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4 HNO3 −→ 2 H2 O + 4 NO2 + O2
HNO3 concentration, wt % Density (20 ◦ C), g/cm3 mp, ◦ C bp, ◦ C Partial pressure (20 ◦ C), kPa
HNO3 H2 O
tion at 900 – 1400 kPa. Some older plants still atomic oxygen adsorbed on the catalyst to yield
employ atmospheric combustion and medium- hydroxylamine. This in turn reacts with molec-
pressure absorption. ular oxygen to form nitrous acid, which then
Intensive work on ammonia combustion as dissociates to nitrogen monoxide and hydroxyl
well as the oxidation and absorption of nitro- ions:
gen oxides has been well documented since the
early 1920s. Up to now the combustion of am- O2
2 O (adsorb.)
monia has been considered as a heterogeneous O (adsorb.) + NH3 −→ NH2 OH
catalytic surface reaction with undesirable side
reactions. The oxidation of nitrogen monoxide NH2 OH + O2 −→ HNO2 + H2 O
is a rare example of a homogeneous third-order HNO2 −→ NO + OH−
gas-phase reaction. The absorption of NOx is a
heterogeneous reaction between fluid (i.e., gas 2 OH− −→ H2 O + O
and liquid) phases. In oxidation experiments under high vacuum,
Bodenstein and coworkers detected both hy-
droxylamine and nitrous acid as intermediate
1.3.1. Oxidation of Ammonia products on the platinum catalyst. Later studies
with a mass spectrometer showed that no such
The oxidation of ammonia to nitrogen monoxide intermediate products are found above 400 ◦ C
is described by the equation [8]. In these tests, both molecular and atomic
4 NH3 + 5 O2 −→ 4 NO + 6 H2 O ∆H = −904 kJ/mol (4) oxygen was found on the catalyst surface. A di-
rect reaction between oxygen and ammonia was
Over a suitable catalyst, 93 – 98 % of the feed therefore postulated according to the following
ammonia is converted to nitrogen monoxide. equations:
The remainder participates in undesirable side
reactions leading to dinitrogen monoxide (ni- NH3 + O2 −→ NO + H2 O + H
trous oxide, laughing gas)
NH3 + O −→ NO + H2 + H
4 NH3 + 4 O2 −→ 2 N2 O + 6 H2 O
∆H = −1105 kJ/mol (5) In fast reactions such as the combustion of
ammonia (the reaction time for Eq. 4 is ca.
and to nitrogen 10−11 s), however, the possible intermediates
4 NH3 + 3 O2 −→ 2 N2 + 6 H2 O ∆H = −1268 kJ/mol(6) most likely cannot be detected because they are
very short-lived and present in very low concen-
Other undesirable reactions are the decomposi- trations. Nowak [9] has compared the numer-
tion of the nitrogen monoxide product ous theories of ammonia combustion. Pignet
2 NO −→ N2 + O2 ∆H = −90 kJ/mol (7)
and Schmidt present a classical Langmuir –
Hinshelwood treatment of the process [10]. The
and its reaction with ammonia possibility that the combustion of ammonia may
be considered as a homogeneous catalytic reac-
4 NH3 + 6 NO −→ 5 N2 + 6 H2 O
tion is now being discussed.
∆H = −1808 kJ/mol (8)
At low temperature (200 – 400 ◦ C), the rate
of ammonia oxidation is limited by the reac-
tion kinetics. The byproducts nitrogen, and es-
Reaction Mechanism. Early theories of the pecially dinitrogen monoxide, are formed pref-
mechanism for the oxidation of ammonia dif- erentially. Between 400 and 600 ◦ C, the reaction
fered as to which intermediate product was rate 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 ammo-
(imide theory, 1927), and Bodenstein (hy- nia through the gas film to the catalyst surface.
droxylamine theory, 1935) [3]. According to The product in this reaction regime is nitrogen
the hydroxylamine theory, ammonia reacts with monoxide.
Nitric Acid, Nitrous Acid, and Nitrogen Oxides 5
The catalyst surface experiences a very low Precious-metal catalysts are usually em-
partial pressure of ammonia and a diminished ployed in the form of closely stacked, fine-mesh
partial pressure of oxygen due to mass-trans- gauzes. At the beginning of a campaign they
fer limitations. The catalytic side reaction bet- have a smooth surface and therefore only slightly
ween ammonia and nitrogen monoxide is accel- limit mass transfer in the gas phase. This gives an
erated by an increase in the partial pressures of initially lower yield of nitrogen monoxide. Af-
both species on the catalyst surface. If catalyst ter a short time in service, however, the surface
poisoning occurs,the number of active centers area of the catalyst increases greatly because
decreases and the partial pressure, particularly of microstructural changes and interactions with
that of ammonia, increases at the remaining ac- volatilizing constituents of the catalyst (Fig. 3).
tive centers. The result is increased formation of Catalyst growth increases the limitation of mass
undesirable byproducts. In practice, this shift is transfer in the gas phase and thus the yield of
offset by raising the temperature, i.e., the reac- nitrogen monoxide.
tion is again displaced into the region limited by
gas-film diffusion. 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 ra-
tio is, however, employed for a variety of rea-
sons, the most important being that conversion
decreases with too high a ratio; ammonia and
air also form an explosive mixture. Because the
mixing of ammonia and air in industrial prac-
tice is incomplete, locally higher ratios may oc-
cur. A ratio that includes a safety margin be-
low the explosion limit is therefore necessary.
The explosion limit declines with pressure so
that high-pressure burners can operate with up
to 11 % ammonia, whereas 13.5 % ammonia is
possible in low-pressure systems. The explosion
limit also depends on the flow velocity (Table 2,
see also [3]) and the water content of the reaction
mixture [11].
Table 2. Explosion limits of ammonia – air mixtures at
atmospheric pressure
0 15.5 27.5
3 28 38
5–8 30 40
12 32 37
14 none none
nitrogen monoxide decreases because of the slip crease greatly (Fig. 5). The usual way to main-
(leakage) of ammonia which reacts with it ac- tain the conversion toward the end of a campaign
cording to Equation (8). If the gas velocities are in spite of catalyst deactivation and losses, is
too low or too many gauzes are used, decompo- to raise the temperature. The ammonia – air ra-
sition of nitrogen monoxide according to Equa- tio is directly related to the reaction tempera-
tion (7) is promoted. Table 3 gives typical gas ture: a 1 % increase in the proportion of ammo-
velocities. nia increases the temperature by ca. 68 K. If the
temperature is too low, conversion to nitrogen
monoxide decreases. The reaction temperature
also depends on the temperature of the inlet gas
mixture. The following formula provides an ap-
proximate value in ◦ C:
the metal surface becomes enriched in rhodium, inum loss. Catalyst poisons include iron oxide
thus improving catalytic activity [17]. Because (rust) and dust in the process air, which is es-
rhodium is more expensive than platinum, a rho- pecially concentrated in the vicinity of fertilizer
dium content of 5 – 10 % has proved optimal. plants. Any material deposited on the catalyst
Figure 6 shows the efficiency of conversion to surface acts as a poison. A multistage filter is
nitrogen monoxide and the platinum loss as a used to prevent these substances from reaching
function of the rhodium content of the alloy [18]. the catalyst (see Section 1.3.3.1).
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:
Pt + O2 −→ PtO2 (g)
where H NO is the Henry coefficient for nitrogen kg = gas-side mass-transfer coefficient, m/s
monoxide in m3 atm/kmol and c ist the concen- po = partial pressure in the bulk gas, atm
tration in kmol/m3 . The rate constant is defined pi = partial pressure at the interface, atm
by At higher NO2 /N2 O4 concentrations in the reac-
6200 tion gas, primarily dinitrogen tetroxide crosses
logk= − + 20.1979 (25)
T the interface and reacts in the fast first-order re-
action (Eq. 20) to form nitric and nitrous acids.
Equations (23) and (25) were derived by Hoff-
Nitrous acid dissociates (Eq. 21), and the result-
mann and Emig [31] and are based on experi-
ing nitrogen monoxide is transported back into
mental data from [32].
the gas space.
