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Nitric acid synthesis

Nitric acid
Production world wide: 65 million t/a
Applications: fertilizers, explosives, organic synthesis, polymers
(e g nylon)
(e.g.

AN ammonium nitrate
CN calcium
l i
nitrate
i
CAN calcium ammonium nitrate
ASN ammonium sulfate nitrate
NP nitrophosphates

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History of Nitric Acid Production

Middle Ages

Produced from salpeter, KNO3

19th century

Produced from Chile salpeter, NaNO3

20th century

Catalytic oxidation of ammonia with air

CF Industries: Urea and UAN

plants at Donaldsonville

Synthesis of nitric acid by oxidation of ammonia

Main challenge in the production of nitric acid is the selectivity for

catalytic
t l ti oxidation
id ti off ammonia
i tto nitric
it i oxide.
id Sid
Side reactions
ti
are
decomposition into N2 and H2 or H2O and formation of N2O.

Direct oxidation of NH3 to NO2 is thermodynamically unfavorable under

the process conditions.

Therefore, the reaction mixture needs cooling

g before non-catalytic
y
conversion of NO to NO2.

Finally, NO2 is absorbed in water to give HNO3.

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Reactions and thermodynamics

NH3 + 2 O2

HNO3 + H2O

H298= -330 kJ/mol

(1)

4 NH3 + 5 O2

NO + 6 H2O

H298= -907
907 kJ/mol

(2)

2 NO + O2

2 NO2

H298= -1261 kJ/mol

(3)

3 NO2 + H2O

2 HNO3 + NO

H298= -1261 kJ/mol

(4)

Side reaction:
4 NH3 + 3 O2

2 N2 + 6 H2O

H298= -1261 kJ/mol

(5)

Equilibrium constants at 900oC:

K(5) = 1015
K(4) =1011

A catalyst with high selectivity for ammonia

oxidation to NO is necessary.

Thermodynamic consideration

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The Ostwald process

Three main steps:

Oxidation of NH3
4 NH3 + 5 O2 4 NO + 6 H2O
Oxidation of NO
2 NO + O2 2 NO2
Absorption of NO2 in H2O
3 NO2 + H2O 2 HNO3 + NO

Ostwald process plant

52-65 %

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Typical process data (Ostwald plant)

KRUPP-UHDE process-dual pressure azeotropic HNO3

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Catalysts for nitric acid production

Pt-Rh alloy (containing 10 wt% Rh) in the form of wire gauze
(Dupont, 1934)
Pt shows
h
hi
high
h selectivity
l ti it ttowards
d NO fformation
ti
Rh addition enhances mechanical strength of Pt gauze and
decreases the volatility of Pt during the high temperature/high
pressure reaction

Several gauze configurations: knitted

gauzes lower N2O emission and
increase mechanical strength

Catalyst deactivation
Catalysts are deactivated by poisoning, fouling and loss of active Pt
Pt metal losses cause a reduction in mechanical strength of the
catalyst gauze (limiting the lifetime of the catalyst) and a gradual
increase of the Rh content on the catalyst surface
Increased Rh leads to decreased activities and a higher production
of N2O and N2, at the expense of NO

In situ Pt recovery process

Use of a woven gauze 90-10%Pd-Au gauze just after the oxidation gauze
to capture the Pt species
PtO2 (g) + Pd

Pt-Pd (alloy) + O2

Up to 80% recovery of Pt

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Process conditions for NH3 oxidation

Optimal conditions for ammonia oxidation to NO are
high temperature (1073 to 1223 K)

short residence time 10-3 - 10-4 s

low pressure 1 to 6.5 bar in dual-pressure plants and

ammonia-to-air ratio in the feed should be 1:9 (i.e. 10 vol.%

NH3)
3 to 50 layers of gauzes stacked in the reactor (burner)

Elementary reaction steps in NH3 oxidation

NH3 + NH3
O2 + 2 2 O
NH3 + O NH2 + OH
NH2 + O NH + OH
NH + O N + OH
N + O NO +
NO NO +
N + N N2 + 2
OH + OH H2O + O +
NH + O NO + H
NH + 2O NO + OH
NO N + O
NH2 + NO N2 + H2O + 2
NO + N N2 + O +
NO + N N2O +
N2O N2O +

At low temperatures (473

( 473 K): NN
coverage dominates the catalyst
surface leading to N2.
At higher temperatures O-coverage
increases and more oxidized
products are formed.
Under industrial conditions the
oxygen-coverage is dominant,
leading to NO.

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Formation of nitric acid by absorption

Mass transport and film diffusion determine overall reaction kinetics.

Environmental concerns in nitric acid production

5.5 kg N2O (green house gas) per tonne of nitric acid produced
Total emissions of N2O from nitric acid manufacture in Europe
can be estimated in 130 kt/a, which is equivalent to 40 Mtonne
of CO2.

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Current developments
Oxide-based combustion catalysts
Lower cost than Pt catalysts
Lower N2O emissions
Lower specific activity 2 orders of magnitude
Sintering, reduction of the oxides because of NH3
Co3O4 doped with Ce, La, selectivity of NH3 to N2O <0.5%
Single metal oxides or mixed oxides (perovskites and spinels) based on
Co, Fe, Bi, Mn, Cr, and Ni.

Combined beds consisting of Pt gauzes and oxides have been successfully

proposed for industrial applications.