Patent Description:
Environmental regulations for emissions of internal combustion engines are becoming increasingly stringent throughout the world.

Operating a lean-burn engine, for example a diesel engine, provide the user with excellent fuel economy due to their operation at high air/fuel ratios under fuel lean conditions. However, diesel engines also emit exhaust gas emissions containing particulate matter (PM), unburned hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx), wherein NOx describes various chemical species of nitrogen oxides, including nitrogen monoxide and nitrogen dioxide, among others. The two major components of exhaust particulate matter are the soluble organic fraction (SOF) and the soot fraction. The SOF condenses on the soot in layers and is generally derived from unburned diesel fuel and lubricating oils. The SOF can exist in diesel exhaust either as a vapor or as an aerosol (i.e., fine droplets of liquid condensate), depending on the temperature of the exhaust gas. Soot is predominately composed of particles of carbon.

Oxidation catalysts comprising a precious metal, such as platinum group metals (PGM), dispersed on a refractory metal oxide support, such as alumina, are known for use in treating the exhaust of diesel engines in order to convert both hydrocarbon and carbon monoxide gaseous pollutants by catalyzing the oxidation of these pollutants to carbon dioxide and water. Such catalysts have been generally contained in units called diesel oxidation catalysts (DOC), which are placed in the exhaust flow path from diesel power systems to treat the exhaust before it vents to the atmosphere. Typically, the diesel oxidation catalysts are formed on ceramic or metallic substrates upon which one or more catalyst coating compositions are deposited. In addition to the conversion of gaseous HC and CO emissions and particulate matter (SOF portion), oxidation catalysts that contain PGM promote the oxidation of NO to NO<NUM>. Catalysts are typically defined by their light-off temperature or the temperature at which <NUM>% conversion is attained, also called T<NUM>.

Catalysts used to treat the exhaust of internal combustion engines are less effective during periods of relatively low temperature operation, such as the initial cold-start period of engine operation, because the engine exhaust is not at a temperature sufficiently high for efficient catalytic conversion of noxious components in the exhaust. To this end, it is known in the art to include a sorbent material, which may be a zeolite, as part of a catalytic treatment system in order to adsorb and/or absorb gaseous pollutants, usually hydrocarbons, and retain them during the initial cold-start period. As the exhaust gas temperature increases, the stored hydrocarbons are driven from the sorbent and subjected to catalytic treatment at the higher temperature.

NOx is contained in exhaust gases, such as from internal combustion engines (e.g., in automobiles and trucks), from combustion installations (e.g., power stations heated by natural gas, oil, or coal), and from nitric acid production plants. Various treatment methods have been used for the treatment of NOx-containing gas mixtures to decrease atmospheric pollution.

One effective method to reduce NOx from the exhaust of lean-burn engines, such as gasoline direct injection and partial lean-burn engines, as well as from diesel engines, requires trapping and storing of NOx under lean burn engine operating conditions and reducing the trapped NOx under stoichiometric or rich engine operating conditions or under lean engine operation with external fuel injected in the exhaust to induce rich conditions. The lean operating cycle is typically between <NUM> minute and <NUM> minutes and the rich operating cycle is typically short (<NUM> to <NUM> seconds) to preserve as much fuel as possible. To enhance NOx conversion efficiency, the short and frequent regeneration is favored over long but less frequent regeneration. Thus, a lean NOx trap catalyst article generally must provide a NOx trapping function and a three-way conversion function. Three-way conversion (TWC) generally refers to converting HC + CO to CO<NUM> + H<NUM>O and reducing NOx to N<NUM>.

Some lean NOx trap (LNT) catalyst articles contain alkaline earth elements. For example, NOx sorbent components include alkaline earth metal oxides, such as oxides of Mg, Ca, Sr or Ba. Other LNT catalyst articles can contain rare earth metal oxides such as oxides of Ce, La, Pr or Nd. The NOx sorbents can be used in combination with platinum group metal catalysts such as platinum dispersed on an alumina support for catalytic NOx oxidation and reduction. The LNT catalyst article operates under cyclic lean (trapping mode) and rich (regeneration mode) exhaust conditions during which the NO produced by the engine during combustion is converted to N<NUM>.

Another effective method to reduce NOx from the exhaust of lean-burn engines requires reaction of NOx under lean burn engine operating conditions with a suitable reductant such as ammonia or hydrocarbon in the presence of a selective catalytic reduction (SCR) catalyst. The SCR process uses catalytic reduction of nitrogen oxides with a reductant (e.g., ammonia) in the presence of atmospheric oxygen, resulting in the formation predominantly of nitrogen and steam:.

4NO+4NH<NUM>+O<NUM> → 4N<NUM>+<NUM><NUM>O (standard SCR reaction).

2NO<NUM>+4NH<NUM> → 3N<NUM>+<NUM><NUM>O (slow SCR reaction).

NO+NO<NUM>+NH<NUM> → 2N<NUM>+<NUM><NUM>O (fast SCR reaction).

Current catalysts employed in the SCR process include molecular sieves, such as zeolites, ion- exchanged with a catalytic metal such as iron or copper.

A useful SCR catalyst component is able to effectively catalyze the reduction of the NOx exhaust component at temperatures below <NUM>, so that reduced NOx levels can be achieved even under conditions of low load which typically are associated with lower exhaust temperatures.

European application <CIT> discloses an exhaust gas treatment device comprising an ammonolysis module wherein ammonia is supplied from stored urea that is converted to ammonia under thermolytic conditions followed by conversion of the ammonia to hydrogen and nitrogen which is then used in treatment of exhaust. However, <CIT> relies on heated systems to generate hydrogen and does suggest storage and use of hydrogen under cold start conditions.

Increasingly stringent emissions regulations have driven the need for developing emission gas treatment systems with improved CO, HC and NO oxidation capacity to manage CO, HC and NO emissions at low engine exhaust temperatures. In addition, development of emission gas treatment systems for the reduction of NOx (NO and NO<NUM>) emissions to nitrogen has become increasingly important. Further, it is observed that precious metals tend to agglomerate and form charged particles under operating conditions, resulting in loss of catalytic activity.

While methods exist for the abatement of HC and NOx during cold-start conditions, improved methods are desired. Methods do not yet exist for the abatement of CO during cold-start conditions.

The present invention is aimed at on-board vehicle hydrogen generation, storage and use as a reductant in exhaust gas streams of internal combustion engines. Generated hydrogen may serve to aid oxidation of CO and/or HC and/or NO<NUM>/NOx formation in an exhaust gas stream, especially during a cold-start period. Hydrogen reductant is, for example, suitable to regenerate precious metals, for instance precious metals present in a diesel oxidation catalyst (DOC). Further, hydrogen reductant may minimize nitrate formation which inhibits the precious metals from dissociating the molecular oxygen needed for low temperature oxidation.

The disclosure provides a system and related methods for abatement of pollutants in an exhaust gas stream of an internal combustion engine, the system comprising a hydrogen injection article configured to introduce hydrogen upstream of a catalytic article.

Accordingly, in one aspect is provided a system for abatement of pollutants in an exhaust gas stream of an internal combustion engine, the system comprising a catalytic article downstream of and in fluid communication with the internal combustion engine, a hydrogen injection article in fluid communication with the catalytic article and with the exhaust gas stream of the internal combustion engine and configured to introduce hydrogen into the exhaust gas stream upstream of the catalytic article, and a hydrogen storage article.

In some embodiments, the hydrogen injection article is configured to introduce hydrogen intermittently on-demand. According to the invention, the hydrogen injection article is configured to introduce hydrogen from the hydrogen storage article. In some embodiments, the hydrogen injection article comprises a valve configured to prevent the exhaust gas stream from entering the hydrogen storage article.

According to the invention, the hydrogen injection article is configured to introduce stored hydrogen during a cold-start period. According to the invention, the hydrogen injection article is configured to introduce hydrogen when the exhaust gas stream entering the catalytic article is at a temperature of from <NUM> to <NUM>. Advantageously, the injection or release of stored hydrogen is intermittent and/or during a cold-start period.

In some embodiments, the system is effective for the abatement of one or more pollutants in an exhaust gas stream, the pollutants selected from the group consisting of CO, HC, NOx, and combinations thereof.

In some embodiments, the catalytic article is a diesel oxidation catalyst (DOC).

In some embodiments, the system is integrated with a vehicle electronic management system.

According to the invention, the system is associated with a hydrogen generation system. According to the invention, the hydrogen generation system comprises an ammonia decomposition article configured to generate hydrogen.

In another aspect is provided a vehicle comprising the system for abatement of pollutants in an exhaust gas stream as described herein.

In a further aspect according to the invention, provided is a method for abatement of pollutants in an exhaust gas stream of an internal combustion engine, the method comprising generating hydrogen on-board a vehicle in an ammonia decomposition article;wherein generating hydrogen comprises: isolating ammonia from an ammonia/organic solvent solution or releasing ammonia from an ammonia storage tank;decomposing ammonia in a catalytic reactor to provide hydrogen;collecting the hydrogen; storing the hydrogen; and introducing stored hydrogen via a hydrogen injection article into the exhaust gas stream downstream from the internal combustion engine and upstream of a catalytic article; comprising introducing stored hydrogen during a cold-start period wherein the exhaust gas stream entering the catalytic article is at a temperature from <NUM> to <NUM>.

