piseth som master program in chemical and environmental engineering 07 january 2014 applications of...

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


13

Parameters Value Limited effluent**

pH 10 6.5-8.5

COD (mg/L) 15334 < 400

Total Iron (mg/L) 7668 < 0.5

Ferric (Fe3+) (mg/L) 6919 NA

TDS (mg/L) 25190 < 5000

TSS (mg/L) 0.006 < 150

Conductivity (µS/cm) 30150 NA

Ammonia Nitrogen (mg/L) 6990 < 1.1

Nitrite nitrogen (mg/L) 2000 < 45

Nitrate Nitrogen (mg/L) 1600 NA

**Pollution Control Department, PCD at www.pcd.go.th


Materials• Jar Test Apparatus• pH meter • Portable TSD meter• Multiple parameters

Photometer• Hotplate• UV-Vis spectrophotometer• Drying Oven• Centrifugal Machine • supporting glassware

14


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)


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


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


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


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


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


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


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?


• 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


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

tkCOD

CODapp

t 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

piseth som master program in chemical and environmental engineering 07 january 2014 applications of...

Documents