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OZONE TECHNOLOGY FOR
WASTEWATER TREATMENT
: APPLICATION & LIMITATION
CHANGHYEON BAK
2017.06.08
1
CONTENTS
 Introduction
 Background
 What is Ozone?
 Ozone’s strength
 Application to wastewater treatment
 Actual cases
 AOP (Advanced Oxidation Process)
 Combination application
 Conclusion
2
INTRODUCTION
3
Pathogen & harmful chemicals in wastewater
 Pathogens and harmful chemicals in wastewater can
cause problems in ecosystem.
 So, disinfection and destruction of harmful chemicals is
needed.
 Disinfection technologies
1) UV 2) Chlorine 3) Ozone
4
BACKGROUND
Viruses Bacteria Protozoa Helminths Phenol Cyanide
Comparison
Criteria UV radiation Ozone Chlorine
Harmful byproducts NO NO YES
Environmental impact LOW LOW HIGH
Bacteria removal SOME YES YES
Virus removal NO YES SOME
Lead removal NO YES NO
Manganese removal NO YES SOME
Iron removal NO YES YES
Odor removal NO YES YES
Color removal NO YES SOME
Operational cost MED LOW MED
Capital cost MED HIGH MED
Maintenance HIGH MED MED
5
BACKGROUND
(Marianne, 1997)
What is ozone
 O3
 Unstable structure -> High reactivity
 Pale blue gas
 Distinctively pungent smell
INTRODUCTION
6
 Much higher solubility into water than O2
 Strong oxidizing agent
 Easy to produce with air or oxygen gas and electricity
Ozone’s strength
INTRODUCTION
7
● Oxygen
Reactions :
1) O2 + e → 2O + e
2)O2 + O + M → O3
water
O2
O3
1)
2)
O3 109mg/L ≫ O2 18mg/L at 25℃
(Ozone solutions, 2014)
pH dependence of dissolved ozone
 Dissolved O3 has pH dependence.
 In basic environment, ozone decomposes rapidly.
 And OH-radicals are produced.
 OH-radical is the strongest oxidant.
 The higher pH, the more OH-radicals.
INTRODUCTION
8
(Lenntech, 2010)
 Disinfection
INTRODUCTION
9
Application to wastewater treatment
 Destruction of organic compound
 Deodorization
 Decolorization
 Removal of taste
Ozone can control water quality.
INTRODUCTION
10
H2S + O3 → SO2 + H2O
Cyanides : CN− + O3 → CNO − + O2
CNO- + OH- + H2O → CO32- + NH3
2CNO- + 3O3 + H2O → 2HCO3- + N2 + 3O2
Urea : (NH2)2CO + O3 → N2 + CO2 + 2 H2O
Before After
Application to wastewater treatment
 Reactions with metal ions
 Iron
 Manganese
 Lead
Ozone makes precipitation with metal ions.
And those can be filtered.
INTRODUCTION
11
2 Fe2+ + O3 + 5 H2O → 2 Fe(OH)3(s) + O2 + 4 H+
2 Mn2+ + 2 O3 + 4 H2O → 2 MnO(OH)2(s) + 2 O2 + 4 H+
PbS + 4 O3 ⟶ PbSO4(s) + 4 O2
Application to wastewater treatment
ACTUAL CASES
12
 Ozone treatment system is placed at the end of
wastewater treatment system.
ACTUAL CASES
Ozone treatment system
13
Wastewater treatment system
Disinfection performance
14
Coliform : E.coli-like
(Hoveid H. et al, 2008)
ACTUAL CASES
 Bacteria totally removed in 10 min. of contact time and
with 1ppm of ozone concentration
Decolorization performance
15
(Abidin. et al, 2016)
ACTUAL CASES
 Red dye RR120 decomposed all in 10 min. with an
ozone flow rate of 10.2 mg/min.
COD removal performance
16
(Preethi V. et al, 2009)
ACTUAL CASES
 COD of tannery effluent decreases by ozonation.
 COD removal efficiency is related to concentration of
ozone and pH.
AOP (advanced oxidation process)
 AOP is a set of chemical treatment procedure to remove
organic materials in wastewater by oxidation through
reactions with the strongest oxidant ·OH.
