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The water salinity is unchanged, only the hardness has been replaced by sodium.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.

Treated water quality (residual hardness)

Co-flow regeneration: Depends on water composition
and regenerant level
Reverse flow regeneration: < 0.02 meq/l (1 mg/l as CaCO3)

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 Degassed water

The salinity has decreased. Temporary hardness is gone.

Treated water quality (after degasifier)

Temporary hardness Practically 0
Total hardness = FMA
pH value 6 to 7

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

SAC (H) DEG

Decat + degassed
Raw water Decationised water
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.

Treated water quality (after degasifier)

Total hardness 0
Na (co-flow regen.) 0.5 to 1 mg/L
Na (reverse flow regen.) < 0.1 mg/L
pH value 2 to 5
FMA Unchanged
CO2 0.2 to 0.3 meq/L
If hardness is not zero, there is a malfunction in≤ the system.

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 demineralisation 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 insead 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
(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– H2O

What happens to the water

1: Cation exchange removing all cations (as in decationisation) followed by degassing:

SAC (H) DEG

Decat + degassed
Raw water Decationised water
water
2: Anion exchange removing all anions (strong and weak acids):
 SBA (OH)

Decat + degassed
Demineralised water
water
Treated water quality
Conductivity (co-flow regen.) 5 to 25 µS/cm
Conductivity (reverse flow regen.) < 1 µS/cm
Silica residual (co-flow) 50 to 200 µg/L
Silica residual (reverse flow) 5 to 40 µg/L
Sodium residual See decationisation above
pH value In principle > 7
Don't use pH as a control parameter

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.
Note that the pH value should not be used as a process control, as it is impossible to measure
the pH of a water with less than say 5 µS/cm conductivity.

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

1 & 2: Cation exchange beginning with the removal of temporary hardness (WAC, as in
dealkalisation) followed by the removal of all remaining cations (SAC):

WAC (H) SAC (H)

Raw water Decarbonated water Decationised water

3 & 4: Anion exchange begining after degassing with the removal of strong acids (WBA)
followed by the removal of weak acids (SBA):

WBA (FB) SBA (OH)

Decat + degassed Partially

Demineralised water
water demineralised

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. See also Condensate polishing.
 Process water for many applications in the chemical, textile and paper industries.
 Water for batteries.
 Water for laboratories.
 Rinse water used in production of computer chips and other electronic devices.
See Ultrapure water.

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 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.
The pH value should not be used as a process control, as pH meters are unable to operate at
1 µS/cm conductivity or below.

Treated water quality

Conductivity < 0.1 µS/cm
Silica residual 1 to 10 µg/L
pH value Cannot be measured
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.

Treated water quality

Depends on water composition, regenerant level and mode of regeneration.

Use reverse flow regeneration only. Expected NO3 leakage with RFR: 2 to 10 mg/L.
Use IXCalc for accurate estimates. A high sulphate background will increase leakage.

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 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
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. Degasifiers as well, and basic principles
of plant design.

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