Patent Application
20100101221
The present disclosure relates generally to exhaust emissions systems and catalysts for use in emissions systems of combustion engines.
The fuel-air mixture used in an engine is selected to achieve desired performance characteristics in the combustion process. Fuel-air mixtures that include excess oxygen are known as “lean” mixtures and are used in lean-burning engines. Alternatively, if the mixture includes a stoichiometric amount or excess amount of fuel, the mixture is rich.
Exhaust from lean burning engines may include relatively high emissions of NOx as compared to combustions engines that operate under fuel rich conditions.
Conversion of the NOx component of exhaust streams to innocuous components generally requires specialized NOx abatement strategies for operation under fuel-lean conditions. Several catalytic systems for reducing NOx in the exhaust of lean burning engines are currently in use and/or under development. Examples of catalysts that may be used for abatement of NOx in the exhaust of lean burning engines include NOx storage reduction (NSR) catalysts, ammonia selective catalytic reduction (NH3-SCR) catalysts, and hydrocarbon selective catalytic reduction catalysts (HC-SCR).
NSR catalysts (also known as “NOx traps”) contain NOx sorbent materials capable of adsorbing or “trapping” oxides of nitrogen under lean burning conditions and platinum group metal components to provide the catalyst with oxidation and reduction functions. In operation, the NSR catalyst promotes a series of elementary steps which are depicted below in Equations 1-5. While several reactions are depicted in equations 1-5, those skilled in the art will recognize that additional and/or different reactions may occur.
In an oxidizing environment, NO is oxidized to NO2 (Equation 1), which is an important step for NOx storage. At low temperatures, this reaction is typically catalyzed by the platinum group metal component. Further oxidation of NO2 to nitrate, with incorporation of an atomic oxygen, is also a catalyzed reaction (Equation 2). There is little nitrate formation in the absence of the platinum group metal component even when NO2 is the main NOx source. The platinum group metal component has the dual functions of oxidation and reduction. For its reduction role, the platinum group metal component first catalyzes the release of NOx upon introduction of a reductant, e.g., CO (carbon monoxide) or HC (hydrocarbon) (Equation 3) to the exhaust. The released NOx is then further reduced to gaseous nitrogen (N2) in a rich environment (Equations 4 and 5). NOx release may be induced by fuel injection even in a net oxidizing environment. However, the efficient reduction of released NOx by CO requires rich conditions.
Oxidation of NO to NO2
NO+½O2→NO2 (1)
NOx Storage as Nitrate
2NO2+MCO3+½O2→M(NO3)2+CO2 (2)
NOx Release
M(NO3)2+2CO→MCO3+NO2+NO+CO2 (3)
NOx Reduction to N2
NO2+CO→NO+CO2 (4)
2NO+2CO→N2+2CO2 (5)
An alternative strategy for the abatement of NOx in the exhaust of lean burning engines uses selective catalytic reduction (SCR) catalyst technology. SCR catalyst technology uses a reductant and an SCR catalyst to reduce NOx to N2. The NH3-SCR catalysts use ammonia as a reductant and typically use catalysts composed of base metals. This technology is capable of reducing NOx by more than 90%. One of the potential disadvantages of NH3-SCR technology is the use of a reservoir to house the ammonia source (e.g., urea). Another potential disadvantage of NH3-SCR technology is the commitment of operators of these machines to replenish the reservoirs with urea as needed and infrastructure for supplying urea to the operators.
Yet another alternative strategy for the abatement of NOx in the exhaust of lean burning engines achieves selective catalytic reduction using hydrocarbon as a reductant instead of ammonia. These catalysts are referred to as HC-SCR catalysts. HC-SCR catalysts may be advantageous because the hydrocarbon is readily available on many machines, thereby eliminating the need for a separate system to house an ammonia source. Unfortunately, HC-SCR catalyst technology typically does not work with the catalyst used for the NH3-SCR system (e.g., copper zeolite), due to a lack of sufficient catalytic activity. Consequently, HC-SCR catalysts typically include a catalytic component that is configured for selectively reducing NOx at lean burning conditions using a hydrocarbon (e.g., platinum (Pt) supported on alumina).