 Better than ozonation alone
 Combinations
1) O3/H2O2 : peroxonation
2) O3/UV : ozone photolysis
3) H2O2/UV
4) H2O2/Fe2+/UV
17
(Mehmet A. et al, 2014)
.
.
.
AOP
Peroxonation (O3/H2O2)
 Reaction
 H2O2 accelerates the decomposition rate of O3.
 It produces a larger number of very reactive ·OH
radicals.
 Peroxonation process is more efficient than ozonation
alone.
 Essential step of disinfection
18
AOP
(Mehmet A. et al, 2014)
Ozone photolysis (O3/UV)
 Reaction
 Effective on eliminating various volatile chlorinated
organic compounds
ex) CHCl3, CCl4, trichloroethylene(TCE) etc.
19
(Mehmet A. et al, 2014)
AOP
AOP in Petrochemical wastewater treatment
 190 tons/months of phenolic wastes disposes by petrochemicals,
pharmaceuticals, and polymer industries.
 2-Nitrophenol(2NP) is a main pollutant from petrochemical
wastewater.
 Shokri applied ozone to degrade 2NP.
 Ozonation at high pH (pH = 9) generates OH-radical rapidly. (=AOP)
20
(Shokri A., 2015)
AOP
Removal rate (%)
2NP 99.8
TOC 31
COD 72.5
Coking wastewater treatment
 O3 & H2O2/O3 is applied to remove cyanide from coking wastewater.
 Oxidation process is combined with coagulation-flocculation-
decantation and lime-soda ash softening pretreatment.
 Using lower concentrations of ozone, cyanide is not removed.
 Ozone consumption without softening pretreatment is twice as much
as that with softening pretreatment because wastewater contains
bicarbonate ions.
21
(Pueyo N. et al, 2016)
COMBINED TREATMENT
Textile wastewater treatment
 Textile wastewater contains acute toxic chemicals.
 Pazdzior et al studied the effect of ozonation & biodegradation on
toxicity.
 Ozonation is combined with aerobic biodegradation.
22
(Pazdzior K. et al, 2016)
COMBINED TREATMENT
Toxicity removal
O3 →Bio 76.2 – 92.2%
Bio→ O3 93.7 – 94.2%
Bio→ O3 →Bio ~ 96%
raw
O
3
Bio
O
3
→Bio
Bio
→
O
3
Bio
→
O
3
→
Bio
Toxicity after treatment
Oilfield wastewater treatment
3 steps to enhance biodegradability of oilfield produced water(OPW)
1. Microwave demulsification : to remove oil
2. Ozone oxidation : to enhance the biodegradability of wastewater
3. Biological aerated filter : aerobic digestion
 BOD5/COD shows the biodegradability of wastewater.
 The optimum ozone treatment condition
- Dosage : 7mg/L
- Contact time : 15min
23
(Kang J. et al, 2015)
Parameter Initial value
pH 6.6
COD (mg/L) 648
BOD5 (mg/L) 45
BOD5/COD 0.07
Oil (mg/L) 68
TPH (mg/L) 76
SO4
2- (mg/L) 34
NH3-N (mg/L) 52
PS (mg/L) 589
TSS (mg/L) 3,346
Microtoxicity (EC50, %) 8.6
▶Charateristics of OPW
(Rajakovic V. et al 2006)
COMBINED TREATMENT
Oilfield waster treatment
 Result
 After biological treatment, effluent satisfies Chinese discharge
standard.
 Ozone decomposes complex chemicals biodegradable.
24
(Kang J. et al, 2015)
Parameter Initial value After microwave treatment After ozonation
COD (mg/L) 648 382 260
BOD5 (mg/L) 45 21 86
BOD/COD 0.07 0.08 0.33
Oil (mg/L) 68 25 16
TPH (mg/L) 76 28 18
NH3-N (mg/L) 52 43 37
PS (mg/L) 58 58 12
Microtoxicity (EC50, %) 8.6 8.8 31
COMBINED TREATMENT
Conclusion
 Ozone can degrade various types of chemicals or microbe with its
strong oxidizing power.
 Many studies proved that ozonation is effective not only on
municipal wastewater but also on industrial wastewater.
 pH of wastewater and concentration of ozone is important on
effectiveness of ozonation.
 Basic environment(>pH 7) is favorable for ozonation.
 Lower concentration of ozone may not be effective.
 Ozonation can need pretreatments according to condition of
wastewater.
