Emission catalyst solutions for Euro 5 and beyond

Emission catalyst solutions for Euro 5 and beyond ECT 2011, New Delhi November 9-10, 2011 Dr Toni Kinnunen CTO, Ecocat Group toni.kinnunen@ecocat.com www.ecocat.com

Complete diesel aftertreatment system Lightoff DOC/ POC H-cat SCR ASC DPF UREA INJECTION Regeneration Based on application, normally only some of above are needed Ecocat has the whole range of catalysts in portfolio; substrates and coatings Ecocat has technology for both SCR and active DPF systems

Portfolio of Products and Technology by Segments 3-way Catalyst and Selective Catalytic Reduction (SCR) Diesel Oxidation Catalyst (DOC) Industrial and Off-road Catalyst Particle Oxidation Catalyst (POC) Diesel Particulate Filter (DPF)

Chemistry in key role Tailor made interactions Ready made Powder or Slurry PM PM PM Ready made Powder or Slurry PM PM PM PM PM PM Pd, Rh, Pt, La, Al, Ce, Zr, Pr, Sr, Nd, Y, Ba, Si, Ti, W etc. mainly as oxides

Chemistry in key role Challenges in exhaust gas catalysis chemistry Need for continuous development - better cost efficiency ( better and cheaper ) - improved durability (temperature, poisons) Molecular scale modifications and analyses Nanotechnology Additional challenges - impurities of poor biodiesels and batch-to-batch variations - other alternative fuels require tailoring case by case - regulations vs. dirty fuels (developing countries, off-road) - city driving conditions in big cities

Chemistry in key role Computational chemistry in daily use Path Mechanism Reaction E a (ev) k (s -1 ) 1/2 LH * * CO Os CO 2 (g) vacancy 0.66 10 7 3 ER * CO(g) Os CO2(g) vacancy 0.70 10-3 * * * 4 LH CO O CO (g) O 2 2 0.57 10 8 (-3.20eV) (-2.65eV)

SCR technology PM reduction technologies Natural gas catalysis

SCR systems Urea Hydrolyser V-SCR catalyst (and ASC) dosing units and control

Reactions in SCR systems PreOxicat Hydrolysis SCR catalyst standard SCR NO + O 2 NO 2 CO(NH 2 ) 2 CO + H 2 O 2 NH 3 + CO 2 4 NO + 4 NH 3 + O 2 4 N 2 + 6 H 2 O PostOxicat fast SCR NO 2 -SCR NO + 2 NH 3 + NO 2 4 N 2 + 3 H 2 O 4 NH 3 + 3 NO 2 3.5 N 2 + 6 H 2 O 4 NH 3 + 3 O 2 2 N 2 + 6 H 2 O

Metallic substrate for mixers and H-catalysts EcoXcell Welded, mixer-type structure for coated catalysts having efficient 3D mass and heat transfer EcoXcell 20 for SCR applications Hydrolysis catalyst coating SCR catalyst coating

ppm N H cat only laboratory experiments Product distribution with empty reactor Nominal inlet: 1000 ppm NO, no NO 2, 500 ppm Urea, 10 % O 2, 8 % H 2 O, N 2 balance Standard flow rate Urea hydrolysis products- empty reactor 1200 1000 unreacted urea ~50 % of urea unreacted 800 600 N2O NOx 400 200 HNCO NH3 0 180 205 230 260 300 350 450 Temperature before cat, C

ppm N H cat only laboratory experiments Product distribution with HT700 KH1.1+KH2.2 (good adhesion/improved selectivity) Nominal inlet: 1000 ppm NO, no NO 2, 500 ppm Urea, 10 % O 2, 8 % H 2 O, N 2 balance SV = 100 000 h -1 Urea hydrolysis products- KH1.1+KH2.2 (w8090-200 cpsi) HT700 aged 1200 unreacted urea 1000 Almost only NH 3!! no by-products 800 600 400 N2O NOx HNCO NH3 200 0 180 205 230 260 300 350 450 Temperature before cat, C

NOx conversion, % (NH3 < 20 ppm) Engine 6.9 L; Catalyst 12.8L, 500 cpsi Ecocat 100 NOx conversion curve 80 60 28.000 h -1 465 ppm NO x 16.500 h -1 51.000 h -1 930 ppm NO x 1420 ppm NO x 61.000 h -1 1170 ppm NO x 57.000 h -1 990 ppm NO x 40 20 0 200 250 300 350 400 450 500 550 Temperature, C

