Lecture 19_Sulphuric acid

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Pilani Campus
Starting with Sulfur Acid
Physical properties of H2SO4
• Colorless
• Viscous liquid
• Specific gravity: 1.8357
• Normal boiling point: ~274 oC
• Largest volume chemical commodity produced
• Is sold or used commercially in a number of different
concentrations
• As various oleums (fuming sulfuric acid, H2SO4 + SO3)

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Uses of Sulfuric Acid
• Production of basic chemicals
• Fertilizers
• Alkylation process in oil refineries
• Copper leaching process
• Pulp & paper industry

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H2SO4
Sulfuric Acid is not one-RM product
– About 58% of the world’s production was based on
elemental Sulfur, 25% on Pyrite, and 17% on other
sources
Sulfuric acid can be produced from
– Chamber Process
– Contact Process
– DCDA Process
– Haldor Topsoe Catalyst Process
– PCUK Process
– CIL Process

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Starting with Sulfur
• Sulfuric Acid is produced from catalytic oxidation of SO2
to SO3
• It is dissolved in water to form sulfuric acid

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Chamber process
Dr. Roebuck of Birmingham, England introduced the lead
chamber process in 1746

– Can produce large amounts in lead chambers, which was less

expensive & stronger, column heights can be increased (vs glass)
– Looks like simple and requires simple equipment but reactions
involved are not simple

– Rxns which produce SO3 & H2SO4 take place in huge lead
chambers or in packed tower

– Method used nitrogen oxides as oxygen carrying catalysts for

conversion of SO2 to SO3

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Chamber process
Reactions

2NO  O 2  2NO2
2SO 2  2NO2  2H 2O  2H 2SO 4  NO

Overall Reaction

2SO2  O2  2H2O  2H2SO4

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 Chamber process
• Sulfur or iron pyrites is burned with sufficient
excess air
– so that the concentration of oxygen is slightly
higher than that of sulfur dioxide
• Gases are conveyed through a combustion
chamber
– where they are deprived of some of the dust
present in them
• Gas then enters the base of the Glover tower
– where it meets the downward flow of the Gay-
Lussac acid or nitrous vitriol
Chamber process
• Gas is cooled here and picks up part of the
moisture (steam) for the acid making process
• Nitrous vitriol becomes de nitrated
– gets concentrated by the heat supplied from the
gas
• Gas from the top of the Glover tower is
conveyed through the lead chambers
• These vary in number from three or four to
twelve, depending on the capacity of the plant
• Water is sprayed from the top of these chambers
by means of atomizers
Chamber process
Chamber process
Chamber process

Glover tower: Large packed tower that is situated before the chambers in the chamber
process of making sulfuric acid and that serves especially to cool the hot mixture of
sulfur dioxide and air on its way to the chambers, to supply water vapor, to remove the
nitrogen oxides from nitrous vitriol entering at the top from the Gay-Lussac tower, and to
concentrate sulfuric acid also entering at the top from the chambers

Gay Lussac tower: a large packed tower that is situated after the chambers in the
chamber process of making sulfuric acid and that contains strong sulfuric acid for
absorbing nitrogen oxides from the spent gases with the formation of nitrous vitriol
Chamber process
• Important Design Factors
– Reaction rate for Oxidation of Nitric Oxide
• Exothermic Reaction
• Rate constant decreases with temperature
• Gases are to be cooled before entering the chamber and that is how
GLOVER Tower has come into picture
– Concentration of Acid in Chamber
• Conc. Of H2SO4 should be less than 72.75 percent; otherwise it
absorbs the excessive quantities of nitrogen dioxides, which result in
severe corrosion in Lead Chamber
– Molar Ratio of NO to NO2 in Gay-Lussac Tower
• NOx in the ratio of nitric oxide to nitrogen dioxide equal to 1, are
absorbed rapidly by circulating acid in the Gay-Lussac tower
• An excess of NO2 will react with water to produce Nitric Acid
• Nitric Acid forms a white fog and escapes from top of the tower
Contact process
• Contact process originally used a supported platinum
catalyst, but from the 1920s on this has been
gradually replaced by a vanadium catalyst
• Pt is replaced with vanadium catalysts because of high price of platinum and its
sensitivity to poisons

• Life time of an active catalyst is 10–20 years

• Another significant change occurred in the early 1960s with the

introduction of the so-called double absorption process,
in which part of the formed sulfur trioxide is removed between
two conversion stages

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Contact process: Reactions
involved

1. 1st reaction is exothermic, & increases temp considerably

2. That means, there is a scope of heat integration

3. Even 2nd & 3rd reactions are exothermic

4. In 3rd reaction, sulphuric acid is used to absorb SO3 as both SO3 & H2O forms
mist

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 Current sulfur dioxide
oxidation catalysts this
means a
minimum temperature of
680–715 K

