Water Softening 1712086475
Water Softening 1712086475
TOPICS
• Water Hardness
• Calculating Calcium Hardness as CaCO3
• Calculating Magnesium Hardness as CaCO3
• Calculating Total Hardness
• Calculating Carbonate and Noncarbonate Hardness
• Alkalinity Determination
• Determining Bicarbonate, Carbonate, and Hydroxide Alkalinity
• Lime Dosage Calculation for Removal of Carbonate Hardness
• Calculation for Removal of Noncarbonate Hardness
• Recarbonation Calculation
• Calculating Feed Rates
• Ion Exchange Capacity
• Water Treatment Capacity
• Treatment Time Calculation (Until Regeneration Required)
• Salt and Brine Required for Regeneration
WATER HARDNESS
Hardness in water is caused by the presence of certain positively charged metallic ions in solution in
the water. The most common of these hardness-causing ions are calcium and magnesium; others
include iron, strontium, and barium. The two primary constituents of water that determine the hardness
of water are calcium and magnesium. If the concentration of these elements in the water is known,
the total hardness of the water can be calculated. To make this calculation, the equivalent weights of
calcium, magnesium, and calcium carbonate must be known; the equivalent weights are given below.
Equivalent Weights
Example 21.1
Problem
A water sample has calcium content of 51 mg/L. What is this calcium hardness expressed as CaCO3?
211
212 Mathematics for Water/Wastewater Treatment Plant Operators
Solution
Referring to Equation 21.1:
x mg L 51 mg L
=
50.045 20.04
51 × 50.045
x=
20.45
= 124.8 mg L Ca as CaCO3
Example 21.2
Problem
The calcium content of a water sample is 26 mg/L. What is this calcium hardness expressed as
CaCO3?
Solution
Again referring to Equation 21.1:
x mg L 26 mg L
=
50.045 20.04
26 × 50.045
x=
20.45
= 64.9 mg L Ca as CaCO3
Example 21.3
Problem
A sample of water contains 24 mg/L magnesium. Express this magnesium hardness as CaCO3.
Solution
Referring to Equation 21.2:
x mg L 24 mg L
=
50.045 12.15
24 × 50.045
x=
12.15
= 98.9 mg L
Example 21.4
Problem
The magnesium content of a water sample is 16 mg/L. Express this magnesium hardness as CaCO3.
Water Softening 213
Solution
x mg L 16 mg L
=
50.045 12.15
16 × 50.045
x=
12.15
= 65.9 mg L Mg as CaCO3
Example 21.5
Problem
A sample of water has calcium content of 70 mg/L as CaCO3 and magnesium content of 90 mg/L
as CaCO3.
Solution
Referring to Equation 21.3:
Example 21.6
Problem
Determine the total hardness as CaCO3 of a sample of water that has calcium content of 28 mg/L
and magnesium content of 9 mg/L.
Solution
Express calcium and magnesium in terms of CaCO3:
x mg L 28 mg L
=
50.045 20.04
x = 69.9 mg L Mg as CaCO3
214 Mathematics for Water/Wastewater Treatment Plant Operators
x mg L 9 mg L
=
50.045 12.15
x = 37.1 mg L Mg as CaCO3
When the alkalinity (as CaCO3) is greater than the total hardness, all the hardness is carbonate
hardness:
Total hardness (mg/L) as CaCO3 = carbonate hardness (mg/L) as CaCO3 (21.5)
When the alkalinity (as CaCO3) is less than the total hardness, then the alkalinity represents
carbonate hardness and the balance of the hardness is noncarbonate hardness:
Example 21.7
Problem
A water sample contains 110 mg/L alkalinity as CaCO3 and 105 mg/L total hardness as CaCO3.
What is the carbonate and noncarbonate hardness of the sample?
Water Softening 215
Solution
Because the alkalinity is greater than the total hardness, all the hardness is carbonate hardness:
Example 21.8
Problem
The alkalinity of a water sample is 80 mg/L as CaCO3. If the total hardness of the water sample
is 112 mg/L as CaCO3, what is the carbonate and noncarbonate hardness (in mg/L as CaCO3)?
