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ORNL is managed by UT-Battelle for the US Department of Energy ORNL is managed by UT-Battelle for the US Department of Energy Emissions Control for Lean Gasoline Engines Jim Parks (PI), Todd Toops, Josh Pihl, Vitaly Prikhodko Oak Ridge National Laboratory ACE033 June 9, 2016 Sponsors: Gurpreet Singh, Ken Howden, and Leo Breton Advanced Combustion Engines Program U.S. Department of Energy This presentation does not contain any proprietary, confidential, or otherwise restricted information

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Page 1: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

ORNL is managed by UT-Battelle for the US Department of EnergyORNL is managed by UT-Battelle for the US Department of Energy

Emissions Control for Lean Gasoline EnginesJim Parks (PI), Todd Toops, Josh Pihl, Vitaly Prikhodko

Oak Ridge National Laboratory

ACE033June 9, 2016

Sponsors: Gurpreet Singh, Ken Howden, and Leo Breton

Advanced Combustion Engines ProgramU.S. Department of Energy

This presentation does not contain any proprietary, confidential, or otherwise restricted information

Page 2: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

2 DOE VTO Annual Merit Review – ace033

Project OverviewTimeline

Budget

Barriers Addressed

Collaborators & Partners• FY16: $400k (Task 2*)

• General Motors• Umicore• University of South Carolina• Cross-Cut Lean Exhaust

Emissions Reduction Simulations (CLEERS)

• Barriers listed in VT Program Multi-Year Program Plan:

– 2.3.1B: Lack of cost-effective emission control

– 2.3.1C: Lack of modeling capability for combustion and emission control

– 2.3.1.D: Emissions control durability

• Year 1 of 3-year program• Builds on previous R&D in FY13-

FY15

*Task 2: Lean Gasoline Emissions Control

Part of large ORNL project “Enabling Fuel Efficient Engines by Controlling Emissions”(2015 VTO AOP Lab Call)

Page 4: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

4 DOE VTO Annual Merit Review – ace033

Objectives and Relevance Enabling lean-gasoline vehicles to meet emissions regulations

will achieve significant reduction in petroleum use• Objective:

– Demonstrate technical path to emission compliance that would allow the implementation of lean gasoline vehicles in the U.S. market. • Lean vehicles offer 5–15% increased efficiency

over stoichiometric-operated gasoline vehicles • Compliance required: U.S. EPA Tier 3

– Investigate strategies for cost-effective compliance• minimize precious metal content while

maximizing fuel economy

• Relevance:– U.S. passenger car fleet is dominated by gasoline-fueled vehicles. – Enabling introduction of more efficient lean gasoline engines can provide

significant reductions in overall petroleum use• thereby lowering dependence on foreign oil and reducing greenhouse gases

EPA Tier 3 Emission Regulations

>70% less NOx

>85% less

NMOG

70% less PM

Page 5: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

5 DOE VTO Annual Merit Review – ace033

Cars34.1%

Light Trucks39.0%Motorcycles

0.3%

Buses0.9%

Class 3-6 Trucks4.9%

Class 7-8 Trucks20.9%

gasoline95.5%

diesel4.5%

gasoline99.4%

diesel0.6%

Relevance: small improvements in gasoline fuel economy significantly decreases fuel consumption

Lean gasolinevehicles can

decrease US gasoline

consumption by ~13 billion gal/year

• US car and light-truck fleet dominated by gasoline engines• 10% fuel economy benefit has significant impact

– Potential to save 13 billion gallons gasoline annually• HOWEVER…emissions compliance needed!!!

