CTB3365x – Introduction to Water Treatment

D4 – Conditioning and softening

Luuk Rietveld

How do we avoid corrosion and scaling of our water

installations?
How can we condition our water?
How do we remove hardness from drinking water?
Welcome at the lecture about conditioning and softening of
drinking water.

After this lecture you will be able to explain the motivations

for incorporating conditioning and softening into the drinking
water treatment plant design, the principles underlying
conditioning and softening processes as well as
which parameters affect the calcium carbonate equilibrium.

For all drinking water production plants, care should be taken

to obtain the calcium carbonate equilibrium to avoid scaling or
corrosion of pipe material.
For soft and desalinated waters, conditioning implies an
increase in pH, bicarbonate (HCO3-) and calcium
concentration to sufficient levels.
When water is too hard, thus having a high calcium and
magnesium concentration, the water should be softened to
avoid scaling of heating devices, like coffee machines, dish
washers, and washing machines, to diminish staining of cloths,
and soap consumption.
An additional advantage of softening is an increase in pH
which diminishes uptake of heavy metals from internal piping
material, being a benefit for public health and the
environment.

What is the optimal water composition to avoid corrosion or

scaling?
The optimal water composition is with a pH between 7.5 and
8.5 and a calcium concentration between 0.5 and 1.25
mmol/L, depending on the magnesium concentration this
gives a total hardness of about 0.75-1.5 mmol/L.
Conditioning of the water is needed when the raw water isn’t
in the range of optimal water composition.

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When the raw water has a low hardness and low pH it should
be passed through a calcium carbonate filter to dissolve
calcium and bicarbonate as well as to increase the pH.
Furthermore, when the raw water has a sufficient hardness,
but a low pH, carbon dioxide should be stripped out to
increase the pH.
Finally, when the water has a high hardness, the calcium
concentration should be diminished and pH increased. In the
Netherlands, this is done by pellet softening.

Conditioning with aeration is based on stripping carbon

dioxide out of the water.
To see the effect of stripping on water composition, the so
called Tillmans’ curve is used.
Aggressive water that has a corrosive effect on pipe material
will reach equilibrium when the concentration of carbon
dioxide isn’t too high and in equilibrium with the bicarbonate
concentration, resulting in a point on Tillmans’ curve.

Conditioning with limestone or marble filtration is based on

the dissolution of calcium carbonate in water.
This is only possible when sufficient carbon dioxide is
available.
Sometimes additional carbon dioxide dosing is required.

Limestone filtration is performed in the same way as rapid

sand filters are operated, even with the possibility for
backwashing.
However, due to the dissolution of the limestone, frequent
addition of new material is needed.

The dissolution of calcium carbonate with carbon dioxide

results in the formation of 2 moles of bicarbonate per 1 mole
of carbon dioxide, increasing the alkalinity and buffering
capacity of the water and decreasing the aggressiveness,
bringing the water into chemical equilibrium.

From the raw and clear water characteristics it is possible to

analyse what treatment was performed to condition the
drinking water.
In the example, the incoming water has a low pH, and a low
calcium and bicarbonate concentration. After treatment, the
pH, calcium concentration and bicarbonate concentration
increased.
This means that conditioning must have been performed with
limestone filtration.

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When raw water is too hard, softening should be applied.
Hardness is mostly indicated in mmol/L, but also eq/L, German
degrees, French degrees, and equivalent concentration of
calcium carbonate are used.
As said before, the optimal hardness is between 0.75 and 1.5
mmol/L.

How is softening with pellet reactors performed?

Pellet reactors consist of a fluidised bed reactor with seeding
material (sand grains), where caustic soda, lime or soda ash is
dosed.
The increase in pH results in the formation of carbonate that
crystallises with calcium on the grains/pellets.
The resulting pellets are about 1 mm in diameter, are almost
pure calcium carbonate and can be reused in industry or
agriculture avoiding the production of a waste stream.