In some embodiments, the method comprises intermittent introduction of the stored hydrogen, optionally, upon instruction from a vehicle electronic management system. In some embodiments, the method comprises introducing stored hydrogen during a cold-start period wherein the exhaust gas stream entering the catalytic article is at a temperature from <NUM> to <NUM>.

In some embodiments, the method is effective in providing an increase in % conversion of one or more of CO, HC and NOx relative to the % conversion in the absence of injection or release of stored hydrogen, wherein the increase in % conversion is ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>% or ≥ <NUM>%.

In some embodiments, the catalytic article comprises a diesel oxidation catalyst (DOC), a NOx- adsorber DOC (NA-DOC), or a lean NOx-trap (LNT) catalyst composition.

According to the invention, the method comprises generating hydrogen on-board a vehicle in an ammonia decomposition article. Not according to the invention is, generating hydrogen comprises collecting and/or storing water, splitting the water into hydrogen and oxygen, collecting the hydrogen and storing the hydrogen. According to the invention, generating hydrogen comprises isolating ammonia from an ammonia/organic solvent solution or releasing ammonia from an ammonia storage tank, decomposing the ammonia in a catalytic reactor to provide hydrogen, collecting the hydrogen, and storing the hydrogen. In some embodiments, one or more of the collecting, storing, splitting, isolating, releasing, and decomposing functions are performed via a vehicle on-board integrated system comprising articles configured for each function.

The present disclosure includes, the following embodiments:.

These and other features, aspects, and advantages of the disclosure will be apparent from a reading of the following detailed description together with the accompanying drawings, which are briefly described below. The invention includes any combination of two, three, four, or more of the above-noted embodiments as well as combinations of any two, three, four, or more features or elements set forth in this disclosure, regardless of whether such features or elements are expressly combined in a specific embodiment description herein. This disclosure is intended to be read holistically such that any separable features or elements of the disclosed invention, in any of its various aspects and embodiments, should be viewed as intended to be combinable unless the context clearly dictates otherwise. Other aspects and advantages of the present invention will become apparent from the following.

In order to provide an understanding of embodiments of the invention, reference is made to the appended drawings, in which reference numerals refer to components of exemplary embodiments of the invention. The drawings are exemplary only, and should not be construed as limiting the invention. The disclosure described herein is illustrated by way of example and not by way of limitation in the accompanying figures. For simplicity and clarity of illustration, features illustrated in the figures are not necessarily drawn to scale. For example, the dimensions of some features may be exaggerated relative to other features for clarity. Further, where considered appropriate, reference labels have been repeated among the figures to indicate corresponding or analogous elements.

The articles "a" and "an" herein refer to one or to more than one (e.g. at least one) of the grammatical object. Any ranges cited herein are inclusive. The term "" used throughout is used to describe and account for small fluctuations. For instance, "" may mean the numeric value may be modified by ±<NUM>%, ±<NUM>%, ±<NUM>%, ±<NUM>%, ±<NUM>%, ±<NUM>%, ±<NUM>%, ±<NUM>%, ±<NUM>%, ±<NUM>% or ±<NUM>%. All numeric values are modified by the term "" whether or not explicitly indicated. Numeric values modified by the term "" include the specific identified value. For example " <NUM>" includes <NUM>. Where ranges are disclosed herein, each combination of lower endpoint and upper endpoint explicitly define a range that is contemplated as an embodiment of the invention.

The present invention is directed to systems, articles and methods for on-board vehicle hydrogen generation for use as a reductant in an exhaust gas stream of an internal combustion engine. The invention is also aimed at systems, articles and methods for on-board hydrogen generation from ammonia. Present systems comprise one or more "functional articles" or simply "articles". Functional articles comprise one or more certain functional elements, for instance reservoirs, tubing, pumps, valves, batteries, circuitry, meters, nozzles, reactors, filters, funnels and the like. The systems are integrated, that is, having interconnected articles and/or elements.

The term "associated" means for instance "equipped with", "connected to" or in "communication with", for example "electrically connected" or in "fluid communication with" or otherwise connected in a way to perform a function. The term "associated" may mean directly associated with or indirectly associated with, for instance through one or more other articles or elements. The term "associated" means for instance "equipped with", "connected to" or in "communication with", for example "electrically connected" or in "fluid communication with" or otherwise connected in a way to perform a function. The term "associated" may mean directly associated with or indirectly associated with, for instance through one or more other articles or elements.

The term "catalyst" refers to a material that promotes a chemical reaction. The catalyst includes the "catalytically active species" and the "carrier" that carries or supports the active species. For example, molecular sieves including zeolites are carriers/supports for copper active catalytic species. Likewise, refractory metal oxide particles may be a carrier for platinum group metal catalytic species.

The catalytically active species are also termed "promoters" as they promote chemical reactions. For instance, the present copper- or iron-containing molecular sieves may be termed copper- or iron-promoted molecular sieves. A "promoted molecular sieve" refers to a molecular sieve to which catalytically active species are intentionally added.

The term "catalytic article" in the invention means an article comprising a substrate having a catalyst coating composition.

The term "configured" as used in the description and claims is intended to be an open-ended term as are the terms "comprising" or "containing". The term "configured" is not meant to exclude other possible articles or elements. The term "configured" may be equivalent to "adapted".

In general, the term "effective" means for example from <NUM>% to <NUM>% effective, for instance from <NUM>%, <NUM>%, <NUM>% or <NUM>% to <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, or <NUM>%, regarding the defined catalytic activity or storage/release activity, by weight or by moles.

The term "exhaust stream" or "exhaust gas stream" refers to any combination of flowing gas that may contain solid or liquid particulate matter. The stream comprises gaseous components and is for example exhaust of a lean burn engine, which may contain certain non-gaseous components such as liquid droplets, solid particulates and the like. An exhaust stream of a lean burn engine typically further comprises
combustion products, products of incomplete combustion, oxides of nitrogen, combustible and/or carbonaceous particulate matter (soot) and un-reacted oxygen and/or nitrogen.

The term "functional article" in the invention means an article comprising a substrate having a functional coating composition disposed thereon, in particular a catalyst and/or sorbent coating composition. "Platinum group metal components" refer to platinum group metals or one of their oxides. "Rare earth metal components" refer to one or more oxides of the lanthanum series defined in the Periodic Table of Elements, including lanthanum, cerium, praseodymium and neodymium.

As used herein, the term "promoted" refers to a component that is intentionally added to the molecular sieve material, typically through ion exchange, as opposed to impurities inherent in the molecular sieve. In order to promote the selective catalytic reduction of nitrogen oxides in the presence of ammonia, in one or more embodiments, a suitable metal is independently exchanged into the molecular sieve. According to one or more embodiments, the molecular sieve is promoted with copper (Cu) and/or iron (Fe), although other catalytic metals could be used without departing from the invention, such as manganese, cobalt, nickel, cerium, platinum, palladium, rhodium or combinations thereof. Typical amounts of promoter metal include <NUM> to <NUM>% by weight of the SCR catalyst material.

As used herein, the term "selective catalytic reduction" (SCR) refers to the catalytic process of reducing oxides of nitrogen to dinitrogen (N<NUM>) using a nitrogenous reductant. As used herein, the terms "nitrogen oxides" or "NOx" designate the oxides of nitrogen.

The term "sorbent" refers to a material that adsorbs and/or absorbs a desired substance, in this invention, a NOx and/or CO and/or HC and/or NH<NUM>. Sorbents may advantageously adsorb and/or absorb (store) a substance at a certain temperature and desorb (release) the substance at a higher temperature.

As used herein, the term "substrate" refers to the monolithic material onto which the catalyst composition, that is, catalytic coating, is disposed, typically in the form of a washcoat. In one or more embodiments, the substrates are flow-through monoliths and monolithic wall-flow filters. A washcoat is formed by preparing a slurry containing a specified solids content (e.g., <NUM>-<NUM>% by weight) of catalyst in a liquid, which is then coated onto a substrate and dried to provide a washcoat layer.

As used herein, the term "washcoat" has its usual meaning in the art of a thin, adherent coating of a catalytic or other material applied to a substrate material, such as a honeycomb-type carrier member, which is sufficiently porous to permit the passage of the gas stream being treated. The washcoat containing the metal-promoted molecular sieve of the invention can optionally comprise a binder selected from silica, alumina, titania, zirconia, ceria, or a combination thereof. The loading of the binder is <NUM> to <NUM> wt. % based on the weight of the washcoat.

The term "vehicle" means for instance any vehicle having an internal combustion engine and includes for instance passenger automobiles, sport utility vehicles, minivans, vans, trucks, buses, refuse vehicles, freight trucks, construction vehicles, heavy equipment, military vehicles, farm vehicles and the like.

