U.S. patent application number 12/953714 was filed with the patent office on 2012-05-24 for apparatus for removing mixed nitrogen oxides, carbon monoxide, hydrocarbons and diesel particulate matter from diesel engine exhaust streams at temperatures at or below 280 degrees c.
This patent application is currently assigned to AirFlow Catalyst Systems, Inc.. Invention is credited to Thomas A. Iacubucci, Thomas Richard Roberts.
Application Number | 20120124976 12/953714 |
Document ID | / |
Family ID | 46063020 |
Filed Date | 2012-05-24 |
United States Patent
Application |
20120124976 |
Kind Code |
A1 |
Roberts; Thomas Richard ; et
al. |
May 24, 2012 |
APPARATUS FOR REMOVING MIXED NITROGEN OXIDES, CARBON MONOXIDE,
HYDROCARBONS AND DIESEL PARTICULATE MATTER FROM DIESEL ENGINE
EXHAUST STREAMS AT TEMPERATURES AT OR BELOW 280 DEGREES C
Abstract
Disclosed is a catalytic unit that removes contaminates and
particulates, including nitrogen oxides and soot, from diesel
engine emissions without the use of chemical agents. The disclosed
apparatus comprises a flow through device in fluid communication
with a reduction unit, which is in fluid communication with a
diesel particulate filter. The flow through device is coated with
hematite and bixbyite in a ratio ranging from 1:1 to 9:1. The
reduction unit is a catalytic substrate comprising one or more
transition metals supported on a molecular sieve coated with an
oxide catalyst. The diesel particulate filter has an oxide coating
and a noble metal coating. The flow through device converts nitric
oxide into nitrogen dioxide. The reduction unit converts most of
the nitrogen dioxide into nitrogen, water, carbon monoxide and
carbon dioxide. The diesel particulate filter traps remaining soot
and coverts it and the carbon monoxide into carbon dioxide.
Inventors: |
Roberts; Thomas Richard;
(Rochester, NY) ; Iacubucci; Thomas A.;
(Brockport, NY) |
Assignee: |
AirFlow Catalyst Systems,
Inc.
Rochester
NY
|
Family ID: |
46063020 |
Appl. No.: |
12/953714 |
Filed: |
November 24, 2010 |
Current U.S.
Class: |
60/299 |
Current CPC
Class: |
B01D 2255/20738
20130101; B01D 53/9477 20130101; B01D 2255/2073 20130101; B01D
2255/20769 20130101; F01N 13/0097 20140603; B01D 53/944 20130101;
F01N 2370/04 20130101; Y02A 50/2341 20180101; B01D 2255/20761
20130101; F01N 3/035 20130101; F01N 3/2066 20130101; B01D 2255/106
20130101; B01J 23/8892 20130101; B01J 37/0215 20130101; B01D
53/9418 20130101; F01N 3/0231 20130101; B01D 2255/2092 20130101;
Y02T 10/12 20130101; B01D 2255/40 20130101; Y02T 10/24 20130101;
B01J 29/064 20130101; B01D 2255/50 20130101; B01D 2255/1021
20130101; B01D 2255/2065 20130101; B01D 2255/20746 20130101; B01D
2255/1023 20130101; F01N 2370/02 20130101; Y02A 50/20 20180101;
B01D 2255/104 20130101; B01D 2255/2094 20130101; B01D 2255/9155
20130101; F01N 2510/0684 20130101; B01D 2255/20715 20130101 |
Class at
Publication: |
60/299 |
International
Class: |
F01N 3/10 20060101
F01N003/10 |
Claims
1. An apparatus for removing contaminants and particulates,
including nitrogen oxides and soot, from diesel engine emissions,
comprising: a flow through device coated with a first catalyst
comprising hematite (Fe.sub.2O.sub.3) and bixbyite
((Mm.sub.1.5,Fe.sub.0.5)O.sub.3) wherein the ratio of hematite to
bixbyite ranges from 1:1 to 9:1; wherein said flow through device
is in fluid communication with an reduction unit comprising a
catalytic substrate coated with a second catalyst, said substrate
comprising one or more transition metals supported on a molecular
sieve and said second catalyst comprising one or more stabilizing
oxides coating the molecular sieve; wherein said reduction unit is
in fluid communication with a diesel particulate filter coated with
a first coating comprising tin oxide, aluminum oxide and zirconium
oxide and a second coating comprising gold, silver, palladium or
platinum.