References: Transportation Energy Data Book, Ed. 34 (2013 petroleum/fuel use data)

Fuel Use:Cars

Fuel Use:Lighttrucks

Highway Transportation PetroleumConsumption by Mode

Page 6: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

6 DOE VTO Annual Merit Review – ace033

Milestones

• FY2015, Q4: Simulate transient load/speed operation of passive SCR on BMW lean gasoline engine platform

• FY2016, Q1: Complete bench flow reactor assessment of Pd-only and TWC/NSC formulations for NH3 production during Passive SCR

CompleteQuarterly Milestones

• FY2015: Determine effect of aging and/or poisoning on TWC NH3formation through flow reactor experiments

• FY2017: Achieve EPA Tier 3 level emissions with 15% fuel economy gain vs. stoichiometric operation and less than 4 g Pt-equivalent per liter engine with commercial feasibility assessment including material costs

Annual SMART Milestones

• FY2017, Q2: criteria based on FY2017 SMART Milestone

GO/NO-GO Decisions

CompleteFurther studies ongoing

CompleteFurther studies ongoing

Page 7: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

7 DOE VTO Annual Merit Review – ace033

Approach focuses on catalyst and system optimization of Passive SCR (and LNT+SCR)

TWC

LeanGasolineEngine

Key Principle: system fuel efficiency gain depends on optimizing NH3production during rich operation and NOx reduction during lean operation

Other Core Principles:• Expand range of temperature operation• Materials must be durable to temperature and poisons (S)• Understand Pt group metals utilization to minimize cost

Minimize rich period of lean-rich cycle

Minimize engine out Lean NOx emissions

Add NOx storage for lean NOx storage and rich phase NH3 production

Minimize NH3oxidation (keep

NH3 stored)

Maintain high NOx conversion over

temperature range

Control emissions during lean-rich

transitions

Lean

Maximize engine out Rich NOx emissions

Minimize engine out Rich CO/HC

emissions

Maximize NOx to NH3conversion efficiency

Maximize CO and HC oxidation efficiency

Clean up CO/HC emissions (if needed)

Rich

Minimize engine out Lean NOx emissions

Add NOx storage for lean NOx storage and rich phase NH3 production

Minimize NH3oxidation (keep

NH3 stored)

Maintain high NOx conversion over

temperature range

Control emissions during lean-rich

transitions

Lean

Page 8: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

8 DOE VTO Annual Merit Review – ace033

Iterative Bench Reactor + Engine Study Approach

Bench Flow Reactor with cycling and multi-catalyst (close-coupled

and underfloor) capabilitiesBMW 120i lean gasoline engine platform with

National Instruments (Drivven) open controller

Define exhaust conditions

Formulation-dependent TWC performance TWC performance vs. AFR with

realistic HC and H2 characterization

Controlled TWC+SCR system performance Realistic TWC+SCR system performance

with fuel efficiency measurement

TWC+SCR performance with refined load step cycle Combustion parameter optimization to

maximize NH3 production

Collaborations with modeling community and CLEERS

System study guidance

Prototype catalysts

Page 9: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

9 DOE VTO Annual Merit Review – ace033

Collaborations and PartnersPrimary Project Partners• GM

– guidance and advice on lean gasoline systems via monthly teleconferences

• Umicore– guidance (via monthly teleconferences) and catalysts for

studies (both commercial and prototype formulations)• University of South Carolina (Jochen Lauterbach)

– Catalyst aging studies with student Calvin Thomas

Additional Collaborators• CDTi: catalysts for studies• CLEERS: Share results/data and identify research needs• LANL: Engine platform used for NH3 sensor study (M. Mukundan, E. Brosha, C. Kreller)• MECA: GPF studies via Work For Others contract• University of Minnesota: Collaboration on DOE funded project at U of Minn. related to lean GDI PM

(PI: Will Northrop)• CTS (Filter Sensing Technologies): Small business technical assistance on RF sensors for GPF

on-board diagnostics• DOE VTO Fuel and Lubricant Technology Program: Engine platform used for ethanol-based

HC-SCR studies

(3) Lean GDI PM Projects

Page 10: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

10 DOE VTO Annual Merit Review – ace033

Responses to 2015 Reviewers

Category ScoreApproach 3.50Tech Accomplishments 3.50Collaboration 3.50Future Research 3.50Weighted Average 3.50

