Integrated MBR and AOP processes for organics removal from pharmaceutical wastewater

Transcription

1 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Integrated and AP processes for organics removal from pharmaceutical wastewater G. Mascolo 1, A. Pollice 1, A. Massone 2 1 CR-IRSA (ational Research Council Water Research Institute Via F. de Blasio, Bari ITALY 2 Austep S.r.l. Via Mecenate, 76/ Milano

2 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Presentation outline Focusing the problem; Potential benefits of integrating biological processes and APs; Results obtained treating a real pharmaceutical wastewater (using 3 or UV/ 2 2 as AP: - Process performance through gross-parameters monitoring - removal of main organics; - by-products formation; - by-products degradation; - integrated vs sequential /AP configuration; Conclusions.

3 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium FCUSIG TE PRBLEM The removal of residual pharmaceutical compounds from industrial pharmaceutical wastewater is very challenging due to: Presence of non-biodegradable solvents and synthesis intermediate; The simultaneous presence of high fraction of easily biodegradable carbon and lower amounts of recalcitrant organics; A high saline content. Combination of biological and APs are then necessary to reach the target discharge limits. If AP is used as a post-treatment step, organic by-products are likely to be present in the final.

4 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium ow is it possible to limit the formation of by-products? Long contact time of the AP step (high operational costs. Biotreat. AP Integration of biological treatment and AP (the investigated approach that was employed for two different pharmaceutical wastewaters within the project. AP 3 A Membrane BioReactor ( was used with both 3 or UV/ 2 2 step; rganics and by-products were identified by LC/MS and LC/MS-MS.

5 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Composition of pharmaceutical wastewater Parameter Unit Amount p 4 Conductivity ms cm -1 7 DC mg L CD mg L mg L -1 <0.1 Acetate mg L alidixic acid mg L nalidixic acid (a synthetic antibacterial agent Cl - mg L P 3-4 mg L -1 <0.1 S = 4 mg L a mg L -1 2 TSS mg L concentration of added nutrients P 3-4 = 18.9 mg L = 49.2 mg L -1 VSS mg L

6 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Lab-scale plant set-up: operational conditions 1 phase: alone PARMACEUTICAL WASTEWATER PARMACEUTICAL WASTEWATER 2 phase: /AP AP PERMEATE 3 PERMEATE 3 Parameter Unit Amount reactor L 6 Feed flow rate L d RT d 3.75 SRT d 30 VLR g CD L -1 react d Membrane flux L m -2 h Relaxation cycle 15 min every 3 h zone dosed mg L -1 min zone dosed mg mg -1 CD 0.22 zonation time min 15 UV lamp (254 nm W 40 UV reaction time* min mm 0.5 *UV reactor volume: 0.5 L

7 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Gross parameters integrated with 3 integrated with UV/ 2 2 M L S S, M LVSS (g /L, CST STEADY STATE ZATI 100% 80% 60% 40% 20% 0% M LSS M LVSS-1, % CD REMVAL M L S S, M LVSS (g /L, CST STEADY STATE UV/ % 80% 60% 40% 20% 0% M LSS M LVSS-1, % CD REMVAL MLSS MLVSS CST CD REMVAL MLSS MLVSS CST CD REMVAL o significant sludge reduction was observed after integration with AP

8 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium TK and 4+ removal TK inf = 59.1 mg /L, 4, inf = 37.8 mg /L TK inf = 51.5 mg /L, 4, inf = 31 mg /L integrated with 3 STEADY STATE ZATI integrated with UV/ 2 2 STEADY STATE UV/ 2 2 Effluent ( m g /L Effluent ( m g /L TK effl 4 effl TK effl 4 effl

9 [nalidixic acid], mg/l eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Concentration of nalidixic acid in the and % of removal ( nalidixic acid removal (% [nalidixic acid], mg/l UV/ 2 2 (+UV/ UV/ nalidixic acid removal (% ozonation time: 15 min AP 0 3 UV/ 2 2 reaction time: 5 min

10 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Performance of the two investigated integrations 100% 80% 60% 40% 20% 0% +3 +UV/22 CD Removal DX Removal TK Removal 4 xidation VSS/TSS

11 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Characterization of nalidixic acid real wastewater: 48 organics identified compound number MW ret. time (min 1, , , , 2.2 5, , 5.3 7, , 4.1 8, 10, , 3.6, , , , , , , , , , 27, , 7.0, , 31, 41, , 7.7, 8.3, , , 7.2, , 38, , 8.0, , , , , organic n. 6 organic n. 8 organic n. 10 organic n. 13 organic n. 16 organic n. 17 organic n. 21 organic n. 24 organic n. 25 organic n. 28 organic n. 29 organic n. 31 organic n. 33 organic n. 34 organic n. 36 organic n. 35 organic n. 37 organic n. 39 organic n. 44 organic n. 47

