critical materials in catalysis: precious vs base metals...
TRANSCRIPT
Sept 29, 2011 1
Critical Materials in Catalysis:
Precious vs Base Metals in
Automotive Catalyst Systems
Christine Lambert Ford Research and Advanced Engineering
The Role of Chemical Sciences in Finding Alternatives to Critical
Resources Workshop
September 29th-30th, 2011
The National Academy of Sciences
Sept 29, 2011 2
Outline
• Overview of modern automotive catalysts
• Why Base Metals are not effective TWCs
• Where Base Metals do work
• Example of a Cu/zeolite catalyst system
• Other Base Metal catalyst research
• Summary
Sept 29, 2011 3
What are Automotive Catalysts?
http://www.umicore.com/en/cleanTechnologies/autocats/
Catalysts are used to reduce
the amount of regulated
pollutants from gasoline and
diesel vehicles:
• hydrocarbons (HC)
• carbon monoxide (CO)
• nitrogen oxides
(NOx = NO + NO2)
• particulate matter (PM)
N2, CO2 and H2O
Sept 29, 2011 4
Automotive Three-Way Catalyst “Staying in the Window”
Catalytic converter:
Typical operating conditions:
• 350 – 650 C (extremes: ambient to 1050 C)
• near-stoichiometric exhaust gas
• 60 – 300 ms contact time
Heck and Farrauto
Shelef and McCabe
<1% oxygen at stoichiometry
Sept 29, 2011 5
Modern Automotive TWC Electron microprobe view of washcoat (2000):
Typical catalyst composition (2000):
cordierite 70 wt%
-Al2O3 13
CeO2 6
ZrO2 4
La2O3/Nd2O3 3
BaO/SrO 2
NiO 1.5
Pt/Pd/Rh 0.5
Gandhi 2004
substrate
wall inner
layer
outer
layer
substrate
wall
substrate
wall
substrate
wall
Sept 29, 2011 6
What Are Precious Metals vs Base Metals?
Precious
Metals
Platinum Group Metals (PGM)
Transition
Metals
Base metals are non-precious,
i.e., oxidize or corrode easily.
www.wpclipart.com
Sept 29, 2011 7
PCV
System
Spark
Control,
PVS,
etc.
EGR
valves
Therm-
actor
Technologies Deployed to Meet
Increasing Stringent
Emission Standards
1960 1965 1970 1975 1980 1985 1990 1995 2000 2005
Oxidation
Catalysts,
some
electronics,
some
feedback
carb
(EEC I &
EEC II)
More
Electronics
(S/D)
More F/B
(EE III & V)
Pt/Rh TWC
Throttle
Body
Injection
Port
Injection
(S/D)
(EEC IV)
High-tech
TWC
Mass
Air
(EEC V)
Pd/Rh TWC
Pd-only TWC
Adv. Washcoat
Fore/Aft O2
sensor
OBD II
Adapt. fuel
Misfire
Detection
Sealed
Fuel Vapor
System
Zone-coat TWC
High cell density
TWC
NOx Trap
PTEC
Controller
Gandhi 2003/2004
• Base metals, Ag & Au: low activity and/or durability
• Ru, Ir, and Os: form volatile oxides
• Pt and Pd: suitable for oxidation catalysts
• Rh added for NOx control
• Oxygen storage components added (Ce)
• Stabilized alumina (Ba, La)
• Pd enabled by unleaded fuel
• Layers & metal segregation
• Stabilized cerium oxides
• More effective PGM use
Sept 29, 2011 8
Supply Chain for Automotive Catalysts
Partially derived from
Platinum 2011
Substrate
Manufacturers
Catalyst
Coaters Canners
Automotive
Assemblers
Catalytic
Promoter
Suppliers
Raw
Material
Suppliers
Customers
PGM
Market
“open loop”
recycled
PGM
PGM
mining
Jewelry Electrical Industrial
Catalysts
PGM
Refining PGM
Recycling
PGM
Recycling
Sept 29, 2011 9
PGM Supply and Demand
Platinum 2011
