Acid strengths
Associated end uses
Percent
H2SO4
35.67
Uses
Storage batteries, electric utilities
62.18
Normal superphosphate and other fertilizers
69.65
77.67
80.00
Copper leaching
93.19
98-99
104.50
Surfactants, nitrations, hydrofluoric acid
106.75
109.00
Explosives
111.25
113.50
114.63
About 220 million tonnes of sulfuric acid are produced/consumed per year.
Sulfuric acid
Sulfuric acid is made from SO2, O2 and water.
SO2 comes from:
burning molten elemental sulfur with dry air
smelting and roasting metal sulfide minerals
decomposing contaminated (spent) sulfuric acid catalyst
Sulfur burning is far and away the largest source.
SO2 in the gas is made into sulfuric acid by
catalytically oxidizing it to SO3
reacting this SO3 with the H2O() in 98.5 mass% H2SO4(),
1.5 mass% H2O()
Contact process
Three Step Process
1) S + O2
SO2
2) SO2 + 1/2O2
SO3
3) SO3 + H2O
H2SO4
Plant
Drying
H2O + H2SO4 H2SO4.H2O
To avoid:
(a) accidental formation of H2SO4 by the reaction of H2O(g) with the
SO3 product of catalytic SO2 oxidation
(b) condensation of the H2SO4() in cool flues and heat exchangers
(c) corrosion.
Oxidation of Sulfur
1) S (l)
S(g)
2) S (g) + O2 (g) SO2 (g)
Sulfur
Steam
10-12% SO2
Water
Air
Process:
93% H2SO4
H = 99 kJ.mol-1
SO2 Gas
Gas
Cooling
SO3 Gas
Lechatelier principle is usually taken into account in deciding how to optimize the equilibrium. This
states that when an equilibration system is subjected to stress, the system will tend to adjust itself
in such a way that part of the stress is relieved.
Maximizing SO3
Removal of heat a decrease in temperature will
favor the formation of SO3 since this is an exothermic
process
Increased oxygen concentration
Removal of SO3 (as in the case of the double
absorption process)
Raised system pressure
Selection of the catalyst to reduce the working
temperature (equilibrium)
Increased reaction time
SO2 Gas
Kinetic Effects
- Oxidation of sulfur dioxide is
slow and reversible
Gas
Cooling
SO3 Gas
93% H2SO4
Absorption
Catalytic oxidations SO3 product is
made into H2SO4() by contacting
catalytic oxidations exit gas with
strong sulfuric acid. The reaction is:
SO3 + H2O H2SO4
H2SO4() is not made by reacting
SO3(g) with pure H2O(). This is
because Reaction is so exothermic
that the product of the reaction
would be hot H2SO4 vaporwhich is
difficult and expensive to condense.
Oleum Production
Sulfuric acid with additional SO3 absorbed
20% Oleum contains 20% SO3 by weight in the oleum
Common strengths of oleum are 20, 30, 40, 65 percent.
To produce 20 and 30 percent oleum, only requires an additional
absorption tower.
%H2SO4 = 100 + 18/80 * % oleum
20% oleum is equivalent to 104.5% H2SO4
Oleum is used in reactions where water is excluded
SO3 + H2SO4
H2S2O7
(disulfuric acid)
Production Considerations
Metal corrosion is a big issue in the manufacture of sulfuric acid.
Special alloy metals must be used to guard against excessive
corrosion.
Nickel, chromium, molybdenum, copper, an silicon are the
most important elements that enhance corrosion resistance of
alloys.
Recent developments
The three main recent developments in sulfuric acid making have
been: