Chapter: 3

Nitric acid industries

By Mr. Biniyam Abera (M.Sc.)

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 3.1. Introduction

 Nitric acid is an inorganic compound with the formula HNO₃.

 Nitric acid is one of the oldest chemicals and was known in ancient
times as ‘Aqua Fortis’ and it was primarily used to separate gold
and silver.
 Nitric acid is a very common and heavily used chemical in the world
and is manufactured on a large scale by global manufacturers.
 Precaution Continued exposure to vapor may cause chronic
bronchitis and chemical pneumonitis may occur.
 It is a highly corrosive mineral acid.

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 Brief summary about characteristics of nitric acid

 Characteristics of Nitric acid should be thoroughly examined because those

characteristics affect the Production process, Safety, and Storage facilities
during the production process.

• A strong acid: Aqueous HNO3 acid is a strong acidic solution and reacts with
metals it is the only acid to dissolve Cu.

• A strong oxidizing agent: As aqueous HNO3 becomes a strong acid, it is a

strong oxidizing agent because Nitric acid can be reduced to lower oxidation
states such as Nitric oxide (NO) or Nitrogen dioxide (NO2) while other
chemicals are being oxidized.

• Decomposes when exposed to sunlight: Nitric acid decomposes to Nitrogen

dioxide, oxygen, and water when exposed to sunlight or higher temperatures.
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Specific gravity 1.502

Viscosity 1.62cp

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• If the concentration of nitric acid is between 68-95% then it is called red-fuming
nitric acid which is primarily used in the rocket fuel industry

• If the concentration of nitric acid is above 95% then it is called white fuming nitric
acid and it primarily finds its use in the etching industry

• The concentration that is most common and commercially available to buy in the
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market is about 68% nitric acid.
3.2. Uses and applications of nitric acid in industries

 To produce fertilizers

 To produce explosives

 Important chemical

 Dissolve metals

 To produce metal nitrates

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 Other uses of Nitric acid

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3.3. Production and consumption of Nitric acid

Nitric acid is prepared in two ways

1. Labratorically on a small scale

2. Industrially on a large scale such as

A. Ammonia oxidation process (Ostwald’s process)

B. NaNO3 + H2SO4 process (Chile Salt Peter
process)
C. N2 fixation from the air (Wisconsin process)
D. Nitrogen fixation by nuclear fission fragment (new)

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Prepare nitric acid in the laboratory in small scale requirements

• Nitric acid can be produced in an analytical laboratory on a small scale

under safety conditions under an experienced technical supervisor.

• Use a fume hood to eliminate any toxic gases formed duration the
procedure and wear all personnel protective equipment (PPEs).

Raw materials are Potassium nitrate and concentrated sulfuric acid

• The reaction of potassium nitrate and concentrated sulfuric acid can be
used to prepare nitric acid in the laboratory. When the mixture is heated,
formed nitric acid can be separated by the distillation process.

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1. Ammonia gas (NH3) as the source of nitrogen

• Ammonia is used as the source of Nitrogen for Nitric acid

manufacturing.

• Ammonia gas is industrially manufactured by the Haber Process.

Ammonia is fed to the reactor as a gas for further reactions.

• Storage and handling of ammonia gas should be handled with care.

2. Oxygen gas (O2) to oxidize ammonia and Nitric oxide

• Oxygen gas is used to oxidize ammonia to Nitric oxide and Nitrogen

dioxide before Nitric acid production. Purified Oxygen gas can be
separated from ambient air. 12
3. Water to produce Nitric acid

Water is used in the last stage of Nitric acid manufacturing when

Nitrogen dioxide gas is dissolved in water.

Though water is not only used as a raw material, it can be used as a

coolant where necessary.

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3.4. Process Technology of Nitric Acid Industries

A. Reactor
Reactions occurring in the reactor are;
1) 4NH3+5O2 4NO+6H2
2) 4NH3+3O2 2N2+6H2O
B. Tail gas heater and heat recovery boiler
The Reaction occurring are;
2NO + O2 2NO2
C. Cooler or Condenser
The reaction occurring in the equipment is;
3NO2 + H2O 2HNO3 + NO

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D. Oxidation tower

Reaction occurring in oxidation tower;

NO2 + 2HNO3 3NO2 + H2O

E. Compressor

The reaction taking place in the compressor is;

2NO + O2 2NO2

F. Distillation Column

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 3.4.1. The sodium nitrate sulphuric acid process