Solution
Alkalinity is less than total hardness; therefore, both carbonate and noncarbonate hardness will be
present in the hardness of the sample. Referring to Equation 21.6,
112 mg L = 80 mg L − x mg L
112 mg L − 80 mg L = x mg L
x = 32 mg L noncarbonate hardness
ALKALINITY DETERMINATION
Alkalinity measures the acid-neutralizing capacity of a water sample. It is an aggregate property
of the water sample and can be interpreted in terms of specific substances only when a complete
chemical composition of the sample is also performed. The alkalinity of surface waters is primarily
due to the carbonate, bicarbonate, and hydroxide content and is often interpreted in terms of the
concentrations of these constituents. The higher the alkalinity, the greater the capacity of the water
to neutralize acids; conversely, the lower the alkalinity, the less the neutralizing capacity. To detect
the different types of alkalinity, the water is tested for phenolphthalein and total alkalinity, using
Equation 21.8 and Equation 21.9:
A × N × 50, 000
Phenolphthalein alkalinity ( mg L ) as CaCO3 = (21.8)
mL of sample
B × N × 50, 000
Total alkalinity ( mg L ) as CaCO3 = (21.9)
mL of sample
where
A = titrant (mL) used to pH 8.3
B = titrant (mL) used to titrate to pH 4.5
N = normality of the acid (0.02 N H2SO4 for this alkalinity test)
50,000 = a conversion factor to change the normality into units of CaCO3
216 Mathematics for Water/Wastewater Treatment Plant Operators
Example 21.9
Problem
A 100-mL water sample is tested for phenolphthalein alkalinity. If 1.3-mL titrant is used to pH 8.3
and the sulfuric acid solution has a normality of 0.02 N, what is the phenolphthalein alkalinity of
the water?
Solution
Referring to Equation 21.8:
A × N × 50, 000
Phenolphthalein alkalinity ( mg L as CaCO 3 ) =
mL of sample
Example 21.10
Problem
A 100-mL sample of water is tested for alkalinity. The normality of the sulfuric acid used for
titrating is 0.02 N. If 0 mL is used to pH 8.3, and 7.6 mL titrant is used to pH 4.5, what is the
phenolphthalein and total alkalinity of the sample?
Solution
Example 21.11
Problem
A water sample is tested for phenolphthalein and total alkalinity. If the phenolphthalein alkalinity
is 10 mg/L as CaCO3 and the total alkalinity is 52 mg/L as CaCO3, what are the bicarbonate,
carbonate, and hydroxide alkalinities of the water?
Water Softening 217
TABLE 21.1
Interpretation of Results Values
Alkalinity (mg/L as CaCO3)
Results of Bicarbonate Carbonate Hydroxide
Titration Alkalinity Alkalinity Alkalinity
P =0 T 0 0
P <½T T – 2P 2P 0
P =½T 0 2P 0
P >½T 0 2T – 2P 2P – T
P =T 0 0 T
Solution
Based on titration test results, phenolphthalein alkalinity (10 mg/L) is less than half of the total
alkalinity (52 mg/L ÷ 2 = 26 mg/L; see Table 21.1); therefore, each type of alkalinity is calculated
as follows:
Bicarbonate alkalinity = T − 2 P
= 52 mg L − 2(10 mg L )
= 52 mg L − 20 mg L
= 32 mg L as CaCO3
Carbonate alkalinity = 2 P
= 2(10 mg L )
= 20 mg L as CaCO3
Example 21.12
Problem
Results of alkalinity titrations on a water sample are as follows:
Solution
Now use Table 21.1 to calculate the other alkalinity constituents (P > ½ T):
Carbonate alkalinity = 2 T − 2 P
= 2(24 mg L ) − 2(14 mg L )
= 20 mg L as CaCO3
Hydroxide alkalinity = 2 P − T
= 2(14 mg L ) − (24 mg L )
= 4 mg L as CaCO3
Quicklime (CaO2) 56
Hydrated lime (Ca(OH)2) 74
Magnesium (Mg2+) 24.3
Carbon dioxide (CO2) 44
Magnesium hydroxide (Mg(OH)2) 58.3
Soda ash (Na2CO3) 100
Alkalinity (as CaCO3) 100
Hardness (as CaCO3) 100
where
A = CO2 in source water (mg/L as CO2 × 56/44)
B = bicarbonate alkalinity removed in softening (mg/L as CaCO3 × 56/100)
C = hydroxide alkalinity in softener effluent (mg/L as CaCO3 × 56/100)
D = magnesium removed in softening (mg/L as Mg2+ × 56/24.3)
1.15 = excess lime dosage (using 15% excess)
Note: For hydrated lime dosage, use Equation 21.10 as given for quicklime, except substitute 74
for 56 when determining A, B, C, and D.
