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Article No : a17_293
Nitric Acid, Nitrous Acid, and Nitrogen Oxides

MICHAEL THIEMANN, Uhde GmbH, Dortmund, Federal Republic of Germany
ERICH SCHEIBLER, Uhde GmbH, Dortmund, Federal Republic of Germany
KARL WILHELM WIEGAND, Uhde GmbH, Dortmund, Federal Republic of Germany
1. Nitric Acid . . . . . . . . . . . . . . . . . . . . . . . 177 1.4.1. Wastewater . . . . . . . . . . . . . . . . . . . . . . . 211

1.1. Introduction. . . . . . . . . . . . . . . . . . . . . . 177 1.4.2. Stack Gas . . . . . . . . . . . . . . . . . . . . . . . . 211
1.2. Properties . . . . . . . . . . . . . . . . . . . . . . . 178 1.4.2.1. Emission Limits . . . . . . . . . . . . . . . . . . . 211
1.3. Industrial Production. . . . . . . . . . . . . . . 179 1.4.2.2. Analysis . . . . . . . . . . . . . . . . . . . . . . . . . 212
1.3.1. Oxidation of Ammonia . . . . . . . . . . . . . . 180 1.4.2.3. Control of NOx Emissions . . . . . . . . . . . . 212
1.3.2. Oxidation and Absorption of Nitrogen 1.5. Storage and Transportation. . . . . . . . . . 216
Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . 184 1.6. Uses and Economic Aspects . . . . . . . . . . 216
1.3.3. Equipment. . . . . . . . . . . . . . . . . . . . . . . . 191 2. Nitrous Acid . . . . . . . . . . . . . . . . . . . . . 217
1.3.3.1. Filters and Mixers . . . . . . . . . . . . . . . . . . 191 3. Nitrogen Oxides . . . . . . . . . . . . . . . . . . . 218
1.3.3.2. Burners and Waste-Heat Boilers. . . . . . . . 192 3.1. Dinitrogen Monoxide . . . . . . . . . . . . . . . 218
1.3.3.3. Compressors and Turbines . . . . . . . . . . . . 193 3.2. Nitrogen Monoxide . . . . . . . . . . . . . . . . 219
1.3.3.4. Heat Exchangers and Columns . . . . . . . . . 195 3.3. Nitrogen Dioxide and Dinitrogen
1.3.3.5. Construction Materials. . . . . . . . . . . . . . . 198 Tetroxide . . . . . . . . . . . . . . . . . . . . . . . . 220
1.3.4. Processes . . . . . . . . . . . . . . . . . . . . . . . . 200 3.4. Dinitrogen Trioxide . . . . . . . . . . . . . . . . 221
1.3.4.1. Weak Acid Processes. . . . . . . . . . . . . . . . 200 3.5. Dinitrogen Pentoxide . . . . . . . . . . . . . . . 222
1.3.4.2. Concentrated Acid Processes . . . . . . . . . . 206 4. Toxicology and Occupational Health . . . 222
1.4. Environmental Protection . . . . . . . . . . . 211 References . . . . . . . . . . . . . . . . . . . . . . . 223
1. Nitric Acid The direct combustion of air in an electric arc,

developed by BIRKELAND and EYDE, was aban-
1.1. Introduction doned because of its poor energy efficiency.
Later direct processes, such as thermal nitrogen
Nitric acid is a strong acid that occurs in nature monoxide synthesis with fossil fuels or nitrogen
only in the form of nitrate salts. When large-scale monoxide synthesis in nuclear reactors, did not
production of nitric acid began, sodium nitrate gain widespread acceptance. Ammonia produc-
(soda saltpeter, Chile saltpeter) was used as the tion from calcium cyanamide was of only transi-
feedstock. At the beginning of the 20th century tory value. Ammonia produced from nitrogen
the reserves of Chile saltpeter were thought to be and hydrogen by the Haber – Bosch process
nearing exhaustion, so processes were developed (! Ammonia, 2. Production Processes) is,
for replacing nitrogen from natural nitrates however, still used as feedstock for nitric acid
with atmospheric nitrogen. Three techniques production.
were used industrially: The crucial step in nitric acid production,
the catalytic combustion of ammonia, was
1. Production of nitrogen monoxide by reacting developed by OSTWALD around the turn of the
atmospheric nitrogen and oxygen at > 2000 century. The most important design parameters
for a nitric acid plant were determined first in
C (direct processes)
2. Production of ammonia by hydrolysis of laboratory tests and later in a pilot plant. The
calcium cyanamide under pressure first production facility employing the Ostwald
3. Production of ammonia from nitrogen and process came on stream in 1906 at Gerthe in
hydrogen Germany [1–3].
2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a17_293
178 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

Heat of vaporization (20 C) 626.3 J/g
Most of the nitric acid produced is used to Specific heat
form inorganic fertilizers (! Phosphate Fertili- at 0 C 1.7601 J g1 K1
zers); it is mostly neutralized with ammonia to at 20 C 1.7481 J g1 K1
form ammonium nitrate (! Ammonium Com-
pounds, Section 1.2.1.). The decomposition of nitric acid makes its
physical properties difficult to determine at high-
er temperature. Up to ca. 50 C, conventional
1.2. Properties methods of measurement are possible; beyond
this, indirect thermodynamic calculations or
Nitric acid was known to the ancient Egyptians special short-time measuring methods must be
because of its special ability to separate gold employed. Figure 1 illustrates the vapor pressure
and silver. Many well-known alchemists in the curve of pure nitric acid. Table 1 lists important
Middle Ages experimented with the acid. In the physical properties of aqueous nitric acid. A
middle of the 17th century, GLAUBER reported its comprehensive review of the physical and chem-
preparation from saltpeter and sulfuric acid. ical properties of nitric acid is given in [6].
Physical Properties. Nitric acid [7697-37- Chemical Properties. Concentrated nitric

2], Mr 63.013, is miscible with water in all acid, with nitrogen in the þ 5 oxidation state,
proportions. At a concentration of 69.2 wt %, it acts as a strong oxidizing agent. The reaction
forms a maximum-boiling azeotrope with water.
The azeotropic mixture boils at 121.8 C. Pure NO þ
3 þ4 H
NOþ2 H2 O
anhydrous nitric acid boils at 83 – 87 C; the goes to the right for all substances with oxidation
reason a range of boiling points are cited in potentials more negative than þ 0.93 V [7]. For
the literature is that the acid decomposes on example, copper (þ 0.337 V) and silver
heating [4]: (þ 0.799 V) are dissolved by nitric acid, where-
4 HNO3 !2 H2 Oþ4 NO2 þO2 as gold (þ 1.498 V) and platinum (þ 1.2 V) are
resistant. In practice, 50 % nitric acid (aqua
The nitrogen dioxide formed on decomposi-
tion colors the acid yellow or even red at higher
concentrations. Because the vapors can also
absorb moisture, the term ‘‘red fuming nitric
acid’’ is used. In the pure anhydrous state, nitric
acid is a colorless liquid.
The most important physical properties of
pure nitric acid follow:
fp 41.59 C
bp 82.6 0.2 C
Density, liquid
at 0 C 1549.2 kg/m3
at 20 C 1512.8 kg/m3
at 40 C 1476.4 kg/m3
Refractive index n24
D 1.3970
Dynamic viscosity
at 0 C 1.092 mPa s
at 25 C 0.746 mPa s
at 40 C 0.617 mPa s
Surface tension
at 0 C 0.04356 N/m
at 20 C 0.04115 N/m
at 40 C 0.03776 N/m
Thermal conductivity (20 C) 0.343 W m1 K1
Standard enthalpy of formation
Liquid 2.7474 J/g
Gas 2.1258 J/g Figure 1. Vapor pressure curve for pure nitric acid
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 179
Table 1. Physical properties of aqueous nitric acid as a function of

composition [5]
HNO3 Density mp, C bp, C Partial

concentration, (20 C), pressure
wt % g/cm3 (20 C), kPa
HNO3 H2O
0 0.99823 0 100.0 2.23

10 1.0543 7 101.2 2.26
20 1.1150 17 103.4 2.02
30 1.1800 36 107.0 1.76
40 1.2463 30 112.0 1.44
50 1.3100 20 116.4 0.03 1.05
60 1.3667 22 120.4 0.12 0.65
70 1.4134 41 121.6 0.39 0.35
80 1.4521 39 116.6 1.4 0.12
90 1.4826 60 102.0 3.6 0.03
100 1.5129 42 86.0 6.0 0
fortis) is used for separating gold from silver.

Some base metals, such as aluminum and chro-
mium, are attacked by nitric acid only at their
surfaces because a thin oxide layer is formed, Figure 2. Ostwald process
which protects (i.e., passivates) the core against
further oxidation. As a result of this passivation,
alloyed steel equipment can be used in nitric acid
technology.
2 NOþO2 !2 NO2
N2 O4 ð2Þ
Highly diluted nitric acid is almost completely
dissociated
2. Absorption of the nitrogen oxides to yield
HNO3 þH2 O
H3 Oþ þNO
3 nitric acid:
and does not attack copper and more noble 3 NO2 þH2 O!2 HNO3 þNO ð3Þ
metals. Due to its acid nature, however, it reacts
with base metals, liberating hydrogen and form-
ing nitrates.
A mixture (volume ratio 3 : 1) of concentrated The way in which these three steps are
nitric acid and concentrated hydrochloric acid implemented characterizes the various nitric acid
(aqua regia) also dissolves gold. processes. In monopressure (single-pressure)
processes, ammonia combustion and NOx ab-
sorption take place at the same working pressure.
1.3. Industrial Production These include medium-pressure (230 –
600 kPa) and high-pressure (700 – 1100 kPa)
The industrial production of nitric acid by the processes. Very few plants currently employ low
Ostwald process is described in this section. The pressure (100 – 220 kPa) for both combustion
process involves three chemical steps (Fig. 2): and absorption.
In dual-pressure (split-pressure) processes,
1. Catalytic oxidation of ammonia with atmo- the absorption pressure is higher than the com-
spheric oxygen to yield nitrogen monoxide: bustion pressure. Modern dual-pressure plants
feature combustion at 400 – 600 kPa and ab-
4 NH3 þ5 O2 !4 NOþ6 H2 O ð1Þ sorption at 900 – 1400 kPa. Some older plants
Oxidation of the nitrogen monoxide product still employ atmospheric combustion and medi-
to nitrogen dioxide or dinitrogen tetroxide: um-pressure absorption.
Intensive work on ammonia combustion as O2 À 2 Oðadsorb:Þ

well as the oxidation and absorption of nitrogen
oxides has been well documented since the early O ðadsorb:ÞþNH3 !NH2 OH
1920s. Up to now the combustion of ammonia
has been considered as a heterogeneous catalytic NH2 OHþO2 !HNO2 þH2 O
surface reaction with undesirable side reactions.
The oxidation of nitrogen monoxide is a rare HNO2 !NOþOH
example of a homogeneous third-order gas-phase
reaction. The absorption of NOx is a heteroge- 2 OH !H2 OþO
neous reaction between fluid (i.e., gas and liquid)
phases. In oxidation experiments under high vacuum,
BODENSTEIN and coworkers detected both hydrox-
ylamine and nitrous acid as intermediate pro-
1.3.1. Oxidation of Ammonia ducts on the platinum catalyst. Later studies with
a mass spectrometer showed that no such inter-
The oxidation of ammonia to nitrogen monoxide mediate products are found above 400 C [8]. In
is described by the equation these tests, both molecular and atomic oxygen
was found on the catalyst surface. A direct reac-
4 NH3 þ5 O2 !4 NOþ6 H2 O DH ¼ 904kJ=mol ð4Þ tion between oxygen and ammonia was therefore
postulated according to the following equations:
Over a suitable catalyst, 93 – 98 % of the feed
ammonia is converted to nitrogen monoxide. The NH3 þO2 !NOþH2 OþH
remainder participates in undesirable side reac-
tions leading to dinitrogen monoxide (nitrous NH3 þO!NOþH2 þH
oxide, laughing gas)
In fast reactions such as the combustion of
4 NH3 þ4 O2 !2 N2 Oþ6 H2 O DH ¼ 1105 kJ=mol ð5Þ ammonia (the reaction time for Eq. 4 is ca.
1011 s), however, the possible intermediates
and to nitrogen most likely cannot be detected because they are
very short-lived and present in very low concen-
4 NH3 þ3 O2 !2 N2 þ6 H2 O DH ¼ 1268 kJ=mol ð6Þ
trations. NOWAK [9] has compared the numerous
Other undesirable reactions are the decompo- theories of ammonia combustion. PIGNET and
sition of the nitrogen monoxide product SCHMIDT present a classical Langmuir – Hinshel-
wood treatment of the process [10]. The possi-
2 NO!N2 þO2 DH ¼ 90 kJ=mol ð7Þ bility that the combustion of ammonia may be
considered as a homogeneous catalytic reaction
and its reaction with ammonia
is now being discussed.
4 NH3 þ6 NO!5 N2 þ6 H2 O DH ¼ 1808 kJ=mol ð8Þ At low temperature (200 – 400 C), the rate
of ammonia oxidation is limited by the reaction
kinetics. The byproducts nitrogen, and especially
Reaction Mechanism. Early theories of the dinitrogen monoxide, are formed preferentially.
mechanism for the oxidation of ammonia dif- Between 400 and 600 C, the reaction rate
fered as to which intermediate product was becomes limited by mass transfer, which is
formed. The classical theories were proposed by then dominant above 600 C. Control by mass
ANDRUSSOV (nitroxyl theory, 1926), RASCHIG transfer relates to the diffusion rate of ammonia
(imide theory, 1927), and BODENSTEIN (hydroxyl- through the gas film to the catalyst surface. The
amine theory, 1935) [3]. According to the hydrox- product in this reaction regime is nitrogen
ylamine theory, ammonia reacts with atomic monoxide.
oxygen adsorbed on the catalyst to yield hydrox- The catalyst surface experiences a very low
ylamine. This in turn reacts with molecular partial pressure of ammonia and a diminished
oxygen to form nitrous acid, which then dissoci- partial pressure of oxygen due to mass-transfer
ates to nitrogen monoxide and hydroxyl ions: limitations. The catalytic side reaction between
ammonia and nitrogen monoxide is accelerated

by an increase in the partial pressures of both
species on the catalyst surface. If catalyst
poisoning occurs,the number of active centers
decreases and the partial pressure, particularly
that of ammonia, increases at the remaining
active centers. The result is increased formation
of undesirable byproducts. In practice, this shift
is offset by raising the temperature, i.e., the
reaction is again displaced into the region limited
by gas-film diffusion.
Precious-metal catalysts are usually em-
ployed in the form of closely stacked, fine-mesh
gauzes. At the beginning of a campaign they
have a smooth surface and therefore only slightly
limit mass transfer in the gas phase. This gives an
initially lower yield of nitrogen monoxide. After
a short time in service, however, the surface area
of the catalyst increases greatly because of
microstructural changes and interactions with
volatilizing constituents of the catalyst (Fig. 3).
Catalyst growth increases the limitation of mass
transfer in the gas phase and thus the yield of
nitrogen monoxide.
Reaction Engineering. From an engineer-

ing standpoint, the combustion of ammonia is
one of the most efficient catalytic reactions
(maximum possible conversion 98 %). Accord-
ing to the stoichiometry of Equation (4), the
ammonia – air reaction mixture should contain
14.38 % ammonia. A lower ammonia – air ratio Figure 3. Photograph of platinum – rhodium gauze (Degus-
is, however, employed for a variety of reasons, sa, FRG) taken with a scanning electron microscope (enlarge-
the most important being that conversion ment 100 : 1) A) Initial stage; B) Highly activated stage
decreases with too high a ratio; ammonia and
air also form an explosive mixture. Because the nitrogen monoxide decreases because of the slip
mixing of ammonia and air in industrial (leakage) of ammonia which reacts with it ac-
practice is incomplete, locally higher ratios may cording to Equation (8). If the gas velocities are
occur. A ratio that includes a safety margin below too low or too many gauzes are used, decompo-
the explosion limit is therefore necessary. The sition of nitrogen monoxide according to Equa-
explosion limit declines with pressure so that tion (7) is promoted. Table 3 gives typical gas
high-pressure burners can operate with up to velocities.
11 % ammonia, whereas 13.5 % ammonia is
possible in low-pressure systems. The explosion Table 2. Explosion limits of ammonia – air mixtures at atmospheric
pressure
limit also depends on the flow velocity (Table 2,
see also [3]) and the water content of the reaction Flow velocity, Lower explosion Upper explosion
mixture [11]. m/s limit, % NH3 limit, % NH3
According to Le Chatelier’s principle, the 0 15.5 27.5
increase in volume in Equation (4) implies that 3 28 38
conversion declines as pressure rises (Fig. 4). 5–8 30 40
12 32 37
If the gas velocities are too high or the number
14 none none
of catalyst gauzes is insufficient, conversion to
Figure 4. Conversion of ammonia to nitrogen monoxide on

