Sulphuric Acid

Engr. Muhammad Sajid

Lecturer
Department of Chemical Engineering
University of Gujrat
Contents
1. History of Manufacture Development
2. Properties
3. Importance
4. Production
5. Process Chemistry
6. Raw Material
7. Process Description
8. Waste management
9. Health and safety
10. Usage
Introduction
 Oil of vitriol
 King of acids
 Economy indicator
 World Production of Sulfuric Acid

Canada
Mexico
Others
Japan
Latin America
F-USSR
Europe
Africa
U.S.
Asia

0.0 5.0 10.0 15.0 20.0 25.0 30.0

Share (percent)
 World Supply / Demand for Sulfuric Acid
(thousands of metric tons, 100% H2SO4)

250,000
200,000
150,000
100,000
50,000
0
1985

1988

1991

1994

1997

2000
Annual Capacity Production
 History of Manufacture of Sulfuric Acid

 One of the oldest industrially applied processes. Discovered by a

Persian alchemist in the tenth century.
 Saltpeter and sulfur were mixed in a glass container and burned in a
moist atmosphere. Acid was collected from the condensed vapors.
 In England, 1746, the lead chamber reactor was invented. This
invention allowed for higher production rates (<78%).
 In England, 1831, a patent was filed that described the oxidation of
sulfur dioxide over a platinum catalyst, the Contact Process. This new
process increased yields of reaction from 70 to above 95%.
 In 1913, BASF was granted a patent for the use of vanadium
pentoxide as a catalyst for the Contact Process
 By the 1930‟s, vanadium pentoxide was becoming the dominate
catalyst used because of insensitivities to poisons and lower cost.
 In 1960 a patent application was filed by Bayer using the so called
double-catalyst process (double absorption).
Properties
 Sulfuric acid is a highly corrosive strong
mineral acid with the molecular formula
H2SO4.
 It is a colorless to slightly yellow viscous
liquid which is soluble in water at all
concentrations.
 Strong oxidizing and dehydrating agent.
 Density: 1.84 g/cm³
 Molar mass: 98.079 g/mol
 Boiling point: 337 °C
 Importance

 One of the most important of all chemicals.

 The most important uses of sulfuric acid include:
 Lead-acid batteries
 Ore processing

 Fertilizer manufacturing

 Oil refining

 Wastewater processing

 Chemical synthesis
Production

Sulphuric Acid can be

manufactured by two
processes:
• Lead Chamber Process
• Contact Process
 Lead Chamber Process

 Earliest method (presented in1746) for Production of

H2SO4.
 Process Chemistry:
NO2

2SO2 + 2 H2O + O2 -----------> 2 H2SO4

 Sulfuric acid produced in the lead chambers is limited
to about 35% concentration.
 At higher concentrations, Nitrosylsulfuric acid
precipitates on the lead walls as chamber crystals.
 This process is completely replaced by Contact Process
Contact Process
 This process was patented in 1831 by the British
vinegar merchant Peregrine Phillips.
 In this process, SO3 is absorbed into 98.5 % to 99
% H2SO4 in the presence of catalyst.
 Large plants can produce 1.3 tons in excess per
metric ton of acid by this process.
Contact Process

S  SO2  SO3  H2SO4

Process Chemistry

 The Contact Process is based on three steps:

 Step I: Oxidation of S

 Step II: Conversion of SO2 to SO3

 Step III: Absorption of SO3

Process Chemistry
 The following chemical reaction is avoided in
contact process:
Raw Materials

Sulfur Air for Water

Oxygen
 Raw Material
SULFUR
Property Value
 Sulfur of greater Appearance: Yellow Flake, Amber to yellow
than 99% purity is liquid/solid

used for the Odor: Faint odor., rotten egg odor

Solubility: Insoluble in water
production of sulfuric Specific Gravity: 2.07 at 20C (68F) solid,
acid. Sulfur normally 1.811 Kg/L molten sulfur
present in the form Boiling Point: 444.6 0C (833 F)

of flakes or granules. Melting Point/range: 112 – 120 0C

Auto Ignition 232 0C
At proper operating Temperature:
conditions one ton of Flash Point: 207 oC, (405 oF)

sulfur produced three Vapor Density (Air=1): 8.9

Vapor Pressure (mm 10 @ 246C (475F)
tones of sulfuric acid. Hg):
Vapor Pressure: 4x10-6 mm Hg @ 30 oC (86 oF)
Raw Material
WATER
 Demineral water is used for the production of
sulfuric acid to avoid difficulties in process
equipments. It raw water is used scaling will be
deposit at heat exchanging areas. At proper
operating conditions one mole of water is required
for every mole of sulfuric acid.
Air
 Dust free dry air
Catalyst
 Catalyst used is vanadium penta oxide (V2O5).
 Pellet Shape

 Ring Shape

 Star or Daisy Shape

PROCESS DESCRIPTION

Absorption of
Sulfur and Sulfur Conversion of SO3 gas and
Burning SO2 to SO3 Production of
Acid
Role of Catalyst
1. The sulfur dioxide is oxidized to sulfur trioxide by the vanadium (V)
oxide. In the process, the vanadium (V) oxide is reduced to vanadium
(IV) oxide.