The following equation can be written for the
Mass Transfer. For more than 50 years sci-
absorption rate of dinitrogen tetroxide [34]:
entists have studied the transport of nitrogen ox- q
ides in water and in dilute and concentrated ni- JN2O4 =HN2O4 pN2O4 kDN2O4 (27)
tric acid. A variety of mechanisms have been
proposed depending on the gas composition and where
the acid concentration. These are partly in agree- H = Henry coefficient, m3 atm/kmol
ment with the absorption model of Figure 8. k = rate constant, s−1
In the NOx absorption region important for D = diffusion constant, m2 /s
acid formation, dinitrogen tetroxide transport is
Numerous measurements in laboratory ab-
considered to be the rate-limiting step. The quan-
sorbers support this mechanism. Interpretations
tity of dinitrogen tetroxide transported from the
of measurements in absorption columns have
bulk gas to the interface depends chiefly on the
given the following correlations for the mass-
NO2 – N2 O4 equilibrium [28,33]:
transfer coefficients [35]:
kgNO2 o
JN2O4 = pNO2 − piNO2 1) Bubble-cap trays
2RT
kgN2O4 o
+ pN2O4 − piN2O4 (26)
RT
where
J = absorption rate, kmol m−2 s−1
Nitric Acid, Nitrous Acid, and Nitrogen Oxides 11
nitric acid and water. Up to a nitric acid concen- pN ˜O2 =pNO2 + 2pN2O4 (36)
tration of 65 wt % and an inlet nitrogen oxide
partial pressure of 100 kPa, however, the vapor The nitrogen dioxides, considered as completely
pressures from the binary system HNO3 – H2 O dissociated, are assumed to react according to
can be used to determine K 2 (Fig. 9).
Figure 10 shows how K 1 depends on the
acid concentration and the temperature. This pa- This hypothetical reaction leads to the equilib-
rameter is particularly interesting from an en- rium relation
gineering standpoint because it allows the acid
strength to be determined if the gas concentra- Kp =K1 ·K2
tion is known. pNO p2
If the equilibrium is based on the overall re- whereK1 = 3
and K2 = HNO3 (38)
p ˜ pH2O
action N O2
y ∗i = mole fraction of i-th component in liq- each phase, so that the temperature may differ in
uid phase at the phase boundary both phases of a single stage. The mathematical
ν = stoichiometric coefficient treatment of this model is described in [52].
Analogously for the liquid phase (subscript l)
come overloaded and cause an excessive pres- excesses in the burner are a risk for plant safety
sure drop. Filter life depends on the particulate (explosion limit) and may also cause overheat-
load in the air (typically 0.8 mg/m3 ). In areas ing of the catalyst gauze. Poor mixing lowers the
where sandstorms may occur (maximum load- conversion of ammonia to nitrogen monoxide
ing 500 mg/m3 ), the use of a sand separator and increases platinum loss from the catalyst.
(a centrifugal collector) as a prefilter is recom- The efficiency of a given mixing operation is
mended. described by the standard deviation σ of mea-
sured samples from the theoretical value x̄ a cer-
Ammonia Filters. The liquid ammonia fil- tain distance downstream from mixing. In nitric
ter removes solid contaminants, especially small acid plants, the deviation should be < 1 %. If the
rust particles; 99.9 % of all particles larger than theoretical ammonia concentration in a mixture
3 µm should be eliminated. Selection of a liq- is 10 %, for example, measured values fluctuate
uid ammonia filter requires consideration of the between 9.9 and 10.1 % [54]. Only static mix-
fact that traces of oils and chlorides are also ers are used (e.g., the Uhde tubular mixer or the
present in ammonia. Proven filter materials are Sulzer three-element mixer).
Teflon and sintered metals. Polypropylene and
ceramic filter candles (cartridges) are also em-
ployed. Magnetic filters have found some use 1.3.3.2. Burners and Waste-Heat Boilers
but have limited capacity.
Filtration of ammonia gas should remove
99.9 % of oil and solid particles larger than
0.5 µm. The principal filter media are glass
fibers, sintered metals, and ceramics. The pres-
sure drop is up to 10 kPa, depending on filter
type.
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
The heat of reaction liberated during am- tects the downstream superheater against exces-
monia combustion is utilized to produce steam sive temperature. The superheater is followed by
and preheat the tail gas. Steam is produced in a the main evaporator. Evaporator tubes are also
waste-heat boiler located immediately below the installed at the wall to cool it and protect it from
burner (Fig. 15). The burner consists of a burner excessive temperature.
basket packed with filling material to ensure uni- Figure 16 shows how heat from the waste-
form distrubution of the downward flowing reac- heat boiler is used to raise steam. Boiler feed-
tion gas. Platinum recovery gauzes ( page 7) are water is led through the economizer (b) into a
located above the filling material. The catalyst steam drum (c). Water at thermal equilibrium
gauzes ( page 6) are located above the recovery with the steam is pumped from the drum through
gauzes. The burner basket is clamped between the evaporators. Steam from the drum goes first
the flanges of the burner head and the waste- to the lower superheater (g) and is then cooled
heat boiler. To ensure better distribution of the in the drum so that the desired temperature can
reaction mixture, the burner head also contains be attained in the upper superheater (f).
a perforated plate or honeycomb grid. Hydro- Systems with an economizer integrated in the
gen burners rotating above the surface are of- waste-heat boiler have also proved serviceable
ten used for ignition. The gauze temperature is (Fig. 17, see next page). Here, as in the waste-
measured, and the space above the gauze can be heat boiler of Figure 15, the heat-exchanger
observed through inspection glasses. The gauzes tubes can be arranged spirally in disk form or
glow bright red during catalysis. The throughput in a square pack.
per element can produce up to 1200 t of 100 % A shell-and-tube evaporator with natural cir-
nitric acid per day. culation can also be used (Fig. 18, see next page).
Waste-heat boilers up to 6 m in diameter are The superheater tubes (e) are again arranged as
used. Figure 15 shows a waste-heat boiler for a flat spiral. These waste-heat boilers are partic-
medium-pressure burning. The preevaporator is ularly suitable for smaller plants or those using
located directly below the burner basket and pro- low steam pressure.
18 Nitric Acid, Nitrous Acid, and Nitrogen Oxides
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 20 shows a medium-pressure pro- for these two devices comes from a multistage
cess (400 – 600 kPa), as preferred for small- tail-gas turbine (e) and a steam turbine (f) or
or medium- capacity plants (≤ 600 t/d 100 % electric motor. These systems are preferred for
HNO3 ). The machinery for this process includes large- capacity plants (≥ 400 t/d 100 % HNO3 ),
a radial or axial air compressor (a) without in- especially in Europe.
terstage cooling, a single-stage tail-gas turbine High-pressure plants (Fig. 22) are preferred
(d), and a steam turbine (e) or electric motor. in the United States because of lower investment
A dual-pressure process with medium-pres- costs. The machinery includes an air compres-
sure combustion and high-pressure absorption sor with interstage cooling. Radial devices are
calls for both an air compressor and nitrous gas generally used, but the low-pressure section in
compressor (Fig. 21). The air for combustion is larger machines may be axial. The tail-gas tur-
delivered at 400 – 600 kPa by an uncooled radial bine is usually a multistage reaction machine.
or axial air compressor (a). The radial nitrous The nitrous gas compressors are virtually al-
gas compressor (c) produces the 1.0 – 1.2 MPa ways of radial design, but axial machines are
pressure needed for absorption. The drive power available. The design and operation of the com-
20 Nitric Acid, Nitrous Acid, and Nitrogen Oxides
Figure 21. Flow sheet of a nitric acid process with medium-pressure combustion and high-pressure absorption
a) Air compressor; b) Reactor with waste-heat recovery system; c) Nitrous gas compressor; d) Absorption tower; e) Tail-gas
turbine; f) Steam turbine; g) Cooling system; h) Heat exchanger network
Figure 22. Flow sheet of a nitric acid process with high-pressure combustion and high-pressure absorption
a) Air compressor; b) Reactor with waste-heat recovery system; c) Absorption tower; d) Tail-gas turbine; e) Steam turbine;
f) Heat exchanger network; g) Interstage cooler
pressors must take particular account of the fol- highly toxic, it must not be allowed to escape
lowing properties of the gas stream: from the compressor. The machine is therefore
1) Nitrites and nitrates may be formed equipped with air-purged labyrinth seals. Chem-
2) The nitrous gas is toxic and highly corrosive ical reactions must be considered in the design
3) Chemical reactions take place when nitrous of nitrous gas compressors. The endothermic
gas is compressed dissociation of dinitrogen tetroxide to nitrogen
dioxide removes heat from the stream [56] and
When the nitric acid plant is started up or can cool the gas by 20 ◦ C or more.
in continuous operation, unreacted ammonia is Because of their large capacities, modern ni-
present in the burner exit gas. The level in con- tric acid plants usually employ axial air com-
tinuous operation is ca. 30 ppm of ammonia. As pressors. The possibility of surging in the com-
a result, nitrates and nitrites would accumulate pressor, especially during plant start-up, requires
in the nitrous gas compressor if they were not the installation of appropriate surge protection.
removed regularly. If the temperature exceeds Adjustable inlet guide vanes allow operation at
240 ◦ C, combustion or explosion is possible. To various plant capacities.
