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
1.1. Introduction aban-doned because of its poor energy
efficiency. Later direct processes, such as
Nitric acid is a strong acid that occurs in nature thermal nitrogen monoxide synthesis with fossil
only in the form of nitrate salts. When large- fuels or nitrogen monoxide synthesis in nuclear
scale production of nitric acid began, sodium reactors, did not gain widespread acceptance.
nitrate (soda saltpeter, Chile saltpeter) was used Ammonia produc-tion from calcium cyanamide
as the feedstock. At the beginning of the 20th was of only transi-tory value. Ammonia
century the reserves of Chile saltpeter were produced from nitrogen and hydrogen by the
thought to be nearing exhaustion, so processes Haber – Bosch process (! Ammonia, 2.
were developed for replacing nitrogen from Production Processes) is, however, still used as
natural nitrates with atmospheric nitrogen. feedstock for nitric acid production.
Three techniques 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
C (direct processes) for a nitric acid plant were determined first in
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].

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

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

Most of the nitric acid produced is used to Heat of vaporization (20 C) 626.3 J/g
Specific heat
form inorganic fertilizers (! Phosphate Fertili- at 0 C 1.7601 J g
1
K1
zers); it is mostly neutralized with ammonia to 1
at 20 C 1.7481 J g 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 comprehensive review of the physical and chem-
its preparation from saltpeter and sulfuric acid. ical properties of nitric acid is given in [6].

Physical Properties. Nitric acid [7697-37-2], Chemical Properties. Concentrated nitric

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 þ
water. The azeotropic mixture boils at 121.8 C. NO3 þ4 H NOþ2 H2O
Pure anhydrous nitric acid boils at 83 – 87 C; goes to the right for all substances with oxidation
the 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 (þ 0.799
heating [4]: V) are dissolved by nitric acid, where-as gold (þ
4 HNO3!2 H2Oþ4 NO2þO2 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
3
at 0 C 1549.2 kg/m
at 20 C 1512.8 kg/m3
at 40 C 1476.4 kg/m3
24
Refractive index n 1.3970
D

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 m 1 K 1
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
3
wt % g/cm (20 C), kPa
HNO3 H2 O

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
Figure 2. Ostwald process
surfaces because a thin oxide layer is formed,
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 N 2O 4 ð2Þ
Highly diluted nitric acid is almost
completely dissociated
þ
2. Absorption of the nitrogen oxides to yield
HNO3þH2O H3O þNO3 nitric acid:
and does not attack copper and more noble 3 NO2þH2O!2 HNO3þNO 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
(aqua regia) also dissolves gold. acid processes. In monopressure (single-
pressure) processes, ammonia combustion and
NOx ab-sorption take place at the same working
1.3. Industrial Production pressure. 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
Ostwald process is described in this section. The low pressure (100 – 220 kPa) for both
process involves three chemical steps (Fig. 2): combustion 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 NH3þ5 O2!4 NOþ6 H2O ð1Þ sorption at 900 – 1400 kPa. Some older plants
still employ atmospheric combustion and medi-
Oxidation of the nitrogen monoxide product
to nitrogen dioxide or dinitrogen tetroxide: um-pressure absorption.
 1 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24
80

O2 \2 Oðadsorb:Þ
Intensive work on ammonia combustion as well
as the oxidation and absorption of nitrogen oxides
has been well documented since the early 1920s.O
Up to now the combustion of ammonia has been
considered as a heterogeneous catalytic surface ðadsorb:ÞþNH3!NH2OH NH2OHþO2!HNO2þH2O HNO2!
reaction with undesirable side reactions. The NOþOH
oxidation of nitrogen monoxide is a rare example
of a homogeneous third-order gas-phase reaction. 2 OH !H2OþO
The absorption of NOx is a heteroge-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-ducts
on the platinum catalyst. Later studies with a mass
1.3.1. Oxidation of Ammonia spectrometer showed that no such inter-mediate
products are found above 400 C [8]. In these tests,
The oxidation of ammonia to nitrogen monoxide both molecular and atomic oxygen was found on
is described by the equation the catalyst surface. A direct reac-
ð4Þ tion between oxygen and ammonia was therefore
4 NH3þ5 O2!4 NOþ6 H2O DH ¼ 904kJ=mol postulated according to the following equations:
Over a suitable catalyst, 93 – 98 % of the feed
NH3þO2!NOþH2OþH
ammonia is converted to nitrogen monoxide. The
remainder participates in undesirable side reac-
tions leading to dinitrogen monoxide (nitrous NH3þO!NOþH2þH
oxide, laughing gas)
In fast reactions such as the combustion of
4 NH3þ4 O2!2 N2Oþ6 H2O DH ¼ 1105 kJ=mol ð5Þ ammonia (the reaction time for Eq. 4 is ca.
11
10 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 NH3þ3 O2!2 N2þ6 H2O DH ¼ 1268 kJ=mol ð6Þ trations. NOWAK [9] has compared the numerous
theories of ammonia combustion. PIGNET and
Other undesirable reactions are the decompo-
SCHMIDT present a classical Langmuir – Hinshel-
sition of the nitrogen monoxide product
wood treatment of the process [10]. The possi-
2 NO!N2þO2 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 6 NO 5 N2 6 H2O DH 1808 kJ=mol 8 At low temperature (200 – 400 C), the rate

þ ! þ ¼ ðÞ
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
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 181

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-sa,
is, however, employed for a variety of reasons, FRG) taken with a scanning electron microscope (enlarge-ment
the most important being that conversion 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
mixing of ammonia and air in industrial slip (leakage) of ammonia which reacts with it
practice is incomplete, locally higher ratios may ac-cording to Equation (8). If the gas velocities
occur. A ratio that includes a safety margin are too low or too many gauzes are used,
below the explosion limit is therefore decompo-sition of nitrogen monoxide
necessary. The explosion limit declines with according to Equa-tion (7) is promoted. Table 3
pressure so that high-pressure burners can gives typical gas velocities.
operate with up to 11 % ammonia, whereas
13.5 % ammonia is possible in low-pressure Table 2. Explosion limits of ammonia – air mixtures at atmospheric
systems. The explosion limit also depends on pressure
the flow velocity (Table 2, see also [3]) and the Flow velocity, Lower explosion Upper explosion
water content of the reaction 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
182 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

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
A high reaction temperature promotes ammo- temperature and catalyst composition [5] a) Pt; b) Pt – Rh
98/2; c) Pt – Rh 90/10
nia combustion (Fig. 4), but high temperature
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
greatly (Fig. 5). The usual way to maintain the conversion is lower. Another disadvantage of
conversion toward the end of a campaign in spite non-noble-metal catalysts is that they are more
of catalyst deactivation and losses, is to raise the quickly poisoned [13].
temperature. The ammonia – air ratio is directly The usual form of catalyst is a fine-mesh gauze
2
related to the reaction temperature: a 1 % increase (standardized at 1024 mesh/cm ). Manu-facturers
in the proportion of ammonia increases the offer wire diameters of 0.060 and 0.076 mm. The
temperature by ca. 68 K. If the temperature is too Johnson Matthey ‘‘Tailored Pack’’ combines
low, conversion to nitrogen monoxide decreases. gauzes made of different wire diameters [14]. The
The reaction temperature also de-pends on the upstream gauzes have a wire diameter of 0.076
temperature of the inlet gas mixture. The mm and the downstream ones 0.060 mm to
following formula provides an approximate value optimize the catalyst surface area.
in C: High-pressure plants also utilize ‘‘fiber packs’’
in which a fraction of the fibrous catalyst material
treactor ¼ tgas mixtureþr 68 where r ¼ NH3=ðNH3þairÞ ð9Þ is held between two gauzes [15]. The packs have
the advantage of reduced platinum loss and thus
longer run times. ‘‘Fiber packs’’ have not yet
Catalysts. [12]. Since the introduction of the been used in medium-pressure ammonia
industrial production of nitric acid by the Ostwald combustion because fewer gauzes are used in
process, several hundred materials have been medium-pressure than in high-pressure processes
tested as catalysts for ammonia combustion. (see Table 3), so the lower pressure drop results in
Platinum catalysts have proved most suitable and poorer distribution.
are used almost exclusively today. Oxides of non- To reduce catalyst consumption, particularly
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
face becomes enriched in rhodium, thus improv-
m/s C HNO3 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-tent
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
of 5 – 10 % has proved optimal. Figure 6 shows
the efficiency of conversion to nitrogen
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 183

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!PtO2ðgÞ

Mechanical losses are accelerated by impuri-

ties in the reaction mixture, which can lead to
Figure 6. Conversion of ammonia to nitrogen monoxide on the formation of whiskers at the grain
platinum gauze (a) and platinum losses (b) as a function of boundaries. The whiskers are more easily
catalyst composition broken off by the flowing gas.

monoxide and the platinum loss as a function of Recovery of Precious Metals. Precious-metal
the rhodium content of the alloy [18]. losses from the catalyst have a significant effect
If a low reaction temperature (< ca. 800 C) is on the operating costs of a nitric acid plant. The
unavoidable, a pure platinum catalyst should be approximate losses and resulting costs can be
employed, because otherwise rhodium(III) determined from the ammonia combustion
oxide would accumulate at the catalyst surface temperature and the loading. Losses increase with
and decrease catalytic activity [18]. temperature and loading; however, smaller losses
Palladium is also used in catalyst alloys. may be measured at higher loadings because a
Laboratory studies on the catalytic activity of 90 more uniform incoming flow causes less
% Pt – 10 %Rh and 90 %Pt – 5 %Rh – 5 % Pd movement of the gauzes relative to one another
gauzes reveal no great differences in nitrogen and thus reduces mechanical losses. Table 3 lists
monoxide yield [19]. The ternary catalyst is of 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 has most important drawback is their large pressure
been initiated, crystal growth rapidly in-creases drop, which can reach 25 kPa between filter
the surface area. The highest conversion on the changes.
catalyst is obtained after a few days use. Specially Mechanical filters recover 10 – 20 % plati-
pretreated platinum gauzes that reach maximum num, but recovery rates up to 50 % have been
activity after just a few hours are also on the reported [22]. These filters have the advantage of
market [20]. Start-up problems with plati-num low capital costs and the disadvantage of high
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) In low-pressure burners, marble chips 3 – 5
and dust in the process air, which is especially mm in length were used immediately down-
con-centrated in the vicinity of fertilizer plants. stream of the catalyst gauzes [23]. At high reac-
Any material deposited on the catalyst surface tion temperature, the marble is converted to
acts as a poison. A multistage filter is used to calcium oxide, whose high absorption capacity for
prevent these substances from reaching the platinum and rhodium permits up to 94 %
catalyst (see Section 1.3.3.1). recovery. During reactor shutdown, however, the
184 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

