NITRIC ACID

PRODUCTION

ENGR. MUHAMMAD
SAJID
LECTURER
DEPARTMENT OF
CHEMICAL ENGINEERING
UNIVERSITY OF
GUJRAT,PAKISTAN
 CONTENTS
Introduction

Properties

History

Process description

Chemistry of reactions

Uses

Health safety and environment

INTRODUCTION
 Nitric acid is a strong mineral acid. It is a mono-basic acid. It is a strong
oxidizing agent and can oxidize metals and nonmetals easily.
 It is used in the manufacture of fertilizers, silk industry, explosive materials
such as (T.N.T) etc
 Nitric acid (HNO3), also known as aqua fortis (strong water) and spirit of
niter, is a highly corrosive strong mineral acid. The pure compound is
colorless, but older samples are yellowish in color due to the
accumulation of oxides of nitrogen. Commercially available nitric acid
having concentration of 68% HNO3, while the solution containing
more than 86% HNO3, is referred to as fuming nitric acid.
Depending on the amount of nitrogen dioxide present, fuming nitric
PROPRTIES
acid is further characterized as white fuming
nitric acid or red fuming nitric acid, at
concentrations above 95%.
General

Nitric acid

Systematic name Nitric acid

Other names Aqua fortis
Spirit of nitre
 Salpetre acid

Molecular formula HNO3

SMILES [N+](=O)(OH)[O-]
Acidic Ion Concentration pH = -2 (1 N)
Molar mass 63.01 g/mol
Appearance Clear, colorless liquid
CAS number 7697-37-2

Properties

Density and phase 1.51 g/cm³

Solubility in water miscible

Melting point -42°C (231 K)

Boiling point 83°C (356 K)

Acidity (pKa) -2

HISTORY
Throughout History, Nitric Acid has been called Aqua Regina, which is
Latin meaning "royal water", by ancient scientists and chemists who first
discovered it. Nitric Acid has the name Aque Regina due to the fact that
beacuse to its corrosive behavior, it is one of few "reagents" that can
dissolve metals such as gold and platinum.
HISTORY
The first known person to write a
decription and discuss their method of
sythesizing nitric acid was named Jabir
ibn Hayyan (born in Persia c.
721 and died in Iraq c. 815) In his
decription he says:

"Take a pound of Cyprus vitriol, a pound

and a half of Saltpetre, and a quarter of a
pound of alum. Submit the whole to
distillation, in order to withdraw a liquor
which has a high solvent action. The
dissolving power of the acid is greatly
augmented if it be mixed with some sal
ammoniac, for it will then dissolve gold,
silver and sulphur“[1]

HISTORY
After the discovery from Jabir ibn
Hayyan, a Dutch Chemist named
Johann Rudolf Glauber (16041670) made a new discovery, he
was the first to make the compound Nitric Acid, with the
distillation of salt peter and sulfuric acid. The compound that
he created, was later named "Glaubers Salt", after the man who
discovered it.

LABORATORY SYNTHESIS
In laboratory, nitric acid can be made by thermal decomposition of copper(II)
nitrate producing nitrogen dioxide and oxygen gases, which are then passed
through water to give nitric acid.[2]
2 Cu(NO3)2 → 2 CuO (s) + 4 NO2 (g) + O2 (g)
An alternate route is by reaction of approximately equal masses of any nitrate
salt such as sodium nitrate with 96% sulfuric acid (H2SO4), and distilling this
mixture at nitric acid's boiling point of 83 °C. A nonvolatile residue of the
metal sulfate remains in the distillation vessel. The red fuming nitric acid
obtained may be converted to the white nitric acid.
 2 NaNO3 + H2SO4 → 2 HNO3 + Na2SO4
The dissolved NOx are readily removed using reduced pressure at room
temperature (10–30 min at 200 mmHg or 27 kPa) to give white fuming nitric
acid. This procedure can also be performed under reduced pressure and
temperature in one step in order to produce less nitrogen dioxide gas.

PRODUCTION OF NITRIC ACID

Commercially Nitric acid is made from ammonia in a three-step
process known as the Ostwald process.

Raw Materials:

 Ammonia gas

 Water

 Oxygen gas Production Process:

Step 1: Oxidation of NH3 to NO .

