Reducing fresh water consumption in high water volume consuming industries by recycling AOP-

treated effluents “AOP4Water”

Zmanjševanje porabe svežžžže vode v industriji s ponovno uporabo (recikliranjem) oččččišččččenih odpadnih voda

Predstavitev zaključčččnih rezultatov projekta

Gospodarska zbornica Slovenije, 19.6.2013

Era-net Cornet projekt za industrijska združžžženja, januar 2011- junij 2013 (www.cornet-aop4water.eu)

Projekt se izvaja v okviru programa Cornet sofinanciranega s strani MGRT

Projektni partnerji

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Glavni cilji AOP4Water projekta:

�Zagotavljanje novih virov vode za potrebe industrije, ki so

veliki porabniki vode, s ponovno uporabo očiščenih odpadnih

voda iz papirne, tekstilne in živilsko predelovalne industrije ter

očiščenih komunalnih odpadnih voda

�Ključ do ponovne uporabe (recikliranja) vode je izboljšana

učinkovitost čiščenja odpadnih voda s pomočjo kombinacije

različnih AOP in biološkega čiščenja

�Uporaba minimalnih količin O3 z namenom prepustiti končno

razgradnjo cenejši biološki stopnji čiščenja in tako zmanjšati

celokupne stroške čiščenja odpadne vode.

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5

Začčččetno stanje

• O3 za napredno čiščenje odpadnih vod � veliko prednosti, dobri rezultati in

izkušnje

• VENDAR: ni vedno ekonomična rešitev

• Da bi čiščenje z O3 naredili bolj privlačno � kombinacija z H2O2, UV,

ultrazvokom

• Regije s pomanjkanjem pitne vode � potrebni so novi viri vode

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AOP pri ččččišččččenju odpadnih vod

• Ozon:

�Spremeni preostanek KPK v biološko razgradljive komponente

�KPK ↓, BPK5 ↑, BPK5/KPK ↑

ozoniranje biofilterbiološko čiščenjeproizvodnja papirja

izpust v vodno telo

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Cilj

• Ponovna uporaba AOP-očiščenih odpadnih vod namesto sveže pitne vode

• Ponovna uporaba v:

• proizvodnji papirja in celuloze

• tekstilni industriji

• Vir so odpadne vode iz:

• proizvodnje papirja in celuloze

• živilskopredelovalne industrije

• tekstilne industrije

• komunalne odpadne vode

Ključ do ponovne uporabe:

• Izboljšati učinkovitost AOP-čiščenja z namenom:

� zagotoviti optimalno kvaliteto vode

� pokazati možne uporabe očiščenih odpadnih vod.

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Izvedba

WP 8

sustainability studies

WP 2Factory investigations

WP 3AOP trials with effluents

(paper mills, textile, municipal, food)

WP 4 Biodegradability-trials

WP 5 Mathematical Modelling (Data

analyses and system identification)

WP 6Impact of water(re-)use on process

water and product quality

WP 7Water-treatment concepts

AQP

AQP

UL

UL

PTS

Celabor

Celabor

WP 1Coordination

WP 9

Dissemination and use

PTS

PTS

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AOP pilotna naprava

rezervoar

UV> 40 mJ/cm2λ = 253nmMax. discharge: 15 L/min

Redox, pH, O2

Vodna črpalka

2.4 L/min

Ozon generator: 500 mg/h

Zračna črpalka: 4-5 L/min

Ventouri ozon injektor

Analizator

ozona

BMT 964 C,

Messetechnik

Katalizato

r

Rotameter

Ozon reaktor

Sušilec zraka

Papirna odpadna voda

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0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Original O3 O3 + H2O2 UV + H2O2 O3 + UV O3 + UV + H2O2

Rem

ain

ing

CO

D-s

har

e

Outlet Final Clarifier Outlet AOP Outlet Biofilter

1,0 g O3/g COD0 0,8 g O3/g COD0

+ 0,2 g H2O2/g COD0

0,8 g O3/g COD0

+ UV 60 kWh/m³

0,8 g O3/g COD0

+ 0,2 g H2O2/g COD0

+ UV 60 kWh/m³

UV 60 kWh/m³

+ 0,2 g H2O2/g COD0

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Mill A +B: O3 – BOD5/COD

0

2

4

6

8

10

12

14

16

18

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4

SOD [g O3/g COD0]

