ADDIS ABABA UNIVERSITY

ADDIS ABABA INSTITUTE OF TECHNOLOGY

SCHOOL OF CHEMICAL AND BIO ENGINEERING

CBEg 3151: Chemical Process Industries

Lecture 5: Process Technology of Chloro-Alkali

Industries

BY: Yeayneabeba Tadesse

May 15, 2021

OUTLINE
 Introduction
 Sodium carbonate production

1) Leblanc process
2) Solvay process
 Sodium bicarbonate production

 Sodium hydroxide production

1) Electrochemical process
2) Lime soda process
 Hydrochloric acid production

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Introduction
Chloro-Alkali
Refers to the two chemicals (chlorine and an alkali)
which are simultaneously produced as a result of the
electrolysis of saltwater.
 The chloro-alkali industry is a major contributor to
national economic activity.
The major product that are considered as a chloro-
alkali are: sodium carbonate, sodium bicarbonate,
caustic soda, chlorine, hydrogen, hydrochloric acid,
sodium hypochlorite (NaOCl), lime/ calcium oxide,
calcium hydroxide and calcium hypochlorite.
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Sodium Carbonate
 Sodium Carbonate is the disodium salt of carbonic
acid with alkalinizing property.
 is a white, anhydrous, powdered or granular
material.
 Also Know as
 Washing Soda
 Soda Ash
 Soda Crystal

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Properties
 Hydroscopic: means when it exposed to air, it can
spontaneously absorb water molecules.
 Soluble in water
 Slightly soluble in Alcohol
 Alkaline taste
 Effervescence: When it is placed in a slightly acidic
solution, it decomposes and forms bubbles.

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Uses of sodium carbonate
 Water softener,
 Food processing aid,
 pH modifier,
 Swimming pool chemical and electrolyte.
 It is also used in the manufacture of glass, paper,
soaps and detergents, and many other useful
chemicals.

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 Production technology of sodium
carbonate
 Types of process for soda ash production
1) Leblanc process
2) Solvay process
3) Trona purification process

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1. Leblance process
 In 1791, the French chemist Nicolas Leblanc
patented a process for producing sodium carbonate
from salt, sulfuric acid, limestone, and coal.
 First, sea salt (sodium chloride) was boiled/burn in
sulfuric acid to yield sodium sulfate and hydrogen
chloride gas.
 RAW MATERIALS:
1)Sulfuric acid
2)sodium Chloride
3)calcium Carbonate And Coal

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Process description
 Common salt is first mixed with the conc. H2SO4 in
equivalent quantities and heated in a cast iron
furnace to yield NaHSO4 along with HCl gas.
 HCl is passed to tower packed with coke and is
absorbed through a spray of water comes down in
the tower.
 The paste of NaHSO4 is then taken out and heated
to a high temperature on the hearth of a furnace
along with some more common salt.

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 NaHSO4 is thus converted into sodium sulfate,
known as salt cake.
NaCl + H2SO4 NaHSO4 + HCl
NaHSO4 + NaCl Na2SO4 + HCl
 The salt cake is broken or pulverized, mixed with
coke and limestone and charged into black ash
rotary furnace consisting of refractory lined steel
shells.
 The mass is heated by hot combustion gases
entering at one end and leaving at the others.

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 The molten porous gray mass thus formed known
as black ash is separated from the calcium sludge
and then crushed and leached with water in
absence of air in a series of iron tank.
Na2SO4 + 2C Na2S + 2CO2
Na2S + CaCO3 Na2CO3 + CaS
 The extract containing Na2CO3, NaOH, and other
impurities is sprayed from the top of a tower in
counter current to flow of hot gases from the black
ash furnace.

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 The sodium carbonate thus obtained is
concentrated in open pans and then cooled to get
sodium carbonate.
 The product is calcined to get soda ash which is re-
crystallized to Na2CO3.10H2O.
 The sludge containing mostly CaS is left behind as
alkali waste
Na2S + CaCO3 Na2CO3 + CaS

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Process flow diagram and major unit operation

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Main reactions in Leblanc process

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 The hydrochloric acid produced by the Leblanc
process can be marketed and the calcium sulphide
by product has a waste disposal issues.
 The major drawback of Leblanc process was its
environmental impact with the emission of HCl gas
and the production of calcium sulphide solid waste.
 This process is also an energy intensive process
and utilize relatively expensive inputs which make
it uncompetitive and as a result it become an
obsolete technology since 1900.

