A HIGH TEMPERATURE

VI!'

18 INt4D~USTRlAL AND ENGINEERING CHEMISTRY

SUPERPHOSPHORIC ACID PLANT
H. Y. ALLGOOD
F. E. LANCASTER, JR.
J. A. McCOLLUM
J. P. SIMPSON
The effects of the main operating variables in
various pieces of equipment have been analyzed
while the plant was being operated under routine
and special tests conditions. The plant burns ele-
mental phosphorus to produce ortho- and super-
phosphoric acids at concentrations equivalent to
85 to 115% H3P04. Operating conditions can be
easily changed to produce acid of the desired
concentration.
or several years TVA has operated thermal phos-
Fphoric acid units of carbon and graphite con-
struction to produce 75 to 90% phosphoric acid from
elemental phosphorus for experimental fertilizer produc-
tion (7). Pilot-plant studies showed that more highly
concentrated phosphoric acids could be easily produced
(70). T o test these findings on a plant scale, one of the
old units was modified in 1956 so that dilute acid could be
added in the hydrator and more heat could be removed
from the product acid by use of an external heat ex-
changer. With these changes, the acid produced con-
tained about 76% PZOEor the equivalent of 105%
(8).
Studies of the properties and potential uses of this
superphosphoric acid in the fertilizer field (5, 6, 9)
showed that the acid could be ammoniated to produce
liquid fertilizer base solutions, such as 10-34-0 and 11-
37-0, as well as a 12-40-0 suspension. The polyphos-
phates in this acid or its base solutions sequester solids
and thereby make possible the production of clear mixed
fertilizer solutions, such as 10-5-5, 8-16-8, and 5-15-10,
and the production of high-analysis fertilizer suspensions,
such as 15-15-15, 10-30-10, and 9-18-27. Sequestra-
tion also permits the incorporation of more secondary
nutrients and micronutrients, such as salts of iron, zinc,
manganese, and molybdenum. With this acid, more
concentrated solid fertilizers such as high-analysis super-
phosphate (0-54-0) and ammonium polyphosphate
(15-61-0) can be produced (3, 4). Tests showed that
the solids in wet-process phosphoric acid can be seques-
tered by the addition of 1 5 to 50% of superphosphoric
acid or its ammoniated products ( 7 7).
These developments were well received in the fer-
tilizer industry (7). Therefore, TVA decided to produce
enough superphosphoric acid to demonstrate the feasi-
bility of the process and to provide acid and ammoniated
fluid fertilizers for evaluation and testing. Accordingly,
in 1961 about 52,000 tons of this acid was produced in
the old modified plants, but the higher temperatures
required for making superphosphoric acid caused more
rapid deterioration of the cemented joints between the
graphite blocks, and this resulted in loss of acid and
excessive maintenance.
T o avoid such maintenance and to decrease the losses
of acid, TVA had a stainless steel unit built for the
production of superphosphoric acid. This unit, which
went into operation in 1962, was designed to burn 6000
lb. of elemental phosphorus per hour to produce acid
containing 76y0 PzO6 (equivalent to 105% H3P04).
This plant has demonstrated the ability to produce acid
with concentrations as high as 80 to 8370 P z O (equiva-
~
lent to 110 to 115y0 HsP04). Major objectives of the
new plant were to lower maintenance expense, to in-
crease efficiency of acid recovery, to produce a large
part of the superphosphoric acid needed in TVAs
experimental fertilizer program, and to provide design
and operational information about this type of plant
for the industry.
From a brief outline of essential features of the plant
and the process, this paper moves to a more detailed
discussion of operating experience-the problems, effects
of operating variables, and operating indexes. More
comprehensive information on the plant, particularly on
the considerations underlying the design, will be pre-
sented in a bulletin to be published by TVA.
DESCRIPTION OF PROCESS FLOWS
AND EQUIPMENT
Production of phosphoric acid by the thermal process
involves the primary steps of oxidizing (burning)
elemental phosphorus to produce PzOh, hydrating the
PZOSwith dilute acid or water to produce phosphoric
acid, and recovering the acid from the vapor stream.
In the stainless steel unit, cooling of equipment in contact
with hot process gases and acid streams is very essential
to good service life.
Figure 1 is a perspective sketch of the plant. Mainly
the plant is comprised of two parallel combustion cham-
bers, a hydrator, a venturi scrubber, and a separator
tower. Two combustion chambers were provided to
permit continued plant operation at reduced capacity
if one should fail for any reason. Operating experience
has shown that a single, larger combustion chamber
should be feasible, and this would be recommended for
any future plant. Auxiliary equipment consists of
systems for storing and feeding phosphorus, filtering and
compressing combustion air, controlling atomizing air,
VOL. 5 9 NO. 6 J U N E 1 9 6 7 19
 cooling and recycling product acid, collecting and dis-
tributing dilute acid, treating cooling water, and storing
and pumping product acid. Supply or service con-
nections available from outside the plant are liquid
phosphorus, compressed air for atomizing phosphorus
and the operating pneumatic instruments, filtered water
for hydrating P206, process water for cooling the equip-
ment, steam for heating the phosphorus and the water in
phosphorus pipe jackets, aqua ammonia for neutraliziiig
water over the phosphorus supply, and electricity. A
small amount of sulfuric acid is used for adjusting the p H
of the incoming process cooling water to minimize
scaling.
All of the equipment exposed to PzO5 vapor and phos-
phoric acid at elevated temperatures is constructed of
Type 316L stainless steel. Piping and jackets that con-
duct cooling water are made of Type 304 stainless steel.
