Industrial Chemistry I

Unit 3
Hydrochloric,Hydrofluoric and Sulphuric
acids
By Ediget L.(M.Sc.)
Debark university, CNCS, Chemistry department, April,26 2022
3.1. Methods of manufacture of hydrochloric acid and
its uses
A. Methods of manufacture of hydrochloric acid
Hydrochloric Acid can be manufactured either
purposely or as a by-product.

However, the volume of hydrochloric acid

manufactured as a by-product is so important that
hydrochloric acid is not often produced purposely.
o Burner Process (inorganic direct synthesis),
o Organic By-product Synthesis,
o Waste Incineration.
Burner Process
 Chlorine and hydrogen react exothermally to form hydrogen
chloride gas as follows:

 Both gases pass through a burner nozzle, and are ignited inside a
graphite combustion chamber, which is cooled by water. The
hydrogen chloride gas produced is cooled, and absorbed into
water to give hydrochloric acid at the desired concentration.
Organic By-product Synthesis
 Hydrochloric acid is made during chlorination of organic
products as follows:

 Hydrochloric acid is also made during fluorination of chlorinated

organic products to manufacture (hydro)chlorofluorocarbons as
follows:

Organic Waste Incineration

 Hydrochloric acid is made during Incineration, at high
temperatures, of chlorinated wastes as follows:
B. Uses of Hydrochloric Acid
Hydrochloric acid is a strong inorganic acid that is used in many
industrial processes such as refining metal.
Pickling of steel
to remove rust or iron oxide scale from iron or steel
before subsequent processing
Production of inorganic compounds

Numerous products can be produced with hydrochloric

acid in normal acid-base reactions, resulting in
inorganic compounds.

These include water treatment chemicals such as

iron(III) chloride and polyaluminium chloride (PAC)
Fe2O3 + 6 HCl → 2 FeCl3 + 3 H2O (iron(III) chloride from magnetite)
Both iron(III) chloride and PAC are used as flocculation and coagulation
agents in sewage treatment, drinking water production, and paper production.

Other inorganic compounds produced with hydrochloric acid include road

application salt calcium chloride, nickel(II) chloride for electroplating, and
zinc chloride for the galvanizing industry and battery production.

pH Control and neutralization

Hydrochloric acid can be used to regulate the acidity (pH) of
solutions

Regeneration of ion exchangers

used in the regeneration of ion exchange resins.
Cation exchange is widely used to remove ions such as Na+ and
Ca2+ from aqueous solutions, producing demineralized water. The
acid is used to rinse the cations from the resins. Na+ is replaced with
H+ and Ca2+ with 2 H+.
Hydrochloric acid (HCl) is a versatile chemical that has a number of
different industrial uses.
 Some examples are
 hydrometallurgical processing (e.g., production of alumina
and/or titanium dioxide),
 chlorine dioxide synthesis,
 hydrogen production,
 activation of petroleum wells, and
 miscellaneous cleaning/etching operations including metal
cleaning (e.g., steel pickling).
 Also known as muriatic acid, HCl is used by masons to clean
finished brick work.
3.2. Industrial manufacture of hydrofluoric acid and its uses

Anhydrous hydrogen fluoride is

manufactured by the action of
sulfuric acid on calcium fluoride.
Powdered acid-grade fluorspar
(≥97% CaF2) is distilled with
concentrated sulfuric acid; the
gaseous hydrogen fluoride that
leaves the reactor is condensed and
purified by distillation
USE
 Hydrogen fluoride is the most important compound of
fluorine.

 Anhydrous hydrogen fluoride

 is used in the production of most fluorine-containing
chemicals.
 It is used in the production of
 refrigerants,
 herbicides,
 pharmaceuticals,
 high-octane gasoline,
 aluminum,
 plastics,
 electrical components, and
 fluorescent light bulbs.
 Aqueous hydrofluoric acid
 is used in
 stainless steel pickling,
 glass etching,
 metal coatings,
 exotic metal extraction, and
 quartz purification
 The most important use of hydrogen fluoride
 is in the production of fluorocarbon chemicals,
 including
 hydrofluorocarbons,
 hydrofluorochlorocarbons, and
 fluoropolymers; 60% of production is used
for this purpose.
 The next most important uses of hydrogen fluoride are:
 chemical derivatives, 18%;
 aluminum manufacturing, 6%;
 stainless steel pickling, 5%;
 petroleum alkylation catalysts, 4%; and
 uranium chemicals production, 3%.
 Miscellaneous other uses include
 glass etching,
 herbicides, and
 rare metals
3.3. Chamber process and contact process of
manufacture of sulphuric acid and its handling

Introduction
 During the 19th century, the German chemist Baron
Justus von Liebig discovered that sulphuric acid,
when added to the soil, increased the amount of soil
phosphorus available to plants.

