Nitric Acid Manufacturing Processes

Module 4
Dr. N. K. Patel
Lecture: 16 Nitric acid
Module: 4
Lecture: 16
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.
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.
NPTEL 96
Module 4
Dr. N. K. Patel
Raw materials
Basis: 1000kg Nitric acid (95% yields)

Sodium Nitrate = 1420kg
Sulfuric acid = 1638kg
Sources of raw material

Sulfuric acid can be obtained by contact process as described in Module: 4,
Lecture: 18.
Sodium nitrate can be obtained from caliche ore. Also, it is manufactured by

neutralization of soda ash with nitric acid as well by reaction of ammonium nitrate
and sodium hydroxide.
Reaction
NaNO3 + H2SO4 NaHSO4 + HNO3
Manufacture
Cooled Silica
Pipes
Cast Iron
Retort Water
out
Water in
NaNO3 + H2SO4 Water or Dil. HNO3
Stoneware
Balls
Furnace HNO3
Conc. HNO3
Dil. HNO3
Figure: Manufacture of nitric acid from chile saltpetre or nitrate
Block diagram of manufacturing process
Diagram with process equipment
Animation
NPTEL 97
Module 4
Dr. N. K. Patel
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
N2 + O2 2NO H = + 43.2 kcals

2NO + O2 2NO2 H = - 26.92 kcals
4NO2 + 2H2O + O2 4HNO3
Manufacture
Na2CO3
Water
Solution
Cooling
water
Oxidation
Air
Tower
Absorption Soda
Towers Tower
Boiler Na2CO3 Tower
50 % Nitric
Electric Arc Acid
Furnace
Figure: Manufacturing of Nitric Acid by Arc Process
NPTEL 98
Module 4
Dr. N. K. Patel
Animation
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
NPTEL 99
Module 4
Dr. N. K. Patel
Water = 120000kg
Steam credit = 1000kg @ 200psig
Power = 10-30KWH

Ammonia can be synthesized by Haber Bosch or Modern process as
described in Module: 2, Lecture: 6.
Reaction
Major reactions
4NH3 + 5O2 4NO + 6H2O H = - 216.6kcals ---- (1)
2NO+O2 2NO2 H = - 27.1kcals ---- (2)
Side reactions
4NH3 + 3O2 2N2 + 6H2O H = - 302.7kcals ---- (3)
2NH3 N2 + 3H2 H = + 26.7 kcals ---- (4)
2NH3 + 2O2 N2O + 3H2O H = - 65.9kcals ---- (5)
4NH3 + 6NO 5N2 + 6H2O + 432.25kcal H = - 431.9kcals ---- (6)
Nitrous oxide oxidation and absorption
2NO+O2 2NO2 H = - 27.1kcals ---- (7)
3NO2 + H2O 2HNO3+ NO H = - 32.2kcals ---- (8)
2NO2 N2O4 H = - 13.9kcals ---- (9)
2NO2 + H2O HNO3 + HNO2 H = - 27.7kcals ---- (10)
HNO2 H2O + NO + NO2 ---- (11)
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.
Animation
NPTEL 100
Module 4
Dr. N. K. Patel
Process Steam
Vaporizer
Tail Gas
NH3
storage
Water cooling
Converter Water
800 0C cooling
Absorption
Compresed Super
Tower
preheated air heater
Oxidation
Tower
Heat Tail gas
Recovery heater
Boiler
Steam
Catalyst Economiser
Convertor Recovery Air
Filter Air
Turbine Compressor 57-60 % HNO3 solution for use or

Eapander Concentrated to 95% HNO3
Make up
Water
Exhaust
Air Gas
Water Condense
Figure: Manufacturing of Nitric acid from by oxidation of ammonia
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
NPTEL 101
Module 4
Dr. N. K. Patel
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
4NH3 + 3O2 2N2 + 6H2O H = - 302.64kcal ---- (12)

4NH3 + 6NO 5N2 + 6H2O H = - 432.25kcal ---- (13)
2NO N2 + O2 H = - 43kcal ---- (14)
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.
4NH3 + 5O2 4NO + 6H2O
Ammonia oxidation reaction has an extremely favourable equilibrium

constant so that one step, high temperature converter design may be used.
NPTEL 102
Module 4
Dr. N. K. Patel
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.
4NH3 + 6NO 5N2 + 6H2O
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
NPTEL 103
Module 4
Dr. N. K. Patel
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. 410 %
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.
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
NPTEL 104
Module 4
Dr. N. K. Patel
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.
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 ions
NPTEL 105
Module 4
Dr. N. K. Patel
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.
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.
NPTEL 106
Module 4
Dr. N. K. Patel
Lecture: 17 Sulfuric acid
Module: 4
Lecture: 17
SULFURIC ACID
INTRODUCTION
Sulfuric acid (H2SO4) is a highly corrosive strong mineral acid. It is a colorless to

slightly yellow viscous liquid which is soluble in water at all concentrations. It is one of
the most important heavy industrial chemicals due to it has a number of large-scale
uses particularly in the phosphate fertilizer industry. About 60 % of the sulfuric acid
produced is utilized in fertilizer manufacture.
Sulfuric acid was called "oil of vitriol" by Medieval. The study of vitriol began in
ancient times. Sumerians had a list of types of vitriol that classified according to
substance's colour.
Johann Glauber prepared sulfuric acid by burning sulfur together with

saltpeter (potassium nitrate, KNO3), in the presence of steam in the 17th century.
Decomposition of saltpeter followed by oxidation produces SO3, which combines
with water to produce sulfuric acid. Joshua Ward used the method for the first large-
scale production of sulfuric acid in 1736.
John Roebuck, produce less expensive and stronger sulfuric acid in lead-lined
chambers in 1746. The strength of sulfuric acid by this method is 65%. After several
refinements, this method, called the "lead chamber process" or "chamber process",
remained the standard for sulfuric acid production for almost two centuries.
The process was modified by Joseph Louis Gay-Lussac and John Glover which
improved concentration to 78%. However, the manufacture of some dyes and other
chemical processes require a more concentrated product. Throughout the 18th
century, this could only be made by dry distilling minerals in a technique similar to
the original alchemical processes.
Pyrite (iron disulfide, FeS2) was heated in air to yield iron(II) sulfate, FeSO4,
which was oxidized by further heating in air to form iron(III) sulfate, Fe 2(SO4)3, which,
when heated to 4800C, decomposed to iron(III) oxide and sulfur trioxide, which
could be passed through water to yield sulfuric acid in any concentration. But the
production expenses are very high.
NPTEL 107
Module 4
Dr. N. K. Patel
More economical process i.e. the contact process was patented by

Peregrine Phillips in 1831. Today, nearly all of the world's sulfuric acid is produced
using this method.
MANUFACTURE
The Industrial manufacture of sulfuric acid is done mainly by two processes
1. The Lead Chamber process

2. The Contact process
1. The lead chamber process
The Lead Chamber process for the manufacture of sulfuric acid dates back
about 200 years. Although less efficient than the contact process, it is still of
considerable commercial importance.
Raw Materials
Basis: 1000kg Sulfuric acid (98% yield)
Sulfur = 400kg
Air = 399kg
Reaction
S + O2 SO2 H = - 70.9kcals
4FeS2 + 11O2 2Fe2O3+ 8SO2
SO2 + NO2 SO3 + NO
SO3 + H2O H2SO4 H = - 92.0kcals
NO + O2 2NO2 H = - 27.12kcals
NaNO3 + H2SO4 NaHSO4 + HNO3
2HNO3 + 2SO2 2SO3 + H2O + NO + NO2
NO + NO2 + 2H2SO4 2NO.HSO4 + H2O
2ON.O.SO2OH + H2O H2SO4 + NO2 + NO
Manufacture
Animation
NPTEL 108
Module 4
Dr. N. K. Patel
Conc. H2SO4
Nitrated Acid
Chamber Acid Watrer Spray
Chamber I Chamber II Chamber III
To Chimney
Gay - lussac Tower

Nitre Pot
Burners
Conc. Acid Chamber Acid
Figure: Manufacturing of Sulfuric acid by Chamber process
Sulfur dioxide is obtained by burning sulfur or by roasting pyrites. There are two
function of burner
1. To oxidize sulfur to maximum extent