An example of an HC-SCR catalyst that reduces NOx at lean burning conditions using a hydrocarbon are disclosed in US Patent Application 2008/0069743 to Castellano. Castellano teaches the use of silver tungstate in an HC-SCR catalyst to improve the operating temperature at which the HC-SCR catalyst reduces NOx.
The catalysts, systems, and methods disclosed herein provide for reduced NOx emissions in the exhaust stream of a lean burning engine. The catalysts include two different types of selective catalytic reduction (SCR) catalysts (i.e., two different types of catalysts that may catalytically reduce NOx using a reductant). The first catalyst is an SCR catalyst having a composition that produces a reductant and the second catalyst is an SCR catalyst having a composition that reduces NOx using the reductant produced by the first SCR catalyst. The second SCR catalyst is associated with the first SCR catalyst such that the reductant produced by the first catalyst may be used by the second SCR catalyst to reduce NOx.
Methods for removing nitrogen oxides (NOx) from an exhaust stream are also disclosed. The method may include first providing an initial exhaust gas stream from a lean burning engine where the initial exhaust gas stream includes NOx. The initial exhaust gas stream is introduced into a hydrocarbon selective catalytic reduction (HC-SCR) catalyst under lean burning conditions and produces ammonia, thereby yielding an intermediate exhaust gas stream that includes ammonia and NOx. The intermediate exhaust gas stream is introduced into an ammonia (NH3-SCR) catalyst and at least a portion the ammonia and NOx is converted to N2.
A. Emissions Treatment Systems
The SCR catalysts described herein may be included in an emissions system for lean burning engines. Referring to
The first SCR catalyst 116 and the second SCR catalyst 118 may be part of an emissions system that includes one or more additional components including, but not limited to, diesel oxidation catalysts, catalyzed soot filters, soot filters, NO2 traps, NSR catalysts, partial hydrocarbon oxidation catalysts, air pumps, external heating devices, precious metal catalysts, sulfur traps, phosphorous traps, and the like. The first SCR catalyst 116 and the second SCR catalyst 118 may be deposited on or associated with the foregoing components, alone or in combination, and in any way, so long as the SCR catalysts can perform their desired catalytic function as described below. For example, one or more of the foregoing additional components may be positioned between engine 113 and first SCR catalyst 116; between first SCR catalyst 116 and second SCR catalyst 118, and/or after second catalyst 118.
The catalyst compositions described herein may be part of a hydrocarbon SCR (HC-SCR) system 100 where the hydrocarbons are supplied by engine controls or engine management. For example, fuel injected into engine 113 may be increased such that excess fuel is present in the exhaust stream 124 from engine 113. Alternatively, the catalyst compositions may be part of an HC-SCR system 100 in which the hydrocarbons are supplied by a separate injection device. For example, hydrocarbons may be injected into gas stream 124 within conduit 110 between engine 113 and first catalyst 116. In another embodiment, an HC-SCR system may have hydrogen added to the emissions system 100, for example using a partial oxidation reactor (POX reactor), an on board supply of hydrogen, or by using compounds or complexes that release hydrogen when they are decomposed. An HC-SCR system may be provided in which 1% or more of the first reductant contains an oxygenated carbon-containing molecule such as an aldehyde, alcohol or carbon monoxide.
The first SCR catalyst 116 is a catalyst that converts at least a portion of NOx to N2 using a first reductant and also produces a second reductant. For example, in one embodiment, the first SCR catalyst 116 may be an HC-SCR catalyst that produces ammonia and the second SCR catalyst 118 may be an NH3-SCR. The first and second SCR catalysts 116 and 118 respectively may be associated in any way so long as the second reductant produced by the first SCR catalyst 116 may be utilized to convert NOx to N2 using the second SCR catalyst 118.
Referring to
With reference to
The second SCR catalyst 118 is typically deposited on the substrate 120 in an amount sufficient to ensure suitable durability and reactivity for reducing NOx using the second reductant (i.e., the reductant produced by the first SCR catalyst). In one embodiment the second SCR catalyst 118 composition may be deposited in a range from roughly 1.0 g/in3 to roughly 3.6 g/in3.
The first and/or the second SCR catalysts (116 and 118) may be in the form of self-supporting catalyst particles, as a honeycomb monolith formed of the SCR catalyst compositions, or other configurations, or combinations thereof. In one or more embodiments, the SCR catalysts 116 and/or 118 are disposed as a washcoat or as a combination of washcoats on a ceramic or metallic substrate 120, such as but not limited to a honeycomb flow-through substrate.