2. An apparatus according to claim 1 wherein the second coating
comprises platinum.
3. An apparatus according to claim 2 wherein the molecular sieve is
zeolite.
4. An apparatus according to claim 2 wherein in the molecular sieve
is zeolite and the transition metal includes one or more of Cu, Co,
Fe, Ag and Mo.
5. An apparatus according to claim 2 wherein the molecular sieve is
zeolite and the transition metal is Cu.
6. An apparatus according to claim 2 wherein the molecular sieve is
zeolite and the transition metal is Fe.
7. An apparatus according to claim 2 wherein the transition metal
includes one or more of Cu, Co, Fe, Ag and Mo.
8. An apparatus according to claim 2 wherein the transition metal
is Cu.
9. An apparatus according to claim 2 wherein the transition metal
is Fe.
10. An apparatus according to claim 2 wherein the stabilizing oxide
is cerium oxide.
11. An apparatus according to claim 2 wherein the molecular sieve
is zeolite and the stabilizing oxide is cerium oxide.
12. An apparatus according to claim 2 wherein the molecular sieve
is zeolite, the transition metal includes on or more of Cu, Co, Fe,
Ag and Mo, and the stabilizing oxide is cerium oxide.
13. An apparatus according to claim 2 wherein the molecular sieve
is zeolite, the transition metal is Cu, and the stabilizing oxide
is cerium oxide.
14. An apparatus according to claim 2 wherein the molecular sieve
is zeolite, the transition metal is Fe and the stabilizing oxide is
cerium oxide.
15. An apparatus according to claim 1 wherein the molecular sieve
is zeolite.
16. An apparatus according to claim 15 wherein the transition metal
includes one or more of Cu, Co, Fe, Ag and Mo.
17. An apparatus according to claim 15 wherein the transition metal
is Cu.
18. An apparatus according to claim 15 wherein the transition metal
is Fe.
19. An apparatus according to claim 15 wherein the stabilizing
oxide is cerium oxide.
20. An apparatus according to claim 15 wherein the transition metal
includes one or more of Cu, Co, Fe, Ag and Mo and the stabilizing
oxide is cerium oxide.
21. An apparatus according to claim 15 wherein the transition metal
is Cu and the stabilizing oxide is cerium oxide.
22. An apparatus according to claim 15 wherein the transition metal
is Fe and the stabilizing oxide is cerium oxide.
23. An apparatus according to claim 1 wherein the transition metal
includes one or more of Cu, Co, Fe, Ag and Mo.
24. An apparatus according to claim 23 wherein the stabilizing
oxide is cerium oxide.
25. An apparatus according to claim 1 wherein the transition metal
is Cu.
26. An apparatus according to claim 1 wherein the transition metal
is Fe.
27. An apparatus according to claim 1 wherein the transition metal
is Cu and the stabilizing oxide is cerium oxide.
28. An apparatus according to claim 1 wherein the transition metal
is Fe and the stabilizing oxide is cerium oxide.
29. An apparatus according to claim 1 wherein the stabilizing oxide
is cerium oxide.
30. An apparatus for removing contaminants and particulates,
including nitrogen oxides and soot, from diesel engine emissions,
comprising: a flow through device coated with a first catalyst
comprising hematite (Fe.sub.2O.sub.3) and bixbyite
((Mn.sub.1.5,Fe.sub.0.5)O.sub.3), wherein the ratio of hematite to
bixbyite ranges from 1:1 to 9:1; wherein said flow through device
is in fluid communication with a reduction unit comprising a
catalytic substrate coated with a second catalyst, said substrate
comprising one or more transition metals supported on a molecular
sieve and said second catalyst comprising one or more stabilizing
oxides coating the molecular sieve.