• Used in the early days

• Double Displacement (Metathesis) reaction

• Extracted from Chile saltpeter 35-60% NaNO3, some KNO3, and rest
of NaCl

Step 1
The mixture is heated in a cast iron retort

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Step 2
The vapor of HNO3 is cooled and
condensed

Step 3
The acid is collected in a stoneware
receiver
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 Figure The sodium nitrate sulphuric acid process flow
chart

 The reaction of the production of nitric acid from sodium nitrate

sulphuric acid process

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3.4.2. Nitric acid production by ammonia oxidation - Ostwald method

Step 1

The aim is to prepare nitric oxide (NO)

• Ammonia (NH3) gas and Oxygen (O2) gas are mixed to a 1:9 volume
ratio.

• The mixture is heated up to 850 - 1000 0C temperature.

• The mixture is sent through a Pt/Rh catalyst.

• Then exothermic reactions happen and produce NO and H2O as a result.

• Due to exothermic reaction (heat is generated as a result of reaction), the

reaction happens easily after it was started.
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The reactions

4NH3(g) + 5O2(g) → 4NO + 6H2O(g) + ΔH ΔH0 = -904 kJmol-1

• The reaction happens under high-pressure conditions

• To create a higher pressure, more reactants has to be entered to the

reaction. This will increase more impact between reactants and catalysts.

• This increases the reaction rate to produce more products.

• Excess air will confirm the completeness of ammonia oxidization to

Nitric oxide (NO).

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Step 2

• The aim is to prepare Nitrogen dioxide (NO 2)

• Next reaction gives us Nitrogen dioxide (NO 2(g)) as the result of

furthermore oxidation of Nitric oxide.

• This reaction should be done at a lower temperature than the

previous reaction. (<1500C).

• Hence produced Nitric oxide is cooled

• The cold air mixed with Nitric oxide (NO reacts with excess O2)

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The reaction
NO(g) + O2(g) → NO2(g) + ΔH ΔH0 = -115 kJmol-1

Step 3

The Aim is to Prepare nitric acid as the final product

Produced Nitrogen dioxide (NO2(g)) in the second step is now cooled

before it is sent to the water.

Nitrogen dioxide is absorbed very well in the water and produces Nitric acid
as a result of furthermore oxidization.

3NO2(g) + H2O(l) → 2HNO3(aq) + 4NO(g)

• Released nitric oxide (NO) in step 3 is resent back to the step 2 to oxidize to
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Nitric oxide.
 Requirements for industrial nitric acid manufacturing

1. Pressure: 4-10 atm

2. Temperature: 850- 10000C
3. Pt catalyst (10% Rh content)

Figure Flowcharts for the production of nitric acid 23

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 3.4.3. Major unit operations of Nitric acid production by
Ammonia Oxidation

All plants for the production of nitric acid are currently based on the
same basic chemical operations:-

– Oxidation of ammonia with air to give nitric oxide

– Oxidation of the nitric oxide to nitrogen dioxide and

– Absorption in water to give a solution of nitric acid

The main unit operations involved in the nitric acid process are the
same for all types of plants and in sequential order, these are:-

– Air filtration, – Air compression, – Air/ammonia mixing

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– Air/ammonia oxidation over catalytic gauzes
– Energy recovery by steam generation and/or gas re-heating
– Gas cooling
– Gas compression, energy recovery, and cooling (dual pressure plants
only)
– Absorption, with the production of nitric acid
– Waste gas (tail gas) heating
– Energy recovery by the expansion of the waste gas to the
atmosphere, in a gas turbine

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 3.5. High and low strength Nitric Acid Production

1. Weak Nitric Acid Production

This process typically consists of 3 steps:

(1) ammonia oxidation,

(2) nitric oxide oxidation, and

(3) Absorption

The most commonly used catalyst is made of 90 percent platinum

and 10 percent rhodium.

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2. High-Strength Nitric Acid Production

A high-strength nitric acid (98 to 99 percent concentration) can be

obtained by concentrating the weak nitric acid (30 to 70 percent
concentration) using extractive distillation

The weak nitric acid cannot be concentrated by simple fractional

distillation.

The distillation must be carried out in the presence of a dehydrating

agent

Concentrated sulfuric acid (typically 60 percent sulfuric acid) is most

commonly used for this purpose.
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Flow diagram of high-strength nitric acid production from weak nitric
acid.

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Thank you
-The end-
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