Presentation 2007-03-24 Mobile Source Emissions and Biofuels An

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Presentation 2007-03-24 Mobile Source Emissions and Biofuels An Powered By Docstoc
					Mobile Source Emissions
& Biofuels:
An Overview of Selected
Canadian Federal R&D
Outline
• Emissions Research and Measurement
  Division Facility
• Biodiesel Targeted Measure
• Light duty ethanol programs
• Biofuels and advanced combustion strategies
• Summary of major findings




                      2
Acknowledgements
•   The work presented is the           •   Chemistry Lab Staff
    product of the ERMD team                –   Trevor Connolly
    along with our many partners.           –   Anthony Tong
•   Fred Hendren, Division Chief            –   Diane Dey
•   Project Management                      –   Kerri Longlade
    –   Greg Rideout                    •   Vehicle and Engine Operations
    –   Debbie Rosenblatt                   –   Peter Barton
    –   Jill Hendren                        –   Jacek Rostkowski
    –   Norman Meyer                        –   Christopher Beregszaszy
    –   Sheri Belisle                       –   Steve Rutherford
    –   Cara Baas                           –   Guy Bracewell
•   Sample Collection                       –   Mike White
    Technologists                           –   Ron Moodie
    – Scott Dey                             –   Brent Gauthier
    – Shannon Furino                        –   Wayne Baas

                                    3
Emissions Research and
Measurement Division
• Regulatory
  – Canadian Environmental Protection Act compliance
     • Light duty vehicles, heavy duty engines, off-road engines
• Research
  – Detailed emissions characterization
     • Advanced fuels, aftertreatment, combustion strategies
  – Collaborative R&D
     • Health effects, emissions inventories, source
       apportionment, real-world emissions measurements
• Support for Technology Development
  – Private sector clients
     • Aftertreatment, fuels, vehicle technologies, engine
       technologies

                               4
    Facility
•   Four light duty chassis
    dynamometers
     – One in cold cell
     – One 4WD to be commissioned
•   Motorcycle/ATV chassis
    dynamometer
•   HD chassis dynamometer
     – in cold cell
•   Two HD engine dynamometers
•   Three small engine
    dynamometers
     – Chainsaws to light duty vehicle
       engines
•   Two SHEDs
•   Field sampling

                                         5
Biodiesel Activities
A Decade of Biodiesel Studies
• Biodiesels for a Mining Application
   MSED #95-26745
• Evaluation of Biodiesel in an Urban Transit Bus
  Powered by 1998 DDECII6V2 TA and DDC8V71
  Engine
   MSED #95-26743
• Evaluation of Heavy Duty Engine Exhaust
  Emissions Using Biodiesel and Oxidation Catalyst
  DDC 6V71
   MSED # 96-01
• Emissions Evaluation of Biodiesel Blends on a Late
  Model Diesel Truck
   ERMD # 98-26718

                           7
Biodiesel Targeted Measure
• Announced in 2003
  – 500 M litres/year production of biodiesel by 2010
  – Reduction of GHG emissions from on/off-road
    vehicles by 1.1 Mt by 2012
• Allocated $ 11.9 M (2003-2007)
  – Support programs that encourage wider usage of
    biodiesel
  – Identify and remove barriers to commercialization of
    biodiesel production in Canada
Biodiesel Targeted Measure
• Activities:
   – On-road and off-road end user technology
     demonstrations
   – Emissions analysis, fuel specifications, fuel
     property analysis
   – Technology R&D and pilot plants (feedstock
     handling, process conversion)
   – International technology linkages
   – Public awareness, education, outreach

                          9
    Emissions Studies
•   Urban Transit Buses                             •   Criteria emissions
     – BioBus                                            – CO, NOX, TPM, HC
     – Halifax Transit Authority                         – Fuel consumption
     – GVRD Bus Technology Demo                     •   Detailed emissions characterization
•   Class 8 Highway Trucks                               – NMHC, carbonyls
     – Biodiesel Byway                                   – organic acids
     – Effect of Biodiesel on Criteria Air               – semiquantitative analysis for
       Contaminants                                        oxygenated compounds
•   HDE’s & Advanced After-Treatment                     – CH4, N2O
    Technologies                                         – SO2, NH3
     – Biodiesel fuel matrix                             – OC-EC
     – Diesel Particulate Filters                        – PM ions, metals
          • Both Passive and Active                      – PM/SVOC characterization
            Regeneration Strategies
                                                             • PAH, NO2PAH
     – SCR Technologies (2 manufacturers)                    • Alkanes, biomarkers,
•   Non-Road                                                   alkylcyclohexanes
     – BioMer – river tour boats in Montreal
     – BioShip – Cargo Vessel Auxiliary
       Engine
     – Gen Sets

                                               10
  Urban Buses
• Test Engines:
   – 98 Cummins 8.3L
     mechanical fuel injection
   – 02 Cummins 8.3L
     electronic fuel injection
   – 1999 NOVA LFS
     Cummins ISC 250
   – 1994 NOVA Classic DDC
     6V92
• Test Fuels: B5, B20
• Feedstocks include canola,
  animal tallow, recycled
  yellow grease, fish oil

                                 11
Urban Buses
• Whether on-road testing, chassis
  dynamometer testing or engine dynamometer
  testing
  – ↓ 2 to 30% PM
  – ↓ 70% EC
  – ↓ 9 to 18% SO4
  – No change or small ↓ NOX,
  – ↓ 9 to 31% CO
  – ↓ 11 to 30% HC