• Main use for Rh is autocatalysts
• Pt & Pd are also used in jewelry, industrial
catalysts, and investment
• Recently the demand for Pt and Pd is higher than
the supply
• Recycled PGM can help offset this deficit
Sept 29, 2011 10
PGM Price Volatility Pt, Pd, and Rh prices since 1992
• Catalyst design with PGM is made
more difficult by price volatility
• Metal type is kept varied to offer
several TWC design options, i.e.,
Pt/Rh vs Pd/Rh vs Pd only
• Base metals such as copper are
far less expensive
www.kitco.com
Sept 29, 2011 11
Base Metal TWC Research (1980 Assessment)
1) PGM less affected by sulfur <500C
2) PGMs have higher specific activity
3) PGM is more thermally resistant to loss of low temperature activity
Kummer, 1980
Sept 29, 2011 12
Base Metal TWC Performance Example of Cu TWC on Modern Gas Engine
• Cu and Cu/Cr tested in lab
and on engine
• 4wt%Cu/2wt%Cr provided
highest net NOx conversion
• A rich bias was required,
lowering fuel economy
• Copper catalysts must be
close-coupled to the engine
(hotter location) to avoid
sulfur poisoning and
increase activity
rich
bias
Theis, SAE 922251
Sept 29, 2011 13
Summary of 30+ Years of TWC • Base metals, Ag & Au not active or durable enough
• Ru, Ir, and Os all form volatile oxides
• Pt and Pd were left for the oxidation catalysts
• Rh added for NOx control
• Oxygen storage components added (Ce); later stabilized with Zr
• Stabilized alumina with Ba, La
• Pd/Rh and Pd-only options enabled by Pb-free fuel
• Cu and Cu/Cr retested on modern gas engine; found rich bias required and sulfur still an issue
Sept 29, 2011 14
Diesel Fraction of New U.S. Vehicle Sales
Year
1990 1995 2000 2005 2010
% D
iese
l M
ark
et
Sh
are
0.1
1
10
100
Cars
Class 1 + Class 2 trucks
Class 2b + Class 3 trucks
Class 2b trucks
Class 2b trucks (Ford+GM+Chrysler)
Class 3 trucks (Ford+GM+Chrysler)
Wallington et al., in review
Trucks
Class 1: < 6,000 lbs
Class 2: 6,001-10,000 lbs
Trucks
Class 3: 10,001-14,000 lbs
Class 2b: 8,501-10,000 lbs
Cars
Sept 29, 2011 15
A Brief History of U.S. Diesel Aftertreatment
Model Year
1990 1995 2000 2005 2010 2015
Em
issio
n s
tandard
s a
pplic
able
fo
r m
ediu
m-d
uty
die
sels
(g/[
bhp h
r])
0.01
0.1
1
10
NOx
PM
Evolution of emissions standards for NOx and PM.
• mid-1990s: Diesel oxidation catalysts (DOCs)
with ceria and alumina for PM oxidation
• 2007:
• ultra-low sulfur diesel,
• particulate filters for PM control
• high precious metal DOCs
• lean NOx control (NOx traps)
• 2010:
• lean NOx control (urea SCR)
Wallington et al., in review
Sept 29, 2011 16
An Example of U.S. Diesel Aftertreatment 2011 MY Ford Diesel Super Duty
Cu/zeolite Pd-rich Pt/Pd
Aqueous urea tank
(refilled at oil change)
HC + O2 CO2
CO + O2 CO2
NH3 + NOx N2 C + O2 CO2
media.ford.com
Sept 29, 2011 17
-700
-600
-500
-400
-300
-200
-100
0
100
200
300
400
500
600
700
0 200 400 600 800 1000 1200
Test Time (s)
Tem
pera
ture
(C
)
0
20
40
60
80
100
120
Veh
icle
sp
eed
(m
ph
)
Ford 2011MY Diesel (9500 lbs)
Ford 3.5L GTDI (5250 lbs)
Exhaust Gas Temperatures
λ = intake air / theoretical air req.
