Jan. 21, 1936. E.

LOscHER 2,028,402
PROCESS FOR THE PRODUCTION OF conCENTRATED NITRIC ACID
Filed May 27, 1933 2 sheets-Sheet 1

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Jan. 21, 1936. E, LUSCHER 2,028,402
PROCESS FOR THE PRODUCTION OF conceNTRATED NITRIC ACID
Filed May 27, 1933 . 2 sheets-Sheet 2

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 Patented Jan. 21, 1936
2,028,402

UNITED STATES PATENT OFFICE

2,028,402
PROCESS FOR THE PRODUCTION OF
CONCENTRATED NITRC; ACD
Emil ischer, Base, Switzerland, assignor to
onza. Elektrizitatswerke and Chemische Fab
riken Aktiengesellschaft (Gampel), Basel, Swit
zerland
Application May 27, 1933, Serial No. 673,153
n Germany June 4, 1932
Claims. (Cl. 23-160)
This invention relates to the continuous pro anhydrous nitric acid occurring in the middle
duction of concentrated nitric acid. part of the column is already free from nitrogen
It is known that concentrated and also highly tetroxide, whilst below this point only fractiona
Concentrated nitric acid can be prepared from tion of diluted nitric acid takes place in the col
5 Water or dilute nitric acid, nitrogen oxides and umn with the result that at the lower end of the
oxygen- under pressure and at elevated tem
perature, column a Weaker nitric acid, entirely freed from
nitrogen oxides and having a water content cor
It has been proposed to carry out the afore responding to the temperature prevailing at this
Said conversion continuously in a vertical column, point, is obtained.
into which water is introduced at the top, liquid In contradistinction thereto it has been foun O
nitrogen tetroxide at a somewhat lower level and according to this invention that, when carrying
Oxygen at the botton. A considerable excess of out the interaction between Water or dilute nitric
nitrogen tetroxide is maintained during the op acid, excess of nitrogen oxides, for example
eration, the quantity of N2O4 relatively to the nitrogen tetroxide, and oxygen at elevated pres
water being always at least in the ratio 15:1. sure in a column or column-type apparatus 5
The temperature in the lower end of the column whilst supplying heat to the lower part of the
is raised to about 50 to 60° C. and the top part column and condensing the vapourS formed in
of the column is cooled. Two immiscible liquid the upper part of the column, for example by
phases are formed inside the column, of which water- or air-cooling, considerable technical and
the upper phase consists principally of liquid economical advantages are obtained if the heat
nitrogen tetroxide and the lower of concen supply to the lower part of the column is so 20.
trated nitric acid, which continuously discharges regulated whilst introducing the oxygen into the
from the bottom of the vertical column. lower part of the column that, at this point, the
It is also known that the interaction between temperature only reaches the boiling point at
Water or dilute nitric acid, nitrogen oxides and the prevailing pressure of the nitric acid having 25
Oxygen can be accelerated by ensuring fine dis the desired maximum content of HNO3 and a
tribution between the liquid and gaseous phases. content of about 5 to 20% of N2O4 occurring at
It has accordingly already been proposed to carry this point and does not in any part of the column
out this interaction in a fractionating column reach the boiling point of nitric acid free from
30 charged with fillers by introducing water or nitrogen oxides and water at the prevailing pres
dilute nitric acid, nitrogen tetroxide and oxygen sure. The lower oxides of nitrogen formed dur 30
at the top of the column, the oxidation of the ing the reaction are thereby constantly removed
nitrogen oxides and the formation of nitric acid up the column, whilst such a quantity of nitrogen
taking place in the upper part of the column, tetroxide is left in the liquid trickling down in
whilst fractionation of the downwardly trickling the column in counter-current to the ascending 35
acid is effected by heating the lower part of the oxygen and lower nitrogen oxides that fresh
column to 100° to 125° C., in such a manner that HNO3 is constantly formed in the downwardly
an aqueous nitric acid collects in the lower part trickling liquid and a liquid nitric acid having
of the column, whilst at the level in the middle the desired maximum content of HNO3 together
s part of the column where the temperature is with a content of N2O4 amounting, to about 5 to 40
from 85 to 90° C. anhydrous HNO3 in the form 20%, collects at the lower end of the column.
*Of vapour is present and can be drawn off at this
OOInt.