The substrate 120 may be any material typically used for preparing catalysts, and typically includes a ceramic or metal honeycomb structure. Examples include monolithic substrates of the type having fine, parallel gas flow passages extending therethrough from an inlet or an outlet face of the substrate, such that passages are open to fluid flow therethrough (referred to as honeycomb flow through substrates). The passages, which are typically straight paths from their fluid inlet to their fluid outlet, are defined by walls on which the catalytic material may be coated as a washcoat so that the gases flowing through the passages contact the catalytic material. The flow passages of the monolithic substrate 120 are generally thin-walled channels, which may be of any suitable cross-sectional shape and size such as trapezoidal, rectangular, square, sinusoidal, hexagonal, oval, circular, etc. Such structures may contain from about 60 to about 600 or more gas inlet openings (i.e., cells) per square inch of cross section.
The substrate 120 may also be a wall-flow filter substrate, where the channels are alternately blocked, allowing a gaseous stream entering the channels from one direction (inlet direction), to flow through the channel walls and exit from the channels from the other direction (outlet direction). Either NSR and/or SCR catalyst composition may be coated on the wall-flow filter. If such substrate is utilized, the resulting system will be able to remove particulate matters along with gaseous pollutants. The wall-flow filter substrate may be made from materials, such as, but not limited to, cordierite or silicon carbide.
The ceramics useful for substrate 120 may be made of any suitable refractory material, e.g., cordierite, cordierite-alumina, silicon nitride, zircon mullite, spodumene, alumina-silica magnesia, zircon silicate, sillimanite, a magnesium silicate, zircon, petalite, alumina, an aluminosilicate, a material of comparable functionality, or combinations thereof.
The substrates 120 useful for the catalysts (SCR catalyst 116 or 118) may also be metallic in nature and be composed of one or more metals or metal alloys. The metallic substrates may be employed in various shapes such as corrugated sheet or monolithic form. Suitable metallic substrates may include heat resistant metals and metal alloys such as titanium and stainless steel as well as other alloys in which iron is a substantial or major component. Such alloys may contain one or more of nickel, chromium and/or aluminum, and the total amount of these metals may advantageously comprise at least 15 wt % of the alloy, e.g., 10-25 wt % of chromium, 3-8 wt % of aluminum and up to 20 wt % of nickel. The alloys may also contain small or trace amounts of one or more other metals such as manganese, copper, vanadium, titanium and the like. The surface of the metal substrates 120 may be oxidized at high temperatures, e.g., 1000° C. and higher, to improve the resistance to corrosion of the alloys by forming an oxide layer on the surfaces of the substrates. Such high temperature-induced oxidation may enhance the adherence of the refractory metal oxide support and catalytically promote metal components to the substrate.
In alternative embodiments, one or more catalyst compositions may be deposited on an open cell foam substrate 120. Such substrates are typically formed of refractory ceramic or metallic materials. Substrates 122, 320, 420, and 520, described above, may be configured the same or similar to substrate 120.
B. Catalyst Compositions
According to one or more embodiments, the catalyst compositions and/or emissions systems may include any first SCR catalyst 116 that is configured to catalyze the reduction of NOx using a first reductant and also produce a second reductant. The first SCR catalyst 116 may include a catalytic metal that is substantially free of a platinum group metal. Also, the first SCR catalyst 116 is typically supported on a support material.
In one embodiment, the first SCR catalyst 116 is sized and configured to reduce NOx using a carbon-based reductant (herein referred to as “hydrocarbon SCR catalyst” or “HC-SCR catalyst”). Examples of carbon based reductants include, but are not limited to, diesel, carbon monoxide, and/or other hydrocarbons or oxides of carbon. The HC-SCR catalyst 116 may produce quantities of ammonia while reducing NOx using a hydrocarbon reductant. In one embodiment, the HC-SCR 116 produces ammonia in a concentration in a range from roughly 5 ppmv to roughly 50 ppmv.
