Separation Processes: Electrodialysis

Introduction
Electrodialysis (ED) is a membrane separation process that utilizes an
electrical potential difference as a driving force for moving salt ions in
solutions. The membrane is selective in that it'll only permit the
passage of either anions or cations but not both. Thus separation is
due to charge rather than size differences. This process can be used to
separate differently charged molecules of similar sizes. The process is
based on the principle that most salts that dissolved in water are ionic,
being either positively charged (cation, such as Na+, Ca2+, Mg2+) or
negatively charged (anion, such as Cl-, CO32-). These ions are attracted
to electrodes with an opposite electric charge (i.e. anion to cathode or
positively-charged electrode, and cation to anode or negatively-
charged electrode).
• In the ion-exchange membranes, charged groups are attached to the polymer
backbone of the membrane material. The fixed charged groups partially or
completely exclude ions of the same charge from the membrane. This means that an
anionic membrane with fixed positive groups excludes positive ions but is freely
permeable to negatively charged ions. Similarly, a cationic membrane with fixed
negative groups exclude negative ions but is freely permeable to
positively charged ions.
Electrodialysis cell
Characteristics
A typical ED system has up to 100 or more unit cells (cell pairs) in a plate
and-
frame arrangement where the cation and anion exchange membranes are
placed in an alternating pattern between the anode and cathode
electrodes of a direct current source.
The cation-selective and anion-selective membranes are arranged in
alternative fashion. The space (channel) bounded by the 2 different
membranes is called a cell. A unit cell or cell pair is made up of 2 cells: - the
ion-depleted cell for the passage of fresh water (the fresh water channel or
desalted water channel), and the ion-concentrated cell for the passage of
brine (the brine channel). The cells alternate between the fresh water
channel and the brine channel. Each cell is connected by its own
feed/product stream and brine stream. The unit cells and electrodes are
arranged horizontally or vertically. The entire unit is called a stack. The entire
stack is commercially available from manufacturers as such.
• Salt solution (such as seawater) enters in parallel path through all the
cells while an electric potential is maintained across the electrodes.
The positively charged cations in the solution migrate toward the
cathode, and the negatively charged anions migrate toward the
anode.
• Cations easily pass through the negative charged cation exchange
membrane but are retained by the positively charged anion exchange
membrane. Similarly anions pass through the positively charged anion
exchange membrane but are retained by the negatively charged cation
exchange membrane.
• For example, in the fresh water channel, the anions are attracted and
diverted towards the cathode, while at the same time, the cations are
 attracted and diverted towards the anode, in an opposite direction to the
movement of anions. The anions pass through the anion-selective
membrane into the brine channel. The anions cannot pass through the
next membrane because it is a cation-selective membrane. The anions are
therefore trapped in the brine channel.
• Likewise, the cations pass through the cation-selective membrane into the
brine channel. The cations are also trapped in the brine channel as the next
membrane is anion-selective.
• Thus, the freshwater channel is depleted of both cations and anions
through migration across the membranes. At the same time, the brine
channel next to the freshwater channel becomes enriched in cations and
anions.
Categories of Ion exchange membranes
 • Ion exchange membranes fall into 2 broad categories: homogeneous
and heterogeneous. Most ion exchange membranes are produced as
homogeneous films 50 - 200 mm thick. Typically the membrane is
reinforced by a net or fabric to maintain the shape and to minimise
swelling.
• In homogeneous membranes, the charged groups are uniformly
distributed through the membrane matrix. In heterogeneous
membranes, the ion exchange groups are contained in small domains
distributed throughout an inert support matrix, which provide
mechanical support.
Materials of Ion exchange membranes
Cation-selective membranes are usually made of cross-linked polystyrene (with
divinyl benzene) that has been sulfonated (with 98% sulphuric acid) to produce
sulfonate (---- SO3-) attached to the polymer.

Anion-selective membranes are usually made of cross-linked polystyrene containing

quaternary ammonium groups (----- NR3+). This can be achieved by post-treating the
polystyrene with monochloromethyl ether and aluminium chloride to introduce
chloromethyl group into the benzene ring followed by formation of quaternary
amines with trimethylamine.
Heterogeneous Membrane
• The simplest form has very finely powdered cation or anion exchange
particles uniformly dispersed in polypropylene. A much finer
heterogeneous dispersion of ion exchange particles, and consequently
a more stable membrane, can be made with a poly vinyl chloride
plastisol.
FLOW SYSTEM
 • A simplified flow system for a typical ED stack is shown in the Figure
below. An ED plant consists of several elements:
• A feed pretreatment system
• The membrane stack
• The power supply and process control unit
• The solution pumping system
Flow system
Pretreatment
• Prefilter removes large charged organic molecules and colloids such as humic acid. These
materials are particularly troublesome impurities because they are drawn by their charge
to the membrane surface but are too large to permeate. Thus they tend to accumulate at
 the dilute solution side of the membrane and precipitate.

• The type and complexity of the feed pretreatment system depend on the content of the
feedwater to be treated. Sterilization by chlorination is used to prevent bacterial growth
on the membrane. However, the chlorine must be removed (via activated carbon filters or
NaHSO3addition) before the water enters the ED stack, because chlorine degrades the
membranes. Sodium metahexaphosphate can be added to prevent membrane surface
fouling by precipitation of sparingly soluble salts such as calcium sulfate.
• After the pretreatment step, the feedwater is pumped through the ED stack. The stack
contains 100 or more membrane cell pairs each with a membrane area of 1 - 2 m 2.

