August, 1941

INDUSTRIAL A N D ENGINEERING CHEMISTRY

within coatings that are properly formulated never reaches

a concentration sufficiently high to satisfy the conditions
requisite for electrochemical corrosion. The impermeability
of bituminous coatings to electrolytic ions constitutes an
additional bar to corrosion of the protected metal. Practical
corrosion tests in the laboratory and field have fully substantiated the above statements. It fOllOwS that asphalt will be
effective in preventing the corrosion of coated metal pipes as
long as the asphalt coating remains macroscopically intact.

Literature Cited

A. 0.. Badger, R. M., Gullehon, E. E., and Stevenson, D. P., IND.ENO.CHEM.,33,984 (1941).

(1) Beckman,

995

(2) Boggs, C. R.,and Blake, J. T.,

Ibid., 18,224 (1926).

ftl$;zz7
~~~~,52ur.

sei.
Papers, 16,327 (1920).
( 5 ) Herrmann, D. B.,Be22 Lab. Record, 13,45 (1934).
(6) Hickman, K.C. D., J. Franklin Inst., 221, 215, 383 (1936).
H H.t and Kohmang G* T * tJ * Phys*
31p23
(7) (1927).
(8) Mallison, H., Vedag-Buch, p. 144, Berlin, Vereinigte Da&
pappen-Fabriken, 1936.
(9) Morris, V. N., and Street, J. N., IND.ENQ.CHEM.,21, 1215

(1929).
(10) Taylor, R. L., Herrmann, D. B., and Kemp, A. R., Ibid., 28,
1255 (1936).
(11) Thomas, G.O.,J . Inst. Engineers, Australia, 6 , 337 (1934).
(12) Walther, H., Oel Kohle, Erdoel Teer, 12, 191 (1936).

Superphosphoric Acid by
Absorption of Phosphorus
Pentoxide Vapor
__

J. H. WALTHALL AXD M. M. STRIPLIN, JR.

Tennessee Valley Authority, Wilson Dam, Ala.

The pilot-plant development of a new process for manufacturing phosphoric acid is

described. Phosphorus is burned with
dried air, and the resulting phosphorus
pentoxide vapor is absorbed in concentrated aqueous solutions containing about
85 per cent phosphorus pentoxide (superphosphoric acid). Concentrated solutions, of low water vapor pressure, and dried
air are employed to avoid the formation of
an acid mist resulting from hydration of
the phosphorus pentoxide in the vapor
phase. The absorption step is carried out
at temperatures high enough to prevent
condensation of phosphorus pentoxide to
the solid phase.
The resulting phosphorus pentoxide solution is a viscous liquid which can be diluted
with water to yield either pyrophosphoric
or orthophosphoric acid, depending upon
the quantity of water used for dilution.
The advantages of the process over the present method used to produce weaker acid
are discussed.

HE customary procedure in the manufacture of phosphoric acid by furnace methods is either to burn the gas
directly as it comes from the furnace, or to separate the
phosphorus from the carbon monoxide by condensation and
then burn the phosphorus. After combustion, water is
sprayed into the gas to cool it and t o hydrate the phosphorus
pentoxide. This treatment produces a mist of finely divided
phosphoric acid particles which usually are separated from
the gas stream electrostatically. An exception to the electrostatic method of separation is the recently developed packedtower method. It has been shown (3) that effective collection
of the phosphoric acid mist may be obtained mechanically in
a packed tower. The use of a packed tower for this purpose
should not be confused with gas absorption, since the material
to be recovered enters the tower as a finely divided suspension
of liquid droplets and is therefore not required to undergo a
change of phase when collected.
Satisfactory mechanical separation of a mist from a gas
stream is usually difficult to accomplish. For instance, in the
packed-tower process referred t o above, a high-pressure drop
across the tower is required t o obtain good recovery of acid.
It seemed worth while, therefore, to investigate the absorption of phosphorus pentoxide vapor by phosphorio acid. If
phosphoric acid could be recovered by absorption of the vapor
of its anhydride, the dficulties inherent in separating small
suspended liquid particles from a gas stream could be avoided.
