NITRIC ACID

HNO3

Lecture By: Engr. Mina Arshad

INTRODUCTION
 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

colour 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
acid is further characterized as white fuming nitric acid or red fuming
nitric acid, at concentrations above 95%
Lecture By: Engr. Mina Arshad
PROPERTIES
Physical Properties
 Molecular formula : HNO3
 Molecular weight : 63.013gm/mole
 Appearance : Colorless liquid
 Odour : Pungent
 Boiling point : 83°C
 Melting point : -42°C
 Density : 1.5129gm/mL (liquid)
 Solubility : Miscible with water in all proportions
 The impure nitric acid is yellow due to dissolved oxides of nitrogen, mainly
NO2
 It has a corrosive action on skin and causes painful blisters
Lecture By: Engr. Mina Arshad
MANUFACTURING PROCESS
Nitric acid is manufactured by three methods;
1. From Chile saltpetre or nitrate
2. Arc process or Birkeland and Eyde process
3. Ostwald's process or Ammonia oxidation process

Lecture By: Engr. Mina Arshad

The Ostwald Process
Nitric acid is made by the oxidation of ammonia, using platinum or
platinum-rhodium 2- 10% as catalyst, followed by the reaction of the
resulting nitrogen oxides with water.

Lecture By: Engr. Mina Arshad

The Ostwald Process
1. Catalytic Combustion
4NH3 + 5O2 4NO + 6H2O

2. Oxidation of NO
2NO + O2 2NO2 N2O4

3. Absorption
3NO2 + H2O 2HNO3 + NO
Lecture By: Engr. Mina Arshad
Ostwald's Process or Ammonia Oxidation Process
Raw Materials
Basis: 1000kg nitric acid (100%)
 Ammonia = 290kg
 Air = 3000Nm3
 Platinum = 0.001kg
 Water = 120000kg
 Steam = 1000kg at 200psig
 Power = 10-30KWH

Lecture By: Engr. Mina Arshad

Reactions
 Major reactions
4NH3 + 5O2 4NO + 6H2O
2NO+O2 2NO2

 Side reactions
4NH3 + 3O2 2N2 + 6H2O
2NH3 N2 + 3H2
2NH3 + 2O2 N2O + 3H2O
4NH3 + 6NO 5N2 + 6H2O

Lecture By: Engr. Mina Arshad

 Nitrous Oxide Oxidation And Absorption

2NO+O2 2NO2
3NO2 + H2O 2HNO3+ NO
2NO2 N2O4
2NO2 + H2O HNO3 + HNO2
2HNO2 H2O + NO + NO2

Lecture By: Engr. Mina Arshad

Lecture By: Engr. Mina Arshad
Lecture By: Engr. Mina Arshad
The process involves four steps;

1. Catalytic oxidation of ammonia with atmospheric oxygen to yield

nitrogen monoxide
2. Oxidation of the nitrogen monoxide product to nitrogen dioxide or
dinitrogen tetroxide
3. Absorption of the nitrogen oxides to yield nitric acid
4. Concentration of nitric acid

Lecture By: Engr. Mina Arshad

Process Description
 Compressed air is mixed with anhydrous ammonia, fed to a shell and
tube convertor designed so that the preheater, super heater and
steam heat recovery boiler are within the same reactor shell

 The convertor section consists of 10-30 sheets of Pt-Rh alloy in the

form of 60-80 mesh wire gauge packed in layers inside the tube

 The reaction is very exothermic. The catalyst temperature may range

from 800°C - 925°C

Lecture By: Engr. Mina Arshad

 The temperature of the gases from the converter is above 600°C
 The converter gases are a mixture of nitric oxide, water, oxygen, and
nitrogen

 It is necessary to cool these gases so that they may be absorbed.

There are various arrangements to accomplish this purpose. The heat
from the gases leaving the converter is used as the source of heat in
the compressed air preheater and also to produce steam in a waste
heat boiler

 Product gases from the reactor which contain 10-12% NO, are sent
through heat recovery units consisting of heat recovery boiler, super
heater and quenching unit for rapid cooling to remove large fraction
of product heat, and into the oxidizer-absorber system
Lecture By: Engr. Mina Arshad
 It is necessary to further cool the gases in water-cooled condensers.
The condensing system usually includes chambers to allow time for
the oxidation reaction to proceed

 Air is added to convert NO to NO2 at the more favorable temperature

(40-50°C) environment of the absorption system

 Air from the air compressor unit may be introduced at the base of the
tower to bleach the acid by desorbing the dissolved nitrogen dioxide
and at the same time provide additional oxygen to oxidize the nitric
oxide formed as a reaction byproduct

Lecture By: Engr. Mina Arshad

Reactions in Absorption Unit
3NO2 + H2O 2HNO3 + NO

N2O4 + H2O HNO2 + HNO3

3HNO2 HNO3 + H2O + 2NO

Lecture By: Engr. Mina Arshad

 The equipment in the absorption tower may be series of packed or
sieve tray vertical towers or a series of horizontal cascade absorbers

 The product from this water absorption system is 57-60% HNO3

solution which can be sold as or concentrated as follows;
1.Concentration by H2SO4
2.Concentration by Mg(NO3)2

Lecture By: Engr. Mina Arshad

1. Concentration by H2SO4
Rectification with 93% H2SO4 in silicon-iron or stoneware tower produces
concentrated nitric acid and 70% H2SO4 which can be re-evaporated to 93% H2SO4
or used as it is.