 Ozonation shows better performance when it is combined with
other water treatment technologies.
25
CONCLUSION
26
Thank you!

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Ozone_treatment_for_wastewater_treatment.pptx

  • 1. OZONE TECHNOLOGY FOR WASTEWATER TREATMENT : APPLICATION & LIMITATION CHANGHYEON BAK 2017.06.08 1
  • 2. CONTENTS  Introduction  Background  What is Ozone?  Ozone’s strength  Application to wastewater treatment  Actual cases  AOP (Advanced Oxidation Process)  Combination application  Conclusion 2
  • 4. Pathogen & harmful chemicals in wastewater  Pathogens and harmful chemicals in wastewater can cause problems in ecosystem.  So, disinfection and destruction of harmful chemicals is needed.  Disinfection technologies 1) UV 2) Chlorine 3) Ozone 4 BACKGROUND Viruses Bacteria Protozoa Helminths Phenol Cyanide
  • 5. Comparison Criteria UV radiation Ozone Chlorine Harmful byproducts NO NO YES Environmental impact LOW LOW HIGH Bacteria removal SOME YES YES Virus removal NO YES SOME Lead removal NO YES NO Manganese removal NO YES SOME Iron removal NO YES YES Odor removal NO YES YES Color removal NO YES SOME Operational cost MED LOW MED Capital cost MED HIGH MED Maintenance HIGH MED MED 5 BACKGROUND (Marianne, 1997)
  • 6. What is ozone  O3  Unstable structure -> High reactivity  Pale blue gas  Distinctively pungent smell INTRODUCTION 6
  • 7.  Much higher solubility into water than O2  Strong oxidizing agent  Easy to produce with air or oxygen gas and electricity Ozone’s strength INTRODUCTION 7 ● Oxygen Reactions : 1) O2 + e → 2O + e 2)O2 + O + M → O3 water O2 O3 1) 2) O3 109mg/L ≫ O2 18mg/L at 25℃ (Ozone solutions, 2014)
  • 8. pH dependence of dissolved ozone  Dissolved O3 has pH dependence.  In basic environment, ozone decomposes rapidly.  And OH-radicals are produced.  OH-radical is the strongest oxidant.  The higher pH, the more OH-radicals. INTRODUCTION 8 (Lenntech, 2010)
  • 10.  Destruction of organic compound  Deodorization  Decolorization  Removal of taste Ozone can control water quality. INTRODUCTION 10 H2S + O3 → SO2 + H2O Cyanides : CN− + O3 → CNO − + O2 CNO- + OH- + H2O → CO32- + NH3 2CNO- + 3O3 + H2O → 2HCO3- + N2 + 3O2 Urea : (NH2)2CO + O3 → N2 + CO2 + 2 H2O Before After Application to wastewater treatment
  • 11.  Reactions with metal ions  Iron  Manganese  Lead Ozone makes precipitation with metal ions. And those can be filtered. INTRODUCTION 11 2 Fe2+ + O3 + 5 H2O → 2 Fe(OH)3(s) + O2 + 4 H+ 2 Mn2+ + 2 O3 + 4 H2O → 2 MnO(OH)2(s) + 2 O2 + 4 H+ PbS + 4 O3 ⟶ PbSO4(s) + 4 O2 Application to wastewater treatment
  • 13.  Ozone treatment system is placed at the end of wastewater treatment system. ACTUAL CASES Ozone treatment system 13 Wastewater treatment system
  • 14. Disinfection performance 14 Coliform : E.coli-like (Hoveid H. et al, 2008) ACTUAL CASES  Bacteria totally removed in 10 min. of contact time and with 1ppm of ozone concentration
  • 15. Decolorization performance 15 (Abidin. et al, 2016) ACTUAL CASES  Red dye RR120 decomposed all in 10 min. with an ozone flow rate of 10.2 mg/min.
  • 16. COD removal performance 16 (Preethi V. et al, 2009) ACTUAL CASES  COD of tannery effluent decreases by ozonation.  COD removal efficiency is related to concentration of ozone and pH.
  • 17. AOP (advanced oxidation process)  AOP is a set of chemical treatment procedure to remove organic materials in wastewater by oxidation through reactions with the strongest oxidant ·OH.  Better than ozonation alone  Combinations 1) O3/H2O2 : peroxonation 2) O3/UV : ozone photolysis 3) H2O2/UV 4) H2O2/Fe2+/UV 17 (Mehmet A. et al, 2014) . . . AOP
  • 18. Peroxonation (O3/H2O2)  Reaction  H2O2 accelerates the decomposition rate of O3.  It produces a larger number of very reactive ·OH radicals.  Peroxonation process is more efficient than ozonation alone.  Essential step of disinfection 18 AOP (Mehmet A. et al, 2014)
  • 19. Ozone photolysis (O3/UV)  Reaction  Effective on eliminating various volatile chlorinated organic compounds ex) CHCl3, CCl4, trichloroethylene(TCE) etc. 19 (Mehmet A. et al, 2014) AOP
  • 20. AOP in Petrochemical wastewater treatment  190 tons/months of phenolic wastes disposes by petrochemicals, pharmaceuticals, and polymer industries.  2-Nitrophenol(2NP) is a main pollutant from petrochemical wastewater.  Shokri applied ozone to degrade 2NP.  Ozonation at high pH (pH = 9) generates OH-radical rapidly. (=AOP) 20 (Shokri A., 2015) AOP Removal rate (%) 2NP 99.8 TOC 31 COD 72.5
  • 21. Coking wastewater treatment  O3 & H2O2/O3 is applied to remove cyanide from coking wastewater.  Oxidation process is combined with coagulation-flocculation- decantation and lime-soda ash softening pretreatment.  Using lower concentrations of ozone, cyanide is not removed.  Ozone consumption without softening pretreatment is twice as much as that with softening pretreatment because wastewater contains bicarbonate ions. 21 (Pueyo N. et al, 2016) COMBINED TREATMENT
  • 22. Textile wastewater treatment  Textile wastewater contains acute toxic chemicals.  Pazdzior et al studied the effect of ozonation & biodegradation on toxicity.  Ozonation is combined with aerobic biodegradation. 22 (Pazdzior K. et al, 2016) COMBINED TREATMENT Toxicity removal O3 →Bio 76.2 – 92.2% Bio→ O3 93.7 – 94.2% Bio→ O3 →Bio ~ 96% raw O 3 Bio O 3 →Bio Bio → O 3 Bio → O 3 → Bio Toxicity after treatment
  • 23. Oilfield wastewater treatment 3 steps to enhance biodegradability of oilfield produced water(OPW) 1. Microwave demulsification : to remove oil 2. Ozone oxidation : to enhance the biodegradability of wastewater 3. Biological aerated filter : aerobic digestion  BOD5/COD shows the biodegradability of wastewater.  The optimum ozone treatment condition - Dosage : 7mg/L - Contact time : 15min 23 (Kang J. et al, 2015) Parameter Initial value pH 6.6 COD (mg/L) 648 BOD5 (mg/L) 45 BOD5/COD 0.07 Oil (mg/L) 68 TPH (mg/L) 76 SO4 2- (mg/L) 34 NH3-N (mg/L) 52 PS (mg/L) 589 TSS (mg/L) 3,346 Microtoxicity (EC50, %) 8.6 ▶Charateristics of OPW (Rajakovic V. et al 2006) COMBINED TREATMENT
  • 24. Oilfield waster treatment  Result  After biological treatment, effluent satisfies Chinese discharge standard.  Ozone decomposes complex chemicals biodegradable. 24 (Kang J. et al, 2015) Parameter Initial value After microwave treatment After ozonation COD (mg/L) 648 382 260 BOD5 (mg/L) 45 21 86 BOD/COD 0.07 0.08 0.33 Oil (mg/L) 68 25 16 TPH (mg/L) 76 28 18 NH3-N (mg/L) 52 43 37 PS (mg/L) 58 58 12 Microtoxicity (EC50, %) 8.6 8.8 31 COMBINED TREATMENT
  • 25. Conclusion  Ozone can degrade various types of chemicals or microbe with its strong oxidizing power.  Many studies proved that ozonation is effective not only on municipal wastewater but also on industrial wastewater.  pH of wastewater and concentration of ozone is important on effectiveness of ozonation.  Basic environment(>pH 7) is favorable for ozonation.  Lower concentration of ozone may not be effective.  Ozonation can need pretreatments according to condition of wastewater.  Ozonation shows better performance when it is combined with other water treatment technologies. 25 CONCLUSION