AVECC Conference April 29, 2004

Catalyst Based Diesel Emission Control Technology

DPX™ Catalyzed Particulate Filter

1

Engelhard DPXTM Catalyzed HD Diesel Soot Filter Technology Development Shows Continual Improvement Early CSF’s, High Pt

1980’s

1st Generation, Pt + BMO’s,

2nd Generation, Improved Materials, 3rd Generation, Improved Materials, Preparation Methods 4th & 5th Generation, Improved Materials, Controlled Catalyst Placement

Off-Road, FLT

1993

1998

1999

Retrofit Applications: USA, Europe, Asia Diesel OEM’s: “Emitless” “Green Diesel” Other

2001+

US 2007 Passive-Active Filter

Engelhard’s DPX™ Catalyzed Soot Filter (CSF) Technologies Can Be Supported on a Myriad of Supports z

Engelhard’s soot filter catalysts can be applied to virtually any type of soot filter media: cordierite, silicon carbide (traditional & Octa Design), composite, sintered metal, open cell metallic foams.

2

Regeneration Methods will Determine the System Design z

Passive regeneration Î Aggregate soot burning rate > aggregate soot accumulation rate Î Dependent on engine-out soot rate, duty cycle and exhaust temperature » Catalytic Soot Burn Rate is dependent on temperature and oxidants present » Passive regeneration increases time interval required between active regeneration events.

z

Active regeneration Î Required to insure soot burning over light load, low temperature conditions, (i.e. net soot accumulation conditions). Î Fuel induced Exotherm to provide heat for soot combustion.

Studies Demonstrate the Superiority of Catalyzed Soot Filter 3-Step Soot Loading / Regeneration Test

Slope of DP/Time During Regeneration 2.0

190

450

400

170

1.0

150

0.0 250

130

CSF 300

110 250

90

200

150 0

20

40

60

Time (min)

80

d ( ∆ P )/d t ( m b a r/m in )

DPF

Exh-BackPress (m Bar)

Exh -T em p s (°C)

Tin 350

-2.0 -3.0

70

-4.0

50

-5.0

100

300

350

400

450

500

550

600

-1.0

DPF CSF DOC+DPF DOC+CSF

Regeneration Temp °C

3

Modeling Analysis Shows Large Advantage for CSF over DOC + Un-catalyzed Filter System at Low Engine-Out NOx 1 Input Level DOC + DPF (1g) DOC + DPF (4g) CSF (1g) CSF (4g)

0.9

0.7

A-Speed / High Torque Burn-Off

0.6

A-Speed / Low Torque Soot Loading 0.5 0.4 0.3 0.2 0.1 0 0

2000

4000

6000

8000

10000

12000

Time (s)

Simulated Transient Cycle Test of Field Return DPXTM After 191,000mi - Note stable DP vs time indicating good passive regeneration durability 375

20

350

18

325

16

275

14

250 225

12

200

10

175 150

8

125

6

100 75

CSF Pres Drop, kPa

300

4

50

2

25 13:57

13:11

12:30

11:48

9:42

11:06

8:55

10:24

8:14

7:32

6:50

6:08

5:26

4:41

3:57

3:16

2:34

1:52

1:10

0:28

23:42

23:00

22:18

21:36

20:54

20:12

19:25

18:43

18:00

17:17

16:34

15:52

0 15:06

0 14:16

Temp., C

Soot Loading (g/L)

0.8

Time T_Cat_In deg C

T_Cat_Out deg C

dP_CSF_avg1s kPa

4

Passive Regeneration Continues to Improve 18

300 --TBC01,

---------------------------------------------------TBC01,

CIT=0 N.m------------------------------------

---TBC02,

CIT=0 N.m-

17 16 15

250

14 13 12 11 10 9

150

kPa

Temperature, C

200

8 7 6

100

5 4 3

50

2 1 0

0 0

4

9

14

19

24

28

Time in Hours T_Cat_In

T_CSF_Out

dP_CSF

Catalyzed Particulate Filter Conclusions z

DPX™ Filter Technology has improved Significantly over the last 5 years Î Regeneration now occurring at very low temperatures

z

DPX™ Catalyzed Particulate Filter Technology Durability is proven on a wide variety of applications with in use operation in excess of 450,000 miles on road

z

DPX™ Catalyzed Particulate Filters can be used in Low NOx applications with minimal change in Regeneration Performance

z

DPX™ Technology can be applied to numerous substrate technologies and configurations for the enhanced Passive and Active Regeneration necessary to meet 2007 emission standards.

