CHAPTER : SEVEN

CHLOR-ALKALI INDUSTRY
PRESENTED TO:
 3rd year industrial chemistry
PRESENTED BY:
 Biniyam Abera (MSc.)
 Outlines
7.1. Application and use of products of Chlor-alkali industries

7.2. Production of Caustic soda

7.3. Process Technology of Soda Ash Production

7.4. Production of Sodium bicarbonate

 Introduction
• The term Chlor- alkali refers to the two chemicals Chlorine and Alkali

• Chlor-alkali process is an industrial process for the electrolysis of NaCl.

• Currently 95% of world chlorine production is obtained by chlor- alkali

process.

• Chlorine, Sodium Hydroxide, and Sodium Carbonate Are Primary

Products of the Chlor-Alkali Industry

• Large-scale electrolysis technology is used by industry for the

manufacture of chlor alkali products such as chlorine (Cl2) and sodium
hydroxide (NaOH / caustic soda), through the electrolysis of sodium
chloride (NaCl).
 The main technologies applied for chlor-alkali production are mercury,
diaphragm and membrane cell electrolysis.

 The chlorine-alkali (chlor-alkali) industry is an important part of the

chemical industry, and produces chlorine and sodium hydroxide
through the electrolysis of table salt (NaCl).
 The main Problem occur when Cl2 and NaOH are produced together
 Cl2 combines with the NaOH to form ClOˉ and Clˉ ions. This
produces NaClO3, NaClO, a component of household bleach.
 History of Chlor-alkali Industry

The diaphragm cell process and the mercury cell process were both
introduced in late 1800s.

The membrane cell process was developed much more recently

(1970).

Each of these processes represents a different method of keeping

chlorine produced at the anode separate from caustic soda and
hydrogen produced at the cathode.

During the last half of 19th century, chlorine was used almost
exclusively in the textile and paper industry.
7.1. Application and use of products of chlor-alkali industries
• The application of the chlor-alkali process is to produce 3 main
chemicals: chlorine, caustic soda and caustic potash.
Products of
chlorine

• Primarily, chlorine is used to make chemical compounds or organic

chemicals such as

• phosgene for polycarbonate,

• methyl-chloride for silicones,

• polyvinyl chloride (PVC) and methylene chloride for adhesives,

• polyurethanes, sulphur chlorides for crop protection and dyes, and
titanium dioxide for catalysts.

• Construction (PVC windows, water pipes, flooring, roofing

materials)

• Energy (batteries, solar panels, wind turbine blades)

• Food (crop protection, thickening agents)

• Health & personal care (bleaches, cosmetics, detergents, dental

treatments/cements, deodorants, dry cleaning, textiles)

• Home Care (paints, adhesives, refrigerants)

Products made from chlorine are used in a variety of sectors, which
include:
• Paper (inks, coatings, pulp)
• Pharmaceuticals (cancer treatment)
• Safety (water treatment)
• Sport (exercise equipment, clothing)
• Technology (circuit boards, fiber-optics, semiconductors, smartphones)
• Transportation (car parts, brake fluid, anti-freeze)
 Products made from caustic soda

are used in many sectors, including:

• Construction (carbon fibre, mining, metal plating)

• Energy (oil refining, wind turbines)

• Health & personal care (soaps, toothbrushes,

anticoagulants, shampoo, vitamins)

• Household (cooking equipment, foils, doors and windows)

• Sport (bicycles, tennis rackets, sails)

 Products made from caustic potash
feature in sectors such as :
• Agriculture (fertilizer)

• Energy (batteries)

• Food (additives, wine, chocolate)

• Industry (steel foundry, rubber, titanium dioxide, fire suppressant,

welding)

• Transport (de-icing fluid)

7.2. Production of Caustic soda

• Caustic soda is a strong alkaline compound with the chemical

formula NaOH.

• Its remarkable properties stem from its ability to dissociate in water,

forming hydroxide ions.

• This characteristic makes it highly reactive, particularly in solutions,

where it exhibits both acidic and basic qualities.

• The corrosive nature of caustic soda is crucial to its applications,

ranging from chemical manufacturing to water treatment.
-Production of Caustic Soda-

 The production of caustic soda involves

several methods, with each contributing to the
availability of different forms, including
caustic soda pearls.
 Nearly all caustic soda is generated by the
electrolysis of sodium chloride solution using
one of three cell types:
1. Mercury
2. Diaphragm and
3. Membrane cells.
• The primary raw material is common salt, usually in the form of
underground deposits which are brought to the surface as a solution
in a pumped high-pressure water supply.

• The sodium chloride solution is often called brine.

In the mercury cell,

1. Sodium is discharged in the form of a mercury sodium amalgam

and chloride ions as chlorine.

