U.S. patent application number 16/702344 was filed with the patent office on 2020-04-02 for zirconia-based compositions for use in passive nox adsorber devices.
The applicant listed for this patent is Magnesium Elektron Limited, University of Kentucky Research Foundation. Invention is credited to Mark CROCKER, John G. DARAB, Deborah Jayne HARRIS, Yaying JI, David Alastair SCAPENS.
Application Number | 20200101436 16/702344 |
Document ID | / |
Family ID | 1000004509694 |
Filed Date | 2020-04-02 |
United States Patent
Application |
20200101436 |
Kind Code |
A1 |
HARRIS; Deborah Jayne ; et
al. |
April 2, 2020 |
ZIRCONIA-BASED COMPOSITIONS FOR USE IN PASSIVE NOx ADSORBER
DEVICES
Abstract
A passive NO.sub.X adsorbent includes: palladium, platinum or a
mixture thereof and a mixed or composite oxide including the
following elements in percentage by weight, expressed in terms of
oxide: 10-90% by weight zirconium and 0.1-50% by weight of least
one of the following: a transition metal or a lanthanide series
element other than Ce. Although the passive NO.sub.X adsorbent can
include Ce in an amount ranging from 0.1 to 20% by weight expressed
in terms of oxide, advantages are obtained particularly in the case
of low-Ce or a substantially Ce-free passive NOx adsorbent.
Inventors: |
HARRIS; Deborah Jayne;
(Manchester, GB) ; SCAPENS; David Alastair;
(Manchester, GB) ; DARAB; John G.; (Flemington,
NJ) ; CROCKER; Mark; (Georgetown, KY) ; JI;
Yaying; (Lexington, KY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Magnesium Elektron Limited
University of Kentucky Research Foundation |
Manchester
Lexington |
KY |
GB
US |
|
|
Family ID: |
1000004509694 |
Appl. No.: |
16/702344 |
Filed: |
December 3, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
15945770 |
Apr 5, 2018 |
10500562 |
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16702344 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01D 2257/404 20130101;
B01D 2253/1122 20130101; B01D 53/9481 20130101; B01J 20/3236
20130101; B01J 20/3214 20130101; B01D 53/04 20130101; B01J 20/0225
20130101; B01J 20/3204 20130101; B01D 53/9418 20130101; B01D
2253/25 20130101; B01J 20/06 20130101 |
International
Class: |
B01J 20/06 20060101
B01J020/06; B01J 20/02 20060101 B01J020/02; B01J 20/32 20060101
B01J020/32; B01D 53/94 20060101 B01D053/94; B01D 53/04 20060101
B01D053/04 |
Claims
1-20. (canceled)
21. A passive NOx adsorbent comprising: palladium, platinum or a
mixture thereof and a mixed or composite oxide comprising the
following elements in percentage by weight, expressed in terms of
oxide: 10-90% by weight zirconium; and 0.1-50% by weight of least
one of the following: a lanthanide series element other than Ce,
comprising Pr; and a transition metal comprising at least one of
the following metals selected from W, Mn, and Fe.
22. A passive NOx adsorbent according to claim 21 further
comprising at least one of Y, La and Nd as said lanthanide series
element other than Ce.
23. A passive NOx adsorbent according to claim 21, comprising Mn as
said transition metal in an amount of 0.1 to 20% by weight and Pr
as said lanthanide series element other than Ce in an amount of 0.5
to 30% by weight, wherein a total amount of Pr and Mn is not more
than 50% by weight.
24. A passive NOx adsorbent according to claim 23 further
comprising at least one of W and Fe as said transition metal.
25. A passive NOx adsorbent according to claim 23 further including
at least one of Y, La and Nd as said lanthanide series element
other than Ce.
26. A passive NOx adsorbent according to claim 23 further
comprising an element from Group 14 of the Periodic Table in an
amount ranging from 0.1 to 20% by weight expressed in terms of
oxide.
27. A passive NOx adsorbent according to claim 21 comprising Ce in
an amount ranging from 0.1% to not more than 20% by weight
expressed in terms of oxide.
28. A passive NOx adsorbent according to claim 21 comprising Ce in
an amount ranging from 0.5 to not more than 5% by weight expressed
in terms of oxide.
29. A passive NOx adsorbent according to claim 21 with the proviso
that the passive NOx adsorbent is substantially free of Ce.
30. A passive NOx adsorbent according to claim 21 with a minimum
fresh NOx storage capacity of 7.5 .mu.mol/g after 5 minutes at
120.degree. C.
31. A passive NOx adsorbent according to claim 21 with a minimum
aged NOx storage capacity of 5 .mu.mol/g after 5 minutes at
120.degree. C.
32. A passive NOx adsorbent according to claim 21 in which the
mixed or composite oxide includes Mn as said at least one
transition metal and optional Ce, with a minimum fresh NOx storage
capacity of at least 40 .mu.mol/g after 5 minutes at 120.degree.
C.
33. A passive NOx adsorbent according to claim 21 in which the
mixed or composite oxide includes Mn as said at least one
transition metal and optional Ce, with a minimum aged NOx storage
capacity of at least 19 .mu.mol/g after 5 minutes at 120.degree.
C.
34. A passive NOx adsorbent according to claim 21 in which the
mixed or composite oxide includes Mn as said at least one
transition metal, with a minimum fresh NOx storage capacity of at
least 50 .mu.mol/g after 5 minutes at 120.degree. C.
35. A passive NOx adsorbent according to claim 21 in which the
mixed or composite oxide includes Mn as said at least one
transition metal, with a minimum aged NOx storage capacity of at
least 45 .mu.mol/g after 5 minutes at 120.degree. C.
36. A monolithic substrate supporting a washcoat, said washcoat
comprising said passive NOx adsorbent according to claim 21.
37. A passive NOx adsorbent according to claim 21 in combination
with a Selective Catalytic Reduction catalyst.
