sorbent materials for the cleaning of sewage biogas...

Sorbent materials for the cleaning of sewage biogas

in high temperature fuel cell plants

Davide Papurello1, Andrea Lanzini1, Federico Smeacetto2, Massimo Santarelli11, Politecnico di Torino – DENERG, Corso Duca degli Abruzzi, 24, 10129, Turin, Italy.2, Politecnico di Torino – DISAT, Corso Duca degli Abruzzi, 24, 10129, Turin, Italy.

6 - 9 novembre 2013

Politecnico di Torino

2Politecnico di Torino

Summary:

1. SOFCOM mission overview

2. Biogas from SMAT (WWTPs)

3. Trace compounds detection

4. Sorbent material apparatus

5. Experimental investigation on cleaning system – sorbent

materials (effect of biogas water content)

6. Conclusions and future works

Politecnico di Torino

3

SOFCOM is an applied research project devoted to demonstrate the technical

feasibility, the efficiency and environmental advantages of CCHP plants based on

SOFC fed by different typologies of biogenous primary fuels (locally produced) also

integrated by a process for the CO2 separation from the anode exhaust gases.

SOFCOM layout: Demo plant


Air blower

Air pre-heater

Air CHP

Reformer

SOFC

Cleaning system

Oxy-combustor

Cooling CO2 separation


Biogas from SMAT – waste water treatment plant

Greatest waste water treatment plant in Italy,

serving 2.2 millions equivalent inhabitants in Turin

metropolitan area (26000 m3/h).

Waste water treatment area: 4 parallel lines: biological “tertiary” treatment with nitrogen and phosphorus removal

Sludge treatment line: pre-dewatering, anaerobic digestion, post-dewatering, drying. Treats over 6000 m3/day of sludge (2%tss)

In absence of oxygen anaerobic microorganisms

turn organic substances of sludge into biogas, a mix

of methane (60-65%) and carbon dioxide (35-40%).

> 6 digesters each 12000 m3, 17-20 day mean residence time;

> 33000 Nm3/day biogas (2010)

SMAT Castiglione Torinese WWTP


Biogas trace compounds

ContaminantSMAT Analysis

Feb 2012

SMAT Analysis

May 2012

DIGESTOR

CA 3033

DIGESTOR

CA 3033

DIGESTOR

CA 3034

H2S 78,4 148,5 150,6

Total 120 200 220

Alkene % Vol. % Vol % Vol

C2H4 1 1,2 1,4

Total

chlorine compounds (as HCl) 165.1 211.4

Total 165.1 211.4

Siloxanes ppbv ppbv ppbv

1,1,3,3,5,5-esametiltrisilossano <8 <13 <14,9

decametilciclopentasilossano D5 89.1 277 202

decametiltetrasilossano L4 <8 <13 <14,9

dodecametilpentasilossano L5 <8 <13 <14,9

esametilciclotrisilossano D3 11.4 157 187

esametildisilossano L2 <8 13.7 <14,9

ottametilciclotetrasilossano D4 71.8 253 129

Total 172.3 839.7 553.4

1,2-dichloroethylene (cis) 69.9 N/A N/A

1,2-dichloroethylene (trans) 0.6 N/A N/A

1,2-dichloropropane 2.5 N/A N/A

chloroform 0.7 N/A N/A

chloromethane <0.13 N/A N/A

vinyl chloride <0.119 N/A N/A

dibromochloromethane <0.0811 N/A N/A

dichlorodifluoromethane <0.114 N/A N/A

dioxane 2.8 N/A N/A

hexachlorobutadiene <0.13 N/A N/A

dichloromethane 8.8 N/A N/A

tetrachloroethylene 76.3 N/A N/A

trichloroethylene 11.2 N/A N/A

trichlorofluoromethane <0.155 N/A N/A

Total 172.9 N/A N/A

Chlorine compounds: essentially HCl

(100-400 ppbv)

Siloxane compounds: essentially D4-

D5 (70-400 ppbv)

Sulfur compounds: essentially

H2S (70-180 ppmv)


H2S

Chlorine compounds:

Siloxane compounds


Sorbent material apparatus for the sulfur compound removal

CH4/CO2

+

H2S

+

H2O

Blank line

Filter line

PDMS

filter

Heated

trap

HPR 20

MS

Filter

The experimental set-up adopted for the

sorbent material test with simulated biogas

(CH4/CO2 = 1.5), H2S at 30.72 ppm(v) and

demineralized water at 7.28% vol.


