Inc., New Wales Operations, is the largest
single site phosphate complex in the United States. From
raw materials of phosphate rock, sulfur, limestone, soda ash
and ammonia the plant produces six fertilizer products,
six animal feed products and uranium oxide as a by-product.
Pitman-Moore, Inc., a wholly owned subsidiary of IMC is
responsible for the production of animal feeds and health
products. The phosphate based animal feed products are
produced at the New Wales complex which is operated by IMc
Fertilizer, Inc.
Phosphorus and calcium are needed in animals for the
formation and composition of the bones, teeth and muscles.
Normally, animals get their nutrients from plants; but in
recent years the nutrients are supplemented by the farmer to
help in developing the animals quickly. An ideal source of
phosphorus is phosphate rock, and the majority of the
phosphate based animal feed supplements are made from
phosphoric acid, zi
Phosphoric acid produced by the wet process method generally
contains fluoride compounds in excess of what is considered
suitable for animal consumption. Small amounts of fluoride
may be beneficial for the animals' development. However,
the ingestion of excessive fluorides can cause poor
development of the skeleton and teeth, resulting in brittle
bones and lameness. Excessive tooth wear, a reduction in
weight gain and milk production due to reduced eating and
drinking of water are other problems that can occur.
Feed-grade phosphates must contain no more than 1 pars of
fluorine to 100 parts of phosphorus (P/F=100). Most states
require the minimum ratio of phosphorus to fluorine (P/F) in
animal feed products to be 100. However, some states
require an even higher minimum ratio of 17
Therefore, for the phosphoric acid produced by the wet
Process to be used in the production of animal feeds,
Gefluorination is necessary.
Two different methods of defluorination exist at New Wales.
Rotary kilns are utilized for defluorination in producing
one of the products. All the other products are produced
by steam stripping the phosphoric acid, This paper will
discuss the steam stripping process.The animal feed granulation plants at New Wales produce
calcium and ammonium phosphate products. They produce five
different dry products, and a defluorinated liquid
phosphate.
CHEMISTRY
In Florida rock there is about 3-4% fluorine present after
beneficiation, The fluorine is present in the rock as
calcium fluoride, calcium fluosilicate, and calcium
phosphate fluoride complexes.
When the rock is reacted with sulfuric acid in the
Phosphoric Acid plant, hydrogen fluoride (HF) and silicon
tetrafluoride (Sify) are volatilized as shown in equations
(1), (2) and (3).
Cary + H2S0, -----> CaS04 + 2HF a
Casife + H2S04 -----> Caso, + HySirg (2)
HySikg <---> SIP y + 2H a)
Some of the fluorine remains in the phosphoric acid as
hydrogen fluoride (HF), as fluosilicic acid (HySiF,g), as
fluosilicate salts (especially sodium and potassidm), and as
metal fluoride complexes (especially aluminum and iron).
The stripping of the fluorine from the acid is more easily
attained when the fluorine is present in the silicon tetra
fluoride form, Silicon tetrafluoride is more volatile than
hydrogen fluoride, Silicon dioxide is added to the
phosphoric acid to allow the chemical reactions necessary
for producing the silicon tetrafluoride. Equations (4) —
(8) show the primary reactions that occur wher excess silica
is present in the phosphoric acid.
2H2SiFg + Sic, 3SiPy + 2H20 (4)
4HP + Sio, Sify + 2H20 (5)
2Na2SiPg + Sid, 38iFy + 2Na20 (6)
2K2SiFg + Sid, 3SiFy + 2K20 7)
4AlF3 + 35102 -------> 38iFy + 2A1203 (8)
Equations (4) and (5) occur very rapidly, and the silicon
tetrafluoride is evolved. However, the fluorine present in
the acid as fluosilicates and metal complexes, as shown in
Equations (6), (7) and (8), reacts slowly, requiring heat
and time to occur.Figure 1 shows the solubility curves for sodium and
potassium fluosilicates in phosphoric acid (1). The
solubility of sodium fluosilicate decreases with increasing
P205 strength, and its lowest level appears to be in the 55%
strength acid. This is one of the factors that affects the
slow reaction rate because the sodium fluosilicate has to be
soluble to react with the silicon dioxide. The solubility
of potassium fluosilicate in 55% acid is higher than sodium
fluosilicate, Unfortunately, there is more sodium than
potassium present in the phosphoric acid, and so more sodium
fluosilicates are formed.
The presence of impurities in the acid affects the form in
which the fluorine is present. It appears that the higher
the impurity levels, the higher the fluorine level. The
worst culprit is aluminum,
High levels of dissolved aluminum present in the phosphoric
acid can cause various complexes of the fluorine to form
such as chukhrovite, Ca4so4(Alf¢)(Sifg)(OH).12H20, and
cryolite (Na,K) Alf (2). ‘The reaétion Of these fluoride
complexes with silicon dioxide is very slow. It is possible
that the silicon tetrafluoride in the solution has to be
below a certain level before the aluminum fluoride complex
will react with the silicon dioxide.