a platinum gauze as a funtion of temperature [5] a) 100 kPa;
b) 400 kPa
Figure 5. Losses of precious metals in the combustion of
ammonia to nitrogen monoxide as a function of temperature
A high reaction temperature promotes ammo- and catalyst composition [5] a) Pt; b) Pt – Rh 98/2; c) Pt –
nia combustion (Fig. 4), but high temperature Rh 90/10
decreases the conversion. Maximum tempera-
tures up to 950 C have been realized, but cata-
lyst losses, chiefly due to vaporization, increase cost less than platinum catalysts, but conversion
greatly (Fig. 5). The usual way to maintain is lower. Another disadvantage of non-noble-
the conversion toward the end of a campaign in metal catalysts is that they are more quickly
spite of catalyst deactivation and losses, is to poisoned [13].
raise the temperature. The ammonia – air ratio is The usual form of catalyst is a fine-mesh
directly related to the reaction temperature: a 1 % gauze (standardized at 1024 mesh/cm2 ). Manu-
increase in the proportion of ammonia increases facturers offer wire diameters of 0.060 and
the temperature by ca. 68 K. If the temperature is 0.076 mm. The Johnson Matthey ‘‘Tailored
too low, conversion to nitrogen monoxide Pack’’ combines gauzes made of different wire
decreases. The reaction temperature also de- diameters [14]. The upstream gauzes have a wire
pends on the temperature of the inlet gas mixture. diameter of 0.076 mm and the downstream ones
The following formula provides an approximate 0.060 mm to optimize the catalyst surface area.
value in C: High-pressure plants also utilize ‘‘fiber
packs’’ in which a fraction of the fibrous catalyst
treactor ¼ tgas mixture þr 68 where r ¼ NH3 =ðNH3 þairÞ ð9Þ material is held between two gauzes [15]. The
packs have the advantage of reduced platinum
loss and thus longer run times. ‘‘Fiber packs’’
Catalysts. [12]. Since the introduction of have not yet been used in medium-pressure
the industrial production of nitric acid by the ammonia combustion because fewer gauzes
Ostwald process, several hundred materials have are used in medium-pressure than in high-
been tested as catalysts for ammonia combustion. pressure processes (see Table 3), so the lower
Platinum catalysts have proved most suitable and pressure drop results in poorer distribution.
are used almost exclusively today. Oxides of To reduce catalyst consumption, particularly
non-noble metals can also be employed; these in gauzes at the bottom of the reactor, ceramic
grids coated with platinum – rhodium have also
been developed [16].
Table 3. Typical design data for ammonia burners Platinum is usually alloyed with 5 – 10 %
rhodium to improve its strength and to reduce
Pressure, Number Gas Reaction Catalyst catalyst loss. During combustion, the metal sur-
MPa of gauzes velocity, temperature, loss, g/t
m/s
C HNO3
face becomes enriched in rhodium, thus improv-
ing catalytic activity [17]. Because rhodium is
0.1 – 0.2 3–5 0.4 – 1.0 840 – 850 0.05 – 0.10 more expensive than platinum, a rhodium con-
0.3 – 0.7 6 – 10 1–3 880 – 900 0.15 – 0.20
0.8 – 1.2 20 – 50 2–4 900 – 950 0.25 – 0.50
tent of 5 – 10 % has proved optimal. Figure 6
shows the efficiency of conversion to nitrogen
Platinum loss during operation is caused by

vaporization and abrasion. Vaporization loss
predominates, but if heavy vaporization loss
weakens the structure then abrasion can substan-
tially lower burner efficiency. Platinum loss due
to vaporization is thought to involve the forma-
tion of short-lived platinum dioxide:
PtþO2 !PtO2 ðgÞ
Mechanical losses are accelerated by impuri-

ties in the reaction mixture, which can lead to the
Figure 6. Conversion of ammonia to nitrogen monoxide on formation of whiskers at the grain boundaries.
platinum gauze (a) and platinum losses (b) as a function of The whiskers are more easily broken off by the
catalyst composition flowing gas.
monoxide and the platinum loss as a function of Recovery of Precious Metals. Precious-
the rhodium content of the alloy [18]. metal losses from the catalyst have a significant
If a low reaction temperature (< ca. 800 C) effect on the operating costs of a nitric acid plant.
is unavoidable, a pure platinum catalyst should The approximate losses and resulting costs can
be employed, because otherwise rhodium(III) be determined from the ammonia combustion
oxide would accumulate at the catalyst surface temperature and the loading. Losses increase
and decrease catalytic activity [18]. with temperature and loading; however, smaller
Palladium is also used in catalyst alloys. losses may be measured at higher loadings
Laboratory studies on the catalytic activity of because a more uniform incoming flow causes
90 % Pt – 10 %Rh and 90 %Pt – 5 %Rh – 5 % less movement of the gauzes relative to one
Pd gauzes reveal no great differences in nitrogen another and thus reduces mechanical losses.
monoxide yield [19]. The ternary catalyst is of Table 3 lists typical loss rates.
economic interest because palladium costs much Platinum recovery systems are installed in
less than platinum or rhodium. most nitric acid plants to improve process
Platinum gauzes are pretreated by the manu- economics.
facturer (Degussa and Heraeus, FRG; Johnson Mechanical Filters. Mechanical filters are
Matthey and Engelhard, UK) so that they do not made of glass, mineral wool, or ceramic or
need to be activated after installation in the asbestos fibers. They are normally installed
burner. The reaction is ignited with a hydrogen where the gas temperature is < 400 C. Their
flame until gauzes glow red. After the reaction most important drawback is their large pressure
has been initiated, crystal growth rapidly in- drop, which can reach 25 kPa between filter
creases the surface area. The highest conversion changes.
on the catalyst is obtained after a few days use. Mechanical filters recover 10 – 20 % plati-
Specially pretreated platinum gauzes that reach num, but recovery rates up to 50 % have been
maximum activity after just a few hours are also reported [22]. These filters have the advantage of
on the market [20]. Start-up problems with plati- low capital costs and the disadvantage of high
num gauzes are discussed in [21]. The prolonged operating costs resulting from the large pressure
decline in activity after the conversion maximum drop across the filter. For economic reasons, they
is due to catalyst poisoning and platinum loss. are only employed in mono-high-pressure plants.
Catalyst poisons include iron oxide (rust) and In low-pressure burners, marble chips 3 –
dust in the process air, which is especially con- 5 mm in length were used immediately down-
centrated in the vicinity of fertilizer plants. Any stream of the catalyst gauzes [23]. At high reac-
material deposited on the catalyst surface acts as tion temperature, the marble is converted to
a poison. A multistage filter is used to prevent calcium oxide, whose high absorption capacity
these substances from reaching the catalyst (see for platinum and rhodium permits up to 94 %
Section 1.3.3.1). recovery. During reactor shutdown, however, the
calcium oxide must be protected against recovery efficiency on wire diameter and mesh
moisture. fineness [24]. A method for selecting the opti-
Recovery Gauzes. A technically elegant mum platinum recovery gauze system for a
approach to platinum recovery is to install, just particular nitric acid plant is described in [25].
downstream of the catalyst gauzes, a material The captured platinum diffuses into the palla-
that is stable at high temperature and that can dium gauze and forms an alloy. The topmost
absorb platinum oxide vapor and form an alloy gauze is often designed to reach saturation in one
with it. The first recovery gauzes in production campaign, usually 180 d. Determining the eco-
plants (supplied by Degussa in 1968) consisted of nomic optimum for a recovery system (the most
a gold – palladium alloy (20/80). Nowadays important criterion is the weight of palladium
most such gauzes are gold-free but have a low required) necessitates taking into account the fact
content of nickel (ca. 5 %) to enhance their that palladium is lost. This loss corresponds to
strength. The gauzes have 100 – 1350 mesh/cm2 about one-third of platinum recovery.
and are made of wire with a diameter of 0.2 – ‘‘Getter’’ systems can recover more than 80 %
0.06 mm. Several recovery gauzes with different of the platinum lost from the catalyst. The mech-
specifications are usually installed. Loss of plati- anism of rhodium recovery has not yet been fully
num from the catalyst is greater than that of elucidated. Up to 30 % of rhodium from the
rhodium; for example, the calculated loss com- catalyst is captured by recovery systems.
position for a 90/10 Pt – Rh gauze is 95/5. A
‘‘recovery factor’’ can be determined for each
recovery gauze, indicating how much of the 1.3.2. Oxidation and Absorption of
available platinum is retained by the gauze. This Nitrogen Oxides
recovery factor depends on the specifications
of the gauze, the operating pressure, and the After the combustion of ammonia, the nitrogen
loading. Figure 7 shows the dependence of the monoxide product gas is cooled en route to
absorption and, if necessary, compressed. As
a result, part of the nitrogen monoxide is oxidized
to nitrogen dioxide or dinitrogen tetroxide
(Eq. 2), which is converted to nitric acid by
absorption in water (Eq. 3).
Absorption is usually performed in plate col-
umns where the nitrous gases are converted to
nitric acid in the liquid phase on the plates.
Nitrogen monoxide is constantly reformed in
this step and prevents complete absorption of
the inlet gases. Oxidation of nitrogen monoxide
occurs mainly in the gas phases between the
plates, but also in the gas phase of the bubble
layer on them.
Gas Phase. The gas phase is the site of

nitrogen monoxide oxidation
2 NOþO2 !2 NO2 DH ¼ 1127 kJ=mol ð10Þ
as well as nitrogen dioxide dimerization

2 NO2
N2 O4 DH ¼ 58:08 kJ=mol ð11Þ
and dinitrogen trioxide formation

NOþNO2
N2 O3 DH ¼ 40 kJ=mol ð12Þ
Figure 7. Performance of a palladium-based recovery gauze Reaction of the oxidized nitrogen oxides
as a function of mesh size and wire diameter with water vapor leads to formation of nitrous
and nitric acids. These reactions are of According to [27], the equilibrium constant can
secondary importance from an engineering be determined as
standpoint.
pN2 O3 4740
To describe the kinetics of nitrogen monoxide Kp ¼ ¼ 65:3 109 exp ð19Þ
pNO pNO2 T
oxidation (Eq. 10), a third-order rate equation is
used [26]:
kp 2
r¼ p pO ð13Þ Liquid Phase. The large number of reactive
RT NO 2
components in the gas phase (NO, NO2, N2O3,
where N2O4) means that the reaction model for
r ¼ reaction rate, kmol m3 s1 absorption is complicated. Figure 8 shows
kp ¼ reaction rate constant, atm2 s1 a sophisticated model devised by HOFTYZER and
R ¼ universal gas constant, m3 atm kmol1 K1 KWANTEN [28].
T ¼ temperature, K The main route for the formation of nitric
p ¼ partial pressure, atm acid in this model involves two steps in the
The rate constant is defined by liquid phase. First, dissolved dinitrogen tetrox-
652:1 ide reacts with water, yielding nitric and nitrous
logkp ¼ 1:0366 ð14Þ acids:
T
N2 O4 þH2 O!HNO3 þHNO2 DH ¼ 87:0 kJ=mol ð20Þ
Nitrous acid then dissociates to nitric acid,

This reaction is unusual because it goes to the water, and nitrogen monoxide, the latter being
right faster at low temperature than at high transported across the interface into the bulk
temperature, i.e., the reaction rate has a negative gas:
temperature coefficient.
Because equilibrium in the nitrogen dioxide 3 HNO2 !HNO3 þH2 Oþ2 NO DH ¼ 15:3 kJ=mol ð21Þ
dimerization system is reached very quickly, an
equilibrium formula
According to ANDREW and HANSON [29],
a first-order equation can be written for the rate
kp pN O
r¼ p2NO2 2 4 ð15Þ of dinitrogen tetroxide hydrolysis:
RT Kp
r ¼ kcN2 O4 ð22Þ
can be assumed where Kp is the equilibrium
constant. The dimerization rate is virtually inde- where cN2 O4 is the concentration of dinitrogen
pendent of temperature [27], so the rate constant tetroxide in kmol/m3. The rate constant is given
at 25 C by
4139
kp ¼ 5:7 105 atm1 s1 ð16Þ logk ¼ þ16:3415 ð23Þ
T
can be used at all temperatures of technical
interest. The kinetics of nitrous acid dissociation
HOFTYZER and KWANTEN [28] give the follow- were studied by ABEL and SCHMID [30], with the
ing equation for the NO2 – N2O4 equilibrium following result:
constant:
c4HNO2 k c4HNO2
pN O 6866 r¼k 2
¼ 2 ð24Þ
Kp ¼ 22 4 ¼ 0:698 109 exp ð17Þ pNO HNO c2NO
pNO2 T
where HNO is the Henry coefficient for nitrogen
An equilibrium formula can also be written for monoxide in m3atm/kmol and c ist the concen-
dinitrogen trioxide formation: tration in kmol/m3. The rate constant is defined
by

kp pN O
r¼ pNO pNO2 2 3 ð18Þ 6200
RT Kp logk ¼ þ20:1979 ð25Þ
T
Figure 8. Nonstoichiometric model of absorption of nitrogen oxides in water [28]
Equations (23) and (25) were derived by HOFF- the interface and reacts in the fast first-order
MANN and EMIG [31] and are based on experimen- reaction (Eq. 20) to form nitric and nitrous acids.
tal data from [32]. Nitrous acid dissociates (Eq. 21), and the result-
ing nitrogen monoxide is transported back into
Mass Transfer. For more than 50 years the gas space.
scientists have studied the transport of nitrogen
oxides in water and in dilute and concentrated The following equation can be written for the
nitric acid. A variety of mechanisms have been absorption rate of dinitrogen tetroxide [34]:
proposed depending on the gas composition and pffiffiffiffiffiffiffiffiffiffiffiffiffiffi
the acid concentration. These are partly in agree- JN2 O4 ¼ HN2 O4 pN2 O4 kDN2 O4 ð27Þ
ment with the absorption model of Figure 8.
In the NOx absorption region important for where
acid formation, dinitrogen tetroxide transport is H ¼ Henry coefficient, m3 atm/kmol
considered to be the rate-limiting step. The quan- k ¼ rate constant, s1
tity of dinitrogen tetroxide transported from the D ¼ diffusion constant, m2 /s
bulk gas to the interface depends chiefly on the Numerous measurements in laboratory absor-
NO2 – N2O4 equilibrium [28], [33]: bers support this mechanism. Interpretations of
measurements in absorption columns have given
KgNO2 o
JN2 O4 ¼ pNO2 piNO2 the following correlations for the mass-transfer
2RT
ð26Þ coefficients [35]:
kgN O
þ 2 4 poN2 O4 piN2 O4
RT
1. Bubble-cap trays
where
J ¼ absorption rate, kmol m2 s1
kg ¼ gas-side mass-transfer coefficient, m/s
po ¼ partial pressure in the bulk gas, atm
pi ¼ partial pressure at the interface, atm
At higher NO2 /N2O4 concentrations in the reac-
tion gas, primarily dinitrogen tetroxide crosses
2. Sieve trays
where
H ¼ Henry coefficient, m3kPa/kmol
T ¼ temperature, K
W ¼ mass fraction
The absorption of NO2 – N2O4 in concentrat-
ed nitric acid can be treated as pure physical
absorption [36]. Deviations from the described
Figure 9. Vapor pressures of nitric acid and water as
chemisorption also occur at low gas-phase a function of acid strength and temperature [28] 1mm
NO2 – N2O4 concentrations [29]. Hg ¼ 133.2 mPa
Absorption Equilibrium. Equilibrium solved in the dilute acid affect the activities of
considerations allow determination of the maxi- nitric acid and water. Up to a nitric acid concen-
mum possible acid concentration for a given tration of 65 wt % and an inlet nitrogen oxide
composition of the inlet gas. For example, partial pressure of 100 kPa, however, the vapor
suppose the overall reaction is pressures from the binary system HNO3 – H2O
can be used to determine K2 (Fig. 9).
3NO2 ðgÞþH2 OðlÞ
2HNO3 ðlÞþNOðgÞ DH ¼ 72:8kJ=mol
Figure 10 shows how K1 depends on the acid
ð30Þ
concentration and the temperature. This param-
and the equilibrium constant is defined as eter is particularly interesting from an engineer-
ing standpoint because it allows the acid strength
p2HNO3 pNO to be determined if the gas concentration is
Kp ¼ ð31Þ
p3NO2 pH2 O known.
with the partial pressures of nitrogen monoxide If the equilibrium is based on the overall
( pNO) and nitrogen dioxide (pNO2 ) in the gas reaction
phase and the vapor pressures of nitric acid 3=2 N2 O4 ðgÞþH2 OðlÞ
2 HNO3 ðlÞ ð33Þ
(pHNO3 ) and water (pH2 O ) over the dilute acid. In þNO3 ðgÞ DH ¼ 75 kJ=mol
industrial absorption the equilibrium constant
depends only on temperature. The equilibrium the equilibrium constant is
constant is conventionally split into two terms:
Kp ¼ K1 K2
Kp ¼ K1 K2 pNO p2HNO3
where K1 ¼ and K2 ¼ ð34Þ
pNO p2 ð32Þ 3=2
where K1 ¼ 3 and K2 ¼ HNO3 pN2 O4 pH2 O
pNO2 pH2 O
K2 depends on the acid concentration and the Again Figure 9 gives the K2 values. In
temperature. Gases ( N2O4, N2O3, HNO2 ) dis- this formulation, K1 is a function of the acid
Figure 11. Value of K1 from Equation (34) as a function of

acid concentration
The equilibrium constant Kp can be estimated

with the following equation [38]:
2:64
logKp ¼ 7:35þ ð39Þ
T
Figure 10. Value of K1 from Equation (32) as a function of Then K1 can be determined from Kp, and the K2
acid concentration and temperature [28] values obtained from Figure 9. The parameter K1
determines the equilibrium curves for constant
temperature and constant acid concentration
concentration and does not depend on temperature when pNO2 is plotted against pNO (Fig. 12). The
(Fig. 11). The curve of Figure 11 can be fitted by an K1 values are necessary to calculate the absorp-
empirical equation [37]: tion of nitrous gases according to TONIOLO [39].
The application of the Toniolo diagram is de-
2
logK1 ¼ 7:41220:29WHNO3 þ32:47WHNO scribed in [40].
3
3
ð35Þ
30:87WHNO 3
Modeling of the Absorption Tower. The

where W denotes the mass fraction.
literature offers many methods for calculating the
Another way of describing the absorption
absorption of nitrous gases; they can be classified
equilibrium is to start with the hypothetical com-
according to the number of reactions, the reaction
ponent NO2 denoted as ‘‘chemical NO2’’:
kinetics, or the type of mathematical method:
pNO~2 ¼ pNO2 þ2pN2 O4 ð36Þ
1. Number of Reactions. The simplest calcula-
The nitrogen dioxides, considered as completely tion model uses Equation (30) to describe the
dissociated, are assumed to react according to events on an absorption plate and a kinetic
formula to describe nitrogen monoxide oxi-
dation between two oxidation plates [41].
Extended models [42–45] also take into
account the dimerization of nitrogen dioxide
This hypothetical reaction leads to the equi- to dinitrogen tetroxide. In this way it is possi-
librium relation ble to describe nitric acid formation not just
Kp ¼ K1 K2
via nitrogen dioxide but also via dinitrogen
pNO p2 tetroxide [46–49].
where K1 ¼ and K2 ¼ HNO3 ð38Þ
3
pN~O2 pH2 O Models that include the formation and disso-
ciation of nitrous acid in the liquid phase give
to-plate calculations are generally described

in the literature. The relaxation method [31]
and a special stage-to-stage calculation [52],
however, have also been used for the design of
absorption towers.
By way of example, an equilibrium model

and a transport model are described in more
detail.
Equilibrium Model. The equilibrium model
is based on Equations (11) and (33). If a gas of
known composition is fed to the plate and an
acid of known strength leaves the plate, the
calculation begins at the bottom of the tower.
If the gas throughput is taken to be constant
(because of the high content of inerts), the
following mass balance is obtained for the n-
th plate:
3ðyn;NO yn1;NO Þ ¼ ðyn1;NO2 þ2yn1;N2 O4 Þ
ð40Þ
ðyn;NO2 þ2yn;N2 O4 Þ
where y is the mole fraction in the vapor phase.

