Ar is t o t le Un ive r s it y o f T h e s s a lo n iki De p a r t m e n t o f C h e m i c a l E n g i n e e r i n g

Chemical Process Engineering Research Institute Centre for Research and Technology Hellas

Production of H2 and C2 Hydrocarbons from Methane in a Proton Conducting Solid Electrolyte Cell
V. Kyriakou, C. Athanasiou, I. Garagounis, A. Skodra and M. Stoukides

International Conference on H2 Production 2011

Outli

 Goal and approach of this research  Solid state membrane reactors  Dimerization of methane  Experimental Results  Conclusions  Future work

The Goal of this Research

The development of a novel approach of upgrading methane towards either:  simultaneous production/separation of H2 and C2 hydrocarbons  cogeneration of electrical power and C2 hydrocarbons

The Approach

The reaction was studied in solid state proton (H+) conducting cells, which would operate either as:

 H+ pumps  chemical cogenerative fuel cells

Proton Conducting Cell

 Operation modes: a) Open circuit , b) Fuel cell mode, c) Proton pumping mode

Oxidative Coupling of Methane

Conversion of methane to versatile industrial raw materials, such as ethane or ethylene: 2 CH4 + 1/2 2 CH4 + CH4 + 2
2

C2H6 + H2O C2H4 + 2 H2O CO2 + 2 H2O

2 2

 Selectivity to C2's decreases with increasing conversion and thus, the C2 yield is usually limited  To achieve industrially acceptable C2 yields, numerous catalysts and reactor designs have been tested including solid electrolyte membrane reactors

Methane Dimerization in a Proton Conducting Membrane Reactor

Cell Overall Reaction:

2 CH4
Side reaction:

2 H2 + C2H4

CH4

C + 2 H2

Cell Operation
Proton Pumping mode Fuel Cell mode

Overall: 2 H2O + 3 CH4

6 H2 + C2H4 + CO2

Overall: 3 O2 + 3 CH4

4 H2O+ C2H4 + CO2

Experimental

Double Chamber Cell Reactor

Reactants Products N2 , H2 or Air, H2O (FC)

N2 or Air (FC)

Reactor head Cooling Water

Quartz tube Working ElectrodeCatalyst Counter Electrode

YSZ tube Glass Sealant SZY proton conductor

5Ce5Ce-5Na2WO4/SiO2-Au (Open Circuit Studies)

 Dominant product is CO2  H2 incr as

it

CH4

 Elimination of H2 at ig

O2

5Ce5Ce-5Na2WO4/SiO2-Au (Closed Circuit Studies)

2 increase

with current

 FS = Separated 2/ Produced 2

5Ce5Ce-5Na2WO4/SiO2-Au (Summary)

 Significant C2 rate improvement with O2 addition  Dominant product was CO2 in all cases

drastic increase of
 Current application

constant C2 rates
 Non-conductive catalyst
PEROVSKITES

La0.6Sr0.4Co0.8Fe0.2O3 (Open Circuit Studies)

 Comparable C2 - CO2

 Hig er formatio rate of H2

La0.6Sr0.4Co0.8Fe0.2O3 (Closed Circuit Studies)

 C s a d H i cr as with curr

 Al

st c

l t s

arati

fH

La0.6Sr0.4Co0.8Fe0.2O3 (Cogeneration Preliminary Studies)

 Positive affection of current

 Lo

o er ensities

Conclusions

 LSCF is better from good but not conductive C2 catalysts  Very good
2

separation with LSCF perovskite

 Cogeneration also improved the C2 production rates

Future Work

 More perovskites to be tested  igher concentration of steam  Thinner electrolytes

Thank you for your attention