Chassis FTP-75 Cycle
Sept 29, 2011 18
Exhaust Gas Oxygen Content
-40
-30
-20
-10
0
10
20
30
40
50
0 200 400 600 800 1000 1200
Test Time (s)
Lam
bd
a
0
20
40
60
80
100
120
140
160
180
veh
icle
sp
eed
(m
ph
)
Ford 2011MY Diesel (9500 lbs)
Ford 3.5L GTDI (5250 lbs)
λ = intake air / theoretical air req.
Chassis FTP-75 Cycle
Sept 29, 2011 19
Diesel Lean NOx Control Options
• HC SCR using Pt
• Lean NOx Trap with Pt, Pd and Rh
• EtOH SCR using Ag
• Urea SCR with Cu/zeolite SAE 2004-01-1292
SAE 2005-01-1082
Sept 29, 2011 20
Basics of Urea SCR
• Urea is injected into the exhaust pipe upstream of the catalyst as an aqueous solution at 32.5 wt% (eutectic)
• Non-toxic, commodity chemical that forms ammonia
• Tradename in U.S. is “Diesel Exhaust Fluid” – DEF
• SCR needs oxygen for high conversions
H2N NH2
C
O
HNCO NH3+
CO2 NH3+H2O
heat
heat
urea decomposition:
NOx reduction:
4NO O2+ 4NH3 + 4N2 6H2O+
2NH3 NO NO2+ + 2N2 3H2O+
6NO2+ 8NH3 7N2 12H2O+
urea
Sept 29, 2011 21
SCR Catalyst Options
0
10
20
30
40
50
60
70
80
90
100
100 150 200 250 300 350 400 450 500 550 600 650
Inlet Gas Temperature (ºC)
Gro
ss
NO
x c
on
ve
rsio
n (
%)
Cu-Based SCR
Fe- Based SCR
Vanadium Based SCR
FTP US06
• Cu/zeolites are best
at low temperatures
• Fe/zeolites perform
well at high
temperatures
• Vanadium based
SCRs are not
appropriate for US
Diesels with Filters
SAE 2007-01-1575
Sept 29, 2011 22
What are Zeolites? • Zeolites are composed of aluminum oxide and silicon
oxide in a crystalline structure
• Some zeolites are found in nature but most are
synthesized for high purity
• Zeolites are in widespread use as water softeners,
absorbents, dessicants, oil refining
• Also called “molecular sieves” due to varying cage sizes
on the angstrom scale
Beta (BEA) Chabazite (CHA)
www.iza-structure.org/databases/
Sept 29, 2011 23
Small Pore Zeolites Enabled
Use of Cu Automotive Catalyst
• Cu/CHA development enabled Cu/zeolite for automotive use • Related patents and publications:
– Zones “Zeolite SSZ-13 and its method of preparation” US4544538, 1985
– Bull et al., “Copper CHA zeolite catalysts”, US7601662, 2009
– Kwak et al., “Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NOx with NH3”, J. Catal. 275 (2010) 187-190
– McEwen et al., “Integrated operando X-ray and DFT characterization of Cu-SSZ-13 exchange sites during the selective catalytic reduction of NOx with NH3”, Catal. Today, in press.