FY2015 AMR Review(5 Reviewers)

[scores: 1 (min) to 4 (max)]

Relevant to DOE Objectives?YES (100%)

Sufficiency of ResourcesInsufficient

(40%)Sufficient

(60%)

Summary of Reviewers’ Feedback:• Generally positive feedback on:

– Approach (bench+engine)

– Collaborations with industry

– Project design, relevance, future plans

– Inclusion of S, aging effects

• More interest in OEM perspectives• Consider deS and desoot fuel penalties and

CO/HC emissions• Consider N2O (relative to GHG* standard)• Fundamental questions on ceria, Rh effects• Want more soot and modeling R&D

*N2O Greenhouse Gas (GHG) cap is 10 mg/mile

Page 11: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

12 DOE VTO Annual Merit Review – ace033

Responses to 2015 Reviewers

Category ScoreApproach 3.50Tech Accomplishments 3.50Collaboration 3.50Future Research 3.50Weighted Average 3.50

FY2015 AMR Review(5 Reviewers)

[scores: 1 (min) to 4 (max)]

Relevant to DOE Objectives?YES (100%)

Sufficiency of ResourcesInsufficient

(40%)Sufficient

(60%)

Summary of Reviewers’ Feedback:• Generally positive feedback on:

– Approach (bench+engine)

– Collaborations with industry

– Project design, relevance, future plans

– Inclusion of S, aging effects

• More interest in OEM perspectives• Consider deS and desoot fuel penalties and

CO/HC emissions• Consider N2O (relative to GHG* standard)• Fundamental questions on ceria, Rh effects• Want more soot and modeling R&D

*N2O Greenhouse Gas (GHG) cap is 10 mg/mile

Project Adjustments/Responses:• Project directly addressing OEM concerns• Will calculate deS/desoot effects• N2O data collected; more analysis occuring• Surface science studies (DRIFTS/XPS)• Resource limited, but project leveraged for

(3) PM/GPF projects & CLEERS database

“…feedback from OEMs on value of passive systems, lessons learned and technical challenges would improve rating to outstanding. Several OEMs indicate passive system challenges are constraining use especially predictability of efficiently producing NH3.”

Project results shared with Ford and FCA. Lots of questions on feasibility, transient control, and net fuel efficiency gain. References: J. Theis et al. CLEERS 2015, SAE 2015-01-1004, SAE 2015-01-1006; Doornbos et al. SAE 2015-01-0776, SAE 2015-24-2504, SAE 2016-01-0935

Page 12: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

13 DOE VTO Annual Merit Review – ace033

Responses to 2015 Reviewers

Category ScoreApproach 3.50Tech Accomplishments 3.50Collaboration 3.50Future Research 3.50Weighted Average 3.50

FY2015 AMR Review(5 Reviewers)

[scores: 1 (min) to 4 (max)]

Relevant to DOE Objectives?YES (100%)

Sufficiency of ResourcesInsufficient

(40%)Sufficient

(60%)

Summary of Reviewers’ Feedback:• Generally positive feedback on:

– Approach (bench+engine)

– Collaborations with industry

– Project design, relevance, future plans

– Inclusion of S, aging effects

• More interest in OEM perspectives• Consider deS and desoot fuel penalties and

CO/HC emissions• Consider N2O (relative to GHG* standard)• Fundamental questions on ceria, Rh effects• Want more soot and modeling R&D

*N2O Greenhouse Gas (GHG) cap is 10 mg/mile

Project Adjustments/Responses:• Project directly addressing OEM concerns• Will calculate deS/desoot effects

Page 13: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

14 DOE VTO Annual Merit Review – ace033

Responses to 2015 Reviewers

Category ScoreApproach 3.50Tech Accomplishments 3.50Collaboration 3.50Future Research 3.50Weighted Average 3.50

FY2015 AMR Review(5 Reviewers)

[scores: 1 (min) to 4 (max)]

