PILLS Final Conference19th / 20th September 2012

Development & Investigation of

wastewater treatment technologies

at local sourcesat local sources

Sven Lyko, Emschergenossenschaft

Christian Köhler, Centre de Recherche Henri Tudor

(on behalf of the PILLS partners)

Outline

• 4 pilot plants at 4 hospitals

Outline

• Applied technologies (pilot plants)

• Removal efficiency and operational performance

• MBR

• O3 (+H2O2)

• UV/TiO2, UV/H2O2

• Activated Carbon (GAC, PAC)

• Energy consumption

• Costs

• Key messages

Overview of the applied technologies

Conventional WWTPs

PILLS pilots MBRAdvanced

Treatment

Advanced

Treatment

Membrane filtration Oxidation processesAdsorption(Activated carbon)

Ultrafiltration /

Reverse osmosis

� Ozonation� Powdered activated

carbon

�Advanced oxidation processes

(UV/TiO2, UV/H2O2,, O3/H2O2)

� Granulated activated

carbon filtration

Illustrating the range:

Over pilot scale...

From lab scale...

To full scale.

Treated Wastewater > 80,000 m³

No. Samples > 3,000

Pre-treatment Advanced Treatment Post Treatment

GAC filter

PAC reactorSandfilter

Ultrafiltration

Investigated pilot plants

MBR

Ozonation (+H2O2)

UV/TiO2/H2O2

Sandfilter

GAC filter

Moving bed BR

Process performance of the MBR

MLSS

g/L

SRT

d

HRT

h

F/M

kgCOD/kgMLSS/d

T

C

LP

L/m²/h/bar

DE 10 249 60 0.040 26 170

9

Venditti, S., Köhler, C., Arenz-Leufen, M., O'Nagy, O., Cornelissen, A., Klepiszewski, K., 2011. Conference proceedings - Membrane bioreactor process as pre-treatment for hospital effluents, 8th IWA Leading-Edge Conference on Water and Wastewater Technologies, Amsterdam, The Netherlands.

DE 10 249 60 0.040 26 170

NL 10 <180 53 0.073 19

LU 10-13 30-40 8 0.08-0.10 18 148 - 100

CH 2 30-50 32 0.06-0.10 29

MBR effluent quality

Effluent DE NL CH LU

COD mg/L 31 23 30 27

DOC mg/L 11.0 8.7 7.0

Ptot mg/L 2.0 9.3 5.3

N mg/L 3.3 53.0 3.8 (NH +NO ) 17.0

10

• MBR with excellent effluent quality due to biochemical processes (C-, N-, (P-)

Elimination) and high MLSS retention efficiency

• Disinfection and bathing water quality

• Suitable pre-treatment step for advanced technologies

Ntot mg/L 3.3 53.0 3.8 (NH4+NOx) 17.0

Pharmaceuticals removal by MBR

DE

%

NL

%

CH

%

LU

%

n=6 n=6 n=3 n=2

Diclofenac 18 35 ±21 -5 ± 3 44

Naproxen 90 97 ±2 n.a. 34

Carbamazepine -29 -63±73 -6 ± 12 10

Atenolol 94 89±6 99 ± 1 80

Bezafibrate 95 98 >91 n.a.

Lidocaine n.a. 79 ±21 56 ± 13 20

Ciprofloxacin n.a. 79 ±7 51 ± 13 -3

Clarithromycin 98 34 ±43 50 ± 12 50

Sulfamethaxozole 13 85 ±11 7 ± 57 -76

Sulfamethaxozole&N4-

Acetylsulfamethoxazolen.a. n.a. 36 ± 28 91

Erythromycin 90 -3 ±82 <60 >98

Diatrizoate -12 -460±800 -5 ± 16 n.a.

Iopamidol 31 n.a. -29 ± 218 n.a.

Iopromide 38 n.a. 31 ± 2 n.a.

Cyclosphosphamide n.a. 26 ±19 <20 13

Ifosfamide n.a. -780±1200 <LOD <LOQ

≥ 80 Inconsistent ≤ 50

NSAIDs in effluent of the advanced

treatment

2,00

1,50

2,00

2,50

conc. (ug/L)

Ibuprofen

Diclofenac

Indometacin

Naproxen

n = 7

12

0,05 0,02 0,020,10

0,82

<LOQ <LOQ <LOQ

0,026 <LOQ <LOQ0,00

0,50

1,00

MBR effluent MBR + 5mg O3/L MBR + 20 mgPAC/L + SF

Nafo, I. et al., 2012. Full-scale plant for the elimination of pharmaceuticals in hospital wastewater – Comparison of advanced treatment technologies. 16th International EWA Symposium Sustainable Wastewater Management - New solutions for new problems, Munich, Germany.

