OZONE OXIDATION ENABLES WATERS TO BE RE-USED - Aquafit 4 Use … Conference... · · 2011-01-26OZONE OXIDATION ENABLES WATERS TO BE RE-USED Dr. Jörg Mielcke ... food industry Quality

Water & Wastewater

OZONE OXIDATION ENABLES WATERS TO BE RE-USED

Dr. Jörg Mielcke( - WED)

VII ANQUE`S International Congressand

Mid-term AquaFit4Use Conference

Ozone enables waters to be re-used

Oviedo; June,15th 2010

2

Water & Wastewater

Outline

� Requirements for waters to be re-used

� Concepts for waste water treatment

� Principle aspects using ozone for waste water treatment

� Principle aspects about process combination (treatment trains)

- biology and oxidation

- AOP treatment

� Large scale plants

� Cost situation

� Conclusions



3

Water & Wastewater

Motivation



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Water & Wastewater

…..…..…..…..……(other more)

100--------

Colony forming

units [CFU/100ml]

15050 - 40065 - 7065 - 7060Calcium [mg/L]

--500 - 1700------

Conductivity

[µS/cm]

--7.1 - 8.16.5 - 87 – 86.5 – 7.5pH

5150 - 450500 – 200020020 - 50COD [mg/L]

20--none visiblenone visiblenone visibleColour [mg/L Pt]

Quality for

cleaning

water

food industry

Quality for

sanitary paper

paper industry

Low quality water

textile industry

Moderate quality water

textile industry

High quality water

textile industry

Parameter(excerpt)

Recommend maximum levels of different parameters for industrial waterindustrial water re-use qualities



5

Water & Wastewater

Treatment Concepts for Waste Water Reuse

Inlet Biology ClarifierPrimary

RO

AOP:- UV / H2O2

- UV / O3

- O3 / H2O2

MF

Outfall/ River

Reuse

Drinkingwater

Bio/Filtration UVOzone

AOP:- UV / H2O2

- UV / O3

- O3 / H2O2

A-Carbon

A-Carbon

Conventional WW Treatment

Disinfection(Optional)



6

Water & Wastewater

Treatment steps for waste water and principle effects

DisinfectionPhoto-oxidation

Effects UV

COD removal

Persistant sub-stances removal

Disinfection

Color, Odor

Threadworms

Disinfection effect

e.g. on sand filter

(reduction of threadworms)

Reduction of ToxicityIncrease of BOD

Effects Ozone

MembraneOzone (AOP)

UVA-carbon

SedimentationSand filterDifferent membrane filters

Activated sludgeFixed bed

Different kind of reactors

FlocculationCoagulation

SedimentationFiltration

Technique

Additional treatment

Clarifier/FilterBiological treatmentPrimary

treatment



7

Water & Wastewater

MEMBRANEMEMBRANE

OXIDATIONOXIDATION

Waste Water

Tool boxes for treatment concepts of WW

Carbon

RecyclingBiology

SEVERAL TREATMENT TRAINS POSSIBLE

Separation

In situ

AquaFit4Use concept



8

Water & Wastewater

COD elimination by Ozone - example -

0

100

200

300

400

500

600

700

800

900

0 500 1000 1500 2000 2500

Ozone dose [mg/l]

CO

D [

mg

/l]

0

10

20

30

40

50

60

70

80

90

CO

D E

lim

inati

on

[%

]

COD

COD elimination



9

Water & Wastewater

Specific oxidation: e.g. Kresol degradation

0

2000

4000

6000

8000

10000

12000

14000

16000

0 500 1000 1500 2000 2500

Ozone dose [mg/l]

CO

D [

mg

/l]

0

100

200

300

400

500

600

700

800

Kre

so

l [m

g/l

]

COD Kresol



10

Water & Wastewater

AOX- / COD- elimination Deodorisation

Decolorisation

Disinfection

0 1 5 10 25 50 100 200 ozone dosage (g O3 / m³)

General effects



11

Water & Wastewater

� Improvement of:

� BOD/COD-ratio

� flocculation / filtration

� Reduction of:

� color

� toxic compounds (e.g. EDC)

� odor (e.g. H2S)

� bacteria

� further COD reduction

� Mineralisation of:

� CKW´s

� TOC

ozone oxidationin waste water

partial oxidation(cracking)

complete oxidation

Oxidation with OZONE / principle aspects



12

Water & Wastewater

“Biology - Ozone” - basic effects

hardly biodegradable COD

biodegradableCOD

COD

biologicaltreatment plant

Ozone

Goal: Improve biodegradability



13

Water & Wastewater

Treatment effects using „Biology-Ozone“

raw raw ozoneozone biologybiology ozoneozone biobio--filterfilter

water water treatment Itreatment I treatment IItreatment II

ozone ozone 0 50-100 0 400-600 0

dosage: g/m³ g/m³

effects:effects: no detoxification cracking effects reduction of : reduction of : reduction of : reduction of :

- phenol - biol. COD - partly COD - COD/BOD

- color - BOD color, odor, foam - odor removal

disinfectionspecific compoundse.g. EDC

CODCOD

reductionreduction 0%0% 5%5% 60%60% 80%80% 90%90%



14

Water & Wastewater

� Improvement of:

� BOD/COD-ratio

� flocculation / filtration

� Reduction of:

� color

� toxic compounds (e.g. EDC)

� odor (e.g. H2S)

� bacteria

� further COD reduction

� Mineralisation of:

� CKW´s

� TOC

ozone oxidationin waste water

partial oxidation(cracking)

complete oxidation

Oxidation with OZONE / principle aspects



15

Water & Wastewater

O3

•OH+ P

+ PPox

P´ox

+ OH-

O3 : specific (direct ozone reaction)

•OH: fast, not specific

Oxidation: ozone and radical reaction



16

Water & Wastewater

How to create more Hydroxyl Radicals?