38. A method for reducing nitrogen oxides (NOx) present in a lean
gas stream comprising at least one of nitric oxide (NO) and
nitrogen dioxide (NO.sub.2), comprising the steps of: (i) providing
the passive NOx adsorbent according to claim 21 in the lean gas
stream; (ii) adsorbing NOx from the lean gas stream on or in the
passive NOx adsorbent at a temperature below 200.degree. C.; (iii)
thermally net desorbing NOx from the passive NOx adsorbent in the
lean gas stream at 200.degree. C. and above; (iv) catalytically
reducing the NOx on a downstream catalyst situated downstream of
the passive NOx adsorbent, with at least one of the following
reductants: a nitrogenous reductant, a hydrocarbon reductant,
hydrogen and a mixture thereof.
39. A method according to claim 38 wherein the lean gas stream
emanates from a gasoline fueled or diesel fueled engine.
Description
TECHNICAL FIELD
[0001] This disclosure relates to treating gas streams so as to
remove nitrogen oxides (NOx) therefrom and in particular, to
passive NOx adsorbents (PNA) that store NOx at lower temperatures
and then release the NOx at higher temperatures.
TECHNICAL BACKGROUND
[0002] Urea-SCR (Selective Catalytic Reduction) is a well-known
solution for treating the NOx emissions from diesel engines, but
requires the exhaust temperatures to be above 200.degree. C. [1].
The heating rate on diesel engines/exhaust can be relatively slow,
and this results in a delay between switching the engine on and
being able to dose urea and effectively remove NOx by SCR
("cold-start" period). The NOx emissions during this cold start
period comprise a large portion of the total emissions during the
FTP-75 and NEDC test protocols for example, and this has
significant implications for real world driving.
[0003] In Europe, the legislated NOx limits for diesel vehicles
have been constantly falling since the introduction of the Euro
standard, and the current Euro VI limit is 0.080 g/km (September
2014).
[0004] One solution is to utilize a "passive NOx adsorbent" (PNA)
material upstream of the SCR catalyst, which is capable of storing
NOx below 200.degree. C. (i.e., during the cold start period) and
then releasing it above this temperature (i.e., once the SCR
catalyst is active).
[0005] Standard lean NOx trap materials (e.g.,
Pt/Ba/Al.sub.2O.sub.3) which require the oxidation of NO to
NO.sub.2 are useful at higher temperatures but do not tend to store
NOx efficiently below 150.degree. C. In this regard, an alternative
class of materials are necessary that are more active at lower
temperatures (from ambient up to 200.degree. C.).
[0006] In addition to the low temperature NOx storage capability,
PNA materials must also have suitable thermal stability. Depending
on the location (e.g., on DOC), it may experience temperatures up
to 800-850.degree. C. (hydrothermal) under high engine load
conditions. The PNA will always be upstream of the SCR catalyst but
may be downstream of a filter, which could be regenerated actively
or passively. Hence the PNA must maintain its low temperature
activity after such thermal excursions.
[0007] Further to these thermal stability demands, candidate PNA
materials should also be robust to the presence of
sulfur-containing species in the exhaust gas. This implies that the
materials have a relatively low propensity for adsorbing sulfur
species, but also tend to de-sulfate under suitable conditions
(e.g. preferably below 700.degree. C. in lean conditions).
[0008] U.S. Pat. No. 8,105,559 refers to the use of palladium on
ceria (Pd--CeO.sub.2) as an effective PNA candidate. NOx is
allegedly stored effectively at 120.degree. C., 160.degree. C. or
200.degree. C., and is allegedly desorbed almost immediately upon
ramping the temperature. However, no data is provided on the effect
of sulfur in the feed gas.
[0009] U.S. Pat. No. 8,920,756 refers to the use of an
Ag/Al.sub.2O.sub.3 component in combination with another material
to create a passive NOx adsorber system. The second material may
contain manganese, but only in combination with ceria, and this is
likely to be inherently sulfur-intolerant. In addition to this, the
function of the second component is to store NOx once the
temperature is above 190.degree. C. (NOx during the initial cold
start period being stored on the Ag/Al.sub.2O.sub.3 component).
[0010] U.S. Pat. No. 9,687,811 discusses the use of various
materials/combinations for use in the PNA application. Specific
mention is made of manganese, but this is used/added as a bulk
Mn.sub.3O.sub.4 component (i.e., not part of a solid solution)
which is expected to lead to poor thermal stability and low
sulfur-tolerance. Further to this, the Mn.sub.3O.sub.4 component is
always added in combination with a ceria component.
[0011] Zhao-shun Zhang and co-workers (Appl. Cat. B: Environmental,
165 (2015) 232-244) investigated the addition of manganese into a
model lean NOx trap (Pd/Ba/Al.sub.2O.sub.3). They demonstrated
enhanced NO oxidation activity but required temperatures above
300.degree. C. for efficient NOx storage.
[0012] Li-Hong Guo and co-workers (Catal. Today, June 2017) also
investigated model manganese oxide systems under more relevant NOx
storage conditions (i.e., <200.degree. C.) and found that NOx
could be stored effectively. However, although MnO.sub.2 had the
greatest NOx storage capacity, the strong adsorption of NOx meant
that desorption was more difficult, and Mn.sub.2O.sub.3 showed more
facile NOx release. So, when designing manganese-containing PNA
materials, one should consider the state of the Mn species and the
impact of other components of the mixed or composite oxide on this.
Oxidation of NO to NO.sub.2 is not always beneficial, with surface
nitrites being generally less stable than nitrates, and thus more
easily desorbed.
[0013] U.S. Patent application publication No. 2009/0191108 refers
to the use of praseodymia-zirconia mixed oxides (optionally
containing ceria) in NOx trapping applications for lean burning
internal combustion engines. Although the materials showed improved
sulfur-tolerance compared to Ba/Al.sub.2O.sub.3 reference (after
rich regeneration at 550.degree. C.), there is no low temperature
activity promoting element (such as a transition metal) and these
materials require temperatures of 200-300.degree. C. for suitable
NOx storage.
[0014] And finally, the palladium-on-zeolite system has received a
lot of attention for the PNA application, such as U.S. published
patent application No. 2012/0308439. Although efficient low
temperature NOx storage is observed, the palladium usage can be
quite high (>50 g/ft.sup.3) which has cost implications, and
these materials also tend to adsorb hydrocarbons which may or may
not be advantageous.