Ozone

- Strong chemical oxidant

- Reacts directly and indirectly

- Can be combined with H2O2 � AOP

Dose

mg/L

HRT

min

Dose

gO3/gDOC

DE 5 30 0.45

source: www.lenntech.com

DE 5 30 0.45

NL 13 40 1.50

LU 6-15 6-16 0.24-1.28

CH 4-7 10-30 0.60-1.10

Pharmaceuticlas transformation by

ozonation

DE%

NL%

CH%

CH%

LU%

g O3/g DOC 0.45 1 1.08 0.64 1.28

Diclofenac >95 99.7 100 100 99

Naproxen >60 90 n.a. n.a. >88

Carbamazepine 88 99,7 >99 >99 >99

Atenolol >17 97 >23 >23 >95

Bezafibrate >57 n.a. 87 n.a. n.a.

Lidocaine n.a. 99 >98 >98 >99Lidocaine n.a. 99 >98 >98 >99

Ciprofloxacin n.a. 99.9 100 100 91

Clarithromycin 80 n.a. 100 100 >97

Sulfamethaxozole 97 99 99 96 >99

Erythromycin1) >90 n.a. >93 >93 >33

Diatrizoate 21 45-60 16 7 n.a.

Iopamidol 43 n.a. 55 31 n.a.

Iopromide 0 n.a. 60 37 n.a.

Cyclosphosphamide n.a. 78-85 57 33 58

Ifosfamide n.a. 80-90 62 20 n.a.

≥ 80 50 - 80 ≤ 50

Ozone - dosage

- O3 reasonable dosage: 0.5 – 1.0 gO3/gDOC

- Depending on wastewater composition (e.g. bulk compounds)

- No mineralisation – Formation of by-products

0.20

0.25

7.20

7.40

DOC UV254 a) b)

60

80

100

Re

mo

va

l ra

te [

%]

0.24 gO3/gDOC 0.48 gO3/gDOC 1.28 gO3/gDOC

5

6

7

TOC (mg/L) DOC (mg/L)

0.00

0.05

0.10

0.15

0.20

6.00

6.20

6.40

6.60

6.80

7.00

0 5 10 15 20 25 30 35

UV

-25

4 (

nm

)

DO

C

(mg

l-1

)

Residence time (min)

0

20

40

60

Re

mo

va

l ra

te [

%]

10 mg/L ozone, 1.8 g ozone / g DOC

Christa S. McArdell, Lubomira Kovalova, Hansruedi Siegrist, 2011, Input and Elimination of Pharmaceuticals and Disinfectants from Hospital Wastewater - final report -, Dept. of Environmental Chemistry and Dept. of Process Engineering, Eawag, Dübendorf

Venditti, S., Arenz-Leufen, M., Köhler, C., Klepiszewski, K., Cornelissen, A., 2012. Treatment of pharmaceutical wastewater by O3 and O3/H2O2 processes: a pilot scale study in Luxembourg, in: IWA (Ed.), Conference ecoSTP - EcoTechnologies for Wastewater Treatment. IWA, Santiago de Compostela, Spain.

0

1

2

3

4

MBR permeate After ozonation After biofilter

Pharmaceuticals transformation by

UV/H2O2/TiO2

NL CH CH LU LU LU LU

Medium Pressure/

Low PressureMP LP LP LP LP MP MP

UV/H2O2 UV/TiO2 UV UV UV/H2O2 UV UV/H2O2

Fluence (J/m2) 6440 2754 7425 29700 29700 101250 101250

H2O2 (g/L) - - - - 1.1 - 1.1

Fluence

J/m²

HRT

s

H2O2

mg/L

TiO2

DE - - - -

NL 6,440 15 5-15 -

LU 7,425–101,250 18-71 0-1.1 -

CH 800-7,200 18-162 fibre

Diclofenac 97 90 >98 >99 97 >99 >99

Naproxen 50 n.a. n.a. n.a. >94 n.a. n.a.