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 that The captured platinum diffuses into the palla-
is stable at high temperature and that can absorb dium gauze and forms an alloy. The topmost
platinum oxide vapor and form an alloy with it. gauze is often designed to reach saturation in one
The first recovery gauzes in production plants campaign, usually 180 d. Determining the eco-
(supplied by Degussa in 1968) consisted of a gold nomic optimum for a recovery system (the most
– palladium alloy (20/80). Nowadays most such important criterion is the weight of palladium
gauzes are gold-free but have a low content of required) necessitates taking into account the fact
nickel (ca. 5 %) to enhance their strength. The that palladium is lost. This loss corresponds to
2 about one-third of platinum recovery.
gauzes have 100 – 1350 mesh/cm and are made
of wire with a diameter of 0.2 – 0.06 mm. Several ‘‘Getter’’ systems can recover more than 80 %
recovery gauzes with different specifications are of the platinum lost from the catalyst. The mech-
usually installed. Loss of plati-num from the anism of rhodium recovery has not yet been fully
catalyst is greater than that of rhodium; for elucidated. Up to 30 % of rhodium from the
example, the calculated loss com-position for a catalyst is captured by recovery systems.
90/10 Pt – Rh gauze is 95/5. A ‘‘recovery factor’’
can be determined for each recovery gauze,
indicating how much of the available platinum is 1.3.2. Oxidation and Absorption of
retained by the gauze. This recovery factor Nitrogen Oxides
depends on the specifications of the gauze, the
operating pressure, and the loading. Figure 7 After the combustion of ammonia, the nitrogen
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 N2O4 DH ¼ 58:08 kJ=mol ð11Þ

and dinitrogen trioxide formation

NOþNO2 N2O3 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
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 185

and nitric acids. These reactions are of According to [27], the equilibrium constant can
secondary importance from an engineering be determined as
standpoint. p
N O3 4740
To describe the kinetics of nitrogen
monoxide oxidation (Eq. 10), a third-order rate 2

p p
equation is used [26]: Kp ¼ NO NO2 ¼ 65:3 10 exp
9
T ð19Þ

kp 2

r¼ RT pNOpO2 ð13Þ Liquid Phase. The large number of reactive

components in the gas phase (NO, NO2, N2O3,
where
N2O4) means that the reaction model for
3 1
r ¼ reaction rate, kmol m s 2 1 absorption is complicated. Figure 8 shows
k reaction rate constant, atm s
p ¼ 3
1 1 a sophisticated model devised by HOFTYZER and
R ¼ universal gas constant, m atm kmol K 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-
ide reacts with water, yielding nitric and nitrous
652:1

logkp ¼ T 1:0366 ð14Þ acids:

N2O4þH2O!HNO3þHNO2 DH ¼ 87:0 kJ=mol ð20Þ

This reaction is unusual because it goes to the

right faster at low temperature than at high
temperature, i.e., the reaction rate has a
negative temperature coefficient.
Because equilibrium in the nitrogen dioxide
dimerization system is reached very quickly, an
equilibrium formula

p
kp 2 N2 O4

p K
r ¼ RT NO2 p ð15Þ
can be assumed where Kp is the
equilibrium constant. The dimerization
rate is virtually inde-
pendent of temperature [27], so the
rate constant at 25 C
 Nitrous acid then dissociates to nitric acid, water, and
nitrogen monoxide, the latter being transported across the
interface into the bulk gas:
3 HNO2!HNO3þH2Oþ2 NO DH ¼ 15:3 kJ=mol ð21Þ

According to ANDREW and HANSON [29], a first-order

equation can be written for the rate of dinitrogen tetroxide
hydrolysis:
r k
¼ cN2 O4 ð22Þ
where cN2O4 is the concentration of dinitrogen tetroxide in
3
kmol/m . The rate constant is given by

4139

5 1 1
kp ¼ 5:7 10 atm s ð16Þ logk ¼ T þ16:3415 ð23Þ

can be used at all temperatures of technical

interest. The kinetics of nitrous acid dissociation were
HOFTYZER and KWANTEN [28] give the follow- studied by ABEL and SCHMID [30], with the
ing equation for the NO2 – N2O4 equilibrium following result:
constant:
4 4
p c k c
N2 O4 6866 HNO2 HNO2

2 2 2
9 r ¼ k pNO ¼ HNO cNO ð24Þ
Kp 0:698 10 exp
2
¼ pNO 2 ¼ T
where HNO is the Henry coefficient for nitrogen
3
An equilibrium formula can also be written for monoxide in m atm/kmol and c ist the concen-
3
dinitrogen trioxide formation: tration in kmol/m . The rate constant is defined
by

p
kp N2 O3

6200
p p
r ¼ RT NO NO2 K ð18Þ logk 20:1979 25
p ¼ T þ ð Þ
186 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

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
tal data from [32]. acids. Nitrous acid dissociates (Eq. 21), and the
result-ing nitrogen monoxide is transported
Mass Transfer. For more than 50 years back into 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
nitric acid. A variety of mechanisms have been the absorption rate of dinitrogen tetroxide [34]:
proposed depending on the gas composition and
N2 O4 ¼ N2 O4 N2 O 4 pffiffiffiffiffiffiffiffiffiffiffiffiffiffi24 ð Þ
the acid concentration. These are partly in agree-
ment with the absorption model of Figure 8. J H p kDN O 27
In the NOx absorption region important for where
acid formation, dinitrogen tetroxide transport is 3
H ¼ Henry coefficient, m atm/kmol k ¼ rate
considered to be the rate-limiting step. The quan- 1
constant, s
tity of dinitrogen tetroxide transported from the 2
bulk gas to the interface depends chiefly on the D ¼ diffusion constant, m /s
Numerous measurements in laboratory
NO2 – N2O4 equilibrium [28], [33]:
J o i absor-bers support this mechanism.
¼ 2RT2pNO pNO 2
N2 O4
K
gNO
2
Interpretations of measurements in absorption
columns have given the following correlations
k for the mass-transfer coefficients [35]:
gN2 O4 o i ð26Þ
p p
þ RT N2 O4 N2 O4

where 1. Bubble-cap trays

2 1
J ¼ absorption rate, kmol m s
kg ¼ gas-side mass-transfer coefficient, m/s
o i
p ¼ partial pressure in the bulk gas, atm p
¼ partial pressure at the interface, atm
At higher NO2 /N2O4 concentrations in the reac-
tion gas, primarily dinitrogen tetroxide crosses
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 187

2. Sieve trays

where
3
H ¼ Henry coefficient, m kPa/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 a
chemisorption also occur at low gas-phase NO2 –
N2O4 concentrations [29]. function of acid strength and temperature [28] 1mm 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
mum possible acid concentration for a given concen-tration of 65 wt % and an inlet nitrogen
composition of the inlet gas. For example, oxide partial pressure of 100 kPa, however, the
suppose the overall reaction is vapor pressures from the binary system HNO 3 –
3 NO2ðgÞþH2OðlÞ 2HNO3ðlÞþNOðgÞ DH ¼ 72:8 kJ=mol
H2O can be used to determine K2 (Fig. 9).
ð30Þ Figure 10 shows how K1 depends on the acid
concentration and the temperature. This param-
and the equilibrium constant is defined as eter is particularly interesting from an engineer-
p 2 p ing standpoint because it allows the acid
HNO 3 NO
strength to be determined if the gas
Kp ¼ 3 concentration is known.
pNO 2 pH2 O ð31Þ
with the partial pressures of nitrogen monoxide If the equilibrium is based on the overall
( pNO) and nitrogen dioxide (p NO2 ) in the gas reaction
phase and the vapor pressures of nitric acid 3=2 N2O4ðgÞþH2OðlÞ 2 HNO3ðlÞ ð33Þ
(pHNO3 ) and water (pH2 O) over the dilute acid. In
industrial absorption the equilibrium constant þNO3ðgÞ DH ¼ 75 kJ=mol
depends only on temperature. The equilibrium the equilibrium constant is
constant is conventionally split into two terms:
p p 2
p p 2
Kp ¼ K1 K2 NO HNO 3
Kp ¼ K1 K2 NO HNO 3 p
where K1 ¼ p3=2 and K2 ¼ H2 O ð34Þ
N2 O 4
3 p
where K1 ¼ pNO 2 and K2 ¼ H2 O ð32Þ
K2 depends on the acid concentration and the Again Figure 9 gives the K2 values. In this
temperature. Gases ( N2O4, N2O3, HNO2 ) dis- formulation, K1 is a function of the acid
188 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

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 T ð39Þ
Figure 10. Value of K1 from Equation (32) as a function of
acid concentration and temperature [28]
Then K1 can be determined from Kp, and the
K2 values obtained from Figure 9. The
parameter K1 determines the equilibrium
curves for constant temperature and constant
concentration and does not depend on acid concentration when pNO2 is plotted against
temperature (Fig. 11). The curve of Figure 11 pNO (Fig. 12). The K1 values are necessary to
can be fitted by an empirical equation [37]: calculate the absorp-tion of nitrous gases
according to TONIOLO [39]. The application of
2
logK1 ¼ 7:412 20:29WHNO3 þ32:47WHNO 3 35 the Toniolo diagram is de-scribed in [40].
30:87W 3
ð Þ