2. The vanadium (IV) oxide is then re-oxidised by the oxygen

present in the stream

Overall reaction is as under

Contact Process
Single-Contact Single
Absorption Process
Single-Contact Double
Absorption Process
Double- Contact double
Absorption Process
 SINGLE-
CONTACT
SINGLE
ABSORPTION
PROCESS
Single-Contact Single Absorption
Process

SO3 is produced in 4 pass converter

Absorbed in Sulfuric acid

Remaining gases discarded to atmosphere

No recycle of un reaccted SO2

SINGLE-CONTACT DOUBLE
ABSORPTION PROCESS
Description of Process
 Drying Tower
 Sulphur Burner
 Waste Heat Boiler
 Hot Gas Filter
 4-Passs Converter
 Oelum Tower
 Absorption Tower
 Acid Coolers
Drying Tower
 Moisture in air may poison the
catalyst.
 Drying tower removes the moisture
content from air.
 98-99% H2SO4 is sprayed over the
moist air which absorbs the water.
 After drying 93-97% H2SO4 leaves
the drying tower.
 The dried air is further used in
 Sulphur Burner
 4-Pass Converter
 Heat Exchanger
 Sulphur Burner
 Furnace similar to that used for burning fuel oils.
 Molten Sulphur and Air is introduced.
 Sullphur is burned and the oxidation of S takes place:

Sulfur
Steam

10-12% SO2

Water
- Air drying tower with acid
Air
- Sulfur is injected into burner
- Reaction Temperature 2000°F
93% H2SO4
- Exothermic reaction must be cooled
- Steam recovered
 Waste Heat Boiler
 Removes heat from sulfur burner gas
and uses the heat to make steam
 It takes the boiler feed water and
coverts it to steam thus increasing the
energy efficiency of the process.
 The gas leaving has tem 425-440 oC.
Hot Gas Filter
 Takes SO2 gas from waste heat
boiler.
 Removes dust, CO2 and other
contaminants form the gas.
 4-Pass Converter
 The “Heart” of the whole process
 Has 4 stages each stage containing
V2O5 catalyst packed trays.
 The following reversible reaction is
carried out:

 According to Le Chatelier's Principle,

this reaction will be favoured if you
lower the temperature.
 So the temperature is lower between
stages to ensure 99.7% conversion of
SO2 to SO3.
Oxidation of Sulfur Dioxide

SO2 Gas
SO2 Gas

Gas
Cooling

SO3 Gas

SO3 Gas 93% H2SO4

Temperature Ranges
in 4-Pass Converter
Converter
 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
atmosphere
 Nearly complete conversion
from sulphur dioxide to sulphur
trioxide is achieved. SO?
over to you...
 Use Le Chatelier‟s principle to determine what
temperatures and pressure is desired for this
reaction.

 Also, would excess reactants be employed?

 Excess products? Why/Why not?

 What about dilution?

Le Chatelier
 Temperature: Because the reaction is exothermic Le
Chatalier predicts the reaction will become more
product favoured when the temperature is decreased

 Because the generation of products decreases

pressure, an increase in pressure will push the reaction
forward

 By supplying excess reactants the system will try to re-

establish equilibrium by getting rid of those reactants.
This will also push the reaction forward
Rate of reaction
 What factors will increase the rate of reaction?

 High Temperature

 High Pressure

 The use of a catalyst

Le Chatelier VS Speed:
Path to Victory
 In most instances both a product favoured reaction and
a speedy reaction desire the same factors.
 Excess oxygen is used as the excess reactant
 Even though increased pressure increases the rate of
reaction and pushes it forwards, manufacturers do not
bother as high yields are achieved without this costly
addition.
 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?!
 Kinetic Effects
- Oxidation of sulfur dioxide is slow and reversible
- The reaction requires a catalyst and 426.7°C temperatures
-The reaction is exothermic and sensitive to excessive heat

• Equilibrium Constant (The degree at which the reaction proceeds is temp. dependent)

log Kp = 4.956 - 4.678

T

T = absolute temp. in kelvin

Kp = equilibrium constant as a function of partial pressure of gases

Kp = ( PSO3 )
PSO2 PO2
Temperature Profile
 Temperature profile
Catalyst
 Luckily, the 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 Catalyst Distribution

Catalyst % Catalyst Conversion %

Bed
1 19.4 56
2 25.0 87
3 26.7 99.1
4 28.9 99.7
Oelum Tower
 SO3 enters from the bottom and H2SO4 is
sprayed over it.
 H2SO4 absorbs the SO3 and oelum is
formed:

 Oelum is cooled by the acid cooler to

remove the heat of absorption.
 Cooled oelum is recycled back to ensure
maximum absorption.
Absorption Tower

 The final operational is carried

out in absorption tower.
 Oelum enters the bottom and
95-97% H2SO4 is sprayed over
it.
 99% H2SO4 comes out from the
bottom of the tower.
 Absorption of SO3
 Absorption of SO3

