U.S. patent application number 09/749650 was filed with the patent office on 2001-11-01 for sulfur trap in nox adsorber systems for enhanced sulfur resistance.
Invention is credited to Bailey, Owen, Dou, Danan, Molinier, Michel.
Application Number | 20010035006 09/749650 |
Document ID | / |
Family ID | 22654469 |
Filed Date | 2001-11-01 |
United States Patent
Application |
20010035006 |
Kind Code |
A1 |
Dou, Danan ; et al. |
November 1, 2001 |
Sulfur trap in NOx adsorber systems for enhanced sulfur
resistance
Abstract
An exhaust gas catalyst system, comprises: a sulfur trap warm-up
catalyst, housed within the exhaust stream and comprising: a sulfur
scavenger component; and a NO.sub.X adsorber catalyst, housed
within the exhaust stream downstream from said sulfur trap in an
underfloor position. The method of reducing sulfur poisoning of a
nitrogen oxide adsorber, housed within an exhaust gas catalyst
system, comprises: placing a sulfur trap within the exhaust stream
upstream from a NO.sub.X adsorber, wherein said sulfur trap
comprises: a sulfur scavenger component.
Inventors: |
Dou, Danan; (Tulsa, OK)
; Molinier, Michel; (Houston, TX) ; Bailey,
Owen; (Clarmore, OK) |
Correspondence
Address: |
Vincent A. Cichosz
DELPHI TECHNOLOGIES, INC.
1450 West Long Lake
Troy
MI
48007
US
|
Family ID: |
22654469 |
Appl. No.: |
09/749650 |
Filed: |
December 27, 2000 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60178927 |
Feb 1, 2000 |
|
|
|
Current U.S.
Class: |
60/274 ; 60/285;
60/301 |
Current CPC
Class: |
B01D 2255/204 20130101;
B01D 53/949 20130101; F01N 13/009 20140601; F01N 3/0878 20130101;
F01N 2610/03 20130101; F01N 3/0821 20130101; Y02A 50/20 20180101;
F01N 3/085 20130101; Y02A 50/2344 20180101; B01D 53/9422 20130101;
F01N 2570/14 20130101; Y02T 10/22 20130101; F01N 2570/04 20130101;
F01N 3/0807 20130101; B01D 2255/102 20130101; F02D 41/028 20130101;
F01N 3/0842 20130101; F01N 3/0871 20130101; B01D 53/945 20130101;
F01N 3/0814 20130101; Y02T 10/12 20130101 |
Class at
Publication: |
60/274 ; 60/285;
60/301 |
International
Class: |
F01N 003/00; F01N
003/10 |
Claims
1. An exhaust gas catalyst system, comprising: a sulfur trap
disposed within an exhaust stream, said sulfur trap comprising a
sulfur scavenger component; and a NO.sub.X adsorber catalyst
disposed within the exhaust stream, downstream from said sulfur
trap.
2. The exhaust gas catalyst system of claim 1, wherein said sulfur
scavenging component is an inorganic material having an affinity
for sulfur species such that said sulfur scavenging component traps
sulfur components within an exhaust stream flowing over said sulfur
scavenging component.
3. The exhaust gas catalyst system of claim 2, wherein said sulfur
scavenging component is a trapping element selected from the group
consisting of Ag, Al, Ba, Ce, Co, Cu, La, Li, Mg, Nd, Rb, Sn, Sr,
Zn, and mixtures and alloys comprising at least one of the
foregoing trapping elements.
4. The exhaust gas catalyst system of claim 1, wherein said sulfur
scavenging component is loaded on a porous support selected from
the group consisting of alumina, gamma-alumina, alpha-alumina,
zeolite, zirconia, ceria, magnesium oxide, titania, silica, and
mixtures comprising at least one of the foregoing supports.
5. The exhaust gas catalyst system of claim 1, further comprising
an oxidation catalyst.
6. The exhaust gas catalyst system of claim 5, wherein said
oxidation catalyst is selected from the group consisting of
platinum, palladium, rhodium, and mixture s comprising at least one
of the foregoing catalysts.
7. The exhaust gas catalyst system of claim 1, further comprising a
lean NO.sub.X catalyst.
8. The exhaust gas catalyst system of claim 7, wherein said lean
NO.sub.X catalyst comprises: a support selected from the group
consisting of Al.sub.2O.sub.3, SiO.sub.2, ZrO.sub.2, CeO.sub.2,
La.sub.2O.sub.3, TiO.sub.2, and mixtures comprising at least one of
the foregoing supports; one or more zeolitic materials; and one or
more precious metals.
9. The exhaust gas catalyst system of claim 1, further comprising a
three-way catalyst positioned downstream of the NO.sub.X adsorber
or within the NO.sub.X adsorber washcoat.
10. The exhaust gas catalyst system of claim 1, further comprising
a particulate filter, housed in an underfloor position, upstream of
said NO.sub.X adsorber.
11. The exhaust gas catalyst system of claim 1, further comprising
a sulfur trap bypass valve for spraying injected fuel directly in
front of said NO.sub.X adsorber.
12. The exhaust gas catalyst system of claim 11, further comprising
a particulate filter, housed in an underfloor position, upstream of
said NO.sub.X adsorber.
13. The exhaust gas catalyst system of claim 1, further comprising
a three-way valve, between the sulfur trap and the NO.sub.X
adsorber, for diverting a short, rich exhaust period around said
NO.sub.X adsorber catalyst.
14. The exhaust gas catalyst system of claim 13, further comprising
a particulate filter, housed in an underfloor position, upstream of
said NO.sub.X adsorber.
15. The exhaust gas catalyst system of claim 1, wherein said sulfur
trap is housed in a close-coupled position relative to an internal
combustion engine.
