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Lecture
WATER TREATMENT WATER TREATMENT

Chapter 5
AERATION
IRON AND MANGANESE
REMOVAL

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IRON AND MANGANESE REMOVAL AERATION

Contents Theory of Aeration

• Solubility of gas in water

• Aeration
CS = kD. Ca
• Principles of iron and manganese removal
• kD: depends on kind of gas
– high kD = high solubility , hard to remove
• Methods
– low kD = low solubility , easy to remove

• concentration in the air --> Ca

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AERATION AERATION

Theory of Aeration Theory of Aeration

Table: Value of kD diffusion coefficient
• Henry’s law

CS = kD. Ca kD
Kind of air M (g/mol)
0oC 10oC 20oC 30oC

CS = saturation concentration of the gas in water [g/m3] O2 32 0.0493 0.0398 0.0337 0.0296

H2S 34 4.690 3.650 2.870

Ca = concentration of gas in air [g/m3]
CO2 44 1.710 1.230 0.942 0.738
kD= diffusion coefficient [-]
O3 48 0.641 0.539 0.395 0.259

Air 0.0288 0.0234 0.0200 0.0170

5 Source: Trinh Xuan Lai (2004). Water treatment for domestic and industrial application. 6

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AERATION

Theory of Aeration Theory of Aeration

• Universal gas law Partial pressure

• Partial pressure depends on the composition of the air:

• p = partial pressure of the gas [Pa]
• (78.084% N2; 20.948% O2; 0.934% Ar; 0.032% CO2; 0.002% other
• V = total gas volume [m3]
gases.
• n = number of mol of the gas [-]
• Partial pressure of oxygen at a standard pressure of 101325 Pa (1
• R = universal gas constant = 8,3142 J/(K*mol)

• T = temperature of the gas [oK] atmosphere)

• M = molecular weight [g/mol] PO2= 0.21*101325 = 21.226 kPa

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AERATION C.5

What is the saturation concentration of carbon dioxide in water Aeration kinetic

(pressure = 101325 Pa, T = 10°C)? M = 44 g/mol, T = 283oK

Gas Distribution coefficient kD Volume percentage [%]

CO2 1.23 0.034

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Aeration kinetic Aeration efficiency

Example of determine of k2:

Aeration efficiency
K = 1 – exp(-k2.t)
Dissolved oxygen concentration measured at various time for a submerged

aerator. Determine of k2:

With spray aeration: C = C0 + K (CS – C0)
Time (min) 4 7 10 13 16 19 22

DO, mg/L 0.8 1.8 3.3 4.5 5.5 6.2 7.3

Assumed: saturated DO = 10.17 mg/L (at 15oC) tc : hydraulic retention time, s

h: height from spray to water level, m

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Aeration efficiency Aeration efficiency

With air, water downward:

With cascade: C = CS - (CS – C0)(1 – K /n)n

n: number of steps
K = total efficiency

With air upward, water downward:

http://what-when-how.com/petroleum-
refining/description-of-reactors-petroleum-refining/

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Aeration efficiency Aeration example 2:

– R : air-water ratio, A co-current tower aerator has a R of 5 and a contact time of 20s, height
of aeration tower h = 6 m. What is the CO2 concentration after aeration if
– Cs: saturation concentration at initial condition
the influent concentration is 65 mg/l and the saturation concentration for
– Co: initial air concentration, mg/l
CO2 in water is 1,0 mg/l? Assumed: kD of CO2 =1.2 and k2 = 0.2 s-1.
– KD : diffusion coefficient air into water

– k2 : gas separation factor If h is increased from 6 to 8 m, calculate the effluent concentration with
the same loading rate?
– t : contact time, s; t = h / q ,

h: aeration tower height, What is the efficiency of counter current tower aeration if we use the
q: loading rate, 36 – 150 m3/m2.h same conditions (h = 6m and t = 20s)
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IRON AND MANGANESE REMOVAL IRON AND MANGANESE REMOVAL

Definition Definition

What problems are caused by iron and manganese? Chemistry of iron and manganese in water:

• Clothing washed in water containing excessive Fe and Mn may

Fe and Mn can be present in water in one of three basic forms:
become stained a brownish color.
1. Dissolved: ferrous (Fe2+) and manganous (Mn2+)
• The taste of beverages, such as tea and coffee, may also be
2. Particulate: ferric (Fe3+) and manganic (Mn4+) states
affected by Fe and Mn.
3. Colloidal: very small particles (difficult to settle and filter).

