Jan. 8, 1935. R. R.

FULTON 1,986,889
PREPARATION OF AMMONIUM SULPHATE
Filed Sept. 5, 193l 2. Sheets-Sheet l

sSS
S. Ny.

INVENTOR.
M62aoe/7/6/2/72/2
(? ATAOR Y.
Jan. 8, 1935. R. R. FULTON 1986,889
PREPARATION OF AMMONIUM SULPHATE
Filed Sept. 5, 1931 2 Sheets-Sheet 2

INVENTOR.
Aroate/YMe M2/7t/7
 Patented Jan. 8, 1935
1986,889

. .. .. .
ES 1986,889
PREPARATION OF AMMONIUM sulPHATE
Robert R. Fulton, Pittsburgh, Pa., assignor to . . . -
The Koppers Company of Delaware, a corpora-
tion of Delaware
a
Application September 5, 1931, serial No. 561,415
5 Claims. (CI. 23-119)
This invention relates to processes of prepar the top through a pipe 3 controlled by a valve 3’.
ing ammonium sulphate.
An object of the present invention is to pro Columns from six feet to about sixty feet in
Wide a process of preparing ammonium sulphate employed. up to ten feet or more in width are
height and
by the oxidation of ammonium sulphite. An fhe column is filled to any desired level with 5
other object.is to provide improvements in meth solution containing ammonium sulphite. . . .
ods of oxidizing ammonium sulphite so as to An oxidizing gas such as air, ionized air, oxy
make feasible the efficient production of am gen, or gases containing oxygen or ozone are
sum Sulphate therefrom
SCae. s
on .."a ". commercial
..
passed through a porous plate 4 at the base of the
. . . I have found in the manufacture of ammonium column 1. The oxidizing gas is introduced be-l
Sulphate by the oxidation of ammonium sulphite, aneath the plate 4 through a pipe 5 controlled by
valve 6. , ... . . . . . . . . .... .
particularly when the latter is in solution, that The plate 4 may be of any fine porous material
When the oxidizing gas is finely dispersed sub which will produce fine bubbles in the sulphite
stantially throughout the body of the solution: solution and which will permit the passage of the 15
treated, increased yields of ammonium sulphate
are obtained. It is particularly advantageous to
gas at a fairly rapid rate. The bubbles are rep
have the gas in a finely divided state at the place resented in the drawing by small circles. Plates
made of fritted glass or the fine grades of alun
at which the gas is introduced into the solution. dum plates are suitable. The rate of passage of
Oxidizing gas is preferably introduced at the the gas must be kept below that at which the 20
base of a relatively tall column of the liquid con gas tends to lift the solution bodily out of the
taining ammonium sulphite for the purpose of tak column; but the rate is high enough to keep the
ing advantage of the hydrostatic pressure. This solution in a foaming state. A meter 7 is provid
increased pressure at the base combined with the ed for measuring gas. . . . . . . . .. .
introduction of oxidizing gas in extremely finely The pressure employed for forcing, the oxidiz- 25
divided condition in a region at the base of the ing gas through the porous plate and the column
column brings about rapid oxidation of the am of solution, depends upon the fineness of the
monium sulphite. The column is preferably of pores in the plate and upon the height of the
Such a height that substantially no union of the column. , , ,' . . . . .. . .
gas bubbles occurs in the upper regions of the . Means are provided for recirculating gas or
column. . . . . . . . . . . . . . . . . . . . solution or both through the column 1. During
Good results are obtained by treating an alka the passage of gas into the solution, the latter
line solution of sulphite, but the present process passes out near the top of the column, down
operates more efficiently when the sulphite solu wardly through a pipe 8 and back into the botton
tion is in neutral or preferably in acid condition of the column through the turned-up end 9 of
while contacting with an oxidizing gas. The the pipe 8.
preferred pH value is from about 5.5 to 7.0. Am The gas passing upwardly through the solu
monia-containing gases or sulphur dioxide-con tion, collects in a chamber 10 at the top of the
taining gases may be passed into the sulphite so column 1 and is withdrawn either through a .
lution intermittently or continuously either to pipe. 11 controlled by a valve 12, or by closing the 40
vary the hydrogen ion concentration or to main
tain it constant.
valve 12 the gas is passed into a pipe 13 controlled
by a valve 14 and by means of a pump 15, is
Other features of the present invention will be forced into the pipe 5 and through the plate 4
set forth in a further description of the process into the solution in the column 1. . . . . -
which may be carried out in apparatus such as The alkalinity or acidity of the ammonium 4