In addition to producing ammonia, the HC-SCR catalyst 116 may produce an intermediate gas stream 126 with a desired ratio of NO2 to NO. For example, the HC-SCR catalyst 116 may yield an intermediate gas stream (i.e., the gas stream between catalyst 116 and 118) with a ratio of NO2 to NO in a range from roughly 40:60 to 60:40, or alternatively, roughly 45:55 to roughly 55:45.
Examples of catalysts that may be sized and configured to reduce NOx in an exhaust gas stream 126 using a first reductant and produce a second reductant include, but are not limited to, catalysts having a silver tungstate active component. The silver tungstate catalysts may be supported on a support material and may include silver in an amount between roughly 1 wt % and roughly 10 wt %.
In one embodiment, the support may be alumina such as, but not limited to, hydroxylated alumina. As used herein, the term “hydroxylated” refers to alumina that has a high concentration of surface hydroxyl groups that are introduced as the alumina is obtained. Examples of hydroxylated alumina include boehmite, pseudoboehmite or gelatinous boehmite, diaspore, nordstrandite, bayerite, and gibbsite. Pseudoboehmite and gelatinous boehmite are generally classified as non-crystalline or gelatinous materials, whereas diaspore, nordstrandite, bayerite, gibbsite, and boehmite are generally classified as crystalline. According to one or more embodiments, the hydroxylated alumina is represented by the formula Al(OH)xOy where x=3−2y and y=0 to 1 or fractions thereof. In their preparation, such types of alumina are typically not subject to high temperature calcination, which would drive off many or most of the surface hydroxyl groups.
According to embodiments disclosed herein, substantially non-crystalline hydroxylated alumina in the form of flat, plate-shaped particles, as opposed to needle-shaped particles, may be useful in preparing catalysts. The shape of the hydroxylated alumina used in one or more embodiments is in the form of a flat plate and has an average aspect ratio of 3 to 100 and a slenderness ratio of a flat plate surface of 0.3 to 1.0. The aspect ratio is expressed by a ratio of “diameter” to “thickness” of a particle. The term “diameter” as used herein refers to a diameter of a circle having an area equal to a projected area of the particle, which may be obtained by observing the alumina hydrate through a microscope or a Transmission Electron Microscope (TEM). The slenderness ratio refers to a ratio of a minimum diameter to a maximum diameter of the flat plate surface when observed in the same manner as in the aspect ratio. Hydroxylated, flat, plate-shaped particulate aluminas which may be used in producing the first SCR catalyst 116 according to embodiments are commercially available.
Alternatively, a calcined alumina may be treated in a manner to add surface hydroxyl groups, for example, by exposing the alumina to steam for a period of time. In one or more embodiments, the alumina used for silver impregnation is substantially free of gamma alumina. The final catalyst after silver impregnation, drying, calcination, and/or hydrothermal treatment, may comprise gamma alumina or other high temperature alumina phases.
In one or more embodiments, the alumina is impregnated with a solution containing silver tungstate. The silver tungstate catalysts 116 have HC-SCR activity for the treatment of emissions from lean burning engines. The stoichiometric compound Ag2WO4 (or multiples thereof) supported on an alumina such as gamma alumina, boehmite or pseudoboehmite or mixtures thereof may effectively convert NOx to N2 in the presence of a hydrocarbon reducing agent. Compared to a silver only compound on an alumina HC-SCR catalyst 116, similar conversions of NOx may be obtained with approximately one half the net silver loading using silver tungstate. The 2% silver tungstate on alumina catalyst may give similar NOx conversion as 2% silver (as Ag2O) on the same alumina, although the silver (Ag2O) loading for the silver tungstate catalyst is only one half that of silver only catalyst.
The silver tungstate catalyst 116 may be made by dissolving commercially available silver tungstate in an ammonium hydroxide solution and impregnating the alumina to the desired silver tungstate level. The resulting material is then dried and calcined to a temperature of about 540° C. The material may then be heated in 10% steam at 650° C. It has been found that silver tungstate catalysts 116 may provide high conversions over a broad temperature range of about 275° C. to 525° C.
The deposition of silver onto the surface of alumina may be achieved by various impregnation methods, including incipient wetness and wet impregnation. In the wet impregnation process, an excess amount of solution is mixed with the support, followed by evaporation of the excess liquid. The deposition of silver may also be achieved by other coating techniques such as chemical vapor deposition.