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Recovery of sulfur from alkali waste

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 The computation between both Leblanc and Solvay
processes lasted many years, but relative simplicity,
reduced operating costs and above all reduced
environmental impact of the Solvay process
ensured its success.
 Because the Solvay process recycles its ammonia, it
consume only limestone and brine, and has calcium
chloride as its only waste product.
 This made it sustainably more economical than
Leblanc process , and it soon came to dominate
world sodium carbonate production.

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2. Solvay process

 In 1861, the Belgian industrial chemist Ernest

Solvay developed a method to convert sodium
chloride to sodium carbonate using ammonia.
 The Solvay process centered around a large hollow
tower.
 At the bottom, calcium carbonate (limestone) was
heated to release carbon dioxide.

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Advantages
1) It is cheap process.
2) Raw material easily available.
3) CO2 recover in Calcination tower and Ammonia
also recover in Ammonia Recovery Tower.
4) Pollution free.
5) Only 1 waste product that is CaCl2
6) Na2CO3 of very high purities obtained.

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Main raw materials
1. Sodium chloride (Nacl)+ water (H2O)=Brine
2. Limestone (CaCO3)
3. Ammonia (NH3)

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Manufacturing steps in Solvay process
Step 1: Brine purification
 Saturated solution of NaCl is used.
 Impurities such as calcium, magnesium, iron and
sulphate are removed by precipitation with calcium
carbonate, sodium hydroxide and calcium chloride,
eg.

 Brine solution is filtered and passed through

ammonia tower to dissolve ammonia.

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Step 2: Shift brine in ammonia tower/Absorber and
 
make ammonical brine
The purified brine is allowed to percolate down
the ammonia tower in which ammonia gas is passed
through the bottom in a counter current fashion.
The brine solution thus takes up the necessary
amount of ammonia and liberates heat.
The ammonia in the Solvay process is used to
reduce the acidity of the solution so that the
sodium bi carbonate can precipitate out.
It also buffer the solution so that when the CO2 is
added to the solution it does not increase the
acidity of the solution and thus stops the
precipitation process.

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Carbonation tower
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Step 6:Ammonia recovery

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Main reactions in Solvay process

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3. Trona purification process

 Sodium carbonate is also produced from large

deposits of mineral Trona or high Trona-soda ash
bine.
 It is cheaper to mine or extract sodium carbonate
than to manufacture it.
 Furthermore, the CaCl2 by-product of Solvay
process has not found sufficient use as a chemical
to enhance the economic value of the Solvay
process.
 Several processes are used to refine Trona ore and
are simpler than Solvay process.
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 They are two types
1. Trona ore is first calcined to impure soda ash,
which is then purified.
2. To extract the soda ash from high Trona lake
or other sources through solar evaporation
and followed by calcination of crystallized
trona.
 The letter route is now used predominantly at
Abijata soda ash Enterprise of Ethiopia.

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 Sodium bicarbonate/NaHCO3
 Sodium bicarbonate is an inorganic white, odorless,
crystalline powder salt.
 It decompose in to soda ash, CO2 and water when
heated.
 It is also known as sodium hydrogen carbonate is
used as leaving agent in baking industry. This is why
it is called baking soda.
 Baking powder contains anticaking agents such as
starch and weak acid such as alum and tartaric acid.
These weak acids reacts with sodium bicarbonate,
releasing CO2 gas which causes cake batter and
bread dough to rise and produces the tiny holes in
cake and breads.
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 Major unit operations of sodium
bicarbonate production
1. Soda ash dissolution tank
2. CO2 supply system
3. Absorption and carbonation tower.
4. Crystallizer
5. Filter and
6. Low temperature dryer

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Process description

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 The operation of tower is so controlled that the
temperature is reduced to effect high absorption
and at the same time adjusted not to effect
crystallization of NaHCO3 at the bottom of the
tower where the very saturated liquor is drown.
 Thus, by maintaining proper temperature gradient
in column, the process is very much controlled for
optimum production.
 The saturated solution of sodium bicarbonate is
finally subjected to crystallization, filtration and low
temperature drying processes to give solid NaHCO3

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 Caustic soda and chlorine production by
electrochemical process
 Chlorine, caustic soda and hydrogen are produced
via electrolysis of salt solution, and this process
require large inputs of electricity.
 Elecrolysis is a process of breaking down a
compound into its constituent elements by passing
electricity through it.
 Electricity is a major cost element in chlor-alkali
production cost (60% of variable cost)

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 The electrolysis process and technology
types
 The processing of brine electrolysis to produce
caustic soda, chlorine, and hydrogen is called the
electrolytic (chlor- alkali) process.
 In this process there are three types of electrolytic
cell:
1) Diaphragm Cell
2) Mercury Cell
3) Membrane Cell

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 Each process represents a different method of
keeping the chlorine produced at the anode and
hydrogen including sodium hydroxide at the
cathode
 The main difficulty during the electrolysis of NaCl
solutions was that of achieving Continuous
separation of chlorine generated at the anode and
sodium hydroxide produced at the cathode
 Chlorine ions are oxidized and chlorine (Cl2) is
formed at the anode in all of the three cells.

