Water Treatment Water Treatment: Lecture 6: Softening
Water Treatment Water Treatment: Lecture 6: Softening
Water Treatment Water Treatment: Lecture 6: Softening
University of Gaza ‐Environmental Engineering Department
Water Treatment
Water Treatment
EENV 4331
Lecture 6: Softening
Dr. Fahid Rabah
1
6. Hardness and Softening in water Treatment
6.1 Definition of hardness:
A. Hardness is the term often used to characterize a
water that :
water that :
Dose not form a foam or lather well and cause
soap scum
p
Ca2+ + (Soap)‐ Ca(Soap)2 (s) (soap scum)
This increase the amount of soap needed for
washing
cause scaling on pipes and hot boilers.
cause valves to stick due to the formation of
cause valves to stick due to the formation of
calcium carbonate crystals
leave stains on plumbing fixtures
p g
2
6. Hardness and Softening in water Treatment
Figure 6.1:
Figure 6.1:
Scaling due to calcium and magnesium
precipitation
3
6. Hardness and Softing in water Treatment
B. Hardness is defined as the sum of the divalent
metal cations (in consistent units) existing in
water such as :
Ca 2+
2 , Mg 2+
2 , Fe 2+
2 , Mn 2+
2
4
6. Hardness and Softening in water Treatment
D Hard water classification
D. Hard water classification
5
6. Hardness and Softening in water Treatment
E Formation of Hardness
E. Formation of Hardness
Precipitation
Topsoil
Subsoil
CO2 + H2O H2CO3
6
6. Hardness and Softening in water Treatment
F. Carbonate and non carbonate Hardness
Carbonate Hardness ( CH)
• Ca2+, Mg2+ associated with HCO3‐, CO32‐
• Oft
Often called "temporary hardness" because
ll d "t h d "b
heating the water will remove it. When the
water is heated, the insoluble carbonates will
,
precipitate and tend to form bottom deposits in
water heaters.
Non Carbonate Hardness ( NCH)
Non‐Carbonate Hardness ( NCH)
• Ca2+, Mg2+ associated with other ions, Cl‐, NO3‐,
SO42‐
• NCH = TH – CH
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6. Hardness and Softening in water Treatment
F. Hardness Units
Total Hardness = ∑ (Ca 2+ + Mg 2+ )
The hardness unit is the same as that consistent unit used for both of the above
ions. The most used units are:
Where,
EW = equivalent weight
S i
Species = Ion or Radical or Compound
I R di l C d
Radical: such as CO32‐, SO4 2‐
Compounds: such as CO2, CaSO
Compounds: such as CO CaSO4
8
6. Hardness and Softening in water Treatment
MW For radicals and
EW
El t i l Charge
Electrical Ch compounds
MW
EW For ions
Valance
MW = molecular weight of the Species
Example 3.1 : a) Find the EW of Mg 2+ that has a concentration of 10 mg/L as
the ion in water. b)
h b) Find the EW of CaCO
d h f 2 as mg/L
2+
3 c)) find concentration of Mg
f d f /
CaCO3.
9
6. Hardness and Softening in water Treatment
b) Finding the EW for CaCO
Finding the EW for CaCO3 :
g mg
MW 100 MW 100
mole mmole
2 meq
Electrical charge (n)
2 eq Electrical charge
mole mmole
MW 100 mg 1 mg
EW EW .[ ] EW 50
Electrical Charge mmole 2 meq/mmole meq
D) Finding the Mg 2+ concentration as CaCO3 :
C CO 3 mg/L i
EW of CaCO 3
mg/L
/L as CaCO /L as species
EW of species
Mg 2+ conc.
10
Ground
Water
Rapid Mixing Flocculation Sedimentation Recarbonation
Figure 6.2: Softening Treatment Plant Single stage
softening
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6. Hardness and Softening in water Treatment
6.2 Relation between Alkalinityy and hardness:
A. Definition of Alkalinity
Alkalinity is a very important parameter in water chemistry and
Alkalinity is a very important parameter in water chemistry and
related very closely to hardness and softening process. The
following equation is used to measure the alkalinity in water:
Alkalinity = (HCO ) (CO32‐
Alk li it (HCO3‐) + (CO 2 ) + (OH
) (OH‐) ‐
) (H+)
• Where the concentrations are in meq/L or mg/L as CaCO3
Usually the (OH‐) and (H
Usually the (OH ) and (H+) are negligible.
) are negligible.
• The relation between the alkalinity species is given by the following three
equations:
10 -10.33
[H ][CO 23 ]
[HCO3-]
, 10 -14
H
OH
, H 10
pH
Where the concentrations are moles/ L in these three equations
12
Various Forms of alkalinity and CO2 relative to pH in water at 25 oC.