16. A method of reducing sulfur poisoning of a nitrogen oxide
adsorber, housed within an exhaust gas catalyst system, comprising:
placing a sulfur trap within the exhaust stream upstream from a
NO.sub.X adsorber, housed in an underfloor position, wherein said
sulfur trap comprises: a sulfur scavenger component; removing
sulfur species from said exhaust stream into said sulfur trap
according to the sulfur affinity of said sulfur scavenger
component; and directing the resulting exhaust stream, having a
reduced sulfur species concentration, to said NO.sub.X
adsorber.
17. The method of claim 16, wherein said sulfur scavenging
component is an inorganic material having an affinity for sulfur
species such that said sulfur scavenging component traps sulfur
components within an exhaust stream flowing over said sulfur
scavenging component.
18. The method of claim 17, wherein said sulfur scavenging
component comprises a trapping element selected from the group
consisting of Ag, Al, Ba, Ce, Co, Cu, La, Li, Mg, Nd, Rb, Sn, Sr,
Zn, and mixtures and alloys comprising at least one of the
foregoing trapping elements.
19. The method of claim 16, wherein said sulfur scavenging
component is loaded on a porous support selected from the group
consisting of alumina, gamma-alumina, alpha-alumina, zeolite,
zirconia, ceria, magnesium oxide, titania, silica, and a mixture
comprising at least one of the foregoing supports.
20. The method of claim 16, wherein said sulfur trap further
comprises an oxidation catalyst.
21. The method of claim 20, wherein said oxidation catalyst is
selected from the group consisting of platinum, palladium, rhodium,
and mixtures and alloys comprising at least one of the foregoing
catalysts.
22. The method of claim 16, wherein said sulfur trap further
comprises a lean NO.sub.X catalyst.
23. The method of claim 22, wherein said lean NOx catalyst
comprises: a support selected from the group consisting of
Al.sub.2O.sub.3, SiO.sub.2, ZrO.sub.2, CeO.sub.2, La.sub.2O.sub.3,
TiO.sub.2, and mixtures comprising at least one of the foregoing
supports; one or more zeolitic materials; and one or more precious
metals.
24. The method of claim 16, wherein the exhaust gas catalyst system
further comprises a three-way catalyst positioned downstream of the
nitrogen oxide adsorber or within the NO.sub.X adsorber
washcoat.
25. The method of claim 16, further comprising spraying injected
fuel directly in front of said NO.sub.X adsorber via a bypass valve
such that oxygen is consumed on said NO.sub.X adsorber prior to
exposure to a sulfur rich pulse.
26. The method of claim 25, further comprising filtering
particulate materials from said exhaust stream via a particulate
trap, housed between the sulfur trap and the NO.sub.X adsorber.
27. The method of claim 26, wherein spraying fuel directly in front
of said NO.sub.X via said bypass valve occurs during regeneration
of said particulate trap.
28. The method of claim 16, further comprising diverting a short,
fuel-rich exhaust pulse around said NO.sub.X adsorber catalyst via
a three-way valve, located between the sulfur scavenging component
and said NO.sub.X adsorber prior to exposure of said NO.sub.X
adsorber to a sulfur rich pulse.
29. The method of claim 28, further comprising filtering
particulate materials from said exhaust stream via a particulate
trap, housed between the sulfur trap and the NO.sub.X adsorber.
30. The method of claim 29, wherein diverting said exhaust gas
around said NO.sub.X adsorber by way of said three way valve to
said NO.sub.X adsorber occurs immediately prior to regeneration of
said particulate trap or of said sulfur trap warm-up catalyst.
31. The method of claim 16, wherein said sulfur trap is housed in a
close-coupled position relative to an internal combustion engine.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of the Provisional
Application Ser. No. 60/178,927 filed Feb. 1, 2000, which is hereby
incorporated by reference.
TECHNICAL FIELD
[0002] The present disclosure relates to nitrogen oxide adsorption
materials used in exhaust systems of internal combustion
engines.
BACKGROUND
[0003] It is well known in the art to use catalyst compositions,
including those commonly referred to as three-way conversion
catalysts ("TWC catalysts") to treat the exhaust gases of internal
combustion engines. Such catalysts, containing precious metals like
platinum, palladium, and rhodium, have been found both to
successfully promote the oxidation of unburned hydrocarbons (HC)
and carbon monoxide (CO) and to promote the reduction of nitrogen
oxides (NO.sub.X) in exhaust gas, provided that the engine is
operated around stoichiometry balanced for combustion ("combustion
stoichiometry"; i.e., an air to fuel (A/F or .lambda.) ratio of
about 14.7 and 14.4, in the case of a gasoline engine).
[0004] Fuel economy and global carbon dioxide (CO.sub.2) emissions
have made it desirable to operate the engine under lean-burn
conditions, where the A/F ratio is somewhat greater than combustion
stoichiometry (i.e., greater than 14.7 and generally between 19 and
35), to realize a benefit in fuel economy. When lean-burn
conditions are employed, three way catalysts are efficient in
oxidizing the unburned hydrocarbons and carbon monoxides, but are
inefficient in the reduction of nitrogen oxides.
[0005] One approach for treating nitrogen oxides in exhaust gases
of engines operating under lean-burn conditions has been to
incorporate NO.sub.X adsorbers in exhaust lines along with
three-way catalysts. Conventional exhaust systems contemplate any
number of configurations, including for example, use of NO.sub.X
adsorbers in the same canister along with three-way catalysts or
use of a NO.sub.X adsorber in a separate can upstream of the
three-way catalyst, among others.