The aforesaid method of operating is based on
the recognition of the fact that the following re
The result of the regulation of the temperature actions take place in the column.
in this latter process, in such a way that the The formation of concentrated nitric acid by 45
temperature in the middle part of the column the interaction of nitrogen tetroxide with Water
already exceeds the boiling temperature of an and oxygen proceeds in accordance with the fol
hydrous HNO3 (86° C.) and increases in the lowing combined equation:
downward direction. until it reaches. 100° to 125
C. in the lower part of the column, is that all the i. 2N2O4+2H2O+O2=4HNO3. 50
nitrogen oxides, i.e. both the lower oxides (NO The individual chemical and physical reactions
and N2O3) and also the nitrogen tetroxide, are which take place in this case are, however, ex
removed from the acid chiefly formed in the up tremely numerous and complicated, so that the
per part of the column during its passage down interestion does not actually proceed according
Wards through the fractionating zone, so that the to the above equation, especially since molecular ss
 2 2,028,402
oxygen is not capable, even under pressure, of ascending gases and vapours. The result of the
aforesaid limitation of the heat supply is that
oxidizing N2O4 to N2O5 and the nitrous acid, under
the lower oxides of nitrogen, such as N2O3 and
the conditions in question, is not oxidized direct
NO or HNO2 formed according to the hereinbe
to HNO3. fore mentioned Equations 2 and 3, are continuous
5 The following intermediate equations perhaps ly and extensively removed by the ascending
show the course of the different reactions bet gases and vapours from the downwardly trickling
ter than the above combined Equation 1: liquid during its passage through the column,
On the one hand the N2O4 reacts with Water
or dilute nitric acid with the formation of HNO2 with considerable assistance by the oxygen flow
ing from below upwards, but that by far the O
10 and HNO3 according to the equation: greatest part of the nitrogen tetroxide not yet
converted into HNO3 according to Equation 2 re
On the other hand the HNO2 formed according mains in the liquid.
As a result of this procedure opportunity is af
to Equation 2 dissociates under the prevailing re forded along the entire passage of the down
action conditions chiefly into N2O3, and H2O ac Wardly trickling
cording to the equation: liquid for the formation of fresh
nitric acid in accordance with the above con
bined Equation 1, whilst, owing to the continuous
removal of the lower nitrogen oxides primarily
The N2O3 formed, for example, according to this formed
equation, insofar as sufficient oxygen is present, thereby according to Equations 2 and 3, 20
20
is oxidized to N2O4 according to the equation: the said lower oxides are to a great extent pre
vented from exerting a reducing action on the
already formed HNO3 in accordance with Equa
The remaining N2O3, however, reacts with al tion tion 2 reversed and Equation 5. By the Co-Opera
ready formed HNO3 according to the equation: of the aforementioned factors and the at- :
tendant promotion of the processes favouring the
formation of acid and counteracting the Suppres
The reactions according to Equations 2, 3 and 5 sion of the formation of acid, the present inven
proceed substantially in the liquid phase, whilst tion enables concentrated acid to be produced in
the reaction according to Equation 4 proceeds the shortest conceivable time and under the most
substantially in the gaseous phase. advantageous economic conditions imaginable.
The reactions according to Equations 3 and 5 A further advantage of the process according
counteract the formation of HNO3, according to to this invention is that the material of the ap
Equation 2. The essential factor in this case is paratus is subjected to uniform pressure and
that N2O4 is inert towards concentrated nitric temperature conditions, whereby shearing and 3
35
acid, whilst HNO2 and N2O3 are rapidly oxidized blistering of the acid-resisting linings, which are
by concentrated nitric acid according to Equation otherwise to be feared, are to a great extent
2 reversed and according to Equation 5, So that avoided.
as the content of HNO3 in the acid already present The reaction which proceeds exothermically is,
increases, the redisintegration of the HNO3 with as is known, influenced by the temperature and 40
40 elimination of Water in accordance with Equation the pressure, in that for the production of highly
2 reversed and Equation 5 takes place with in concentrated acids correspondingly higher tem
creasing rapidity. peratures and pressures are necessary. The re
Accordingly the object of the present invention action temperature may also be regulated by heat
is to carry out the interaction known per se be exchange, for example between the discharging 45
tween water or dilute nitric acid, nitrogen oxides hot acid and the introduced oxygen, in heat
and OXygen in a column or column-type appa exchange devices known per se. For carrying
ratus under Such conditions that the formation of the process into effect a distillation column con
fresh HNO3 in accordance with Equation 2 is taining distributing elements, such as perforated
promoted along the entire passage of the liquid plates, Raschig rings or the like, may be employed, 50
trickling down in the column, and the re-disin which is provided at its lower end with a liquid
tegration of the HNO3 formed in accordance with Sump, capable, for example, of being heated with
Equation 2 reversed and Equation 5 is as far as the aid of a steam packet, and at its upper end
possible prevented. with a dephlegmator, the water or the dilute
This object is attained in accordance with nitric acid being introduced into the upper part
this invention in contradistinction to the afore and the oxygen into the lower part of the coluinn.
