Lowering laboratory and real driving particle emissions of direct injection spark ignition engines with n-butanol and isobutanolblends.

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1 19 th ETH Conference on Combustion Generated Nanoparticles Zurich, Switzerland, June 28-July 1, 2015 Lowering laboratory and real driving particle emissions of direct injection spark ignition engines with n-butanol and isobutanolblends. Michal Vojtisek-Lom Lom, Vít t Beránek, Vojtěch Klír Faculty of Mechanical Engineering,, Czech Technical University in Prague michal.vojtisek@fs.cvut.cz (+420) Jitka Štolcpartová,, Jan Topinka Institute of Experimental Medicine, Academy of Sciences of the Czech Republic Jaroslav Schwarz, Petr Vodička Institute of Chemical Processes of the Czech Academy of Sciences Miroslav Cigánek, Miroslav Machala Veterinary Research Institute, Brno, Czech Republic Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29,

2 Overview of the study 2013 / EURO 6 Ford Focus car with EcoBoostDISI engine Gasoline, E15, 25% n-butanol, 25% isobutanol Chassis dynamometer - NEDC, WLTP, Artemis, USO6 HC, CO, NO, NO2, PM, PN (PMP), PN (EEPS), Unregulated: FTIR, PAH, genotoxicity(dna adducts, ) 55-km real driving loop - size distribution (onboard EEPS) Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29,

3 Issues adressed in this study Particle emissions from DISI engines: - emissions from production / in-use engines - effects of driving cycle / off-cycle emissions -particles smaller than 23 nm - volatile nanoparticles Real driving emissions and their measurement WLTP vs. NEDC, Artemis, USO6,..., real driving Effect of renewable alcohol fuels on particle emissions Butanol as a potential alternative to ethanol Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29,

4 Project BIOTOX Mechanisms of Toxicity of Particles from Biofuels PM measurement and sampling using high-volume samplers Gasoline MPI and direct injection, diesel, Traditional and alternative fuels (ethanol, butanol, biodiesel, NExBTL, blends) Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29,

5 Real driving emissions measurement Portable on-board monitoring systems (PEMS) Celý den jezdí auty sem a tam, aby ukázali, že ježděníautem je špatnépro životní prostředí. (Steve Taylor, New York) Cars, buses, trucks, tractors, loaders, mowers, small airplanes,mopeds, ferries, locomotives, construction machinery Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29,

6 Research PEMS : On-board FTIR (gaseous compounds), EEPS (size distributions), CPC (particle counts) Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29,

7 Studentprojects: E85, n-butanol, isobutanolin unmodified gasoline engines in Škoda cars Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, On-board FTIR ~ 30 kg ~ W 3 hours on 26 kg of batteries

8 (Diesel) ICE exhaust particulate matter Small particles (units to hundreds of nm) formed by incomplete combustion of fuel and engine lubricating oil and wear metals Complex mixture of compounds, many known to be carcinogenic More premature deaths(> 400 K per year in EU)than traffic accidents(< 40 K per year) One of the most pressing urban environmental problems Liati A., Dimopoulos P.E., Combustion and Flame 157 (2010) Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29,

9 Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, Spořilov ambient concentrations of nmparticles (thousands per cm3) March 26, 2014

10 Roadside & neighborhood ambient PM Spořilov, February2014, average of40 locations, typical concentrations particles/cm 3 (max /cm 3 ) normalized particle number concentration ~ 10 nm ~ nm Mean (error bars - st.dev.) Geometric mean Median particle electric mobility diameter [nm] Vojtíšek a kol., NanoCon Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, Diesel exhaust Ronkko a kol, EST 2013

11 Is diesel PM becoming more of a question of public policy rather than technology? With DPF Euro 5 with no DPF (Prague, CZ) Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29,

12 Gasoline engine PM: Number vs. Mass limits by driving cycle WLTP is not as lame as NEDC, but does it cover the problem enrichment at high load (prohibited by EPA)? US06 and Artemis motorway cycles as a supplement? particle number emissions [#/km] 4.0E E E E E E E E E+00 EURO 5 PM mass limit WLTP NEDC Artemis urban-rural Artemis 130 Artemis 150 USO particle mass emissions [mg/km] Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, EURO 5 PN limit

13 Gasoline engine real-driving PM emissions Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29,

14 Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, Gasoline engine on-road PM emissions steady speed vs. full-power acceleration PM in raw exhaust [mg/m3] PM mass emissions [ug/s] PM [ug/s] PM [mg/m3] km/h GPS road speed [km/h] acceleration [m/s2] Instantaneous PM emissions 0 12:15:00 12:25:00 12:35:00 12:45: :55:00 13:05:00 Area of each mark is 5 Instantaneous fuel consumption proportional to the 4 instantaneous PM emissions in mg/s Fuel consumption vehicle speed [km/h] acceleration [m/s2] vehicle speed [km/h]