Unless otherwise indicated, all parts and percentages are by weight. "Weight percent (wt. %)," if not otherwise indicated, is based on an entire composition free of any volatiles, that is, based on dry solids content.

The present invention now will be described more fully hereinafter.

The present systems and methods include on-board vehicle hydrogen generation and thus the systems are integrated with a hydrogen generation system. Hydrogen is generated on-board from ammonia. Outside the invention, hydrogen may be stored outside a vehicle in a gaseous, liquid or solid state and brought and placed on-board and replenished as needed. Generated hydrogen is advantageously injected into an exhaust gas stream of an internal combustion engine, where it will suitably function as a reductant in certain catalytic processes and/or catalyst regeneration processes. Catalytic processes include oxidation of CO and/or HC and/or formation of NO<NUM>/NOx for downstream reduction by an SCR catalyst to abate pollutants.

Hydrogen may be stored in a hydrogen storage article, for example stored in a gas storage tank or reservoir. Hydrogen may be stored in a gaseous, liquid or solid state. Hydrogen may be stored for instance in a solid state, for example in silicon or a hydrogen storage alloy. Solid state hydrogen storage is taught for example in <CIT>, <CIT>, <CIT>, <CIT> and <CIT> Hydrogen storage alloys reversibly store hydrogen and are disclosed for example in <CIT> and <CIT> and U. Pre-Grant Pub. No. <NUM>/<NUM>. Hydrogen storage alloys are for example modified ABx type metal hydride (MH) alloys where in general, A is a hydride forming element and B is a weak or non-hydride forming element. A is in general a larger metallic atom with <NUM> or less valence electrons and B is in general a smaller metallic atom with <NUM> or more valence electrons. Suitable ABx alloys include those where x is from <NUM> to <NUM>. The present alloys are capable of reversibly absorbing (charging) and desorbing (discharging) hydrogen. ABx type alloys are for example of the categories (with simple examples), AB (HfNi, TiFe, TiNi), AB<NUM> (ZrMn<NUM>, TiFe<NUM>), A<NUM>B (Hf<NUM>Fe, Mg<NUM>Ni), AB<NUM> (NdCo<NUM>, GdFe<NUM>), A<NUM>B<NUM> (Pr<NUM>Ni<NUM>, Ce<NUM>Co<NUM>) and AB<NUM> (LaNi<NUM>, CeNi<NUM>).

Not according to the invention, a hydrogen generation system may comprise a water-splitting functional article (water-splitting article). The water-splitting article may comprise an electrolytic cell configured to split water into hydrogen and oxygen via an electrochemical reaction. For instance, the water-splitting article may comprise a photoelectrode configured to initiate the electrochemical reaction. A photoelectrode is associated with a light source. Advantageously, the light source is a light emitting diode (LED), for example a blue light emitting diode. The light source will advantageously be associated with a battery. The battery is for example the main rechargeable vehicle battery.

Devices for hydrogen generation are disclosed for example in U. Pre-Grant Pub. <NUM>/<NUM> and <NUM>/<NUM>.

The water source may advantageously be atmospheric water. For instance, the water source may be atmospheric water condensed by an air-conditioner condenser. Such water is otherwise lost to the roadway or parking lot. The present system may therefore comprise an article configured to collect and/or store water (a water collection article). The water collection article may be associated with an air-conditioner. The water collection article may be associated with a filter. The water source may also be for example bottled water. The water may be supplied to the water-splitting article in the form of steam. The water may be heated to steam via captured heat generated by the internal combustion engine. Thus the system may comprise a heating article configured to convert water to steam. The heating article may be associated with an internal combustion engine or exhaust gas stream.

Generated hydrogen may be collected via a hydrogen collection article. For example, a hydrogen collection article may comprise a hydrogen separation membrane. Hydrogen separation membranes may comprise palladium or palladium alloys and may for instance be ≤ <NUM> thick. Hydrogen separation membranes may also comprise for example polymer, silica, ceramic or porous carbon. For example, the membrane is ≤ <NUM> thick, for example the membrane is from <NUM>, from <NUM> or from <NUM> thick to <NUM>, <NUM> or <NUM> thick. The membrane may be supported with a perforated stainless steel sheet, for instance <NUM> thick. Alternatively, the membrane may be supported on a porous ceramic tube or rod. The membrane may be associated with a heating element, e.g. an electrical heating element, to maximize the flow of hydrogen and separation from oxygen.

A hydrogen generation system according to the invention includes a catalytic article ("catalytic reactor") configured to decompose ammonia into nitrogen and hydrogen (ammonia decomposition article).

The source of ammonia may be from an on-board ammonia reservoir or may be from ammonia brought on-board, for example in a tank adapted to contain gaseous or liquid ammonia (and adapted to release ammonia as needed). For instance, the system may comprise a tank adapted to contain ammonia and release ammonia (ammonia storage tank) and a catalytic reactor configured to decompose ammonia into hydrogen and nitrogen. According to the invention, the system comprises an ammonia generation system and a catalytic reactor configured to decompose ammonia to hydrogen and nitrogen. An ammonia generation system may comprise a reservoir containing an ammonia/organic solvent solution which can be mounted (for example, on a vehicle) in proximity to other emission control system components. The ammonia/organic solvent solution will, in some embodiments, readily liberate gaseous ammonia. Advantageously, the organic solvent in the ammonia/organic solvent solution comprises an alkanol and/or a glycol, for example a solvent selected from the group consisting of ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, ethylene glycol, propylene glycol, isomers thereof and mixtures thereof. In certain embodiments, the organic solvent comprises n-butanol and/or ethylene glycol.

The ammonia/organic solvent solution may, for example, comprise from <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>% or <NUM>%, to <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, or <NUM>% ammonia by weight, based on the weight of the ammonia/organic solvent solution. These concentrations are at ambient conditions of <NUM> and <NUM> atm of pressure.

In some embodiments, the ammonia generation system comprises a reservoir containing an ammonia/organic solvent solution and a phase separator configured to isolate ammonia from the solution.

The phase separator may operate in a similar fashion to a distillation column and is configured to isolate lower-boiling ammonia gas from higher-boiling organic solvent. The phase separator may be in thermal communication with a heat exchanger. In the context of this disclosure, two objects "in thermal communication" means that heat from one of the two objects may be used to drive a catalytic reaction in or cause gas to desorb from the other object. Thus, heat may be applied to the phase separator. Heat applied may be, for example, from <NUM> or <NUM> to <NUM> and the source of heat may be, for instance, waste heat generated from the engine during operation or the heat may be applied electrically.

The system may further comprise an ammonia storage container configured to store isolated ammonia, which may simply be for instance a suitable tank to hold ammonia gas. The container may be associated with a catalytic reactor configured to catalytically decompose ammonia into hydrogen and nitrogen.

The ammonia generation system may advantageously comprise a reservoir containing an ammonia/organic solvent solution, a phase separator configured to isolate ammonia from the solution, an ammonia storage container, and an ammonia injection article. The system is integrated with the articles and elements associated with each other.

An exemplary ammonia generation system <NUM> is shown in <FIG>. Reservoir <NUM> is configured to contain an ammonia/organic solvent solution. Ammonia may be directed to a phase separator <NUM> configured to isolate ammonia from the ammonia/organic solvent solution. Isolated ammonia may be directed to an ammonia storage container <NUM>. One or more articles may be associated with a heat exchanger, for example reservoir <NUM> and/or phase separator <NUM>, which heat exchanger(s) may be associated with waste heat from an engine.

The hydrogen generation system may, in some embodiments, comprise the articles and elements of the ammonia generation system described above. The catalytic reactor may be termed an "ammonia decomposition article.

The hydrogen generation system may comprise a phase separator and/or an ammonia storage container integrated with the reservoir and with the catalytic reactor.

The catalytic reactor may comprise an ammonia decomposition catalyst disposed on an inner surface thereof and/or onto high surface area supports which may be present within the volume of the reactor. The catalytic reactor may comprise a heat exchanger configured to provide waste heat generated from the internal combustion engine to the catalyst (to heat the catalyst). The ammonia decomposition catalyst may also be heated through the combustion of a fixed amount of ammonia and air.

For instance, the catalytic reactor may contain a coating composition comprising an ammonia decomposition catalyst disposed on an inner surface thereof and/or on a high surface area support present within the volume thereof. The catalytic reactor may advantageously be associated with a heat exchanger where for example the heat exchanger is associated with an internal combustion engine and adapted to provide waste heat from the engine to the reactor to heat the decomposition catalyst. Alternatively, the decomposition catalyst may be heated if desired through combustion of a fixed amount of ammonia and air.