Said known processes, on the one hand by so lim The nitrogen oxides may be introduced into the
iting the heat Supplied to the lower part of the upper part or, particularly in the production of
column, that at this point the temperature only very highly concentrated acids, also into the 60
reaches the boiling point at the prevailing pres lower part of the column.
60
Sure of the nitric acid having the desired maxi The nitrogen oxides are employed in exceSS in
mum content of HNO3 and a content of N2O4, such a way that the finished acid contains about
amounting to about 5 to 20% and that therefore 5 to 20% of N2O4. The finished acid after re
the boiling temperature at the prevailing pres by moval from the apparatus can then be bleached
(35
Sure of nitric acid free from nitrogen oxides and thethe usual methods. It is advisable to effect
bleaching in a separate distillation column
Water or even of aqueous nitric acid free from directly connected with the reaction column, in
nitrogen oxides is not reached in any part of the
column and on the other hand by introducing which event the distilled off nitrogen oxides can
be separately condensed and be then again intro
the oxygen into the lower part of the column. duced into the reaction column together with 70
70 The result of the last mentioned procedure is
that the formation of fresh N2O4, by the oxidation fresh N2O4. -
of the N2O3 present by the oxygen introduced By suitably proportionating the liquid sump
disposed in the lower part of the column, the time
from below, can take place in the gaseous phase
that the reaction liquid remains in the pressure
along the entire passage of the liquid trickling
down in the column in countercurrent to the apparatus can be regulated in accordance with
 2,028,402 3
actual requirements. Such a sump may also be electric Safety, devicer; it the control valve for the
replaced by a sufficient number of suitable column discharge of the concentrated nitric acid.
bases or be sub-divided into smaller sumps. The apparatus of Fig. 2 is made for low pres
The oxygen necessary for the process is intro-. Sures and temperatures according to Example 1.
5 duced into the lower portion of the column either f is the device for blowing off waste gases, which
above the surface of the liquid or, as is particu comes from the top of the column and paSS the
larly advisable, into the liquid itself, or beforced liquid Seal S; K1 the inlet for nitrogen Oxides;
under pressure through the aforementioned liquid l the liquid Sump; in the inlet for oxygen; S the
Sump in a state of fine division, for example by liquid seal for the continuous discharge of the
0 employing finely perforated plates, concentrated nitric acid and Waste gases; it are 10
The uniform inti'oduction of N2O4 and water control valves.
or dilute nitric acid which is necessary in order The results obtained on carrying out the pres
to maintain a constant proportion of the reac ent process are, for example, as follows:
tion components, is preferably effected with the
5 aid of cog wheel pumps. It may, however, also 15
be effected by other conveying means, such as I II III
plunger pumps or rotating slide valve pumps.
In order to prevent the partial pressure of the Total pressure in atmospheres.- 0.8-1.2 3.2 50
Oxygen from being too extensively detrinentally Average temperature in degrees
centigrade------ - - - - - - - - - - - - - - 25-35 30-40. Approx. 100
influenced by impurities in the Oxygen, Such as Time of flow through the col
nitrogen, argon, and the like, a little waste gas, Inn in seconds (approxi
mately).---------------------- 60 40-50 60
for example about 10 to 20% of the compressed Concentration of the finished
acid, percent---------- 70-80 84-85 97
gases, is preferably allowed constantly to escape Waste gas, percent---- 0-20 10-20 10-20
from the upper part of the column. eight of column inn
Diameter of column in imms.
