Removal of Removal of Iron (Fe) and Manganese (MN) : DR Liu Yu

Removal of
Iron (Fe2+) and Manganese (Mn2+)
Dr Liu Yu
1
Problems with
ith iron and manganese
•. Many Fe2+ and Mn2+-related chemical compounds have colors,

also contribute to water turbidity
• Fe2+ and Mn2+ consume the dissolved

•. oxygen in water
•. Fe2+ and Mn2+ cause the taste of water even at very low conc
2
Healthy Concern
US EPA h
has established
t bli h d "secondary"
" d " limits
li it for
f Fe/Mn
F /M in
i drinking
d i ki water.
t
Fe 0.30 mg/L
g
Mn 0.05 mg/L
There is
Th i a health
h lth concern with
ith hi
high
h levels
l l off manganese in
i drinking
d i ki
water because manganese may affect neurological and muscle
function in humans.
3
Iron and Manganese Chemistry
Element Precipitate Reaction
Fe2+ Fe(OH)2 In absence of O2 and CO32-, pH≥10
Fe2+ FeCO3 In absence of O2 and S2-, pH>8,

pH>8 alk>0.01
alk>0 01 eq/L
Fe2+→Fe3+ Fe(OH)3 4Fe2+ + 2H+ + O2 → 4Fe3+ + 2OH-

2Fe2+ + Cl2 → 2Fe3+ +2Cl-
3Fe2+ + 4H+ + MnO4- → 3Fe3+ + MnO2 + 2H2O
Mn2+→Mn4+ MnO2 Mn2+ + 2H+ + 0.5O2 → Mn4+ + H2O
Mn2+ + Cl2 → Mn4+ + 2 Cl-
3Mn2+ + 2Mn7+ → 5Mn4+
Question: How to removeFe2+ and Mn2+?

4
Removal of Fe2+ and Mn2+ by Chemical Oxidation
Basic idea:
●. Iron and manganese are oxidized to form precipitates
Oxidants: O2, Cl2 and KMnO4
●. The p
precipitates
p are removed by
y sedimentation or filtration
Questions:
- How to estimate the chemical dosage?
- How to design a process to realize such chemical oxidation?
5
How to calculate chemicals required?
Example:
A well water supply contains 3.2

3 2 mg/L of iron and 0
0.8
8
mg/L of manganese at pH7.8. Estimate the dosage of
potassium permanganate
p p g required
q for iron and
manganese oxidation?
(Mn=55; Fe=56; K=39; O=16; H=1)
6
●. Fe2+ oxidation by permanganate:
3Fe2+ + 4H+ +MnO4- → 3Fe3+ + MnO2 + 2H2O

3×56 55+64
1 mg Fe2+ oxidized = (55+64)/(3×56) = 0.71 mg MnO4-
= 0.95 mg KMnO4
●. Mn2+ oxidation by permanganate:
3Mn2+ + 2Mn7+ → 5Mn4+

3×55 2×55
1 mg Mn2+ oxidized = 0.67 mg Mn7+ = 1.92 mg KMnO4

7
Summary:
●. 1 mgg Fe2+ oxidized = 0.95 mgg KMnO4
●. 1 mg Mn2+ oxidized = 1.92 mg KMnO4
KMnO4 required = (3.2 mg Fe2+/L)×0.95 + (0.8 mg Mn2+/L)×1.92
= 4.6 mg/L
8
Briefing
g of iron oxidation by
y oxygenation
yg
In the absence of NOM and water pH >5.5,

5.5,
[ 2+ ]
d[Fe
− = k[Fe 2+ ][OH − ]2 PO2
dt
Effect of pH:
The rate of oxidation of Fe2+ increased by 100-fold per pH unit
Effect of complexing agents:

NOM can bind or complex iron
iron, thus slow down the kinetics of
oxidation
9
Question:
How to show the effect of pH on iron oxidation rate?
d[Fe 2+ ]
− = k[Fe 2+ ][OH − ]2 PO2
dt
10
Typical
yp Fe and Mn Removal Process
Chemical injection
Filter
Finished
Fi ih d
water
Raw water
Mixing tank Reaction tank
Chemical
slurry
Fe and Mn Precipitates Backwash unit
11
Question:
Why a filter rather than a sedimentation tank

is used in the Fe-Mn removal process?
12
Some Design Criteria for Iron and Manganese Control
Element Units
Reaction tank:
Retention time 5-30 min at average flow after chemical feed
Filt
Filter:
Filter media 1.5 mm effective size or greater anthracite
Surface flow rate,, Q
Q/A gpm/ft2 to 10 gp
5 gp gpm/ft2
Backwash tank:
Backwash Q/A 15 25 gpm/ft2
15-25
Backwash tank size 20 min flow at 5 times normal filtration Q/A
13
Example:
To design a backwash tank with a diameter of 6 m,

m
and filtration Q/A is fixed at 5 m3/m2 h.
Calculate its volume.
14
• Cross section area A = πR2 = π×(3 m)2 = 28 m2
• Given Q/A = 5 m3/m2 h for filtration, thus flow rate for backwash:
Q = (5 × 5 m3/m2 h) × (28 m2) = 700 m3/h
• Retention time in the backwash tank = 20 min
V = Q × retention time = (700 m3/h) × (20/60 h)
= 233 m3
Configuration of the backwash tank:

