1. Reducing fresh water consumption in high water volume consuming industries by recycling AOP- treated effluents “AOP4Water” Zmanjševanje porabe sveže vode v industriji s ponovno uporabo (recikliranjem) očiščenih odpadnih voda 13. oktober 2011, Ljubljana Pregled in koncept projekta ter prvi rezultati Trajanje: 01 januar 2011 – 31 december 2012 dr. Aleksandra Krivograd Klemenčič

2. 2 outline  Initial situation  AOPs for advanced effluent treatment  Project objectives  Execution, time frame

3. 3 Initial situation  O 3 for advanced effluent treatment : many advantages, good results and experience  BUT: not always economical worthwhile  Make O 3 -treatment more attractive:  Combination with H 2 O 2, UV, Ultrasound  Regions with a lack of freshwater  new water sources needed

4. 4 AOP in effluent treatment  Ozone:  turns residual COD into biodegradable compounds  COD ↓, BOD 5 ↑, BOD 5 /COD ↑ ozone stage biofilter biological treatment paper production receiving water

5. 5 Goal  (re-)use of AOP-treated effluents instead of freshwater  (re-)use in Pulp and paper mills Textile industry  Source: effluents from Pulp and paper mills Food processing industry Textile industry Municipal waste water Key to (re-)use:  improve the efficiency of AOP-treatment  to ensure optimum water quality  to show the possible use of the treated water

6. 6 Execution WP 8 sustainability studies WP 2 Factory investigations WP 3 AOP trials with effluents (paper mills, textile, municipal, food) WP 4 Biodegradability-trials WP 5 Mathematical Modelling (Data analyses and system identification) WP 6 Impact of water(re-)use on process water and product quality WP 7 Water-treatment concepts AQP UL PTS Celabor WP 1 Coordination WP 9 Dissemination and use PTS

7. 7 Time frame

8. Selected textile industries  TSP Maribor d.d.  POLZELA socks and stockings factory d.d. 8

9. 9 Options of reuse of AOP-treated wastewater in textile industry - in dyeing process - in washing process - ?

10. 10 Reservoir System pump 2.4 L/min Ozonation Generator: 200-400 mg/h Internal air pump: 4-5 L/min Ventouri ozone injector Hydrogen Peroxide pump, 2.7 mL/min Hydrogen Peroxide UV > 40 mJ/cm2 λ = 253nm Max. discharge: 15 L/min Redox, pH, O 2 samplers IzVRS and ECHO Ltd. designed and constructed lab-scale pilot plant for performing AOP-trials

11. UV TRIALS O 3 TRIALS H 2 O 2 TRIALS Task 3.2: AOP trials – technologies used individually  Two parameters were chosen to be followed in the preliminary trials: COD and colouration.  Sampling point (at POLZELA socks and stockings factory): wastewater from the production of textiles – outflow from the equalization pond (where partial self-neutralization is present as acidic and alkaline wastewater is mixed)

12. Results: UV TRIALS DateNumber of cycles Processing time (min) Processing time (s) COD (mg/L)Colour (455 nm) [units PtCo] Colour residue (%) 1.7.201100' start0340-- 1.7.201111'60335-- 1.7.201122'120331-- 1.7.201155'300328-- 1.7.20111010'600333-- 1.7.20112020'1200327-- 1.7.20115050'3000330-- 1.7.2011100100'6000323-- 1.7.2011200200'12000287-- 4.7.201143203days25920018877546,69 4.7.20113days - raw sample 3171660100 12

13. 13 Results: UV TRIALS λ = 253 nm Q = 2.4 L/min V = 2.4 L

14. Results: O 3 TRIALS DateNumber of cycles Processing time (min) Processing time (s) COD (mg/L)Colour (455 nm) [units PtCo] Colour residue (%) 4.7.201100' start0312-- 4.7.201112'120304-- 4.7.201124'240299-- 4.7.2011510'600298-- 4.7.20111020'1200303-- 4.7.20112040'2400283-- 4.7.201150100'6000263497100 4.7.2011100200'1200023427956 5.7.20117201 day86400799419 14

15. Results: O 3 TRIALS 15 Q = 2.4 L/min V = 4.8 L Q O 3 = 500 mg/h

16. Results: H 2 O 2 TRIALS DateNumber of cycles Processing time (min) Processing time (s) COD (mg/L)Colour (455 nm) [units PtCo] 7.7.201100' start02861803 7.7.201112'12010011779 7.7.201124'24014191744 7.7.2011510'60025741712 7.7.20111020'120046841611 7.7.20112040'2400111001499 7.7.201150100'6000152001497 7.7.2011100200'12000159001295 8.7.20117201d86400 16

17. Results: H 2 O 2 TRIALS 17 Q = 2.7 L/min V = 4.8 L 2.7 mL of 30% H 2 O 2 per min added

18. CONCLUSIONS COD decrease: ozonation at the applied ozone concentration proved to be more efficient compared to UV irradiation (25% remaining COD at ozonation compared to 55% at UV irradiation) COLOURATION: ozonation proved to be much more efficient compared to peroxide application in colour removal (19% remaining colouration at ozonation compared to 72% at peroxide application) The amount of H 2 O 2 added needs to be adjusted and surplus avoided 18

19. FURTHER TRIALS Task 3.2: AOP trials – technologies used individually POLZELA (Textile factory A):  Repetitions of experiments with separately applied methods (UV, O 3 and H 2 O 2 ) (Autumn 2011)  Performing experiments with Cavitation (Autumn 2011)  Parameters to be analyzed: COD, BOD5, Colour, Nitrate, Nitrite, TSS, pH, Total hardness, Sulphate, Chloride, Iron, Manganese, Copper, Alkalinity, Turbidity 19 TSP (Textile factory B)?, municipal wastewater, removal of pharmaceuticals Trials planned to be performed in 2012

20. FURTHER TRIALS Task 3.3: AOP trials – technologies used combined POLZELA (Textile factory A):  UV +O 3 (Autumn 2011)  H 2 O 2 + O 3 (Autumn 2011)  US + O 3 (Autumn 2011)  US +UV (Autumn 2011)  US+ H 2 O 2 + O 3 (Autumn 2011) 20 TSP (Textile factory B), municipal wastewater, removal of pharmaceuticals Trials planned to be performed in 2012