2. To produce and constant supply of gas containing maximum concentration
of SO2
The burner of the furnace should expose large surface of melted sulfur and
should be provided secondary air in order to burn sublimed burner. This is necessary
due to low heat of combustion and high vapour pressure of sulfur. At about 400 0C,
pyrite (FeS2) decompose in to FeS and sulfur vapour, the later oxidized to SO 2 in
presence of excess air. The residual FeS also oxidizes to Fe2O3 and SO2. Iron oxide
(Fe2O3) slightly catalyzed oxidation of SO2 to SO3. Burner gas should contain sufficient
oxygen for carry out further oxidation of SO2 to SO3.
The burner gases which contain SO2, N2, O2 and dust or fine particle of pyrites
are passed through dust chamber followed by Cottrell electrical precipitator or
centrifugal separator in order to remove dust or fine particle of ore. Dust chambers
are provided with horizontal shelves or baffles followed by filtration through crushed
coke or similar material.
Now, burner gases are passed through niter oven made of cast iron in which
equimolecular proportion of NaNO3 and H2SO4 is heated. Resulting nitric acid reacts
with SO2 to give mixture of nitric oxide (NO) and nitrogen dioxide (NO2) which are
carried with burner gases.
NPTEL 109
Module 4
Dr. N. K. Patel
In modern plant oxides of nitrogen are produced by passing mixture of

ammonia and air through heated platinum gauze acting as catalyst (same as
manufacture of HNO3 by ammonia oxidation process)
After passing burner gases to dust chamber and niter oven, they pass through
5 meter square and 10 -15meter high Glower tower which is packed with flint stone,
quartz, tile or acid resisting bricks. The packing in the tower is loosely stacked at the
bottom to facilitate mixing of hot gases. The hot burner gases passes up this tower is
at 450 - 6500C and dilute H2SO4 from the lead chamber and nitrosyl sulfuric acid from
Gay-Lussac tower are made to trickle down the Glower tower by means of sprayers.
Here, burner gases are cooled down to 70-800C, dilute chamber acid is
concentrated up to 78% and nitrosyl sulfuric acid (nitrous vitriol) is denitrated by
action of water.
The tower acid is drawn off from the bottom of the tower and collected in the
container called acid egg. The acid from base of Glower tower is cooled to 40 0C by
air coolers.
The mixture of SO2, Oxides of nitrogen and air is then passed to series of
rectangular vessels made of lead (lead chamber) having 15-45 meter length,
6-7 meter width and 7 meter length. The number of chambers depends upon the
size of plant, but usually they are 3 to 6 in number. The chambers are arranged in
two parallel rows. Steam from low pressure boiler or pure filtered water is sprayed
from top of the chamber. Mixture of gases is converted into H 2SO4 having 65-70%v
strength is collected at the bottom of the chamber. Dilute sulfuric acid obtained in
any of the chamber is called chamber acid. A part of chamber acid is pumped to
Glower tower, and the rest is sent for concentration.
The unabsorbed remaining gases contain oxides of nitrogen and SO 2 from

lead chamber are then passed through Gay-Lussac tower at the top of which
Glower acid is sprayed to recover oxides of nitrogen.
The oxides of nitrogen recovered in the form of nitroso sulfuric acid are
pumped to Glower tower to again regenerate oxides of nitrogen.
When pyrite is used as raw material, the chamber acid may contain arsenious
oxide (from pyrite), lead sulfate from lead chamber are removed by treatment of
H2S and dilution of acid respectively. Dilute acid may be further concentrated into
Glower tower.
Kinetics and thermodynamics
2NO+O2 2NO2 H0 =-27.118kcals
NPTEL 110
Module 4
Dr. N. K. Patel
Above reaction is rate controlling step in the chamber process. The

exothermic forward reaction is favoured by decrease in temperature. As the
reaction proceeds with decrease in volume, the formation of NO2 would be
favoured by increase in pressure. It has been observed that the rate of oxidation is
slow at ordinary temperature and rate is proportional to the square of the absolute
pressure. At lower temperature, the production of chamber acid has been found to
be greater. All these facts are in good agreement with the fact that the oxidation of
NO to NO2 is the rate controlling step in this process.
The dilution of nitrosyl sulfuric acid within the Glover tower leads to its
decomposition and nitrous fumes produced catalyze the synthesis of sulfuric acid
when they come in contact with sulfur dioxide and water.
2HSO4.NO + H2O 2H2SO4 + NO + NO2 ---- (1)

NO + NO2 + SO2 + H2O H2SO4 + 2NO ---- (2)
Reaction (2) can be shown in chain as follow
NO + NO2 N2O3 + H2O 2HNO2 + SO2 H2SO4 + 2NO
Reaction (2) can be repeated cyclically by the partial reoxidation of the nitric
oxide produced by excess air which forms part of the sulfurous gas coming from the
combustion chamber.
2NO + 1/2 O2 NO + NO2 ---- (3)
Reaction (2) and (3) mainly occur in chambers following the Glover tower
until the SO2 has been exhausted.
The recovery of nitrous gases is important task of Gay Lussac towers but it is
difficult. A reverse reaction of reaction (1) is taking place here. This is in effect, a
typical equilibrium reaction which is particularly sensitive to the mass action effect
by water
2H2SO4 + NO + NO2 2HSO4.NO + H2O
or reversible reaction
2HSO4.NO + H2O 2H2SO4 + NO + NO2
Above reaction is displaced to the right in the Glover tower where water is
relatively abundant and to the left in the Gay Lussac tower which is supplied with
sulfuric acid which is transformed into nitrosyl sulfuric acid by absorbing
equimolecular mixture of NO and NO2 on account of its high concentration (78%).
NPTEL 111
Module 4
Dr. N. K. Patel
Reason for obsolesce
As discussed above, overall reaction consisting of number of partial reactions

which takes place in liquid phase, the development of surfaces which are covered
in this liquid is a factor of fundamental importance in promoting the synthesis of
sulfuric acid. Maximum strength of sulfuric acid obtained by chamber process is 78%.
However, in manufacture of some dyes and chemical processes require more

concentrated H2SO4. There so, the process is largely replaced by contact process.
NPTEL 112
Module 4
Dr. N. K. Patel
Module: 4
Lecture: 18
SULFURIC ACID (continued)

2. The contact process for sulfuric acid
Almost all sulfuric acid is manufactured by the contact process.
Raw Materials
Basis: 1000kg sulfuric acid (100%)
Sulfur dioxide or pyrite (FeS2) = 670kg
Air = 1450-2200Nm3

The sources of sulfur and sulfur dioxide are as follows
Sulfur from mines
Sulfur or hydrogen sulfide recovered from petroleum desulfurization
Recovery of sulfur dioxide from coal or oil-burning public utility stack gases
Recovery of sulfur dioxide from the smelting of metal sulfide ores
2PbS + 3O2 2PbO + 2SO2
Isolation of SO2 from pyrite
Reactions
S + O2 SO2 H = - 71.2kcals
2SO2 + O2 2SO3 H = - 46.3kcals
SO3 + H2O H2SO4 H = - 31.1kcals
Manufacture
Animation
NPTEL 113
Module 4
Dr. N. K. Patel
Preheater SO2 + O2 + N2
(suphurous gases)
Steam Water Conc. H2SO4
Cooling lead 100 % H2SO4

pipe Hot gases
Tyndall
box H.E.-1 Waste
Gases
Air
Sulphur H.E.-2
pyrites Dust Scrubber Drying Arsenic
burner chamber Tower Purifier H.E.-3
Absorber
Oleum
SO3
Figure: Manufacturing of Sulfuric acid by Contact process
Steps in the Contact Process
The steps in this process are as follow.
1. Burning of sulfur
2. Catalytic oxidation of SO2 to SO3
3. Hydration of SO3
1. Burning of sulfur
Burning of sulfur in presence of dry air is carried out in sulfur pyrite burner. As
SO2 is needed for the catalytic oxidation and prevention of corrosion, dry air is used
in the combustion process. If sulfur contains carbonaceous impurities, the molten
material has to be filtered to avoid poisoning the catalyst and forming water from
burning hydrogen.
2. Catalytic oxidation of SO2 to SO3

When using sulfur from sources 1 and 2, purification of the SO2 gas is normally
not needed. Other sources of SO2 require wet scrubbing followed by treatment of
the gas with electrostatic precipitators to remove fine particles. The catalyst used is
vanadium pentoxide (V2O5) and the pressure is 1.2-1.5 atmospheres. The
temperature has to be kept around 4500C. If it rises above 4500C, the equilibrium is
displaced away from SO3. Temperature should reach around 4500C for the catalyst
to be activated. This process is strongly exothermic. The catalytic reactor is designed
as a four-stage fixed-bed unit. The gas has to be cooled between each step. Four
passes, together with "double absorption, described below, are necessary for overall
conversion of 99.5-99.8% (three passes, 97-98%). The temperature rises to over 6000C
with the passage of the gas through each catalyst bed. The doubled absorption
consists of cooling the gases between each bed back to the desired range by
sending them through the heat exchanger and then back through the succeeding
beds. Between the third and fourth beds, the gases are cooled and sent to an
NPTEL 114
Module 4
Dr. N. K. Patel
absorption tower. This is to shift the equilibrium to the right by absorbing SO3. The
gases are then sent to the heat exchanger to warm them to 410-4300C and then on
to the fourth catalyst bed.
3. Hydration of SO3
After the catalytic oxidation process, the resulting SO3 is hydrated by
absorption in packed towers filled with 98-99% sulfuric acid. This is the H2SO4
azeotrope of minimum total vapour pressure. The catalytic oxidation has to proceed
in high yield to avoid air pollution problems. SO2 has a low solubility in 98% H2SO4. At
lower acid concentrations, sulfuric acid and SO3 form a troublesome mist and at
higher concentrations emissions of SO3 and H2SO4 vapour become significant. The
absorption acid concentration is kept within the desired range by exchange as
needed between the H2SO4 in the drying acid vessel that precedes the combustion
chamber with the H2SO4 in the absorption tower. The acid strength can be adjusted
by controlling the streams of H2SO4 to give acid of 91 to 100% H2SO4 with various
amounts of added SO3 and water. The conversion of sulfur to acid is over 99.5%.

