Lecture 21_Nitric acid

process
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Pilani Campus
Oxidation of NO to NO2 is the slowest reaction

• Equilibrium is more favorable at lower temperatures

• Because of decrease in volume, this reaction is favored under high pressure
• Nitrogen dioxide (NO2)is in equilibrium with its dimer dinitrogen tetroxide
(N2O4)
HNO3
1. Absorption process of nitrogen dioxide in water is quite
complex because several reactions can occur, both in
the liquid phase and in the gas phase

2. A peculiar point is that in the reaction not only is the

desired product (HNO3) formed but also part of the
reactant (NO) is formed back

3. In addition, absorption reaction takes place in the liquid

phase, while NO oxidation occurs in the gas phase, the
rate of mass transfer between the gas and liquid phase
plays a major role

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HNO3
Optimal conditions for ammonia oxidation are:
– High temp

– Short residence time (minimize side & consecutive reactions taking place)

– Low pressure

But absorption of NO2 is favored at high pressure

So dilemma exist?????

– Should low pressure is applied both for oxidation & absorption?

– Should it operate like low pressure in oxidation reactor & high pressure for
absorption process?

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HNO3
There are two types of nitric acid plants
– High mono pressure process

• Its lower capital cost

• Lower energy and ammonia prices
– Dual-pressure process

• Favored in Europe
• Allowable capital payback periods and energy
costs have traditionally been higher

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Mono pressure process
• Either medium pressure (3 – 6 atm) or high pressure (7 –
12 atm)

• Process….

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Mono pressure process
• Either medium pressure (3 – 6 atm) or high pressure (7 –
12 atm)

• Higher operating pressure reduce equipment size and

capital cost
– Capital cost is about 10 – 14% lower than that of the dual-pressure process

• Higher temperature and operating pressures

accommodate a more efficient recovery of process
energy
– either as steam or as reheated tail gas, providing power for air compression

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Single pressure plants operate at either medium (1.7 and 6.5bar) or high (between
6.5 and 13 bar) pressure

Yield of nitric oxide depends on pressure and temperature as indicated in the table
1 below
Dual pressure process
• It has a medium pressure (0.3 – 0.6 MPa) front end for
ammonia oxidation and a high pressure (1.1 – 1.5 MPa)
tail end for absorption

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1. Main change in the flow scheme is the addition of a compressor between the
ammonia conversion stage and the absorption stage
2. Another difference in this scheme is the way in which NOx abatement is
achieved, that is, by extended absorption
1. Extended absorption is a technique to reduce NOx emissions by increasing
absorption efficiency (i.e., acid yield)
2. This option can be implemented by installing a single large absorption tower,
extending the height of an existing tower, or by adding a second tower in series
with the existing tower
3. Increase in the volume and number of trays in the absorber results in more NOx
recovered as nitric acid

• Waste tail gas is heated in the ammonia oxidation heat exchanger, expanded in a power
recovery turbine and expelled from the effluent stack to the atmosphere

• Final step expands the gas in the power-recovery turbine and thermal energy
produced in this turbine can be used to drive the compressor
Dual pressure process
• It has a medium pressure (0.3 – 0.6 MPa) front end for
ammonia oxidation and a high pressure (1.1 – 1.5 MPa)
tail end for absorption

• Compared to high mono pressure plants

– lower oxidation pressure improves ammonia yield and catalyst performance
– platinum losses are significantly lower and production runs are extended by a
longer catalyst life

• Reduced pressure also results in weaker nitric acid

condensate from the cooler condenser
– which helps to improve absorber performance

• Due to the split in operating conditions

– the dual pressure process requires a specialized stainless steel NOx compressor

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BITS Pilani, Pilani Campus
For many reasons the compression and expansion operations may be
considered extremely important step for the nitric acid process
Dual pressure process

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