Relevant to DOE Objectives?YES (100%)

Sufficiency of ResourcesInsufficient

(40%)Sufficient

(60%)

Summary of Reviewers’ Feedback:• Generally positive feedback on:

– Approach (bench+engine)

– Collaborations with industry

– Project design, relevance, future plans

– Inclusion of S, aging effects

• More interest in OEM perspectives• Consider deS and desoot fuel penalties and

CO/HC emissions• Consider N2O (relative to GHG* standard)• Fundamental questions on ceria, Rh effects• Want more soot and modeling R&D

*N2O Greenhouse Gas (GHG) cap is 10 mg/mile

Project Adjustments/Responses:• Project directly addressing OEM concerns• Will calculate deS/desoot effects• N2O data collected; more analysis occuring

Page 14: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

15 DOE VTO Annual Merit Review – ace033

Responses to 2015 Reviewers

Category ScoreApproach 3.50Tech Accomplishments 3.50Collaboration 3.50Future Research 3.50Weighted Average 3.50

FY2015 AMR Review(5 Reviewers)

[scores: 1 (min) to 4 (max)]

Relevant to DOE Objectives?YES (100%)

Sufficiency of ResourcesInsufficient

(40%)Sufficient

(60%)

Summary of Reviewers’ Feedback:• Generally positive feedback on:

– Approach (bench+engine)

– Collaborations with industry

– Project design, relevance, future plans

– Inclusion of S, aging effects

• More interest in OEM perspectives• Consider deS and desoot fuel penalties and

CO/HC emissions• Consider N2O (relative to GHG* standard)• Fundamental questions on ceria, Rh effects• Want more soot and modeling R&D

*N2O Greenhouse Gas (GHG) cap is 10 mg/mile

Project Adjustments/Responses:• Project directly addressing OEM concerns• Will calculate deS/desoot effects• N2O data collected; more analysis occuring• Surface science studies (DRIFTS/XPS)

Page 15: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

16 DOE VTO Annual Merit Review – ace033

Responses to 2015 Reviewers

Category ScoreApproach 3.50Tech Accomplishments 3.50Collaboration 3.50Future Research 3.50Weighted Average 3.50

FY2015 AMR Review(5 Reviewers)

[scores: 1 (min) to 4 (max)]

Relevant to DOE Objectives?YES (100%)

Sufficiency of ResourcesInsufficient

(40%)Sufficient

(60%)

Summary of Reviewers’ Feedback:• Generally positive feedback on:

– Approach (bench+engine)

– Collaborations with industry

– Project design, relevance, future plans

– Inclusion of S, aging effects

• More interest in OEM perspectives• Consider deS and desoot fuel penalties and

CO/HC emissions• Consider N2O (relative to GHG* standard)• Fundamental questions on ceria, Rh effects• Want more soot and modeling R&D

*N2O Greenhouse Gas (GHG) cap is 10 mg/mile

Project Adjustments/Responses:• Project directly addressing OEM concerns• Will calculate deS/desoot effects• N2O data collected; more analysis occuring• Surface science studies (DRIFTS/XPS)• Resource limited, but project leveraged for

(3) PM/GPF projects & CLEERS database

Page 16: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

17 DOE VTO Annual Merit Review – ace033

Summary of Technical Accomplishments• Bench Reactor Studies:

– Cold start selectivity as a function of λ defined for catalyst sample matrix

• Engine Studies:– Completed study of effects of NH3:NOx on fuel efficiency and NOx/NH3/N2O slip

• Aging and S Effects:– Materials characterization conducted on Malibu-1 catalyst (PGM size) after aging– S exposure study during lean-rich cycling completed (data analysis ongoing)

sample ID Description Pt (g/l) Pd (g/l) Rh (g/l) OSC NSCMalibu-1 Front half of TWC 0 7.3 0 N NMalibu-2 Rear half of TWC 0 1.1 0.3 Y N