                      12
Urban Buses
• Common Themes
  – PM
    • Mechanical control engines showed greater
      decreases than electronic control engines
  – NOX
    • If observed, electronic control engines showed
      decrease. No change for mechanical control
      engines.
  – Fuel Consumption
    • No statistically significant difference compared
      to ULSD

                         13
Class 8 Highway Trucks
• Three Class 8 highway
  tractors
   – Engines: Cummins,
     Caterpillar, Mercedes
• Full emissions
  characterization on
  chassis dynamometer
  (HD-UDDS)
• Test Fuels:
   – LSD, Biodiesel Blends; B2,
     B5, B20, B100
   – One test with ULSD/B20
   – One test with B5 @ -10oC


                                  14
Class 8 Highway Trucks
•   All emission changes from LSD to B100 were statistically significant, except
    CO2.
     – ↓ 25 to 80% for CO, THC and PM with B100
     – ↑ 4 to 22% for NOX with B100
•   B20 trends were similar to B100 but smaller in magnitude.
     – With B20, the Cummins powered rig showed a modest decrease in NOX.
•   For B2 and B5
     – No difference in NOX emissions
     – ↓ 9% for PM for B5
     – No difference in PM for B2.

•   Two trucks tested on ULSD and B20/ULSD
     – The Cummins powered rig showed no change in NOX
     – The Mercedes powered rig
          • ↑ 2% for NOX and ↓ 15% for PM.
•   Fuel consumption
     – ↑ with B100 fuel
     – No measurable change with B2, B5, and B20



                                          15
    HDE’s & Advanced After-Treatment
    Technologies
•   Fuel Matrix Component of NYC                   •    Biodiesel Fuel Matrix
    Transit Clean Diesel                                 – 2004 CAT C11 ACERT
    Demonstration Project                                – 2004 Cummins ISM
    – 2000 International DT466                               • B5 & B20 blended with ULSD
        • 10 fuels, 4 after-treatment and engine             • Soy, Canola, and Tallow
          configurations                                 – FTP Transient and Steady State
        • B20/ULSD tested with DOC, CRDPF,                 Operation
          and CRDPF with EGR
                                                         – Detailed emissions characterization
    – FTP Transient test
    – Detailed emissions characterization




                                                   16
             HDE’s & Advanced After-Treatment
             Technologies

                                    ULSD                 B20                                                   Engine Out         CRT ULSD          CRT B20

                 7.0                                                                                   8.0
                                     2001 International 466 (230 hp)
                                                                                                       7.0                  2001 International 466 (230 hp)
                 6.0                         FTP Hot Tests
                                                                                                                                    FTP Hot Tests




                                                                            Emission Rate (g/bhp-hr)
                                                                                                       6.0
                 5.0
NOX (g/bhp-hr)




                                                                                                       5.0
                 4.0
                                                                                                       4.0
                 3.0
                                                                                                       3.0
                 2.0
                                                                                                       2.0

                 1.0                                                                                   1.0

                 0.0                                                                                   0.0
                       Engine Out     DOC         CRT       EGR/CRT                                          PM*100   NOX           NO        HC        CO




                                                                       17
HDE’s & Advanced After-Treatment
Technologies
             PM             NOx            CO

                           -12%
                                                     3%      B20 Animal
   -35%
                                         -1%
                                                     3%      B20 Canola
                  -21%
                                          0%
                                                    3%       B20 Soy
                  -20%
                           -12%
                                                0%           B5 Animal
                                   -7%
                                          0%
                                                0%           B5 Canola
                                   -7%
                                   -7%
                                                1%           B5 Soy
                                                      5%

 -40%     -30%       -20%        -10%          0%          10%
                       % Difference


                                  18
    HDE’s & Advanced After-Treatment
    Technologies
•   1998 Caterpillar 3126E with a            •   Use of prototype SCRT with B20
    prototype exhaust after treatment            & ULSD:
    system
                                                 – ↓ >95% TPM, CO, THC
     – Regenerating DPF with SCR                 – ↓ 70% NOX
•   ULSD and B20 Canola                          – ↑ ratio of NO2 / NOX
•   FTP Transient                                – ↑ N2O
                                                 – Presence of NH3
                                                 – ↓ PAH, VOC, Carbonyls
                                                 – B20 vs. ULSD without emission
                                                   control
                                                    • ↓ 16% THC
                                                    • ↓ 7% CO
                                                 – Power and performance changes
                                                   were not evident during testing




                                        19
            HDE’s & Advanced After-Treatment
            Technologies
             • 2005 Mack 300 HP with internal EGR with active regeneration
               DPF (fuel injection for trap regeneration)
             • >90% PM reduction
             • Operation on B20 does not negatively affect emissions

                        TPM Mass Emissions using ULSD and B20 with
                              Various Exhaust Configurations

                                                                                                               NOx Mass Emissions using ULSD and B20 with
TPM Mass Emissions




                     0.10
                     0.08
                                                                                                                     Various Exhaust Configurations
    (g/bhp.hr)




                     0.06                                               ULSD


                                                                                    NOx Mass Emissions
                                                                                                         5.0
                     0.04                                               B20
                                                                                                         4.0

                                                                                        (g/bhp.hr)
                     0.02
                                                                                                         3.0                                                  ULSD
                     0.00
                                                                                                         2.0                                                  B20
                               EO         Clean Filter       Burn OFF
                                                                                                         1.0
                                     Exhaust Configuration
                                                                                                         0.0
                                                                                                                     EO         Clean Filter       Burn OFF
                                                                                                                           Exhaust Configuration




                                                                               20
HDE’s & Advanced After-Treatment
Technologies                                            2.5
                                                                 DOC               SCR 1            SCR 2