An exemplary on-board hydrogen generation system is configured to generate hydrogen via catalytic decomposition of ammonia and comprises a catalytic reactor configured to decompose ammonia to hydrogen and nitrogen, as shown in <FIG>. In system <NUM>, ammonia may be directed to a catalytic reactor <NUM>. In one embodiment, ammonia may be directed to a catalytic reactor <NUM>, configured to decompose ammonia into hydrogen and nitrogen. Catalytic reactor <NUM> may contain an ammonia decomposition catalyst disposed on an inner surface thereof and/or on high surface area supports present within the reactor volume. The catalytic reactor <NUM> may comprise a hydrogen separation membrane <NUM>, which membrane may comprise a catalytic coating composition comprising an ammonia decomposition catalyst disposed on an outer surface of the membrane. The membrane is configured so that ammonia contacts the outer surface containing the decomposition catalyst. Ammonia decomposition catalysts include for example precious metals on silica, for example supported ruthenium. One or more articles may be associated with a heat exchanger, for example, catalytic reactor <NUM>, which heat exchanger(s) may be associated with waste heat from an engine. Not shown are any necessary check valves, a hydrogen injector, nor a nitrogen vent valve.

Ammonia decomposition catalysts include, for example, precious metals on silica, for example, supported ruthenium. Hydrogen separation membranes may comprise palladium or palladium alloys and may for instance be ≤ <NUM> thick. Hydrogen separation membranes may also comprise for example polymer, silica, ceramic or porous carbon. For example, the membrane is ≤ <NUM> thick, for example the membrane is from <NUM>, from <NUM> or from <NUM> thick to <NUM>, <NUM> or <NUM> thick. The membrane may be supported with a perforated stainless steel sheet, for instance <NUM> thick. Alternatively, the membrane may be supported on a porous ceramic tube or rod. The membrane may be associated with a heating element, e.g. an electrical heating element, to maximize the flow of hydrogen and separation from oxygen.

The catalytic reactor may comprise a hydrogen separation membrane as above. The reactor may comprise a catalytic coating composition comprising an ammonia decomposition catalyst disposed on an inner space of the reactor and outside the membrane. The membrane is configured so that ammonia contacts the surface of the decomposition catalyst.

According to the invention hydrogen generated via catalytic ammonia decomposition is stored in a hydrogen storage article on-board as described above.

The hydrogen generation article will advantageously contain a hydrogen injection article configured to introduce hydrogen into an exhaust gas stream of an internal combustion engine where it will suitably function as a reductant in certain catalytic processes and/or catalyst regeneration processes. The hydrogen injection article may be in fluid communication with an oxidation catalyst and configured to introduce hydrogen upstream of the oxidation catalyst, for example a diesel oxidation catalyst (DOC). The hydrogen injection article will typically be downstream of and in fluid communication with an internal combustion engine.

An exemplary system <NUM> according to the present disclosure for generating hydrogen from ammonia for use in an emission control system is shown schematically in <FIG>. In one embodiment, system <NUM> incorporates hydrogen generation system <NUM>, as shown in <FIG> and described herein above. In one embodiment, ammonia may be directed to a catalytic reactor <NUM>, configured to decompose ammonia into hydrogen and nitrogen. Catalytic reactor <NUM> may contain an ammonia decomposition catalyst disposed on an inner surface thereof and/or on high surface area supports present within the reactor volume. The catalytic reactor <NUM> may comprise a hydrogen separation membrane <NUM>, which membrane can separate hydrogen from an ammonia-hydrogen mixture. Ammonia decomposition catalysts include for example precious metals on silica, for example supported ruthenium.

The catalytic reactor may be vented to release generated nitrogen. The membrane may serve to isolate hydrogen, which is directed to a hydrogen storage article <NUM>. Isolated hydrogen may be directed to a DOC article <NUM>, for example, be introduced upstream of a DOC article. One or more articles may be associated with a heat exchanger, for example catalytic reactor <NUM>, which heat exchanger(s) may be associated with waste heat from an engine. Not shown are any necessary check valves, hydrogen injector, an ammonia injector or a nitrogen vent valve.

In some embodiments, a system is provided that comprises system <NUM>, in some embodiments, a system is provided that comprises system <NUM>, in some embodiments, a system is provided that comprises both system <NUM> and system <NUM>, and in some embodiments, a system is provided that comprises system <NUM>, system <NUM> and system <NUM>.

The present system suitably contains one or more hydrogen injection articles, for instance a valve configured to prevent the exhaust gas stream from entering the hydrogen storage article, and, configured to introduce hydrogen into an exhaust gas stream. Hydrogen will advantageously be "pulsed" or released intermittently into the exhaust gas stream to perform a desired reducing function upon demand (on- demand).

The system may advantageously be integrated into the engine electronic management algorithm (electronic management system), for instance as is urea injection for SCR functions.

The oxidation catalyst, such as a DOC article, is suitable for example to oxidize NO and/or CO and/or HC components of exhaust gas. Suitable oxidation catalysts advantageously comprise a platinum group metal (PGM) dispersed on a refractory metal oxide support.

Oxidation catalysts comprising a precious metal, such as platinum group metals (PGM), dispersed on a refractory metal oxide support, such as alumina, are known for use in treating the exhaust of diesel engines in order to convert both hydrocarbon and carbon monoxide gaseous pollutants by catalyzing the oxidation of these pollutants to carbon dioxide and water. Such catalysts have been generally contained in DOCs, which are placed in the exhaust flow path from diesel power systems to treat the exhaust before it vents to the atmosphere. Typically, the diesel oxidation catalysts are formed on ceramic or metallic substrates upon which one or more catalyst coating compositions are deposited.

The support material on which the catalytically active PGM is deposited for example comprises a refractory metal oxide, which exhibits chemical and physical stability at high temperatures, such as the temperatures associated with gasoline or diesel engine exhaust. Exemplary metal oxides include alumina, silica, zirconia, titania, ceria, praseodymia, tin oxide and the like, as well as physical mixtures or chemical combinations thereof, including atomically-doped combinations and including high surface area or activated compounds such as activated alumina.

Included are combinations of metal oxides such as silica-alumina, ceria-zirconia, praseodymia-ceria, alumina-zirconia, alumina-ceria-zirconia, lanthana-alumina, lanthana-zirconia-alumina, baria-alumina, baria- lanthana-alumina, baria-lanthana-neodymia-alumina and alumina-ceria. Exemplary aluminas include large pore boehmite, gamma-alumina and delta/theta alumina. Useful commercial aluminas used as starting materials in exemplary processes include activated aluminas, such as high bulk density gamma-alumina, low or medium bulk density large pore gamma-alumina and low bulk density large pore boehmite and gamma-alumina.

High surface area metal oxide supports, such as alumina support materials, also referred to as "gamma alumina" or "activated alumina," typically exhibit a BET surface area in excess of <NUM><NUM>/g, often up to <NUM><NUM>/g or higher. An exemplary refractory metal oxide comprises high surface area γ-alumina having a specific surface area of <NUM> to <NUM><NUM>/g. Such activated alumina is usually a mixture of the gamma and delta phases of alumina, but may also contain substantial amounts of eta, kappa and theta
alumina phases. "BET surface area" has its usual meaning of referring to the Brunauer, Emmett, Teller method for determining surface area by N<NUM> adsorption. Desirably, the active alumina has a specific surface area of <NUM> to <NUM><NUM>/g, for example from <NUM> to <NUM><NUM>/g.

In certain embodiments, metal oxide supports useful in the catalyst compositions disclosed herein are doped alumina materials, such as Si-doped alumina materials (including, but not limited to <NUM>-<NUM>% SiO<NUM>-Al<NUM>O<NUM>), doped titania materials, such as Si-doped titania materials (including, but not limited to <NUM>-<NUM>% SiO<NUM>-TiO<NUM>) or doped zirconia materials, such as Si-doped ZrO<NUM> (including, but not limited to <NUM>-<NUM>% SiO<NUM>-ZrO<NUM>).

Advantageously, a refractory metal oxide may be doped with one or more additional basic metal oxide materials such as lanthanum oxide, barium oxide, strontium oxide, calcium oxide, magnesium oxide or combinations thereof. The metal oxide dopant is typically present in an amount of <NUM> to <NUM>% by weight, based on the weight of the catalyst composition. The dopant oxide materials may serve to improve the high temperature stability of the refractory metal oxide support or function as a sorbent for acidic gases such as NO<NUM>, SO<NUM> or SO<NUM>.

The dopant metal oxides can be introduced using an incipient wetness impregnation technique or by addition of colloidal mixed oxide particles. Preferred doped metal oxides include baria-alumina, baria-zirconia, baria-titania, baria-zirconia- alumina, lanthana-zirconia and the like.

Thus the refractory metal oxides or refractory mixed metal oxides in the catalyst compositions are typically selected from the group consisting of alumina, zirconia, silica, titania, ceria, for example bulk ceria, manganese oxide, zirconia-alumina, ceria-zirconia, ceria-alumina, lanthana-alumina, baria-alumina, silica, silica-alumina and combinations thereof. Further doping with basic metal oxides provides additional useful refractory oxide supports including but not limited to baria-alumina, baria-zirconia, baria-titania, baria-zirconia- alumina, lanthana-zirconia and the like.