6 m in diameter
or 2×6m×4m
2×6 ×4
8 m in depth
15
Other Methods for Iron and Manganese Control
•. Ion exchange
g
Due to the divalent nature of Fe2+ and Mn2+, they are readily
removed on ion exchange g materials
●. Membrane separation
Question:
What type of membrane
membrane, MF
MF, UF
UF, NF and RO?
16
Chemical costs for iron and manganese removal
Oxidant $/mil gala

Cl2b 21
2.1
KMnO4c 5.8
Aeration 05
0.5
a Concentration of Fe = 1 mg/L; Mn = 0.5 mg/L

b Cl : $0.11/1b
2
c KMnO : $0.55/1b
4
17
Solids produced from Fe2+ and Mn2+ removal process:
● Fe(OH)
( )2
● FeCO3
● Fe(OH)3
● MnO
M O2
Depends on chemical oxidation process employed!
18
Remarks:
If you have
h intension
i t i tot use chemical
h i l oxidation
id ti process,
● The amount of chemical slurry generated must be

estimated;
● Proper method to handle that slurry should be

recommended
● The treatment cost of slurry should be accounted for in

overall cost
19
Treatment Types NOT Recommended
- Magnetic/Electronic Fe/Mn Removal Devices
So far, there is no proof that magnetic/ electronic Fe/Mn removal

devices are effective. It is difficult to obtain objective test data for
methodologies that do not remove the contaminants.
- Reverse Osmosis
This process will become clogged by rust particles, Fe/Mn bacteria,

silt and cannot be regenerated.
silt, regenerated New membranes would be required
frequently.
20

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Removal of

Iron (Fe2+) and Manganese (Mn2+)

•. Many Fe2+ and Mn2+-related chemical compounds have colors,

• Fe2+ and Mn2+ consume the dissolved

Element Precipitate Reaction

Fe2+ Fe(OH)2 In absence of O2 and CO32-, pH≥10

Fe2+ FeCO3 In absence of O2 and S2-, pH>8,

Fe2+→Fe3+ Fe(OH)3 4Fe2+ + 2H+ + O2 → 4Fe3+ + 2OH-

Question: How to removeFe2+ and Mn2+?

Oxidants: O2, Cl2 and KMnO4

A well water supply contains 3.2

(Mn=55; Fe=56; K=39; O=16; H=1)

3Fe2+ + 4H+ +MnO4- → 3Fe3+ + MnO2 + 2H2O

1 mg Fe2+ oxidized = (55+64)/(3×56) = 0.71 mg MnO4-

●. Mn2+ oxidation by permanganate:

3Mn2+ + 2Mn7+ → 5Mn4+

1 mg Mn2+ oxidized = 0.67 mg Mn7+ = 1.92 mg KMnO4

●. 1 mgg Fe2+ oxidized = 0.95 mgg KMnO4

●. 1 mg Mn2+ oxidized = 1.92 mg KMnO4

KMnO4 required = (3.2 mg Fe2+/L)×0.95 + (0.8 mg Mn2+/L)×1.92

In the absence of NOM and water pH >5.5,

Effect of complexing agents:

Mixing tank Reaction tank

Why a filter rather than a sedimentation tank

To design a backwash tank with a diameter of 6 m,

Calculate its volume.

Q = (5 × 5 m3/m2 h) × (28 m2) = 700 m3/h

• Retention time in the backwash tank = 20 min

V = Q × retention time = (700 m3/h) × (20/60 h)

Configuration of the backwash tank:

Oxidant $/mil gala

a Concentration of Fe = 1 mg/L; Mn = 0.5 mg/L

Depends on chemical oxidation process employed!

● The amount of chemical slurry generated must be

● Proper method to handle that slurry should be

● The treatment cost of slurry should be accounted for in

- Magnetic/Electronic Fe/Mn Removal Devices

So far, there is no proof that magnetic/ electronic Fe/Mn removal

This process will become clogged by rust particles, Fe/Mn bacteria,

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