2. The amalgam flows to a totally separate compartment where it

reacts with water to yield sodium hydroxide solution and
hydrogen gas.
 The diaphragm cell

• Usually manufactured of asbestos, allows a flow of brine from the anode

to the cathode but separates the chlorine and hydrogen gas spaces.

• As hydrogen ions are discharged, hydroxide ions accumulate in the

cathode compartment with the aqueous sodium ions to produce sodium
hydroxide.

• Back migration of the hydroxide ions from the cathode to the anode is
prevented by the velocity of the liquid flow from one compartment to the
other.

• The chlorine formed at the anodes rises through the brine into a space
formed by the cell’s cover.
 In the membrane process

• The ion exchange membrane acts as a barrier to all gas and liquid
flows and only allows the passage of sodium ions between
compartments.

• The sodium ions pass in hydrated form to produce sodium hydroxide

in the cathode where hydrogen is given off. Chlorine gas is liberated
at the anode.

• The membrane is a copolymer of tetra fluoro ethylene or a similar

fluorinated monomer.
 Comparison

Mercury cells are cheaper to operate than diaphragm cells when

electricity costs are low and produce the product at the required
concentration and high purity, but mercury must be removed from the
effluent.

Diaphragm cells need plenty of thermal energy to concentrate the

caustic solutions but can be cheaper than mercury cells when steam
costs are low and have relatively cheap construction costs.

The use of membrane cells is growing due to lower capital and energy
costs and an absence of environmental problems. Therefore Membranes
can handle varying current densities and maximize production at cheap
electricity prices.
 Applications Across Industries
• Chemical Manufacturing:
Caustic soda is a key ingredient in the production of various
chemicals, including plastics, solvents, and dyes. Its role as a
strong base and versatile reactant makes it indispensable in
chemical synthesis.
• Water Treatment:
The alkaline properties of caustic soda make it an effective agent
in water treatment processes. It neutralizes acidity, adjusts pH
levels, and aids in the removal of heavy metals from wastewater.
• Textile Industry:
In textile manufacturing, caustic soda is used to mercerize cotton,
enhancing its strength and appearance. It is also involved in
dyeing processes, contributing to the vibrancy of colored fabrics.
• Soap and Detergent Production:

The saponification process, essential for soap and detergent production,

relies on caustic soda. It reacts with fats and oils to form soap, a
fundamental step in the manufacturing of cleaning products.

• Alumina Refining:

Caustic soda is a critical component in the Bayer process for alumina

refining, where it facilitates the extraction of aluminum from bauxite ore.
 7.3. Process Technology of Soda Ash Production

 Soda Ash also known as sodium carbonate.

 Na2CO3, is a sodium salt of carbonic acid.
 Sodium carbonate is domestically well known for its everyday use
as a water softener.
 It can be extracted from the ashes of many plants or seaweed.
 It is synthetically produced in large quantities from salt (sodium
chloride) and limestone by a method known as the Solvay process.
 MANUFACTURING OF SODA ASH SOLVAY
PROCES

 The Solvay process, also called ammonia soda process

 Uses salt (NaCl) and limestone (CaCO3) as raw materials.
 The raw material of this process is found every where in the world.
 The Solvay process produces “light soda ash”, which is used for the
detergent market and certain chemical intermediates.
 Recrystallization of light soda ash produce dense “soda ash”.
 MAIN CHEMICAL
REACTIONS
 The two main components: sodium chloride and calcium carbonate.
2NaCl + CaCO3 → Na2CO3 + CaCl2 IT IS NOT
EASY
 In practice this direct way is not possible and it needs the
participation of other substances and many different process steps to
get the final product: soda ash. The steps are :
(Step1) NaCl + H2O + NH3  NaCl + NH4OH
(Step2) 2NH4OH + CO2  (NH4)2CO3 + H2O
(Step3) (NH4)2CO3 + CO2 + H2O  2NH4HCO3
(Step4) 2NH4HCO3 + 2NaCl  2NaHCO3 ↓ + 2NH4Cl
 Sodium bicarbonate crystals are separated from the mother liquor by
filtration. sodium bicarbonate is decomposed thermally into sodium
carbonate, water and carbon dioxide (5).
2 NaHCO3 → Na2CO3 + H2O + CO2 (5)

The ammonium chloride filtrate (4) is reacted with alkali, generally

milk of lime (6), followed by steam stripping to recover free gaseous
ammonia:

2NH4Cl + Ca(OH)2 → CaCl2 + 2NH3 ↗ + 2 H2O (6)

 Carbon dioxide and calcium hydroxide originate from limestone
calcination (7)

CaCO3 → CaO + CO2 ↗ (7)

CaO + H2O → Ca(OH)2 (8)

 Brine (NaCl) has to be treated before the input in the process to
remove impurities : calcium and magnesium.
 If not removed they would react with alkali and carbon dioxide to
produce insoluble salts contributing to scale formation inside
equipment.