avoid an explosion, water or steam is briefly Tail-gas turbines can be single-stage or mul-
sprayed into the suction of the nitrous gas com- tistage devices of axial or radial design. For part-
pressor every 8 h [55]. Because nitrous gas is
Nitric Acid, Nitrous Acid, and Nitrogen Oxides 21
load operation, these machines are equipped condensate has a concentration of, for exam-
with a group of valve-controlled nozzles or ad- ple, ca. 40 wt % at medium pressure. Suitable
justable guide vanes in the inlet. materials of construction are discussed in Sec-
Steam turbines may be condensing or back- tion 1.3.3.5. The thermal design of a gas cooler –
pressure machines with or without an extrac- condenser is difficult because the cooling step
tion/side stream. involves chemical reactions in both the gas and
the condensed liquid phases. In the apparatus
shown in Figure 24, nitrous gas passes into the
1.3.3.4. Heat Exchangers and Columns shell side through two inlets; each of the par-
tial streams reverses direction four times. Heat
Heat Exchangers. The shell-and-tube de- is absorbed by cooling water.
sign predominates for tail-gas heat exchangers,
with hot nitrous gas on the tube side and cool tail Absorption Tower. Absorption tower design
gas on the shell side. The pressure drop should is governed by the calculations for the oxida-
be kept as low as possible to secure a favorable tion process (i.e., tower height, see also Sec-
energy balance for the plant as a whole. tion 1.3.2) and thermal design. Because oxida-
tion proceeds more slowly as the NOx content in
Ammonia Evaporator. Various types of the tower decreases, the spacing between plates
equipment can be used for ammonia evapo- increases. Figure 25 shows an absorption tower
ration. Figure 23 shows a shell-and-tube heat for a plant with a daily production capacity of
exchanger with mist collector. Cooling water 1830 t of 100 % nitric acid. Acid formation takes
on the tube side is cooled on evaporation. In place chiefly in the bottom third of the tower,
medium-pressure plants, the heat of vaporiza- whereas NOx is reduced in the upper two-thirds.
tion is also taken from chilled water used as As a result, most of the heat must be withdrawn
coolant in the absorption step. The shell-side in the lower third; this is done with cooling coils
heat-transfer coefficients for ammonia can be on the plates. The coils on the upper plates pri-
calculated according to [57]. marily cool the nitrogen monoxide gas against
chilled water, because oxidation proceeds faster
Gas Cooler – Condenser. In the cooler – at lower temperature. Most modern absorption
condenser, the temperature is lowered below the towers have sieve plates. Compartments built
dew point of the inlet nitrous gas. The nitric acid into the bottom of the tower separate acid of
medium strength from weak acid in case of plant
22 Nitric Acid, Nitrous Acid, and Nitrogen Oxides
Figure 24. Cooler – condenser with feedwater preheaters attached to nitrous gas inlets
of these steels decreases with increasing tem- the passive region E p (see Section 1.2) is reached
perature. Normal austenitic steels are generally sooner. Furthermore, chromium lowers the cor-
not stable above 70 %. The chromium content rosion rate in the passive state and raises the
determines the corrosion resistance; its anticor- transpassive potential E tr . The last point is im-
rosive action is influenced by the carbon con- portant because the corrosion potential of stain-
tent of steel. The chromium in the alloy forms less steel in strong (highly concentrated) nitric
a carbide (Cr3 C2 ) at the grain boundaries; only acid often reaches the limit of the transpassive
small amounts of free chromium remain at high potential. In the transpassive range the passive
carbon contents, and the steel is therefore less layer starts to dissolve. A steel with too lit-
corrosion resistant. If excess chromium remains tle chromium or with elements that lower the
after the amount needed for carbide formation transpassive potential tends to corrode at a high
is consumed, only this excess is responsible for rate [58].
the anticorrosion properties. Steels of a given specification behave differ-
ently under nitric acid attack because of per-
mitted batch-to-batch variations in composition.
The only way to be sure that a selected steel is
suitable for an apparatus in contact with nitric
acid is to perform tests. The best known method
is the Huey test, in which a clean, polished piece
of steel is immersed in boiling 65 % nitric acid at
ambient pressure [59]. The specimen is exposed
to these conditions for five successive 48-h pe-
riods, the acid being renewed at the beginning
of each test period. The Huey test gives a good
indication of how individual alloy constituents
affect intergranular corrosion.
To ensure good weldability, the carbon con-
tent is limited to 0.03 %; alternatively, titanium
or niobium is added as a stabilizer.
The stainless steels generally used in nitric
acid plants are those classified unter material
no. 1.4306 (AISI 304L); in the Federal Republic
Figure 26. Anodic polarization curve for stainless steel
of Germany, however, the corresponding stabi-
Cr denotes the effect of chromium on the anodic polarization lized qualities, material no. 1.4541 (AISI 321)
rate and 1.4550 (AISI 347), are also employed (Ta-
ble 4). These steels are usually specified for tow-
The effect of chromium on the corrosion rate ers and heat-exchanger shells, and also for many
is shown in the anodic polarization curve of Fig- heat-exchanger tubes. The 1.4335 steel (AISI
ure 26. When chromium is present in the alloy, 310L) has a very low corrosion rate and is used
24 Nitric Acid, Nitrous Acid, and Nitrogen Oxides
particularly where corrosive attack is severe, for The energy of compression can be partially reco-
example, if the temperature is below the dew vered with a tail-gas turbine. To circumvent the
point of nitrous gas, even at higher temperatures difficulty of operating a compressor for nitrous
[59]. These conditions normally occur at the in- gas and obtain a further decrease in plant vol-
let to the tail-gas preheater, in the dew point re- ume, to ammonia was also oxidized at medium
gion of the cooler – condenser, and at the outlet pressure. This type of process is particularly eco-
of the feedwater preheater. Corrosion at these nomical for smaller capacities and is thus de-
locations is caused mainly by reevaporation of scribed first.
nitric acid condensate, which brings the acid As plant capacities continued to grow and
concentration up to the azeotropic level (69 % lower tail-gas levels of NOx were necessary the
HNO3 ). The acid is then very aggressive, even in absorption pressure was increased still further.
the vapor phase. Corrosion can take place in the Lower energy costs and shorter depreciation pe-
boiler feedwater preheater if condensate forms riods in the United States have led to a pref-
at the outlet. Reheating of the condensate by the erence for the high-pressure process, whereas
hot process gas can lead to critical conditions. more favorable consumption and production fig-
Process design parameters should normally be ures in Europe have favored the dual-pressure
selected so as to avoid condensation; material process with medium-pressure combustion and
no. 1.4306 is then adequate. If, however, con- high-pressure absorption.
densation or reboiling occurs and this steel can- The principle of medium- and high-pressure
not be used, 1.4335 should be employed [60]. (monopressure) plants is that air for ammonia
oxidation and NOx absorption is compressed to
In plants producing concentrated nitric acid, the desired pressure. The “primary” air for oxi-
aluminum (99.8 %), ferrosilicon, tantalum, and dation is then mixed with ammonia and forced
special austenitic steels are used. Because tanta- through the burner. The “secondary” air for strip-
lum is very expensive, it is employed only with ping dissolved NOx out of the raw acid and ox-
boiling concentrated nitric acid. Ferrosilicon can idizing the intermediate nitrogen monoxide is
be used only in castings because of its brittle- supplied upstream of the absorption tower. The
ness. tail gas is heated and then expanded in a tur-
bine (on a common shaft with the compressor)
to produce mechanical energy. The remaining
1.3.4. Processes drive power is supplied by a steam turbine run-
ning on process steam.
Figure 14 illustrates the steps necessary for im-
plementation of the Ostwald process. Industrial Medium-Pressure Process. Figure 27 is a
processes differ in the sequence and design of flow sheet of a medium-pressure process (ca.
these steps. This section describes processes for 550 kPa). Liquid ammonia is evaporated at ca.
the production of weak acid [61, pp. 61 – 98] and 700 kPa in the ammonia evaporator (a). The
strong acid [61, pp. 99 – 130]. cold generated can be used in the absorption
step. Water is removed from liquid ammonia in
an ammonia stripper (b). The ammonia – water
1.3.4.1. Weak Acid Processes blowdown mixture is evaporated batchwise with
steam. Residual aqueous ammonia can be used
The first industrial plants for the production of in fertilizer production. The ammonia vapor is
weak acid employed atmospheric combustion heated with steam to ca. 90 ◦ C in the ammonia
and low-pressure absorption [3]. This type of preheater (c) and then filtered (d). If necessary, a
plant is no longer built. It was followed by a small stream of ammonia is diverted to tail-gas
process employing atmospheric combustion and treatment.
absorption at medium pressure. This process has All the air needed for the process is sucked
the advantage of lower absorption costs because in through the air filter (f ) by the air compressor
the marked improvement in absorption obtained (g). The compressed air is divided into two sub-
with the pressure generated by a nitrous gas com- streams in a tail-gas preheater (h). The secondary
pressor allows the apparatus to be downsized. air goes to the bleacher (x) for stripping raw acid.