 Step 2: Oxidation of NO to NO2 .
Step 3: Absorption and reaction of NO2 with water

PRODUCTION OF NITRIC AC
PROCESS CONDITIONS
The conditions favouring the formation of the products at suitable
reaction rates for the reaction are:
 High pressure
 Excess air
 A catalyst
 As high a temperature as is consistent with practicable
reaction rates, catalyst efficiency and operating pressure Most
plants operate with:
 Moderate pressures (10-13 atm)
 Oxygen (air)
 An alloy of platinum and rhodium as catalyst
 Temperatures at ca 1200 K
 PROCESS CLASSIFICATIONS

The oxidation and absorption steps can be classified as:-

– Low pressure (pressure below 1.7bar)

– Medium pressure (pressure between 1.7 and 6.5bar)

– High pressure (pressure between 6.5 and 13bar)

UNIT OPERATIONS INVOLVED

The main unit operations involved in the nitric acid process are the same for all
types of
plant and in sequential order these are:-
– Air filtration
– Air compression
– Air/ammonia mixing
– 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 expansion of the waste gas to atmosphere, in a gas turbin
PROCESS FLOW DIAGRAM

16

BLOCK FLOW DIAGRAM

 17

PRODUCTION OF NITRIC OXIDE

Catalytic Combustion

The combustion of ammonia is one of the most efficient catalytic reactions with
possible conversions up to 98 percent.
The catalyst is platinum and the reaction occurs at 900 oC. The catalyst is a Pt-
Rh fine-mesh gauze, where the Rh provides strength.
The biggest issue with this method is the loss of precious metal at the reactor
temperatures.
Recovery gauze is typically used to absorb platinum oxide vapor and form an
alloy. This gauze can periodically be removed and platinum recovered.
PRODUCTION OF NITRIC OXIDE
Nitrous oxide, nitrogen and water are also simultaneously formed in this step,
as shown below.
Conditions are carefully controlled in the converter in order to ensure that
nitrogen monoxide (NO) is the main product, rather than nitrogen gas (N2) or
nitrogen (I) oxide (N2O).

The yield of nitric oxide depends on the pressure and temperature as shown
below.

Temperature Considerations

Even though higher yields would be obtained at lower temperatures (the

forward reaction is exothermic), the process is carried out at high temperatures
(820 930oC ). This is because the rate at which the reaction proceeds at low
temperatures is too slow to be commercially viable. To compensate for the
resultant loss in product yield, the gas mixture is passed over a catalyst a
number of times to produce a moderate yield of NO .
Pressure Considerations
At the high temperatures employed, the NO formed decomposes to form

nitrogen and oxygen.

To avoid this, the gas mixture is passed across the catalyst very rapidly
(contact time is approximately 0.003 sec). To achieve this high flow rate, the
reaction is performed at high pressures even though lower pressures would
result in a higher product yield. The consequential loss in yield of NO is
compensated for by the increased reaction rates and the quality of product
obtained.
BURNER DESIGN

Burner Head

Typical conditions
Platinum Gauze
for the production of
NO are therefore:

High temperatures Super Heater

(820 930oC )

High pressures (11

atm) Feedwater Preheater

Nitrous Gas Outlet

PRODUCTION OF NITRIC OXIDE

Catalytic Combustion
 PRODUCTION OF NITRIC OXIDE
Catalytic Combustion

BURNER
EFFICIENCY

Even with all the

compromises that are
required in this step,
the yield of NO is in
the order of 95%.
Effect of Rh on the Platinum Gauze
PRODUCTION OF NITRIC OXIDE
 The gas mixture entering the converter is filtered to remove catalytic
poisons, which increases the efficiency of the catalysts and hence
decreasing the pressure (and energy) required to force the gas
through the catalyst bed.
 Heat exchangers are employed to remove heat released by the
reaction in the converter and then using it to heat incoming gases or
generate electricity.
 At the high temperatures and pressures used in the converter, the
catalyst slowly vaporises and is lost. Gases leaving the converter are
passed through a filter to recover the metals and minimise the impact
of these vapours on the environment.
 Specific catalysts are added to the converter to decompose any N2O
formed.
OXIDATION OF NITRIC OXIDE

The NO is cooled en route to the absorption tower and, if necessary,

compressed.
As a result of this process, part of the NO is oxidized to nitrogen dioxide and
dinitrogen tetroxide.
To describe the kinetics of NO oxidation, a third-order rate equation is used.
This reaction is unusual because the reaction is quicker at lower
temperatures. The reaction rate has a negative temperature coefficient.