SUMMARY OF THE DISCLOSURE
[0015] This disclosure features a composition for a passive NOx
adsorbent comprising Zr-based mixed or composite-oxides. The
passive NOx adsorbent includes at least one of the following: a
transition metal (e.g., Mn, W, Fe) and a lanthanide series element
(e.g., Pr). In some instances structural promoters, for example, an
oxide of Y, La or Nd, may be used to improve the thermal durability
of Zr-based mixed or composite-oxides [Applied Catalysis, 1991;
Topics in Catalysis, July 2004].
[0016] The passive NOx adsorbents of this disclosure compensate for
a deficiency in performance of conventional catalysts in removing
NOx in gasoline and diesel engine exhaust from motor vehicles. The
passive NOx adsorbents herein are able to store or adsorb NOx from
the lean exhaust gas stream at lower temperatures (e.g., below
200.degree. C.) at a point when conventional catalysts do not
perform well. Then, above 200.degree. C. the passive NOx adsorbents
herein release or desorb the NOx at a point when the conventional
catalysts can perform well. For example, the passive NOx adsorbent
of the disclosure releases the NOx at temperatures above
200.degree. C. to a downstream and different SCR catalyst device
which reduces the NOx to nitrogen gas so as to satisfy stringent
NOx emission regulations for motor vehicles.
[0017] A first aspect of this disclosure features a passive
NO.sub.X adsorbent including: palladium, platinum or a mixture
thereof and a mixed or composite oxide. The mixed or composite
oxide includes the following composition: 10-90% by weight
zirconium and 0.1-50% by weight of at least one of the following: a
transition metal or a lanthanide series element other than Ce.
[0018] It should be appreciated that in the mixed or composite
oxides of this disclosure, for example, the recited weight
percentages of elements on an oxide basis are based on a total
weight of the mixed or composite oxide and when combined equal
100%. Further, use of "comprising" transitional claim language does
not exclude additional, unrecited elements or method steps.
Moreover, the disclosure also contemplates use of "consisting
essentially of" transitional claim language, which limits the scope
of the claim to the specified materials or steps and those that do
not materially affect the basic and novel characteristic(s) of the
claimed invention which include the function of the mixed or
composite oxide as a passive NOx adsorbent. When numerical ranges
are used, the range includes the endpoints unless otherwise
indicated.
[0019] Specific features of the first aspect of the disclosure will
now be described. The mixed or composite oxide can include at least
one of W, Mn and Fe as the transition metal. The transition
metal(s) can be present in an amount ranging from 0.1% to 20% by
weight of the mixed or composite oxide, on an oxide basis.
[0020] Particular mixed or composite oxides include the following:
Pr--Zr; Mn--Zr; W--Zr; and Mn--Pr--Zr; any of the foregoing
including Fe; and any of the foregoing including optional amounts
of Ce or being substantially free of Ce as discussed further in the
Summary of the Disclosure below.
[0021] In another feature, the mixed or composite oxide can include
at least one of Pr, Tb, or a mixture of Pr and Tb, as the
lanthanide series element other than Ce.
[0022] Yet another feature is that the mixed or composite oxide can
include Pr as the lanthanide series element other than Ce, and at
least one of the following metals selected from W, Mn, and Fe as
the transition metal.
[0023] A further feature is that the mixed or composite oxide can
include at least one of Y, La and Nd as the lanthanide series
element other than Ce, present in an amount of up to 20% by weight,
in particular, in an amount ranging from 0.5 to 20% by weight. In
the case of rare earth elements including at least one of Y, La,
Nd, when an amount greater than or equal to 0.5 wt % is recited,
this indicates that the element(s) are intentionally added.
[0024] Another feature is that the mixed or composite oxide can
include Pr and at least one of Y, La and Nd as the lanthanide
series element other than Ce in an amount ranging from 0.5% to 20%
by weight, and at least one of the following metals selected from
W, Mn, and Fe as the transition metal in an amount ranging from
0.1% to 20% by weight.
[0025] A further feature is that the mixed or composite oxide can
include an element from Group 14 of the Periodic Table (e.g., Si or
Sn) in an amount ranging from 0.1 to 20% by weight expressed in
terms of oxide.
[0026] Other features are that the mixed or composite oxide can
include Mn as the transition metal in an amount of 0.1 to 20% by
weight and Pr as the lanthanide series element other than Ce, in an
amount of 0.5 to 30% by weight, the total amount of Mn and Pr being
not more than 50% by weight. The following specific features may
apply to the above feature. In one feature, the mixed or composite
oxide can further include at least one of W and Fe as the
transition metal. In addition, the mixed or composite oxide can
further include at least one of Y, La and Nd as the lanthanide
series element other than Ce. Moreover, the mixed or composite
oxide can include an element from Group 14 of the Period Table
(e.g., Si or Sn) in an amount ranging from 0.1 to 20% by weight
expressed in terms of oxide.
[0027] The mixed or composite oxide of the passive NOx adsorbent
can include Ce in the following amounts: not more than 20% by
weight expressed in terms of oxide; in particular, in an amount
ranging from 0.1% to 20%; further ranging from 0.1 to less than 5%;
further still ranging from 0.5 to less than 5%; and in particular,
the passive NOx adsorbent can be substantially free of Ce.
[0028] The passive NOx adsorbent as a fresh material can have a
minimum NOx storage capacity of 7.5 .mu.mol/g after 5 minutes at
120.degree. C.
[0029] Further, the passive NOx adsorbent as an aged material can
have a minimum NOx storage capacity of 5 .mu.mol/g after 5 minutes
at 120.degree. C.
[0030] Another feature is a passive NOx adsorbent according to the
first aspect in which the mixed or composite oxide includes Mn as
the at least one transition metal and includes optional element X,
wherein when element X is present it is: at least one of Ce; or Pr
as the lanthanide series element other than Ce, with a minimum
fresh NOx storage capacity of at least 40 .mu.mol/g after 5 minutes
at 120.degree. C.
