1. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain 1 Politecnico di Milano Dipartimento di Energia Research Activities Nov 2009-May 2010 at Laboratory of Catalyis and Catalytic Processes Gianpiero Groppi, Pio Forzatti, Djamela Bounechada, Paola Castellazzi

2. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain OUTLINE Powder catalysts –Lean vs stoichiometric conditions –S-poisoning / regeneration behaviour ECOCAT honeycomb catalyst –Kinetic tests under T-ramp, constant conditions  -sweep vs constant -Hydrothermal ageing and S-poisoning 2SPB2

3. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain 3 Lean vs stoichiometric conditions Assessment of conversion performances depending on support and Pd load: Upon activation the investigated Pd supported systems exhibit lower CH 4 conversion performaces than the reference Ecocat catalyst, but at 1/3 Pd load (2% w/w vs 6.3% w/w) CH 4 0.5%; O 2 4%; H 2 O 1%; He/Ar; 93.5%; T: 350°C, GHSV = 150.000 Ncm 3 /gcat/h CH 4 0.5%; O 2 1%; H 2 O 1%; He/Ar; 93.5%; T: 350°C, GHSV = 150.000 Ncm 3 /gcat/h

4. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain Catalysts 0.8 g Adsorbed SO 2 (µmol) ECOCAT 190 2% Pd/Al 2 O 3 278 2% Pd/CeO 2 -Al 2 O 3 235 2% Pd/La 2 O 3 -Al 2 O 3 264 2% Pd/ZrO 2 76 CH 4 0,5% ; H 2 0,33%; O 2 1,17%; H 2 O 5%; SO 2 55 ppm; N 2 at balance T = 300°C for 6 h; GHSV : 22500 Ncm 3 /g cat /h 4 S-poisoning on powder catalysts

5. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain POLITECNICO DI MILANO T-step regeneration procedure DIPARTIMENTO DI ENERGIA - LCCP Regeneration treatments performed at different T-steps Activity measurements made at 350°C (lean)

6. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain Lean conditions: 0.5% CH 4, 4% O 2, 1.1% H 2 O, 2% N 2, He at balance 6 Regeneration under lean conditions  Ecocat reference catalyst exhibits higher resistance to S poisoning, catalyst supported on non sulphating ZrO 2 shows the worst behavior.  Only Pd/ZrO 2 is significantly regenerated under lean conditions @ 750 °C

7. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain Alternated lean combustion (0.5% CH 4, 4% O 2, 1.1% H 2 O, 2% N 2, He at balance) – reducing pulses (0.5% CH 4, 1.1% H 2 O, He at balance) 7 Regeneration under rich pulses conditions  Much more effective regeneration obtained under rich conditions (below 600°C)  Regeneration behaviour almost independent on the support

8. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain TPR: 0.5% CH 4, 1.1% H 2 O, He at balance, 15°C/min up to 900°C 8 SO 2 release in TPR experiments

9. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain Sliding termocouple in a channel of the monolith for the measurement of T axial profile 36 cm 15.2 cm 1.63 cm 1.3 cm Honeycomb sample: Experimental setup Standard feed gas mixture: CH 4 1500 ppm CO0.6 Vol.% H2H2 0.1 Vol.% NO1300 ppm O2O2 0.58/0.95 Vol.% H2OH2O10 Vol.% CO 2 10.7 Vol.% N2N2 balance Lambda1.00/1.02 GHSV50000 h -1 9

10. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain O 2 effect: CO 2 effect: T ramp (cooling) λ = 1.02 Kinetic study under T-ramp experiments H 2 O effect: k oxCH4 @ 773K [mol/g cat /s/atm] 1.53E-03 E oxCH4 [kJ/mole]106.5 [mol/g cat /s] DB2.4

11. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain Reproducibility/stability at constant λ=1.00-1.01-1.02 T ramp (cooling) λ = 1.02 11

12. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain Reproducibility stability under λ-sweep 12 t = 20s

13. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain First order kinetic PFR balance From T-ramp: E att = 120 kJ/mol k 0 = 67 s -1 From λ-sweep: E att = 120 kJ/mol k 0 = 1450 s -1 13 20 fold activity enhancement! E att = 125 kJ/mol k 0 = 70 s -1 E att = 135 kJ/mol k 0 = 2066 s -1 30 fold activity enhancement!

14. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain Effect of frequency on λ-sweep 14

15. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain CO molar fraction 15 Effect of frequency on λ-sweep

16. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain H 2 molar fraction 16 Effect of frequency on λ-sweep

17. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain Time evolution of concentration profiles λ-sweep t = 60s O 2 balances show that both Pd and (partly) CeO 2 are involved in the redox process

18. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain Hydrothermal Ageing Ageing I 10h @ 800°C Air, H 2 O ~ 10% Ageing II 10h @ 950°C Air, H 2 O ~ 10% quartz wool thermocouple Gas out Gas in Monolithic catalyst λ-sweep t = 20s 18

19. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain 19 Hydrothermal Ageing

20. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain Ageing with sulfur Short ageing with sulfur (1g S /l cat ) 1h @ 300°C Standard mixture (without NO) + 14ppm SO 2 Long ageing with sulfur (3g S /l cat ) 3h @ 300°C Standard mixture (without NO) + 14ppm SO 2 Integral: SO 2,in = 1.01 g S /l cat SO 2,ads = 81% Integral: SO 2,in = 2.99 g S /l cat SO 2,ads = 73% 20

21. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain CH 4 conversion 21 Ageing with sulfur

22. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain Short ageing with sulfur (1g S /l cat ) 1h @ 300°C Standard mixture (without NO) + 14ppm SO 2 On aged (II) catalyst On degreened catalyst Integral: SO 2,in = 1.02 g S /l cat SO 2,ads = 57% Integral: SO 2,in = 1.01 g S /l cat SO 2,ads = 81% 22 Ageing with sulfur

23. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain 23 Ageing with sulfur CH 4 conversion

24. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain Effect of ageing procedures λ-sweep t = 20s 24

25. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain Effect of regeneration 25 λ-sweep t = 20s

26. INGAS 18 th month meeting, Paris, May 20-21 2010 INGAS INtegrated GAS Powertrain Conclusions and future work Al 2 O 3 supported Pd catalyst show lower but comparable conversion performances than Ecocat with 1/3 Pd load All the catalyst suffer from S-poisoning, but Ecocat is much more resistant Significant regeneration under rich conditions at 600°C Operations under -sweep conditions provide superior (more than one order of magnitude activity enhancement) and more stable performances of Ecocat honeycomb catalyst Ecocat catalyst resists to hydrothemal ageing at 800°C, but suffer from significant deactivation at 950°C Ecocat catalyst show good resistence towards S-poisoning Preparation and testing of Au/Pd catalysts Higher Pd load (up to 6% w/w) Kinetic tests under -sweep conditions