Basic ion exchange processes

in water treatment
Introduction
The ion exchange technology is used for different water treatment applications:

Softening (removal of hardness)

De-alkalisation (removal of bicarbonate)

Decationisation (removal of all cations)

Demineralisation (removal of all ions)

Mixed bed polishing

Nitrate removal

Selective removal of various contaminants

You will find here a description of the above processes, the exchange reactions and the changes in
water. Resin types are described in another page, as well as regeneration methods. See also the
general introduction to ion exchange, and an overview of ion exchange column designs in other pages.

Softening
Natural water contains calcium and magnesium ions (see water analysis) which form salts that are
not very soluble. These cations, together with the less common and even less soluble strontium
and barium cations, are called together hardness ions. When the water evaporates even a little,
these cations precipitate. This is what you see when you let water evaporate in a boiling kettle on
the kitchen stove.
Hard water also forms scale in water pipes and in boilers, both domestic and industrial. It may
create cloudiness in beer and soft drinks. Calcium salts deposit on the glasses in your dishwasher if
the city water is hard and you have forgotten to add salt.
Strongly acidic cation exchange resins (SAC, see resin types) used in the sodium form remove these
hardness cations from water. Softening units, when loaded with these cations, are then
regenerated with sodium chloride (NaCl, table salt).
Reactions
Here the example of calcium:

2 R-Na + Ca++

R2-Ca + 2 Na+

R represents the resin, which is initially in the sodium form. The reaction for magnesium is
identical.
The above reaction is an equilibrium. It can be reversed by increasing the sodium concentration on
the right side. This is done with NaCl, and the regeneration reaction is:
R2-Ca + 2 Na+

2 R-Na + Ca++

What happens to the water

SAC (Na)

Raw water

Softened water

The water salinity is unchanged, only the hardness has been replaced by sodium. A small residual
hardness is still there, its value depending on regeneration conditions.
Uses
Examples for the use of softeners:

Treatment of water for low pressure boilers

In Europe, most dishwashers have a softening cartridge at the bottom of the machine

Breweries and soft drink factories treat the water for their products with food grade resins

Softening the water does not reduce its salinity: it merely removes the hardness ions and replaces
them with sodium, the salts of which have a much higher solubility, so they don't form scale or
deposits.

De-alkalisation
This particular process uses a weakly acidic cation resin. This resin type is capable of removing
hardness from water when it also contains alkalinity. After treatment, the water contains carbon
dioxide, that can be eliminated with a degasifier tower. The cation resin is very efficiently
regenerated with an acid, usually hydrochloric acid.

Reactions
Here the example of calcium:
2 R-H + Ca++(HCO3)2

R2-Ca + 2 H+ + 2 HCO3

and the hydrogen cations combine with the birarbonate anions to produce carbon dioxide and
water:
H+ + HCO3

CO2 + H2O

What happens to the water

WAC (H)

Raw water
Decarbonated water
Recombination of hydrogen and bicarbonate and removal of carbon dioxide with the degasifier:

DEG

Decarbonated water
The salinity has decreased. Temporary hardness is gone.
Uses
De-alkalisation is used:

In breweries

In household drinking water filters

For low pressure boilers

As a first step before the SAC exchange in demineralisation

Degassed water

De-alkalisation reduces the salinity of water, by removing hardness cations and bicarbonate
anions.

Decationisation
The removal of all cations is seldom practiced, except as a first stage of the demineralisation
process, or sometimes in condensate polishing where the decationiser precedes a mixed bed unit.
A strongly acidic cation exchange resin (SAC) is used in the H + form.
Reactions
Here the example of sodium, but all cations react in the same way:
R-H + Na+

R-Na + H+

The equilibrium reaction is reversed for regeneration by increasing the hydrogen concentration on
the right side. This is done with a strong acid, HCl or H2SO4:
R-Na + H+

R-H + Na+

What happens to the water

SAC (H)

Raw water

DEG

Decationised water

Decat + degassed water

In the second step, a degasifier is used again to remove the carbon dioxide formed by combining
the bicarbonate anions and the released hydrogen cation. The water salinity is reduced, and the
water is now acidic. A small sodium leakage is shown.

