Optimization of the chlor-alkali process by
online concentration measurements
Relevant for: Chemical Industry
An accurate control of the required hydrochloric acid and caustic soda concentrations through
the whole chlor-alkali process is important and can easily be accomplished with Anton Paar's
density sensor L-Dens 7400 and sound velocity sensor L-Sonic 5100.
1 Chlor-alkali process
The chlor-alkali process is an important method to
produce many basic chemicals like, hydrochloric acid,
caustic soda, chloride and hydrogen.
There are 3 existing chlor-alkali processes which are
distinguished in the different kinds of anode-cathode
materials and their type of membrane whereby the
membrane cell process is the most common one.
(Figure 1)
Figure 1: Chlor-alkali membrane cell process
The starting material for the chlor-alkali process is
sodium chloride which is used as natural brine with a
concentration of approx. 30%. In the electrolytic cell
the sodium chloride is converted to caustic soda,
chloride and hydrogen. Chloride is further processed
to 37% concentrated hydrochloric acid with water and
hydrogen. The produced caustic soda with 25-32% is
concentrated to 48-50% by evaporation.
The aim of the process is to produce caustic soda and
hydrochloric acid in pure and high concentration.
These chemicals are used in a huge variety of
products and industries as precursor materials.
XDPIA144EN-A
2 Application solution
2.1 Production of NaOH
The brine entering the electrolytic cell is monitored
with sound velocity (S) which guarantees blocking free
measurements. Constant concentration of the brine is
required to prevent quality breakdowns during the
electrolysis and to protect the membrane from
impurities.
In the electrolytical cell, current converts the brine to
chlorine (Cl2), hydrogen (H2) and caustic soda
(NaOH). In the membrane cell process the anode and
cathode are separated by a membrane which only
allows sodium and water to pass.
The membrane cell process generates pure caustic
soda which leaves the electrolysis cell with 25–32%.
Caustic soda concentration must be monitored with
density (D) or sound velocity (S) measurements to
maintain safe concentrations and not to damage the
membranes. In a subsequent evaporation step the
caustic soda solution is further concentrated to
approx. 50%, which is controlled with a density sensor
(D).
2.2 Production of hydrochloric acid
The chlor-alkali process is one of the main processes
to produce chemically pure and concentrated
hydrochloric acid, which happens in two highly
exothermic steps.
First gaseous hydrochloride gas is formed by
combustion of hydrogen and chloride, which are both
produced as byproducts the previous electrolysis. For
optimal combustion conditions and to keep the
amount of free chlorine low, the combustion takes
place with an excess of hydrogen.
Further, the hydrochloride gas is absorbed in a falling
film absorber to generate pure hydrochloric acid with a
1 www.anton-paar.com
concentration up to 37%. In the falling film absorber Sensor NaCl Temperature Accuracy
de-mineralized water absorbs the hydrochloride gas
and by the gravity the hydrochloric acid it transported [%] [°C] [%]
to a collecting tank. The concentration of the L-Sonic 5100
0 … 26 0 … 90 ±0.05
hydrochloric acid is controlled by a density (D) Version MON
measurement to assure constant quality of the pure
Sensor NaOH Temperature Accuracy
concentrated acid.
[%] [°C] [%]
L-Dens 7400
3 Measurement setups 0 … 50 0 … 100 ±0.05
Version INC

3.1 Overview 0 … 34 10 … 80 ±0.1

L-Sonic 5100
Version MON 20 … 80
Special materials and instruments are required for the 30 … 50 ±0.6
strong alkaline nature of NaOH and the corrosive area
Sensor HCl Temperature Accuracy
of HCl. Anton Paar provides the suitable technology [%] [°C] [%]
and materials for all measurements in the chlor-alkali
process. All sensors are produced with outstanding L-Dens 7400 0 … 37 0 … 80 ±0.1
conductive materials to ensure precise values Version TAN
immediately after a temperature change. Table 1: Specifications of sensors used for a chlor-alkali process

NaCl Sound velocity monitor

3.2 Process integration
The sound velocity measurement of NaCl is
performed with the L-Sonic 5100 Version MON with The L-Dens can be installed inline, directly in the main
wetted parts made of Monel, which can be installed pipe or in a bypass. Density sensors are very compact
inline. and modular and can be easily integrated in the
NaOH Density monitor tightest spaces of existing manufacturing plants.
Continuous density measurement of NaOH solutions (Figure 2)
is performed with the L-Dens 7400 Version INC
density sensor with wetted parts made of Incoloy 825,
which can be installed inline or in a bypass to the
main line
NaOH Sound velocity monitor Figure 2: Inline and bypass installation of L-Dens 7400
The sound velocity of NaOH solutions is measured
with the L-Sonic 5100 Version MON with wetted parts In Figure 3 an inline installation of L-Sonic 5100 is
made of Monel 400, using a DN 50 or ANSI 2” flange shown.
for the inline connection to the pipework or stirred
vessels.
HCl Density monitor
The density measurement of HCl is performed with
the L-Dens 7400 Version TAN with wetted parts made
of Tantalum, which can be installed inline or in a Figure 3: Inline installation of L-Sonic 5100
bypass to the main line.
4 Benefits
For all setups the temperature-compensated
concentration values are calculated automatically with ▪Real time monitoring reduces production and
the Pico 3000 transmitter.
recovery costs
▪ Best solution for continuous monitoring of all
Additionally, all sensors are available as explosion-
products maintained in a chlor-alkali process
proof version according to ATEX/ IECEx / FM / UL /
CSA for group IIA and IIB. All Sensors
▪ are maintenance-free,
Table 1 shows the sensor specifications for all points ▪ include automatic temperature compensation,
of the chlor-alkali process, other specifications are ▪ are easy to integrate and to operate.
available on demand.
Contact Anton Paar GmbH
Tel: +43 316 257-0
process@anton-paar.com | www.anton-paar.com

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