Sulfuric Acid

Introduction
Sulfuric acid is a strong mineral acid with the molecular formula H 2SO4. It is soluble in water at
all concentrations. Sulfuric acid has many applications, and is one of the top products of the
chemical industry. It is an essential component to many industries as well as being an essential
ingredient in the operation of deep cycle solar backup batteries. It is such an important chemical
that more of it is produced than any other single substance. The economic wealth of a country
can be estimated by the amount of sulfuric acid it produces.

History
Sulfuric acid was probably discovered by alchemists in the thirteenth century. In the middle ages
it was made by distilling iron (II) sulphate crystals.
2FeSO4.7H2O -------> Fe2O3 + H2SO4 + SO2 + 13H2O
Since iron (II) sulphate was known as green vitriol, the acid formed was called oil of vitriol.

Properties:
Appearance: Colorless oily liquid
Chemical Formula

>H2SO4

Molar mass

>98 g mol-1

Melting point

>10oC

Boiling point

>340oC

Density

>1.83g cm-3

Sulfuric acid is a dense, oily liquid once known as oil of vitriol. Pure sulfuric acid is almost twice
as dense as water (1.98 g cm-2). As water is added the density drops. Car batteries contain
concentrated sulfuric acid. As the battery is discharged the concentration of the acid falls by
measuring the density of the acid the driver can check whether the battery is flat or not.

Action as an oxidizing agent

It behaves as an oxidizing agent only when hot and concentrated:
Cu + 2H2SO4 --> CuSO4 + H2O + SO2
The sulfuric acid is reduced to sulfur dioxide.
Action as a dehydrating agent
Concentrated sulfuric acid has a great affinity for water. (It is important when diluting the
concentrated acid to add the acid to water and NEVER water to acid.) The reaction is highly
exothermic.
So great is its affinity for water that it can dehydrate compounds containing hydrogen and
oxygen:
C12H22O11 + nH2SO4 --> 12C + (11H2O + nH2SO4)
sucrose
+ sulfuric --> Carbon +
(water + sulfuric acid)
acid
CH3CH2OH + nH2SO4 --> CH2 = CH2 + (H2O + nH2SO4)
Ethanol

+ sulfuric
-->
acid

ethene

+ (water + sulfuric acid)

It is used for drying gases, especially SO2 and HCl, but cannot be used to dry a reducing gas such
as H2S or an alkaline gas such as NH3.
Action as a dehydrating agent
The properties of acids are due to the hydrogen ions in solution. Concentrated sulfuric acid
contains molecules, rather than ions. Since it contains very few hydrogen ions it does not react
significantly with metals and can safely be stored in steel containers. A piece of magnesium
ribbon does not dissolve in concentrated sulfuric acid.
Diluted with water, sulfuric acid behaves as a typical acid:

it reacts with metals to form sulphates plus hydrogen gas

it reacts with metal carbonates to form metal sulphates plus carbon dioxide plus water

It neutralizes bases to form sulphates plus water.

Production of sulfuric acid

There are two processes for the production of the sulfuric acid

Lead Chamber Process

In the lead chamber process hot sulfur dioxide gas enters the bottom of a reactor called a Glover
tower where it is washed with nitrous vitriol (sulfuric acid with nitric oxide, NO, and nitrogen
dioxide, NO2, dissolved in it) and mixed with nitric oxide and nitrogen dioxide gases; some of
the sulfur dioxide is oxidized to sulfur trioxide and dissolved in the acid wash to form tower acid
or Glover acid (about 78% H 2SO4). From the Glover tower a mixture of gases (including sulfur
dioxide and trioxide, nitrogen oxides, nitrogen, oxygen, and steam) is transferred to a lead-lined
chamber where it is reacted with more water. The chamber may be a large, boxlike room or an
enclosure in the form of a truncated cone. Sulfuric acid is formed by a complex series of
reactions; it condenses on the walls and collects on the floor of the chamber. There may be from
three to twelve chambers in a series; the gases pass through each in succession. The acid
produced in the chambers, often called chamber acid or fertilizer acid, contains 62% to 68%
H2SO4. After the gases have passed through the chambers they are passed into a reactor called the
Gay-Lussac tower where they are washed with cooled concentrated acid (from the Glover
tower); the nitrogen oxides and unreacted sulfur dioxide dissolve in the acid to form the nitrous
vitriol used in the Glover tower. Remaining waste gases are usually discharged into the
atmosphere.

