Chemical Technology

Subject Code: CH2001

Lecture 6

1
 Sulfur
Phase at STP solid
Appearance lemon yellow sintered microcrystals

Melting point 388.36 K (115.21 °C, 239.38 °F)

Boiling point 717.8 K (444.6 °C, 832.3 °F)
3
alpha: 2.07 g/cm
3
Density (near r.t.) beta: 1.96 g/cm
3
gamma: 1.92 g/cm
3
when liquid (at m.p.) 1.819 g/cm
Critical point 1314 K, 20.7 MPa
Heat of fusion mono: 1.727 kJ/mol
Heat of vaporization mono: 45 kJ/mol
Molar heat capacity 22.75 J/(mol·K)
2
 Sulfur mines
• Sulfur exists in nature as elemental
deposits, sulfides of iron, zinc, lead,
and copper, and sulfates of sodium,
calcium, barium, and magnesium.
• Hydrogen sulfide is often a
component of natural gas and occurs
in many volcanic gases.
• Sulfur is a constituent of many Indonesia’s Ijen crater
proteins and is essential for life. Milos island, Greece
• Sulfur exists in several allotropic
forms. The stable form at room Indonesia’s Ijen crater
temperature contains eight- Saba Islander
membered rings, and so the true
formula is S8.
• Sulfur (group 16) reacts with almost
all metals and readily forms the
sulfide ion, S2−, in which it has as
oxida on state of 2−. Sulfur reacts
with most nonmetals

3
 Videos
• Production video
• https://www.youtube.com/watch?v=yVuyXxsmdUI

• Lecture videos
• https://www.youtube.com/watch?v=mDQBlp7c3n4
• https://www.youtube.com/watch?v=pAO_ihesifY

• Lebowitz, Samuel H. (1931). "A demonstration working model of the

Frasch Process for mining sulfur". J. Chem.
Educ. 8 (8):1630. Bibcode:1931JChEd...8.1630L. doi:10.1021/ed00
8p1630.

4
 Sulfur from mines
• It is the only industrial method of
recovering sulfur from elemental
deposits.
• until the late 20th century, when
sulfur recovered from petroleum
and gas sources.
• The Claus process is the most
significant gas desulfurizing
process, recovering elemental
sulfur from gaseous hydrogen
sulfide.

• In the Frasch process, superheated

water is pumped into the sulfur
deposit; the sulfur melts and is
extracted. The Frasch process is
able to produce high-purity sulfur

5
 Frasch process
• Frasch sulfur process works best on either salt domes or bedded
evaporite deposits, where sulfur is found in permeable rock layers
trapped in between impermeable layer.
• In the Frasch process, three concentric tubes are introduced into the
sulfur deposit.
• Superheated water (165 °C, 2.5-3 MPa) is injected into the deposit
via the outermost tube. Sulfur (m.p. 115 °C) melts and flows into the
middle tube.
• Water pressure alone is unable to force the sulfur into the surface
due to the molten sulfur's greater density, so hot air is introduced
via the innermost tube to froth the sulfur, making it less dense, and
pushing it to the surface.
• The sulfur obtained can be very pure (99.7 - 99.8%). In this form, it is
light yellow in color. If contaminated by organic compounds, it can
be dark-colored; further purification is not economic, and usually
unnecessary.
• The Frasch process can be used for deposits 50–800 meters deep. 3-
38 cubic meters of superheated water are required to produce every
tonne of sulfur, and the associated energy cost is significant.

6
 USES OF SULPHUR
1. It is mainly used for preparation of sulphur dioxide
which is used in manufacture of sulphuric acid.
2. Sulphur is used in the manufacture of gun powder.
3. Sulphur is used in the manufacture of matches
and fireworks.
4. Sulphur is used on vulcanization of rubber.
Natural rubber is soft and sticky. Heating it with
sulphur makes it hard, non-sticky and more
elastic. This process is known as vulcanization.
5. Sulphur is used in ointments for curing skin
diseases.
6. Sulphur is used in beauty parlor to give specific
shape to the hair.