31. An apparatus according to claim 30 wherein the molecular sieve
is zeolite.
32. An apparatus according to claim 31 wherein the transition metal
includes one or more of Cu, Co, Fe, Ag and Mo.
33. An apparatus according to claim 31 wherein the transition metal
includes one or more of Cu, Co, Fe, Ag and Mo and the stabilizing
oxide is cerium oxide.
34. An apparatus according to claim 31 wherein the transition metal
is Cu and the stabilizing oxide is cerium oxide.
35. An apparatus according to claim 31 wherein the transition metal
is Fe and the stabilizing oxide is cerium oxide.
36. An apparatus according to claim 31 wherein the stabilizing
oxide is cerium oxide.
37. An apparatus according to claim 31 wherein the transition metal
is Cu.
38. An apparatus according to claim 31 wherein the transition metal
is Fe.
39. An apparatus according to claim 30 wherein the transition metal
includes one or more of Cu, Co, Fe, Ag and Mo.
40. An apparatus according to claim 39 wherein the stabilizing
oxide is cerium oxide.
41. An apparatus according to claim 30 wherein the transition metal
is Cu.
42. An apparatus according to claim 30 wherein the transition metal
is Fe.
43. An apparatus according to claim 41 wherein the stabilizing
oxide is cerium oxide.
44. An apparatus according to claim 42 wherein the stabilizing
oxide is cerium oxide.
45. An apparatus according to claim 30 wherein the stabilizing
oxide is cerium oxide.
Description
[0001] This disclosure relates to the removal of contaminants and
particulates from exhaust gases generated by diesel engines. More
particularly, this disclosure relates to a passively-regenerated
diesel filter for the removal of several materials from diesel
exhaust gas at low temperatures, including carbon monoxide,
hydrocarbons, diesel particulate matter and various nitrogen
oxides, including nitrous oxide, nitric oxide, nitrogen sesquioxide
and nitrogen dioxide. This invention employs in situ catalytic
units in place of technology using ammonia or ammonia derived from
urea and does not require the application of liquid hydrocarbons or
gaseous hydrocarbons.
BACKGROUND OF THE INVENTION
[0002] The combustion of fossil fuels, such as gasoline or diesel
fuel, leads to the formation of harmful substances. Diesel engines,
in particular, produce four major emissions: nitrogen oxides (NOx),
diesel particulate matter (material suspended in the air in the
form of minute solid particles or liquid droplets), hydrocarbons
and carbon monoxide. Nitrogen oxides react with water to form
nitric acid (HNO.sub.3), which is a major contributor to acid rain.
Nitrogen oxides can also detrimentally react with ozone. The United
States and other jurisdictions have increasingly required NO.sub.X
emission reductions from stationary and mobile sources. Further,
these jurisdictions also regulate the emission of hydrocarbons.
[0003] The exhaust emitted from internal combustion engines needs
to be treated prior to being emitted in order to meet these
increasingly stringent exhaust emission standards. The removal of
various unwanted contaminants from diesel exhaust gas has required
increasingly complex technology. In the context of gasoline
engines, catalytic converters have become ubiquitous in the
industry to attempt to remove harmful materials from the exhaust.
For example, three-way catalysts have been developed to reduce
NO.sub.x in the rich-burn exhaust found in automobiles. These
catalysts, however, are not as effective in the lean-burn
conditions found in diesel vehicles. Further, abatement devices for
diesel engines present different problems than those for gasoline
engines because the formation of complex nitrogen gases, carbon
monoxide, raw hydrocarbons and soot is common in the operation of a
diesel engine.
[0004] Diesel particulate matter includes soot, which consists of
finely divided carbon and hydrocarbons. Soot is particularly
difficult to remove from diesel exhaust. A device known as a diesel
particulate filter (DPF) is one way to remove soot from a diesel
engine. These filters are made of a porous ceramic or metal
substrate that allows the exhaust gases to pass through the filter
but traps the small carbon particles. These filters, however, often
become clogged with the soot generated by the engine, causing a
potentially-harmful backpressure increase in the engine. Higher
backpressure creates a fuel economy penalty. High backpressure can
also cause an engine to stall or result in engine damage.