Carbamazepine n.a. 2 1 21 94 81 97

Atenolol 23-50 0 0 <LOQ 89 >84 <LOQ

Bezafibrate 25 n.a. n.a. n.a. n.a. n.a. n.a.

Lidocaine -86 2 5 21 87 83 99

Ciprofloxacin 72 35 57 n.a. 93 n.a. n.a.

Clarithromycin 17 7 14 7 85 84 >99

Sulfamethaxozole 48 50 85 79 82 >98 >99

Erythromycin*1) 21 0 10 n.a. n.a. n.a. n.a.

Diatrizoate 32-58 73 96 n.a. n.a. n.a. n.a.

Iopamidol n.a. 41 92 n.a. n.a. n.a. n.a.

Iopromide n.a. 63 92 n.a. n.a. n.a. n.a.

Cyclosphospham. 9 3 0 -3 70 58 >75

Ifosfamide 3-15 0 n.a. <LOQ <LOQ <LOQ <LOQ

≥ 80 > 30 < 80 ≤ 30

UV + 1.1 mg/L H2O2 – Pharmaceuticals

removal vs. energy demand

Köhler, C., Venditti, S., Igos, E., Klepiszewski, K., Benetto, E., Cornelissen, A., 2012. Elimination of pharmaceutical residues in biologically pre-

treated hospital wastewater using advanced UV irradiation technology: A comparative assessment. HAZMAT in press.

Pharmaceuticals removal by activated

carbon

Dose

mg/L

HRT

min

EBCT

min

Size

mm

DE 20 30

NL - - 60 0.5-1.5

LU - - - -

DE%

NL%

CH%

CH%

PAC-SF GAC PAC-UF PAC-UF

dosage PAC (mg/L) 20 - 23 43

Naproxen >54 >93 n.a. n.a.

Diclofenac 59 98 98 99

Lidocaine n.a. >98 100 100

Cyclosphosphamide n.a. >97 73 >73CH 8-43 60

„Accumulating of dissolved

compounds“

Cyclosphosphamide n.a. >97 73 >73

Ifosfamide n.a. >97 >60 >60

Ciprofloxacin n.a. >99 >99 >99

Clarithromycin >80 >99 100 100

Erythromycin1) >90 >99 >88 >88

Sulfamethaxozole 12 >96 33 62

Diatrizoate 1 98 14 18

Iopamidol 23 n.a. 69 80

Iopromide 0 n.a. 85 91

Carbamazepine >72 98 99 100

Bezafibrate >59 n.a. >86 >86

Atenolol >7 >97 >88 >88

≥ 80 > 30 < 80 ≤ 30

Energy consumption

Pre treatment

kWh/m³

Bioreactor

kWh/m³

Membranes

kWh/m³

Ozonation

kWh/m³

Activated carbon

kWh/m³

UV

kWh/m³

Air treatment

kWh/m³

NL 0.6 0.3 0.6 0.9* 0.2 (GAC) 0.50 - 1.07 0.1

CH 0.1-0.2CH 0.1-0.2

LU 0.5 1

DE 0.3 0.9 0.5* 0.45 (PAC-SF) 2**

GAC: Granular activated carbon filtration; PAC-SF: Powdered activated carbon and sand filtration

* Oxygen generation on-site from ambient air; ** Exhaust air treatment by Photoionisation incl. heating

Cost considerations

MBR

EUR/m³

GAC

EUR/m³

O3

EUR/m³

UV/H2O2

EUR/m³

Investment cost 3.25 0.10 0.15 0.30

Variable cost 1.45 0.20 0.10 0.20

Total cost 4.70 0.30 0.30 0.50

Key messages

• Decentralized treatment of pharmaceuticals concentrated wastewater was successfully demonstrated

• MBR is a suitable pre-treatment step � C-, N-, (P-) removal and part of pharmaceuticals

• Advanced treatment options showed good pharmaceuticals removal performance performance

• Regarding energy demand and costs, O3 and activated carbon have advantages (not considering process handling and local requirements)

• Advanced treatments showed lower removal rates for some substances like X-ray contrast media

• Full-scale plants � stable process operation

24

Thank to all the supporters of the PILLS project

www.pills-project.eu

Dr. Jochen Stemplewski and Dr. Emanuel Grün, Kirsten Adamczak, Can Aksüt, Klaus Baumers, Eva Böhling, Carsten Bräuer, Bernhard Hehn, Dirk Hellmich, Eberhard

