Lecture_Sulphuric acid

BITS Pilani
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 (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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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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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 range 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 environmental concerns

• Gas after passing through 3 catalyst bed goes to first

absorption tower where SO3 is removed

• Gas is then heated to 420 degree C, passed through

catalyst bed, then cooled & sent to the 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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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 average bed temp is reduced at every bed,

eqm approach temp delta T also declines &
hence rate constant decreases

• Thus average 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”.
Sulphur production
• Elemental sulfur was simply produced from deposits, in
particular those of volcanic origin

• Nowadays sulfur is nearly completely produced as a by-

product of the processing of sulfur-containing feed stocks,
which produce an off-gas rich in hydrogen sulfide

• Hydrogen sulfide obtained by amine absorption (Section

5.4) from hydrogen sulfide-containing gas such as sour
natural gas, and off-gas from hydro-treating units (Section
3.4.5) or coal gasification plants (Section 5.3), is frequently
converted to elemental sulfur by the “Claus” process
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Sulphur production
• Elemental sulfur was simply produced from deposits, in
particular those of volcanic origin

• Nowadays sulfur is nearly completely produced as a by-

product of the processing of sulfur-containing feed stocks,
which produce an off-gas rich in hydrogen sulfide

• Hydrogen sulfide obtained by amine absorption (Section

5.4) from hydrogen sulfide-containing gas such as sour
natural gas, and off-gas from hydro treating units (Section
3.4.5) or coal gasification plants (Section 5.3), is frequently
converted to elemental sulfur by the “Claus” process
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• By this process 95–97%, H2S is converted

• To obtain greater conversions several technologies are in

use
• Some are already proven technology, others are under
development

• In the Claus process, elemental sulfur is produced by partial

oxidation of hydrogen sulfide in a furnace.

• Overall, reaction may be represented simply by the highly

exothermic reaction:, but in real, chemistry is very complex
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• In practice, the overall reaction is accomplished in two steps.

• One third of the hydrogen sulfide is oxidized to sulfur and water, and then the remaining
hydrogen sulfide reacts with the formed sulfur dioxide converting it into sulfur:

• At the high temperature of the furnace, oxidation rates are very high and in
agreement with thermodynamics, sulfur dioxide is formed

• Because only a sub stoichiometric amount of oxygen is fed to the plant, sulfur
can be formed in a consecutive reaction

• Sulfur recovery in this thermal step is limited to 50−70% due to the equilibrium,
which shifts to the left at higher temperature
• H2S containing gas is fed to an oxidation chamber where it is partially
combusted with air to form sulfur dioxide, which then reacts with the
remaining hydrogen sulfide to form elemental sulfur

• Heat of reaction is recovered in a waste heat boiler by raising high-pressure

steam. Gas leaving the combustion chamber is cooled to about 450 K for
sulfur condensation

• The gas is then reheated (to 520 K) and passed into the first Claus
reactor, where the Claus equilibrium is re-established and additional
sulfur is formed.

• After each reactor, sulfur is removed by condensation. In the

condensers low-pressure steam is generated

• Tail gas, which besides residual hydrogen sulfide and sulfur dioxide
contains small amounts of carbon disulfide (CS2) and carbonyl sulfide
(COS), is either further processed (Boxes 8.1 and 8.2) or incinerated
and emitted to the atmosphere, depending on emission regulations.