Nitric Acid, Nitrous Acid, and Nitrogen Oxides 25
The secondary airstream exiting the bleacher is the feedwater preheater (n), which is located di-
laden with NOx and is added to the nitrous gas rectly on the inlet of the cooler – condenser (o).
before it enters the absorption tower ( p). The Additional water of combustion condenses out
greater part of the process air, the primary air, in the cooler – condenser before the nitrous gas
is mixed with the superheated ammonia in the stream is mixed with the NOx -laden secondary
ammonia – air mixer (e); it then flows through air and admitted to the absorption tower (p). The
the mixed-gas filter (not illustrated) and, now acid condensate from the feedwater preheater
cleaned, enters the reactor (i) where ammonia and the cooler – condenser flows directly into the
reacts with oxygen in the primary air over the bottom of the gas cooler – condenser. This acid
platinum – rhodium catalyst, yielding nitrogen condensate is then delivered by an acid conden-
monoxide and water. The reaction is exother- sate pump to a tray with the appropriate concen-
mic and proceeds at ca. 890 ◦ C. The nitrous gas tration in the absorption tower.
stream is cooled in the waste-heat boiler ( j), In the lower part of the tower, the nitrous
raising steam. Nitrogen monoxide is oxidized gas is oxidized further, thus reaching the neces-
to nitrogen dioxide in the downstream piping sary degree of oxidation before entering the ab-
and equipment, heating the nitrous gas stream. sorption section. The tower contains sieve trays
Further heat recovery takes place in the tail-gas through which the gas flows countercurrent to
preheater (k) and the economizer (l). After ex- the acid. The product acid concentration is at-
iting the economizer, the nitrous gas stream is tained on the lowermost absorption tray of the
cooled in a second tail-gas preheater (m). Con- tower. The acid is then pumped to the bleacher
densate can form in the next unit downstream, (x), where dissolved NOx is stripped, before the
26 Nitric Acid, Nitrous Acid, and Nitrogen Oxides
acid is stored in tanks. Chlorides in the absorp- mixture is evaporated with low-pressure steam
tion tower feed accumulate on trays where the in the ammonia stripper (b). The residual am-
acid concentration is ca. 21 wt %. Because of the monia concentration is ca. 2.5 %.
danger of corrosion, these trays must be emp- Ammonia exiting the evaporator system is
tied into the product acid tank from time to time. heated to ca. 130 ◦ C in the ammonia preheater
Cooling water flowing through coils on the sieve (c), and contaminants are removed in the ammo-
trays removes heat generated by the oxidation nia gas filter (d).
of nitrogen monoxide to nitrogen dioxide and Air is sucked in through the air filter (f ) and
its further conversion to nitric acid. Part of the compressed to ca. 1 MPa in an air compressor
heat absorbed by the cooling water is utilized (g) with interstage cooling (h). The primary air
to evaporate ammonia. A demister in the head (ca. 80 % of the total) is heated to ca. 180 ◦ C
of the tower collects liquid droplets entrained in against nitrous gas in the air heater (m) and then
the tail gas; the condensate runs back to the last fed to the ammonia – air mixer (e). The mixed
tray of the absorption tower. gas stream has a temperature of ca. 175 ◦ C and
The tail gas absorbs heat from the secondary contains 10.7 vol % ammonia. It passes through
air and the nitrous gas in three tail-gas pre- a filter (not illustrated) into the reactor (i) where
heaters. In the BASF catalytic tail-gas treatment the ammonia and atmospheric oxygen react over
(r; see also Section 1.4.2.3), ca. 60 vol % of the the platinum – rhodium catalyst at ca. 900 ◦ C to
NOx in the tail gas is selectively reacted with form mainly nitrogen monoxide and water.
ammonia. Hot tail gas containing < 200 ppm The reaction gases next pass through the
NOx goes to the tail-gas expansion turbine (s), waste-heat boiler ( j), where they are cooled to
in which mechanical energy is produced to drive ca. 400 ◦ C. The heat is used to raise high-pres-
the air compressor. Finally, the tail gas is dis- sure steam and superheat it to 500 ◦ C in the pree-
charged to the atmosphere via the stack. vaporator, superheater, and reevaporator of the
The tail-gas expansion turbine supplies part boiler.
of the power needed to drive the air compres- The boiler system is fed with condensate from
sor. The rest is generated by a condensing steam the steam turbine condenser (w) plus demineral-
turbine supplied with product steam. The tur- ized water from the battery limit. Both streams
bine may be bled. The steam turbine conden- are led to a tank and from there go through the
sate goes to the boiler feedwater preheater (n) feedwater preheater (n) to the deaerator mounted
where it absorbs heat from the NOx gas and then on the feedwater tank (t) and operating at a slight
flows through the deaerator into the feedwater gauge pressure. The tank serves as suction ves-
tank (t). Nondeaerated feedwater from the bat- sel for the feedwater pumps, which deliver water
tery limitalso flows via a preheater into the feed- through the economizer into the boiler drum (u).
water tank. The boiler feedwater pump raises the The water – steam mixture in the evaporator
pressure of the deaerated feedwater to the requi- is circulated by the boiler circulation pump. Sat-
site boiler pressure. Product steam is raised with urated steam and water are separated in the boiler
heat from ammonia combustion in the waste- drum (u).
heat boiler ( j). After leaving the waste-heat boiler ( j), the
Most of the steam generated in the waste-heat nitrous gas is cooled to ca. 260 ◦ C in a tail-gas
boiler drives the condensing steam turbine. The preheater (k). After passing through a run of pip-
remainder can be utilized in the ammonia pre- ing for oxidation, nitrous gas gives up more use-
heater and stripper and for deaerating the feed- ful heat in the economizer (l), and its tempera-
water; any excess is exported as product steam. ture falls to ca. 210 ◦ C. After another oxidation
run, the stream is led into the air heater (m) and
High-Pressure Process. Figure 28 shows a cooled to ca. 180 ◦ C. The heat recovered is used
high-pressure process running at ca. 1 MPa. Liq- to preheat the primary air.
uid ammonia is fed into the evaporator (a), where Before the nitrous gas is led into the gas
it is evaporated at ca. 1.15 MPa against warm wa- cooler – condenser (o), it passes through feed-
ter. The evaporation temperature rises slightly water preheaters and through the warm-water
above 35 ◦ C as the water content builds up in heater (n) both mounted on the two inlets of the
the evaporator. The ammonia – water blowdown cooler – condenser. The nitrous gas is cooled to
Nitric Acid, Nitrous Acid, and Nitrogen Oxides 27
ca. 115 ◦ C and partly condensed before entering Tail gas exits the absorption tower at ca. 20 –
the cooler – condenser. 30 ◦ C. It is heated to ca. 80 ◦ C in a tail-gas pre-
In the water- cooled cooler – condenser (o), heater (q) against the tail-gas stream from the ex-
the gas is cooled to < 50 ◦ C so that water formed pansion turbine. The tail gas is further heated to
during ammonia oxidation condenses to pro- 140 ◦ C against low-pressure steam (r) and then
duce ca. 45 % acid. This product is delivered to to ca. 375 ◦ C in a tail-gas preheater (k). It is sub-
the appropriate tray of the absorption tower (p) sequently expanded in the tail-gas turbine (s);
by the acid condensate pump. The NOx -laden this step produces ca. 70 % of the energy re-
secondary air recycled from the bleacher (x) is quired to drive the air compressor.
mixed with the nitrous gas stream before it is fed Tail gas exits the turbine at ca. 135 ◦ C and is
into the tower ( p). led to a tail-gas preheater (q), where it is cooled
In the sieve-tray absorption tower ( p) the ni- to ca. 90 ◦ C before being discharged through the
trous gas flows countercurrently to the process stack.
water fed at the column head, and nitric acid is The rest of the power needed to drive the
formed. Heat from the absorption tower is trans- air compressor can be supplied by a pass-out
ferred to the cooling water. Raw acid from the condensing steam turbine (v). The superheated
absorption tower is treated with secondary air in steam is delivered to the steam turbine or ex-
the bleacher (x), then delivered to battery limit ported. Part of the steam supplied to the turbine is
with the aid of the system pressure. withdrawn as low-pressure steam before admis-
sion to the condensing section. This low-pres-
28 Nitric Acid, Nitrous Acid, and Nitrogen Oxides
sure steam is used in the plant or exported. The content builds up in the evaporator. Ammonia
rest of the steam supplied to the turbine passes evaporator II is designed so that the entire am-
through the condensing section and is condensed monia stream can be evaporated in it, if neces-
in the steam turbine condenser (w). sary, at a maximum temperature of 20 ◦ C. If the
water content or the evaporation temperature in
Dual-Pressure Process. The dual-pressure ammonia evaporator II is too high, the ammo-
process combines the favorable economics of nia – water mixture is blown down and fed to
medium-pressure combustion with the effi- the ammonia stripper (b). Ammonia is stripped
ciency of high-pressure absorption. Figure 29 is to a residual content of ca. 2.0 % as the tempera-
a flow sheet of such a plant with ammonia com- ture is raised to 150 ◦ C with low-pressure steam.
bustion at 0.5 MPa and absorption at 1.1 MPa. The residue, greatly depleted in ammonia, is dis-
Liquid ammonia is fed to the ammonia evap- charged.
orator (a), which is under a pressure of ca. Gaseous ammonia from the evaporator sys-
0.65 MPa. The entire stream then goes to ammo- tem 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 am- Air is sucked through the filter (f) and com-
monia 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 am-
against cooling water. The evaporation temper- monia – air mixer (e). The mixed gas stream has
ature increases from 12 ◦ C to ca. 20 ◦ C as water a temperature of ca. 220 ◦ C and contains ca.