• 2004 CAT ACERT                                        2.0




                                        NOx (g/hp-hr)
   – 2 selective catalytic reduction                    1.5


     systems (DOC+SCR)                                  1.0

   – ULSD and B20 Canola                                0.5

   – FTP Transient                                      0.0
                                                               HDTC          ESC           HDTC         ESC
   – ESC steady state 13 mode                                         ULSD                        B20

                                                                      DOC          SCR 1          SCR 2

• ↓PM with B20 vs. ULSD with                            0.06


  DOC                                                   0.05


• ↓PM when SCR#1 is added
                                                        0.04




                                        PM (g/hp-hr)
• ↓NOX with both SCR systems
                                                        0.03

                                                        0.02

• B20 does not negatively affect                        0.01

  PM or NOX emissions                                   0.00
                                                               HDTC          ESC           HDTC         ESC

                                                                      ULSD                        B20


                                   21
    Marine Applications
• BioMer Demonstration
•   12 vessels, operating out of 2 ports,       •   Engine Dyno Results
    used biodiesel from May to Oct 2004
                                                    – ↓ 13-36% CO (B5-B100)
     – B100, B20, B10, B5
                                                    – ↓ 36% THC (B100, NSD for
•   Field Trials                                      B5 and B20)
     – 3 boats tested while in service with         – ↑5-10% NOX (B20-B100,
       B100                                           NSD for B5)
     – Steady states @ varying speeds               – ↓31-82% PM (B5-B100)
     – Portable emissions sampling system           – FC
       with fuel flow meter                            • ↓1.8% B5
     – CO, NOX, PM, CO2                                • NSD B20
•   Engine Dyno Emissions                              • ↑3.3% B100
     –   CAT 3176E Marine Engine
     –   ISO 8178-4 cycle E5
     –   B5, B20, B100 (recycled cooking oil)
     –   Complete Emissions Characterization


                                          22
 Marine Applications
• Merchant vessel Anna
  Desgagnés
  – 17850 ton ship
  – cargo of heavy machinery,
    trucks and freights to ports
    along the Atlantic coast into
    Resolute Bay (cold temp)        % DIFF B20 vs Marine Diesel Oil
                                       CO               -5.6
  – one of four generators
                                       CO2              -1.5
    powered with B20 rendered
                                      NOX               -4.5
    animal fats and cooking oils       HC               -16
                                       PM               +25
                                       FC               -1.6

                               23
    Mobile Generators                                                 Génératrice de 1 000 kw
                                                                        Comparaison NOx


•   1000 kw and 60 kw generators                      6.0

    – Caterpillar 51.8L Mechanical                    5.0


    – Cummins 3.9L Electronic                         4.0                                                                    D2




                                              kg/hr
                                                      3.0                                                                    B5
•   LSD #2, B5 and B20                                2.0

    – Blend of animal fats and cooking oil            1.0


•   ISO 8178-1:1996 test cycle D2                     0.0
                                                              100     75           50        25        Ralenti   Moy. Pon.

•   Both PM and NOX reductions                                                  Charge appliqué en %


    observed with B20
                                                                       Génératrice de 1 000 kw
                                                                          Comparaison PM
                                                      160.0
                                                      140.0
                                                      120.0
                                                                                                  D2
                                                      100.0                                       B5




                                              g/hr
                                                       80.0
                                                       60.0
                                                       40.0
                                                       20.0
                                                        0.0
                                                                100        75           50        25      Ralenti     Moy.
                                                                                                                      Pon.
                                                                                  Charge appliqué en %




                                         24
For more information on Biodiesel
Targeted Measure Projects contact:

Greg.Rideout@ec.gc.ca
or
Debbie.Rosenblatt@ec.gc.ca
Ethanol Activities
Two Recent Studies
• Tailpipe and Evaporative Emissions from
  Light Duty Vehicles of 4 Different
  Technologies Operating on Gasoline and
  Ethanol-Gasoline Blends (E10 and E20)

• Tailpipe Emissions from Two Flex-Fuel
  Vehicles Operating on Gasoline and E85




                      27
4 Vehicle Technologies
•   4 light duty gasoline vehicles of different technologies
     –   Tier 1 (1998 Ford Escort)
     –   California SULEV w/zero evap. emissions (2001 Nissan Sentra)
     –   LEV LDT Flex-Fuel (2003 Dodge Caravan)
     –   Gasoline Direct Injection vehicle (Japanese LEV, 2000 Mitsubishi Dion)

•   4 test fuels
     – Vary fuel ethanol content (E0, E10, E20) while holding sulphur content, RVP,
       distillation and Octane Number constant.
     – Splash blend at 10% with base fuel

•   Standard (20 oC) and cold (-10 oC) temperature testing

•   FTP and US06 driving cycles

•   Evaporative emissions (heat build and hot soak)

                                        28
  CO Emissions
• FTP CO emissions                               1.6
                                                 1.4
                                                                     E0




                         CO (g / mile) FTP
  decrease for all                               1.2
                                                 1.0
                                                                     E10
                                                                     E10-Spl
  vehicle technologies                           0.8                 E20
                                                 0.6
                                                 0.4
                                                 0.2
                                                 0.0
                                                            Escort   Sentra        Caravan   Dion

• US06 CO emissions
                                                 16
  decrease for all                               14                      E0
                            CO (g / mile) US06



                                                 12                      E10
  vehicle technologies                           10                      E10-Spl
                                                  8                      E20
                                                  6
                                                  4
                                                  2
                                                  0
                                                            Escort   Sentra        Caravan   Dion



                                                       29
NOX Emissions
• FTP NOX                                           0.40
                                                    0.35         E0
  emissions