The crucial step is the oxidation of SO2 to SO3. At normal conditions, the
equilibrium lies far to the left and the amount of SO3 formed is very small. To improve
the yield of SO3, the reaction is carried out at around 4500C and 1.5-1.7atm pressure
in presence of V2O5 or Pt as catalyst.
2SO2 + O2 2SO3 H = - 46.98kcal
These conditions are chosen by applying Le Chatelier's principle as explained

below.
Effect of temperature
Since the forward reaction is exothermic, at higher temperatures the
backward reaction i.e., the dissociation of SO2 is more favoured. However, at very
low temperature, the rate of combination of SO2 and O2 is very slow and at higher
temperature of about 4500C, the rate of formation of SO3 is high and rate of
decomposition of SO3 is minimum. Hence, the temperature range which best meets
kinetics and thermodynamics requirements for high yield in the synthesis of SO 3 is
located in between 4000C to 5000C, with optimum temperature at about 4500C.
Effect of pressure
In the forward reaction i.e. formation of sulfur trioxide, the number of moles of
gaseous components is decreasing.
ng = (2) - (2+1) = -1
NPTEL 115
Module 4
Dr. N. K. Patel
The formation of SO3 takes place with decrease in volume and hence
increase in pressure is expected to increase the rate of formation of SO 3, i.e., rate of
forward reaction. However, it has been observed that there is no appreciable
change in the yield at higher pressures. Also, higher pressure will increase the rate of
corrosion of iron tower used in the process. Hence pressure of 1.5-1.7atm is usually
satisfactory.
The equilibrium constant in terms of partial pressure is given by
The amount of SO3 at various concentrations of SO2 and O2 can be estimated

by using partial pressures of the gases. If a and b are the moles of SO 2 and O2
respectively and X is the mole of SO3 formed at equilibrium, then Kp is given by,
( )
( ) ( )
Rate of contact reactions

The main steps involved in the rate of contact reactions in heterogeneous
catalyst are as follows
Diffusion of the reacting gases to the catalyst

Adsorption of the gases on the surface of the catalyst
Chemical reactions taking place on the surface of the catalyst
Desorption of the reaction products from the surface of the catalyst
Diffusion of the reacted molecules away from the catalyst
It has been observed that the rate of oxidation of SO2 on the surface of
platinum catalyst is proportional to the pressure of SO2 and inversely proportional to
the square root of the pressure of SO3. The rate is independent of the pressure of
oxygen. The energy of activation on platinum surface is about 10kcal/mole as
against an activation energy of about 23-34kcal/mole for the promoted vanadium
catalyst. Maximum value of 34kcal/mole has actually been observed for pure V2O5
catalyst. The rate of oxidation of SO2 to SO3, on the surface of vanadium catalyst
largely depends upon the pressure of oxygen and weakly upon the pressure of SO2.
The rate of oxidation is determined by the following three steps.
Rate of absorption of reacting gases ( SO2 and O2) on the surface of the
catalyst
Chemical reactions between absorbed SO2 and O2 on the surface of the
catalyst
The rate of desorption of SO2 from the surface
NPTEL 116
Module 4
Dr. N. K. Patel
The actual reactions are very complicated, as they involve a series of

reactions between the gas, the catalyst, the promoters and the carriers.
Comparison of vanadium and platinum catalyst

Aspect Vanadium catalyst Platinum catalyst
Conversion Higher Lower and decrease with use
Investment Initially less, 5% replacement is
High, Lower life and highly
required per year fragile
Catalyst poisoning Relatively immune to poison
Poisoned, especially by
arsenic
Handling of SO2 Less (7-8%) High (8-10%)
Requirement per 14kg catalyst mass containing 189gms
1000kg 7-8%V2O5
(100% acid)/day
Operation of multistage convertor
SO2 + O2 + N2
(sulfurous gases)
H.E.-1
Access
ports
H.E.-2
H.E.-3
SO3
Figure: Multistage reactor for the conversion of SO2 into SO3
NPTEL 117
Module 4
Dr. N. K. Patel
The apparatus in which SO2 is converted into SO3 is as shown in figure. It is

designed so as to achieve high rate of conversion along with highest possible
thermodynamic yields. The convertor is subdivided into several compartments
having separate layers of catalytic mass supported by meshes.
In four compartment reactor, upon entering the reactor from top , the
sulfurous gases have been heated to about 4000C by heat exchange carried out
earlier on the sulfurous gases themselves, the added air or the mixture of them are
heated up to about 6000C where upon they react. The rate of reaction is high but
the yield does not exceed 75%.
Upon leaving the first compartment the temperature of the partially

converted gases is lowered by 1000C in the gas-gas heat exchanger (HE-1), and
they are returned to the converter where, in correspondence with the temperature
of the catalytic bed in the second compartment, they are brought up to about
5000C and react to form further SO3 from SO2. The rate of reaction is lower but the
yield goes up to 85%.
The gases are again sent out of the reactor and their temperature is reduced
again by 1000C by means of heat exchanger (HE-2). Then returned to third
compartment where yields raised up to 95% by passing through the catalytic bed at
4800C. The rate of reaction is further lowered, but now only small amounts of gas to
be converted into SO3.
After lowering the temperature third time by external heat exchange (HE-3),
the gases are passed back to the reactor where they undergo on the catalytic bed
in the fourth compartment, final conversion at about 4500C, which gives yield of 98-
99%.
Major engineering problems
Design of multistage catalytical convertor for highly exothermic reaction.

Earlier two stage converter is used but nowadays the design of three or four
stages rather than conventional two stage operation are developed.
To optimize space velocity in catalyst chamber because it deals with
pumping cost or fixed charges of reactor
Thin catalyst beds of 30-50cm height used to avoid above difficultties. Yield
can drop due to longitudinal mixing if the convective gas velocity through
the bed is low
Removal of heat of absorption of SO3 in acid. Pipe coolers with water dripping
over external surface have been replaced by cast iron pipe with internal fins
to promote better heat transfer.
Pressure drop must be low, so, 8cm stacked packing is often used.
NPTEL 118
Module 4
Dr. N. K. Patel
PROPERTIES
Physical Properties
Molecular formula : H2SO4
Appearance : Water white slightly viscous liquid
Boiling point : 2900C
Melting point : 100C
Solubility : Miscible with water in all proportions
Viscosity : 26.7cP (200C)
Aqueous sulfuric acid solutions are defined by their H2SO4 content in weight-
percent terms.
Anhydrous (100%) sulfuric acid sometimes referred to as monohydrate,
which means that it is the monohydrate of SO3.
Dissolve any quantity of SO3, forming oleum (fuming sulfuric acid).
The physical properties of sulfuric acid and oleum are dependent on H 2SO4
and SO3 concentrations, temperature, and pressure.
Chemical Properties
1. Dehydrating agent
Has a great affinity for water and the reaction is extremely exothermic.
A large amount of heat is produce due to formation of mono and dehydrates
(H2SO4.H2O and H2SO4.2H2O) on mixing acid with water. So while preparing
dilute solutions of H2SO4 the acid should be added to water slowly with
constant stirring. Never add water to the acid.
Used for drying almost all gases, except NH3 and H2S.
Its corrosive action on skin is also due to dehydration of skin which then burns
and produces itching sensation.
Due to dehydrating property, it chars sugar to give carbon.
C12H22O11 12C + 11H2O
Also, paper, starch, wood etc. are charred by conc. H2SO4 due to the
removal of water. It is also used in removing water from various substances
such as oxalic acid and formic acid.
COOH-COOH H2O + CO + CO2
2. Oxidising agent
Gives O2 on strong heating, hot conc. H2SO4 also acts as an oxidising agent.
3. Pickling agent
Finds application in pickling in which layers of basic oxides are removed
before electroplating, enameling, galvanizing and soldering.
NPTEL 119
Module 4
Dr. N. K. Patel
4. Acidic nature
Strong dibasic acid and forms two series of salts with alkalis. These are
bisulfates (HSO4-) and sulfates (SO4-2).
USES
The largest single use is in the fertilizer industry.

Mostly in production of phosphoric acid, which in turn used to manufacture
fertilizers such as triple superphosphate, mono and diammonium phosphates
Used for producing superphosphate and ammonium sulfate.
Used as an acidic dehydrating reaction medium in organic chemical and
petrochemical processes involving such reactions as nitration, condensation,
and dehydration, as well as in oil refining, in which it is used for refining,
alkylation, and purification of crude-oil distillates
In the inorganic chemical industry e.g. in the production of TiO2 pigments,
hydrochloric acid, and hydrouoric acid
In the metal processing industry e.g. for pickling and descaling steel, for
leaching copper, uranium, and vanadium ores in hydrometallurgical ore
processing, and in the preparation of electrolytic baths for nonferrous-metal
purification and plating
Certain wood pulping processes in the paper industry require sulfuric acid,
used in textile and chemical fiber processes and leather tanning
In manufacture of explosives, detergents and plastics
In production of dyes, pharmaceuticals
NPTEL 120
Module 4
Dr. N. K. Patel
Lecture: 19 Hydrochloric acid
Module: 4
Lecture: 19
HYDROCHLORIC ACID
INTRODUCTION
Hydrochloric acid (HCl), also known as muriatic acid, is a solution of hydrogen

chloride in water. HCl exists in solid, liquid, and gaseous states and is water soluble in
all proportions.
The first hydrochloric acid was prepared through heating common salt and
sulfuric acid by Benedictine Monk and Basil Valentine in 15th century. Also, Libavius
prepared free hydrochloric acid by heating salt in clay crucibles in 16th century.
In the 17th century, Johann Rudolf Glauber used NaCl and H2SO4 for the
preparation of sodium sulfate in the Mannheim process, releasing hydrogen chloride
gas as a by-product. Joseph Priestley prepared pure HCl in 1772, and chemical
composition includes hydrogen and chlorine was proven by Humphry Davy in 1818.
Demand for alkaline substances increased during the Industrial Revolution in