[0005] So-called active regeneration devices exist that use heat or
chemicals (or a combination of both) to remove soot from the
filter. Some of these devices operate by spraying raw diesel fuel
into the filter chamber and igniting the fuel and soot in situ.
This process, along with the presence of oxygen, ignites the soot
at a sufficiently high temperature (600.degree. C.) to convert it
into either carbon monoxide or carbon dioxide. This process
temporarily clears the filter. These devices require a backpressure
monitoring apparatus, a fuel injection system and instrumentation
to control the monitoring of the filter and the cleaning
system.
[0006] Some applications use off-board regeneration. That process,
however, requires operator intervention because the device must be
plugged into a wall/floor mounted regeneration station, or the
filter must be removed from the machine and placed in the
regeneration station. Off-board regeneration is generally not used
in connection with on-road vehicles, such as diesel vehicles,
except in situations where the vehicles are parked in a central
depot when not in use.
[0007] Passive regeneration can also be used to remove soot from
the filter. Passive regeneration occurs when the soot in the diesel
particulate filter spontaneously combusts during the engine's
normal work cycle. This combustion only occurs when the exhaust
temperatures are sufficiently hot, requiring high temperatures (as
high as 650.degree. C.). Certain techniques have been developed
that can lower the temperature required for passive regeneration,
including coating the surface of the substrate used in the filter
with noble metal catalysts such as platinum. This technique,
however, has the undesirable effect of increasing the emission of
nitrogen dioxide (NO.sub.2), a harmful gas. Further, these passive
regeneration devices also use large amounts of platinum or other
noble materials, driving up the cost.
[0008] The NO.sub.x series, including nitrous oxide (N.sub.2O),
nitric oxide (NO), nitrogen sesquioxide (N.sub.2O.sub.3) and
nitrogen dioxide (NO.sub.2), is also difficult to remove from
diesel exhaust. New technologies have been created to remove
NO.sub.X from exhaust streams. As noted above, three-way catalysts
have been developed to reduce NO.sub.X in the rich-burn exhaust
found in automobiles. These catalysts, however, are not as
effective in lean-burn conditions found in diesel vehicles. In the
oxygen-rich environment of diesel exhaust, chemically reducing NOx
to molecular nitrogen is difficult. This conversion of NO.sub.x in
the exhaust stream requires a reductant (HC, CO or H.sub.2) and,
under typical engine operating conditions, sufficient quantities of
reductant are not present to facilitate the conversion of NO.sub.x
to nitrogen.
[0009] For stationary sources, ammonia may be used to reduce
NO.sub.X. For example, urea ((NH.sub.2).sub.2CO.sub.2) is used to
convert NOx gases to N.sub.2 and H.sub.2O. This method of reducing
NO.sub.X is not preferred for mobile sources such as diesel
vehicles because of the toxic nature of ammonia and the storage
requirements. Further, the use of ammonia as a method of reducing
NO.sub.X is hampered by the lack of availability. Unlike with
regular gasoline or diesel fuel, there are few readily-available
commercial sources of refueling and disposal for ammonia-based
reductants. Further, these reactions occur at relatively high
temperatures and the materials are difficult to use because of
their corrosive nature and relatively high freezing point.
[0010] There are also systems which use diesel fuel which is dosed
onto the catalyst body in order to accomplish the selective
reduction of the NOx gases. As noted above, controlling NOx
emissions from a diesel engine is difficult because diesel engines
are designed to run lean. Some lean NOx catalyst systems inject
diesel fuel or another reductant into the exhaust upstream of the
catalyst. The fuel or other hydrocarbon reductant acts as a
reducing agent for the catalytic conversion of NOx to N.sub.2.