1. Graph shows the influence of the temperature on the

equilibrium conversion of SO2
2. Oxidation of sulfur dioxide is thermodynamically favored by
low temperature
3. At 680 K, almost 100 % conversion is achieved
As with all exothermic equilibrium reactions, however, the ideal
temperature must be a ______between achievable conversion
(thermodynamics) and the rate at which
this conversion can be attained (_______) (kinetics)
Contact process: Reactor
• Important that sulfur dioxide is converted to sulfur
trioxide nearly quantitatively,
• not only for plant economic reasons but, more importantly, for environmental
reasons

• Oxidation of sulfur dioxide is an exothermic equilibrium

reaction

• Consequently, with increasing conversion the

temperature rises, leading to lower attainable equilibrium
conversions

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Contact process: Reactor
• For example:

• equilibrium conversion at 710 K is about 98%

• But, due to the adiabatic temperature rise, conversions

of only 60–70% are obtainable in a single catalyst bed

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Contact process: Reactor
• In practice, this is overcome by using multiple catalyst
beds (usually four) with intermediate cooling

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Conversion efficiency of any sulphuric acid plant is presented in eqm-
stage process
• Fig. represents eqm-stage diagram of sulphur
burning using 8% SO2 burner gas

• Slopes of adiabatic temp rise lines are directly

proportional to sp. heat capacity of process gas,
which is reasonably constant for any degree of
conversion

• For a given gas composition, adiabatic temp rise

lines can approach eqm curve, but never crosses
it

• As avg bed temp is reduced at every bed, eqm

approach temp delta T also declines & hence rate
constant decreases

• Thus avg reaction rate decreases in each

successive beds & hence more catalyst is
needed in subsequent beds
 • Major part of the conversion is obtained in the first bed.
Inlet temperature of the first bed is around 700 K and
the exit temperature is 865 K or more, depending on
concentration of sulfur dioxide in the gas

• Successive lowering of the temperature between the

beds ensures an overall conversion of 98–99%

• Still, this is not enough to meet current environmental

standards.

• Therefore, modern sulfuric acid plants use

intermediate sulfur trioxide absorption after the
second or, more commonly, the third catalyst bed

Intermediate removal of sulfur trioxide from the gas stream enables the
conversion of sulfur dioxide “beyond thermodynamic equilibrium”.
Modern H2SO4 plant
• Three main sections can be distinguished,

• That is, combustion of sulfur to produce sulfur dioxide (sulfur

burner),

• Catalytic oxidation of sulfur dioxide to form sulfur trioxide, and

• Absorption of sulfur trioxide in concentrated sulfuric acid

(absorption towers)

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 In first absorption tower, most
Double absorption
SO converts intoprocess
SO at
2 3
of the sulfur trioxide produced
is absorbed in a circulating
around 400 deg C
stream of sulfuric acid
More sensitive catalyst,
better conversion but

Gas (SO2& O2)from

top of tower enters 4th
bed in converter

final absorption tower

removes this sulfur
After leaving catalyst, gases are
trioxide from the gas
cooled to around 400 – 450 deg
stream before release
C & passed through economizer
to the atmosphere.
where temp is further reducedBITS Pilani, Pilani Campus
DCDA H2SO4 plant
• Sulphuric acid is maintained at desired concentration
(98% H2SO4) by addition of water & its temp is controlled
in the desired ranged of 70 to 90 deg C measured at
tower inlet by cooling the recirculated bed

• In single absorption process; recovery of sulphur as

sulphuric acid is 97-98% & remainder is lost to
atmosphere as Sox

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DCDA H2SO4 plant
• Purpose of Double absorption towers:
• mainly cause of env concerns
• Gas after passing through 3 catalyst bed goes to first absorption tower where
SO3 is removed
• Gas is then heated to 420deg C, passed through catalyst bed, then cooled & sent
to second absorption tower

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DCDA H2SO4 plant
• Small amounts of sulfuric acid mists or aerosols are
always formed in sulfuric acid plants when gas streams
are cooled or sulfur trioxide reacts with water below the
sulfuric acid dew point

• Formation of sulfuric acid mists is highly undesirable

because of corrosion and process stack emissions.

• Therefore, the absorbers in sulfuric acid plants are

equipped with demisters, consisting of beds of small-
diameter glass beads or Teflon fibers

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Modern H2SO4 plant
• Sulfuric acid plants can be operated as cogeneration
plants.

• Much of the heat produced in the combustion of sulfur is

recovered as high-pressure steam in waste heat boilers,
while some of the heat produced in the
catalytic sulfur dioxide oxidation is also recovered by
steam production in so-called economizers

• Steam production in modern large sulfuric acid plants

exceeds 1.3 t/t of sulfuric acid produced

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Catalysts deactivation
• Life of modern vanadium catalysts may be as long as 20
years, typically at least five years for the first and second
bed and at least 10–15 years for the third and fourth bed

• Main reasons for loss of activity of vanadium catalysts

are physical breakdown giving dust, which could plug the
catalyst bed, and chemical changes within the catalyst
itself

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