[0031] Yet another feature is a passive NOx adsorbent according to
the first aspect in which the mixed or composite oxide includes Mn
as the at least one transition metal and optional element X,
wherein when element X is present it is: at least one of Ce; or Pr
as the lanthanide series element other than Ce, with a minimum aged
NOx storage capacity of at least 19 .mu.mol/g after 5 minutes at
120.degree. C.
[0032] Another feature is a passive NOx adsorbent according to the
first aspect in which the mixed or composite oxide includes Mn as
the at least one transition metal and Pr as the lanthanide series
element other than Ce, with a minimum fresh NOx storage capacity of
at least 50 .mu.mol/g after 5 minutes at 120.degree. C.
[0033] Still further is featured a passive NOx adsorbent according
to the first aspect in which the mixed or composite oxide includes
Mn as the at least one transition metal and Pr as the lanthanide
series element other than Ce, with a minimum aged NOx storage
capacity of at least 45 .mu.mol/g after 5 minutes at 120.degree.
C.
[0034] Another feature is a monolithic substrate supporting a
washcoat, the washcoat comprising the passive NOx adsorbent of the
first aspect of the disclosure.
[0035] Further the passive NOx adsorbent of the first aspect of the
disclosure can be used in combination with a Selective Catalytic
Reduction catalyst.
[0036] A second aspect of the disclosure features a method for
reducing nitrogen oxides (NOx) present in a lean gas stream
including at least one of nitric oxide (NO) and nitrogen dioxide
(NO.sub.2), including the following steps. The passive NOx
adsorbent of the first aspect of the disclosure is provided in the
lean gas stream. NOx is adsorbed from the lean gas stream on or in
the passive NOx adsorbent at a temperature below 200.degree. C.
NO.sub.X is thermally net desorbed from the passive NOx adsorbent
in the lean gas stream at 200.degree. C. and above. The NO.sub.X is
catalytically reduced on a downstream catalyst situated downstream
of the passive NO.sub.X adsorbent, with at least one of the
following reductants: a nitrogenous reductant, a hydrocarbon
reductant, hydrogen and a mixture thereof.
[0037] In one specific feature of the second aspect the lean gas
stream emanates from a gasoline fueled or diesel fueled engine.
[0038] Many additional features, advantages and a fuller
understanding of the disclosure will be had from the Detailed
Description that follows. It should be understood that the above
Summary of the Disclosure describes the subject matter of the
disclosure in broad terms while the following Detailed Description
describes the subject matter of the disclosure more narrowly and
presents particular embodiments that should not be construed as
necessary limitations of the broad subject matter of the
disclosure.
DETAILED DESCRIPTION
[0039] Fresh Mn-zirconia passive NOx adsorbents and Mn--Pr-zirconia
passive NOx adsorbents exhibit NO.sub.X storage values after, for
example, 5 minutes at 120.degree. C. comparable to those of
analogous fresh materials containing Ce but drop off after 15
minutes at 120.degree. C. As known in the art, aging represents
expected behavior of a material after being in use for a period of
time. Looking at aged PNA materials, the Mn--Pr-zirconia passive
NOx adsorbent compositions of this disclosure exhibit NO.sub.X
storage values after all times up to 15 minutes at 120.degree. C.
comparable or considerably greater than those of the Ce-containing
analogues.
[0040] The term "passive NOx adsorbent (PNA)" as used in this
disclosure means an adsorbent disposed in a gas stream, which
stores NOx from the gas stream at temperatures up to 200.degree. C.
and releases the stored NOx into the gas stream at temperatures
greater than 200.degree. C. If an SCR catalyst is used, the PNA can
be located upstream of the SCR catalyst, for example. When the term
"fresh" is used in this disclosure it means an adsorbent material
that has only been calcined under such conditions as to decompose
any precursor constituents into an "active" form, and hasn't
undergone any accelerated and/or in-use ageing.
[0041] Tungstated zirconia (WO.sub.3--ZrO.sub.2) passive NOx
adsorbent material has also been shown to exhibit considerably
greater NO.sub.X storage values compared to pure zirconia (in the
presence of Pt or Pd, and tested fresh).
[0042] Equally important for passive NOx adsorbents, the stored
NO.sub.X can be thermally desorbed from the adsorbent with high
efficiency in the working temperature range of 200-350.degree. C.
The tungstated zirconia adsorbent discussed above has also been
shown to exhibit a greater percentage of the amount of NO.sub.X
desorbed to the amount stored compared to other materials presented
here. Similarly, the addition of Pr to Mn-zirconia adsorbent has
been shown to be beneficial in terms of facilitating thermal
NO.sub.X release between 200 and 250.degree. C. compared to non-Pr
containing and Ce-containing analogues.
[0043] Therefore, comparable properties and even definite
advantages are obtained in the passive NOx adsorbents of this
disclosure when avoiding use of Ce, compared to Ce containing
compositions. The passive NOx adsorbents of this disclosure
advantageously can limit Ce to the following amounts on an oxide
basis: Ce in an amount not more than 20% by weight; Ce in an amount
ranging from 0.1 to 20% by weight; Ce in an amount less than 5% by
weight; Ce ranging from 0.5% to less than 5% by weight; and in
particular, the composition is substantially free of Ce.
[0044] While the addition of Fe to Ce-zirconia passive NOx
adsorbent material provides for less overall NO.sub.X storage
compared to a Mn--Ce-zirconia passive NOx adsorbent material, the
Fe-containing adsorbent material exhibits a greater percentage of
the amount of NO.sub.X desorbed to the amount stored. By
extrapolation, it is believed this desorbing behavior resulting
from use of Fe would also be evident in non-ceria containing
passive NOx adsorbent material or low-ceria containing passive NOx
adsorbent material.