Malibu-combo Full TWC 0 4.0 0.16 Y NORNL-1 Pt + Pd + Rh 2.47 4.17 0.05 Y YORNL-2 Pd + Rh 0 6.36 0.14 N NORNL-6 Pd 0 6.50 0 N NORNL-5 Pd + OSC high 0 6.50 0 H NORNL-4 Pd + OSC med 0 4.06 0 M NORNL-3 Pd + OSC low 0 1.41 0 L N

Catalyst Sample Matrix [OSC=oxygen storage capacity; NSC=NOx storage capacity]

Page 17: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

18 DOE VTO Annual Merit Review – ace033

Extensive flow reactor investigations show impact of TWC formulation, λ on light-off performance for passive SCR

• Gas composition has a large effect on light-off performance

– best combination of NOx reduction, NH3 production, and HC conversion achieved at λ 0.97 for all 5 TWCs evaluated

– same as optimum rich λ for passive SCR operation

• Conversion of NO and CO, production of NH3 all light-off at around 150°C

• Formulation has only a minor influence on light-off performance among TWCs tested

– T50 (Temperature at >50% conversion) and T90 (Temperature at >90% conversion) shown at right (dark bars=T50; light bars=T90)

NO

C3H8

CO

N2O

NH3

Malibu (Pd) TWC catalyst light-off at λ=0.97

NOx C3H8 CO

Page 18: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

19 DOE VTO Annual Merit Review – ace033

050

100150200250300350400

0.95 0.96 0.97 0.98 0.99 1

Tem

pera

ture

for

N2O

<10%

yie

ld (C

)

λ

λ affects NH3 and N2O formation during light-off as well

• NH3 formed at >80% yield starting at ~150°C for Malibu-1 catalyst (Pd)

• Temperature for N2O to decrease to <10% yield a function of λ

• Note: inlet temperature shown

050

100150200250300350400

0.95 0.96 0.97 0.98 0.99 1

Tem

pera

ture

for

NH 3

>80%

yie

ld (C

)

λ

NH3>80% Yield N2O<10% Yield

NO

C3H8

CO

N2O

NH3

Malibu (Pd) TWC catalyst light-off at λ=0.97

Page 19: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

20 DOE VTO Annual Merit Review – ace033

050

100150200250300350400

0.95 0.96 0.97 0.98 0.99 1

Tem

pera

ture

for

N2O

<10%

yie

ld (C

)

λ

λ affects NH3 and N2O formation during light-off as well

• NH3 formed at >80% yield starting at ~150°C for Malibu-1 catalyst (Pd)

• Temperature for N2O to decrease to <10% yield a function of λ

• Note: inlet temperature shown

050

100150200250300350400

0.95 0.96 0.97 0.98 0.99 1

Tem

pera

ture

for

NH 3

>80%

yie

ld (C

)

λ

NH3>80% Yield N2O<10% Yield

λ=0.97 during cold start gives best NH3production with least N2O

NO

C3H8

CO

N2O

NH3

Malibu (Pd) TWC catalyst light-off at λ=0.97

Page 20: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

21 DOE VTO Annual Merit Review – ace033

Engine-based studies show NH3:NOx>1 critical to achieving highest NOx conversion

0

20

40

60

80

100

90

92

94

96

98

100

0.90 1.00 1.10 1.20 1.30

NO

Xco

nver

sion

, %

SCR

loading, %

• NOx conversion reaches >99% at NH3:NOx=1.13

• Increasing NH3:NOx to 1.20 results in NH3 slip• N2O primarily forms over SCR during lean

phase (~2ppm) and not affected by NH3:NOx• N2O spike over TWC observed at lean to rich

transition (~8ppm)