The combustion chambers, the hydrator, the venturi,
the bottom third of the separator tower, the ducts
connecting these vessels, and the acid piping from the
hpdrator to the product acid cooler are fully water
jacketed. This stainless steel equipment is exposed to the
phosphorus flame and P 2 0 5at temperatures as high as
5000" F. or to heated acid at temperatures up to 365" F.
The key to protection of the metal is rapid and continuous
removal of heat from the metal to the cooling water.
In contrast with an old carbon-graphite plant, the
new plant has the following features: construction of
stainless steel cooled by treated water in jackets, operation
under pressure of 3 to 4.5 lb. p.s.i.g. by forced airflow,
operational control by more instrumentation, and
capacity to burn 6000 lb. instead of about 3000 lb.
phosphorus per hour in process equipment of equal or
smaller size.
Oxidation of Phosphorus
Phosphorus is transferred by a centrifugal pump from
a feed tank through hot water-jacketed piping, a control
valve, and a rotameter to the atomizing-type burner in
the combustion chamber. Rates are between 1.5 and
4.5 g.p.m.
Atomizing air from the general plant supply flows
at 80 to 120 c.f.p.m. through a condensate trap, a flow
control valve, and thence at 9 to 16 p.s.i.g. into the
burner shown in Figure 2. This burner comprises a
central pipe for phosphorus surrounded by successively
larger annular channels for steam, atomizing air, and
cooling water. Air passes through a gap between the
phosphorus jet and burner tip and atomizes the stream
of phosphorus.
Combustion air at 3000 to 6000 c.f.p.m. flows through
a dust filter, a damper flow controller, a centrifugal
AUTHORS H. Y. Allgood, F. E. Lancaster, Jr., J . A .
McCollum, and J . P. Simpson are engineers for the Tennessee
Valley Authority, Muscle Shoals, Ala. T h e authors wish to
acknowledge that M . M . Striplin, Jr., D.McKnight, B. P.
Dana, and S. A . Hardin were primarily responsible for planning
and designing the plant.
20 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
blower, a flow element, and thence through a 14-in.
pipe to the combustion air nozzle at the combustion
chamber.
The atomized phosphorus discharges into an excess
of combustion air and burns at a temperature of 3000"
to 5000" F. in the bottom of a vertical combustion
chamber that is 6.3 ft. in diameter and 29.3 ft. high.
Then the PzO6 vapor, nitrogen, and excess air flow
upward, lose heat through the water-cooled shell, and
leave at 1200 to 1650" F. through a 3.5-ft.-diameter
duct in the conical top. Water vapor present in com-
bustion air reacts with P205 to form polyphosphoric
acids, some of which deposit as a protective coating 0.1
to 0.3 in. thick on the walls of a chamber. Thus, the
combustion chambers serve for oxidation of phosphorus
to PzOb and for removal of heat from the products of
combustion.
Hydration of PBOS
Gas from the combustion chambers enters the conical
top of the hydrator tower that is 9 ft. wide and 29.8 ft.
high and flows downward with three streams of acid
spray. One spray is dilute acid added at a controlled
rate to hydrate the PzOj in the gas stream and yield
product phosphoric acid of a desired concentration.
The other two acid sprays are cooled product acid for
cooling the gas stream. Sprays of cooled product acid
also enter below the conical top to form a falling film
that cools the vertical walls and the dished bottom of the
tower. Acid collects in the bottom of the tower and
flows by gravity to a cooler. Gas and acid mist leave
through a duct connected to the side near the bottom
of the tower. Thus, the hydrator serves for hydration of
Pz06, for recovery of about one half of the product
acid, and for cooling the gas stream.
Recovery of Acid Mist
Gas and acid mist from the hydrator flow into the
horizontal venturi scrubber unit that is 15 ft. long. A
9-in.-high dam near the inlet of the unit prevents back-
flow of dilute acid into the hydrator. The gas passes
through a spray of dilute acid added to dissolve any
solid acid from the walls and then through a spray of
about 250 g.p.m. of dilute acid in the 3- by 3- by 42-in.
venturi throat. I t is important to maintain a pressure
differential of 35 to 60 in. of water at the venturi to
obtain essentially complete recovery of PzOb. Con-
sequently, the venturi hydrates the remaining PzOj
vapor, coalesces acid mist, and cools the gas.
The gas and acid then flow into the centrifugal section
of the separator tow-er where the acid separates. The
gas passes upward through an internal duct and enters a
spray section. The spray consists of a controlled flow of
make-up water and recycled dilute acid. The small
amount of moisture in the combustion air and this make-
up water provide all the water needed for hydration of
P z 0 5 .The gas then flows through a mist eliminator pad
made of Type 31 6L stainless steel mesh and into a stack.
Dilute acid collected in the bottom of the tower flows by
gravity to a dilute acid receiver. In summary, the
separator recovers liquid and mist from the gas, pro-
duces dilute acid, and releases heat in the stack gas.
Acid and Wahr Systems
Product acid at 450 to 600 g.p.m. and 200' to 350" F.
flows by gravity from the hydrator into the main cooler
tank that is 9 ft. in diameter and 11.5 ft. high. The
cooler tank contains 36 Platecoils with a total area of
1044 sq. ft. Water flowing through these coils and
that spmyed-on the outside of the cooler tank cool the
hot acid. An agitator unit with two turbine-type im-
pellers is provided in the cooler tank. An improvised
, make-up water, and air, and then the phosphorus feed.
auxiliary cooler is used when higher production rates are
required. The product is collected in a receiver tank.
Recycled cool acid passes through a strainer that removes
solid plyphosphoric acid and is pumped to spray