                               NOx (g / mile) FTP
                                                    0.30         E10
                                                    0.25         E10-Spl
  increase for all                                  0.20         E20

  vehicle                                           0.15
                                                    0.10
  technologies                                      0.05
                                                    0.00
                                                                 Escort     Sentra     Caravan   Dion


• US06 NOX                                          0.8

  emissions                                         0.7                      E0
                      NOx (g / mile) US06



                                                    0.6                      E10
  essentially                                       0.5                      E10-Spl
                                                                             E20
  unchanged for all                                 0.4
                                                    0.3

  vehicle                                           0.2
                                                    0.1
  technologies                                      0.0
                                                                Escort     Sentra      Caravan   Dion



                                                           30
 Cold Temperature Effects
• Cold temperature                              7.0
                                                                             E0
                                                6.0
  – increases FTP CO                                                         E10




                            CO (g / mile) FTP
                                                5.0                          E10-Spl
    emissions                                   4.0                          E20

  – increases US06                              3.0

    CO emissions of                             2.0

    Escort, not of                              1.0
                                                0.0
    Sentra.                                                Escort   Sentra

• FTP CO emissions                              18
  unchanged to slight                           16                           E0
                                                                             E10
                        CO (g / mile) US06



  decrease with                                 14
                                                12                           E10-Spl

  ethanol                                       10
                                                 8
                                                                             E20


• US06 CO emissions                              6
                                                 4
  unchanged with                                 2

  ethanol                                        0
                                                           Escort   Sentra



                                                      31
Cold Temperature Effects
• Cold temperature                                 1.40
                                                                E0
                                                   1.20
                                                                E10




                              NOX (g / mile) FTP
   – increases FTP NOX                             1.00         E10-Spl
     emissions                                     0.80         E20

                                                   0.60
   – increases US06 NOX
                                                   0.40
     emissions                                     0.20

• FTP NOX emissions                                0.00
                                                                          Escort   Sentra
  unchanged with
  ethanol                                          4.5
                                                   4.0        E0
• US06 NOX emissions
                          NOX (g / mile) US06

                                                   3.5        E10
                                                   3.0        E10-Spl
  unchanged with                                   2.5        E20

  ethanol                                          2.0
                                                   1.5
                                                   1.0
                                                   0.5
                                                   0.0
                                                                        Escort     Sentra


                                                         32
  Effect of Ethanol Blend
  on NMOG                                      0.20
                                               0.18        E0
                                                           E10




                        NMOG (g / mile) FTP
                                               0.16

• At 20 oC,                                    0.14
                                               0.12
                                                           E10-Spl
                                                           E20
                                               0.10
   – FTP NMOG                                  0.08
     emissions are                             0.06
                                               0.04
     unchanged with                            0.02
                                               0.00
     ethanol                                               Escort    Sentra   Caravan   Dion

   – US06 NMOG                                 0.10
                                                                                        E0
                                               0.09
     emissions appear   NMOG (g / mile) US06
                                               0.08                                     E10
                                                                                        E10-Spl
     to decrease with                          0.07
                                               0.06                                     E20
     ethanol                                   0.05
                                               0.04
                                               0.03
                                               0.02
                                               0.01
                                               0.00
                                                           Escort    Sentra   Caravan   Dion


                                                      33
 Effect of Ethanol Blend
 on NMOG
                                                   0.60
                                                                                 E0
                                                   0.50                          E10




                             NMOG (g / mile) FTP
                                                                                 E10-Spl
                                                   0.40
• At -10 oC, emissions                                                           E20
                                                   0.30
  are 2-10x higher                                 0.20
  than at 20 oC                                    0.10

   – FTP NMOG                                      0.00
                                                               Escort   Sentra
     emissions are
     unchanged with                                0.14
                                                                                 E0
     ethanol             NMOG (g / mile) US06      0.12
                                                                                 E10
                                                   0.10                          E10-Spl
   – US06 NMOG                                     0.08                          E20
     emissions appear                              0.06

     to increase with                              0.04

     ethanol                                       0.02
                                                   0.00
                                                               Escort   Sentra


                                                          34
Ozone Specific Reactivity
                                                   7
                                                        E0
                                                   6
• Small differences                                     E10




                              FTP g O3 / g NMOG
                                                   5    E10-Spl
  among vehicle                                    4    E20

  technologies                                     3

• Ethanol has little effect                        2
                                                   1
  on specific reactivity
                                                   0
• (not shown) Cold                                      Escort    Sentra   Caravan      Dion

  temperature increases                            7
                                                                              E0
  specific reactivity                              6                          E10
                              US06 g O3 / g NMOG   5                          E10-Spl
   – 25% for Sentra                                                           E20
                                                   4
   – 17% for Escort on                             3
     FTP                                           2

   – Decrease of 17% for                           1

     Escort on US06                                0
                                                        Escort    Sentra   Caravan      Dion



                                                   35
  Ozone Forming Potential
                                                    1.0
• Greatest factor                                   0.9
                                                    0.8
                                                          E0
                                                          E10

  appears to be vehicle




                              FTP g O3 / mile
                                                    0.7   E10-Spl
                                                    0.6   E20
  technology followed by                            0.5
                                                    0.4
  driving conditions                                0.3
                                                    0.2

• Ethanol has little effect                         0.1
                                                    0.0
                                                          Escort    Sentra   Caravan   Dion
• Higher NMOG
  emission rates and                                1.0
                                                                                       E0
                                                    0.9
  higher specific                US06 g O3 / mile
                                                    0.8                                E10
                                                    0.7                                E10-Spl
  reactivity increases                              0.6                                E20
                                                    0.5
  ozone forming                                     0.4
                                                    0.3
  potential in cold                                 0.2
                                                    0.1
  temperatures                                      0.0
                                                          Escort    Sentra   Caravan   Dion