Holtmeier, Till Möller, Issa Nafo, Ekkehard Pfeiffer, Ulrike Raasch, Prof. Burkhard Teichgräber, Michael Walkstein, Ingo Werner, Daniel Wischniewski, Peter Weingarten and

Frank Netz (Marienhospital Gelsenkirchen) Herr Lange, Regina Di Febo, Julianne Joseph (Municipality of Gelsenkirchen, Referat Umwelt), Jörg Alda, Dietmar Loch, Andreas

Schiffers (Tutthas & Meyer Ingenieurgesellschaft mbH), Christian Högel, Susanne Zander-Hauck, Harald Jakobs, Hans-Dietrich Eschke, Joanna Will (joint laboratory of

Ruhrverband, Emschergenossenschaft and Lippeverband), Monika Hammers-Wirtz (gaiac at the RWTH Aachen University), Axel Magdeburg (BiK Frankfurt), Jochen Türk (IUTA

Duisburg), Prof. Elke Dopp, Jessica Richard (IWW Mülheim), Herman Evenblij, Hans Huijsman, Dirk Kievit, Jan Luijten, Warry Meuleman, Arjan de Mink, Mirabella Mulder

(Mirabella Mulder Waste Water Management), Karl Borger (Vitens), Martijn Tas (Vitens), Jacques van Paassen (Vitens), Evert-Jan van den Brandhof (RIVM), Wilko Verweij

(RIVM), Marja Woutersen (RIVM), Erik Steenbergen (RIVM), Nico Wortel (Pharmafilter) and the Isala Clinics, Waterboard Groot Salland, Innovatieprogramma KRW, Province

Overijssel, the Municipality Zwolle, Vitens, STOWA., Alain Arend, Martina Arenz, Emmanuelle Becker, Enrico Benetto, Alex Cornelissen, Melanie Guiton, Elorri Igos, Collins Jury,

Kai Klepiszewski, Guy Kneip, Christian Köhler, Oliver O’Nagy, Paul Schosseler, Silvia Venditti, Ministry of higher Education and Research, Daniel Cardao, Henri Hinterscheid,

Marcel Klesen, André Weidenhaupt, Jean-Paul Lickes, Luc Zwank, Prof. Johannes Pinnekamp, Silvio Beier, Christopher Keysers, David Montag

Silvio Canonica, Andreas Eggmann (Hospital Baden), Jack Eugster, Cornelia Kienle (Ecotox Center, Eawag/EPFL), Lubomira Kovalova, Judit Lienert, Christa S. McArdell,

Stefan Kötzsch (UMik, Eawag), Ruedi Moser (Hunziker Betatech AG), Michael Schärer (FOEN), Hansruedi Siegrist, Michael Thomann (Holinger AG, Liestal), Urs von Gunten,

Heinz Wernli (Hospital Baden), Federal Office for the Environment, Swiss State Secretariat for Education and Research (SER)/COST Cantons AG, BE, BL, GE, SG, SH, SO, SZ,

TG, VD, ZH; Prof. A. Reller, University of Augsburg, Kantonsspital Baden, Federal Office for Spatial Development (ARE), Colin Dalglish, Karin Helwig, Colin Andrew Hunter,

JiaQian Jiang, John MacLachlan, Moyra McNaughtan, Ole Pahl, Joanne Roberts, Dainis Sudmalis, Zhengwei Zhou, Bill Dickie, Bill Glass, Philip Grieve, Hugh Hamill, Victoria

Hepworth, Jed Mather, Kevin Milne, Jenny Webb, Mark Heggie, Andrew Rawlins, Ian Ridgway, Ashley Roberts, Scottish Water, Ken Allinson, Brian Ellor, Mark Haffey, Archie

Johnston, Harry Keddie, Willie Lindsay, George O’Sullivan, Stuart Pheasant, Adam Zyndul, Olivier Barraud, Magali Casellas, Christophe Dagot, Corinne Maftah, Marie-Cécile

Ploy, Thibault Stalder, Dupuytren Hospital, the city of Limoges, Joint Technical Secretariat of the NWE Interreg programme: Daniel von Hugo, Isabelle Lecroart , Scientific Board

members: Florian Keil, Thomas Schwartz (KIT Karlsruhe), Thomas Steger-Hartmann (Bayer Health Care) and Pim de Voogt (IBED University of Amsterdam).

… and you for your attention!