[0006] These adsorbers generally comprise a catalytic metal, such
as platinum, palladium and/or rhodium, in combination with an
alkali and/or alkaline earth element (hereinafter the "alkali
material"), loaded on a porous support such as alumina,
gamma-alumina, zirconia, alpha-alumina, cerium oxide (ceria), or
magnesium oxide. The catalytic material in the adsorber acts first
to oxidize NO to NO.sub.2. NO.sub.2 then reacts with the alkali and
alkaline earth materials to form stable nitrate salts. In a
stoichiometric or rich environment, the nitrate is
thermodynamically unstable, and the stored NO.sub.X is released for
catalysis, whereupon NO.sub.X is reduced to N.sub.2 gas.
[0007] For practical incorporation of the supported catalytic
materials into internal combustion engine exhaust systems, the
support will, itself, be deposited on a chemically stable and
thermally insulating substrate, or metallic substrate. Particularly
useful substrates include cordierite and mullite, among others. The
substrate may be of any size or shape, such as is required by the
physical dimensions of the designed exhaust system. Similarly, the
internal configuration of the substrate may be any known or
commonly employed configuration. Substrates are typically formed as
monolithic honeycomb structures, layered materials, or spun fibers,
among other configurations.
[0008] U.S. Pat. No. 5,727,385 to Hepburn, which is herein
incorporated by reference, discloses a NO.sub.X trap, comprising
(i) at least one precious metal selected from platinum and
palladium loaded on a porous support; and (ii) at least one alkali
or alkaline earth metal (a) loaded on a porous support or (b)
present as an oxide thereof. Hepburn optionally includes a
three-way catalyst located either between the two components or
after the NO.sub.X trap.
[0009] Although the NO.sub.X adsorbers remove the NO.sub.X from the
exhaust stream during lean burn conditions and/or low temperatures,
they are plagued with the problem of sulfur poisoning under such
conditions. Sulfur, a contaminant present in fuel, adsorbs onto the
NO.sub.X adsorber, reducing the sites available for trapping
NO.sub.X.
[0010] What is needed in the art is an exhaust gas catalyst system
having improved durability, as well as NO.sub.X and sulfur
management, over extended operating time.
SUMMARY
[0011] The above-described and other disadvantages of the prior art
are overcome by an exhaust gas catalyst system. The exhaust gas
catalyst system comprises: a sulfur trap disposed within an exhaust
stream, said sulfur trap comprising a sulfur scavenger component;
and a NO.sub.X adsorber catalyst disposed within the exhaust
stream, downstream from said sulfur trap.
[0012] The above-described and other features and advantages of the
present invention will be appreciated and understood by those
skilled in the art from the following detailed description,
drawings, and appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Referring now to the accompanying drawings, which are meant
to be exemplary, not limiting, and wherein like elements are
numbered alike in the several Figures, in which:
[0014] FIG. 1 is a graphic representation of sulfur concentration
vs. adsorption time, showing fresh sulfur adsorption of a sulfur
trap at 400.degree. C. and an A/F ratio of 20, with 100 ppm (parts
per million) sulfur dioxide (SO.sub.2). High sulfur adsorption
efficiency for the sulfur trap is established.
[0015] FIG. 2 is a graphic representation of sulfur concentration
vs. release time, showing fresh sulfur release from a sulfur trap
at 700.degree. C. and an A/F ratio of 13, following exposure to
sulfur as depicted in FIG. 1. High sulfur regenerability for the
sulfur trap is established.
[0016] FIG. 3 is a graphic representation of sulfur concentration
vs. adsorption time, showing sulfur adsorption of a fresh sulfur
trap as a function of temperature (200-700.degree. C. lines) at
high space velocity. High sulfur adsorption efficiency across a
wide temperature window for the sulfur trap is established.
[0017] FIGS. 4 and 5 shows graphic representations of sulfur
concentration vs. release time, showing sulfur release from a fresh
sulfur trap at 600.degree. C. (FIG. 4) and at 700.degree. C. (FIG.
5) with an A/F ratio of 13, 13.6 and 14 after adsorption with 100
ppm SO.sub.2 at 400.degree. C. for 40 minutes. Regenerability of
the sulfur trap is established.
[0018] FIGS. 6 and 7 shows graphic representations of sulfur
concentration vs. adsorption time at 400.degree. C. for 40 minutes
at an A/F ratio of 20 (FIG. 6) and sulfur concentration vs. release
time at 700.degree. C. for 10 minutes with an A/F ratio of 13,
(FIG. 7). Establishes good sulfur storage and good sulfur release
after repeated sulfur poisoning and regeneration.
[0019] FIG. 8 is a graphic representation of sulfur concentration
vs. adsorption time at 400.degree. C. for 40 minutes at an A/F
ratio of 20 (with 100 ppm SO.sub.2 in feed gas) of a fresh and two
aged warm-up catalysts, aged at 900.degree. C. and 950.degree. C.
for 16 hours in air and water.
[0020] FIG. 9 is a graphic representation of sulfur concentration
vs. adsorption time for fresh and aged sulfur trap warm-up
catalysts at different flow rates (SV=45,000 to 90,000 per hour).
High sulfur trap efficiency at modest flow rate for the fresh and
aged warm-up catalysts is established.
[0021] FIG. 10 is a graphic representation of sulfur concentration
vs. release time, showing sulfur release at 700.degree. C. and
.lambda. of 13 from a fresh and two thermally aged sulfur traps
after sulfur adsorption at 400.degree. C. for 40 minutes and an A/F
ratio of 20 with 100 ppm SO.sub.2.
[0022] FIG. 11 is a graphic representation of NO.sub.X adsorption
performance of the sulfur trap at 300.degree. C. vs. adsorption
time, showing NO.sub.X adsorption of fresh and aged (at 900.degree.
