Chemical Process Technology

Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk

Sulfuric Acid Industry

Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk

 Manufacturing of Sulfuric Acid
• Technological Options for the Production of SULFURIC ACID:
• 1. Contact Process (Platinum and Vanadium catalyst)
• 2. Lead Chamber Process (homogeneous catalyst: Nitrogen
oxides)

• High price of platinum and its sensitivity to poisons.

• Nowadays, the life time of an active catalyst is 10–20 years

Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk

 Manufacturing of Sulfuric Acid
• Lead Chamber Process:
• Sulfur dioxide is oxidized with moist air, using gaseous
nitrogen oxides as catalysts, the reaction takes place
primarily in a series of large, boxlike chambers of sheet lead.

Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk

 A Brief Summary of the Contact Process
• First elemental sulfur is converted to sulfur dioxide
• 2S (l) + O2(g) → 2SO2(g) rH298 = −298.3 kJ/mol
• The sulfur dioxide is converted into sulfur trioxide by the reversible
reaction taking place at the heart of the catalytic converter.
• SO2(g) + ½ O2(g) → SO3(g) rH298 = −98.5 kJ/mol
• The sulfur trioxide is first brought in to contact with a spray of lean
sulfuric acid in the absorption tower wherein OLEUM is formed
which on the addition of water finally gives rise to concentrated
sulfuric acid.
• H2SO4 (l) + SO3 (g)→H2S2O7 (l)
• H2S2O7 (l) + H2O (l) → H2SO4 (l) rH298 = −130.4 kJ/mol

Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk

Sulfuric Acid PFD

Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk

Sources of Sulfur
• Elemental Sulfur from Crude/ natural gas refineries
• Hydrogen Sulfide
• Metal Smelting

CuFeS2 + SiO2 + O2 → Cu2S・FeS + 2FeO・SiO2 + SO2 + Reaction heat

Cu2S・FeS + SiO2 + O2 → Cu + 2FeO・SiO2 + SO2 + Reaction heat

Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk

 Sulfur Burning
• Dried air and atomized molten sulfur are introduced at one end of the sulfur burner,
which is a horizontal, brick-lined combustion chamber.
• A high degree of atomization and good mixing are key factors.
• Atomization typically is accomplished by pressure spray nozzles or by mechanically
driven spinning cups.
• Some sulfur burner designs contain baffles or secondary air inlets to promote mixing.
• Handling of molten sulfur requires keeping the temperature between 410 and 425 K,
where its viscosity is lowest. Therefore, it is transported through heated lines.

Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk

Sulfur Burning

Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk

Sulfur Burning

Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk

 SO2 Conversion
• Quantitative conversion of SO2→SO3 is desirable for Plant
economics and environmental Purposes
• Permissible limits in US → 2kg of SO2/ Matric Ton of Sulfuric acid
(100%) Produced.
• The catalytic oxidation of sulfur dioxide is carried out in adiabatic
fixed bed reactors
• Vanadium oxide supported on a porous inorganic support

Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk

 SO2 Conversion
• The oxidation of SO2 is thermodynamically
favored by low temperature.
• The conversion is (nearly) complete up to
temperatures of about 700 K. As with all
exothermic equilibrium reactions, however,
the ideal temperature must be a compromise
between achievable conversion
(thermodynamics) and the rate at which this
conversion can be attained (kinetics).
• With the current sulfur dioxide oxidation
catalysts this means a minimum temperature
of 680–715 K. Equilibrium conversion of SO2 to SO3 (p = 1 bar;
• Elevated pressure is thermodynamically shaded area indicates range of practical operating
temperature)
favorable, but the effect of pressure is small.
Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk
 SO2 Conversion
The major part of the conversion is obtained
in the first bed. The inlet temperature of the
first bed is around 700 K and the exit
temperature is 865 K.

The successive lowering of the temperature

between the beds ensures an overall
conversion of 98–99%.

Still, this is not enough to meet current

environmental standards. Therefore, modern
sulfuric acid plants use intermediate sulfur
trioxide absorption after the second or, more
commonly, the third catalyst bed.

The intermediate removal of sulfur trioxide

from the gas stream enables the conversion
of sulfur dioxide “beyond thermodynamic
equilibrium

Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk

SO2 Conversion

Effect of inter-stage absorption of SO3 on SO2 oxidation

Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk
 Demisters
• Small amounts of sulfuric acid mists or aerosols are always
formed in sulfuric acid plants when gas streams are cooled or
sulfur trioxide reacts with water below the sulfuric acid dew
point.
• Formation of sulfuric acid mists is highly undesirable because
of corrosion and process stack emissions. Therefore, the
absorbers in sulfuric acid plants are equipped with demisters,
consisting of beds of small-diameter glass beads or Teflon
fibers.

Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk

 Waste Heat boilers
• Sulfuric acid plants can be operated as cogeneration plants.
• Much of the heat produced in the combustion of sulfur is
recovered as high-pressure steam in waste heat boilers, while
some of the heat produced in the catalytic sulfur dioxide
oxidation is also recovered by steam production in so-called
economizers.
• Steam production in modern large sulfuric acid plants exceeds
1.3 t/t of sulfuric acid produced.

Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk

 Catalyst Deactivation
• The life of modern vanadium catalysts may be as long as 20
years, typically at least 5 years for the first and second bed
and at least 10–15 years for the third and fourth bed.
• The main reasons for loss of activity of vanadium catalysts are
physical breakdown giving dust, which could plug the catalyst
bed, and chemical changes within the catalyst itself.
• The former is overcome by regular screening of the catalyst
(first bed annually, others less frequently).
• The latter is the result of migration of the molten vanadium
oxide from catalyst particles into adjacent dust and increases
with increasing temperature.
Assistant Professor: Engr. Dr. Asim Riaz | Email: asim.riaz@kfueit.edu.pk