Obviously, recovery of phosphoric acid in a packed tower
might result from the absorption of phosphorus pentoxide
vapor, the mechanical collection of liquid droplets, or the condensation and solution of solid phosphorus pentoxide. It
was necessary, therefore, in the present development work, t o
understand the behavior of phosphorus pentoxide and phosphoric acid under various conditions and to employ an experimental technique which would permit a study of absorption with a minimum of interference by the other two methods
of recovery. The most logical procedure was to operate the

INDUSTRIAL AND ENGINEERING CHEMISTRY

996

tower under conditions which would prevent the phosphorus

pentoxide vapor from undergoing a change of phase prior
to its absorption by the acid. To accomplish this it was necessary to operate the system a t a temperature high enough to
avoid condensation of phosphorus pentoxide to the solid
phase, and also under anhydrous conditions to a.t.oid mist
formation which would result in conversion of phosphorus
pentoxide vapor to the liquid phase.

.:c

PARTIAL PRESSURE P,O,;MM

MERCURY
38.424.0
17.4
13.7
11.2
9.6
8.3
280

EXCESS AIR-PER CENT

FIGURE1. THE P4Ol0 DEW POINT

OF
GAS PRODUCEDBY BURXIKG
PHOSPHORUS
IN DRYAIR

Vol. 33, No. 8

I n the development of the original conception of the process,

it was realized that to bring about true gaseous absorption
would require both the introduction of the phosphorus pentoxide into the tower as a vapor and preservation of the
vapor state within the tower until absorption could occur.
Should an attempt be made to absorb phosphorus pentoxide
vapor in a liquid that exerts an appreciable vapor pressure of
water, the phosphorus pentoxide upon entering the absorption
apparatus would first come in contact with water vapor which
had evaporated from the liquid into the gas stream. Because
of the rapidity with which P4O10
and water vapor react, an acid
mist would undoubtedly be formed before the P4O10could
reach the surface of the liquid and be absorbed. Finely
divided liquid particles suspended in a gas have negligible
diffusion velocities and, as a result, are effectively insulated
from contact with the main body of the liquid by a gas film (7).
I n all probability this accounts for the poor recovery obtained
when attempts are made to absorb phosphorus pentoxidevapor
in either water or dilute aqueous solutions of phosphoric acid.
Because of the effect of the presence of water vapor, it was
necessary to keep the atmosphere within the absorption
tower substantially dry by employing as the absorbent phosphoric acid of sufficiently high P205 content to exert a very
low vapor pressure. Lack of vapor pressure data for phosphoric acid containing in excess of 72.4 per cent P20s
(100 per
cent H3P04) prevented estimation of a suitable strength of
acid that might have been used as the absorbent. However,
it was apparent that the acid would have to contain more than
72.4 per cent phosphorus pentoxide because acid of this
strength exerts an appreciable vapor pressure of water even
at lower temperatures than those required to avoid condensation of phosphorus pentoxide (Figure 1).
The present study was undertaken t o determine whether the
concept as to the fundamental principles of the process was
sound, t o determine the strength of acid that could be produced by the process, and to obtain data for comparison of
the process with other methods of producing phosphoric acid.
Although it is customary to interpret absorption data in
terms of capacity coefficients, the accumulation of sufficient
data for the proper application of this method was considered
beyond the scope of the present study.

When phosphorus is burned with a limited excess of dry

air, enough heat is liberated to vaporize and superheat the
resulting phosphorus pentoxide. If the gas containing the
phosphorus pentoxide is then permitted t o lose heat, a temperature will finally be reached a t which it becomes saturated
with phosphorus pentoxide. I n the absence of supercooling
the loss of additional heat will result in the condensation of
phosphorus pentoxide as a solid. The vapor pre,sure measurements of Southard and Nelson (6) were used to calculate this
temperature for gaseous mixtures obtained by burning phosphorus with various amounts of air. The results are given in
Figure 1. In calculating these temperatures it was necessary
to know the molecular weight of phosphorus pentoxide vapor.
Southard and Nelson (6) estimated the vapor to consist
essentially of P4Oi0. Therefore, a molecular weight of 284,
which corresponds to P4010,was used in the calculations.
Equipment and Procedure
From this figure it was posiible to estimate the lowest temThe upper diagram of Figure 2 shows the pilot plant as first
perature at which the gas could be introduced into the
assembled. The equipment for drying air with phosphoric
absorption tower and maintain the phosphorus pentoxide in
acid has been described (6) and is not shown.
the vapor state.
To prevent the PaOlo from undergoing a
change of phase before entering the absorption tower, it is necessary not only to maintain the gas a t a temperature above the dew
point but also, as pointed out above, to exclude the presence of any appreciable quantity
of water vapor. Even though phosphorus
is burned usually with air which contains some
water vapor, it is customary to refer to the
product as phosphorus pentoxide. This is not
the case, however, because any water introduced with the air combines with the phosphorus pentoxide to produce acid. Since a
small amount of water will partially hydrate
a comparatively large amount of phosphorus
pentoxide, it appeared necessary to guard
against mist formation prior to the absorption step by drying the air used for combustion.
The most logical method for carrying out the
drying operation was to bring the air into contact with the phosphoric acid produced continuously in the process and thereby eliminate
P I L E O F SUPERPHOSPHATE FERTILIZER
PREPARED BY REACTING ROCK
PHOSPHATE WITH PHOSPHORIC
ACID
the necessity of regenerating a drying agent.

August, 1941

INDUSTRIAL AND ENGINEERING CHEMISTRY

997

to deliver the hot phosphoric acid to

the top of the packed tower. Water
was directed on the outside of the packing gland to increase the life of the
packing. No difficultywas experienced
in
pumping the acid. The pump ordiFILTER
narily required repacking after about
5 days of continuous operation.
Eleven runs were made with the
pilot plant assembled as shown in the
COOLER
upper diagram, Figure 2. I t was then
modified as sketched below to permit a
study of the absorption of phosphorus
gentoxide vapor from gas obtained by
urning phosphorus with a much
greater excess of air than that used in
making the first eleven runs. The
original combustion chamber was replaced with a smaller refractory-lined
chamber. A phosphorus vaporizer and
I
an air preheater %ere added. These
changes were necessary to obtain gas
temperatures at the inlet of the absorption tower well above the dew
point of phosphorus pentoxide. . The
phosphorus vaporizer consisted of a
28-inch section of 6-inch pipe closed
at each end by flanges, and was electrically heated by strip heaters fastened
to the outer surface of the pipe. The
air preheater consisted of eight 20-foot
sections of 2-inch pipe connected by
return bends and placed in a box containing loose heat-insulating material.
Electrical contacts were made at each
end of the 160-foot len th of pipe, and
the pipe itself was usecf as an electrical
resistor. The air to be preheated was
passed through the pipe. With this
arrangement 2500 cubic feet of air per
hour could be heated to 450' C. (842'
F.) with 750 amperes at 75 volts.
The concentration of the acid being
recirculated was prevented from increasing by frequent additions of
weaker acid containing about 55 per
cent phosphorus pentoxide. Acid wm
used for dilution instead of water because the latter would have flashed to
steam at the temperatures prevailing
in the tank.
Phosphorus pentoxide recovery was
determined by deducting the amount
of phosphorus pentoxide contained in
the exhauat gas from the amount entering the tower. The phosphorus pentoxide content of the exhaust gas was
determined by diverting a measured
amount of the gas and passin it
through a filter tube packed with Jass
wool. When sampling the gas, the
velocity in the sampling tube was ke t
OF ORIGINAL
(above) AND OF MODIFIED
PILOT
PLANT
(below)
FIQKJRE
2. DIAGRAM
amroximatelv the same as that in tEe
exhaust line, "After passing gas through
the glass wool filter for 10 minutes, the
A brick-lined cylinder was used for the combustion chamber.
tube was removed and washed with hot water to dissolve the
Dry molten phosphorus was fed at 60" C. (140' F.) into it from
phosphorus pentoxide. The hosphorus pentoxide content of
calibrated cylinders by displacement with water. A small orifice
the wash water was obtainex by chemical analysis, and the
meter calibrated in terms of phosphorus was employed to
result was used to compute the amount of phosphorus pentmeasure the rate a t which water was used for this pur ose.