 This discovery gave rise to an increase in the

commercial production of sulphuric acid and led to
improved methods of manufacture.
Raw Materials

 Raw materials for sulphuric acid are

those that produce sulphur dioxide
when reacted with oxygen.

 The commonly used raw materials are:

 Elemental sulphur
 Sulphides such as pyrites
 Hydrogen sulphide from petroleum
refineries
Manufacturing process
 Two processes:

 Lead-chamber and

 Contact processes
 are used for the production of sulphuric acid

 In their initial steps, both processes require the use of sulphur

dioxide.
The Lead-chamber process
This process employs:
 reaction vessels of large lead-sheathed brick
towers
Process

 Sulphur dioxide is introduced with steam and

oxides of nitrogen into the reaction vessels
 where the gases are sprayed down with water
and chamber acid.

 The sulphur dioxide and nitrogen dioxide dissolve

and over a period of approximately 30 minutes the
sulphur dioxide is oxidized to sulphuric acid.
The Lead-chamber process

 The presence of nitrogen dioxide is necessary for

the reaction to proceed.

 The process is highly exothermic, and a major

consideration of the design of the chambers was to
provide a way to dissipate the heat formed in the
reactions.
 Almost all the nitrogen oxides are recovered

 Sulphuric acid produced in this way is only about 62

to 70 per cent H2SO4. The rest is water.

 The chamber process has become obsolete and has

been replaced by the contact process due to the
following reasons:

i. An increased demand for strong, pure acid and

oleum

ii. Contact process plants are cheaper and more

compact
The Contact Process

The second method of manufacturing sulphuric acid, the contact

process, which came into commercial use about 1900:
 depends on oxidation of sulphur dioxide to sulphur trioxide,
SO3, under the accelerating influence of a catalyst.

The first contact plants (before 1920) were built using platinum
catalysts.
Finely divided platinum, the most effective catalyst, has two
disadvantages:
 it is very expensive, and
 it is deactivated by certain impurities in ordinary sulphur dioxide.
 They include compounds of arsenic, antimony and lead.
 In the middle of 1920s, vanadium catalysts started and have
since then replaced platinum.
 By 1930, the contact process could compete with the
chamber process and because it produces high strength
acid, it has almost replaced the chamber process.

 Since the oxidation of sulphur and sulphur dioxide releases

large amounts of energy, major changes in the manufacturing
plant design were introduced to utilise this heat energy in the
production of steam for generating electrical power.
 This combination of a chemical plant and electrical
generation is known as co-generation.
The main steps in the contact plant are:
Production of sulphur dioxide gas
Purifying and cooling the gas
The gas conversion of SO2 into sulphur

trioxide (SO3) by passing it through a

converter containing the catalyst
Absorbing the sulphur trioxide in
sulphuric acid
Production of SO3
Sulphur is burned in the sulphur burner to produce sulphur dioxide:

 Before combustion, sulphur, is first melted by heating it to

135°C.
 Combustion is carried out at between 900 and 1800°C.
 The combustion unit has a process gas cooler.
 The SO2 content of the combustion gases is generally around

18% by volume and the O2 content is low but higher than 3%.

 The gases are generally diluted to 9-12% SO 2 before entering

the conversion process.
Conversion of SO2 into SO3

• The design and operation of sulphuric

acid plants are focused on the following
gas phase chemical reaction in the
presence of a catalyst:
 • From thermodynamic and stoichiometric considerations, the
following methods are available to maximise the formation of
SO3 for the O2/SO2/SO3 system.

• heat removal: the formation of SO3 is exothermic, so a

decrease of temperature will be favourable
• increased oxygen concentration
• removal of SO3
• raising the system pressure
• catalyst selection to reduce the working temperature
• longer reaction time
• This reaction is a reversible reaction and the conditions used are a compromise
between equilibrium and rate considerations.
 It is necessary to shift the position of the equilibrium as far as possible to
the right in order to produce the maximum possible amount of sulphur
trioxide in the equilibrium mixture.
 Even though excess O2 would move the SO2 formation to the right, the
1:1 mixture gives the best possible overall yield of sulphur trioxide.