Equilibrium Equations (34) for Kp1 and (17)
for Kp2 give the equation
ay3n;NO2 þby2n;NO2 þyn;NO2 þd ¼ 0
pffiffiffi
with a ¼ 3ðKp1 pÞðKp2 pÞ1:5
ð41Þ
b ¼ 2ðkp2 pÞ
d ¼ ð3yn1;NO þyn1;NO2 þ2yn1;N2 O4 Þ
This formula allows the compositions of the gas

Figure 12. Toniolo diagram for an absorption tower [39] leaving the n-th plate and the acid arriving at the
A ! B absorption process; B ! C oxidation process n-th plate to be determined.
Before the (n þ 1)-th plate is calculated, the
oxidation of nitrogen monoxide must be deter-
the best description of known chemical events
mined. The flow behavior of the nitrous gases in
[50], [50]. A model that permits nitrous acid
an absorption tower is not known exactly, so
formation in the gas phase has also been
the oxidation space can be described as either
proposed [51].
a tubular or a stirred-tank reactor. Actual con-
2. Reaction Kinetics. Most design computations
ditions probably lie somewhere between the two
use equilibrium equations for the basic reac-
[28], but trends can be identified on the basis of
tions. These static methods have the drawback
plate type. The stirred-tank model is preferred
of requiring the introduction of efficiency
for bubble-cap trays [47], but flow-through con-
factors [51] that take into account limitation
ditions can be expected in the case of sieve
of transport of the reactants across the inter-
plates. Because virtually all absorption towers
face. Dynamic methods do not need empirical
today are fitted with sieve plates, only these are
efficiency factors because they describe mass
discussed.
transfer in terms of physical and chemical
When the reaction is carried out isothermally,
laws [28], [31], [50], [52].
integration of the rate equation
3. Mathematical Methods. In view of the large
number of nonlinear equations to be solved in dpNO
¼ kp2NO pO2 ð42Þ
both equilibrium and dynamic models, plate- dt
gives a solution
2
q¼
kð2pO2 pNO Þ
( 2 3)
ð43Þ
x 1 42pO2 pNO x5
ln
pNO ð1xÞ 2pO2 pNO 2pO2 ð1xÞ
where
q ¼ residence time, s
k ¼ rate constant, atm2 s1
p ¼ partial pressure, atm
t ¼ time, s
x ¼ fraction of oxidized nitrogen monoxide
in which x must be determined by iteration from
the residence time q and the inlet partial pressures
of nitrogen monoxide ( pNO) and oxygen (pO2 )
[47]. The partial pressures of the other compo-
nents leaving the reactor can be calculated from
the fraction x of oxidized nitrogen monoxide. Figure 13. Hydrodynamic model of absorption tower g ¼
molar gas flow rate of a component; G ¼ molar flow rate of
If an excess of oxygen is assumed to be gas; L ¼ molar flow rate of liquid; p ¼ pressure; T ¼ temper-
ature; Tcw ¼ temperature of cooling water; V ¼ volume; x ¼
present, the rate equation can be simplified mole fraction in liquid phase; y ¼ mole fraction in gas phase
[53] as
dpNO
¼ kp2NO ð44Þ Transport Model. A transport model for the
dt
absorption tower is based on a series of units,
so that the partial pressure of nitrogen monoxide each containing a bubble- column reactor and an
at the reactor outlet ( p0 NO) can be determined: adiabatic plug flow reactor (Fig. 13) [52]. The
bubble-column reactor, modeled as two ideal
1 1 kq stirred-tank reactors, simulates the liquid with
0 ¼ þð2pO2 pNO Þ ð45Þ
pNO pNO 2 gas bubbles on a tray (absorption space). The
adiabatic plug flow reactor simulates oxidation
Because the oxidation reaction is highly exother- between plates (oxidation space).
mic, the tubular reactor can be designed for
isothermal operation only when conversion is The balances are carried out with the equa-
very low (e.g., when the tail gas contains little tions
NO). Otherwise, adiabatic reaction conditions pn
Gn yn;i Gn1 yn1;i kg;i aV ðy yn;i Þ
must be assumed. To describe the reaction under RTn n;i
adiabatic conditions the oxidation space is divid- X
Mg ð47Þ
ed into n layers, in each of which the reaction is ¼ Vg ng;ij rg;j
j¼1
isothermal. The temperature increase from one
Pk
layer to the next is given by [33] i ¼ N2, O2, NO, NO2, N2O4 and i¼1
CNO;0 ðDHR Þ GNO;0 GNO
yn;i ¼ 1 for the components in the gas phase
DT ¼ 1=2 ð46Þ (subscript g) where
r0 Cp GNO;0
a ¼ interfacial area per unit volume, m2 /m3
where G ¼ molar gas flow rate, kmol/s
CNO, 0 ¼ initial concentration of NO, kmol/m3 kg ¼ gas-side mass-transfer coefficient
Cp ¼ molar heat capacity, kJ kmol1 K1 Mg ¼ number of reactions in the gas phase
GNO ¼ molar gas flow rate, kmol/s n ¼ plate number
GNO, 0 ¼ initial gas flow rate, kmol/s r ¼ reaction rate, kmol m3 s1
DHR ¼ reaction enthalpy, kJ/kmol V ¼ volume of bubble layer
r0 ¼ initial density, kg/m3 Vg ¼ volume of gas phase in bubble layer
yi ¼ mole fraction of i-th component in liquid differ in both phases of a single stage. The
phase mathematical treatment of this model is de-
y *i ¼ mole fraction of i-th component in liquid scribed in [52].
phase at the phase boundary
n ¼ stoichiometric coefficient
Analogously for the liquid phase (subscript l) 1.3.3. Equipment
Ln xn;i Lnþ1 xnþ1;i þkl;i aVcn ðxn;i xn;i Þ
Figure 14 summarizes the equipment needed
X
Ml ð48Þ to implement the three chemical steps involved
L~n x~n;i ¼ Vl nl;ij rl;j in nitric acid production (Fig. 2). In addition to
j¼1
P
k producing nitric acid, a nitric acid plant also
i ¼ NO, N2O4, HNO2, HNO3, H2O and xn;i ¼ 1 where generates steam or mechanical energy from the
i¼1
chemical energy liberated.
c ¼ molar concentration, kmol/m3
L ¼ molar liquid flow rate, kmol/s 1.3.3.1. Filters and Mixers
x ¼ mole fraction in liquid phase
L~ ¼ side stream To obtain the highest possible conversion of
Ml ¼ number of reactions in the liquid phase ammonia on the catalyst and a long catalyst life,
Thermodynamic equilibrium is assumed at the the starting materials (air and ammonia) must be
interface, purified. The air must be very clean to prevent
catalyst poisoning (Section Catalysts).
yn;i ¼ Hn;i xn;i ð49Þ
where H is the Henry coefficient and the formula Air Filter. A multistage filter is normally
pn
used on the air intake to a nitric acid plant and
kg;i ðyn;i yn;i Þ ¼ kl;i cn ðxn;i xn;i Þ should remove 99.9 % of all particles larger than
RTn ð50Þ
0.5 mm.
i ¼ NO; N2 O4
Typical filter media are plastic and glass
is used for dynamic mass transfer between fibers. Filter frames should be made of stainless
phases. A separate heat balance is performed steel. Air filters must be replaced regularly
for each phase, so that the temperature may because filter bags can tear or filter mats can
Figure 14. Equipment needed in a nitric acid plant

become overloaded and cause an excessive is important in both cases. Local ammonia
pressure drop. Filter life depends on the particu- excesses in the burner are a risk for plant
late load in the air (typically 0.8 mg/m3 ). In safety (explosion limit) and may also cause
areas where sandstorms may occur (maximum overheating of the catalyst gauze. Poor mixing
loading 500 mg/m3 ), the use of a sand lowers the conversion of ammonia to nitrogen
separator (a centrifugal collector) as a prefilter monoxide and increases platinum loss from the
is recommended. catalyst.
The efficiency of a given mixing operation is
Ammonia Filters. The liquid ammonia fil- described by the standard deviation s of mea-
ter removes solid contaminants, especially small sured samples from the theoretical value x
rust particles; 99.9 % of all particles larger than a certain distance downstream from mixing. In
3 mm should be eliminated. Selection of a liquid nitric acid plants, the deviation should be
ammonia filter requires consideration of the fact < 1 %. If the theoretical ammonia concentra-
that traces of oils and chlorides are also present in tion in a mixture is 10 %, for example, mea-
ammonia. Proven filter materials are Teflon and sured values fluctuate between 9.9 and 10.1 %
sintered metals. Polypropylene and ceramic filter [54]. Only static mixers are used (e.g., the Uhde
candles (cartridges) are also employed. Magnetic tubular mixer or the Sulzer three-element
filters have found some use but have limited mixer).
capacity.
Filtration of ammonia gas should remove 1.3.3.2. Burners and Waste-Heat Boilers
99.9 % of oil and solid particles larger than
0.5 mm. The principal filter media are glass The heat of reaction liberated during ammonia
fibers, sintered metals, and ceramics. The pres- combustion is utilized to produce steam and
sure drop is up to 10 kPa, depending on filter preheat the tail gas. Steam is produced in a
type. waste-heat boiler located immediately below the
burner (Fig. 15). The burner consists of a burner
Filters for the Mixed Gas. The mixed-gas basket packed with filling material to ensure
filter provides final cleaning of the ammonia – uniform distrubution of the downward flowing
air mixture and improves the mixing of the air reaction gas. Platinum recovery gauzes (Section
and ammonia; it should remove 99.8 % of all Recovery of Precious Metals) are located above
particles larger than 1.5 mm. Contaminants in the the filling material. The catalyst gauzes (Section
gas mixture not only originate externally (in the Catalysts) are located above the recovery gauzes.
process air and ammonia) but are also formed by The burner basket is clamped between the flanges
corrosion inside the system (rust). The gas mix- of the burner head and the waste-heat boiler. To
ture filter should therefore be installed as near as ensure better distribution of the reaction mixture,
possible to the burner. Ceramic filter cartridges the burner head also contains a perforated plate or
are generally used in which silicon dioxide is the honeycomb grid. Hydrogen burners rotating
dominant constituent. For a filter cartridge with above the surface are often used for ignition.
a surface loading of 250 m3 /m2, the maximum The gauze temperature is measured, and the
pressure drop in the clean state is 10 kPa. space above the gauze can be observed through
inspection glasses. The gauzes glow bright red
Mixers. Static gas mixers are used for two during catalysis. The throughput per element can
purposes in nitric acid plants: produce up to 1200 t of 100 % nitric acid per day.
Waste-heat boilers up to 6 m in diameter are
1. To mix ammonia and air in a ratio of ca. 1 : 10 used. Figure 15 shows a waste-heat boiler for
for catalytic oxidation (see Section 1.3.1) medium-pressure burning. The preevaporator is
2. To mix ammonia and tail gas in a ratio of located directly below the burner basket and
1 : 100 for the catalytic reduction of NOx as protects the downstream superheater against ex-
part of tail-gas treatment (see Section 1.4.2.3). cessive temperature. The superheater is followed
by the main evaporator. Evaporator tubes are also
From an economic standpoint, homogeneous installed at the wall to cool it and protect it from
mixing of the gas streams upstream of the reactor excessive temperature.
Stress cracking corrosion is a special threat to

economizer tubes. Start-up always leads to the
formation of ammonium salts; nitrous and nitric
acids may also condense. To prevent very rapid
corrosive attack, the equipment is therefore heat-
ed before start-up and the feedwater is preheated
to a high temperature.
Waste-heat boilers can be designed for
pressures up to 10 MPa and temperatures up to
550 C in the superheater. The steam is used to
drive a turbine or is exported.
1.3.3.3. Compressors and Turbines
Machines on a common shaft are used to

deliver and compress the gases and supply
the drive power needed for this purpose. Pow-
er sources are the tail-gas turbine and a steam
turbine or electric motor. The tail-gas turbine
can supply 35 – 100 % of the compression
energy required for the process, depending on
the degree of preheating; the remainder comes
from the steam turbine. The machinery used
Figure 15. Reactor for catalytic ammonia oxidation with depends on the nitric acid process and may
waste-heat recovery system (Lentjes) a) Burner head; b) consist of an air compressor, a nitrous gas
Perforated plate; c) Platinum gauzes and platinum recovery compressor, a tail-gas turbine, and a steam
gauzes; d) Inspection glass; e) Superheater and evaporator
tubes; f ) Hydrogen ignition; g) Refractory packing; h) Ni-
turbine or an electric motor.
trous gas outlet Figure 19 shows the nitric acid process with
atmospheric combustion and medium-pressure
(400 – 600 kPa) absorption. The nitrous gas
compressor (b) sucks the reaction mixture
through the burner and simultaneously provides
Figure 16 shows how heat from the waste-heat the pressure needed for absorption. This com-
boiler is used to raise steam. Boiler feedwater is pressor does not have interstage cooling and can
led through the economizer (b) into a steam drum be of radial or axial design. The tail gas from the
(c). Water at thermal equilibrium with the steam absorption column is expanded in a tail-gas
is pumped from the drum through the evapora- turbine (d), usually a single-stage device. The
tors. Steam from the drum goes first to the lower rest of the power required to drive the nitrous gas
superheater (g) and is then cooled in the drum so compressor is supplied by the steam turbine or an
that the desired temperature can be attained in the electric motor.
upper superheater (f). Figure 20 shows a medium-pressure process
Systems with an economizer integrated in the (400 – 600 kPa), as preferred for small- or me-
waste-heat boiler have also proved serviceable dium- capacity plants ( 600 t/d 100 % HNO3 ).
(Fig. 17). Here, as in the waste-heat boiler of The machinery for this process includes a radial
Figure 15, the heat-exchanger tubes can be or axial air compressor (a) without interstage
arranged spirally in disk form or in a square pack. cooling, a single-stage tail-gas turbine (d), and
A shell-and-tube evaporator with natural a steam turbine (e) or electric motor.
circulation can also be used (Fig. 18). The A dual-pressure process with medium-pres-
superheater tubes (e) are again arranged as a flat sure combustion and high-pressure absorption
spiral. These waste-heat boilers are particularly calls for both an air compressor and nitrous gas
suitable for smaller plants or those using low compressor (Fig. 21). The air for combustion is
steam pressure. delivered at 400 – 600 kPa by an uncooled radial
Figure 16. Water and steam connections of heat exchangers (Lentjes) downstream of catalysis a) Reactor; b) Economizer;
c) Steam drum; d) Boiler feedwater pumps; e) Preevaporator; f ) Upper superheater; g) Lower superheater; h) Main evaporator
or axial air compressor (a). The radial nitrous gas When the nitric acid plant is started up or in
compressor (c) produces the 1.0 – 1.2 MPa pres- continuous operation, unreacted ammonia is
sure needed for absorption. The drive power for present in the burner exit gas. The level in
these two devices comes from a multistage tail- continuous operation is ca. 30 ppm of ammonia.
gas turbine (e) and a steam turbine (f) or electric As a result, nitrates and nitrites would accumu-
motor. These systems are preferred for large- late in the nitrous gas compressor if they were not
capacity plants ( 400 t/d 100 % HNO3 ), removed regularly. If the temperature exceeds
especially in Europe. 240 C, combustion or explosion is possible.
High-pressure plants (Fig. 22) are preferred To avoid an explosion, water or steam is briefly
in the United States because of lower invest- sprayed into the suction of the nitrous gas com-
ment costs. The machinery includes an air pressor every 8 h [55]. Because nitrous gas is
compressor with interstage cooling. Radial highly toxic, it must not be allowed to escape
devices are generally used, but the low-pres- from the compressor. The machine is therefore
sure section in larger machines may be axial. equipped with air-purged labyrinth seals. Chem-
The tail-gas turbine is usually a multistage ical reactions must be considered in the design of
reaction machine. nitrous gas compressors. The endothermic
The nitrous gas compressors are virtually dissociation of dinitrogen tetroxide to nitrogen
always of radial design, but axial machines dioxide removes heat from the stream [56] and
are available. The design and operation of the can cool the gas by 20 C or more.
compressors must take particular account of the Because of their large capacities, modern
following properties of the gas stream: nitric acid plants usually employ axial air
compressors. The possibility of surging in the
1. Nitrites and nitrates may be formed compressor, especially during plant start-up,
2. The nitrous gas is toxic and highly corrosive requires the installation of appropriate surge
3. Chemical reactions take place when nitrous protection. Adjustable inlet guide vanes allow
gas is compressed operation at various plant capacities.
Figure 18. Reactor for catalytic ammonia oxidation with