Criteria NOx conversion, % (20 ppm NH3) Effect of NH3 slip criteria limit 100 Urea-SCR engine results- MAN 6.9L, 15 h aged KSCR2, 500 cpsi, 12.7L 90 80 70 60 30.000 h -1 51.000 h -1 61.000 h -1 58.000 h -1 50 40 30 20 10 16.500 h -1 KSCR2, 20 ppm NH3 KSCR2, 10 ppm NH3 0 200 250 300 350 400 450 500 550 Temperature, C No significant changes in performance without any additional NH3 slip catalyst

Criteria NO x conversion, % (20 ppm NH3) Effect of cell density (surface area) 100 90 80 70 60 50 40 30 20 10 0 Ecocat 350 cpsi -1 30.000 h 16.500 h -1 Extruded ref 51.000 h -1 61.000 h -1 58.000 h -1 200 250 300 350 400 450 500 550 Temperature, C Ecocat 500 cpsi Ecocat 220 cpsi krit eeri2_14dec07 Target conversions Euro 6/US2010 Euro 5 Euro 4 Catalyst amounts: Ecocat 500 cpsi 170 g/l Extruded 300 cpsi ~ 500 g/l Ecocat volume/engine volume = 1.86

Criteria NOx conversion, % (20 ppm) SCR Activity after burner ageings 100 90 80 70 60 50 40 30 20 10 66 79 77 230 C 20.000 h -1 93 98 95 96 98 98 97 99 98 260 C 19.000 h -1 Pt-DOC+KSCR2-300 cpsi FRESH 310 C 400 C 43.000 h -1 48.000 h -1 Pt-DOC+KSCR2 300 cpsi - Burner aged 570 C/100h Pt-DOC+KSCR2-300cpsi+4Pt/ASC- Burner aged 570 C/100h 95 Effect of ASC 77 88 480 C 51.000 h -1 0 MODE 10 (230 C) MODE 9 (260 C) MODE3 (310 C) MODE2 (400 C) MODE1(480 C) - Good durability by burner ageing at 570 C/100 h expect a slight deacrease in mode 1 point Compensation by the use of ASC

Ecocat SCR: the first EPA and CARB approval for V-SCR (off-road)

Urea Dosing System Urea Tank Injection nozzle Electrical Air Pump Aftertreatment Control Unit

DOC position Turbolader NO x Sensor Motor: Iveco F1C E4 3l 4 cylinder 130kW Horiba Gas Analyzer

PM reduction technologies coated DPF POC-F (4th generation POC ) active regeneration systems

Sol-gel coating for DPF Uncoated 150 cpsi SiC KF1 20 g/l coated 150 cpsi SiC Very thin layer (< 2µm) on pore walls Pores are kept open to keep filtration and p properties similar to uncoated DPF

Sol-gel coating for DPF Pore volume [ml/g] Poresize distribution of 200 cpsi SiC 0,25 0,2 21,5 21,8 0,15 0,1 0,05 0 10 Pore diameter (µm) 100 SiC 200 uncoated SiC 200 KF1 60 g/l

Sol-gel coating for DPF Coating on pores by sol-gel coating and process: Surface area of coating >200 m 2 /g as fresh Very thin layer (< 2µm) on pore walls Can be coated on e.g. SiC, ceramic and sintered metal filters Pt (or Pd) is added as active material on coating Higher surface area for active component Higher activity and stability

soot mass [g] Soot load Ecocat CDPFs vs. serial CDPF 20 18 16 soot load serial DPF soot load Ecocat DPF 7556.1 [30g/ft³] 35 g/cft Pt 30 g/cft Pt 14 12 10 8 6 4 2 0 0 500 1.000 1.500 2.000 2.500 distance [km]

percentage EURO IV [%] Results Ecocat CDPF vs. Serial sample MVEG-B test Opel serial 2500km (measured with winter tires) Ecocat NP7556.1 2500km (measured with winter tires) 90,0 80,0 70,0 60,0 50,0 40,0 30,0 20,0 10,0 0,0 CO NOx HC + NOx PM

POC-F applicable for diesel Euro4/5 and GDI Euro6

POC Particulate Oxidation Catalyst Cost competitive solution for particulate removal Proven efficiency and durability in both LDD and HDD applications. Tailored coating recommended for particulate collection efficiency and maintenance free operation (regeneration). Cost efficient production technology.

