Oxidation Case Studies

Oxidation Case Studies
J(Hans) van Leeuwen
3/9/2013
Disinfection applications
Introduction
Summary
and explanation Simple calculations Show some applications

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3/9/2013 Disinfection applications
DISINFECTION KINETICS
Chicks Law
dN dt
-kN
N is the number of microorganisms at time t, and k is a constant (dimension : t-1).
This constant applies only for a fixed concentration of a certain disinfectant
INTEGRATION OF CHICKs LAW Integrating for N, N=No at t = 0
ln N/N0 = -kt
N/N0 = e-kt
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Watsons Law
Cnt = constant
Simplified:
Ct = constant Applies only for a fixed rate of kill a certain organism a specific disinfectant
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Example
Ct value for ozone is 1.0 mgL-1min.
We could achieve that with 1 mg/L ozone residual for 1 minute
Or: 0.4 mg/L for 2.5 minutes
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CHLORINE RESIDUALS
Free HOCl and OClCombined NH2Cl, NHCl2 Total = Free + combined
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CHLORINE REACTIONS WITH AMMONIA

Cl2 + H2O HOCl + NH3 HOCl + H+Cl-
NH2Cl + HOH
HOCl + 2NH2Cl N2 + 3H+Cl- + H2O

Net reaction: 2 x 2nd + 3rd :
3 HOCl + 2 NH3 N2 + 3H+Cl- + 3H2O

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CHLORINE REACTIONS WITH AMMONIA

Cl2 + H2O HOCl + NH3 HOCl + H+Cl-
NH2Cl + HOH
HOCl + 2NH2Cl N2 + 3H+Cl- + H2O

Net reaction: 3 x 1st + 2 x 2nd + 3rd :
3 Cl2 + 2 NH3
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N2 + 6H+ClDisinfection applications
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MEASUREMENT OF CHLORINE (OR CHLORAMINES)

DPD pink color develops
KI solution I-1 oxidized to I, forms I2

Color of DPD or I2 can be measured, or I2 titrated with FAS solution
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formation
Other oxidation reactions
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DISINFECTION BYPRODUCTS THMs - CHX3, e.g. CHCl3 Chlorite and chlorate, ClO2ClO3 Bromoform - CHBr3 Bromate - BrO3-
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ClO2 made from Sodium Chlorite

Acidification of Chlorite 5 ClO2- + 4 H+ 4 ClO2 + 2 H2O + ClOxidation of Chlorite by Chlorine 2 NaClO2 + Cl2 2 NaCl + 2 ClO2
Oxidation of Chlorite by Persulfate 2 NaClO2 + Na2S2O8 2 ClO2 + 2 Na2SO4

From Sodium Hypochlorite and Sodium Chlorite NaOCl + 2 NaClO2 + 2 HCl 2 ClO2 + 3 NaCl + H2O Electrochemical oxidation of chlorite ClO2- ClO2 + eDry chlorine/chlorite (laboratory method) NaClO2 + 1/2 Cl2 --> ClO2 + NaCl (solid) 13
OZONE PRODUCTION
Electron bombardment UV irradiation at < 200 m Electrolytically
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Corona Discharges in Ozone Generation
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Large Ozone Generators
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Toxicity of ozone to humans

Ozone concentration ppm
0.1
0.1
10
100
1000 10000
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10 100 1000 Exposure time (minutes)
10000
COMPONENTS OF AN OZONATION SYSTEM

INFLUENT
OZONE GENERATOR OZONE CONTACT CHAMBER OZONE DESTRUCTOR
AIR/OXYGEN PREPARATION
AIR
VENT
OTHER OXYGEN APPLICATIONS EFFLUENT Alternative paths for enriched oxygen recycle
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BUBBLE COLUMN CONSTRUCTION DETAILS
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50m m 50
Deep Shaft Ozonation System 30

0.8 0.7 Ozone dose A

OZONE RESIDUAL (mg/l)
0.6 0.5 0.4 0.3 Ozone dose B 0.2 0.1 0 0 1 2 3 4 5 TIME (min) 6 7 8 9 10
Pre-ozonation
Ozone Disinfection
Raw Water
Screening
Clarification
Filtration
G A C
Distribution
Residual Disinfection
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OTHER USES OF OZONE IN WATER TREATMENT Iron and Mn removal Color removal Geosmin and 2-MIB Cyanotoxins cylindrospermopsin,
microcystin, anatoxin*
Microflocculation Biodegradability
*Produced by Cylindrospermopsis, Microcystis and Anabena genera
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Scarce Water Resources near Mines
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Further Applications of Ozone in The Water Technology Field

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Wastewater treatment Effluent disinfection Cooling water treatment Swimming pools Ozonated ice Ozonated air AOP (advanced oxidation processes)
Mine Water Cooling
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Case Study: Mining Application
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DUST
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POSSIBLE INHIBITORS
High temperatures Heavy metals Disinfectant byproducts or residues
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Ozonation Bubble Column
Sand Filters
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Oxidation of cyanides, thiocyanate and TOC in the Reclamation of Water in Steel Processing
BHP near Wollongong, Australia reuses wastewater after biological and activated carbon treatment Cyanides interfere with biological treatment and need to be lowered to 200 mg/L before activated sludge Cyanates are incompletely removed if over 250 mg/L
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BHP Ozonation Investigations
Ozone was tested to observe efficacy to remove CN- and SCNOzone requirements due to competitive reactions observed Ozone needs to replace or enhance activated carbon treatment
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CYANIDE REMOVAL FROM COG
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CYANIDE REMOVAL FROM BHP
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CYANATE REMOVAL FROM BHP