The oxidation catalyst composition may comprise any of the above-named refractory metal oxides and in any amount. For example refractory metal oxides in the catalyst composition may comprise at least <NUM>, at least <NUM>, at least <NUM>, at least <NUM> or at least <NUM> wt. % (weight percent) alumina where the wt. % is based on the total dry weight of the catalyst composition. The catalyst composition may for example comprise from <NUM> to <NUM> wt. % alumina, from <NUM> to <NUM> wt. % alumina or from <NUM> to <NUM> wt. The oxidation catalyst composition comprises for example from <NUM> wt. %, <NUM> wt. %, <NUM> wt. %, or <NUM> wt. %, to <NUM> wt. %, <NUM> wt. %, <NUM> wt. %, <NUM> wt. % ,or <NUM> wt. % alumina based on the weight of the catalytic composition. Advantageously, the oxidation catalyst composition may comprise ceria, alumina and zirconia or doped compositions thereof.

Catalyst compositions may be prepared using a binder, for example, a ZrO<NUM> binder derived from a suitable precursor such as zirconyl acetate or any other suitable zirconium precursor such as zirconyl nitrate. Zirconyl acetate binder provides a coating that remains homogeneous and intact after thermal aging, for example, when the catalyst is exposed to high temperatures of at least <NUM>, for example, <NUM> and higher and high water-vapor environments of <NUM>% or more. Other potentially suitable binders include, but are not limited to, alumina and silica. Alumina binders include aluminum oxides, aluminum hydroxides and aluminum oxyhydroxides. Aluminum salts and colloidal forms of alumina many also be used. Silica binders include various forms of SiO<NUM>, including silicates and colloidal silica. Binder compositions may include any combination of zirconia, alumina and silica.

The oxidation catalyst composition coated onto a substrate may comprise a PGM component from <NUM> wt. % (weight percent), <NUM> wt. %, <NUM> wt. %, <NUM> wt. %, or <NUM> wt. %, to <NUM> wt. %, <NUM> wt. %, <NUM> wt. %, <NUM> wt. %, <NUM> wt. %, <NUM> wt. %, <NUM> wt. %, <NUM> wt. %, <NUM> wt. %, <NUM> wt. %, <NUM> wt. %, or <NUM> wt. %, based on the weight of the dry composition.

The PGM component of the oxidation catalyst composition is, for example, present from <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, or <NUM>/ft<NUM>, to <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, <NUM>/ft<NUM>, or <NUM>/ft<NUM>, based on the volume of the substrate.

The oxidation catalyst composition in addition to the refractory metal oxide support and catalytically active metal may further comprise any one or combinations of the oxides of lanthanum, barium, praseodymium, neodymium, samarium, strontium, calcium, magnesium, niobium, hafnium, gadolinium, terbium, dysprosium, erbium, ytterbium, manganese, iron, chromium, tin, zinc, nickel, cobalt or copper.

In one or more embodiments, the oxidation catalyst compositions as disclosed herein are disposed on a substrate to form a catalytic article. Present substrates for catalytic articles are <NUM>-dimensional, having a length and a diameter and a volume, similar to a cylinder. The shape does not necessarily have to conform to a cylinder. The length is an axial length defined by an inlet end and an outlet end. The diameter is the largest cross-section length, for example the largest cross-section if the shape does not conform exactly to a cylinder.

Any suitable substrate for the catalytic articles disclosed herein may be employed, such as a monolithic substrate of the type having fine, parallel gas flow passages extending there through from an inlet or an outlet face of the substrate such that passages are open to fluid flow there through ("flow-through monolith"). Another suitable substrate is of the type have a plurality of fine, substantially parallel gas flow passages extending along the longitudinal axis of the substrate where, typically, each passage is blocked at one end of the substrate body, with alternate passages blocked at opposite end-faces ("wall-flow filter"). Flow-through substrates and wall-flow filters will be further discussed herein below.

In one or more embodiments, the substrate is a ceramic or metal having a honeycomb structure. Ceramic substrates may be made of any suitable refractory material, e.g. cordierite, cordierite-α-alumina, aluminum titanate, silicon titanate, silicon carbide, silicon nitride, zircon mullite, spodumene, alumina-silica-magnesia, zircon silicate, sillimanite, a magnesium silicate, zircon, petalite, α-alumina, an aluminosilicate and the like.

Substrates may also be metallic, comprising one or more metals or metal alloys. The metallic substrates may be employed in various shapes such as pellets, corrugated sheet or monolithic foam. Specific examples of metallic substrates include heat-resistant, base-metal alloys, especially those in which iron is a substantial or major component. Such alloys may contain one or more of nickel, chromium, and aluminum, and the total of these metals may advantageously comprise at least <NUM> wt. % (weight percent) of the alloy, for instance, <NUM> to wt. % chromium, <NUM> to <NUM> wt. % of aluminum, and from <NUM> to <NUM> wt. % of nickel.

Examples of metallic substrates include those having straight channels; those having protruding blades along the axial channels to disrupt gas flow and to open communication of gas flow between channels; and those having blades and also holes to enhance gas transport between channels allowing for radial gas transport throughout the monolith.

Flow-through monolith substrates have fine, parallel gas flow passages extending from an inlet end to an outlet end of the substrate such that passages are open to fluid flow. The passages, which are essentially straight paths from their fluid inlet to their fluid outlet, are defined by walls on which a catalytic coating is disposed so that gases flowing through the passages contact the catalytic material. The flow passages of the monolithic substrate are thin-walled channels, which can be of any suitable cross-sectional shape and size such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, etc. The flow- through monolith is ceramic or metallic as described above.

Flow-through monolith substrates for example have a volume of from <NUM> in<NUM> to <NUM> in<NUM>, a cell density (inlet openings) of from <NUM> cells per square inch (cpsi) to <NUM> cpsi or up to <NUM> cpsi, for example from <NUM> to <NUM> cpsi and a wall thickness of from <NUM> to <NUM> microns or <NUM> microns.

In one or more embodiments, the substrate is selected from one or more of a flow-through honeycomb monolith or a particulate filter, to which the catalytic material(s) are applied to the substrate as a washcoat. <FIG> illustrate an exemplary substrate <NUM> in the form of a flow-through substrate coated with a catalyst composition as described herein. Referring to <FIG>, the exemplary substrate <NUM> has a cylindrical shape and a cylindrical outer surface <NUM>, an upstream end face <NUM> and a corresponding downstream end face <NUM>, which is identical to end face <NUM>. Substrate <NUM> has a plurality of fine, parallel gas flow passages <NUM> formed therein. As seen in <FIG>, flow passages <NUM> are formed by walls <NUM> and extend through carrier <NUM> from upstream end face <NUM> to downstream end face <NUM>, the passages <NUM> being unobstructed so as to permit the flow of a fluid, e.g., a gas stream, longitudinally through carrier <NUM> via gas flow passages <NUM> thereof. As more easily seen in <FIG>, walls <NUM> are so dimensioned and configured that gas flow passages <NUM> have a substantially regular polygonal shape. As shown, the catalyst composition can be applied in multiple, distinct layers if desired. In the illustrated embodiment, the catalyst composition consists of both a discrete bottom layer <NUM> adhered to the walls <NUM> of the carrier member and a second discrete top layer <NUM> coated over the bottom layer <NUM>. The present invention can be practiced with one or more (e.g., <NUM>, <NUM>, or <NUM>) catalyst layers and is not limited to the two-layer embodiment illustrated in <FIG>. Further coating configurations are disclosed herein below.

Wall-flow filter substrates useful for supporting the catalytic coatings have a plurality of fine, substantially parallel gas flow passages extending along the longitudinal axis of the substrate. Typically, each passage is blocked at one end of the substrate body, with alternate passages blocked at opposite end-faces. Such monolithic carriers may contain up to <NUM> or more flow passages (or "cells") per square inch of cross-section, although far fewer may be used. For example, the substrate may have from <NUM> to <NUM>, more usually from <NUM> to <NUM>, cells per square inch ("cpsi"). The cells can have cross-sections that are rectangular, square, circular, oval, triangular, hexagonal, or are of other polygonal shapes.

The wall-flow filter may have a volume of for instance from <NUM><NUM>, <NUM><NUM>, <NUM><NUM>, <NUM><NUM>, <NUM><NUM>, <NUM><NUM>, <NUM><NUM>, <NUM><NUM>, <NUM><NUM>, <NUM><NUM> or <NUM><NUM> to <NUM><NUM>, <NUM><NUM>, <NUM><NUM>, <NUM><NUM>, <NUM><NUM>, <NUM><NUM>, <NUM><NUM> or <NUM><NUM>.

Wall-flow substrates typically have a wall thickness from <NUM> microns to <NUM> microns, for example from <NUM> microns to <NUM> microns or from <NUM> microns to <NUM> microns.

