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Determining an Effective

Coagulant Dosage
Raymond D. Letterman
Department of Civil and Environmental
Engineering, Syracuse University

Edwin C. Tifft, Jr.


Water Supply Symposium
September 22, 2010

The material in this talk is from:


Raymond D. Letterman and Sotira Yiacoumi,
Chapter 8, Coagulation and Flocculation,
Water Quality and Treatment, 6th Edition,
James K. Edzwald, Technical Editor, McGrawHill, NY (2010)
Expected publication date is December 2010.

The focus of this talk:

A method* for:
selecting the coagulant type
estimating the coagulant dosage
estimating acid or base requirements, if any
Hydrolyzing metal salt coagulants
Removal of NOM (natural organic material)

*Evaluating design alternatives and estimating treatment costs

The method uses:

The effective acid content of hydrolyzing


metal salt (HMS) coagulants.

An understanding of the effect of pH on the


solubility of the metal hydroxide precipitate
[Al(OH)3 and Fe(OH)3].

A simple relationship between the initial NOM


concentration (TOC) and the HMS dosage.

Equilibrium chemistry calculations that relate


alkalinity pH total inorganic carbon conc.

Effective Acid Content of Hydrolyzing


Metal Salt Coagulants

Hydrolysis of Al (and Fe)


Aluminum ion

Al(H 2 O)

Aluminum hydrolysis product

3+
6

Al(OH)(H2 O)

Bicarbonate ion

Hydrogen ion

2+
5

+ H

Carbon dioxide

2H + HCO H 2 CO 3 (CO 2 + H 2 O) + H
3

Alkalinity and pH decrease

Hydrolysis of Al (and Fe)


Al(H2O)36 +

aquo aluminum ion


Low pH

Al(OH)(H2O)52 +

mononuclear species

Al13O4 (OH)724+

polynuclear species

Al(OH)3 (s)

aluminum hydroxide precipitate

Al(OH)-4

aluminate ion species

High pH

Calculating the Effective Acid Content


Prehydrolyzed product solutions
300 3B
Effective acid content (meq /mg metal) =
100(AW)
B = basicity of the product (0 to < 83%)
A W = atomic weight of the metal (Al, AW = 27 g and Fe, AW = 55.9 g)

Calculating the Effective Acid Content


Acidified (acid supplemented) product solutions
300
A
Effective acid content (meq/mg
metal)
=
+
100( AW ) EW ( M )
A = weight percent of pure acid (H2SO4 or HCl)
EW = equivalent weight of the acid (H2SO4, EW = 49 g/eq and HCl, EW =
36.5 g/eq)
AW = atomic weight of the metal (Al, AW = 27 g and Fe, AW = 55.9 g)
M = metal content (weight % Al or Fe) of the coagulant product solution

Example calculation of the effective acid


content using numbers from product data
sheets

Product Data Sheet Example


Product A

Product A Example Calculation


300 3B 300 3(0)
Effective acid content =
=
= 0.111 meq /mg Al
100(AW)
100(27)

Alum

Product Data Sheet Example


Product B

=B

Product B Example Calculation


300 3B 300 3(75)
Effective acid content =
=
= 0.028 meq /mg Al
100(AW)
100(27)

Prehydrolyzed Al product
with B = 75%

Product Data Sheet Example


Product C

=M
=A

Product C Example Calculation


Effective acid content =

300
A
300
10
+
=
+
= 0.181 meq/mg Al
100(AW) EW(M) 100(27) 49(2.9)

Alum with 10% H2SO4

Effective Acid Content - Examples


Coagulant
Solution

Basicity (B, %)

A, weight %
pure acid

M, weight %
metal

Calculated Effective Acid


Content (meq/mg metal)

Aluminum
Sulfate (Alum)

4.3 (Al)

0.111

Polyaluminum
Chloride
(PACl)

80

12.3 (Al)

0.022

Acid
Supplemented
Alum
(Acidized
Alum)

10 (H2SO4)

2.8 (Al)

0.184

Ferric Sulfate
(with 2%
excess acid)

2 (H2SO4)

10 (Fe)

0.058

The effective acid content can also be measured by titration with strong base.

