Elemental sulfur

Elemental sulfur extraction process

Frasch Process:
Melting the sulfur underground or under the sea and then pumping it
up to the surface.
Equipment:
Ordinary oil-well equipment is used to bore the surface to the bottom
of the sulfur-bearing stratum.
3 concentric pipes (20, 10 and 3 cm) are used to pass through the
sulfur bearing stratum.
A 10 cm pipe is passed through the 20 cm pipe so that an annular
space exists between the two pipes.
The outer pipe should be reached up to the anhydrite area (anhydrous
calcium sulphate)
Elemental sulfur extraction process
Frasch Process:
Melting the sulfur underground or under the sea and then pumping
it up to the surface.
Equipment:
The inner pipe should be ended up at the middle of sulfur bearing
calcite, so that it seals the annular space
An air pipe of 3 cm inside the others reaches to the depth slightly
above the collar of the calcite.
20 cm pipe is perforated at two different levels of the sulfur
bearing calcite
Elemental sulfur extraction process
Frasch Process:
Melting the sulfur underground or under the sea and then pumping
it up to the surface.
Equipment:
The upper set of perforation permits the escape of hot water and
molten sulfur enters through the system.
Hot water at about 160˚C is passed down the annular space
between 20 and 10 cm pipes.
It discharges through the perforation in to the porous
formationnear to the calcite.
Elemental sulfur extraction process
Frasch Process:
Melting the sulfur underground or under the sea and then pumping it
up to the surface.
Equipment:
The temperature of calcite are is raised above the melting point of
sulfur about 115 ˚C.
Molten sulfur being heavier than the water, sinks and form a pool
around the base of the well.
It enters through the lower perforation section and raises in the space
between 10 an 3 cm pipes.
Elemental sulfur extraction process
Frasch Process:
Melting the sulfur underground or under the sea and then pumping it
up to the surface.
Equipment:
Compressed air, forced down the 3 cm pipe aerates and reduces the
density of the liquid sulfur so that it will raise to the surface.
The compressed air volume is regulated so that the production rate is
equalized with the sulfur melting rate.
On the surface the liquid sulfur moves through steam-heated lines to
separate the air
 THE CONTACT PROCESS
Raw Materials
Basis: 1000kg sulfuric acid (100%)
Sulfur dioxide
Sources of raw material
The sources of sulfur and sulfur dioxide are as follows
 Sulfur from mines
 Sulfur or hydrogen sulfide recovered from petroleum desulfurization
 Recovery of sulfur dioxide from coal or oil-burning public utility stack gases
 Recovery of sulfur dioxide from the smelting of metal sulfide ores

2PbS + 3O2 = 2PbO + 2SO2

 Isolation of SO2
Reactions

Reactions

S + O2 = SO2 ΔH The steps in this process are as follow.

1. Burning of sulfur
2SO2 + O2 = 2SO3 ΔH 2. Catalytic oxidation of SO2 to SO3
3. Hydration of SO3
SO3 + H2O= H2SO4 ΔH
Process description
Burning of sulfur : Burning of sulfur in presence of dry air is carried out in sulfur pyrite burner.
As SO2 is needed for the catalytic oxidation and prevention of corrosion, dry air is used in the
combustion process. If sulfur contains carbonaceous impurities, the molten material has to be
filtered to avoid poisoning the catalyst and forming water from burning hydrogen.
Catalytic oxidation of SO2 to SO3 When using sulfur from sources 1 and 2, purification of the
SO2 gas is normally not needed. Other sources of SO2 require wet scrubbing followed by
treatment of the gas with electrostatic precipitators to remove fine particles. The catalyst used is
vanadium pentoxide (V2O5) and the pressure is 1.2-1.5 atmospheres.
The temperature has to be kept around 4500C. If it rises above 4500C, the equilibrium is
displaced away from SO3. Temperature should reach around 4500C for the catalyst to be
activated. This process is strongly exothermic.
The catalytic reactor is designed as a four-stage fixed-bed unit.
The gas has to be cooled below, are necessary for overall conversion of 99.5-99.8% (three
passes, 97-98%). The temperature rises to over 6000C with the passage of the gas through each
catalyst bed.
Hydration of SO3 After the catalytic oxidation process, the resulting SO3 is hydrated by
absorption in packed towers filled with 98-99% sulfuric acid.
The catalytic oxidation has to proceed in high yield to avoid air pollution problems. SO2 has a
low solubility in 98% H2SO4. At lower acid concentrations, sulfuric acid and SO3 form a
troublesome mist and at higher concentrations emissions of SO3 and H2SO4 vapour become
significant.
Major engineering problems
 Design of multistage catalytical convertor for highly exothermic reaction.
 Earlier one or two stage converter is used but nowadays the design of three or four stages
rather than conventional two stage operation are developed.
 To optimize space velocity in catalyst chamber because it deals with pumping cost or fixed
charges of reactor
 Thin catalyst beds of 30-50cm height used to avoid above difficulties. Yield can drop due to
longitudinal mixing if the convective gas velocity through the bed is low
 Removal of heat of absorption of SO3 in acid. Pipe coolers with water dripping over external
surface have been replaced by cast iron pipe with internal fins to promote better heat transfer.
 Pressure drop must be low, so, 8cm stacked packing is often used.
Utilizations
 The largest single use is in the fertilizer industry.
 Mostly in production of phosphoric acid, which in turn used to manufacture fertilizers such as
superphosphate, mono and diammonium phosphates, ammonium sulfate
 Used as an acidic dehydrating reaction medium in organic chemical production
 petrochemical processes involving such reactions as nitration, condensation, and dehydration,
as well as in oil refining, in which it is used for refining, alkylation, and purification of crude-
oil distillates
Sulfur burning single-absorption sulfuric acid plant
with air injection cooling process
Contact sulfuric acid
Contact Process equipment:

1. Burners
2. Treatment of the burner gas
3. Heat exchangers and coolers
4. Converter
5. Absorption process unit