September 1995 Vol. 1 No.

Electrochemical Salt Splitting

by David Genders

Salt splitting is a relatively new technology dependent on the availability of modern

membranes. Its development has usually been driven by one of two major factors,
both environmentally based. The first is the desire to produce caustic soda without
the co-production of chlorine, and the second is the increased cost of disposing of
heavily laden salt solutions.

Caustic is in Demand

Caustic soda is produced in the USA at a rate of 14 million tons per year, almost
entirely by the electrolysis of brine. In this process chlorine is produced at the anode
and caustic soda at the cathode in stoichiometric quantities. There is a growing
awareness of the need for new processes for the manufacture of high purity sodium
hydroxide that do not lead to co-production of chlorine. This requirement exists
because the chlorine and sodium hydroxide markets are rarely in balance. Despite
the high demand for chlorine in the last two years, it is still expected that
environmental pressures on chlorine will lead to an increased demand for caustic
over the coming decade. Predictions are for a long-term trend in which the demand
for sodium hydroxide will outstrip that for chlorine. Several present markets for
chlorine are expected to experience significant downturns due to environmental
pressures or concerns about health hazards; these include pulp and paper
bleaching, fluorocarbons, water treatment and chlorinated hydrocarbons. At the
same time, the demand for sodium hydroxide is predicted to continue to grow.
Another trend is towards modular plants that allow the manufacture of chemicals on
various scales including generation on a relatively small scale at the site of use.

Recycling Process Streams

Increasingly, environmental regulations are putting more stringent limitations on the

amount of solid and liquid waste that may be discharged. Recycling salt solutions as
acids and bases not only avoids a waste disposal problem, but also provides credit
in lieu of the raw material that would otherwise need to be purchased.

Splitting Sodium Sulfate to Caustic and Sulfuric Acid

Sodium sulfate can be effectively split electrochemically into sulfuric acid and
sodium hydroxide in a three compartment cell (1) such as shown schematically in
Figure 1.

72 Ward Road, Lancaster, NY 14086
Tel: 716-684-0513,
[email protected]
www.electrosynthesis.com

 September 1995 Vol. 1 No. 1

Sodium sulfate is passed through the central compartment; under the influence of
the potential field, the sulfate is transported through the anion permeable
membrane into the anolyte and sodium ions pass through the cation permeable
membrane into the catholyte. The anode and cathode reactions generate proton
and hydroxide respectively and hence the sulfuric acid and caustic soda accumulate
in the anolyte and catholyte. One of the limitations of this approach is the
concentrations of acid and base that can be efficiently formed in the cell. As the acid
concentration builds in the anolyte compartment, the current efficiency for the
process drops markedly. This loss in current efficiency is primarily due to the back
migration of protons from the anolyte compartment across the anion exchange
membrane into the central compartment. This makes the pH in the central
compartment acidic, thereby also reducing the current efficiency for production of
sodium hydroxide. The back migration of protons across anion exchange
membranes is well known and several manufacturers have developed membranes
specifically designed to minimize this leakage. One such membrane is Tokuyama
Neosepta ACM. However, even with these specialty membranes the pH in the
central compartment still drops.

One of the consequences of having a low pH in the central compartment is a

limitation on the type of cation exchange membrane that can be used. High
performance, bilayer cation exchange membranes (for example DuPont Nafion®
902) contain perfluorinated polymers with sulfonic acid exchange groups on one
side and carboxylic acid exchange groups on the other side. The weak acid
exchange material limits the back migration of hydroxide ions during the production
of caustic allowing higher caustic concentrations (32% by weight) to be reached at
good current efficiencies. However, to maintain conductivity in the membrane, the
carboxylic acid functionality must not become protonated. Since these weak acid
exchange groups have a pKa of 2 - 3, the pH in the central compartment cannot be

72 Ward Road, Lancaster, NY 14086
Tel: 716-684-0513,
[email protected]
www.electrosynthesis.com

 September 1995 Vol. 1 No. 1

such that a significant portion of the charge is carried by protons. If the central
compartment does become acidic, then membranes with strong acid exchange
groups must be used (for example DuPont Nafion® 324 or 350). This limits the
caustic concentration that can be achieved at good current efficiency to 15 - 20% by
weight.

Salt Splitting To Caustic and Ammonium Sulfate

Several strategies have been used to mediate the effects of proton back migration.
A good example of this is found in technology developed at The Electrosynthesis
Company (ESC) in conjunction with Ormiston Mining (2). Figure 2 shows a
schematic of a process in which the products are caustic soda and ammonium
sulfate. Clearly, one advantage of such a process is that protons generated at the
anode are neutralized by the addition of ammonia gas. This prevents the central
compartment from becoming acidic and, therefore, improves the current efficiency
for caustic production. In addition, the possibility exists for using high performance
bilayer membranes to make higher product concentrations directly in the
electrochemical cell. The anode product in this process, ammonium sulfate, is used
extensively as a fertilizer.

The process operates efficiently producing high concentrations of caustic soda and
ammonium sulfate. The cell is operated in a three compartment mode separated by
a Neosepta® AMH anion exchange membrane from Tokuyama and a Nafion 902
bilayer cation exchange membrane from DuPont. The pH of the anolyte is
maintained between 1 and 2. The cell operates at current densities of up to
2.5 kA m-2 producing 32% caustic at current efficiencies in excess of 95%.

72 Ward Road, Lancaster, NY 14086
Tel: 716-684-0513,
[email protected]
www.electrosynthesis.com

 September 1995 Vol. 1 No. 1

Bipolar Membranes

An alternative method for salt splitting utilizes bipolar membranes (3). These
membranes allow for the formation of hydroxide and protons from the splitting of
water without the coproduction of hydrogen and oxygen. Figure 3 shows a diagram
of part of a cell stack using this technology. A typical stack may have >100 bipolar
membranes with assorted anion and cation membranes between a pair of
electrodes. This technology has the advantage of reduced power requirements and
potentially cheaper cell stacks. However, to date these membranes still suffer
stability problems as well as unwanted transport across the membrane interface. In
the above example, the latter would lead to sulfate contamination in the caustic
stream, or sodium contamination in the sulfuric acid stream.

Gas Diffusion Electrodes

Power cost is almost always an important consideration in electrochemical salt

splitting operations. One approach to reducing this, through lower cell voltages, is to
use a hydrogen depolarized anode. In these cells the hydrogen gas produced at the
cathode is returned to the anode and oxidized to protons at a gas diffusion
electrode. This technique can lower the cell voltage by over a volt. The Hydrina™
process piloted by DeNora (4) is a good example of this. Here a cation exchange
membrane is also placed immediately adjacent to the anode to prevent the anode
from flooding under the hydraulic head of the electrolyte solutions.

72 Ward Road, Lancaster, NY 14086
Tel: 716-684-0513,
[email protected]
www.electrosynthesis.com

 September 1995 Vol. 1 No. 1

Caustic Without Chlorine

Processes that produce caustic soda without the coproduction of chlorine afford the
opportunity to redress the balance in caustic chlorine production. We have already
discussed the importance of power costs in the economics of such processes and it
therefore follows that any process that produces caustic as a commodity chemical
must operate at a very low overall cell voltage. This point is particularly important
when an economic credit for waste disposal of a salt cannot be taken.

The Electrosynthesis Company has been developing a process for the production of
caustic from sodium carbonate that is expected to meet these requirements (5). The
basis of the technology is shown in Figure 4. The process takes advantage of gas
diffusion electrode technology to accomplish low cell voltages; moreover, the high
anolyte pH allows additional power savings. Figure 5 shows current potential curves
for the oxidation of hydrogen at a platinum catalyzed gas diffusion electrode. As
would be expected, there is a considerable voltage advantage realized by running
the electrode in a basic environment compared to the acidic electrolyte. The
potential of the electrode in the carbonate solution is controlled by the pH of the
electrolyte at the catalyst site. Hence at higher current densities, the protons are
formed more rapidly, sending the pH within the electrode structure more acidic.
Clearly, in designing electrodes for this process one would fabricate the structure
such that the highest pH is maintained at the catalyst surface.

72 Ward Road, Lancaster, NY 14086
Tel: 716-684-0513,
[email protected]
www.electrosynthesis.com

 September 1995 Vol. 1 No. 1

The process is able to produce high purity caustic at concentrations up to 32% at

current densities of 2.5 kA m-2 with a cell voltage of less than 1.6 volts. This
corresponds to a total power consumption of less than 1200 kWHr/ton of caustic.
Table 1 shows a comparison of the power consumptions required for several caustic
producing technologies.