Ave

SCR

OU

Tco

nc.,

ppm

0

5

10

15

20

25

30

35

0.96 1.09 1.13 1.19 1.20 1.25

Average SCRout NOx, ppm

Average, NH3 slip, ppm

Average, N2O slip, ppm

NH3:NOX at TWC outlet

NOXNH3N2O

NH3:NOX at TWC outlet

0

5

10

15

NH3

0

5

10

15

NOX

lean rich lean rich

NH3:NOX=1.20

time, s

0

5

10

15

50 150 250 350

N2O

conc

entr

atio

n, p

pm

TWC Tinlet=470°C

SCR Tinlet=350°C

Page 21: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

22 DOE VTO Annual Merit Review – ace033

Reducing cycle timing enables >99% NOx conversion at NH3:NOx=1 (engine studies)

0

20

40

60

80

100

90

92

94

96

98

100

0.90 1.00 1.10 1.20 1.30

NO

Xco

nver

sion

, % SCR

loading, %

NH3:NOX at TWC outlet

0

20

40

60

80

100

90

92

94

96

98

100

50 100 150 200 250

NO

Xco

nver

sion

, % SCR

loading, %

loading

conversion

cycle timing, s

NH3:NOX = 1

3 X

0

2

4

6

8

10

12

0.90 1.00 1.10 1.20 1.30

% fu

el b

enef

it

BSFC-based

NH3:NOX at TWC outlet

cycle timing, s

0

2

4

6

8

10

12

50 100 150 200 250

BSFC-based

% fu

el b

enef

it

Page 22: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

23 DOE VTO Annual Merit Review – ace033

PGM sintering occurs mostly in early aging hours but continues to 100 hours

This research was performed, in part, using instrumentation (FEI Talos F200X S/TEM) provided by the Department of Energy, Office of Nuclear Energy, Fuel Cycle R&D Program and the Nuclear Science User Facilities. STEM images collected by Michael Lance (ORNL).

Pd map and HAADF for 50hr aged Malibu-1

0%5%

10%15%20%25%30%

0 20 40 60 80

Part

icle

s in

Bin

[% o

f tot

al p

artic

les]

PGM Particle Size (nm)

Fresh25 hours50 hours100 hours

RecallFY15 AgingData

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24 DOE VTO Annual Merit Review – ace033

Sulfur impact evaluated on hydrothermally aged TWC while cycling; some effects observed but recoverable

1. Began with Hydrothermally aged Pd TWC (Malibu-1)

HC

Note: Preliminary Results Shown

0%

20%

40%

60%

80%

100%

350 400 450 500 550 600 650

NH 3

Sele

ctiv

ity

Temperature (°C)

NH3

Measure“Clean”

ReactivityWhile Cycling

With no S

4-modeAging at900°C

CleanAged

No ST=350°C

λ=0.97T=650°C

λ=0.97T=650°C

CleanSulfatedDesulfated

80%

85%

90%

95%

100%

350 400 450 500 550 600 650Pr

opan

e Co

nver

sion

Temperature (°C)

Page 24: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

25 DOE VTO Annual Merit Review – ace033

Sulfur impact evaluated on hydrothermally aged TWC while cycling; some effects observed but recoverable

1. Began with Hydrothermally aged Pd TWC (Malibu-1)2. S aged TWC while lean-rich cycling (fixed load shown)

HC

Note: Preliminary Results Shown

0%

20%

40%

60%

80%

100%

350 400 450 500 550 600 650

NH 3

Sele

ctiv

ity

Temperature (°C)

0%

20%

40%

60%

80%

100%

350 400 450 500 550 600 650

NH 3

Sele

ctiv

ity

Temperature (°C)

NH3

Measure“Sulfated”Reactivity

While CyclingWith no S

Add ST=350°C

Measure“Clean”

ReactivityWhile Cycling

With no S

4-modeAging at900°C

Clean SulfatedAged

No ST=350°C

λ=0.97T=650°C

λ=0.97T=650°C

CleanSulfatedDesulfated

80%

85%

90%

95%

100%

350 400 450 500 550 600 650Pr

opan

e Co

nver

sion

Temperature (°C)

80%

85%

90%

95%

100%

350 400 450 500 550 600 650Pr

opan

e Co

nver

sion

Temperature (°C)