Schneider, CLEERS Telecon, Sept 2011
Chabazite (CHA)
www.iza-structure.org/databases/
Sept 29, 2011 24
A Few Challenges Faced During Commercial
Urea SCR System Development
• Stabilization of Pt
• Stabilization of Cu/zeolite
• HC poisoning/coking of Cu/zeolite
• Sulfur effects on Cu/zeolite
• Urea specifications and refill
Sept 29, 2011 25
Thermal Stability of DOC
0
0.2
0.4
0.6
0.8
1
100 150 200 250 300
Convers
ion E
ffic
iency
Temperature (Deg C)
HC Light-Off Conversion2-Mode 100 hrs / 300 ppm S + 20 mgP/gal
20:1
2:1
1:4
Pt only
0%
10%
20%
30%
40%
50%
150 200 250 300 350 400 450 500 550
% N
O2
of
To
tal N
Ox
Temperature (C)
NO2:NOx
Pt only20:1
2:1
1:4
• Addition of Pd to Pt has a
stabilizing effect for HC oxidation
during cold-start
• Pd also stabilizes Pt for NO
oxidation but has no inherent
activity itself
Sept 29, 2011 26
Precious Metal Poisoning of SCR
• Pt from upstream DOC can volatilize and interfere with SCR function
• Prime indicators are increased NH3 oxidation and N2O production
• Front section of catalyst most affected and can be regenerated
• Pt DOC may be stabilized with addition of Pd and lower exotherm Ts
EVALUATION of DYNAMOMETER
AGED FeSCR CATALYST
Lab flow reactor Pt poisoning of Cu
SCR by upstream DOC
-50
-25
0
25
50
75
100
100 150 200 250 300 350 400 450 500 550 600
Inlet Gas Temperature (ºC)
NO
x C
on
ve
rsio
n (
%)
Non - Contaminated
Contaminated
0
10
20
30
40
50
60
70
80
90
100
100 150 200 250 300 350 400 450 500 550 600
Catalyst Temperature (ºC)
NO
x C
on
ve
rsio
n (
%)
1st Inch (Inlet)
2nd Inch
3rd Inch
4th Inch
5th Inch
6th Inch (Outlet)
SAE 2008-01-2488
SAE 2009-01-0627
Sept 29, 2011 27
Thermal Stability of SCR Catalyst
• Thermal stability of
Cu/zeolite recently
improved from 750 to
900 C (Cu/beta
Cu/CHA)
• NO2 no longer needed for
low temp conversion
• Lower cost aftertreatment
now possible
SAE 2008-01-1025
4NH3 + 4NO + O2 4N2 + 6H2O
Sept 29, 2011 28
HC Poisoning/Coking of Zeolitic SCR
0
10
20
30
40
50
60
70
80
90
100
NO
x C
on
vers
ion
(%
)
0
2
4
6
8
10
12
14
16
18
20
Cu
mu
lati
ve H
Cs (
g/l
cata
lyst)
% NOx Conv.
Cum. HC's
Degreened
Activity
(250°C,
20% NO2
in feed)
Start HC
Addition
500°C,
10 min
Activity
Regained
End HC
Addition
SCR Catalyst Durability: HC
• HC poisoning is reversible after 500°C, lean
HC Inhibition HC Storage/Exotherm
Both issues were resolved by transition from Cu/beta to Cu/CHA
DEER 2004
Sept 29, 2011 29
Sulfur Effects on Cu/zeolite
0
10
20
30
40
50
60
70
80
90
100
150 200 250 300 350 400 450 500 550 600 650
Catalyst Temperature (°C)
NO
x c
on
vers
ion
(%
)
degreened
120k mi sulfated
after regen at 650°C
• Sulfur affects NOx activity below 300C
• Sulfur can be removed by lean filter regeneration conditions >650C
• Amount adsorbed between regens can be tolerated based on 15 ppm-
wt S in diesel fuel
Effect of 20ppm SO2 at 200°C
(Calculated miles based on 15ppm fuel sulfur)
0
10
20
30
40
50
60
70
80
90
100
160 180 200 220 240 260 280 300
Temperature(°C)%
NO
x C
on
vers
ion
0 miles
500miles
Effect of 120K mi at 15ppm fuel sulfur
DEER 2004
Sept 29, 2011 30
Urea Specifications and Refill
• OEMs and suppliers formed
USCAR working group to define
specifications
• Aqueous urea is sold as “Diesel
Exhaust Fluid” or “DEF”
• Current refill uses bottles, drums,
totes, and bulk dispensers
• ~ $2.79/gal in bulk
• ~ $4.65/gal in bottles http://www.dieselexhaustfluid.com/
Mattina, 16th Annual Fleet Fueling Conference, Sept
2010.
• Websites offer DEF locations
http://www.factsaboutscr.com
Sept 29, 2011 31
Diesel MDV Impact on Sustainability
Year
1995 2000 2005 2010 2015
CO
2 (
g/k
Wh)
at P
eak T
orq
ue
600
700
800
900
1000
Gasoline
Diesel
Comparison of Class 2b / Class 3 peak torque brake specific
CO2 for medium-duty vehicles 1998 - 2011 calendar years.