integrated waste-heat recovery system (Steinm€uller) a) Burn-
er head; b) Perforated plate; c) Platinum gauzes; d) Packing;
e) Superheater tubes; f ) Evaporator; g) Nitrous gas outlet
with hot nitrous gas on the tube side and cool tail
gas on the shell side. The pressure drop should be
kept as low as possible to secure a favorable
energy balance for the plant as a whole.
Ammonia Evaporator. Various types of

equipment can be used for ammonia evapora-
Figure 17. Reactor for catalytic ammonia oxidation with
tion. Figure 23 shows a shell-and-tube heat
integrated waste-heat recovery system (Steinm€uller) a) Burn- exchanger with mist collector. Cooling water
er head; b) Perforated plate; c) Platinum gauzes and platinum on the tube side is cooled on evaporation. In
recovery gauzes; d) Inspection glass; e) Superheater and medium-pressure plants, the heat of vaporiza-
evaporator tubes; f ) Feedwater preheater; g) Nitrous gas
outlet
tion is also taken from chilled water used as
coolant in the absorption step. The shell-side
heat-transfer coefficients for ammonia can be
Tail-gas turbines can be single-stage or calculated according to [57].
multistage devices of axial or radial design. For
part-load operation, these machines are equipped Gas Cooler – Condenser. In the cooler –
with a group of valve-controlled nozzles or condenser, the temperature is lowered below the
adjustable guide vanes in the inlet. dew point of the inlet nitrous gas. The nitric acid
Steam turbines may be condensing or back- condensate has a concentration of, for example,
pressure machines with or without an extraction/ ca. 40 wt % at medium pressure. Suitable mate-
side stream. rials of construction are discussed in Section
1.3.3.5. The thermal design of a gas cooler –
condenser is difficult because the cooling step
1.3.3.4. Heat Exchangers and Columns involves chemical reactions in both the gas and
the condensed liquid phases. In the apparatus
Heat Exchangers. The shell-and-tube de- shown in Figure 24, nitrous gas passes into the
sign predominates for tail-gas heat exchangers, shell side through two inlets; each of the partial
Figure 19. Flow sheet of a nitric acid process with atmospheric combustion and medium-pressure absorption a) Reactor with
waste-heat recovery system; b) Nitrous gas compressor; c) Absorption tower; d) Tail-gas turbine; e) Steam turbine; f ) Cooling
system; g) Heat exchanger network
Figure 20. Flow sheet of a nitric acid process with medium-pressure combustion and medium-pressure absorption a) Air
compressor; b) Reactor with waste-heat recovery system; c) Absorption tower; d) Tail-gas turbine; e) Steam turbine; f ) Heat
exchanger network
Figure 21. Flow sheet of a nitric acid process with medium-pressure combustion and high-pressure absorption a) Air
compressor; b) Reactor with waste-heat recovery system; c) Nitrous gas compressor; d) Absorption tower; e) Tail-gas turbine;
f ) Steam turbine; g) Cooling system; h) Heat exchanger network
Figure 22. Flow sheet of a nitric acid process with high-pressure combustion and high-pressure absorption a) Air compressor;
b) Reactor with waste-heat recovery system; c) Absorption tower; d) Tail-gas turbine; e) Steam turbine; f ) Heat exchanger
network; g) Interstage cooler
streams reverses direction four times. Heat is tower, whereas NOx is reduced in the upper two-
absorbed by cooling water. thirds. As a result, most of the heat must be
withdrawn in the lower third; this is done with
Absorption Tower. Absorption tower cooling coils on the plates. The coils on the upper
design is governed by the calculations for the plates primarily cool the nitrogen monoxide gas
oxidation process (i.e., tower height, see also against chilled water, because oxidation pro-
Section 1.3.2) and thermal design. Because oxi- ceeds faster at lower temperature. Most modern
dation proceeds more slowly as the NOx content absorption towers have sieve plates. Compart-
in the tower decreases, the spacing between ments built into the bottom of the tower separate
plates increases. Figure 25 shows an absorption acid of medium strength from weak acid in
tower for a plant with a daily production capacity case of plant shutdown. The collected acids
of 1830 t of 100 % nitric acid. Acid formation are pumped back to the tower at restart so that
takes place chiefly in the bottom third of the a steady state is reached more quickly. Before the
Figure 23. Ammonia evaporator a) Evaporator tubes; b) Sparger; c) Drop separator

Figure 24. Cooler – condenser with feedwater preheaters attached to nitrous gas inlets
tail gas leaves the tower, entrained acid droplets

are collected in the demister.
Bleacher. The NOx gases contained in

the acid are stripped out with secondary air in
the bleacher. A distribution tray delivers the acid
evenly onto the Raschig ring packing. The pack-
ing rings are made of stainless steel, material
no. 1.4301 (AISI 304) or 1.4306 (AISI 304L).
1.3.3.5. Construction Materials
Because of the special behavior of nitric acid

toward metals (see Section 1.2), materials of
construction for nitric acid plants must be select-
ed very carefully. When industrial production
began, acid-resistant masonry linings were used
for plant components that came in contact with
the product. By the 1920s, materials technology
had advanced to the point that high chromium
contents could be incorporated into alloy steels.
Today, the principal materials of construction in
nitric acid plants (< 70 % HNO3 ) are austenitic
chromium – nickel steels containing 18 % chro-
mium and 10 % nickel. The corrosion resistance
of these steels decreases with increasing temper-
Figure 25. Absorption tower a) Nitrous gas inlet; b) Inner ature. Normal austenitic steels are generally not
compartment; c) Outer compartment stable above 70 %. The chromium content de-
point is important because the corrosion potential

of stainless steel in strong (highly concentrated)
nitric acid often reaches the limit of the trans-
passive potential. In the transpassive range the
passive layer starts to dissolve. A steel with too
little chromium or with elements that lower the
transpassive potential tends to corrode at a high
rate [58].
Steels of a given specification behave differ-
ently under nitric acid attack because of permit-
ted batch-to-batch variations in composition.
The only way to be sure that a selected steel is
suitable for an apparatus in contact with nitric
acid is to perform tests. The best known method
is the Huey test, in which a clean, polished piece
of steel is immersed in boiling 65 % nitric acid at
ambient pressure [59]. The specimen is exposed
to these conditions for five successive 48-h per-
Figure 26. Anodic polarization curve for stainless steel Cr iods, the acid being renewed at the beginning of
denotes the effect of chromium on the anodic polarization rate each test period. The Huey test gives a good
indication of how individual alloy constituents
termines the corrosion resistance; its anticorro- affect intergranular corrosion.
sive action is influenced by the carbon content of To ensure good weldability, the carbon con-
steel. The chromium in the alloy forms a carbide tent is limited to 0.03 %; alternatively, titanium
(Cr3C2 ) at the grain boundaries; only small or niobium is added as a stabilizer.
amounts of free chromium remain at high carbon The stainless steels generally used in nitric
contents, and the steel is therefore less corrosion acid plants are those classified unter material
resistant. If excess chromium remains after the no. 1.4306 (AISI 304L); in the Federal Republic
amount needed for carbide formation is con- of Germany, however, the corresponding stabi-
sumed, only this excess is responsible for the lized qualities, material no. 1.4541 (AISI 321)
anticorrosion properties. and 1.4550 (AISI 347), are also employed
The effect of chromium on the corrosion rate (Table 4). These steels are usually specified
is shown in the anodic polarization curve of for towers and heat-exchanger shells, and also
Figure 26. When chromium is present in the for many heat-exchanger tubes. The 1.4335 steel
alloy, the passive region Ep (see Section 1.2) (AISI 310L) has a very low corrosion rate and is
is reached sooner. Furthermore, chromium low- used particularly where corrosive attack is
ers the corrosion rate in the passive state and severe, for example, if the temperature is below
raises the transpassive potential Etr. The last the dew point of nitrous gas, even at higher
Table 4. Chemical analyses (wt %) of standard and special stainless steels [59]
Type of steel C max. Si max. P max. S max. Cr Ni Other
AISI 304L 0.035 0.75 0.040 0.030 18 – 20 8 – 13