+25ppm-hrSO2

Equivalent to Low Temp Oxidation Protocol

Page 25: Emissions Control for Lean Gasoline Engines Control for Lean Gasoline Engines Jim Parks ... •Lean vehicles offer 5–15% ... Collaboration on DOE funded project at U of Minn. related

26 DOE VTO Annual Merit Review – ace033

Sulfur impact evaluated on hydrothermally aged TWC while cycling; some effects observed but recoverable

1. Began with Hydrothermally aged Pd TWC (Malibu-1)2. S aged TWC while lean-rich cycling (fixed load shown)3. After S aging, deS at 650°C and λ=0.97 while lean-rich cycling4. After deS: 350°C and 650°C data show good performance recovery

HC

Note: Preliminary Results Shown

0%

20%

40%

60%

80%

100%

350 400 450 500 550 600 650

NH 3

Sele

ctiv

ity

Temperature (°C)

0%

20%

40%

60%

80%

100%

350 400 450 500 550 600 650

NH 3

Sele

ctiv

ity

Temperature (°C)

NH3

Measure“Sulfated”Reactivity

While CyclingWith no S

Add ST=350°C

Measure“Clean”

ReactivityWhile Cycling

With no S

4-modeAging at900°C

Clean Sulfated deSulfatedAged

No ST=350°C

λ=0.97T=650°C

λ=0.97T=650°C

λ=0.97T=650°C

0%

20%

40%

60%

80%

100%

350 400 450 500 550 600 650

NH 3

Sele

ctiv

ity

Temperature (°C)

CleanSulfatedDesulfated

80%

85%

90%

95%

100%

350 400 450 500 550 600 650Pr

opan

e Co

nver

sion

Temperature (°C)

80%

85%

90%

95%

100%

350 400 450 500 550 600 650Pr

opan

e Co

nver

sion

Temperature (°C)

80%

85%

90%

95%

100%

350 400 450 500 550 600 650Pr

opan

e Co

nver

sion

Temperature (°C)

+25ppm-hrSO2

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27 DOE VTO Annual Merit Review – ace033

0%

2%

4%

6%

8%

10%

12%

14%

16%

Fuel

Con

sum

ptio

n Be

nefit

(vs.

Sto

ich.

)

FY13 FY14 FY15 FY16 FY17

Remaining Challenges

0

1

2

3

4

5

6

7

8

9Pt

-Equ

ival

ent (

g/Li

ter e

ngin

e)

FY13 FY14 FY15 FY16 FY17B

etter

Fuel Economy PGM [Cost]

BMW 120iTWC+LNT

• Improve system level fuel economy (reduce NH3 production fuel penalty)• Address catalyst performance during transients and rich-lean transitions• Determine technique to enable NSC functionality over temperature range • Broaden aging studies to include SCR

max

0

1

2

3

4

5

BMW 120i Passive SCR

Cata

lyst

Vol

ume

(lite

rs)

LNT

TWCTWC

SCR

Size

Bench Flow Reactor StatusEngine-Based Study Status

max

calc

max

max

Bet

ter

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28 DOE VTO Annual Merit Review – ace033

Future Work: Addressing Remaining Challenges• Catalyst formulation studies on bench flow reactor

– Examine SCR formulations for NH3 oxidation and compare resulting data with engine-based data

• Continue aging studies including studying select prototype formulations– Perform materials characterization [TEM, BET/Chemi, XRD]– Continue aging of TWC formulations with sulfur while cycling– Characterize aged SCR (aging complete)

• Continue engine-based studies to maximize system fuel efficiency – Repeat existing studies with TWC formulation that contains NSC– Understand transient and switching effects on Passive SCR/LNT+SCR– Define method to predict transient emissions and fuel efficiency

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29 DOE VTO Annual Merit Review – ace033

SummaryRelevance Enabling lean gasoline vehicles will significantly reduce US

petroleum use

Approach

Focus on non-urea Passive SCR and LNT+SCR

Evaluate catalyst formulations on bench flow reactor for cost-effective emissions control