15 Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, PM (light scattering) [g] E-85_1 E-85_2 E-85_3 Gasoline_1 Gasoline_2 Gasoline_ elapsed distance [km] 4000 ŠkodaFelicia passenger car, Euro liter MPI SI engine 3 runs on gasoline 3 runs on E85 PM length [km] Effects of E85 on real driving emissions in an ordinary car 14 km test route (SAE ) E-85_1 E-85_2 E-85_3 Gasoline_1 Gasoline_2 Gasoline_3 Cumulative PM length elapsed distance [km]

16 Laboratory tests Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, Vehicle: 2013 Ford Focus, Euro 6 EcoBoost 1.0-liter engine Direct ignition gasoline Fuels: Gasoline (no ethanol), E15 (15% ethanol) 25% n-butanol 25% isobutanol Cycles: Fuel change & adaptation, WLTP preconditioning, WLTP cold, WLTP hot, 4 x Artemis

17 Dilution tunnel instrumentation Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, High-volume samplers Rotating disc Microdiluter & EEPS Full-flow Dilution tunnel Laboratory FTIR Portable FTIR PMP-compliant particle counter

18 Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, Effect of cycle & effect of PN definition: PN (PMP), PN (EEPS nm), PN (EEPS nm) Gasoline, PM is gravimetric on TX40HI20-WW Emfab filters mg/km #/km 20.0 x 10^ PM mass [mg/km] PN (PMP) [#/km x 10^12] PN EEPS nm PN EEPS nm 0.0 WLTP cold WLTP hot NEDC hot Art urb Art rur Art 130 US06

19 Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, Fuel effect on HC, CO, NOx, CO2: 4 runs of Artemis cycle g/km HC Gas E0 E15 nbu25 ibu25 g/km NOx Gas E0 E15 nbu25 ibu HC NO x SAE in review Art urb Art rur Art Art urb Art rur Art 130 g/km CO Gas E0 E15 nbu25 ibu CO g/km CO2 Gas E0 E15 nbu25 ibu CO Art urb Art rur Art Art urb Art rur Art 130

20 Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, Fuel effect on PM, PN (PMP), PN (EEPS, and nm) mg/km PM Gas E0 E15 nbu25 ibu25 #/km PN-EEPS > 23 nm Gas E0 E15 nbu25 ibu E PM - gravimetric 5.0E+12 PN - EEPS nm E E E E Art urb Art rur Art E+00 Art urb Art rur Art 130 #/km PN (PMP) Gas E0 E15 nbu25 ibu25 2.5E E E E E+11 PN - PMP #/km PN-EEPS nm Gas E0 E15 nbu25 ibu25 4.5E E E E E E E E E+12 PN - EEPS nm SAE in review 0.0E+00 Art urb Art rur Art E+00 Art urb Art rur Art 130

21 Fuel effect on PM mass gravimetric and EC Artemis cycle(4 runs on each fuel) Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, mg/km PM Gas E0 E15 nbu25 ibu EC - E0 EC - E15 EC - nbu25 EC - ibu25 Gravimetric: TX40HI20-WW Filters EC: Quartz fiber filter EC/OC split: EUSAAR 2 protocol Art urb Art rur Art 130

22 Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, Non-volatile component of PM and PN Are solid particles mostly larger, and volatiles smaller??? Or artefact??? Artemis cycle (4 runs on each fuel) Volatile fraction of PM 120% 100% EC/PM - E0 EC/PM - nbu25 PMP/EEPS - E0 PMP/EEPS - nbu25 EC/PM - E15 EC/PM - ibu25 PMP/EEPS - E15 PMP/EEPS - ibu25 Solid PM fraction: EC (from EC/OC) total PM mass 80% 60% Solid PN fraction: PN-PMP EEPS nm no volatile removal 40% 20% 0% Art urb Art rur Art 130

23 Effects of fuel on *normalized* size distribution Normalized particle number concentration WLTP cold e0 e15 nbut25 ibut25 Normalized size distributions mostly similar among fuels particle size [nm] 0.14 WLTP hot 0.25 Artemis motorway 130 Normalized particle number concentration e0 e15 nbut25 ibut25 Normalized particle number concentration e0 e15 nbut25 ibut particle size [nm] particle size [nm] Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29,

24 Effects of fuel on polyaromatic hydrocarbons (PAH) Artemis cycle, all parts, all runs Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, Extractable organic matter (ug/km) Sum of PAHs (ng/km) Sum of 16 US EPA PAHs (ng/km) Sum 7 cpah (ng/km) Gasoline E15 nbu25 ibu25

25 Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, Effects of fuel on polyaromatic hydrocarbons (PAH) Emissions of 7 carcinogenic PAH [ng/km] Artemis cycle, all parts, all runs Benz[a]anthracene Chrysene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[a]pyrene Indeno[1,2,3-cd]pyrene Benzo[ghi]perylene Gasoline E15 nbu25 ibu25

26 Toxicity assays: Ongoing, will report later Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29,

27 On-board instrumentation EEPS, mini-pems, batteries Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, Rotating disc microdiluter, (150 C, DR 300:1)sampling from the tailpipe-> -> EEPS (5-560 nm, 1 Hz)

