piseth som
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Applications of Fenton and Fenton-like Reactions with Subsequent Hydroxide Precipitation for Derusting Wastewater Treatment. Piseth Som. Master Program in Chemical and Environmental Engineering 07 January 2014. Outline. Background and Problems Rational and Importance - PowerPoint PPT PresentationTRANSCRIPT
Piseth Som
Master Program in Chemical and Environmental Engineering
07 January 2014
Applications of Fenton and Fenton-like Reactions with Subsequent Hydroxide Precipitation for Derusting
Wastewater Treatment
Outline
• Background and Problems
• Rational and Importance
• Theoretical and Empirical Reviews
• Materials and Experiment
2
Background and Problem
• Cleaning operations of pipes and boilers
3
• To dissolve rust– hydrochloric acid or Alkali
Flushing– Hot and cold water flushing– Ammoniated Ethylene Diamine
Tetraacetic Acid (EDTA) Pickling– Pasivative agent (Sodium
Nitrite)– Ammonia rinsing (Bansal, 2012)
www.fourquest.com/chemicalcleaning
Rust (Fe2O3)
Background and Problem
• High content of metal and organic chelating agent– 5000-10000 mg/L of iron – <100 mg/L of Copper (Huang et al.,
2000)
4
Kation Power (2010)
• Organic acid (EDTA and Citric Acid) cause metal-complexation (Fu et al., 2012; Chitra et al., 2011 )
Generation of Complex Wastewater
www.chemicool.com/defination/ligand
Rational and Importance
5
• Metal-EDTA Complex (Fe-EDTA)
Derusting Wastewater
Ability of Fenton reaction for organic degradation and industrial wastewater treatment (Buatista et al., 2008)
Rational and Importance
6
• Fenton and Fenton-like reactions for derusting wastewater is not well documented
• Feasibility for NiEDTA and CuEDTA treatment, so they may do for FeEDTA (Fu et a., 2009, and Lan et al., 2012)
• Originated Iron (Fe2+/Fe3+ ) and iron oxide (Fe2O3) in
wastewater could be used as catalyst for Fenton-like reaction (Lan et al. 2012)
Objectives
7
1. To determine optimum initial parameters of Fenton and Fenton-like reactions (initial pH, [Fe2+ ], and [H2O2]) for treatment of derusting wastewater
2. To determine the optimum reaction time and reaction kinetics
3. To determine the optimum precipitation pH for Fenton and Fenton-like reactions
4. To investigate the effects of Fenton and Fenton-like reactions on ammonia, nitrate and nitrite removal
Scope and Limitation
8
• Real derusting wastewater is used in the study
• Jar Test apparatus is conducted at laboratory room temperature at DChE, BUU
• Objective Parameters: TCOD, SCOD, Total Iron, Soluble Iron, Fe2+, Fe3+, Ammonium, Nitrate, Nitrate, TDS
• Kinetic degradation organic chelating agents are monitored in term of COD
• Oxidation Products or intermediate are NOT monitored
Theoretical Reviews
9
• Fenton Reactions as Advanced Oxidation Processes (AOP) using hydroxyl radical (OH•) (E0
= 2.8V) (Neyens & Baeyens, 2003)
OH • + Organic Compound Oxidized Products
H2O2 + Fe2+pH ~ 3 - 4
Fe3+ + OH• + OH− (Fenton)
H2O2 + Fe3+pH ~ 3 - 4
Fe2+ + HO2• + OH−
H2O2 + Fe2+pH ~ 3 - 4
Fe3+ + OH• + OH− (Fenton-like)
Feo(ZVI)+ 2H+ pH ~ 3 - 4
Fe2+ + H2
H2O2 + Fe2+pH ~ 3 - 4
Fe3+ + OH• + OH− (Fenton-like)
Theoretical Reviews (Cont’)
10
Reaction Mechanism Pathways
RH + •OH → (OH)RH•
(Hydroxyl Radical Addition)(Matthew Tarr, 2003)
RH + •OH → R• + H2O(Hydrogen Abstraction)(Neyens & Baeyens, 2003)
RH + •OH → (RH)• + + OH−
(Direct Electron Transfer)(Munter, 2001)
R• + Fe3+ -oxidation → R+ + Fe2+ R• + Fe2+ -reduction → R− + Fe3+
(Fe2+/3+ inducing) (Kim et al., 2010)
Empirical Reviews
11
Huang et al., (2000)
Electro-chemicaltreatment
EDTA recovery94.16% of metal removed
15.5 mA/Cm2
Materials and Experiment
12
Derusting Wastewater – Boilers cleaning processes– Kation Power Company located in Rayong Province
Materials and Experiment
13
Parameters Value Limited effluent**