 SO3 (g) + H2O (l)  H2SO4 (aq) Δ H = -130 kj mol-1

 Direct reaction with water is very exothermic which results in the

formation of steam. Sulfuric acid as a gas is very difficult to collect
so an absorption tower is used instead:

 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)
Acid Coolers

 Used in three places:

 Oelum Cooler
 Drying Acid Cooler
 Absorption Acid Cooler

 Their function is to remove the

heat of absorption.
 Reduces the temperature from
250 oC to room temperature.
DOUBLE- CONTACT DOUBLE
ABSORPTION PROCESS
Double- Contact double Absorption
Process
After 3rd pass converted gases are absorbed in inter absorption tower

Unabsorbed/unconverted gases are returned back to 4th pass

After 4th pass gases are reabsorbed in final absorption tower

Unabsorbed gases from FAT are discarded to atmosphere

Double- Contact double Absorption
Process

The latest process

Recently 4th is reshaped to 4th A and 4th B.

No environmental pollution

SOx as low as 200 PPM

Mist Eliminators
 In double-absorption method there is
a higher chance of acid mist
formation due to greater capacity
than single-absorption process.
 To avoid it mist eliminators are
installed.
 Mist Eliminators can be:
 Packed bed separators
 Wire mesh mist eliminators
 Electrostatic precipitators
 Sonic agglomerators
 Porous ceramic filter tubes
Green Energy?
 “The „Contact Process‟
actually reduces
pollution!”

 Prove or disprove this

statement.
GREEN
 By using the sulphur by products
of other reactions it prevents
these pollutants escaping into
the atmosphere.
 This helps to prevent acid rain.
Yay!

 More energy is produced in the

process than is used by it.
Another yay!
 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.
Critical Parameters
 Sulfur temperature
 Sulfur flow rate
 Burner temperature
 Boiler Pressure
 Converter beds temperature
 Acid circulation rate
 Acid concentrate
 Acid temperature
 ACT level
Uses
 P Manufacture of paper
 Di Manufacture of drugs
 Di Manufacture of dyes has a ...
 P Manufacture of pigments
 H Household
 D Detergent (manufacture ) in...
 Beats As the electrolyte in car batteries
 Per Petroleum refining
 Minute Metallurgical processes
Uses
 75% of the Sulfuric Acid that is produced is used to
make fertilisers such as
 Superphosphate
 Ammonium sulphate and
 Ammonium phosphate.
Industries in Pakistan
S.No Industry Location Capacity Process
1 Agritech-HPFL Haripur 110 MT/Day DCDA
2 Suraj Fertilizers Sahiwal 220 MT/Day DCDA
3 Atta Chemicals Multan 100 MT/Day SCSA
4 Tufail Chemicals Manga mandi 50 MT/Day DCDA
5 Akbari Chemicals Multan road 70 MT/Day DCDA
Lahore
6 Faras Combine Phol Nagar 200 MT/Day SCDA
Marketing Company (Lahore)
7 POF Wah Cantt 60 MT/Day SCDA
 Waste Management
 Sulfuric acid plants use sulfur or sulfur dioxide that is
a by-product from other industries.
 To maximise their conversion of sulfur dioxide to sulfur
trioxide most plants now use a double absorption
process.
 Any unreacted gas from the absorption tower is
passed over the catalytic beds again and re passed
through the absorption tower.
 This improves the percentage of sulfur dioxide
converted from 98% to better than 99.6%
 Waste Management

 Emissions from the plant have to be continuously

monitored for sulfur dioxide as this can cause acid
rain.
 The amount of sulfuric acid mist emitted from the
process is minimised by controlling the operating
temperature of the absorber, gas flow rates and
concentrations.
 Waste Management
 Improvements in conversion have also been made
by adding small amounts of caesium to the
vanadium oxide catalyst to increase its efficiency
and allow it to operate at lower temperatures
 Caesium-doped catalysts are about 3x more
expensive than the usual vanadium oxide catalyst.
 Waste Management
 There is relatively little solid waste produced from
sulfuric acid manufacturing.
 The catalyst is dumped in landfill after recovering
the mildly toxic vanadium.
 The cooling water is recycled.
 All three processes are exothermic, meaning energy
is produced. This energy is used to generate its
electricity or as a source to produce other chemicals.
Waste Management
Health and Safety
 Sulfuric acid is highly corrosive and can burn skin and
eyes severely.
 It can cause blindness and third degree burns on
contact.
 Exposure to sulfuric acid mist can cause other health
problems.
 Workers in sulfuric acid plants can also be exposed to
the acid through breathing air contaminated with
emissions containing oxides of sulfur
Health and Safety
 Strict safety procedures including adequate methods
to trap the fumes are required to minimise the risks to
workers and the environment in the case of accidently
release
 Work areas must be well ventilated and employees
wear protective clothing.
 Acid spills are contained using materials such as
earth, clay or sand and then slowly diluted with water
before being neutralised with a base such as
limestone or sodium carbonate