1. Methane Powered Heavy Duty Engine with Low Fuel Consumption and Euro VI Emission Compliance X. Auvray 1, N. Sadokhina 1, G. Smedler 2, U. Nylén 3, M. Holmström 4, Louise Olsson 1 1 Chalmers University of Technology, Chemical Engineering; Competence Center for Catalysis, 412 96, Göteborg, Sweden 2 Johnson Matthey AB, 421 31, Västra Frölunda, Sweden 3 Scania CV AB, 151 87 Södertälje, Sweden 4 AVL MTC Motortestcenter AB, Box 223, 13623, Haninge, Sweden

2. The target for this project proposal is to address the problem of combining low energy- specific fuel consumption with low GHG and very low toxic emissions for a state-of-the-art CNG/CBG engine.  The project will support the introduction of renewable fuels for Euro VI vehicles.  Euro VI emissions will be met by engine tuning and by developing next generation of exhaust aftertreatment system for methane powered engines.  Reduction of CO 2 emissions will be reduced by 10 %.  Catalyst model for methane exhaust system for both stoichiometric and mixed lean combustion  Project time: 2013-03-01 - 2015-08-30  Program: Energy and Environment  Funded: 50% from The Swedish Energy Agency Methane Powered Heavy Duty Engine with Low Fuel Consumption and Euro VI Emission Compliance

3. Compressed Natural Gas as vehicle fuel To decrease mineral oil consumption To decrease greenhouse gas and pollutants emissions 3

4. Compressed Natural Gas as vehicle fuel: emissions Natural gas is mainly composed of methane Natural gas impurity content (ex: S) is low CNG vehicles emit less: – CO 2 – NO x – Particulate matters (PM) – Volatile Organic Compounds (VOC) CNG vehicles emit methane (GHP= 23) 4

5. Date Refuelling StationsNatural Gas VehiclesCountry Natural gas vehicles: worldwide count www.iangv.org 5

6. Support: 20 wt.% Ce-Al 2 O 3 (S = 114 m 2 /g) calcined in air at 900 o C, 2 h; Catalyst preparation: The catalyst contains 3.2 wt.% of Pd and 0.6 wt.% Pt on 20 wt.% Ce-Al 2 O 3 Pretreatment: 1. Reduction T = 500 o C; 2% H 2 ; Ar; 30 min 2. Lean/rich/lean cycle T = 700 °C Lean: 0,03% CO; 0,05% NO; 0,05% CH 4 ; 8% O 2 ; 5% H 2 O; Ar; 60 min Rich: 2% H 2 ; 5% H 2 O; Ar; 20 min 3. Ageing T = 700 C; 8% O 2 ; 5% H 2 O; Ar; 30 min Ramp test (Lean conditions): Heating/cooling cycle T = 150 - 700 o C; ramp = 5 °/min Catalytic activity measurement: Ceramic monolith: 400 cpsi; l = 20 mm, d = 21 mm; Washcoat: 500 mg calcined in air, 600 o C, 2 h Pre-treatmentRamp test 1 2; 3 6

7. Methane oxidation: simple gas composition Conditions: 0.05% CH 4 ; 8% O 2 ; Ar T = 150 - 700 o C; ramp = 5 °/min Temperature of 50% conversion CH 4, o C Gas mixtureHeatingCooling CH 4 + O 2 329305 24 o C Mixture: CH 4 + O 2 heatingcooling E act = 101 kJ/molE act = 77 kJ/mol

8. Methane oxidation: complex gas composition Conditions: 0.05% CH 4 ; 8% O 2 ; 0.03% CO; 0.05% NO; Ar T = 150 - 700 o C; ramp = 5 °/min Temperature of 50% conversion CH 4, o C Gas mixtureHeatingCooling Amplitude CH 4 + O 2 32930524 o C CH 4 + O 2 + CO + NO34833216 o C Mixture: CH 4 + O 2 + CO + NO heatingcooling E act = 115 kJ/molE act = 83 kJ/mol Inhibiting effect of CO + NO: -Increase of E act -Increase of T 50 -Decrease of hysteresis amplitude

9. Reaction order calculation: complex gas composition Conditions: without H 2 O; 0.05% CH 4 ; 0.05% NO; 0.03% CO; 8% O 2 ; Ar T = 305 o C Reaction order CO conc.CH 4 conc.O 2 conc.NO conc. 100; 300; 500; 700; 800 ppm; Order is 0 200; 500; 800; 1100; 1400 ppm; Order is 0.4 0.14; 2; 5; 8; 12 %; Order is 0.1 100; 300; 500; 700; 1100 ppm; Order is – 0.3 CH 4 change O 2 change NO change CO change 0 CO0 CH 4 0 O 2 0 NO O 2 treatment 700 - 305 o C O 2 treatment 700 - 305 o C O 2 treatment 700 - 305 o C 100 ppm 800 ppm 200 ppm 1400 ppm 0.14 % 12 % 100 ppm 1100 ppm 60 50 40 30 20 10 0 CH 4 conversion (%) 0120240360480 600 720840 Time (min) 960 1080

10. Kinetic modeling Reaction:CH 4 + 2O 2  CO 2 + 2H 2 O Reaction rate: r= k [CH 4 ] α [ O 2 ] β Rate constant: k=A exp(-E act /(RT)) Build a model and implement kinetic parameters experimentally measured to model experimental data

11. Kinetic modeling: global model Atuned E101784 (exp) Model Exp heating Exp cooling Inlet gas temperature (°C) CH 4 conversion (%) Simple mixture: CH 4 + O 2 r= k [CH 4 ] α [ O 2 ] β k=A exp(-E act /(RT))

12. Acknowledgments Swedish Energy agency (FFI 37179-1) is greatfully acknowledged for the financial support.