AL-MUTHANNA UNIVERSITY

COLLEGE OF CHEMICAL ENGENEERING

SUBJECT OF THE REPORT: PRODUCTION OF NITRIC

ACID

REPORT DONE BY:TARIQ FAREED ABDULLAH

SUPERVISED BY: DR. HAMEED DAWOOD.

2020-2019
 NITRIC ACID

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
colourless, 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%.

First Nitric acid was mentioned in Pseudo-Geber's De Inventione

Veritatis which is prepared by calcining a mixture of saltpetre (Niter
KNO3), alum and sulfuric acid. Also, described by Albertus in the 13th
century and by Ramon Lull, who prepared it by heating niter and clay
and called as "eau forte" (aqua fortis)

. Glauber invent the process to obtain HNO3 by heating niter with strong
sulfuric acid. In 1776 Lavoisier showed that it contained oxygen, and in
1785 Henry Cavendish determined its precise composition and
synthesized it by passing a stream of electric sparks through moist air.
PROPERTIES
Physical Properties
 Molecular formula : HNO3
 Molecular weight : 63.013gm/mole
 Appearance : Colourless liquid
 Odour : Pungent
 Boiling point : 1210C (68% HNO3 solution)
 Melting point : -420C
 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.

Chemical Properties
 Acidic properties: It is a strong monobasic acid and ionization in aqueous
solution.
 Oxidizing properties: It acts as a powerful oxidizing agent, due to the
formation of nascent oxygen.
 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 ionswhile
HNO3 is reduced to NO, NO2. N2O, NH2OH or NH3, depending upon the
conditions such as temperature, nature of metal and concentration of theacid.
 Nitric acid has ability to separate gold and silver.
USES
 As a starting material in the manufacture of nitrogen fertilizers such as
ammonium nitrate, ammonium phosphate and nitrophosphate. Large
amounts are reacted with ammonia to yield ammonium nitrate.
 Weak acid are used to digest crude phosphates.
 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 nitroaromatics.
 Used in the production of adipic acid.
 Used in fibers, plastics and dyestuffs industries
 Used in metallurgy and in rocket fuel production

 As the replacement of sulfuric acid in acidulation of phosphate rock

METHODES OF MANUFACTURE
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

1. From Chile saltpeter or nitrate

It is the first commercial process of manufacture of nitric acid from sodium
nitrate extracted from Chile saltpeter. The process is now become obsolete since
second decade of nineteenth century.

Raw materials
Basis: 1000kg Nitric acid (95% yields)
Sodium Nitrate = 1420kg
Sulfuric acid = 1638kg
Reaction

Manufacture

Equal weight of sodium nitrate (or potassium nitrate) and sulfuric acid is
charged to cast iron retort having outlet provided at bottom to take out solution of
sodium bisulfate. The reactants are heated to about 2000C by the hot furnace
gases. The furnace gases are produced by combustion of coal in the furnace. Then
the vapour of nitric acid are cooled and condensed in water cooled silica pipes.
The cooled acid is collected in stoneware receiver. The un-condensed vapours are
scrubbed with water in absorption tower which is packed with stone ware balls and
cooled by cold water. The dilute acid is re-circulated till it becomes concentrated.
The residual sodium bisulfate is removed by outlet provided at the bottom of retort.
2. Arc process or Birkeland and eyde process
Raw materials
Basis: 1000kg Nitric acid (98% yield)

