CENG 5711 Water Treatment 2012/13 A.Y.

, Lecture Note

5. Miscellaneous Treatment Processes

5.1. Water Softening

Water hardness is largely the result of geological formations of the water source. Public acceptance
of hardness varies from community to community, consumer sensitivity being related to the degree
of hardness to which consumer is accustomed. Hardness of more than 300 – 500 mg/l as caCO3 is
considered excessive for a public water supply and results in high soap consumption as well as
objectionable scale in plumbing fixtures and pipes.

The reduction of hardness, or softening, is a process commonly practiced in water treatment.

Softening may be done by the water utility at the treatment plant or by the consumer at the point of
use, depending on the economics of the situation and the public desire for soft water. Generally
softening of moderate water (50 to 150 mg/L hardness) is best left to the consumer, while harder
water should be softened at the water treatment plant. Softening processes commonly used are
chemical precipitation and ion exchange, either of which may be employed at the utility-owned
treatment plant. Home-use softeners are almost exclusively ion exchange units.

5.1.1. Chemical Precipitation

The different species of hardness have different solubility limits. The least soluble forms are
calcium carbonate and magnesium hydroxide. Chemical precipitation is accomplished by
converting calcium hardness to calcium carbonate and magnesium hardness to magnesium
hydroxide. This can be accomplished by the lime-soda ash process or by the caustic soda process.

Lime-soda ash: It uses lime, Ca(OH)2 and soda ash, Na2CO3, to precipitate hardness from
solution. All forms of carbonate hardness as well as magnesium non-carbonate hardness can be
converted to the precipitating species by the addition of lime (CaO). In the following equations, the
symbol s is used to indicate that a solid precipitate forms and that it is sufficiently dense to settle
by gravity.

Ca2+ + 2(HCO3)- + CaO + H2O 2CaCO3 S + 2H2O

Mg2+ + 2(HCO3)- + CaO + H2O 2CaCO3 S + Mg2+ + CO32-

Mg2+ + CO3 2- + CaO + H2O 2CaCO3 S + Mg(OH)2 S

SO42 - SO4 2-
2+
Mg + 2Cl - + CaO + H2O Ca 2+
+ Cl2 - + Mg(OH)2 S
2NO3 - 2NO3 -

As can be seen above, the removal of magnesium non-carbonate hardness results in the formation
of calcium noncarbonated hardness. This calcium non carbonate hardness, as well as any initially
present in the water, can be removed by the addition of soda ash (Na2CO3):

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CENG 4402 Water Supply & Urban Drainage Lecture Note

SO42 - SO4 2-
Ca2+ + Cl - + Na2 + CO3 CaCO3 S + 2Na+ + 2Cl -
2NO3 - 2NO3 -

Precipitation softening cannot produce water completely free of hardness because of the solubility
of calcium carbonate and magnesium hydroxide. Furthermore, completion of the chemical
reactions is limited by physical considerations, such as adequate mixing and limited detention time
in settling basins. Therefore the minimum practical limits of precipitation softening are 30 mg/l of
Ca2+ and 10 mg/l of Mg2+, both expressed as CaCO3. Hardness levels of 80 – 100 mg/l are
generally considered acceptable for public water supply, but the magnesium content should not
exceed 40 mg/l as CaCO3 in a softened municipal water.

The precipitation of CaCO3 and Mg(OH)2 is pH-dependent. The optimum pH for CaCO3
precipitation by lime addition is from 9 to 9.5, while effective precipitation of Mg(OH)2 under
water treatment plant conditions requires a pH of about 11.0. Since natural water has a pH
considerably below these values, it is often necessary to artificially raise the pH. This can be
accomplished by the addition of an excess amount of lime. The addition of about 1.25 mequiv/L of
lime is sufficient to raise the pH to 11.0.

Ca2+ + H2O Ca2+ + 2OH-

If dissolved carbon dioxide is present in water it will also react with lime.

CO2 + CaO CaCO3 S

Also this reaction does not reduce hardness, it does consume lime. Removal of supersaturated CO2
by aeration is often practiced to reduce lime requirements. If CO2 exceeds 10 mg/L it may be
economically advantageous to remove it prior to softening.

A two stage system is preferred for excess lime treatment. Lime is applied in first stage mixing and
sedimentation to precipitate both calcium and magnesium. Carbon dioxide is applied to neutralize
the excess lime. And soda ash is added to reduce noncarbonated hardness. Solids formed in these
reactions are removed by secondary settling and subsequent filtration.

Caustic Soda: All forms of hardness can also be converted to the precipitating species by the
addition of caustic soda (NaOH).

CO2 + 2NaOH 2Na+ + CO32- + H2O

Ca2+ + 2(HCO3)- + 2NaOH 2CaCO3 S + 2Na+ + CO3 2- + 2H2O

Mg2+ + 2(HCO3)- + 4NaOH Mg(OH)2 S + 2Na+ + CO32- + 2H2O

Mg2+ + SO4 2- + 2NaOH Mg(OH)2 S + 2Na+ + SO42-

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CENG 5711 Water Treatment 2012/13 A.Y., Lecture Note

Chemical requirement: the quantity of chemicals to soften water can be calculated using the
appropriate formulas.

Example
Water defined by the following analysis is to be softened by excess-lime treatment in a two stage
system.
CO2 = 8.8 mg/l as CO2
Ca2+ = 70 mg/l
Mg2+ = 9.7 mg/l
Na+ = 6.9mg/l
Alk (HCO3-) = 115 mg/l as CaCO3
SO42- = 96 mg/l
Cl- = 10.6 mg/l

The practical limits of removal can be assumed to be 30 mg/l of CaCO3 and 10 mg/l of Mg(OH)2,
expressed as CaCO3. Sketch a meq/l bar graph and list the hypothetical combinations of chemical
compounds in the raw water. Calculate the quantity of softening chemicals required and the
theoretical CO2 needed to provide a finished water with one-half of the alkalinity converted to
bicarbonate ion. Draw a bar graph for the softened water after re-carbonation and filtration.

Solution:
Component Mg/l Equivalent weight Meq/l
CO2 8.8 22.0 0.40
Ca2+ 70 20.0 3.50
Mg2+ 9.7 12.2 0.80
Na+ 6.9 23.0 0.30
Alk 115 50.0 2.30
SO42- 96 48.0 2.00
Cl- 10.6 35.5 0.30

The meq/l bar graph of the raw water is shown below, and the hypothetical combinations are
listed.

0 3.5 4.3 4.6

2+ 2+ +
Ca Mg Na
CO2
HCO3- SO42- Cl-

0.4 2.3 meq 1.2 meq 0.8 meq 0.3

CO2
Bar graph and hypothetical chemical combinations in the raw water.

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CENG 4402 Water Supply & Urban Drainage Lecture Note

Component Meq/l Lime Soda ash

CO2 0.4 0.4 0
Ca(HCO3)2 2.3 2.3 0
CaSO4 1.2 0 1.2
MgSO4 0.8 0.8 0.8
Total 3.5 2.0

Lime Required = stoichiometric quantity + excess lime

= 3.5 * 28 + 35 = 133 mg/l of CaO
Soda ash required = 2.0 * 53 = 106 mg/l of Na2CO3

A hypothetical bar graph for the water after addition of softening chemicals and first stage
sedimentation is shown below. The dashed box is the excess-lime addition, 35 mg/l of CaO = 1.25
meq/l. The 0.6 meq/l of Ca2+ (30mg/l as CaCO3) and 0.20 meq/l of Mg2+ (10 mg/l as CaCO3) are
the practical limits of hardness reduction. The 2.0 meq/l of Na2SO4 results from the addition of
soda ash. Alkalinity consists of 0.20 meq/l of OH- associated with Mg(OH)2 and 0.60 meq/l of
CO32- related to CaCO3.

0 0.6 0.8 3.1

Ca2+ Ca2+ Mg2+ Na+

OH- OH- CO32- SO42- Cl-

1.25 meq 0.8 meq 2.0 meq

Excess lime hardness soda ash addition

5.2. Iron and Manganese Removal

Iron and manganese in concentrations greater than 0.3 mg/l of iron and 0.05 mg/l of manganese
stain plumbing fixtures like taps, wash basins, white glazed sanitary wares and laundered clothes.
Although discoloration from precipitates is the most serious problem associated with water
supplies having excessive iron and manganese, foul tastes and odours can be produced by growth
of iron bacteria in water distribution mains. This filamentous bacteria, using reduced iron as
energy source, precipitate it, causing pipe incrustations. Decay of the accumulated bacterial slims
creates offensive tastes and odours.

Dissolved iron and manganese often found in groundwater from wells located in shale, sandstone
and alluvial deposits. Impounded surface water supplies may also have troubles with iron and
manganese. An anaerobic hypolimnion (stagnant bottom-water layer) in a reservoir dissolves
precipitated iron and manganese from the bottom mud, and during periods of overturn these
minerals are dispersed throughout entire depth.

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CENG 5711 Water Treatment 2012/13 A.Y., Lecture Note

They are usually present as soluble bicarbonates. The iron is converted into insoluble ferric oxide.
The CO2 gas is expelled and ferric oxide is converted into precipitate of Fe(OH)3. The floc of
Fe(OH)3 is removed when this water reaches settling tanks and filters. Sometimes when they are
present as combined with organic matter, the aeration alone will not remove them. For this the
addition of lime is necessary. The Cl2 and KMnO4 solutions can also be used. The complete
process in this case will be lime or chlorine treatment, aeration, sedimentation and filtration.

5.2.1. Aeration-Filtration
The simplest form of oxidation treatment uses plain aeration. The units most commonly employed
are the tray type, where a vertical rise pipe distributes the water on top of series of trays, from
which it then drops and spatters down through a stack of three or four of them. Soluble iron is
readily oxidized by the following reaction:

2Fe(HCO3)2 + 0.5O2 + H2O 2Fe(OH)3 +4CO2

Manganese can’t be oxidized as easily as iron and aeration alone is generally not effective. If,
however, the pH is increased to 8.5 or higher (by the addition of lime, soda ash, or caustic soda)
and if aeration is accompanied by contact with coke beds coated with oxides in the aerator,
catalytic oxidation of the manganese occurs. The oxidized iron and manganese is then removed by
a granular-media filter.

5.2.2. Aeration-Chemical Oxidation-Sedimentation Filtration

This sequence of processes is the usual method for removing iron and manganese from well water
without softening treatment. Contact tray aeration is designed to displace dissolved gasses (i.e.
CO2) and initiate oxidation of the reduced iron and manganese.

Chlorine, potassium permanganate, ozone or chlorine dioxide can chemically oxidize both iron and
manganese. When chlorine is utilized, a free available chlorine residual maintained throughout the
treatment process. The rate of manganese II oxidation by chlorine depends on the pH, the chlorine
dosage, mixing conditions and other factors.
Potassium permanganate oxidation is many times faster than chlorine for the oxidation of
manganese. Also the rate of reaction is relatively independent of the hydrogen ion concentration
within the pH range of 5-9.

Filtration following chemical oxidation is very important. Practice has shown that filters pass
oxidized manganese unless grains of the media are coated with manganese oxides serving as a
catalyst. This covering develops naturally during filtration of manganese-bearing water.

Ozone oxidizes manganese faster than other oxidants, but if the dosage is too high, it may convert
the manganese to permanganate and thereby cause the water to turn pink.

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CENG 4402 Water Supply & Urban Drainage Lecture Note

5.3. Processes used for Saline Water Conversion

Careful use of available water resources can make them last longer, but countries with a per capita
availability of less than 1000 m3/year (i.e. the water scarce countries) will need technological
solutions such as seawater desalination and reuse of reclaimed wastewater to augment fresh water
supplies in the future. Desalination, along with water reuse and water importation, can provide a
means of increasing the supply of fresh water. Some experts predict that desalinated seawater will
become an important water source in this century, as 70% of the world’s population lives within 50
miles of the sea. Given the almost unlimited availability of seawater, desalination could provide
sustainable water supply to many municipalities and industry.

For domestic water supply in large cities, desalination will become a realistic alternative to
conventional drinking water treatment, when costs are comparable. Industrial development
demands large amounts of clean water, and desalination may be the technology of choice to
develop industry in regions of water scarcity.

5.3.1. Desalination methods

Saline water is water that contains a significant amount of total dissolved solids (TDS). It is
divided into three categories. Freshwater generally covers water with a TDS up to 1000 mg/l,
brackish water from 1000 to 10,000 and seawater above 35,000 mg/l. In certain cases brackish
water may contain 10,000 to 35,000 mg/l TDS and it is then referred to as “difficult” brackish
water. Saline water also contains small amounts of organic matter and dissolved gases but the
majority of dissolved materials are inorganic salts.

Desalination technology can basically be divided in two types: thermal desalting technology and
membrane desalting technology. Thermal desalting technology comprises multi-stage flash
distillation (MSF), multi-effect distillation (MED) and vapour compression (VC), while membrane
technology includes electrodialysis (ED) and reverse osmosis (RO). In all types of desalting
technology, saline water is separated into two streams: a freshwater stream with a low salt
concentration and a brine or concentrate stream with a high salt concentration. Both types of
technology require energy to operate. While both distillation (MSF, MED or VC) and membrane
processes (RO) are widely used for seawater desalination, RO is also applied for brackish and low
salinity water. ED is only suitable for fresh or brackish water. The energy consumption of
membrane processes depends on the salinity of the raw water, whereas in distillation processes the
(thermal) energy consumption is constant and does not depend on feed water salinity.

Energy consumption in RO and ED for brackish and low salinity water is much lower than in
distillation processes. Recent innovations in seawater RO have reduced the energy consumption
further. However, it is difficult to make a general statement that in seawater desalination one
thermal or membrane process is better than another without in-depth information on site conditions
and the specific application. In general, thermal systems are robust and have high tolerance for
variable feed water quality, while membrane systems have lower capital and energy costs but are
sensitive to fouling.