oxide contained in the jexhaust gas. During the 10-minute
After being dried, the air was passed through a calibrated %enperiod required to take a gas sample, the oxygen content of the
turi meter and then into the combustion chamber. The moisture
exhaust gas was obtained with an Orsat apparatus, and a sample
content of the air was calculated from wet- and dry-bulb temof acid was removed from the acid tank. The amount of phosperatures.
phorus pentoxide that entered the tower was calculated from an
oxygen balance. The accuracy of this procedure was verified
An indirect gas cooler, constructed by jacketing a section of
durin runs 8 and 10 by means of material balances which insheet-iron pipe, was employed to control the temperature of the
clude$ the weight of acid produced.
gas entering the packed tower. The packed tower was 11.8
inches in diameter and was packed to a depth of 7 feet with 1inch porcelain Raschig rings. The rings were supported by a
Experimental Results
perforated metal plate. Acid drained from the tower through a
The absorption data are given in Table I. With the
pipe which extended to the bottom of an upright cylinder located
in the acid tank. Acid overflowed at the top of the cylinder
exception of run 10, during which a n aqueous solution of orthothrough a calibrated weir provided to measure the acid rate.
phosphoric acid was used as absorbent, the experimental conThe temperature of the acid entering the tower was controlled
ditions were favorable to the absorption of phosphorus
by regulating the flow of cooling water through a coil of pipe
pentoxide vapor. The acid was at a temperature high enough
contained in the acid tank. A centrifugal pump was employed

1.-

998

INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 33, No. 8

TABLEI. EXPERIMENTAL
AND CALCULATED
DATA
Phosphorus
Rate,
Lb./Hr.

Air for Combustion

Rate
Humidity,
(9.T. P.).
lb. H % 0 /
Per cent
Ou. ft./hr.
Ib. dry air
excess

Absorption Tower
Inlet GasTempeiature, Velocity
ft./sec.b'
C.

Acid
Rate.
lb./hr.j

sq. ft.

Per cent
P206

Temp., C.
Tower
Tower
inlet
outlet

Phosphorus Pentoxide
Tower loss,
Per cent
lb./hr.
recovery

Run 1
19.8
19.6
19.6
19.5

2055
2038
2038
2028

0.0005
0,0006
0.0006
0.0006

50
50
50
50

360
285
300
320

1.5
1.5
1.4
1.4

1250
1250
1250
1250

78.2
79.2
79.5
79.9

177
182
186
196

192
202
214
218

3.8
4.8
5.8
5.8

91.6
89.3
87.1
87.0

24.4
23.9
24.6

2685
2555
2570

0.0041
0.0039
0.0039

53
54
51

340
350
350

1.9
1.9
1.9

625
625
625

82.3
82.9
83.8

179
185
168

254
277
274

3.6
2.3
3.6

93.6
95.8
93.6

25.1
25.1

2620
2620

0.0044
0.0038

51
51

390
392

2.1
2.1

2890
2890

82.3
85.3

185
185

204
200

3.0
2.6

94.8
95.5

22.9
22.8
22.4
22.5
22.6
22.6

2615
2600
2600
2610
2620
2620

0.0032
0,0027
0.0027
0.0019
0.0019
0 0019

65
65
68
67
67
67

375
380
390
397
415
415

2.0
2.1
2.1
2.1
2.2
2.2

2890
2890
2890
1088
1860
1860

82.7
83.1
83.7
