OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

Fuel-Borne Reductants for NOx Aftertreatment: Preliminary EtOH SCR Study

Diesel Engine Emissions Reduction WorkshopAugust 28, 2003

Oak Ridge National Laboratory: John Thomas, Mike Kass, Sam Lewis,John Storey, Ron Graves, Bruce Bunting

Caterpillar: Alexander Panov, Paul Park

Other contributors: Williams-Pekin: Fuel grade ethanolGE Betz: Blending agent, blend testingGromark: Blended fuelIllinois DOCCA: Coordinated delivery

Sponsor: US DOE, OFCVT, Team Leader: Steve Goguen

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

Background Leading to Current Effort

1. Previous work: E-diesel, urea SCR, adsorber catalysts. 2. HC SCR receiving less attention than other aftertreatment

technologies.3. ORNL formulated concepts for fuel-borne reductant systems.

EtOH seen as a removable fuel-borne reductant for HC SCR4. Caterpillar marketed an EtOH SCR system for stationary

diesels. Co-operative effort developed between Caterpillar and ORNL

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

Comparison of Urea SCR to EtOH SCR

Urea SCR

Commercial technology for stationary engines

NOx Reduction > 90% achievable for 300-500°C

Uses ~ 1:1 NH3/NOx mol ratio

Aqueous solution injected into exhaust

32.5% urea freezes at 12°F

Can produce/slip NH3, N2O, inert PM, reactive solids

EtOH SCR

R&D, utility being explored

NOx Reduction ~ 80% thought to be possible for 400-500°C?

Uses ≥ 3:1 C/NOx mole ratio

Used undiluted, can be fuel-borne

Freezing not an issue

Unwanted products/slip likely:, NH3, N2O, aldehydes, HC

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

Initial Project Objectives:

• Evaluate performance of EtOH reductant, Ag-Alumina SCR catalyst system on diesel exhaust. Look at unregulated emissions

• Demonstrate EtOH stripping from E-diesel & its usefulness for NOx reduction.

• Later: consider other fuel-borne reductants, catalysts

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

Ethanol Was Stripped From 15% E-Diesel

Using “mild distillation” nearly all EtOH was removed and then recovered

NTRC Analytical Lab.

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

Experimental Configuration

• Donated 1999 Cummins ISB, 5.9 L, With Cummins provided cooled EGR, upgraded fuel system, turbo., controls. Configured for “Near-2004” emissions.

• 285 hp DC motoring dynamometer• Measured gases in exhaust via

standard benches• FTIR and GC-MS used to look for

specific HCs, N2O, NH3, Acetaldehyde

FTIR

Analytical Bench: O2NOx, CO, HC, CO2

Analytical Bench: O2NOx, CO, HC, CO2

Injector

Ag Catalyst

Engine

UEGO NGK NOx sensor

PhotoacousticSpectrometer

GC-MSBag SampleMicrodilution

Tunnel

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

Cummins 5.9 L Engine

BU

RN

ER

•

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

Reductant Injector and Catalyst in the ExhaustORNL/NTRC Cell 3

7 L catalyst located 1 m downstream of the injector.

Automotive EFI injector downstream of turbo outlet.

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

SCR Performance Experimental Methodology• Shakedown, de-green catalyst for ~10 hours at 400°C.

• Performance Investigation at Two Engine Conditions / Space Velocities:compared conversion at a low & high space velocity while maintaining similar catalyst temperature and NOx flux.

Test Speed Torque SV Cat T NOxSetting RPM ft-lbs 1/h °C g/min

AVL8-M3 1115 230 21000 360-400 ~1.5~AVL8-M6 2225 180 57000 360-400 ~2.1

Fuel-Reductant Combinations: Fuel Reductant

1. ECD-1 fuel-grade EtOH2. ECD-1 “stripped” fuel-grade EtOH3. E-diesel “stripped” fuel-grade EtOH4. ECD-1 reagent grade EtOH

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

Excellent NOx Conversion Was Achieved at 21000/h, 360-400°C

NOx conversion vs C/N ratio, 1115 RPM

0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5 6 7 8 9 10carbon/nitrogen ratio (2X Ethanol/NO2)

NO

x co

nver

sion

(%)

ECD1, fuel EtOH, test 1

Space Velocity ~ 21,000 1/hCatalyst temperature: 360-390 C

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

Excellent NOx Conversion Was Achieved at 21000/h, 360-400°C

NOx conversion vs C/N ratio, 1115 RPM

0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5 6 7 8 9 10carbon/nitrogen ratio (2X Ethanol/NO2)

NO

x co

nver

sion

(%)

ECD1, fuel EtOH, test 1

ECD1, fuel EtOH, test 2

ECD1, stripped EtOH, test 3

Space Velocity ~ 21,000 1/hCatalyst temperature: 360-390 C

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

NOx Conversion Was Excellent at 21000/h and 360-400°CSelectivity appeared to improved as catalyst is exposed to more sulfur

NOx conversion vs C/N ratio, 1115 RPM

0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5 6 7 8 9 10carbon/nitrogen ratio (2X Ethanol/NO2)

NO

x co

nver

sion

(%)

