CHEMICAL PROCESS INDUSTRIES

Production of CHLORINE

Introduction

Chlorine, along with its important by-product, sodium hydroxide, is

produced from the readily available starting material, rock salt
(sodium chloride).  It is well known for its use in sterilizing drinking
water and in particular swimming pool water.  However, most
chlorine is used in the chemical industry in the manufacture of other
products.  Sometimes chlorine is in the product molecule but on
other occasions it is used to produce intermediates in the
manufacture of products that do not contain chlorine and the
element is recycled.
 

Uses of chlorine
The largest use is in the manufacture of poly(chloroethene), PVC.  Other
major polymers produced using chlorine include the polyurethanes.
Although chlorine does not appear in the polyurethane molecule, chlorine is
used to make the intermediates, the isocyanates.  The oxygenates (Figure
1) are principally epoxypropane (propylene oxide) and propane-1,3-diol,
which are used to make polyols.  These, like the isocyanates, are used in
turn to make polyurethanes.
1-Chloro-2,3-epoxypropane has many industrial uses, the most important
being in the manufacture of the epoxy resins. Among the uses of the
chloromethane are the manufacture
of silicones and poly(tetrafluoroethene), PTFE.
The solvents (including trichloroethene) are used in dry cleaning.
Chlorine is also used in the manufacture of many inorganic compounds,
notably titanium dioxide and hydrogen chloride.
Most chlorine is produced on the site on which it is going to be used, for
example, to make hydrochloric acid and the other compounds described
above.
 However, some chlorine needs to be transported for example, when it is to
be used to purify water. For this, the chlorine is dried by passing it through
concentrated sulphuric acid and then compressed and liquefied into
cylinders, ready for transportation.

Annual production of chlorine

World 65 million tonnes1

U.S. 11 million tonnes1

Europ 10 illion tonnes2

e

Manufacture of chlorine
Most chlorine is manufactured by the electrolysis of sodium chloride
solutions.  The other main commercial product is sodium hydroxide.  The
primary raw material for this process is rock salt (sodium chloride), available
worldwide usually in the form of underground deposits of high purity.  It is
pumped to the surface with high pressure water as a concentrated solution.
This solution is often called brine.
A solution of sodium chloride contains Na+(aq) and Cl-(aq) ions and, from
the dissociation of water, very low concentrations of H+(aq) and OH-(aq)
ions.  During the electrolysis of the solution, chlorine and hydrogen gases
are produced:
As the hydrogen ions are discharged, more water dissociates forming more
hydrogen and hydroxide ions.  This results in a gradual build up of the
concentrations of hydroxide ions around the cathode, thus producing a
solution of sodium hydroxide.  The essential requirement is to maintain an
effective and economic means of separating the anode and cathode
reactions so that the products, chlorine and caustic soda, will not react to
form sodium hypochlorite.  This separation has been achieved historically
by the mercury amalgam and diaphragm processes.  However, these are
being phased out and most new plants use ion exchange membranes,
which are the most environmentally and economically sound means of
chlorine production.

(a) Cation exchange membrane cell

The cation exchange membrane does not allow any
gas or negative ions to flow through it but it allows
Na+ ions to move between the brine and caustic
compartments.
(b) Mercury amalgam cell
In the flowing mercury cathode process sodium ions
are discharged in the form of a mercury sodium
amalgam and chloride ions are converted to chlorine.
The amalgam flows to a totally separate compartment,
the decomposer (denuder) in which it reacts with water
to yield sodium hydroxide solution and hydrogen gas.
(c) Percolating diaphragm cell
A percolating diaphragm, usually of asbestos, allows a
through flow of brine from anode to cathode. It
separates the chlorine and hydrogen gas spaces. The
migration of OH- ions from the cathode to the anode is
prevented by the velocity of liquid flow against them.

(a) Cation exchange membrane cell

The anodes are made of titanium coated with ruthenium dioxide.  The
cathodes are nickel, often with a coating to reduce energy consumption.
The anode and cathode compartments are completely separated by an ion-
permeable membrane .  The membrane is permeable to cations, but not
anions; it allows the passage of sodium ions but not chloride or hydroxide
ions . Sodium ions pass through in hydrated form (Na.xH2O)+ so some water
is transferred, but the membrane is impermeable to free water molecules.
The sodium hydroxide solution leaving the cell is at ca 30% (w/w)
concentration. It is concentrated by evaporation using steam, under
pressure, until the solution is ca 50% (w/w), the usual concentration needed
for ease of transportation and storage.

The membrane (0.15-0.3 mm thick) is a co-polymer

of tetrafluoroethene (and a similar fluorinated monomer with anionic
(carboxylate and sulfonate) groups.

When hydrogen ions migrate to the cathode, hydrogen is liberated.