321 0.08 0.75 0.040 0.030 17 – 20 9 – 13 Ti
347 0.08 0.75 0.040 0.030 17 – 20 9 – 13 Nb
ISO 1.4306 0.03 1.0 0.045 0.030 17 – 20 10 – 12.5
1.4541 0.10 1.0 0.045 0.030 17 – 19 9 – 11.5 Ti
1.4550 0.10 1.0 0.045 0.030 17 – 20 9 – 11.5 Nb
Sandvik 3R12* 0.030 0.60 0.030 0.030 18.5 10.5
2R12* 0.020 0.10 0.015 0.010 18.5 11
2RE10** 0.020 0.30 0.020 0.015 24.5 20.5
*
ISO material no. 1.4306.
**
ISO material no. 1.4335.
temperatures [59]. These conditions normally um pressure. This type of process is particularly
occur at the inlet to the tail-gas preheater, in the economical for smaller capacities and is thus
dew point region of the cooler – condenser, and described first.
at the outlet of the feedwater preheater. Corrosion As plant capacities continued to grow and
at these locations is caused mainly by reevapora- lower tail-gas levels of NOx were necessary the
tion of nitric acid condensate, which brings the absorption pressure was increased still further.
acid concentration up to the azeotropic level Lower energy costs and shorter depreciation
(69 % HNO3 ). The acid is then very aggressive, periods in the United States have led to a prefer-
even in the vapor phase. Corrosion can take ence for the high-pressure process, whereas more
place in the boiler feedwater preheater if conden- favorable consumption and production figures in
sate forms at the outlet. Reheating of the Europe have favored the dual-pressure process
condensate by the hot process gas can lead to with medium-pressure combustion and high-
critical conditions. Process design parameters pressure absorption.
should normally be selected so as to avoid con- The principle of medium- and high-pressure
densation; material no. 1.4306 is then adequate. (monopressure) plants is that air for ammonia
If, however, condensation or reboiling occurs oxidation and NOx absorption is compressed to
and this steel cannot be used, 1.4335 should be the desired pressure. The ‘‘primary’’ air for oxi-
employed [60]. dation is then mixed with ammonia and forced
In plants producing concentrated nitric acid, through the burner. The ‘‘secondary’’ air for
aluminum (99.8 %), ferrosilicon, tantalum, and stripping dissolved NOx out of the raw acid and
special austenitic steels are used. Because tanta- oxidizing the intermediate nitrogen monoxide is
lum is very expensive, it is employed only with supplied upstream of the absorption tower. The
boiling concentrated nitric acid. Ferrosilicon can tail gas is heated and then expanded in a turbine
be used only in castings because of its brittleness. (on a common shaft with the compressor) to
produce mechanical energy. The remaining drive
power is supplied by a steam turbine running on
1.3.4. Processes process steam.
Figure 14 illustrates the steps necessary for im- Medium-Pressure Process. Figure 27 is
plementation of the Ostwald process. Industrial a flow sheet of a medium-pressure process
processes differ in the sequence and design of (ca. 550 kPa). Liquid ammonia is evaporated at
these steps. This section describes processes ca. 700 kPa in the ammonia evaporator (a). The
for the production of weak acid [61, pp. 61 – cold generated can be used in the absorption
98] and strong acid [61, pp. 99 – 130]. step. Water is removed from liquid ammonia in
an ammonia stripper (b). The ammonia – water
1.3.4.1. Weak Acid Processes blowdown mixture is evaporated batchwise with
steam. Residual aqueous ammonia can be used in
The first industrial plants for the production of fertilizer production. The ammonia vapor is heat-
weak acid employed atmospheric combustion ed with steam to ca. 90 C in the ammonia
and low-pressure absorption [3]. This type of preheater (c) and then filtered (d). If necessary,
plant is no longer built. It was followed by a small stream of ammonia is diverted to tail-gas
a process employing atmospheric combustion treatment.
and absorption at medium pressure. This process All the air needed for the process is sucked in
has the advantage of lower absorption costs through the air filter (f ) by the air compressor (g).
because the marked improvement in absorption The compressed air is divided into two sub-
obtained with the pressure generated by a nitrous streams in a tail-gas preheater (h). The secondary
gas compressor allows the apparatus to be down- air goes to the bleacher (x) for stripping raw acid.
sized. The energy of compression can be partially The secondary airstream exiting the bleacher is
recovered with a tail-gas turbine. To circumvent laden with NOx and is added to the nitrous gas
the difficulty of operating a compressor for before it enters the absorption tower ( p). The
nitrous gas and obtain a further decrease in plant greater part of the process air, the primary air, is
volume, to ammonia was also oxidized at medi- mixed with the superheated ammonia in the
Figure 27. Simplified flow sheet of a medium-pressure process a) Ammonia evaporator; b) Ammonia stripper; c) Ammonia
preheater; d) Ammonia gas filter; e) Ammonia – air mixer; f ) Air filter; g) Air compressor; h) Tail-gas preheater III; i) Reactor;
j) Waste-heat boiler; k) Tail-gas preheater I; l) Economizer; m) Tail-gas preheater II; n) Feedwater preheater; o) Cooler –
condenser; p) Absorption tower; q ) Ammonia – tail-gas mixer; r) BASF catalytic tail-gas reactor; s) Tail-gas expansion
turbine; t) Feedwater tank with deaerator; u) Steam drum; v) Steam turbine; w) Steam turbine condenser; x) Bleacher
ammonia – air mixer (e); it then flows through ary air and admitted to the absorption tower (p).
the mixed-gas filter (not illustrated) and, now The acid condensate from the feedwater preheat-
cleaned, enters the reactor (i) where ammonia er and the cooler – condenser flows directly into
reacts with oxygen in the primary air over the the bottom of the gas cooler – condenser. This
platinum – rhodium catalyst, yielding nitrogen acid condensate is then delivered by an acid
monoxide and water. The reaction is exothermic condensate pump to a tray with the appropriate
and proceeds at ca. 890 C. The nitrous gas concentration in the absorption tower.
stream is cooled in the waste-heat boiler ( j), In the lower part of the tower, the nitrous gas is
raising steam. Nitrogen monoxide is oxidized to oxidized further, thus reaching the necessary
nitrogen dioxide in the downstream piping degree of oxidation before entering the absorp-
and equipment, heating the nitrous gas stream. tion section. The tower contains sieve trays
Further heat recovery takes place in the tail-gas through which the gas flows countercurrent to
preheater (k) and the economizer (l). After exit- the acid. The product acid concentration is at-
ing the economizer, the nitrous gas stream is tained on the lowermost absorption tray of the
cooled in a second tail-gas preheater (m). Con- tower. The acid is then pumped to the bleacher
densate can form in the next unit downstream, the (x), where dissolved NOx is stripped, before the
feedwater preheater (n), which is located acid is stored in tanks. Chlorides in the absorption
directly on the inlet of the cooler – condenser tower feed accumulate on trays where the acid
(o). Additional water of combustion condenses concentration is ca. 21 wt %. Because of the
out in the cooler – condenser before the nitrous danger of corrosion, these trays must be emptied
gas stream is mixed with the NOx-laden second- into the product acid tank from time to time.
Cooling water flowing through coils on the sieve rest is generated by a condensing steam turbine
trays removes heat generated by the oxidation of supplied with product steam. The turbine may be
nitrogen monoxide to nitrogen dioxide and its bled. The steam turbine condensate goes to the
further conversion to nitric acid. Part of the heat boiler feedwater preheater (n) where it absorbs
absorbed by the cooling water is utilized to heat from the NOx gas and then flows through the
evaporate ammonia. A demister in the head of deaerator into the feedwater tank (t). Nondeaer-
the tower collects liquid droplets entrained in the ated feedwater from the battery limit also flows
tail gas; the condensate runs back to the last tray via a preheater into the feedwater tank. The boiler
of the absorption tower. feedwater pump raises the pressure of the deaer-
The tail gas absorbs heat from the secondary ated feedwater to the requisite boiler pressure.
air and the nitrous gas in three tail-gas preheaters. Product steam is raised with heat from ammonia
In the BASF catalytic tail-gas treatment (r; see combustion in the waste-heat boiler ( j).
also Section 1.4.2.3), ca. 60 vol % of the NOx in Most of the steam generated in the waste-heat
the tail gas is selectively reacted with ammonia. boiler drives the condensing steam turbine. The
Hot tail gas containing < 200 ppm NOx goes to remainder can be utilized in the ammonia
the tail-gas expansion turbine (s), in which me- preheater and stripper and for deaerating the
chanical energy is produced to drive the air feedwater; any excess is exported as product
compressor. Finally, the tail gas is discharged to steam.
the atmosphere via the stack.
The tail-gas expansion turbine supplies part of High-Pressure Process. Figure 28 shows
the power needed to drive the air compressor. The a high-pressure process running at ca. 1 MPa.
Figure 28. Simplified flow sheet of a high-pressure process a) Ammonia evaporator; b) Ammonia stripper; c) Ammonia
preheater; d) Ammonia gas filter; e) Ammonia – air mixer; f ) Air filter; g) Air compressor; h) Interstage cooler; i) Reactor;
j) Waste-heat boiler; k) Tail-gas preheater; l) Economizer; m) Air preheater; n) Feedwater and warm-water preheaters;
o) Cooler – condenser; p) Absorption tower; q) Tail-gas preheater; r) Tail-gas preheater; s) Tail-gas expansion turbine;
t) Feedwater tank with deaerator; u) Steam drum; v) Steam turbine; w) Steam turbine condenser; x) Bleacher
Liquid ammonia is fed into the evaporator (a), Before the nitrous gas is led into the gas
where it is evaporated at ca. 1.15 MPa against cooler – condenser (o), it passes through feed-
warm water. The evaporation temperature rises water preheaters and through the warm-water
slightly above 35 C as the water content builds heater (n) both mounted on the two inlets of the
up in the evaporator. The ammonia – water cooler – condenser. The nitrous gas is cooled to
blowdown mixture is evaporated with low-pres- ca. 115 C and partly condensed before entering
sure steam in the ammonia stripper (b). The the cooler – condenser.
residual ammonia concentration is ca. 2.5 %. In the water- cooled cooler – condenser (o),
Ammonia exiting the evaporator system is the gas is cooled to < 50 C so that water formed
heated to ca. 130 C in the ammonia preheater during ammonia oxidation condenses to produce
(c), and contaminants are removed in the ammo- ca. 45 % acid. This product is delivered to the
nia gas filter (d). appropriate tray of the absorption tower (p) by
Air is sucked in through the air filter (f) and the acid condensate pump. The NOx-laden
compressed to ca. 1 MPa in an air compressor (g) secondary air recycled from the bleacher (x) is
with interstage cooling (h). The primary air mixed with the nitrous gas stream before it is fed
(ca. 80 % of the total) is heated to ca. 180 C into the tower (p).
against nitrous gas in the air heater (m) and then In the sieve-tray absorption tower (p) the
fed to the ammonia – air mixer (e). The mixed nitrous gas flows countercurrently to the pro-
gas stream has a temperature of ca. 175 C and cess water fed at the column head, and nitric
contains 10.7 vol % ammonia. It passes through acid is formed. Heat from the absorption tower
a filter (not illustrated) into the reactor (i) where is transferred to the cooling water. Raw acid
the ammonia and atmospheric oxygen react over from the absorption tower is treated with
the platinum – rhodium catalyst at ca. 900 C to secondary air in the bleacher (x), then deliv-
form mainly nitrogen monoxide and water. ered to battery limit with the aid of the system
The reaction gases next pass through the pressure.
waste-heat boiler ( j), where they are cooled to Tail gas exits the absorption tower at ca. 20–
ca. 400 C. The heat is used to raise high-pres- 30 C. It is heated to ca. 80 C in a tail-gas
sure steam and superheat it to 500 C in the preheater (q) against the tail-gas stream from the
preevaporator, superheater, and reevaporator of expansion turbine. The tail gas is further heated
the boiler. to 140 C against low-pressure steam (r) and
The boiler system is fed with condensate from then to ca. 375 C in a tail-gas preheater (k). It
the steam turbine condenser (w) plus deminer- is subsequently expanded in the tail-gas turbine
alized water from the battery limit. Both streams (s); this step produces ca. 70 % of the energy
are led to a tank and from there go through the required to drive the air compressor.
feedwater preheater (n) to the deaerator mounted Tail gas exits the turbine at ca. 135 C and is
on the feedwater tank (t) and operating at a slight led to a tail-gas preheater (q), where it is cooled to
gauge pressure. The tank serves as suction vessel ca. 90 C before being discharged through the
for the feedwater pumps, which deliver water stack.
through the economizer into the boiler drum (u). The rest of the power needed to drive the air
The water – steam mixture in the evaporator compressor can be supplied by a pass-out con-
is circulated by the boiler circulation pump. densing steam turbine (v). The superheated
Saturated steam and water are separated in the steam is delivered to the steam turbine or ex-
boiler drum (u). ported. Part of the steam supplied to the turbine is
After leaving the waste-heat boiler ( j), the withdrawn as low-pressure steam before admis-
nitrous gas is cooled to ca. 260 C in a tail-gas sion to the condensing section. This low-pressure
preheater (k). After passing through a run of steam is used in the plant or exported. The rest of
piping for oxidation, nitrous gas gives up more the steam supplied to the turbine passes through
useful heat in the economizer (l), and its temper- the condensing section and is condensed in the
ature falls to ca. 210 C. After another oxidation steam turbine condenser (w).
run, the stream is led into the air heater (m) and
cooled to ca. 180 C. The heat recovered is used Dual-Pressure Process. The dual-pressure
to preheat the primary air. process combines the favorable economics of
medium-pressure combustion with the effi- ammonia – water mixture is blown down and fed
ciency of high-pressure absorption. Figure to the ammonia stripper (b). Ammonia is stripped
29 is a flow sheet of such a plant with ammo- to a residual content of ca. 2.0 % as the tempera-
nia combustion at 0.5 MPa and absorption at ture is raised to 150 C with low-pressure
1.1 MPa. steam. The residue, greatly depleted in ammonia,
Liquid ammonia is fed to the ammonia is discharged.
evaporator (a), which is under a pressure of ca. Gaseous ammonia from the evaporator
0.65 MPa. The entire stream then goes to ammo- system is passed through the ammonia gas filter
nia evaporator I, where ca. 80 % of the ammonia (c) to remove contaminants, then heated to ca.
is evaporated against cold water at a constant 150 C in the ammonia preheater (d).
temperature of ca. 12 C. Residual liquid ammo- Air is sucked through the filter (f) and com-
nia is fed to ammonia evaporator II (not illus- pressed to 0.5 MPa in the compressor (g). About
trated) and evaporated at varying temperatures 86 % of the air is fed as primary air to the
against cooling water. The evaporation tempera- ammonia – air mixer (e). The mixed gas stream
ture increases from 12 C to ca. 20 C as water has a temperature of ca. 220 C and contains
content builds up in the evaporator. Ammonia ca. 10 vol % ammonia. It is transported through
evaporator II is designed so that the entire the gas-mixture filter (not illustrated) to the
ammonia stream can be evaporated in it, if reactor (h). Here, ammonia reacts on the
necessary, at a maximum temperature of 20 C. platinum – rhodium catalyst with atmospheric
If the water content or the evaporation tempera- oxygen at 890 C to produce a 96.5 % yield of
ture in ammonia evaporator II is too high, the nitrogen monoxide and water.
Figure 29. Simplified flow sheet of a dual-pressure process a) Ammonia evaporator; b) Ammonia stripper; c) Ammonia gas
filter; d) Ammonia preheater; e) Ammonia – air mixer; f ) Air filter; g) Air compressor; h) Reactor; i) Waste-heat boiler; j) Tail-
gas preheater III; k) Economizer; l) Tail-gas preheater II; m) Feedwater preheater; n) Cooler – condenser I; o) Cooler –
condenser II; p) Nitrous gas compressor; q ) Tail-gas preheater I; r) Cooler – condenser III; s) Absorption tower; t) Tail-gas
expansion turbine; u) Feedwater tank with deaerator; v) Steam drum; w) Steam turbine; x) Steam turbine condenser; y) Bleacher
The reaction gases next pass through the and is mixed with the raw acid from the absorp-
waste-heat boiler (i) and are cooled to 355 C. tion column.
The heat is used to raise high-pressure steam in From cooler – condenser III the nitrous gas,
the preevaporator, superheater, and reevaporator now at least 90 % oxidized, enters the absorption
of the boiler. tower (s). The gas first passes through oxidation
The boiler system is fed with condensate from trays that receive only a slight flow of liquid, to
the steam turbine condenser (x) plus deminera- attain the degree of oxidation needed for equi-
lized water from the battery limit. Both streams librium with 68 % acid. In the absorption
are led to a tank and then pass through the section, gas and liquid move countercurrently.
feedwater preheater (m) to the deaerator mounted Required process water is pumped to the tower
on the feedwater tank (u). The tank serves as head. The 68 % raw acid is withdrawn from
a suction vessel for the feedwater pumps, which the first absorption tray and then treated with
deliver the water through the economizer (k) into secondary air in the bleacher (y). It is delivered
the steam drum (v). to the battery limit with the aid of the system
The water – steam mixture in the evaporator pressure.
is circulated by the boiler circulation pump. Approximately 80 % of the heat generated by
Saturated steam and water are separated in the absorption is transferred to the cooling water and
steam drum (v). the remainder to the chilled water employed in
After exiting the waste-heat boiler and pass- the last part of the absorption step where very
ing through a run of piping for oxidation, the little heat of reaction is liberated.
nitrous gas is cooled from 390 to 280 C in tail- The tail gas contains < 150 – 200 ppm NOx
gas preheater III (j). After further oxidation, it and exits the absorber at 20 C. It is heated to
enters the economizer (k), where it is cooled 110, 200, and finally 350 C in the three down-
from 310 to 200 C. The nitrous gas gives up stream tail-gas preheaters (q, l, and j) before
further useful heat to the tail gas in tail-gas being expanded in the tail-gas turbine (t). The
preheater II (l) and its temperature falls to ca. turbine supplies ca. 67 % of the power required
170 C. by the air and the nitrous gas compressors. The
The gas passes through the feedwater preheat- expanded tail gas has a temperature of ca. 100 C
er (m), mounted on the cooler – condenser inlet and is discharged through a stack.
and thereby cools to ca. 100 C. In the water- The remaining power required to drive the
cooled cooler – condenser I (n), the gas is cooled rotating machinery can be obtained from a pass-
to < 50 C so that the water formed during out condensing steam turbine (w). Superheated
ammonia oxidation condenses. A ca. 43 % acid steam is fed to the turbine or exported. Part of the
results and is pumped to the appropriate tray of steam supplied to the turbine may be withdrawn
the absorption tower (s). The secondary air laden as low-pressure steam before it enters the con-
with NOx and recycled from the bleacher (y) is densing section. This low-pressure steam may
now mixed with the nitrous gas stream. The be used in the plant or exported. The remainder of
mixed stream is then led into cooler – condenser the steam fed to the turbine passes through the
II (o), where it is cooled to ca. 45 C against condensing section and is condensed in the steam
chilled water. More water condenses and a ca. turbine condenser (x).
52 % acid is formed, which is forwarded for
absorption along with acid formed in cooler – Comparison of Medium- and High-
condenser I. The gas is passed through a mist Pressure Processes. [62]. Two trends can be
collector (not illustrated) upstream of the nitrous seen in the worldwide development of weak acid
gas compressor (p). processes. First, from the process-engineering
The nitrous gas is compressed to 1.1 MPa in standpoint, a progression occurs from low-
the compressor ( p) and has an outlet temperature through medium- to high-pressure processes
of ca. 130 C. It passes to tail-gas preheater I (q ), [5]. Second, capacities continue to increase;
where it is cooled to ca. 75 C. Downstream of single-train plants producing up to 2000 t of
the preheater is cooler – condenser III (r), which nitric acid per day are now being built. In Europe,
the nitrous gas leaves at 50 C. The resulting acid the dual-pressure design is preferred for larger
condensate has a concentration of ca. 58 wt % plants, whereas smaller ones employ the mono-
Table 5. Comparison of significant specific consumption figures for nitric acid plants (values are given per tonne of 100 % HNO3, the tail gas
contains < 200 ppm of NOx )
Parameter Monopressure processes Dual-pressure process
Medium pressure High pressure
Operating pressure, MPa 0.55 1.080 0.45/1.1

Ammonia, kg 282* 283 279
Electric power, kW h 8.5 8.0 9.0
Platinum, g 0.14 0.30 0.11
Cooling water, t (Dt ¼ 10 C)** 120 125 130
Process water, t 0.3 0.3 0.3
Low-pressure heating steam, t 0.1 0.1 0.1
High-pressure excess steam, t (2.5 MPa, 400 C) 0.87 0.78 0.81
*
Includes 1 kg NH3 for NOx reduction from 600 to < 200 ppm.
**
Includes water for steam turbine compressor.
pressure design. Where feedstock and energy acid and then led to a reactor where it is reacted
prices are low, monopressure operation offers with oxygen and water (or weak acid) under
special advantages; low investment costs ensure pressure to yield concentrated acid. Second,
a quick payout, particularly in North America. If, nitrous gases can be reacted with azeotropic acid
on the other hand, feedstock and energy prices to form a concentrated acid that can be converted
are very high (as in Europe), yield and energy easily to concentrated and azeotropic acid by
efficiency must be maximized, so higher invest- distillation. The latter product is either complete-
ment costs are acceptable. Table 5 compares ly recycled or used in the production of ordinary
consumption figures per unit product for mono- weak acid.
pressure and dual-pressure processes. In the indirect processes, concentration is
New pollution control regulations and the based on extractive distillation and rectification
energy crisis of the mid-1970s have also led to with sulfuric acid or magnesium nitrate.
the development of new processes or the im-
provement of existing ones. To avoid the need Direct Process. The essential feature of the
for catalytic tail-gas treatment in large-tonnage classical direct process (Fig. 30) is that liquid
plants (and thus an increase in specific ammonia dinitrogen tetroxide is produced and reacted
consumption), new facilities employ higher under pressure with pure oxygen and a certain
absorption pressures. quantity of dilute nitric acid. A detailed account
of concentrated acid production via azeotropic
1.3.4.2. Concentrated Acid Processes nitric acid is given in [61, pp. 99 – 130].
Industrially produced nitric acid contains 50 – Ammonia Oxidation. As in weak acid pro-
70 wt % HNO3. This is high enough for fertilizer cesses, feed ammonia is evaporated, superheat-
production, but nitration processes in industrial ed, and filtered (see Section 1.3.4.1). Evaporation
organic chemistry call for concentrated acid takes place with the aid of water heated with
(98 – 100 %). Distillation, the simplest way to process heat. Because traces of water and oil
concentrate dilute acid, fails because nitric acid accumulate in the ammonia evaporator the sump
and water form an azeotrope (68.4 % HNO3 at must be drained into the steam-heated stripper
atmospheric pressure). from time to time. Air for ammonia combustion
Concentrated nitric acid is manufactured is sucked through a filter (a) and mixed with
directly or indirectly [63]. In the direct process, purified ammonia in the mixer ( b). The ammonia
the water generated in ammonia combustion is content of the mixture is held in the range 11.5–
withdrawn by rapid cooling to give a nitrous gas 12.3 vol %, depending on the temperature. The
mixture from which concentrated acid can be optimal combustion temperature is 830 –
produced directly in one of two ways. First, the 850 C. Ammonia oxidation takes place over
completely oxidized NOx can be separated in conventional platinum – rhodium catalysts in
liquid form by absorption in concentrated nitric the reactor (d). The heat of reaction is used to
Figure 30. Simplified flow sheet of a process for direct production of strong nitric acid with oxygen a) Air Filter;
b) Ammonia – air mixer; c) Gas mixture filter; d) Reactor; e) Cooler; f ) Compressor; g) Cooler; h) Oxidation tower;
i) Recirculating acid tank; j) Postoxidizer; k) Cooler; l) Cooler; m) Absorption tower; n) Final absorber; o) Raw acid tank;
p) Cooler; q ) Precondenser; r) Stirred tank; s) Reactor; t) Bleacher; u) Cooler
raise steam in a waste-heat boiler and an econo- acid from the tower bottom is pumped (recircu-
mizer. The process gas exits the economizer at lated) to the head.
ca. 170 C and is then cooled to 25 C in
a cooler – condenser (e), giving an acid contain- Final Oxidation of Nitrogen Monoxide. The
ing ca. 2 – 3 wt % nitric acid. The cooler – nitrous gases leaving the oxidation tower
condenser is specially designed to condense as are approximately 95 % oxidized and are led to
much water as possible without much NOx a final oxidizer ( postoxidizer) (j) where they are
absorption. Part of the process heat is also trans- completely oxidized by desorption of concen-
ferred to the warm water used for ammonia trated nitric acid. The acid moves countercur-
evaporation. The weak condensate generated in rently to the nitrous gases. Water produced in this
the cooler – condenser is used as scrub liquor for reaction dilutes the concentrated acid; acid leav-
final absorption. ing the postoxidizer contains ca. 75 % HNO3.
Flow control of the concentrated nitric acid feed
Oxidation of Nitrogen Monoxide. Secondary into the postoxidizer is important because too
air is mixed with the cooled process gas to high a rate lowers the output of concentrated acid,
oxidize nitrogen monoxide to nitrogen dioxide. whereas too low a rate displaces final oxidation
The amount of secondary air must be sufficient to into the absorber, with the result that the concen-
ensure that the tail gas has a minimal oxygen trated nitric acid entering the absorption tower is
content (2.5 – 3.5 vol %) before it is discharged too dilute. The product gas is saturated with
to the atmosphere. The concentrated nitric acid nitric acid vapor. For the next step, absorption,
venting system is connected to the secondary air the process gas is cooled to 10 C against
intake in such a way that oxygen and nitrogen brine in a cooler ( l). Virtually all the nitrogen
oxides liberated on venting are recycled to the dioxide is dimerized to dinitrogen tetroxide at
process. The nitrogen monoxide gas and second- this temperature.
ary air are compressed together to ca. 0.14 MPa
(f ). After further cooling (g) to remove the heat Absorption of Dinitrogen Tetroxide. The
of compression, the mixture enters the oxidation nitrous gases are completely dimerized to dini-
tower (h), which is usually equipped with sieve trogen tetroxide and, in this condition, are fed
trays. Tube coils on the trays remove the heat of into the absorber (m). The absorber consists of
oxidation. To maintain a liquid level on all trays, four sections, each packed with ceramic Raschig
rings. The dinitrogen tetroxide is absorbed in > 98 wt % nitric acid requires a higher R factor.
concentrated nitric acid that comes from the The economically most favorable R factor can
bleacher and is cooled to ca. 10 C (k, u). The be found only by empirical means; the ratio can
acid leaving the absorption tower contains ca. be varied to achieve optimal operating condi-
25 – 30 wt % dinitrogen tetroxide and is tions. The makeup acid used to maintain the
pumped to the raw acid tank (o). water balance of the raw acid mixture is taken
from the bottom of the final absorber (n).
Final Absorption. The gas exiting the ab- Concentrated nitric acid is formed in the
sorption tower is practically free of nitrogen reactor (s) at ca. 5.0 MPa and 60 – 80 C. High
dioxide but saturated with nitric acid vapor. The mechanical strength and corrosion resistance
vapor is removed by scrubbing in the final ab- are needed, but these two requirements cannot
sorber (n), which consists of two sections. The be satisfied by any one material. The reactor
scrub liquor (weak nitric acid from the cooler – thus has a carbon steel jacket to provide me-
condenser) is recirculated or used to make up the chanical strength and a pure aluminum inner
water balance in the stirred tank. shell to provide corrosion resistance. Unreacted
oxygen is supplied to the suction of the nitrous
Dinitrogen Tetroxide Production. The laden gas blower via the venting system. The con-
concentrated nitric acid is sent from the raw acid centrated nitric acid product is led to the
tank (o) to the bleacher (t), which consists of raw acid tank (o) and then to the bleacher.
a stripping section and a reboiler. The acid enters The bleached concentrated acid is cooled to
the head of the tower and flows downward þ 30 C (u). Most of the concentrated nitric
countercurrently to the nitric acid vapor, which acid is returned to the absorption tower and
strips nitrogen dioxide from the concentrated final oxidation.
nitric acid. The bleached concentrated acid goes
to the reboiler section of the bleacher, where it is Indirect Processes. Two types of indirect
partially evaporated and partially withdrawn as process are used to produce concentrated
product acid. The vapor exiting the bleacher nitric acid (i.e., product containing > 97 wt %
contains ca. 95 % nitrogen dioxide and 5 % nitric HNO3 ):
acid. Most of the vapor condenses in a down-
stream precondenser (q). Dinitrogen tetroxide 1. Sulfuric acid process
is liquefied in the liquefier and fed to a stirred 2. Magnesium nitrate process
tank (r).
Both concentration techniques are based on
Production of Concentrated Nitric Acid. extractive distillatfication. Weak acid is first
The formation of concentrated nitric acid in the produced by a conventional process (Section
reactor (s) is described by the following equation: 1.3.4.1), then a third component is added to
extract the water so that up to ca. 99 %
4 NO2 ð
2 N2 O4 ÞþO2 þ2 H2 O
4 HNO3
nitric acid can be distilled from the ternary
This requires a N2O4 – H2O molar ratio of mixture.
1 : 1 and a weight ratio of 5.11 : 1. The reaction The starting product is ordinary commercial
time can be considerably shortened if dinitrogen nitric acid (ca. 55 – 65 % HNO3 ). Weaker acids
tetroxide is present in excess. On the other can be preconcentrated in a single-stage or mul-
hand, an excess of dinitrogen tetroxide lowers tistage process to give ca. 68 wt % nitric acid.
the production rate of the reactor and increases Figure 31 illustrates a single-stage apparatus.
the dinitrogen tetroxide recycle rate, resulting in Preconcentration takes place in a continuous
higher steam consumption for bleaching and a countercurrent distillation tower (a), which can
greater cold requirement for dinitrogen tetroxide be of either the packed or the bubble-tray type.
liquefaction. The system includes one or, if appropriate, two
The N2O4 – H2O ratio, denoted the R factor, preheaters, a recirculating evaporator system for
is the most important criterion for monitoring the tower bottom, a stripping and rectifying
reactor operation. In practice, it fluctuates be- section for the tower, an overhead condenser,
tween 6.5 and 7. A product concentration of and a reflux separator (b).
Table 6. Consumption figures for the production of 1 t of 99 % HNO3