Experimental investigation on cleaning system – sorbent materials

Sorbent materialApparent density

(kg m-3)

Relative density

(kg m-3)

Grain

dimension

s (µµµµm)

Note

Activated carbon,

RST3 Norit200-600 2100 100-180

Zinc oxide,

Actisorb S2 ZnO Clariant 1090 100-180

Activated carbon,

Carb-OX Air dep520 1650 100-180

The best performance are achieved with low

fraction of oxygen and water – manufacturer

SEM 10000x SEM 2000x

C, Fe, CuZn, O


Experimental investigation on cleaning system – effect of biogas water content

0

10

20

30

40

50

60

70

80

90

100

0 200 400 600 800 1000 1200 1400 1600 1800

C/Co (%)

Time (s)

RST3 - H2O 7.28%

ZnO - H2O 7.28%

Carb-ox - H2O 7.28%

0

10

20

30

40

50

60

70

80

90

100

0 200 400 600 800 1000 1200 1400 1600 1800

C/Co (%)

Time (s)

RST3

ZnO

Carb-ox


3 sorbent materials were tested for the H2S removal. (Biogas)

Figure depicts the removal performance as the ratio between the outlet

concentration (C) and the inlet concentration (C0) of the filter cartridge.

The best performance are achieved by ZnO and RST3 activated carbon for the sulfur

removal. Carb-ox activated carbon decreases the filer performance around 9% in dry

conditions. At stationary conditions this material removes only 30% whereas the

other two sorbents 60%.

Under wet conditions the filter performance decrease for RST3 and ZnO around 36%

and 28% respectively, whereas in case of Carb-ox they improve of +17%.

Conclusions


Further works on the pollutants removal is needed, especially considering chlorines

(HCl, C2Cl4) and siloxane (D4) compounds effect and the contemporary presence of

water.

Future works

At the moment we are testing the same set-up apparatus with:

• Single effect of H2S on RST3, ZnO and air-dep sorbent material plus biogas water

effect;

• Single effect of HCl on RST3, ZnO and air-dep sorbent material plus biogas water

effect;

• Double effect of H2S + HCl on RST3, ZnO and air-dep sorbent material plus biogas

water effect…


References

www.polito.it/sofcom/

Papurello, D, et al. Monitoring of volatile compound emissions during dry

anaerobic digestion of the Organic Fraction of Municipal Solid Waste by

Proton Transfer Reaction Time-of-Flight Mass Spectrometry. Bioresource

Technology 126, 254–265

Papurello, D, et al. Biogas from dry anaerobic digestion of the organic

fraction of municipal solid waste: production, cleaning and direct use in a

Solid Oxide Fuel Cell. Waste Management (Under revision)

Papurello, D., Lanzini, L., Santarelli, M., Leone, P., 2013. Solid Oxide Fuel Cell

energy production from biogas – impact of contaminants (COS, C2H4) on fuel

cell performance. ATI 2013.

Papurello, D., Schuhfried, E., Lanzini, A., Romano, A., Cappellin, L., Märk, T.D.,

Silvestri, S., Biasioli, F., 2013. Influence of co-vapors on biogas filtration for fuel

cells monitored with PTR-MS (Proton Transfer-Reaction Mass Spectrometry).

Fuel Processing Technology 2014; 118: 133-140.(0378-3820/$ -

http://dx.doi.org/10.1016/j.fuproc.2013.08.011)

14

Thanks for the attention

Davide Papurello – [email protected] – 3402351692

Politecnico di Torino – DENERG, Corso Duca degli Abruzzi, 24, 10129,

Turin, Italy.

sorbent materials for the cleaning of sewage biogas...

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