Journal of the Air Pollution Control Association

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Nitric Acid Manufacture

Informative Report No. 5

To cite this article: (1964) Nitric Acid Manufacture, Journal of the Air Pollution Control Association,
14:3, 91-93, DOI: 10.1080/00022470.1964.10468252

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NITRIC ACID MANUFACTURE
Informative Report No. 5
N litric acid is a strong inorganic
acid produced in a large volume.
There are approximately 50 privately
owned plants producing nitric acid in
this country. The total annual produc-
tivity capacity of these commercial
plants is estimated to be on the order
of 4.1 million tons. Government facil-
ities in stand-by condition or operation
have an additional capacity of about 2.3
million tons per year. Production of
nitric acid (100% basis) in 1961 as
reported by the U. S. Department of
Commerce was 3,378,000 tons.
The largest use of nitric acid is in the
production of fertilizers. This usage
accounts for 75% of all the nitric acid
produced. About 15% of the produc-
tion is used in the manufacture of ex-
plosives and 10% is distributed among
a wide variety of outlets. These in-
clude the manufacture of synthetic
fibers, dyes, and plastics.
Process
Nitric Acid by the Ammonia
Oxidation Process
Essentially all of the nitric acid pro-
duced is made by the ammonia oxida-
tion process. With the proper catalyst,
ammonia (NH3) can be oxidized with
air to yield nitric oxide (NO) and water.
The chemical equation is as follows:
4 NH3 + 502 = 4NO + 6H2O
The nitric oxide is further oxidized
with excess air to yield nitrogen di-
oxide (NO2).*
2NO + O2 = 2NO2
The nitrogen dioxide may then be ab-
sorbed in water to form a water solu-
tion of nitric acid.
* Nitrogen dioxide exists in equilibrium
with its dimer, nitrogen tetraoxide (2NO2
= N2O4). Lower temperature and higher
concentrations favor dimer formation.
The mixture of both is often referred to as
nitrogen dioxide and calculations are made
on the basis that the gas is nitrogen diox-
ide.
March 1964 / Volume 14, No. 3
This report, published as Informa-
tive Report No. 5 of the Air Pollution
Control Association's TI-2 Chemical
Committee, began to move through
the 14 step approval procedure, as
outlined in the March 1963 Journal,
on January 10, 1964. Comments
made by members of the Technical
Council were considered in the prepa-
ration of the final report. It is now
published as representing the "best
thinking of the Association." It is an
extremely timely and informative
report.
3NO2 + H2O = 2HNO3 + NO
In general, the process for nitric
acid manufacture consists of preheating
the air, mixing it with ammonia gas,
passing it over a platinum catalyst,
extracting the heat produced from this
reaction by using it to preheat the
incoming air and then cooling further,
adding secondary air and then absorb-
ing the nitrogen dioxide in water to form
nitric acid.
In more detail, air is compressed,
filtered, and preheated to about 300 °C
by passing it through a heat exchanger.
Ammonia gas is continuously vaporized
from anhydrous liquid ammonia in a
steam-heated evaporator. The com-
pressed air and ammonia are mixed
in a mixing chamber to produce a mix-
ture containing 8 to 10% ammonia by
volume.
The ammonia-air mixture is then
passed through the converter, which
contains the platinum-rhodium (2 to
10% rhodium) catalyst. This is in the
form of sheets of very fine wire gauze,
packed in layers (10 to 30 sheets).
The reaction is very exothermic. The
catalyst temperature may range from
800°C to 925°C. The temperature
of the gases from the converter is
above 600°C. The converter gases
are a mixture of nitric oxide, water,
oxygen, and nitrogen.
It is necessary to cool these gases
so that they may be absorbed. There
are various arrangements to accomplish
TI-2 Chemical Industry Committee
this purpose. The heat from the gases
leaving the converter is used as the
source of heat in the compressed
air preheater and also to produce steam
in a waste heat boiler. It is necessary
to further cool the gases in water-cooled
condensers. The condensing system
usually includes chambers to allow
time for the oxidation reaction to pro-
ceed.