83.7
83.1
83.1

188
196
204
183
202
202

224
213
218
232
246
246

1.8
2.2
2.5
1.3
2.1
1.6

96.6
95.8
95.1
97.5
95.9
96.9

23.4
23.0

2597
2555

0.0028
0.0027

60
60

450
445

2.3
2.2

2890
2890

83.2
83.1

206
210

225
229

2.6
2.1

95.1
96.0

29.5
29.2
28.7
29.2
29.2

3070
3040
2980
2980
2980

0.0010
0.0015
0.0018
0.0020
0.0021

50
50
50
47
47

440
455
510
530
515

2.6
2.6
2.8
2.8
2.8

2890
2890
2890
2890
2890

83.1
84.5
82.6
82.5
82.7

204
204
204
204
204

279
221
229
229
228

3.4
2.1
2.8
3.5
3.1

95.0
96.9
93.7
94.8
95.4

18.5
18.5
18.2

2020
1925
1925

0.0061
0.0058
0.0058

58
50
53

395
395
385

1.6
1.5
1.5

2890
2890
2890

83.4
83.2
83.0

206
207
199

216
22 1
224

1.4
1.9
2.2

96.7
95.5
94.7

23.8
24.0
22.3
24.3
24.9
23.8
24.6
22.6

2500
2490
2475
2475
2490
2475
2510
2495

0.0046
0.0061
0.0060
0.0052
0.0048
0.0040
0.0039
0.0038

51
50
60
46
44
50
47
60

450
442
458
450
460
450
450
460

2.2
2.1
2.2
2.1
2.2
2.1
2.2
2.2

1860
1860
1860
1860
1860
1860
1860
1860

82.8
82.8
82.9
83.2
83.0
83.4
82.5
82.6

207
210
213
204
204
204
204
204

243
240
238
227
238
224
22 1
229

4.3
5.2
4.8
3.5
3.4
3.5
3.7
5.5

92.1
90.5
90.6
93.7
94.1
93.6
93.4
89.3

23.6
23.6
22.8
23.6

2525
2525
2525
2525

0.0028
0.0023
0.0020
0.0025

54
54
60
54

455
450
460
4b0

2.2
2.2
2.2
2.2

2890
2890
2890
2890

84.7
84.9
85.0
85.0

216
216
218
218

229
224
229
235

1.7
2.3
2.5
2.5

96. 9
95.7
95.2
95.4

21.8
21.8
22.8
22.6
23.0
23.0

2620
2620
2620
2600
2600
2600

0.0069
0.0066
0.0066
0.0065
0.0063
0.0063

73
73
66
66
63
63

340
345
375
380
390
393

1.9
2.0
2.0
2.0
2.1
2.1

9630
9630
9630
9630
9630
9630

71.7
71.7
69.8
69.8
70.0
70.0

85
85
82
82
82
82

93
93
93
93
93
93

13.8
22.9
24.2
21.0
18.1
21.6

72.3
54.1
53.6
59.5
65.6
58.9

24.8
24.1
23.9
23.5
25.2

2440
2460
2465
2465
2540

0.0028
0.0020
0.0031
0.0018
0.0024

42
47
49
52
46

563
578
573
573
506

Run 11
2.3
2.3
2.3
2.3
2.2

2555
2688
2555
2555
2815

86.0
86.4
85.3
86.5
87.0

232
232
252
252
282

248
252
271
285
293

0.75
0.61
1.56
0.58
0.54

98.7
98.9
97.1
98.9
99.2

4.8
4.8
3.3
3.0
3.2

2355
2405
2405
2405
2385

0.0023
0.0009
0.0022
0.0020
0.0019

610
630
960
1065
980

490
500
490
495
500

2.4
2.4
2.4
2.4
2.4

2285
2336
2367
2362
2338

85.3
84.9
85.4
86.0
85.7

251
254
251
251
249

267
260
254
260
260

0.16
0.38
0.22
0.19
0.28

98.5
96.5
97.1
97.2
96.2

Run 2

Run 3

Run 4

Run 5

Run 6

Run 7

Run 8

Run 9

Run 10

Run 12

a
b

The absorption tower exit gas tempcrature waB essentially the same as the absorption tower inlet acid temperature.
Based on e m p w tower.

to avoid condensation of phosphorus pentoxide and concentrated enough to prevent the evaporation of appreciable
quantities of water. In all of the runs reported, the gaseous
mixture was kept in a substantially dry condition and was
introduced into the absorption tower at a temperature high
enough to ensure the phosphorus pentoxide being in the vapor
phase.

