Sulfur & sulfuric acid

Sulfur

Sulfur is a non metallic, odourless, tasteless chemical

element, insoluble in water. It may appear as a gas,
liquid, or solid phase. It is the basic raw material for
manufacture of sulfuric acid, which is considered as the
barometer of India's industrial progress.

Sulfur
As a mineral, sulphur appears as a pale yellow, brittle
crystalline form, which is known as native sulphur.
When the element is burned, it produces the familiar
smell of sulphur (rotten egg smell).
If sulphur is combined with other metallic elements,
it forms a sulfide such as iron sulfide (fools gold).
If sulphur is combined with other metallic elements and
oxygen, it becomes a sulfate such as gypsum
(hydrous calcium sulfate).

Rhombic & monoclinic crystals of sulfur

Properties of sulfur
When burns sulfur melts to a blood-red
liquid and emits a blue flame that is best
observed in the dark.

Occurance
Sulfur is found mainly in volcanic regions, and in salt
domes. It also occurs in natural gas and petroleum
crudes. Underground deposits of sulfur associated with
salt domes in limestone rock provides a substantial
portion of the words supply of the element.

Sulfur deposits

Sulfur deposits in
salt domes
Sulfur is accumulated in the
cap rock in salt dome

Classification of Processes
1.

Elemental sulfur mining from salt domes (Frasch process)

2.

Hydrogen sulfide conversion from natural gas and industrial

gases (Indian refineries and many U.S. refineries)

3.

Iron pyrites from Amjhore in Bihar State

1. Elemental Sulfur Mining (Frasch

Process)
Raw materials
Sulfur deposits in salt domes
Large supply of hot water

Frasch Process


Process description

Wells drilled into free sulfur-bearing salt domes.

Treated hot water is pumped into deposit melt

sulfur; water moves upward and outward to bleeder
wells on outer periphery of area where it is aerated
and discharged.

Molten sulfur sinks to bottom of casing and is jet

pumped with compressed air to sump-separation
units and shipment or storage.

Filtration

is

sometimes

used

carbonaceous and mineral matter.

to

remove

Major engineering problems

Heat transfer in melting and shipping operations
Finding suitable sources of treated water
Corrosion

2. Oxidation-reduction of H2S
Raw materials
H2S from natural (sour) gas and petroleum refinery
streams. Recovered by scrubbing with ethanol amines
and high-temperature stripping.
Chemical reactions

Process description :

H2S and air burns and produces SO2.

The product SO2 reacts with H2S in a two-stage catalytic

converter with intercooling and condensing.

Final waste gas is scrubbed with molten sulfur.

Major engineering problems:

a)

Two-stage reactor design for exothermic SO 2 oxidation of

H2S. 70-80% conversion in first stage at 300-400C range
followed by 250-300C operation in second reactor to
obtain favorable equilibrium.

b)

Heat exchange for molten sulfur handling

c)

Corrosion

d)

Final clean-up of stack gases

3. Elemental Sulfur from Pyrites

(Finnish Process)

Process description:

Pyrites ore is dried in a rotary kiln with flue gases and

ground to 200 mesh.

It is dispersed at the top of a vertical circular shaft

furnace (5.5m diameter x 10m height).

Heat of dissociation and fusion is transferred to the FeS 2

as it moves downward in the suspension.

At the bottom of the vertical shaft the gases change 90

and move horizontally.

The liquid droplets of FeS are caught in the molten horizontal batch
and any silica gangue is trapped and fluxed with lime which floats
on top of the molten FeS matte.

The liquid FeS is tapped periodically and granulated in water to

produce 4 mm grains for further roasting operations.

Hot gases at 1,300C move through a high-pressure heat recovery

boiler section (70 atms. Steam).

Dust is next separated by electrostatic precipitation.

The first step in S recovery is done in a high temperature catalytic
reactor, where carbon compounds with S are eliminated.

The reaction gases, still containing SO2 and H2S, are cooled to 150C by
passing through a low-pressure heat recovery boiler (4.5 atms. gage).

This is followed by "cold stage" catalytic reaction where aluminum oxide

catalyzes the H2S + SO2 reaction to produce S, vapor.