The cooled gas then enters the ab-
sorption system. This may consist
of a large bubble cap tower. In this
case the gases enter the bottom of the
tower and contact nitric acid descend-
ing the tower. Fresh make-up water
in small amounts is introduced to the
top of the tower. Weak acid previ-
ously condensed out in the cooling
system is introduced at an intermediate
point in the absorption tower. The
heat of solution of nitrogen dioxide in
water is removed by cooling coils.
Nitric acid ranging from 55 to 60%
in strength is withdrawn from the
bottom of the tower. Air from the
air compressor unit may be introduced
at the base of the tower to bleach the
acid by desorbing the dissolved nitro-
gen dioxide and at the same time pro-
vide additional oxygen to oxidize the
nitric oxide formed as a reaction by-
product.
The absorption system in other plants
may consist of a series of tanks equipped
with cooling coils and one bubble
cap plate in each tank. A series of
packed absorption towers may also be
used. In all cases, the function is the
same, i.e., to obtain intimate contact
of the nitrogen dioxide in the gas
phase with the absorbing acid. The
heat of solution must be removed to
accomplish this efficiently.
._The,,exit.,gases from the absorption
tower or system are still under pressure
and in some plants this energy may be
used to supply power for the compressed
air requirements and after serving this
purpose the gases are discharged to
the atmosphere. These gases consist
essentially of nitrogen, oxygen, water
91
 Data vapor, nitric oxide and nitrogen di-
Physical Other oxide. It is these gases which are
Name Properties Odor Toxicity Effects visible as a red-brown plume.
Nitric 0 Colorless gas — Nitric Acid Concentration Process
oxide BP 152°C
Nitrogen Red-brown gas Strong, Irritating to upper respiratory Corrosive to For many purposes, 55 to 60% nitric
dioxide acrid tract. Threshold limit for 8 metals in acid is satisfactory. However, for
hours of continuous exposure in moist at- nitrations and other applications a
the work environment—5 ppm. mosphere more concentrated nitric acid is re-
Nitric Colorless liquid Acrid Irritating to upper respiratory Corrosive to
acid BP 86°C (of- tract. Threshold limit for 8 metals quired. This is done by distilling a
ten yellow to hours of continuous exposure in mixture of the dilute nitric acid with
red due to the work environment—10 ppm. three or four times its weight of con-
dissolved ni- centrated sulfuric acid.
trogen oxides)
Ammonia Colorless gas Strong Irritating to upper respiratory This is generally done on a continuous
tract. Threshold limit for 8 basis in a packed tower. 92 to 95% sul-
hours of continuous exposure in furic acid is introduced to the top of
the work environment—100 ppm. the tower and 55 to 60% nitric acid
° Nitric oxide in the atmosphere is rapidly converted to nitrogen dioxide. is introduced at an intermediate point
92-95%
above the middle of the tower. Heat
Sulfuric is supplied to the tower by heating the
Acid tower bottoms with steam in a heat
exchanger or by introducing super-
heated steam directly to the bottom
of the tower.
The sulfuric acid and nitric acid feeds
6O°/« flow down countercurrent to ascending
Nitric nitric acid vapor and water vapor.
Acid The sulfuric acid retains the water
and the concentrated nitric acid is vola-
tilized from the top of the tower, and
9 0 - 9 8 % HNO3 to Storage is subsequently condensed. The con-
centration of nitric acid produced is
greater than 90% and usually ranges
between 95 and 98% as desired to meet
specific requirements.
The tower bottoms (70 to 85% sul-
furic acid) must then be processed
through conventional sulfuric acid con-
centrators to recover the sulfuric acid.
Air Pollution Control Aspects
Nitric oxide and nitrogen dioxide are
the atmospheric contaminants from
nitric acid manufacture.