                                         36
 Evaporative Emissions
                                                                 Heatbuild

• Evaporative emissions                         12
                                                      E0
                                                10
  are difficult to quantify                           E10




                              NMOG (g / test)
                                                 8    E10-Spl

  with good precision                            6
                                                      E20

                                                 4
  using these                                    2

  procedures                                     0
                                                      Escort    Sentra       Caravan   Dion

• Effect of emission
                                                                  Hot Soak
  standards is very                             2.0
                                                      E0

  apparent                    NMOG (g / test)
                                                1.5
                                                      E10
                                                      E10-Spl
                                                      E20
• Total NMOG emissions                          1.0


  are higher for heat                           0.5


  build than hot soak                           0.0
                                                      Escort    Sentra       Caravan   Dion



                                         37
 Evaporative Emissions
                                                                Heatbuild
                                               600
• Even our careful                             500
                                                      E0




                           Ethanol (mg/test)
                                                      E10
  attention to vehicle                         400    E10-Spl
                                               300    E20
  and canister                                 200

  conditioning resulted                        100

  in ethanol detected in                         0
                                                     Escort     Sentra      Caravan   Dion

  E0 fuel tests
                                                                 Hot Soak

• Hot soak emissions                           600
                                                     E0
                                               500
                           Ethanol (mg/test)
  of ethanol are higher                        400
                                                     E10
                                                     E10-Spl

  than heat build                              300   E20

                                               200
  emissions except for                         100

  the Dion                                       0
                                                     Escort     Sentra      Caravan   Dion



                                    38
  Evaporative Specific Reactivity
                                                         3.5




                              Heat Build g O3 / g NMOG
                                                                                           E0
• Specific reactivity                                    3.0
                                                                                           E10
                                                         2.5                               E10-Spl
   – Evaporative                                         2.0                               E20

     emissions are less                                  1.5
                                                         1.0
     reactive than tailpipe                              0.5

     emissions                                           0.0
                                                               Escort   Sentra   Caravan   Dion
   – Largest factor is
     vehicle technology                                  3.5
                                                                                 E0

                              Hot Soak g O3 / g NMOG
                                                         3.0                     E10
   – Ethanol has little                                  2.5                     E10-Spl
                                                                                 E20
     effect                                              2.0
                                                         1.5
                                                         1.0
                                                         0.5
                                                         0.0
                                                               Escort   Sentra   Caravan   Dion



                                                         39
Evaporative Ozone Forming
Potential                                       18
                                                16    E0




                       Heat Build g O3 / test
                                                      E10
• Largest factor is                             14
                                                12
                                                      E10-Spl
                                                      E20
  vehicle technology                            10
                                                 8
                                                 6
• Ethanol has little                             4
                                                 2
  effect                                         0
                                                      Escort    Sentra   Caravan   Dion


                                                18
                                                16    E0
                       Hot Soak g O3 / test     14    E10
                                                12    E10-Spl
                                                10    E20
                                                 8
                                                 6
                                                 4
                                                 2
                                                 0
                                                      Escort    Sentra   Caravan   Dion


                                                 40
 GHG Emissions
                                                    50
                                                         E0
• Methane




                            CH4 (mg / mile) FTP
                                                    40   E10
                                                         E10-Spl
  – both FTP and US06                               30   E20


    emissions unchanged                             20


    with ethanol                                    10

                                                     0
  – except for the Tier 1                                Escort    Sentra       Caravan   Dion

    vehicle
                                                    50
                                                                      E0

                             CH4 (mg / mile) US06
                                                    40                E10
                                                                      E10-Spl
                                                    30                E20

                                                    20

                                                    10

                                                     0
                                                         Escort    Sentra       Caravan   Dion



                                                    41
GHG Emissions
                                                  30
                                                                E0
• Nitrous oxide                                   25




                            N2O (mg / mile) FTP
                                                                E10
                                                  20            E10-Spl
  emissions show no                               15
                                                                E20

  consistent pattern.                             10

• Effects depend on                                5

                                                   0
  both driving cycle                                   Escort   Sentra     Caravan   Dion

  and on vehicle                                  30
  technology                                                     E0

                        N2O (mg / mile) US06
                                                  25             E10
                                                  20             E10-Spl
                                                                 E20
                                                  15

                                                  10

                                                   5

                                                   0
                                                       Escort   Sentra     Caravan   Dion



                                                  42
Vehicle Emissions
• 2 Studies

  – Tailpipe and Evaporative Emissions from
    Light Duty Vehicles of 4 Different
    Technologies Operating on Gasoline and
    Ethanol-Gasoline Blends (E10 and E20)

  – Tailpipe Emissions from Two Flex-Fuel
    Vehicles Operating on Gasoline and E85

                       43
Flex-Fuel Vehicles
• Two flex-fuel vehicles tested over Federal Test Procedure
   – 2002 Chrysler Caravan
      • US EPA NLEV LEV LDT and California LEV 1 LDT
   – 2004 Chrysler Sebring
      • US EPA Interim Non-Tier 2 Bin 8 and California ULEV 1

• Test Fuels
   – Tier 2 certification gasoline
   – E85 from local distributor

• Emissions measured
   – Regulated emissions (CO, NOX, NMOG)
   – GHGs (CO2, CH4 and N2O)
   – Detailed NMOG analysis


                                     44
2002 FFV Caravan: Regulated
Emissions
• CO and NOX emissions decrease with E85
• NMOG emissions unchanged
• Fuel sensor reached only 64% on E85
                           FFV Caravan
               1.00
                                         Tier 2   E85
               0.80

