Applications of Fenton and Fenton-like Reactions for De-rusting Wastewater Treatment

Mr. Piseth Som (55910117)Degree Program in Chemical and Environmental

Engineering31 August 2013

BURAPHA UNIVERSITYFACULTY OF ENGINEERING

Content

• Introduction• Theoretical and Empirical Reviews• Materials and Methods• Expected Results• Research Time Frame

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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

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• 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)

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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

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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, Fe2+ /Fe3+

Fenton and Fenton-like ReactionsFe2+ /Fe3+ + H2O2 HO

Problem for • Ion Exchange• Precipitation • Coagulation • Adsorption • Biological Method

• Destruct EDTA • Free Iron/ Metal

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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

Scope and Limitation

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• 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

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• 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

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Theoretical and Empirical Reviews

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• 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

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Oxidizing agent EOP, (V)

Fluorine Hydroxyl radical (HO·)Oxygen (atomic) Ozone Hydrogen peroxide Hypochlorite Chlorine Chlorine dioxide Oxygen (molecular)

3.062.802.422.081.781.491.361.271.23

RH + •OH → R• + H2O + CO2

RH + •OH → (OH)RH•

RH + •OH → (RH)• + + OH−

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No. Reactions Rate constants(k)

(1) Fe2+ + H2O2 → Fe3+ + OH• + OH− ( chain initiation) 70 M-1s-1

(2) Fe2+ + •OH → Fe3+ + OH− (chain termination) 3.2 108 M-1s-1

(3) Fe2+ + HO2• → Fe3+ + HO2

− 1.3 106 M-1s-1

(4) •OH + H2O2 → HO2• + H2O (scavenging effects) 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

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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)

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Fu et al., Chistra et al. ,

2004 2009 2012 201320102005

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Research Method

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• Cleaning Wastewater – Pipe, boilers, and tanks cleaning processes– Kation Power Company in Rayong Province

Parameters Value Limited effluent pH 9COD (mg/L) 150000BOD (mg/L) 0TSS (mg/L) 4390TDS (mg/L) 22870Turbidity (NTU) 12Total Iron (mg/L)

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ZVI + 35% w/w H2O2 , 150 rpm for 60 min Jar Test Apparatus

Wastewater

adjust pH 3

H2SO4

adjust pH11.5 NaOH

Settling for 15 min 80 rpm for 10 min

FeCODTSSTDS

turbidity

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nkCdtdC

)exp(0 ktCC

ktCC

0

11

)exp(0 tkCC app

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• 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

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Activities 2013 20141 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5