Typically, in these systems, a computer monitors one or more
sensors that measure backpressure and/or temperature, and the
computer makes decisions on when to activate the regeneration
cycle. The additional fuel is generally supplied by a metering
pump. Running the cycle too often while keeping the backpressure in
the exhaust system low uses extra fuel. Not running the
regeneration cycle soon enough increases the risk of engine damage
and/or uncontrolled regeneration (from an excess of accumulated
soot) and possible filter failure. Therefore, these methods are
complicated and significantly impact fuel efficiency.
[0011] Selective catalytic reduction (SCR) of NO.sub.X with
hydrocarbons has been used under lean-burn conditions such as those
found in diesel engines. Materials found to be catalytically active
for SCR include metal-exchanged zeolites, such as Cu-ZSM-5,
Co-ZSM-5 and Fe-ZSM-5. These zeolites are very active for SCR using
C.sub.3 hydrocarbons. These materials, however, lose much of their
activity when water is added to the exhaust stream, which is common
due to the presence of water in exhaust. Although the exact cause
of the loss of activity due to the introduction of water is
unknown, delumination of the zeolite framework may occur, reducing
the number of active sites, or the metal sites may over-oxidize and
lose their activity.
[0012] Marshall, et al., U.S. Pat. No. 7,220,692 (the "'692
Patent"), discloses a zeolite-based catalyst that demonstrates
increased stability in water. Disclosed are bifunctional catalysts
that combine active-metal exchanged molecular sieves with a
separate metal oxide stabilizing phase forming an oxide coating
thereon. The material is in essence a two-phased catalyst
comprising one or more transition metals supported on a molecular
sieve and one or more stabilizing oxides coating the sieve
material. The preferred embodiment of the material is a catalyst
composed of a zeolite-supported copper metal impregnated with a
ceria stabilizing oxide. The catalyst, however, can be comprised of
any number of zeolite materials including zeolite Y, zeolite Beta,
mordenite, ferrierite, ZSM-5 or ZSM-12.
[0013] The use of the material disclosed in the '692 Patent,
however, requires the use of organic reductants, primarily diesel
fuel. Therefore, the use of that zeolite-based catalyst requires
the use of additional fuel, reducing the fuel efficiency rating of
the vehicle in which it is used and creating additional
expense.
SUMMARY OF THE INVENTION
[0014] The present invention relates to a passively-regenerated
diesel filter for the removal of several materials from diesel
exhaust gas at low temperatures, including carbon monoxide,
hydrocarbons, diesel particulate matter and various nitrogen
oxides, including nitrous oxide, nitric oxide, nitrogen sesquioxide
and nitrogen dioxide. It is the object of this invention to provide
an in situ catalytic unit that does not require the use of chemical
agents such as ammonia or additional fuel as a reducing agent. It
is a further object of this invention to allow the removal of
contaminants and particulates from diesel exhaust gas at
temperatures typical in diesel engines (at or below 280.degree.
C.).
[0015] The disclosed invention is an apparatus for removing
contaminants and particulates, including nitrogen oxides and soot,
from diesel engine emissions. The preferred embodiment of this
apparatus comprises a flow through device in fluid communication
with a reduction unit, which is in turn in fluid communication with
a diesel particular filter. The flow through device is preferably
coated with a catalyst comprising hematite (Fe.sub.2O.sub.3) and
bixbyite ((Mn.sub.1.5,Fe.sub.0.5)O.sub.3) where the ratio of
hematite to bixbyite ranges from 1:1 to 9:1. The reduction unit
preferably comprises a catalytic substrate coated with a catalyst,
with the substrate comprising one or more transition metals
supported on a molecular sieve and the catalyst comprising one or
more stabilizing oxides coating the molecular sieve. The diesel
particulate filter is coated with a first coating comprising tin
oxide, aluminum oxide and zirconium oxide and a second coating
comprising platinum, palladium, silver or gold.
[0016] The flow through device and reduction unit may be used with
other filters. Another embodiment of the invention is an apparatus
for removing contaminants and particulates, including nitrogen
oxides and soot, from diesel engine emissions, comprising: a flow
through device coated with a catalyst comprising hematite
(Fe.sub.2O.sub.3) and bixbyite ((Mn.sub.1.5,Fe.sub.0.5)O.sub.3),
where the ratio of hematite to bixbyite ranges from 1:1 to 9:1. The
flow through device is in fluid communication with a reduction unit
comprising a catalytic substrate coated with a catalyst, with the
substrate comprising one or more transition metals supported on a
molecular sieve and the catalyst comprising one or more stabilizing
oxides coating the molecular sieve.