Demineralisation
For many applications, all ions in the water must be removed. In particular, when water is heated
to produce steam, any impurity can precipitate and cause damage. As there are cations and anions
in the water, we must use two different types of resins: a cation exchanger and an anion
exchanger. This combined arrangement produces pure water, as presented in the general
introduction. Demineralisation is also called deionisation. The cation resin is used in the hydrogen

form (H+) and the anion resin in the hydroxyl form (OH ), so that the cation resin must be
regenerated with an acid and the anion resin with an alkali.
A degasifier is used to remove the carbon dioxide created after cation exchange when the water
contains a significant concentration of bicarbonate.
The cation resin is usually located before the anion resin: otherwise if the water contains any
hardness, it would precipitate in the alkaline environment created by the OH form anion resin as
Ca(OH)2 or CaCO3, which have low solubility.

Layout SAC (DEG) SBA

Let us first consider a simple deminineralisation system comprising a strong acid cation exchange
resin in the H+ form, a degasifier (optional) and a strong base anion exchange resin in the OH
form. The first step is decationisation as shown above:
RSAC-H + Na+

RSAC-Na + H+

With calcium instead of sodium (also valid for magnesium and other divalent cations):
2 RSAC-H + Ca++

(RSAC)2-Ca + 2 H+

In the second step, all anions are removed with the strong base resin:
RSBA-OH + Cl

RSBA-Cl + OH

The weak acids created after cation exchange, which are carbonic acid and silicic acid (H 2CO3 and
H2SiO3) are removed in the same way:
RSBA-OH + HCO3

RSBA-HCO3 + OH

And finally, the H+ ions created in the first step react with the OH ions of the second step to
produce new molecules of water. This reaction is irreversible:
H+ + OH

H2O

What happens to the water

Cation exchange (as in the decationisation process above):

SAC (H)

Raw water

DEG

Decationised water

Decat + degassed water

Anion exchange:

SBA (OH)

Decat + degassed water

Demineralised water

Demineralised water is completely free of ions, except a few residual traces of sodium and silica,
because the SAC and SBA resins have their lowest selectivity for these. With a simple
demineralisation line regenerated in reverse flow, the treated water has a conductivity of only
about 1 S/cm, and silica residual between 5 and 50 g/L depending on the silica concentration in
the
feed
and
on
regeneration
conditions.
Note that the pH value should not be used as a process control, as it is impossible to measure the
pH of water with less than say 5 S/cm conductivity.
Regeneration
The SAC resin is regenerated with a strong acid, HCl or H 2SO4:
R-Na + H+

R-H + Na+

And the SBA resin is regenerated with a strong alkali, NaOH in 99 % of the cases:
RSBA-Cl + OH

RSBA-OH + Cl

Layout WAC/SAC DEG WBA/SBA

Because weakly acidic and weakly basic resins offer a high operating capacity and are very easy to
regenerate, they are used in combination with strongly acidic and strongly basic resins in large
plants. The first step with the WAC resin is dealkalisation (removal of bicarbonate hardness), and
the second step with the SAC removes all the remaining cations. A WAC resin is used when both
hardness and alkalinity are present in large relative concentrations in the feed water.
WBA resins remove only the strong acids after cation exchange. They are not capable of removing
the weak acids such as SiO 2 and CO2. In the regenerated, free base form, they are not dissociated,
so no free OH ions are available for neutral anion exchange. On the other hand, their basicity is
enough to adsorb the strong acids created after cation exchange:
RWBA + H+Cl

RWBA.HCl

In the last step, a SBA resin is thus required to remove the weak acids, as shown in the preceding
section:
RSBA-OH + HCO3

RSBA-HCO3 + OH

What happens to the water

Cation exchange beginning with dealkalisation followed by the removal of all remaining cations:

WAC (H)

SAC (H)

Raw water
Decarbonated water
Decationised water
Anion exchange begins with the removal of strong acids after degasification:

WBA (FB)

Decat + degassed water

SBA (OH)

Partially demineralised

Demineralised water

A full demineralisation line is shown below, with a cation exchange column (WAC/SAC), a
degasifier, an anion exchange column (WBA/SBA), and a polishing mixed bed unit. The use of a
weakly acidic resin and the degasifier column are conditioned by the presence of hardness and
alkalinity in the feed water, as explained in the previous sections.