10 vol % ammonia. It is transported through the ture of ca. 130 ◦ C. It passes to tail-gas preheater
gas-mixture filter (not illustrated) to the reac- I (q ), where it is cooled to ca. 75 ◦ C. Down-
tor (h). Here, ammonia reacts on the platinum – stream of the preheater is cooler – condenser III
rhodium catalyst with atmospheric oxygen at (r), which the nitrous gas leaves at 50 ◦ C. The
890 ◦ C to produce a 96.5 % yield of nitrogen resulting acid condensate has a concentration of
monoxide and water. ca. 58 wt % and is mixed with the raw acid from
The reaction gases next pass through the the absorption column.
waste-heat boiler (i) and are cooled to 355 ◦ C. From cooler – condenser III the nitrous gas,
The heat is used to raise high-pressure steam in now at least 90 % oxidized, enters the absorption
the preevaporator, superheater, and reevaporator tower (s). The gas first passes through oxidation
of the boiler. trays that receive only a slight flow of liquid, to
The boiler system is fed with condensate from attain the degree of oxidation needed for equilib-
the steam turbine condenser (x) plus demineral- rium with 68 % acid. In the absorption section,
ized water from the battery limit. Both streams gas and liquid move countercurrently. Required
are led to a tank and then pass through the feed- process water is pumped to the tower head. The
water preheater (m) to the deaerator mounted 68 % raw acid is withdrawn from the first ab-
on the feedwater tank (u). The tank serves as a sorption tray and then treated with secondary air
suction vessel for the feedwater pumps, which in the bleacher (y). It is delivered to the battery
deliver the water through the economizer (k) into limit with the aid of the system pressure.
the steam drum (v). Approximately 80 % of the heat generated by
The water – steam mixture in the evaporator absorption is transferred to the cooling water and
is circulated by the boiler circulation pump. Sat- the remainder to the chilled water employed in
urated steam and water are separated in the steam the last part of the absorption step where very
drum (v). little heat of reaction is liberated.
After exiting the waste-heat boiler and pass- The tail gas contains < 150 – 200 ppm NOx
ing through a run of piping for oxidation, the ni- and exits the absorber at 20 ◦ C. It is heated to
trous gas is cooled from 390 to 280 ◦ C in tail-gas 110, 200, and finally 350 ◦ C in the three down-
preheater III (j). After further oxidation, it enters stream tail-gas preheaters (q, l, and j) before be-
the economizer (k), where it is cooled from 310 ing expanded in the tail-gas turbine (t). The tur-
to 200 ◦ C. The nitrous gas gives up further use- bine supplies ca. 67 % of the power required by
ful heat to the tail gas in tail-gas preheater II (l) the air and the nitrous gas compressors. The ex-
and its temperature falls to ca. 170 ◦ C. panded tail gas has a temperature of ca. 100 ◦ C
The gas passes through the feedwater pre- and is discharged through a stack.
heater (m), mounted on the cooler – condenser The remaining power required to drive the
inlet and thereby cools to ca. 100 ◦ C. In the rotating machinery can be obtained from a pass-
water- cooled cooler – condenser I (n), the gas is out condensing steam turbine (w). Superheated
cooled to < 50 ◦ C so that the water formed dur- steam is fed to the turbine or exported. Part of the
ing ammonia oxidation condenses. A ca. 43 % steam supplied to the turbine may be withdrawn
acid results and is pumped to the appropriate tray as low-pressure steam before it enters the con-
of the absorption tower (s). The secondary air densing section. This low-pressure steam may
laden with NOx and recycled from the bleacher be used in the plant or exported. The remainder
(y) is now mixed with the nitrous gas stream. The of the steam fed to the turbine passes through
mixed stream is then led into cooler – condenser the condensing section and is condensed in the
II (o), where it is cooled to ca. 45 ◦ C against steam turbine condenser (x).
chilled water. More water condenses and a ca.
52 % acid is formed, which is forwarded for Comparison of Medium- and High-
absorption along with acid formed in cooler – Pressure Processes [62]. Two trends can be
condenser I. The gas is passed through a mist seen in the worldwide development of weak acid
collector (not illustrated) upstream of the nitrous processes. First, from the process-engineering
gas compressor ( p). standpoint, a progression occurs from low-
The nitrous gas is compressed to 1.1 MPa in through medium- to high-pressure processes [5].
the compressor ( p) and has an outlet tempera- Second, capacities continue to increase; single-
30 Nitric Acid, Nitrous Acid, and Nitrogen Oxides
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 )
∗ Includes 1 kg NH3 for NOx reduction from 600 to < 200 ppm. ∗∗Includes water for steam turbine compressor.
train plants producing up to 2000 t of nitric acid produced directly in one of two ways. First, the
per day are now being built. In Europe, the dual- completely oxidized NOx can be separated in
pressure design is preferred for larger plants, liquid form by absorption in concentrated ni-
whereas smaller ones employ the monopressure tric acid and then led to a reactor where it is
design. Where feedstock and energy prices are reacted with oxygen and water (or weak acid)
low, monopressure operation offers special ad- under pressure to yield concentrated acid. Sec-
vantages; low investment costs ensure a quick ond, nitrous gases can be reacted with azeotropic
payout, particularly in North America. If, on the acid to form a concentrated acid that can be con-
other hand, feedstock and energy prices are very verted easily to concentrated and azeotropic acid
high (as in Europe), yield and energy efficiency by distillation. The latter product is either com-
must be maximized, so higher investment costs pletely recycled or used in the production of or-
are acceptable. Table 5 compares consumption dinary weak acid.
figures per unit product for monopressure and In the indirect processes, concentration is
dual-pressure processes. based on extractive distillation and rectification
New pollution control regulations and the en- with sulfuric acid or magnesium nitrate.
ergy crisis of the mid-1970s have also led to the
development of new processes or the improve- Direct Process. The essential feature of the
ment of existing ones. To avoid the need for cat- classical direct process (Fig. 30) is that liquid
alytic tail-gas treatment in large-tonnage plants dinitrogen tetroxide is produced and reacted un-
(and thus an increase in specific ammonia con- der pressure with pure oxygen and a certain
sumption), new facilities employ higher absorp- quantity of dilute nitric acid. A detailed account
tion pressures. of concentrated acid production via azeotropic
nitric acid is given in [61, pp. 99 – 130].
Ammonia Oxidation. As in weak acid pro-
1.3.4.2. Concentrated Acid Processes cesses, feed ammonia is evaporated, super-
heated, and filtered (see Section 1.3.4.1). Evap-
Industrially produced nitric acid contains 50 – oration takes place with the aid of water heated
70 wt % HNO3 . This is high enough for fertil- with process heat. Because traces of water and
izer production, but nitration processes in indus- oil accumulate in the ammonia evaporator the
trial organic chemistry call for concentrated acid sump must be drained into the steam-heated
(98 – 100 %). Distillation, the simplest way to stripper from time to time. Air for ammonia
concentrate dilute acid, fails because nitric acid combustion is sucked through a filter (a) and
and water form an azeotrope (68.4 % HNO3 at mixed with purified ammonia in the mixer ( b).
atmospheric pressure). The ammonia content of the mixture is held in
Concentrated nitric acid is manufactured di- the range 11.5 –12.3 vol %, depending on the
rectly or indirectly [63]. In the direct process, temperature. The optimal combustion temper-
the water generated in ammonia combustion is ature is 830 – 850 ◦ C. Ammonia oxidation takes
withdrawn by rapid cooling to give a nitrous gas place over conventional platinum – rhodium cat-
mixture from which concentrated acid can be
Nitric Acid, Nitrous Acid, and Nitrogen Oxides 31
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
alysts in the reactor (d). The heat of reaction is acid from the tower bottom is pumped (recircu-
used to raise steam in a waste-heat boiler and lated) to the head.
an economizer. The process gas exits the econ- Final Oxidation of Nitrogen Monoxide. The
omizer at ca. 170 ◦ C and is then cooled to 25 ◦ C nitrous gases leaving the oxidation tower are ap-
in a cooler – condenser (e), giving an acid con- proximately 95 % oxidized and are led to a final
taining ca. 2 – 3 wt % nitric acid. The cooler – oxidizer ( postoxidizer) ( j) where they are com-
condenser is specially designed to condense as pletely oxidized by desorption of concentrated
much water as possible without much NOx ab- nitric acid. The acid moves countercurrently to
sorption. Part of the process heat is also trans- the nitrous gases. Water produced in this reac-
ferred to the warm water used for ammonia evap- tion dilutes the concentrated acid; acid leaving
oration. The weak condensate generated in the the postoxidizer contains ca. 75 % HNO3 . Flow
cooler – condenser is used as scrub liquor for fi- control of the concentrated nitric acid feed into
nal absorption. the postoxidizer is important because too high
Oxidation of Nitrogen Monoxide. Secondary a rate lowers the output of concentrated acid,
air is mixed with the cooled process gas to oxi- whereas too low a rate displaces final oxidation
dize nitrogen monoxide to nitrogen dioxide. The into the absorber, with the result that the concen-
amount of secondary air must be sufficient to trated nitric acid entering the absorption tower is
ensure that the tail gas has a minimal oxygen too dilute. The product gas is saturated with ni-
content (2.5 – 3.5 vol %) before it is discharged tric acid vapor. For the next step, absorption, the
to the atmosphere. The concentrated nitric acid process gas is cooled to −10 ◦ C against brine
venting system is connected to the secondary air in a cooler ( l). Virtually all the nitrogen diox-
intake in such a way that oxygen and nitrogen ox- ide is dimerized to dinitrogen tetroxide at this
ides liberated on venting are recycled to the pro- temperature.
cess. The nitrogen monoxide gas and secondary Absorption of Dinitrogen Tetroxide. The ni-
air are compressed together to ca. 0.14 MPa (f ). trous gases are completely dimerized to dini-
After further cooling (g) to remove the heat of trogen tetroxide and, in this condition, are fed
compression, the mixture enters the oxidation into the absorber (m). The absorber consists of
tower (h), which is usually equipped with sieve four sections, each packed with ceramic Raschig
trays. Tube coils on the trays remove the heat of rings. The dinitrogen tetroxide is absorbed in
oxidation. To maintain a liquid level on all trays, concentrated nitric acid that comes from the
bleacher and is cooled to ca. −10 ◦ C (k, u). The
32 Nitric Acid, Nitrous Acid, and Nitrogen Oxides
acid leaving the absorption tower contains ca. of the raw acid mixture is taken from the bottom
25 – 30 wt % dinitrogen tetroxide and is pumped of the final absorber (n).
to the raw acid tank (o). Concentrated nitric acid is formed in the re-
Final Absorption. The gas exiting the absorp- actor (s) at ca. 5.0 MPa and 60 – 80 ◦ C. High
tion tower is practically free of nitrogen dioxide mechanical strength and corrosion resistance are
but saturated with nitric acid vapor. The vapor is needed, but these two requirements cannot be
removed by scrubbing in the final absorber (n), satisfied by any one material. The reactor thus
which consists of two sections. The scrub liquor has a carbon steel jacket to provide mechanical
(weak nitric acid from the cooler – condenser) is strength and a pure aluminum inner shell to pro-
recirculated or used to make up the water bal- vide corrosion resistance. Unreacted oxygen is
ance in the stirred tank. supplied to the suction of the nitrous gas blower
Dinitrogen Tetroxide Production. The laden via the venting system. The concentrated nitric
concentrated nitric acid is sent from the raw acid acid product is led to the raw acid tank (o) and
tank (o) to the bleacher (t), which consists of then to the bleacher. The bleached concentrated
a stripping section and a reboiler. The acid en- acid is cooled to + 30 ◦ C (u). Most of the con-
ters the head of the tower and flows downward centrated nitric acid is returned to the absorption
countercurrently to the nitric acid vapor, which tower and final oxidation.
strips nitrogen dioxide from the concentrated ni-
tric acid. The bleached concentrated acid goes to Indirect Processes. Two types of indirect
the reboiler section of the bleacher, where it is process are used to produce concentrated nitric
partially evaporated and partially withdrawn as acid (i.e., product containing > 97 wt % HNO3 ):
product acid. The vapor exiting the bleacher con-
tains ca. 95 % nitrogen dioxide and 5 % nitric 1) Sulfuric acid process
acid. Most of the vapor condenses in a down- 2) Magnesium nitrate process
stream precondenser (q). Dinitrogen tetroxide is
Both concentration techniques are based on
liquefied in the liquefier and fed to a stirred tank
extractive distillatfication. Weak acid is first
(r).
produced by a conventional process (Sec-
Production of Concentrated Nitric Acid. The
tion 1.3.4.1), then a third component is added
formation of concentrated nitric acid in the re-
to extract the water so that up to ca. 99 % nitric
actor (s) is described by the following equation:
acid can be distilled from the ternary mixture.
4 NO2 (
2 N2 O4 ) + O2 + 2 H2 O
4 HNO3
can be preconcentrated in a single-stage or mul- lier technologies that reduces steam consump-
tistage process to give ca. 68 wt % nitric acid. tion by as much as 50 %.
Figure 31 illustrates a single-stage apparatus. The materials of construction are highly cor-
Preconcentration takes place in a continuous rosion resistant. Towers are made of borosili-
countercurrent distillation tower (a), which can cate glass, enameled steel, and steel – polytetra-
be of either the packed or the bubble-tray type. fluoroethylene. Heat exchangers are made of
The system includes one or, if appropriate, two glass, polytetrafluoroethylene, stainless steel,
preheaters, a recirculating evaporator system for tantalum, titanium, high-purity aluminum, and
the tower bottom, a stripping and rectifying sec- special alloys.
tion for the tower, an overhead condenser, and a Figure 32 is a flow sheet of a plant making
reflux separator (b). concentrated nitric acid by the sulfuric acid pro-
Sulfuric Acid Process. Sulfuric acid can be cess. The feed nitric acid, concentrated to about
used as extracting agent (see also → 4. Distilla- 68 wt %, is preheated (e) and then fed into the
tion and Rectification). The concentrated nitric distillation tower (a). At least 80 wt % sulfuric
acid product is clear and colorless; it contains acid is fed to the head of the tower. The part of
98 – 99 wt % nitric acid and < 0.05 % nitrogen the tower above the nitric acid inlet, which is
dioxide. irrigated with sulfuric acid, can be regarded as
Consumption figures for the production of 1 t the rectifying section, with the sulfuric acid also
of 99 % nitric acid from dilute nitric acid are functioning as reflux. The part of the tower be-
given in Table 6. low the nitric acid inlet is the stripping section.
A circulating evaporator system takes care of
Table 6. Consumption figures for the production of 1 t of 99 %
HNO3 from dilute nitric acid by the sulfuric acid process∗ bottom heating. The ca. 70 % sulfuric acid leav-
ing the bottom of the tower goes to the concen-
Parameter Starting HNO3
concentration, wt %
trator (c), which operates under vacuum (8 kPa).
The overhead vapor product from the tower is
55 60 65 condensed to form 99 % nitric acid and then
Heating steam (1.0 – 1.8 MPa), t 2.0 1.75 1.45 deaerated (b). The tail gases, which still con-
Cooling water, m3 80 60 50 tain nitric acid vapor, are scrubbed with dilute
Electric energy, kW · h 17 14 11
Water evaporated, t 0.82 0.66 0.53
nitric acid (d).
Magnesium Nitrate Process. In this process
∗ Source: Plinke – NASAC plant data. a magnesium nitrate solution is used to extract
The nitric acid concentration step now oper- water from the nitric acid. The resulting dilute
ates with indirect heating, an advance over ear- magnesium nitrate solution is restored to the de-
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
34 Nitric Acid, Nitrous Acid, and Nitrogen Oxides
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
1) Mass of substances emitted as mass concen- term exposure (IW1), 0.08 mg/m3 ; short-term
tration in units of g/m3 or mg/m3 , referred exposure (IW2), 0.2 mg/m3 .
to the volume of stack gas at standard con-
ditions (0 ◦ C, 101.3 kPa) after deducting the
moisture content of water vapor, or to the 1.4.2.2. Analysis
volume of stack gas at standard conditions
(0 ◦ C, 101.3 kPA) before deducting the mois- The guidelines for the measurement and mon-
ture content of water vapor; and itoring of NOx emissions from nitric acid pro-
2) Mass of substances emitted, referred to time, duction are specified in [67, 70,71]. Photometry
as mass velocity in units of kg/h, g/h, or mg/h; without auxiliary chemical reaction and chemi-
and luminescence [71, c – e] are suitable for the con-
3) Ratio of the mass of substances emitted to tinuous measurement of NOx emissions [65].
the mass of products generated or processed Difficulties in gas sample preparation due to
(emission factors), as mass ratio in units of condensation are discussed in [71, c – g]. Ad-
kg/t or g/t. ditonal apparatus-related problems occur when
chemiluminescence is used to measure emis-
The usual concentration unit ppm (mL/m3 ) sion of moist stack gases at higher NOx lev-
can be converted to the prescribed mass concen- els. A chemiluminescence analyzer with a max-
tration (mg/m3 ) with the following factor [69]: imum range of 0 – 10 000 ppm has been devel-
1 ppm = 1.88 mg/m3 (based on monomeric NO2 oped [72].
at 101.3 kPa and 298 K and ideal-gas behavior). For stack gases containing traces of ammo-
The TA-Luft [67] states that the emission nia, precipitation of ammonium salts in the mea-
of nitrogen monoxide and nitrogen dioxide in suring cells has prevented continuous measure-
the stack gas of nitric acid plants must not ex- ments. Two methods useful for the discontinu-
ceed 0.45 g/m3 as nitrogen dioxide. Further- ous measurement of nitrogen oxide emissions
more, stack gases may be discharged only if col- [65] are acidimetric titration and the photomet-
orless; as a rule, this is the case if the mass con- ric phenoldisulfonic acid technique [71, a, b].
centration of nitrogen dioxide in the stack gas
does not exceed the value given by the follow-
ing formula: 1.4.2.3. Control of NOx Emissions
Massconcentrationof nitrogen dioxide mg/m3 Four basic approaches are used to reduce tail-
1200 gas NOx levels: improved absorption, chemical
=
Internaldiameterof stackorifice (dm) scrubbing, adsorption, and catalytic tail-gas re-
duction. Recent decades have seen intense re-
The requirement of a colorless discharge sets search and development effort invested in these
a practical limit of < 200 ppm NOx . Older low- methods. More stringent environmental restric-
and medium-pressure plants should comply with tions have lent special urgency to development
these standards by March 1, 1996. in this area. The most important techniques are
Plants whose emission of nitrogen monox- covered in this section.
ide and nitrogen dioxide (as nitrogen dioxide)
exceeds a rate of 30 kg/h must be equipped with Improved Absorption. Absorption effi-
devices that continuously measure the mass con- ciency depends chiefly on the absorption pres-
centration of nitrogen oxides. Quantitative re- sure, the number of stages, and the tempera-
lationships between emission and ground-level ture. The temperature of the gas between stages
concentration are also described, thus setting is especially important because it governs the
guidelines for stack design. progress of oxidation, which is the limiting
If ground-level concentration limits are ex- quantity for the entire absorption process (see
ceeded, the TA-Luft emission limits are further Section 1.3.2). In an already existing nitric acid
reduced by the relevant authorities. The ground- plant, the options are to expand the absorption
level concentration limits for gaseous pollutants volume and/or lower the absorption temperature.
in air are as follows [67]: nitrogen dioxide, long- In the first approach, large additional volumes
Nitric Acid, Nitrous Acid, and Nitrogen Oxides 37
only result in small reductions of tail-gas NOx safe process based on scrubbing the tail gas with
levels because the oxidation of nitrogen monox- ammonium nitrate solution; nitrite formation is
ide to nitrogen dioxide proceeds very slowly suppressed by aeration and the presence of free
when the NOx concentration is low. The draw- acid. The tail gas is then led through an am-
back to this method is that added absorption moniacal scrub liquor, pH 7.5 – 8.5. The scrub-
volume in stainless steel is very expensive. The bing product is a 30 – 50 % ammonium nitrate
advantage is that it does not require any new solution. The tail gas has a residual level of ca.
technology. The absorption volume is added 200 ppm NOx .
in the form of a second tower; new absorption Hydrogen peroxide scrubbing is based on the
tower designs with very few stages have been following overall reactions:
devised [73].
The use of cold energy in the absorption pro- NO + NO2 + 2 H2 O2 −→ 2 HNO3 + H2 O
cess greatly accelerates oxidation of nitrogen 2 NO2 + H2 O2 −→ 2 HNO3
monoxide to nitrogen dioxide. The disadvantage
of this method is that the necessary refrigeration The reactions are carried on sieve trays or in
equipment and piping demand further invest- packed towers with recirculation of the hydro-
ment. Another technique involving the use of gen peroxide solution. The advantage of this
cold to lower the NOx level is to cool the nitrous scrubbing process is that the reaction time is
gas so that more dinitrogen tetroxide than nitro- very fast; the disadvantage, that the hydrogen
gen dioxide is formed. The dinitrogen tetroxide peroxide scrub liquor is expensive.
is then scrubbed with nitric acid at ca. 0 ◦ C; it A solution containing 20 % urea and 10 %
can be stripped out, and converted to nitric acid free nitric acid has also been suggested for scrub-
by the reaction bing tail gas to remove NOx . The process is car-
ried at ca. 50 ◦ C. Both nitrogen oxides are se-
N2 O4 + 1/2 O2 + H2 O −→ 2 HNO3 lectively reduced to nitrogen by urea, which de-
composes to yield nitrogen and carbon dioxide.
in an absorption reactor at ca. 60 – 80 ◦ C. The The process, developed by Norsk Hydro in Nor-
technique is similar to that in concentrated ni- way, has the advantage that urea is readily avail-
tric acid production. The method is, however, able and relatively cheap. The resulting stack gas
more suitable for investment in a plant being de- plume is colorless but heavily laden with water
signed than for the expansion or upgrading of an vapor.
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 inte- and other problems have prevented its adop-
grated chemical plant, which is usually the case. tion. A patent granted to Kernforschungsan-
However, in some instances a nitric acid plant lage Jülich GmbH has a similar object [82], but
or sections of a fertilizer complex must operate again industrial experience is slight. A “wet”
independently. The following scrub liquors have adsorption system has also been developed by
been proposed: aqueous suspension of magne- Cofaz (France). A carbon- containing adsorbent
sium carbonate and magnesium hydroxide [74]; is sprayed with water or dilute nitric acid and
solution of vanadium in nitric acid [75]; ammo- brought in contact with the tail gas. This pro-
nium sulfide and bisulfide [76]; milk of lime cess has been installed in three monopressure
[77]; ammonia [78]; hydrogen peroxide [79]; plants [83].
and urea [80].
Ammonia scrubbing is used in the United Catalytic Reduction. Catalytic reduction
States. Goodpasture (Texas) has developed a was the first method used to reduce NOx emis-
38 Nitric Acid, Nitrous Acid, and Nitrogen Oxides
sions; as early as 1924, a patent for such a pro- to nitrogen monoxide. The stack gas is then de-
cess was issued to Fauser [84]. A fuel is added, colorized; in some countries, this is sufficient.
at a level below the flash point, to the nitro- Complete NOx removal generally requires pre-
gen oxides which then react on the catalyst sur- heating, multiple fixed-bed catalysts (with cool-
face to form nitrogen and water vapor. Most ing between beds to prevent overheating), and
fuels (e.g., hydrocarbons and hydrogen), how- careful heat recovery to offset part of the fuel
ever, react preferentially with the free oxygen cost.
that is always present in tail gases from nitric Most nitric acid plants constructed or mod-
acid production. As a result, the nitrogen ox- ified by Weatherly use nonselective catalytic
ides are not destroyed until free oxygen has been NOx abatement units with tail-gas exit tempera-
consumed. Under these conditions the reactions tures of 650 – 675 ◦ C. Some plants have gas exit
with methane can be described as temperatures > 815 ◦ C, which is higher than the
maximum for admission to the tail-gas expan-
CH4 + 2 O2 −→ CO2 + 2 H2 O sion turbines. The tail gas must then be cooled,
CH4 + 4 NO −→ CO2 + 2 H2 O + 2 N2 either against tail gas entering the catalytic unit
or with the aid of waste-heat boilers.
CH4 + 2 NO2 −→ CO2 + 2 H2 O + N2
In the process marketed by Du Pont the tail
Ammonia can also be used as a reducing agent, gas is dried, preheated, and then heated in two
preferentially reducing the nitrogen oxides: stages. The gas is subsequently divided into two
streams. One substream is heated further, mixed
6 NO + 4 NH3 −→ 5 N2 + 6 H2 O with methane, and led over the first fixed-bed
6 NO2 + 8 NH3 −→ 7 N2 + 12 H2 O catalyst. The second substream is mixed with
methane without further heating and led over
NO + NO2 + 2 NH3 −→ 2 N2 + 3 H2 O the second fixed-bed catalyst, along with the first
4 NO + O2 + 4 NH3 −→ 4 N2 + 6 H2 O substream. Hot tail gases exit the bottom of the
reactor and are led through the tail-gas expan-
Catalytic reduction processes are accordingly sion turbine, which recovers part of the work of
classified as nonselective or selective. compression.
Catalysts for nonselective reduction pro- Ammonia is the only economically relevant
cesses are usually based on platinum, vanadium reducing agent for selective catalytic processes.
pentoxide, iron oxide, or titanium. The fuel re- The consumption of reducing agent in the se-
quirement is the stoichiometric amount needed lective treatment of NOx is much smaller than
to reduce all the oxygen present (free and in ni- in nonselective processes. Furthermore, the tail-
trogen oxides) plus a small excess (ca. 0.5 vol % gas temperature after reduction is significantly
CH4 ). lower, allowing the use of simpler, cheaper con-
Unfortunately, the principal byproducts of struction materials. The optimal catalyst service
this process are carbon monoxide (≤ 1000 ppm) temperature is 250 – 350 ◦ C, but operation at up
and hydrogen cyanide. When hydrocarbon fuels to 500 ◦ C is possible. The costs due to the use
are used, the tail gas must be preheated before of expensive ammonia must, however, also be
the reaction on the catalyst proceeds at all. The considered. To prevent formation of ammonium
preheat temperature depends directly on the fuel nitrate (a potential explosion hazard) in the ex-
selected: pansion turbine or downstream, emissions must
Natural gas 450 – 480 ◦ C be monitored for ammonia (10 – 20 ppm).
Propane 340 ◦ C When BASF, Ludwigshafen [85] began work
Butane 340 ◦ C
Naphtha 340 ◦ C
on catalytic NOx reduction in the early 1960s,
Hydrogen 250 ◦ C existing patents indicated the use of ammonia
together with noble-metal (Pt, Rh, Ru, Pd) and
The use of hydrogen allows the preheat tem- iron-group (Fe, Co, Ni) catalysts [86, 87]. Alter-
perature to be lowered to 150 – 200 ◦ C but is gen- natives were found: vanadium pentoxide, tung-
erally too expensive. sten oxide, and molybdenum oxide gave excel-
If the quantity of fuel is not enough to reduce lent results. Vanadium pentoxide on an alumina
all the oxygen, nitrogen dioxide is reduced only support proved to be most economical.
Nitric Acid, Nitrous Acid, and Nitrogen Oxides 39
Selective processes also require oxygen, Ammonia is uniformly mixed with the tail-
which oxidizes part of the nitrogen monoxide gas stream in static mixers. The performance of
to nitrogen dioxide to ensure roughly equal lev- the treatment process is monitored by measur-
els of these two oxides (the best condition for ing the temperature rise during reduction (ca.
reduction). Because the BASF process operates 10 ◦ C/1000 ppm NOx ).
at 200 – 350 ◦ C, side reactions between ammo- Uhde, Dortmund, as licensee, has retrofitted
nia and oxygen can be neglected. The reaction 14 plants with the BASF process. The tail
is not affected by dinitrogen monoxide, carbon gas, usually containing 500 – 1000 ppm NOx , is
dioxide, or water vapor. heated to about 260 ◦ C. Ammonia gas is added
For a plant with a tail-gas stream of to the tail-gas stream in a mixer and then led
37 000 m3 /h (STP) operating at a pressure of through the reactor. The pressure drop is ca.
730 kPa with an inlet NOx concentration of 25 kPa. The effluent meets the requirement of
500 –1000 ppm, this process (270 ◦ C) gives an colorlessness.
exit concentration of 50 – 150 ppm NOx . The The HGW – Didier process, developed
treated tail gas contains < 20 ppm ammonia jointly by Hamburger Gaswerke (HGW) and
(usually ca. 5 ppm), and the nitrogen dioxide Didier, Essen uses a chromium oxide catalyst
level is 30 –50 ppm. The stack gas is generally with a service temperature of 265 – 350 ◦ C. The
colorless. Careful temperature monitoring at the nitric acid plant planned for DSM Miststoffen
tail-gas expansion turbine and measurement of (Geleen, Netherlands) is designed for a tail-gas
the ammonia level can prevent the deposition stream of 76 000 m3 /h (STP) with a maximum
of ammonium nitrate. To minimize the pressure NOx level of 2200 ppm. The exit concentration
drop, the reactor features an annular design with will not exceed 100 ppm NOx . The tail gas is
inward flow (Fig. 34). preheated before entering the reactor. To meet
the strict emission limit of < 100 ppm, the cat-
alyst is located in three beds. Ammonia can
be admitted separately over each. The following
distribution has proved most efficient: 70 % over
the first bed, 20 % over the second, and 10 %
over the third catalyst bed.
Other companies also have selective catalytic
reduction processes for nitric acid tail gases. For
example, Mitsubishi Chemical has developed a
process operating at 400 – 500 ◦ C under pressure
[88,89]. The “DN-Cat” catalyst is installed bet-
ween the heat exchanger and the tail-gas expan-
sion turbine in the conventional flow sheet.
The Weatherly selective catalytic process op-
erates at 250 – 310 ◦ C. The noble-metal catalysts
are the same ones employed in nonselective pro-
cesses, except that the fuel is replaced by ammo-
nia.
The Bergbauforschung – Uhde process [90]
is chiefly employed for stack-gas cleanup at
power plants but may later find use in emission
abatement at nitric acid plants. The Bergbau-
forschung – Uhde process for simultaneous sul-
fur and NOx removal from stack gases is uti-
lized at the cold end of the power-plant boiler,
i.e., downstream of the air preheater and elec-
trostatic filter. It employs the adsorptive and
catalytic properties of “activated coke” at 50 –
Figure 34. BASF tail-gas reactor for NOx reduction 150 ◦ C. The reducing agent is again gaseous am-
a) Hole plate; b) Catalyst; c) Wire gauze
40 Nitric Acid, Nitrous Acid, and Nitrogen Oxides
monia. The technique combines a selective cat- large amounts are reacted with ammonia to yield
alytic process for NOx and an adsorptive one for ammonium nitrate (→ Ammonia Compounds,
sulfur dioxide. The catalyst is therefore installed Chap. 1.2.1.). Weak acid (ca. 60 % HNO3 ) is
in a moving-bed reactor. most suitable for this purpose. Smaller amounts
of weak acid are used to digest crude phos-
phates. About 75 – 85 % of the nitric acid pro-
1.5. Storage and Transportation duced is used in the fertilizer sector. In addition,
porous ammonium nitrate prills are still an im-
As a rule, nitric acid is stored in stainless steel
portant component of explosives (→ Explosives,
tanks and transported in stainless steel contain-
Chap. 7.2.).
ers.
Nitric acid is used as a nitrating agent in
The regulations for transport by rail [91, 92]
the preparation of explosives (→ Explosives)
and road [93,94] differentiate among > 70 % ni-
and organic intermediates such as nitroalka-
tric acid, 55 – 70 % nitric acid, and < 55 % ni-
nes (→ Nitro Compounds, Aliphatic) and ni-
tric acid, and also between mixtures with sul-
troaromatics (→ Nitro Compounds, Aromatic).
furic acid (“mixed acid”) containing > 30 % ni-
It is also used in the production of adipic acid
tric acid and those containing < 30 % nitric acid.
(→ Adipic Acid, Chap. 4.1.).
Similar regulations [95] apply to transport by
Other applications include use as a chemical
ship. Important transport regulations for > 70 %
in metallurgy (e.g., as an etchant and pickling
nitric are as follows:
agent for stainless steels) and in rocket fuel pro-
IMDG Code Class 8, D 8261, E – F 8186 duction.
UN No. 2032
RID/ADR Class 8, no. 2 a
Worldwide output of nitric acid in 1987 was
CFR 49: 172.101, Cor. M 26.882×106 t, representing a slight increase of
ca. 4 % over 1976. Production in industrialized
Regulations for < 70 % nitric acid are countries has stagnated or even declined, but in
1976 – 1985 increases in capacity in less indus-
IMDG Code Class 8, D 8260, E – F 8185
UN No. 2031 trialized countries occurred [96]. Production fig-
RID/ADR Class 8, no. 2 b ures for nitric acid in 1987 follow (106 t):
CFR 49: 172.101, Cor. M
Europe, total 16.472
Provisions range from details of technical United States 6.553
Eastern Europe 4.289
equipment to labeling and give instructions in Asia 1.544
case of accidents. Regulations for the road trans- Federal Republic of Germany 2.112
port of nitric acid (≤ 70 % HNO3 emphasize Poland 2.136
the associated hazards ( poisoning by inhalation Belgium 1.470
Spain (1986) 1.249
of vapors, danger of chemical burns on contact Italy 1.195
with flammable substances, formation of nitrous Hungary 1.018
gases). Protective equipment includes respira-
tory protection apparatus, goggles, and clothing
affording complete coverage, as well as an eye- 2. Nitrous Acid
wash bottle with pure water. In case of accident,
the fire and police departments are to be notified Nitrous acid [7782-77-6], HNO2 , Mr 47.01, is a
immediately. Spilled nitric acid must not be ab- moderately strong to weak acid. Its dissociation
sorbed with sawdust or other flammable material constant K in highly dilute solutions at 18 ◦ C is
(because of the fire hazard); instead, its spread 4.5×10−4 . The acid is stable only in cold dilute
must be prevented by the construction of earth aqueous solution. It can be prepared as follows:
barriers.
Ba ( NO2 )2 + H2 SO4 −→ 2 HNO2 + BaSO4
1.6. Uses and Economic Aspects On heating in the presence of sand, glass splin-
ters, or other sharp-edged objects, or even at low
The principal use of nitric acid is as a starting ma- temperature, it disproportionates as
terial in the manufacture of nitrogen fertilizers;