Applications of Fenton and Fenton-like Reactions for De-rusting Wastewater Treatment Mr. Piseth Som ( ) Degree Program in Chemical and Environmental Engineering 31 August 2013 BURAPHA UNIVERSITY FACULTY OF ENGINEERING

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

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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

7 Rational App. of Fenton and Fenton- like reactions for De-rusting wastewater is NOT well documented Utilization of existing Ferrous/Ferric ion in Wastewater Ease of application, Biodegradability improvement and detoxification Presence of Chelating Agents (EDTA) results in inapplicability for conventional process Controversy of Chelating agents in Fenton reaction NiEDTA and CuEDTA were conducted but FeEDTA is not well document

8 Mixed Wastewater (COD, Metal, EDTA waste...) Precipitation M(OH) n  / Fe(OH) 3  Cleaning Solution ( EDTA, NaOH, DTS, Ammonia) Cleaning Processes (Pipe, boilers, Tanks,...) Metal-EDTA complex, Fe 2+ /Fe 3+ Fenton and Fenton-like Reactions Fe 2+ /Fe 3+ + H 2 O 2  HO  Problem for Ion Exchange Precipitation Coagulation Adsorption Biological Method Destruct EDTA Free Iron/ Metal

9 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, Fe 2+ / Fe 3+, H2O2 and reaction time) on treatment efficiency 3. To investigate the kinetic of degradation organic compounds in term of COD

Scope and Limitation 10 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

11 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

Theoretical and Empirical Reviews 12

Theoretical and Empirical Reviews 13 Discovered by Mr. Fenton in 1894 : mixture of Fe 2+ with H 2 O 2 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

14 Oxidizing agent EOP, (V) Fluorine Hydroxyl radical (HO·) Oxygen (atomic) Ozone Hydrogen peroxide Hypochlorite Chlorine Chlorine dioxide Oxygen (molecular) RH + OH → R + H 2 O + CO 2 RH + OH → (OH)RH RH + OH → (RH) + + OH −

15 No.ReactionsRate constants(k) (1)Fe 2+ + H 2 O 2 → Fe 3+ + OH + OH − ( chain initiation)70 M -1 s -1 (2)Fe 2+ + OH → Fe 3+ + OH − (chain termination) 3.2  10 8 M -1 s -1 (3)Fe 2+ + HO 2 → Fe 3+ + HO 2 − 1.3  10 6 M -1 s -1 (4) OH + H 2 O 2 → HO 2 + H 2 O (scavenging effects) 3.3  10 7 M -1 s -1 (5)Fe 3+ + H 2 O 2 → Fe 2+ + H + + HO M -1 s -1 (6)Fe 3+ + HO 2 → Fe 2+ + H + + O  10 6 M -1 s -1

16 Scavenging effects results from overdoing of [H 2 O 2 ] and Fe 2+/3+ in the system Fe 2+ + OH → Fe 3+ + OH − Fe 2+ + HO 2 → Fe 3+ + HO 2 − Fe 3+ + HO 2 → Fe 2+ + H + + O 2 H 2 O 2 + OH → HO 2 + H 2 O Fe 2+ + H 2 O 2 → Fe 3+ + OH + OH − (Fenton oxidation) Fe 3+ + H 2 O 2 → Fe 2+ + HO 2 + OH − (Fenton-like reaction)

17 Factor Effecting Fenton and Fenton-like Reaction pH suitable with At low pH  decompose H 2 O 2 into O 2 and H 2 O by Fe 2+ and reaction between OH and H + occurs (Neyens & Baeyens, 2003) - At high pH  Precipitate Fe(OH) 3  decompose H 2 O 2 into O 2 and H 2 O 2 without OH and stable Fe-complex is formed (Bautista et al.,2007&2008)

18 Fu et al., Chistra et al., Lan et al., Fu et al.,

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Research Method 21 Cleaning Wastewater – Pipe, boilers, and tanks cleaning processes – Kation Power Company in Rayong Province ParametersValueLimited effluent pH9 COD (mg/L) BOD (mg/L)0 TSS (mg/L)4390 TDS (mg/L)22870 Turbidity (NTU)12 Total Iron (mg/L)

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23 ZVI + 35% w/w H 2 O 2, 150 rpm for 60 min Jar Test Apparatus Wastewater adjust pH 3 H 2 SO 4 adjust pH11.5NaOH Settling for 15 min80 rpm for 10 min Fe COD TSS TDS turbidity

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25 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

26 Activities