Air = 198kg
Water = 145kg

Reaction

Air freed from CO2 and moisture is passed through electric arc chamber
having two copper electrodes which are continuously circulated by cold water and
are connected with AC dynamo. A powerful electromagnet placed at right angles
to the electrodes spreads the arc in the form of a disc. The chamber is also provided
with inside suction pumps for rapid circulation of air across the flame through
holes of refractory fire work. Nitrogen and oxygen of air combines at 20000C
temperature to form nitric oxide. The hot exit gases (10000C) leaving the chamber
is passed through tube fire boiler for steam generation. The temperature of gases
leaving the boiler is significantly reduced up to 1500C. The gases are allowed to
pass through oxidation chambers made of iron and lined inside with acid proof
stone. Here, nitric oxide is further oxidizing to nitrogen peroxide in presence of air.
The exit gases from oxidation towers are passed through series of absorption tower
filled with broken quartz through which cold water or dilute nitric acid is
continuously sprayed from top. The gases which enter from the base of 1st tower
are leave at the top. Continuous counter current flow of gases in each tower is
maintained by centrifugal fan. The 3rd tower is fed with cold water and the dilute
nitric acid is collected at the base is re-circulated to the top of the preceding tower.
50% HNO3 is obtained at the base of 1st tower. The gases leaving the last
absorption tower contains traces of nitrogen oxides. The gases are allowed to pass
through two wooden towers which are sprayed down by dilute solution of soda
ash. The solution at the base of sodium carbonate tower is evaporated to collect
crystal of sodium nitrate.
Engineering aspects
The conversion of NO to HNO3 was carried out by means of oxidation and
hydration processes which is same as product obtained from oxidation of ammonia
Reason for obsolesce
High electrical energy consumed. There were enormous amounts of gas in
circulation compared to low concentration of NO which was formed (about 2%) on
account of the fact that high temperature also promote the reverse dissociation
reaction.
3. Ostwald's process or Ammonia oxidation process
Raw Materials
Basis: 1000kg nitric acid (100%)
Ammonia = 290kg
Air = 3000Nm3
Platinum = 0.001kg
Water = 120000kg
Steam credit 1000kg @ 200psig
Power = 10-30KWH
Reaction
Major Reactions:

Side reactions

Nitrous oxide oxidation and absorption

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

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

Compressed air is mixed with anhydrous ammonia, fed to a shell and

tube convertor designed so that the preheater and steam heat recovery
boiler-super heater 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. Contact time and of the gas
passes downward in the catalyst zone 2.5 X 10-4sec and are heated at
8000C.

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. Air is added to
convert NO to NO2 at the more favourable temperature (40-500C)
environment of the absorption system. The equipment in the absorption
train 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
Concentration by H2SO4
Rectification with 93% H2SO4 (660Be) 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.

Concentration by Mg(NO3)2
Magnesium nitrate solution containing 70-75% Mg(NO3)2 is fed to
dehydrating tray along with dilute HNO3 from the absorption tower. The
salt solution acts as an extractive distillation agent, removing water at
1000C or higher, thus allowing rectification with azeotropic formation.
The dilute Mg(NO3)2 solution re-concentrated by evaporation.

Advantages
 Operating cost is half compare to H2SO4 process
 Acid quality and yield improved
Disadvantage
 Increase in 70% capital expenditure
Engineering aspects
Thermodynamics and kinetics

All the above exothermic reaction takes place in more or less extent.
Reaction 12 and 13 occurs with decrease in enthalpy with increase in number of
moles followed by increase in entropy
Ammonia oxidation reaction has an extremely favourable equilibrium
constant so that one step, high temperature converter design may be used.

Further, ammonia air mixture exhibit explosion limits. At STP it is 15.6%

ammonia, while temperature above 6000C and 1atm pressure, the limit is lowered
to 10.5%
The following condition should be fulfilled to convert NH3 into NO
 Explosion limit
The explosion limits are avoided by employing quantity of air such that the
amount of ammonia mixed with it is less than 10.5vol% of total volume.
 Thermodynamics
The thermodynamics of competing reactions (12) and (13) are rendered
unfavourable by working above 5000C, while the reaction (14) are not favoured if
the process is carried out under 12000C
 Kinetics
Kinetics of reaction (1) is speeded up by use of catalyst. This is also done by
preventing any reduction in the velocity of the reaction brought about by presence
of inert gas nitrogen in the reaction zone.
Reaction kinetics in ammonia oxidation stage
 Rate of reaction is directly proportional to system pressure
 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
 Rate of NO formation very nearly corresponds to diffusional transport of
ammonia molecules to the catalyst surface.

There is slight equilibrium advantage to operation at atmospheric pressure.

This is more than offset by increased capacity in a given reactor volume with
subsequent catalyst and reactor savings when operating high pressures (3-8atm.)
Oxidation of nitrogen oxide does not have as large equilibrium constant.
There so, the reaction predominates in water and absorption portions of the
process, which operates at low temperature at 40-500C. All the nitrogen oxide
liberated on absorption of NO2 must be reoxidized in absorption tower.

Absorption of nitrogen oxides into water

Following design criteria should be considered
 Rate of abortion 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
Process design modification
Most plants operate at higher pressure (3-8atm) 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

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.

4–10 % 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 diameter0.05mm 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. 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.

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
freed from all above impurities along with suspended particles of lubricants, fats,
fine dust and abrasive powder. Also, suspension of Fe2O3 from ammonia is
removed. For that efficient filtration system along with magnetic separators are
provided.