Chapter 2: Sulfur & Sulfuric acid

Sulfur & Sulfuric acid

Sulfuric acid
 Sulfuric acid, H2SO4, is a colorless, viscous liquid with a normal boiling
point of 294 OC.
 It is the largest volume chemical commodity produced and it is sold
or used commercially in a number of different concentrations: 78%,
93%, 96%, 98-99%, 100% and as various oleums.
 Sulfuric acid has a number of large-scale uses not only within the chemical
industry, but in other industries as well, such as:

Phosphate fertilizer industry Man-made fibres

Petroleum refining Batteries
Pigment production In pharmaceuticals
Steel finishing Dehydrating agent

Electronic chips Oxidizing agent

Detergents
Plastics and rubber
Sulfur & Sulfuric acid
Sulphur & Sulphur dioxide (Raw Material)
 The sources of sulfur and sulfur dioxide are:
 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.
 Isolation of SO2 from pyrite (FeS2 (iron (II) disulfide).
Frasch Sulfur mining process
Sulfuric acid manufacturing
 Almost all sulfuric acid is manufactured by the contact process. This
process involves three stages.
Reactions
1. Solid sulfur, S(s), is burned in the air to form SO2
S(s) + O2(g) -----> SO2(g)
2. In the presence of a vanadium catalyst (vanadium (V) oxide) –
production of SO3(g)
2SO2(g) + O2(g) -----> 2SO3(g)
3. SO3(g) is dissolved in 98% (18M) H2SO4, to produce disulfuric acid
or pyrosulfuric acid, also known oleum, H2S2O7
SO3(g) + H2O(l) -----> H2SO4(l) (slow and mist formation)

SO3(g) + H2SO4 ------> H2S2O7

4. Water is added to H2S2O7 to form H2SO4

H2S2O7(l) + H2O(l) -----> 2H2SO4(l)
Sulfuric acid manufacturing
1) Solid sulfur storage Raw Materials
2) Sulfur melting
3) Liquid sulfur filtration
4) Liquid sulfur storage
5) Air filter and silencer
6) Air dryer
7) Sulfur combustion, two burners with individual air supply
8) Steam drum, feed-water tank, waste heat boiler
9) Converter
10) Intermediate absorber
11) Final absorber
12) Heat exchangers, economizers and super-heater
Sulfuric acid manufacturing
Stage 1:
 Air is cleaned by electrostatic precipitation, dried then heated to approx.
600oC.
 If solid sulfur is the starting point, it is made molten and then sprayed under
pressure into a furnace.
 It will then combust in air to produce SO2
 The high surface area of molten S results in a very fast combustion reaction.
 S(l) + O2(g)  SO2 (g) Δ H = -297 kJ mol-1
 Temperature may reach 1000°C so SO2 needs to be cooled.

If sulfur contains

carbonaceous Sulfur
Steam
impurities, the molten
material has to be 10-12% SO2
filtered to avoid Water
poisoning the catalyst Air
and forming water from
burning hydrogen.
93% H2SO4
Sulfuric acid manufacturing
Stage 2:
 In the next stage, the sulfur dioxide is converted to sulfur trioxide using
V2O5 as a catalyst
 2SO2 (g) + O2(g) (with V2O5 ) 2SO3 (g) Δ H = -197 kj mol-1
 The reaction happens on the catalyst of vanadium (V) oxide to speed up the
reaction. As much SO2 as possible is changed into SO3.
 SO2 is mixed with air and passed through trays containing loosely packed
porous pellets of the catalyst V2O5.
 Because the reaction is so exothermic it must continually be cooled.
 The temperature in the converter is maintained at 400 - 500°C and a pressure of
1 atm.
 The following methods are available to maximize the formation of SO3:
 Removal of heat—a decrease in temperature will favor the formation of SO3
since this is an exothermic process.
 Increased oxygen concentration in the input side.
 Removal of SO3 (double contact double absorption process) from the reaction
zone.
 Raised system input pressure.
 Selection of the catalyst to reduce the working temperature (equilibrium).
 Increased reaction time.
Sulfuric acid manufacturing
Sulfuric acid manufacturing
Convertor
Sulfuric acid manufacturing

 To maximize conversion of SO2 and hence minimize emissions of this gas into the
atmosphere, most plants now employ the “double absorption” process.
 In this process, unreacted gases in the absorption tower are recycled to the
converter for one or two additional passes over the catalyst beds, and then
returned to the absorption tower.
Sulfuric acid manufacturing
Sulfuric acid manufacturing
 Le Chatelier dictates that a low temperature will push the reaction forward.
However, the rate of reaction will slow with reduced temperature. What to
do?

 Luckily, the V2O5 catalyst saves the day by making lower temperatures
viable.

 The effect of the catalyst is maximised by spreading it over trays which

increases the surface area.

 The catalyst can become ‘poisoned’ and rendered ineffective by dust.

Therefore the air and sulphur dioxide pass through electrostatic
precipitators before they enter the converter.
Typical Conversions Values
Catalyst Bed % Catalyst Conversion %
1 19.4 56
2 25.0 87
3 26.7 99.1
4 28.9 99.7
Sulfuric acid manufacturing
Stage 3:
 Absorption of SO3
SO3 (g) + H2O (l)  H2SO4 (aq) Δ H = -130 kj mol-1

 SO3 cannot be directly reacted with H2O to produce H2SO4. As this reaction
is highly exothermic, a net back reaction is favoured, reducing the
yields of sulfuric acid. Furthermore, at higher temperatures, the acid forms a
mist which is difficult and expensive to collect.

 So, the solution will be:

H2SO4 (aq) + SO3 (g)  H2S2O7 (l) This product is called oleum

 Very little reactant is left. Oleum is then mixed with water:

H2S2O7 (l) + H2O (l)  2H2SO4 (l)

 Sometimes the reactions occur simultaneously:

H2SO4 (aq) + SO3 (g) + H2O (l)  2H2SO4 (l)
Sulfuric acid manufacturing
Sulfuric acid manufacturing
 The ‘Contact Process’ actually reduces pollution!

 By using the sulphur by-products of other reactions it prevents

these pollutants escaping into the atmosphere.
 This helps to prevent acid rain.

 More energy is produced in the process than is used by it.

 This energy is recycled by the plant and can even be sold to other
plants for use in chemical manufacture.
 Sometimes the energy is used to produce ‘green’ electricity.
Wastes Management
 To minimize SO2 emissions and hence the formation of acid rain, most
plants use a double absorption processes. In this way the percentage
of sulfur dioxide converted can be increased from 98% to 99.6%.
 The amount of sulfuric acid mist emitted from the process is
minimized by controlling the operating temperature of the absorber,
gas flow rates, and concentrations.
 Small amounts of caesium are added to the vanadium(V) oxide catalyst to
increase its efficiency (and hence maximise yields of SO3) and allow it to
operate at lower temperatures.
 Cooling water is usually recycled.
 The heat exchanger removes the heat produced during the exothermic
reaction. The heat collected is recycled and is used to heat the incoming
gas. This reduces costs associated with process and conserves energy.
 The oxidation of sulfur dioxide to sulfur trioxide is highly exothermic,
generating sufficient heat energy to meet the energy needs of the rest of
the plant. Surplus energy is produced and converted to electricity.