After catalysis, sulfur gas is condensed on molten sulfur droplets in a spray

condenser.

The heat of fusion is recovered via low-pressure steam boiler (0.7 atm.
gauge).

The exit gases are next washed with water in another tower to further
recover entrained and uncondensed sulfur.

The sulfur usually contains arsenic which attacks the vanadium or

platinum catalyst in the SO2> SO3 contact process for H2SO4.

It can be removed by contacting molten sulfur with milk of lime in

a continuous autoclave.

Sulfur as SO2 for sulfuric acid can be obtained by roasting the

granulated FeS from Ithe smelting furnace.

Fluidized roasting at 1,000C produces SO2 gas which is cooled in

waste heat boiler, cleaned by cyclones and electrostatic
precipitation.

The hot cinders of iron oxide, suitable for blast furnace sinter cake,
are cooled on conveyors and shipped to steel plants.

Major engineering problems

a) Pyrites ore beneficiation
The process was developed for pyrites ores of Finland
which have 1.5% SiO2. Indian ore at Amjhore has 5-7%
SiO2 and requires either flotation initially or extra
limestone to flux out the silica. The latter is preferred
since there is a 30% loss of ore in beneficiation.

b) Grinding
The particle size range of 200 mesh was an economic balance

between heat transfer rate from combustion gases plus residence

time, as dictated by rate of fall of particles, tower height, and
grinding costs.
c)

Substitution of coal for fuel oil

Low-grade fuel oil is only available at the Amjhore site at high

costs. Smelting with coal would represent a savings of 20% in the
cost of sulfur produced. Use of coal is being considered for pilot
plant development in India. The question of using pulverized coal
directly in the smelter burners or working with secondary
combustion gases after ash has been removed must be resolved.

d) Gaseous reactions in the smelting furnace

Complete combustion of fuel without excess air is desirable

to avoid unbalance of the H2S-SO2 ratio which can be shifted
with only minor changes in the oxygen/fuel ratio. The
smelter feed system requires close instrumental control.

e) Two-stage catalytic reactor design

Plant first operated only with cold stage so that COS and CS 2
remained unconverted to free sulfur. By first using a hightemperature catalyst, these compounds can also be oxidized
and the sulfur yield increased from 85 to 92%. Design of the
cold stage is similar to Process 3.3.

f)

Heat

recovery

and

generation

of

electric energy

Despite the initial endothermic smelting

step and the high electrical energy usage
for grinding, the overall process has excess
heat energy which is converted via three
stages of steam boiler heat recovery to
electric energy with a net production of
1,400 KWH/ton of S.

Sulfuric acid(H2SO4)

Cautions in using sulfuric

acids

The picture says

it all.

Sulfuric Acid

Sulfuric acid is produced in greater quantities than any

other chemical worldwide.

Annual worldwide production is estimated at about 170

million tonnes.

Sulfuric Acid

Transport and storage of sulfuric acid are hazardous.

A high proportion of the acid is used close to the site

of manufacture.

Most sulfuric acid plants are located near smelting

and refining industries that produce waste sulfur
dioxide, a raw material for the production of sulfuric
acid.

Uses of sulfuric acid

It is used in the
manufacturing of paper,
household detergents,
pigments, dyes, and
drugs.
It is the electrolyte in
car batteries.
Tanning leather
Cleansing metal

Why in fertilizers

Sulfuric acids is used as a dehydrating agent to prevent

the soil from over hydrating, thus the plant will be able
to survive.

Use of sulfuric acids

(In tanning leather)

Sulfuric acid is used in tanning to bring down the pH of

collagen to a very low level so as to facilitate the penetration
of mineral tanning agent into the substance.

Use of sulfuric acids

(In cleaning metals)

The acid is used in pickling which is a

surface treatment used to remove
impurities such as stains, inorganic
contaminants, rustor scale from
ferrousmetals,copper, andaluminum
alloys.

Methods of production
Contact Process
2. Chamber Process
. Both processes are based on SO . Chamber process was
2
developed first (1746), but this process produces acid
of concentration less than 80%. Contact process yields
98% H2SO4 and higher which can be diluted, if
necessary.
. Chamber process is virtually obsolete.
1.

The contact process

Sulfuric Acid is manufactured in stages from sulfur
dioxide.
These involve oxidation of sulfur dioxide to sulfur
trioxide.
Followed by conversion to the acid.
The process can be summarised:
SO2(from various sources) SO3 H2SO4

The contact process

The contact process raw

materials
The sulfur dioxide used to produce sulfuric acid is obtained
from two principal sources
Combustion of sulfur recovered from natural gas and crude
oil.
Sulfur dioxide formed during the smelting of sulfide ores of
copper, zinc or lead.
A third process can be used from mining of the
underground deposits of elemental sulfur.

Steps in contact process

Contact process is a three step process

Stage
1

Stage 2

Step1: Burning of Sulfur

If sulfur is used as a raw material, the first step is to

spray molten sulfur under pressure into a furnace up
to 1000C.

Here it burns in air to produce sulfur dioxide gas.

The sulfur dioxide gas is then cooled for the next
step.

The high surface area of the sulfur spray allows

combustion to be rapid.
S(l) + O2(g) SO2(g); H = -297 kJ mol-1

Step 2: Catalytic oxidation of

sulfur dioxide

Sulfur dioxide gas is oxidised to sulfur trioxide gas by

oxygen, using Vanadium oxide as a catalyst

2SO2(g) + O2(g)

2SO3(g); H = -197 kJ mol-1

This step is performed in a reaction vessel called a

converter.

PROCESS D ESC RIPTI ON

Sulfur dioxide is mixed with air and passed through

trays containing loosely packed porous pellets of
catalysts.
The converter contains several catalyst beds and the
gas mixture passes over each in succession.
Because the reaction is exothermic it is necessary to
cool the gas mixture as it passes from one tray to
another to maintain the desired reaction temperature.
The temperature in the converter is maintained
between 400C and 600C and the pressure is close
to 1 atm.
Nearly complete conversion of sulfur dioxide to
sulfur trioxide is achieved.

Advantages & disadvantages of vanadium

oxide as catalyst

Step 2: Equilibrium yield

Using Le Chateliers principal, the equilibrium yield of
sulfur trioxide will increase:
As temperature decrease: Since the reaction is
exothermic a decrease in temperature will favour
the forward reaction.
As pressure increases: Since there are more gas
particles on the reactants the forward reaction will
result in a decreased pressure.
If excess reactants are added.

Step 3: Absorption of sulfur trioxide

Sulfur trioxide reacts with water to form sulfuric acid:
SO3(g) + H2O(l) H2SO4(aq); H = -130 kJ mol-1

However direct reaction with water is not used, because

large amount of heat evolves when sulfur trioxide is
added to water and a fine mist of acid is produced which
is difficult to collect.

Instead, sulfur trioxide gas is passed into concentrated

sulfuric acid in an absorption tower. This reaction occurs
in two steps

Stage 3: Absorption of sulfur

trioxide
1.

The sulfur trioxide gas dissolves almost totally in

the acid to form a liquid known as oleum.
SO3(g) + H2SO4(l) H2S2O7(l)

2.

Oleum obtained from the absorption tower is then

carefully mixed with water to produce sulfuric acid:
H2S2O7(l) + H2O(l) H2SO4(l)

Stage 3
Sulfur trioxide is converted to
sulfuric acid. The sulfur trioxide gas is
absorbed into very concentrated
sulfuric acid (98% solution of H2SO4 in
water), producing a thick fuming liquid
called oleum.
The oleum is mixed carefully with
water, and the sulfuric trioxide in the
oleum reacts with the water to produce
H2SO4.
SO3 (g)+H2O(l)-> H2SO4(l)

Major engineering problems

Design of multistage catalytic converter for a highly

exothermic reaction: Some designs contain 3 or 4
stages rather than conventional two-stage operation
for large capacity plants.

Corrosion problems: Optimization studies show that

equilibrium yield can be increased by square root of
system pressure (PT) at a given temperature, but
compression cost as well as corrosion problem
increases., so low pressure operation (1 atm) is used.