In theory, there are several technologies that exist for advanced oxidation,

(AOP) such as:

- Hydrogen Peroxide + Ultraviolet Light- Hydrogen Peroxide + Ozone

- Ozone + Ultraviolet

Known methods, but not commercialized:

- Titanium Dioxide + Ultraviolet Light

- The photo-Fenton Process (Fe(OH)2+ hv → Fe2+ + ·OH)

- Oxidation in combination with electrolysis

- Various Catalytic Processes (oxidant chemical + catalyst)

- ………

These are the technical

relevant ones



17

Water & Wastewater

COD reduction with ozone and ozone/H2O2

0

20

40

60

80

100

120

140

160

180

200

0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600

03-Dosage react [g/m³]

CO

D [

mg

02

/L] O3/H2O2

O3



18

Water & Wastewater

Ozone treatment – key technique to process waste water for various targets



19

Water & Wastewater

ozone generator

energy(400 V)

coolingwater

5 - 32 °C

feed gas

O3

grounded

air / O2

electrodes

5,5 kV

offgas

reaction tank

Scheme of an ozone system



20

Water & Wastewater

MWWTP Kalundborg, DK - start up: 02/2003

Target: COD removal; 1200 m³/h

High input of industrial waste water

COD(effluent biology): 120–180 mg/l

Limit < 70 mg/l COD

Ozone installation: 2 x 90 kg ozone/h

Oxygen production onsite

Off-gas for biology aeration



21

Water & Wastewater

“Ozone” - application for different water types

� Municipal waste water

- pre treatment part stream or polishing final effluent

reduction of: colored substances, AOX, phenols, PAH,

COD, bacteria, pharmaceuticals, etc. ozone dose: 5.0 to 150 g O3/m

3

� Drinking water

- Ozone ( pre- / main / post- ozonisation)

reduction of: bacteria, THM precursors, taste&odor (and other goals) ozone dose: 0.5 to 5.0 g O3/m

3

� Industrial waste water

- different combinations Ozone - BIO - Ozone - BIO

reduction of: specific chemicals, color, COD, etc.ozone dose: 50 to 1000 g O3/m

3



22

Water & Wastewater

Cost situation / example calculations

� cost for ozone production:- 1.5 – 2.0 Euro/kg ozone

(invest ozone generation + operation – no reaction system)

� end up in:- 5 g O3/m³ 0.0075 to 0.01 Euro/m3

- 50 g O3/m³ 0.075 to 0.10 Euro/m3

- 200 g O3/m³ 0.30 to 0.40 Euro/m3

- 1000 g O3/m³ 1.5 to 2.0 Euro/m3

� necessary ozone dosage:- polishing effluent: 5 – 20 g/m3

- slight COD reduction, decolourisation: 30 – 200 g/m3

- intensive COD reduction: 200 – 2000 g/m3



23

Water & Wastewater

Conclusions

• Oxidation (mainly OZONE) is a powerful technique to be used in treatment trains to make-up waters for re-use ( in situ ).

• For special tasks Advanced Oxidation Processes (AOP) might be required.(there is no „one is the best AOP“ – decision matrix)

• Decision criteria:

- treatment requirements/goals

- treatment efficiency (type of water, contaminants, )

- part of treatment train (harmony, synergies)

- foot print

- capital and operating cost

• Some parameters are affected effectively – some not!

(COD, color, odor, germs) (hardness, conductivity)

Oxidation for re-use?



24

Water & Wastewater

Waste water treatment technologies

0,1

1,0

10,0

100,0

1.000,0

10.000,0

100.000,0

0,1 1,0 10,0 100,0 1.000,0 10.000,0

Flow [m³/h]

CO

D [

mg

/l]

Aerob biological Treatment

(activated sludge, MBR, Biofilter)

electrolytic ozone generators / LBT UV Systems incl. MB

(PHARMA)

Incineration /

Evaporation

Wet Air Oxidation

OZONE /AOP (OZONE + H2O2)

AOP

(Fenton)

Anaerob biological

Treatment

AOP (UV/H2O

2)



25

Water & Wastewater

…..…..…..…..……(other more)

100--------

Colony forming

units

[CFU/100ml]

15050 - 40065 - 7065 - 7060Calcium [mg/L]

--500 - 1700------

Conductivity

[µS/cm]

--7.1 - 8.16.5 - 87 – 86.5 – 7.5pH

5150 - 450500 – 200020020 - 50COD [mg/L]

20--none visiblenone visiblenone visibleColour [mg/L Pt]

Quality for cleaning

water

food industry

Quality for

sanitary paper

paper industry

Low quality water

textile industry

Moderate quality

water

textile industry

High quality water

textile industry

Parameter(excerpt)

Recommend maximum levels of different parameters for industrial waterindustrial water re-use qualities

��

��

Do youremember?

O3

O3O3

O3O3

O3

O3

O3

AOP

AOP

AOP

UV



26

Water & Wastewater

Source: watereducation.organisation(www.watereducation.org)

Our Mission



27

Water & Wastewater

Thank you for your attention!

ANY QUESTIONS, COMMENTS?

UV Disinfection Ozone Oxidation Advanced Oxidation

Documents

OZONE OXIDATION ENABLES WATERS TO BE RE-USED - Aquafit 4 Use … Conference... · · 2011-01-26OZONE OXIDATION ENABLES WATERS TO BE RE-USED Dr. Jörg Mielcke ... food industry Quality