nozzles in the hydrator.
Dilute acid from the separator flows by gravity to a
1800-gal. receiver tank from which it is pumped to the
sprays in the hydrator, the separator tower, and the
venturi scrubber.
River water is used for cooling. In its untreated
state, it contains about 150 p.p.m. of dissolved solids and
m Several times during initial start-up with one com-
L u*
e ..
< - increase in .phosphorus
I,
I- I" 0.0. ;,g$~~,.,:
.5 'i.;
.L
. ,
~
has a pH of 7 to 8. It is passed through a strainer to
remove large solids and then is treated with sulfuric acid
to adjust the pH to 5.6 to 6.0. This treatment has
prevented the formation of significant scale on the heat
transfer surfaces when the temperature of the effluent
water has been limited to 120" F.
OPERATION TO PRODUCE ACID OF
DIFFERENT CONCENTRATIONS
Start-up of the plant is a straightforward operation
that involves starting flows of cooling water, acids,
After combustion of phosphorus is started, operators
adjust process flows to attain operating conditions within
set control limits.
Shutdown of the plant involves stopping the flow of
phosphorus and then the flow of dilute acid to the hy-
drator and the make-up water to the separator. Circula-
tion of other streams continues until the combustion
chamber and hydrator are sufficiently cooled. Con-
ckntration of acid in the plant, the duration of the shut-
down period, and the atmospheric temperature deter-
mine whether acid must be drained from equipment to
avoid crystallization.
When changing from the production of an acid of one
concentration to another in the range 60 to 83% Pros
content, operators change the dilute acid flow rate to the
hydrator to cause the product acid concentration to
change about 1 to 2% PzOoper hour until the desired
concentration is being made. They also adjust operating
conditions to control the temperatures within prescribed
limits for a particular concentration of acid.
Start-up, shutdown, and change in acid concentration
in the new plant can be handled easily and cause no
damaging expansion or contraction as was characteristic
in the old plants.
OPERATING AND EQUIPMENT PROBLEMS
Studies, frequent inspections, and observations have
been made to improve the plant and to increase its
production capability.
Opeding Problems and Methods for Alleviating Them
bustion chamber in service, malfunction of the atomizing
air controller caused a sudden decrease in airflow and a
large - flow which resulted in the
blowing of the water safety seal at the combustion
, chamber. Without this seal, the excessive pressure
. 'could have caused severe damage to the thin-walled
process vessels. Figure 3 shows that a decrease in
atomizing airflow has a marked effect on the flow of
phosphorus in the atomizing-type phosphorus burner.
As the phosphorus burning rate was being gradually
increased during plant start-up to produce 76% PPOS
acid, the temperature of the acid leaving the hydrator
. and cooler soon reached the maximum limits prescribed
to avert corrosion in uncooled piping and pumps. So
it was necessary to l i i i t the phosphorus burning rate to
about 4500 lb. per hour until modifications demibed
V O L 5 9 NO. 6 J U N E 1 9 6 7 21
 r at 250" F. did not excessively corrode uncooled Type
0 4u w w IW IZJ IKI IW 1w 203
Atoniziq lir M a 10hmr, C. F. M.
Figure 3. Effectof air rata on thcjow of p h p h in thc atmizing-
type p h o s p h burnn
later were made. At the reduced phosphorus burning
rate, the pressure differential at the venturi was less than
20 in. of water, and the stack gas carried some acid mist
that fell into the plant area. Therefore, a damper was
installed upstream from the venturi throat to permit
control of the pressure differential in a range of 35 to
60 in. of water to cause the mist to coalesce and to be
recovered in the separator tower.
Several minor modifications of the plant as originally
built were made to increase the phosphorus burning
rate from 4500 to 6000 lb. per hour when producing acid
of 76% PIOS content. These changes resulted in the
plant previously described. They included the in-
stallation of a water jacket around the acid pipe between
the hydrator and cooler, an external water-cooled gas
seal at the cooler, an auxiliary product acid cooler, and
a second product acid spray in the top of the hydrator.
These changes also permitted the phosphorus burning
rate to be increased to 7800 lb. per hour when acid of
80% PIOScontent was being produced.
The development of 11-37-0 liquid fertilizer required
acid with 75 to 85% of its P,Os in plyphosphate form.
Most of the acid produced in the plant has been of 78
to 80% PZOScontent to satisfy this requirement. Be-
cause acid of this concentration crystallizes at room
temperature, it is kept at 150' to 170' F. in plant storage
until used in a fertilizer process.
During the first few months, operating experience
had shown that several minor changes were needed to
overcome operating problems and to produce acid with
83% PZOScontent. It was necessary to install the
following equipment in the plant: a strainer in the
product acid cooler to retain and to permit dissolution
of solid acids, a dilute acid spray to dissolve solids that
deposited on the walls upstream from the venturi, and
reinforced framework to secure the Platecoils in the
turbulent viscous acid in the cooler. Also, the tem-
perature of the acid leaving the hydrator was allowed to
increase to about 350" F. and that leaving the cooler to
about 250 F. These changes resulted in lower acid
viscosity which permitted increased cooling of this acid.
Tests had shown that acid containing 78 to 83% P106
22 INDUSTRIAL A N D EN GIN E E R I N G .C H EM1S T R Y
31 6L stainless steel. Water-cooled stainless steel resisted
attack by the acid at 350" F.
Sludge that has about 30% phosphorus, 8% solids