Europe, Nicolas Leblanc developed cheap large-scale production of sodium
carbonate (soda ash). Using common salt, sulfuric acid, limestone and coal which
release HCl as a by-product. Until the British Alkali Act 1863 and similar legislation in
other countries, the excess HCl was vented to air. After the passage of the act,
waste gas is absorbed in water, producing hydrochloric acid on an industrial scale.
In the twentieth century, the Leblanc process was effectively replaced by the
Solvay process without hydrochloric acid by-product. Since hydrochloric acid was
already fully settled as an important chemical in numerous applications, the
commercial interest initiated other production methods, some of which are still used
today. After the year 2000, hydrochloric acid is mostly made by absorbing by-
product hydrogen chloride during a chemical manufacturing process such as
chlorination of hydrocarbons.
Since 1988, hydrochloric acid has been listed as a Table II precursor under the
1988 United Nations convention against illicit traffic in narcotic drugs and
psychotropic substances because of its use in the production of heroin, cocaine,
and methamphetamine.
NPTEL 121
Module 4
Dr. N. K. Patel
MANUFACTURE
HCl is manufactured by various methods as follows
1. Synthesis from hydrogen and chlorine

2. From salt and sulfuric acid
3. As by-product from chemical processes
4. From incineration of waste organics
5. Hydrochloric acid solutions
1. Synthesis from Hydrogen and Chlorine
There is large demand in the market for water white acid. Such acid is
obtained by synthetic method, and most of the plants are based on this process.
Raw materials
Basis: 1000kg of Hydrochloric acid (98% yield)
Hydrogen = 28.21kg
Chlorine = 999.21kg

Both hydrogen and chlorine can be obtained during electrolysis of brine for
manufacturing of NaOH as described in Module: 3, Lecture: 13.
Also, hydrogen can be synthesized from any one methods of following which
are described in detail in Module: 2, Lecture: 4.
1. Lane process or iron steam process

2. Steam hydrocarbon process
3. Liquefaction of coal gas and coke oven gas
4. Bosch process or water gas-steam process
Reaction
H2 + Cl2 2 HCl H = - 43.9kcals
Manufacture
Animation
NPTEL 122
Module 4
Dr. N. K. Patel
Dilute acid or water

added under control
Cold water
inlet
Exit for
exhaust
Combustion Hydrogen Exhaust gas
chamber burning fan
in chlorine
Chlorine Water
outlet
Hydrogen
Hydrochloric
acid
storage tank
Figure: Manufacturing of Hydrochloric acid from hydrogen and chlorine combustion
The plant consists of combustion chamber of structural carbon or lined with

silica bricks provided with cooling device which may consist even of cold-water
circulation in the shell. To ensure all the chlorine reacts with hydrogen, excess of 10%
hydrogen compare to chlorine is charged from the bottom of combustion chamber.
Also, care should be taken that the combustion chamber and length of ducting
which leads the gas to absorber should be sufficiently specious, otherwise
hydrochloric acid will contain free chlorine. The burning of hydrogen is started by
igniting the burner with an external air-hydrogen torch. Dry chlorine is passed into the
combustion chamber, where hydrogen burns in an atmosphere of chlorine to
produce HCl. The exothermic nature of the direct combination of both gases (H2
and Cl2) is such as to raise the temperature of the reagents, and the reaction
products to a point where they are incandescent. The reaction is carried out at
24000C with greenish flame. The gases are always kept above dew point to avoid
corrosion. The combustion chamber is then cooled externally by water and gas tight
lid is fitted at the top of the reactor which suddenly opens to allow the gases to
escape in case of emergency. Hydrochloric acid gas is cooled absorbed in water
or dilute HCl solution by passing through cooler and absorber through the
connecting pipe. The strength of acid produced is generally 32-33 %. The heat of
absorption of HCl in water is removed by spray of cold water outside the absorber.
The solution of HCl flows into a storage tank.
Anhydrous hydrogen chloride

Hot gases originating from combustion chamber are passing over anhydrous
CaCl2 or washing them with 98% sulfuric acid and then cooled and compressed to
60atm pressure. The cooled and compressed gas having 99.9% purity is filled in steel
cylinders.
NPTEL 123
Module 4
Dr. N. K. Patel
In another process, absorb the combustion gas into water and distilled it to
36% concentration of HCl. If one is to obtain 97% HCl at the top of the column. The
35% acid is cooled to -120C and aqueous liquid containing 50% HCl is left to
condense, while residual gases, when they have been de nebulized as compressed
to 60atm are of purity exceeding 99.5%.
Thermodynamics and kinetics

H2 + Cl2 2HCl H = - 44kcal
Above exothermic reaction is much favoured by both by large evolution of

energy and the product gas leaving the chamber, thereby circumventing the fact
that equilibrium would otherwise be attained. The very fact that equilibrium is not
established also precludes the large increase in temperature from having a negative
effect on the yield of highly exothermic reaction.
On account of the existence of large energy barrier to the reaction, mixture

of molecular H2 and Cl2 is stable at ambient temperatures and in absence of
suitable wavelengths. Photons with frequencies which are able to furnishing the
activation energy can be produced by creating an electrical spark in a mixture of
molecular H2 and Cl2 or by first burning mixture of H2 with air and then gradually
replacing air with chlorine.
The initiation, propagation and termination of the chain reactions are as

follows
Initiation
Cl2 + h 2Cl
Propagation
Cl + H2 HCl + H+
H + Cl2 HCl + Cl
Termination
Cl + Cl Cl2 + heat
H + H H2 + heat
H + Cl HCl +heat
A large amount of heat is developed both from chain propagation reactions

and from chain termination processes, the continued renewal of the chain
propagators by thermal route is ensured over the long term. In brief reaction
between hydrogen and oxygen to produce hydrogen chloride is a chain reaction
with a high quantum yield.
NPTEL 124
Module 4
Dr. N. K. Patel
Engineering aspect
The combustion chamber and ducting to absorber should be sufficiently
specious for avoiding wall effect. From physicochemical point of view if the walls of
reactor in which chain reactions takes place by their varying nature, development,
shape and orientation as to affect the chain carriers is called wall effect. In the
present case wall tends to interrupt the process by promoting the chain breaking
reaction (termination reactions). Physico chemically, chain terminators act as a third
body in a system which already consists of the reactant bodies.
2. The SaltSulfuric acid process
The reaction between NaCl and sulfuric acid occurs in two endothermic
stages.
Raw materials
Basis: 1000kg Hydrochloric acid
Sodium Chloride = 3206kg

Sodium chloride can be obtained from sea water, salt lake and sub soil
water as described in Module: 3, Lecture: 8.
Sulfuric acid can be obtained by contact process as described in Module: 4,

Lecture: 18
Reaction
NaCl + H2SO4 NaHSO4 + HCl
NaCl + NaHSO4 Na2SO4 + HCl
Manufacture
Animation
NPTEL 125
Module 4
Dr. N. K. Patel
Off
gases H2O
Salt
H2SO4
H2O Cooler
Scrubber
Cooler
Reactor
Absorber
Na2SO4
HCl
Fuel H2SO4 Storage
Figure: Manufacturing of Hydrochloric acid from salt and sulfuric acid
Salt (NaCl) and sulfuric acid are charged to the furnace. It is desirable to
keep one of the components in the reaction mixture in a liquid form in both steps.
The first step is carried out at the lower temperature compare to second step. Even
so, for liquefaction of NaHSO4, which is required to carry out in second step, material
is heated up to 4000C. Sodium sulfate in form of sludge is collected from the bottom
of the furnace. The product and unconverted sulfuric acid is sent to further
processing in which recovery of sulfuric acid and nitric acid in cooling tower and
absorber respectively.
3. As by-product from chemical processes
Over 90% of the hydrogen chloride produced as a by-product from various

chemical processes. The crude HCl generated in these processes is generally
contaminated with impurities such as unreacted chlorine, organics, chlorinated
organic and entrained catalyst particles. A wide variety of techniques are
employed to treat these HCl streams to obtain either anhydrous HCl or hydrochloric
acid. Some of the processes in which HCl is produced as by-product is the
manufacture of chlorouorohydrocarbons, manufacture of aliphatic and aromatic
hydrocarbons, production of high surface area silica, and the manufacture of
phosphoric acid and esters of phosphoric acid.
4. From incineration of waste organics
Environmental regulations regarding the disposal of chlorine-containing

organic wastes have motivated the development of technologies for burning or
paralyzing the waste organics and recovering the chlorine values as hydrogen
chloride. Several catalytic and non-catalytic processes have been developed to
treat these wastes to produce hydrogen chloride.
NPTEL 126
Module 4
Dr. N. K. Patel
5. From hydrochloric acid solutions
Gaseous hydrogen chloride is obtained by partially stripping concentrated

HCl acid using an absorberdesorber system. The stripper is operated at a pressure
of 100200kPa (12atm) for improved recovery of HCl. The overhead vapors
consisting of 97% HCl and 3% H2O is cooled to remove most of the water as
concentrated HCl, and the residual water vapor is removed by drying the gas with
sulfuric acid.
PROPERTIES
Molecular formula : HCl

Appearance : Colourless liquid
Odour : Pungent
Boiling point : -850C
Melting point : -1140C
Density : 1.179gm/mL (35.2% HCl )
Solubility : Extremely soluble in water
Water solubility depends on temperature. At 760mmHg (1atm) pressure 1liter
of water dissolves 525.2 liters of HCl at 00C (46.15%w of HCl) and at 180C,
451.2 liter of HCl are dissolved (42.34%w of HCl).
Forms azeotropic mixture with water, containing 20.24% HCl which boils at
1100C.
Commercially available in 27.9%, 31.5% and 35.2%wt HCl solution in water.
Anhydrous HCl is available in steel cylinders because completely dry HCl is not
very reactive. But dry HCl often reacts only in the presence of catalysts.
Solution of hydrogen chloride in a polar solvent is strong acid and, therefore,
an aggressive reagent.
USES
Hydrogen chloride and the aqueous solution, muriatic acid, find application
in many industries.
Anhydrous HCl is consumed for its chlorine value, whereas aqueous

hydrochloric acid is often utilized as a non-oxidizing acid.
Used in metal cleaning operations, chemical manufacturing, petroleum well
activation, and in the production of food and synthetic rubber.
Used for the manufacture of chlorine and chlorides, e.g. Ammonium chloride
used in dry cell.
In the manufacture of glucose from corn starch.
For extracting glue from bones and purifying boneblack.
A saturated solution of zinc chloride in dilute HCl is used for cleaning metals
before soldering or plating.
NPTEL 127
Module 4
Dr. N. K. Patel
It is also used in medicine and as laboratory reagent.