POC Particulate Oxidation Catalyst Test engine: Cummins, 4,5 Litre, Euro 4 Basics of POC sample: D240, L300, 300cpsi, 10g/m 2, Pt10g/ft 3 ESC 11 load 25% ESC 3 load 50% ESC 12 load 75% ESC 10 load 100%

SEM images of the coated POC- fibers from the inlet One location Other location Carbon adhesive on holder Coating Fiber

NO2 formation POC-F vs. Cordierite in E6 engine POC-F

PM g/km Percentage changes Steady point POC- F PM results average of three tests 0,100 0,090 0,080 0,070 100 % 90 % 80 % 70 % 0,060 60 % 0,050 0,040 0,030 0,020 0,010 0,000 RAW 0,044 0,061 0,071 NP 9881 POC F partially closed by silica fiber 60 km/h 80 km/h 120 km/h 0,012 0,015 0,015 %-changes 72,4 % 74,7 % 78,9 % Constant speed 50 % 40 % 30 % 20 % 10 % 0 % RAW NP 9881 POC F partially closed by silica fiber %-changes

POC and Gasoline (GDI) Could POC be the solution for PM/ PN emission challenges in Euro6? Audi3 1.4 ltr (GDI, Euro4) vehicle in collaboration with Darmstadt Hochschule (GER) POC-L (143 x 152 mm) in addition to original TWC as first trial, followed by POC-F with identical dimensions Target to reduce both particle mass (PM) and number (PN) closer to the Euro6 limit especially fuel-efficient GDI engines have a big challenge to meet the limit partial filtering devices without any active regeneration would be feasible Note: more detailed information planned to be published in SAE World Congress 2012

POC and GDI Gidney J.T. et al., Environ. Sci. Technol. 2010, 44, 2562 2569

POC-L and Gasoline (GDI)

POC-F and Gasoline (GDI) PM average 0,0020 0,0015 0,0010 0,0005 0,0000 Serial TWC 1 Serial TWC + POC (2nd sample) 2,E+12 2,E+12 PN average 1,E+12 5,E+11 0,E+00 Serial TWC 1 Serial TWC + POC (2nd sample)

On-road trial for POC-F PM and PN efficiency after 14 400 km on-road/ GDI

Active regeneration systems

Alternative fuels - case CNG and LPG -

Alternative fuels need for catalyst tailoring New type of fuel, new type of emissions and conditions durability and selectivity requirements can vary Some molecules are difficult to convert methane from CNG poor selectivity can yield new type of pipe out emissions aldehydes, N 2 O, NH 3 etc. Impurities of bio-based fuels might bring new challenges for chemistry itself and the whole afterteatment system

Alternative fuels need for catalyst tailoring PGM loadings and ratios (Pt-Pd-Rh) Interaction with active sites and carrier Stabilizing, promoting Adsorption properties and selectivity tuning by varying the composition Different layers Zone coating

Natural gas potential solution Advantages Lower CO 2 emissions compared to gasoline and diesel No particulate emissions! Significantly lower NOx emissions Other benefits Global natural gas sources Lower noise level Odourless exhaust gas Disandvantages In heavy duty, need for engine development Methane emissions specific CNG catalysts is needed

Methane oxidation major challenge CH 4 + 2O 2 809 kj CO 2 + 2H 2 O To tackle the high energy barrier is common to use high loaded catalysts To avoid this effect a promoter is needed High loadings affect dispersion negatively Extending durability Promoter stabilizes the surface Slowing sintering Enhancing activity

Emissions g/km Promoter Effect on Emissions: K5.7 for CNG only applications Results Correspond to Aged Samples Effect of promoter on Activity/ CNG engine test 0,600 0,533 0,500 0,400 0,410 0,300 0,200 0,100 0,138 0,122 0,057 0,040 0,000 THC CO Nox K5.7 Without promoter K5.7 With promoter

engine optimisation with our K5.7, enhancing CH 4 conversion Ideal operation point is correlated to temperature and lambda Sligthly rich operation under transient conditions improves CH 4 conversion

LPG growing fast Advantages Lower CO 2 emissions compared to gasoline Significantly lower PM and NOx emissions than diesel Easy logistics, resources and distribution Safety issues vs. CNG Catalysts are typically low-loaded, optimized TWC catalysts Disandvantages Low power output from powertrain Performance under cold conditions

Summary V-SCR technology is durable, robust and shown to be a feasible solution also by EPA/ CARB SCR catalysts combined with PreOxicat, PostOxicat, hydrolysis catalyst or/and catalyzed particulate filters can be designed by the application On DPF uniform coating through the wall provides good stability Active regeneration needed when driving conditions do not ensure passive systems (POC-F and DPF) Alternative fuels and new engine technologies are coming, catalyst tailoring is needed

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