- 5 5 6
In order to carry out the process. Successfully (approximately).-------------- 250 250 300 25
it is important to introduce the reaction compo Output-metric tons/day (ap
proximately)----------------- 15 5 - 15
nents and to remove the finished crude acid as
regularly as possible. The continuous discharge
of the acid is most suitably ensured with the aid Eacamples
3) of one or more floating elements of sufficiently
large construction. In the event of any disturb 1. (See Fig. 2.) A 5 metre high column having 30
ance of the float taking place, electric safety an average diameter of about 250 mms. and filled
devices or contacts are with advantage provided, with Raschig rings of white ware was employed
which operate in such a way that when the level for the continuous production of a 70-80% nitric
3. 5 Of the liquid rises too high in the reaction appara acid. At its lower end a liquid sump was situ SS
tus, the gas and liquid inflow are automatically ated, having a capacity of about 20 litres and
interrupted. connected with a liquid Seal for the continuous
In the case of processes operating at relatively blowing off of the acid. A perforated plate WaS
low pressures, such as are employed for less further disposed in the liquid Sump, through
4.) highly concentrated acids, the acid discharge can which the oxygen was forced under pressure in
further also be effected for example through a a state of fine division into the liquid. At the
liquid seal. For the continuous discharge of the upper end of the column a dephlegmator cooled
Waste gases, regulating members such as are usul with water was disposed. The waste gas was
ally employed in high pressure plants are, with continuously drawn off through a liquid seal.
advantage, provided. The waste gases can like By regulating the quantities of steam and Of the
wise be removed through a liquid seal which is cooling water in the dephlegmator, the tempera
advantageous particularly in the case of relatively ture conditions in the column could be so ad
low pressure processes. justed that the reinforced distilling and rectify
The parts of the apparatus exposed to the ac ing effects, necessary for attaining the maximum
50 tion of acid are with advantage constructed, in output, took place therein. The temperature in
50
accordance with the concentration and composi the Sump was maintained by heating at 30-35° C.
tion of the acid in question, from ferro-silicon, The dilute nitric acid. is introduced at a point
tantalum, quartz, aluminium or the like corro two-thirds up the height of the column and the
'sion-resisting material, or are lined with such nitrogen oxides were introduced at a point % up
material. the height of the column. The working pressure
in the accompanying drawings two apparatus prevailing in the column was approximately 0.8
suitable for carrying the process into effect are to 1.2 atmospheres and the average temperature
diagrammatically illustrated by way of example. about 25-35 C. The nitric acid and the N2O4
The two apparatus have the following common flowed under their own hydrostatic pressure into
80 parts: a, is a fractionating column with perforated the reaction column. The quantity of nitric acid
bottoms b; c the dephleginator with cooling water introduced per day amounted to approximately
jacket d e the safety valve; g the inlet for water 8.3 metric tons of 50% nitric acid and the quan
or dilute nitric acid with the aid of the cog wheel tity of the nitrogen oxides to approximately 9.5
pump h. and the throttle valve i; l the liquid metric tons. The nitric acid produced per day
Sul). amounted to about 15 metric tons calculated. On 65
The apparatus of Fig. 1 is made for the pro the already bleached 78-80% acid. The crude
duction of nitric acid under high pressure accord acid containing 15-20% of tetroxide was bleached
immediately after the process, the nitrogen
ing to the Example 2. f is the device for blowing Oxides distilled over being again employed. The
off the Waste gases on the top of the column; quantity of oxygen forced in amounted to ap
k; the inlet for nitrogen oxides; m, a steam jacket; proximately 1,000 cubic metres of 96% O2 per 70
in the inlet for oxygen through the perforated day. The nitrogen oxides present in the waste
plate o; p and p1 respectively are the inlet and gases Were recovered.
outlet for steam; q a floating element for the 2. For the production of an approximately
continuous discharge of the nitric acid. With the 97% nitric acid an apparatus constructed for a 75
 4. 2,028,402
working pressure of 50 atmospheres was emi flowing pressure which comprises bringing downwardly
ployed (see Fig. 1). liquid reaction components and reaction
The reaction column had a diameter of 300 . products in intimate contact with upwardly rising
Oxygen and with upwardly rising reaction prod
nam.S. and a height of 6 metres and was pro lucts in the form of gases or vapors through a 5
vided with dephlegmator and liquid Sump. It temperature gradient, said temperature gradient
contained 20 perforated plates, over which the being obtained by heating the acid accumulating
reaction liquid trickled downwards, whilst oxygen at the lowest point
flowed through from below upwards. The dilute riched by the HNO3 of the path of the liquid en
formed during its downward
nitric acid and the nitrogen oxides are intro fiOW and containing excess N2O4 to a temperature O
O duced at a point about two-thirds up the height corresponding at the pressure used to the boiling
of the column.