Aqua regia used for dissolving metal
NPTEL 128
Module: 4
Dr. N. K. Patel
Lecture: 20 Phosphorous
Module: 4
Lecture: 20
PHOSPHOROUS
INTRODUCTION
Phosphorus is the chemical element that has the symbol P and atomic
number 15. As phosphorus was the 13th element to be discovered and can be used
in explosives, poisons and nerve agents is referred as "the Devil's element". It is
essential for life. It is a component of DNA, RNA, ATP, and also the phospholipids that
form all cell membranes.
Hennig Brand discovered phosphorous during his experiment on urine in 1669.

Robert Boyle was the first to use phosphorus to ignite sulfur-tipped wooden splints,
forerunners of our modern matches, in 1680.
Due to its high reactivity, phosphorus is never found as a free element on

Earth. Phosphorus as a mineral is present in its maximally oxidized state, as inorganic
phosphate rocks from which it can be extracted out. Phosphorous which is primarily
extracted from calcium phosphate rocks consider as an expensive mineral but, with
the increasing demand of phosphorous products like phosphoric acid, synthetic
fertilizer and phosphate salts. The situation demands modification in extraction
method as well as product manufacture.
Elemental phosphorus exists in two major forms
White phosphorus
Red phosphorus,
White phosphorus was first made commercially, for the match industry in the
19thcentury, by distilling off phosphorus vapour from precipitated phosphates, mixed
with ground coal or charcoal, which was heated in an iron pot, in retort. The
precipitated phosphates were made from ground up bones that had been
degreased and treated with strong acids. Carbon monoxide and other flammable
gases produced during the reduction process were burnt off in a flare stack. This
process became obsolete when the submerged arc furnace for phosphorus
production was introduced to reduce phosphate rock. The electric furnace method
allowed production to increase to the point where phosphorus could be used in
weapons of war.
NPTEL 129
Module: 4
Dr. N. K. Patel
PHOSPHATE ROCK
Phosphate rock is a natural mineral found as a geological deposit on a large
scale in the form of sedimentary rocks containing various amounts of calcium
phosphates. India alone is estimated to have about 140 million tons of rock
phosphate deposits, most of which are however, of low grade and with substantial
impurities unsuitable for the production of phosphate fertilizers.
Phosphate rock is used as a phosphatic fertilizer after grinding called

phosphorite or mineral phosphate, or as a primary source of phosphorus. Finely
ground rock (60-100mesh size) phosphate can be applied directly to the acidic soil.
For neutral or alkaline soils acid-treated rock phosphate (like superphosphate) is
used. Powdered rock phosphate is free-flowing and is easily amenable to handling
and storage. Crops like rubber, tea, coffee, apples and fruit plantations of oranges
are suitable for direct application of rock phosphate.
Francolite (calcium carbonate-fluorapatite) of formula [Ca5(PO4,CO3)3(F,OH)

is the most predominant mineral of phosphate. Four kinds of phosphate rocks are
recognized: hard rock phosphate, soft rock phosphate, land pebble phosphate and
river pebble phosphate, with the phosphorus content varying from 2 to 21 %.
Phosphate rock contains phosphorous in an apatite form which is water

insoluble. The citrate solubility can vary from 5 to 17 % of the total phosphorus,
depending on the chemical nature of the rock and the size to which it is ground.
The efficiency of the ground rock phosphate can be increased by
Mixing with soluble phosphorus and fertilizers

Mixing with elemental sulfur or sulfur-producing compounds
Using phosphate solubilizing micro-organisms
More than 90% of rock phosphate is used for production of superphosphate

and phosphoric acid. Less than 8 % is used directly as soil fertilizer and about 2 % as
animal and poultry feed.
Purification
Calcium phosphate is obtained after removal of various impurities present in
phosphate rock. The up grading of ore and removal of impurities is carried out by
Floatation of phosphate rock.
Clays (kaolinite, illite, smectites and attapulgite), quartz and other silicates
(feldspars), carbonates (calcite and dolomite), secondary phosphates (phosphates
bearing iron and aluminum) and iron oxides (geothite, hematite and magnetite) are
the common impurities which are associated with phosphate rock.
NPTEL 130
Module: 4
Dr. N. K. Patel
Phosphate ore beneficiation is done by many methods. Froth floatation is a

widely used technique in the phosphate industry. Froth floatation is generally
employed with siliceous ores when other less expensive or less complicated
techniques fail to produce phosphate concentrates suitable for chemical
processing. Prior to its conditioning for floatation, the floatation feed of phosphate
rocks is delimed.
In the floatation of phosphate ores, apatite particles are generally directly

transferred to the froth fraction (direct floatation) by using anionic collectors such as
fatty acids. The anionic collectors selectively attach themselves to the phosphate
particles, render them hydrophobic and lift them to the surface by the froth and air
bubbles formed. The mineral bearing froth may simply overflow the cells or paddles
or may be skimmed off. Quartz and other silicates are removed from the bottom of
the floatation cells.
A second stage of floatation may be required to remove silica from the

phosphate-rich float by cationic collectors (usually amines), when silica is floated
and the phosphate particles settle to the underflow.
A selective floatation of carbonates from phosphate rock is rather difficult

owing to the similarity in the physicochemical properties of the carbonate and
phosphate minerals. Several treatments have been proposed, including floatation,
calcination, acid washing, magnetic separation and heavy media separation for
the removal of free carbonates from the phosphates.
Uses
The most important use of phosphate rock is in fertilizers. Table is a compilation
of phosphate-rock treatment processes.
NPTEL 131
Module: 4
Dr. N. K. Patel
Table: Phosphate-rock processing, products and byproducts
Process Raw materials Main products By- products

and reagents and derivatives
Acidulation Phosphate rock, Superphosphate, Fluorine
Sulfuric acid, phosphoric acid (wet compounds
phosphoric acid, process) triple vanadium,
hydrochloric acid super phosphate , mono uranium (limited)
ammonia, ammonium phosphate,
potassium chloride diammonium phosphate,
Electric-furnace Phosphate rock, Phosphorus, phosphorus Fluorine
reduction siliceous flux, coke pentoxide and halides, compounds,
(for reduction), phosphoric acid, triple CO, slag
electrical energy, superphosphate, various (for RR ballast
condensing water Na,K,NH4,Ca salts; mono aggregate,
potassium phosphate fillers,
ferrophosphorus
Calcium Phosphate rock, Calcium metaphosphate Fluorine
metaphosphate phosphorus, air or compounds
oxygen, fuel
Calcination or Phosphate rock Defluorinated phosphate Fluorine
defluorination silica, water or compounds
steam, fuel
YELLOW PHOSPHORUS
Raw materials
Basis: 1000kg Phosphorus
Calcium phosphate = 6804kg
Sand = 2018kg
Coke = 1202kg
Carbon electrode consumption = 22.68kg
Electricity = 13000kWH
Reaction
2Ca3(PO4)2 + 10C + 6SiO2 CaSiO3 + P4 + 10CO
Manufacture
Animation
NPTEL 132
Module: 4
Dr. N. K. Patel
Phosphate
Rock
Grinder
Sinterer
Screen
Coke and Sand CO
Electrostatic Yellow
Hopper
Precipitator Phosphorous
Fines to Waste
A Cooler
Molten Electric Furnace
Slag
Figure: Manufacturing of Yellow Phosphorous
Rock phosphate is crushed as fine powder, so that complete transformation

to phosphorous pentoxide (P2O5) and finally element phosphorous is possible. The
powdered rock phosphate is mixed with sand and coke powder in the required
proportion and charged into electric furnace having electrodes at bottom. The
base of furnace is heated with carbon blocks as the temperature increases due to
electrical heating. Reaction of rock phosphate with sand starts at about 11500C
resulting into calcium silicate and P2O5. Further increasing the temperature to 15000C
carbon particle reacted with P2O5 there by phosphorous and carbon monoxide
formed which is collected from top outlet. Residual calcium silicate settles down at
bottom in form of slag which is taken out time to time from the outlet provided at
bottom of the furnace.
Product gases which is mixture of phosphorous and carbon monoxide is

cooled in a water cooler thereby phosphorous solidify and carbon monoxide gas is
separated. Purification of phosphorous is carried out by melting it and treating with
chromic acid (mixture of K2Cr2O7 and H2SO4). The carbon and silicon impurities are
removed due to oxidation. Pure phosphorous which is pale yellow colour is washed
with water before it is casted into sticks.
NPTEL 133
Module: 4
Dr. N. K. Patel
Recovery of the products

The fumes emerging from the furnace are first freed from any mineral and
other fine reagents which may have been carried up at less than 3000C so that the
phosphorous is not condensed out. The remaining gases consist of phosphorous, CO
and SiF4, are sent to a bottom of tower in which water is sprayed from two different
heights. Care should be taken that temperature should not drop below 600C. The
phosphorous condenses out but does not solidify, is collected under water which
reacts with the SiF4 gas, converting into metasilicic and fluorosilicic acids.
SiF4 + 3H2O H2SiO3 + 2H2SiF6
The fluorinated components are subsequently recovered from the solution.