ABSORPTION
 Water is mixed with the nitrogen dioxide gas in absorption towers to form dilute
solutions of nitric acid according to the following overall reaction;
  This is a redox reaction in which produces nitrogen in its highest oxidation state
(+5 in nitric acid).

 The towers contain large number of inert plates packed with inert granular
materials designed to increase the contact between the gases and water.
 The absorption tower is governed by the calculations for the oxidation process.
Oxidation proceeds more slowly as the NOx concentration decreases in the top
of the tower, therefore the spacing between the plates increase.
 This reaction is exothermic and continuous cooling is needed. The conversion is
favored by low temperatures and significant reaction occurs until the gases
leave the towers.
 Nitrogen dioxide gas is pumped at 5 to 10 atm across the inert packing material,
through which water is trickled from above.

ABSORPTION
 Reaction between the water and the gas produces nitric acid, which then
dissolves in the remaining water. Small quantities of NO are also produced,
which reacts with oxygen from the air in the tower to produce NO2 which
then reacts as before.
 The coils on the upper plates work to keep the NO gas cool for fast reaction.
 Oxidation proceeds more slowly as the NOx concentration decreases in the
top of the tower, therefore the spacing between the plates increase.
 Acid formation takes place chiefly in the bottom third of the reactor, whereas
NOx is reduced in the upper two thirds.
 As a result, most of the heat of reaction is withdrawn in the lower third of the
tower.
 A solution of nitric acid may be produced that is about 45–60% HNO3 . This
can easily be increased to 68% (equivalent to 16M ) by distilling off some of
the water.
ABSORPTION
TOWER
ABSORPTION OF NITRIC OXIDES
 HIGHER CONCENTRATIONS
OF NITRIC ACID
 Nitric acid can be concentrated to about 68% in water with the above
described process.
 This concentration is adequate for most fertilizer applications but not for
chemical nitration reactions.
 However, there are ways to overcome the azeotrope (68% in water) and go to
higher acid concentrations.

 Concentrated Acid Processes:

1) Direct - injecting or absorbing NOx into weak nitric acid under
pressure.
2) Indirect - extractive distillation and rectification with sulfuric acid or
magnesium

REACTIONS
4 NH3 (g) + 5O2 (g) → 4NO (g) + 6H2O (g)
 2 NH3 (g) + 2O2 (g) → N2O (g) + 3H2O (g)
4 NH3 (g) + 3O2 (g) → 2N2 (g) + 6H2O (g)
4 NH3 (g) + 6NO2 (g) → 5N2 (g) + 6H2O (g)

2NO (g) + O2 (g) → 2NO2 (g)

3NO
2 (g) + H
2 O (l) → 2HNO
3 (aq) + NO (g)

2NO2 (g) + H2O (l) → HNO3 (aq) + HNO2 (aq) N2O4

(g) + H2O (l) → HNO3 (aq) + HNO2 (aq)
N2O3 (g) + H2O (l) → 2HNO2 (aq)

USES
 Used during the manufacture of explosives (ex. trinitrotoluene- TNT)
 Fertilizers
  Aid detection of metals in solutions
 Works as an oxidizing agent
 Used as oxidizer in liquid fuel rockets
 The compound can be used in a colorimetric test while differentiating
the difference between heroin and morphine

USES
Annual production of nitric acid

World 60 million
tonnes
Europe 20 million
tonnes
 NITRIC ACID USES
•Nitric Acid is commonly used in industry and
agriculture.
• It is highly used in the manufacturing of
explosives.
• It is a component of solid rocket fuels, and acts
as an oxidizer.
• It is used as a chemical reagent to identify
various other metals.
 NITRIC ACIDS USES
•Nitric acid is used In woodworking to ‘age’ wood
(in very diluted forms).
•Nitric acid can be used as an inexpensive process
to identify and assess the purity of gold,
particularly in low-grade alloys.
•Nitric acid in a solution of alcohol and water can
be used to etch metals.
NITRIC ACID USES
Nitric acid is highly used in making fertilizers
because it can make plants grow faster. The
downside is if it is used in soil that drains easily it
can contaminate rivers and streams making algae
grow faster and deoxygenating the water. This
can inhibit the growth of other plants and animal
life.
USES
 Nitric acid is a component of acid rain
 Nitric acid is a powerful oxidizing agent, and the reactions of nitric acid with
compounds such as cyanides carbides, and metallic powders can be
explosive
 Reactions of nitric acid with many organic compounds, such as turpentine,
are violent and hypergolic (i.e., self-igniting).
 Concentrated nitric acid dyes human skin yellow due to a reaction with the
protein keratin These yellow stains turn orange when neutralized.
 One use for IWFNA is as an oxidizer in liquid fuel rockets.
 One use for nitric acid is in a colorimetric test to distinguish heroin and
morphine.
 Nitric acid is also used in school laboratories to perform experiments
involving the testing of chloride. The sample is added with silver nitrate
solution and nitric acid to see if a white precipitate, silver chloride, remains.
HEALTH SAFET & ENVIRONMENT
Nitric acid is a dangerous chemical and should be
handled with regard to its corrosive and oxidizing
properties. Avoid contact with acid and use protective
equipment, most particularly eye protection. If spilled
on the skin, it can cause yellow discoloration, and
larger quantities or concentrations can cause fatal
burns. Do not breathe fumes given off when mixed
with metals or organic compounds—the effects may be
delayed but still fatal. Stay away from any red-brown
fumes! Nitric acid does not itself burn, but it oxidizes
organic matter and makes it highly flammable.