               0.60
      g/mile




               0.40

               0.20

               0.00
                      CO          NOx         NMOG

                                 45
2004 FFV Sebring: Regulated
Emissions
• CO and NOX emissions decrease with E85
• NMOG higher with E85 (cold start)
                          FFV Sebring
              1.00
                                          Tier 2   E85
              0.80

              0.60
     g/mile




              0.40

              0.20

              0.00
                     CO             NOx        NMOG

                               46
Unburned Ethanol
• Unburned ethanol is included in NMOG
• Found predominantly on cold engine start
                              Unburned Ethanol
              250
                                      FFV Caravan     FFV Sebring
              200
    mg/mile




              150

              100

               50

                0
                    Phase 1     Phase 2     Phase 3     Composite

                                       47
2002 FFV Caravan: Carbonyl
Compounds
• Carbonyl compounds emitted predominantly on cold start
• E85 results in increases in formaldehyde, acetaldehyde and
  acrolein emissions
                                    FFV Caravan Carbonyl Compounds
              20
                                                                    Benzaldehyde
              18
                                                                    Isobutyraldehyde & Butyraldehyde
              16                                                    Methyl Ethyl Ketone
              14                                                    Methacrolein
                                                                    Crotonaldehyde
    mg/mile




              12                                                    Propionaldehyde
              10                                                    Acetone
                                                                    Acrolein
               8
                                                                    Acetaldehyde
               6                                                    Formaldehyde
               4
               2
               0
                   T2         E85        T2         E85      T2          E85          T2         E85

                        Phase 1               Phase 2             Phase 3              Composite


                                                        48
2004 FFV Sebring: Carbonyl
Compounds
• Acetaldehyde emissions increase with E85
   – 25x for Caravan
   – 50x for Sebring
                                    FFV Sebring Carbonyl Compounds
              25
                                                                    Benzaldehyde
                                                                    Isobutyraldehyde & Butyraldehyde
              20                                                    Methyl Ethyl Ketone
                                                                    Methacrolein
                                                                    Crotonaldehyde
    mg/mile




              15
                                                                    Propionaldehyde
                                                                    Acetone
              10
                                                                    Acrolein
                                                                    Acetaldehyde
               5                                                    Formaldehyde


               0
                   T2         E85        T2         E85      T2          E85          T2         E85

                        Phase 1               Phase 2             Phase 3                 Composite


                                                        49
2002 FFV Caravan: Toxic
Emissions
• Toxic hydrocarbon emissions are reduced with E85
• With both fuels, found predominantly on cold engine start
                                            FFV Caravan Toxics
            80
                                                                              o xylene
            70
                                                                              m&p xylene
            60                                                                Ethyl benzene
            50                                                                Toluene
  mg/mile




                                                                              Benzene
            40
                                                                              1,3 butadiene
            30

            20

            10

             0
                 T2             E85   T2             E85    T2         E85   T2          E85

                      Phase 1              Phase 2               Phase 3      Composite


                                                       50
2004 FFV Sebring: Toxic
Emissions

                                       FFV Sebring Toxics
           80
                                                                         o xylene
           70
                                                                         m&p xylene
           60
                                                                         Ethyl benzene
           50
                                                                         Toluene
 mg/mile




           40                                                            Benzene
           30                                                            1,3 butadiene

           20

           10

            0
                T2         E85   T2         E85        T2         E85   T2          E85

                     Phase 1          Phase 2               Phase 3      Composite



                                                51
 Specific Reactivity
• The specific
  reactivity of E85                                      Specific Reactivity
                                          4.5
  is lower than the                       4.0




                       g Ozone / g NMOG
  Tier 2 fuel                             3.5
                                          3.0
                                          2.5
                                          2.0
• The specific                            1.5
                                          1.0
  reactivity of the                       0.5
                                          0.0
  emissions from                                T2             E85             T2             E85
  the newer vehicle                                  Caravan                        Sebring
  technology are
  lower than the old
  technology

                                                52
 Ozone Forming Potential
• The ozone forming
  potential of E85 is                                       Ozone Forming Potential
  lower than the Tier                     0.35
                                          0.30
  2 fuel

                         g Ozone / mile
                                          0.25
                                          0.20
                                          0.15
• The ozone forming                       0.10
  potential of the                        0.05

  emissions from the                      0.00
                                                      T2             E85        T2              E85
  newer vehicle
                                                           Caravan                    Sebring
  technology are
  slightly higher than
  the old technology

                                                 53
  GHG Emissions
                                                     M e th a n e Em issio n s
                                       60

• Methane emissions                    50
                                       40




                            mg/mile
   – Increase with E85                 30
                                       20

   – Very similar for two              10
                                        0
     vehicles                               T2                 E85             T2                  E85

                                                 C a ra va n                        S e b rin g



• Nitrous oxide emissions              60
                                                 N i tro u s O x i d e Em i ssi o n s

                                       50
  – Decrease with E85        mg/mile
                                       40
                                       30
  – Decrease with more                 20

    stringent emission                 10
                                        0
    standard                                T2                  E8 5           T2                  E8 5

                                                 C a ra v a n                       S e b ri n g



                               54
    Fuel Consumption
•   E85 has lower energy density,
                                                           Fuel Consumption
    therefore a larger volume is
    consumed for the same amount                      20
    of driving                                        18                Tier 2   E85

                                                      16
•   Actual CO2 emission rates were
                                                      14
    within 2% of expected based on
    complete conversion of fuel C to                  12




                                            L/100km
    CO2                                               10
                                                       8
•   CO2 emission rates were within
    3% between the fuels                               6
                                                       4
•   Lower carbon content of fuel                       2
    offset by lower energy density.
•   CO2 benefits are not achieved                      0
    at the tailpipe.                                       Caravan         Sebring


                                       55
Summary
• For the vehicles tested, low ethanol gasoline blends
  (E10, E20)
   – Reduce FTP and US06 CO emissions
   – Increase FTP NOX emissions; US06 emissions
     unchanged
   – Had little effect on FTP and US06 NMOG emissions
   – Had little effect on Specific Reactivity of NMOG
     emissions
   – Had little effect on CH4 and N2O emissions
   – Had little effect on the evaporative NMOG emissions
     nor their specific reactivity.