insoluble in benzene, 20% oils and tars, and 42% water
gradually accumulates on the surface of the phosphorus
in the feed tanks. It must be pumped from the tanks
to a phosphorus recovery unit at intervals of 1 to 3
months.
Impurities in the phosphorus, atomizing air, and
filtered combustion air deposit residue in combustion
chambers. This accumulates in the pool of poly-
phosphoric aeid in the bottoms of the chambers and is
removed about once a year. The product acid has less
than 0.01% solid impurities.
A multipoint conductivity recorder is utilized to in-
dicate any acid leaks into cooling water streams from the
jackets and ducts. Leaks can be detected immediately
and repairs made. Value of this instrumentation was
proved when leakage of acid at a flexible pipe connection
was stopped within 5 minutes after it started. Without
this conductivity meter the leakage might have continued
undetected and resulted in serious acid loss, corrosion,
and stream pollution.
Equipment Problems
During early operation while acid of 80% Pa05
content was being made, an internal weir for distributing
acid for cooling the shell of the hydrator corroded
through. This resulted from a stoppage caused by
crystallized acid in the weir trough or from a low flow of
acid to the trough. To correct this problem, the weir
was removed, a water jacket was installed in this area,
and four nozzles were inserted to spray a falling film down
the inside walls of the hydrator.
Failure of the shaft and bearings of one of the com-
bustion air blowers was attributed to impeller imbalance
caused by gradual accumulation of dust that passed
through the air filter. Further failures were averted by
periodically cleaning the blowers, and by doubling the
area of the filter unit. While repairs were being made to
the blower, the plant was operated at a reduced produc-
tion rate with the other blower and one combustion
chamber.
Some equipment did not perform well and was
eliminated. Gear-type metering pumps for phosphorus
and the graphite rupture disk required with them were
replaced with valves to control flow from existing cen-
trifugal pumps in the feed tanks. Diaphragm pumps for
metering sulfuric acid were eliminated, and compressed
air was used to feed the acid into the cooling water.
Carbon Intalox saddle packing was not needed so it was
removed from the separator tower. Flexible hose sec-
tions for phosphorus and acid were replaced with
rigid piping. Screwed fittings in acid piping were
replaced with flanges. A rubber-lined pipe in which
the sulfuric acid and process cooling water were mixed
was replaced with a section of stainless steel pipe.
Efforts to repair a crack in a horizontal weld in a
combustion chamber resulted in progressive cracking.
Thedore, a 1-ft. band, 6 in. above and below the bad
weld, was sawed out of the chamber and replaced by a
I-ft. band properly welded in place.
Corrosion
Corrosion of equipment has not presented major
problem$ in the plant. Audigage measurements taken
periodically have shown no apparent change in the
thickness of metal in the combustion chamber, hydrators,
and separator, or ducts that connect them. However,
nome problems have been encountered at other locations.
Leakage at welds required the relining of the bottom
of the dilute acid receiver. Type 316L stainless steel
unwetted by acid but exposed to vapor above the acid has
required repairs because of corrosion. This corrosion
is attributed partly to trace amounts of fluoride from
impurities in phosphorus but mainly to the chloride
(about 20 p.p.m.) present in the make-up water. A
depmit found above the mist eliminator pad in the
separator tower contained 0.01% fluoride and 1.0%
chloride. Failure of acid piping and spray nozzles
exposed to Pro, vapor at 1200' to 1600" F. inside the
hydrator has occurred, but could be prevented by
water jacketing.
After service periods of 6 to 9 months, the phosphorus
burners originally installed had to be repaired because
of corrosion at the end of the burner. Mcdiied burners
provided with improved cooling have lasted 15 to 18
months.
Corrosion in the vapor space of the mild steel phos-
phorus feed tanks is minimized by keeping the tanks
filled with water so that floating particles of phosphorus
cannot burn to produce acid.
The percentages of heat removed will vary from those
shown when heat removal in the combustion chambers is
changed by operating steps described later. Heat flow
through a square foot of metal shell of the combustion
chambers was 20,000 B.t.u. per hour or about three times
the flow through the shell of the hydrator and cooler.
Because of the exceptionally high heat removal possible
in a combustion chamber, it would seem that the metal
surface in a plant could be saved by increasing the area
exposed to the hot combustion gas. However, the size
of the area must be limited because excessive cooling of
the gases condenses polyphosphoric acids and then
PIOsto form a thick lining that restricts heat flow through
the metal to cooling water. Coatings of polyphosphoric
acid are approximately 0.25 in. thick on the inside
surfaces of the combustion chambers and as much as
0.75 in. thick in the ducts at the inlet of the hydrator.
Thickness of the coating may increase with an increase
in water vapor content in atomizing and combustion air,
with a decrease in the temperature of the combustion
products, and with a decrease in the temperature of the
cooling water in the jackets. Water vapor in the air has
ranged from 2 to 22 lb. per 100 lb. of phosphorus.
Oxidation of Phosphorus
Figure 4 shows that increasing the phosphorus burning
rate in a combustion chamber increases the temperature
of the effluent gas, the heat removal per square foot,
the total heat removal, and the overall heat transfer
coefficient. The percentage of the beat input removed
in the combustion chamber decreases with an increase