[0045] The mixed or composite oxide compositions of the passive NOx
adsorbents of this disclosure may include the listed elements as
oxides. However, a portion of the elements may be in a form of
hydroxides or oxyhydroxides. The passive NOx adsorbents can be in
the form of a powder. Typical characteristics of the PNA powder
include: particle size; d.sub.50 may range from about 1 .mu.m to
about 100 .mu.m, although for washcoated materials the d.sub.50
will generally be <10 .mu.m. The surface area of the fresh PNA
powder will typically fall in the range 40-250 m.sup.2/g. The total
pore volume of the fresh PNA powder will typically fall in the
range 0.10-1.0 cm.sup.3/g. Impurity levels of the fresh PNA powder
are <500 ppm of Na or Cl and <0.1% SO.sub.4 typical
impurities. Naturally occurring HfO.sub.2 may be present in an
amount of 1-2% in the ZrO.sub.2 used in the adsorbents of this
disclosure. The PNA powder may be applied as an aqueous washcoat
that coats a substrate, for example, onto a monolithic substrate,
and in particular, onto a honeycomb shaped monolithic substrate.
Examples of monolith coating methods suitable for use in this
disclosure can be found in US2011/0268634A1 and WO2017/144493A1,
which are incorporated herein by reference in their entireties,
although other techniques could be used.
[0046] The passive NOx adsorbents of this disclosure may be used in
various gas streams containing NOx and, in particular, in lean gas
streams. An example lean gas stream includes the following
components in the indicated percentages by volume: CO.sub.2 about
12%, H.sub.2O about 11%, O.sub.2 about 9%, NOx 50-1000 ppm, CO
100-500 ppm, PM 1-30 mg/m.sup.3, HC 20-300 ppm. One particular
application is in an exhaust stream of a gasoline fueled engine of
a motor vehicle. Another application is in the exhaust stream of a
diesel fueled engine of a motor vehicle. Non-automotive
applications such as trains and ships are also relevant with regard
to use of the materials of this disclosure, along with stationary
emissions sources such as power stations, refineries, and general
industrial facilities that generate NOx.
[0047] Given that interest in this type of automotive application
is growing (in an effort to decrease cold start emissions from
lean-burn engines), the commercial application of these devices can
be expected in the near future.
[0048] Suitable methods for preparing the passive NOx adsorbents of
this disclosure may include (but are not limited to) the methods
described in the following references, all of which are
incorporated herein by reference in their entireties: [0049] 1.
Cauqui, M. A.; Rodriguez-Izquierdo, J. M. J. Non-Cryst. Solids,
1992, 147/148, 724. (Sol-gel method); [0050] 2. J. A. Navio, et
al., Chem. Mater. 1997, 9, 1256-1261. (Alkaline precipitation);
[0051] 3. Kolen'koa Y., et al., Mater. Sci. Eng. C, 2003, 23, 1033
(Hydrothermal synthesis); [0052] 4. Kasilingam Boobalan, et al., J.
Am. Ceram. Soc. 2010, 11, 3651-3656 (Combustion method); [0053] 5.
U.S. Pat. No. 7,431,910; [0054] 6. U.S. Pat. No. 7,632,477; [0055]
7. U.S. Pat. No. 7,794,687.
[0056] The subject matter of the disclosure will now be described
by reference to the following examples, which are for purposes of
illustration and should not necessarily be used to limit the
subject matter herein.
Example 1
[0057] A portion of tungstated zirconia mixed or composite oxide
(15.75% WO.sub.3/84.25% ZrO.sub.2) (e.g., can be made using the
process described in U.S. Pat. No. 7,632,477) was used as a support
to make the "Pt--W--Zr" and "Pd--W--Zr" materials. All amounts of
compounds in this disclosure are in % by weight that together equal
100% of the composition, unless otherwise indicated. It is assumed
the zirconia includes an amount of HfO.sub.2 up to 2% even if this
is not indicated.
[0058] Pt and Pd were deposited on the support by means of
incipient wetness impregnation. The support material was first
dried in a vacuum oven at 70.degree. C. overnight then impregnated
with an aqueous solution of tetra-ammine platinum (II) nitrate (or
tetra-ammine palladium nitrate). Pt and Pd loadings were kept at 1
wt % for single metal catalysts, the remainder being the mixed or
composite oxide. If bimetallic catalysts are used, Pt and Pd can be
simultaneously loaded on the support by co-impregnation using a
mixture of Pt and Pd tetra-ammine nitrate solution. For bimetallic
catalysts, Pt and Pd loadings can be 0.5 wt % for each metal, the
remainder being the mixed or composite oxide. After drying at
50.degree. C. overnight in a vacuum oven, the impregnated samples
were calcined at 500.degree. C. for 3 h.
[0059] For some of the Examples and Comparative Example, fresh and
aged PNA powders had characteristics recited in Table 3 below.
[0060] A microreactor loaded with about 150 mg of PNA powder (free
flowing powder, having a particle size of less than 0.2 mm) was
employed to study the NO.sub.X adsorption and desorption properties
of the adsorbents. In all the cases, a total flow rate of 120 sccm
was used, corresponding to a gas hourly space velocity (GHSV) of
about 30,000 h.sup.-1.
[0061] Effluent gases were analyzed using a mass spectrometer (QMS
200). Unless otherwise stated, the adsorbents were first pretreated
at the desired NO.sub.X storage temperature under lean gas
containing 5% O.sub.2, 5% CO.sub.2 and 3.5% H.sub.2O until the
samples were saturated (based on a comparison of the feed and
effluent gas concentrations); typically this required 15
minutes.
[0062] NO.sub.X storage was performed at three different
temperatures (80, 100 and 120.degree. C.) by adding 300 ppm NO to
the lean feed gas. After NO.sub.X storage for a specified period of
time, the feed gas was switched to bypass mode and the NO flow was
switched off.
[0063] When the NO concentration had dropped to zero, the gas was
re-directed to the reactor and temperature-programmed desorption
was carried out to study NO.sub.X desorption behavior using a ramp
rate of 10.degree. C./min from the storage temperature up to
500.degree. C. The results are presented in Table 1.
Comparative Example 1
[0064] A portion of undoped zirconia (e.g., can be made using the
process described in U.S. Pat. No. 7,794,687) was used as a support
to make the "Pt--Zr" and "Pd--Zr" materials and then tested based
on the procedures detailed in EXAMPLE 1. The results are presented
in Table 1.