The inflow of N2O4 amounted to approximately temperature of an acid having the highest desired
12 metric tons and that of the dilute, i. e. 50% about 5 to 20% N2O4, and
HNO3 concentration having a content of
and condensing by cooling
HNO3, to approximately 5.6 metric tons per day. at the highest point of the gas path the rising 5
15 Both liquids were continuously forced in a uni hydrous vapors whereby the reaction process is
form Stream into the reaction apparatus by
means of cog wheel pumps. The oxygen required carried out in the form of a fractional distillation,
for the Oxidation amounted to 60 cubic metres the lower nitrogen oxides are continuously car
ried upwards, and nitrogen tetroxide remains in
per hour. Such quantity in the liquid trickling downwards ;
20 The heating conditions were so regulated that that fresh HNO3 is constantly formed in said
an increased partial fractional distiliation took downwardly trickling liquid, and liquid nitric
place in the courinn. For this purpose the lower acid having the desired highest content of HNO3
part of the column was slightly heated with
steam, whilst the resulting vapours were again and at
a content of about 5 to 20% N2O4 is obtained
the lower end of its path and may be con 25
25 condensed by the dephlegmator disposed high tinuously removed, and in which process the inert
The acid obtained in the continuous operation gases accumulating at the highest point of the
er lip. -

and thereafter immediately bleached possessed to path of the liquid are removed at least from time
a final concentration of about 97% HNO3. The time.
30 output amounted to 14-16 metric tons per day.
3. A process for the production of concentrated e
t

What I claim is: nitric acid which comprises mixing at a pressure

1. Method of continuously producing concen higher than atmospheric a downwardly flowing
trated nitric acid from Water or dilute nitric Stream of Water and nitrogen oxides with a stream
acid, nitrogen OXides and oxygen at Superat of Oxygen flowing counter-current thereto, and
35 mospheric pressure which comprises bringing establishing in said mixed counterflowing streams
downwardly flowing liquid reaction components a, thermal gradient corresponding at the upper
and reaction products in intimate contact with region thereof to the condensation point of
upwardly rising oxygen and with upwardly ris hydroUS vapors and at the lower region thereof to
ing reaction products in the form of gases or the temperature corresponding at the prevailing
vapors through a attemperature gradient, said pressure to the boiling point of concentrated nitric 40
tempreature gradient being obtained by heating acid containing about 5% to about 20% NaO,
the acid accumulating at the lowest point of the whereby liquid concentrated nitric acid contain
path of the liquid enriched by the HNO3 formed ing about 5% to about 20% N2O4 is collected at
during its downward flow and containing an ex Said lower region of the mixture and excess
ceSS N2O4 to a temperature corresponding at the nitrogen oxides and vapors are swept into the 45
pressure used to the boiling temperature of an upper cooler regions thereof by said upward
acid having the highest desired HNO3 concen Stream of oxygen.
4. The process set forth in claim 3 in which the
tration and having a content of about 5 to 20% aScending
N2O4, and condensing by cooling at the highest a State ofOXygen fine
is mixed under pressure and in
division with said downward
50 point of the gas path the rising hydrous vapors, Stream.
whereby the reaction process is carried out in the 5. The process set forth in claim 3 in which the
form of a fractional distillation, the lower nitro upward stream of oxygen is mixed with said
gen oxides are continuously carried upwards and down Ward stream at a point above the surface
nitrogen tetroxide remains in such quantity in
55 the liquid trickling downwards that fresh HNO3 of 6.the liquid nitric acid collected.
The process set forth in claim 3 in which the
is constantly formed in said downwardly trickling upWard stream of oxygen is introduced in the
liquid and the liquid nitric acid having the de
sired highest content of HNO3 and a content of liquid nitric acid collected.
7. The process set forth in claim 3 in which the
about 5 to 20% N2O4 is obtained at the lower 60
60 end of its path and may be collected therefrom. liquid nitric acid formed is allowed to collect
2. Method of continuously producing concen and is withdrawn in a substantially continuous
lane.
trated nitric acid from water or dilute nitric acid, EMTL LÜSCHER.
nitrogen oxides and oxygen at Superatmospheric