MEMBRANE ELECTROLYSIS OF NaCl

SOLUTION
(Chlor-Alkali Technology)
OUTLINE
• Electrochemistry Fundamentals
• Ion Exchange Membranes
• Brine (NaCl) Electrolysis (Chlor-Alkali)
• Mercury cell process
• Diaphragm cell process
• Membrane cell process
• Membrane electrolysis of Borax solution
 Electrochemistry Fundamentals
• Redox reactions

• Electrochemical reactions:
▫ Heterogeneous Electrolyte-Electrode reactions
 ∆G>0 / ∆G<0=> Nonspontaneous/spontaneous =>input/output of
electrical energy
Electrochemistry Fundamentals
• Thermodynamics
• Free energy, electrical work
• ∆G0=-n.F. E0
• Cell Potential
• E0=E0anode - E0cathode
• Standard potentials (1M, 298K, 1 bar)
• Nerst equation;
Electrochemistry Fundamentals
Electrochemistry Fundamentals
• Faraday’s Law
• m, mass produced; Q, total electric charge in C; n valence number;
M, molar mass
• Current Efficiency => Actual/Theorical
• Side reactions
• Kinetics=>overpotential, tafel eq., exchange current
density, electrocatalysis etc.
Electrochemistry Applications
• Fuel Cells and Batteries
• Primary metal production (electrowinning): Al, Mg,
Na
• Metal refining: Cu, Ni - also electroplating
• Inorganic chemicals: Cl2/NaOH; H2O2 and other
peroxy compounds; O3; chromic acid; KMnO4
• Organic compounds: adiponitrile
• Waste water purification and recycling
Some common types of electrode processes
Ion Exchange Membranes
• Polymeric structure
• Seperates anode and cathode compartments.
• Permselectivity to counter ions
• Permselectivity to specific-valent-ions.
Ion Exchange Membranes
Ion Exchange Membranes
NaCl Electrolysis (Chlor-Alkali Ind.)
• Overall reaction:

• Different electrodes => different reactions are

possible thermodynamically
• 3 known methods
• Mercury process
• Diaphragm process
• Membrane process
• Diphragm and membrane=> same anodic-cathodic
reactions; mercury => different cathodic reaction.
NaCl Electrolysis (Chlor-Alkali Ind.)
• Mercury process
• The oldest, 1890s
• Cl2 evolving anode (graphite, Ti), mercury cathode.
Mercury cell
process
flowsheet
NaCl Electrolysis (Chlor-Alkali Ind.)
• Diaphragm process
• A permeable asbestos (or metal oxide with polymer) based diaphragm
is used to separate the anode products from the cathode products.
• Product contains NaCl and NaOH. NaOH(s)
can be crystallised out.
Diaphragm
process
flowsheet
NaCl Electrolysis (Chlor-Alkali Ind.)
• Membrane Process
• Ion-exchange membrane selectively allows Na+ and water to flow to
the cathode compartment but prevents products from
moving between compartments.
• Favoured method => no hazardous waste, very
pure NaOH, lowest energy input.
• SS or Ni cathode & Ti anode.
• Same reaction mechanism as
diaphragm process
Ca-Mg removal
(to ppb level)

Ion exchange eq.:

R-Na2+Ca2+ =>
R-Ca + 2Na+

Membranepro
cess flowsheet
NaCl Electrolysis (Chlor-Alkali Ind.)
Mercury Cell Diaphragm Cell Membrane Cell
cathode Na depositing => mercury H2 evolving => stainless steel, Ni, Ni coated SS
flowing over steel (H2O reduced)
(Na+ reduced)

cathode product Na/Hg amalgam NaOH, H2 (+NaCl) NaOH, H2

(Cl2 and brine are removed (have to be separated) (membrane will not let Cl– or
separately) OH– through)

decomposer + - -
anode Cl2Evolving => unstable “graphite” replaced by “RuO2 coated Ti”, which is “DSA”. RuO2 =>
catalytic activity.
anode product Cl2
purity of NaOH 50 % 11 % 30-40 %
electrical energy 4-4.5 volts 4-5 volts 3-4 volts and lower

cell temp. (°C) 90-95 75-85 88-90

environmental use of Hg & its disposal older cells contain asbestos -

NaCl Electrolysis (Chlor-Alkali Ind.)
NaCl Electrolysis (Chlor-Alkali Ind.)

Percentage of the 3 Production capacities of

processes in different the 3 processes in
geographies Japan