Example 2
[0065] A portion of undoped zirconia (same material as used in
COMPARATIVE EXAMPLE 1) was first impregnated with an aqueous
solution of manganese nitrate, then dried and calcined at
500.degree. C. for 3 h. The resulting Mn--ZrO.sub.2 oxide (20.0%
MnO.sub.2/80.0% ZrO.sub.2) was subsequently impregnated with
aqueous tetra-amine palladium (II) nitrate and further calcined at
500.degree. C. for 3 h. Pd loading in the catalysts was maintained
at 1 wt %.
[0066] The material of EXAMPLE 2 was then tested based on the
procedures detailed in EXAMPLE 1. The results are presented in
Table 1.
Example 3
[0067] A portion of a ceria-zirconia mixed or composite oxide
(25.7% CeO.sub.2/74.3% ZrO.sub.2) (e.g., can be made using the
process described in U.S. Pat. No. 7,431,910) was first impregnated
with an aqueous solution of manganese nitrate, then dried and
calcined at 500.degree. C. for 3 h. The resulting Mn--Ce--ZrO.sub.2
oxide (20.0% MnO.sub.2/20.6% CeO.sub.2/59.4% ZrO.sub.2) was
subsequently impregnated with aqueous tetra-amine palladium (II)
nitrate and further calcined at 500.degree. C. for 3 h. Pd loading
in the catalysts was maintained at 1 wt %.
[0068] The material of EXAMPLE 3 was then tested based on the
procedures detailed in EXAMPLE 1. The results are presented in
Table 1.
Example 4
[0069] A portion of manganese-zirconia mixed or composite oxide
(13.3% MnO.sub.2/86.7% ZrO.sub.2) was used as a support for
palladium and tested based on the procedures detailed in EXAMPLE
1.
[0070] This mixed or composite oxide can be made using the process
described in U.S. Pat. No. 7,632,477, which is incorporated herein
by reference in its entirety. The results are presented in Table
1.
Example 5
[0071] A portion of EXAMPLE 4 (with palladium added) was
hydrothermally aged and then tested based on the procedures
detailed in EXAMPLE 1. All hydrothermal ageing carried out in this
disclosure is under the conditions of 750.degree. C. for 16 hours
in 10% O.sub.2, 5% CO.sub.2, 5% H.sub.2O, balance N.sub.2 gas. The
results are presented in Table 1.
Example 6
[0072] A portion of a manganese-praseodymia-zirconia mixed or
composite oxide (14.3% MnO.sub.2/14.0% Pr.sub.6O.sub.11/71.7%
ZrO.sub.2) was used as a support for palladium and then tested
based on the procedures detailed in EXAMPLE 1.
[0073] This mixed or composite oxide can be made using the process
described in U.S. Pat. No. 7,632,477. The results are presented in
Table 1.
Example 7
[0074] A portion of a manganese-ceria-zirconia mixed or composite
oxide (13.0% MnO.sub.2/10.0% CeO.sub.2/77.0% ZrO.sub.2) was used as
a support for palladium and then tested based on the procedures
detailed in EXAMPLE 1. The results are presented in Table 1.
[0075] This mixed or composite oxide can be made using the process
described in U.S. Pat. No. 7,431,910.
Example 8
[0076] A portion of a manganese-praseodymia-zirconia mixed or
composite oxide (7.0% MnO.sub.2/13.6% Pr.sub.6O.sub.11/79.4%
ZrO.sub.2) was used as a support for palladium and then tested
based on the procedures detailed in EXAMPLE 1.
[0077] This mixed or composite oxide can be made using the process
described in U.S. Pat. No. 7,632,477. The results are presented in
Table 1.
Example 9
[0078] A portion of EXAMPLE 8 (with palladium added) was
hydrothermally aged and then tested based on the procedures
detailed in EXAMPLE 1. The results are presented in Table 1.
Example 10
[0079] A portion of a manganese-ceria-zirconia mixed or composite
oxide (6.3% MnO.sub.2/9.7% CeO.sub.2/84.0% ZrO.sub.2) was used as a
support for palladium and then tested based on the procedures
detailed in EXAMPLE 1.
[0080] This mixed or composite oxide can be made using the process
described in U.S. Pat. No. 7,431,910. The results are presented in
Table 1.
Example 11
[0081] A portion of EXAMPLE 10 (with palladium added) was
hydrothermally aged and then tested based on the procedures
detailed in EXAMPLE 1. The results are presented in Table 1.
Example 12
[0082] A portion of a manganese-ceria-zirconia mixed or composite
oxide (20.0% MnO.sub.2/10.0% CeO.sub.2/70.0% ZrO.sub.2) was used as
a support for palladium and then tested based on the procedures
detailed in EXAMPLE 1.
[0083] This mixed or composite oxide can be made using the process
described in U.S. Pat. No. 7,431,910. The results are presented in
Table 1.
Example 13
[0084] A portion of EXAMPLE 12 (with palladium added) was
hydrothermally aged and then tested based on the procedures
detailed in EXAMPLE 1. The results are presented in Table 1.
Example 14
[0085] A portion of an iron-ceria-zirconia mixed or composite oxide
(20.0% Fe.sub.2O.sub.3/10.0% CeO.sub.2/70.0% ZrO.sub.2) was used as
a support for palladium and then tested based on the procedures
detailed in EXAMPLE 1.
[0086] This mixed or composite oxide can be made using the process
described in U.S. Pat. No. 7,431,910. The results are presented in
Table 1.
Example 15
[0087] A portion of an iron-ceria-zirconia mixed or composite oxide
(10.0% Fe.sub.2O.sub.3/10.0% CeO.sub.2/80.0% ZrO.sub.2) was used as
a support for palladium and then tested based on the procedures
detailed in EXAMPLE 1.
[0088] This mixed or composite oxide can be made using the process
described in U.S. Pat. No. 7,431,910. The results are presented in
Table 1.
Example 16
[0089] A portion of an iron-ceria-zirconia mixed or composite oxide
(5.0% Fe.sub.2O.sub.3/10.0% CeO.sub.2/85.0% ZrO.sub.2) was used as
a support for palladium and then tested based on the procedures
detailed in EXAMPLE 1.
[0090] This mixed or composite oxide can be made using the process
described in U.S. Pat. No. 7,431,910. The results are presented in
Table 1.