                            56
Summary
• For the vehicles tested, a higher ethanol gasoline
  blend (E85)
   – Reduced FTP CO and NOX
   – Had little effect on FTP NMOG
   – Significantly increased carbonyl emissions
      • Acetaldehyde 25-50x greater
   – Decreased toxic hydrocarbons
      • Fuel dilution effect
   – Reduced the specific reactivity of FTP emissions
     thereby reduced ozone forming potential
   – Increased CH4 emissions
   – Decreased N2O emissions

                               57
Biofuels and Advanced
Combustion Strategies
    HCCI
•   Homogeneous Charge
    Compression Ignition is a low
    temperature combustion strategy
    that can result in very low NOX
    and PM emissions with high
    thermal efficiency.
•   HCCI is an auto-ignition process
    – start of combustion is controlled
      by temperature and pressure not
      spark (SI) or fuel injection (CI)
•   Because it is a low temperature
                                                                   UofA HCCI facility
    process, engine out CO and                 Waukesha CFR engine and dynamometer
    unburned HC emissions are high
    in a relatively cool exhaust gas
    – Very challenging for conventional
      TWC or OC technologies


                                          59
HCCI
• Two collaborative projects looking at gasoline-like and diesel-like
  fuels in HCCI combustion in a research engine
   – University of Alberta – ideal fuels with different octane numbers
      prepared from iso-octane and heptane or ethanol and heptane
   – National Research Council of Canada – ideal fuel of n-heptane
      studying effect of engine parameters and EGR on combustion
      efficiency.
• Dilute exhaust samples were collected in canisters and analyzed
  by GC-FID and GC-MS for NMHC, oxygenated organics, CH4
  and N2O
   – NRC study also included carbonyl sampling with DNPH
      cartridges
• Ideal fuels allow chemical reaction mechanisms to be studied
   – Provides information useful in computer modeling of HCCI
      combustion

                                  60
Effect of Ethanol on HCCI
Combustion
• Ethanol has an octane number similar to iso-octane
  when measured in the standard manner.
• Ethanol's latent heat of vaporization is about twice
  that of iso-octane, providing a strong cooling effect
  on the intake charge, particularly as the mixture is
  made more fuel-rich.
   – This led to experimental problems of transferring the
     engine from its initial CNG-fueled, spark-ignition
     operation to HCCI as well as problems in maintaining
     a constant intake mixture temperature and thus
     controlling combustion.
• HCCI combustion is much more sensitive to fuel
  properties than conventional SI combustion.


                            61
NMOG Emissions from HCCI
• Unburned fuel compounds account for 58-75% of the NMOG
  emissions, depending on conditions.
• Partial combustion products, alkenes and carbonyls are the next
  most prominent components of NMOG
   – Low molecular weight alkenes (ethylene, propylene, isobutene
     and 1-butene) account for 7-25% of NMOG
   – Carbonyl compounds account for 12-33% of NMOG.
   – Formaldehyde dominates carbonyl emissions (41-50%).
   – Methane emissions are also significant (1-5% of NMOG)
• HCCI combustion appears to form unsaturated cyclic compounds
  (cycloalkenes and aromatics).
   – Whether these compounds come from the lubrication oil or the
     combustion process is still not clear.



                                62
  Carbon Balance of HCCI Emissions
• Fraction of carbon emitted as CO and HC increases with
  decreasing combustion temperature
• The HC fraction becomes more “reactive” and contains more
  unburned fuel components
                                              Carbon Balance as a Function of AFR
   % Fuel C as CO2, CO and




                             100%

                             80%

                             60%                                                              %C as THC
             THC




                                                                                              %C as CO
                             40%                                                              %C as CO2
                             20%

                              0%
                                    38   45       48      50         52   56        58   60
                                                               AFR



                                                                63
                                                          NMOG Emissions from HCCI
                                                                             Alkane Distribution by Carbon Number                                                                        Alkene Distribution by Carbon Number
                                                                                                                                  1                                         8000
                                                          16000
                                                                                                                                  2




                                                                                                                                               Emission Rate (mg/kg fuel)
                                                                                                                                                                            7000
                             Emission Rate (mg/kg fuel)




                                                          14000                                                                                                                                                                           2
                                                                                                                                  3
                                                          12000                                                                                                             6000                                                          3
                                                                                                                                  4
                                                                                                                                                                            5000                                                          4
                                                          10000                                                                   5
                                                                                                                                                                                                                                          5
                                                           8000                                                                   6                                         4000
                                                                                                                                                                                                                                          6
                                                                                                                                  7                                         3000
                                                           6000                                                                                                                                                                           7
                                                                                                                                  8
                                                           4000                                                                                                             2000                                                          8
                                                                                                                                  9
                                                                                                                                                                            1000                                                          9
                                                           2000                                                                   10
                                                               0                                                                  11                                          0
                                                                        38         45        48    50         52   56   58   60   12                                               38      45     48     50         52   56     58   60
                                                                                                        AFR                                                                                                   AFR