EFFECTS O F OPERATING VARIABLES

Ha)R m o w l by Unih of Cho Plant
When the plant is being operated with any particular
phosphorus feed rate and percentage of excess combustion
air, the same percentage of the total heat input that is
removed in any unit of the plant remains about the
same regardless of the concentration of acid being made.
However, when the concentration of the acid being made
is decreased, the gas leaving the hydrator and separator
removes a slightly higher percentage of the heat input
because it carries out more heat in the water vapor.
The following tabulation shows the typical heat removal
in main components of the plant while phosphorus was
being burned at rates between 3500 and 4300 lb. per
hnu:

by. cnruya B.t.u.1

Wow, Totd of Wr.1
Heat h U a i in Sq. Ft. B.t.u./Hr. InpuI (Sq. Ft.)
Coonbustionchamh 1311 26,500,000 57.4 20,OOO
Hydrator 903 6,700,000 14.7 7,400
Roduet acid cmler 1300 9,100,000 19.7 7,000
fhsphwur )uln!q h,u. PJ HK.
Venturi scrubber 157 400,000 0.8 2,300
Separatortowerbottom 396 900,000 2.0 2,400 Figure 4. Efftct of phosphorus burning rata ana' exctss air on h a t
Gar leaving separator . .. 2,400,000 5.4 . .. removal from n combustion chamber

V O L 5 9 NO. 6 J U N E 1 9 6 7 23
 in burning rate. With a lower percentage of excess air, 70 (96.71
the heat removal and gas temperature also increase, but
the overall heat transfer coefficient remains about the
same. 65 (89.81
7
At a constant phosphorus burning rate, the heat
removal from the combustion chamber may be increased 60 (82.91
by lowering the percentage of excess combustion air to
increase the temperature of the combustion products.
An increase in the temperature of effluent cooling water
to the maximum allowable limit decreases the thickness
of the acid film in the chamber and also increases heat
removal. If these steps do not sufficiently decrease heat
3 55 (76.01
s -t-t I

in the effluent gas, as an operational control the phos-

phorus burning rate must be decreased.
Metal walls near the bottom of the combustion
chamber apparently have not been attacked by the
phosphorus flame and gas at temperatures as high as
5180' F. In tests of about 2-hour duration, phosphorus
was burned at a rate of about 5000 lb. per hour in one 35 (48.31
chamber and the temperature of gas leaving was 1800
to 1840' F. No apparent attack occurred on the walls
30 (41.41
of the chamber. These tests indicate that burning
rates in a combustion chamber might be safely raised,
but steam might have to be added at a controlled rate to 25 134.5)
provide a protective coating of polyphosphoric acid to (82.9) (89.8) (96.7) (103.6) (110.5)
60 65 70 75 80
avert corrosive attack by the gas. ?r&a Add Cornrntrotion, X Q, 0 ,

Hydration of P,Os Figure 5. Effeci of cowenfration of acid being produced on cowenfra-

