Chemical Technology

Subject Code: CH2001

Lecture 4

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 Chloro alkali industry
• The Chloralkali Industry: Applications of Electrolysis
• https://www.youtube.com/watch?v=ueeHNwL5lSE
• https://www.chemicalsafetyfacts.org/sodium-hydroxide/
• Chlor-Alkali Industry in the country produces mainly Caustic
Soda, Chlorine and Soda Ash.
• The geographic distribution of Chlor-alkali processes world-
wide differs appreciably (production capacity of chlorine):
-Western Europe, predominance of mercury cell process (June
2000): 55%
-United States, predominance of diaphragm cell process: 75%
-Japan, predominance of membrane cell process: >90%
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 NaOH Properties
Chemical formula NaOH Solubility in methanol 238 g/L
−1
Molar mass 39.9971 g mol Solubility in ethanol <<139 g/L
Appearance White, waxy, opaque crystals Vapor pressure <2.4 kPa (at 20 °C)
+ –
Odor odorless Basicity (pKb) -0.56 (NaOH(aq) = Na + OH )
3 −6 3
Density 2.13 g/cm Magnetic −15.8·10 cm /mol (aq.)
Melting point 323 °C (613 °F; 596 K) susceptibility (χ)
Boiling point 1,388 °C (2,530 °F; 1,661 K) Refractive index (nD) 1.3576
Solubility in water 418 g/L (0 °C)
1000 g/L (25 °C)
3370 g/L (100 °C)
Solubility soluble in glycerol
negligible in ammonia
insoluble in ether
slowly soluble in propylene
glycol

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 Sodium Hydroxide
Key Concepts
• Sodium hydroxide, NaOH, is also known as lye or caustic soda.
• Sodium hydroxide is a commonly used base.
• It is stable towards heat.
• It is highly soluble in water and a considerable amount of heat is evolved due to the formation of a number of hydrates,
e.g., NaOH.H2​O, NaOH.2H2​O. It is also soluble in alcohol.
• Aqueous solution of sodium hydroxide is strongly alkaline due to its complete dissociation into Na+ and OH−

Electrolysis of concentrated sodium chloride solutions (brine) produces chlorine gas, hydrogen gas and aqueous sodium hydroxide.
• 2NaCl(aq) + 2H2O(l) → H2(g) + Cl2(g) + 2NaOH(aq)
• Cl2(g) is produced at the anode (positive electrode).
• H2(g) and NaOH(aq) are produced at the cathode (negative electrode).

Three types of electrolytic cell are used to produce sodium hydroxide from brine:
• Castner-Kellner Cell (Mercury Process)
• Nelson Diaphragm Cell
• Membrane Cell
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 Production/consumption of caustic soda

Annual growth is
around 5.4 %

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 NaOH uses

• Domestic oven and drain cleaner

• Pulp and paper production
• Manufacture of rayon and other synthetic fibres
• Soap and detergent production
• Extraction of alumina from bauxite (Bayer Process)
• Removal of sulfur dioxide and hydrogen sulfide in petroleum
refining

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 Classification of process (NaOH)

✓Electrolytic process producing chlorine, NaOH, and H2 as co-

products.
✓Diaphragm electrolytic cell-uses saturated NaCl solution and
produces 10-12% caustic.
✓Other process membrane cell
✓Mercury electrolytic cell-uses saturated NaCl solution with
solid salt make-up

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 Classification of process

✓Chlorine processes without co-products

• HCl-air oxidation with Fe2O3 catalyst
• HCl-air-Cl2 oxychlorination processes
• HNO3-NaCl-air process
✓NaOH process with no Cl2 co-product
✓Na2CO3-Ca(OH)2, no further investment allocated as process
not competitive.

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 Electrolytic Cells for the Production of Sodium Hydroxide
Castner-Kellner Cell (Mercury Process)
Anode: titanium
Anodic reaction (oxidation):
2Cl-(aq) → Cl2(g) + 2e-
Cathode: mercury flowing along bottom of cell
Cathodic reaction (reduction):
Na+(aq) + e- → Na(s)

Na(s) dissolves in the liquid mercury to form an amalgam which is

removed to the decomposer.
In the decomposer the amalgam reacts with water to form sodium
hydroxide, hydrogen gas and mercury.
2Na/Hg + 2H2O(l) → 2Na+ + 2OH- + H2(g) + 2Hg(l)
Sodium hydroxide solution and hydrogen gas are collected.
Mercury is recycled through the electrolytic cell.
Mercury is toxic so care must be taken to prevent mercury losses.
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 FEATURES MERCURY CELL
• Electric current flowing through the cell decomposes the brine
passing through the narrow space between the electrodes,
liberating chlorine gas at the anode and metallic sodium at the
cathode.
• The chlorine gas is accumulated above the anode assembly and
discharged to the purification process.
• As it is liberated at the surface of the mercury cathode and the
sodium immediately forms an amalgam (a 'mixture' of two metals)
• 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-free mercury is fed back into the electrolyser and
reused.
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 Nelson Diaphragm Cell
• Porous diaphragm of asbestos or metal oxide with polymer
separates anode and cathode compartments.
• Diaphragm prevents hydroxide ions entering anode compartment
and prevents chloride ions entering cathode compartment.
• Saturated brine enters anode compartment where chlorine gas is
produced.