Contact Process
In the contact process, purified sulfur dioxide and air are mixed, heated to about 450C, and
passed over a catalyst; the sulfur dioxide is oxidized to sulfur trioxide. The catalyst is usually
platinum on a silica or asbestos carrier or vanadium pentoxide on a silica carrier. The sulfur
trioxide is cooled and passed through two towers. In the first tower it is washed with oleum
(fuming sulfuric acid, 100% sulfuric acid with sulfur trioxide dissolved in it). In the second
tower it is washed with 97% sulfuric acid; 98% sulfuric acid is usually produced in this tower.
Waste gases are usually discharged into the atmosphere. Acid of any desired concentration may
be produced by mixing or diluting the products of this process.

Chemistry
There are three stages in the manufacture of sulfuric acid:

Burn sulfur to form sulfur dioxide:

S + O2 --> SO2

Oxidize sulfur dioxide to sulfur trioxide in the presence of a catalyst:

2SO2 + O2 <==> 2SO3

Combine sulfur trioxide with water to form sulfuric acid:

SO3 + H2O --> H2SO4

Each of these reactions is exothermic. The heat released is used to make steam which is used to
supply the energy needs of the factory and to generate electricity for sale.

Sulfuric acid at Alhamad Chemical and Fertilizer Limited

Production of sulfuric acid in Alhamad Chemicals is 100 MT per day there are two plants with
50 tones each.

Raw Material
At Al-Hamad Chemical and Fertilizer sulfur comes from different refineries it is elemental
form. Sulfur normally brought through trucks. It is stored in the sulfur storage sheds in the form
of piles. And is fed to plant through dozers. Sulfur comes from refineries as almost 99.9% pure
sulfur.
Steps involved in the production of sulfuric acid give below;

1-Melting
Sulfur is fed to melting pits through conveyer belt. These pits are provided with steam coils.
Here steam is used as heating medium and the pressure of steam provided by boiler is 100 to 120
psig. In pits an agitator is also provided to maintain constant temperature and or proper melting.
Temperature in sulfur melting pits is about 135-140 oC. It is noticed that temperature of sulfur
will not increase much that it exceeds its flash point1.

2-Combustion
Furnace is made of mild steel lined with refractory bricks. In furnace molten sulfur is pumped at
the top of furnace. At the top of furnace molten sulfur is mixed with air 2 and in the furnace
combustion takes place and the following reaction took place;
S(s) + O2(g) ---> SO2(g)

H = -296 kJ mol-1

1 Flash point of sulfur is 160 oC and auto ignition temperature is 232 oC.
2 Air comes from main blower after drying.

The combustion of sulfur is and exothermic reaction . Temperature of combustion gases 3

increased to 800- 850 oC. Temperature of combustion gases depends upon quantity of sulfur fed
to the furnace. The quantity of sulfur is manipulated by the gear pump.
In furnace there are arrangements for startup. At the bottom natural gas line and air line comes
into furnace which is used in case of start up. Air feed to the furnace is about 150 oC hot.

3-Waste Heat Boiler

As the combustion gases are at above 800 oC. In waste heat boiler that heat is recovered in waste
heat boiler . This boiler in Alhamad chemical is fire tube boiler. There are 86 nos of tubes in
boiler. Boiler feed Water comes from water softening plant and is fed through multi stage pump.
Steam generated is of 130 psi this steam is used to melt the sulfur in melting pits. Here
combustion gases loose their energy. The lines comes out from boiler goes to hot gas filter.

Hot gas Filter

Gases come from the waste heat boiler and bypass line 4 feed to the hot gas filter from the top.
Gas passes through the bed of quartz stones of different sizes. Hat gas filter used to filter the any
mud content or ash. At inlet of the hot gas filter temperature is maintained at 440 to 450 oC.

SO3 Converter
This converter is also a reactor and contains for beds of catalyst. Vanadium pentaoxide is used as
a catalyst. Gas comes from hot gas filter at about 440 oC. Sulfur dioxide and oxygen is fed at the
top of the converter. At first bed there is 1ft height of the catalyst bed and 9000 liter 5. Sulfur
dioxide reacts with the oxygen in the presence of catalyst and sulfur trioxide forms;
2SO2 + O2 <==> 2SO3

H= -196 kJmol-1

This reaction is also exothermic. In converter first bed there is 75% conversion took place.
Gases exit from the first bed passes through cooling loops 6. This loop low the temperature of the
gases. And these gases pass through the second bed. At second bed of catalyst about 17% of
conversion takes place. In second bed there is also in increase in temperature . Then the exit
3 These combustion gases composed of SO2 , O2 , N2, etc.
4 This line is used to control the temperature it is employed with the valves called
damper
5 9000 liter shows adsorption capacity of the catalyst.
6 These cooling loops are cooled with air.

gases are cooled with air cooling loop. Then the gases enter at the third bed. In third bed there is
2-4% conversion took place. Heat generated at third bed removed with the radiation plate. Then
finally gases comes in 4th bed at 4th bed 1- 2% conversion take place. Here the exit gases contain
SO3, N2, and traces of unconverted SO2 and temperature is about 442 oC.