5

NOx Adsorbers

NOx-Trap System Must be Designed for the Application z

z

Light-Duty Î Regulated drive cycles operate low on torque curve » Cold start and high efficiency between 150-200°C required » Max temperature on cycle may not exceed 350-400°C Î Catalyst / System Implications » Desulfation can be conducted at 550-600°C » 1X catalyst volume / engine displacement ratio being considered » Space velocity may not exceed 50-80K/hr. Medium, Heavy-Duty Î NTE requirements necessitate operation at all speed/load conditions » Cold start requirements minimized » Max temperature can reach 550-600°C Î Catalyst / System Implications » Desulfation will require >700°C » 2X catalyst volume / engine displacement ratio being considered » With this volume space velocity may exceed 150K/hr at NTE points

6

NOx Removal Efficiency and NOx Storage Capacity are a Function of Space Velocity 100

Normalized NOx Storage Capacity as a Function of SV

NOx Conversion as a Function of Space Velocity 2.5

90

2.0

NS50 (g NO2/L)

70 60 50 40 30

1.5

1.0

-1

-1

GHSV=25000 h -1 GHSV=37500 h -1 GHSV=75000 h

20 10

SV = 25,000 h -1 SV = 37,500 h -1 SV = 75,000 h

0.5

0.0

0 200

250

300

350

400

200

450

250

300

350

400

450

o

o

Temperature ( C)

Temperature ( C)

Heavy-Duty NOx-traps Require Activity at High Temperatures NOx Capacity (90% Eff.) of Catalyst System 5 z

z

Heavy-Duty NOx-Traps are designed to have higher NOx Storage Capacity at Higher Temperature. At NTE conditions the system needs to be correctly sized for the high exhaust flow rates.

Capacity, (g NO2/L)

NOx Conversion (%)

80

4.5

35K 70K 105K 140K

4 3.5 3 2.5 2 1.5 1 0.5 0 200

250

300

350

400

450

500

550

600

Temperature, (°C)

7

NOx Storage Capacity has been Correlated to NOx Removal Efficiency NOx Trapping Capacity @350°C

z

Example of Laboratory Capacity Measurement Since it is estimated that 90% NOx removal efficiency will be required for the application, capacity measure is limited to 10% breakthrough.

100 90

Trapping Efficiency, %

z

80 70 60

capacity = 1.06 g NO2/L

50 40 30 20 10 0 0

1

2

3

4

5

6

Time on Stream, min.

Light Duty NOx Adsorber Can Be Stable for Multiple Sulfation / Desulfation Cycles NOx Capacityof LNTDuring DeSOx Process

z

z

120,000 mi durability will require approximately 55 DeSOx cycles. New NOx-trap can be desulfated efficiently at 600°C. Durable to end-of-life simulation.

2 1.8

Capacity @ 350C, g NO2/L

z

sulfation

35KVHSV

desulfation

1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56

Cycles

8

Comparison of Performance Window After Multiple Sulfation and Desulfation Cycles Cycle NOx Performance of Low Temp LNT z

Low Temperature system has excellent activity window at low SV.

100 90 80

NOx efficiency maintained through endof-life simulation.

NOx Conv (%)

70

z

60

60s L/ 3s R (0.27 g NO2/L flux/min)

50 40

after 20 DeSOx

30

after 55 DeSOx

20

35K VHSV

10 0 150

200

250

300

350

400

450

500

Inlet Temperature (°C)

NOx-Trap Performance on Medium-Duty Engine with Rich Control by Engine Management Catalyst System Undersized to Demonstrate SV Importance. Î 1.3X Engine Displacement

Mode A-25

SV (hr –1)

Temp (°C)

42.7

288

169

2.6

A-50

70.5

355

311

3.9

96.7

397

523

5.6

A-100

118.4

426

652

6.5

z z

90

Catalyst Durable in End-of Life Simulation. Rich Quality During DeSOx Mode Impacts Aged Performance. Total Activity Can be Improved by Optimization of Catalyst Size.