The second SCR catalyst 118 is an SCR catalyst configured to reduce NOx in an exhaust stream of a lean burning engine using the second reductant (i.e., the reductant produced by the first SCR catalyst 116). The second SCR catalyst 118 may include any material or combination of materials that may adsorb the second reductant produced by the first SCR catalyst 116 and/or facilitate the reaction of NOx with the second reductant to yield nitrogen.
In one embodiment, the second SCR catalyst 118 is an ammonia SCR catalyst. The NH3-SCR catalyst 118 may include a base metal catalyst on a high surface area support such as, but not limited to, alumina, silica, titania, zeolite or a combination of these. The NH3-SCR catalyst 118 may include a base metal selected from the group consisting of copper (Cu), iron (Fe) and cerium (Ce) and/or a combination of these metals, although other base metals may be used, including, but not limited to indium (In), copper (Cu), silver (Ag), zinc (Zn), cadmium (Cd), cobalt (Co), nickel (Ni), iron (Fe), molybdenum (Mo), tungsten (W), titanium (Ti), vanadium (V), and zirconium (Zr), oxides thereof, alloys thereof, or combinations thereof. Base metals generally are able to effectuate NOx conversion using ammonia while both the base metals and the high surface support material serve to readily adsorb the NH3. The base metal and high surface area support such as zeolite selected may be one that adsorbs NH3 over a relatively wide temperature range. Likewise, the base metal selected may be one that may converts NO and NO2 to N2 across a desired temperature range and desired range of NO/NO2 ratios.
The second SCR catalyst 118 is associated with the first SCR catalyst 116 such that the second reductant (i.e., the reductant produced by the first SCR catalyst) is in fluid communication with the second SCR catalyst 118. The association between the first and second SCR catalysts 116 and 118, respectively, may be provided by depositing the first and second SCR catalysts on one or more substrates and/or including the catalysts within an emissions treatment system 100. Moreover, any of the foregoing components described herein with respect to SCR catalyst 116, SCR catalyst 118, and/or substrates 120 and 122 may be included in the corresponding components of systems 300, 400, and/or 500, described above (e.g., components of catalyst 116 are suitable for components of catalyst 316, etc).
C. Methods For Manufacturing Compositions
The catalyst composite may be readily prepared in one or more layers on a monolithic honeycomb substrate 120. For a two-layer washcoat, the bottom layer, finely divided particles of a high surface area refractory metal oxide such as gamma alumina may be slurried in an appropriate vehicle, e.g., water. The substrate may then be dipped one or more times in such slurry or the slurry may be coated on the substrate 120 (e.g., honeycomb flow through substrate) such that there will be deposited on the substrate 120 the desired loading of the catalytic component. Components such as the silver metals, precious metals or platinum group metals, transition metal oxides, stabilizers, promoters and the NOx sorbent component may be incorporated in the slurry as a mixture of water soluble or water-dispersible compounds or complexes. Thereafter, the coated substrate 120 is typically calcined by heating, e.g., at 400 to 600° C. for 1 to 3 hours.
In one or more embodiments, the slurry may be comminuted to result in substantially all of the solids having particle sizes of less than 20 microns, e.g., 1-15 microns, in an average diameter. The comminution may be conducted in a ball mill or other similar equipment, and the solids content of the slurry may be, e.g., 20-60 wt % or alternatively 35-45 wt %.
Each layer is thereafter prepared and deposited on the previously formed layer of the calcined composite in a manner to yield a catalyst as described above with respect to
D. Methods For Reducing NOx
The present disclosure includes a method for reducing NOx in the exhaust stream of a lean burning engine using two different SCR catalysts, one of which produces a reductant. The method includes providing an initial exhaust gas stream 124 having a concentration of NOx. The initial exhaust gas stream 124 is obtained from the engine 113 and delivered over a hydrocarbon selective catalytic reduction (HC-SCR) catalyst 116 under lean burning conditions and the HC-SCR catalyst produces ammonia, thereby yielding an intermediate exhaust gas stream 126 that includes ammonia and NOx. The intermediate exhaust gas stream 126 is delivered over an ammonia (NH3-SCR) catalyst 118 and at least a portion of the NOx is converted to N2 using the ammonia produced by the HC-SCR catalyst 116.