Air Pre Heater

Gases exit from converter are at higher temperature. Then these gases passed through heat
exchanger called air pre heater. It is shell and tube heat exchanger. In this heat exchanger gases
pass through tubes and air through shell. Here gases loose their energy and heat up air which is
later used in furnace. Then these gases passes through cooling loops and these further loose their
energy.

Absorption Tower
Finally SO3 gas passes through absorption tower. Gas fed from bottom and Sulfuric acid from the
top of the tower. Sulfuric acid of 98.5% concentration in water is sprayed with the help of
nozzles. At the top of tower, there are about 59 nozzles in absorption tower. Absorption tower
consist a bed of packing which include Pall ring, Raching rings, and broken pieces of both. In
packing sulfuric acid and SO3 gas comes in contact and absorption took place. The purpose of
packing is to increase interfacial area. The circulating sulfuric acid temperature is maintained at
70 oC for maximum absorption.

Circulation Tank

In this tank oleum comes from absorption tower is stored and there is a mixing of water to form
the sulfuric acid from oleum. And from circulation tank two lines comes out of sulfuric acid
which passes through coolers and then goes to the absorption tower and drying tower
respectively. In circulation tank a conduct meter is employed which moniter the concentration of
the Sulfuric acid.

Utilities
Drying tower
This tower removes the moisture contents of air. In this tower sulfuric acid is used for the
removal of moisture. Here temperature increases due to the brisk reaction. In drying tower
packing is used. And nozzles spraying system is used. If moisture contents are not removed in
drying tower this will cause the corrosion and also poison the catalyst.

Scrubber
On scrubber is also employed to remove SO 2 from waste gases. This will only used when we
start the plant because there is not efficient conversion from SO 2 to SO3. This is a vertical tower,
where Soda Ash solution is sprayed from the top and waste gases from the bottom. Where a
chemical reaction took place and sodium sulphate solution forms, thus removing SO2 from waste
gases. And the soda ash comes from soda ash tank, where we maintain the pH 13.

Softening Plant
At softening plant raw water is softened by passing through Sodium zeolite resin. This water is
fed to the boiler by multistage pump. After four days resin is regenerated with brine solution.

Chemical Safety Data: Sulfuric acid

Common
synonyms

Sulfuric acid, vitriol, oil of vitriol

Formula

H2SO4

Physical
properties

Form: Colorless oily liquid when concentrated; colorless liquid when diluted
Stability: Stable, but hygroscopic.
Melting point: -2 C
Water solubility: Miscible in all proportions (dissolution is very exothermic)
Specific gravity: 1.84 (concentrated), close to 1 (dilute)

Principal
hazards

**Contact with the eyes or skin can cause serious permanent damage
**Concentrated
solutions
of
acid
are
extremely corrosive
** Dissolution of sulfuric acid in water is very exothermic; enough heat may be
released to make the water boil

Safe
handling

Always wear safety glasses. Do not allow the acid or a solution of it to come
into contact with your skin. Concentrated sulfuric acid should not be diluted by
inexperienced users! When diluting acid always wear eye protection, and
ALWAYS add acid to water (not the reverse) slowly and with great care. Use
constant stirring (sulfuric acid is much denser than water, and if you do not stir
when adding acid to water, a layer of concentrated acid may form at the bottom
of the beaker, creating a substantial temperature gradient where acid and water
meet). Note that freshly-prepared solutions will be warm or hot, and will as a
consequence be more corrosive than a cool solution.

Emergency

Eye contact: Immediately flush the eye with plenty of water. Continue for at

least ten minutes and call for immediate medical help.

Skin contact: Wash off with plenty of water. Remove any contaminated
clothing. If the skin reddens or appears damaged, call for medical aid.
If swallowed: Drink plenty of water and call for immediate medical help.
Disposal

Small amounts of dilute sulfuric acid can be flushed down a sink with a large
quantity of water, unless local rules prohibit this. Larger amounts should be
neutralized before disposal. Concentrated acid should not be flushed down a
sink.

Protective
equipment

ALWAYS wear safety glasses when handling sulfuric acid or its solutions. If
you need gloves, use neoprene, butyl rubber, natural rubber, polyethylene or
PVC for handling solutions at concentrations of up to 70%. Use butyl rubber or
polyethylene for concentrated sulfuric acid.