Catalytic article for exhaust systems of natural gas engines

Abstract

The present invention relates to a catalyst article for the exhaust system of a natural gas engine having improved sulfur and / or moisture tolerance. The catalyst article includes a doped alumina-supported palladium catalyst, the alumina-supported palladium catalyst being doped with manganese and / or zinc. The present invention further relates to an exhaust gas treatment system, a natural gas combustion engine, and a method for the treatment of exhaust gas from a natural gas combustion engine.

Description

[Technical Field]

[0001] The present invention relates to catalyst articles for the exhaust systems of natural gas engines, and in particular to catalyst articles having improved sulfur and water resistance due to the presence of additional Mn and / or Zn in an alumina-supported Pd catalyst. [Background technology]

[0002] Natural gas is gaining interest as an alternative fuel for vehicles and stationary engines that traditionally use gasoline and diesel fuel. Natural gas is composed primarily of methane (typically 70-90%), with varying proportions of other hydrocarbons such as ethane, propane, and butane (up to 20% in some deposits) and other gases. It can be produced commercially from oil or natural gas fields and is widely used as a combustion energy source for power generation, industrial cogeneration, and home heating. It can also be used as a vehicle fuel.

[0003] Natural gas can be used as a transportation fuel in the form of compressed natural gas (CNG) and liquefied natural gas (LNG). CNG is carried in tanks pressurized to 3600 psi (approximately 248 bar) and has an energy density per unit volume that is approximately 35% that of gasoline. LNG has 2.5 times the energy density of CNG and is primarily used in heavy vehicles. LNG is cooled to liquid form at -162°C, resulting in a 600-fold reduction in volume, which means that LNG is easier to transport than CNG. Bio-LNG, a potential alternative to natural (fossil) gas, is produced from biogas, obtained by anaerobic digestion of organic matter such as landfill waste or manure.

[0004] Natural gas has many environmental advantages: it is a cleaner burning fuel, typically containing fewer impurities, has a higher energy per carbon (Bti) than traditional hydrocarbon fuels, resulting in lower carbon dioxide emissions (25% fewer greenhouse gas emissions), and lower PM and NO emissions compared to diesel and gasoline. x Biogas can reduce these emissions even further.

[0005] Further drivers for adopting natural gas include its high abundance and lower cost compared to other fossil fuels.

[0006] Natural gas engines produce significantly lower PM and NO emissions compared to heavy and light duty diesel engines. x (up to 95% and less than 70%, respectively). However, the exhaust gases produced by NG engines often contain significant amounts of methane (so-called "methane slip"). Regulations limiting emissions from these engines currently include Euro VI and the U.S. Environmental Protection Agency (EPA) Greenhouse Gas Act. These impose emission limits for methane, nitrogen oxides (NOx), and particulate matter (PM).

[0007] The two main operating modes used in methane-fueled engines are stoichiometric conditions (λ = 1) and lean-burn conditions (λ ≥ 1.3). Palladium-based catalysts are known to be the most active type of catalyst for methane oxidation under both conditions. Regulated emission limits for both stoichiometric and lean-burn compressed natural gas engines can be met by applying either a palladium-rhodium three-way catalyst (TWC) or a platinum-palladium oxidation catalyst, respectively.

[0008] The development of this Pd-based catalyst technology depends on overcoming challenges related to cost and catalyst deactivation by sulfur, water, and heat aging.

[0009] Methane is the least reactive hydrocarbon, requiring high energy to break the primary C-H bond. The ignition temperature of alkanes generally decreases with increasing fuel-air ratio and with increasing hydrocarbon chain length, which correlates with C-H bond strength. It is known that the light-off temperature for methane conversion on Pd-based catalysts is higher than that for other hydrocarbons ("light-off temperature" refers to the temperature at which the conversion rate reaches 50%).

[0010] When operated under stoichiometric conditions (λ=1), the TWC can be used as an effective and cost-effective aftertreatment system for combusting methane. -3 Most bimetallic Pd-Rh catalysts with high total platinum group metal (pgm) loadings exceeding 1000 MPa are required for high levels of methane conversion to meet end-of-life total hydrocarbon (THC) regulations due to the very low reactivity of this hydrocarbon and catalyst deactivation by thermal and chemical effects. The use of high pgm loadings improves total HC conversion in stoichiometric CNG engines. However, high methane conversion can be achieved at relatively low pgm based on engine calibration, i.e., by controlling the air-fuel ratio to operate near or richer than stoichiometric. The pgm loading can also be varied to accommodate local legislative requirements for methane and non-methane conversion.