&on of dilutu acid in tha snubber-separator system
Cooled product acid sprayed into the top of the
hydrator cools the hot gas stream and controls the tem-
perature of the gas leaving. The dilute acid sprayed
into the top hydrates the PeOa and controls the con-
centration of product acid. The falling film of acid
on the inner wall is cooled by jacket water, and an
increase in its flow rate lowen the overall temperature of
acid leaving the hydrator: These flows are the main
ones used to control the operation of the hydrator.
The heat removed by the cooling water and by the
product acid generally increases with the temperature,
heat content, and mass flow of the inlet gas. Acid
concentrations or acid flow rate within ranges used seem
to have no apparent significant effect on PzOl removal.
The hydrator recovers from 40 to 70% (average of about
55%) of the PnOs fmm the process gas stream. The
remainder of the PzOa is recovered effectively in the -4 I
venturi as described in the following section. Evidently
the gas and acid 'spray do not intimately mix and come to 30
equilibrium as they flow through this large (9-ft. diam-
eter) tower.
As shown in Figure 5, the dilute acid in the scrubber-
$1
separator system increases in P,06 content as the PzOs sa
5
content of the product acid is increased. An increase 5:
in acid production rate or in acid concentration causes -5

IO
a rise in the temperature of the dilute acid. d

5
R r o v w y of Acid Mist
In the venturi scrubber, the PzOsladen gas at 0
20 30 40 50 60
550" F. comes in intimate contact with sprays of rela- hnrurs Differordial krmr Venturi, In. H,O
tively cool dilute acid and expands because of a decrease Figure 6. Typical effect of gas pressure &ffmential at tha wntun on
in pressure of 35 to 60 in. of water. Evaporation of PtOa lossin gas to xtwk and on gar cooling

24 INDUSTRIAL A N D ENGINEERING CHEMISTRY

water from the acid and expansion of the gas quickly Heat Transfer
cool the gas stream to the temperature of the acid. Overall
Coefficient
I

The P206 vapor is hydrated, and the acid mist coalesces Acid B.t.u./Hr. B.t.u./(Hr.)
into droplets that separate as a liquid. The venturi- % pzos O F. (Sq.Ft.)(O F.) (Sq. Ft.)
separator tower unit recovers more than 98% of the 65 180 120-140 5000-10,000
P2Os in the gas when the gas pressure differential across 76 200 67-95 7000-9000
the venturi throat is less than 20 in. of water. However, 80 250 41-113 5000-12,000
a higher pressure differential, between 35 and 60 in. of 83 250 40-55 5000-7000
water, must be imposed to recover 99.9yo of the Pzos
from the gas. Figure 6 shows the effect of gas pressure polyphosphoric acids may crystallize on the cool Plate-
differential on the P2O5 loss in stack gas and on cooling coils and decrease the heat transfer rate. Reduced
of the gas. At a differential of 35 in. of water or water rates and resultant high effluent water tempera-
higher, the gas stream is actually cooled a few degrees tures minimize crystallization of polyphosphoric acid on
below the temperature of the acid fed to the venturi. the surface of the Platecoils and cause a substantial in-
The rate of acid flow to the venturi throat also affects the crease in efficiency. At a temperature of 250' F.
differential as shown in Table I. product acid containing 80 to 83% P205 will not sig-
The centrifugal separator, spray section, and mist nificantly corrode the Platecoils even if the temperature
eliminator in the separator tower effectively separate and of the outlet cooling water is allowed to rise above 120"
recover acid from the gas leaving the venturi. F. and solids deposit to restrict heat transfer. At times
the effluent water has been permitted to reach 190' F.
Cooling of the Product Acid Water leaving at a temperature of 189' F. permitted
In the product acid cooler, the agitator rapidly mixes the high transfer rate of 12,000 B.t.u. per hour per sq.
the 450 to 600 g.p.m. of incoming acid at temperatures ft. for the acid containing 80% P20s.
between 200" and 350" F. with the 3700 gal. of acid in
the tank. The temperature of acid in the tank varies Permissible Phosphorus Burning Rates
no more than =k4" F. throughout the tank. Generally, Table I1 shows the maximum permissible acid tem-
overall heat transfer coefficients between the acid and the peratures and phosphorus burning rates for the plant
water in the Platecoils decrease when the concentration when it is producing acids of different concentrations.
and viscosity of acid increase. However, the coefficients Plant operating conditions for attainment of these
sometimes vary for acids of the same concentration. rates are as follows: 20% excess air for phosphorus com-
Since an increase in temperature significantly decreases bustion; cooled product acid flow to two sprays in the
the viscosity of an acid, the acid being cooled is con- top of the hydrator and a total flow of 550 to 600 g.p.m.
trolled at the maximum temperature permissible'without of acid from the hydrator to the coolers; and the use of
excessive corrosion. Ranges of the heat transfer rates the main and auxiliary cooler with effluent cooling
measured for acids of different P 2 0 5content are tabulated water at temperatures up to 150 F.
below. When cooling the acids of high P205 content, Higher phosphorus burning rates than those shown