C. or 950.degree. C.) sulfur trap warm up catalyst. Establishes
that the sulfur trap provides a modest NO.sub.X trapping
function.
[0023] FIG. 12 is a graphic representation of NO.sub.X conversion
percentage vs. evaluation temperatures, showing NO.sub.X
conversions of fresh and aged (at 900.degree. C. or 950.degree. C.)
sulfur trap at high SV. Establishes that the sulfur trap provides a
modest NO.sub.X conversion function.
[0024] FIG. 13 is a graphic representation of sulfur concentration
vs. release time at 700.degree. C., and at an A/F ratio 13, of an
aged (900.degree. C. in air) sulfur trap for palladium,
palladium/platinum, and palladium/ platinum/rhodium precious group
metal loadings.
[0025] FIG. 14 is a graphic representation of NO.sub.X adsorption
percentage at 300.degree. C. of NO.sub.X adsorbers with and without
sulfur trap protection.
[0026] FIG. 15 is a graphic representation of NO.sub.X conversion
percentage at (30 seconds lean/2 seconds rich) of NO.sub.X
adsorbers with and without sulfur trap protection.
[0027] FIG. 16 shows a simple scheme for an exhaust gas catalyst
system, comprising a sulfur trap, located in close coupled position
with an internal combustion engine, and a NO.sub.X adsorber, placed
in underfloor position.
[0028] FIG. 17 shows a more complex scheme for an exhaust gas
catalyst system in a diesel engine, further comprising a
particulate trap.
[0029] FIG. 18 is a graphical illustration of transmittance of
sulfur through a NO.sub.X adsorber during continuous
regeneration.
[0030] FIG. 19 is a bar graph illustrating that after severe aging
at 995.degree. C. maximum bed temperature for 100 hours, start up
catalysts with (lines 16,18,20) and without (lines 15,17,19) sulfur
scavengers have substantially equivalent light off performance.
[0031] FIGS. 20 and 21 are graphical illustrations showing lean
adsorption and rich release of sulfur from two platinum based
sulfur traps, wherein lines 21 and 30 represent temperature, while
lines 22 and 31 represent sulfur concentration. Clearly the second
formulation (FIG. 21) releases sulfur at 300.degree. C., and is
therefore suitable for a continuous regeneration strategy, while
the first formulation (FIG. 20) releases no sulfur at 300.degree.
C., and is thus suitable for a periodic regeneration strategy.
[0032] FIG. 22 is a graphical illustration of the rich and lean
adsorption of different sulfur species by a NO.sub.X adsorber; line
221 represents H.sub.2S at an A/F of 13, line 222 represents
SO.sub.2 at an A/F of 13, and line 223 represents SO.sub.2 at an
A/F of 20.
[0033] FIG. 23 is a graphical illustration of NO.sub.X adsorber
conversion efficiency after aging for 20 hours with no sulfur (line
232) or in the presence of H.sub.2S (line 233) or SO.sub.2 (line
231) in a rich environment (A/F is 13.2).
[0034] FIG. 24 is a graphical representation of the projection of
frequency of sulfur trap regeneration (periodic regeneration
strategy) as a function of ppm sulfur content in the fuel for two
different sulfur trap formulations, both platinum based.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0035] The exhaust gas catalyst system provides improved management
of NO.sub.X and sulfur components through incorporation of a sulfur
trap upstream from a NO.sub.X adsorber, the sulfur trap comprises a
sulfur scavenging component and optionally an oxidation catalyst
and/or a lean NO.sub.X catalyst.
[0036] Additionally, the nature of sulfur species released during
periodic regeneration, including hydrogen sulfide (H.sub.2S) or
sulfur dioxide (SO.sub.2), can be tuned depending on the materials
utilized to build the sulfur scavenging sulfur trap. The sulfur
trap comprises a sulfur scavenging component and optionally a
catalytic component (NO.sub.X and/or oxidation catalyst) comprising
one or more precious metals, e.g., an oxidation catalyst and/or a
NO.sub.X catalyst, disposed on a substrate. Parameters in selecting
sulfur scavenging components for the sulfur trap include the
temperatures at which these components release sulfur species and
the level of exhaust richness required to trigger such release.
These parameters may be adjusted to the particular exhaust design,
and materials selected, accordingly. The sulfur scavenging
component comprises trapping element(s) having a sufficient
affinity for sulfur to enable adsorption in a lean exhaust
environment (e.g., at an A/F ratio of about 17 and above) and
optionally, a support. Materials are also preferably selected on
their ability to release sulfur at relatively low temperatures
under rich exhaust conditions. Trapping elements including silver
(Ag), aluminum (Al), barium (Ba), cerium (Ce), cobalt (Co), copper
(Cu), lanthanum (La), lithium (Li), magnesium (Mg), sodium (Na),
neodymium (Nd), rubidium (Rb), tin (Sn), strontium (Sr), and zinc
(Zn), among others, as well as combinations and alloys comprising
at least one of the foregoing elements, have been found to be
optimally effective and are accordingly preferred. Combinations of
two or more elements are particularly preferred since such
combination provides a more balanced adsorption performance over
wider A/F ratio and temperature ranges.
[0037] The trapping element(s) may be applied to supporting
materials as is known in the art. Suitable support materials
include high surface area materials (e.g., a surface area of about
50 m.sup.2/g or greater), such as alumina (gamma-alumina, alpha
alumina, theta alumina, and the like), zeolite, zirconia, magnesium
oxide, titania, silica, and combinations comprising at least one of
the foregoing support materials, among others. Since ceria stores
oxygen in lean phases which translates to a fuel economy penalty
during lean to rich modulations where storage of O.sub.2 in lean
phase consumes additional reductants, ceria within the sulfur trap
catalyst should be minimized or eliminated. Desirably, the support
material has a surface area above about 300 square meters per gram
(m.sup.2/g).