[0017] In the various embodiments of the invention, the second
coating for the diesel particulate filter may be comprised of
platinum. Further, the molecular sieve is preferably comprised of
zeolite. The transition metal coating for the catalytic substrate
may include one or more of Cu, Co, Fe, Ag or Mo or may be comprised
of copper or iron. The stabilizing oxide may preferably be cerium
oxide.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] The FIGURE depicts a preferred embodiment of the claimed
apparatus. Exhaust is generated by the engine 1 and flows into a
sealed container 2 housing the catalytic elements. The exhaust gas
first passes through the flow through device 3, through the
reduction unit 4, and then into the diesel particulate filter 5.
The treated exhaust gas is then emitted from the sealed contained
through an opening 6.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The present invention relates to an apparatus that removes
harmful pollutants from a diesel engine exhaust system at
relatively low temperatures (at or below 280.degree. C.). The
invention prevents the plugging of diesel particulate filters while
converting carbon monoxide (CO) to carbon dioxide (CO.sub.2),
nitrogen oxides (NOx) to nitrogen (N.sub.2) and passively
regenerating the soot trap portion of the device. Specific
catalysts in the flow through device alter the composition of the
exhaust gases so that the gases react with the carbon and
hydrocarbons formed in the diesel engine during combustion. The
reaction of the carbon and hydrocarbons in the reduction unit forms
carbon monoxide. After further reaction, gaseous carbon dioxide
forms, which no longer can plug the filter.
[0020] The disclosed invention is comprised of three different
elements contained in a single catalytic converter. The first
element converts nitric oxide (NO) into nitrogen dioxide
(NO.sub.2). The second element is an area where selective catalytic
reduction (SCR) occurs, converting most of the nitrogen oxide (NOx)
into nitrogen (N.sub.2), water (H.sub.2O), carbon monoxide (CO),
and carbon dioxide (CO.sub.2). The third element traps any
remaining soot and converts it to CO.sub.2 while simultaneously
converting CO into CO.sub.2.
[0021] The first element consists a device with a ceramic coating
comprised of hematite (Fe.sub.2O.sub.3) and bixbyite
((Mn.sub.1.5,Fe.sub.0.5)O.sub.3). The device oxidizes NO to
NO.sub.2, increasing the amount of NO.sub.2 by approximately 30 to
50%. The increased amount of NO.sub.2 flowing into the diesel
particulate filter allows more effective oxidation of the soot. The
coating for the substrate comprises hematite (Fe.sub.2O.sub.3) and
bixbyite ((Mn.sub.1.5,Fe.sub.0.5)O.sub.3), with a ratio of hematite
to bixbyite ranging from 1:1 to 9:1.
[0022] The second element has a reduction unit comprising a
catalytic substrate coated with a specially prepared zeolite-based
catalyst. The nitrogen dioxide-enhanced exhaust flows through this
unit and is converted into nitrogen, water, carbon monoxide and
carbon dioxide. The remaining NO.sub.x is partially reduced to
N.sub.2 and the soot is converted to water vapor, CO and CO.sub.2.
The coating is in essence a two-phased catalyst comprising one or
more transition metals supported on a molecular sieve and one or
more stabilizing oxides coating the sieve material. A preferred
embodiment of this coating is a catalyst composed of a
zeolite-supported copper metal impregnated with a ceria stabilizing
oxide. Another preferred embodiment of this coating is a catalyst
composed of a zeolite-supported iron metal impregnated with a
stabilizing oxide.
[0023] The zeolite coating material is blended with a tin oxide
catalyst. This material is described in Summers et al., U.S. Pat.