TABLE I. EFFECT O F D I L U T E A C I D FLOW O N GAS PRESSURE D I F F E R E N T I A L AND O U T L E T T E M P E R A T U R E A T

T H E VENTURI"
Dilute Acid Pressure
Pressure at Daperential
Spray Inlet, across Venturi, -. Gas at Venturi, O F.
Flow, G.P.M. Temp., F. P.S.I.G. In. Water Inlet O U l:let

225 161 95 55 540 162

169 163 65 46 540 168
113 163 40 38 520 165
56 162 12 22 530 182
0 ... 0 12 ... 280+
a Operating conditions: phosphorus burning rate, 7100 lb./hr.; excess air, 18%; PzOd i n product acid, 80.1 7 0 Hap04 in dilute acid, 74.8%; and damper removed from
venturi throat.

TABLE II. M A X I M U M PERMISSIBLE A C I D TEMPERATURES A N D PHOSPHORUS B U R N I N G RATES

Acid Being Temfi. of Acid Leaving, ' F. Phosphorus Burning Rate, Lb./Hr.b
Produced, Dilute Acid with Cooling Water at
% P20P Hydrator Cooler Receiver 45' F. 85' F.
63 (87) 280 200 180 7300 7000
76 (105) 280 200 180 6000 6000
80 (111) 350 250 200 7800 7800
83 (115) 350 250 200 3800 3800
a Hap04 equivalent in parenthesis.
In both combustion chambers.

VOL. 5 9 NO. 6 J U N E 1 9 6 7 25
 Figure 7. Op&'ng data on predudion of phorphic add of diffmmt cowntralion