                                                                             Alkynes Distribution by Carbon Number                                                                      Carbonyl Distribution by Carbon Number
                                          250                                                                                                                               7000
                                                                                                                                                                                                                                          1




                                                                                                                                               Emission Rate (mg/kg fuel)
Emission Rate (mg/kg fuel)




                                                                                                                                                                            6000
                                          200                                                                                                                                                                                             2
                                                                                                                                                                            5000                                                          3
                                          150                                                                                         2                                                                                                   4
                                                                                                                                                                            4000
                                                                                                                                      3                                                                                                   5
                                                                                                                                                                            3000                                                          6
                                          100                                                                                         4
                                                                                                                                                                            2000                                                          7
                                                          50                                                                                                                                                                              8
                                                                                                                                                                            1000
                                                                                                                                                                                                                                          9
                                                          0                                                                                                                   0
                                                                   38         45        48        50         52    56   58   60                                                    38      45     48     50         52   56     58   60
                                                                                                       AFR                                                                                                    AFR




                                                                                                                                          64
Advanced Emissions
Characterization
    What else is in there?
•   Semiquantitative GC-MS / GC-FID analysis strategy developed to identify
    organic “unknowns” in gas phase emissions
     – Carbonyls not in TO-11 method
     – FAME fragments
     – Other oxygenated species (e.g. furans)
•   Cryogenic preconcentration GC-MS operated with same parameters as GC-
    FID method for NMHC analysis
•   Qualitative identification by GC-MS by library search and peak purity tools
     – No co-eluting compounds
     – Library search criteria better than 900 for identification
•   Semiquantitative analysis by GC-FID by relative retention time identification
    and average response factor of NMHC.
•   For carbonyl compounds found in TO-11 method
     – semiquantitative analysis agreed between within ±20%
     – linearity better than 0.94 over order of magnitude concentration.

•   Information from this method will be used to determine what compounds to
    include in an oxygenated compound method.
                                            66
Biodiesel Emissions
• Low Molecular Weight FAMEs
   – Produced by cracking of higher MW fuel FAMEs
   – Other than Acetic Acid Methyl Ester, FAMEs are unsaturated
• Furans
   – Concentration appears not to change from Diesel to B100
• Nitro-compounds
   – Nitromethane
   – Nitrophenol in diesel, B20 and B100 emissions
• Carbonyl compounds not in TO-11 method
   – At least 10 carbonyl compounds were identified, many
      unsaturated.
• Unusual Finds
   – MTBE appears to be produced by the combustion process.
      Levels are above dilution air concentrations
   – Isobutyl formate was identified but its occurrence is not
      consistent

                                 67
Biodiesel Emissions
 Compound                    Structure       Compound               Structure               Compound          Structure

                                                                                            4-
                                     O       Isovaleraldehyde
                                                                                            Pentenoic
 Furan                                       (3-                                                                          O
                                                                                            Acid Methyl
                                             Methylbutanal)     O                                                 O
                                                                                            Ester
                                     O       Methyl isopropyl
 Methyl Acetate                                                                                                       O
                                             ketone                 O                       2-
 (acetic acid methyl
                                             (3-Methyl-2-                                   Heptanone
 ester)                          O
                                             Butanone)
                             O                                                          O
 Trimethylacetaldehyde                                                                                                    O
                                             4-Penten-2-one                                 Heptanal
 (2-Methyl-2-propanal)
                                                                                                              O
                             O                                              O               5-Hexenoic
                                             2-Methyl
 2,3-Butanedione                                                                            Acid Methyl
                                             tetrahydrofuran                                              O
                                         O                                                  Ester
 Methyl Acrylate                     O                                              O
                                             Ethyl Vinyl
 (2-Propenoic Acid           O                                                              Octanal
                                             Ketone                                                       O
 Methyl Ester)
                                                                                            6-                O
                                                                                O
                                             3-Butenoic Acid                                Heptenoic
 Isobutyl Formate        O                                          O
                                             Methyl Ester                                   Acid Methyl   O
                                 O
                                                                                            Ester
                                                                                O
                                             Paraldehyde                O
                                                                                O




                                                     68
HCCI Emissions
• The GC-MS qualitative analysis found that partial
  oxidation of hydrocarbons had taken place, resulting
  in a variety of alcohols, aldehydes, ketones,
  oxiranes and furans in the dilute exhaust.
• A number of hydrocarbons were identified that were
  not present in the quantitative analysis. These
  compounds were mostly branched pentadienes. A
  number of of these pentadiene isomers were found
  but correctly identifying them was difficult as the
  mass spectra are nearly identical.


                          69
HCCI Emissions
Structure       Name                    Structure        Name      Structure             Name
                                                                   O
                acetaldehyde            HO               allyl
                                                                                         propylene oxide
 O                                                       alcohol
                                                         methyl
                                                                                         1,2-
                isobutryaldehyde                         allyl
 O                                      HO                                           O   Epoxybutane
                                                         alcohol
                                        O                                   O
                                                         acetone
 O
                butyraldehyde                                                            furan

                                                 O       methyl         O
 O
                                                         vinyl
                trimethylacetaldehyde                                                    2-methyl furan
                                                         ketone

                                                 O       methyl             O
                crotonaldehyde                           ethyl                           Tetrahydrofuran
 O                                                       ketone

                                                     O
                                                         t-3-
                methacrolein                                                             2,5-
 O                                                       penten-
                                                                                         dimethylfuran
                                                         2-one                  O
                                                                   O


 O
                hexanaldehyde                                          N+       O-       nitromethane

            O
                heptanaldehyde
                octanaldehyde
 O



                                            70
71