that shown by way of example in the accom sulphite solution in the column may be con
panying drawings, in which, . . . . . trolled by admitting ammonia-containing gas or
Figure 1 is a vertical sectional view partly in sulphur dioxide-containing gas into the solution.
elevation of one form of apparatus, and . . . These gases are preferably passed into the Solu
Fig. 2 is an elevational view, partly in cross sec
tion through the plate 4 in which case they are 9 .
tion of another form of apparatus. . . . . admitted separately into the pipe 5. To prevent
In the apparatus shown in Fig.1, a solution deposition of solid ammonium salt, after am--
containing ammonium sulphite is passed into a monia has been fed into the pipe 5through a
tall narrow column 1 through a pipe 2 controlled pipe 17 for instance, controlled by a valve 18,
5. by a valve 2 near the base of the column or into the ammonia gas is swept through the plate 4 55
 2 1,986,889
by the oxidizing gas before admitting sulphur phatetaining the concentration of ammonium Sul
high enough, the Solution and gases may
dioxide gas through a pipe 19 controlled by a be recirculated in the column 1 until crystals of
valve 20, and Sulphur dioxide is swept out before ammonium sulphate
ammonia is admitted. form and the resulting
The ammonia-containing gas or the Sulphur slurry may be withdrawn from the column and
dioxide-containing gas may be, if desired, passed passed to the drain table 33 where the Solid
annoniunin Sulphate is separated,
. . through the porous plate along with the stream
of oxidizing gas either intermittently or con beUnder increased pressures the oxidation may
speeded up and higher-yields of aminonium
tinuously. By the proper regulation of the Sulphate are obtained. Although the present O
10 Valves, the proportions of the gases may be con process may be carried on at any pressure, par
trolled. ticularly at atmospheric pressure and above, it
The gases before leaving the top of the column. preferable to increase the
1, and particularly if they are withdrawn isstages pressure in the later
of the conversion. The last traces of am
through the pipe 11, may be sprayed by means, naonium-Sulphite. are difficult to convert to Sul
15 of a Spray 21 controlled by a valves 22, with ann phate, but by increasing the pressure, 100 per
monia solution or with acid sulphite solution or cent conversion is obtained. Alternatively, the
dilute sulphuric acid depending on the sulphur . addition of a Small amount of Sulphuric acid,
dioxide or ammonia content of the gases.
The temperature of the solution in the coli. SeleVeS to change traces of Sulphite to Sulphate.
In the apparatus shown in Fig. 1, the pressure :
20 umn, if desired, is controlled by any suitable in the column 1 is built up by closing the valve
means. If the temperature used is above atmos 12 in the pipe 11, forcing oxidizing gas into the
pherie; a heating jacket 23, for instance, is used.
column through the pipe 5 until the desired pres
Steam or other heating fluid is admitted through Sure is reached, and then closing the. Valve 6.
a pipe 24 controlled by a valve 25 and withdrawn The valve 14 in the pipe 13 is opened and the gas
through a pipe-26 controlled by a valve 27. A is repeatedly circulated through the Solution by
pipe 28 controlled by a valve 29 may be provided ineans of the pump 15. .
for withdrawal of condensates. The heating fluid Pressures in the lower regions and at the bot
may be substituted by a cooling fluid if necessary.
A thermometer 30 is provided for determining tom of the column may be...raised or lowered by
varying the height of the column of solution 36
30 the temperature of the solution in the column 1. treated. The column may be filled to a rela
Good results are obtained by maintaining a
temperature during oxidation of substantially tively
and
low level at the beginning of the process
after the reaction has proceeded for a time,
30° C. to 45° C. Temperatures as high as 60° C. the level may be raised by the addition of fresh
or even 80° C. may be employed. When con Sulphite solution or previously aerated solution.
35 ducting the oxidation under superatmespheric instance, in some cases a saturated solution
pressure, the temperatures may even be higher ofForammonium sulphate may be added or a solu
than those mentioned. tion of substantially.the same composition as
The temperature of the solution in the column
may also be controlled by withdrawing heated that which is being treated in the column, may 40
be added. . . . . . ."
40 solution through a pipe 31 controlled by a valve A trough 41 is provided to catch any liquid
