INGAS 18 th month meeting, Paris, May 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

INGAS 18 th month meeting, Paris, May 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

INGAS 18 th month meeting, Paris, May 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 = Ncm 3 /gcat/h CH 4 0.5%; O 2 1%; H 2 O 1%; He/Ar; 93.5%; T: 350°C, GHSV = Ncm 3 /gcat/h

INGAS 18 th month meeting, Paris, May INGAS INtegrated GAS Powertrain Catalysts 0.8 g Adsorbed SO 2 (µmol) ECOCAT 190 2% Pd/Al 2 O % Pd/CeO 2 -Al 2 O % Pd/La 2 O 3 -Al 2 O % 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 : Ncm 3 /g cat /h 4 S-poisoning on powder catalysts

INGAS 18 th month meeting, Paris, May 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)

INGAS 18 th month meeting, Paris, May 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 750 °C

INGAS 18 th month meeting, Paris, May 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

INGAS 18 th month meeting, Paris, May 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

INGAS 18 th month meeting, Paris, May 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 ppm CO0.6 Vol.% H2H2 0.1 Vol.% NO1300 ppm O2O2 0.58/0.95 Vol.% H2OH2O10 Vol.% CO Vol.% N2N2 balance Lambda1.00/1.02 GHSV50000 h -1 9

INGAS 18 th month meeting, Paris, May 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 773K [mol/g cat /s/atm] 1.53E-03 E oxCH4 [kJ/mole]106.5 [mol/g cat /s] DB2.4

INGAS 18 th month meeting, Paris, May INGAS INtegrated GAS Powertrain Reproducibility/stability at constant λ= T ramp (cooling) λ =

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

INGAS 18 th month meeting, Paris, May 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 fold activity enhancement! E att = 125 kJ/mol k 0 = 70 s -1 E att = 135 kJ/mol k 0 = 2066 s fold activity enhancement!

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

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

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

INGAS 18 th month meeting, Paris, May 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

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

INGAS 18 th month meeting, Paris, May INGAS INtegrated GAS Powertrain 19 Hydrothermal Ageing

INGAS 18 th month meeting, Paris, May INGAS INtegrated GAS Powertrain Ageing with sulfur Short ageing with sulfur (1g S /l cat ) 300°C Standard mixture (without NO) + 14ppm SO 2 Long ageing with sulfur (3g S /l cat ) 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

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

INGAS 18 th month meeting, Paris, May INGAS INtegrated GAS Powertrain Short ageing with sulfur (1g S /l cat ) 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

INGAS 18 th month meeting, Paris, May INGAS INtegrated GAS Powertrain 23 Ageing with sulfur CH 4 conversion

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

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

INGAS 18 th month meeting, Paris, May 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