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06 Aug 2014
Introduction
The ion exchange technology is used for different water treatment applications:
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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 RNa + Ca++
R 2Ca + 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:
R 2Ca + 2 Na+
2 RNa + Ca++
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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The water salinity is unchanged, only the hardness has been replaced by sodium.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.
Dealkalisation
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 RH + Ca++(HCO3)2
R 2Ca + 2 H + + 2 HCO3
and the hydrogen cations combine with the birarbonate anions to produce carbon dioxide and water:
H + + HCO3
CO2 + H 2O
WAC (H)
Raw water
Decarbonated water
Recombination of hydrogen and bicarbonate and removal of carbon dioxide with the degasifier:
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DEG
Decarbonated water
Degassed water
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
Top
Here the example of sodium, but all cations react in the same way:
RH + Na+
RNa + 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:
RNa + H +
RH + Na+
SAC (H)
Raw water
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DEG
Decationised water
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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.
R SACNa + H +
With calcium insead of sodium (also valid for magnesium and other divalent cations):
2 R SACH + Ca++
(R SAC)2Ca + 2 H +
In the second step, all anions are removed with the strong base resin:
R SBAOH + Cl
R SBACl + OH
The weak acids created after cation exchange, which are carbonic acid and silicic acid (H2CO3 and H2SiO3) are
removed in the same way:
R SBAOH + HCO3
R SBAHCO3 + 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
H 2O
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SAC (H)
DEG
Raw water
Decationised water
SBA (OH)
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 1S/cm, and a silica residual
between 5 and 50g/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 5S/cm conductivity.
Regeneration
The SAC resin is regenerated with a strong acid, HCl or H2SO4:
RNa + H +
RH + Na+
And the SBA resin is regenerated with a strong alkali, NaOH in 99% of the cases:
R SBACl + OH
R SBAOH + Cl
R WBA.HCl
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In the last step, a SBA resin is thus required to remove the weak acids, as shown in the preceding section:
R SBAOH + HCO3
R SBAHCO3 + OH
WAC (H)
Raw water
SAC (H)
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)
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.
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Demineralised water
Nothing is left
Mixed bed polishing produces a water with less than 0.1S/cm conductivity. With sophisticated design and
appropriate resins, the conductivity of pure water (0.055S/cm) can be achieved. Residual silica values can
be as low as 1g/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 predemineralised 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 ultrapure water for the semiconductors industry
Service deionisation (with offsite 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:
R SBACl + NO3
R SBANO3 + Cl
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 (nonselective) sulphate is removed. Bicarbonate
is only removed partially at the beginning of the service run.
Uses
Mainly municipal water treatment
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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.
Franois de Dardel
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