CENG 420 – Water Treatment Lecture Note
Chapter 8 Miscellaneous treatment processes
8.1. Softening
Sedimentation and plain filtration remove only suspended and colloidal solids from raw water.
Still water contains some dissolved mineral matter like calcium, magnesium, iron, manganese,
sodium, potassium, and strontium, and so on in association with bicarbonates, carbonates,
sulphates, chlorides and nitrates. The minerals in natural water may be of alkaline, neutral and
acidic in nature. Alkaline minerals may cause alkalinity or alkalinity and hardness. The removal
of such dissolve objectionable substances from water by the addition of some chemicals to
convert them into insoluble substances is known as chemical precipitation.
Softening is the removal of hardness from water. It can be achieved by lime-soda softening or
ion exchange. Hard water is usually defined as water which contains a high concentration of
calcium and magnesium ions. Measurements of hardness are given in terms of the calcium
carbonate equivalent, which is an expression of the concentration of hardness ions in water in
terms of their equivalent value of calcium carbonate (Table 8.1).
Table 8.1 Degree of hardness
Mg/L as CaCO3 Degree of hardness
0-75 Soft
75-150 Moderately hard
150-300 Hard
> 300 Very hard
Water softening is needed when hardness is above 150-200 mg/L; Hardness 50-80 is acceptable
in treated water.
Hardness is a problem because it interferes with soaps and detergents and leaves a white crusty
scale around faucets.
Ca2+ + (soap)- Ca(soap)2
Two types of hardness can be identified- carbonate and non-carbonate hardness.
Carbonate hardness compounds Non-carbonate hardness compounds
Calcium carbonate (CaCO3) Calcium sulfate (CaSO4)
Magnesium carbonate (MgCO3) Magnesium sulfate (MgSO4)
Calcium bicarbonate (Ca(HCO3)2) Calcium chloride (CaCl2)
Magnesium bicarbonate (Mg(HCO3)2) Magnesium chloride (MgCl2)
Calcium hydroxide (Ca(OH)2)
Magnesium hydroxide (Mg(OH)2)
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AAU, FoT, Department of Civil Engineering Instructor: Zerihun Alemayehu
CENG 420 – Water Treatment Lecture Note
Carbonate hardness is sometimes called temporary hardness because it can be removed by
boiling water. Non-carbonate hardness cannot be broken down by boiling the water, so it is also
known as permanent hardness. In general, it is important to distinguish between the two types of
hardness because the removal method differs for the two.
Total Hardness (TH) = Sum of Ca2+ and Mg2+ ions measured as mg/L of CaCO3
Total Hardness (as CaCO3) = (eq/L of cation charge) x (50g CaCO3/Charge eq) x 1000mg/g
Example Hardness Calculations:
⎛ 1 mg ⎞⎛ 2 chg eq ⎞⎛ mole ⎞⎛ 50,000 mg ⎞
TH (Ca 2 + ) = ⎜ ⎟⎜ ⎟⎜⎜ ⎟⎟⎜⎜ ⎟⎟ = 2.50 mg asCaCO3
⎝ L ⎠⎝ mole ⎠⎝ 40,000 mg ⎠⎝ chg eq ⎠ L
⎛ 1 mg ⎞⎛ 2 chg eq ⎞⎛ mole ⎞⎛ 50,000 mg ⎞
TH ( Mg 2 + ) = ⎜ ⎟⎜ ⎟⎜⎜ ⎟⎟⎜⎜ ⎟⎟ = 4.12 mg asCaCO3
⎝ ⎠⎝ ⎠⎝ L
L mole 24,300 mg ⎠⎝ chg eq ⎠
Softening methods
1. Boiling
2. Lime treatment
3. Lime-soda process
4. Ion-exchange method
Boiling. Boiling reduces only calcium carbonate hardness but not non-carbonate hardness.
Ca(HCO3)2 CaCO3 + H2O + CO2
Lime treatment. Addition of lime to hardwater converts soluble bicarbonate into insoluble
CaCO3. If CO2 is present in water, some amount of lime is required to neutralize it.