Ca2+ + CO3 2- → CaCO3 ↓ (9)

Mg2+ + 2 OH- → Mg(OH)2 ↓ (10)

 Sodium carbonate formed (equation 5) is called "light soda ash"
because its bulk density is approximately 0.5 t/m3.
 A subsequent operation called densification enables this value to be
doubled by crystallization into sodium monohydrate, by adding water
(equation 11) then followed by drying (equation 12). Final product is
"dense soda".
Na2CO3 + H2O -------- > Na2CO3.H2O (11)
Na2CO3.H2O --------- > Na2CO3 + H2O ↗ (12)
ADVANTAGES OF SOLVAY PROCESS
 Can use low-grade brine
 Less electric power and Less corrosion problems
 No co-products to dispose of
 Does not require ammonia plant investment
DISADVANTAGES OF SOLVAY PROCESS
 Higher salt consumption and steam consumption
 Higher investment in ammonia recovery unit verses crystallization units for
ammonium chloride
 Waste disposal of calcium chloride brine stream
 Higher capacity plant for economic break-even operation
 With current fertilizer shortage, all of the ammonium chloride will be used as
a mixed chemical fertilizer ingredient, so co-product disposal no problem.
HANDLING AND STORAGE
 Handling: Do not breathe dust, vapor, mist, or gas. Do not get in eyes,
on skin, or on clothing. Use only in a chemical fume hood.
 Storage: Store in a cool, dry place. Store in a tightly closed container.
 7.4. Production of Sodium bicarbonate

 Sodium bicarbonate is the chemical compound with the formula NaHCO3.

Because it has long been known and is widely used.

 The salt has many other names including sodium hydrogen carbonate, sodium

bicarb, baking soda, bread soda, cooking soda, bicarb soda or bicarbonate of

soda.

 The word saleratus, from Latin sal æratus meaning "aerated salt", was widely used

in the 19th century.

 In the year 1971, NaHCO3 was first manufactured by a French chemist named

Nicolas Leblanc. It was in the year 1846, John Dwight and Austin Church started a

manufacturing unit to produce baking soda using sodium carbonate and carbon

dioxide.
 Used for the production of both sodium bicarbonate and potassium bicarbonate.

 It is soluble in water.

• Sodium bicarbonate is a white solid that is crystalline but often appears as a

fine powder.

• It has a slight alkaline taste resembling that of sodium carbonate.

• It is a component of the mineral natron and is found dissolved in many

mineral springs. The natural mineral form is known as nahcolite.

• NaHCO3 is mainly prepared by the Solvay process, which is the reaction of

calcium carbonate, sodium chloride, ammonia, and carbon dioxide in water.

 Preparation of Baking Soda

• Solvay process is used for the production of sodium bicarbonate and sodium

carbonate industrially.

• In this process, carbon dioxide, water, ammonia and brine solution in its

concentrated form, are used as raw materials.

• This process is used mainly because it is inexpensive and less raw materials are

used to produce necessary chemicals.

• The important chemical reaction that is used in the production of baking soda and

sodium carbonate is:

CO2 + H2O + NH3 + NaCl → NaHCO3 + NH4Cl

2NaHCO3 → Na2CO3 + CO2 + H2O

Properties of Sodium Bicarbonate

• It is non-flammable.

• Powder dust is not explosive.

• It has a melting point of 500C

• NaHCO3 is a white crystalline solid which is odorless.

• It is basic in nature.
 Application of baking soda

Sodium bicarbonate is primarily used in cooking (baking) where it

reacts with other components to release carbon dioxide, that helps
dough "rise."

The acidic compounds that induce this reaction include

cream of tartar, lemon juice, yogurt etc., hence sodium bicarbonate
can be substituted for baking powder provided sufficient acid reagent
is also added to the recipe.

Many forms of baking powder contain sodium bicarbonate

combined with cream of tartar.
 It is used as a fabric softener in laundry

 Sodium bicarbonate has been used as a performance enhancer for

sprinters

 Baking soda can be used as a low-cost alternative to raising pH in

swimming pools.

 Sodium bicarbonate is used in Dry Chemical fire extinguishers as an

alternative to the corrosive ammonium phosphate in ABC

extinguishers.

 Sodium bicarbonate is often used in the pharmaceutical industry as an

additive to cell culture media.

 It acts as a weak buffer.

• It is used in a process for cleaning paint called soda blasting.

• It is used as a base in the production of crack cocaine.

• It is used as an effective anti-dandruff treatment.

• It can be used as a carbon sequestration agent, as demonstrated by

the Sky mine process, to trap Carbon Dioxide greenhouse gas
emissions in solid form, as one potential tool against global
warming.
THANK YOU
THE END