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 In the cathode section of mercury process a
sodium/mercury amalgam is formed and hydrogen
(H2) and hydroxide ions (OH-) are formed by the
reaction of sodium in the amalgam with water in
the denuder to finally form caustic soda.
 In the cathode compartment of the membrane and
diaphragm cells, water decomposed to form
hydrogen (H2) and hydroxide (OH-) at the cathode
to react with sodium ion to produce caustic soda.

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 Raw materials:
1. Sodium chloride
2. Water
 Salt is first dissolved in the dissolution tank. The
obtained saturated brine(salt) is then sent to a
purification tank to remove impurities.
 Industrial water is also purified before entering the
cell
 Electricity is needed in electrolytic cell.

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1. Diaphragm cell
 In the diaphragm cell process, all reactions takes
place within one cell and the cell effluent contains
both salt and caustic soda.
 The diaphragm is usually made of asbestos and
separate the feed brine (anolyte) from the caustic-
containing catholyte.
 The anode compartment was filled with saturated
brine get ionized by the action of electrical energy.
 During the electrolysis of brine, chlorine is
generated the anode.

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 The sodium ions, along with sodium chloride and
water, percolated through the diaphragm in to
cathode compartment from which sodium
hydroxide is produced at the cathode.

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 The diaphragm prevents the reaction of the
caustic soda with the chlorine.
 A diluted caustic brine leaves the cell.
 Diaphragm cell require multiple effect evaporation
to concentrate the alkali solution coming out of
the cell 10-12% NaOH to 50% NaOH.

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Diaphragm process
Advantage:
1. Utilization of less pure brine than required by
membrane cell
2. Operate at lower voltage than mercury process

Disadvantage:
1. NaOH produced is both dilute and evaporation
is required.
2. Chlorine gas contains oxygen

3. Avoidance of asbestoses emission required

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2. Mercury cell process
 Mercury cell process involves two cells. The first cell
is called primary cell or electrolizer while the second
one is known as secondary cell or
denuder/decomposer.
 Electric current flowing through the cell decomposes
the brine passing through the narrow space between
the electrodes, liberating chlorine gas (Cl2) at the
anode and metallic sodium (Na) at the cathode.
 The chlorine gas is accumulated above the anode
assembly and discharged to the purification process.

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 As sodium ion is liberated at the surface of the
mercury cathode it immediately forms an amalgam
(a 'mixture' of two metals) with mercury.
 The liquid amalgam flows from the electrolytic cell
to a separate reactor, called the decomposer, where
it reacts with water in the presence of a graphite
catalyst to form caustic soda (sodium hydroxide) and
hydrogen gas.
 The sodium hydroxide produced at the denuder has
a concentration of about 50%.
 The sodium-free mercury is fed back into the
electrolyser and reused.
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Mercury process:
Advantages:
1. Pure 50% NaOH solution and less steam
energy is required
2. Pure chlorine gas
Disadvantage:
1. Operate at higher voltage than diaphragm and
membrane cell.
2. More stringent brine purification required
3. The amalgam process inherently release of
mercury which make the mercury process
environmentally unfriendly which limit its
wider application.
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3. Membrane cell
 This technology uses water-impermeable ion-
conducting membrane.
 The membrane is made of a special resin which
permits cations (positive ions) to pass through.
 The anode chamber of a membrane electrolytic cell
is filled with brine, and the cathode chamber with
water.
 The brine in the anode chamber contains sodium
(Na+) and chloride (Cl-) ions.