Figure 2 shows a very strong correlation between increasing
levels of aluminum in the phosphate rock and increasing
levels of fluorine in the 54% phosphoric acid. As
expected, an increase in the level of fluorine present in
the phosphoric acid results in an increase in the
defluorination times. Figure 3 shows the relationship
obtained between increasing aluminum in the phosphate rock
and the defluorination batch times. These correlations were
developed from an intensive study of acid defluorination
Parameters at New Wales.
SILICA DELIVERY and UNLOADING
At New Wales the facilities for receiving silica allow
delivery in either pneumatic trucks or railcars. The silica
is transferred from the carrier into a storage bin via a
filter/receiver located on top of the bin, The
filter/teceiver discharges directly into the storage bin.
Located below the silica storage bin is a slurry tank. Here
an operator mixes a “batch" of silica with fresh water. The
% solids of the silica "batch" is monitored. A chart shows
the approximate volume of silica slurry to be transferred to
the tanks containing the phosphoric acid solution, depending
on the $ F in the acid and the % solids in the silica
slurry.FLOW SHEET
The stripping of the fluorine from the phosphoric acid is
accomplished with forced circulation evaporators. This is a
“batch” process. Figure 4 shows the flow sheet. Either 40%
acid, 54% unclarified acid (ROP) or 54% centrifuged acid
(merchant acid) is received from the Phosphoric Acid plant
and stored in an agitated tank, referred to as a batch
tank, When the acid transfer is complete, the silica
slurry is added, and the reactions to form silicon
tetrafluoride start.
The acid is then pumped to an evaporator where heating and
stripping of the fluorine begins. The acid is circulated
through the evaporator and returned to the batch tank. This
closed loop operation is continued until the P/F ratio for
that particular batch is greater than 100.
In the evaporator, steam is added to the heat chest, the
acid is heated and water vapor is evolved, The fluorine
disengages from the acid in a gaseous form, as either
silicon tetrafluoride or hydrogen fluoride, Fresh make-up
water is added to the evaporator at a rate equal to the
quantity of water vapor evolved, The strength of the acid
is maintained between 55-57% P205 because the fluorine
evolution is faster.
when the batch is completed, that is, the ratio of the P/F
is greater than 100, the feed to the evaporator is stopped.
The acid is then transferred from the batch tank to a
defluorinated acid storage tank. Another batch of acid is
then received from the Phosphoric Acid plant, and the
process is started again.
The option exists of dumping the evaporator after each batch
or starting a new batch with an evaporator full of
defluorinated acid. This is an economic evaluation
depending on the size of the evaporator units and the batch
tanks involved, because the time required to dump and refill
the evaporators also has to be considered.PROCESS DESCRIPTION
The key to the operation of the process is the evaporators.
The units are Swenson forced circulation evaporators with a
barometric condenser and two-stage ejector set with an
intercondenser for vacuum control.
The defluorination evaporators operate at higher
temperatures (200-220°F) than the evaporators in a
Phosphoric Acid plant. A double layered rubber consisting
of a chlorobutyl layer with a Triflex backing is used to
allow for the higher temperatures.
The acid feed flow to the evaporators is controlled with a
flowmeter, The evaporators are controlled by two of the
following three variables, with the third one being a
result. They are:
(i) temperature
(ii) pressure
(idi) concentration
Normally, the first two parameters are controlled and the
concentration is a result, To ensure that the fluorine is
evolved with the water vapor, temperatures over 210°F are
required. The lower the absolute pressure, the higher the
resulting acid concentration will be, which will facilitate
fluorine stripping. Acid strength between 55-57% P205 is
good for stripping the fluorine. ‘The higher the P205
strength the better the fluorine evolution, but the
viscosity of the acid becomes a problem above 58% P205.
ANALYSES
Samples are taken every two hours, and the fluorine level is
analyzed and monitored by the operators inthe plant. 1f
the fluorine remains the same for two consecutive samples,
prior to the completion of a batch, additional silica is
added to the batch tank to improve or restart the reaction.
When the level of the fluorine falls below 0.30%, the
samples are submitted to the Quality Control Laboratory
where the percent P205 and F are determined so that the P/F
ratio can be obtained. Samples are then collected and
submitted on an hourly basis. Operating policy requires two
consecutive samples with a P/F ratio better than 100 (or 175
to meet some states requirements) before the batch is
considered complete.DEFLUORINATION PROCESS
Figure 5 shows the change in fluorine with time during a
Gefluorination cycle. The initial fluorine is lost very
rapidly, and the slope of the curve is very steep. It is
believed that the steep section of the curve corresponds
with the evolution of the silicon tetrafluoride that is
readily available in the acid.