An attempt t o start a run with a cold system clearly demonstrated that condensation of phosphorus pentoxide would
have to be prevented, not only for the purpose of distinguishing between the different methods of recovery, but also for the
proper functioning of the packed tower. Large quantities of
phosphorus pentoxide condensed in the pipe lines and in the
packed tower. Some of it could be observed floating in an

INDUSTRIAL AND ENGINEERING CHEMISTRY

August, 1941

999

pentoxide content is much less viscous and can be pumpcd

satisfactorily a t slightly elevated temperatures. Some of the
properties of acids containing more than 72.4 per cent P205
were discussed by Lum, Malowan, and Durgin (4).
Run 12 was made to determine whether good recovery could
be obtained from gas containing much less phosphorus pentoxide than that produced by burning phosphorus with an
excess of air of the order of 50 per cent. During run 12,
recovery was determined when burning condensed phosphorus

unwetted condition on the surface of the acid draining from

the packed tower. The remainder accumulated in the packing and restricted the flow of gas and acid through the tower.
Thereafter the system was preheated before starting a run.
When the temperatures of inlet gas and acid were high enough
to avoid condensation, the plant functioned smoothly, and
no solid phosphorus pentoxide could be observed in the acid.
The gas velocity and the acid rate were varied between
rather narrow limits without a noticeable influence on phosphorus pentoxide recovery. The principal factor affecting
recovery wag the concentration of the acid employed as the
absorbent. As Figure 3 shows, the recovery improved markedly with increase in acid concentration. This was expected because of the effect of acid concentration upon the
partial pressure of water vapor in the absorption tower. It
is unfortunate that vapor pressure data for phosphoric acids
containing more than 72.4 per cent PzO6 are not available so
that a direct plot can be made. However, Figure 3 serves to
illustrate the principle involved.
Some idea of the quantity of water vaporized from two
acids of different concentrations and its effect on recovery can
be obtained from the material balances given in Table 11.
For comparison with runs in which stronger acid was used,
run 10 was made with acid containing about 71 per cent
phosphorus pentoxide which is equivalent to 98 per cent
HaP04. During this run 47 pounds of water were vaporized
from the acid in 5.3 hours, and only 56 per cent of the phosphorus pentoxide was recovered. During run 8 in which
stronger acid containing about 83 per cent phosphorus pentoxide was used, only 1 pound of water was volatilized in 13.8
hours, and there was 92 per cent recovery. The highest recovery, 99.2 per cent, was obtained with acid of 87 per cent
phosphorus pentoxide content (Table I).
Assuming that any water vapor given up by the acid combines with phosphorus pentoxide vapor to form metaphosphoric acid according t o the equation,

with about 600 per cent excess air and also with about 1000
per cent excess air. The results in Table I show that recoveries
of the same order were obtained as when using the more concentrated gas. This is of considerable importance because of
the water vaporized during run 8 was sufficient to hydrate only
1.2 per cent of the phosphorus pentoxide, whereas during
the possible desirability of using this process to recover
phosphorus pentoxide directly from oxidized electric furnace
run 10 the water vaporized was enough t o hydrate ail of the
phosphorus pentoxide. This seems to be the explanation for
or oxidized blast furnace gas without first condensing the
the poor recovery obtained when weaker acid was used.
phosphorus.
The most concentrated acid produced contained 87.0 per
The partial pressure of P4010 in gas produced by burning
cent phosphorus pentoxide (run 11, Table I) and was entirely
condensed phosphorus with 50 per cent excess air has been
calculated to be about 24 mm. of mercury. This is probably
too viscous to pump a t room temperature. Therefore it would
seem advantageous when producing acid of this concentration
the most concentrated gas that would be encountered in the
to dilute it to about 84-85 per cent phosphorus pentoxide
commercial application of this process because the use of a
smaller excess of air might result in incomplete oxidation of
before allowing it to cool. Acid of 8485 per cent phosphorus
phosphorus- during unsteady
operation. Oxidation of the
phosphorus contained in
phosphate blast furnace gas
TABLE11. MATERIAL
BALANCES
FOR RUNS8 AND 10
would probably yield a gas
c
Run 8
-Run
IO------.