[0011] NO x The reduction of NO and oxidation of methane are also more difficult under highly oxidizing conditions. For lean-burn CNG applications, Pd-Pt with high total pgm loadings (>200 gft-3) is required for methane combustion at lower temperatures. Unlike stoichiometric engines, NO is reduced in the presence of excess oxygen. x A reducing agent must also be injected into the exhaust stream so that NO can be reduced. This is usually in the form of ammonia (NH3). Therefore, lean-burn applications require a completely non-stoichiometric catalyst system where efficient NO xReduction can be achieved using CO or HC under slightly rich or stoichiometric conditions.

[0012] Due to the non-reactive (or low-reactive) properties of methane at low temperatures, increased methane emissions occur during cold starts and idle conditions, primarily in lean burn situations where exhaust temperatures are lower than stoichiometric. To improve methane reactivity at lower temperatures, one option is to use higher pgm loadings, but this increases cost.

[0013] Natural gas catalysts, especially Pd-based catalysts, can suffer from poisoning by water (5-12%) and sulfur (<0.5 ppm SO2 in lubricating oil), especially under lean conditions, which results in a dramatic decline in catalyst conversion over time. Water deactivation is significant due to the formation of hydroxyls, carbonates, formates, and other intermediates on the catalyst surface. Activity is reversible and can be fully restored when the water is removed. However, this is impractical because methane combustion feed always contains high levels of water due to the high H content in methane.

[0014] HO can be either an inhibitor or promoter, depending on the air-fuel ratio, i.e., λ. Under stoichiometric and reducing conditions (λ > 1), HO can act as a promoter for hydrocarbon oxidation via the steam reforming reaction in both CNG and gasoline engines. However, in lean-burn CNG operating at λ > 1, HO acts as an inhibitor of methane oxidation. Understanding the water-inhibitory effect and designing catalysts that are more tolerant to the presence of HO is important. This allows for improvements when trying to control methane emissions from lean-burn CNG.

[0015] Although sulfur levels in engine exhaust are very low, Pd-based catalysts are significantly deactivated upon sulfur exposure due to the formation of stable sulfates. Regenerating catalysts to restore activity after sulfur poisoning is difficult and typically requires high temperatures, rich operation, or both. This is easily achievable under stoichiometric operation but is more difficult under lean-burn conditions. Lean-burn vehicles operate at much higher air-fuel ratios than stoichiometric vehicles and require much higher concentrations of reductant injection to switch to rich operation. Thermal deactivation, resulting from a high level of misfire events due to poor engine transient control and ignition systems, destroys the catalyst and results in correspondingly high levels of exhaust emissions.

[0016] The catalyst deactivates under both conditions, but sulfur poisoning has a more dramatic effect than heat aging under lean operation. Sulfur poisoning can be ameliorated by adding small amounts of Pt to the Pd catalyst. This is because sulfur inhibition due to the formation of palladium sulfate can be significantly reduced by adding Pt. However, adding Pt also increases costs.

[0017] It is therefore desirable to provide an improved catalyst for natural gas burning engines to reduce methane emissions by addressing catalyst deactivation due to sulfur, water, thermal aging, etc., without increasing the cost of the catalyst. It is an object of the present invention to address this problem and to address the shortcomings associated with the prior art, or at least to provide a commercially useful alternative thereto. Summary of the Invention

[0018] According to a first aspect, there is provided a catalyst article for the treatment of exhaust from a natural gas burning engine, the catalyst article comprising a doped alumina supported palladium catalyst, the alumina supported palladium catalyst doped with manganese (Mn) and / or zinc (Zn).

[0019] In the following sections, different aspects / embodiments are defined in more detail. Each aspect / embodiment so defined can be combined with any other aspect / embodiment or aspects / embodiments, unless expressly indicated otherwise. In particular, any feature indicated as being preferred or advantageous can be combined with any other feature or features indicated as being preferred or advantageous.

[0020] Catalyst articles are components suitable for use in exhaust gas systems. Typically, such articles are honeycomb monoliths, sometimes referred to as "bricks." They have a high surface area configuration suitable for contacting the gas to be treated with the catalytic material to effect conversion or transformation of components of the exhaust gas. Other forms of catalyst articles are known, including plate configurations, as well as wrapped metal catalyst substrates. While the catalysts described herein are suitable for use in all of these known forms, the honeycomb monolith form is particularly preferred, as it offers a good balance between cost and simplicity of manufacture.

