Advanced oxidation for aromatic amine mineralization after ...

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Advanced oxidation for aromatic amine mineralization

after aerobic granular sludge treatment

of an azo dye containing wastewater

Ana M. T. Mata(1,2), Nídia D. Lourenço(1), Helena M. Pinheiro(1)

(2) iBB, Instituto Superior Técnico, Universidade de Lisboa, Av.

Rovisco Pais, 1049-001 Lisboa, Portugal

(1) Instituto Politécnico de Setúbal, Rua Vale de Chaves, Campus

do IPS, Estefanilha, 2910-761 Setúbal, Portugal

Introduction

Textile wastewater

- negative environmental impact

- heavily loaded regarding organic carbon

and color (70% from azo dyes)

Colorless dye persisten metabolites

→ 2 phase biological treatment

anaerobic ↔ dye reduction (color removal)

aerobic ↔ further oxidation (COD removal)

Aerobic Granular Sludge

Sequencial Batch Reactor

(AGS-SBR)

Acid Red 14:

Intense color

p-4A1NS (stable amine)

o-amine(unstable)

colorless colorless

e-

13th IWA SWWS and 5th ROS, Athens 14-16 SET. 2016Ana Mata

13th IWA SWWS and 5th ROS, Athens 14-16 SET. 2016

The aim of this work was:

- Apply advanced oxidation processes (AOP) in simple configuration, as a

post-treatment of an AGS-bioreactor to promote the mineralization of the

azo dye metabolites

• Ozonation

• UV irradiation

- The recirculation of the AOP treated effluent back to the AGS-bioreactor

was also tested to evaluate the improvement of the overall removal of

organic load (COD)

Aim

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Experimental System

13th IWA SWWS and 5th ROS, Athens 14-16 SET. 2016

Textile Wastewater

40 mg/L Dye (AR14)

1000 mg/L COD Emsize1

6h cycle

AGS-SBR

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Experimental System

13th IWA SWWS and 5th ROS, Athens 14-16 SET. 2016

Fill

Anaerobic

Aeration

Settling

Discharge

Iddle

AGS-SBR effluent 6h cycle

2h

3h

3 to 5 min

AGS-SBR

Textile Wastewater

40 mg/L Dye (AR14)

1000 mg/L COD Emsize1

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Experimental System

13th IWA SWWS and 5th ROS, Athens 14-16 SET. 2016

Fill

Anaerobic

Aeration

Settling

Discharge

Iddle

AGS-SBR effluent 6h cycle

2h

3h

3 to 5 min

AGS-SBR

Textile Wastewater

40 mg/L Dye (AR14)

1000 mg/L COD Emsize1

Color and COD

removal > 80%

but

Recalcitrant aromatic

amine (41ANS)

AGS-SBR effluent

collected along

a period of 2 days

for following experiments

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Experimental System

13th IWA SWWS and 5th ROS, Athens 14-16 SET. 2016

AGS-SBR effluent

Color and COD

removal > 80%

but

Recalcitrant aromatic

amine (41ANS)

Ozonation

post-treatment

60-watt Electronic Ozonizer

5 L/min

Sample: 800 mL in

an 1L cylinder

Ozone fed for 60 minutes

samples collected at

0, 5, 10, 20, 30, 45 and 60 min

Followed by

HPLC

UV-vis

COD

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Experimental System

13th IWA SWWS and 5th ROS, Athens 14-16 SET. 2016

AGS-SBR effluent

Color and COD

removal > 80%

but

Recalcitrant aromatic

amine (41ANS)

Ozonation

post-treatment

UV irradiation

post-treatment

60-watt Electronic Ozonizer

5 L/min

Sample: 800 mL in

an 1L cylinder

150-watt, medium pressure

mercury lamp (200-600 nm)

Sample: 600 mL in

a 850-mL photoreactor

Ozone fed for 60 minutes

samples collected at

0, 5, 10, 20, 30, 45 and 60 min

30 min irradiation

samples collected at

0, 5, 10, 20 and 30 min

Followed by

HPLC

UV-vis

COD

Followed by

HPLC

UV-vis

COD

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Experimental System

13th IWA SWWS and 5th ROS, Athens 14-16 SET. 2016

Recirculation

of the AOP treated effluent

back to the AGS-bioreactor was also studied

Followed by

HPLC

UV-vis

COD

TSS

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13th IWA SCWWS and 5th SCROS, Athens 14-16 SET. 2016