Membrane Stack

• In a stack, the membrane sheets are separated from each other by spacer
gaskets. 2 membranes and 2 spacer gaskets form a simple cell pair. Holes
 in the spacer gaskets are aligned with holes in the membrane sheets to
form the manifold channels that distribute the feed to the proper
channels and remove the product and brine streams.
• The distance between membranes (i.e. the cell thickness) needs to be as
small as possible to minimise electrical resistance. The spacer maintains
the shape of the membranes, control solution flow distribution in the
stack, and minimise the film thickness on the membrane which in turn
limits the effects of concentration polarization.
• It is necessary to have uniform flow distribution in the manifold channels,
and to prevent internal leakage, particularly from the ion-concentrating cell
to the ion-depleting cell.
• The tortuous path design, a spacer gasket creates a labyrinthine flow and
extends the path length within the cell. The solution takes several 180o bends
between the entrance and exit ports locate in the middle of the spacer.
• In the sheet flow design, the solution flows in a relatively straight line from the
 entrance to the exit ports, which are located on opposite sides. If the length-to
width ratio of the spacer is sufficiently large, the entrance and exit ports can be
located at the corners.
• The end plate of the stack is a rigid, plastic frame containing the electrode
compartment. The anode is constructed of stainless steel, and the cathode is
made of platinum-coated tantalum, niobium or titanium.
• The entire arrangement is compressed together with bolts between the 2 end
flow plates. The perimeter gaskets of the gasket spacers are tightly pressed
into the membranes to form the cells.

Power Supply, Control Unit and Pumping System

• Initial ED plants are operated uni-directionally, i.e. the polarity of the 2 electrodes
and hence the position of the dilute and concentrated cells in the membrane
stack were fixed. In this mode of operation, formation of scale on the membrane
surface by precipitation of colloids and insoluble salts was often a severe
problem. Feed pretreatment is required as previously discussed.
• Most ED plants include brine recycling because this converts more feedwater to
product, i.e. higher conversion. Also, brine recycling reduces electrical
consumption because it is more conductive than the dilute feed stream.
However, brine recycling is limited by the scaling potential of raw water.
• Typical ED plants operate at 50 - 90% conversion. Conversion is controlled by the
brine re-circulation rate. ED system can operate over a broad pH (1 - 13) and
temperature range (up to 43 oC).
• ED systems use large amounts of dc power: for a 200-cell pair stack containing 1
m2 of membrane, the total voltage is about 200 - 400 V and the current is about
400 A per stack.
• The energy used in solution pumping system increases as the average
 salt concentration of the feed decreases and can become dominant in
low concentration solutions (less than 500 ppm salt). The pressure
drop per stack varies from 15 - 30 psi for sheet flow cells to as much as
70 - 90 psi for tortuous path cells.
• Depending on the separation required, the fluid will be pumped
through 2 - 4 cells in series, requiring inter-stage pumps for each stack
• Multiple ED stacks can be arranged in series or parallel. A parallel
arrangement (see Figure) is used if a higher production rate cannot be
obtained by a single ED stack. In this configuration, each stack is
connected to the feed, product and brine recycle by manifolds.
Typically each stack is controlled and monitored by its own gages and
flow meters. Although the parallel configuration increases production
rate, product quality remains the same
• Because concentration polarization becomes more important as the
solution becomes more dilute, the solution velocity increases in the
stacks processing the most dilute solution. The velocity is controlled
 by the number of cell pairs through which the solution passes in each
stack. The number of cell pairs decreases from the first to the last
stack. This is known as the taper of the system.
• Typically, large ED plants have 2 - 3 stacks in series to achieve a
product containing 500 mg/L TDS from a feed having about 3,000
mg/L TDS. Each stack removes 30 - 50% of the salt.
Concentration Polarization and Limiting Current

• Concentration polarization controls the performance of practical ED system.

Consider a salt solution in which the ions are transported across the membrane.
The resistance to ion transport in ED system can be represented by a thin film
adjacent to the membrane surface. Because ions selectively permeate the
membrane, the concentration of some of the ions in the solution immediately
 adjacent to the membrane surface becomes significantly depleted compared to
the bilk solution concentration.
• As the voltage across the stack is increase to raise the flux of ions through the
membrane, the solution next to the membrane surface becomes increasingly
depleted of the permeating ions.
• Depletion of ions at the membrane surface means that an increasing fraction of
the voltage drop is dissipated in transporting ions across the thin film rather than
through the membrane. Therefore the energy consumption per unit of ions
transported increases significantly.
• A point can be reached at which the ion concentration at the membrane
surface is zero. This represents the maximum transport rate of ions through
the thin film. The current through the membrane at this point is called the
limiting current density, i.e. current per unit area of membrane (mA/cm2).

• Once the limiting current density is reached, any further increase in voltage
 difference across the membrane will not increase ion transport or current
through the membrane.
• The limiting current density for an electrodialysis system operated at the
same feed solution flow rate is a function of the feed solution salt
concentration, as shown in the equation for a cation:
• Determining the limiting current in industrial-scale ED system is not so
easy, as the thin film thickness will vary from place to place across the
membrane surface.
• As the salt concentration in the solution increases, more ions are available
to transport current in the thin film, so the limiting current density also
increases. For this reason large ED systems with several stacks in series will
operate with different current densities in each stack reflecting the change
in the feed water concentration as salt is removed.
• In practice, systems are operated at currents substantially below the
limiting value. Concentration polarization is controlled by circulating the
solutions through the stack at a high rate.