Example 21.13
Problem
A water sample has a carbon dioxide content of 4 mg/L as CO2, total alkalinity of 130 mg/L as
CaCO3, and magnesium content of 26 mg/L as Mg2+. Approximately how much quicklime (CaO ×
90% purity) will be required for softening? (Assume 15% excess lime.)
Solution
Calculate the A to D factors:
= 4 mg L × (56 44)
= 73 mg L
Quicklime dosage ( mg L ) =
(5 mg L + 73 mg L + 0 + 60 mg L ) × 1.15
0.90
= 176 mg L CaO
Example 21.14
Problem
The characteristics of a water sample are as follows: 4 mg/L CO2 as CO2, 175 mg/L total alkalinity
as CaCO3, and 20 mg/L magnesium as Mg2+. What is the estimated hydrated lime (Ca(OH)2) (90%
pure) dosage required for softening (in mg/L)? (Assume 15% excess lime.)
220 Mathematics for Water/Wastewater Treatment Plant Operators
Solution
Determine the A to D factors:
= 4 mg L × (74 44)
= 130 mg L
Example 21.15
Problem
A water sample has a total hardness of 250 mg/L as CaCO3 and a total alkalinity of 180 mg/L.
What soda ash dosage will be required to remove the noncarbonate hardness (in mg/L)?
Solution
Calculate the noncarbonate hardness using Equation 21.11:
x = 70 mg L
Example 21.16
Problem
Calculate the soda ash required (in mg/L) to soften water if the water has a total hardness of 192
mg/L and a total alkalinity of 103 mg/L.
Solution
Determine noncarbonate hardness:
192 mg L = 103 mg L + x mg L
192 mg L − 103 mg L = x
89 mg L = x
RECARBONATION CALCULATION
Recarbonation involves the reintroduction of carbon dioxide into the water, either during or after
lime softening, lowering the pH of the water to about 10.4. After the addition of soda ash,
recarbonation lowers the pH of the water to about 9.8, promoting better precipitation of calcium
carbonate and magnesium hydroxide. Equation 21.13 and Equation 21.14 are used to estimate
carbon dioxide dosage.
[
Total CO 2 dosage ( mg L ) = Ca (OH)2 excess (mg L ) × ( 44) 74 + ]
(21.14)
[Mg 2+
]
residual (mg L ) × ( 44) 24.3
Example 21.17
Problem
The A, B, C, and D factors of the excess lime equation have been calculated as follows: A = 14 mg/L;
B = 126 mg/L; C = 0; and D = 66 mg/L. If the residual magnesium is 5 mg/L, what is the carbon
dioxide (in mg/L) required for recarbonation?
Solution
Calculate the excess lime concentration:
= 31 mg L
222 Mathematics for Water/Wastewater Treatment Plant Operators
= 18 mg L + 9 mg L
= 27 mg L
Example 21.18
Problem
The A, B, C, and D factors of the excess lime equation have been calculated as: A = 10 mg/L; B =
87 mg/L; C = 0; D = 111 mg/L. If the residual magnesium is 5 mg/L, what carbon dioxide dosage
would be required for recarbonation?
Solution
The excess lime is:
= 208 × 0.15
= 31 mg L
= 18 mg L + 9 mg L
= 27 mg L CO 2
Feed rate (lb/day) = Flow rate (MGD) × chemical dose (mg/L) × 8.34 lb/gal (21.15)
Example 21.19
Problem
Jar tests indicate that the optimum lime dosage is 200 mg/L. If the flow to be treated is 4.0 MGD,
what should be the chemical feeder setting in lb/day and lb/min?
Solution
Calculate the lb/day feed rate using Equation 21.15:
Feed rate (lb/day) = Flow rate (MGD) × chemical dose (mg/L) × 8.34 lb/gal
= 6672 lb/day
6672 lb day
Feed rate (lb min) =
1440 min day
= 4.6 lb min
Example 21.20
Problem
What should be the lime dosage setting (in lb/day and lb/hr) if the optimum lime dosage has been
determined to be 125 mg/L and the flow to be treated is 1.1 MGD?