[0038] There are no real upper limits for the amount of sulfur
scavenging and/or catalytic components that can or should be loaded
onto the support, except in as much as overloading of the support
material can cause undesirable backpressures and pressure drops
within the exhaust system. Similarly, there are no real lower
limits for the amount of sulfur scavenging and/or catalytic
components that can be loaded onto the support, it being recognized
that the effectiveness of the trapping elements increase as the
amount of the trapping elements loaded onto the support increases.
Exemplary sulfur scavenging components comprise barium in an amount
of up to about 1,480 grams per cubic foot (g/ft.sup.3); strontium
in an amount of up to about 940 g/ft.sup.3; and magnesium in an
amount of up to about 500 g/ft.sup.3. A particularly preferred
sulfur scavenging component designed to provide optimal amounts of
trapping elements while reducing backpressure, comprises a
combination of about 370 to about 740 g/ft.sup.3 barium, about 235
to about 375 g/ft.sup.3 strontium, and about 125 to about 250
g/ft.sup.3 magnesium.
[0039] For example, a sulfur trap composition could have a
catalytic component comprising up to about 95 wt % sulfur
scavenging component, up to about 25 wt % catalyst (NO.sub.X and/or
oxidation), and optionally up to about 40 wt % stabilizers,
disposed on a substrate; with about 40 wt % to about 90 wt % sulfur
scavenging component, about 2 wt % to about 20 wt % catalyst, and
about 2 wt % to about 40 wt % stabilizers preferred; and about 60
wt % to about 85 wt % sulfur scavenging component, about 3 wt % to
about 10 wt % catalyst, and about 5 wt % to about 30 wt %
stabilizers especially preferred; based upon the total weight of
the catalytic component. For example the catalytic component of the
sulfur trap could comprise about 40 wt % Ba, about 25 wt % Sr,
about 6 wt % Ce, about 6 wt % precious metals, and about 23 wt %
stabilizers. Alternatively, the catalytic component of the sulfur
trap could comprise about 50 wt % Ba, about 32 wt % Sr, about 7 wt
% precious metals, and about 11 wt % stabilizers.
[0040] To provide structural integrity to the sulfur trap the
support is, itself, carried on a high temperature, insulating
substrate. Particularly useful substrates, which are stable in high
temperatures (e.g., temperatures up to about 1,200.degree. C.),
include cordierite, mullite, and metal substrates, among others.
This substrate, which may be in any known or commonly employed
configuration, is typically formed as a monolithic honeycomb
structure, layered materials, or spun fibers, among other
configurations.
[0041] As mentioned above, the sulfur scavenging component obtained
may be utilized alone, or combined with precious metals, including
palladium, platinum, gold, rhodium, osmium, iridium, and ruthenium,
as well as combinations and alloys comprising at least one of the
foregoing metals. A preferred sulfur trap catalyst precious metal
(PM) loading comprises: up to about 60 g/ft.sup.3 platinum, up to
about 250 g/ft.sup.3 palladium, and up to about 30 g/ft.sup.3
rhodium. A particularly preferred sulfur trap catalyst has a PM
loading, designed for optimal performance, comprising: about 10 to
about 40 g/ft.sup.3 platinum, about 40 to about 100 g/ft.sup.3
palladium, and about 3 to about 10 g/ft.sup.3 rhodium.
[0042] Not to be bound by theory, platinum generally enhances
palladium-based light off functions by facilitating nitrogen oxide
(NO) to nitrogen dioxide (NO.sub.2) and sulfur dioxide (SO.sub.2)
to sulfite (SO.sub.3) oxidation, thereby improving both NO.sub.X
and sulfur oxides (SO.sub.X) trapping efficiencies. Rhodium,
located on the sulfur trap surface, enhances NO.sub.X reduction,
both at stoichiometry and during lean to rich modulations and also
promotes high steady state hydrocarbon conversions. Accordingly, a
tri-metallic formulation is preferred to provide effective storing
of NO.sub.X (to the extent that it occurs in the sulfur trap) and
SO.sub.X and for converting stored NO.sub.X during lean to rich
modulations.
[0043] Rhodium addition to platinum and palladium improves sulfur
release under rich conditions. Not to be limited by theory, this is
believed to be attributable to enhanced rates of steam reforming,
which results in the production of hydrogen (H.sub.2) gas; a very
effective constituent for NO.sub.X and sulfate reduction.
Consistent with this, the tri-metallic formulation is also found to
be more effective for the release of sulfur during high temperature
rich desulfation than palladium only and platinum/palladium
formulations of the same support architecture. FIG. 13 shows that
after high temperature aging (900.degree. C. in air), the
platinum-palladium-rhodium catalyst (line 121) has better sulfur
release at 700.degree. C. and A/F ratio 13, than the
platinum-palladium (line 122) and palladium (line 123)
catalysts.
[0044] The sulfur trap catalyst itself may be made out of the sole
sulfur scavenger component, or it may be made as a mixture (or
juxtaposition) of the sulfur scavenger component and either of an
oxidation catalyst or a lean NO.sub.X catalyst. Where either of the
oxidation catalyst or lean NO.sub.X catalyst accompanies the sulfur
scavenging component, the sulfur trap catalyst may be formed by any
conventional technique.
[0045] The one of three main production techniques are preferred.