BO

D5 [

mg

/l]

0,00

0,04

0,08

0,12

0,16

0,20

0,24

0,28

0,32

0,36

BO

D5/C

OD

[-]

BOD5 Mill A

BOD5 Mill B

BOD5/COD Mill A

BOD5/COD Mill B

BOD5/COD

BOD5

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surova tekstilna odpadna voda

AOP-očiščena tekstilna odpadna voda

Tekstilna odpadna voda

Tekstilna odpadna voda

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Tekstilna odpadna voda

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Komunalna odpadna voda

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ŽŽŽŽivilsko predelovalna odpadna voda

Najbolj učinkovita se je izkazala kombinacija ozona + UV

�Učinkovita dezinfekcija

�Učinkovito razbarvanje

�Zmanjšanje motnosti

�Zmanjšanje KPK in BPK5

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Primerjava papirne in tekstilne odpadne vode

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0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

O3 H2O2 UV + H2O2

Rem

ain

ing

sh

are

COD a436nmCOD a436nm

paper

textile

Dezinfekcija komunalne odpadne vode

Ozonation

• TCB and E. coli – removal

within 20 minutes (8,3 g

O3/m3)

AOPs combinations – higher

efficiency for microbes removal

not proven

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Estrogen hormones removal – overview of AOPs tested

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Example: BOD5/COD

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Results of modelling with Weka

Construction of different ML models

Example: BOD5/COD with M5P Model Tree

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Rule: 4

BODvsCOD_r = 0.1283 * SOD + 0.0135 * UVvsCOD + 0.0287 * H2O2vcCOD

+ 0.0054 * CODvsDOC_i - 0.4014 * BODvsCOD_i + 0.0493

Correlation coefficient 0.9295

Vpliv uporabe AOP oččččišččččene vode na barvo papirja

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-5

-3

-1

1

3

5

7

9

11

-11 -9 -7 -5 -3 -1 1 3 5 7 9 11

a*

b*

Ref. Sc_1 Sc_2 Sc_3 Sc_4 Sc_5 Sc_6

blue redgreen

yellow

50 % WW 1

50 % AOP

Paper

100 % AOP

50 % WW 1

50 % AOP 100 % AOP

50 % WW 1

50 % AOP 100 % AOP

Food processing Municipal wastewater

100 % WW 1

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0

250

500

750

1000

1250

1500

1750

2000

2250

2500

2750

3000

3250

3500

3750

4000

Basis Sz_1 Sz_2 Sz_3 Sz_4 Sz_5 Sz_6

0,0

0,5

1,0

1,5

2,0

2,5

3,0

3,5

4,0

Modulus of elasticity N/mm² Tensile strength kN/m

Breaking elongation % Bending stiffness Nmm

50 % WW

50 % AOP

Paper

100 % AOP

50 % WW

50 % AOP 100 % AOP

50 % WW

50 % AOP 100 % AOP

Food processing Municipal Wastewater

100 %

WW

Vpliv uporabe AOP oččččišččččene vode na mehanske lastnosti papirja

Modul elastičnosti N/mm2Raztezek pri utrgu

Natezna trdnost kN/mUpogibna togost N mm

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Bleaching testsH2O2 35 % 5 hours at 80 °C at pH 9 - Unbleached cotton.

Bleaching before light dye, no need if dark color

Check pH stability before and after bleaching

CIE whiteness at daylight (ISO11475 :2004) CIE

Control tissue A (no bleaching) 21.33

Control tissue B (no bleaching) 20.61

Bleached with agro food treated water A 37.60

Bleached with agro food treated water B 37.98

Bleached with textile 2 treated water A 58.29

Bleached with textile 2 treated water B 58.04

Bleached with textile 1 treated water A 57.89

Bleached with textile 1 treated water B 57.58

Bleached with paper mill treated water A 28.22

Bleached with paper mill treated water B 27.64

Bleached with tap water A 57.31

Bleached with tap water B 57.78

0 black100 white

Duplicate comparable:uniform bleaching

Treated water

- from textile = as tap water

- from agro food - paper =

not for bleaching (color, hardness,

particles), only re-used for dark dyes.