HEALTH HAZARDS OF NITRIC ACID

 Nitric acid is a strong acid and a
powerful oxidizing agent. Nitric acid can
cause severe burns to the eyes and skin. If
the gases are inhaled they can cause
burns to your respiratory tract.

HEALTH HAZARDS OF NITRIC ACID

•Nitric Acid can cause nausea, vomiting, diarrhea
and abdominal pain.
•It can affect you when inhaled and may pass
through the skin.
•Nitric acid has also been tested and is believed to
possibly cause reproductive damage.

HOW TO HANDLE SPILLS AND EMERGENCIES

If nitric acid is spilled or leaked and personnel are

involved you should evacuate them right away. Only
properly trained personnel should attempt to clean up spills.
You should ventilate the area of the spill or leak and try to
neutralize it with an alkaline. You should absorb the liquid
 with a non-combustible material like sand and put it in
sealed containers. It may be necessary to dispose of it as
Hazardous Material.

OTHER SAFETY PRECAUTIONS

Long-term exposure
Maintain PEL and STEL as dictated by OSHA
Noise

Governed by OSHA, PEL of 90 dB

 Maintain & lubricate equipment, sound barriers,
limiting exposure
General protection
Insulate or guard heated surfaces on working floor
Good lighting
Railings & non-slip surfaces
Training, safety checklists
FIREFIGHTER HAZARDS OF NITRIC ACID
If involved in a fire, firefighters should use water spray,
alcohol-resistant foam, dry chemical or carbon dioxide to
fight the fire. Firefighters should avoid inhaling the gas of
nitric acid and use full protective gear including full turn
out gear and a self-contained breathing apparatus.
UNUSUAL FIRE AND EXPLOSION HAZARDS

Nitric acid will increase the flammability of organics

like wood, and can cause explosions with metal
powders, carbides, and turpentine. Firefighters should
use extreme care.
PROPER PERSONAL PROTECTIVE EQUIPMENT

Anyone handling nitric acid should wear

personal protective equipment that is made from
materials that can not be permeated or degraded
by it. This personal protective equipment should
include: suits, gloves, footwear, eye protection,
and a respirator.
WASTES MANAGEMENT
 The Ostwald process is very energy efficient and produces little waste.
 The oxidation of ammonia is highly exothermic, generating sufficient
heat energy to meet the energy needs of the rest of the plant.
 The main gaseous emissions from the Ostwald process include NO and
2 NO . Both gases contribute to photochemical smog, and therefore,
careful attention must be paid to minimizing how much of these gases
are emitted into the atmosphere.
 One approach involves the heating of these gases using a fuel such as
natural gas, naphtha or hydrogen, over a catalyst, so that the NOx is
reduced to N2 .
WASTES MANAGEMENT

In addition, the absorption tower may be modified by increasing its

size or operating pressure so as to maximise conversion of NOx
to nitric acid.

1. Thomas H. Chilton, Strong Water; Nitric Acid: Sources,

Methods of Manufacture, and Uses (Cambridge, MA: M.I.T.
Press, 1968). OCLC 237255.
2. Allan, D. R.; Marshall, W. G.; Francis, D. J.; Oswald, I. D. H.;
Pulham, C. R.; Spanswick, C. (2010). "The crystal structures of
the low-temperature and high-pressure polymorphs of nitric
acid". Dalton Trans. 39: 3736–3743. doi:10.1039/B923975H.