32, and by passing in solution of lower tempera which flows over the top of the column 1 and
ture-through the pipe 2 or the pipe 3 or through the overflow is drawn off through a seal 42.
both. The concentration of the solution in the : The sulphur dioxide used in the present process
column may also be controlled in this way. . may be derived from various, Sources as for in
Solutions containing various proportions of stance by roasting metallic Sulphides, or by burn
ammonium sulphite or ammonium bisulphite or ing sulphur or hydrogen sulphide.
both may be treated. Solutions containing sub The annonia, may be. Synthetic ammonia, or
stantially 10% to 20% ammonium sulphite give annonia obtained by treating ammonium com
Satisfactory yields of ammonium sulphate. How pounds with alkali or alkaline. earth hydroxides,
50 ever a highly satisfactory method is to treat or it may be obtained from ammonia liquor ob
Solutions at such temperatures that when cooled tained in the treatment of coal gases.
to lower temperatures a supersaturated solution Crude ammonia, liquors from coal gas plants
of ammonium sulphate forms and crystals of this contain besides ammonium hydroxide, Varying
salt readily separate out. - amounts of sulphides, and cyanides, as well as 5
55 In the latter case the solution is withdrawn Organic materials. Such as pyridine, tar acid oils,
from time to time through the pipe 3i and naphthalene and other compounds. When treat
passed into a drain table 33 to permit settling out ing ammonia liquors, it is highly advantageous
of crystals of ammonium sulphate. The solid to removes the oily, materials present therein. 6)
ammonium sulphate 34 with adhering mother These materials tend to retard the oxidation
60 liquor is passed: into a centrifuge 35 and the
dried ammonium sulphate is then ready for ship reaction. They rise to the surface and may
ment. .. . . . . . .. . . .. .
be removed from the liquid in the column 1 by
The mother liquor from the drain table 33 permitting them to overflow into the trough 41.
drains out through a pipe 36 and is joined in Also, when treating ammonia, liquors, it is ad
65 a tank 37 with liquor coming from the centrifuge vantageous to add sulphur dioxide in excess of 65
35 through a pipe 38. The mother liquor in the the amount required to neutralize the ammonia
tank 37 is pumped by means of a pump 39 and other alkaline Substances, in order to de
through a pipe 40 into the top of the column 1. compose the sulphides and cyanides, which are
It has been found that the presence of am driven off later as hydrogen sulphide, and hy
70 monium Sulphate in the sulphite solution is high drogen cyanide. If the sulphite liquor is left
ly. beneficial and aids in the nore rapid and com alkaline, the sulphides and cyanides form thio
plete oxidation of the sulphite. A sulphite solu sulphate and thiocyanate which are undesirable
impurities in ammonium sulphate. Further
tion containing up to about 35% and preferably more when the liquor is acid, the effect of
not more than substantially .40% ammonium i.
75 Sulphate gives. Satisfactory results. By main pyridine is eliminated since it is converted to
 . . . . . . . . 1,988,889 -3
aAlso,saltdispersion
which dissolves in the sulphite
of the oxidizing gasi
liquoi o the column of solution above a gas inlet. By
anThe
acidpresences
medium. of. certain
. . . impuritie
. n rotating the propeller the gas is beaten... ...
... solution. . . . . . . . . . . . . . . . .
into the
aqua, . . Another means for injecting oxidizing gas into
ammonia, such as primary amines, causes the for the
mation of formaldehyde in the very last stages ever,sulphite
since it
solution is a perforated pipe. How-s:
is important to produce a uniform
of the oxidation period. The detection of the mixture of finely divided gas and solution, per
first traces of formaldehyde serves as an indi
cation of practically the end of the oxidation. forated plates are preferred and are employed
as shown in the drawings. Minute bubbles are
period and for some purposes the oxidation may thereby
be stopped at this time. distributed over a large area at the base 10
In the apparatus shown in Fig. 2, a series ofInsteadthe column.
of providing indirect heating means
arrangement of columns is shown. Although only for the columns as shown, heated oxidizing gas.
two columns 45 and 46 are shown, any number
15 may be used. The columns shown are con may be injected into the solution, whereby direct
structed similarly to the column shown in Fig.1. heating
and are provided with heating jackets 47 and the
is accomplished. If the temperature of
solution rises above any desired point, cooled
5