13
6. Hardness and Softening in water Treatment
Example 6.1:
l
A sample of water having a pH of 7.2 has the
A sample of water having a pH of 7 2 has the
following concentrations of ions
Ca2+ 40 mg/L
40 mg/L
Mg2+ 10 mg/L
Na+ 11.8 mg/L
K+ 7.0 mg/L
7.0 mg/L
HCO3‐ 110 mg/L
SO42‐ 67.2 mg/L
Cl‐ 11 mg/L
g/
• Construct a bar chart of the ions in term of mg/L CaCO3
• Calculate the TH, CH, NCH, Alkalinity
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6. Hardness and Softening in water Treatment
Example 6 1:
Example 6.1:
Ion Conc. M.W. n Eq. Wt. Conc. Conc.
mg/L mg/mmol mg/meq meq/L mg/L as
CaCO3
Ca2+ 40.0 40.1 2 20.05 1.995 99.8
Mg2+ 10.0 24.3 2 12.15 .823 41.2
Na+ 11.8 23.0 1 23.0 .51 25.7
K+ 70
7.0 39 1
39.1 1 39 1
39.1 .179
179 8 95
8.95
HCO3- 110.0 61.0 1 61.0 1.80 90.2
SO42- 67.2
67 2 96 1
96.1 2 48 05
48.05 1 40
1.40 69 9
69.9
Cl- 11.0 35.5 1 35.5 .031 15.5
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6. Hardness and Softening in water Treatment
Check The ionic balance:
(cations) = (anions)
175.6 = 175.6 mg/L as CaCO3 O.K
3 51
3.51 = 3.23 meq/L O.K
3 23 /L OK
Note: (error in the range of ± 10% is accepted)
Note: one check is enough ( either as {mg/L as CaCO3 } or as {meq/L} )
16
6. Hardness and Softening in water Treatment
• Alkalinity = (HCO3‐) + (CO32‐) + (OH‐) ‐ (H+)
a. Since pH = 7.2
[H+] = 10‐pH = 10‐7.2 mole/L = 10‐7.2 g/L
eq/L
10-7.2 g H /L H 10
-7.2
eq/L
1 g/eq
b. 10-14
14
H OH = 10 -14
14
1 0 -7.2
72
OH
OH 10
-6.8
68
mole/L
OH 10
-6.8
mole/L 17 *10 -6.8
g/L eq/L
17 *10-6.8 g OH /L
17 g/eq
OH 10
- -6.8
eq/L
17
6. Hardness and Softening in water Treatment
d Find the carbonate concentration:
d. Find the carbonate concentration:
[H ][CO 23 ] 10-7.2 x[CO 23 ]
10 -10.33
10 -10.33
[HCO3-] 1.8 x 10-3
[CO32‐]= 1.33 x 10‐6 mole/L = 79.8 x 10‐6 g/L
79.8 *10-6 g /L = 2.66 x 10‐6 eq/L
q/
2‐
CO3 in eq/L
30 g/eq
Alkalinity = (1.80 x 10‐33) + (2.66 x 10‐66) + 10‐6.8
6 8 ‐ 10‐7.2
7 2 = 1.801 x 10‐3
3 eq/L
/
Alkalinity = 1.801 x 10‐3 x 1000 x 50 = 90.1 mg/L as CaCO3
Note: it is clear that the most effective form of alkalinity is bicarbonate,
this is always true when the pH is 8.3 or less.
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6. Hardness and Softening in water Treatment
• Carbonate Hardness
Carbonate Hardness
the portion of the hardness associated with carbonate or bicarbonate
‐ Alkalinity = 90.1 mg/L as CaCO3
TH = 141 mg/L as CaCO3
CH = 90.2 mg/L as CaCO3
‐ Non‐carbonate Hardness:
NCH = TH ‐ CH
= 141 ‐ 90.1= 50.9 mg/L as CaCO3
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6. Hardness and Softening in water Treatment
Construct the bar chart of the ions in term of mg/L CaCO3
Construct the bar chart of the ions in term of mg/L CaCO
TH
00
0.0 99 8
99.8 141 166 7 175.6
166.7 175 6
Ca 2+ Mg 2+ Na + K +
HCO3‐ SO4 2‐ Cl‐
0.0 90.2 160.1 175.6
CH NCH
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6. Hardness and Softening in water Treatment
6.3 Softening definition:
g
a) Softening is the chemical processes in which hardness
causing ions ( Ca 2+ , Mg2+ ) are removed from water ether
completely or partially
completely or partially.
b) Softening may be a chivied by chemical precipitation using
the Lime‐ Soda Ash method or by ion exchange.
c) In the chemical precipitation method the objective is to
produce CaCO3 and Mg(OH)2 :
+ CO32‐ 2CaCO3(s)
Ca2+ + CO 3( )
Mg2+ + 2OH‐ Mg(OH)2(s)
These two reactions are achieved by the
These two reactions are achieved by the
addition of Lime [Ca(OH)2] and Soda ash [
Na2CO3] as will be shown.
] as will be shown
21
6. Hardness and Softening in water Treatment
f)) A common water treatment goal is to provide a
g p
water with a hardness in the range of 75 to 120 mg/L
as CaCO3
g) To precipitate CaCO3 and Mg(OH)2 we need to raise the pH to 10.3 by
the addition of Lime [Ca(OH)2]. The addition of the OH‐
t HCO3‐ to CO
will convert HCO
ill t CO32‐
h) To precipitate Mg(OH)2 we need to raise the pH to 11 by the addition
f Soda ash [ Na
of ] This will add the CO322‐ ion
Soda ash [ Na2CO3]. This will add the CO ion
needed to react with the remaining Ca 2+
i) Some of the
Some of the added lime [Ca(OH)
added lime [Ca(OH)2] is consumed to
] is consumed to
remove CO2 which is necessary to raise the pH.
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6. Hardness and Softening in water Treatment
6.4 Chemistry of Lime‐ Soda Ash Softening
softening reactions
• Neutralization of carbonic acid
[To raise the pH we need first to neutralize any acid in the water]
CO2 + Ca(OH)2 CaCO3(s) + H2O
• Precipitation of CH due to calcium:
[To raise the pH to 10.3 all the HCO3‐ is converted to CO32‐]
Ca2+ + 2HCO3‐ + Ca(OH)2 2CaCO3(s) + 2H2O
• Precipitation of CH due to magnesium
Precipitation of CH due to magnesium
[To raise the pH to 11 add more lime]
Mg2+ + 2HCO3‐ + Ca(OH)2 Mg2+ + CO32‐+ CaCO3(s)+ 2H2O
Mg2+
2+ + CO + Ca(OH)2 MgOH2(s)+ CaCO
+ CO322‐ + Ca(OH) + CaCO3(s)
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6. Hardness and Softening in water Treatment
6.4 Chemistry of Lime‐ Soda Ash Softening
• Removal of NCH due to calcium
Ca2+ + SO4‐2 + Na2CO3 CaCO3(s) + 2Na+ + SO4‐2
Ca2+ + 2Cl‐1 + Na2CO3 CaCO3(s) + 2Na+ + 2Cl‐1
• Removal of NCH due to magnesium
+ Ca(OH)2 MgOH2(s)
Mg2+ + Ca(OH) + Ca2+
2( )+ Ca
Ca2+ + Na2CO3 CaCO3(s) + 2Na+
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6. Hardness and Softening in water Treatment
6.4 Chemistry of Lime‐ Soda Ash Softening
Softening process limitations:
f l
1. Lime‐Soda softening cannot produce a water completely free of hardness
because of the solubility of CaCO3 and Mg(OH)2, limitations of mixing
and reaction time .
2. Thus , the minimum calcium hardness that can be achieved is
30 mg/L as CaCO3 , the minimum Magnesium hardness that can be achieved
is 10 mg/L as CaCO3 , this gives a minimum hardness of 40 mg/L as CaCO3.
3. However, normally the water is treated to give a hardness in the range of 75 to
120 mg/L as CaCO
mg/L as CaCO3. .
4. An Excess lime beyond the stoichiometric amount is usually added to
remove Mg 2+ hardness . The minimum excess lime is usually 20 mg/L
as CaCO3 , maximum excess lime is 62.5 mg/L as CaCO
as CaCO maximum excess lime is 62 5 mg/L as CaCO3 (1.25 meq/L).
(1 25 meq/L)
5. Mg 2+ in excess of 40 mg/L as CaCO3 is not desired as it forms scale in
water heaters. Mg 2+ is expensive to remove, so we only remove Mg 2+
i
in excess of 40 mg/L as CaCO
f 40 /L C CO3.
25
6. Hardness and Softening in water Treatment
6.4 Chemistry of Lime‐ Soda Ash Softening
Chemicals requirements:
h l
According to the softening chemical reactions:
‐Lime
Lime is added at the ratio of 1:1 for each carbonate hardness
is added at the ratio of 1:1 for each carbonate hardness
compound except for Mg(HCO3) the ratio is 2:1 [i.e. 2 lime for
each 1 Mg(HCO3) ].
g
‐Lime is also added at the ratio of 1:1 for each Magnesium NCH
compound such as MgSO4
‐Soda ash is added at the ratio of 1:1 for each Magnesium or
p
Calcium NCH compound such as MgSO g 4 4 ,, and CaSO4.
‐ CO2 needed is 1:1 ratio with the excess lime added, and 1:1
ratio with CaCO3 remaining after softening, 2:1 ratio with
g( )2 remaining after softening.
Mg(OH) g g
‐ The units of the chemicals are either in meq/L or mg/L CaCO3
‐ Example 6.2 illustrates the chemical requirements
calculations.
calculations.
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6. Hardness and Softening in water Treatment
6.5 Excess Lime Softening example
Example: 6.2
A water with the ionic characteristics shown below is to be softened to the
A ih h i i h i i h b l i b f d h
minimum possible hardness by lime‐soda‐ash excess lime process. Calculate
the required chemical quantities in meq/L. Draw a bar diagram of the softened
water. Assume that a residual of CaCO3 of 0.60 meq/L and a residual of Mg(OH)2
of 0.20 meq/L will remain in the softened water.
3.4 6.4 7.4
Ca 2+ Mg 2+ Na 2+
CO2 HCO3‐ SO4‐2
06
0.6 00
0.0 4.9 7.4
27