First, all components can be mixed in the same washcoat and applied
to the substrate. Alternately, the sulfur scavenging component and
either of the oxidation catalyst or lean NO.sub.X catalyst can be
applied as separate layers (in any order) on the same catalyst
brick (monolith). As a third alternative, the components can be
banded onto a dual brick system, where the sulfur scavenging
component and either of the oxidation catalyst or lean NO.sub.X
catalyst can be applied to separate bricks or separate areas of one
brick.
[0046] These sulfur traps can be employed in various manners: (a)
sulfur trap close-coupled brick and NOx adsorber underfloor brick;
(b) sulfur trap close-coupled brick and a dual brick underfloor
arrangement with the first portion being a sulfur trap and the
second portion being a NOx adsorber; and (c) sulfur trap
close-coupled brick with a NOx adsorber underfloor brick with a
sulfur trapping function incorporated via the use of the sulfur
scavenging components.
[0047] Experimentally, the startup catalyst adsorbs sulfur with
nearly 100% efficiency at temperatures of about 200.degree. C. to
about 700.degree. C., whether fresh or after severe thermal aging
at about 700.degree. C. to about 950.degree. C. for 16 hours. The
following Figures detail experimental performance characteristics
for a sulfur trap catalyst, comprising approximately: 40 g/ft.sup.3
platinum, 80 g/ft.sup.3 palladium, 11 g/ft.sup.3 rhodium, 740
g/ft.sup.3 barium, and 472 g/ft.sup.3 strontium.
[0048] FIG. 1 shows fresh sulfur adsorption for a sulfur scavenging
component at 400.degree. C. and an A/F ratio of 20, with 100 ppm
(parts per million) SO with sulfur breakthrough, or unadsorbed
sulfur, measured in total sulfur mode, in which all species of
sulfur are analyzed. In contrast, FIG. 2 shows fresh sulfur release
for a sulfur scavenging component at 700.degree. C. and an A/F
ratio of 13. These Figures indicate a high sulfur adsorption and
release efficiency for the sulfur scavenging component.
[0049] FIG. 3 shows sulfur adsorption of a fresh sulfur scavenging
component at high space velocity as a function of temperature
(200-700.degree. C. (the line numbers correlate with the
temperatures in .degree. C.)). Sulfur breakthrough was measured in
total sulfur mode. A new sample was used in each adsorption test.
As can be seen in FIG. 3, the fresh sulfur scavenging component
shows high sulfur adsorption efficiency across a wide temperature
window for the sulfur scavenging component.
[0050] FIGS. 4 and 5 show sulfur release from a fresh sulfur
scavenging component at 600.degree. C. and at 700.degree. C.,
respectively, over three A/F ratios, 13 (lines 41, 51), 13.6 (lines
42, 52), and 14 (lines 43, 53), after adsorption with 100 ppm
SO.sub.2 at 400.degree. C. for 40 minutes. Temperature was ramped
up to 600.degree. C. or 700.degree. C. in nitrogen gas, whereupon
synthetic gas simulating exhaust, at the particular A/F ratio, was
switched online for 10 minutes. Sulfur emission was measured in
total sulfur mode. FIGS. 4 and 5 show that the sulfur scavenging
component is regenerable.
[0051] FIGS. 6 and 7 show sulfur adsorption of a fresh sulfur
scavenging component at 400.degree. C. at an A/F ratio of 20 and
100 ppm SO.sub.2 for 40 minutes (FIG. 6) and sulfur release of a
fresh sulfur scavenging component at 700.degree. C. at an A/F ratio
of 13 and 100 ppm SO.sub.2 for 10 minutes (FIG. 7). Sulfur
breakthrough was measured in total sulfur mode. FIGS. 6 and 7 show
good sulfur storage and release performance after repeated sulfur
poisoning and regeneration.
[0052] FIG. 8 shows sulfur adsorption at 400.degree. C. of a fresh
(line 73) and of two aged (900.degree. C. (line 72) and 950.degree.
C. (line 71) for 16 hours in air and water) sulfur trap catalysts
at an A/F ratio of 20 for 40 minutes (100 ppm SO.sub.2 in feed
gas). Good adsorption performance of fresh and aged sulfur
scavenging components is established.
[0053] FIG. 9 shows sulfur adsorption at 400.degree. C., A/F ratio
of 20 and 10 ppm SO.sub.2 for fresh (line 82) and 900.degree. C.
aged (lines 81 and 83) sulfur trap catalysts at different flow
rates, 45,000 (line 83 (1 inch (") by 1"))and 90,000 per hour (line
81 (1" by 0.5"); line 82 (1".times.0.5")). This figure indicating a
high sulfur trap efficiency at modest flow rate for both the fresh
and aged catalysts.
[0054] FIG. 10 shows sulfur release at 700.degree. C. and an A/F
ratio of 13 from a fresh (line 93) and two thermally aged
(900.degree. C., line 92 and 950.degree. C., line 91) sulfur
scavenging components after sulfur adsorption at 400.degree. C. at
an A/F ratio of 20, for 40 minutes with 100 ppm SO.sub.2.
Temperature was ramped up to 700.degree. C. under nitrogen gas,
whereupon rich gas was switched online for 10 minutes. Sulfur
emission was measured in total sulfur mode. FIG. 10 further
establishes that the thermally aged sulfur scavenging component is
regenerable.
[0055] As mentioned above, the sulfur scavenging component may
additionally possess some NO.sub.X adsorption and conversion
properties. FIG. 11 shows NO.sub.X adsorption of fresh (line 101)
and aged sulfur scavenging components (line 102 aged at 900.degree.
C. in air/H.sub.2O; line 103 aged at 950.degree. C. in
air/H.sub.2O) at high space velocity ("SV", which is the flow of
exhaust gas over the catalyst in one hour divided by the catalyst
volume) of 61,000 hr.sup.-1, showing that the sulfur scavenging
components provide a modest NO.sub.X trapping function. For the
sulfur scavenging component in FIG. 11, the component was aged at
900.degree. C. (line 102) or 950.degree. C. (line 103) in air and
water for 16 hours.
