PI 0.414 u.414 ... ... ~. ... ... ...

C
SiF.
+
0 1.199
0.072
( 0 )o.54!1
~ . .
(01 u:bir
... 0'0.14
... ...
...
U.lKU
... n:ois
~ . . 0:47,
...
...
...
n*o 0.096 ... ... ... . . ... 0:096 ... ...
v. c. .M. a.nn9 . . ~ ... . ~ . . . ... .. ... ... ... 0.00Q
cnniiow 11*or;rnr>risi ~ ~ ~~- -~~ , .~-S,.ro .*x,i.,x,r r- ___ PlOS B*L.,*cE:-~--
PeOa + 5C Pa + 5C0 1.unii x 0 423 0.423
++c3C= =zcoFe* + 8CCJ
~

x n.m
~

FclOi o.040 o.226 =

COI

creased by increase of temperature iiritil sucli iircrciise ei'leat,,. ( 3 ) The ~J~W'IIWUS may be wliected in elemental state,
a statc of physical change by brillging tile otilcr followed by a step ill wlrich the 0nid:ition and hydration are per-
P*06arid carbon into further contact. This usually r(:- fi,rmcil in r:ont,inuity.

control, since the synclironisinl: of several steps for continuous

The C a M i O I ratio may vary considerably frolri the 3 to 2, as
shown, but this combination is known to result in satisfathory
operation. As above statcd, this reaction is involved in
substantially every thermal process that has tiad any degree
of successful employment. Where ptiosplioric acid is the
desired final product, there rmrst be siibseqiierit operatioils d
reoxidation and hydration. The oxidation fiinetion is
usually written
operation demands marc careful design in the solution of
prolAems arising than in control of tire individual step func-
tions. However, the disconnected processes involve greater
uttendant costs and processing losses than connected or
continuous processes. The conversion of a process from
separated or intermittent stage operation to one of continuity
usriallv involves ovcrcomine" manv difficulties in desinn.,
etinstruction, and operation before successful outcome re-
~~

Pz 5CO + +
10 ( 0 ) = €'&a 5 0 1 + snlt,s.
Ti<-hvdrat,ion i s ,in-
_ _ i _ ....
ELWXROTEERMAI.
derstood as PRocEss

PrOa + 3Hn0 =
21I*POI
Tlie electrothermal
phosphoric acid proc-
ess inuseatAnniston,
The steps shown in Ala., was conceived
the three f o r e g o i n g upon the above prin-
r e a c t i o n s may be, ciple of greater econo-
and are in different miesfrnm process eon-
instances, conducted tinuity. Its develop
separately or in con- ment to a commcr-
tinuity: cia1 silecess required
s o l u t i o n of m a n y
(1) All threc may
be conducted &s R con- problems not foreseen
tinuous meration. i 11 t 11e disconnected
(2) Ail t h r e e may step process. There
heconducted s e p a - had heen several pre-
vious a t t e m p t s at
production of phos-
lected. then'oxidieed Dhoric acid tlrrouxh I

with separate collection reduetioil of phos-

of the P,Oa u-hieh is ON C ~ a n r . m cPLATFORM
PxrosPtxoktIc! ACIDFuux~ces,1,oo~tnoDOWN PROM
then h y d r a t e d to CRANE phorus, with imme-
H,PO,. All fuinhoes are operetins under full load. diate reoxidation and
liydration in i:o~itinuuosprocess. For various rcasoiis, largely
technical, none had been sufficiently profitablc t o justify
continuance in t.lie field.
'Po explain more clearly some of the problems encountered
and solved in the development of the Anniston (Swann
C!orporation) process, a review of the cliemical and tliermal
fundamentals is of advantage. In Table I is given a
theoretical metallurgical halancc of phosphate-smelting, based
uunn tsnical mate-
Wl1e11 the pliosphorus and carbun iiionoxide are burned with
cold air, using about 25 per cent excess, the temperature
of couibustion is around 1800O C. This heat must be re-
moved from these gases sufficiently to bring the tempera-
ture down to wound 200" C. before the Pros may be hy-
drated to H,PO*. Whether this available heat in the gases
is utilized by transference to the incoming cold charge or
other useful purposes, or is wasted in such cooling, there is a
serious nroblem of