 The forward reaction is exothermic and is favoured by low temperature.

However, too low a temperature slows the reaction. To get the gases to
reach equilibrium within a very short time, a compromise temperature of
400–450 oC is used.
 According to Le Chatelier’s principle high pressures favour the forward
reaction. However, even at relatively low pressures of 1 to 2 atmospheres,
there is a 99.5% conversion of sulphur dioxide into sulphur trioxide.

 In the absence of a catalyst the reaction is quite slow and is therefore

carried out in the presence of a vanadium oxide catalyst which has a
long life because it is not easily poisoned. Further more, vanadium
catalyst has high conversion efficiency. Its only disadvantage is that it
requires use of low sulphur dioxide concentration which makes plant
capital cost to be high.
In summary, optimum conditions for sulphuric acid production in the
contact process are:
 A temperature of about 4300C
 A pressure of 2 atmospheres
 Vanadium pentoxide catalyst
Absorption of SO3

 Sulphuric acid (H2SO4) is obtained from the absorption of SO3 into

sulphuric acid with a concentration of at least 98%, followed by the
adjustment of the strength by the controlled addition of water.

 SO3, will react with water to form sulphuric acid. However, converting the
sulphur trioxide into sulphuric acid cannot be done by simply adding water
to the sulphur trioxide. Direct mixing of sulphur trioxide with water by the
following reaction is uncontrollable. The exothermic nature of the reaction
means it generates a fog or mist of sulphuric acid, which is more difficult to
work with than a liquid.
 Instead, the sulphur trioxide is first dissolved in concentrated (98%)
sulphuric acid to form a product known as fuming sulphuric acid or
oleum.

 The oleum can then be reacted safely with water to produce

concentrated sulphuric acid.
Environmental Issues
 Sulphuric acid is a constituent of acid rain, formed by atmospheric
oxidation of sulphur dioxide in the presence of water.
 Sulphur dioxide is released when fuels containing sulphur such as oil and
coal are burned. The gas escapes into the atmosphere forming sulphuric
acid.
 Sulphuric acid is also formed naturally by oxidation of sulphide ores.
Uses of sulphuric acid
 Sulphuric acid is the most widely used chemical.
 The largest single use of sulphuric acid is for making phosphate and
ammonium sulphate fertilizers.
 Other uses include production of phosphoric acid, trisodium phosphates
for detergent making.
 Sulphuric acid is also used in large quantities in iron and steel making as a
pickling agent to remove oxidation, rust and scale from the metals.
 It is an oxidizing and dehydrating agent. Its dehydrating action is vital in
absorbing water formed in chemical conversions such as nitration,
sulphonation, and esterification. It vigorously removes water from, and
therefore chars, wood, cotton, sugar, and paper.
 As a strong oxidizing agent it is capable of dissolving such relatively
unreactive metals as copper, mercury, and lead to make compounds of
these metals.
 It is used in the manufacture of aluminium sulphate for application in paper
pulp production and in water treatment.
 It is also used as an electrolyte in lead acid batteries found in cars.

Various concentrations of sulphuric acid are available depending on the

application purpose. These include:
 Summary
Production of sulfuric acids ( The contact process)
The most important process for making sulfuric acid.
Consists of 3 stages.

Stage3

Stage 1

Stage 2
Production of sulfuric acids
(Stage 1)

In the first stage of the process, sulfur is burned in air to

make sulfur dioxide gas.

Sulfur + oxygen->sulfur dioxide

S(I)+ O2(g) -> SO2(g)
Production of sulfuric acids
(Stage 2)
This is the stage where sulfur dioxide is
converted to sulfur trioxide.

Sulfur dioxide+ oxygen -> sulfur

trioxide
2So2(g)+O2(g) -> 2SO3(g)
<-

The reaction happens on catalyst of

vanadium(V) oxide to speed up the
reaction. As much sulphur dioxide as
possible is changed to sulphur trioxide,
and releases of sulphur dioxide are
prevented such that acid rains will not
be caused.
Production of sulfuric acids
(Stage 3)
In the final stage, sulfur trioxide is
converted to sulfuric acid. The sulfur
trioxide gas is absorbed into very
concentrated sulfuric acid (a 98 per cent
solution of H2SO4 in water), producing a
thick fuming liquid called oleum. The oleum
is mixed carefully with water, and the
sulfuric trioxide in the oleum reacts with the
water as follows:
Sulfur trioxide+ water -> sulfuric acid
SO3(g)+H2O(l)-> H2SO4(l)