2. Concentration by Mg(NO3)2
Extractive distillation to break nitric acid and water azeotrope to produce
concentrated nitric acid. Magnesium nitrate solution containing 70-75% Mg(NO3)2
is fed to dehydrating tray along with dilute HNO3 from the absorption tower.
 Advantages
Operating cost is half compare to H2SO4 process
Lower capital and maintenance cost
Acid quality and yield improved
 Disadvantage
Increase in 70% capital expenditure (slightly more steam is required as compared to
sulfuric acid to fulfill energy requirements)
Lecture By: Engr. Mina Arshad
Reaction Kinetics in Ammonia Oxidation Stage
 Rate of reaction is directly proportional to system pressure (4-10atm)
 Alloying of platinum with rhodium improves yield at given set of
conditions
 Reaction to form NO is favoured by increasing temperature until an
optimum is reached which increases with higher velocities. This
results from the prevention of back diffusion of NO into higher NH3
concentration region. If this occurs the following reaction is quite
probable and should be avoided for high NO yield.
4NH3 + 6NO 5N2 + 6H2O
 Rate of NO formation very nearly corresponds to diffusional transport
of ammonia molecules to the catalyst surface

Lecture By: Engr. Mina Arshad

Absorption of nitrogen oxides into water
Following design criteria should be considered
 Rate of absorption depends on concentration of NO2 in gas phase. In
absorber where concentration of NO2 is greater than 5%, the
controlling reaction is solution of N2O4 accompanied by hydrolysis of
HNO3 and HNO2.

 Low temperature is beneficial for absorber operation efficiency

 Increasing pressure favours physical absorption rate and shift

chemical equilibrium to produce higher acid strength

Lecture By: Engr. Mina Arshad

Process design modification
Most plants operate at higher pressure (4-10atm) rather than complete
atmospheric pressure. Some operates at a combination of 1atm pressure
oxidation and high pressure absorption. Very high pressure is limited due to
cost of pressure vessel.
Advantages and disadvantages of elevated pressure are as follows
Advantages
 Higher acid strength
 Lower investment cost
 Higher reaction rate and lower volume in both oxidation and absorption
equipment
Disadvantages
 Lower oxidation yield
 Higher power require if recovery units are not specified
 Higher catalyst loss unless good catalyst recovery procedure are not used
Lecture By: Engr. Mina Arshad
Catalyst for oxidation of ammonia
 Platinum/rhodium alloy containing 10% rhodium is the only
industrially viable catalyst. Rhodium not only improves the catalytic
properties of platinum but also improves mechanical and anti-
abrasive properties of material under the operating condition such as
to counter the severe corrosion and oxidation atmosphere
 2–10% of rhodium used in Pt/Rh supported catalyst. Higher
efficiencies and smaller platinum losses can be achieved by knitted
gauzes
 The metallic alloy catalyst is prepared into very fine threads of
diameter 0.05mm which are woven into meshes with more than
1000stiches/cm2. Two to four or even more of these meshes are
placed on top of one another inside the reactors when these are put
into operation
Lecture By: Engr. Mina Arshad
knitted Gauzes for Ammonia Oxidation
Lecture By: Engr. Mina Arshad
 Catalyst threads are smooth, bright and less active at initial stage, as
the time progresses they becomes dull and wrinkled whereupon their
activity rises to the maximum. Finally they become spongy with
activity falling off. When it is in most active state, ammonia oxidation
yields up to 98% of NO are obtained

 Ammonia conversion efficiency is a function of pressure and

temperature. As the pressure increases, higher temperatures are
needed to obtain the high conversion efficiency. An increased flow
rate and the presence of several layers of the catalyst help to
minimize undesirable side reactions. However, high flow rates
increase the catalyst loss which leads to search for non-platinum
catalysts for ammonia oxidation. The most prospective non-platinum
catalysts are based on oxides of Co, Fe or Cr
Lecture By: Engr. Mina Arshad
Catalyst Poison
 Sulfates, H2S, chlorides, Arsenic and its oxide, Si, P, Pb, Sn and Bi are
permanently poisoning the catalyst
 These elements lead to the formation of inactive compounds in the
wires resulting in decreasing of the catalytic activity
 Traces of acetylene, ethylene, Cr, Ni and Fe temporarily reduce the
conversion efficiency which can be restored by treatment with HCl
 There so air should be free from all above impurities along with
suspended particles of lubricants, fats, fine dust and abrasive powder.
For that, efficient filtration system along with magnetic separators
are provided

Lecture By: Engr. Mina Arshad

Chemical Properties
 Acidic properties: It is a strong monobasic acid and ionizes in
aqueous solution
 Oxidizing properties: It acts as a powerful oxidizing agent

 Action on metals: It reacts with almost all the metals, except noble
metals, like Pt and Au. The metals are oxidized to their corresponding
positive metal ions while HNO3 is reduced to NO, NO2, N2O, NH2OH or
NH3, depending upon the conditions such as temperature, nature of
metal and concentration of the acid
 Nitric acid has ability to separate gold and silver

Lecture By: Engr. Mina Arshad

USES
 As a starting material in the manufacture of nitrogen fertilizers such
as ammonium nitrate, ammonium phosphate and nitrophosphate
 As a nitrating agent in the preparation of explosives such as TNT,
nitroglycerine, cellulose polynitrate, ammonium picrate
 In manufacture of organic intermediates such as nitroalkanes and
nitro-aromatics
 Used in the production of adipic acid ( C6H10O4)
 Used in fibers, plastics and dyestuffs industries
 Used in metallurgy and as an oxidizer in rocket propellants
 As the replacement of sulfuric acid in acidulation of phosphate rock

Lecture By: Engr. Mina Arshad