Anode: carbon (graphite) or titanium coated with Ru-Ti oxide.

Anode reaction (oxidation):2Cl-(aq) → Cl2(g) + 2e-

Cathode: steel mesh

Cathode reaction (reduction):2H2O(l) + 2e- → H2(g) + 2OH-(aq)

Na+ migrates across diaphragm to cathode compartment combining with OH- to form NaOH.
Overall cell reaction (showing Na+ spectator ions):
2H2O(l) + 2Cl-(aq) + 2Na+(aq) → 2Na+(aq) + 2OH-(aq) + H2(g) + Cl2(g)
Product contains sodium chloride and sodium hydroxide. NaOH(s) can be crystallised out.

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 FEATURES DIAPHRAGM CELL
• In the diaphragm cell process, there are two compartments
separated by a permeable diaphragm.
• Brine is introduced into the anode compartment and flows
into the cathode compartment.
• Similarly to the Membrane Cell, chloride ions oxidized at the
anode to produce chlorine, and at the cathode, water is split
and caustic soda and hydrogen are formed.
• The diaphragm prevents the reaction of the caustic soda with
the chlorine.
• A diluted caustic brine leaves the cell.
• The caustic soda must usually be concentrated to 50% and
the salt removed. This is done using an evaporative process.
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 Membrane Cell
• Favoured method for producing sodium hydroxide as there is no hazardous
waste, very pure sodium hydroxide is produced and it has the lowest energy
requirements.
• Ion-exchange membrane selectively allows Na+ and water to flow to the cathode
compartment but prevents products from moving between compartments.
• Saturated brine enters the anode compartment where chlorine gas is formed.
Anode (positive electrode): titanium
Anode reaction (oxidation):
2Cl-(aq) → Cl2(g) + 2e-
Cathode (negative electrode): nickel
Cathode reaction (reduction):
2H2O(l) + 2e- → H2(g) + 2OH-(aq)

Na+ migrates across the membrane to cathode compartment combining with OH- to form NaOH.
Overall cell reaction (showing Na+ spectator ions):
2H2O(l) + 2Cl-(aq) + 2Na+(aq) → 2Na+(aq) + 2OH-(aq) + H2(g) + Cl2(g)
• Product is concentrated sodium hydroxide.

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 FEATURES 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.
• 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.
• Water in the cathode chamber partly dissociates into hydrogen and hydroxide ions.
• The hydrogen ions capture electrons on the cathode surface to form hydrogen gas.
• 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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 Chlorine properties
Phase at STP gas
Melting point (Cl2) 171.6 K ​(−101.5 °C, ​−150.7 °F)

Boiling point 239.11 K ​(−34.04 °C, ​−29.27 °F)

Density (at STP) 3.2 g/L

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when liquid (at b.p.) 1.5625 g/cm
Critical point 416.9 K, 7.991 MPa
Heat of fusion 6.406 kJ/mol
Heat of vaporisation 20.41 kJ/mol
Molar heat capacity 33.949 J/(mol·K)

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 Chlorine consumption in India

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 Hydrogen and Chlorine uses

• margarine • PVC (polyvinyl chloride)

• nylon • dry-cleaning solvent
• HCl (gas and acid) • HCl (gas and acid)
• bleaches
• weed-killers
• paints and dyes
• anti-bacterial agent in water

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 Chlorine-caustic soda production process
Raw materials
• 10-15 % NaCl or solid salt.
• Na2CO3 and NaOH for salt purification.
• Sulfuric acid for Cl2 drying.
Quantitative requirement (basis)
• 1 ton of Cl2
• 1.15 15 tons of NaOH (98%)
• 283 Nm3 of H2 (26 kg)
• 1.3 tons of salt
• 26 kg soda ash (58% Na2O)
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• Sulfuric acid (98%) 5-6 kg.
• Sodium hydroxide 10-15 kg
• Steam 11 tons
• Electricity 2900 kWh
Plant capacities: 100-1000
tons/days of cl2 in a series of
electrolysis units each
producing 0.5-2 tons cl2 per
day.
Electrolytic process for chlorine-caustic soda production

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 Process description

• A combination of diaphragm and mercury cell processes will be

described.
• Brine solution flows through pipeline to storage reservoir and
then through a brine treatment system.
• Caustic soda, soda ash and barium carbonate removes calcium,
magnesium and iron salts which would clog up diaphragms.
• This purified saturated brine ( 25-28% NaCl) is heated and
electrolyzed in a diaphragm cell. The cell operating at 45-55%
decomposition efficiency, discharges a 10-12% caustic soda with an
equal concentration of NaCl

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• Multiple effect evaporation concentrates the cell liquor to 50%
NaOH solution.
• The precipitated salt is separated and then treated with brine.
• Salt separated overflow is 50% caustic soda product
containing 2% NaCl and 0.1 -0.5% NaClO on dry basis.
• This commercial caustic grade can be evaporated to produce
saturated 73% NaOH liquor.
• The characteristics of the cell configuration are already
explained.
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Advantages and Disadvantages of Chlor-Alkali
Processes

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 Major engineering problems/Economics

• Choice of cell design

• Corrosion
• Plant location
• Caustic-chlorine-hydrogen balance
• Lime-soda process
• Choice of electrolytic cell
• Power costs

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