[0056] FIG. 12 shows NO.sub.X conversions of fresh (line 111) and
aged sulfur scavenging components (line 112 aged at 900.degree. C.
C in air/H.sub.2O; line 113 aged at 950.degree. C. C in
air/H.sub.2O; both for 16 hours) at high SV, showing that the
sulfur scavenging components provide a modest NO.sub.X conversion
function. For FIG. 12, NO.sub.X conversions were plotted at
different temperatures for fresh and aged sulfur scavenging
component at a SV of 61,000 per hour, with 500 ppm of NO.sub.X and
with 30 second to 2 second lean to rich modulations.
[0057] Experimentally, the sulfur trap exhibits light-off
performance equivalent to that of standard three-way catalysts of
comparable precious metal (PM) loading. The sulfur trap also
provides reasonable levels of NO.sub.X conversion and acceptable NO
to NO.sub.2 oxidation efficiencies even at high space velocities
(e.g., SV of up to about 60,000 hr.sup.-), such performance being
dependent on PM loadings, aging conditions, catalyst volumes, among
other parameters. Experimental values showed 8% NO to NO.sub.2
oxidation for fresh sulfur scavenging component and 1% NO to
NO.sub.2 oxidation for sulfur scavenging component aged at
900.degree. C. in air and water.
[0058] Because the sulfur trap is proximal to the engine, NO.sub.X
conversion over the sulfur trap catalyst occurs before the
temperature at the underfloor location is sufficient to fully
adsorb NO.sub.X species. As a result, overall system performance is
enhanced. Further, NO to NO.sub.2 oxidation over the sulfur trap
also improves NO.sub.X trapping efficiency on the downstream
NO.sub.X adsorber. The desulfation of this sulfur trap catalyst is
also facilitated when it is closely proximal to the engine
manifold, where it is exposed to higher average exhaust
temperatures, allowing at least partial sulfur regeneration under
modest driving conditions.
[0059] The NO.sub.X adsorber used in conjunction with the sulfur
trap may be any NO.sub.X adsorber as can be found in the prior art.
The NO.sub.X adsorber should comprise a catalyst capable of
catalyzing NO.sub.X under rich conditions and a material capable of
adsorbing NO.sub.X under lean conditions. Typically, the NOx
adsorber comprises catalyst, such as a precious metal, metal oxide,
alkali and/or alkaline earth metal, disposed on a support such as
alumina, titania, zirconia, ceria, lanthanum oxide, zeolite,
silica, magnesia or a combination comprising at least one of the
foregoing. An exemplary NO.sub.X adsorber is described in U.S. Pat.
No. 5,727,385 to Hepburn, which discloses a NO.sub.X adsorber,
comprising: (i) at least one precious metal selected from platinum
and palladium loaded on a porous support; and (ii) at least one
alkali or alkaline earth metal (a) loaded on a porous support or
(b) present as an oxide thereof.
[0060] In one embodiment, the sulfur trap is employed upstream of a
NO.sub.X adsorber located in an underfloor position in any type of
exhaust system, including diesel. Consequently, the NO.sub.X
adsorber is protected from sulfur poisoning in the first instance,
and purged of sulfur buildup when required.
[0061] The sulfur trap and NO.sub.X adsorber may simultaneously
adsorb, during lean phases, and release, during rich pulses, sulfur
species and NO.sub.X species, in which case the sulfur maintenance
strategy is referred to as continuous regeneration mode. FIG. 21
shows a sulfur trap component consistent with continuous
regeneration, i.e. capable of releasing sulfur at low temperature
(300.degree. C.).
[0062] However, a system whereby the sulfur scavenging component
would adsorb sulfur species for an extended period of time,
regardless of the A/F ratio, at low temperature (between about
200.degree. C. to about 500.degree. C.), and then release sulfur
during events specifically aimed towards sulfur trap regeneration
(for example, longer rich periods at temperatures of about
500.degree. C. to about 700.degree. C. or more), is preferred as is
supported by FIGS. 20, 22 and 23. FIG. 22, as well as FIG. 23, show
that in the rich mode, much less sulfur is adsorbed on a NO.sub.x
adsorber than in the lean mode. Essentially, if sulfur is trapped
upstream from a NO.sub.x adsorber in the lean mode, and then
released from the sulfur trap in the rich mode; since the NO.sub.x
adsorber has much less capacity for sulfur in the rich mode,
poisoning of the NO.sub.x adsorber will be less severe. In fact, as
is illustrated by the dashed lines in FIGS. 16 and 17, if the NOx
adsorber is bypassed during the rich releases of sulfur, poisoning
would be completely eliminated. The periodic strategy is preferred
to the continuous strategy because less sulfur releases mean less
opportunities for the sulfur to readsorb on the downstream NOx
adsorber and thus slower poisoning of the NOx adsorber.
[0063] With reference to FIG. 16, for example, the exhaust gas
system comprises a sulfur trap (3), located within the exhaust
stream and a NO.sub.X adsorber (4) downstream of the sulfur trap
(3), in an underfloor position. As discussed above, depending on
the application, the sulfur trap (3) can optionally be solely a
sulfur scavenger component, the combination of an oxidation
catalyst and a sulfur scavenging component or the admixture of a
lean NO.sub.X catalyst and sulfur scavenging component.