[0021] Preferably, the doped alumina-supported palladium catalyst is provided as a washcoat on a substrate. Alternatively, the doped alumina-supported palladium catalyst is provided as a component of an extruded substrate. Preferably, in either case, the substrate is a flow-through monolith. Preferably, when the catalyst is provided as a washcoat on a substrate, the substrate is a flow-through ceramic monolith.

[0022] The catalytic article is for the treatment of exhaust from a natural gas combustion engine. That is, the catalytic article is for catalytic treatment of exhaust gas from a natural gas combustion engine for converting or transforming components of the gas before releasing them into the atmosphere to meet exhaust gas regulations. When natural gas is combusted, it produces both carbon dioxide and water, but the exhaust gas also contains additional amounts of methane (and other short-chain hydrocarbons) that need to be catalytically removed before the exhaust gas is released into the atmosphere. The exhaust gas also typically contains significant amounts of water and sulfur, which can accumulate and deactivate the catalyst.

[0023] In mobile applications, the natural gas combustion may be configured to operate in a lean or stoichiometric configuration. By "mobile application," it is meant that the system may generally be suitable for use in an automobile or other vehicle (e.g., an off-road vehicle), where there may be changes in fuel supply and demand during operation depending on operator requirements such as acceleration. In mobile applications, the system may generally be run temporarily in a rich mode, which is associated with a significant increase in temperature to help burn off catalyst-poisoning sulfur and remove accumulated water.

[0024] In stationary systems, natural gas combustion can also be configured to operate under lean or stoichiometric conditions. Examples of stationary systems include gas turbines and power generation systems, where combustion conditions and fuel composition are generally kept constant over long periods of operation. This means that there are fewer opportunities to have regeneration steps to remove sulfur and moisture contaminants compared to mobile applications. Therefore, the benefits described herein can be particularly beneficial in stationary applications. That is, it is particularly desirable to provide a catalyst with high sulfur and moisture tolerance when opportunities for catalyst regeneration are limited.

[0025] Although the above "dilute" and "stoichiometric" systems are described as "mobile" and "stationary," it should be understood that both system types can be used across a range of different applications.

[0026] The catalytic article comprises a doped alumina-supported palladium catalyst. That is, the article comprises a catalyst comprising an alumina support provided as a support for supporting palladium and a dopant as components (preferably as the only catalytically active components). Alumina is a very common support for use in catalytic applications, and selecting an appropriate alumina is common in the art. The selection of the appropriate amount of alumina to form the catalyst depends on the substrate morphology, as discussed herein.

[0027] Alumina may be provided in one or more different crystalline forms. Gamma alumina is generally most preferred due to its thermal stability. The alumina may contain one or more dopants to help improve its stability; typical dopants include Si and La. Dopants for stabilizing the alumina are preferably present in an amount less than 15% by weight of the alumina, more preferably less than 10% by weight. These dopants for alumina may be present in an amount of 1-10% by weight of the alumina.

[0028] Depending on the form of the catalyst article, the catalyst may further comprise additional non-catalytic components. For example, it is conventional to include binders containing clay and other alumina components in washcoats. For example, it is conventional to include additional fillers and processing aids such as glass fibers and clay in extruded catalyst monoliths.

[0029] Preferably, the catalyst article has a surface roughness of 50 to 300 g / ft 3 , preferably 70 to 250 g / ft 3 , more preferably 100 to 200 g / ft 3 These levels are effective in treating methane in exhaust gases and can be significantly higher than those for TWC.

[0030] The alumina supported palladium catalyst is doped with manganese and / or zinc. Most preferably the catalyst is doped with either Mn or Zn. Preferably the catalyst article has a doping density of 5 to 100 g / ft 3 , preferably 20 to 80 g / ft 3 , more preferably 40 to 60 g / ft 3 The catalyst has a total loading of Mn and / or Zn of 1000 Mn / 2000 Mn / 2000 Zn / 2 ...

[0031] Preferably, the catalyst article has a ratio of Pd loading to total Mn and / or Zn loading of greater than 1:1, preferably between 1:1 and 10:1, more preferably between 2:1 and 5:1, and most preferably about 3:1. Because the Mn and / or Zn are present to promote the reaction effected by the Pd, the amount of dopant is generally less than or equal to the amount of promoted Pd.

