Technology Profile

Chlorine Production from NaCl (Chlor-Alkali)

By Intratec Solutions

hlorine is among the most important chemical commodities

it is used in the manufacture
of a multitude of end products (for example, plastics, solvents, pesticides,
pharmaceuticals, disinfection chemicals
and others), as well as in processes
that produce industrial chemicals via
organochlorine intermediates, such
as polycarbonates, silicones, polyurethanes and others.

The process
The following describes chlorine production by the electrolysis of aqueous
sodium chloride (brine) using a conventional membrane process (Figure 1).
Brine purification. Initially, recycled,
depleted brine is mixed with water and
re-saturated with fresh sodium chloride. Since other metal ions (such as
Ca2+ and Mg2+) present in the brine
would harm the membranes, the brine
is treated with precipitants, so that the
metals precipitate. The precipitated
solids form a sludge, which is removed
by settling in a clarifier. Subsequently,
the clarified solution is filtered and purified by ion-exchange resins to remove
residual hardness and achieve acceptable levels of Ca2+ and Mg2+ ions.
Electrolysis. The ultrapure brine and
electricity are the main inputs for the
electrolysis section. The brine is fed
into the anolyte compartments (electrolyte near the anode) of the electrochemical cells. These are separated
from the catholyte by cation-exchange
membranes. Chlorine gas is generated at the anodes and sodium ions
migrate through the membranes into
the catholyte solution. The depleted
Sodium
chloride

Water

Precipitants

NaCl, electricity

Electrolysis
(membrane)

NaCl, electricity

Electrolysis
(diaphragm)

NaCl, electricity

Electrolysis
(mercury)

HCl, electricity

Oxidation

HCl, oxygen

Chlorine

n Raw material n Process n Main product

FIGURE 2. Several viable pathways exist for industrial chlorine production

brine from the anode compartments is

dechlorinated downstream and then
returned to the brine saturation step.
On the catholyte side, water is electrolyzed, generating H2 gas and hydroxyl (OH) ions. Membranes prevent
the migration of OH ions into the anolytes, in such a way that hydroxyl ions
combine with the sodium ions to form
caustic soda (NaOH). The addition of
demineralized water keeps the catholyte concentration at the desired level.
Product recovery. Hydrogen from
the electrolysis process is compressed for sale to consumers. The
caustic soda solution is concentrated
to a saturated 50 wt.% NaOH solution the traditional commercial form
of the material. The Cl2 gas produced
is sent to drying towers where concentrated sulfuric acid circulates as a
dehydrating agent. The dry Cl2 gas is
compressed and liquefied before being sent to storage.

Chlorine pathways
Most chlorine produced at commercial scale is based on electrolysis of
aqueous sodium chloride (chlor-alkali
process). Aside from the process described above, electrolytic production
of chlorine can be accomplished by
two other basic processes: diaphragm
cell and mercury cell processes. Fig-

ure 2 shows these electrochemical

processes and other pathways for
chlorine production.

Economic performance
The total capital investment estimated to be required to construct
a plant with a capacity of 500,000
metric tons per year of chlorine in
the U.S. is about $820 million (data
from the first quarter of 2014). The
capital investment includes fixed
capital, working capital and additional capital requirements. The production costs (raw materials, utilities,
fixed costs, corporate overhead and
depreciation costs) are about $500
per metric ton of chlorine produced
(credits from sales of hydrogen and
caustic soda co-products were not
taken into account).
This column is based on Chlorine
Production from Sodium Chloride
Cost Analysis, a report by Intratec.
It can be found at: www.intratec.us/
analysis/chlorine-production-cost. n
Edited by Scott Jenkins
Editors note: The content for this column is supplied by Intratec Solutions LLC (Houston; www.intratec.us) and edited
by Chemical Engineering. The analyses and models presented
are prepared on the basis of publicly available and nonconfidential information. The content represents the opinions
of Intratec only. More information about the methodology for
preparing analysis can be found, along with terms of use, at
www.intratec.us/che.

Demineralized
water

Hydrogen

Electrolysis

Chlorine

10

4
Residues

Water vapor

ST

Caustic soda
(50 wt.%)
8

ST

11

CW

12

6
RF

13

1. Brine saturation
2. Precipitation
3. Filtration
4. Ion exchange
5. Electrolysis
6. Dechlorination
7. H2 compression
8. NaOH evaporation
9. CI2 drying
10. CI2 liquefaction
11. Steam boiler
12. Cooling tower
13. Refrigeration unit
CW Cooling water
ST Steam
RF Refrigerant

FIGURE 1. The above diagram shows chlorine production by the electrolysis of aqueous sodium chloride via a conventional membrane process
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AUGUST 2016

39