Water treatment:

softening

Sudha Goel, Ph.D.

Dept. of Civil Eng., IITKgp
Kharagpur 721 302

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 Hardness

Hardness: due to presence of multivalent cations like Ca, Mg (mainly),
and Fe, Mn, Sr, Al, etc.
 Formation of soap curd (lack of frothing or foaming that is essential
for bringing dirt particles into solution), increased soap requirement
and subsequent difficulty in all cleaning activities
 On heating, scale formation or precipitation of these ions, CaCO3
and Mg(OH)2, leads to reduced efficiency of heating elements, and
failure (eg. Equation 6.8)

Synthetic detergents can reduce the problem but not eliminate it

General level of acceptance is <= 150 mg/L

Carbonate hardness
 Due to anions like carbonates and bicarbonates
 Also called temporary hardness, since it can be precipitated by
boiling

Non-carbonate hardness
 Amount of hardness in excess of carbonate hardness
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GMM, 1998
Hardness

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 Hardness classification

Description Hardness, meq/L Hardness, mg/L

Soft <1 <50 to 75

Moderately hard 1 to 3 50 or 75 – 150

Hard 3 to 6 150 - 300

Very hard >6 > 300

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GMM, 1998
 Alkalinity

Alkalinity is the measure of a water’s

ability to absorb hydrogen ions without
significant pH change
 Eq. 6.9
 Buffering capacity of water

5
GMM, 1998
 Softening

Surface waters are generally softer than GWs
 For hardness levels < 200 mg/L as CaCO3, no
softening is required

Softening is often required for GW
 Especially when hardness is > 1000 mg/L

Processes
 Lime-soda
 Ion exchange

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GMM, 1998
 Lime-soda process

Quick lime (CaO) or hydrated lime (Ca(OH)2) is added to water

See Equation 6.12 (Masters text, pg.284), carbonates of Ca precipitate out
of solution; similarly, Mg(OH)2 precipitates

If insufficient bicarbonate alkalinity is present, soda ash is added to
precipitate Mg and Ca

Can bring hardness down to 40 mg/L of CaCO3 and 10 mg/L of Mg(OH)2
 Solubility of Ca carbonate is 15 mg/L at 0 deg C and 14 mg/L at 25 deg C
(Sincero2)
 Solubility of Mg hydroxide is 17 mg/L (as CaCO3) at 0 deg C and 15.5 mg/L (as
CaCO3) at 18 deg C
 Therefore, the above conc will always be there no matter how much lime is
added
 If higher removal is required, adsorption is the only method for removing Ca and
Mg to a greater extent

Extent of precipitation is a function of pH for Ca and Mg species

Optimum pH for CaCO3 is 9 to 9.5 while for Mg(OH)2 it is above 11
 Equilibrium pH for CaCO3 in a closed system is 9.96 and in an open system is
8.35, no pH adjustment is generally done
 For Mg removal, 1.25 meq/L of lime are added to bring pH to 11
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 Mineral

Calcium carbonate 15
Calcium chloride 336000
Calcium sulphate 1290
Calcium hydroxide 2390
Magnesium bicarbonate 37100
Magnesium carbonate 101
Magnesium chloride 362000
Magnesium hydroxide 17
Magnesium sulphate 170000
Sodium bicarbonate 38700
Sodium carbonate 61400
Sodium chloride 225000
Sodium hydroxide 370000
Sodium sulphate 33600
Loewenthal RE and GvR Marais [1982] Carbonate Chemistry of Aquatic Systems, Theories and Application, Volume 1, 8
433 pp. Ann Arbor Scienc Publishers, Collingwood, Michigan, USA.
Softening reactions

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 Carbon dioxide in the lime-soda process

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Recarbonation

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Split treatment

If water has high Mg hardness it is treated by
split treatment

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 Ion Exchange

Type of ion exchange adsorbents
 Zeolites: can be natural or synthetic
 Ion exchange resins: cationic or anionic

Na-R is exchanged for Ca and Mg, does not contribute to
hardness

Regeneration required

Ion exchange is displacement of one ion by another
 Displaced ion is originally part of a solid matrix
 Displacing ion is originally in solution
 The insoluble part of the exchange material is the ‘host’

Objective: to remove low levels of TDS in water
 Not efficient where high levels of TOC, SS and TDS exist, since
porous bed reactors that are generally used get choked and the resin
is ‘blinded’ to the ions that can be exchanged
 Can be used for the removal of toxic heavy and radioactive metals
like As, Cr, Ra, U, Se, etc.

Operations: Batch or continuous flow systems are possible
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 Ion exchange

Applications
 Softening: removal of Ca, Mg, and other polyvalent cations

Nitrates, arsenate, chromate and selenate

 Hazardous waste: removal of radium, uranium, etc.

 Activated alumina adsorption

Removal of F and As

 Generally, used in lab (high-grade analytical applications) and

industrial applications for getting ‘ultra-pure’ water
 Analytical equipment based on ion-exchange principle

Ion chromatography in liquid phase (IC, HPLC)

Gas chromatography (GC)

 For water supply systems, often ‘split’ treatment is used

A specific fraction of the total volume is demineralized and then mixed
with main stream to provide a known amount of TDS in the final stream

Pre-filtration is almost always used (it is necessary!)

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Ion exchange process

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 Ion exchange

Feasibility of process depends on
 Water quality (TDS level)
 Competing ions
 Alkalinity
 Contaminant concentration
 Affinity of resin or alumina for contaminant vs. competing
ions

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AWWA – ch9, 1990
 Ion exchange adsorbers

Natural or synthetic zeolites: crystalline aluminosilicates

Activated alumina: most popular adsorbent is an ion exchanger
 Ligand exchange
 Chemisorption

Synthetic resins:
 Types

Strong and weak acid cation exchangers

Strong and weak base anion exchangers

 faster exchange rate

 longer life
 higher capacity

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 Zeolites

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Wikipedia 2007
 Design consideration and parameters

Design principles for ion exchange columns are exactly the same as for AC
adsorption columns

Generally, run in granular packed-bed reactors
 Downflow reactors
 Column backwashed after exhaustion to remove trapped solids and then
regenerated with regenerant solution
 Synthetic resins are more efficient than natural zeolites
Typical design parameters:
 Conc of TDS in initial and final water, degree of demineralization
 Average design flow
 Typical bed depths: 1 to 2 m
 Flow rates: 0.2 to 0.4 m3/m2-min
 Total exchange capacity: 50,000 to 80,000 g/m3 as CaCO3
Four basic steps in operation

Exhaustion

Backwashing

Regeneration

Slow and fast rinse 21

 Ion exchange process

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http://www.ionindia.com/company.html
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