In the reaction in which nitrogen di-
oxide reacts with water to form nitric
acid,
•» 70-85% H 2 S0 4 to Rework
3NO2 + H2O = 2HNO3 + NO
NITRIC ACID CONCENTRATION it is apparent that nitric oxide is formed
as a byproduct of the reaction. The
nitric oxide must be reoxidized to
nitrogen dioxide which can then be
reacted with additional water and the
reaction chain is repeated. It is not
possible to completely absorb oxides
of nitrogen by absorption in water.
It is essential, however, that efficient
absorption of the nitrogen dioxide be
Gos
Converter Cooler obtained. The evolution of oxides to
1 Weak the atmosphere results in a loss of
v
HNO 3 yield and thus a severe economic loss.
Ammonia
There are two factors which are
Storage u Vaporizer
important in the absorption reaction.
They are pressure and temperature.
Increased pressure increases the rate of
absorption. The older nitric acid plants
operated at essentially atmospheric pres-
sure. The new plants operate at
NITRIC ACID MANUFACTURE
approximately 100 lb per square inch
pressure. This permits the produc-
tion of more concentrated nitric acid

92 Journal of the Air Pollution Control Association

(60% rather than 50% nitric) and
higher throughput.
Lower temperatures are beneficial
to absorber operating efficiency. The
temperatures obtained are largely a
function of the temperature of the
cooling water employed. Thus, in
summer weather where cooling water is
obtained from a river, the absorption
efficiency is lower and as a result the
stack gases from the plant will have
a higher concentration of oxides of
nitrogen.
As a part of the routine operating
procedure, analyses are performed on
the nitrogen dioxide content and the
oxygen content of the stack gases
and also on the ammonia content of
the air-ammonia mixture introduced
to the converter. These analyses are
performed every four hours and serve
as controls on the operation of the plant.
The operator, therefore, does not de-
pend on visual observation of the stack
gases from the plant as is the case in
some operations. Rigid control of the
composition of the exhaust gases is
maintained.
The color of the mixed oxides varies
from colorless to chocolate brown de-
pending on the concentration of nitro-
gen dioxide present (both nitric oxide
and nitrogen tetraoxide are colorless).
As evolved from the stack of a plant
producing nitric acid, the color of the
gas is red-brown. This unusual color
is apt to create in the mind of someone
who is not familiar with the chemical
industry, the impression that the gases
are much more dangerous than they
actually are.
A typical nitric acid plant may have
a rated capacity of 55 tons of nitric
acid (as 100% HN03) per day. A plant
of this size would require air compres-
sors having a capacity of approxi-
mately 5500 cfm of free air. Approxi-
mately 100 cfm of air is required per
ton of rated capacity.
The oxygen in the air is partially used
in the oxidation reaction. Air supplied
contains 21% oxygen by volume and
the exit gases from the process usually
contain about 3% oxygen. Therefore,
by a material balance the volume of
gases exhausted from a 55-ton nitric
acid plant approximates 4500 cfm.
The stack gases may contain 0.2 to 0.4%
(vol) oxides of nitrogen expressed as
nitrogen dioxide.
The concentration of nitric acid by
distillation with sulfuric acid does not
involve an absorption reaction as does
the ammonia oxidation process. The
nitric acid concentration process in-
volves the condensation of nitric acid
which has been volatilized. This is
done by condensers very efficently.
There is little or no loss of oxides of
nitrogen. Air is not introduced in
the system at any point so, therefore,
the volume of gases exhausted is very
March 1964 / Volume 14, No. 3
Air Pollution Bills Pending in Legislature
Arizona
H. 45 Air Pollution—Provides that
violation of air pollution laws or
regulations thereunder shall be a mis-
demeanor. Introduced by Wilcox
January 14, 1964; referred to House
Judiciary County, and Health Com-
mittees January 15, 1964.