Results Ozonation post-treatment

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13th IWA SCWWS and 5th SCROS, Athens 14-16 SET. 2016

Results Ozonation post-treatment

● 5 min O3 -> 85% conversion of 4A1NS

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220 254

0

0,5

1

1,5

2

2,5

3

3,5

190 290 390 490 590 690 790

Ab

sorb

ance

Wavelength (nm)

B

0 min (SBR effluent)

10 min Ozonation

60 min Ozonation

● disappearance amine peak at 320 nm

4A1NS concentracion by HPLCUV-vis spectra

HPLC chromatogram

● General disappearance of residual peaks

or retention time reduction ● COD value was unchanged (no

mineralization)

Results UV irradiation post treatment

13th IWA SCWWS and 5th SCROS, Athens 14-16 SET. 2016

Results UV irradiation post treatment

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220 254

0

0,5

1

1,5

2

2,5

3

3,5

190 290 390 490 590 690 790

Ab

sorb

ance

Wavelength (ƞm)

B

SBR effluent (0 min)

10 min UV irradiation

30 min UV irradiation

4A1NS concentracion by HPLCUV-vis spectra

● need 20min UV -> 85% conversion of 4A1NS

● at 10min amine peak at 320 nm still remains

● disappearance of all residual metabolites

● COD value almost unchanged (no

mineralization)

HPLC chromatogram

13th IWA SCWWS and 5th SCROS, Athens 14-16 SET. 2016

Results Recirculation to bioreactor after AOP

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13th IWA SCWWS and 5th SCROS, Athens 14-16 SET. 2016

Results Recirculation to bioreactor after AOP

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0

0,5

1

1,5

2

2,5

3

3,5

190 290 390 490 590 690 790

Ab

sorb

ance

λ (nm)

beginning of biological cycle (O3)

end of biological cycle (O3)

beginning of biological cycle (UV)

end of biological cycle (UV)

UV-vis spectra

● no change of the ozonised effluent

● a slight absorbance decrease of UV-irradiated effluent

● HPLC essentially unchanged both for Ozone an UV-irradiated effluent

● recirculation to bioreactor increments COD removal by

20% - ozonised effluent

15% - UV-irradiated effluent

13th IWA SCWWS and 5th SCROS, Athens 14-16 SET. 2016

Conclusions

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13th IWA SCWWS and 5th SCROS, Athens 14-16 SET. 2016

Conclusions

- The conversion of the recalcitrant 4A1NS amine was successfully achieved

using the two AOP tested as post-treatments

- A removal efficiency of 85% for the recalcitrant amine could be obtained with

either 5 min of ozonation or 20 min of UV irradiation.

- COD removal in both AOP treatments was insignificant, but a simulated

recirculation of these effluents back to the biological treatment achieved removal

yields of 15 to 20%.

- It can be concluded that ozonation and UV irradiation are promising options as

polishing treatments for the effluents coming from AGS-SBR treatment of textile

wastewaters, aiming to eliminate recalcitrant aromatic amines resulting from azo

dye bioreduction.

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13th IWA SCWWS and 5th SCROS, Athens 14-16 SET. 2016

Acknowledgements

- This work was financed by Fundação para a Ciência e a Tecnologia (FCT, Portugal) through

the BIOTEXTILE project (PTDC/EBB-EBI/120624/2010) and the funding received by iBB -

Institute for Bioengineering and Biosciences (UID/BIO/04565/2013).

- A.M.T. Mata and N.D. Lourenço acknowledge the financial support of FCT through doctoral

(SFRH/BD/49432/2009) and post-doctoral (SFRH/BPD/88095/2012) research grants,

respectively.

- Instituto Politécnico de Setúbal is also acknowledged for financial support granted to A.M.T.

Mata.

- Funding received by iBB from Programa Operacional Regional de Lisboa 2020 (Project N.

007317) is also acknowledged.

Thank you for your attention!anatavaresmata@gmail.com

Ana Mata