Wt., Concn.
PlOs, Water,
Wt., Conon., PlOs, Water,
containing about 3 to 5 mm.
lb.
% P20; lb.
lb.
lb.
yo P10s lb.
lb.
partial pressure of P4O10.
Material in
Acid in tank at start of run
400
83.8
335
65
376
72.9
274
102
These partial pressures correAcid added during run
401
55.3
222 179
118
0
... 118
spond roughly to that obTotal
801
557
ZG
m
274
tained when oxidizing conMaterial out
Acid removed from tank during run
548
83.1
456
92
584
0.3
411
densed phosphorus with 1000
906
83.3
765 1
s
... 7....
... 173
...
Acid removed from tank at end of run
and with 600 per cent excess
Total
1454
1211
243
air, respectively. The partial
Summary
Water vaporized from acid =
244 - 243 = 1 Ib.
220 - 173 = 47 lb.
pressure of P401o in gas obP2Oa recovered =
1211 - 557
6541b.
411 - 274 = 1371b.
tained by oxidizing the phosPaOs content of exhaust gas =
4.2 lb. per hr.0
20.3 Ib. per hr.b
Lennth of run =
13 81 hr.
5.30 hr
phorus in phosphate electric
P2O;lost in exhaust gas =
4.2 X 13.81 = 58 Ib.
20.3 X 5.30 = 108 lb.
P2Os recovery =
[654/(654 f 58)] 100 = 92.0%
furnace gas would probably
[137/(137 f l08)l 100 = 56%
be between 3 and 25 mm.,
a Average value for run 8, taken from Table I.
b Average value for run 10, taken from Table I
which is within the range
studied.
Pa010

+ 2Hz0 = 4HP08

1000

INDUSTRIAL AND ENGINEERING CHEMISTRY

Although no systematic study was made to determine

what effect the humidity of the air used for combustion had on
recovery, about a fourteen fold variation in this factor occurred during the investigation. However, any influence it
may have had on recovery was no greater than that of uncontrollable variations in operation and hence could not be
evaluated. The most humid air used contained about 0.007
pound of water per pound of dry air. This is less moisture
than that contained in air from most localities during periods
of high humidity. Therefore] it cannot safely be said that
it is unnecessary to provide a means of drying the air. Further
study will be required to settle this question.
When condensed phosphorus was burned with undried air
during periods of high humidity] and extremely viscous material] presumably phosphoric acid of very high phosphorus
pentoxide content, was deposited in the pipe through which
the products of combustion passed. Upon cooling, this material changed to a glassy solid which was extremely difficult
to remove from the pipe. Drying the air used for combustion
practically eliminated the formation of this material and
therefore might be worth while from this standpoint alone.

Advantages
The process appears to have several important advantages
over others now in use for producing less concentrated acid.
Probably the most important, in view of the ever increasing
demand for new products, is that the process yields acid containing 85 per cent phosphorus pentoxide as compared to
the common product containing only about 55 per cent. Acid
of 85 per cent Pz06content can be readily diluted with water
or with dilute phosphoric acid to give pyrophosphoric acid or
orthophosphoric acid of any strength desired.
It is possible by shipping acid of high Pz06
content to avoid
handling a portion of the water contained in weaker acid.
For acids of 85 and 55 per cent phosphorus pentoxide content, this would amount to a saving in freight of about 35
per cent. Where the transportation of acid is required, this
economy might well become the deciding factor in favor of the
present process. Furthermore] acid of 85 per cent phosphorus pentoxide content is comparatively noncorrosive a t
room temperature and could probably be handled in less
expensive containers than those required for acid of 55 per
cent phosphorus pentoxide content.
I n spite of these advantages, use of the process commercially might not be justified at present unless i t could be
employed to produce acid which, after dilution, would compare favorably in cost with acid manufactured by processes
now in use. Determination of this point would require
economic studies beyond the scope of the present paper. I n
making a comparison on a phosphorus pentoxide unit cost
basis, however, several important advantages of the present
process should be considered.
