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ChE 308
Lecture 3
Chlor-Alkali Industries: Caustic
soda, Chlorine, Soda Ash
Chlor-Alkali Industry
Lime stone and Fuel
Ammonia
Sodium Chloride
Carbon dioxide
Electrolyte Process
Chlorine
Pulp and Paper
Solvents
Pesticides
Plastics
Sanitation
Refrigeration
Fluid
Soda Ash
Sodium bicarbonate
Caustic Soda
Soap, Rayon, Dyes,
Paper, Foods,
rubber, Textiles,
Chemicals,
Bleaching,
Petroleum,
Metallurgy
Soap
Glass
Drugs
Paper
Ceramics
Sugar
Photography
Leather
Drugs
Beverages
Baking
Powder
Food products
Fire
extinguisher
Manufacture of Chlorine and Caustic Soda
Sodium Hydroxide:
White, solid material that picks up moisture from air.
If put in water, it produces a large amount of heat.
Very corrosive and can cause severe burns
Caustic Soda and Chlorine Processes
Sodium Chloride solution (brine)is electrolytically decomposed to
elemental chlorine (in the anode compartment), and sodium
hydroxide solution and elemental hydrogen (in the cathode
compartment) in all the processes
The overall reaction for the electrolytic production of caustic soda
and chlorine is:
2 NaCl (aq) + 2 H2O = Cl2 (gas) + H 2 (gas) + 2 NaOH (aq)
Anode
Cathode
Manufacture of Chlorine and Caustic Soda contd
Reactions:
Decomposition Voltage and voltage efficiency:
Where, E= Theoretical decomposition voltage
H= enthalpy change of reaction
J= electrical equivalent of heat
T= absolute temperature
F= Faraday constant
n= number of equivalents involved
Manufacture of Chlorine and Caustic Soda contd
Decomposition Voltage and voltage efficiency (contd):
The ratio of theoretical voltage to that actually used is the Voltage
efficiency of the cell(ranges from 60-75%).
The ratio of the theoretical to the actual current consumed is defined as the
Current efficiency(ranges from 95-97%).
The product of voltage efficiency and current efficiency is the energy
efficiency of the cell.
Manufacture of Chlorine and Caustic Soda contd
Methods of manufacture
1. Chemical: Lime soda Process
2. Electrochemical: Chloro Alkali Process
Diaphragm Cell
Mercury Cell process
Membrane cell process
Electrochemical methods of manufacture
Diaphragm cell process:
This process uses a steel cathode, and the anode area is separated from
the anode area by a permeable diaphragm.
A diluted caustic brine leaves the cell.
The caustic soda must usually be concentrated to 50% and the salt
removed.
Mercury cell process:
Sodium metal forms an amalgam at a mercury cathode.
This sodium is then reacted with water to produce NaOH.
Membrane cell process:
This process is similar to the diaphragm cell process.
Here a Naflon membrane is used to separate the cathode and the anode
reactions. Only sodium ions and a little water pass through the membrane.
It produces a high quality of NaOH.
Of the three processes , it requires the lowest consumption of electric
energy and the amount of steam needed for the concentration of the caustic
soda is relatively small.
Electrochemical methods of manufacture contd
Diaphragm Cell type Process
Electrochemical methods of manufacture contd
Mercury Cell type Process
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Electrochemical methods of manufacture contd
Membrane Cell type Process
Electrochemical methods of manufacture contd
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Electrochemical methods of manufacture contd
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Advantages and Disadvantages of Electrochemical
methods of manufacture
Process
Diaphragm
Process
Mercury
Process
Membrane
Process
Advantages
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Disadvantages
Use of well brine
Low electricity consumption
Use of asbestos
High steam consumption
Low purity caustic
Low chlorine quality
50% caustic direct from cell
High purity chlorine and hydrogen
Simple brine purification
Use of mercury
Expensive cell operation
Large floor space
Costly environment protection
Low energy consumption
Cost of membrane
Use of solid salt, high purity brine
Low capital investment
High oxygen content in chlorine
High purity caustic
Insensitivity to cell load variations
and shutdowns
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Comparison of cell technologies
Mercury
Diaphragm
Membrane
Operating current density(KA/m2)
8-13
0.9-2.6
3-5
Cell voltage (V)
3.9- 4.2
2.9- 3.5
3.0-6.0
NaOH strength(wt%)
50
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33-35
Energy Consumption(KWh/MT Cl2)
3360
2720
2650
Steam Consumption (KWh/MT Cl2)
for concentration to 50% NaOH
610
180
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Membrane cell process Flow sheet
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Dorr Continuous Causticization
Process
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Other Chlor-Alkali
Products
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Liquid Chlorine
Chemical Formula: Cl2
Appearance: Clear amber color
Product Quality: Cl2 purity 99.5%
Uses:
Manufacture of various chemical compounds e.g., carbon tetrachloride,
chlorinated lime, PVC, HCl, etc.
Water purification, manufacture of metallic chlorides, chlorinated lime,
chlorobenzene, etc.
Shrink proofing wool, in flame-retardant compounds, manufacture of
trichloroethylene, neoprene etc.
Processing of meat, fish, vegetables and fruit, in special batteries (with
lithium or zinc)
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Hydrochloric acid
Chemical Formula: HCl
Product quality: 30-32% HCl
Appearance: Colorless or slightly yellow fuming liquid
Uses:
Metal picking and cleaning, industrial acidizing, boiler scale removal
Processing of bone in gelatin manufacturing industry, food processing (corn
syrup, sodium glutamate).
Manufacture of dyestuffs, casein, pharmaceuticals, synthetic rubber,
laboratory reagent etc.
Effluent treatment and the regeneration of ion-exchange resin in water
treatment.
Bangladesh demand: 150- 200 TPD
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Sodium Hypochlorite
Chemical Formula: NaOCl
Product quality: Available Cl2
Appearance: Pale greenish liquid
Uses:
Disinfection, odor control, specification, bleaching.
Chlorination of drinking and process water, oil refineries, petroleum
refineries.
Textile industry, pulp and paper industry, soap manufacturing, food
processors, wood processing.
Elimination of slime and algae in swimming pool and boiler water.
Bangladesh demand: 40- 50 TPD
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Stable Bleaching Powder
Chemical Name: chlorinated lime
Chemical Formula: Ca(OCl)Cl
Product quality: 30-32% HCl
Appearance: Dry free flowing dull white powder
Product quality: Available chlorine conc. 35-37% min
Uses:
Sewage disposal, odor control, BOD reduction and removal of poisonous
matter.
Potable water purification, mosquito control, control of epidemic etc.
Bleaching agent (paper & textile), algaecide, bactericidal and deodrant.
Elimination of algae and slime in swimming pool, sanitation and general
hygiene.
Bangladesh demand: 100- 150 TPD
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Na2CO3
Shall be discussed on next class