Example 17
[0091] A manganese-silica-praseodymia-zirconia mixed or composite
oxide was prepared (7.0% MnO.sub.2/13.6% Pr.sub.6O.sub.11
5.0%SiO.sub.2/74.4% ZrO.sub.2); analogous to EXAMPLE 8 but with
silica present.
[0092] This mixed or composite oxide can be made using the process
described in U.S. Pat. No. 7,632,477.
CONCLUSIONS
[0093] Conclusions drawn from the test results described in the
discussed in EXAMPLES 1-16 and COMPARATIVE EXAMPLE 1 are shown in
Table 1 and discussed below. In the discussion, amounts of the
elements in the mixed or composite oxides are rounded to the
nearest whole number.
TABLE-US-00001 TABLE 1 Results of testing the Indicated PNA
materials for a storage temperature of 120.degree. C. and a
desorption time of 15 minutes. % of Amount Desorbed to Amount
NO.sub.X Stored at 120.degree. C. Amount NO.sub.X Desorbed Amount
Stored (.mu.mol/g) (.mu.mol/g) 15 min <350.degree. Material 1
min 2 min 5 min 15 min 15 min <250.degree. C. 15 min
<350.degree. C. C./15 min Comparative 4.97 9.71 14.62 29.42 7.56
11.09 38 Example 1 (Pt) Comparative 3.59 5.62 10.73 23.45 8.91
16.81 72 Example 1 (Pd) Example 1 (Pt) 3.67 5.01 7.77 12.99 7.26
10.30 79 Example 1 (Pd) 9.42 15.76 24.19 30.65 24.88 29.35 96
Example 2 (Pd) 10.69 21.10 45.73 80.06 32.80 64.61 81 Example 3
(Pd) 10.19 19.19 43.59 92.47 23.23 55.91 60 Example 12 (Pd) 11.10
21.47 53.78 145.78 30.32 102.70 70 Example 13 (Pd) 10.41 18.23
27.30 34.42 15.15 23.71 69 Example 4 (Pd) 10.96 21.65 53.64 126.87
45.73 111.67 88 Example 5 (Pd) 9.61 13.87 20.10 31.88 14.86 19.96
63 Example 7 (Pd) 10.78 21.24 53.55 136.66 34.44 100.70 74 Example
6 (Pd) 10.70 21.35 53.34 113.94 36.72 75.04 66 Example 8 (Pd) 10.68
21.33 52.88 118.95 36.33 58.74 49 Example 9 (Pd) 10.47 20.62 46.53
69.91 16.26 48.41 69 Example 10 (Pd) 10.76 21.43 53.63 114.76 41.26
75.03 65 Example 11 (Pd) 10.62 20.30 31.95 37.69 22.81 36.23 96
Example 14 (Pd) 2.79 4.87 10.55 25.59 12.86 22.77 89 Example 15
(Pd) 2.99 5.30 11.22 27.75 13.53 24.11 87 Example 16 (Pd) 2.99 5.11
10.79 26.62 16.58 27.83 100
Example 1 (Pd)
[0094] The Pd--W--Zr material exhibits greater NO.sub.X storage at
120.degree. C. at all times explored compared to the Pd--Zr
material (see COMPARATIVE EXAMPLE 1 (Pd)) and greater percentage of
the amount NO.sub.X desorbed to the amount stored. In particular,
the Pd--W--Zr material exhibits an amount of NO.sub.X desorbed to
the amount stored of 96%.
Example 2 (Pd)
[0095] The Pd--Mn(20)-Zr material exhibits NO.sub.X storage values
after 5 minutes at 120.degree. C. comparable to those of the
Pd--Mn(20)-Ce(21)-Zr material (see EXAMPLE 3 (Pd)) but less storage
after 15 minutes at 120.degree. C. However, the Pd--Mn(20)-Zr
material exhibits considerably better NO.sub.X desorption at all
temperatures explored relative to the amount stored, compared to
the Pd--Mn(20)-Ce(21)-Zr material. This illustrates a definite
advantage over materials that include Ce, for use as passive NOx
adsorbents.
Example 4 (Pd)
[0096] The Pd--Mn(13)-Zr material exhibits NO.sub.X storage values
after 5 minutes at 120.degree. C. comparable to those of the
Pd--Mn(13)-Ce(10)-Zr material (see EXAMPLE 7 (Pd)) but less storage
after 15 minutes at 120.degree. C. However, the Pd--Mn(13)-Zr
material exhibits a greater percentage of the amount NO.sub.X
desorbed to the amount stored. This shows a definite advantage over
Ce containing adsorbent material.
Example 6 (Pd)
[0097] The Pd--Mn(14)-Pr(14)-Zr material exhibits NO.sub.X storage
values after 5 minutes at 120.degree. C. comparable to those of the
Pd--Mn(13)-Ce(10)-Zr material (see EXAMPLE 7 (Pd)).
Example 8 (Pd)
[0098] The Pd--Mn(7)-Pr(14)-Zr material exhibits NO.sub.X storage
values after 5 minutes at 120.degree. C. comparable to that of the
Pd--Mn(6)-Ce(10)-Zr material (see EXAMPLE 10 (Pd)).
Example 9 (Pd)
[0099] The Pd--Mn(7)-Pr(14)-Zr (HT aged) material exhibits
comparable or better NO.sub.X storage values at 120.degree. C. at
all times explored with respect to the Pd--Mn(6)-Ce(10)-Zr (HT
aged) material (see EXAMPLE 11 (Pd)). In particular, the
Pd--Mn(7)-Pr(14)-Zr (HT aged) material of Example 9 (Pd) exhibited
the greatest amount of NO.sub.X storage of all the aged materials
explored in these EXAMPLES and COMPARATIVE EXAMPLES at about 70
.mu.mol/g.
Example 14 (Pd)
[0100] While the Pd--Fe(20)-Ce(10)-Zr material exhibits less
NO.sub.X storage compared to a Pd--Mn--Ce-zirconia material (e.g.
see EXAMPLE 12 (Pd)), the Pd--Fe(20)-Ce(10)-Zr material exhibits a
large percentage of the amount of NO.sub.X desorbed to the amount
stored. By extrapolation, this behavior resulting from use of Fe
would also be evident in non-ceria containing materials.