Effective Acid Content


8.0
Raw water - pH = 7.3, alkalinity = 38.5 mg/L as CaCO3 (0.77 meq/L)

Ferric sulfate

7.0

Alum

pH

PACl (B=75%)
PACl (B=50%)

6.0

Alum (A=5%)
Alum (A=10%)
Ferric Chloride
PACl (B=10%)

5.0

4.0
0

10

20

Coagulant dosage (mg M/L)

30

Coagulant Product Solutions Used in


the Titrations Plotted in the Graph
Effective Acid Content
(EAC, meq/mg M)

Coagulant Product Solution

Label in
Figures

Acid supplemented alum with A =10%

Alum (A=10%)

0.168

Acid supplemented alum with A = 5%

Alum (A=5%)

0.135

Conventional Alum (A = 0 and B = 0%)

Alum

0.111

Polyaluminum chloride with B = 10%

PACl (B=10%)

0.100

Polyaluminum chloride with B = 50%

PACl (B=50%)

0.056

Ferric Chloride

Ferric Chloride

0.054

Ferric Sulfate

Ferric Sulfate

0.054

Polyaluminum chloride with B = 75%

PACl (B=75%)

0.028

Effective Acid Content


8.0
Raw water - pH = 7.3, alkalinity = 38.5 mg/L as CaCO3 (0.77 meq/L)
Ferric sulfate

7.0

Alum
PACl (B=75%)

pH

PACl (B=50%)

6.0

Calculated
Alum (A=5%)
Alum (A=10%)
Ferric Chloride

5.0

PACl (B=10%)

4.0
0.0

0.5

1.0

1.5

2.0

Coagulant dosage, strong acid equivalents (meq/L)

meq/L = mg/L x effective acid content

Solubility of the Metal Hydroxide


Precipitate
Minimize Residual Aluminum
Establish a Target pH for the
Coagulation Process

Aluminum Hydroxide Solubility Diagram


-2
-3
-4

Al(OH)3 precipitate

log[Al(III)]

-5

Temperature =
25C

-6
-7
-8

Al(OH)4-

AlOH2+

-9
Al3+

-10
-11
4

8
pH

10

11

Ferric Hydroxide Solubility Diagram


-5

Temperature = 25 C
-6

log[Fe(III)]

-7

-8
Fe(OH)3 precipitate

-9
FeOH2+

-10
Fe(OH)2+

-11
Fe(OH)4-

Fe3+

-12
4

8
pH

10

11

pH of Minimum Al(OH)3 Solubility


pHm - pH at minimum soluble Al concentration
6.9
6.8
6.7
6.6

pHm

6.5
6.4
6.3
6.2
6.1
6.0
5.9
0

10

15

20

Temperature (degrees C)

25

30

Minimum Soluble Al Concentration


Minimum soluble aluminum concentration Alm vs temperature

Minimum Soluble Al (microgram Al/L)

25

20

15

10

0
0

10

15

20

Temperature (degrees C)

25

30

Alum addition to a solution with an initial alkalinity = 100 mg/L


as CaCO3 and initial pH = 8.5
10

10

0.1
9

Soluble Al

0.01

pH

Soluble Al Concentration (mg Al/L)

Al added

0.001
0.01

0.1

1
Al Dosage (mg Al/L)

10

100

4
0.01

0.1

1
Al Dosage (mg Al/L)

10

100

Alum addition to a solution with an initial alkalinity = 10 mg/L as


CaCO3 and initial pH = 7.5

10

Al added

1
7

0.1
pH

Soluble Al Concentration (mg Al/L)

100

0.01

Soluble Al
5

0.001
0.01

0.1

1
Al Dosage (mg Al/L)

10

100

4
0.01

0.1

1
Al Dosage (mg Al/L)

10

100

Relationship between the initial NOM


concentration (TOC) and the HMS
dosage

Models for describing HMS dosage


NOM concentration relationship

Adsorption isotherm approach


Steve Dentel, Marc Edwards, Kastl, et al.

Simple proportionality
Van Benschoten and Edzwald, and others

HMS dosage, m = R x TOCo


m = hydrolyzing metal salt
dosage in mg metal/L

TOCo = raw water total


organic carbon concentration
in mg C/L

Magnitude of R (proportionality constant)


5.0
4.5
M = Fe

4.0
3.5

R (mg M/mg C)

iron salts

M = Al

3.0
2.5
2.0

aluminum
salts

1.5
1.0
0.5
0.0
3

6
pH

The pH on the xaxis is the final


value after the acid
from the HMS
coagulant has
reacted with the
alkalinity of the
solution.

Removal of TOC (when m = R x TOCo)


Archer-Singer (2006)

Pernitsky-Edzwald (2006)

Edzwald-Kaminski (2009)

Tambo-Kamei-Itoh (1989)

TOC removal %
does not depend
on the final pH.
The SUVA of the
raw water NOM
is an important
indicator.

Linear (Archer-Singer (2006))


90

Percent TOC Removal

80
y = 13.871x - 7.1312
R2 = 0.5497

70
60
50
40
30
20
10
0
0.0

1.0

2.0

3.0

SUVA (L/m mg)

4.0

5.0

SUVA = UV light
absorbance at
=254 nm
divided by TOCo.