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IRON AND MANGANESE REMOVAL IRON AND MANGANESE REMOVAL

Treatment technologies Treatment technologies

• If Mn is present, a strong pre-oxidant (KMnO4) or Cl2 bleach

• Aeration
is required for filtration to be effective.
• Chemical oxidation
• Air is also used as a pre-oxidant for Fe, but is insufficient for
• Other methods
Mn oxidation.

• If Fe alone is present, aeration followed by filtration provides

effective treatment.
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IRON AND MANGANESE REMOVAL

Treatment technologies - Aeration Principles of iron removal

• Aeration method  filtration

Goal:
– Fe < 10 mg/l, no Mn
• Increase O2 concentration (anaerobic ground water)
– High alkalinity (> 2 meq/l)
 oxidize Fe2+ and Mn2+
– pH > 7, H2S < 0.2 mg/l, NH3 < 1 mg/l
• Decrease CO2 concentration – O2 demand = DOC + 0.47 H2S + 0.15 Fe2+ <= 7 mg/L

 aggressive water  corrosion of pipes Purpose:

• Remove dissolved gasses e.g. CH4, H2S, VOCs – Remove CO2  increase alkalinity increase pH
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– Diffuse O2 into water  increase DO concentration

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IRON AND MANGANESE REMOVAL IRON AND MANGANESE REMOVAL

Principles of Iron removal Principles of Iron removal

• Aeration:
Manganese oxide catalyst layer
– Oxidation of Fe2+  Fe3+ and precipitates
- Increase oxidation efficiency Fe2+  Fe3+ even with low pH (pH<5)
– Separation of iron precipitate by sedimentation and filtration

4Fe2+ + 8 HCO3- + O2 + 2 H2O  4 Fe(OH)3 + 8 CO2 + 8 H2O MnO.Mn2O7 + 4Fe(HCO3)2 + 2 H2O →3MnO2 + 4Fe(OH)3 + 8CO2

– Oxidation of iron depends on: 3 MnO2 + O2  MnO.MnO7

• low pH  oxidation rate decrease

- Practically, use KMnO4 to produce MnO.MnO7 layer
• DO, temperature
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• CO2, alkalinity

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IRON AND MANGANESE REMOVAL IRON AND MANGANESE REMOVAL

Treatment technologies - Aeration Treatment technologies - Aeration

• Oxidation of Mn(II) with oxygen:

• Oxidation of Fe(II) with oxygen:

4Fe2+ + O2 + 4H+ → 4Fe3+ + 2H2O

[Fe(II)] = concentration of ferrous iron, mol/L

rFe(II) = overall oxidation rate of ferrous iron, mol/L.min
t = time, min
PO2 = partial pressure of oxygen, atm
kapp = apparent rate constant, 1/min.atm
[Mn2+] = concentration of ferrous iron, mol/L
k3 = rate constant, L2/mol2.min.atm
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k = pseudo-first-order constant, min−1 = k3PO2 [OH−] 26

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IRON AND MANGANESE REMOVAL IRON AND MANGANESE REMOVAL

Treatment technologies - Aeration Treatment technologies - Aeration

Partial pressure • Cascade aeration

• Partial pressure depends on the composition of the air: • Multiple tray aeration
• (78.084% N2; 20.948% O2; 0.934% Ar; 0.032% CO2; 0.002% other
• Tower aeration
gases.

• Partial pressure of oxygen at a standard pressure of 101325 Pa (1 atm)

PO2= 0.21*101325 = 21.226 kPa

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IRON AND MANGANESE REMOVAL IRON AND MANGANESE REMOVAL

Treatment technologies - Aeration

Treatment technologies - Aeration
• Multiple trays method
Cascade aeration - Simple aeration method
– Natural aeration
– Spray on the surface with the height from the overflow to water
– Remove: 75 -80% CO2 , increase DO
level > 0.6 m
– Surface loading: 5 -10 m3/m2.h
– Removal efficiency: 30 -35% CO2

– Filtration rate: 5 -7 m/h

– Washing backwash 10 -12 l/s.m2

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IRON AND MANGANESE REMOVAL IRON AND MANGANESE REMOVAL

Treatment technologies –Aeration Tower Treatment technologies – Filtration by Green sand

o High loading aeration: air and water flow countercurrent • Manganese Greensand = a glauconite

greensand.
o Remove 85 -90% CO2 , increase DO
• Capable of reducing Fe, Mn and H2S from
o Loading: 40 -50 m3/m3.h
water through oxidation and filtration.