Solution
The lb/day feed rate for lime is:
= 1147 lb day
1147 lb day
Lime (lb min) =
24 hr day
= 48 lb hr
sodium; bicarbonate, sulfate, and chloride are the normal negatively charged ions of concern. An
ion exchange medium, called resin, is a material that exchanges a hardness-causing ion for another
one that does not cause hardness, holds the new ion temporarily, and then releases it when a
regenerating solution is poured over the resin. The removal capacity of an exchange resin is generally
reported as grains (gr) of hardness removal per cubic foot (ft3) of resin. To calculate the removal
capacity of the softener, we use:
Exchange capacity (grains) = Removal capacity (grains/cu ft) × media volume (cu ft) (21.17)
Example 21.21
Problem
The hardness removal capacity of an exchange resin is 24,000 grains/cu ft. If the softener contains
a total of 70 cu ft of resin, what is the total exchange capacity (in grains) of the softener?
Solution
Referring to Equation 21.17:
= 1,540,000 grains
Example 21.22
Problem
An ion-exchange water softener has a diameter of 7 ft. The depth of resin is 5 ft. If the resin has
a removal capacity of 22-kilograins/cu ft, what is the total exchange capacity of the softener (in
grains)?
Solution
Before the exchange capacity of a softener can be calculated, the cu ft resin volume must be known:
= 0.785 × 7 ft × 7 ft × 5 ft
= 192 cu ft
= 4,224,000 grains
Example 21.23
Problem
An ion-exchange softener has an exchange capacity of 2,455,000 grains. If the hardness of the
water to be treated is 18.6 grains/gallon, how many gallons of water can be treated before regen-
eration of the resin is required?
Solution
Referring to Equation 21.18:
Example 21.24
Problem
An ion-exchange softener has an exchange capacity of 5,500,000 grains. If the hardness of the
water to be treated is 14.8 grains/gallon, how many gallons of water can be treated before regen-
eration of the resin is required?
Solution
Again referring to Equation 21.18:
Example 21.25
Problem
The hardness removal capacity of an ion-exchange resin is 25 kilograins/cu ft. The softener contains
a total of 160 cu ft of resin. If the water to be treated contains 14.0 gpg hardness, how many gallons
of water can be treated before regeneration of the resin is required?
Solution
Both the water hardness and the exchange capacity of the softener must be determined before the
gallons of water can be calculated:
= 4,000,000 grains
Example 21.26
Problem
An ion-exchange softener can treat a total of 642,000 gallons before regeneration is required. If
the flow rate treated is 25,000 gph, how many hours of operation do we have before regeneration
is required?
Solution
Referring to Equation 21.19:
Example 21.27
Problem
An ion exchange softener can treat a total of 820,000 gallons of water before regeneration of the
resin is required. If the water is to be treated at a rate of 32,000 gph, how many hours of operation
are there until regeneration is required?
Solution
Again referring to Equation 21.19:
Salt required (lb) = Salt required (lb/kgrains removed) × hardness removed (kgrains) (20.20)
Water Softening 227
To determine the brine solution (the lb salt per gal brine factor used in Equation 21.21), we must
refer to the salt solutions table below:
10 0.874 6.69
11 0.990 7.41
12 1.09 8.14
13 1.19 8.83
14 1.29 9.63
15 1.39 10.4
Example 21.28
Problem
An ion-exchange softener removes 1,310,000 grains hardness from the water before the resin must
be regenerated. If 0.3 lb salt is required for each kilograin removed, how many pounds of salt will
be required for preparing the brine to be used in resin regeneration?
Solution
Salt required (lb) = Salt required (lb/1000 grains) × hardness removed (kg)
= 393 lb
Example 21.29
Problem
A total of 430 lb of salt is required to regenerate an ion exchange softener. If the brine solution is
to be a 12% brine solution, how many gallons of brine will be required? (See Salt Solutions table
to determine the lb salt/gal brine for a 12% brine solution.)
Solution
430 lb salt
=
1.09 lb salt gal brine
= 394 gal of 12% brine
Thus, 430 lb salt to make up a total of 394 gallons of brine will result in the desired 12% brine
solution.