Fresh System A Aged System B

80

[NOx] BS NOx (ppm) (g/kW.h)

A-75 z

100

70

Efficiency [%]

z

60 50 40 30 20 10 0 A100

A75

Mode

A50

A25

9

Performance Evaluated on a Light-Duty Application Showing NOx Activity can be Maintained if Lean/Rich is Optimized Catalyst System Correctly Sized for LD application with 1.7X Engine Displacement SV (hr –1)

Temp (°C)

[NOx] (ppm)

30 mph

10.3

220

112

45 mph

18.3

285

183

60 mph

21.6

320

230

Mode

Effect of Aging Time on NOx Performance 30 miles/hour Steady-State Condition 100 90 50 hr

80

NOx Conversion (%)

z

600 hr

70 60 50 40 30 20 10

z

Excellent activity can be maintained if NOx storage capacity is not exceeded

0 30 Lean / 3 Rich 60 Lean / 3 Rich 90 Lean / 3 Rich 120 Lean / 3 Rich 150 Lean / 3 Rich

Lean / Rich Timing During Evaluation

NOX Adsorber Conclusions z z z z z z

NOx Trap technology has greatly improved over the last few years. 90% NOx Reduction Efficiency has been demonstrated over a wide operating range New Catalysts have been designed for with lower desulfation temperatures and improved thermal durability Catalyst durability has been proven in excess of 200,000 miles NOx trap systems must be designed and integrated in conjunction with specific engine platforms and technology in mind. Catalyst sizing and NOx regeneration strategy is critical for proper performance and durability

10

Selective Catalytic Reduction

SCR Technology Continues to Improve z z z z

Improved Low temperature Performance is needed to meet future emissions standards (Particularly US 2010) New Generation SCR catalysts show better low temperature NOx performance compared to traditional system System Configuration is critical for optimized performance. SCR technology is capable of reducing NOx by 90%

11

SCR System Configuration

SCR Catalyst

Optional NH3 Clean up Volvo D7B260, 6.73 liter, Euro 2

Optional Oxidation Cat

Urea Sol’n., AirAssist Injector

In a standard configuration Vanadia catalyst shows improved performance compared to low temperature Zeolite catalysts above 300 C 100 90

NOx conversion, %

80 70 60 50 40

Blank + Zeolite + Zeolite

30

Blank + Zeolite + Clean up

20

Blank + Vanadia + Clean up

10

Blank + Vanadia + Vanadia

0

150

200

250

300

350

400

450

Test Temperature

12

The addition of an Oxidation catalyst before the Low Temperature Zeolite SCR catalyst significantly improves performance 100 90

NOx conversion, %

80 70 60

Blank + Zeolite + Zeolite

50

Blank + Zeolite + Clean up

40

Low Oxi + Zeolite + Zeolite

30

Low Oxi + Zeolite + Clean up

20

High Oxi + Zeolite + Clean up

10

High Oxi + Zeolite + Zeolite

0

150

200

250

300

350

400

450

Test Temperature

Oxidation catalysts performance improvement of Vanadia based SCR catalysts is less than the improvement for Zeolite SCR catalysts 100 90

NOx conversion, %

80 70 60 50 40

Blank + Vanadia + Vanadia

30

Blank + Vanadia + Clean up

20

Low Oxi + Vanadia + Vanadia High Oxi + Vanadia + Clean up

10

High Oxi + Vanadia + Vanadia

0

150

200

250

300

350

400

450

Test Temperature

13

Increasing fuel sulfur from 5 to 35 ppm has a limited effect on SCR catalyst performance 100 90 80

60 50

Blank + Vanadia + Vanadia

40

Blank + Vanadia + Vanadia (35 ppm S) Low Oxi + Vanadia + Vanadia

30

Low Oxi + Vanadia + Vanadia (35 ppm S)

20

High Oxi + Zeolite + Zeolite

10

High Oxi + Zeolite + Zeolite (35 ppm S)

0 150

200

250

300

350

400

450

Test Temperature, C

ESC Test results for low temperature Zeolite SCR: 90+ NOx conversion,