CO which is completely freed from phosphorous and fluorine compounds is then
cooled, dried and subsequently used as a fuel.
The slags consisting of CaSiO3, which are produced in the furnace and
subsequently discharged from outlet provided at base of furnace, are good
additives for cements, air-port runway construction and antiskid conglomerates.
The liquid phosphorous, after decolouration with activated carbon is filtered

and solidify to yellow phosphorous. It is stored under water.

It is important to ensure that three component i.e. phosphate minerals, silica
and coke are thoroughly and homogeneously mixed with one another. To do this if
they are obtained from flotation processes, the phosphate mineral must be
agglomerated or converted into nodules after addition of a small amount of
quartzite in rotating furnaces which are heated by utilizing the combustion of
carbon monoxide, which is formed during the process, in conjugation with that of
fuel oil.
The arc resistance furnace is responsible for providing the energy, by the
conversion of electricity into thermal energy, required for the above endothermic
reaction which requires 5894kcal/kg.
India has abundant supply of calcium phosphate, salt and coke, but the
manufacture of phosphorus largely depends upon the production of cheap electric
power.
RED PHOSPHORUS
Raw material
Yellow phosphorous
NPTEL 134
Module: 4
Dr. N. K. Patel
Manufacture
Burning
Phosphorus
Iron safety tube
Thermometer Na2CO3 Water
Casr iron
Temp.
pot
Cooler
240 0 C Fire brick
setting
Charged with Coke

white or yellow Furnace
phosprus Ashpit
Washer Washer Dryer Red
Phosphorous
Figure: Manufacturing of Red Phosphorous
Animation
Batch process
Yellow phosphorous obtain from earlier process is taken into iron pot provided
with safety outlet and thermometer jackets. Conversion of yellow phosphorous to
red phosphorous is exothermic reaction and strict maintenance of temperature in
range 2400C to 2500C in required as conversion do not take place below 2400C and
above 2500C accident chances are there. After complete conversion product is
washed with NaOH solution as yellow phosphorous is soluble but red phosphorous is
not soluble in NaOH
Continuous process
In the process liquid white phosphorous is maintained at boiling point for
5-6hrs to achieve 35 to 50% conversion. The product is taken into screw conveyer in
which unreacted phosphorous vaporizes which is recrystallize and recycled. The red
phosphorous is of high purity and therefore doesn't require further purification.
PROPERTIES
Molecular formula :P
Molecular weight : 30gm/mole
Appearance : White, red and black solid
Odour : Irritating odour
Boiling point : 280.50C
NPTEL 135
Module: 4
Dr. N. K. Patel
Melting point : 44.20C

Density : 2.2-2.34gm/ml
Solubility : Insoluble in water and soluble in carbon disulfide
White phosphorus is a highly reactive, waxy, white-yellow, transparent solid
with acrid fumes. It emits a weak green glow (luminescence) in the presence
of oxygen. White phosphorus ignites spontaneously in air.
USES
Red phosphorus is used in fireworks, smoke bombs and pesticides.
Black phosphorus no significant commercial uses due to least reactivity.
White phosphorus and zinc phosphate are mainly used as a poison for rats.
Used in making incendiary bombs, tracer bullets and for producing smoke
screen
Used in fertilizers, which provides phosphate as required for all life and is often
a limiting nutrient for crops.
Used in the manufacture of PCl3, PCl5, P2O5 and phosphorus bronze
Organophosphorus compounds used in detergents, pesticides and nerve
agents, and matches
Phosphorus is one of the most essential mineral in the body and is ranked
second to calcium. However, the deficiency of phosphorous is relatively rare
About 80% of all phosphorus is present in human body in the form of calcium
phosphate in the teeth and bones.
It also participates in several vital functions of the body, such as energy
metabolism, synthesis of DNA and the absorption and utilization of calcium.
Phosphorus plays a role in facilitating optimal digestion.
It helps in the normal functioning of the kidneys and ensures proper discharge
of wastes.
Adequate levels in body is essential to maintain normal brain functions
Phosphorus helps maintain a good hormonal equilibrium.
NPTEL 136
Module: 4
Dr. N. K. Patel
Lecture: 21 Phosphoric acid
Module: 4
Lecture: 21
PHOSPHORIC ACID
INTRODUCTION
Phosphoric acid (H3PO4), also known as orthophosphoric acid or

phosphoric(V) acid, is a mineral (inorganic) acid. Orthophosphoric acid molecules
can combine with themselves to form a variety of compounds which are also
referred to as phosphoric acids.
Amongst the mineral acids, phosphoric acid stands an special status as it is

used for specialty application including anticorrosive and food industry out of
number of processes available only the latest are discussed below which includes
applications of electric furnace, blast furnace and process including oxidation and
hydration of phosphorous or the wet process which uses sulfuric acid and rock
phosphate.
The continuous process of phosphoric acid production uses liquid white

phosphorous at the boiling condition for 5 to 6hrs so that about 35 - 50 % white
phosphorous is converted to red phosphorous. The hot red phosphorous is taken in a
screw conveyer which along with inert gases gives a solid pure red phosphorous as
product. Red phosphorous finds the application in manufacturing of matchsticks,
chlorides of phosphorous as PCl3, PCl5, phosphorous oxide as P2O5 and phosphor
bronze etc.
MANUFACTURE
The modern manufacturing methods of phosphoric acid are following:
1. Using phosphate rock and blast furnace

2. Using phosphate rock and electric furnace
3. Oxidation and hydration of phosphorous
4. Wet process or from sulfuric acid and phosphate rock
1. Using phosphate rock and blast furnace
The blast furnace process was widely used in the first three decades of 20 th
century. Resulting phosphoric acid can be used in manufacturing of insecticide,
pesticides, detergents etc. but not for fertilizers.
NPTEL 137
Module: 4
Dr. N. K. Patel
Raw materials
Basis: 1000kg phosphoric acid (100%)
Phosphate rock = 2290kg
Sand (Silica) = 6800kg
Coke = 3175kg
Briquette binder = 227kg
Air = 450000ft3
Reactions
Ca3(PO4)2 + 3SiO2 + 5C 2P + 5CO + 3CaSiO3
2P + 5CO + 5O2 P2O5 + 5CO2
P2O5 + 3H2O 2H3PO4 85-90% yield
Manufacture
Steam
To phosphorous plant
Dust Phosphporous Steam Water
precipitator
collector vapour boiler
Cottrell
Binder Coke
Sand
Briquetic
Phosphate Water
press
Hydrater
rock pressure
5000 psi Compressed
Air
air
Hot
Blast
blast
Furnace
stove
Phosphoric
acid
Slag
Ferro
phosphorous
Figure: Manufacturing of Phosphoric acid using blast furnace
Animation
Phosphate rock is pulverized and mixed with coke powder and binder is
compressed to 5000 psi resulting into the briquettes. Briquettes are dried and
charged along with sand and additional coke powder from top of the blast furnace.
The preheated air (1000 11000C)is charged from bottom of the blast furnace via
tuyere. A tuyere is cooled copper conical pipe numbering 12 in small furnace and
up to 42 in large furnace through which hot air is blown in to the furnace. Preheated
air leads to burning of briquettes giving temperature rise up to 13700C. The coke acts
NPTEL 138
Module: 4
Dr. N. K. Patel
as reducing agent as well as fuels. About 760kg of coke is consumed in reduction of

phosphate rock to phosphorous and remaining generates heat by combustion with
air. Reaction is completed in the furnace itself producing P2O5 and calcium silicates
as slag. The product gases also contain carbon monoxide and nitrogen along with
dust particles. For purification, it is passed through cyclone separator and
phosphorous condenser. Thus, P2O5 and elemental phosphorous are separated out.
Hot P2O5 gases are cooled in the heat exchanger. Therefore, superheated steam is
produced and a part of gas is taken into regenerative blast furnace. As a result the
entire phosphorous and phosphorous pentoxide is cooled and purified before taken
into hydrating towers. Purification of phosphoric acid includes removal of arsenic by
hydrogen sulfide treatment followed by filtration.
Engineering aspects
Blast furnace
Blast furnace is made of high temperature resistant refractories brick. Blast
furnace have accessories of hot blast stove for supply of compressed preheated air
having temperature 1000 11000C, briquette press for preparation of briquettes of
Phosphate rock and coke, dust collector (cyclone separator) for removal of dust
particles from product stream. Also, two outlets for removal of slag and
ferrophosphorous are provided at the bottom of the furnace.
The top of the blast furnace is closed as it operates at high top pressure. There
are two different systems are used for charging of briquettes, coke and silica. One is
having double bell system which is often equipped with movable throat armour and
other is bell less top as shown in figure.
Also, there are two construction techniques to support the blast furnace as
shown in figure.
NPTEL 139
Module: 4
Dr. N. K. Patel
Animation
One utilized lintel or support ring at the bottom of the shaft upon which the
higher level of the furnace rests. The other is free standing construction requiring
and independent support for the blast furnace top and gas system. The required
expansion both thermal as well as pressure for the installation is below for the lintel
i.e. in bosh/belly area in lintel type furnace, while compensator for expansion in the
free standing furnace is at the top.
2. Using phosphate rock and electric furnace
Raw materials
Sand (silica) = 680kg
Coke breeze = 400kg
Caron electrode = 8kg
Air = 100000ft3
Electricity = 4070KWH
Reactions
Ca3(PO4)2 + 3SiO2 + 5C 2P + 5CO + 3CaSiO3 H = - 364.8 kcals
2P + 5CO + 5O2 P2O5 + 5CO2
P2O5 + 3H2O 2H3PO4 87-92% yield H = - 44.9 kcals
NPTEL 140
Module: 4
Dr. N. K. Patel
Manufacture
Water CO2
Sand
Coke Sand
breeze filter
precipitator
Water
Cottrell
Sintering
Phosphate
&
Hydrater
rock
Sizing
Water
Size Electric
Ferro Furnace Purifier
phosphorous 2400 oF H2S / H2O
Phosphoric acid 85 %
Air
Figure: Manufacturing of Phosphoric acid using Electric furnace
Animation
The phosphate rock is reduced to elemental phosphorous by the action of