HNO3 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 according to the number of reactions, the reaction
com-ponent NO2 denoted as ‘‘chemical NO2’’: kinetics, or the type of mathematical method:

p p p 1. Number of Reactions. The simplest calcula-

NO~2 ¼ NO2 þ2 N2 O4 ð36Þ
tion model uses Equation (30) to describe the
The nitrogen dioxides, considered as completely events on an absorption plate and a kinetic
dissociated, are assumed to react according to 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 to
dinitrogen tetroxide. In this way it is possi-ble
This hypothetical reaction leads to the equi- to describe nitric acid formation not just via
librium relation
nitrogen dioxide but also via dinitrogen
p p tetroxide [46–49].
2
Kp ¼ K1 K2 NO HNO 3 Models that include the formation and disso-
ciation of nitrous acid in the liquid phase give
p
where K1 ¼ p3 and K2 ¼ H2 O ð38Þ
N~O2
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 189

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:
y y y y
3ð n;NO n 1;NOÞ ¼ð n 1;NO2 þ2 n 1;N2 O4 Þ ð40Þ
y y
ð n;NO2 þ2 n;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
ay 3 by 2 y d
n ;NO2 þ n ;NO2 þ n;NO2 þ ¼0
p 1:5
with a ¼ 3ðKp1 ffiffiffipÞðKp2 pÞ ð41Þ
b ¼ 2ðkp2 pÞ
d ¼ ð3
y y
n 1;NOþ n 1;NO2 þ2
y
n 1;N2 O4 Þ
This formula allows the compositions of the gas
Figure 12. Toniolo diagram for an absorption tower [39] A !
leaving the n-th plate and the acid arriving at
the n-th plate to be determined.
B absorption process; B ! C oxidation process
Before the (n þ 1)-th plate is calculated, the
oxidation of nitrogen monoxide must be deter-
the best description of known chemical mined. The flow behavior of the nitrous gases
events [50], [50]. A model that permits in an absorption tower is not known exactly, so
nitrous acid formation in the gas phase has the oxidation space can be described as either a
also been proposed [51].
tubular or a stirred-tank reactor. Actual con-
2. Reaction Kinetics. Most design computations ditions probably lie somewhere between the
use equilibrium equations for the basic reac-tions. two [28], but trends can be identified on the
These static methods have the drawback of basis of plate type. The stirred-tank model is
requiring the introduction of efficiency factors preferred for bubble-cap trays [47], but flow-
[51] that take into account limitation of transport through con-ditions can be expected in the case
of the reactants across the inter-face. Dynamic of sieve plates. Because virtually all absorption
methods do not need empirical efficiency factors towers today are fitted with sieve plates, only
because they describe mass transfer in terms of these are discussed.
physical and chemical laws [28], [31], [50], [52].
When the reaction is carried out
3. Mathematical Methods. In view of the large isothermally, integration of the rate equation
number of nonlinear equations to be solved in
both equilibrium and dynamic models, plate-
dp
NO 2

¼ kp p
dt NO O2 ð42Þ
190 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

gives a solution
2

q ¼ kð2pO2 pNOÞ
ð43Þ
O2
2
(p NO 1 x 2p p ln 2p 1 x 3 )
x 1
2p pNOx

ð Þ 4 ð Þ5
where
q ¼ residence time, s
2 1
k ¼ rate constant, atm s 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
Figure 13. Hydrodynamic model of absorption tower g ¼ molar
nitrogen monoxide ( pNO) and oxygen (pO2 ) [47]. gas flow rate of a component; G ¼ molar flow rate of gas; L ¼
The partial pressures of the other compo-nents molar flow rate of liquid; p ¼ pressure; T ¼ temper-ature; Tcw
leaving the reactor can be calculated from the ¼ temperature of cooling water; V ¼ volume; x ¼ mole
fraction x of oxidized nitrogen monoxide. fraction in liquid phase; y ¼ mole fraction in gas phase

If an excess of oxygen is assumed to be Transport Model. A transport model for the

present, the rate equation can be simplified [53] absorption tower is based on a series of units,
as each containing a bubble- column reactor and
dpNO 2 an adiabatic plug flow reactor (Fig. 13) [52].
The bubble-column reactor, modeled as two
¼ kpNO
ideal stirred-tank reactors, simulates the liquid
dt ð44Þ
with gas bubbles on a tray (absorption space).
so that the partial pressure of nitrogen monoxide The adiabatic plug flow reactor simulates
at the reactor outlet ( p
0 oxidation between plates (oxidation space).
NO) can be determined:

1 1 kq The balances are carried out with the equa-

p tions
pNO ¼0 NO þð2pO2 pNOÞ 2 ð45Þ
pn
Because the oxidation reaction is highly exother- Gy G y k aV y y
mic, the tubular reactor can be designed for ð
n n;i n 1 n 1;ig;i RTn n;i n;iÞ
isothermal operation only when conversion is Mg ð47Þ
very low (e.g., when the tail gas contains little X
¼ Vg ng;ijrg;j j¼1
NO). Otherwise, adiabatic reaction conditions
must be assumed. To describe the reaction under k

adiabatic conditions the oxidation space is divid- i ¼ N2, O2, NO, NO2, N2O4 and P i¼1
ed into n layers, in each of which the reaction is
isothermal. The temperature increase from one
layer to the next is given by [33]
C H
T 1=2 NO;0ð D RÞ GNO;0 GNO 46 yn;i ¼ 1 for the components in the gas phase

D ¼ r0Cp GNO;0 ð Þ (subscript g) where

2 3
where a ¼ interfacial area per unit volume, m /m
3
kmol/m G ¼ molar gas flow rate, kmol/s
C
NO, 0 ¼ initial concentration of NO, 1 1 kg ¼ gas-side mass-transfer coefficient

Cp ¼ molar heat capacity, kJ kmol K Mg ¼ number of reactions in the gas phase

G
NO ¼ molar gas flow rate, kmol/s n ¼ plate number 3 1
G
NO, 0 initial gas flow rate, kmol/s
¼ kJ/kmol r ¼ reaction rate, kmol m s
DHR ¼ reaction enthalpy, 3 V ¼ volume of bubble layer

V
r0 ¼ initial density, kg/m g ¼ volume of gas phase in bubble layer
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 191

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
Lx L x k aVc x x
n n;i nþ1 nþ1;iþ l;i nð n;i n;iÞ Figure 14 summarizes the equipment needed to
Ml
implement the three chemical steps involved in
~ ð48Þ nitric acid production (Fig. 2). In addition to
producing nitric acid, a nitric acid plant also
nl;ijrl;j
Ln x~n;i ¼ Vl j¼1

generates steam or mechanical energy from the

X k
chemical energy liberated.
P
i ¼ NO, N2O4, HNO2, HNO3, H2O and xn;i ¼ 1 where

i¼1
1.3.3.1. Filters and Mixers
3
c ¼ molar concentration, kmol/m
To obtain the highest possible conversion of
L ¼ molar liquid flow rate, kmol/s ammonia on the catalyst and a long catalyst life,
x ¼ mole fraction in liquid phase the starting materials (air and ammonia) must
~ be purified. The air must be very clean to
L ¼ side stream prevent catalyst poisoning (Section Catalysts).
M
¼ number of reactions in the liquid phase
l
Thermodynamic equilibrium is assumed at the Air Filter. A multistage filter is normally
interface, used on the air intake to a nitric acid plant and
y H x 49
should remove 99.9 % of all particles larger
n;i than 0.5 mm.
n;i ¼ n;i ð Þ
where H is the Henry coefficient and the formula Typical filter media are plastic and glass
p fibers. Filter frames should be made of stainless
n y steel. Air filters must be replaced regularly
k y k c x x because filter bags can tear or filter mats can
g;i RTn ð n;in;i Þ¼ l;i nð n;i n;iÞ

ð50Þ

i ¼ NO; N2O4
is used for dynamic mass transfer between
phases. A separate heat balance is performed
for each phase, so that the temperature may
Figure 14. Equipment needed in a nitric acid plant
192 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

become overloaded and cause an excessive is important in both cases. Local ammonia
pressure drop. Filter life depends on the excesses in the burner are a risk for plant safety
particu-late load in the air (typically 0.8 (explosion limit) and may also cause
3
mg/m ). In areas where sandstorms may occur overheating of the catalyst gauze. Poor mixing
3
(maximum loading 500 mg/m ), the use of a lowers the conversion of ammonia to nitrogen
sand separator (a centrifugal collector) as a monoxide and increases platinum loss from the
prefilter is recommended. catalyst.
The efficiency of a given mixing operation is
Ammonia Filters. The liquid ammonia fil-ter described by the standard deviation s of mea-
removes solid contaminants, especially small sured samples from the theoretical value x a
rust particles; 99.9 % of all particles larger than certain distance downstream from mixing. In
3 mm should be eliminated. Selection of a nitric acid plants, the deviation should be
liquid ammonia filter requires consideration of < 1 %. If the theoretical ammonia concentra-
the fact that traces of oils and chlorides are also tion in a mixture is 10 %, for example, mea-
present in ammonia. Proven filter materials are sured values fluctuate between 9.9 and 10.1 %
Teflon and sintered metals. Polypropylene and [54]. Only static mixers are used (e.g., the Uhde
ceramic filter candles (cartridges) are also tubular mixer or the Sulzer three-element
employed. Magnetic filters have found some mixer).
use but have limited 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 fibers, The heat of reaction liberated during ammonia
sintered metals, and ceramics. The pres-sure combustion is utilized to produce steam and
drop is up to 10 kPa, depending on filter type. preheat the tail gas. Steam is produced in a waste-
heat boiler located immediately below the burner
(Fig. 15). The burner consists of a burner basket
Filters for the Mixed Gas. The mixed-gas filter packed with filling material to ensure uniform
provides final cleaning of the ammonia – air distrubution of the downward flowing reaction
mixture and improves the mixing of the air and gas. Platinum recovery gauzes (Section Recovery
ammonia; it should remove 99.8 % of all particles of Precious Metals) are located above the filling
larger than 1.5 mm. Contaminants in the gas material. The catalyst gauzes (Section Catalysts)
mixture not only originate externally (in the are located above the recovery gauzes. The burner
process air and ammonia) but are also formed by basket is clamped between the flanges of the
corrosion inside the system (rust). The gas mix- burner head and the waste-heat boiler. To ensure
ture filter should therefore be installed as near as better distribution of the reaction mixture, the
possible to the burner. Ceramic filter cartridges 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. The
3 2 gauze temperature is measured, and the space
a surface loading of 250 m /m , the maximum
pressure drop in the clean state is 10 kPa. 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 : used. Figure 15 shows a waste-heat boiler for
10 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 1 : located directly below the burner basket and
100 for the catalytic reduction of NO x as part of protects the downstream superheater against
tail-gas treatment (see Section 1.4.2.3). ex-cessive temperature. The superheater is
followed by the main evaporator. Evaporator
From an economic standpoint, homogeneous tubes are also installed at the wall to cool it and
mixing of the gas streams upstream of the reactor protect it from excessive temperature.
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 193

