INGAS 18-months Meeting, Paris, France, May 2010 INGAS INtegrated GAS Powertrain Institute of Catalysis and Surface Chemistry Polish Academy of Sciences 18 months research activities WP2.2 Advanced Catalyst Development

INGAS 18-months Meeting, Paris, France, May 2010 INGAS INtegrated GAS Powertrain Objective: Design of an active and stable catalyst for CH 4 combustion based on transition metal mixed oxides Scope of work: synthesis physico-chemical characterization catalytic testing Innovative aspect: novel precursors - hydrotalcites, pillared clays new compositions/modified synthesis methods for known structures (spinels, perovskites, hexaaluminates) synthesis in the presence of support suitable for washcoat preparation WP2.2 Advanced Catalyst Development Mixed Oxide Catalysts (ICSC PAS)

INGAS 18-months Meeting, Paris, France, May 2010 INGAS INtegrated GAS Powertrain Summary of catalyst synthesis and characterization work (over 80 catalyst formulations):  Spinels and perovskites derived from hydrotalcite-like precursors (metal elements: Cu, Mn, Co, Cr, Ce, Zr, Pd, La, Al, different stoichiometries)  Spinels and perovskites prepared by sol-gel procedure from citrate precursors (metal elements: Cu, Mn, Co, Al, Fe, La, Pd)  Hexaaluminates (metal elements: Mn, Mg,Al, La)  Pillared clays (metal elements: Zr, Al, Pd, clay: montmorillonite) Characterization methods: XRD, chemical analysis (ICP-OES), SEM, XPS, FT-IR, TG/DTG/DSC, TPR, N 2 adsorption at 77 K WP2.2 Advanced Catalyst Development Mixed oxide catalyst (ICSC PAS)

INGAS 18-months Meeting, Paris, France, May 2010 INGAS INtegrated GAS Powertrain WP2.2 Advanced Catalyst Development Spinels/Ht Spinels, Perovskites/Cit PILC Hexaaluminates 24 m 2 /g 19 m 2 /g 257 m 2 /g 197 m 2 /g 185 m 2 /g 229 m 2 /g 239 m 2 /g 182 m 2 /g 229 m 2 /g 265 m 2 /g 280 m 2 /g 200 m 2 /g 215 m 2 /g 114 m 2 /g 98 m 2 /g 101 m 2 /g 118 m 2 /g 94 m 2 /g 85 m 2 /g 66 m 2 /g 18 m 2 /g 76 m 2 /g 324 m 2 /g 33 m 2 /g 17 m 2 /g 30 m 2 /g 66 m 2 /g 86 m 2 /g 104 m 2 /g 98 m 2 /g 55 m 2 /g 237 m 2 /g Perovskites/Cit, Ht 3 m 2 /g 16 m 2 /g 2 m 2 /g 26 m 2 /g 2 m 2 /g 17 m 2 /g  Different structures  Different compositions  Different specific surfaces  Ht – hydrotalcite-derived  Cit – citrate-derived perovskite  PILC – pilllared clays

INGAS 18-months Meeting, Paris, France, May 2010 INGAS INtegrated GAS Powertrain WP2.2 Advanced Catalyst Development  Different morphologies 76 m 2 /g MnAl(2:1)Cit 237 m 2 /g MnAl(2:1)Ht 18 m 2 /g CuMn(1:2)Cit 151 m 2 /g CuMn(2:1)Cit/Puralox 33 m 2 /g LaCo(1:1)Cit 19 m 2 /g MnLaAl(1:1:11)Ha 182 m 2 /g Pd2-Zr-PILC LaFe(1:1)Cit 2 m 2 /g

INGAS 18-months Meeting, Paris, France, May 2010 INGAS INtegrated GAS Powertrain Catalytic testing – summary  hydrotalcite-derived mixed oxide catalysts belong to most active catalysts  hexaaluminates form the least active group  selected citrate-derived mixed oxides and pillared clays also display appreciable activity  all tested mixed oxide catalysts are much less active than the reference noble metal ECOCAT sample. SV=10000 h -1 As received catalysts WP2.2 Advanced Catalyst Development Mixed Oxide Catalysts – Catalytic Screening  over 120 catalytic tests, carried out at SV=10000 and h -1 on as received and thermally aged catalysts

INGAS 18-months Meeting, Paris, France, May 2010 INGAS INtegrated GAS Powertrain WP2.2 Advanced Catalyst Development Supporting on a Puralox carrier (γ-Al 2 O 3 + 5% ZrO 2 and 2% CeO 2 )  Beneficial influence of the support

INGAS 18-months Meeting, Paris, France, May 2010 INGAS INtegrated GAS Powertrain WP2.2 Advanced Catalyst Development Thermal ageing tests – summary λ=1, SV=50000 h -1 5h 600 o C, 10 h 800 o C,

INGAS 18-months Meeting, Paris, France, May 2010 INGAS INtegrated GAS Powertrain WP2.2 Advanced Catalyst Development Thermal ageing tests – most active catalysts Cu-Mn-based mixed oxides form most active group

INGAS 18-months Meeting, Paris, France, May 2010 INGAS INtegrated GAS Powertrain WP2.2 Advanced Catalyst Development Thermal ageing tests λ=1, 5h 600 o C, 10 h 800 o C, SV=50000 h -1 Cu-Mn-based mixed oxide catalysts supported on Puralox (γ-Al 2 O 3 + 5%ZrO 2 + 2%CeO 2 ) show good thermal stability

INGAS 18-months Meeting, Paris, France, May 2010 INGAS INtegrated GAS Powertrain Conclusions  Best catalysts are based on CuMn mixed oxide systems and show activity exceeding that described in literature for mixed oxide systems. However, severe thermal treatment foreseen by InGas boundary conditions causes significant drop in catalytic performance of unsupported active phase.  Use of appropriate support improves thermal stability of mixed oxide active phase and renders the material ready for washcoat preparation. Addition of small amount of Pd at the stage of precursor synthesis is beneficial for the activity. WP2.2 Advanced Catalyst Development Mixed Oxide Catalysts – Conclusions and Outlook

INGAS 18-months Meeting, Paris, France, May 2010 INGAS INtegrated GAS Powertrain Outlook Optimization of selected formulations aimed at enhancement of activity, prevention of sintering and maximization of the specific surface area via:  use of promoters (including noble metals) and carriers  synthesis modification (e.g. reverse microemulsions, ultrafine grinding) trageted especially at increase of dispersion of thermally stable low surface area oxidic phases (perovskites, hexaaluminates) WP2.2 Advanced Catalyst Development Mixed Oxide Catalysts – Conclusions and Outlook

INGAS 18-months Meeting, Paris, France, May 2010 INGAS INtegrated GAS Powertrain Oil phase Surfactant Water (reaction medium) Reverse microemulsion limits particle size of precipitate Ht – reverse microemulsion Ht – conventional synthesis WP2.2 Advanced Catalyst Development Mixed Oxide Catalysts – Conclusions and Outlook