from dilute nitric acid by the sulfuric acid process*
Parameter Starting HNO3

concentration, wt %
55 60 65
Heating steam (1.0 – 1.8 MPa), t 2.0 1.75 1.45

Cooling water, m3 80 60 50
Electric energy, kW h 17 14 11
Water evaporated, t 0.82 0.66 0.53
*
Source: Plinke – NASAC plant data.
polytetrafluoroethylene, stainless steel, tanta-

Figure 31. Simplified flow sheet of a process for preconcen- lum, titanium, high-purity aluminum, and special
tration of nitric acid a) Preconcentrating tower; b) Separator; alloys.
c) Recirculating evaporator system; d) Cooler Figure 32 is a flow sheet of a plant making
concentrated nitric acid by the sulfuric acid
Sulfuric Acid Process. Sulfuric acid can be process. The feed nitric acid, concentrated to
used as extracting agent (see also ! Distillation, about 68 wt %, is preheated (e) and then fed
1. Fundamentals). The concentrated nitric acid into the distillation tower (a). At least 80 wt %
product is clear and colorless; it contains 98 – sulfuric acid is fed to the head of the tower. The
99 wt % nitric acid and < 0.05 % nitrogen part of the tower above the nitric acid inlet,
dioxide. which is irrigated with sulfuric acid, can be
Consumption figures for the production of 1 t regarded as the rectifying section, with the
of 99 % nitric acid from dilute nitric acid are sulfuric acid also functioning as reflux. The part
given in Table 6. of the tower below the nitric acid inlet is the
The nitric acid concentration step now oper- stripping section.
ates with indirect heating, an advance over earlier A circulating evaporator system takes care of
technologies that reduces steam consumption by bottom heating. The ca. 70 % sulfuric acid leav-
as much as 50 %. ing the bottom of the tower goes to the concen-
The materials of construction are highly cor- trator (c), which operates under vacuum (8 kPa).
rosion resistant. Towers are made of borosilicate The overhead vapor product from the tower is
glass, enameled steel, and steel – polytetrafluor- condensed to form 99 % nitric acid and then
oethylene. Heat exchangers are made of glass, deaerated (b). The tail gases, which still contain
Figure 32. Simplified flow sheet of a process for concentrating nitric acid with sulfuric acid (Plinke – NACSAL process)
a) Concentrating tower; b) Condenser – deaerator; c) Sulfuric acid concentrating tower; d) Tail-gas treatment; e) Preheater;
f ) Cooler; g) Blower; h) Separator
Table 7. Consumption figures for the production of 1 t of 99 % HNO3 dewatering tower. The bottom of the tower is
from dilute nitric acid by the magnesium nitrate process *
heated, and the dilute magnesium nitrate solu-
Parameter Starting HNO3 tion, containing < 0.1 % nitric acid, is led to the
concentration, wt % vacuum evaporator (b). Condensed weak acid is
processed in the recovery tower (c) and recycled
55 60 65
if appropriate. The tail gas still contains nitric
Heating steam (1.0 – 1.8 MPa), t 2.0 1.75 1.45 acid vapor and can be scrubbed with dilute nitric
Cooling water, m3 80 70 60 acid (c).
Electric energy, kW h 10 9 8
Water evaporated, t 0.82 0.66 0.53
*
Comparison of Indirect Processes. Which
Source: Plinke – MAGNAC plant data.
concentration process is better suited to a
given task must be decided case by case. From
nitric acid vapor, are scrubbed with dilute nitric a process-engineering standpoint, the magne-
acid (d). sium nitrate process has the following
advantages:
Magnesium Nitrate Process. In this process
a magnesium nitrate solution is used to extract 1. The installation is very compact. No holding
water from the nitric acid. The resulting tanks are needed, which reduces energy
dilute magnesium nitrate solution is restored losses.
to the desired working concentration of 2. Because the reconcentration step for magne-
about 72 % in a vacuum concentrator before sium nitrate is carried out in stainless steel
being returned to the nitric acid concentration vessels, virtually no critical construction
step. materials are required.
Consumption figures for the production of 1 t 3. Magnesium nitrate can be transported in
of 99 % nitric acid from dilute nitric acid are sacks, and is therefore much easier to handle
given in Table 7. than sulfuric acid.
Figure 33 is the flow sheet of a plant making 4. The weak nitric acid condensate, which is
concentrated nitric acid by the magnesium nitrate produced when the magnesium nitrate solu-
process. Weak acid is fed to the dewatering tower tion is reconcentrated, is partly reused in NOx
(a). Extractive distillation with a concentrated absorption. Losses of nitric acid are very
(72 wt %) solution of magnesium nitrate at slight.
140 C gives an overhead product containing
99 % nitric acid. A small fraction of the con- As in weak acid production, development of
densed overhead product is refluxed to the concentrated acid production has followed dif-
Figure 33. Simplified flow sheet of a process for concentrating nitric acid with magnesium nitrate (Plinke – MAGNAC
process) a) Concentrating tower; b) Vacuum evaporator; c) Tail-gas treatment; d) Preheater; e) Cooler; f ) Blower; g) Separator
ferent paths in the United States and the Federal 1.4.2. Stack Gas
Republic of Germany (and, in part, in Europe). In
the United States estimated operating costs are Obsolescent nitric acid plants can be recognized
significantly lower for concentration with mag- by their strongly colored yellow to reddish brown
nesium nitrate than with sulfuric acid. The U.S. plumes of stack gas. The coloration is due to
view is largely that, even after the change from nitrogen dioxide. Some stack gases contain up
autoclaves to continuous direct production, the to 3000 ppm NOx; very old plants may surpass
equipment cost (i.e., investment cost) is too high these values [64].
for the latter process to be competitive. The absorption of nitrous gases with water
forms part of the nitric acid process. However,
the laws of nature prevent complete absorption,
1.4. Environmental Protection and some residual emission cannot be avoided
(see Section 1.3.2). These emissions can be
In recent years, more stringent water pollution minimized by optimizing process conditions,
regulations have taken effect and legislative increasing the efficiency of absorption, or using
provisions for air pollution have been amended. special tail-gas treatment methods.
New processes have been developed and intro- Crucial parameters for the absorption of
duced to significantly reduce pollutant emissions nitrous gases in water are the following [65]:
from nitric acid plants. The problem of nitrogen
oxide pollution is treated in more detail in ! Air, 1. Pressure
2. Effects of Air Pollutants. 2. Temperature
3. Reaction volume
4. The efficiency of the absorption tower
1.4.1. Wastewater 5. The partial pressures of nitrogen oxides and
oxygen
Wastewater problems can be overcome by
appropriate design of the nitric acid plant. An Emissions in the Federal Republic of
especially simple form of wastewater treatment Germany in 1986 totaled ca. 3106 t NOx
can be employed when the nitric acid is pro- [66]. Transportation, households, and small con-
cessed directly for the production of mineral sumers accounted for ca. 66 % of this; power
fertilizers. plants and district heating plants for ca. 25 %;
The solution from ammonia stripping con- and industry, including furnaces, for ca. 9 %.
tains up to 10 % ammonia; it can be neutralized Nitrogen oxides from nitric acid production were
with nitric acid and then subjected to absorption responsible for < 1 % of the total emissions.
along with process water. The acid product
then contains a small amount of ammonium 1.4.2.1. Emission Limits
nitrate, but this is not a problem when the acid
is processed into mineral fertilizers. Heightened sensitivity to environmental con-
Leaks from pumps, vessels, etc., are pumped cerns, coupled with the need for larger and more
into a separate acid drain tank, and then pro- efficient production systems, will lead to further
cessed directly or indirectly. The apparatus used reductions in NOx emissions. Legislators are
for this purpose is completely separate from the following this trend and modifying pollution
sewage system and thus prevents contamination limits in accordance with changing technical
of wastewater. capabilities.
If heat is removed by recooling systems, cool- At the beginning of the 1980s the first
ing water blowdown is fed into the wastewater general administrative regulation was issued
system to limit thickening of the cooling water. in the Federal Republic of Germany under the
Fresh water must be supplied to compensate for Federal Pollution Control Act: the Technische
the blowdown and evaporation losses. Corrosion Anleitung zur Reinhaltung der Luft (TA-Luft;
inhibitors, hardness stabilizers, and in some Technical Instructions for Air Pollution Con-
cases, biocides are also carried out of the system trol) [67]. This regulation and the correspond-
by blowdown. ing VDI guidelines [68] form the basis for
issuing operating permits. Regulations in exceeds a rate of 30 kg/h must be equipped

many other countries are based on these with devices that continuously measure the mass
guidelines. concentration of nitrogen oxides. Quantitative
The designation NOx is commonly used to relationships between emission and ground-level
specify emission and concentration values concentration are also described, thus setting
because stack gases always include mixtures of guidelines for stack design.
nitrogen oxides. For the purpose of standardiza- If ground-level concentration limits are ex-
tion, the oxides are calculated in terms of nitro- ceeded, the TA-Luft emission limits are further
gen dioxide. The acceptable concentrations from reduced by the relevant authorities. The ground-
TA-Luft 1986 [67] are level concentration limits for gaseous pollutants
in air are as follows [67]: nitrogen dioxide, long-
1. Mass of substances emitted as mass concen- term exposure (IW1), 0.08 mg/m3; short-term
tration in units of g/m3 or mg/m3, referred to exposure (IW2), 0.2 mg/m3.
the volume of stack gas at standard conditions
(0 C, 101.3 kPa) after deducting the mois-
ture content of water vapor, or to the volume 1.4.2.2. Analysis
of stack gas at standard conditions (0 C,
101.3 kPA) before deducting the moisture The guidelines for the measurement and
content of water vapor; and monitoring of NOx emissions from nitric acid
2. Mass of substances emitted, referred to time, production are specified in [67], [70], [71].
as mass velocity in units of kg/h, g/h, or mg/h; Photometry without auxiliary chemical
and reaction and chemiluminescence [71c – e] are
3. Ratio of the mass of substances emitted to the suitable for the continuous measurement of NOx
mass of products generated or processed emissions [65].
(emission factors), as mass ratio in units of Difficulties in gas sample preparation due to
kg/t or g/t. condensation are discussed in [71c – g].
Additonal apparatus-related problems occur
The usual concentration unit ppm (mL/m3 ) when chemiluminescence is used to measure
can be converted to the prescribed mass concen- emission of moist stack gases at higher NOx
tration (mg/m3 ) with the following factor [69]: levels. A chemiluminescence analyzer with a
1 ppm ¼ 1.88 mg/m3 (based on monomeric maximum range of 0 – 10 000 ppm has been
NO2 at 101.3 kPa and 298 K and ideal-gas developed [72].
behavior). For stack gases containing traces of ammo-
The TA-Luft [67] states that the emission of nia, precipitation of ammonium salts in the
nitrogen monoxide and nitrogen dioxide in the measuring cells has prevented continuous
stack gas of nitric acid plants must not exceed measurements. Two methods useful for the
0.45 g/m3 as nitrogen dioxide. Furthermore, discontinuous measurement of nitrogen oxide
stack gases may be discharged only if colorless; emissions [65] are acidimetric titration and the
as a rule, this is the case if the mass concentra- photometric phenoldisulfonic acid technique
tion of nitrogen dioxide in the stack gas does [71a, b].
not exceed the value given by the following
formula: 1.4.2.3. Control of NOx Emissions
3
Mass concentration of nitrogen dioxide ðmg=m Þ
1200 Four basic approaches are used to reduce tail-gas
¼
Internal diameter of stack orifice ðdmÞ NOx levels: improved absorption, chemical
scrubbing, adsorption, and catalytic tail-gas
The requirement of a colorless discharge sets reduction. Recent decades have seen intense
a practical limit of < 200 ppm NOx. Older low- research and development effort invested in these
and medium-pressure plants should comply with methods. More stringent environmental restric-
these standards by March 1, 1996. tions have lent special urgency to development in
Plants whose emission of nitrogen monoxide this area. The most important techniques are
and nitrogen dioxide (as nitrogen dioxide) covered in this section.
Improved Absorption. Absorption effi- plant or sections of a fertilizer complex must