No. 7,056,856 (the "'856 Patent), which describes a tin oxide
catalyst employing precious metals. The material is a three-way
tin-oxide based catalytic material that is stable at exhaust gas
temperatures of internal combustion engines when the tin oxide
lattice includes hafnium and/or any of several rare earth oxide
components in the lanthanide series, such as oxides of La, Pr and
Nd. The rare earth oxides replace or supplement the transition
metal oxide promoters in prior art tin oxide catalysts. This
replacement or supplementation provides a high degree of thermal
stability as measured by the Brunauer/Emmett/Teller (BET) surface
area in the range of temperatures required for automotive uses.
[0024] The third element is a diesel particulate filter (DPF)
coated with a ceramic composition comprising, among other things,
tin oxide, aluminum oxide and zirconium oxide. This element acts to
trap any remaining soot and convert the remaining by-products to
N.sub.2, CO.sub.2 and water vapor. After the filter is coated with
the ceramic composition, a coating of platinum is precipitated onto
the filter. Again, this process occurs at a temperature lower than
280.degree. C. The lower temperature removal of soot is beneficial
because it occurs at normal exhaust temperatures. Further, the
increased NO.sub.2 generation from the preceding elements within
the device decreases the amount of platinum required in the filter,
lowering the cost of the soot removal apparatus.
[0025] A preferred embodiment of the apparatus includes a flow
through device in fluid communication with an reduction unit, which
is in turn in fluid communication with a catalyzed diesel
particulate filter. Preferably, the flow through device, reduction
unit and the diesel particulate filter will be placed in a sealed
container, such as one made of stainless steel or other suitable
material, to prevent the escape of gases. The diesel exhaust is
received by the flow through device and passes through the device
and the reduction unit, and into the filter before being emitted
into the atmosphere.
[0026] The flow through device may be made from cordierite,
stainless steel, or a primarily nonferrous metal. Alternatively,
the flow through device may be made from a ceramic material or any
other material common to use in the art. The substrate is coated
with an oxide formulation of hematite (Fe.sub.2O.sub.3) and
bixbyite ((Mn.sub.1.5,Fe.sub.0.5)O.sub.3), wherein the ratio of
hematite to bixbyite ranges from 1:1 to 1:9. The optimum ratio of
hematite to bixbyite for low temperature removal of soot is about
1:7, where the NO.sub.2 formation increases by up to 50% at
temperatures lower than 100.degree. C. Ratios from 4:1 to 9:1 also
increase NO.sub.2 formation at temperatures lower than 100.degree.
C. This material is disclosed in a pending patent application which
is incorporated by reference.
[0027] In one preferred embodiment, the substrate is coated using
solution made from a ferric salt and a manganese salt prepared by
the coprecipitation method. The substrate is coated immediately
after the ferric salt and manganese salt are combined. The coated
substrate is dried and calcinated at 500.degree. C. for two hours.
During the drying, the coating undergoes a shrinkage process which
causes micro-cracks to form in the surface, increasing the surface
area of the coating. The heating, among other things, stabilizes
the oxidation state of the composition and bonds the individual
grains to the surface of the substrate. Crystallographic changes
also occur during the heating process, where the small precipitates
become crystals, further increasing the surface area. Thereafter,
the material goes through a shrinkage process during the heating
due to water loss and sintering. It is understood that the coating
may be prepared in any other manner that creates the correct
proportion of hematite and bixbyite and results in a thin layer of
the coating covering the surface of the substrate.
[0028] The second element of the device is a reduction unit in
fluid communication with the flow through device. In the preferred
embodiment of the invention, this element converts between 20% and
99% of the NO.sub.x into N.sub.2. The reduction unit is made by
coating a suitable substrate (consisting of ceramic material, metal
or porous metal foam) with a cerium-copper zeolite material which
has been specially prepared for coating. Marshall, et al., U.S.