coke and heat in the presence of sand in electric arc furnace subsequent oxidation
of phosphorous gives phosphorous pentoxide which on hydration gives the product
phosphoric acid.
Phosphate rock after proper grinding and primary purification is taken into
sintering oven where it is nodulized and granulized so that fast oxidation of the
separated phosphorous takes place. Temperature of 10950C is maintained in electric
furnace so that maximum amount of elemental phosphorous extracted out and
oxidation takes place. Since fluoride of phosphorous and calcium are the common
impurity which reacts with sand giving flourosilicates as the slag.
The gases from the furnace, phosphorous and carbon monoxide are
removed by the suction process and the oxidation product P2O5 is taken into
hydration column which gives P2O5 to H3PO4 at about 850C. Purification of
phosphoric acid is carried out by H2S to remove Arsenic, H2SO4 to remove calcium
salts and Silica to remove fluorides. All the byproducts are removed before
concentrating the acid and filtering it as final product.
NPTEL 141
Module: 4
Dr. N. K. Patel
Advantages of electric arc furnace over other methods

The advantage of the electric furnace process lies in its ability to use a low-
grade phosphate rock, provided the major impurity is silica. Also, iron and aluminum
oxides are not objectionable as in the wet process. Siliceous rocks containing 24%
phosphorus as P2O5 are acceptable. The by-product carbon monoxide, is used as a
fuel for calcination.
3. Oxidation and Hydration of phosphorous
Raw materials

Phosphorus = 300kg
Air = 46000ft3
Steam = variable
Water = variable
Reactions
2P + 2O2 P2O5
P2O5 + 3H2O 2H3PO4 (94 97% yield)
Manufacture
At the locations away from phosphate rocks mines from purified elemental
phosphorous is oxidized and hydrated to give phosphoric acid. In the manufacturing
process molten phosphorous is sprayed into combustion chamber along with
preheated air and superheated steam. Combustion of phosphorous increases the
temperature up to 19800C. Furnace design depends on the requirement with
respect to quantity and quality. They are made of acid proof structural bricks,
graphite, carbon and stainless steel.
Animation
NPTEL 142
Module: 4
Dr. N. K. Patel
Water
COMBUSTION
CHAMBER
Hydrater
Phosphorous
seperator
Cyclone
Glass wool
Air
filter
Steam
Seperator
Vent
Cooler
85% Phosphoric acid
Figure: Manufacturing of Phosphoric acid by Oxidation and Hydration
The gases from furnace which mainly contains P2O5, steam, N2 and small
quantity of oxygen is taken into a hydration column where counter current mixing of
dilute phosphoric acid and the gases gives the product concentrated H 3PO4 of 75%
to 85% concentration. Remaining acid is trapped into packed column or
electrostatic precipitator.
4. Wet process or from sulfuric acid and phosphate rock
The wet process is according to the acids (sulfuric acid, nitric acid or
hydrochloric acid) used to decompose the phosphate rock. The process using
sulfuric acid is the most common among all particularly for producing fertilizer grade
phosphoric acid.
The wet process phosphoric acid, also called as green acid. Depending upon
the hydrate forms of calcium sulfate produced during the wet process, it is classified
as anhydrate, hemi hydrate and dihydrate. The hydrate form is controlled mainly by
temperature and acid concentration.
NPTEL 143
Module: 4
Dr. N. K. Patel
Anhydrite (n=0) process is not commercially viable due to high temperatures

requirement and the higher rate of corrosion.
The dihydrate process is the most popular due to simplicity and ability to use
a wide variety of phosphate rocks in the process. Hemihydrate processes produce
phosphoric acid of a relatively high concentration without the need of the
concentration step. There is also some attentiveness in the two-stage processes that
involve crystallization in the hemi-hydrate form followed by recrystallization in the
dihydrate form, with or without filtration or centrifugation.
Raw materials
Reaction
Ca10F2(PO4)6 + 10H2SO4 + 20H2O 10CaSO4.2H2O + 2HF + 6H3PO4
Manufacture
There are two processes i.e. dihydrate and hemihydrates (CaSO4.2H2O and
CaSO4.1/2H2O) are used for production of phosphoric acid.
Aspect Dihydrate process Hemihydrate process

Strength of sulfuric acid 78% 95%
Operating temperature Below 800C 1000C
Resistance to material Less High
Digestion time High Short
P2O5 content in product 33% 38%
Quantity of calcium sulfate High Small
Sulfuric acid on reaction with phosphate rock along with precipitation of

calcium sulfate results into the formation of phosphoric acid. The process is simple
and requires grinding of phosphate rock reacting with dilute phosphoric acid so that
melt is produced which in a reactor as mixed with concentrated sulfuric acid for 4 to
8hrs in the temperature range of 75-800C. Lot of air is required to control the
temperature. Resulting gases includes HF and P2O5 which in the absorption tower is
separated and finally treated to give fluorosilicates and dilute phosphoric acid. The
main product in the liquid form which is phosphoric acid and calcium sulfate is
filtered and washed. Thus, gypsum and phosphoric acid are separated and after
minor purification the phosphoric acid is concentrated into the evaporator.
NPTEL 144
Module: 4
Dr. N. K. Patel
Recycled Weak Phosphoric Acid
Sulphuric acid Cooling Air

To Fluorine
Phosphate rock Scrubber
Tank Reactor Filter

Feed
Tank
Hot
Air Water
Suction Water
Vaccum
Titing Pan Filter
Gypsum
To Product acid
Waste
Figure: Manufacturing of Phosphoric acid by Wet process
Animation
Throughout the plant, corrosion resistant materials of construction must be

used. The most common ones are structural carbon or nickel alloy for evaporator
heat exchangers; rubber or carbon-brick for reactor linings; polyester-fiber glass in
pipes, ducts, and small vessels. Yield of phosphoric acid based on phosphorus
content of raw material is 95%
NPTEL 145
Module: 4
Dr. N. K. Patel

The average retention time in the reactor system is about eight hours. The
direct contact between phosphate rock and sulfuric acid are prevented, so that
maximum phosphorous is extracted from the rock and formation of easily filterable
crystal of gypsum. A high concentration of free sulfuric acid would result in the
formation of a coating of calcium sulfate on the phosphate rock, thereby blocking
further reaction. On the other hand, a high concentration of calcium ions in the
slurry would increase the amount of phosphate co- crystallized with gypsum. In order
to maintain a uniform composition of slurry, the incoming stream of sulfuric acid and
phosphate rock is mixed and agitated as rapidly and as completely as possible to
ensure homogeneity. Most of the modern plants use about 96 % pure sulfuric acid. Its
mixing with dilute phosphoric acid generates heat which is used to evaporate the
water and volatilize fluorine compounds (mainly SiF, and HF).
Three methods of cooling are generally in use: (a) blowing air on to the slurry,
(b) blowing air across the slurry, and (c) flash cooling under vacuum.
The fumes emerging from the reactors and the digesters are sent to the
fluorine recovery unit, while the suspension of the digesters are filleted in the first
compartment of a continuous filter, which yields phosphoric acid containing about
33% of P2O5.
Engineering aspects
Selection of phosphate rock
The plant is designed in such a way that can be used for blend of rocks from
different sources. The plants have extra capacity for grinding, filtration and slurry
handling systems to take care of variation in the rock composition. As phosphate
rock is a complex raw material that affects plant operation in numerous ways, a
thorough chemical and mineralogical evaluation of the quality should be made
before selecting a phosphate rock or changing the source to another. However, a
trial run in a pilot plant is needed for complete evaluation of the rock. The
phosphate rock used in the process is of as high a grade as possible, usually ranging
from 30 to 35 % P2O5 and 1 to 4 % iron and aluminum.
Before attack by acids, mineral must be crushed so that 60 70 % of it passes

through 200 mesh sieve. Crushed mineral is calcined to remove organic impurities,
because the presence of organic substances promotes the formation of foams
which makes it difficult to filter off calcium sulfate. The purified mineral is again
crushed to powder form by milling and is premixed first with recycled phosphoric
acid and then fed with sulfuric acid. The recycle phosphoric acid contributes to
attack on the mineral and disperse both heat of reaction and heat of dilution of
H2SO4, thereby facilitating crystallization of the calcium sulfate. Also, these steps
favours both precipitation, of readily filterable chalk consisting of minutes crystals of
NPTEL 146
Module: 4
Dr. N. K. Patel
CaSO4.2H2O or CaSO4.1/2H2O which act as crystallization nuclei, as well as digestion

in suitable containers, after the attach of reaction mixture.
Grinding of rock materials