CO2: CO2 + Ca(OH)2 ↔ CaCO3 ↓ + H20
Calcium carbonate hardness: Ca(HCO3)2 + Ca(OH)2 ↔ 2 CaCO3↓+ 2 H2O
Magnesium carbonate hardness: Mg(HCO3)2 + Ca(OH)2 ↔ CaCO3↓ + MgCO3 + 2 H2O
Excess lime treeatment: MgCO3 + Ca(OH)2 ↔ Mg(OH)2 ↓ + CaCO3 ↓
Noncarbonate hardness: MgSO4 + Ca(OH)2 ↔ Mg(OH)2 ↓ + CaSO4
MgCl2 + Ca(OH)2 ↔ Mg(OH)2 ↓ + CaCl2
Addition of excess lime raises the pH to 10.5. The excess lime is neutralized by CO2 to reduce
the pH to about 8.0 before filtratration. This is called re-carbonation.
CO2 + Ca(OH)2 ↔ CaCO3 ↓ + H20
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AAU, FoT, Department of Civil Engineering Instructor: Zerihun Alemayehu
CENG 420 – Water Treatment Lecture Note
Lime-soda process: Used to remove both carbonate and non-carbonate hardness. Lime and soda
ash (sodium carbonate) are used to convert calcium and magnasium into insoluble calcium
carbonate and magnesium hydroxide flocculated suspensions. These supensions are removed by
sedimentation and filtration.
Reaction with soda ash
CaSO4 + Na2CO3 ↔ CaCO3 ↓ + Na2SO4
CaCl2 + Na2CO3 ↔ CaCO3 ↓ + 2NaCl
Lime and soda-ash requirements are computed as follows:
[Ca(OH)2] = [CO2] + [HCO3-] + [Mg2+] + [excess lime]
[Na2CO3] = [Ca2+] + [Mg2+] – [Alkalinity]
Where,
[Ca(OH)2] = amount of lime required for softening in meq/L
[Na2CO3] = amount of soda-ash required for noncarbonate softening in meq/L
[CO2] = concentration of CO2 in meq/L
[HCO3-] = concentration of HCO3- in meq/L
[Ca2+] = concentration of Ca2+ in meq/L
[Mg2+] = concentration of Mg2+ in meq/L
[Excess lime] = additional lime to maintain elevated pH value (usually 1 or 1.25 meq/L)
[Alkalinity] = concentration of alkalinity in meq/L
Chemical dosing design:
• Softening goals: TH = 75 to 120 mg/L Mg2+ hardness = 40 mg/L max.
• Practical softening limits: Ca2+ = 30 mg/L min.; Mg2+ 10 mg/L min.
• Excess chemical requirements: 20 mg/L
Ion-exchange
Softnening by ion-exhange involves passing rhe water through a column containing a special
ion-exhange material. Several different types of ion-exchange materials are in use, icluding
natural substances called zeolites and synthetic resins. When water containing calcium and
magnesium ions is in contact with these materials, an exchange of ions takes place. The calcium
and magnesium ions are taken up by the resin, whereas sodium ions, Na+, are released inti the
water.
The ion-exchange process is illustrated schematically in Figure 5.12. eventually, the exchange
capacity of the zeolite or resin is used up and the ion exchanger must be regenerated for further
use. This done by washing the exchanger with a sodium chloride, NaCl, solution.
Softening by ion exchange can produce water with almost zero levels of hardness, but this in not
really desirable. Very soft water may be aggressive, or corrosive, causing damage to metal pipes
and plumbing. Hardness level of about 100mg/L are considered optimal for drinking water.
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AAU, FoT, Department of Civil Engineering Instructor: Zerihun Alemayehu
CENG 420 – Water Treatment Lecturee Note
Zeolite can
c be expreessed as soddium aluminno silicate. Zeolites
Z are either availlable naturallly or
prepared artificially (synthetic
( zeeolites). Greeen sand or gluconite are some of thee natural zeolites.
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AAU, FoT,, Departmentt of Civil Engin
neering Instructor: ZZerihun Alemaayehu