7
 Pyrite Fool's Gold
• The mineral pyrite or iron pyrite, also known as fool's gold, is an iron
sulfide with the chemical formula FeS2 (iron (II) disulfide).
• Pyrite's metallic luster
• pale brass-yellow

• Nicknames:
brass, brazzle,
and Brazil,

• "stone or mineral which

strikes fire“

• associated with other

sulfides or oxides in quartz
veins, sedimentary rock,
and metamorphic rock,

8
 Sulfur from pyrites (Finnish process)
Chemical Reactions
Quantitative requirement
• 1 ton of elemental ‘S’ (basis)
• 4.4 ton pyrites ore
• 0.65 ton limestone
• 0.76 ton fuel oil
• 25 ton water
• 1800 kWh
• 1.2 ton SO2 from FeS
• 2.8 ton Fe2O3 from FeS roasting

9
 Sulfur and sulfur dioxide from pyrites
• Pyrites ore is dried in a rotary kiln with
flue gases and ground to 200 mesh. It is
dispersed with hot combustion gases
from oil burners at the tip of a vertical
circular shaft furnace.
• The liquid droplets of FeS are caught in
the molten horizontal batch and any
silica gangue is trapped and fluxed with
lime, floating on the top of the molten
FeS matte.
• The liquid FeS is trapped periodically
and granulated in water to produce 4
mm grains for further roasting
operations.

10
 Process description
• Hot gases at 1300 C move through a high-pressure heat recovery boiler, colling to 300 C. Dust is
next separated by electrostatic precipitation.
• The first step in combined 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 atm). This is followed by cold-
stage catalytic reaction where aluminium oxide catalyze the H2S + SO2 reaction to produce S6
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). The exit gases are next washed with
water in another tower to further recovery entrained and uncondensed sulfur.
• The sulfur usually contains arsenic which attacks the vanadium or platinum catalyst in the SO2 to
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 granulated FeS from smelting furnace.
Fluidized roasting at 1000C 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 conveyor and shipped to steel plant.

11
 Major engineering problems
Pyrites ore beneficiation
• The process was developed for pyrite ore of Finland which have 1.5% SiO2. Indian ore at amjhore has 5-7%
SiO2 and require either flotation initially or extra limestone to flux out the silica. The latter is preferred since
there is 30% loss of ore in beneficiation.
Grinding
• The particle size range of 200 mesh was an economic balance b/w heat transfer rate from combustion gases
and residence time, as dictated by rate of fall of particles, tower height and grinding cost.
Substitution of coal for fuel oil
• Low grade fuel oil is only available at the ore site at high cost. Smelting with coal would represent a saving of
20% in the cost of S produced. Use of coal is being considered for pilot plants developed in India.
Gaseous reaction in the smelting furnace
• Complete combustion of fuel without excess air is desirable to avoid unbalance of h2S to SO2 ratio which
can be shift with only minor changes in the oxygen/fuel ratio. The smelter feed system requires close
instrumental control.
Two-stage catalytic reaction
Heat recovery and generation of electric energy

12
 Sulfur production by oxidation-reduction of H2S
Oxidation-reduction of H2S

2H2S + 3O2 → 2SO2 + 2H2O;

∆H = -247.89 kcal

4H2S + 2SO2 → S6 + 4H2O;

∆H = 42.24 kcal

13
 Process
Raw materials
• H2S from natural gas
Basis 1 metric ton of sulfur
• 1.2 tons of H2S and 1700 Nm3 requirement.
Process
• H2S and air is burned. The product SO2 oxidizes H2S by reaction in a two-stage
catalytic convertor with intercooling and condensing. Final wate gas is scrubbed with
molten sulfur.
Major engg problem:
• Two-stage reactor design
• Heat exchanger for molten sulfur handling
• Corrosion
• Final clean-up of stack gases.

14