Study fuel penalty and realistic performance on lean gasoline engine research platform

CollaborationsPrimary: GM, Umicore, and Univ. of South Carolina

Additional: CDTi, LANL, MECA, Univ. of Minnesota, CTS(FST)

Technical Accomplishments

Characterized NOx/HC/CO light-off and NH3/N2O formation vs. temperature on bench flow reactor of Umicore catalyst matrixDetermined optimal NH3:NOx of 1.13 for fuel efficiency and NOx/NH3/N2O slip performanceMeasured PGM peak size shift from 3.5 nm to ~37 nm withaging time

99% NH3 yield at 350°C after S during lean-rich cycling + deS

Future Work Bench reactor, aging, and engine studies ongoing toward project goals of fuel efficiency and cost (Pt-equivalent)

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30 DOE VTO Annual Merit Review – ace033

Technical Backup slides

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31 DOE VTO Annual Merit Review – ace033

Project Goals Defined by Industry

FY13 FY14 FY15 FY16 FY17Fuel economy gain over stoichiometric 7% 10% 10% 12% 15%

Total emissions control devices Pt* (g/Lengine) 8 7 6 5 4

* - will use Pt equivalent cost to account for different costs of Pt, Pd and Rh; 5-year average value fixed at beginning of project

5-year Average($/troy oz.) Pt-equivalent

Platinum $ 1,504 /troy oz. 1.0

Palladium $ 463 /troy oz. 0.3

Rhodium $ 3,582 /troy oz. 2.4

Gold $ 989 /troy oz. 0.7

In addition to milestones, a set of project goals has been adopted to ensure progression towards goal of low-cost emissions control solution for fuel efficient lean-burn gasoline vehicles

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32 DOE VTO Annual Merit Review – ace033

BMW 120i engine features three main combustion modes

0

200

400

600

-360 -300 -240 -180 -120 -60 0 60 120 180 240 300 360

Inje

ctor

Driv

e Vol

tage

(V) [

data

offs

et b

y 20

0 V]

Crank Angle Degrees (CAD)

Lean Stratified

Lean Homogeneous

Stoich Homogeneous

=Main Spark

=Restrike 1500 rpm, 26% Loadλ=1.9

1500 rpm, 65% Loadλ=1.38

1500 rpm, 31% Loadλ=1.0

• Spray guided combustion system design

• Piezoelectric injectors operate at different voltages as well as different durations

• Multiple sparks enable ignition under lean operation

• In addition to three main combustions modes, there is also an OEM rich homogeneous mode for LNT control of NOX emissions to meet EURO V NOXemission standards

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33 DOE VTO Annual Merit Review – ace033

Conducted transient flow reactor experiments to estimate TWC effects on fuel consumption• Used feedback-controlled

cycles on flow reactor to evaluate dynamic TWC response in context of passive SCR

• Evaluated two different simulated engine cycles (fixed load, load step)

fixed load load steprich lean rich lean

load (BMEP) 2 bar 2 bar 8 bar 2 bar

SV (h-1) 27000 45000 60000 45000

NOx (ppm) 600 360 1200 360

max lean time 50% 80%simulates cruise “hill” transient

Rich Leanλ 0.95 0.96 0.97 0.98 0.99 1.00 2

O2 (%) 0.96 1.02 1.07 1.13 1.17 1.22 10

CO (%) 2.0 1.8 1.6 1.4 1.2 1.0 0.2

H2 (%) 1.0 0.9 0.8 0.7 0.6 0.5 0

NO (ppm) 600 (or 1200) 360

C3H8 (ppm C1) 3000 1900

H2O (%) 11 6.6

CO2 (%) 11 6.6

TWC SV (hr-1) 27000 (or 60000) 45000

• Compositions & flows selected to mimic BMW GDI engine exhaust

• Space velocity changed with λand load

• C3H8 chosen as challenging HC