The walls of the wall-flow filters are porous and generally have a wall porosity of at least <NUM>% or at least <NUM>% with an average pore size of at least <NUM> microns prior to disposition of the functional coating. For instance, the wall-flow filter will have a porosity of ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>% or ≥ <NUM>%. For instance, the wall-flow filters will have a wall porosity of from <NUM>%, <NUM>%, <NUM>% or <NUM>% to <NUM>%, <NUM>% or <NUM>% and an average pore size of from <NUM> microns, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> microns to <NUM> microns, <NUM>, <NUM>, <NUM> or <NUM> microns prior to disposition of a catalytic coating. The terms "wall porosity" and "substrate porosity" mean the same thing and are interchangeable. Porosity is the ratio of void volume divided by the total volume of a substrate. Pore size may be determined according to ISO15901-<NUM> (static volumetric) procedure for nitrogen pore size analysis. Nitrogen pore size may be determined on Micromeritics TRISTAR <NUM> series instruments. Nitrogen pore size may be determined using BJH (Barrett-Joyner-Halenda) calculations and <NUM> desorption points. Useful wall-flow filters have high porosity, allowing high loadings of catalyst compositions without excessive backpressure during operation.

A cross-section view of a wall-flow filter section is illustrated in <FIG>, showing alternating plugged and open passages (cells). Blocked or plugged ends <NUM> alternate with open passages <NUM>, with each opposing end open and blocked, respectively. The filter has an inlet end <NUM> and outlet end <NUM>. The arrows crossing porous cell walls <NUM> represent exhaust gas flow entering the open cell ends, diffusing through the porous cell walls <NUM>, and exiting the open outlet cell ends. Plugged ends <NUM> prevent gas flow and encourage diffusion through the cell walls. Each cell wall will have an inlet side 404a and outlet side 404b. The passages are enclosed by the cell walls. The dark squares in <FIG> are plugged ends <NUM> and white squares are open ends <NUM>.

Useful wall-flow filters typically have an aspect ratio (length/diameter or L/D) of from <NUM> to <NUM>, for example from <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> to <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM>. By aspect ratio is meant the ratio of length to diameter of the filter. For instance, the wall-flow filters may have an aspect ratio of from <NUM> to <NUM>. The high aspect ratio will allow the wall-flow filter to be fitted in a close-coupled position close to the engine. This allows for fast heat-up of the catalyst composition; the exhaust gas will heat up the catalyst composition to the operating (catalytic) temperature faster than if it were in an under-floor position. A close-coupled position is, for instance, within <NUM> inches (in) from the exhaust manifold (i.e., where individual cylinder exhaust pipes join together). In some embodiments, the distance from the exhaust manifold to the upstream end of the DOC unit is from <NUM> in to <NUM> inches. In some embodiments, the distance is <NUM> in, <NUM> in, <NUM> in, <NUM> in, <NUM> in, <NUM> in, <NUM> in, <NUM> in, <NUM> in, <NUM> in, <NUM> in, <NUM> in or <NUM> in. Metallic substrates, in particular, are advantageously employed in certain embodiments in a close-coupled position, allowing for fast heat-up.

The porous wall flow filter can be catalyzed in that the wall of the substrate has thereon one or more catalytic materials. Catalytic materials may be present on the inlet side of the substrate wall alone, the outletside alone, both the inlet and outlet sides, or the wall itself may consist all, or in part, of the catalytic material. In another embodiment, this invention may include the use of one or more catalyst layers and combinations of one or more catalyst layers on the inlet and/or outlet walls of the substrate.

Catalyzed wall-flow filters are disclosed for instance in <CIT>. This reference teaches a method of applying a catalytic coating such that the coating permeates the porous walls, that is, is dispersed throughout the walls. Flow- through and wall-flow substrates are also taught, for example, in <CIT>. Loading of the catalytic coating on a wall-flow substrate will depend on substrate properties such as porosity and wall thickness and typically will be lower than the catalyst loading on a flow-through substrate.

The catalytic coating that provides the oxidation catalyst composition of a DOC article may comprise more than one thin adherent layer, the layers in adherence to each other and the coating in adherence to the substrate. The entire coating comprises the individual "coating layers". The catalytic coating may advantageously be "zoned", comprising zoned catalytic layers. This may also be described as "laterally zoned". For example, a layer may extend from the inlet end towards the outlet end extending <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>% or <NUM>% of the substrate length. Another layer may extend from the outlet end towards the inlet end extending <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>% or <NUM>% of the substrate length. Different coating layers may be adjacent to each other and not overlay each other. Alternatively, different layers may overlay a portion of each other, providing a third "middle" zone. The middle zone may for example extend from <NUM>% to <NUM>% of the substrate length, for example <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>% or <NUM>% of the substrate length.

Different layers may each extend the entire length of the substrate or may each extend a portion of the length of the substrate and may overlay or underlay each other, either partially or entirely. Each of the different layers may extend from either the inlet or outlet end.

Different catalytic compositions may reside in each separate coating layer. For example, one coating layer could comprise an oxidation catalyst composition without any optional sorbent compositions and a second layer could include (or consist entirely of) one or more optional sorbent compositions. Thus, discussion related to different layers may correspond to any of these layers. The catalytic coating may comprise <NUM>, <NUM> or <NUM> or more coating layers. The one or more coating layers together comprise the <NUM> catalytic compositions.

Zones of the present disclosure are defined by the relationship of coating layers. With respect to different coating layers, there are a number of possible zoning configurations. For example, there may be an upstream zone and a downstream zone; there may be an upstream zone, a middle zone and a downstream zone; there may four different zones, etc. Where two layers are adjacent and do not overlap, there are upstream and downstream zones. Where two layers overlap to a certain degree, there are upstream, downstream and middle zones. Where for example, a coating layer extends the entire length of the substrate and a different coating layer extends from the outlet end a certain length and overlays a portion of the first coating layer, there are upstream and downstream zones.

Different coating layers may be in direct contact with the substrate. Alternatively, one or more "undercoats" may be present, so that at least a portion a catalytic coating layer or coating layers are not in direct contact with the substrate (but rather with the undercoat). One or more "overcoats" may also be present, so that at least a portion of the functional coating layer or layers are not directly exposed to a gaseous stream or atmosphere (but rather are in contact with the overcoat).

Different coating layers may be in direct contact with each other without a "middle" overlapping zone. Alternatively, different coating layers may not be in direct contact, with a "gap" between the two zones. In the case of an "undercoat" or "overcoat" the gap between the different layers is termed an "interlayer. " An undercoat is a layer "under" a coating layer, an overcoat is a layer "over" a coating layer and an interlayer is a layer "between" two coating layers. The interlayer(s), undercoat(s) and overcoat(s) may contain one or more functional compositions or may be free of functional compositions. The present catalytic coatings may comprise more than one identical layer.

In some embodiments, the substrate may have, for example, two coating layers, e.g., one oxidation catalyst material as described herein and a second catalyst material (which can be an oxidation catalyst material or can be another type of catalyst material). <FIG>, <FIG> and <FIG> show some possible coating layer configurations for a substrate with two such coating layers. Shown are substrate walls <NUM> onto which coating layers <NUM> and <NUM> are disposed. This is a simplified illustration, and in the case of a porous wall-flow substrate, not shown are pores and coatings in adherence to pore walls and not shown are plugged ends. In <FIG>, coating layer <NUM> (e.g., the oxidation catalyst material) extends from the inlet <NUM> to the outlet <NUM><NUM>% of the substrate length; and coating layer <NUM> (e.g., the second catalyst material) extends from the outlet to the inlet <NUM>% of the substrate length and the coating layers are adjacent each other, providing an inlet upstream zone <NUM> and an outlet downstream zone <NUM>. In <FIG>, coating layer <NUM> (e.g., the second catalyst material) extends from the outlet <NUM>% of the substrate length and layer <NUM> (e.g., the oxidation catalyst material) extends from the inlet greater than <NUM>% of the length and overlays a portion of layer <NUM>, providing an upstream zone <NUM>, a middle zone <NUM> and a downstream zone <NUM>. In <FIG>, coating layers <NUM> and <NUM> each extend the entire length of the substrate with layer <NUM> overlaying layer <NUM>. The substrate of <FIG> does not contain a zoned coating configuration. <FIG>, <FIG> and <FIG> may be useful to illustrate coating compositions on a wall-flow or flow-through substrate, e.g., of an oxidation catalytic article as described herein.

As mentioned, catalysts used to treat the exhaust of internal combustion engines are less effective during periods of relatively low temperature operation, such as the initial cold-start period of engine operation, because the engine exhaust is not at a temperature sufficiently high for efficient catalytic conversion of noxious components in the exhaust. Accordingly, an aspect of the present invention is directed to exhaust gas treatment systems and methods.

In the present exhaust gas treatment systems and methods, the exhaust gas stream is received into the catalytic article or treatment system by entering the upstream end and exiting the downstream end. The inlet end of a substrate is synonymous with the "upstream" end or "front" end. The outlet end is synonymous with the "downstream" end or "rear" end. A substrate will have a length and a diameter. The treatment system is in general downstream of and in fluid communication with an internal combustion engine.