Steps to Selecting a HMS Coagulant

Select a target final pH (pHf) based on


minimum precipitate solubility (Al salts).

Estimate the required coagulant dosage


using R at pHf. (m = R x TOCo)

Calculate the final alkalinity at pHf (alkf)


and the change in the alkalinity (alko
alkf)

Estimating the change in alkalinity


with HMS coagulant addition

Use the initial pH (pHo), initial alkalinity


(alko), and water temperature to
determine the total inorganic carbon
concentration of the solution (CT).

Estimating the change in alkalinity


with HMS coagulant addition (cont.)

Assume CT remains constant during


coagulation (closed-to-atmospheric CO2
assumption) and use the selected value
of pHf with CT to determine the final
alkalinity (alkf) of the solution.
Spreadsheet programs
Special nomographs
Deffeyes diagram

Tools for making


this calculation

Deffeyes Diagram Method


25 degrees C

Alkalinity (milliequivalents/L)

alko = 1.5 meq/L

pHo = 7.7

pHf =

3.0

6.12

2.5

7.0

2.0

7.5

1.5

8.5

1.0

0.5

alkf = 0.6 meq/L

0.0
0

Inorganic Carbon Concentration, CT (millimoles/L)

mg/L as CaCO3 = 50 x meq/L

Selecting the type of coagulant


Initial
alkalinity
(meq/L)

Calculated final
alkalinity (meq/L)

Dosage of any pH adjustment chemical


(e.g., NaOH or H2SO4) in meq/L

alk o - alk f
X
= EAC of coagulant solution (meq/mgM)
m
m
Calculated dosage of
coagulant (mg M/L)
m = R x TOCo

Calculating the dosage of pH


adjustment chemical(s)
This image cannot currently be displayed.

alk o - alk f
mg of additive
Dosage (mg/L) = m
- EAC

m
meq

mg
alk - alk f

Note : When o
quantity is a negative number.
- EAC < 0 the additive must be a base and the
meq
m

pH adjustment chemicals
Additive
Sodium
Bicarbonate
(NaHCO3)
Sodium
Carbonate
(Na2CO3)
Hydrated Lime
(Ca(OH)2
Sodium
Hydroxide
(NaOH)
Sulfuric Acid
(H2SO4)
Hydrochloric
Acid (HCl)
Carbon Dioxide
(CO2)

Additive
Dosage

Change in
alkalinity
(meq/L)

Change in inorganic
carbon concentration, CT
(moles C/L)

1 mg/L

1.19 x 10-2

1.19 x 10-5

1 mg/L

1.89 x 10-2

9.43 x 10-6

1 mg/L

2.7 x 10-2

1 mg/L

2.5 x 10-2

1 mg/L

-2.04 x 10-2

1 mg/L

-2.82 x 10-2

1 mg/L

2.0 x 10-5

Example calculation

TOCo = 11.5 mgC/L


SUVA = 3.5 L/m mg

Temperature = 25 C
alko = 1.5 meq/L (75 mg/L as CaCO3)
pHo = 7.5

Select target (final) pH

pHf = 6.1

pH - minimum solubility of Al(OH)3 at


T = 25C
-2
-3
-4
log[Al(III)]

-5
-6
-7
-8
-9
-10
-11
4

8
pH

10

11

Determine HMS coagulant dosage (m)


pHf = 6.1
R = 0.5 mg Al/mg C
m = R x TOCo = 0.5 x 11.5 mg C/L = 5.7
mg Al/L

5.0
4.5

M = Fe

4.0

M = Al

R (mg M/mg C)

3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
3

6
pH

Determine the final alkalinity (alkf)

Use pHo = 7.5 and alko = 1.5 meq/L


CT = 1.6 x 10-3 moles C/L

Use pHf = 6.1 and CT = 1.6 x 10-3 moles C/L


alkf = 0.6 meq/L

Alkalinity (milliequivalents/L)

25 degrees C

pHf =

3.0

6.12

2.5

7.0

2.0

7.5

1.5

8.5

1.0

0.5

0.0
0

Inorganic Carbon Concentration, CT (millimoles/L)

Determine the effective acid content


of the coagulant (or coagulant +)
alk o - alk f
1.5 - 0.6
meq
X
=
= 0.158
= EAC
m
5.7
mg Al
m
Options:
1) Use alum with EAC = 0.111 meq/mg Al and supplemental strong acid
(X/m = 0.158 0.111 = 0.047 meq/mg Al or X = 0.047 x 5.7 = 0.27
meq/L
2) Use acid supplemented alum with A/M = 2.5 % H2SO4/% Al
Effective acid content (meq/mg
=
metal)

300
A
+
100( AW ) EW ( M )