Wet or dry grinding of Phosphate rocks is required depending upon the raw
materials. Fine grinding is required in case of multi-compartment digesters and poor
sulfate control. Most of the old plants use dry grinding, and a majority of the new
plants use wet grinding with a ball mill or ring roller mills having air classification. Slurry
containing 62 to 70% solid is produced. Wet grinding requires about 30 to 40% less
power and there is no atmospheric pollution by dust. The main disadvantages of this
process are that the balls and the mill lining wear out faster, and the amount of
recycled waste water that may be required in phosphoric acid production is
reduced. Also, it is necessary to maintain the ratio of solids while grinding.
Handling and storage of phosphate rock

Phosphate rock are stored in dry conditions and protected against rain, wind
and freezing weather. Relatively coarse rocks can be stored in piles. To ensure the
constant supply, the storage capacity should ideally be 1.5 times the largest
shipment.
Amount of sulfuric acid

As the by-product acid may contain some impurities, most phosphoric acid
plants have on site facilities for producing sulfuric acid from sulfur or pyrites. Sulfuric
acid of 93 to 98% concentration is used. The sulfuric acid requirement is calculated
assuming its amount required to combine with calcium present in the rock to form
calcium sulfate. Also, considering that about 15% of fluorine combines with calcium
oxide to form calcium fluoride, the sulfuric acid requirement is calculated. For a high
grade phosphate rock, H2SO4 required is 2.5 tons per ton of phosphorus; and for low
grade rocks, it is 3.15 tons per ton of phosphorus.
Filtration of gypsum
Filtration is carried out as efficiently and economically as possible. All modern
plants use continuous horizontal vacuum filters. The other widely used filters are tilting
pans, rotary filters, rotary table filters and belt filters. Some of the product acid is
recycled to the digestion step to control the percentage of solids in the slurry, which
is normally 35 to 45 %.
Filters are characterized by their surface area and the rate of rotation (in a
rotary filter) or the rate of travel (in a belt filter). The filtration rate is also affected by
the size and shape of gypsum crystals which, in turn, are decided by the type of
phosphate rock, crystal shape modifiers, control of reaction conditions, sulfate
concentration, slurry re-circulation, phosphoric acid concentration, etc.
NPTEL 147
Module: 4
Dr. N. K. Patel
The filtration rate is also affected by temperature, concentration, viscosity of

the acid, the desired recovery, the amount of vacuum, the design of the filter and
insoluble impurities in the rock like clay. The normal filtration rates reported in the
production are 2 to 18 tons/m2/day.
Purification
Phosphoric acid which is intended for use in fertilizers does not require any
purification but for chemical and food products it must be purified. The block
diagram of purification processes is as follows.
H3PO4
NaOH or Na2CO3 (Impure)
Adjustment to pH
Na2SiF6
=2
H2S BaCO3
Adjustment to pH
As2S3, BaSO4, PbS, etc.
=5
Fe
Reductions
Ca(OH)2
Adjustment to pH
Al(OH)3, Fe(OH)3, Mn(OH)2,
= 8.5
H2SO4 MnO(OH) etc.
Precipitation of
anhydrous and hydrated
CaSO4
Filtration Removal of precipitates
H3PO4
Purified
Figure: Purification of Phosphoric acid
Sludge disposal
The sludge usually contains gypsum, fluosilicates, iron and phosphate
compounds. Acids containing sludge can be used for onsite fertilizer (triple
NPTEL 148
Module: 4
Dr. N. K. Patel
superphosphate) production. Most of the phosphorus (as P2O5) in the sludge is

citrate-soluble but not water-soluble.
The sludge may be used in the production of non- granular mono-ammonium

phosphate which is used as an intermediate in the production of compound
fertilizers. There is no economical method for using sludge solids where phosphate
fertilizers are sold on the basis of water solubility. Precipitation after concentration to
54 % phosphorus (as P2O5) is slow and never so complete as more precipitate will
form on standing.
PROPERTIES
Molecular formula : H3PO4
Appearance : White solid or colourless viscous liquid above 420C
Boiling point : 1580C (decompose)
Melting point : 42.350C (anhydrous)
29.320C (hemihydrate)
1.685gm/mL (85% solution)
2.030gm/mL (crystal at 250C)
Solubility : Soluble in water
Viscosity : 147cP (100%)
USES
Used for preparation of hydrogen halides

Used as a "rust converter", by direct application to rusted iron, steel tools, or
surfaces. It converts reddish-brown iron(III) oxide, Fe2O3 (rust) to black ferric
phosphate, FePO4
Food-grade phosphoric acid is used to acidify foods and beverages such as
various colas.
Used in dentistry and orthodontics as an etching solution, to clean and
roughen the surfaces of teeth where dental appliances or fillings will be
placed.
As an ingredient in over-the-counter anti-nausea medications that also
contain high levels of sugar (glucose and fructose).
Used in many teeth whiteners to eliminate plaque.
Used as an external standard for NMR and HPLC
As a chemical oxidizing agent for activated carbon production
As the electrolyte in phosphoric acid fuel cells and is used with distilled water
(23 drops per gallon) as an electrolyte in oxyhydrogen (HHO) generators.
Also, used as an electrolyte in copper electro polishing for burr removal and
circuit board planarization.
As a flux by hobbyists (such as model railroaders) as an aid to soldering.
NPTEL 149
Module: 4
Dr. N. K. Patel
As common wet etching agent in compound semiconductor processing,

Hot phosphoric acid is used in micro fabrication to etch silicon nitride (Si 3N4). It
is highly selective in etching Si3N4 instead of SiO2, silicon dioxide.
As a cleaner by construction trades to remove mineral deposits, cementitious
smears, and hard water stains.
As a chelant in some household cleaners aimed at similar cleaning tasks.
Used in hydroponics pH solutions to lower the pH of nutrient solutions.
As a pH adjuster in cosmetics and skin-care products.
As a dispersing agent in detergents and leather treatment.
As an additive to stabilize acidic aqueous solutions within specified pH range
NPTEL 150

Nitric Acid Manufacturing Processes

Caricato da

Informazioni sul documento

Titolo originale

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Nitric Acid Manufacturing Processes

Caricato da

Copyright:

Formati disponibili

Module 4

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

Nitric acid is manufactured by three methods.

1. From Chile saltpetre or nitrate

1. From Chile saltpeter or nitrate

It is the first commercial process of manufacture of nitric acid from sodium

Basis: 1000kg Nitric acid (95% yields)

Sources of raw material

Sodium nitrate can be obtained from caliche ore. Also, it is manufactured by

NaNO3 + H2SO4 NaHSO4 + HNO3

NaNO3 + H2SO4 Water or Dil. HNO3

Figure: Manufacture of nitric acid from chile saltpetre or nitrate

Block diagram of manufacturing process

Diagram with process equipment

2. Arc process or Birkeland and eyde process

Basis: 1000kg Nitric acid (98% yield)

N2 + O2 2NO H = + 43.2 kcals

Figure: Manufacturing of Nitric Acid by Arc Process

Block diagram of manufacturing process

Diagram with process equipment

The conversion of NO to HNO3 was carried out by means of oxidation and

Reason for obsolesce

High electrical energy consumed. There were enormous amounts of gas in

3. Ostwald's process or Ammonia oxidation process

Sources of raw material

Block diagram of manufacturing process

Diagram with process equipment

Turbine Compressor 57-60 % HNO3 solution for use or

Figure: Manufacturing of Nitric acid from by oxidation of ammonia

The process involves four steps

1. Catalytic oxidation of ammonia with atmospheric oxygen to yield nitrogen

Thermodynamics and kinetics

4NH3 + 3O2 2N2 + 6H2O H = - 302.64kcal ---- (12)

4NH3 + 5O2 4NO + 6H2O

Ammonia oxidation reaction has an extremely favourable equilibrium

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

The following condition should be fulfilled to convert NH3 into NO

Reaction kinetics in ammonia oxidation stage

There is slight equilibrium advantage to operation at atmospheric pressure.

Oxidation of nitrogen oxide does not have as large equilibrium constant.

Absorption of nitrogen oxides into water

Process design modification

Advantages and disadvantages of elevated pressure are as follows

Catalyst for oxidation of ammonia

Ammonia conversion efficiency is a function of pressure and temperature. As

As a starting material in the manufacture of nitrogen fertilizers such as

Sulfuric acid (H2SO4) is a highly corrosive strong mineral acid. It is a colorless to

Johann Glauber prepared sulfuric acid by burning sulfur together with

More economical process i.e. the contact process was patented by

The Industrial manufacture of sulfuric acid is done mainly by two processes

1. The Lead Chamber process

1. The lead chamber process

Block diagram of manufacturing process

Diagram with process equipment

Chamber Acid Watrer Spray

Chamber I Chamber II Chamber III

Gay - lussac Tower

Conc. Acid Chamber Acid

Figure: Manufacturing of Sulfuric acid by Chamber process

1. To oxidize sulfur to maximum extent

In modern plant oxides of nitrogen are produced by passing mixture of

The unabsorbed remaining gases contain oxides of nitrogen and SO 2 from

Kinetics and thermodynamics