1. Decreasing the non- biodegradable component of Pulp & Paper effluent, combining AGAR® technology and Advanced Oxidation Processes (AOP) Maital Helman Presented by: Ramiro Garza September 2014 IPN-ISRAEL WATER WEEK

2. Proprietary and confidential Problem definition  In certain industrial wastewater, the remaining non-biodegradables concentration out of biological treatment exceed required effluents regulations  In thus cases the present practice would be either tertiary treatment or separate discharge of specific streams IsraelIndiaChinaEurope COD < 100ppm ZLD COD < 700ppmCOD < 160ppm Discharge to river COD 800-2000ppm -COD < 500ppm Discharge to WWTP COD < 150ppm-- Irrigation for agriculture Examples of COD industrial effluents standards

3. Proprietary and confidential Pulp & Paper Industry  The 3 rd largest polluter in the US  The WW are contaminated with large quantities of organic materials, which results with only 85-90% of bd. COD  Due to the parallel efforts for reducing water usage in the process, the non- biodegradable (NBD) fraction is increasing hence, compliance with effluent COD standards becomes much more complicated  Increasing WW biodegradability might allow almost complete remove of COD compounds and possible reuse of more WW

4. Proprietary and confidential Suggested Solution  The oxidation treatment is proposed for effluent biodegradability increase that will than be reintroduce back to a biological treatment  Appropriate AOP technology will be adopted based on effluent characteristics Inlet Air Carriers Outlet Fenton NiO Recirculation MBBR AOP Recirculation back to biological treatment Inlet Air Carriers Fenton NiO Air Carriers Outlet MBBR AOP MBBR Discharged to second biological reactor Combining AOP technologies with MBBR

5. Proprietary and confidential Advanced Oxidation Process (AOP) 1.Formation of strong oxidation agents (e.g. hydroxyl radicals) 2.Reaction between oxidants and organic compounds may result with biodegradable intermediates 3.Optional - Reaction of biodegradable intermediates with oxidants referred to as mineralization The AOP involves several steps

6. Proprietary and confidential Fenton  Fenton is an oxidation reaction, developed over a century ago, using hydrogen peroxide and Iron sulfate at low pH of 2.5-3.5  The process is tested in a batch mode

7. Proprietary and confidential Nickel Oxide  Nickel oxide is a Catalyst for oxidation processes for WW treatment  The Colonna contains granular catalyst, while an Hydrogen peroxide is fed at different concentrations to form the radicals  The pH inside the Colonna should be kept >8.5

8. Proprietary and confidential Objectives  Define optimal condition - applying Fenton reaction to reach higher BOD/COD ratio  Define optimal condition - applying Nickel Oxide catalyst to reach higher BOD/COD ratio  Performing Partial oxidation (15% removal of COD) to increase biodegradability to 0.3

9. Results

10. Proprietary and confidential Fenton  Increase in BOD/COD ratio obtained at different Fe +2 to H 2 O 2 ratio, oxidizing 50 ppm COD, at different Fe +2 -H 2 O 2 ratios

11. Proprietary and confidential Fenton  To evaluate the influence of pH correction, experiments were performed at pH 4 (after correction) and pH 8 (w/o correction) at Fe-H 2 O 2 molar ratio of 1:10 and oxidation of 50ppm COD at 35 ˚C

12. Proprietary and confidential Fenton  Different COD level were oxidized  The influence of the COD con. that was to be oxidized, on biodegradability, was evaluated

13. Proprietary and confidential Nickel oxide  Influence of H 2 O 2 concentration on the increase in BOD/COD ratio between time zero and at the end of the experiment

14. Summary & Conclusions

15. Proprietary and confidential Conclusions  Increase in BOD/COD ratio was exhibited in all tested system, for both NiO and Fenton reactions  Fenton’s reagent was succeeding to maintain high removal percentage at different Peroxide concentration  Using Nickel oxide catalyst, optimal operation conditions are with 0.05% oxidizer concentration and 60°C  Average COD Removal Rate in Nickel oxide & Fenton experiments were 26% and 15%, respectively.

16. QA

17. Contact Information Contact us for further information about Aqwise solutions Email Maital@aqwise.com Maital Helman R&D Engineer Website www.aqwise.com Telephone +972-9-9591901