Nitric acid (HNO3)

HNO3 is also one of the largest bulk chemicals produced throughout the world. Major uses
of nitric acid are in the production of fertilizers, explosives, specialty chemicals and as a
precursor in nylon manufacture. HNO3 is manufactured as 60-62 wt% HNO3 in water.
The three major steps in the commercial production of HNO3 are:
a) oxidation NH3 to NO; 4 3 + 5 2 4 + 6 2 , = 907 /
b) oxidation of NO to NO2; 2 + 2 2 2 , = 113.8 /
c) Absorption of NO2 in water to form HNO3. 3 2 + 2 2 3 + ,
= 1261 /
A side reaction in which NH3 is oxidized to N2 is also possible:
4 3 + 3 2 4 2 + 6 2 ,

= 1261 /

Oxidation of NH3
To improve selectivity toward NO, a catalyst, mixture of 90% Pt 10% Rh, is chosen. This
catalyst, as you can guess, is expensive. It is known that in the presence of catalyst, the side
reaction proceeds slowly than the NO formation reaction.
Choose the operating conditions for the above reactions. Think what conditions achieve high
rates and less side products.
A.
B.
C.
D.

high temperature
low temperature
high residence time
low residence time

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Select an appropriate reactor for NH3 oxidation to NO

a) Fixed bed adiabatic reactor

b) Multi Tubular Reactor

c) Gauge reactor

in

in

in

Steam
out

out

Shallow
catalyst
bed

Steam
in
out

out

What could be the primary concern in deciding composition of NH3air mixture input into
the reactor?
A. Rate of main reaction
B. Safety
C. Side product formation
UFL = 25 % NH3, LFL = 16 % NH3 for the feed mixtures. Beyond the limits, that is
mixtures having >25% or < 16% do not explode. Between the limits, the mixtures are highly
inflammable. Typical feed is approximately 10% NH3.

SAFETY IS UTMOST IMPORTANT IN CHEMICAL PLANTS

As an engineer, is distribution of feed mixture over catalyst bed a great concern to you?
Why?

A small fraction of Pt vaporizes and is lost during the reaction (see next page). A fellow
engineer suggests that the reactor operating temperature could be raised to 900 oC from 800
o
C to improve the rate of reaction and conversion without significant increase in Pt loss. His
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suggestion was followed but, the conversion did not rise. (Hint: Think about various steps
involved in the reaction)
100
90
80

% Pt loss

70
60
50
40
30
20
10
0
600

700

800

900

1000

1100

1200

Temperature, oC

Compare the reactor configuration for H2SO4 oxidation and NH3 oxidation. List and explain
similarities and differences.

Could we operate the reactor at > 25% NH3 in the feed mixture? What are the implications
on rate of reaction, residence time, gas distribution etc.

The gases exiting the shallow catalyst bed are cooled. The heat recovered from the gases
converts water to steam.

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Oxidation of NO
The second main reaction in nitric production is oxidation of NO to NO2. This is one of the
five known third-order-homogeneous-reactions.
2
02 =
02

The reaction mechanism proposed for oxidation of NO is as follows:

2 ()2 ()
()2 + ()2 () 22 ()

()2 is an intermediate compound. It is assumed that the first reaction is fast and attains
equilibrium quickly. The second reaction is slow and thus it is the rate controlling step.
Write equation for equilibrium constant, , for ()2 formation: =

Derive equation for rate of

formation. Your equation should contain only .

Speculate why 02 is lower at higher temperatures.

Based on the kinetics of 2 formation, what is done to the gases exiting the ammonia
oxidation reactor?

When the effluent gases are cooled to about 30-40 oC, under pressure, what is (are) expected
to form?
(A) 2

(B) HNO3

(C) Both

Is the produced HNO3 is dilute or concentrated?

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The steam exiting the heat exchanger (condenser) is a gas-liquid mixture; gas phase consists
of predominantly NO2, little NO, and a little HNO3; liquid phase consists of HNO3 mostly.
These two phases are separated.
How do we handle the two separated phases? Look at the reactions listed at the beginning of
this topic.
Draw block diagram for nitric acid production

Absorption is favored at high pressures. Oxidation of NH3 and NO do not need high
pressure; however, experiments indicate that high pressures give high selectivity toward NO.
Should we adopt high pressure for the entire process or low pressure for oxidation and high
pressure for adsorption?
Both processes are used commercially as shown in next couple of pages.

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On the trays shown in absorbed what are the reactions happening in gas phase and liquid
phase?
Gas phase reaction:
Liquid phase reaction:

What is the purpose of cooling the gas above trays? These trays are to be cooled by a
refrigerant to achieve low temperatures. Suggest a coolant. Hint: In what state is NH3
supplied to the plant?

What is purpose of adding stripping air?

In the dual pressure process, vent gas is expanded while gas fed to the absorber is
pressurized. Is there scope for energy conservation?

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Pollution abatement
Even after cooling, some NOx escapes the absorption tower. NOx levels are brought down by
installing a single, long absorption tower OR by adding a second tower in series with the first.
This is called extended absorption.
Alternatively, NOx levels are lowered below the threshold limit of ~200 ppm by catalyst
reduction to N2.
4 + 43 + 2 4 2 + 6 2 = 408 /
22 + 43 + 2 3 2 + 6 2 = 669 /

What could be one reason for which this reduction is attractive in nitric acid plants?

The catalyst for NOx reduction is expensive. A research article developed an adsorption
system, using molecular sieves, to adsorb NOx from tail gas (i.e gas leaving from absorption
tower) and recycling the adsorbed gases. Would you do to convince management about the
system?
A) concentration of NOx leaving the system
B) cost of the system
C) pay back period

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It turns out that tail gas (i.e gas leaving the absorption tower) cannot be heated to the
desired temperature in the second heat exchanger after the ammonia oxidation reactor.
Installing another heat exchanger achieves this temperature. An ingenious way to
combine the heat exchange and reaction is proposed below. Think for yourself first and
then discuss with your neighbor working principle and benefits of the proposal.

Feed

catalyst

Product

First half of cycle

Product

Feed

Second half of cycle

catalyst

Valve open

Inert beads

Valve closed

This portion is not included for the exams

Absorption column in nitric acid plant is probably the most complex unit of its kind in
chemical industry.
The column achieves HNO3 production and NOx abatement
simultaneously.
NOx gases consist of NO, NO2, N2O3, N2O4, HNO2 and HNO3. The liquid phase contains
two acids HNO2 and HNO3. NO has low solubility in water but it reacts with NO2 to form
N2O3 which dissolves in water to form HNO2. Hence there are reactions occurring in gas
phase, absorption accompanied by reactions happening in liquid phase.
High temperature favors reactions in liquid phase but retard NO oxidation. High pressure
promotes absorption and oxidation of NO but adds to the cost.
It is possible to simulate nitric acid plant with all these complexities in APSEN or by writing
a computer code. Simulations aid in optimizing the performance of the plant defined to
minimize cost, emissions of NO etc.

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