366 CHAPTER 10 Specialized and Advanced Water Treatment Processes

10.3 THE LIME-SODA PROCESS

P OF SOFTENING
The aim of the lime-soda process is to convert calcium and magnesium compounds to the virtually
insoluble forms, calcium carbonate (CaCO3) and magnesium hydroxide (Mg(OH)2).
Magnesium carbonate (MgCO3), unlike calcium carbonate, does not precipitate in cold water.
The stages of treatment involved are set out in Table 10.1. Lime is added to remove the temporary
hardness and soda ash is added to remove the permanent hardness. Several applications of lime
and soda ash are needed to remove magnesium hardness. In practice complete removal of hard-
ness is undesirable because this renders a water highly aggressive. Since in most hard waters the
calcium temporary hardness forms the major component it often suffices to remove only this by the
addition of lime. Caustic soda (sodium hydroxide: NaOH) can be used in place of lime for carbon-
ate and non-carbonate hardness removal; alkalinity reduction is only 50% that of lime softening.
Soda ash is formed in the reactions and sometimes it may be supplemented by soda ash addition to
remove non-carbonate hardness. The advantages of caustic soda are that it is easier to handle than
lime, only one chemical may be required and the quantity of calcium carbonate sludge produced is
less (Section 9.2). The drawbacks are its higher cost, it is a hazardous chemical, and that sodium
is added to the treated water. Chemical softening, due to its high operating pH (9.5–10.5), also
removes, by precipitation, many of the heavy metals (Section 10.14), arsenic, iron and manganese.

Table 10.1 Lime-soda softening processes

Reaction Equation number

To remove carbon dioxide in water add LIME (not a softening reaction):

H2CO3  Ca(OH))2  CaCO3  2H2O 10.1

To remove calcium temporary hardness add LIME:

Ca(HCO3)2  Ca(OH))2  2CaCO3  H2O 10.2

To remove calcium permanent hardness add SODA ASH:

CaSO4  Na2CO3  CaCO3  Na2SO4 CaCl2  Na2CO3  CaCO3  2NaCl 10.3

To remove magnesium temporary hardness add LIME more LIME, Stage 1:

Mg(HCO3)2  Ca(OH)2  MgCO3  CaCO3  2H2O 10.4

The calcium carbonate precipitates but the magnesium carbonate does not, so
further LIME is added, Stage 2:
MgCO3  Ca(OH)2  Mg(OH)2  CaCO3. 10.5
The magnesium hydroxide and calcium carbonate precipitate.

To remove magnesium permanent hardness add LIME and SODA ASH:

MgCl2  Ca(OH)2  Mg(OH)2  CaCl2 MgSO4  Ca(OH)2  Mg(OH)2  CaSO4. 10.6
The addition of soda ash then converts the calcium chloride and calcium
sulphate to calcium carbonate as in 10.3 above.

Notes: Compounds in bold are those being added and compounds in italic are those precipitating.
H2CO3—carbonic acid (carbon dioxide in water); Ca(HCO3)2—calcium bicarbonate; Ca(OH)2—calcium hydroxide (hydrated
lime); CaCO3—calcium carbonate; CaSO4—calcium sulphate; CaCl2—calcium chloride; H2O—water; Na2CO3—sodium car-
bonate (soda ash); Mg(HCO3)2—magnesium bicarbonate; Mg(OH)2—magnesium hydroxide; MgCO3—magnesium carbonate;
MgCl2—magnesium chloride; MgSO4—magnesium sulphate.
 10.5 Water Softening by Crystallisation 367

10.4 SOFTENING PLANT

Lime is used in the hydrated form, which is a dry powder and is dosed as a slurry (Section 7.20).
The soda ash is a powder and a solution is prepared for use. The concentration of saturated solution
varies with temperature (Table 7.5). Usually a solution of about 60% of the saturated concentration
at the lowest anticipated water temperature is prepared. Clarification is in hopper-bottom clarifiers
of the sludge-blanket type or solids recirculation clarifiers (Section 7.16).
An excess of up to 10% of both lime and soda ash should be added over the dose stoichio-
metrically required in order to complete the reactions in reasonable time. If magnesium is present,
a portion of it may also cause precipitation but the reaction is slower than that of calcium. Softening
reduces the hardness value to 35–50 mg/l as CaCO3. If the water to be softened contains suspended
solids and organic matter such as colour, these can be removed concurrently although coagulants
and coagulant aids have to be added. The coagulants used are usually of the iron type, because of
their high coagulation pH values, but aluminium sulphates can also be used; at high pH insoluble
magnesium aluminate and not aluminium hydroxide is formed. Normally softeners are operated at
surface loading rates in the range 3–4 m3/h.m2; when magnesium is to be removed the rates are about
2–2.5 m3/h.m2 because of the gelatinous nature of the precipitate.
The dosages of lime required for softening are high, being of the order of 100–200 mg/l. The
process produces a large amount of liquid sludge due to the precipitation of hardness and coagula-
tion of suspended solids and colour (see Sections 9.4 to 9.6 for treatment and disposal).

10.5 WATER SOFTENING BY CRYSTALLISATION

Softening reactions can be accelerated by using sand grains for seeding the crystallisation of
calcium carbonate. Softening takes place in a cylindrical reactor partially filled with filter sand
(0.2–0.6 mm). The water is injected with the softening chemical and passed upwards at a surface
loading rate of 50–120 m3/h.m2 to fluidize the sand bed. Calcium carbonate deposits on the sand
grains which grow to form pellets of about 1–2 mm in diameter and accumulate at the base of the
reactor, from where they can be periodically removed. Make up sand is added either from the top or
at the base. The reaction tanks, called pellet reactors, are typically about 6 m deep and up to 4 m in
diameter (Fig. 10.1). Lime is used when the ratio of carbonate hardness to total hardness is high; in
the intermediate hardness range caustic soda is used; and when carbonate hardness is very low soda
ash is used. Van Dijk (1991) reported that crystal growth is adversely affected when the phosphate
content of a water exceeds 0.5 mg/l as PO4 (0.15 mg/l as P). Fluffy pellets are formed when iron is
present in the water above about 1 mg/l as Fe (van der Veen, 1988).
The advantages of the pellet reactor over the conventional softening process are its high surface
loading rate, pellets are easier to handle than sludge and only a small excess of softening chemical
is required. The disadvantages of the process are that it does not remove magnesium, the hardness
after softening is in the range 50–100 mg/l as CaCO3 (van Honwelingen, 1994) and is therefore
unsuitable for most industrial uses, suspended solids in the product is high (up to 30 mg/l) and the
removal of turbidity and colour in raw water by coagulants cannot be performed in the same reactor.
However, it is therefore ideal for softening ground waters.
Lime is used as slurry of 10–100 g/l. The use of lime water (saturated lime) is not usually practical
because of its low lime content (e.g. 1.76 g/l at 10 °C); the volume to be added would be over 10% of
the volume of water to be softened. Nevertheless there are plants operating with lime water. Use of