[0064] The sulfur scavenging component requires regenerations that
are achieved by rich excursions either in a continuous or in a
periodic way. The duration of the regenerations is depending on the
adopted maintenance strategy, and tuned to create both sufficient
richness and sufficient exotherm over the sulfur trap (3) to cause
sulfur release. Where the trapping efficiency of sulfur scavenging
components can be mapped, regeneration requirements can be
established on a time basis, or, optionally, a sensor can be
employed to determine when sulfur purges must be achieved. For
example, the sulfur trap is operated at temperatures up to about
600.degree. C. or so, and typically about 150.degree. C.
550.degree. C., with lean/rich modulations at appropriate intervals
to maintain the desired sulfur removal from the exhaust stream,
i.e., a continuous regeneration mode. Generally, the lean cycle is
up to about 300 seconds(s) or so, with about 10 to about 250
seconds preferred, and about 30 to about 240 seconds especially
preferred. Meanwhile, the rich cycle is up to about 15 seconds or
so, with up to about 10 seconds preferred, and about 1 to about 5
seconds especially preferred (see FIG. 18, illustration of a
continuous regeneration). Lean/rich modulations can be achieved via
an in cylinder fuel injection (2A) or via an in exhaust injection
(2B), as illustrated in FIG. 16 and 17.
[0065] The beneficial effects gained by inclusion of the sulfur
trap within an exhaust system may be seen by monitoring the
resulting improved NO.sub.X adsorption efficiencies and NO.sub.X
conversion efficiencies. Reference is made to FIGS. 14 and 15,
where each Figure shows improved adsorption and conversion
performance using the sulfur trap (lines 132 and 142, respectively)
relative to the performance of a NO.sub.X adsorber in an exhaust
system lacking the sulfur trap (lines 131 and 141, respectively).
NOx adsorption was measured at 300.degree. C., and adsorption and
conversion efficiencies were measured on NO.sub.X adsorbers after
30 hours of modulation aging with 10 ppm SO.sub.2 at 400.degree.
C.
[0066] Though the sulfur species expelled during regeneration
generally must travel through the NO.sub.X adsorber in the
underfloor position, such species only do so during higher
temperature phases and in a rich exhaust atmosphere. Sulfur
poisoning of the NO.sub.X adsorber is thus reduced over operating
time.
[0067] On the other hand, where the sulfur scavenging component is
not used, sulfur poisoning is far more detrimental, since sulfur
species are present in the exhaust stream during lean periods and
at lower temperatures. In light of this contrast, it is easily
recognized that by using the present invention, high efficiency
duration of a NO.sub.X adsorber in an underfloor position can be
considerably increased.
[0068] The exhaust gas catalyst system having high sulfur storage
capacity across a range of temperatures and A/F ratios, and
effective prevention of NO.sub.X adsorber sulfur poisoning while
providing additional catalytic components, will preferably be
located in a close coupled position. The sulfur trap provides high
sulfur protection maintained via periodic or continuous
regenerations, and good durability in trapping efficiencies despite
aging and regenerations along with multifunctional properties,
allowing for substantive performance in sulfur adsorption, warm-up
catalytic activity, and lean NO.sub.X catalysis. Further, as for
the NO.sub.X adsorber in an underfloor position, utilization of
sulfur protection significantly extends NO.sub.X adsorber
high-activity periods. Consequently, NO.sub.X adsorber
desulfurization is rarely required, translating to better fuel
economy.
[0069] The sulfur trap presented in FIG. 20, which is suitable for
a periodic regeneration strategy, can comprise, for example, any
sulfur scavenging components including, but not limited to, Ag, Zn,
Ce, Co, Ba, Mg, and the like, noble metals including, but not
limited to, Pd, Rh, and the like, and of support including alumina
and titania, and the like, as well as mixtures comprising at least
one of the foregoing materials. The sulfur trap presented in FIG.
21, which is suitable for continuous regeneration strategy, can
comprise, for example, any sulfur scavenging components including,
but not limited to, Ag, Zn, Ba, Sr, and the like, noble metal
catalysts including Pt, Pd, Rh, and support including alumina,
titania and zeolite, and the like, as well as mixtures comprising
at least one of the foregoing materials.
[0070] FIG. 24 is a projection of sulfur trap regeneration
frequency as a function of sulfur content in the fuel, in the case
of a periodic regeneration strategy (which incorporates average
speed, space velocities and similar assumptions). For the best
sulfur trap, at 10 ppm sulfur in the fuel, a regeneration of the
sulfur trap would be required about every 5,000 miles only. If the
NOx adsorber downstream from the sulfur trap survives 10
regenerations of the sulfur trap before it needs a desulfurization
itself, then the NOx adsorber desulfurization will be required
about every 50,000 miles, with NOx adsorber desulfurization
required whenever the NOx conversion ratio falls below the required
level (e.g., about 60%, 70%, 80%, or more, depending on the
application). On the other end, a calculation based similar
approximations shows that the current generation of NOx adsorber
would be completely deactivated (i.e., would provide 0% NOx
conversion), after 28,000 miles of driving with a fuel containing
10 ppm of sulfur.
[0071] Other advantages include the fact that the sulfur trap
functions at start-up, and functions to remove hydrocarbons and NOx
(due to the presence of the NOx and oxidation catalysts), thereby
substantially eliminating a light-off penalty. See FIG. 15 which
shows that after severe aging (e.g., an engine aging with a
sequence of 4 minutes at A/F 14 (rich), 8 minutes at A/F 14.56
(stoichiometric), 20 seconds at A/F 18.2) at 995.degree. C. for 100
hours, the light-off performance is not affected by the
incorporation of a sulfur trap.
[0072] While preferred embodiments have been shown and described,
various modifications and substitutions may be made thereto without
departing from the spirit and scope of the invention. Accordingly,
it is to be understood that the present invention has been
described by way of illustration and not limitation.
* * * * *