ECD1, fuel EtOH

ECD1, fuel EtOH

ECD1, stripped EtOH

E-diesel, stripped EtOH

ECD1, fuel EtOH

ECD1, high-grade EtOH

Space Velocity ~ 21,000 1/hCatalyst temperature: 360-390 C

1.5% fuel penalty: energy basis

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

Good NOx Conversion Achieved at 57000/h and 360-400°C

NOx conversion vs C/N ratio, 2225 RPM

0

10

20

30

40

50

60

70

80

90

100

0 2 4 6 8 10 12carbon/nitrogen ratio (2X Ethanol/NO2)

NO

x co

nver

sion

(%)

ECD1, fuel EtOH

E-diesel, stripped EtOH

ECD1, fuel EtOH

Space Velocity ~ 57,000 1/hCatalyst temperature: 360-390 C

1.5% fuel penalty: energy basis

NOx conversion very similar for the different fuel-reductant combinations

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

HC Slip Changed with Progression of Experiments

Reagent grade EtOH

HC slip vs C/N ratio, 1115 RPM

0

20

40

60

80

100

120

140

160

0 1 2 3 4 5 6 7 8 9 10carbon/nitrogen ratio

HC

slip

(ppm

)

ECD1, fuel EtOH ECD1, fuel EtOH ECD1, stripped EtOHE-diesel, stripped EtOHECD1, fuel EtOHECD1, high grade EtOH

Space Velocity ~ 21,000 1/hCatalyst temperature: 360-390 C

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

HC slip at high SV was about the same ppm level, mass flux is ~2.7 times greater

HC slip vs C/N ratio, 21,000 1/h & 57,000 1/h

0

50

100

150

200

250

0 2 4 6 8carbon/nitrogen ratio

HC

slip

(ppm

)

low SV, E-diesel, stripped EtOH

low SV, ECD1, fuel EtOH

low SV, ECD1, reagent EtOH

High SV, E-diesel, stripped EtOH

High SV, ECD1, fuel EtOH

Catalyst temperature: 360-390 C

~ 0.5 g/hp-h

~ 0.19 g/hp-h

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

FTIR Results: Ammonia Emissions

0

10

20

30

40

50

60

0 2 4 6 8 10 12C1:NOx Ratio

NH

3 (pp

m)

NH3 @ 21000/hNH3 @ 57000/h

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

In the past, some catalyst formed large amounts of N2O

FTIR Results: N2O Emissions

0

1

2

3

4

5

6

0 2 4 6 8 10 12C1:NOx Ratio

N2O

Lev

el (p

pm)

N2O @ 21000/hN2O @ 57000/h

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

FTIR Results: NOX, Versus Acetaldehyde Emissions

0

10

20

30

40

50

60

0 2 4 6 8 10 12C1:NOx Ratio

Ace

tald

ehyd

e (p

pm)

Acet @ 21000/hAcet @ 57000/h

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

We Have Begun to Look at Other Fuel-borne ReductantsNote: much higher SV and NOx flux

7 liter Ag alumina catalyst, 2225 rpm, 360 deg.C, 90000 SV,

0

10

20

30

40

50

60

70

80

0 1 2 3 4 5 6 7ethanol flow, wt% of fuel flow

% N

OX

con

vers

ion EtOH

Octanol

Heptane

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

Reductant stripping experiments

ethanol 78 20 201-propanol 97 20 181-butanol 117 20 17.5n-hexane 69 20 4.9n-heptane 98 20 51-octanol 196 20 0

REDUCTANT BOILING POINT, deg.C

% BLENDED IN ECD1 FUEL

% SEPARATED (rotovap, 100 CC, 10

minutes, 90 deg.C, 200 mm Hg vacuum)

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

Low Temperature Effectiveness of Catalyst

Low Temperature Evaluation: For low SV, catalyst temperatures near 250°C, 300°C, 340°C and 370°C were examined at two C/N ratios

NOx conversion vs catalyst temperature

0

10

20

30

40

50

60

70

80

90

100

240 260 280 300 320 340 360 380Ag catalyst temperature (C)

NO

x co

nver

sion

(%)

1115 RPMECD1, fuel ethanolSV varies from 17,000 to 21,000 1/h

C/N ~ 6

C/N ~ 3

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

GC-MS Results Clearly Show Different Nature of Slip HC for The 3 EtOH “Grades”

2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.000

200000

400000

600000

800000

1000000

1200000

1400000

1600000

Time-->

Abundance

Reagent grade EtOH

Denatured, fuel grade EtOH: gasoline components seen

E-diesel distilled, fuel grade EtOH: evidence of gasoline & diesel components

SV = 21,000 1/h

C9

C10

OAK RIDGE NATIONAL LABORATORYU.S. DEPARTMENT OF ENERGY

Observations & Conclusions• Ethanol SCR effectively reduced NOx emissions of diesel exhaust for

catalyst temperatures between 360-400°C− moderate C1/NOx ratios− 90% for 21000/h and 80% for 57000/h− Some conversion observed at 250°C

• Saw catalyst performance improve with sulfur exposure• Low levels of N2O (< 6 ppm ) were produced• Ethanol was converted to acetaldehyde: slipped at 57000 1/h• Ammonia was produced (high C/N, low SV), but may not be problematic• Fuel-borne feasibility was demonstrated by stripping EtOH from E-diesel –

use as reductant in the SCR system• Technology may show promise - examining a broader set of

parameters/conditions is warranted