pH 10 6.5-8.5COD (mg/L) 15334 < 400
Total Iron (mg/L) 7668 < 0.5 Ferric (Fe3+) (mg/L) 6919 NA
TDS (mg/L) 25190 < 5000TSS (mg/L) 0.006 < 150
Conductivity (µS/cm) 30150 NA
Ammonia Nitrogen (mg/L) 6990 < 1.1Nitrite nitrogen (mg/L) 2000 < 45
Nitrate Nitrogen (mg/L) 1600 NA
**Pollution Control Department, PCD at www.pcd.go.th
Materials and Experiment
Materials• Jar Test Apparatus• pH meter • Portable TSD meter• Multiple parameters
Photometer• Hotplate• UV-Vis spectrophotometer• Drying Oven• Centrifugal Machine • supporting glassware
14
Materials and Experiment
Chemicals for Fenton and Fenton-like reaction• H2O2 – 35% w/w (AR Grade)
• FeSO4 7H2O (AR Grade)
• H2SO4 , HCl and HNO3 Conc. • NaOH – 10 N• H2SO4 – 5N
15
Chemicals for parameters analysis • Ferrous Ammonium Sulfate (Fe(NH4 )2(SO4)2·6H2O)
• Sodium acetate (NaC2H3O23H2O)
• Hydroxylamine(NH2OH-HCl)
• 1,10-pehnanthroline (C12H8N23H2O )
• Potassium Permanganate (KMnO4)
Materials and Experiment
16
Add Fe2+ under mixing 150 rpm for 10 min
adjust pH= 3
Settling for 30 min
adjust pH =8
Add H2O2 under mixing 50 rpm for
60 min
Analysis of Objective
Parameters
Fill 500 mL of sample
Materials and Experiment
17
initial pH: 2-7
[Fe2+] : 0.005-0.15 M
[H2O2]: 1-3.5 M
Reaction Time 20-120 min
Precipitation pH: 6-11
Input
Fenton-like Reaction
(Add H2O2 only)
Fenton Reaction(Fe2+ + H2O2)
ProcessesTCOD, SCOD
Total Iron, Soluble Iron,
Fe2+, Fe3+
Ammonium, Nitrate, Nitrate
TDS
Output
room temperature (28 0C ), mixing at 150 rpm and 80 rpmControl variables
Materials and Experiment
18
Fenton-like reaction
Add H2O2 only
RT= 60 min
H2O2=2 M
Initial pH
2
4
6
8
10
12
pH=2 pH=4 pH=6 pH=8 pH=10 pH=12
Repeat with pH: 2, 3, 4, 5, 6 7 Best pH
Varying initial pH
Materials and Experiment
19
1M 1.5M 2M 2.5M 3M 3.5MVarying [H2O2]
Best [H2O2]
20 40 60 80 100 120Varying RT (min)
Best RT (min)
6 7 8 9 10 11 Precipitation pH
Materials and Experiment
20
Fenton ReactionRT= 60 min
Fe2+=0.05M
H2O2=2M
Initial pH
2
3
4
5
6
7
Repeat experiment with initial pH around the suitable pH to obtain the best initial pH for Fenton reaction
Materials and Experiment
21
0.005M 0.01M 0.05M 0.08M 0.1M 0.12MVarying [Fe2+]
1M 1.5M 2M 2.5M 3M 3.5MVarying [H2O2]
20 40 60 80 100 120Varying RT (min)
6 7 8 9 10 11 Precipitation pH
Optimum Condition, Impacts of each parameters, Kinetics
Materials and Experiment
22
• TCOD and SCOD are determined by close reflux titrimetric method (Method, 5520)
• Total iron , ferric and ferrous concentration are measure by Phenanthroline method (Method, 3500)
• pH is measured by pH meter (EUTECH)
• TSS is measured according to standard method (Method, 2540)
• TDS is measured by portable TDS meter (OHAUS Starter 300C)
• Ammonium nitrogen, Nitrate and Nitrite are measured by Multiple parameters Photometer (Hana HI 83205-2008)
Outlook
23
Fenton and Fenton-like Reactions
Fe2+?
H2O2?
Initial pH?
Reaction Time (min)?
Outlook
24
Activity Plan
25
26
Thank You for Your Attention !
Q & A?
Materials and Experiment
• Hydroxide Precipitation of Iron Before Fenton and Fenton-like Reaction
27
pH=6 pH=7 pH=8 pH=9 pH=10 pH=11Mixing at 50
rpm for 15 min
Settling down for 30 min
Does Iron precipitate? Hypothesis 1
Materials and Experiment
28
• Kinetic Study of COD degradation
• Rate Equation (r)
Organic Matter (COD )+ OH• Oxidized product (P) + CO2 + H20
CODOHkdt
dCODr ][ Second Order Reaction
CODkdt
dCODr app Pseudo-first order Reaction
)ln0
tkCODCOD
appt Integrated Equation
Skoog and West , 2004 ; Lucas and Peres , 2007 and Samet et al., 2011
29
Digestion Extraction
Reagent adding
UV-Visible Spectro.
Calibration Curve
Iron determination
30
0 50 100 150 200 250 300 350 400 450 5000
0.2
0.4
0.6
0.8
1f(x) = 0.00197419748079877 x − 0.000456190476190277R² = 0.999995281575467
Fe (µg in 100 mL)
Abso
rban
ce
portion mL100
sample mLvolume) final mL 100 (in Fe μg Fe/L mg