However, if oxygen is pumped into this part of the cell, the hydrogen reacts
to form water and the voltage needed for the electrolysis process is reduced
by a third.  This, in turn, reduces the power costs and thus the amount of
carbon dioxide formed in the power station by a third.  This is a great
advantage as electricity accounts for about the total cost of production,  A
disadvantage is that the hydrogen is no longer available as an important
and valuable by-product, together with oxygen being consumed as an
additional raw material.  There have been technical difficulties in applying
this process (known as an oxygen-depolarised cathode, ODC) to the
electrolysis of brine and it was found easier to apply to the electrolysis of
aqueous hydrochloric acid in order to generate chlorine.  Large commercial
plants have been constructed in China and Germany, using ODC
technology.  Now these difficulties have been overcome and a new plant
has been commissioned that uses brine as the starting material.
(b) The mercury cell
Typical modern gas-tight, rubber-lined or PVC-lined steel cells are used,
which measure about 2 m x 15 m.  They have a slightly sloping base over
which flows a thin layer of mercury, acting as a cathode.  The anodes are a
series of titanium plates coated with a precious metal oxide layer, and
positioned about 2 mm from the cathode.  The cells typically operate in
series of approximately 100.
Purified, saturated brine (25% (w/w) sodium chloride solution) at typically
333 K flows through the cell in the same direction as the mercury.  This high
salt concentration and the anode coating ensures the oxidation of chloride
ions rather than that of water which would yield oxygen at the titanium
anodes.

At the mercury cathode, sodium ions are discharged in preference to

hydrogen ions due to the high overvoltage of hydrogen.  The sodium forms
an amalgam with the mercury.
The amalgam contains approximately 0.3% (w/w) sodium. It moves on to a
decomposer cell situated alongside the mercury cell.
The exit brine, containing typically 15-20% (w/w) sodium chloride, is freed
of chlorine by blowing air through it, or subjecting the solution to a vacuum.
The solution is resaturated with sodium chloride and returned to the cell.
The decomposer cell is made of steel and contains graphite blocks fixed in
the flow of amalgam.  Alternatively, the decomposer is a tower packed with
graphite spheres. The decomposer acts as a short circuited cell.  At the
anode sites, sodium is oxidized and the ions pass into solution. At the
cathode sites, hydrogen is discharged.
The mercury is returned to the electrolysis cell and the hydrogen passes out
of the decomposer. A 50% (w/w) solution of sodium hydroxide is produced
in the decomposer and most of it is sold in this form.  Some is concentrated
by evaporation to 75% (w/w) and then heat ed to 750-850 K to obtain solid
sodium hydroxide.
(c) The percolating diaphragm cell
In the diaphragm cell, the anodes are titanium coated with a precious metal
oxide and the cathodes are steel.  There is a porous asbestos diaphragm to
separate chlorine and hydrogen that are liberated during electrolysis.
The hydroxide ions formed in the cathode compartment, together with the
sodium ions, produce a solution of sodium hydroxide. The electrolyte level
is maintained higher in the anode compartment so that the brine percolates
through the diaphragm into the cathode section from where it flows out of
the cell with the sodium hydroxide solution.

The chlorine formed on the anodes rises and is led away.

The cathode solution contains about 10-12% (w/w) sodium hydroxide and
15% (w/w) sodium chloride.  This is evaporated to one-fifth of its original
volume when the much less soluble sodium chloride crystallizes to leave a
solution containing 50% (w/w) sodium hydroxide and less than 1% (w/w)
sodium chloride.
Comparison of mercury, diaphragm and membrane
cells
Factors such as capital and energy costs and environmental concerns all
favour the membrane process (Table) but its development was not possible
until work by Du Pont in the US in the early 1960s, and more recently in
Japan, resulted in the production of the membrane material discussed
above.

  Mercury Diaphragm Membrane

cheaper than
construction costs Expensive relatively cheap
mercury cell
toxic mercury
frequent asbestos
must be low maintenance
Operation diaphragm
removed from costs
replacement
effluent
high purity less pure 12%- high purity 30%-
NaOH product
50%-as needs needs
concentration
required concentration concentration
typical cell energy
consumption (kw
3 360 2 720 2 500
hours per tonne of
chlorine)
steam consumption
per caustic Nil High Medium
evaporation
purity of brine Important important very important

Throughout the world, the use of the mercury cell is being phased out.  For
example, in Europe1, the proportion of chlorine made using the Mercury cell
has fallen from 55% to 6% in 2017.  In contrast, the proportion of chlorine
produced by a diaphragm cell has risen from 20% to 77% over the same
period and the chlorine produced by a membrane cell has dropped from
23% to 12%.

 
 
The chlorine-alkali balance
 For every tonne of chlorine, 2.25 tonnes of 50% sodium hydroxide and
340 m3 of hydrogen (under normal conditions) are also produced. It is
necessary, therefore, to ensure that all these products can be sold.