BURAPHA UNIVERSITY
FACULTY OF ENGINEERING
Applications of Fenton and Fenton-like Reactions for
De-rusting Wastewater Treatment
Mr. Piseth Som (55910117)
Degree Program in Chemical and
Environmental Engineering
31 August 2013
Content
•
•
•
•
•
Introduction
Theoretical and Empirical Reviews
Materials and Methods
Expected Results
Research Time Frame
2
Introduction
• Application of Chelating agents (EDTA, Citric
Acid...) in industries:
— Metal production
— Detergent
— Cleaning process (Boilers, Tanks, Pipes)
• Environmental concerns over utilization of
chelating agents (EDTA)
— Mental-Complexation
— Mobilization of Heavy Metals (Ni, Pb, As, Fe, ...)
— Eutrophication Driven Substance (Lan et al. (2012)
3
4
• Chelated complexation
negatively impact on
–
–
–
–
Iron Exchange
Chemical Precipitation
Biological Processes
Adsorption (Fu et al., 2009,
&2012)
• Therefore, treatment
methods are scanned
and searched
5
• Possibility of Advanced Oxidation Processes (AOP)
– Degradation of variety of organic compounds
– Cost effectiveness
– Ease of application (Poyatos et al., 2010)
• Most common application of Fenton reaction
and Fenton-like reaction among other AOPs for
industrial wastewater (Bautista et al., 2008)
6
Ease of application,
Biodegradability
improvement and
detoxification
NiEDTA and CuEDTA
were conducted but
FeEDTA is not well
document
Presence of Chelating
Agents (EDTA) results in
inapplicability for
conventional process
App. of Fenton and Fentonlike reactions for De-rusting
wastewater is NOT well
documented
Rational
Controversy of
Chelating agents in
Fenton reaction
Utilization of existing
Ferrous/Ferric ion in
Wastewater
7
Cleaning Processes
(Pipe, boilers, Tanks,...)
Cleaning Solution ( EDTA,
NaOH, DTS, Ammonia)
Metal-EDTA
complex, Fe2+ /Fe3+
Problem for
• Ion Exchange
• Precipitation
• Coagulation
• Adsorption
• Biological Method
• Destruct EDTA
Precipitation
Mixed Wastewater (COD,
Metal, EDTA waste...)
Fenton and Fenton-like
Reactions
Fe2+ /Fe3+ + H2O2 HO
• Free Iron/ Metal
M(OH)n / Fe(OH)3
8
1. To determine the applicability and optimum
condition Fenton and Fenton-like reactions for
cleaning wastewater treatment
2. To investigate the impact of operating
parameters ( pH, Fe2+/ Fe3+, H2O2 and reaction
time) on treatment efficiency
3. To investigate the kinetic of degradation
organic compounds in term of COD
9
Scope and Limitation
• Real De-rusting (cleaning) Wastewater is used
• Jar Test Apparatus is conducted at laboratory room
temperature at DChE, BUU
• Objective Parameters: COD and Total Iron, Turbidity, TSS, TDS
• Kinetic degradation organic chelating agents are monitored
in term of COD
• Fonton Oxidation Products are not monitored
10
• Objective Parameters = f ( pH, Temp-,
[Fe2+],[ Fe3+], [H2O], RT, Mixing Speed)
• Independent Variables: COD, Total Iron, TDS, TSS,
Turbidity
• Dependent Variables: pH, [Fe2+],[ Fe3+], [H2O],
Reaction Time
• Control Variables: Temp- , mixing speed and
wastewater characteristics
11
Theoretical and Empirical Reviews
12
Theoretical and Empirical Reviews
• Discovered by Mr. Fenton in 1894 : mixture of Fe2+
with H2O2 in acidic condition
• Advanced Oxidation Processes based on Fenton
Reaction are well-known for
– Ability in degradation of varirous organic compounds
– Ease of application
– Cost Effective
– Biodegradability Improvement (COD/BOD ratio)
– POPs degradation
13
Oxidizing agent
EOP,
(V)
•OH
R•
RH +
→
+ H2O + CO2
RH + •OH → (OH)RH•
RH + •OH → (RH)• + + OH−
Fluorine
3.06
Hydroxyl radical (HO·)
2.80
Oxygen (atomic)
2.42
Ozone
2.08
Hydrogen peroxide
1.78
Hypochlorite
1.49
Chlorine
1.36
Chlorine dioxide
1.27
Oxygen (molecular)
1.23
14
No.
Reactions
Rate constants(k)
(1)
Fe2+ + H2O2 → Fe3+ + OH• + OH− ( chain initiation)
70 M-1s-1
(2)
Fe2+ + •OH
3.2 108 M-1s-1
(3)
Fe2+ + HO2• → Fe3+ + HO2−
1.3 106 M-1s-1
(4)
•OH
3.3 107 M-1s-1
(5)
Fe3+ + H2O2 → Fe2+ + H+ + HO2•
0.001-0.01 M-1s-1
(6)
Fe3+ + HO2• → Fe2+ + H+ + O2
1.2 106 M-1s-1
→ Fe3+ + OH− (chain termination)
+ H2O2 → HO2• + H2O (scavenging effects)
15
Scavenging effects results from overdoing of [H2O2 ] and
Fe2+/3+ in the system
Fe2+ + •OH → Fe3+ + OH−
Fe2+ + HO2• → Fe3+ + HO2−
Fe3+ + HO2• → Fe2+ + H+ + O2
H2O2+ •OH → HO2• + H2O
Fe2+ + H2O2 → Fe3+ + OH• + OH− (Fenton oxidation)
Fe3+ + H2O2 → Fe2+ + HO2• + OH− (Fenton-like reaction)
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Factor Effecting Fenton and Fenton-like Reaction
• pH suitable with 3-6
- At low pH  decompose H2O2 into O2 and H2O by Fe2+ and
reaction between •OH and H+ occurs (Neyens & Baeyens,
2003)
- At high pH  Precipitate Fe(OH)3  decompose H2O2 into O2
and H2O2 without •OH and stable Fe-complex is formed
(Bautista et al.,2007&2008)
17
Fu et al.,
Chistra
et al. ,
2004
2005
2009
2010
2012
2013
Lan et al.,
Fu et al.,
18
19
20
Research Method
• Cleaning Wastewater
– Pipe, boilers, and tanks cleaning processes
– Kation Power Company in Rayong Province
Parameters
pH
COD (mg/L)
BOD (mg/L)
TSS (mg/L)
TDS (mg/L)
Turbidity (NTU)
Total Iron (mg/L)
Value
9
150000
0
4390
22870
12
Limited effluent
21
22
Wastewater
ZVI + 35% w/w H2O2 ,
150 rpm for 60 min
Jar Test Apparatus
H2SO4
adjust
pH 3
NaOH
adjust pH11.5
Fe
COD
TSS
TDS
turbidity
Settling for 15 min
80 rpm for 10 min
23
dC
  kC n
dt
C  C 0 exp( kt)
1
1

 kt
C
C0
C  C 0 exp( k app t )
24
• It is expected to
 optimum condition
 Organic reduction and degradation
 Signeficance of Operating parameters
 degradable Products Monitoring???
 Kinetic of Organic Reduction in term of COD?
 Discussion of Other Parameters and Its Condition affected by
Fenton and Fenton Like?
 What is the differences between Fenton (using Ferrous) and
Fenton-like(using Ferric) ?
 How fast did each Wastewater parameter degraded
according to the Kinetic order ( why First and Why Second)
 What is EDTA situation aftern Fenton and Fenton-like
Oxidaton
25
Activities
2013
2014
1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5
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