volved in the production of phosphorus by thermal means. tlirougli the walls provide3 a sufficient cooling rate to make a
Where no combustion of tlie pliosphorus and carbon monoxide protective coating from the corrosion products themselves,
occurs in contact with the charge within the furnace, the tm- proili~ceda satisfactory solution.
perature of the escaping gases from the furiiaee is, as shown,
about 200" C. However, if the gases are burned in contact FURKACE
~l~ECl~l% lC AS ~ ' H l l ~ I ~ H A l ~ E - ~ ~ ~ DVEHICLE
UcTlos
with the top surface of the charge, a portion of the heat evolved
from such combustion will raise the temperature of the in- The electric furnace its a pliospliate-reduction vehicle has its
coming and descending charge; hence, it will cause tlie gases advantages, not so much in tlie usually assumed purpose of
escaping through t.he charge t o attain 5 liiglier temperature. high-tempcrature producing capacity, as in its reserve quanti-
tative lreat capacity, wliicli is essential for the thermal reduc-
'IABLE 11. THEORETICAL
THERMAL
BALANCE
OF SMELTING
OF tion of pliosphorus from natural phosphate. To illustrate
PH~WIIATE
ROCK this essential point, note the tliermoehemistry of tiie principal
(Per pound Pros charged) reaction,
PaosenATr E30CI- Em-
FAemn
3CitO - 2SiO*
I<**VTl"r; ROCB THERYiC THEBYLC
Polrnda P. C . U." 1'. C. lJ. P. C. ti. _ _ ~ ~+~5~ + ZSiOt = f: + .5CO
(CuO)~P~*.
-
+

01'3200 392000 14.5600 832050

~

Malcoular heat requirement = 323950 P. C. U.