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 These ions migrate when a current is applied: the
positively charged sodium ions pass through the
membrane to the cathode chamber, while the
negatively charged chloride ions are discharged on
the anode surface to form chlorine gas (Cl2).
 Water in the cathode chamber partly dissociates into
hydrogen (H+) and hydroxide (OH-) ions.
 The hydrogen ions capture electrons on the cathode
surface to form hydrogen gas (H2).
 The hydroxide ions are attracted to the anode, but
blocked by the membrane, and react with the
sodium ions from the anode chamber to form
caustic soda (sodium hydroxide, NaOH).
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 The concentration of caustic soda produced by
recirculating the solution before it leaves the cell is
32-35%.
 If needed, to reach a concentration of 50% caustic
soda, the caustic liquor produced has to be
concentrated by evaporation using steam.

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Membrane process:
Advantage:
1. Pure NaOH

2. Electric energy consumption only about 77% of

that of mercury proess
3. No mercury and asbestos required

Disadvantage
1. NaOH content only 33% by weight

2. Chlorine gas contains oxygen

3. Very high purity brine required

4. Present high cost and short lifetime of the

membranes.
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 Electrolysis technology is currently very much
dominant in the production of caustic soda and
chlorine.
 Membrane cell is in the process of replacing the
other two cells. This is due to lower operating costs
and advantages in environmental issues as
compared to those associated with mercury and
asbestos.

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Process flow diagram and major unit
operation

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Main characteristics of the different
electrolysis processes

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End product uses

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Caustic soda production by lime soda
process
 Caustic soda solution is a colorless and odorless
liquid
 Is highly reactive and corrosive
 Readily reacts with metal
 Upon cooling the viscosity of the solution
increases rapidly
 Is hydroscopic and readily absorb water from air,
so it should be stored in airtight container.
 It is very soluble in water with liberation of heat.

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Raw material
 Sodium carbonate : Can be manufactured by
Solvay‘s process.
 Lime stone is obtained from mineral calcite or
aragonite, which can be used after removal of clay,
slit and sand (silica).
Major unit operation and process flow diagram

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Process description
 Series of causticizer tank or agitator are added with
20% solution of soda ash (made with weak liquor
from a previous stage) and milk of lime or slaked
lime.
 The causticizer tanks containing steam line to heat
the mixture to 80–90oC are either fitted with
mechanical stirrer or compressed air as substitute
of agitator.
 After the equilibrium the liquid is allowed to settle
for 2-3hour.

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 The causticising process is completed in the series
of three agitators.
 The mixture of NaOH and CaCO3 from the last
agitator is charged to the first thickener, which
consist of a large shallow cylindrical tank into
which the slurry is fed at the center.
 The over flow liquid from the first thickener is
filtered and filtrate containing 10-11% NaOH is
evaporated to 50 % solution in a triple effect
vacuum evaporator as described earlier.

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 The lime sludge from the bottom of the first
thickener is washed with the water and transferred
in to the second thickener.
 The overflow from the second thickener is used as
a weak liquor to make soda ash solution.
 The sludge from the second thickener is filtered
through rotary drum vacuum filter and washed.
 The filtrate is returned to the second thickener
while the cake is calcined in the lime kiln to form
lime.

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HCl Production
 Hydrochloric acid (HCl), also known as muriatic
acid.
 Is a solution of hydrogen chloride in water.
 HCl exists in solid, liquid, and gaseous states and
is water soluble in all proportions.
 The first hydrochloric acid was prepared through
heating common salt and sulfuric acid by
Benedictine Monk and Basil Valentine in 15th
century.

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Uses
 Used in metal cleaning operations, chemical
manufacturing, petroleum well activation, and in
the production of food and synthetic rubber.
 Used for the manufacture of chlorine and chlorides,
e.g. Ammonium chloride used in dry cell.
 In the manufacture of glucose from corn starch.
 For extracting glue from bones and purifying
boneblack.
 A saturated solution of zinc chloride in dilute HCl is
used for cleaning metals before soldering or
plating.

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Production technology
 HCl is manufactured by various methods as follows.
1. Synthesis from hydrogen and chlorine
2. From salt and sulfuric acid
3. As by-product from chemical processes
4. From incineration of waste organics

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1. Synthesis from Hydrogen and Chlorine
Sources of raw material
Both hydrogen and chlorine can be obtained during
electrolysis of brine for manufacturing of NaOH.
 Reaction
H2 + Cl2 2 HCl

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2. The Salt–Sulfuric acid process
 The reaction between NaCl and sulfuric acid occurs
in two endothermic stages.
Sources of raw material
 Sodium chloride can be obtained from sea water,
salt lake and sub –soil water
 Sulfuric acid can be obtained by contact process

 Reaction

NaCl + H2SO4 NaHSO4 + HCl

NaCl + NaHSO4 Na2SO4 + HCl

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THANK YOU!

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