Vpliv uporabe AOP oččččišččččene vode na beljenje in barvanje tekstila

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Light dyeing testLight dyeing pink with anionic dye – polyester cotton

Visual score: 3.5 2 4 4.5 4.5

Tap water Paper mill Textile 1 Textile 2 Agro –food

After bleaching

After pink dyeing

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3. Light dyeing test

Tissue L* a* b*

Tissue dyed with agro food treated water A 81.26 19.9 -5.99

Tissue dyed with agro food treated water B 81.34 19.74 -5.89

Tissue dyed with textile 2 treated water A 82.06 19.54 -6.7

Tissue dyed with textile 2 treated water B 81.6 20.14 -6.35

Tissue dyed with textile 1 treated water – Extreme pink A 80.73 20.18 -5.02

Tissue dyed with textile 1 treated water – Extreme pink B 80.83 19.91 -4.8

Tissue dyed with textile 1 treated water – Extreme white A 83.2 18.02 -5.36

Tissue dyed with textile 1 treated water – Extreme white B 83.57 17.64 -6.09

Tissue dyed with paper mill treated water – Extreme pink A 78.26 20.48 -4.59

Tissue dyed with paper mill treated water – Extreme pink B 79.51 20.26 -5.01

Tissue dyed with paper mill treated water – Extreme white A 85.48 13.64 -4.79

Tissue dyed with paper mill treated water – Extreme white B 85.19 13.96 -5.49

Tissue dyed with tap water – Extreme pink A 80.65 20.23 -5.1

Tissue dyed with tap water – Extreme pink B 81.3 19.99 -5.17

Tissue dyed with tap water – Extreme white A 82.35 18.51 -5.71

Tissue dyed with tap water – Extreme white B 82.5 18.69 -5.54

Uniform dye: 2 measurements

Non-Uniform dye: 4 measurements

Colorimetric Lab test: L for lightness and a and b for the color-opponent dimensions

For light dyeing: tap water not the best uniform pink color

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• Important step in textile process = bleaching = preliminary step for light dyeing

• Different treated waters = different advantages depending on their use

- For bleaching tests : good results for tap and textile water.

- For light dyeing: agro food water and textile 2

- For bleaching + light dyeing, AOP treated textile water 2 the best.

- For dark dyeing, all treated waters ok.

• If dark dyeing, all treated waters ok. Characteristics needed:

- stable pH with T

- soft water (hardness precipitates the soap during washing).

- few ions in solution

- no heavy metals (catalyzer of bleaching, risks for tissues and human health

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-100,0

0,0

100,0

200,0

300,0

400,0

500,0

600,0

700,0

800,0

Classical treatment Classical treatment and AOP-treatment Classical treatment and AOP-treatment

and reuse

µP

t

Mineral extraction

Non-renewable energy

Global warming

Aquatic eutrophication

Aquatic acidification

Land occupation

Terrestrial acid/nutri

Terrestrial ecotoxicity

Aquatic ecotoxicity

Respiratory organics

Ozone layer depletion

Ionizing radiation

Respiratory inorganics

Non-carcinogens

Carcinogens

The impact on the environment is more than doubled BUT the quality is higher!

If the treated water can be reused, 1m³ of fresh water is avoided and the environmental impact is lower

Zaključčččki

�Kombinacije O3 in H2O2, UV ter kavitacije bolj učinkovite kot samo ozon

(izjema papirna industrija)

�Najbolj učinkovita kombinacija: O3 + UV + biološka faza

�Z uporabo ozona smo zvišali razmerje BPK/KPK – težko biološko

razgradljive snovi so postale lažje biološko razgradljive

�AOP očiščena odpadna voda iz vseh treh preiskovanih industrijskih

sektorjev in AOP očiščena komunalna odpadna voda sta primerni za

ponovno uporabo v proizvodnem procesu tekstilne in papirne industrije

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HVALA ZA POZORNOST!

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