in Table I1 could be permitted if some bottlenedrs the density and viscosity of the acids increased. When
listed in the following tabulation were e l i i a t e d : the plant was producing acid with 66% Pros content,the
low temperature and vapor pressure of the recycle cooled
acid permitted cooling of the effluent gas to 440' F.
at the 7060-lb. phosphorus feed rate. Inadequate flow
63 Exear qaeure from wata Venturi throat of cooled acid to the top spray caused the temperature
vapor m praas gas of effluent gas to reach the maximum allowable tempera-
76 EXMStmpaahlrc of Product add omla ture of 550" F. and limited production of acid containing
cooled produa
80 Inadequate eombuation air Air blowas 79.6% PiOr.
83 Exear tmpmamc of dilute Lack ofa dilute add coola I n the gas scrubber and separator section, the con-
acid centration of the dilute acid increased from 41 to 91%
HaPO, with increasing concentration of product add
OPERATING DATA AND HEAT AND being made.
MATERIAL BALANCE The acid cooler did not have capacity to cool acid of
0-w 76% PIOI content to 200" F. at the full phosphorus
Figure 7 is a flow diagram of the plant with operating burning rate, and thii limited the production rate of
data from NXHduring the production of acid of 66, this acid. Cooling limitations for dilute acid limited
76, 80, and 83y0 P ~ Ocontent.
I When these runs were the production rate of 83% Pro, acid.
made, some modifications previously described had not
been completed, and the plant was being operated near Heal and Mokrial hlanco
its maximum permissible phosphorus burning rates for Figure 8 gives heat and material balance data for
the concentration of acid beiig made. Both combustion production of acid of 79% Pros content at a phosphorus
chambers were beiig operated under essentially the burning rate of 5300 lb. per hour. Combustion of
same conditions. The data show the effeets of im- phosphorus accounts for 90% of the heat input, hydration
portant operating variables. of Pro, for 8.5y0, and ddution of acid in the venturi
With increased phosphorus feed rates, the temperaturu and scrubber for 1.5%. Of the heat output, 54% is
of the gas leaving the combustion chambers increased, removed in the combustion chambers, 18% in the
and the cooling water requirements increased throughout hydrator, 17%' in the cooler, 8% in the scrubber-
the plant. separator, and 2% in product acid to storage.
At the hydrator, the flow of cooled product acid The percentages of heat removed by water in different
delivered by the pump to the top spray decreased when jackets of a combustion chamber vary widely, but are
usually significantly higher in the bottom than in the Table I11 gives operating indexes per ton of PzOa
top jacket. produced when the plant is being operated at maximum
In this test, no dilute acid was sprayed into the separa- permissible burning rates to produce acid of different
tor tower. Tests had shown that this spray had no concentrations. Man-hours of operating and main-
significant effect on P205 recovery in the scrubber- tenance labor, of course, decrease as the phosphorus
separator system. Percentages of material and heat burning rate is increased. Cooling water varies in
accounted for were less than 100 mainly because of temperature from about 42" in winter to about 89' F.
errors in the measurement of the flows of air and stack in summer. Requirements range from 15,000 to 32,000
gas. g.p.m. per ton of P z O in
~ acid. Owing to the method
of flow control, the power for the blowers does not sig-
OPERATING DELAYS AND INDEXES
nificantly change with the combustion air rate. In the
From May 1962 through May 1966 the acid plant was past, two combustion chambers have been operated to
operated 88.5y0of calendar time.. Most of the operating burn 3800 lb. of phosphorus per hour when 83%
delays have been caused by factors outside the plant, P ~ o 5acid was being made. Cost of power for the
such as lack of phosphorus supply, failure of power or blowers could be cut in half by operating only one
water supply, the necessity for removing phosphorus combustion chamber.
sludge from feed tanks, or acid production not required ;
these factors accounted for 6% of the time. Scheduled EVALUATION
inspections and modifications of the plant accounted The stainless steel thermal phosphoric acid plant
for about 3%. The sum of delays for equipment repair described in this paper operates smoothly to produce
was about 38 days or less than 3% of the time. During acid containing 60 to 83y0 P z O ~(equivalent to 83
the past year, the plant was operated 92yC of the time, to 115% H3P04). Only minor adjustments in the
and the average burning rate per operating hour was operating conditions are required to vary the concentra-
5810 lb. of phosphorus. tion of the acid. About 99.9yc of the phosphorus
burned is recovered as acid. Corrosion of the stainless
steel equipment has been negligible and operating and
maintenance costs have been reasonable.
TABLE Ill. OPERATING INDEXES Operating experience and plant studies have shown
Production ways to avert equipment failures, to achieve optimum
Product acid, % Pz05 63.0 76.0 79.6 83.3 operating conditions, and to increase the production
HaPOdequivalent, yo 87 105 110 115 capacity.
Phosphorus rate, lb./hr. 7000 6000 7800 3800 The performance of this plant has demonstrated
Acid production, tons/hr. 12.7 9.0 11 , 2 5.2 that acid containing 83ycP205 or the equivalent of 115%
H3P04 can be easily produced. However, additional
Indexes/ton of P z 0 6in acid
cooling of the dilute acid would be required for the
Labor, man-hours production of more than 5 tons of such acid per hour
Operating in this plant. With careful operational control and
Operator 0.12 0.14 0.13 0.22 preventive maintenance, this plant should continue to
Foreman 0.04 0.04 0.04 0.06 perform well for several years.
Maintenance 0.11 0.13 0.11 0.21 Information gained from the operation of this plant
Materials for mainte- has been helpful to other producers of phosphoric acid.
nance, $ 0.34 0.40 0.34 0.62 Design and operating data from this plant have been
Cooling water, million used by the industry as a basis for the design of several
gai.5 plants of a similar type (2). Product acid is used in the
I n at 45 O F., out at manufacture of other products as well as in fertilizer
120" F. 15 15 15 15 production.
In at 65 O F., out at TVA is constructing another stainless steel plant of
120 F. 20 20 20 20 similar design to replace the remaining older unit.
I n at 85 O F., out at
120" F. 32 32 32 32 LITERATURE CITED
Make-up water, gal. 210 130 126 90 (1) Almond, L. H., Steinbiss, H. K., Chem. Eng. 5 5 , 105-9, (October 1948).
(2) Com. Fertilizer 119 (3), 2 5 , 28 (1966).
Combustion air, million (3) Getsinger, J. G., Siegel, M. R., Mann, H . C., Jr., J . Agr. Food Chem. 10, 341-4
cu. ft. (1 962).
80 80 80 80 (4) Phillips, A. B., Young, R. D., Heil, F. G., Norton, M. M., Ibid., 8, 310-15
Atomizing air, million cu. (1960).
ft. 2 2 2 2
(5) Scott, \V. C.; Wilbanks, J. A,, Burns, M. R., Fertilizer S o h . 9, 6-7, 10-11, 14-15
(November-December 1965).
Electricity, kw.-hr. 56 61 52 (6) Slack, A. V.,Potts, J. M., Shaffer, H . B., Jr., J . Agr. Food Chem. 13, 165-71
80 (March-April 1965).
Electricity for air blowers, ( 7 ) Striplin, M. M., Jr., FerliiizerSoln. 4, 32-4 (1962).
(8) Striplin, M. M. Jr., McKnight, David, Megar, G. H., J . Agr. Food Chem.
kw.-hr. 41 44 39 53 6 , 298-303 (195.3):
Steam, lb. 15 (9) Striplin, M. M., Jr., Stinson, J. M., Wilbanks, J. A . , Ibid., 7, 623-8 (1959).
18 14 25
(10) Walthall, J. H., Striplin, M. M., Jr., IND. ENG.CHEH.33, 995-1000 (1941).
4 Approximateb 2.7 gal. of Q3'7 sulfuric acid is added per 700,000 gal. of river water to (11) Wilbanks, J. A., Nason, M . C . , Scott, W. C., J . Agr. Food Chem. 9, 174-8
prevent scale formation. Water f o/cooizng o i l at blowers is approximately 10 gal./min. (1961).

28 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY