Water Softening

Softening
Richard O. Mines, Jr., Ph.D., F. ASCE, P.E. Director of MSE/MS Programs Professor of Environmental Engineering Mercer University

Water Softening: is a unit process involving the addition of chemicals to water for the removal of hardness causing ions.
Water hardness is caused by divalent metallic cations principally calcium (Ca2+) and magnesium (Mg2+). Other divalent metallic cations that contribute to hardness include: iron (Fe2+), manganese (Mn2+), and strontium (Sr2+). Hardness is not related to any health issues. Hardness produces scale in water heaters and pipes; and consumes more soap and detergent than soft waters.
2

Hardness Classification and Units

Total hardness: is generally calculated by
adding the milliequivalents of the calcium and magnesium ions together and then multiplying by the equivalent weight of calcium carbonate, 50.
Hardness is expressed in units of mg/L of CaCO 3. Soft water: hardness of 0 75 mg/L as CaCO3 Moderately hard water: hardness of 75 150 mg/L as CaCO3 Hard water: hardness of 150 - 300 mg/L as CaCO3 Very hard water: hardness of > 300 mg/L as CaCO 3
3

Water Softening Methods

Chemical precipitation through the addition of lime and soda ash is the primary means of removing hardness from water. Ion exchange is also used, especially for individual residences, in which, calcium and magnesium ions are replaced by sodium ions (Na+) by passing water through a resin or bed. Softening is accomplished when water is passed through a semi-permeable membrane such as those used in reverse osmosis, ultrafiltration, or other membrane processes.
4

Chemical Precipitation
Chemical precipitation of hardness is based on the solubilities of calcium carbonate (CaCO 3) and magnesium hydroxide (Mg(OH)2). The solubility products of CaCO3 and Mg(OH)2 are presented in Equations [1] and [2] below. [Ca2+][CO32-] = Ksp = 5 x 10-9 Equation [1] [Mg2+][OH-] = Ksp = 9 x 10-12 Equation [2] When excess lime treatment is used, the residual total hardness is about 40 mg/L as CaCO 3. 30 mg/L as CaCO3 is associated with CaCO3 solubility and 10 mg/L as CaCO3 is associated with Mg(OH)2 solubility.
5

Calculating solubility of CaCO3

Calculate the solubility of CaCO3 in water at room temperature given the Ksp is 8.710-9 (Benefield and Morgan, 1999).

MW of CaCO3 = 40+ 12+3 16 = 100 g mole

CaCO3 s
Ksp =8.7 10
9

2Ca 2+ + CO3

Ca 2+

2 CO3
6

Calculating solubility of CaCO3 II

Assume that the concentration of Ca 2+
2CO3

Calculating solubility of M(OH)2

X
Calculate the solubility of Mg(OH)2 in water at room temperature given the Ksp is 1.210-11 (Benefield and Morgan, 1999).

X X = 8.7 10

X = 9.327 10

moles CaCO3 L
9.33 mg CaCO3 L

MW of Mg OH 2 = 24.3+ 2 17 = 58.3g mole

X= 9.327 10

moles CaCO3 100 g L mole

1000 mg g

Mg OH

2 s
11

Mg 2+ + 2OH
Mg 2+ OH
2

In practice, the solubility of CaCO3 is approximately equal to 30 mg/L as CaCO3 due to competing reactions, temperature, and process constraints.
7

Ksp =1.2 10

Calculating solubility of M(OH)2 II

Assume that the concentration of Mg 2+ X and OH
4

Lime Softening: Concurrent Removals

2X.
2

X 2X =1.2 10
X=1.4 10 X 14.4
4

11

X =1.4 10

moles Mg OH L
50 g CaCO3 eq

moles Mg OH L

58.3g mole

eq 29.2 g Mg OH

1000 mg g

mg CaCO3 L

In practice, the solubility of Mg(OH)2 is approximately equal to 10 mg/L as CaCO3 due to competing reactions, temperature, and process constraints.
9

As5+ >90% @ pH 11 Ba >90% @ pH 10-11 Cd > 95% @ pH >8.5 Cr3+ >95% @ pH >10 F- >55% @ pH 11-12 Pb >95% @ pH 7-8.5 Ag 70-80% @ pH 7-9 Fe2+ 100% @ pH >9.6 Mn2+ 100% @ pH >9.8
10

Source: Davis, 2011, page 4-26

Lime Softening: Concurrent Removals

Mg(OH)2 precipitation removes:
50-80% of the color 30-60% of the TOC (surrogate for NOM)

Excess Lime Addition

Excess lime required to raise the pH above 10.5 to precipitate Mg(OH)2. Lime dosage above stoichiometric amount ranges from 30 to 70 mg/L as CaCO3. Typically, 1.25 meq/L of lime are added for excess lime treatment.
Source: MWH, 2005, page 1596

CaCO3 precipitation removes:

10-30% of the color 10-30% of the TOC

Turbidity is removed by sweep coagulation.

Source: Davis, 2011, page 4-26

11

12

Calculating pH of Excess Lime

Determine the pH of water by adding 1.25 meq/L of Ca(OH) 2

Schematic of 2-Stage LimeSoda Ash Treatment

Lime
Flocculator/

MW of Ca OH 2 = 40+ 16+1 2 = 74 g mole

CO2 Recarb CO2 Filtration

EW of Ca OH 2 =
OH 1.25 meq 1eq L 1000 meq 37 g eq

74g 37 g = 2eq eq
2 17 g OH 74g Ca(OH) 2 1mole 17 g OH
3

Water Clarifier
1.25 10
3

moles L

CaCO3 Mg(OH)2 Soda Ash

Flocculator/ Clarifier

pOH = -log OH -

-log 1.25 10

2.90

Recarb

pH = 14 pOH = 14

2.90 = 11.1
13

CaCO3
14

Lime-Soda Ash Softening Equations I

CaO H 2O Ca(OH) 2 (1)

Lime-Soda Ash Softening Equations II

MgCl2 Ca OH
2

Mg OH

CaCl2

(7)

CO2

Ca(OH)2

CaCO3

H2 O

(2)

CaSO4

Na 2 CO3

CaCO3

Na 2 SO4

(8)

Ca(HCO3 )2

Ca(OH)2

2CaCO3

2H2 O

(3)

Mg(HCO3 )2

Ca(OH)2

CaCO3

MgCO3 2H2 O (4)

CaCl2
Ca OH

Na 2 CO3
2

CaCO3
CaCO3

2 NaCl
H 2O
2

(9)
(10)

MgCO3

Ca(OH)2

CaCO3
CaSO4

Mg(OH)2
Mg(OH)2
15

(5)
(6)

CO2

MgSO4 Ca(OH)2

CaCO3

CO2

H 2O

Ca HCO3

(11)
16

Recarbonation
First Stage Recarbonation:
Carbon dioxide is added to the water to neutralize the excess lime to calcium carbonate which lowers the pH from 11 to around 10.2 according to Equation [10].

Excess Lime-Soda Ash Example

Calculate the lime and soda ash requirements to achieve the practical limits of hardness removal given the following water analysis. Develop the bar graph showing the original theoretical species in the water and a bar graph of the softened water after recarbonation and filtration if 50% of the remaining alkalinity is assumed to be in the HCO 3- form. CO2 = 8.8 mg/L Na+ = 13.7 mg/L Mg2+ = 14.7 mg/L Alkalinity (HCO3-) = 135 mg/L as CaCO3 Ca2+ = 40 mg/L SO42- = 29 mg/L Cl- = 17.8 mg/L

Second Stage Recarbonation:

Further addition of carbon dioxide to the water converts calcium carbonate alkalinity into calcium bicarbonate alkalinity according to Equation [11]. The final pH will be in the range of 9.5 to 8.5. 17

Table 1 shows all the species and their concentrations in mg/L and meq/L.
18

Theoretical Combinations Page 2

Concentration Component

(mg/L) 8.8 40 14.7 13.7 135 29 17.8

Eq. Calculations Wt. 22 20 23 50 48 8.8/22 = 40/2- = 13.7/23 = 135/50 = 29/48 =

Concentration

Example: Bar Graph Raw Water Page 3

0.4 0.0 Ca+2 CO2 HCO30.4 0.0 2.7
SO4-2 Cl

(meq/L) 0.40 2.00 1.20 0.60 2.70 0.60 0.50

19

2.0

3.2

3.8

CO2 Ca2+ Mg2+ Na+ Alkalinity (HCO3-) SO42Cl-

Mg+2 Na+

12.2 14.7/12.2 =

3.3 3.8

35.5 17.8/35.5 =

20

Ex: Chemical Requirements Page 4

Component Equation Concent.

Ex.:Lime & Soda Ash Quantities Pg 5

The total quantity of lime (CaO) is calculated as follows:
5.55 meq mg CaO 28 L meq 155.4 mg CaO lb MG 8.34 L mg L 1296lb

(meq/L) CO2 Ca(HCO3)2 Mg(HCO3)2 2 3 4&5 0.40 2.00 0.70

CaO Required

Na2CO3 Required

MgSO4 Excess Lime CaO Total

6&8

0.50

(meq/L) 0.40 2.00 2(0.70) = 1.40 0.5 1.25 5.55

(meq/L) 0 0 0

MG

The total quantity of soda ash (Na2CO3) is calculated as follows: 0.5

0.50 mg Na 2CO 3 meq 53 L meq mg Na 2CO 3 L lb MG mg L lb MG

26.5

8.34

221

0 0.5
21 22

Example: Residual Hardness Page 6

The final hardness of the water is assumed to be 40 mg/L as CaCO3 which is equal to 40/50 or 0.8 meq/L. The residual magnesium hardness is associated with magnesium hydroxide whose solubility is approximately 10 mg/L as CaCO3. Therefore, 10/50= 0.2 meq/L of Mg+2. Since the total final hardness is equal to 0.8 meq/L, the residual calcium hardness is equal to 0.8 0.2 = 0.6 meq/L of Ca+2 or 30/50 = 0.6 meq/L of Ca+2.

Example: Residual Ions Page 7

Sodium ion remaining in solution is equal to the original sodium concentration (0.6 meq/L) plus the sodium added from the soda ash (0.5 meq/L) which is 1.1 meq/L. The sulfate concentration remaining is equal to the original sulfate concentration of 0.6 meq/L. The final chloride concentration is equal to the original chloride concentration of 0.50 meq/L. Since the final alkalinity is associated with the final hardness (0.8 meq/L), 50% of the total alkalinity was assumed to be converted to the bicarbonate ion which is 0.4 meq/L. The remaining alkalinity is in the carbonate form and constitutes 0.4 meq/L.
24

23

Example: Bar Graph Finished Water Page 8

0.0 Ca+2 0.6 0.8 1.9 Mg+2

Example:1st Stage Recarbonation Page 9

The quantity of carbon dioxide required for first stage recarbonation is calculated as follows: 10/50=0.2

Na+
SO4-2 1.4

0.2

meq OH L

Mg(OH) 2

1.25

meq excess Lime L

CO3-2 HCO30.0 0.4 0.8

Cl1.9
25

1.45

meq mg CO 2 22 L meq

31.9

mg CO 2 L

26

Example: 2nd Stage Recarbonation Pg 10

The quantity of carbon dioxide required for second stage recarbonation is calculated as follows. Since 50% of the alkalinity is converted to bicarbonate form, 8.8 mg/L of carbon dioxide is required.

0.5 0.8

meq L

0.4

meq mg CO 2 22 L meq

8.8

mg L

The total quantity of carbon dioxide required for first and second stage recarbonation is calculated as follows:

31.9

mg L

8.8

mg L

40.7

mg CO 2 L

8.34

lb MG mg L

339

lb MG
27