Chlor-Alkali Industry

Dependable online, inline, and atline solutions for

your process needs.
 Chlorine and Caustic Soda: Chemical Building Blocks

02 Uses of chlorine
Chlorine (Cl2) ranks number 7 on the list of the most com­­­­­
monly produced chemical substances. Since chlorine is
such an extremely reactive molecule, it is dangerous to
transport and handle after purification. Corrosive acids
can form if the purified Cl2 is exposed to moisture.

It is the ba­­sis for the production of numerous intermediate

sub­­­­­­­­­­stances, which, in turn, are important feedstock ma­­
te­­­rials in the petroleum, aluminum, paper and pulp, or
pharmaceutical industries.

For instance, chlorine is used in the production of an

impressive 80% of drugs. Polyvinyl chloride (PVC, one
of the most widely produced polymers worldwide),
isocyanates, and several chemical solvents can be made
as a result of the generation of chlorine. Another common
use is the disinfection of water sources (drinking water,
swimming pools) to protect human health.

Uses of caustic soda

Caustic soda (sodium hydroxide, NaOH) is another cru­­
cial basic chemical which enables production of or­­ga­nic
chemical products, bleach, detergents, paper, cellulose
products, and several other materials.

The Kraft Process, which is used in paper mills to con­

vert solid wood into pulp, is responsible for a consider­
able percentage of caustic soda consumption.

This product is also used frequently to adjust pH in

several production processes in many industries.
 The Chlor-Alkali Process

By far the largest part – about 95% – of the chlorine pro­­

duced globally is obtained via the chlor-alkali process. In
Safer technologies for the future
The most commonly applied electrolysis technique in
03
this process, caustic and chlorine are created together in Europe is the membrane cell technique (64%). All new
similar proportions via electrolysis of sodium (or po­­tas­ plants are based on membrane cell electrolysis of brine,
sium) chloride brine. which does not include mercury and asbestos like the
other processes.
There are three main methods used to create chlorine
and caustic from brine: In Europe, the top chlor-alkali producers are Germany,
• membrane cell process followed by France, Belgium, and the Netherlands.
• mercury cell process
• diaphragm cell process

Power Supply
Chlorine Gas (Cl2) Hydrogen Gas (H2)

Na+ ions OH-

pass through
H2 + 2OH-

membrane Na+
Cl-
Depleted brine
Cl2 + 2e-

33% NaOH
H2
CATHODE (-)
ANODE (+)

Cl2
2H2O + 2e-

OH- Caustic Soda

2Cl-

30% NaOH (NaOH) 33% NaOH

Na+
Cl-
Evaporation
Diluted Brine Diluted NaOH steps
Saturated brine
Non-permeable Ultrapure
ion exchange membrane H2O

Diagram of membrane cell technique for the production of chlorine. Adapted from www.eurochlor.org.
04

Reduce Risk with Online Process Analysis

Every minute counts Advantages of online process analysis

Performing manual sampling followed by laboratory Metrohm Applikon, with the brand of Metrohm Process
analysis can take up precious time. Inefficient and Analytics instruments, is able to offer several application
cumbersome analytical methods can also miss solutions for the chlor-alkali industry.
significant events such as ion exchange breakthrough
early on, or allow the process to be out-of-specification Process analyzers from Metrohm are designed to offer
until the next measurement is taken, whenever that may fast, reliable, accurate measurements in a rugged hous­
be. When it comes to true process optimization tactics, ing, 24/7 to ensure processes are always running within
every minute counts. specifications. Online analysis with industrial process
analyzers lessens the need for highly-skilled technical
In the membrane cell process, it is imperative that ul­ employees and saves time by automating measurements
trapure brine is used for electrolysis, otherwise the ex­ directly at the sample point. Reducing manual samp­
pensive membranes can become fouled. Even exposure ling lowers costs and increases the safety of plant
to higher levels of hardness for a short time can lead operations.
to premature membrane fouling. This causes a loss in
current efficiency which leads either to higher utility With subsidiaries located worldwide, you can rest easy
costs or lower product yields until the membrane is knowing we can support you locally, wherever you are.
eventually replaced during a scheduled shutdown.