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 turbine or an electric motor.
tubes; f ) Hydrogen ignition; g) Refractory packing; h) Ni-
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
led through the economizer (b) into a steam drum can be of radial or axial design. The tail gas
(c). Water at thermal equilibrium with the from the absorption column is expanded in a
steam is pumped from the drum through the tail-gas turbine (d), usually a single-stage
evapora-tors. Steam from the drum goes first to device. The rest of the power required to drive
the lower superheater (g) and is then cooled in the nitrous gas compressor is supplied by the
the drum so that the desired temperature can be steam turbine or an electric motor.
attained in the 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 % HNO 3 ).
(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
A shell-and-tube evaporator with natural 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 sure combustion and high-pressure absorption
flat spiral. These waste-heat boilers are calls for both an air compressor and nitrous gas
particularly suitable for smaller plants or those compressor (Fig. 21). The air for combustion is
using low steam pressure. delivered at 400 – 600 kPa by an uncooled radial
194 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

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 When the nitric acid plant is started up or in
gas compressor (c) produces the 1.0 – 1.2 MPa continuous operation, unreacted ammonia is
pres-sure needed for absorption. The drive present in the burner exit gas. The level in
power for these two devices comes from a continuous operation is ca. 30 ppm of ammonia.
multistage tail-gas turbine (e) and a steam As a result, nitrates and nitrites would accumu-
turbine (f) or electric motor. These systems are late in the nitrous gas compressor if they were not
preferred for large-capacity plants ( 400 t/d 100 removed regularly. If the temperature exceeds 240
% HNO3 ), especially in Europe. C, combustion or explosion is possible. To avoid
High-pressure plants (Fig. 22) are preferred an explosion, water or steam is briefly sprayed
in the United States because of lower invest- into the suction of the nitrous gas com-pressor
ment costs. The machinery includes an air every 8 h [55]. Because nitrous gas is highly
compressor with interstage cooling. Radial toxic, it must not be allowed to escape from the
devices are generally used, but the low-pres- compressor. The machine is therefore equipped
sure section in larger machines may be axial. with air-purged labyrinth seals. Chem-ical
The tail-gas turbine is usually a multistage 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 are dioxide removes heat from the stream [56] and
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.
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 195

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) exchanger with mist collector. Cooling water on
Burn-er head; b) Perforated plate; c) Platinum gauzes and the tube side is cooled on evaporation. In
platinum recovery gauzes; d) Inspection glass; e) medium-pressure plants, the heat of vaporiza-
Superheater and 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 Gas Cooler – Condenser. In the cooler –
equipped with a group of valve-controlled condenser, the temperature is lowered below the
nozzles or 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 ca. 40 wt % at medium pressure. Suitable mate-
extraction/ 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-sign shown in Figure 24, nitrous gas passes into the
predominates for tail-gas heat exchangers, shell side through two inlets; each of the partial
196 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

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
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 197

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 design is cooling coils on the plates. The coils on the upper
governed by the calculations for the oxidation plates primarily cool the nitrogen monoxide gas
process (i.e., tower height, see also Section 1.3.2) against chilled water, because oxidation pro-ceeds
and thermal design. Because oxi-dation proceeds faster at lower temperature. Most modern
more slowly as the NOx content in the tower absorption towers have sieve plates. Compart-
decreases, the spacing between plates increases. ments built into the bottom of the tower separate
Figure 25 shows an absorption tower for a plant acid of medium strength from weak acid in case of
with a daily production capacity of 1830 t of 100 plant shutdown. The collected acids are pumped
% nitric acid. Acid formation takes place chiefly back to the tower at restart so that a steady state is
in the bottom third of the reached more quickly. Before the

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

198 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

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-
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 199

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
Figure 26. Anodic polarization curve for stainless steel Cr 48-h per-iods, the acid being renewed at the
denotes the effect of chromium on the anodic polarization rate beginning of each test period. The Huey test
gives a good indication of how individual alloy
termines the corrosion resistance; its anticorro- constituents affect intergranular corrosion.
sive action is influenced by the carbon content To ensure good weldability, the carbon con-
of steel. The chromium in the alloy forms a tent is limited to 0.03 %; alternatively, titanium
carbide (Cr3C2 ) at the grain boundaries; only or niobium is added as a stabilizer.
small amounts of free chromium remain at high The stainless steels generally used in nitric acid
carbon contents, and the steel is therefore less plants are those classified unter material no.
corrosion resistant. If excess chromium remains 1.4306 (AISI 304L); in the Federal Republic of
after the amount needed for carbide formation Germany, however, the corresponding stabi-lized
is con-sumed, only this excess is responsible for qualities, material no. 1.4541 (AISI 321) and
the anticorrosion properties. 1.4550 (AISI 347), are also employed (Table 4).
The effect of chromium on the corrosion rate These steels are usually specified for towers and
is shown in the anodic polarization curve of heat-exchanger shells, and also for many heat-
Figure 26. When chromium is present in the exchanger tubes. The 1.4335 steel (AISI 310L)
alloy, the passive region Ep (see Section 1.2) is has a very low corrosion rate and is used
reached sooner. Furthermore, chromium low- particularly where corrosive attack is severe, for
ers the corrosion rate in the passive state and example, if the temperature is below the dew point
raises the transpassive potential Etr. The last 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.
200 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

temperatures [59]. These conditions normally um pressure. This type of process is

occur at the inlet to the tail-gas preheater, in the particularly economical for smaller capacities
dew point region of the cooler – condenser, and at and is thus described first.
the outlet of the feedwater preheater. Corrosion at As plant capacities continued to grow and
these locations is caused mainly by reevapora-tion lower tail-gas levels of NO x were necessary the
of nitric acid condensate, which brings the acid absorption pressure was increased still further.
concentration up to the azeotropic level (69 % Lower energy costs and shorter depreciation
HNO3 ). The acid is then very aggressive, even in periods in the United States have led to a
the vapor phase. Corrosion can take place in the prefer-ence for the high-pressure process,
boiler feedwater preheater if conden-sate forms at whereas more favorable consumption and
the outlet. Reheating of the condensate by the hot production figures in Europe have favored the
process gas can lead to critical conditions. Process dual-pressure process with medium-pressure
design parameters should normally be selected so combustion and high-pressure absorption.
as to avoid con-densation; material no. 1.4306 is The principle of medium- and high-pressure
then adequate. If, however, condensation or (monopressure) plants is that air for ammonia
reboiling occurs and this steel cannot be used, oxidation and NOx absorption is compressed to
1.4335 should be employed [60]. the desired pressure. The ‘‘primary’’ air for
oxi-dation is then mixed with ammonia and
In plants producing concentrated nitric acid, forced through the burner. The ‘‘secondary’’
aluminum (99.8 %), ferrosilicon, tantalum, and air for stripping dissolved NOx out of the raw
special austenitic steels are used. Because tanta- acid and oxidizing the intermediate nitrogen
lum is very expensive, it is employed only with monoxide is supplied upstream of the
boiling concentrated nitric acid. Ferrosilicon can absorption tower. The tail gas is heated and
be used only in castings because of its brittleness. then expanded in a turbine (on a common shaft
with the compressor) to produce mechanical
energy. The remaining drive power is supplied
1.3.4. Processes by a steam turbine running on process steam.