Table 1: Power Consumption for the Production of 1Ton of Caustic

Process Power (kWHr/T)

Chloralkali <2300
ESC/Ormiston Three
600-4000
Compartment Cell
Hydrina™ 1700-2000
ESC Caustic without Chlorine
1200
Process

72 Ward Road, Lancaster, NY 14086
Tel: 716-684-0513,
[email protected]
www.electrosynthesis.com

 September 1995 Vol. 1 No. 1

Salt Splitting of other Inorganic and Organic Salts

Obviously, electrochemical salt splitting has much wider applications and may be
appropriate to virtually any salt providing the economics are favorable. Salts, MX,
could include those for example where M is Li+, Na+, K+, ammonium, quaternary
ammonium; and where X is halide, nitrate, phosphate, borate, formate, acetate, etc.

Using membranes to affect this type of conversion avoids the generation of a salt
thereby eliminating a waste disposal problem. The use of conventional electrodes in
this type of salt splitting will require being sure that the inorganic salt or organic
acids are not oxidized at the electrode. In many cases additional membranes or
bipolar membranes are used to avoid this unwanted oxidation.

An example of this type of salt splitting is the recovery of lactic acid from sodium
lactate (6). The latter is produced from starch in a fermentation process and the
lactic acid is traditionally isolated through several liquid extraction steps, an
esterification process and an ion exchange process. All of these steps are replaced
in the electrochemical process by use of a salt splitting cell incorporating bipolar
membranes. This process is currently being operated in Japan.

Conclusions

Salt splitting processes have been around for several decades. During that time
considerable advances have been made in bringing the power requirements down to
a viable level. However, a successful technology for treatment of sodium sulfate
wastes will likely require additional economic incentives such as the coproduction of
a saleable product (for example ammonium sulfate), or credits for the elimination of
a waste stream. Technologies for the production of commodity quantities of caustic
will need to rely on very low power costs and an increasing imbalance in caustic
chlorine production. Recent increases in the price of caustic should maintain a high
level of interest in these technologies. Moreover, the trend toward modular on-site
production of chemicals will facilitate the implementation of electrochemical
technologies.

72 Ward Road, Lancaster, NY 14086
Tel: 716-684-0513,
[email protected]
www.electrosynthesis.com

 September 1995 Vol. 1 No. 1

References

1 J.P.Millington in Ion Exchange Membranes, D.S.Flett, Ed., p195,

. (1983).
2 J.Thompson and D.Genders, "Process for Producing Sodium
. Hydroxide and Ammonium Sulfate from Sodium Sulfate", US Patent
5,098,532, (March 1992).
3 W.Johnson, "Properties and Applications of a Novel Bipolar
. Membrane", Fourth Forum Proceedings, published by The
Electrosynthesis Company, Inc. (1990).
4 G.Faita, "Caustic Soda without Chlorine Production", Seventh Forum
. Proceedings, published by The Electrosynthesis Company, Inc.
(1993).
5 D.Pletcher, J.D.Genders, N.L.Weinberg, E.F.Spiegel, "Electrochemical
. Methods for the Production of Alkali Metal Hydroxides without the Co-
production of Chlorine", US Patent 5,246,551, (September, 1993).
6 F.Lutin, F.Hanada, "Production of Organic Acids with Bipolar
. Technology", presented at Electrochemical Processing - A Clean
Alternative, Toulouse 1995, proceeding published by ICI C&P.

Dr. David Genders is President at The Electrosynthesis Company, Inc. Current

research activities range from electrosynthesis to salt splitting and from sensors to
batteries. Dr. Genders has co-authored ten patents while at The Electrosynthesis
Company and has recently edited two popular books on electrochemistry:
Electrosynthesis - From Laboratory to Pilot to Production and Electrochemistry For A
Cleaner Environment. Both books are available from The Electrosynthesis Company.

Salt splitting applications are not limited to those discussed in this article. If you
have an application that you consider may benefit from electrochemical salt
splitting, please send e-mail to [email protected].

72 Ward Road, Lancaster, NY 14086
Tel: 716-684-0513,
[email protected]
www.electrosynthesis.com