National Council for Science and Technology, Mexico

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Photometrical analysis of Dr. Bruno Lange , Co. Test cuvettes: ❖ Gas chromatography analysis, APHA 2720 4. ❑ Procedure. ❑ Sample test. A. Gas. B. Liquid.
Biological and Environmental Systems Group Department of Chemical and Process Engineering, The University of Sheffield, U.K

National Council for Science and Technology, Mexico

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ANAEROBIC TREATMENT OF PHENOL IN A TWO-STAGE ANAEROBIC REACTOR: A RENEWABLE SOURCE OF ENERGY Ernesto Hernández1, Robert Edyvean2 1 Sponsored by Consejo Nacional de Ciencia y Tecnología, México 2 Department of Chemical Engineering, The University of Sheffield, U.K. [email protected]

INTRODUCTION

RESULTS

Anaerobic digestion 1:

q Performance results

q Is a natural biochemical process based on enzymatic reactions carried out by bacteria in lack of oxygen q Degrades wastes to produce biogas (fuel) and sludge (fertilizer)

54 %CO2

67 %CH4

45 % N2

32 % CO2

Lbiogas

0.3

Phenolic compounds:

0.82

L reactor×Day

Lbiogas Lreactor×Day

q Are toxic substances that can be accumulated in the environment q Broadly used in many industries including: üPlastics and resins üEtc.

üPharmaceutical üFood processing

Phenol

q Have a strong chemical structure: aromatic ring

Methanogenic

reactor

reactor

+

q Are the second largest source of carbon in nature q Cause inhibition problems to anaerobic

Acidogenic

Protein supplement

bioreactors 2,3

q Phenol is an intermediate product of the anaerobic biodegradation of protocatechuic, 4-Hydroxybenzoic acid, tyrosol, caffeic acid, catechol and gallic acid.

99.2 % Phenol degradation 42 % Phenol deg. 15 % COD deg.

CATHECHOL p-CRESOL PHLOROGLUCINOL HYDROQUINONE 3-CLOROPHENOL

ADIPIC ACID

ACETATE PROPIONATE BUTIRARATE CO2, H2

PHENOL CYCLOHEXANONE

CH4

98 % Phenol deg. 62 % COD deg.

q Monitoring results Gas production GPR1

q Consists in separating acidogenic bacteria and methanogenic bacteria to improve the biodegradation efficiency and methane production

Volume of biogas (L Biogas L reactor-1 Day -1)

CAPROIC ACID

1.2 1 0.8 0.6 0.4 0.2 0

AIMS

2

4

6

q Degrade phenol in a two phase anaerobic digester operating at 35 0C and 101 KPa q Measure:

8 10 12 14 16 18 20 22 24 26 28

ü Biomass concentration

70

CR2 1600 1400 1200 1000 800 600 400 200 0 Time (Days)

COD Degradation

Biomass concentration

%DCODdR2

%DCODdGlobal

SOCR1 SOCR2 2500 2000

60 50 40 30 20

1500 1000 500

10

ü pH evolution

CR1

%DGlobal

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

mg/L SOC

%COD degradation

ü Concentration of organic acids

%DR2

100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0

80

ü Degradation of phenol and chemical oxygen demand

%DR1

Time (Days)

%DCODdR1 90

GPR2

Start

0

ü Biogas production and composition

Degradation of phenol

% Phenol degraded

Two phase anaerobic digestion:

67.8 % COD degradation

mg Phenol/L

üPetroleum üAgrochemicals

0 0

1

2

3

4

5

6

7

8

9

10

11

12

13

14

0

15

0

Time (Days)

1

2

3

4

5

6

7

8

9 10 11 12 13 14 15

Time (Days)

Evolution of pH

METHODS

pHR1

q Analytical methods

OAR1

v Photometrical analysis of Dr. Bruno Lange , Co. Test cuvettes:

8000

8.0

7000

7.5

6000 5000

3000

60 50 40

7.0

30 20

6.0 10

5.5

1000 0 0 1

2 3

4 5 6

7 8

9 10 11 12 13 14 15

Time (Days)

q Procedure

BR2

6.5

4000

2000

v Gas chromatography analysis, APHA 2720 4

BR1

St art

8.5

pH

üOrganic acids LYW 365, APHA 5560 4 üPhenol LCK 346, APHA 5530 4

Gas production (A)

9.0

OAR2

9000

mg Acetic Acid/L

üTotal organic carbon LCK 384, APHA 5310 4 üChemical oxygen demand LCK 014, APHA 5220 4

pHR2

5.0

ml 7.5NaOH/10NaHCO3

Organic acids concentration

0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 Time (Days)

Gas production (A)

CONCLUSIONS

400 ml

q Methane production was 3 times higher than the CO2 production at a concentration of 67%

2.5 gr phenol/L Goes into

Everyday Semi continuously

Goes into

pH = 5.5

pH = 8.5

q Phenol is highly degraded by methanogenic bacteria but not by acidogenic bacteria Methanogenic Reactor

Acidogenic Reactor

Sampling (B) Organic + H2O Matter

q 99.2% of phenol was degraded by the two phase anaerobic digester

anaerobes

Sampling (B)

CH4 + CO2 + New + NH3 + H2S + H2 + N2 + heat Biomass

q Biomass concentration was not affected by the addition of phenol

FUTURE WORK q A deep study to know if acidogenic bacteria promote changes in phenol structure q Anaerobic biodegradability by acidogenic bacteria of protocatechuic, 4Hydroxybenzoic acid, p-tyrosol, Caffeic acid, Catechol, Gallic acid and Oleuropein.

q Sample test A. Gas

REFERENCES [1] Pohland, F. G., and Ghosh, S. (1971). "Developments in anaerobic treatment process." Biotechnology and Bioengineering, 2, 85-106. Headspace

Syringe

Vial filled with N2

Gas Chromatographer

[2] Beccari, M., Bonemazzi, F., Majone, M., and Riccardi, C. (1996). "Interaction between acidogenesis and methanogenesis in the anaerobic treatment of olive oil mill effluents." Water Research, 30(1), 183-189. [3] Young, L. Y., and Rivera, M. D. (1985). "Methanogenic degradation of four phenolic compounds." Water Research, 19(10), 1325-1332.

B. Liquid

[4] APHA. (1998). Standard Methods for the Examination of Water and Wastewater, American Public Health Association, Washington.

ACKNOWLEDGEMENTS Sample

Filter

Cuvette test

Spectrophotometer

The authors want to thank the sponsorship of Consejo Nacional de Ciencia y Tecnologia, Mexico as well as R.T. Bachmann and N. B. Coutelle for their criticism.