or, per pound of I'dh = 2280P. u. c.
The exothermic reactions of fomiation of carbom monoxide
fnmi the reducing carbon and that of the combination of
lime and silica involved in the fusion, above mentioned, to
provide the feature of tile liquid phase for complete reduc-
tion of the PIOr, occur sinmltaneously wit11 the reduction per
se; lienee, they reduce the roquireinent by tliat amount. I t
mmt, liowcvr?r, be borne in mind that tlre 2280 1'. C. U.,
wlrieh is about 54 per cent of the total heat required per
unit of PzO,involved, must be supplied a t a temperature
Pound Centigrade uuiw. of around 1300" t o 1400" C. in order t.o perform any work in
tiie required reduction. In practical furnacing operations,
The combustion of tlic plii~pliorusarid carboii m o ~ i ~ ~ x ithis
d ~ fundamental requiremerit demands a reservoir of heat
evolved in the above typicd example will develop lieat as enerLy available at temperatures above 1300" C. When
follows: such lieat energy is derived from fuel combustioil, with tbe
P, to P&: 0.414 x 58Y5 = 2440 P. C. U. (pound Centigrade difficulty of ~naintaiuingsuch a reserve supply with requisite
units) thermal liead, it is necessary to carry such reserve at the
CO t o CO,: I , 199 X 2430 = 1'. C. U. risk of lienvy condiiction and radiation losses, especially if
Tatid heat evolved 5353 P. c. I,'. convent,ional types of fiirriaces are employed. With the heat
5353 == 1,263 times energy theoreticall>-I'equirad for re- t.rsnsfer from combustion gases, the temperature of the source
Then
4229 actions within fnmnee falls rapidly wit11 effective transfer, so that, iinless the reser-
 374 I N D U S T R I A L ,4N D E N G I N E E R I N G C H E M I S T R Y
voir contains available energy far in excess of that required for
the reactions, the temperature of the gases from which the
reaction demand is supplied may drop to the point a t which
such reaction stops. The heat useful in raising the tempera-
ture of the charge consumes only about 40 per cent of the total
required energy in phosphorus reduction. This may all be
supplied up to 1300" C. After such raise in temperature of
the charge is effected,no additional heat supply is of any value
unless it be kept available a t above 1300" C. This probably
explains the failures resulting from many efforts a t fuel-fired
methods of phosphate smelting, or the low thermal economy
attained in many cases.
I n the electric furnace the reservoir of available heat a t the
required thermal head lies in the power source, since the
transformation from electrical energy to heat energy may be
had instantly and without temperature limitation.
DISADVANTAGES OF ELECTRICAL METHOD
With the above described specific advantage in the electrical
method also lies a possible disadvantage, not discernible
except through actual experience. This consists in the disas-
trous practical effects resulting from excessive temperature in
phosphate smelting. When the temperature of a phosphate-
smelting charge appreciably exceeds the 1400" C. essential
for reduction, a volatilization phenomenon occurs in which
the usually nonvolatile constituents, such as lime, silica,
alumina, magnesia, etc., are carried over with the phosphorus
and carbon monoxide. When such constituents take the
fume state in presence of the oxidation of the phosphorus and
carbon monoxide in the gas phase, there results a series
of complex compounds of Pn06with the silica, lime, etc.,
that renders collection and especially purification of the re-
sulting acid practically impossible, thus defeating the pur-
pose of the operation. This difficulty asserted itself in the
early stages of the Anniston operations to such an extent as to
threaten defeat of the entire project. This was overcome
through the accumulative effect of a number of governing
factors being maintained under exact control. These include
sizing; proportioning and proper mixing of the materials;
maintaining of exact depth of charge; especially avoiding
accumulation of carbon in the reducing zone beyond that
necessary for reduction, as well as preventing arcing a t any
local points; and regulating relative aggregates of the various
materials according to resistivity necessary.
The above-noted fact, that the heat of combustion of the
evolved gases is around one and a quarter times that necessary
for the net smelting-energy requirement, naturally accelerates
efforts toward utilization of this heat through returning it t o
the charge By use of preheated combustion air, the initial
temperature of combustion of the gases bearing PZOSmay
be had over 2000" C., thus giving a thermal head adequate
to transfer a considerabIe portion of the energy to the charge
in the reduction range.
SULFURIN THE UNITEDSTATESIN 1931. Production, ship-
ments, and exports of sulfur in 1931 showed marked decreases
in comparison with 1930, according t o the United States Bureau
of Mines. Sulfur production amounted t o 2,128,930 long tons,
a decrease of 17 per cent from the record output of 2,558,981
tons in 1930. Shipments declined from 1,989,917 tons, valued
at about $35~,800,000,in 1930, t o 1,376,526 tons, valued a t
$24,800,000, in 1931, or 31 per cent both in quantity and
in value, and were the smallest recorded since 1922. Stocks
of sulfur a t the mines increased steadily and amounted t o
3,250,000 tons on December 31, 1931, a net gain of 753,000
tons for the year. These stocks n-ere approximately 250,000
tons higher than the previous record stocks on hand at the
mines at the end of 1923.
As in 1930, Texas was the only sulfur-producing state. The
properties that contributed t o this production were those of the
Vol. 21, No. 4
In addition to the difficulties of finding refractories t o with-
stand such temperatures, there is one outstanding feature that
has defeated the greater number of efforts a t practical applica-
tion of heat transfer in this case. This lies in the avidity of
the nascent Pz06for the compounds in the charge (Ca0)3P205
and silica, probably according to the reactions
+
PtOs Si02 = SiPIO,
+
2P105 4(Ca0)3P20j= 6Ca2P20,
These compounds and analogs have lower melting points
than other constituents of the charge; hence, when formed on
the surface of aggregates thereof, they produce a cohesion of
the mass of the charge which bodily prevents further descent
into the fusion zone and effectively stops operation. Where-
ever the heat transfer from the combustion gases bearing
PZOSis attempted by convection through contact, with the
entering charge, these reactions will defeat the object. It
is therefore necessary that the transfer be made without
actual physical contact of the nascent PzO6 with the (CaO)a-
P206 and silica materials of the charge, in order that the
available benefits may be derived. Partial heat transfer has
been accomplished from this available source. There are yet
a number of practical problems to be solved to carry the
available heat economy to the ultimate degree. The newer
developments in refractories provide means for approaching
the problem with greater hope of success. The thermal
processes for phosphoric acid production have yet great
possibilities in economy. The concentration and purity of the
product offer distinct advantages in production of phosphate
salts demanded in the impending developments in the chemical
fertilizer industry.
The relative fertilizing value of plant food compounds can
only be known with scientific exactness when substantially
pure compounds are available. Nitrogen and potassium
compounds are being offered in the fertilizing field relatively
pure and free from minor elements, the influence of which is
still subject to question. P z O ~compounds in any degree of
purity are available only to a very limited degree for this
field. When such are available in unlimited quantities, there
will probably result some beneficial discoveries and results
in agricultural chemistry. Development of the obvious
possibilities in the thermal phosphoric acid processes carry
contributing potentialities of great importance in agricultural
economics.
LITERATURE
CITED
(1) Jacobs e t al., IND. ENG.CHEM.,20, 1240 (1928).
(2) Jacobs et al., I b i d . , 21, 1126 (1929).
(3) Pike, I b i d . , 22, 242 (1930).
(4) Ross et al., I b i d . , 16, 563-6 (1924).
February 3, 1932.
RECEIVED
Duval Texas Sulphur Co. a t Palangana Dome, Benavides,
Duval County; Freeport Sulfur Co. at Bryan and Hoskins
Mounds, Freeport, Brazoria County; and the Texas Gulf
Sulphur Co. at Long Point Dome, Long Point, Ft. Bend County,
Big Hill Dome, Gulf, Matagorda County, and a t Boling Dome,
Xewgulf, Wharton County:
The average quoted price for sulfur was unchanged at $18
a ton €. 0 . b. mines throughout the year. Open prices were $1
t o $3 a ton higher and prices for sulfur exported n-ere given as
$22 a ton f . a. s. Atlantic ports.
KO imports of sulfur or sulfur ore were recorded for the year
1931. Exports of sulfur or brimstone in 1931 totaled 407,586
long tons, compared with 593,312 tons in 1930, a decrease of
31 per cent. Exports t o all the countries that receive important
quantities of American sulfur, with the exception of those to
France, showed large decreases.