Colorado
H. 1050 Air Pollution—Relates to
air pollution definitions, standards,
results of atmospheric tests, etc.
Introduced by Griffith, et al, January
14, 1964; referred to House Metro-
politan Affairs Committee January
14, 1964.
Massachusetts
H. 435 Pollution Abatement—Pro-
vides financial assistance to munici-
palities for the construction of pollu-
tion abatement facilities. Introduced
by Janas, et al., January 1, 1964;
referred to House Public Health
Committee January 1, 1964. Joint
hearing by House and Senate Public
Health Committee January 28, 1964.
H. 830 Breathing Device—Author-
izes the Department of Public Health
to regulate self contained breathing
apparatus offered for sale to the public
and the type of facilities used for com-
pressing air or other gas mixtures to
be sold or disseminated for use in self
contained breathing apparatus. In-
troduced by Hatch January 1, 1964;
referred to House Public Health Com-
mittee January 1, 1964; joint hearing
by House and Senate Committees
January 30, 1964. Joint hearing by
House and Senate Public Health
Committees January 21 and 30, 1964.
H. 2432 Air Pollution—Resolve
providing for an investigation and
study by a special commission relative
to the enforcement of the laws pro-
hibiting air pollution. Introduced by
Frenning January 1, 1964; referred to
low. A typical nitric concentrator
vents through a two-inch pipe vent.
The oxides of nitrogen evolved from this
vent may be observed as they are a red-
brown color.
The formation and release to the air
of nitrogen oxides is very common,
occurring whenever air is heated to a
high temperature. Lightning flashes
result in the formation of enough nitro-
gen oxides to make an appreciable con-
tribution to soil fertility. Combus-
tion processes such as open fires, home
furnaces, powerhouses, and automobile
operation all produce nitrogen oxides.
It has been estimated that in Los An-
geles County, automobiles, trucks, and
buses put 493 tons of nitrogen oxides
into the air each day.
House Public Health Committee
January 1, 1964. Reported by sub-
stitute bill, SBN 349—January 17,
1964.
S. 349 Air Pollution Study—Resolve
provides for an investigation and
study by the Department of Public
Health relative to the pollution of the
atmosphere within the Metropolitan
Air Pollution Control District and
vicinity. Introduced by Ames and
McCann January 1, 1964; referred to
Senate Public Health Committee
January 1, 1964; joint hearing by
Senate and House Committees Janu-
ary 9, 1964. Reported favorably by
Senate Public Health Committee
January 17, 1964; recommitted to
Senate Ways and Means Committee
January 17, 1964.
New York
A. 58 Fall-out—Extends definition
of air contaminant for air pollution
control to include radio-active fall-
out, not limited to strontium-90 and
iodine. Introduced by Blumenthal
January 8, 1964; referred to As-
sembly Health Committee January
8, 1964.
S. 556 Fall-out—For description of
bill see A. 58, above. Introduced
by Ohrenstein January 8, 1964; re-
ferred to Senate Health Committee
January 8, 1964.
A. 2261 (Same as S. 1410) Air Pol-
lution—Includes counties with other
municipalities which may adopt regu-
lations for control of air pollution,
with exercise of right to relate only to
area outside of city, village, or area of
town having regulation thereof. In-
troduced by Willard January 16,
1964; referred to Assembly Health
Committee January 16, 1964.
S. 1410 Air Pollution—For descrip-
tion of bill see A. 2261, above. Intro-
duced by Metcalf January 16, 1964;
referred to Senate Health Committee
January 16, 1964.
Personalia
Two Wheelabrator Corporation field
men have been named to regional
managers posts, effective immediately,
according to Kenneth E. Blessing, vice
president of sales.
George F. Burditt, formerly of the
dust and fume control division, was
appointed head of the Pittsburgh
Region, and Dean T. Pournaras,
previously regional engineer in Cleve-
land, will be in charge of the
Cleveland Region.
93