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) Rust (Fe 2 O 3 )

Background and Problem High content of metal and organic chelating agent – 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

Rational and Importance 5 Metal-EDTA Complex (Fe-EDTA) Derusting Wastewater Destroy EDTA compound Fee iron molecule Fenton, Fenton- like Reactions M(OH)n  Fe(OH)3  Precipitation 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 (Fe 2+ /Fe 3+ ) and iron oxide (Fe 2 O 3 ) 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, [Fe 2+ ], 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, Fe 2+, Fe 3+, 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 ) (E 0 = 2.8V) (Neyens & Baeyens, 2003) OH + Organic Compound  Oxidized Products H 2 O 2 + Fe 2+ pH ~ Fe 3+ + OH + OH − (Fenton) H 2 O 2 + Fe 3+ pH ~ Fe 2+ + HO 2 + OH − H 2 O 2 + Fe 2+ pH ~ Fe 3+ + OH + OH − (Fenton-like) Fe o (ZVI)+ 2H + pH ~ Fe 2+ + H 2 H 2 O 2 + Fe 2+ pH ~ Fe 3+ + OH + OH − (Fenton-like)

Theoretical Reviews (Cont’) 10 Reaction Mechanism Pathways RH + OH → (OH)RH (Hydroxyl Radical Addition) (Matthew Tarr, 2003) RH + OH → R + H 2 O (Hydrogen Abstraction) (Neyens & Baeyens, 2003) RH + OH → (RH) + + OH − (Direct Electron Transfer) (Munter, 2001) R + Fe 3+ -oxidation → R + + Fe 2+ R + Fe 2+ -reduction → R − + Fe 3+ (Fe 2+/3+ inducing) (Kim et al., 2010)

Empirical Reviews 11 Huang et al., (2000) Electro -chemical treatment EDTA recovery 94.16% of metal removed 15.5 mA/Cm 2 Kim et al., (2010) UV/H2O 2 /Fe2+ UV/H 2 O 2 H 2 O 2 /Fe 2+ UV/H2O 2 /Fe3+ Citric Acid degraded 93% COD removal Fu et al., (2009, 2012) Fenton and Fenton-like reaction for NiEDTA complex > 92.8% of Ni removal 78.8% COD removal Residual Fe = 0.04 mg/L Lan et al., (2012) Interior Micro electrolysis – Fenton – Coagulation (IM-FOC) for CuEDTA complete removal of Cu 87% COD removal

Materials and Experiment 12 Derusting Wastewater – Boilers cleaning processes – Kation Power Company located in Rayong Province

Materials and Experiment 13 ParametersValueLimited effluent ** pH COD (mg/L) < 400 Total Iron (mg/L)7668< 0.5 Ferric (Fe 3+ ) (mg/L)6919NA TDS (mg/L)25190< 5000 TSS (mg/L)0.006< 150 Conductivity ( µ S/cm)30150NA Ammonia Nitrogen (mg/L)6990< 1.1 Nitrite nitrogen (mg/L)2000< 45 Nitrate Nitrogen (mg/L)1600NA ** Pollution Control Department, PCD at

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 H 2 O 2 – 35% w/w (AR Grade) FeSO 4  7H 2 O (AR Grade) H 2 SO 4, HCl and HNO 3 Conc. NaOH – 10 N H 2 SO 4 – 5N 15 Chemicals for parameters analysis Ferrous Ammonium Sulfate (Fe(NH 4 ) 2 (SO 4 ) 2 ·6H 2 O) Sodium acetate (NaC 2 H 3 O 2  3H 2 O) Hydroxylamine(NH 2 OH-HCl) 1,10-pehnanthroline (C 12 H 8 N 2  3H 2 O ) Potassium Permanganate (KMnO 4 )

Materials and Experiment 16 Add Fe 2+ under mixing 150 rpm for 10 min adjust pH= 3 Settling for 30 min adjust pH =8 Add H 2 O 2 under mixing 50 rpm for 60 min Analysis of Objective Parameters Fill 500 mL of sample

Materials and Experiment 17 initial pH: 2-7 [Fe 2+ ] : M [H 2 O 2 ]: M Reaction Time min Precipitation pH: 6-11 Input Fenton-like Reaction (Add H 2 O 2 only) Fenton Reaction (Fe 2+ + H 2 O 2 ) Processes TCOD, SCOD Total Iron, Soluble Iron, Fe 2+, Fe 3+ Ammonium, Nitrate, Nitrate TDS Output room temperature (28 0 C ), mixing at 150 rpm and 80 rpm Control variables

Materials and Experiment 18 Fenton-like reaction Add H2O2 only RT= 60 minH2O2=2 MInitial pH 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 [H 2 O 2 ] Best [H 2 O 2 ] Varying RT (min) Best RT (min) Precipitation pH

Materials and Experiment 20 Fenton Reaction RT= 60 minFe 2+ =0.05MH2O2=2MInitial pH Repeat experiment with initial pH around the suitable pH to obtain the best initial pH for Fenton reaction

Materials and Experiment M 0.01M 0.05M 0.08M 0.1M 0.12M Varying [Fe 2+ ] 1M 1.5M 2M 2.5M 3M 3.5MVarying [H 2 O 2 ] Varying RT (min) 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 )

Outlook 23 Fenton and Fenton- like Reactions Fe 2+ ? H2O2? Initial pH? Reaction Time (min)? Hydroxide Precipitation precipitation pH? Removal Efficiency COD? Total Iron? TDS/TSS? Ammonia, Nitrite and Nitrate

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=11 Mixing 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) + CO 2 + H 2 0 Second Order Reaction Pseudo-first order Reaction Integrated Equation Skoog and West, 2004 ; Lucas and Peres, 2007 and Samet et al., 2011

29 DigestionExtraction Reagent adding UV-Visible Spectro. Calibration Curve Iron determination

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