The present system suitably contains one or more hydrogen injection articles configured to introduce hydrogen into an exhaust gas stream, for instance, the injection article comprises a valve configured to prevent the exhaust gas stream from entering the hydrogen storage article. The hydrogen generation article will advantageously contain a hydrogen injection article configured to introduce hydrogen into an exhaust gas stream of an internal combustion engine where it will suitably function as a reductant in certain catalytic processes and/or catalyst regeneration processes. The hydrogen injection article may be in fluid communication with an oxidation catalyst and configured to introduce hydrogen upstream of the oxidation catalyst, for example a diesel oxidation catalyst (DOC). The hydrogen injection article will typically be downstream of and in fluid communication with an internal combustion engine. Hydrogen will advantageously be "pulsed" or released intermittently into the exhaust gas stream to perform a desired reducing function upon demand (on-demand).

The system may advantageously be integrated into the engine electronic management algorithm (electronic management system), for instance as is urea injection for SCR functions.

One exemplary emissions treatment system is illustrated in <FIG>, which depicts a schematic representation of an emission treatment system <NUM>, downstream of and in fluid communication with an internal combustion engine <NUM>. As shown, an exhaust gas stream containing gaseous pollutants and particulate matter is conveyed via exhaust pipe <NUM> from an engine <NUM> to an optional diesel oxidation catalyst (DOC) <NUM>. Other articles not shown may therefore include reservoirs, pumps, valves, mixing boxes, etc..

The exhaust gas treatment system may comprise a hydrogen injection article, configured to introduce hydrogen upstream of the oxidation catalyst unit <NUM>. For example, the hydrogen injection article can be configured for intermittent injection or release of stored hydrogen. The system may be configured, for example, to introduce stored hydrogen during a cold-start period. In some embodiments, the hydrogen injection article comprises a check valve. Hydrogen may be brought on-board in a hydrogen storage article, or from ammonia decomposition. Ammonia decomposition to provide hydrogen may be performed as described herein, e.g., by catalytic decomposition. A suitable system to provide ammonia is depicted as system <NUM> in <FIG> and is described herein.

Generation of hydrogen from ammonia decomposition is described herein and depicted in <FIG> as system <NUM>. A suitable system for generating hydrogen from ammonia, storing the hydrogen, and providing it to a oxidation catalyst article is depicted in <FIG> as system <NUM>, and is described herein.

The exhaust stream is next conveyed via exhaust pipe <NUM> to optional downstream components, such as, for example, a Catalyzed Soot Filter and/or a Selective Catalytic Reduction (SCR) article, not shown.

The oxidation catalyst composition of DOC <NUM> is suitable for example to oxidize NO and/or CO and/or HC components of exhaust gas. In the optional DOC <NUM>, unburned gaseous and non-volatile hydrocarbons and carbon monoxide are largely combusted to form carbon dioxide and water. In addition, a proportion of the NO component may be oxidized to NO<NUM> in the DOC. Suitable oxidation catalyst compositions advantageously comprise a platinum group metal (PGM) dispersed on a refractory metal oxide support, as disclosed herein. The oxidation catalyst composition of DOC <NUM> may be coated on a flow-through monolith substrate or a wall-flow filter substrate as described herein.

The DOC unit is advantageously in a close-coupled position as described herein.

In one aspect is provided a method for abatement of pollutants in an exhaust gas stream of an internal combustion engine, the method comprising introducing stored hydrogen into the exhaust stream downstream of the internal combustion engine and upstream of a catalytic article.

In some embodiments, hydrogen is pulsed into the exhaust gas stream upstream of an oxidation catalyst composition, for example a diesel oxidation catalyst (DOC) as described herein above, during a cold-start period (i.e., the exhaust gas stream is at a temperature of ≤ <NUM>). Hydrogen serves to enhance low temperature oxidation NO and/or CO and/or HC pollutants. In some embodiments, the method is effective in providing an increase in % conversion of one or more of CO, HC and NO relative to the % conversion in the absence of injection or release of stored hydrogen. In some embodiments, the increase in % conversion is ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>%, ≥ <NUM>% or ≥ <NUM>%. In some embodiments, the method further comprises generating hydrogen on-board a vehicle. In some embodiments, the method further comprises generating hydrogen on-board a vehicle upon instruction from a vehicle electronic management system. According to the invention, the method comprises generating hydrogen on-board a vehicle in an ammonia decomposition article.

Outside of the invention, generating hydrogen comprises collecting and/or storing water, splitting water into hydrogen and oxygen, collecting hydrogen and storing hydrogen. According to the invention, the method comprises introducing stored hydrogen via a hydrogen injection article. In some embodiments, the hydrogen injection article comprises a valve configured to prevent the exhaust gas stream from entering the hydrogen storage article.

Present articles, systems and methods are suitable for treatment of exhaust gas streams from mobile emissions sources such as trucks and automobiles. Articles, systems and methods are also suitable for treatment of exhaust streams from stationary sources such as power plants.

The present invention is more fully illustrated by the following examples, which are set forth to illustrate the present invention and is not to be construed as limiting thereof. Unless otherwise noted, all parts and percentages are by weight, and all weight percentages are expressed on a dry basis, meaning excluding water content, unless otherwise indicated.

A bottom coat catalyst slurry containing milled alumina powder impregnated with Pd (<NUM> wt. %), Ba (<NUM> wt. %) and Pt (<NUM> wt. %) was prepared and adjusted to a pH of <NUM> to <NUM> with nitric acid. The bottomcoat slurry had a solid content of <NUM> wt. A top coat slurry containing alumina/<NUM> wt. % Mn and Pt-amine (<NUM> wt. %) was prepared, milled and adjusted to a pH of <NUM> to <NUM> with nitric acid. The top coat slurry had a solid concentration <NUM> wt. Zeolite beta (<NUM>/in<NUM>) was then added to the top coat slurry.

The bottom coat slurry was applied to the entire core length of a <NUM>" × <NUM>", <NUM> cpsi (cell per square inch) honeycomb substrate via a washcoat technique. The coated substrate was air dried at <NUM> and calcined at <NUM> for <NUM> hour, providing a coating loading of <NUM>/in<NUM>. The top coat slurry was applied over the entire bottom coat and was dried and calcined as the bottom coat, to provide a total coating loading of <NUM>/in<NUM> and a total PGM loading of <NUM>/ft<NUM> with a Pt/Pd weight ratio of <NUM>/<NUM>.

A bottom coat catalyst slurry containing milled alumina powder and a Ce/Al (<NUM>/<NUM> wt. %) powder (weight ratio of <NUM>/<NUM>) was prepared to have a solid concentration of from <NUM> to <NUM> wt. Small amounts of zirconium acetate and alumina sol were added as binders. The slurry was coated on a <NUM> cpsi <NUM>" × <NUM>" honeycomb to provide a bottom coat at <NUM>/in<NUM>.

A middle coat catalyst slurry is prepared by impregnating Pd nitrate on a Mn/Al support (<NUM> wt. % Mn) followed by adding a Ba hydroxide solution. The impregnated powder is added to a Pt solution and the pH is adjusted to <NUM> to <NUM> with nitric acid. This slurry is coated onto the bottom-coated core to provide an additional coating loading of <NUM>/in<NUM> and a Pt/Pd weight ratio of <NUM>/<NUM>.

A top coat slurry was prepared by impregnating Pd nitrate on a Mn/Al support (<NUM> wt. % Mn) followed by Ba hydroxide solution. The impregnated powder was added to a Pt solution and the pH was adjusted to <NUM> to <NUM> with nitric acid. Zeolite beta was added to the slurry. The top coat slurry was applied to the coated onto the coated core, providing a three-layer coated core, with a further coating loading of <NUM>/in<NUM> and Pt/Pd weight ratio of <NUM>/<NUM>. Total PGM loading was <NUM>/ft<NUM>.

The coated cores were hydrothermally aged in a tube furnace at <NUM> for <NUM> hours with a feed gas composition of <NUM>% H<NUM>O, <NUM>% O<NUM>, balance N<NUM>. The aged samples were evaluated in a lab reactor equipped to conduct a simulated NEDC (New European Driving Cycle) with a separate feed line for H<NUM>/N<NUM> serving as the source for H<NUM> pulse. Engine out temperature traces between vehicle and simulator are provided in <FIG>, and engine out CO emissions between the vehicle trace and simulator are provided in <FIG>.

Hydrogen was pulsed into the exhaust stream during the first <NUM> seconds of the cycle with a hydrogen concentration in a feed gas of <NUM>% or <NUM>%. Hydrogen injection was performed via a separate (non-preheated) line carrying the H<NUM>/N<NUM> feed gas. Results were obtained for % conversion of HC, CO and NO for coated core Example <NUM>. The data obtained for the coated substrate of Example <NUM> with <NUM>% H<NUM> pulse vs. no H<NUM> pulse were as follows:.

The data demonstrate that hydrogen pulsing was highly effective towards the abatement of pollutants in an exhaust gas stream.

Hydrogen injection had a significant impact during the cold-start period of the NEDC protocol (<NUM>-<NUM> seconds). NEDC results for % conversion of HC, CO and NOx were as follows for coated core Example <NUM> from <NUM>-<NUM> seconds:.

The average inlet temperature for runs with no H<NUM> was <NUM>. Inlet temperature for runs with <NUM>% H<NUM> was <NUM>.