ciency depends chiefly on the absorption pres- operate independently. The following scrub
sure, the number of stages, and the temperature. liquors have been proposed: aqueous suspension
The temperature of the gas between stages is of magnesium carbonate and magnesium hy-
especially important because it governs the prog- droxide [74]; solution of vanadium in nitric acid
ress of oxidation, which is the limiting quantity [75]; ammonium sulfide and bisulfide [76]; milk
for the entire absorption process (see Section of lime [77]; ammonia [78]; hydrogen peroxide
1.3.2). In an already existing nitric acid plant, [79]; and urea [80].
the options are to expand the absorption volume
and/or lower the absorption temperature. In the Ammonia Scrubbing is used in the United
first approach, large additional volumes only States. Goodpasture (Texas) has developed a safe
result in small reductions of tail-gas NOx levels process based on scrubbing the tail gas with
because the oxidation of nitrogen monoxide ammonium nitrate solution; nitrite formation is
to nitrogen dioxide proceeds very slowly suppressed by aeration and the presence of free
when the NOx concentration is low. The draw- acid. The tail gas is then led through an ammo-
back to this method is that added absorption niacal scrub liquor, pH 7.5 – 8.5. The scrubbing
volume in stainless steel is very expensive. The product is a 30 – 50 % ammonium nitrate solu-
advantage is that it does not require any new tion. The tail gas has a residual level of ca.
technology. The absorption volume is added in 200 ppm NOx.
the form of a second tower; new absorption
tower designs with very few stages have been Hydrogen Peroxide Scrubbing is based on
devised [73]. the following overall reactions:
The use of cold energy in the absorption NOþNO2 þ2 H2 O2 !2 HNO3 þH2 O
process greatly accelerates oxidation of nitrogen
2 NO2 þH2 O2 !2 HNO3
monoxide to nitrogen dioxide. The disadvantage
of this method is that the necessary refrigeration The reactions are carried on sieve trays or in
equipment and piping demand further invest- packed towers with recirculation of the hydrogen
ment. Another technique involving the use of peroxide solution. The advantage of this scrub-
cold to lower the NOx level is to cool the nitrous bing process is that the reaction time is very fast;
gas so that more dinitrogen tetroxide than nitro- the disadvantage, that the hydrogen peroxide
gen dioxide is formed. The dinitrogen tetroxide is scrub liquor is expensive.
then scrubbed with nitric acid at ca. 0 C; it can A solution containing 20 % urea and 10 % free
be stripped out, and converted to nitric acid by the nitric acid has also been suggested for scrubbing
reaction tail gas to remove NOx. The process is carried at
ca. 50 C. Both nitrogen oxides are selectively
N2 O4 þ1=2 O2 þH2 O!2 HNO3
reduced to nitrogen by urea, which decomposes
in an absorption reactor at ca. 60 – 80 C. The to yield nitrogen and carbon dioxide. The pro-
technique is similar to that in concentrated nitric cess, developed by Norsk Hydro in Norway, has
acid production. The method is, however, more the advantage that urea is readily available and
suitable for investment in a plant being designed relatively cheap. The resulting stack gas plume is
than for the expansion or upgrading of an existing colorless but heavily laden with water vapor.
plant.
Adsorption Processes. The adsorption of
Chemical Scrubbing. A number of patents NOx by molecular sieves has long been known
and scientific publications deal with options for but has not yet been tested intensively in full-
scrubbing NOx out of tail gas. Problems related scale nitric acid plants.
to the scrub liquor (cost, regeneration, quantity, The Pura-Siv-N process ( Union Carbide) is
and environmental impact) are encountered in claimed to reduce stack gas levels below 50 ppm
all methods. These problems are always easier nitrogen dioxide [81], but high investment costs
to manage if the nitric acid plant is part of an and other problems have prevented its adoption. A
integrated chemical plant, which is usually the patent granted to Kernforschungsanlage J€ulich
case. However, in some instances a nitric acid GmbH has a similar object [82], but again indus-
trial experience is slight. A ‘‘wet’’ adsorption preheat temperature depends directly on the fuel
system has also been developed by Cofaz selected:
(France). A carbon- containing adsorbent is
sprayed withwateror dilute nitric acidand brought Natural gas 450 – 480 C
in contact with the tail gas. This process has been Propane 340
C
installed in three monopressure plants [83]. Butane 340
C

Naphtha 340 C

Hydrogen 250 C
Catalytic Reduction. Catalytic reduction
was the first method used to reduce NOx emis-
sions; as early as 1924, a patent for such a process The use of hydrogen allows the preheat tem-
was issued to FAUSER [84]. A fuel is added, at a perature to be lowered to 150 – 200 C but is
level below the flash point, to the nitrogen oxides generally too expensive.
which then react on the catalyst surface to form If the quantity of fuel is not enough to reduce
nitrogen and water vapor. Most fuels (e.g., all the oxygen, nitrogen dioxide is reduced only
hydrocarbons and hydrogen), however, react to nitrogen monoxide. The stack gas is then
preferentially with the free oxygen that is always decolorized; in some countries, this is sufficient.
present in tail gases from nitric acid production. Complete NOx removal generally requires
As a result, the nitrogen oxides are not destroyed preheating, multiple fixed-bed catalysts (with
until free oxygen has been consumed. Under cooling between beds to prevent overheating),
these conditions the reactions with methane can and careful heat recovery to offset part of the fuel
be described as cost.
Most nitric acid plants constructed or modi-
CH4 þ2 O2 !CO2 þ2 H2 O
fied by Weatherly use nonselective catalytic NOx
CH4 þ4 NO!CO2 þ2 H2 Oþ2 N2 abatement units with tail-gas exit temperatures
of 650 – 675 C. Some plants have gas exit
CH4 þ2 NO2 !CO2 þ2 H2 OþN2 temperatures > 815 C, which is higher than the
Ammonia can also be used as a reducing maximum for admission to the tail-gas expansion
agent, preferentially reducing the nitrogen turbines. The tail gas must then be cooled, either
oxides: against tail gas entering the catalytic unit or with
the aid of waste-heat boilers.
6 NOþ4 NH3 !5 N2 þ6 H2 O In the process marketed by Du Pont the tail gas
is dried, preheated, and then heated in two stages.
6 NO2 þ8 NH3 !7 N2 þ12 H2 O
The gas is subsequently divided into two streams.
One substream is heated further, mixed with
NOþNO2 þ2 NH3 !2 N2 þ3 H2 O
methane, and led over the first fixed-bed catalyst.
The second substream is mixed with methane
without further heating and led over the second
4 NOþO2 þ4 NH3 !4 N2 þ6 H2 O
fixed-bed catalyst, along with the first substream.
Catalytic reduction processes are accordingly Hot tail gases exit the bottom of the reactor
classified as nonselective or selective. and are led through the tail-gas expansion
Catalysts for nonselective reduction process- turbine, which recovers part of the work of
es are usually based on platinum, vanadium compression.
pentoxide, iron oxide, or titanium. The fuel re- Ammonia is the only economically relevant
quirement is the stoichiometric amount needed reducing agent for selective catalytic processes.
to reduce all the oxygen present (free and in The consumption of reducing agent in the selec-
nitrogen oxides) plus a small excess (ca. tive treatment of NOx is much smaller than in
0.5 vol % CH4 ). nonselective processes. Furthermore, the tail-gas
Unfortunately, the principal byproducts of temperature after reduction is significantly low-
this process are carbon monoxide ( 1000 ppm) er, allowing the use of simpler, cheaper construc-
and hydrogen cyanide. When hydrocarbon fuels tion materials. The optimal catalyst service
are used, the tail gas must be preheated before temperature is 250 – 350 C, but operation at
the reaction on the catalyst proceeds at all. The up to 500 C is possible. The costs due to the use
of expensive ammonia must, however, also be

considered. To prevent formation of ammonium
nitrate (a potential explosion hazard) in the
expansion turbine or downstream, emissions
must be monitored for ammonia (10 – 20 ppm).
When BASF, Ludwigshafen [85] began work
on catalytic NOx reduction in the early 1960s,
existing patents indicated the use of ammonia
together with noble-metal (Pt, Rh, Ru, Pd) and
iron-group (Fe, Co, Ni) catalysts [86], [87].
Alternatives were found: vanadium pentoxide,
tungsten oxide, and molybdenum oxide gave
excellent results. Vanadium pentoxide on an
alumina support proved to be most economical.
Selective processes also require oxygen,
which oxidizes part of the nitrogen monoxide to
nitrogen dioxide to ensure roughly equal levels
of these two oxides (the best condition for re-
duction). Because the BASF process operates at
200 – 350 C, side reactions between ammonia
and oxygen can be neglected. The reaction is not
affected by dinitrogen monoxide, carbon diox-
ide, or water vapor.
For a plant with a tail-gas stream of
37 000 m3 /h (STP) operating at a pressure of
730 kPa with an inlet NOx concentration of 500–
1000 ppm, this process (270 C) gives an exit
concentration of 50 – 150 ppm NOx. The treated
tail gas contains < 20 ppm ammonia (usually Figure 34. BASF tail-gas reactor for NOx reduction a) Hole
plate; b) Catalyst; c) Wire gauze
ca. 5 ppm), and the nitrogen dioxide level is
30–50 ppm. The stack gas is generally colorless.
Careful temperature monitoring at the tail-gas Essen uses a chromium oxide catalyst with
expansion turbine and measurement of the a service temperature of 265 – 350 C. The ni-
ammonia level can prevent the deposition of tric acid plant planned for DSM Miststoffen
ammonium nitrate. To minimize the pressure (Geleen, Netherlands) is designed for a tail-gas
drop, the reactor features an annular design with stream of 76 000 m3/h (STP) with a maximum
inward flow (Fig. 34). NOx level of 2200 ppm. The exit concentration
Ammonia is uniformly mixed with the tail-gas will not exceed 100 ppm NOx. The tail gas is
stream in static mixers. The performance of the preheated before entering the reactor. To meet
treatment process is monitored by measuring the strict emission limit of < 100 ppm, the cata-
the temperature rise during reduction (ca. lyst is located in three beds. Ammonia can be
10 C/1000 ppm NOx ). admitted separately over each. The following
Uhde, Dortmund, as licensee, has retrofitted distribution has proved most efficient: 70 % over
14 plants with the BA\varphiSF process. The the first bed, 20 % over the second, and 10 % over
tail gas, usually containing 500 – 1000 ppm the third catalyst bed.
NOx, is heated to about 260 C. Ammonia gas Other companies also have selective catalytic
is added to the tail-gas stream in a mixer and reduction processes for nitric acid tail gases.
then led through the reactor. The pressure drop is For example, Mitsubishi Chemical has developed
ca. 25 kPa. The effluent meets the requirement of a process operating at 400 – 500 C under pres-
colorlessness. sure [88], [89]. The ‘‘DN-Cat’’ catalyst is installed
The HGW – Didier process, developed joint- between the heat exchanger and the tail-gas ex-
ly by Hamburger Gaswerke (HGW) and Didier, pansion turbine in the conventional flow sheet.
The Weatherly selective catalytic process case of accidents. Regulations for the road
operates at 250 – 310 C. The noble-metal transport of nitric acid ( 70 % HNO3 empha-
catalysts are the same ones employed in nonse- size the associated hazards ( poisoning by
lective processes, except that the fuel is replaced inhalation of vapors, danger of chemical burns
by ammonia. on contact with flammable substances, forma-
The Bergbauforschung – Uhde process [90] tion of nitrous gases). Protective equipment
is chiefly employed for stack-gas cleanup at includes respiratory protection apparatus, gog-
power plants but may later find use in emission gles, and clothing affording complete cover-
abatement at nitric acid plants. The Bergbau- age, as well as an eyewash bottle with pure
forschung – Uhde process for simultaneous water. In case of accident, the fire and police
sulfur and NOx removal from stack gases is departments are to be notified immediately.
utilized at the cold end of the power-plant Spilled nitric acid must not be absorbed
boiler, i.e., downstream of the air preheater with sawdust or other flammable material (be-
and electrostatic filter. It employs the adsorp- cause of the fire hazard); instead, its spread
tive and catalytic properties of ‘‘activated must be prevented by the construction of earth
coke’’ at 50 – 150 C. The reducing agent is barriers.
again gaseous ammonia. The technique com-
bines a selective catalytic process for NOx and
an adsorptive one for sulfur dioxide. The 1.6. Uses and Economic Aspects
catalyst is therefore installed in a moving-bed
reactor. The principal use of nitric acid is as a starting
material in the manufacture of nitrogen ferti-
lizers; large amounts are reacted with ammo-
1.5. Storage and Transportation nia to yield ammonium nitrate (! Ammonium
Compounds, Section 1.2.1.). Weak acid
As a rule, nitric acid is stored in stainless (ca. 60 % HNO3 ) is most suitable for this
steel tanks and transported in stainless steel purpose. Smaller amounts of weak acid are
containers. used to digest crude phosphates. About 75 –
The regulations for transport by rail [91], [92] 85 % of the nitric acid produced is used in the
and road [93], [94] differentiate among > 70 % fertilizer sector. In addition, porous ammoni-
nitric acid, 55 – 70 % nitric acid, and < 55 % um nitrate prills are still an important compo-
nitric acid, and also between mixtures with sul- nent of explosives (! Explosives, Section
furic acid (‘‘mixed acid’’) containing > 30 % 7.2.).
nitric acid and those containing < 30 % nitric Nitric acid is used as a nitrating agent in the
acid. Similar regulations [95] apply to transport preparation of explosives (! Explosives) and
by ship. Important transport regulations for organic intermediates such as nitroalkanes (!
> 70 % nitric are as follows: Nitro Compounds, Aliphatic) and nitroaromatics
(! Nitro Compounds, Aromatic). It is also used
IMDG Code Class 8, D 8261, E – F 8186
in the production of adipic acid (! Adipic Acid,
UN No. 2032 Section 4.1.).
RID/ADR Class 8, no. 2 a Other applications include use as a chemical
CFR 49: 172.101, Cor. M in metallurgy (e.g., as an etchant and pickling
agent for stainless steels) and in rocket fuel
Regulations for < 70 % nitric acid are production.
Worldwide output of nitric acid in 1987
was 26.882106 t, representing a slight in-
UN No. 2031 crease of ca. 4 % over 1976. Production in
RID/ADR Class 8, no. 2 b industrialized countries has stagnated or even
CFR 49: 172.101, Cor. M declined, but in 1976 – 1985 increases in ca-
pacity in less industrialized countries occurred
Provisions range from details of technical [96]. Production figures for nitric acid in 1987
equipment to labeling and give instructions in follow (106 t):
Europe, total 16.472

United States 6.553
Eastern Europe 4.289
Asia 1.544
Federal Republic of Germany 2.112
Poland 2.136
Belgium 1.470
Spain (1986) 1.249
Italy 1.195
Hungary 1.018
2. Nitrous Acid
Nitrous acid [7782-77-6], HNO2, Mr 47.01, is a
moderately strong to weak acid. Its dissociation
constant K in highly dilute solutions at 18 C is
4.5104. The acid is stable only in cold dilute
aqueous solution. It can be prepared as follows:
BaðNO2 Þ2 þH2 SO4 !2 HNO2 þBaSO4
On heating in the presence of sand, glass

splinters, or other sharp-edged objects, or even
at low temperature, it disproportionates as
3 HNO2
HNO3 þ2 NOþH2 O
Figure 35. The system N2O3 – H2O a) Ice; b) Homogeneous
This disproportionation reaction influences liquid, water þ dinitrogen trioxide; c) Liquid phase, two
the properties of nitrous acid solutions and is layers; d) Homogeneous liquid, dinitrogen trioxide þ water
important in the production of nitric acid. Nitrous
acid occurs as an intermediate product when NOx
gases are absorbed in water. Nitrous acid exists in two isomeric forms:
By virtue of the above reaction, nitrous acid can
act as both a reducing and an oxidizing agent.
Strong oxidizing agents such as potassium per-
manganate oxidize nitrous acid to nitric acid. It can
be reduced to less oxygen-rich compounds ( NO2, These structures lead to two series of indus-
NO, H2N2O2, NH3 ) by alkali amalgams or by trially important organic derivatives:
electrolytic means. Its salts (nitrites) are not stable
in aqueous solution because of hydrolysis.
Nitrous acid in aqueous solutions is assumed
to be in dynamic equilibrium with its anhydride:
2 HNO2
N2 O3 þH2 O
An especially important property of nitrous
Aqueous solutions of the acid appear colorless acid is its ability to diazotize organic amines. With
but take on an increasingly blue coloration at 5 % primary amines, the acid forms diazonium salts:
dinitrogen trioxide.
RNH2 þHNO2 þHCl!½RN N
Clþ2 H2 O
Figure 35 shows the phase diagram of the
N2O3 – H2O system with its sizable miscibility These salts are used widely in the manufacture
gap. Mixtures break up into a lighter layer with a of azo dyes (! Azo Dyes, 1. General).
high water content and a heavy layer with a high With secondary amines, nitrosamines are
dinitrogen trioxide content. formed:
R2 NHþHNO2 !R2 NNOþH2 O The compounds listed above are described in

Ammonia and urea react with nitrous acid to more detail in order of their oxidation state. Table 8
yield nitrogen: lists their most important physical properties.
NH3 þHNO2 !N2 þ2 H2 O