200,0 180,0
BHP
160,0 140,0
SCN, mg/L
120,0 100,0 80,0 60,0 40,0 20,0 0,0 0 250 500 750 1000 1250
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Ozone consumed, mg/L 3/9/2013
TOC AND COLOR REMOVAL FROM ACTIVATED SLUDGE EFFLUENT

140
TOC mg/L or PCU
120 100 80 60 40 20 0 0
Color
TOC
10
20
30
40
50
60
70
Time, min
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Cost Implications: CN

Capital cost of ozone installation $ 0.64 million Amortisation, maintenance operation $16,000 per month Present alternative, formaldehyde costs $ 7000 per month, more COD Ozone not cost effective
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Cost implications: SCN
Capital required $ 2.0 million Monthly costs $ 76 000
No other method SCN- removal There will be a much smaller risk in achieving treatment objectives Ozone not economical
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SYNTHETIC ORGANIC REMOVAL BY INTEGRATED OZONOLYSIS/ ACTIVATED SLUDGE

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CONVENTIONAL PREOZONATION + ACTIVATED SLUDGE
Air Air
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POST-OZONATION: Remove degradables first
More Treatment required
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Since ozonolysis results in biodegradable byproducts, more biological treatment required after post-ozonation
This requirement can be resolved in two possible ways: another biological treatment stage recirculation to biological treatment 60
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Biological treatment before and after ozonation
Using a large ozonated recycle

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Ozonated Recycle 3/9/2013 Disinfection applications
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O3
THE SOLUTION INVESTIGATED

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Experimental Set-up
Activated sludge with wastewater containing methylene blue ozonated
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Results
MeBl removal in ozonated activated sludge 95% vs. 40% in control COD removal in ozonated activated sludge 80.5% vs. 79.5% in control Better biomass settling
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Control after settling
Ozonated mixed liquor
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Conclusions
Ozone can be dosed within an activated sludge system for the ozonolysis of non-biodegradables Effect on biomass beneficial, if minimal Byproducts mainly biodegradable Economical integrated procedure

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Pilot Scale Implementation at Van Diest Supply Company, Iowa
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3/9/2013

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Oxidation Case Studies

J(Hans) van Leeuwen

and explanation Simple calculations Show some applications

N is the number of microorganisms at time t, and k is a constant (dimension : t-1).

This constant applies only for a fixed concentration of a certain disinfectant

INTEGRATION OF CHICKs LAW Integrating for N, N=No at t = 0

Or: 0.4 mg/L for 2.5 minutes

Free HOCl and OClCombined NH2Cl, NHCl2 Total = Free + combined

CHLORINE REACTIONS WITH AMMONIA

HOCl + 2NH2Cl N2 + 3H+Cl- + H2O

3 HOCl + 2 NH3 N2 + 3H+Cl- + 3H2O

CHLORINE REACTIONS WITH AMMONIA

HOCl + 2NH2Cl N2 + 3H+Cl- + H2O

MEASUREMENT OF CHLORINE (OR CHLORAMINES)

KI solution I-1 oxidized to I, forms I2

ClO2 made from Sodium Chlorite

Oxidation of Chlorite by Persulfate 2 NaClO2 + Na2S2O8 2 ClO2 + 2 Na2SO4

Corona Discharges in Ozone Generation

Large Ozone Generators

Toxicity of ozone to humans

10 100 1000 Exposure time (minutes)

COMPONENTS OF AN OZONATION SYSTEM

OZONE GENERATOR OZONE CONTACT CHAMBER OZONE DESTRUCTOR

BUBBLE COLUMN CONSTRUCTION DETAILS

Deep Shaft Ozonation System 30

0.8 0.7 Ozone dose A

*Produced by Cylindrospermopsis, Microcystis and Anabena genera

Scarce Water Resources near Mines

Further Applications of Ozone in The Water Technology Field

Mine Water Cooling

Case Study: Mining Application

Ozonation Bubble Column

BHP Ozonation Investigations

CYANIDE REMOVAL FROM COG

CYANIDE REMOVAL FROM BHP

CYANATE REMOVAL FROM BHP

Ozone consumed, mg/L 3/9/2013

TOC AND COLOR REMOVAL FROM ACTIVATED SLUDGE EFFLUENT

TOC mg/L or PCU

Cost implications: SCN

Capital required $ 2.0 million Monthly costs $ 76 000

SYNTHETIC ORGANIC REMOVAL BY INTEGRATED OZONOLYSIS/ ACTIVATED SLUDGE

CONVENTIONAL PREOZONATION + ACTIVATED SLUDGE

POST-OZONATION: Remove degradables first

More Treatment required

Biological treatment before and after ozonation

Using a large ozonated recycle

THE SOLUTION INVESTIGATED

Control after settling

Ozonated mixed liquor

Pilot Scale Implementation at Van Diest Supply Company, Iowa

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