A demineralisation line (click to enlarge)

Regeneration
Regeneration is done in thoroughfare, which means that the regenerant first goes through the
strong resin, which requires an excess of regenerant, and the regenerant not consumed by the
strong resin is usually sufficient to regenerate the weak resin without additional dosage.
The cation resins are regenerated with a strong acid, preferably HCl, because H 2SO4 can
precipitate
calcium.
The anion resins are regenerated with caustic soda.

Regeneration of the demineralisation line (click to enlarge)

The quality obtained is the same as in the simple SAC-SBA layout, but because the weak resins are
practicallly regenerated "free of charge", the regenerant consumption is considerably lower.
Additionally, the weak resins have a higher operating capacity than the strong resins, so the total
volume of ion exchange resins is reduced.
Uses
Examples of demineralisation:

Water for high pressure boilers in nuclear and fossil fuelled power stations and other
industries

Rinse water used in production of computer chips and other electronic devices

Process water for many applications in the chemical, textile and paper industries

Water for batteries

Water for laboratories

Mixed bed polishing

Mixed
bed
unit
in
service
and in regeneration
The last traces of salinity and silica can be removed on a resin bed where highly regenerated
strong acid cation and strong base anion resins are mixed.
Mixed bed units deliver an excellent treated water quality, but are complcated to regenerate, as
the resins must first be separated by backwashing before regeneration. Additionally, they require
large amounts of chemicals, and the hydraulic conditions for regeneration are not optimal.
Therefore, mixed beds are usually only used to treat pre-demineralised water, when the service
run is long.
What happens to the water
Practically nothing is left:

SAC (H) + SBA (OH)

Demineralised water

Nothing is left

Mixed bed polishing produces a water with less than 0.1 S/cm conductivity. With sophisticated
design and appropriate resins, the conductivity of pure water (0.055 S/cm) can be achieved.
Residual
silica
values
can
be
as
low
as
1
g/L.
The pH value should not be used as a process control, as pH meters are unable to operate at 1
S/cm conductivity or below.
Uses

Treatment of water pre-demineralised with ion exchange resins

Polishing of reverse osmosis permeate

Polishing of sea water distillate

Treatment of turbine condensate in power stations

Treatment of process condensate in various industries

Production of ultra-pure water for the semiconductors industry

Service de-ionisation (with off-site regenerated columns)

Nitrate removal
Nitrate can be removed selectively from drinking water using strong base anion resins in the
chloride cycle, i.e. regenerated with a NaCl brine. The reaction is:
RSBA-Cl + NO3

RSBA-NO3 + Cl

What happens to the water

SBA (Cl)

Raw water

Denitrated water

Conventional SBA resins can be used, but they also remove sulphate from water. See the selectivity
table. Depending on the resin type, some (selective resins) or all (non-selective) sulphate is
removed. Bicarbonate is only removed partially at the beginning of the service run.
Uses

Mainly municipal water treatment

Selective removal of various other contaminants

Selective removal of metals and other contaminants is mainly used for drinking water and for
waste. Many of these applications require special resins: chelating resin making stable metal
complexes, for instance.
Examples

Removal of boron (boric acid) from drinking water

Removal of nitrate from drinking water (shown above)

Removal of perchlorate from drinking water

Removal of heavy metals from waste: Cd, Cr, Fe, Hg, Ni, Pb, Zn

In many of these applications, a residual concentration in the g/L range is possible.

Some contaminants are difficult to remove with ion exchange, due to a poor selectivity of the
resins. Examples: As, F, Li. See the periodic system of the elements with some ion exchange data.
See also the page about resin types (selective resins) and a separate page about ion exchange
processes for drinking water.

Other information
Abbreviations
Resin types are usually abbreviated in these pages:

SAC: strongly acidic cation exchange resin

WAC: weakly acidic cation exchange resin

SBA: strongly basic anion exchange resin

WBA: weakly basic anion exchange resin

See a table with a complete list of abbreviations and units.

Water
See details about the water analysis as required
A special page is available about drinking water applications.

for

the

above

processes.

Ion
exchange
Various column types are described in a separate page. Degasifiers as well.
Regeneration
See details about regeneration processes, quantities and concentrations of regenerants.

columns

Ion
exchange
A full page describes reaction equilibrium and chemical reactions of these resins.

reactions