Pat. No. 7,220,692 (the "'692 Patent"), discloses a zeolite-based
catalyst that combines active-metal exchanged molecular sieves with
a separate metal oxide stabilizing phase forming an oxide coating
thereon. The catalyst is in essence a two-phased catalyst
comprising one or more transition metals supported on a molecular
sieve and one or more stabilizing oxides coating the sieve
material. Preferably, the catalyst is composed of a
zeolite-supported copper metal impregnated with a ceria stabilizing
oxide. The catalyst, however, can be comprised of any number of
zeolite materials including zeolite Y, zeolite Beta, mordenite,
ferrierite, ZSM-5 or ZSM-12. In addition, the catalyst may be
composed of a zeolite-supported iron metal impregnated with a
stabilizing oxide.
[0029] Any transition metal may be supported by the molecular
sieve, including the commonly-used transition metals copper,
cobalt, iron, silver, molybdenum, vanadium and combinations
thereof. The supporting oxides that coat the molecular sieve
material can be any one or more of the rare earth oxides such as
cerium oxide and transition metal oxides, such as zirconium oxide,
molybdenum oxide, vanadium oxide and niobium oxide. A preferred
embodiment consists of cerium oxide alone or in combination with
one or more of the other rare earth oxides. All of the preferred
oxides are added in the form of metal oxide sols.
[0030] The diesel particulate filter, which may be of any type
available for purchase, may be coated with a ceramic wash coat
comprised of tin oxide, aluminum oxide and zirconium oxide. In one
embodiment, the molar ratio of the tin oxide will be approximately
0.53, the molar ratio of the aluminum oxide will be approximately
0.14 and the molar ratio of the zirconium oxide will be
approximately 0.24. The coating may also additionally be composed
of silicon oxide and lanthanum oxide. The oxide of any rare earth
element of Group IIIA of the periodic table, including cerium,
praseodymium, neodymium, promethium, samarium, europium, thulium,
gadolinium, terbium, dysprosium, holmium, erbium, ytterbium and
lutetium, may be substituted for the lanthanum oxide. In another
embodiment, the molar ratio of the tin oxide is approximately 0.53,
the molar ratio of the aluminum oxide is approximately 0.14, the
molar ratio of the zirconium oxide is approximately 0.24, the molar
ratio of the silicon oxide is approximately 0.04 and the molar
ratio of the rare earth oxide is approximately 0.05.
[0031] Preferably, the aluminum oxide is gamma alumina coated with
silica. The remaining oxides may be added as salts and hydroxides
which are mixed into the alumina-silica mixture to make a fine
precipitate. Thereafter, the precipitate may be washed and dried,
and thereafter ground to an apparent particle size of approximately
0.1 and 0.9 micrometers prior to coating. The final coating, after
application and drying, will have an average particle size of 20 to
40 nanometers. A coating of platinum, gold, silver or palladium is
placed on the filter after the ceramic coating. Preferably,
platinum will be used and may be applied as a nitrate or a
tera-amine platinum nitrate. The platinum may be applied through
various methods, including submersion, waterfall coating, spraying
or any other recognized coating method. The preferred result of the
coating, regardless of the method, is a uniform nano-sized
dispersion of the platinum metal over the ceramic coating. Any
fairly uniform dispersion of the platinum within commercially
acceptable tolerances may be used, however. The percentage of
platinum may vary with the application and the system design,
ranging from approximately 0.5 grams per liter to 5.0 grams per
liter. The filter is then heat treated at 500.degree. C.
[0032] The invention removes soot from the diesel particulate
filter at low temperatures (at or less than 280.degree. C.). In one
of the preferred embodiments, the Group IIIA elements (including
lanthanum) oxidize CO and HC as well as carbon at low temperatures.
An oxygen removed from the NO.sub.2 combines with the carbon in the
filter to form CO and CO.sub.2. The catalysts in the ceramic
coating act as an environment to store the allotrope of oxygen so
that the reaction may occur at low temperatures. The flow through
device facilitates the operation of the filter because it increases
the NO.sub.2 flowing into the diesel particulate filter. Other
benefits of the disclosed apparatus exist or may be discovered.
[0033] Ideally, the apparatus would use the coated flow through
device, the reduction unit and the coated diesel particulate
filter. The flow through device and reduction unit, however, may be
used with other filters and may have applications other than those
stated.
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