CHEMICAL ENGINEERING

CHAPTER 2
MANUFACTURE OF SULPHURIC ACID

 COURSE OBJECTIVE
The course should enable the students to:
a. Develop an understanding of several chemical process industries here in Oman and
elsewhere
b. Have in-depth understanding of the physical and chemical principles learned and be able to
relate them to realistic situations in chemical engineering

 COURSE OUTCOMES
The students should be able toDescribe in detail the flowsheet, identify raw material
requirement and industrial applications, associated for the sulphuric acid

 COURSE RESOURCES
1. Dryden’s Outlines of Chemical Technology by M. Gopala Rao and Marshall Sittig, East-
West Press, New Delhi, 3rd Edition, 2010
2. Shreve’s Chemical Process Industries by George T.Austin . Tata Mc-GrawHill Book
Company, Newyork, 5th Edition, 2012

 INTRODUCTION
Sulphuric acid is a highly corrosive strong mineral acid.It is the most important heavy
industrial chemical.60% of Sulphuric acid manufactured is used in the manufacture of
phosphoric fertilizer.

 HISTORY
Sulphuric acid is called as Vitriol by Medieval age people. It was first sulphuric acid was
prepared by Johann Glauber in 17th century.He prepared by burning sulfur with saltpeter
(potassium nitrate, KNO3)in presence of steam. Joshua Ward found method for large scale
production of sulphuric acid in 1736

 CHARACTERISTIC PROPERTIES OF SULPHURIC ACID

It is a colorless to slightly yellow viscous liquid which is soluble in water at all
concentrations.Aqueous sulphuric acid solution are defined by the concentration of
sulphuric acid in weight%. The anhydrous sulphuric acid which is 100% sulphuric acid is
called a monohydrate. The Monohydrate mainly contains SO3. Fuming sulphuric acid is
obtained by dissolving SO3 in sulphuric acid. It is also called as Oleum.

 PHYSICAL PROPERTIES:

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Molecular Formula: H2SO4

Molecular Weight: 98.08 g./mole
Boiling Point: 2900C
Melting point: 100C
Density: 1840 kg/m3

 CHEMICAL PROPERTIES:

Sulphuric acid is a strong dibasic acid. Sulphuric acid can act as good dehydrating agent,
oxidizing agent and pickling agent. A dehydrating agent characteristic enables sulphuric acid
in greater affinity for water and releases heat due to formation of mono and
dehydrates.Example: H2SO4.H2O and H2SO4.2H2O. Dehydration behavior is used for drying
gas, remove water from oxalic acid and formic acid
Sulphuric acid is completely miscible with water with large heat of solution. The amount of
SO3 in sulphuric acid gives varying concentration of oleum.

 USES

The major use of sulphuric acid in manufacture of fertilizer and oil of vitriol.
It is used in in the production of phosphoric acid fertilizer which is used in
manufacture of triple superphosphate, mono and di-ammonium phosphate which
are used in agriculture as fertilizer
It is used as dehydrating agent in crude oil purification process.
It is used in production of TiO2 pigments used in the manufacture of
paints,hydrocholoric acid and hydrofluoric acid.
It is used for leaching copper, uranium and vandium
It is used for descaling steel.
It is used in preparing pulp for paper industry, explosives, detergents and plastics
It is used in production of dyes, pharmaceuticals and leather tanning industry.

 METHODS OF MANUFACTURE

Two different methods are used for industrial production viz., Lead Chamber Process and
Contact Process. Both processes depend on SO2 level. The limitation of lead chamber
process is generation of sulphuric acid less than 80%. The high concentration and high yield
of sulphuric acid lead to popularity of Contact Process.

Raw Material for contact process

Basis or Requirement : 1000 kg of Sulphuric Acid

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Sulphur dioxide or Pyrites ( FeS2) = 670 kg and Air = 1450 -2200 Nm3

 SOURCES OF RAW MATERIAL

Raw material has to be in the form of sulphur or sulphur dioxide. The various dependable
sources for sulphur are

• Sulfur from mines

• Sulfur or hydrogen sulfide recovered from petroleum desulfurization
• Sulfur dioxide recovered from coal or oil burning power plant stack (exhaust) gas.
• Sulfur dioxide recovered from smelting of lead ores
• Separated SO2 from pyrites

 CONTACT PROCESS- REACTIONS AND STEPS

 Reactions

S + O2  SO2 ΔH = - 71.2kcals
2SO2 + O22 SO3 ΔH = - 46.3kcals
SO3 + H2O H2SO4 ΔH = - 31.1kcals

 Steps in the contact process

1. Burning of sulfur
2. Catalytic oxidation of SO2 to SO3
3. Hydration of SO3

Fig. 3.1 Manufacture of Sulphuric acid by contact process

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(Ref: Chemical Technology-II N. K. Patel, NPTEL, New Delhi)

Fig. 3.2 – Flow Sheet for manufacture of Sulphuric acid by Contact Process
(Ref: Chemical Technology-II N. K. Patel, NPTEL, New Delhi)

 Step-1: Burning of sulfur

• Device: Sulfur pyrite Burner
• It is used to burn sulfur using dry air to obtain SO2.
• Dry air is used for burning to avoid corrosion.
• Sulfur should be free from carbon like impurities to avoid poisoning of catalyst and
avoid formation of water.

 Step-2:Catalytic oxidation of SO2 to SO3

• Device: Packed Bed catalytic reactor.If fine particles are present as impurities in SO2 from
burner, it is purified by electrostatic precipitator
• The converson of SO2 to SO3 is carried out using vanadium pentoxide at 1.2-1.5
atmospheres and 4500C.
• The reaction is exothermic and less SO3 forms at higher temperature.
• The reaction is carried out in four stages with reduction of temperature in successive stages
for better conversion due to exothermic reaction.
• The maximum conversion is 99.5% -99.8% .

 Step- 3: Hydration of SO3

• Device: Packed Tower
• After the catalytic oxidation process, the resulting SO3 is hydrated by absorption in
packed towers filled with 98-99% sulfuric acid. This is the H2SO4azeotrope of
minimum total vapour pressure

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• The catalytic oxidation has to proceed in high yield to avoid air pollution problems.
SO2has a low solubility in 98% H2SO4. At lower acid concentrations, sulfuric acid and
SO3 form a troublesome mist and at higher concentrations emissions of SO3 and
H2SO4vapour become significant. The absorption acid concentration is kept within
the desired range by exchange as needed between the H2SO4 in the drying acid
vessel that precedes the combustion chamber with the H2SO4 in the absorption
tower. The acid strength can be adjusted by controlling the streams of H 2SO4 to give
acid of 91 to 100% H2SO4 with various amounts of added SO3 and water. The
conversion of sulfur to acid is over 99.5%.

 Major Engineering Problems in Sulphuric Acid Manufacture:

 Design of Multistage catalytic convertor for highly exothermic reaction.

 Corrosion problems: To decrease corrosion problem, dictate low pressure (1 atm.)
operation.
 Adaption of process to various types of gas feeds.
 Removal of heat absorption of SO3 in acid.

*** END OF CHAPTER ***

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