Example 15 (Pd)
[0101] While the Pd--Fe(10)-Ce(10)-Zr material exhibits less
NO.sub.X storage compared to a typical Pd--Mn--Ce-zirconia material
(e.g. see EXAMPLE 7 (Pd)), the Pd--Fe(10)-Ce(10)-Zr material
exhibits a large percentage of the amount NO.sub.X desorbed to the
amount stored. By extrapolation, this behavior resulting from use
of Fe would also be evident in non-ceria containing materials.
Example 16 (Pd)
[0102] While the Pd--Fe(5)-Ce(10)-Zr material exhibits less
NO.sub.X storage compared to a Pd--Mn--Ce-zirconia material (e.g.
see EXAMPLE 10 (Pd)), the Pd--Fe(5)-Ce(10)-Zr material exhibits a
large percentage of the amount NO.sub.X desorbed to the amount
stored. By extrapolation, this behavior resulting from use of Fe
would also be evident in non-ceria containing materials.
[0103] The disclosure now turns to further examples and a
comparative example for illustrating the subject matter of the
disclosure, which should not be used to necessarily limit the
subject matter herein.
Example 18
[0104] A portion of a praseodymia-zirconia mixed or composite oxide
(25.5% Pr.sub.6O.sub.1/74.5% ZrO.sub.2) was used as a support for
palladium and then tested based on the procedures detailed in
EXAMPLE 1.
[0105] This mixed or composite oxide can be made using the process
described in U.S. Pat. No. 7,632,477. The results are presented in
Table 2 below.
Example 19
[0106] A portion of a ceria-praseodymia-zirconia mixed or composite
oxide (20.6% CeO.sub.2/5.1% Pr.sub.6O.sub.11/74.3% ZrO.sub.2) was
used as a support for palladium and then tested based on the
procedures detailed in EXAMPLE 1.
[0107] This mixed or composite oxide can be made using the process
described in U.S. Pat. No. 7,431,910. The results are presented in
Table 2 below.
Comparative Example 2
[0108] A portion of a high ceria-praseodymia-zirconia mixed or
composite oxide (67.9% CeO.sub.2/16.8% Pr.sub.6O.sub.11/15.3%
ZrO.sub.2) obtained from MEL Chemicals was used as a support for
palladium and then tested based on the procedures detailed in
EXAMPLE 1.
[0109] This mixed or composite oxide can be made using the process
described in Applicant's U.S. Pat. No. 7,431,910. The results are
presented in Table 2 below.
CONCLUSIONS
[0110] Conclusions drawn from the test results described in
Examples 18 and 19 and Comparative Example 2 are shown in Table 2
and discussed below.
TABLE-US-00002 TABLE 2 Results of testing the PNA materials for a
storage temperature of 120.degree. C. and a desorption time of 5
minutes. Amount NO.sub.X Amount NO.sub.X Desorbed Stored at
120.degree. C. (.mu.mol/g) (.mu.mol/g) 5 min - 5 min - Material 1
min 2 min 5 min <250.degree. C. <350.degree. C. Example 18
(Pd) 5.02 8.35 16.78 8.63 13.24 Example 19 (Pd) 4.99 8.03 15.68
5.18 10.15 Comparative Example 5.67 10.18 20.65 5.85 7.15 2
(Pd)
[0111] While the praseodymia-zirconia mixed or composite oxide of
Example 18 and the ceria-praseodymia--zirconia mixed or composite
oxide of Example 19 did not have high storage of NOx after 5
minutes at 120.degree. C. minutes compared to other materials
tested, they exhibited a relatively high amount of NOx desorbed.
Although the high ceria-praseodymia--zirconia mixed or composite
oxide of Comparative Example 2 exhibited slightly better storage of
NOx after 5 minutes at 120.degree. C. compared to the adsorbents of
Examples 18 and 19, this is for a significant increase in
ceria/praseodymia level (and therefore expense) and it exhibited
only a comparable or a lesser amount of NOx desorbed at the
temperatures tested (a significant facet of the PNA function).
[0112] Table 3 below shows Surface area, total pore volume and
crystallite size for fresh and aged PNA material of the indicated
EXAMPLES and COMPARATIVE EXAMPLES.
TABLE-US-00003 TABLE 3 Characteristics of Fresh and Aged PNA
materials of the Indicated EXAMPLES and COMPARATIVE EXAMPLES. Air
Aged Hydrothermally aged Fresh (900.degree. C./2 hr) (750.degree.
C./16 hr) SA TPV CS SA TPV CS SA TPV (m2/g) (cm3/g) (nm) (m2/g)
(cm3/g) (nm) (m2/g) (cm3/g) COMP. 84 0.35 EXAMPLE 1 EXAMPLE 1
EXAMPLE 3 EXAMPLE 4 149 0.41 8.2 7 0.03 EXAMPLE 5 -- EXAMPLE 6 153
0.40 4.2 25 0.11 16 EXAMPLE 7 146 0.41 8.3 11 0.05 27 EXAMPLE 8 95
0.45 11 27 0.12 16 EXAMPLE 9 -- 48 0.24 EXAMPLE 10 98 0.39 9.6 13
0.07 26 EXAMPLE 11 -- EXAMPLE 12 103 0.30 EXAMPLE 13 -- 21 0.10
EXAMPLE 14 80 EXAMPLE 15 67 EXAMPLE 16 62 EXAMPLE 17 150 0.63 6.3
46 0.26 11 EXAMPLE 18 80 0.36 12 EXAMPLE 19 82 0.34 7.9 COMPARATIVE
94 0.24 7.1 EXAMPLE 2 SA = Surface Area TPV = Total Pore Volume CS
= Crystallite Size (from XRD)
[0113] Many modifications and variations of the subject matter of
the disclosure will be apparent to those of ordinary skill in the
art. Therefore, it is to be understood that the subject matter of
the disclosure can be practiced otherwise than has been
specifically shown and described.
* * * * *