An NO trace for NEDC testing of Example <NUM> is shown in <FIG>. Reduction of NO emission during the hydrogen injection period was observed. The examples herein were performed in a dynamic testing environment, in which temperature and speed, along with feed concentrations was constantly varied up and down to simulate driving conditions.

Testing was also performed with coated core Example <NUM>. Results were as follows:.

A cumulative CO emission plot, shown in <FIG>, clearly indicates the benefits of hydrogen injection during the first <NUM> seconds of a cold-start period. Hydrogen injection had a significant impact during the cold-start period of the NEDC protocol (<NUM>-<NUM> seconds). NEDC results for % conversion of HC, CO and NOx were as follows for coated core Example <NUM> from <NUM>-<NUM> seconds:.

The average inlet temperature for runs with no H<NUM> was <NUM>. Inlet temperature for runs with <NUM>% H<NUM> was <NUM>.

As the hydrogen impact became dominant only after <NUM> seconds into the NEDC cycle when the DOC inlet temperature was above <NUM>, the hydrogen injection can therefore be tied to the DOC inlet temperature, to maximize the efficiency of hydrogen usage. To illustrate this important aspect of the application, a steady state light-off test was conducted, with H<NUM> injection at different temperatures, the test performed as Example <NUM>.

The same aged core from Example <NUM> was used in the steady-state light-off test. The light-off test conditions were as listed below:.

The results, as CO conversion versus DOC inlet temperature, are shown in <FIG>. The data indicate that H<NUM> injection on the aged Example <NUM> DOC can be effective for CO conversion enhancement at an inlet temperature of above <NUM>, to avoid any water condensation, consistent with <FIG> dynamic (NEDC) testing results. As H<NUM> injection was provided through an unheated line, it is likely to reduce the inlet DOC temperature further during the H<NUM> injection tests, compared to the standard runs without H<NUM> injection. Therefore, it was considered more efficient to have H<NUM> injection starting at a temperature above <NUM>. The H<NUM> injection runs in <FIG>, <FIG>, and <FIG>, with an injection starting temperature above <NUM>, all showed good CO/HC conversions, and good NO<NUM>/NOx values at the low temperature region (from <NUM> to <NUM>). As the values were similar among all the runs with the H<NUM> injection periods varying from the start of the light-off test to <NUM>, from <NUM> to <NUM>, and from <NUM> to <NUM>, the most efficient way to use the least amount of hydrogen was to start H<NUM> injection at a DOC inlet temperature of <NUM>. To further prove this concept, the fresh Example <NUM> DOC was tested in the same light- off protocol (Example <NUM>).

A fresh core from Example <NUM> was used in the same steady-state light-off test of Example <NUM>. The results, as CO conversion versus DOC inlet temperature, obtained are shown in <FIG>. Again, stopping hydrogen injection before the DOC inlet temperature reached <NUM> provided no CO light-off improvement benefits. Stopping hydrogen injection when the DOC inlet temperature reached <NUM> offered an initial CO conversion boost, as shown in <FIG>, but it was not durable. The same phenomenon was observed for HC conversion in <FIG>. Since the light-off curves for CO/HC fell back to the original light-off phenomenon, shown in both <FIG> & <FIG>, without wishing to be bound by theory, hydrogen injection may be viewed as a neutral booster that has no lasting impact on the catalyst itself. To further illustrate this hydrogen injection effect, an aged Example <NUM> DOC was tested in the same light-off protocol, (Example <NUM>).

An aged core from Example <NUM> was used in the same steady-state light-off test as performed in
Examples <NUM> & <NUM>. To ascertain the sustainable light-off with the hydrogen injection, several hydrogen injection periods were tested on this aged Example <NUM> DOC. The results obtained, presented as CO conversion versus DOC inlet temperature, are shown in <FIG>.

The data demonstrate that a sustainable light-off can be obtained if the hydrogen injection period has passed the original light-off temperature (i.e., <NUM>% conversion point), in this case, <NUM>. Therefore, an
early termination of hydrogen injection from the start of the light-off test to the DOC inlet temperature of <NUM> resulted in a CO light-off curve similar to the original light-off curve without the hydrogen injection, as shown in <FIG>. A similar phenomenon was observed in HC light-off, shown in <FIG>.

To explore further why the hydrogen injection promotes CO/HC conversions during the cold start period, Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) experiments were carried
out on an Agilent CARY680 FTIR spectrometer equipped with a mercury cadmium telluride (MCT - HgCdTe) detector and a Linkam high-temperature environmental chamber with a calcium fluoride (CaF<NUM>) window. The sample powder was dehydrated in flowing Ar or reduced in flowing <NUM>% H<NUM> / Ar at <NUM> for <NUM> hour at a flow rate of <NUM>/min. The DRIFTS spectra were collected during the operando reactions carried at various temperatures (<NUM>, <NUM> and <NUM>). The absorbance spectra from the DRIFTS spectra were taken as a ratio to the background spectrum (the initial spectrum in Ar before reaction) and then used for analysis. In order to decouple the reactions for mechanism understanding, several sets of experiments were investigated using operando spectroscopy (Example <NUM>).

Powders were scraped from a fresh Example <NUM> DOC core and investigated using operando spectroscopy. The CO DRIFTS experiments on dehydrated and reduced fresh Example <NUM> DOC powders
were conducted to investigate the H<NUM> and CO interaction on PGM surface. <FIG> shows the DRIFTS spectral data for CO desorption (pre-adsorbed CO by flowing <NUM>/min of <NUM>% CO/Ar for <NUM> minutes) at three temperatures in two environments - argon vs. <NUM>% H<NUM>/Ar. The solid lines represent the desorption in argon, while the dashed lines represent the desorption in <NUM>% H<NUM>/Ar. The peak at <NUM> - <NUM>-<NUM> and the shoulder at <NUM> - <NUM>-<NUM> were assigned to CO linearly adsorbed on metallic Pt and Pd sites, respectively.

The wide and weak features at <NUM> - <NUM>-<NUM> were due to CO bridge-adsorbed on two PGM atoms. A broad peak at ~<NUM>-<NUM> was assigned to CO adsorbed on three PGM atoms, which is an indication of large PGM particle formation. <FIG> demonstrates that the pre-adsorbed CO on the linear adsorption sites can be completely desorbed in Argon within <NUM> minutes, while only a slight decrease was observed for the desorption in H<NUM>. The peak intensity on the double- and triple-bridged CO adsorption sites barely changed
within <NUM> minutes for both desorption environments. Therefore, the introduction of H<NUM> does not remove CO from the PGM surface; without wishing to be bound by theory, the data suggest that the CO adsorption on the PGM surface is stronger than hydride bonding (if any). This simple CO DRIFTS experiments confirm that there is little or no competitive adsorption between CO and H<NUM> on the PGM surface.

Because hydrogen did not apparently aid in removal of adsorbed CO on the precious metal surface, either under the dynamic NEDC testing conditions or under the steady-state light-off conditions, as observed in Examples <NUM> to <NUM>, it was desired to determine the effect of hydrogen injection on the DOC in enhancing CO/HC conversion.

Another experiment was therefore conducted using operando spectroscopy to further explore the role of hydrogen. In this experiment, NO and a mixture of NO + NO<NUM> were added into the original CO+O<NUM> feed gas mixture, respectively (in Example <NUM>).

The powders from an aged Example <NUM> DOC core, (Example <NUM>), were scraped off and used for this CO + O<NUM> + NO / NOx, with /without H<NUM> experiment. The feed gas compositions for the experiments with respect to the mixture of CO + O<NUM> + NO were: CO: <NUM>%, O<NUM>:<NUM>%, NO: <NUM> ppm; balance Ar. When hydrogen was used for the hydrogen impact experiments, <NUM> ppm H<NUM> was added into the feed gas. For the CO + O<NUM> + NOx experiments, an additional <NUM> ppm of NO<NUM> was added.

<FIG> demonstrates that some N<NUM>O was observed in the CO - O<NUM> - NOx experiment (solid line in the bottom portion of <FIG>) at <NUM>-<NUM>, which, without wishing to be bound by theory, may come from NO<NUM> self-decomposition and/or CO and NO<NUM> interaction according to the equation: <MAT>.

Claim 1:
A system for abatement of pollutants in an exhaust gas stream of an internal combustion engine, the system comprising:
a catalytic article downstream of and in fluid communication with the internal combustion engine;
a hydrogen generation system comprising an ammonia decomposition article configured to generate hydrogen, the ammonia decomposition article comprising an ammonia/ organic solvent reservoir or an ammonia storage tank, and a catalytic reactor configured to decompose ammonia into hydrogen and nitrogen from ammonia;
a hydrogen injection article in fluid communication with the catalytic article and with the exhaust gas stream of the internal combustion engine and configured to introduce hydrogen into the exhaust gas stream upstream of the catalytic article; and a hydrogen storage article;
wherein the hydrogen injection article is configured to introduce hydrogen from the hydrogen storage article and is configured to introduce hydrogen during a cold-start period;
wherein the hydrogen injection article is configured to introduce hydrogen when the exhaust gas stream entering the catalytic article is at a temperature of from <NUM> to <NUM>.