SULPHURIC ACID (H2SO4)

Sulphuric Acid Characteristic

 Pure sulfuric acid is an oily, water-white, slightly viscous
liquid with a melting point of 10.4 °C and a boiling point
of 279.6°C.
 It is infinitely miscible with water, forming sulfuric acid
solutions characterized by their weight percent H2S04,
 Oleum may be formed by dissolving S03 in sulfuric acid
to attain fuming sulfuric acid, with concentrations
nominally greater than 100 percent H2S04.
Uses of Sulphuric Acid
 The primary industrial uses of sulfuric acid are in
phosphate fertilizer manufacture, petroleum refining,
copper ore leaching, synthetic rubber and plastics, and
pulp and paper mills.
 It is used as a solvent, a dehydrating agent, a reagent in
chemical reactions or processes, an acid, a catalyst, and an
absorbent, and in many other applications.
RAW MATERIAL
 The starting material for sulphuric acid manufacture is
clean, dry SO2, 8 to 12% in O2, N2, SO2, CO2, SO3 gas.
 The gas is obtained:
 By burning molten waste elemental sulfur (~70% of world
production)
 From high SO2 strength metallurgical off-gases(~20%)
 By decomposing spent (used) sulphuric acid catalyst(~10%)
 Types of Acid Plants
 Three basic types of sulphuric acid plants :
 Sulphur Burning
 Acid Regeneration
 Metallurgical
Sulphur Burning Acid Plants –
Characteristics
 Elemental sulphur is a raw material
 Sulphur handling systems
 Sulphur furnace
 Energy recovery – steam production, electrical power
generation
 Net energy producer
Acid Regeneration Acid Plants -
Characteristics
 Regeneration furnace that decomposed H2SO4 into SO2
and H2O
 Fuel is burned to provide the energy to decompose acid
 Waste heat boiler to recover energy from gas leaving
furnace
 Wet gas cleaning system
Metallurgical Acid Plants – Characteristics

 SO2 gas comes from a wide variety of pyrometallurgical

processes
 Wet gas cleaning system to remove impurities from the gas
 Both high and low SO2 gas strengths
 Variable operation (flow and SO2 concentration)
 Treatment of wet gas cleaning system effluent
Metallurgical Acid Plants
Sulphuruc Acid Producation
 Lead chamber Process
 Contact Process
LEAD CHAMBER PROCESS
 Lead Chamber process is one of the sulphuric acid
production methods which gives only about 50-60 Be
grade acid.
 The main principle behind the process is that the moist
SO2 (sulphur dioxide) in presence of Nitrogenous Oxides
(active catalyst) is oxidized to sulphur trioxide with the
oxygen present in air. Sulphur trioxide is made to react
with water to produce sulphuric acid.
Lead Chamber Process Reactions

 2 NOHSO4+ H2O → 2H2SO4 + NO + NO2

 SO2 + NO2 + H2O → H2SO4 + NO

Limitation of Lead Chamber Process
 Limited in output, quality and concentration of sulphuric
acid product.
CONTACT PROCESS
 Principle: Sulphur dioxide is converted into Sulpur trioxide by
Metal Oxide Catalyst (Platinum or Vanadium Oxide).
 Processing steps involved in contact process are:
 (l) Production of sulfur dioxide;
 (2) cooling and, for smelters, cleaning of the process gas;

 (3) conversion of the sulfur dioxide to sulfur trioxide;

 (4) cooling of the sulfur trioxide gas;

 (5) absorption of the sulfur trioxide in sulfuric acid
Block Diagram of Sulphuric Acid Production
Contact Process : Production of SO2 (1)

 Sulfur is converted to sulfur dioxide by burning molten

sulfur with dried air in a sulfur burner to yield a 1000-
1200°C gas stream containing 10-12 percent S02.
 Gas stream temperature was reduced to 440-420 oC.
Contact Process : Production of SO2 (2)

 Molten sulfur is filtered to remove impurities (Fe or organic

compound). Limestone is added to reduce acidity of molten
sulphur (reduce corrosivity).
 Modification of SO2 production: LURGI, DORR-OLIVER,
BASF, MONSANTO, dll.
Contact Process : Production of SO2 (3)
 Off-gas from roasting and smelting operations may contain
dust, S03, halogens, NOx, arsenic and other toxic metal
fumes, and mercury.  Gas Cleaning Unit is required
 The cleaning plant steps are :
 (1) hot-gas dedusting;
 (2) wet scrubbing;
 (3) gas cooling;
 (4) mist removal;
 (5) mercury removal.
Contact Process : Conversion of SO2 SO3

 Conversion of SO2  SO3 is accomplished

in multi-stage, fixed-bed catalytic converters
equipped with interstage boilers or heat
exchangers to remove the heat of reaction.

