Membrane Cell

technology

Prepared by: Deep Shah

Guided by: Dr. Ranjan Sengupta

Content
Introduction
Procedure of Membrane Cell
Development of Membranes

Introduction

The chlor-alkali industry is the industry that produces chlorine (Cl2) and
alkali, sodium hydroxide (NaOH) or potassium hydroxide (KOH), by
electrolysis of a salt solution. The main technologies applied for chloralkali production are mercury, diaphragm and membrane cell
electrolysis, mainly using sodium chloride (NaCl) as feed or to a lesser
extent using potassium chloride (KCl) for the production of potassium
hydroxide.
The diaphragm cell process (Griesheim cell, 1885) and the mercury cell
process (Castner-Kellner cell, 1892) were both introduced in the late
1800s.
The membrane cell process was developed much more recently (1970).
Each of these processes represents a different method of keeping the
chlorine produced at the anode separate from the caustic soda and
hydrogen produced, directly or indirectly, at the cathode. Currently,
95% of world chlorine production is obtained by the chlor-alkali process.
D.E.Goldman

The membrane cell process has inherent ecological advantages over

the two older processes, as it does not use mercury or asbestos, and
it is the most energy efficient process.

Despite these advantages, the change of technology to membrane

cells has been slow in western Europe because most existing chlorine
plants were installed in the 1970s with a plant life of 40-60 years and
there has been no need for new production capacity. Nor has there
been a legislativedrive to change technology.

With the inputs/outputs of the chlor-alkali sector, it is also relevant to

point out the special importance of safety aspects related to
production, handling and storage of chlorine.

D.E.Goldman

Three production methods are in use. While themercurycell

method produces chlorine-free sodium hydroxide, the use of
several tonnes of mercury leads to serious environmental
problems.
In a normal production cycle a few hundred pounds of mercury
per year are emitted, which accumulate in the environment.
Additionally, the chlorine and sodium hydroxide produced via the
mercury-cell chloralkali process are themselves contaminated with
trace amounts of mercury.
The membrane and diaphragm method use no mercury, but the
sodium hydroxide contains chlorine, which must be removed.

D.E.Goldman

Procedure

Basic membrane cell used in theelectrolysisof brine. At the

anode (A), chloride (Cl) is oxidized to chlorine. The ion-selective
membrane (B) allows the counterion Na+ to freely flow across, but
prevents anions such as hydroxide (OH) and chloride from
diffusing across. At the cathode (C), water is reduced to hydroxide
and hydrogen gas. The net process is the electrolysis of an
aqueous solution of NaCl into industrially useful products sodium
hydroxide (NaOH) and chlorine gas.
The most common chloralkali process involves the electrolysis
ofaqueoussodium chloride(abrine) in amembrane cell.
Saturated brine is passed into the first chamber of the cell where
thechlorideions areoxidisedat theanode, losing electrons to
becomechlorinegas (Ain figure):
2ClCl2+ 2e
At thecathode, positivehydrogen ionspulled from water
molecules arereducedby the electrons provided by the
electrolytic current, to hydrogen gas, releasinghydroxideions into
the solution (Cin figure):
2H2O+ 2e H2+ 2OH

The ion-permeableion exchange membraneat the center of the

cell allows thesodiumions (Na+) to pass to the second chamber
where they react with the hydroxide ions to producecaustic
soda(NaOH) (Bin figure). The overall reaction for the electrolysis
of brine is thus:
2NaCl + 2H2OCl2+H2+ 2NaOH
A membrane cell is used to prevent the reaction between the
chlorine and hydroxide ions. If this reaction were to occur the
chlorine would bedisproportionatedto form chloride
andhypochloriteions:
Cl2+ 2OH Cl+ ClO+H2O
Above about 60C,chloratecan be formed:
3Cl2+ 6OH 5Cl+ClO3+ 3H2O
Because of the corrosive nature of chlorine production, the anode
(where the chlorine is formed) must be made from a non-reactive
metal such astitanium, whereas the cathode (where hydroxide
forms) can be made from a more easily oxidized metal such
asnickel.

In themembrane cell, the anode and cathode are separated by an

ion-permeable membrane. Saturated brine is fed to the
compartment with the catode (the anolyte).
A DC current is passed through the cell and the NaCl splits into its
constituent components. The membrane passes Na+ions to the
anode compartment (catholyte), where it forms sodium hydroxide
in solution.
The membrane allows only positive ions to pass through to
prevent the chlorine from mixing with the sodium hydroxide. The
chloride ions are oxidised to chlorine gas at the anode, which is
collected, purified and stored. Hydrogen gas and hydroxide ions
are formed at the cathode

Development of membranes

Several firms participated in the development of the membrane

cell. Conceptual studies of permselective membranes began in the
mid 1940s. W.Juda of ionics corporation, and S.G. Osborne of
hooker chemical hold early patents on the membrane cell process.
Diamond and Ionics mounted a joint effort to develop the
membrane cell from the early 1960s. This work demonstrated the
feasibility of the concept, but serious problems developed,
including erosion of anodes, high cell voltage, and very short
membrane life. The project was dormant for about 10 years.

M.Seayian and J.H.Austin,Membrane techology for existing chlor alkali plants,27th chlorine plant operation
seminar,Washington(1984)

In the late 1960s, concern over environmental problems

associated with mercury cell plants initiated a revival of interest in
the membrane cell technology. Initial problems associated with
membrane cells were steadily being alleviated in the early 1970s.
The development of metal anodes negated problems associated
with graphite anode erosion. As a spin-off of the space program,
Dupont developed a perfluorinated ion-exchange membrane while
performing fuel cell research. This membrane was initially called
XR and was later trademarked as Nafion. Nafion membranes
were found to have good ion-exchange properties as well as high
resistance to the harsh environment of the chlor-alkali cell.

M.Seayian and J.H.Austin,Membrane techology for existing chlor alkali plants,27 th chlorine plant operation
seminar,Washington(1984)

The first membrane , made from the perfluorosulfonate polymer

Nafion , were practical only at low caustic concentration , as the
caustic efficiency decreased significantly at high caustic strengths.
To overcome this problem , asymmetric membranes having sulfonic
acid groups on the anode side and converted groups on the cathode
side were developed. Later, a perfluorocarboxylate membrane ,
Flemion , which exhibited better resistance to caustic back-migration
was produced .
The low electrical resistivity of persulfonate-based membranes and
the low caustic back-migration characteristics of perfluorocarboxylate
membranes were coupled by converting the sulfonic acid groups of
Nafion to carboxylate groups on the cathode side to realize the
beneficial properties of both the membrane types.
M.Seayian and J.H.Austin,Membrane techology for existing chlor alkali plants,27 th chlorine plant operation
seminar,Washington(1984)

Thank you