IX Home

Basic ion exchange processes

in water treatment Update
23 Jun 2011
Site map
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The water salinity is unchanged, only the hardness has been replaced by sodium.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
converted by Web2PDFConvert.com
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 + H2 O
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 Degassed 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
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

converted by Web2PDFConvert.com
 SAC (H) DEG

Raw water 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:
RSA C-H + Na+ RSA C-Na + H+
With calcium insead of sodium (also valid for magnesium and other divalent cations):
2 RSA C-H + Ca++ (RSA C)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 (H2CO3 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– H2 O
What happens to the water

Cation exchange (as in the decationisation process above):

SAC (H) DEG

Raw water Decationised water Decat + degassed water

Anion exchange:

converted by Web2PDFConvert.com
 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 µS/cm, and a silica residual between 5 and 50 µg/L
depending on the silica concentration in the feed and on regeneration conditions.
Regeneration
The SAC resin is regenerated with a strong acid, HCl or H2SO4:
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 SiO2 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) SBA (OH)

Decat + degassed water 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.

converted by Web2PDFConvert.com
 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 H2SO4 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

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:
Mixed bed unit in service
and in regeneration

SAC (H) + SBA (OH)

Demineralised water Nothing is left

Mixed bed polishing produces a water with less than 0.1 µS/cm conductivity. With sophisticated design and
appropriate resins, the conductivity of pure water (0.055 µS/cm) can be achieved. Residual silica values can be as
low as 1 µg/L.
Uses

converted by Web2PDFConvert.com
 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 drinkinw 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
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

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 µg/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

converted by Web2PDFConvert.com
 See details about the water analysis as required for the above processes.
A special page is available about drinking water applications.
Ion exchange columns
Various column types are described in a separate page.
Regeneration
See details about regeneration processes, quantities and concentrations of regenerants.
Ion exchange reactions
A full page describes reaction equilibrium and chemical reactions of these resins.

© François de Dardel

converted by Web2PDFConvert.com