• Data from EPA HD database.
• Figure from Wallington, et al., in review.
• At light/moderate loads the CO2 advantage for SCR-equipped diesel will be > 10%.
Urea SCR
used on
majority of
diesels in
2010+.
Sept 29, 2011 32
0.00
5.00
10.00
15.00
20.00
25.00
2004 2005 2006 2007 2008 2009 2010 2011 2012
Pre
cio
us
Me
tal
Us
ag
e
Total PGM Pt Equiv
Diesel MDV Impact on Sustainability Precious Metal Usage on Ford Super Duty Trucks
2011MY J1
DOC+SCR+CDPF
2011MY J2
DOC+SCR+CDPF
DOC only
DOC +CDPF
2011MY
TWC
Increasing
Emission
Stringency
Pd-rich
Diesel-
Gasoline
PGM Gap
Sept 29, 2011 33
Potential Use of Base Metal Catalysts: Addition of SCR to TWC or LNT System
TWC+SCR
LNT+SCR
SAE 2009-01-0285
• SCR may enable lower PGM usage • SCR may be a key enabler for lean burn
Li et al., 2009
• Use of SCR depends on lean burn gasoline dev.& LD diesel usage
• Advanced lean aftertreatment depends on availability of low sulfur fuel
Sept 29, 2011 34
Potential Use of Base Metal Catalysts: NO NO2 Oxidation Function
Pd BMO DOCs Pt-free Perovskite LNTs
US2011/0165046
• Low temperature NO oxidation benefits lean NOx reduction.
• Base metals can replace a portion of the precious metals.
• Pd needed for HC oxidation
~ LaMnO3 (Qi, DEER 2010)
• PGM needed for HC and NOx reduction
Sept 29, 2011 35
Summary • TWC is limited to Pt, Pd and Rh after 30+ years of
research and development
• Diesel aftertreatment content has seen rapid growth in last 5 years from DOCs to filters to lean NOx control
• Pd-rich DOCs and Cu/zeolite lean NOx aftertreatment are now in production on medium duty diesel trucks
• Other potential uses of base metals are now in research stages and depend greatly on lean burn engine development
• The availability of lower sulfur fuel enables high efficiency lean NOx aftertreatment
Sept 29, 2011 36
Acknowledgements
• Jeff Hepburn, Robert McCabe, Douglas
Dobson, Carolyn Hubbard, Dominic
Dicicco, Tim Wallington, Kevin Guo (Ford)
• Martyn Twigg (retired Johnson Matthey)
Sept 29, 2011 37
References • Heck and Farrauto, Appl. Catal. A: Gen. 221 (2001) 443-457
• Shelef and McCabe, Catalysis Today 62 (2000) 35-50
• Gandhi and McCabe, ChemCon, Mumbai, 2004
• Gandhi, et al., Journal of Catalysis, Vol. 216, Issues 1-2, 2003, pp. 433-442
• www.wpclipart.com
• Platinum 2011, Johnson Matthey, May 2011
• www.kitco.com
• J.T. Kummer, Prog. Energy Combust. Sci. Vol. 6, pp. 177-199, 1980
• Theis and Labarge, SAE 922251
• media.ford.com
• T.J. Wallington, C.K. Lambert, W.C. Ruona, Energy Policy, in review
• Lambert et al., SAE 2004-01-1292
• Thomas et al., SAE 2005-01-1082
• Jen et al., SAE 2008-01-2488
• Cavataio et al., SAE 2009-01-0627
• Cavataio et al., SAE 2007-01-1575
• www.iza-structure.org/databases
• Cavataio et al., SAE 2008-01-1025
• Lambert et al., DEER 2004
• Xu et al., SAE 2009-01-0285
• W. Li et al., 12th CLEERS Workshop, 2009
• Drews et al., US 2011/0165046 A1
• Qi et al., DEER 2010 Conference