Chlorine

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.

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.

Figure 1 The uses of chlorine.

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 chloromethanes 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.

Figure 2 Although much rock salt

is pumped to the surface as
brine, some is
mined, as is being done in this
large underground deposit in
Cheshire.
By kind permission of the Salt
Association.

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 sulfuric acid and then
compressed and liquefied into
cylinders, ready for transportation.

Annual production of
chlorine

World 65 million tonnes1

U.S. 14 million tonnes1

Europe 10 million tonnes2

Data from:
1 The Chlorine Institute, 2016
2 Euro Chlor, 2016

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.

Table 1 The key features of the

three electrolytic processes.

(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 (Figure 3).
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.

Figure 3 The membrane cell.

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.

The plant shown in Figure 4 is using

the new oxygen depolarized cathode,
ODC, technology to produce
chlorine, following a large research
programme in Germany, led by Bayer.

Figure 4 Chlorine is being

produced in this bank of
membrane cells, using the
latest technology involving
oxygen-depolarised
cathodes, ODC. This photo
shows feed pipes being
checked at the chemical
plant.
By kind permission of Bayer
MaterialScience AG.

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 (Figure
4) 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.

Figure 5 The mercury cell and

decomposer.

The chlorine is led off as shown in

Figure 5.

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 (Figure 5) 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 (Figure 6), 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.

Figure 6 The diaphragm cell.

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
2) 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

construction relatively
expensive
costs cheap

toxic
mercury frequent
must be asbestos
operation
removed diaphragm
from replacement
effluent

high
NaOH less pure
purity
product 12%-needs
50%-as
concentration concentration
required

typical cell
energy
consumption
3 360 2 720
(kw hours per
tonne of
chlorine)

steam
consumption
nil high
per caustic
evaporation

purity of
important important
brine

Table 2 Comparison of the three

cells.

Figure 7 The large vessel is

known as a Horton sphere.
They are used in the chemical