3.1. Dinitrogen Monoxide
3. Nitrogen Oxides Properties (see Table 8). Under normal con-
ditions (i.e., room temperature and atmospheric
Compounds of oxygen with nitrogen are consid- pressure), dinitrogen monoxide [10024-97-2], al-
ered as a class and called nitrogen oxides (often so called nitrous oxide, N2O, Mr 44.01, is a
denoted as NOx ). colorless gas with a weak, pleasant odor and a
The known oxides and their equilibrium reac- sweetish taste. If inhaled, it can bring about a
tions are as follows: spasmodic inclination to laugh and a condition
resembling drunkenness—hence, its historic
name, laughing gas [97]. Two mesomeric forms
in resonance with each other describe the electron
distribution in the molecule [7]:
Production. Dinitrogen monoxide occurs

as a byproduct of denitrification (especially in
the heavy use of nitrogen fertilizers) and, to some
extent, in the nitrification of nitration waste acids.
The compound was first prepared by PRIESTLEY,
who carefully heated ammonium nitrate:
NH4 NO3 !N2 Oþ2 H2 O
Very little is known about nitrogen trioxide This is still a common route for industrial
(NO3 ) or its dimeric form (N2O6 ). production.
Table 8. Physical properties of nitrogen oxides
Compound N2O NO NO2 /N2O4 N2O3 N2O5
Oxidation state þ1 þ2 þ 4/ þ 4 þ3 þ5
TCr, C 36.41 93 157.85
pCr, MPa 7.245 6.485 10.132
rCr, kg/m3 452 520 550
mp, C 90.86 163.65 11.2 100.7 32.4 *
bp, C 88.48 151.77 21.15 40 to þ 3
Specific heat cp, kJ kg1 K1 0.879 0.996 1.326 0.862 0.778
Standard enthalpy of formation
DHF0 , kJ/kg 1864.190 3007.684 721.199 1101.435 104.589
Heat of vaporization at bp, kJ/kg 376.07 459.031 414.257 517.416
Density, kg/m3
Gas (0 C, 101.3 kPa) 1.9775 1.3402 3.4 (20 C) 1.447(2 C) 2.05
Liquid (20 C, 101.3 kPa) 793 1446.8 (solid)
Dynamic viscosity, mPa s
Gas (25 C, 101.3 kPa) 14.874 19.184 12.838
Thermal conductivity, W m1 K1
Gas (25 C, 101.3 kPa) 0.01718 0.02573 0.1124
Liquid (20 C, 101.3 kPa) 0.1336
*
Sublimation point.
In earlier processes [98], high-purity ammo- water, and 0.01 – 0.1 % chloride ion. The impure
nium nitrate was used (contamination by organic product dinitrogen monoxide ascends from the
material and chlorides had to be avoided), and decomposition flask (a) into the tower (b). Am-
temperatures up to 260 C were reached. Today, monia in the gas space neutralizes any entrained
in contrast, ammonium nitrate can be decom- acidic constituents, and this reaction heats the
posed in aqueous solution containing chlorides lower part of the tower (b). The hot gas is cooled
and nitric acid at temperatures as low as 100 – and scrubbed by an aqueous ammonium nitrate
160 C. This synthesis was introduced in 1970 solution fed through a distributor (c). The solu-
by Hoechst [99] (Fig. 36) tion collected in the bottom of the tower (b) has
The decompositon flask (a) is supplied with a temperature of 50 – 110 C; most of it is
gaseous ammonia and nitric acid (30 – 100 %). recycled through the heat exchanger (d). The
Ammonia gas forms the atmosphere for the entire thermal energy recovered serves to heat the
system, including the tower (b). A small amount evaporator (e), which concentrates a small part
of chloride ion (> 0.2 %) is maintained in the of the solution stream for recycling to the de-
aqueous nitric acid solution in the decomposition composition flask (a). If the temperature profile
flask (a) to accelerate the reaction. If appropriate, in the system is not too low, the process does not
catalytically useful amounts of metal ions (man- need a heat supply.
ganese, copper, cerium, lead, bismuth, cobalt, or This process has two main advantages over
nickel) may also be added. Heat liberated during earlier ones: it offers a substantial energy saving
the reaction raises the temperature to 100 – and produces dinitrogen monoxide free of harm-
160 C. The solution contains 15 – 35 % nitric ful byproducts.
acid, 30 – 50 % ammonium nitrate, 15 – 55 % The dinitrogen monoxide can easily by lique-
fied under pressure and is available in steel cy-
linders. Transport regulations for dinitrogen
monoxide (compressed) are as follows:
IMDG Code Class 2.2

UN No. 1070
RID/ADR Class 2, no. 5 a
CFR 49: 172.102 Nonfla. G
Uses. The principal uses of dinitrogen mon-

oxide are as follows:
1. In medicine, as an anesthetic
2. In the munitions – explosives industry, as
a propellant
3. In the food industry, as a foaming agent
(whipped cream)
Production data for dinitrogen monoxide are

given in [100].
3.2. Nitrogen Monoxide
Nitrogen monoxide [10102-43-9], also called

nitric oxide, NO, Mr 30.01, is a colorless, toxic,
nonflammable gas at room temperature. As soon
Figure 36. Industrial production of dinitrogen monoxide
as it comes in contact with atmospheric oxygen,
[99] a) Decomposition flask; b) Scrubbing tower; c) Ammo- it is oxidized to nitrogen dioxide, a brown vapor.
nium nitrate distributor; d) Heat exchanger; e) Evaporator For physical properties, see Table 8.
Nitrogen monoxide is at dynamic equilibrium rous acid in the Glover tower, to yield nitrogen
with its dimer: monoxide and sulfuric acid.
With aqueous iron sulfate solutions, nitrogen
2 NO
N2 O2 DH ¼ 10:5 kJ=mol
monoxide forms dark brown nitroso iron (II)
At high temperature, however, the equilibri- sulfate [(FeNO)SO4], thus affording a detection
um is shifted all the way toward nitrogen mon- method for nitric acid and nitrates.Transport
oxide. Liquid nitrogen monoxide is completely regulation are as follows:
dimerized, probably as angular ONNO mole-
cules. The nitrogen monoxide molecule contains IMDG Code Class 2, D, E – F 2095
a double bond and a three-electron bond [101] UN No. 1660
RID/ADR Class 2, no. 1 ct
CFR 49: 172.101 Nonfla. G
This makes the molecule more stable than the

resonant structure
3.3. Nitrogen Dioxide and Dinitrogen
Tetroxide
so that the heat of dimerization is slight; the
reaction therefore does not occur in the gas phase. Nitrogen dioxide [10102-44-0], NO2, Mr 46.01,
The nitrogen monoxide molecule contains 11 is a brownish red, toxic gas with a pungent odor;
valence electrons and thus, like all gases with for physical properties, see Table 8. It is in
an odd number of electrons, is paramagnetic. equilibrium with its dimer, dinitrogen tetroxide
Laboratory preparation usually involves the [10544-72-6], also called nitrogen peroxide,
reaction of moderately concentrated nitric acid N2O4, Mr 92.01. The equilibrium is strongly
with copper: temperature dependent; at higher temperature
(ca. 100 C), it is shifted almost all the way
8 HNO3 þ3 Cu
3 CuðNO3 Þ2 þ4 H2 Oþ2 NO
toward nitrogen dioxide.
Nitrogen monoxide is very reactive and can, 2 NO2
N2 O4 DH ¼ 57:2 kJ=mol
as a strongly endothermic compound, be pre-
pared from nitrogen and oxygen in an electric Above 150 C, nitrogen dioxide begins to
flame arc: dissociate:
2 NO2
2 NOþO2 DH ¼ 144:1 kJ=mol
N2 þO2 !2 NO DH ¼ 90:4 kJ=mol
This reaction goes to completion at 650 C.
In acidic solution (e.g., chromic acid, acidified Figure 37 illustrates the dissociation of dinitro-
permanganate solution, hydrochloric acid), gen tetroxide and nitrogen dioxide as a function
nitrogen monoxide is oxidized to nitric acid. The of temperature.
combustion of nitrogen (Birkeland – Eyde, The following values for the equilibrium con-
Sch€onherr, Pauling processes) was formerly an stant of the bidirectional reaction are given in
important method of industrial nitric acid pro- [102]:
duction; however, these processes are no longer
used due to the high energy cost of the arc. Nitric Temperature, K 273.2 298.5 323.5 359.7
acid production is now based on the combustion Kp (101.3 kPa) 0.017513 0.1458 0.8492 7.247
of ammonia; nitrogen monoxide is the first
reaction product and has thus gained some According to PAULING, the nitrogen dioxide
importance as an intermediate. molecule probably exists in two mesomeric
Another use of nitrogen monoxide is in forms with two ionic structures:
nitrosation, where chlorine or bromine reacts
with it to yield nitrosyl halides. In the lead-
chamber process for sulfuric acid production,
nitrosyl hydrogen sulfate is treated with sulfu-
comparable in strength to elemental bromine.

They form explosive mixtures with hydrogen;
mixtures with ammonia explode even at low
temperature.
Transport regulations for liquefied nitrogen
dioxide are as follows:

UN No. 1067
RID/ADR Class 2, no. 3 at
CFR A 49
Nitrogen dioxide is involved in the production

of ‘‘photochemical smog’’ and is a major air
pollutant because it is produced in all combustion
processes. It is therefore subject to strict emission
limits (see Section 1.4.2.1) [67].
Dinitrogen tetroxide has many applications
because of its strong oxidizing action. For exam-
ple, it is employed as a catalyst in oxidation
reactions and as an inhibitor in the distillation
Figure 37. Dissociation of dinitrogen tetroxide and nitrogen
of acrylates. It is also used in the manufacture of
dioxide explosives, as a rocket propellant, and as a
bleach.
Dinitrogen tetroxide can be prepared in two For details on the chemistry of liquid dinitro-
structures, 1 exists at room temperature and is in gen tetroxide, see [103].
equilibrium with 2 at low temperature:
3.4. Dinitrogen Trioxide
Dinitrogen trioxide [10544-73-7], also called

nitrous anhydride, N2O3, Mr 76.01, is stable only
below 0 C, taking the form of a deep-blue
Nitrogen dioxide, like nitrogen monoxide, is liquid. When cooled further, it solidifies as
an odd-electron compound and therefore para- pale blue crystals. For physical properties, see
magnetic; dinitrogen tetroxide is diamagnetic. Table 8.
To reach an even electron number, nitrogen Even below 0 C, dinitrogen trioxide dissoci-
dioxide can give up an electron (NOþ 2 , nitronium ates to a considerable extent:
ion) or gain one (NO 2 , nitrite anion).
Industrial production of NO2 – N2O4 em- N2 O3 ðgÞ
NOþNO2 DH ¼ 40:58 kJ=mol
ploys the Ostwald process (catalytic combustion
of ammonia) and constitutes the initial step in the 2 N2 O3 ðgÞ
2 NOþN2 O4 DH ¼ 12:97 kJ=mol
production of nitric acid (see Section 1.3). At 10 C and ambient pressure, only 10 % of
Other commercial processes for producing the molecules are in the form of undissociated
NO2 – N2O4 are the oxidation of nitrosyl chlo- dinitrogen trioxide (as ONNO2 [104]). This
ride yielding chlorine, and the treatment of sodi- dissociation means that a well-defined boiling
um nitrite with nitric acid and oxidation of the point cannot be given for dinitrogen trioxide
liberated nitrogen monoxide to nitrogen dioxide. (bp range 40 to þ 3 C). The compound is
High-purity NO2 – N2O4 is obtained in the prepared by saturating liquid nitrogen dioxide
production of sodium nitrate from sodium chlo- with nitrogen monoxide:
ride and nitric acid. The dioxide and tetroxide
(oxidation state 4) are strong oxidizing agents, NOþNO2
N2 O3
However, because nitrogen dioxide is present place concentrations [108], [109]: MAK value
mainly as the dimer, a eutectic of nitrogen mon- 10 ppm (25 mg/m3 ); TLV-TWA 2 ppm
oxide and nitrogen dioxide can be postulated (5.2 mg/m3 ); TLV-STEL 4 ppm (10 mg/m3 ).
[105] with the empirical composition NO1.56. Nitric acid reacts with and causes spontaneous
The equilibrium constant for the reaction ignition of organic substances such as wood
has been measured at various temperatures shavings, saw dust, cotton, and cellulose. Spilt
[106]. Because the equilibrium is easily shifted, acid should therefore never be absorbed with
a mixture of nitrogen monoxide and nitrogen such substances.
dioxide behaves chemically like dinitrogen Nitric acid is classified as a hazardous
trioxide. substance [109], [110]. Indications of special
Dinitrogen trioxide occurs chiefly in nitric hazards (R warnings) and safety advisories
acid production. As much as 4 vol % of the NOx (S warnings) are given in [109].
may be present as dinitrogen trioxide. The triox-
ide is used in preparing high-purity alkali nitrites Nitric acid > 70 %
from alkali. It also finds use as an oxidizing agent R 8: Danger of fire when in contact with
in special fuel systems. flammable substances
R 35: Causes severe burns
S 23: Do not inhale vapor
S 26: In case of contact with eyes, flush eyes
3.5. Dinitrogen Pentoxide thoroughly with water and call physician
S 36: Wear appropriate protective clothing
Dinitrogen pentoxide [10102-03-1], also called when working
nitrogen pentoxide, N2O5, Mr 108.01, is the Nitric acid 20 – 70 %
R 35: Same as above
anhydride of nitric acid. It is a colorless crystal- S 2: Must be kept away from children
line substance that melts under pressure but S 23, S 26: Same as above
sublimes at atmospheric pressure. For physical S 27: Immediately remove contaminated
properties, see Table 8. or saturated clothing
Mixtures of nitric acid (> 30 % HNO3 ) and sulfuric acid
In the solid state, dinitrogen pentoxide has (nitrating acid)
a salt-like structure [NO2]þ[NO3]. It is not very R 8, R 35: Same as above
stable and can undergo spontaneous explosive S 23, S 26, S 36: Same as above
decomposition [107]: S 30: Never add water to acid
2 N2 O5 !4 NO2 þO2
Protective clothing should be worn to prevent
Dinitrogen pentoxide can be prepared by contact with the skin. The acid must be kept away
treating nitric acid with phosphorus pentoxide. from children. In case of burns, the affected area
It has strong oxidizing properties and reacts should be washed with copious amounts of water
vigorously with organic substances. With water, and a doctor should be consulted. Skin burns
the hygroscopic crystals form nitric acid: itch and become yellow due to the formation of
xanthoproteins.
N2 O5 þH2 O!2 HNO3 DH ¼ 37:66 kJ=mol
Death may occur if large areas of skin are
With boron trifluoride, it forms a binary com- burned. Since regulation of the body temperature
pound N2O5 – BF3 that is stable at room temper- is disturbed, the patient must be kept warm.
ature. This compound is a good nitrifying agent. Protein enters the bloodstream and the patient
Nitrogen pentoxide has not become important in may suffer from shock, appropriate preventive
industry. measures must therefore be taken. In case of
contact with the eye, the eyelids must be opened
and the eye washed with copious amounts of
4. Toxicology and Occupational water. A doctor must be consulted.
Health Nitrous gases are released from nitric acid at
room temperature, a fume cupboard should
Nitric Acid. Nitric acid has a caustic effect therefore be used when working with the acid.
on the skin and mucous membranes. Industrial Use of respiratory protection equipment with a B,
safety regulations stipulate the following work- E, or NO filter is recommended.
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What are the main industrial processes for producing nitric acid?

What are the main industrial processes for producing nitric acid?

What are the main properties of nitric acid?

What are the main properties of nitric acid?

Article No : a17_293

Nitric Acid, Nitrous Acid, and Nitrogen Oxides

1. Nitric Acid . . . . . . . . . . . . . . . . . . . . . . . 177 1.4.1. Wastewater . . . . . . . . . . . . . . . . . . . . . . . 211

1. Nitric Acid The direct combustion of air in an electric arc,

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Physical Properties. Nitric acid [7697-37- Chemical Properties. Concentrated nitric

Table 1. Physical properties of aqueous nitric acid as a function of

HNO3 Density mp, C bp, C Partial

0 0.99823 0 100.0 2.23

fortis) is used for separating gold from silver.

Intensive work on ammonia combustion as O2 À 2 Oðadsorb:Þ

ammonia and nitrogen monoxide is accelerated

Reaction Engineering. From an engineer-

Figure 4. Conversion of ammonia to nitrogen monoxide on

Platinum loss during operation is caused by

Mechanical losses are accelerated by impuri-

Gas Phase. The gas phase is the site of

as well as nitrogen dioxide dimerization

and dinitrogen trioxide formation

Nitrous acid then dissociates to nitric acid,

Figure 8. Nonstoichiometric model of absorption of nitrogen oxides in water [28]

Figure 11. Value of K1 from Equation (34) as a function of

The equilibrium constant Kp can be estimated

Modeling of the Absorption Tower. The

to-plate calculations are generally described

By way of example, an equilibrium model

where y is the mole fraction in the vapor phase.

This formula allows the compositions of the gas

Figure 14. Equipment needed in a nitric acid plant

Stress cracking corrosion is a special threat to

1.3.3.3. Compressors and Turbines

Machines on a common shaft are used to

Figure 18. Reactor for catalytic ammonia oxidation with

Ammonia Evaporator. Various types of

Figure 23. Ammonia evaporator a) Evaporator tubes; b) Sparger; c) Drop separator

tail gas leaves the tower, entrained acid droplets

Bleacher. The NOx gases contained in

1.3.3.5. Construction Materials

Because of the special behavior of nitric acid

point is important because the corrosion potential

Type of steel C max. Si max. P max. S max. Cr Ni Other

AISI 304L 0.035 0.75 0.040 0.030 18 – 20 8 – 13

Parameter Monopressure processes Dual-pressure process

Medium pressure High pressure

Operating pressure, MPa 0.55 1.080 0.45/1.1

Table 6. Consumption figures for the production of 1 t of 99 % HNO3

Parameter Starting HNO3

Heating steam (1.0 – 1.8 MPa), t 2.0 1.75 1.45

polytetrafluoroethylene, stainless steel, tanta-

issuing operating permits. Regulations in exceeds a rate of 30 kg/h must be equipped

Improved Absorption. Absorption effi- plant or sections of a fertilizer complex must

of expensive ammonia must, however, also be

Europe, total 16.472

On heating in the presence of sand, glass

R2 NHþHNO2 !R2 NNOþH2 O The compounds listed above are described in