After that initial loss, the curve then flattens out, and
the majority of the time is required to remove the remaining
fluorine to obtain the P/F ratio of 100 (or 175). ‘The flat
section of the curve probably corresponds with the fluorine
present in the acid as fluosilicates and metal fluorides.
Three different curves are shown in Figure 5 indicating the
possible effect different levels of initial fluorine can
have on the batch times. As a general rule the
batch time is reduced as the percent fluorine present is
reduced. However, this is not always the case, There are
numerous factors that will affect the overall defluorination
rate and therefore the time, Some of these are:
- the form that the fluorine is present in, as
discussed in the chemistry
= the P205 strength of the acid
- the evaporator operating temperature
~ the steam rate to the evaporators
= the absolute pressure on the evaporators
= the quantity of silica available for reaction
~ the reactivity of the silica
Figure 6 shows that the normal trend expected is an increase
in the batch times as the % F in the phosphoric acid
increases. This data was accumulated at the time the trend
with the increasing aluminum in the rock was noted and
corresponds with the data shown in Figures 2 and 3.
the quantity of the solids present in the phosphoric acid
solution is important. A study at New Wales indicated that
at least 35% of the fluorine present in the phosphoric acid
is in the solids phase. Therefore, when the solids
increase, the % F increases. This explains the lower %F
present in merchant acid (centrifuged acid) which normally
results in lower batch times.
Table 1 shows data collected on the changes in the fluorine
content for the combined acid solution, and the liquid and
solid phases separately during a defluorination cycle. This
data is also presented graphically in Figure 7.The fluorine in the liquid phase is reduced very quickly at
the beginning of the process. Conversely, the fluorine in
the solids is reduced at a slower but steady rate and then
it stops. This further supports the chemistry discussed
earlier on the detrimental effect of the complex fluoride
salts which tie up the fluorine in the solids and take a
very long time to react.
PILOT PLANT
The Development Engineering group at New Wales has a small
evaporator that is used for defluorination tests. It is
used primarily to evaluate different silica sources.
Screening tests are done here rather than in the AFI plant.
Figure 8 shows curves from test runs comparing silica
samples obtained from different suppliers. The control
sample is the present silica source that is being used. As
shown, both silica samples 2 and 3 did better than the
control, whereas sample 1 was in progress for a much longer
time and still had not reached a P/F of 100, so the test was
aborted.
with this information, economic calculations are made to
determine if it is feasible to test the material in the
plant, If so, then a plant test will follow with further
evaluation.
Figure 9 shows another test done with different quantities
of stoichiometric silica available for reaction in the
phosphoric acid. The control sample had. no silica added,
and as noted there was very little change in the initial P/F
ratio. At about 60% stoichiometric silica the curves
flatten out at P/F=50; at 90% stoichiometric silica the P/F
ratio of 100 was achieved. The two different silica sources
tested at this time were essentially the same.
This data also shows the need for adequate silica to be
present for the reactions discussed earlier to occur and
reduce the P/F to 100, 90% stoichiometric is a safe
quantity to have present, depending of course on the
reactivity of the silica. Additional silica is required
when defluorinating to higher P/F ratios,
At times different parameters have been tested such as the
quantity of free sulfate present in the acid and its effect
on defluorination. The effect of different types of
chemicals that could possibly reduce defluorination times
have also been tested in the past. To date none of these
tests has shown any significant promise.SUMMARY
With phosphorus being an important element in the growth of
animals, the value of obtaining feed supplements from such
an abundant supply as the phosphate rock is advantageous.
The presence of high levels of fluorine in the phosphoric
acid, which has a detrimental effect on the animals when
received in large quantities, requires an additional step to
remove this fluorine before the phosphoric acid can be used
in animal feeds.
The ability to strip the fluorine using the forced
circulation evaporators to produce a defluorinated acid with
a minimum P/F ratio of 100 (or 175), has allowed the use of
the phosphoric acid in this application, This method is
typical of most feed-grade phosphate manufacturers.
once the fluorine is removed, the acid is considered to be
feed-grade quality. This means that any product added to
the process from this point on has to meet the Food & Drug
Administration (FDA) approvals for feed-grade quality, Even
though further purification would be required for use in
human products, the product is regulated by the FDA.
The defluorinated acid is then used in a granulation plant
to produce various products which will meet the
specifications for the P/F ratio greater than 100 (or 175).
In addition some is sold to customers requiring a liquid
based phosphate for their blending purposes.ql)
(2)
REFERENCES
Becker, P, - "Phosphates and Phosphoric Acid - volume
3”
Slack, A. V. - “Phosphoric Acid - volume
PoThe Effect of Phosphoric
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