48, and porous plates 49 and 50 at their respective gases may be injected to lower the temperature.
To carry on the present process under pressure
bases. , .. . . .. .. s
20 Solution to be treated is passed into the col throughout the oxidation stage or during any
umn 45 through a pipe 51 controlled by a valve portion thereof, the sulphite-containing solution 20
52. The solution is withdrawn from the bottom may be placed in autoclaves provided with an
of the column and by means of a pump53 is inlet and outlet for oxidizing gas. The gas may
pumped into the top through a pipe 54. This be admitted until a desired superatmospheric
25 recirculation may be kept up until any desired pressure is reached after which the autoclave
stage of oxidation has been reached and then may be sealed and the mixture of gas and solu 25
passed into the top of the column 46, through tion agitated by means of paddles or by rotation
of the autoclave.
a pipe 55 for further treatment. By proper ma If desired, the oxidation of the ammonium
nipulation of the valves 56 and 57 the liquid
30 stream passing through the pipe 54 may be di asulphite may be carried on in the presence of
catalyst. The catalysts may be gaseous, liquid 30
vided in any ratio. -
The liquid may be maintained at a higher orThe Solid substances.
temperature in the column 46 than the liquid solutionaddition
greatly
of foaming agents to the sulphite
improves dispersion of the oxi
35
in the column 45 and may be recirculated by dizing gas. The addition of as little as two
pumping it from the bottom to the top by means grams of licorice root extract or Saponin in 35
of a pump 58 through a pipe 59. It may be twenty-five
noted here that the oxidizing gas and sulphite I claim asgallons
my
of solution is very effective.
invention:
solution travel countercurrently in the towers
40 shown in Fig. 2 and concurrently in the tower 1. A process of preparing ammonium Sulphate,
shown in Fig. 1. which comprises introducing an oxidizing gas
into a solution containing, ammonium Sulphite
The oxidizing gas is passed into the bottom in 40
a closed chamber and thereby building up pres
of the column 46 through a pipe 60 controlled sure therein and thereby converting a major por
by a valve 61, out of the top of the column 46 tion of the sulphite to sulphate, and thereafter
45 a pipeinto62.theBybottom
and of the column 45 through
proper control, if air is used as discontinuing the introduction of oxidizing gas
and converting the remainder of the sulphite
the oxidizing gas, the gas leaving the top of to Sulphate by recirculating the gas contained
45
the column 45 through a pipe 63 provided with therein under the so built-up pressure through
a valve 64, is substantially all nitrogen. the solution.
50
Pipes 65 and 66 provided respectively with 2. A process of preparing ammonium Sulphate,
valves 67 and 68, respectively conduct ammonia Which comprises introducing an oxidizing gas in
containing gas and sulphur dioxide-containing finely divided condition into a Solution containing
50
gas into the pipe 60. Pipes 69 and 70 provided ammonium sulphite and thereby converting a ma
respectively with valves 71 and 72, respectively jor portion of the Sulphite to Sulphate, increasing
conduct ammonia-containing gas and sulphur the pressure in the later stages of conversion and,
55 dioxide-containing gas into the pipe 62. thereby continuing conversion as aforesaid and 55 . . . .
Treated solution containing ammonium sul thereby converting the remainder under such in
phate is withdrawn from the top of the column creased pressure. . . . ."
46 through a pipe 73 controlled by a valve 74 3. A process of preparing ammonium Sulphate, . . .
and passed into an evaporator 75 provided with which comprises introducing an oxidizing gas
60 the usual heating means 76. Solution may also
be passed from the bottom of the column to in finely divided condition into the bottom of a 60
the evaporator through the pipe 59, through a column of liquid containing ammonium sulphite
and thereby converting a major portion of sul-,
pipe 77 provided with a valve 78, and then phite
through a part of the pipe 73. to sulphate, and adding a small amount of
65 sulphuric acid to the column during the intro
EThe slurry formed in the evaporator 75 is with
drawn through a pipe 79 by opening a valve duction of the oxidizing gas to change last traces
of sulphite to sulphate. ". .
65
80 and is passed to a centrifuge 81 from which 4. A process of preparing ammonium Sulphate,
practically
tained.
dry ammonium sulphate 82 ist ob which comprises introducing an Oxidizing gas
70 Various modifications may be made in the into liquid containing ammonium sulphite and
... process and apparatus described, and various at ammonium sulphate in a finely divided condition 70
types of apparatus may be employed in the pres the place at which the gas is introduced into
ent process. As a means for distributing the sulphitethe liquid and thereby converting the ammonium
oxidizing gas in the Sulphite Solution, propellers to ammonium sulphate, and maintaining
is may be mounted for rotation in the bottom of , the proportion of ammonium sulphate in the liquid
from about 30% to 40% during the conversion, 5
4. i;986,889
and maintaining the height of the hydrostatic jor portion of the sulphite to sulphate, and there
head of such height that substantially no union after discontinuing the introduction of oxidizing
of gas bubbles occurs in the upper regions of the gas and converting the remainder of the sulphite
to sulphate by recirculating the gas contained
: 5. A process of preparing ammonium-sulphate, therein through the solution under increased 5
hydrostatic column. .. .

which comprises introducing an oxidizing gas into pressure. ROBERTR. FULTON.

a solution under pressure and containing am
monium sulphite and thereby converting the ma