Figure 14 illustrates the steps necessary for im- Medium-Pressure Process. Figure 27 is a
plementation of the Ostwald process. Industrial flow sheet of a medium-pressure process (ca.
processes differ in the sequence and design of 550 kPa). Liquid ammonia is evaporated at ca.
these steps. This section describes processes for 700 kPa in the ammonia evaporator (a). The
the production of weak acid [61, pp. 61 – 98] cold generated can be used in the absorption
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
The first industrial plants for the production of used in fertilizer production. The ammonia
weak acid employed atmospheric combustion and vapor is heat-ed with steam to ca. 90 C in the
low-pressure absorption [3]. This type of plant is ammonia preheater (c) and then filtered (d). If
no longer built. It was followed by a process necessary, a small stream of ammonia is
employing atmospheric combustion and diverted to tail-gas treatment.
absorption at medium pressure. This process has All the air needed for the process is sucked in
the advantage of lower absorption costs because through the air filter (f ) by the air compressor (g).
the marked improvement in absorption obtained The compressed air is divided into two sub-
with the pressure generated by a nitrous gas streams in a tail-gas preheater (h). The secondary
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
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 201

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 the ary air and admitted to the absorption tower (p).
mixed-gas filter (not illustrated) and, now cleaned, The acid condensate from the feedwater preheat-er
enters the reactor (i) where ammonia reacts with and the cooler – condenser flows directly into the
oxygen in the primary air over the platinum – bottom of the gas cooler – condenser. This acid
rhodium catalyst, yielding nitrogen monoxide and condensate is then delivered by an acid
water. The reaction is exothermic and proceeds at condensate pump to a tray with the appropriate
ca. 890 C. The nitrous gas stream is cooled in the concentration in the absorption tower.
waste-heat boiler ( j), raising steam. Nitrogen In the lower part of the tower, the nitrous gas is
monoxide is oxidized to nitrogen dioxide in the oxidized further, thus reaching the necessary
downstream piping and equipment, heating the degree of oxidation before entering the absorp-
nitrous gas stream. Further heat recovery takes tion section. The tower contains sieve trays
place in the tail-gas preheater (k) and the through which the gas flows countercurrent to the
economizer (l). After exit-ing the economizer, the acid. The product acid concentration is at-tained
nitrous gas stream is cooled in a second tail-gas on the lowermost absorption tray of the tower.
preheater (m). Con-densate can form in the next The acid is then pumped to the bleacher (x),
unit downstream, the feedwater preheater (n), where dissolved NOx is stripped, before the acid is
which is located directly on the inlet of the cooler stored in tanks. Chlorides in the absorption tower
– condenser feed accumulate on trays where the acid
(o). Additional water of combustion condenses out concentration is ca. 21 wt %. Because of the
in the cooler – condenser before the nitrous gas danger of corrosion, these trays must be emptied
stream is mixed with the NOx-laden second- into the product acid tank from time to time.
202 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

Cooling water flowing through coils on the rest is generated by a condensing steam turbine
sieve trays removes heat generated by the supplied with product steam. The turbine may be
oxidation of nitrogen monoxide to nitrogen bled. The steam turbine condensate goes to the
dioxide and its further conversion to nitric acid. boiler feedwater preheater (n) where it absorbs
Part of the heat absorbed by the cooling water heat from the NOx gas and then flows through the
is utilized to evaporate ammonia. A demister in deaerator into the feedwater tank (t). Nondeaer-
the head of the tower collects liquid droplets ated feedwater from the battery limit also flows
entrained in the tail gas; the condensate runs via a preheater into the feedwater tank. The boiler
back to the last tray 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 NO x in Most of the steam generated in the waste-
the tail gas is selectively reacted with ammonia. heat boiler drives the condensing steam turbine.
Hot tail gas containing < 200 ppm NOx goes to The 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 a
the power needed to drive the air compressor. The 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
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 203

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
(c), and contaminants are removed in the produce ca. 45 % acid. This product is
ammo-nia gas filter (d). delivered to the appropriate tray of the
Air is sucked in through the air filter (f) and absorption tower (p) by the acid condensate
compressed to ca. 1 MPa in an air compressor (g) pump. The NOx-laden secondary air recycled
with interstage cooling (h). The primary air (ca. from the bleacher (x) is mixed with the nitrous
80 % of the total) is heated to ca. 180 C against gas stream before it is fed into the tower (p).
nitrous gas in the air heater (m) and then fed to the In the sieve-tray absorption tower (p) the
ammonia – air mixer (e). The mixed gas stream nitrous gas flows countercurrently to the pro-
has a temperature of ca. 175 C and contains 10.7 cess water fed at the column head, and nitric
vol % ammonia. It passes through a filter (not acid is formed. Heat from the absorption tower
illustrated) into the reactor (i) where the ammonia is transferred to the cooling water. Raw acid
and atmospheric oxygen react over the platinum – from the absorption tower is treated with
rhodium catalyst at ca. 900 C to form mainly secondary air in the bleacher (x), then deliv-
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
preevaporator, superheater, and reevaporator of the expansion turbine. The tail gas is further
the boiler. heated to 140 C against low-pressure steam (r)
The boiler system is fed with condensate from and then to ca. 375 C in a tail-gas preheater (k).
the steam turbine condenser (w) plus deminer- It is subsequently expanded in the tail-gas
alized water from the battery limit. Both streams turbine (s); this step produces ca. 70 % of the
are led to a tank and from there go through the energy 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
gauge pressure. The tank serves as suction vessel to 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
After leaving the waste-heat boiler ( j), the is withdrawn as low-pressure steam before
nitrous gas is cooled to ca. 260 C in a tail-gas admis-sion to the condensing section. This low-
preheater (k). After passing through a run of pressure steam is used in the plant or exported.
piping for oxidation, nitrous gas gives up more The rest of the steam supplied to the turbine
useful heat in the economizer (l), and its passes through the condensing section and is
temper-ature falls to ca. 210 C. After another condensed in the steam turbine condenser (w).
oxidation run, the stream is led into the air
heater (m) and cooled to ca. 180 C. The heat Dual-Pressure Process. The dual-pressure
recovered is used to preheat the primary air. process combines the favorable economics of
204 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

medium-pressure combustion with the effi- ammonia – water mixture is blown down and
ciency of high-pressure absorption. Figure 29 is fed to the ammonia stripper (b). Ammonia is
a flow sheet of such a plant with ammo-nia stripped to a residual content of ca. 2.0 % as the
combustion at 0.5 MPa and absorption at 1.1 tempera-ture is raised to 150 C with low-
MPa. pressure steam. The residue, greatly depleted in
Liquid ammonia is fed to the ammonia 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 ca.
content builds up in the evaporator. Ammonia 10 vol % ammonia. It is transported through the
evaporator II is designed so that the entire gas-mixture filter (not illustrated) to the reactor
ammonia stream can be evaporated in it, if (h). Here, ammonia reacts on the
necessary, at a maximum temperature of 20 C. If platinum – rhodium catalyst with atmospheric
the water content or the evaporation tempera-ture oxygen at 890 C to produce a 96.5 % yield of
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
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 205

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 now at least 90 % oxidized, enters the
reevaporator of the boiler. absorption tower (s). The gas first passes
The boiler system is fed with condensate from through oxidation trays that receive only a
the steam turbine condenser (x) plus deminera- slight flow of liquid, to attain the degree of
lized water from the battery limit. Both streams oxidation needed for equi-librium with 68 %
are led to a tank and then pass through the acid. In the absorption section, gas and liquid
feedwater preheater (m) to the deaerator mounted move countercurrently. Required process water
on the feedwater tank (u). The tank serves as a is pumped to the tower head. The 68 % raw
suction vessel for the feedwater pumps, which acid is withdrawn from the first absorption tray
deliver the water through the economizer (k) into and then treated with secondary air in the
the steam drum (v). bleacher (y). It is delivered to the battery limit
The water – steam mixture in the evaporator with the aid of the system pressure.
is circulated by the boiler circulation pump. Approximately 80 % of the heat generated
Saturated steam and water are separated in the by absorption is transferred to the cooling water
steam drum (v). and the remainder to the chilled water
After exiting the waste-heat boiler and pass- employed in the last part of the absorption step
ing through a run of piping for oxidation, the where very 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
er (m), mounted on the cooler – condenser inlet C 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 be
now mixed with the nitrous gas stream. The mixed used in the plant or exported. The remainder of
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-Pressure
condenser I. The gas is passed through a mist Processes. [62]. Two trends can be seen in the
collector (not illustrated) upstream of the worldwide development of weak acid
nitrous 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 the single-train plants producing up to 2000 t of nitric
preheater is cooler – condenser III (r), which the acid per day are now being built. In Europe, the
nitrous gas leaves at 50 C. The resulting acid dual-pressure design is preferred for larger plants,
condensate has a concentration of ca. 58 wt % whereas smaller ones employ the mono-
206 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

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 a pressure to yield concentrated acid. Second,
quick payout, particularly in North America. If, nitrous gases can be reacted with azeotropic
on the other hand, feedstock and energy prices are acid to form a concentrated acid that can be
very high (as in Europe), yield and energy converted easily to concentrated and azeotropic
efficiency must be maximized, so higher invest- acid by distillation. The latter product is either
ment costs are acceptable. Table 5 compares complete-ly recycled or used in the production
consumption figures per unit product for mono- of ordinary 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 dinitrogen tetroxide is produced and reacted
ammonia consumption), new facilities employ under pressure with pure oxygen and a certain
higher 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-ed,
production, but nitration processes in industrial and filtered (see Section 1.3.4.1). Evaporation
organic chemistry call for concentrated acid (98 – takes place with the aid of water heated with
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 % HNO 3 at must be drained into the steam-heated stripper
atmospheric pressure). from time to time. Air for ammonia combustion is
Concentrated nitric acid is manufactured 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 – 850 C.
produced directly in one of two ways. First, the Ammonia oxidation takes place over conventional
completely oxidized NOx can be separated in platinum – rhodium catalysts in the reactor (d).
liquid form by absorption in concentrated nitric The heat of reaction is used to
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 207

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-ing ca. 2 Final Oxidation of Nitrogen Monoxide. The
– 3 wt % nitric acid. The cooler – condenser is nitrous gases leaving the oxidation tower are
specially designed to condense as much water approximately 95 % oxidized and are led to a
as possible without much NOx absorption. Part final oxidizer ( postoxidizer) (j) where they are
of the process heat is also trans-ferred to the completely oxidized by desorption of concen-
warm water used for ammonia evaporation. The trated nitric acid. The acid moves countercur-
weak condensate generated in the cooler – rently to the nitrous gases. Water produced in
condenser is used as scrub liquor for final this reaction dilutes the concentrated acid; acid
absorption. leav-ing the postoxidizer contains ca. 75 %
HNO3. Flow control of the concentrated nitric
Oxidation of Nitrogen Monoxide. Secondary acid feed into the postoxidizer is important
air is mixed with the cooled process gas to oxidize because too high a rate lowers the output of
nitrogen monoxide to nitrogen dioxide. The concentrated acid, whereas too low a rate
amount of secondary air must be sufficient to displaces final oxidation into the absorber, with
ensure that the tail gas has a minimal oxygen the result that the concen-trated nitric acid
content (2.5 – 3.5 vol %) before it is discharged to entering the absorption tower is too dilute. The
the atmosphere. The concentrated nitric acid product gas is saturated with nitric acid vapor.
venting system is connected to the secondary air For the next step, absorption, the process gas is
intake in such a way that oxygen and nitrogen cooled to 10 C against brine in a cooler ( l).
oxides liberated on venting are recycled to the Virtually all the nitrogen dioxide is dimerized
process. The nitrogen monoxide gas and second- to dinitrogen tetroxide at this temperature.
ary air are compressed together to ca. 0.14 MPa
(f ). After further cooling (g) to remove the heat of Absorption of Dinitrogen Tetroxide. The
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 into
trays. Tube coils on the trays remove the heat of the absorber (m). The absorber consists of four
oxidation. To maintain a liquid level on all trays, sections, each packed with ceramic Raschig
208 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

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 be
bleacher and is cooled to ca. 10 C (k, u). The found only by empirical means; the ratio can be
acid leaving the absorption tower contains ca. varied to achieve optimal operating condi-tions.
25 – 30 wt % dinitrogen tetroxide and is The makeup acid used to maintain the water
pumped to the raw acid tank (o). 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. mechanical strength and corrosion resistance
The vapor is removed by scrubbing in the final are needed, but these two requirements cannot
ab-sorber (n), which consists of two sections. be satisfied by any one material. The reactor
The scrub liquor (weak nitric acid from the thus has a carbon steel jacket to provide me-
cooler – condenser) is recirculated or used to chanical strength and a pure aluminum inner
make up the 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 raw
tank (o) to the bleacher (t), which consists of a acid tank (o) and then to the bleacher.
stripping section and a reboiler. The acid enters The bleached concentrated acid is cooled to þ
the head of the tower and flows downward 30 C (u). Most of the concentrated nitric acid is
countercurrently to the nitric acid vapor, which returned to the absorption tower and final
strips nitrogen dioxide from the concentrated 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 nitric
product acid. The vapor exiting the bleacher 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 is 1. Sulfuric acid process
liquefied in the liquefier and fed to a stirred tank 2. Magnesium nitrate process
(r).
Both concentration techniques are based on
Production of Concentrated Nitric Acid. The extractive distillatfication. Weak acid is first
formation of concentrated nitric acid in the reactor produced by a conventional process (Section
(s) is described by the following equation: 1.3.4.1), then a third component is added to
4 NO2ð 2 N2O4ÞþO2þ2 H2O 4 HNO3 extract the water so that up to ca. 99 % nitric
acid can be distilled from the ternary mixture.
This requires a N2O4 – H2O molar ratio of
1 : 1 and a weight ratio of 5.11 : 1. The reaction The starting product is ordinary commercial
time can be considerably shortened if nitric acid (ca. 55 – 65 % HNO3 ). Weaker acids
dinitrogen tetroxide is present in excess. On the can be preconcentrated in a single-stage or mul-
other hand, an excess of dinitrogen tetroxide tistage process to give ca. 68 wt % nitric acid.
lowers the production rate of the reactor and Figure 31 illustrates a single-stage apparatus.
increases the dinitrogen tetroxide recycle rate, Preconcentration takes place in a continuous
resulting in higher steam consumption for countercurrent distillation tower (a), which can be
bleaching and a greater cold requirement for of either the packed or the bubble-tray type. The
dinitrogen tetroxide liquefaction. 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, and
tween 6.5 and 7. A product concentration of a reflux separator (b).
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 209

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
3
Cooling water, m 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
tration of nitric acid a) Preconcentrating tower; b) special alloys.
Separator; 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 regarded as the rectifying section, with the
t 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 A circulating evaporator system takes care of
earlier technologies that reduces steam bottom heating. The ca. 70 % sulfuric acid leav-
consumption by 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
210 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24
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-
tion, containing < 0.1 % nitric acid, is led to the
Parameter Starting HNO3
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
3
Cooling water, m 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
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 211

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
nesium nitrate than with sulfuric acid. The U.S. brown plumes of stack gas. The coloration is
view is largely that, even after the change from due to nitrogen dioxide. Some stack gases
autoclaves to continuous direct production, the contain up to 3000 ppm NOx; very old plants
equipment cost (i.e., investment cost) is too high may surpass 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 nitrous gases in water are the following [65]:
emissions from nitric acid plants. The problem
of nitrogen oxide pollution is treated in more 1. Pressure
detail in ! Air, 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
6
especially simple form of wastewater treatment Germany in 1986 totaled ca. 3 10 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 %; and
The solution from ammonia stripping con- industry, including furnaces, for ca. 9 %. Nitrogen
tains up to 10 % ammonia; it can be neutralized 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 nitrate, 1.4.2.1. Emission Limits
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
into a separate acid drain tank, and then pro- more efficient production systems, will lead to
cessed directly or indirectly. The apparatus further reductions in NOx emissions.
used for this purpose is completely separate Legislators are following this trend and
from the sewage system and thus prevents modifying pollution limits in accordance with
contamination of wastewater. changing technical capabilities.
If heat is removed by recooling systems, At the beginning of the 1980s the first
cool-ing water blowdown is fed into the general administrative regulation was issued in
wastewater system to limit thickening of the the Federal Republic of Germany under the
cooling water. Fresh water must be supplied to Federal Pollution Control Act: the Technische
compensate for the blowdown and evaporation Anleitung zur Reinhaltung der Luft (TA-Luft;
losses. Corrosion inhibitors, hardness Technical Instructions for Air Pollution Con-
stabilizers, and in some cases, biocides are also trol) [67]. This regulation and the correspond-
carried out of the system by blowdown. ing VDI guidelines [68] form the basis for
212 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

issuing operating permits. Regulations in many exceeds a rate of 30 kg/h must be equipped with
other countries are based on these guidelines. devices that continuously measure the mass
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 reduced by the relevant authorities. The
from TA-Luft 1986 [67] are ground-level concentration limits for gaseous
pollutants in air are as follows [67]: nitrogen
1. Mass of substances emitted as mass concen- dioxide, long-term exposure (IW1), 0.08
3 3 3 3
tration in units of g/m or mg/m , referred to the mg/m ; short-term exposure (IW2), 0.2 mg/m .
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 of stack gas at 1.4.2.2. Analysis
standard conditions (0 C, 101.3 kPA) before
deducting the moisture content of water vapor; The guidelines for the measurement and
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
suitable for the continuous measurement of
3. Ratio of the mass of substances emitted to
the mass of products generated or processed NOx emissions [65].
(emission factors), as mass ratio in units of kg/t Difficulties in gas sample preparation due to
or g/t. condensation are discussed in [71c – g].
Additonal apparatus-related problems occur
3 when chemiluminescence is used to measure
The usual concentration unit ppm (mL/m )
can be converted to the prescribed mass emission of moist stack gases at higher NO x
3
concen-tration (mg/m ) with the following levels. A chemiluminescence analyzer with a
3
factor [69]: 1 ppm ¼ 1.88 mg/m (based on maximum range of 0 – 10 000 ppm has been
monomeric NO2 at 101.3 kPa and 298 K and developed [72].
ideal-gas 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
3 discontinuous measurement of nitrogen oxide
0.45 g/m as nitrogen dioxide. Furthermore,
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
¼
1200 Four basic approaches are used to reduce tail-
Internal diameter of stack orifice ðdmÞ gas NOx levels: improved absorption, chemical
scrubbing, adsorption, and catalytic tail-gas
The requirement of a colorless discharge sets a reduction. Recent decades have seen intense
practical limit of < 200 ppm NOx. Older low- research and development effort invested in
and medium-pressure plants should comply these methods. More stringent environmental
with these standards by March 1, 1996. restric-tions have lent special urgency to
Plants whose emission of nitrogen monoxide development in this area. The most important
and nitrogen dioxide (as nitrogen dioxide) techniques are covered in this section.
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 213

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
The temperature of the gas between stages is suspension of magnesium carbonate and
especially important because it governs the magnesium hy-droxide [74]; solution of
prog-ress of oxidation, which is the limiting vanadium in nitric acid [75]; ammonium sulfide
quantity for the entire absorption process (see and bisulfide [76]; milk of lime [77]; ammonia
Section 1.3.2). In an already existing nitric acid [78]; hydrogen peroxide [79]; and urea [80].
plant, the options are to expand the absorption
volume and/or lower the absorption Ammonia Scrubbing is used in the United
temperature. In the first approach, large States. Goodpasture (Texas) has developed a
additional volumes only result in small safe process based on scrubbing the tail gas
reductions of tail-gas NOx levels because the with ammonium nitrate solution; nitrite
oxidation of nitrogen monoxide to nitrogen formation is suppressed by aeration and the
presence of free acid. The tail gas is then led
dioxide proceeds very slowly when the NOx
through an ammo-niacal scrub liquor, pH 7.5 –
concentration is low. The draw-back to this 8.5. The scrubbing product is a 30 – 50 %
method is that added absorption volume in ammonium nitrate solu-tion. The tail gas has a
stainless steel is very expensive. The advantage
is that it does not require any new technology. residual level of ca. 200 ppm NOx.
The absorption volume is added in the form of
a second tower; new absorption tower designs Hydrogen Peroxide Scrubbing is based on
with very few stages have been devised [73]. the following overall reactions:
The use of cold energy in the absorption NOþNO2þ2 H2O2!2 HNO3þH2O 2
process greatly accelerates oxidation of nitrogen
monoxide to nitrogen dioxide. The disadvantage NO2þH2O2!2 HNO3
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
ment. Another technique involving the use of cold hydrogen peroxide solution. The advantage of
to lower the NOx level is to cool the nitrous gas so this scrub-bing process is that the reaction time
that more dinitrogen tetroxide than nitro-gen is very fast; the disadvantage, that the hydrogen
dioxide is formed. The dinitrogen tetroxide is then peroxide scrub liquor is expensive.
scrubbed with nitric acid at ca. 0 C; it can be A solution containing 20 % urea and 10 % free
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
N2O4þ1=2 O2þH2O!2 HNO3 ca. 50 C. Both nitrogen oxides are selectively
reduced to nitrogen by urea, which decomposes to
in an absorption reactor at ca. 60 – 80 C. The yield nitrogen and carbon dioxide. The pro-cess,
technique is similar to that in concentrated developed by Norsk Hydro in Norway, has the
nitric acid production. The method is, however, advantage that urea is readily available and
more suitable for investment in a plant being relatively cheap. The resulting stack gas plume is
designed than for the expansion or upgrading of colorless but heavily laden with water vapor.
an existing 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-
214 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

trial experience is slight. A ‘‘wet’’ adsorption system preheat temperature depends directly on the
has also been developed by Cofaz (France). A fuel selected:
carbon- containing adsorbent is sprayed withwater or
dilute nitric acid and brought in contact with the tail
Natural gas 450 – 480 C
gas. This process has been installed in three Propane 340 C
monopressure plants [83]. Butane 340 C
Naphtha 340 C
Catalytic Reduction. Catalytic reduction was Hydrogen 250 C
the first method used to reduce NO x emis-
sions; as early as 1924, a patent for such a The use of hydrogen allows the preheat tem-
process was issued to FAUSER [84]. A fuel is perature to be lowered to 150 – 200 C but is
added, at a level below the flash point, to the generally too expensive.
nitrogen oxides which then react on the catalyst If the quantity of fuel is not enough to
surface to form nitrogen and water vapor. Most reduce all the oxygen, nitrogen dioxide is
fuels (e.g., hydrocarbons and hydrogen), reduced only to nitrogen monoxide. The stack
however, react preferentially with the free gas is then decolorized; in some countries, this
oxygen that is always present in tail gases from is sufficient. Complete NOx removal generally
nitric acid production. As a result, the nitrogen requires preheating, multiple fixed-bed
oxides are not destroyed until free oxygen has catalysts (with cooling between beds to prevent
been consumed. Under these conditions the overheating), and careful heat recovery to
reactions with methane can be described as offset part of the fuel cost.
Most nitric acid plants constructed or modi-
CH4þ2 O2!CO2þ2 H2O
fied by Weatherly use nonselective catalytic NO x
CH4þ4 NO!CO2þ2 H2Oþ2 N2 abatement units with tail-gas exit temperatures of
650 – 675 C. Some plants have gas exit
CH4þ2 NO2!CO2þ2 H2OþN2 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 N2þ6 H2O In the process marketed by Du Pont the tail
gas is dried, preheated, and then heated in two
6 NO2þ8 NH3!7 N2þ12 H2O NOþNO2þ2 NH3!2 N2þ3 stages. The gas is subsequently divided into
two streams. One substream is heated further,
H2O mixed with methane, and led over the first
fixed-bed catalyst. The second substream is
4 NOþO2þ4 NH3!4 N2þ6 H2O
mixed with methane without further heating
and led over the second fixed-bed catalyst,
Catalytic reduction processes are accordingly along with the first substream. Hot tail gases
classified as nonselective or selective. exit the bottom of the reactor and are led
Catalysts for nonselective reduction process- through the tail-gas expansion turbine, which
es are usually based on platinum, vanadium recovers part of the work of 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 this temperature after reduction is significantly low-er,
process are carbon monoxide ( 1000 ppm) and allowing the use of simpler, cheaper construc-tion
hydrogen cyanide. When hydrocarbon fuels are materials. The optimal catalyst service
used, the tail gas must be preheated before the temperature is 250 – 350 C, but operation at up to
reaction on the catalyst proceeds at all. The 500 C is possible. The costs due to the use
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 215

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
3
37 000 m /h (STP) operating at a pressure of
730 kPa with an inlet NO x concentration of
500– 1000 ppm, this process (270 C) gives an
exit concentration of 50 – 150 ppm NOx. The Figure 34. BASF tail-gas reactor for NO x reduction a) Hole
treated tail gas contains < 20 ppm ammonia plate; b) Catalyst; c) Wire gauze
(usually ca. 5 ppm), and the nitrogen dioxide
level is 30–50 ppm. The stack gas is generally
colorless. Careful temperature monitoring at the Essen uses a chromium oxide catalyst with a
tail-gas expansion turbine and measurement of service temperature of 265 – 350 C. The ni-tric
the ammonia level can prevent the deposition of acid plant planned for DSM Miststoffen
ammonium nitrate. To minimize the pressure (Geleen, Netherlands) is designed for a tail-gas
3
drop, the reactor features an annular design stream of 76 000 m /h (STP) with a maximum
with 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 the strict emission limit of < 100 ppm, the cata-
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 %
14 plants with the BA\varphiSF process. The over the first bed, 20 % over the second, and 10
tail gas, usually containing 500 – 1000 ppm % over the third catalyst bed.
NOx, is heated to about 260 C. Ammonia gas is Other companies also have selective catalytic
added to the tail-gas stream in a mixer and then reduction processes for nitric acid tail gases. For
led through the reactor. The pressure drop is ca. example, Mitsubishi Chemical has developed a
25 kPa. The effluent meets the requirement of process operating at 400 – 500 C under pres-sure
colorlessness. [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.
216 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

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 % HNO 3 empha-
catalysts are the same ones employed in nonse-
lective processes, except that the fuel is size the associated hazards ( poisoning by
replaced by ammonia. inhalation of vapors, danger of chemical burns
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-
forschung – Uhde process for simultaneous age, as well as an eyewash bottle with pure
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 with
boiler, i.e., downstream of the air preheater and sawdust or other flammable material (be-cause
electrostatic filter. It employs the adsorp-tive of the fire hazard); instead, its spread must be
and catalytic properties of ‘‘activated coke’’ at prevented by the construction of earth barriers.
50 – 150 C. The reducing agent is again
gaseous ammonia. The technique com-bines a
selective catalytic process for NO x and an 1.6. Uses and Economic Aspects
adsorptive one for sulfur dioxide. The 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 (ca. 60
As a rule, nitric acid is stored in stainless steel
tanks and transported in stainless steel % HNO3 ) is most suitable for this purpose.
containers. Smaller amounts of weak acid are used to
The regulations for transport by rail [91], [92] digest crude phosphates. About 75 – 85 % of
and road [93], [94] differentiate among > 70 % the nitric acid produced is used in the fertilizer
nitric acid, 55 – 70 % nitric acid, and < 55 % sector. In addition, porous ammoni-um nitrate
nitric acid, and also between mixtures with sul- prills are still an important compo-nent of
furic acid (‘‘mixed acid’’) containing > 30 % explosives (! Explosives, Section 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).
IMDG Code Class 8, D 8261, E – F 8186 It is also used in the production of adipic acid (!
UN No. 2032 Adipic Acid, 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
6
IMDG Code Class 8, D 8260, E – F 8185 26.882 10 t, representing a slight in-crease of
UN No. 2031 ca. 4 % over 1976. Production in industrialized
RID/ADR Class 8, no. 2 b countries has stagnated or even declined, but in
CFR 49: 172.101, Cor. M
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 6
follow (10 t):
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 217

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
4.5 10 . The acid is stable only in cold dilute
aqueous solution. It can be prepared as follows:
BaðNO2Þ2þH2SO4!2 HNO2þBaSO4

On heating in the presence of sand, glass

splinters, or other sharp-edged objects, or even
at low temperature, it disproportionates as
3 HNO2 HNO3þ2 NOþH2O
Figure 35. The system N2O3 – H2O a) Ice; b) Homogeneous
This disproportionation reaction influences
the properties of nitrous acid solutions and is liquid, water þ dinitrogen trioxide; c) Liquid phase, two layers;
important in the production of nitric acid. d) Homogeneous liquid, dinitrogen trioxide þ water
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 These structures lead to two series of indus-
( NO2, NO, H2N2O2, NH3 ) by alkali amalgams or trially important organic derivatives:
by 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 N2O3þH2O
An especially important property of nitrous
Aqueous solutions of the acid appear acid is its ability to diazotize organic amines. With
colorless but take on an increasingly blue primary amines, the acid forms diazonium salts:
coloration at 5 % dinitrogen trioxide.
R NH2þHNO2þHCl!½R N N&Clþ2 H2O
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 of azo dyes (! Azo Dyes, 1. General).
a high water content and a heavy layer with a With secondary amines, nitrosamines are
high dinitrogen trioxide content. formed:
218 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

R2 NHþHNO2!R2 N NOþH2O The compounds listed above are described in

more detail in order of their oxidation state. Table
Ammonia and urea react with nitrous acid to
yield nitrogen: 8 lists their most important physical properties.

NH3þHNO2!N2þ2 H2O
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 pressure), dinitrogen monoxide [10024-97-2],
consid-ered as a class and called nitrogen
al-so called nitrous oxide, N2O, Mr 44.01, is a
oxides (often denoted as NOx ).
colorless gas with a weak, pleasant odor and a
The known oxides and their equilibrium sweetish taste. If inhaled, it can bring about a
reac-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:
NH4NO3!N2Oþ2 H2O

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

NO NO
Compound N2O NO NO2 /N2O4 2 3 2 5

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
3
rCr, kg/m 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 kg 1 K 1 0.879 0.996 1.326 0.862 0.778
Standard enthalpy of formation
0
DHF , 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 m 1 K 1
Gas (25 C, 101.3 kPa) 0.01718 0.02573 0.1124
 Liquid (20 C, 101.3 kPa) 0.1336
*
Sublimation point.
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 219

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, in monia in the gas space neutralizes any entrained
contrast, ammonium nitrate can be decom-posed acidic constituents, and this reaction heats the
in aqueous solution containing chlorides and nitric lower part of the tower (b). The hot gas is cooled
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
catalytically useful amounts of metal ions (man- not 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
the reaction raises the temperature to 100 – saving and produces dinitrogen monoxide free
160 C. The solution contains 15 – 35 % nitric of harm-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, it
[99] a) Decomposition flask; b) Scrubbing tower; c) Ammo- is oxidized to nitrogen dioxide, a brown vapor.
nium nitrate distributor; d) Heat exchanger; e) Evaporator For physical properties, see Table 8.
220 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

Nitrogen monoxide is at dynamic rous acid in the Glover tower, to yield nitrogen
equilibrium with its dimer: monoxide and sulfuric acid.
2 NO N2O2 DH ¼ 10:5 kJ=mol
With aqueous iron sulfate solutions, nitrogen
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 a
IMDG Code Class 2, D, E – F 2095
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
valence electrons and thus, like all gases with an odor; for physical properties, see Table 8. It is
odd number of electrons, is paramagnetic. in equilibrium with its dimer, dinitrogen
Laboratory preparation usually involves the tetroxide [10544-72-6], also called nitrogen
reaction of moderately concentrated nitric acid peroxide, N2O4, Mr 92.01. The equilibrium is
with copper: strongly temperature dependent; at higher
8 HNO3þ3 Cu 3 CuðNO3Þ2þ4 H2Oþ2 NO temperature (ca. 100 C), it is shifted almost all
the way toward nitrogen dioxide.
Nitrogen monoxide is very reactive and can, 2 NO2 N2O4 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:

N2þO2!2 NO DH ¼ 90:4 kJ=mol 2 NO2 2 NOþO2 DH ¼ 144:1 kJ=mol

This reaction goes to completion at 650 C.

Figure 37 illustrates the dissociation of dinitro-
In acidic solution (e.g., chromic acid, acidified
gen tetroxide and nitrogen dioxide as a function
permanganate solution, hydrochloric acid),
of temperature.
nitrogen monoxide is oxidized to nitric acid. The
combustion of nitrogen (Birkeland – Eyde, The following values for the equilibrium
Sch€onherr, Pauling processes) was formerly an con-stant of the bidirectional reaction are given
important method of industrial nitric acid pro- in [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-
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 221

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:

IMDG Code Class 2, D 2213, E – F 2099

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 of acrylates. It is also used in the
Figure 37. Dissociation of dinitrogen tetroxide and nitrogen
dioxide manufacture of explosives, as a rocket
propellant, and as a bleach.
Dinitrogen tetroxide can be prepared in two For details on the chemistry of liquid
structures, 1 exists at room temperature and is dinitro-gen tetroxide, see [103].
in 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 pale
an odd-electron compound and therefore para- blue crystals. For physical properties, see Table
magnetic; dinitrogen tetroxide is diamagnetic. 8.
To reach an even electron number, nitrogen Even below 0 C, dinitrogen trioxide dissoci-
þ
dioxide can give up an electron (NO 2, ates to a considerable extent:
nitronium ion) or gain one (NO2 , nitrite anion).
N2O3ðgÞ NOþNO2 DH ¼ 40:58 kJ=mol
Industrial production of NO2 – N2O4 em-ploys
the Ostwald process (catalytic combustion of
ammonia) and constitutes the initial step in the 2 N2O3ðgÞ 2 NOþN2O4 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-ride dinitrogen trioxide (as ON NO 2 [104]). This
yielding chlorine, and the treatment of sodi-um dissociation means that a well-defined boiling
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 N2O3
222 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

However, because nitrogen dioxide is present place concentrations [108], [109]: MAK value
mainly as the dimer, a eutectic of nitrogen mon- 3
10 ppm (25 mg/m ); TLV-TWA 2 ppm (5.2
oxide and nitrogen dioxide can be postulated 3
mg/m ); TLV-STEL 4 ppm (10 mg/m ).
3
[105] with the empirical composition NO1.56. Nitric acid reacts with and causes spontaneous
The equilibrium constant for the reaction has ignition of organic substances such as wood
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 (S
acid production. As much as 4 vol % of the warnings) are given in [109].
NOx may be present as dinitrogen trioxide. The
triox-ide is used in preparing high-purity alkali Nitric acid > 70 %
nitrites from alkali. It also finds use as an R 8: Danger of fire when in contact with
oxidizing agent in special fuel systems. flammable substances
R 35: Causes severe burns
S 23: Do not inhale vapor
3.5. Dinitrogen Pentoxide S 26: In case of contact with eyes, flush eyes
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
In the solid state, dinitrogen pentoxide has Mixtures of nitric acid (> 30 % HNO3 ) and sulfuric acid
þ (nitrating acid)
a salt-like structure [NO2] [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 N2O5!4 NO2þO2
Protective clothing should be worn to
Dinitrogen pentoxide can be prepared by prevent contact with the skin. The acid must be
treating nitric acid with phosphorus pentoxide. kept away from children. In case of burns, the
It has strong oxidizing properties and reacts affected area should be washed with copious
vigorously with organic substances. With amounts of water and a doctor should be
water, the hygroscopic crystals form nitric acid: consulted. Skin burns itch and become yellow
due to the formation of xanthoproteins.
N2O5þH2O!2 HNO3 DH ¼ 37:66 kJ=mol
Death may occur if large areas of skin are
With boron trifluoride, it forms a binary burned. Since regulation of the body
com-pound N2O5 – BF3 that is stable at room temperature is disturbed, the patient must be
temper-ature. This compound is a good kept warm. Protein enters the bloodstream and
nitrifying agent. Nitrogen pentoxide has not the patient may suffer from shock, appropriate
become important in industry. preventive measures must therefore be taken. In
case of contact with the eye, the eyelids must
be opened and the eye washed with copious
4. Toxicology and Occupational amounts of 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
safety regulations stipulate the following work- B, E, or NO filter is recommended.
Vol. 24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides 223

Oral consumption of nitric acid leads to References

attack of the mucous membranes of the mouth,
the esophagus, and the stomach. Shock may 1 J. Brunborg, P. B. Holmesland in C. Keleti (ed.):
result. If concious, the patient should drink Nitric Acid and Fertilizer Nitrates, Marcel Dekker, New
lukewarm water to dilute the acid. York-Basel 1985, pp. 1 – 164.
2 H. Chilton: Strong Water, The M.I.T. Press,
Cambridge, Mass. 1968.
Nitrous Acid. Nitrous acid is toxic because it 3 Ullmann, 3rd ed., 15, 3 – 67
decomposes to form nitric acid and nitrogen 4 E. M. Horn, H. Keiser, K. Schoeller, Monatsh. Chemie
monoxide. 118 (1987) 1205 – 1218.
5 Ullmann, 4th ed., 20, 305 – 332.
Nitrogen Monoxide. Pure nitrogen mon- 6 S. A. Stern, J. T. Mullhaupt, W. B. Kay: ‘‘The
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reacts, however, with hemoglobin to form 7 A. F. Hollemann, E. Wiberg: Lehrbuch der anorga-
methemoglobin, resulting in cyanosis and pos- nischen Chemie, 81st – 90th ed., De Gruyter, Berlin 1976.
sibly death. The TLV-TWA value is 25 ppm 8 Y. Fogel et al., Kinet. Katal. 5 (1964) 496 – 504.
3
(31 mg/m ). 9 E. J. Nowak, Chem. Eng. Sci. 21 (1966) 19 – 27.
10 T. Pignet, L. D. Schmidt, J. Catal. 40 (1975) 212–225.
11 G. Nettesheim, Chem. Ing. Tech. 41 (1969) 773 – 775.
Nitrogen Dioxide. Nitrogen dioxide is an
3 12 Nitrogen 183 (1990) 27 – 32.
irritant gas. Its MAK value is 5 ppm (9 mg/m ),
3 13 S. P. S. Andrew in C. Keleti (ed.): Nitric Acid and
TLV-TWA 3 ppm (5.6 mg/m ), TLV-STEL Fertilizer Nitrates, Marcel Dekker, New York-Basel 1985,
3
5 ppm (9.4 mg/m ). Inhalation of nitrogen diox- pp. 31 – 40.
ide causes pulmonary edema which may result in 14 Johnson Matthey, DE 3 042 362, 1988 (D. J. Stephan-
death (lethal dose 200 ppm). The substance is only son, A. E. Heywood, G. L. Selman).
slightly water-soluble but highly lipid-soluble. It 15 Johnson Matthey, DE 3 039 286, 1981 (A. G.
Knapton, G. L. Selman).
therefore penetrates the alveoli where it damages
16 Johnson Matthey, EP 0 275 681, 1988 (J. R. Handley).
the capillary walls resulting in exu-dative
17 A. R. McCabe, G. D. W. Smith, Platinum Met. Rev.
inflammation. The respiratory tract is obstructed 27 (1983) no. 1, 19 – 25.
due to formation of foam. Concentra- 18 J. K. Bradley, G. Drake: ‘‘Nitric Acid Technology,’’
tions exceeding 60 – 150 ppm produce Paper read before the Fertiliser Society of London, 15th
coughing and a burning sensation in the chest. October 1981.
Pulmonary edema becomes apparent after 2 – 19 R. M. Heck, J. C. Bonacci, W. R. Hatfield, T. H.
24 h. The patient suffers respiratory distress Hsiung, Ind. Eng. Chem. Process Des. Dev. 21 (1982) 73 –
79.
and insomnia. Chronic exposure to low doses
20 A. J. Fischer, M. A. Lang: ‘‘Engelhard’s Role in
results in coughing, headache, loss of appetite, Advancing Nitric Acid Catalyst Technology,’’ Paper read
and gastrointestinal disorders. Patients should before The British Sulphur Society, 14th Int. Conference,
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3
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224 Nitric Acid, Nitrous Acid, and Nitrogen Oxides Vol. 24

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