Sulfur

CHEM 409-S03

Manufacture of Important Inorganic

Compounds

Top Inorganic Chemicals

Sulfur (and Sulfuric Acid Derivatives)
#1 Sulfuric Acid
#7 Phosphoric Acid
#31 Aluminum Sulfate

Sulfur (and Sulfuric Acid Derivatives)

Sulfuric acid is the largest volume
chemical produced and is sometimes
considered as a leading economic
indicator of the strength of many
industrialized nations
Elemental sulfur can be obtained by
mining (Frasch method) or by oxidation of
hydrogen sulfide (Claus process)

Phase Diagram of Sulfur

Frasch Process for Mining Sulfur

Historically was a major method of sulfur
production until 1970s but now
uncommon last USA Frasch sulfur mine
closed in 2000
High purity sulfur (~99%) can be produced
using this method
http://www.youtube.com/watch?v=ODXbzaO7D9I
Old (~20min) Documentary about Sulfur and
Frasch Process:
http://www.youtube.com/watch?v=kwNdlAZWEik

Outline the Frasch process for mining

sulfur:
First used in 1894 to extract sulfur hidden
under quicksand in Louisiana and Texas

The Claus process for Oxidation of

Hydrogen Sulfide:
Process invented in 1883
95+% of sulfur produced by this process
Uses hydrogen sulfide found in natural gas
and in the by-product gases derived from
refining crude (and other industrial
processes)

The main (unbalanced) reaction

equation for the Claus process is:
H2S + O2 S2 + H2O
Balance the equation

Sulfuric Acid
Sulfuric acid is produced from sulfur,
oxygen and water using the contact
process

Contact Process
Combustion Chamber (combustion of sulfur)

Converter (conversion of sulfur dioxide)

Absorption Tower (sulfur trioxide absorbed into

the sulfuric acid mist)

Hydration of oleum to produce sulfuric acid

http://www.youtube.com/watch?v=mym1rRPX6F4
http://s999.photobucket.com/albums/af118/mschleyer/Giulini/?action=view&curr
ent=ProductionProcessSulfurciAcid.mp4

Sulfuric Acid
In the first step, sulfur is burned to produce
sulfur dioxide
(1) S(s) + O2(g) SO2(g)

Sulfuric Acid
This is then oxidised using oxygen in the
presence of a vanadium(V) oxide catalyst
to produce sulfur trioxide
(2) 2 SO2(g) + O2(g) 2 SO3(g)

Contact Process: Step 2

Uses a vanadium (V) oxide catalyst
(reaction yield is 98%). The highly
exothermic reaction heated to 450C and
subjected to a pressure of 101.3- 202.6
kPa (1-2 atmospheres). Why ?
2 SO2(g) + O2(g) 2 SO3(g) H = 197 kJ mol1

Concentration of Reactants
(2) 2 SO2(g) + O2(g) 2 SO3(g)
Equilibrium shift to the right.
Oxygen comes from the air, therefore an
inexpensive way of increasing the
conversion
What is the best sulfur dioxide:oxygen
ratio ?

Pressure
(2) 2 SO2(g) + O2(g) 2 SO3(g)
Avogadro's Law says that equal volumes
of gases at the same temperature and
pressure contain equal numbers of
molecules
3 molecules on the left-hand side of the
equation, but only 2 on the right

Pressure
(2) 2 SO2(g) + O2(g) 2 SO3(g)
Therefore, according to Le Chatelier's
Principle, if you increase the pressure the
system will respond by favouring the
reaction which produces fewer molecules
High pressure reactors expensive
(The reaction will cause the pressure to
fall)

Temperature
(2) 2 SO2(g) + O2(g) 2 SO3(g)
The reaction is exothermic
Therefore, according to Le Chatelier's
Principle, it is favoured by lowering the
temperature
But, the reaction is run at 400+ C.

Temperature
(2) 2 SO2(g) + O2(g) 2 SO3(g)
Remember Kinetics !!!!!
Lower temperature = slower reaction
A manufacturer is trying to produce as much
sulphur trioxide as possible per day
Not economically viable to achieve an
equilibrium mixture which contains a very high
proportion of sulphur trioxide if it takes several
years

Catalyst
(2) 2 SO2(g) + O2(g) 2 SO3(g)
Uses Vanadium (V) Oxide (V205) catalyst
In the absence of a catalyst the reaction is
very slow
The catalyst has no effect whatsoever on
the position of the equilibrium

Sulfuric Acid

Finally (on paper) the sulfur trioxide is treated

with water to produce 98-99% sulfuric acid
(3) SO3(g) + H2O(l) H2SO4(l)

But directly dissolving SO3 in water is highly

exothermic - SO3 can be absorbed into H2SO4
to produce oleum (H2S2O7),
(3a) H2SO4(l) + SO3 H2S2O7(l)
ThenOleum is then mixed with water to form
sulfuric acid
(3b) H2S2O7(l) + H2O(l) 2 H2SO4(l)

Contact Process

Contact Process (Jess 6.3.13)

Ammonium Sulfate and

Aluminum Sulfate:
Both made using sulfuric acid as a starting
material
What type of chemical reaction underlies
the production of these compounds ?
Outline the manufacturing processes

Ammonium Sulfate
Typical polyprotic acid-base reaction

NH3 H2SO4 NH4 HSO4

NH3 HSO4 NH4 SO4

Overall:

2NH3(g) H2SO4(aq) (NH4 )2 SO4(aq)

Conditions
Operating conditions usually at about 50 to
80oC
Higher temperatures may damage equipment

Sulfuric Acid kept below 70%

316/316L Stainless Steel used for
materials
Provide corrosion protection (molybdenum
and chromium alloys) against sulfuric acid

Saturator

Operation under
vacuum to preserve
metastability

Ammonia inserted in
the discharge of the
circulation pump

Concentrated
liquor passed
through centrifuge

Sulfuric acid injected

in the suction side of
the pump

Aluminum Sulfate
Aluminum trihydrate is refined from bauxite ore
Reacted in a stirred vessel to produce Al2(SO4)3
liquor
2Al(OH)3 + 3H2SO4 2Al3+ + 3SO42- + 6H2O
2Al3+ + 3SO42- Al2(SO4)3
Overall:
2Al(OH)3 + 3H2SO4 + 8H2O Al2(SO4)3 .14H2O
Highly Exothermic: H = -156 kJ mol

Aluminum Sulfate: Process

Reaction in stirred pressure-resistant vessel
SO3 content is 1% less than stoichiometric
requirement
Concentration by flash evaporation
Vacuum cooling
Crystallization