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Basic Ion Exchange Processes
Basic Ion Exchange Processes
Basic Ion Exchange Processes
in water treatment
Introduction
The ion exchange technology is used for different water treatment applications:
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
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:
SAC (Na)
The water salinity is unchanged, only the hardness has been replaced by sodium.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
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
and the hydrogen cations combine with the birarbonate anions to produce carbon dioxide and
water:
WAC (H)
DEG
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:
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:
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.
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:
With calcium insead of sodium (also valid for magnesium and other divalent cations):
In the second step, all anions are removed with the strong base resin:
The weak acids created after cation exchange, which are carbonic acid and silicic acid (H2CO3
and H2SiO3) are removed in the same way:
H+ + OH– H2O
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
And the SBA resin is regenerated with a strong alkali, NaOH in 99 % of the cases:
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:
In the last step, a SBA resin is thus required to remove the weak acids, as shown in the preceding
section:
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)
WBA SBA
(FB) (OH)
Decat + degassed
Partially demineralised Demineralised water
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.
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.
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 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.
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.
Uses
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:
SBA (Cl)
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
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
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:
Water
See details about the water analysis as required for the above processes.
A special page is available about drinking water applications.
Regeneration
See details about regeneration processes, quantities and concentrations of regenerants.