Catalytic Filter for Diesel Exhaust

Purification
Neng Ye, Tim Morin and Mark Fokema

Aspen Products Group, Inc.

186 Cedar Hill St.
Marlborough, MA 01752
fokema@aspensystems.com

2009 DEER Conference

Dearborn, MI

August 4, 2009

ASPEN PRODUCTS GROUP, INC.

 Aspen Products Group, Inc.
• Develops materials and systems that promote efficient and
clean liquid fossil fuel use
–Hydrogen generation, hydrogen purification, sulfur removal
–Catalytic combustion
–Exhaust clean-up
• Products developed for military and commercial customers
• Business strategy to become component manufacturer &
supplier

ASPEN PRODUCTS GROUP, INC.

 Motivation
• Particulates emitted from diesel engines pose significant
health hazards
– lung cancer
– cardiovascular disease
– asthma
• Stricter particulate emissions regulations being
implemented worldwide
• While conventional passive and active particulate filters can
achieve desired particulate reductions, they:
– are expensive (Pt loading, control systems)
– reduce engine fuel economy (exhaust backpressure,
parasitics)
– require frequent maintenance
ASPEN PRODUCTS GROUP, INC.
 Objective & Technical Approach
To develop a precious metal-free passive DPF

Approach
• Wall flow filter comprising nano/microfibers that catalyze soot
oxidation
• Continuously oxidize trapped particulate
matter with oxygen present in exhaust Clean Exhaust Out

Cell Plug

at typical exhaust temperatures

Benefits
• reduced filtration system cost
• reduced operating cost
• increased PM capture efficiency Carbon
Dioxide

Catalytic Fiber
Exhaust In: Wall
Soot Soot
Hydrocarbons

ASPEN PRODUCTS GROUP, INC. Carbon Monoxide

Nano/Microfiber Filtration Efficiency
1

0.8
Filtration Efficiency

0.6

Fiber Diameter 95% Efficiency P

(m) (inWC)
0.4
0.2 0.9
1 2.3
0.2
5 6.0

0
0 2 4 6 8 10
Pressure Drop (inWC)

Depth filtration (no soot cake formation)

ASPEN PRODUCTS GROUP, INC.

 Fiber Preparation
• Metal oxide catalytic fibers prepared by wet chemical technique
• Precious metal-free catalyst formulations
• Mean fiber diameter controllable between 0.1 and 10 micron

0.1 m mean diameter 7.2 m mean diameter

ASPEN PRODUCTS GROUP, INC.

 Catalytic Fiber Stability

Fiber Diameter (m)

Treatment
Nanofiber Microfiber
600°C air 0.1 7.3
600°C simulated exhaust - 7.6
800°C air 0.1 -
900°C air - 5.3
1000°C air N/A -

Fibrous morphology maintained at moderately high temperatures

ASPEN PRODUCTS GROUP, INC.

 Catalytic Activity Screening
Evaluate catalyst activity by heating catalyst-soot mixture in air
• Printex U amorphous carbon (Evonik)
• 20:1 catalyst:soot ratio
• Ramp 2.5°C/min to 600°C
• Monitor CO and CO2 in effluent with NDIR

Determine:
• Onset temperature (10% of soot oxidized) and completion
temperature (90% of soot oxidized)
• CO2/(CO2+CO) ratio

ASPEN PRODUCTS GROUP, INC.

 Catalytic Soot Oxidation
1000

Uncatalyzed
Pt catalyst 96%
800
Mn catalyst
Fe catalyst 98%
CO + CO2 (ppm)

600 Co catalyst

400 41%

200

0
0 100 200 300 400 500 600
Temperature (°C)

• Soot oxidation temperature reduced by ~250°C

ASPEN PRODUCTS GROUP, INC.

 Nitric Oxide Effect
air 500 ppm NO/air
Composition
T10 (°C) T90 (°C) T10 (°C) T90 (°C)
no catalyst 471 583 440 581
Fe-based catalyst 309 432 245 362
Co-based catalyst 254 353 174 367

• No upstream NO oxidation catalyst

• NO significantly reduces soot light-off temperature
• NO does not affect temperature required for complete soot
elimination

ASPEN PRODUCTS GROUP, INC.

 Isothermal Catalytic Oxidation Rate
2.0E-06

1.5E-06 Nanofibers with

tight contact
Oxdiation Rate (g C/s)

1.0E-06

Nanofibers with
Microfibers with loose contact
5.0E-07 tight contact

0.0E+00
0.000 0.005 0.010 0.015 0.020 0.025 0.030
Soot Loading

• Complete soot oxidation achieved at 300°C

• Degree of soot-catalyst contact affects oxidation rate

ASPEN PRODUCTS GROUP, INC.

Predicted Catalytic Filtration Performance
Balance soot inflow, soot outflow, soot oxidation, and soot
accumulation

Vin·Cin – Vout·Cout = A·e-Ea/RT·n·SA··V + ·V·d/dt

Soot loading, , is predicted to remain below 0.01 gsoot/gcatalyst

under expected inflow conditions

ASPEN PRODUCTS GROUP, INC.

 Initial Filtration Testing
Bench-scale filter apparatus
• Jing miniCAST soot generator (quenched diffusion flame)
• Heated filter housing Vent
(startup/shutdown)

• Back-up HEPA filter

P ΔP ΔP

propane
nitrogen Soot Generator exhaust
air
back-up
TC HEPA filter
heater TC TC
back
SO2/N2, NOx/N2 gas filter ceramic
face
heater

Measure temperature, pressure drop, exhaust constituents

Typical conditions:
• Flow velocity 0.03 m/s (STP)
• 40 mg/m3 soot, 12% O2, 2% COx

ASPEN PRODUCTS GROUP, INC.

 Catalytic Filtration Performance
500 10

400 8

Pressure Drop (inWC)

Temperature (°C)

300 6

200 4

100 2

0 0
0 50 100 150 200 250 300 350 400
Time (min)

• No measurable particulates downstream of filter

• Balance point temperature of ~350°C

ASPEN PRODUCTS GROUP, INC.

 Catalytic Filter Scale-Up
High geometric surface area wall flow filter
• Coat catalytic fibers onto existing wall flow filter substrate (low
pressure drop, low-cost)
• Form catalytic fibers into self-supporting media

Catalyst may also be used to enhance performance of flow

through filters

ASPEN PRODUCTS GROUP, INC.

 Conclusions
Nano/microfiber catalytic soot filters offer potential for
improved DPF performance
• Complete soot oxidation at 300°C
• High filtration efficiency achieved at low pressure drop
• No precious metals
• No NOx/PM ratio requirement

Durability and engine-based performance need to be assessed

ASPEN PRODUCTS GROUP, INC.

 Acknowledgments
• National Science Foundation

This material is based upon work supported by the National Science

Foundation under Grant No. IIP-0750259.

Any opinions, findings, and conclusions or recommendations expressed in

this material are those of the author(s) and do not necessarily reflect the
views of the National Science Foundation.

ASPEN PRODUCTS GROUP, INC.