Chapter – 2

SULFUR AND SULFURIC ACID

INDUSTRIES

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 Sulfur
Sulfur is the basic raw material for manufacture of sulfuric
acid.
Sulphur is a multivalent non-metal, abundant, tasteless.
In its native form, sulfur is a yellow crystalline solid.
In nature, it occurs as the pure element or as sulfide and
sulfate minerals.
 Although sulfur is infamous for its smell, frequently
compare to rotten eggs, that odor is actually characteristic of
hydrogen sulphide (H2S).
The crystallography of sulfur is complex. Depending on the
specific conditions, sulfur allotropes form several distinct
crystal structures.

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 Sulfur
• Melting point 112.8 deg. C
• It is insoluble in water , but soluble in organic solvents
and liquid ammonia
• Sulfur exists in the following forms : rock , lump, molten,
ground powder and sublimed powder
End uses for elemental sulfur are :
• 85- 90% for sulfuric acid manufacture
• For production of : SO2, SO3, CS2, and P2S5
• Rubber valcunization agents
• gunpowder, sulfur dyes;
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• Putties, sulfur concrete etc.
 Sulfur Production Processes

CLASSIFICATION

1. Elemental Sulfur mining from salt domes

2. Hydrogen Sulfide conversion from natural gas and industrial gases

3. Iron Pyrites

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 1. Elemental Sulfur mining from salt domes
(Frasch process)

 This is the process used for getting Sulphur

from Sulphur beds underground.
 It is named after Hermann Frasch who
invented the process.
 Superheated water and compressed air is
forced into the ground through pipes. This
then forces out molten Sulphur and water.
 After the water and molten Sulphur has left
the pipes, they can be easily separated.
The Sulphur obtained in this way is 99.5%
pure and can be used directly.
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 2. HYDROGEN SULFIDE CONVERSION FROM NATURAL GAS AND INDUSTRIAL GASES (oxidation –
reduction of H2S)

The Claus Sulfur Recovery Process

 Sulfur recovery refers to the conversion of hydrogen sulfide (H2S) to elemental sulfur.
 Hydrogen sulfide is a by-product of processing natural gas and refining high-sulfur crude oils.
 There are many sulfur recovery technologies available for different applications, however the
most common conversion method used is the Claus process.
 Approximately 90 to 95 percent of recovered sulfur is produced by the Claus process.
 The Claus process typically recovers 95 to 98 percent of the hydrogen sulfide feedstream.

CHEMICAL REACTIONS
A. 2H2S + 3O2  2SO2 + H2O
B. 4H2S + 2SO2 S6+ 4H2O

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• RAW MATERIALS: H S from natural (sour) gas and petroleum refinery streams
A. 2H2S + 3O2  2SO2 + H2O
B. 4H2S + 2SO2 S6+ 4H2O

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 SULFURIC ACID
Properties

Molecular formula H2SO4

Molar mass 98.079 g/mol

Appearance Clear, colorless, odorless liquid

Density 1.84 g/cm3, liquid

Melting point 10 °C, 283 K

Boiling point 337 °C, 610 K

Solubility in water miscible

Acidity (pKa) 1.99

Viscosity 26.7 cP (20 °C)
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 Sulfuric acid
 Sulfuric acid (British English: sulphuric acid), H2SO4, is a strong mineral acid.

 It is soluble in water at all concentrations.

 Sulfuric acid has many applications, and is produced in greater amounts than any

other chemical besides water.

 Principal uses include ore processing, fertilizer manufacturing, oil refining,

wastewater processing, and chemical synthesis.

 Many proteins are made of sulfur-containing amino acids (like cysteine and

methionine) which produce sulfuric acid when metabolized by the body.

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 Forms of sulfuric acid
Although 100% sulfuric acid can be made, this loses SO 3 at the boiling point to produce 98.3% acid.
The 98% grade is also more stable for storage, making it the usual form for "concentrated" sulfuric
acid. Other concentrations of sulfuric acid are used for different purposes. Some common
concentrations are:
 10%, dilute sulfuric acid for laboratory use (pH 1)
 33.5%, battery acid (used in lead-acid batteries) (pH 0.5)
 62.18%, chamber or fertilizer acid (pH about 0.4)
 77.67%, tower or Glover acid (pH about 0.25)
 98%, concentrated (pH about 0.1)
 Since sulfuric acid is a strong acid, a 0.50 M solution of sulfuric acid has a pH close to zero.
 It is highly corrosive and produces severe burns on the skin

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 Classification of processes
Contact process:
– It yields 98% acid and higher which can be diluted if necessary
– Mostly used in production of acid
– Processes is based on SO2.
In many countries, the discharge of sulfur dioxide to the atmosphere is
environmentally unacceptable.
Therefore most of the plants use a Double Contact Double Absorption
Process (DCDA)

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Contact Process

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 CHEMISTRY OF SULFURIC ACID PRODUCTION: Contact Process

• S + O2  SO2 -70 KCal

• SO2 + 1/2 O2  SO3 -23.50 KCal

• SO3 + H2O  H2SO4 -32 Kcal

Raw materials:

• The raw materials for sulfuric acid manufacture are chiefly Sulfur, Pyrites,
Spent oxide, anhydrite and gases from the smelting of metalliferous ores,
from the purification of natural gas and from refining operations.
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 Contact Process:Catalyst

• Platinum was once widely used as catalyst but because of

– excessive cost Platinum

– susceptibility to poisoning,

It has been largely replaced by vanadium oxide.

The vanadium pentaoxide is dispersed on a porous Poisoning

carrier in a pellet form.

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 Catalyst: vanadium pentaoxide (V2O5)

• Advantages of the V2O5 catalyst

1. Relatively immune to poisons.
2. Low initial investment and only 5% replacement per year.

• Disadvantages of V2O5 catalyst

1. Must use dilute SO2 input (7-10%).
2. As a catalyst it is less active and requires high oxygen or sulfur dioxide to
give economic conversions
3. Requires larger converters and thus higher initial investment.

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 Sulfur trioxide made into Sulfuric Acid

• Sulfur trioxide will dissolve in water to make sulfuric acid.

• This is the balanced chemical equation for the reaction of sulfur

trioxide with water.

• sulfur trioxide     +      water            sulfuric acid

       SO3(g)         +      H2O(l)              H2SO4(aq)

• The reaction is highly exothermic and produces an acid mist which

is difficult to condense into sulfuric acid. 17
 Sulfur trioxide made into Sulfuric Acid
In industry it is easier to dissolve sulfur trioxide in concentrated (98%) sulfuric acid to
form oleum (oleum is sometimes called fuming sulfuric acid).

the reaction of sulfur trioxide with sulfuric acid.

Sulfur trioxide     +      sulfuric acid                 oleum

       SO3(g)            +          H2SO4(aq)              H2S2O7(l)

Water is carefully added to oleum to remake concentrated (98%)  sulfuric acid.

The reaction of oleum with water.

oleum      +       water           sulfuric acid

H2S2O7(l)    +      H2O(l)             2H2SO4(aq)
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H2O

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 DCDA process
• Operation of the sulphuric acid plant has some advantages,
1. The equipment is smaller and less expensive
2. Less Catalyst is required.
3. Equilibrium condition and reaction rates are more favourable in the
conversion and absorption steps.

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 uses

1)  The acid in a car battery.

2)  Making Detergents.
3)  Metal treatment and anodising.
4)  A Catalyst
5)  A Dehydrating agent.
6)  Making Fertiliser.
7)  Paints and dyes.
8)  To measure economic development.
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Thanks

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