• Soluble Fe and Mn are oxidized and precipitated by contact with

higher oxides of manganese on the greensand granules.

• H2S is reduced by oxidation to an insoluble sulfur precipitate.

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IRON AND MANGANESE REMOVAL IRON AND MANGANESE REMOVAL

Treatment technologies – Filtration by Green sand Treatment technologies – Chemical Oxidation

Lime: (combine with softening process)

Advantages:
+ Water with DO:
• Iron reduction over wide pH range
4Fe(HCO3)2 + O2 + 2H2O + 4Ca(OH)2 → 4Fe(OH)3↓ + 4Ca(HCO3)2
• Effective reduction of hydrogen sulfide in addition to iron
+ Water without DO:
and/or manganese
Fe(HCO3)2 + Ca(OH)2 → FeCO3 + CaCO3 + H2O
• No harmful effects from a chlorine feed
- Needed amount of lime:
• Low attrition for long bed life [CaO] = 0.8 [CO2] + 1.8 [Fe2+]
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IRON AND MANGANESE REMOVAL IRON AND MANGANESE REMOVAL

Treatment technologies – Chemical Oxidation Treatment technologies – Chemical Oxidation

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IRON AND MANGANESE REMOVAL IRON AND MANGANESE REMOVAL

Calculation process Calculation process

STEP 1: Simple aeration:

• Determine oxidation reduction potential : – CO2 after = CO2 initial + 1.6 Fe2+ , mg/l

EFe3+ / Fe2+ = 1.34 – 0.177 pH And alkalinity: Ki = Kio - 0.036 Fe2+ , meq/l

EMn4+ / Mn2+ = 1.29 – 0.12 pH – Based on CO2 and alkalinity Ki  pH after aeration

In which: pH : pH of water after aeration process

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IRON AND MANGANESE REMOVAL IRON AND MANGANESE REMOVAL

Calculation process Calculation process

Multiple tray aeration: Tower aeration:

– CO2 after = 0.5 CO2 initial + 1.6 Fe2+ , mg/l – CO2 after = 0.8 CO2 initial + 1.6 Fe2+ , mg/l

And alkalinity: Ki = Kio - 0.036 Fe2+ , meq/l And alkalinity: Ki = Kio - 0.036 Fe2+ , meq/l

– Based on CO2 and alkalinity Ki  pH after aeration – Based on CO2 and alkalinity Ki  pH after aeration

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IRON AND MANGANESE REMOVAL IRON AND MANGANESE REMOVAL

Treatment technologies - Aeration Treatment technologies - Aeration

Determine initial concentration of CO2
Dissociation constant carbonic acid K1

t oC 10 20 25 30

• K : alkalinity of water, meq/l K1 3.34x10-7 4.05x10-7 4.31x10-7 4.52x10-7

•  : ionic strength,  = 0.000022P

• P : total salt concentration (mg/l) <=1000   = 0.022

• K1 : dissociation constant carbonic acid 41 42

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IRON AND MANGANESE REMOVAL IRON AND MANGANESE REMOVAL
Tính toán khử sắt bằng quá trình làm thoáng
Treatment technologies - Aeration

Determine pH

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Calculation process Calculation process

STEP 2: • The rest concentration after oxidation process

• Determine oxidation reduction potential after aeration O2 = O2 after aeration – [0.47 H2S + 0.143 Fe2++ DOC]

EO2 / H2O = 1.231 - 0.059 pH + 0.0145 lg [O2] – Simple aeration: O2 = 40% Saturated oxygen concentration

– Multiple tray: O2 = 55% saturated oxygen concentration

– Tower aeration: O2 = 70% saturated oxygen concentration

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IRON AND MANGANESE REMOVAL

Calculation process

STEP 3:

• Compare EFe3+ / Fe2+ to EO2 / H2O

If EO2 / H2O > 3 EFe3+ / Fe2+ (practical)

 select this method.

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