In one embodiment, the HC-SCR catalyst 116 may include a silver tungstate active component. Surprisingly, it has been found that HC-SCR catalysts and systems that include silver tungstate may produce intermediate gas streams that include significant amounts of ammonia and/or NO to NO2 ratios that are particularly beneficial for being reduced by ammonia in the presence of an NH3-SCR catalyst. For example, the HC-SCR catalyst 116 may facilitate formation of an intermediate gas stream 126 that has a NO2 to NO ratio in a range from 40:60 to 60:40, alternatively 45:55 to 55:45. These ranges of NOx species are particularly beneficial for removing the NOx in the intermediate gas stream 126 using an NH3-SCR catalyst.
Example 1 describes an emissions system that includes an HC-SCR catalyst 116 in combination with an NH3-SCR catalyst 118 according to one embodiment. The HC-SCR 116 is positioned upstream from the NH3-SCR 118 in an exhaust system from an internal combustion engine operating on diesel under lean burning conditions. The HC-SCR catalyst 116 may include a silver tungstate supported on a hydroxylated alumina support and having a silver tungstate loading of 2.5 g/in3. The NH3-SCR catalyst 118 may include an iron zeolite with an iron loading of 3.0 g/in3.
A hydrocarbon reductant is introduced into the exhaust gas stream 124 above the HC-SCR catalyst 116 and acts as a reductant in the conversion of NOx to N2 in the presence of the HC-SCR catalyst 116. Testing is carried out with a space velocity of 60,000 h−1, 10% oxygen in the initial gas stream, and diesel as the hydrocarbon reductant at a C1 to NOx ratio of 10. Catalyst performance is tested using a down ramp method starting at 550° C. Essentially no ammonia is present in the gas stream 124 going into the HC-SCR catalyst 116 and approximately 5% to 30% of NOx into the HC-SCR catalyst 116 is converted to ammonia. Ammonia out of the HC-SCR catalyst 116 is typically in a range from roughly 5 to roughly 50 ppmv (e.g. for an engine producing between 0.6 g to 1.2 g of NOx/brake horsepower/hour). Of the 5 to 50 ppmv of ammonia, roughly 80% to roughly 95% of NOx is converted to N2 by the ammonia in the NH3-SCR catalyst that is downstream from the HC-SCR catalyst 116. The catalyst of Example 1 and similar catalysts as described above are hereinafter referred to as a “dual SCR catalyst.”
As compared to known NOx reduction systems, the dual SCR catalysts and emissions treatment systems described herein may be used to achieve higher NOx reduction than known HC-SCR catalysts without the need for separate ammonia storage and delivery systems for ammonia. To evaluate the performance of the dual SCR catalysts and exhaust treatment systems described herein, the dual SCR catalysts were compared to traditional HC-SCR and NH3-SCR catalysts systems.
The highest NOx reduction is expected from the NH3-SCR catalyst 620, which requires the use of ammonia as a reductant. However, as can be seen from the graph, emissions system 600, which uses an HC-SCR catalyst and an NH3-SCR catalyst and hydrocarbon as reductant may achieve a NOx reduction more similar to the NH3-SCR catalyst 620. Moreover, these results may be achieved without introducing an external source of ammonia. In addition, the emissions system 600 may have substantially better NOx reduction and/or a wider operating temperature range compared to the silver tungstate HC-SCR 610, while adding the same reductant (i.e., hydrocarbon) to the initial exhaust gas stream 124.
Most diesel engines and some gasoline engines operate at lean burning conditions. The oxygen-rich fuel mixture used in lean burning engines may be advantageous for many reasons, including high fuel economy and low emissions of gas phase hydrocarbons and carbon monoxide.
The disclosed exhaust treatment systems and catalyst may be applicable to any combustion-type device such as, for example, an engine, a furnace, or any other device known in the art where it is desirable to remove NOx from an exhaust flow.
Examples of engines that may include the catalysts, systems, and methods disclosed herein include, but are not limited to gas, diesel, gaseous, propane, and the like. The engines may be used in applications including, but not limited to, on-highway, off road, earth moving, transportation, generators, aerospace, locomotive, marine, pumps, stationary equipment, and the like.
The catalysts, systems, and methods disclosed herein may be embodied in other specific forms without departing from the spirit or essential characteristics of the disclosure. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