 In Sulfuric Acid plant: Bed thickness is about

0.8 m with bed diameter of 10 m.
Catalyst of SO2  SO3 Conversion
 Vanadium pentaoxide (V2O5) with K as promotor in a
silica porous substrate.
Reaction Mechanism of SO2 Catalyst

Total reaction :
Reaction of SO2  SO3

 Reversible exothermic reaction.

 Equilibrium reaction constant :

 Kp is obtained experimentally based on the Pressure

(atm).
 Conversion of SO3 is determined by: temperature,
pressure, products and reactants (Le Catelier Principle)
Le Catelier Principle

 Temperature
 Because heat is generated in the reaction, removing heat will
result in more SO3 formation
 Pressure
 SO2 and O2 represent 1½ volumes of reactants while SO3 is only 1
volume. Therefore increasing the pressure at which the reaction
occurs will result in more SO3 formation.
 Concentration of Products and Reactants
 Removing reaction products will result in the formation of more
products
Graph of SO2 Conversion vs Temperature and SO2
Conversion

Conversion > at low concentration of

SO2, however, when the SO2
concentration is low, gas flow rate >,
more expensive plant.
Operating Conditionin SO2 Conversion
 Effect of temperature on equilibrium conversion and
reaction rate is contradictory.
 In the Contact Process : Gas enters into catalyst bed at
temperature of 425-440 oC and further increase
adiabatically during reaction.
 Reaction rate increase with the increase of temperatur,
however when equilibrium is obtained, the reaction rate
decrease.
 At temperature of 900 oC when 60-70 % of SO2 is
converted, the reaction is stop and gas is cooled.
Graph of Adiabatic and Isothermal Reaction
Graph of SO2 conversion vs Temperature
Single Bed Catalyst for SO2 Conversion
Multi Bed Catalyst for SO2 Conversion
Multi Bed Catalyst for SO2 Conversion
GAS COOLING
Absorption of Sulfur trioxide
 Sulfur trioxide from the converter is absorbed in 98
percent H2S04 recirculated counter currently through a
packed tower maintained at 60-80°C by indirect cooling.
 Absorption of SO3  Single or double absorbtion.

 Absorption of SO3 is influenced by : acid concentration,

tower design (type and packing high), gas-liquid
distribution, gas flow, acid flow, SO3 concentration in gas.
SINGLE ABSORBTION/ SINGLE CONTACT
 Only 1 Absorption tower of SO3
 Designed with 3-4 bed catalyst
-Tidak dapat memenuhi
standar emisi yang diijinkan
- Recovery energy cukup
tinggi
DOUBLE ABSORBTION/ DOUBLE
CONTACT
 Two absorption tower of SO3
-Desain dapat disesuaikan untuk
menghasilkan recovery energy dan
handling gas.
-- Memenuhi standar emisi
- Plant lebih mahal
- Recovery energi lebih kecil
Simple flowsheet : Dual Absorbtion

(1) Burner (2) Boiler (3) Convertor (4) Inner Absorber (5) Final Absorber
(6) Dilution System
Flowsheet sulphur-burning double absorbtion
plant (Monsanto)
Sulphuric Acid Plants in Indonesia
 PT Indonesian Acids Industry Limited (IAI)
 PT Mahkota Indonesia

Location : Bekasi. Type of Plant: Sulpur Burning.

Gas Source: Elemental Sulphur.
Products: 98% Sulphuric Acid, 20 to 30% Oleum
 PT Petro Jordan Abadi
Location : Gresik. Gas Source: Elemental Sulphur.
 PT Timur Raya
Location : Karawang. Product : Sulfuric Acid: 98.2% Min.
SULFUR
 In the Contact Process, source of Sulfur is produced from:
 Sulfur Mining (Frasch Proses)
 Flue gas (Claus Proses )
 Sulfur sulphide such as ZnS or pyrite (FeS 2)
 Oxidation of sulfide  roasting process.
Fluid bed roasting

(1) Fluid Bed Reactor

(2) Cyclone
(3) Electrostatic precipitator
Roasting Process
 Roasting ZnS

 Roasting Pyrite
 Sulfur Production by the Claus Process
 The Claus process consist of:
 Thermal Step. H2S is partially oxidised with air. The oxidation is
carried out in a high temperature furnace (1000-1400 deg C). Sulphur is
obtained as product, however part of H2S is not reacted.
 Catalytic Step. Residue of H2S is reacted with SO2 at low (200-350 deg
C) by Fe2O3 catalyst.
2H2S + SO2 ==> 3S + 2H2O
Frasch Process for Extracting Sulphur