28 Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, On-board monitoring system Mini-PEMS (13 kg) Response approximately proportional to PM mass concentrations for a given engine Nephelometer (laser scattering) Filtered dilution air CAT lpm raw exhaust Before or after DOC, DPF, Condensate and large particle removal Sample cool & reheat Charge meter Modified ionization smoke alarm (a 100 EUR system) -response proportional to total particle length (close to lung deposited surface area?) F-FC-P F-FC-P F-FC-P F-FC-P F-FC-P NDIR-HC,CO,CO2 NDIR-HC,CO,CO2 chem.cell NO chem.cell NO Filter, flow control, pump Engine outflow

29 Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, Test route 55 km, 1-hour 2 times on each fuel Preconditioning: (Artemis or 1 run) + 6 km road speed [km/h] Gas-2 Gas-3 Gas-1 E15-1 E15-2 nbu-1 nbu-2 ibu-1 ibu elapsed distance [km] altitude [m] Gas-2 Gas-1 E15-1 E

30 Instantaneous PN emissions along the test route E0 E15 nbu25 ibu Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29,

31 road speed [km/h] altitude [m] Gas-2 Gas-3 Gas-1 E15-1 E15-2 nbu-1 nbu-2 ibu-1 ibu Instantaneous emissions elapsed distance [km] Gas Gas-1 E E EEPS total PN [#/cm3] EEPS - based mass concentration [mg/m3] 9.E+05 8.E+05 7.E+05 6.E+05 5.E+05 4.E+05 3.E+05 2.E+05 1.E+05 0.E PN EEPSestimated PM mass elapsed distance [km] Gas-1 Gas-2 Gas-3 E15-1 E15-2 nbu-1 nbu-2 ibu-1 ibu elapsed distance [km] Gas-1 Gas-2 Gas-3 E15-1 E15-2 nbu-1 nbu-2 ibu-1 ibu-2 Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29,

32 Cumulative emissions 140 Gas-2 Gas-3 Gas-1 E15-1 E15-2 nbu-1 nbu-2 ibu-1 ibu-2 EEPS based PM mass [g] Gas-1 Gas-2 Gas-3 E15-1 E15-2 nbu-1 nbu-2 ibu-1 ibu elapsed distance [km] road speed [km/h] elapsed distance [km] altitude [m] Gas Gas-1 E E EEPS total PN [#] 6.E+14 5.E+14 4.E+14 3.E+14 2.E+14 1.E+14 Gas-1 Gas-2 Gas-3 E15-1 E15-2 nbu-1 nbu-2 ibu-1 ibu-2 EEPS total PN > 23 nm [#] 5.E+14 4.E+14 3.E+14 2.E+14 1.E+14 Gas-1 Gas-2 Gas-3 E15-1 E15-2 nbu-1 nbu-2 ibu-1 ibu-2 0.E elapsed distance [km] 0.E elapsed distance [km] Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29,

33 Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, PN as a function of engine power Mass air flow used as a surrogate of fuel flow (stoichiometric operation), fuel flow as a surrogate of engine power EEPS - based particle mass concentration [mg/m3] Gas-2 Gas-3 E15-1 E15-2 nbu-1 nbu-2 ibu-1 ibu engine mass air flow [g/s]

34 Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, PN as a function of road speed and engine power PN emissions are dominated by full-power accelerations notably for gasoline, less for E15, and much less for both butanols. 80 engine mass air flow [g/s] Gas E15 nbu ibu road speed [km/h]

35 Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, Summary Particle emissions from DISI engines - emissions from production / in-use engines -- MEASURED - effects of driving cycle / off-cycle emissions investigated & found - particles smaller than 23 nm found, about half of nm total count - volatile nanoparticles found, large part of total PN - non-regulated compounds PAH measured, toxicity tests ongoing Real driving emissions and their measurement onboard mini-pems and EEPS (onboard FTIR to be done later) PM and PN emissions dominated by high power operation Effect of butanol on particle emissions While E15 did not produce consistentpn or PM reduction, both 25% n-butanoland and 25% isobutanolreduced elemental carbon (EC), particle number emissions per PMP, and 7 US EPA priority carcinogenic polyaromatichydrocarbons by roughly one half, with no increase in NOx or other demonstrated problem.

36 Warning: This engine may produce nanoparticles that are harmful when inhaled. Vojtisek-Lom, 19th ETH Conference on Combustion Generated Nanoparticles, June 29, Thank you! European Social Fund, CZ.1.07/2.3.00/ Support of Research Teams at Czech Technical University in Prague. EU LIFE+ program, project MEDETOX - Innovative Methods of Monitoring of Diesel Engine Exhaust Toxicity in Real Urban Traffic (LIFE10 ENV/CZ/651) Czech Science Foundation project BIOTOX ( S): Mechanisms of toxicity of particles from biofuels

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