SULFUR AND

SULFURIC ACID
SULFUR
Sulfur is one of the most important and basic materials in the chemical process
industries
Melting point = 113oC
Found as pure element in many locations
Not soluble in water
It exists in nature both in free state and combined in ores such as pyrite (FeS 2),
sphalerite (ZnS), and chalcopyrite (CuFeS2)
Important constituent of petroleum and natural gas (as H2S)
The largest application of sulfur is in the manufacture of sulfuric acid
SULFUR
A major source of elemental sulfur is H2S, which is a by-product of the
desulfurization of sour (i.e. sulfur containing) natural gas and sour crude oil
Elemental sulfur ores were mined. ores can be burned to make sulfur dioxide
gas, which is used to produce sulfuric acid
Elemental sulfur is also produced by removing hydrogen sulfide from natural
and refinery gases with absorbents such as mono or diethanolamines
The hydrogen sulfide is then converted to elemental sulfur by the Claus or
modified Claus process
FRASCH PROCESS
The major tonnage of all the elemental sulfur of
the world has been obtained from the sulfur-
bearing porous limestones by the Frasch process
Herman Frasch devised his ingenious method of
melting the sulfur underground or under the sea
and then pumping it up to the surface
Ordinary oil-well equipment is used to bore holes
to the bottom of the sulfur-bearing strata, a
distance underground from 150 to 750 m
FRASCH PROCESS
FRASCH PROCESS
One pipe carries super-heated steam (160oC). Super-heated steam is pushed into
deposit melting solid sulfur.
One carries compressed air. Compressed air is used to increase the pressure of the
deposit forcing sulfur-water mixture to the surface.
Last pipe is used to carry sulfur back to the surface
ENVIRONMENTAL IMPACTS
Thermal Pollution
Earth Subsidence
Acid Rain
FROM FUEL GASES
Increasingly hydrogen sulfide is being removed during the purification of sour
natural gas, coke-oven gas, and from petroleum refinery gas by dissolving it in
potassium carbonate solution or ethanolamine, followed by heating to regenerate it
The hydrogen sulfide thus produced is burned to give sulfur dioxide for sulfuric acid
However, the majority is converted to elemental sulfur by various modifications of
the Clauss process
AMINE EXTRACTION
Also known as Gas Sweetening and Acid Gas Removal

Gas containing H2S is passed through an absorber containing an

amine solution
Monoethanolamine (MEA), Diethanolamine (DEA). MDEA, DIPA,
DGA
where the hydrogen sulfide is absorbed along with carbon dioxide
Absorber and regenerator unit
In the absorber, the down-flowing amine solution absorbs H2S and
CO2 (acid gas), the up-flowing sour gas produce sweetened gas
stream (H2S free gas)
Rich amine is then routed into regenerator (stripper with reboiler) to
produce regenerated amine that is recycled for reuse in the absorber
The stripped overhead gas from regenerator is concentrated H2S
and CO2 (acid gas)
CLAUSS PROCESS
Clauss Thermal Stage

Clauss Catalytic Stage

SULFURIC ACID
Very active material
One of the most widely used and most important technical products
Agent for sulfate formation and for sulfonation
Strong acid and cheap
Oxidizing and dehydrating agent
Fertilizer, detergent, dye industry, etc.
CONTACT PROCESS
Depending on the type of raw material used
Catalyst = platina, vanadium
4FeS2 + 11O2  2Fe2O3 + 8SO2

Burners
Heat exchangers and coolers
Converters
Absorbers
CONTACT PROCESS
1. Preparation of SO2
2. Purification of SO2
3. Oxidation of SO2
4. Absorption of SO3
5. Dilution of oleum
OXIDATION
CONTACT TOWER:
Oxidation of SO2 is carried out in contact tower where V2O5 is filled in different pipes. SO2 here reacts
with air (O2) to produce SO3. Under above conditions 98% SO2 is converted into SO3.
2SO2 + O2  2SO3
CONDITIONS NECESSARY FOR MAXIMUM YIELD OF SO3:
Oxidation of SO2 is a reversible and exothermic process in which volume of product is less than
the volumes of reactants. In order to obtain maximum amount of SO 3, according to Le-Chatelier’s
Principle following conditions are necessary.
CONCENTRATION:
Excess of O2.
TEMPERATURE:
A decrease in temperature favour reaction in forward direction. Optimum temperature for this process is
450oC to 500oC.
PRESSURE:
Since volumes of reactants are greater than the product (3:2), therefore, according to Le-Chatelier’s
Principle a high pressure is favourable. Optimum pressure is about 1.5 to 1.7 atmosphere.
USE OF CATALYST:
At low temperature, rate of reaction decreases. To increase rate of reaction a catalyst
ABSORPTION
SO3 is not directly passed in water, because a dense fog of minute particles of H 2SO4
is produced. It is therefore, dissolved in conc.H 2SO4 to form pyrosulphuric acid
(oleum).
SO3 + H2SO4  H2S2O7 (OLEUM)

DILUTION
Oleum is now diluted with water to form H 2SO4 of required concentration.
H2S2O7 + H2O  2H2SO4