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Applications

Process Application Notes for the Chlor-Alkali Industry 05

• Hardness in Brine.
AN-PAN-1005

Improve upon your brine treatment efficiency • Monitor hardness in brine in μg/L to mg/L with
Brine must be pretreated in several steps to reduce im­­ high-precision burette dosing & auto-calibration.
purities such as calcium and magnesium ions (hard­ness). • Available in three versions for maximum application
After primary treatment, the purified brine is passed coverage: potentiometric titration, thermometric
through an ion exchange unit to further minimize conta­ titration, or photometric measurement.
minants before the electrolysis process. • Suitable for other applications such as caustic and
carbonate in brine, hypochlorite in brine, chlorine
Accurate determination of hardness concentrations can in brine & waste streams, and much more.
estimate the efficiency of settling and resin treatments.
Upstream control of brine quality helps overcome costly
membrane remediation procedures before fouling oc­­
curs.

The 2035 Process Analyzer is the perfect solution to

monitor hardness in brine online during all stages of this
process.

The Metrohm Process Analytics 2035 Process Analyzer (L), for The 2035 Process Analyzer configured for photometric mea­
potentiometric titration of high levels of hardness in raw brine. surements (R) is ideal for monitoring low concentrations of
hardness in polished brine prior to the electrolysis process.
 Applications

06 Fast, safe moisture measurements in gases

Moisture determination in the produced gases (Cl2,
Inline near infrared spectroscopy (NIRS), with a reference
method (such as Metrohm Karl Fischer titration) is ideal
H2) is necessary to overcome corrosion in storage for this application. Near real-time analysis of low
containers and transport pipelines. Vaporization of the moisture content without chemical reagents is possible
gases after storage, without proper removal of moisture with the use of flow cells and fiber optic connections.
beforehand, can also clog the container valves and lead
to further handling issues.

• Safe, reagent-free analysis directly inline.

• NIRS XDS is capable of monitoring up to 9 different
process points with the multiplexing capability.
• Measurement technique sensitive to low levels of
moisture.
• Reference method also provided by Metrohm (Karl
Fischer titration).
• Process analyzer is available in ATEX version.

The NIRS XDS Process Analyzer from Metrohm Process

Analytics, configured for ATEX applications, with rugged flow
cells (R) for inline gas measurements.
Applications

Process Application Notes for the Chlor-Alkali Industry 07

• Online Determination of Anions in 50% NaOH and 50% KOH by IC (ASTM E1787-16).
AN-PAN-1046

Impurities in concentrated caustic with Process IC • IC is a robust analysis method suitable for measur-
ASTM method E1787-16 specifies ion chromatography ing several components in a single sample run.
to measure several anions in concentrated NaOH or • Intelligent sample preparation leads to safer analysis
KOH solutions. The many intelligent sample pre­­con­­ and more reproducible results.
ditioning techniques offered by the Metrohm Process • Measures analytes from ng/L to %.
IC make the analysis of anion impurities in con­­centrated • Optional: integration of pressureless ultrapure water
caustic solutions simple and easy to perform online. system for the most reliable automated trace analysis.

The Process Ion Chromatograph TWO from Metrohm Pro­ Model shown with the optional integrated ultrapure water
cess Analytics. Configured to analyze both anions and cations system (ELGA) and several sample preconditioning modules to
simultaneously for the most comprehensive overview of your keep the analyzer running unattended with full protection from
process. Up to 20 sample streams can be connected to a single harsh sample streams.
instrument.
Subject to change without prior notice
Layout by Alyson Lanciki, printed by Metrohm AG, CH-9100 Herisau, Switzerland
8.000.5251EN – 2019-07

www.metrohm.com