12 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Integration of /AP: organics degradation 0.5 +UV/ influent (after recirculation (+UV/ influent (after recirculation ( UV/ 2 2 after (polishing reaction time (min 3 after (polishing reaction time (min Integration: 3 better than UV/ 2 2 Polishing: 3 better than UV/ 2 2 organic n. 34 AP 3 Removal of this organic: integrated /AP (with 3 and UV/ 2 2 AP

13 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Integration of /AP: organics degradation UV/ 2 2 influent (after recirculation (+UV/ influent (after recirculation ( UV/ 2 2 after (polishing reaction time (min 3 after (polishing reaction time (min Integration: 3 better than UV/ 2 2 Polishing: 3 comparable to UV/ 2 2 organic n. 16 AP 3 Removal of this organic: integrated /AP (with 3 and UV/ 2 2 < AP

14 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium alidixic acid real wastewater: 55 by-products identified compound number MW ret. time (min , , 1.7 3, 16, , 3.3, , , 1.9 7, 19, , 3.9, 5.9 9, , , 31, , 6.2, , 21, , 4.4, , 22, 27, , 4.9, 5.4, , 39, , 7.1, , , , , , , , , , , by-product n. 2 by-product n. 3 by-product n. 8 by-product n. 17 by-product n. 32 by-product n. 43 by-product n. 12 by-product n. 22 by-product n. 38 by-product n. 47 by-product n. 14 by-product n. 5 by-product n. 24 by-product n. 39 by-product n. 49 by-product n. 6 by-product n. 16 by-product n. 26 by-product n. 41 by-product n. 50

15 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Integration of /AP: by-products formation/degradation UV/ 2 2 (+UV/ 2 2 ( UV/ 2 2 after (polishing reaction time (min 3 after (polishing 0 reaction time (min by-product n. 36 AP Integration: 3 slightly better than UV/ 2 2 Polishing: 3 better than UV/ 2 2 Formation of this by-product: integrated /AP (with 3 and UV/ 2 2 < AP

16 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Integration of /AP: by-products formation/degradation UV/ (+UV/ 2 2 ( UV/ 2 2 after (polishing reaction time (min 3 after (polishing 0.0 reaction time (min Integration: UV/ 2 2 better than 3 Polishing: UV/ 2 2 better than 3 by-product n. 26 AP 3 Formation of this by-product: integrated /AP (with 3 only < AP

17 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Integration of /AP: by-products formation/degradation UV/ 2 2 (+UV/ UV/ 2 2 after (polishing reaction time (min 2 by-product n ( after (polishing reaction time (min AP Integration: 3 better than UV/ 2 2 Polishing: UV/ 2 2 better than 3 Formation of this by-product: integrated /AP (with UV/ 2 2 only > AP

18 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Integration of /AP: by-products formation/degradation UV/ 2 2 (+UV/ UV/ 2 2 after (polishing reaction time (min by-product n ( after (polishing reaction time (min AP Integration: 3 better than UV/ 2 2 Polishing: UV/ 2 2 better than 3 Formation of this by-product: integrated /AP (with 3 and UV/ 2 2 > AP

19 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Conclusions gross-parameters (CD, CST, nitrification, etc.. The efficiency of was not affected by the integration with AP (for both 3 or UV/ 2 2 ; organics removal. Performance of the sequential /AP system was comparable or even better than the integrated one. Just for few compounds the efficiency of treatment improved by integration with AP ( 3 or UV/ 2 2 ; By-products removal. For most compounds the integrated /AP system was more effective than the sequential one. Integration with 3 was generally better than that with UV/ 2 2.

20 eptune and Innowatech End User Conference January 27th 2010, Congress centre et Pand nderbergen, Gent, Belgium Acknowledgment Austep working team: I. Moscato, L. Migliorisi IRSA working team: Angela Pinto Carlo Salerno Giuseppe Guglielmi Daniela Saturno Giuseppe Laera AP Daniela Cassano Sara Diomede Piera Ielpo atascha Michel Isabel Pariente This study is part of the EU Innowatech project (Contract o , which has been financially supported by the EU Commission within the thematic priority Global Change and Ecosystems of the Sixth Framework Program (FP Global 4 - SUSTDEV II.3.2