The consequence of using small sized seeding material is that

the specific surface area for crystallisation is high, resulting in
a rapid decrease in calcium concentration.
Therefore the surface loading can be high, up to 100 m/h, and
thus the reactor surface area relatively small.
The high loadings are also needed to keep the grains and
pellets in fluidisation, avoiding cementing of the pellets.
Normally, the pellet reactors are high, higher than 5m, to
minimize super-saturation of calcium carbonate in the effluent
of the reactor, creating problems in the downstream
processes.
In practice the remaining super-saturation is neutralized by a
small acid dosing.
The minimum achievable concentration of calcium in the
effluent is about 0.5 mmol/L.
However, depending on the concentration of magnesium in
the water, the required concentration of calcium can be up to
1.25 mmol/L, leading to a total hardness of 1.5 mmol/L since
magnesium isn’t removed by the system.
In that case it is possible to treat only part of the raw water,
so-calledsplit treatment, and mix the treated water with the
raw water.
This minimizes the investment costs and can avoid the acid
dosing for pH neutralization.

Several chemicals can be used for the softening of raw water:

caustic soda, lime and soda ash.
In practice, mainly the first two are used.
The advantage of caustic soda is that it is relatively easy to
handle and reacts rapidly.
The disadvantage however is that sodium is added to the
water, which can be problematic in case of waters with a
relatively high sodium concentration.
Lime is more difficult to handle, reacts slower , leading to
higher reactors, and produces two times more pellets than
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caustic soda.
Lime is therefore only used in case of water with high sodium
concentrations and a high bicarbonate concentration, avoiding
the production of low alkalinity waters.
When water has a low alkalinity soda ash is used, because
with this chemical the water can be softened without the
decrease of the bicarbonate concentration.

When lime or caustic soda is used for softening two different

reactions take place.

First the water should be conditioned, reacting with the

aggressive carbon dioxide, and then the softening process will
take place.
This means that the water is supersaturated with calcium
carbonate, and crystallisation occurs, removing the calcium
carbonate from the solution.
These reactions can be visualised in the Tillmans’ curve.

Several types of softening reactors are on the market.

A common one is the “Amsterdam reactor” that has a flat
bottom and is about 6 m high.
The reactor is designed for the dosing of caustic soda. In
practice different reactors are placed in parallel.
This is to reduce the surface area of the individual reactors
and to promote flexibility in operation.
When the flow is varying because of seasonal fluctuations
more or less reactors can be put in operation.
In addition, when maintenance of one of the reactors is
needed, it can be taken out of operation without affecting the
production of softened water.

The most important part of the reactor is the bottom, where

the water and chemicals are dosed and distributed over the
reactor.
When dosing isn’t evenly distributed local super-saturation of
calcium carbonate can be too high and spontaneous,
homogeneous, crystallisation can occur, clogging the reactor’s
bottom.
Equal distribution of water flow is important as well to avoid
short circuiting and recirculation flows.

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In the bottom a large amount of nozzles are placed to
distribute the water and chemicals over the reactor.
Each nozzle contains both a water and chemical flow stream
outlet and is designed to create sufficient outflow turbulence
to ensure good mixing between the water and chemical
streams, without clogging the nozzles.

The softening reactors are rather high and the fluidised bed
should be as high as possible to maximise the crystallisation
surface.

To avoid the washing out of seeding material that is on the top

of the bed, the reactor widens before the water flows over the
effluent weir.
In addition, washing out of seeding material should be
diminished by avoiding rapid changes in water flow in the
reactor.
The pellets with crystallised calcium carbonate grow until sizes
of about 1 mm and sink to the lower parts of the bed.
There they can be discharged under gravity towards the pellet
storage.

When properly operated, the pellets are rather uniform.

As said before, these pellets are mostly consisting of pure
calcium carbonate with some traces of organic matter and/or
iron, giving the pellets a darker color.
During storage the excessive water is drained and afterwards
the dried pellets are transported by trucks.
Because of the pureness of the pellets, these can be used in
industry and agriculture.

Proper operation and maintenance of the pellet reactors is of

utmost importance.
When nozzles are clogged or when local, excessive, super-
saturation of calcium carbonate takes place, even artificial
stalagmites can be created in the reactor, of course disturbing
the softening process and leading to intensive maintenance
and repair activities.

Thank you for your attention and I hope to see you again for
the next lecture!