Rapid deterioration of equipment in existing phosphoric
acid plants employing furnace methods is a serious problem
(1). Repairs and maintenance due to this factor contribute
appreciably to the cost of the product. I n such plants phosphoric acid mist is present at elevated temperature in practically every unit of the plant, including the combustion chamber, gas mains, collecting equipment, and exhaust fan. The
comparatively short life of this equipment is believed to be
due both to the corrosive action of the hot phosphoric acid
and to the erosive action of the acid mist impinging on the
exposed surfaces. Lining the equipment with acidproof
brick is not a satisfactory solution of the problem because
acid seeps through the lining and attacks the metal.
I n contrast to phosphoric acid mist, dry phosphorus pentcJxide vapor does not attack metal appreciably a t temperatures below red heat. During the present investigation the

Vol. 33, No. 8

vapor was successfully handled a t 700" C. (1290" F.) in an

air-cooled sheet-iron duct. With the present process it should
be possible to confine the presence of water to the absorption
tower and acid handling equipment] and thereby avoid the
formation of acid in other parts of the plant. This should
reduce corrosion and also permit the use of less expensive
materials of construction.
Curtis, Miller, and Junkins (2) have described a modern
phosphoric acid plant. This plant requires the use of electrostatic precipitators. Since the present process employs
comparatively inexpensive packed towers instead of electrostatic precipitators, it seems reasonable to expect a lower
initial cost of installation.

Summary and Conclusions

A suitable process for producing phosphoric acid containing
about 85 per cent phosphorus pentoxide ("superphosphoric
acid") has been developed on a pilot-plant scale. It differs
from other thermal processes used commercially to manufacture less concentrated phosphoric acid in that it involves
the absorption of phosphorus pentoxide vapor, whereas the
others are b a e d on either mechanical or electrostatic separation of an acid mist.
Superphosphoric acid was obtained by passing the oxidation products from the combustion of phosphorus with dried
air into an absorption tower operated under the following
conditions: temperature of inlet gas 460" C. (860' F.),
exit 215" C. (420" F.); superficial gas velocity, 2.2 feet per
second; concentration of acid used as absorbent, about 85
per cent phosphorus pentoxide; temperature of inlet absorbent 218' C. (424" F.), exit 230" C. (446" F.); circulation
rate of absorbent, 2890 pounds per hour per square foot of
tower cross section.
The degree of absorption of phosphorus pentoxide vapor
varied with the concentration of the phosphoric acid used as
the absorbent. The recovery increased markedly with acid
concentration and reached 99.2 per cent when using acid containing 87.0 per cent phosphorus pentoxide. The data were
not sufficiently extensive to indicate the effect of gas velocity
or acid rate.
Phosphoric acid containing 72.4 per cent phosphorus pentoxide (orthophosphoric acid) was found to be unsuitable as
an absorbing medium for phosphorus pentoxide vapor.
Only 56 per cent recovery of phosphorus pentoxide was obtained when using this acid as the absorbent.
Aclcnowledgment
The authors wish to acknowledge the assistance of R. A.
Wilson and other members of the TVA staff who helped with
the experimental work presented in this paper.

Literature Cited
(1) Curtis, H. A., and Miller, A. RII., Chem. & M e t . Eng. 43, 408
(1936).
(2) Curtis, H. A., Miller, A. M., and Junkins, J. N., Ibid., 43, 583
(1936).
(3) Curtis, H.A.. Miller, A. M.,and Newton, R. H., Ibid , 45, 193
(1938).
(4) Lum, J. H., Malowan, J. E., and Durgin, C. B., Ibid., 44, 721
(1937).
(5) Southard, J, D., and ?;elson, R. A., J . Am. Chem. S O C ,59, 911
(1937).
(6) Striplin, M. M.,Jr., IND. EXG.CHEM.,
33, 910 (1941).
(7) Walker, W. H., Lewis, M'. K., McBdams, W. H., and Gilliland,
E. R.. "Princides of Chemical Enainoerinn".
- 3rd ed. D. 38
New York, McGraw-Hill Book Co.,-1937.
PRESBNTED
before t h e Division of Industrial and Engineering Chemistry
a t the lOlst Meeting of the American Chemical Society, St. Louis, hlo.