[0032] The present inventors sought to provide a natural gas engine aftertreatment system capable of burning methane at lower temperatures. Surprisingly, the inventors discovered that the inclusion of Mn and / or Zn has a positive effect on (i) methane conversion performance under wet and dry conditions and (ii) the sulfur tolerance of the catalyst. In particular, experimental SCAT analysis revealed that Mn- and Zn-doped Pd / Al2O3 catalysts exhibited improved light-off activity for methane at low temperatures under both dry and wet conditions. This suggests that doping Pd / Al2O3 with either Mn or Zn improves catalytic performance over Pt-doped Pd / Al2O3 catalysts. Sulfur tolerance tests were also performed on these catalysts, and both the Mn- and Zn-doped catalysts showed similar improvements in sulfur tolerance.

[0033] Without wishing to be bound by theory, it is believed that doping Pd with Mn increases the activation energy (E a ) and is thought to improve resistance to OH poisoning compared to other dopants. Similar performance was observed with Zn.

[0034] Using computer simulations, we developed a model to help understand the fundamentals of these reactions. In this model, a PdO(100) surface was doped with a series of +2 oxidation state elements, as listed in Table 1. The activation energy barrier (E aA model was constructed by calculating the adsorption energies of the cations of ZnO, ZnO, and various intermediate species. The model predicted that doping with either Mn or Zn could decrease the activation energy and improve the resistance to OH or SO2 poisoning.

[0035] [Table 1]

[0036] To confirm the activity of these doped PdO(100) surfaces, three variables were then calculated: δG(CH4_TS * ), δG(OH * ) and δG(O * ) was used to develop a kinetic model, where δG(CH4_TS * ) is the first dissociation step of CH4, which is considered to be the rate-determining step, and δG(OH * ) represents the resistance to water poisoning, and δG(O * ) is the adsorption of oxygen on the Pd surface to generate active sites. Mn was suggested to enhance the activity of the PdO(100) surface at low temperatures.

[0037] Preferably, the doped alumina supported palladium catalyst contains platinum, preferably in an amount of 50 to 300 g / ft 3 , preferably 70 to 250 g / ft 3 , more preferably 100 to 200 g / ft 3 Preferably, the weight ratio of Pt to Pd is less than 1:1, preferably 1:2 to 1:10. Pt is a well-known complementary Pgm that is present to improve the overall oxidation performance of the catalyst.

[0038] The table above clearly shows that Mn and Zn are better than PdO alone under all circumstances. However, the other elements shown represent a balance of advantages and disadvantages. Preferably, the doped alumina-supported palladium catalyst includes one or more additional dopant elements selected from Se, Cu, Cd, Ge, Ba, Sr, and Sn. As shown in the table above, each of these dopants has a different balance of effects on the activation energy, the energy of OH, O, and SO2 absorption. This means that, depending on the specific application required, it may be desirable to add a component with a specific benefit, even if it is offset by some disadvantages. For example, Cd provides a strong improvement in water resistance but only a moderate disadvantage in the activation energy.

[0039] Preferably, the one or more further dopant elements are present in an amount of 5 to 100 g / ft 3 , preferably 20 to 80 g / ft 3 , more preferably 40 to 60 g / ft 3 Preferably, the one or more further dopants are present in a weight ratio relative to the total amount of Mn and Zn of less than 1:1, preferably less than 3:1, and more preferably less than 5:1, since Mn and Zn generally have a positive effect, while further dopants generally provide a secondary benefit.

[0040] According to a further aspect, there is provided an exhaust gas treatment system including the catalytic article described herein. The exhaust gas treatment system generally has an inlet end configured to receive exhaust gas from a combustion chamber and an outlet for releasing treated exhaust gas to the atmosphere. Alongside the catalytic article in the exhaust gas system, there may be one or more other catalytic or filtering components suitable for treating other components of the exhaust gas or for providing additional treatment to methane to avoid slippage.

[0041] According to a further aspect, there is provided a natural gas combustion engine comprising an exhaust gas treatment system as described herein. Preferably, the natural gas combustion engine is configured to operate under lean conditions. The natural gas combustion engine may be a stationary engine. As noted above, catalyst regeneration is more difficult in stationary systems, so it is particularly important that the catalyst be stable to sulfur and moisture contamination. Otherwise, the catalyst would need to be taken offline and separately regenerated, which can lead to process inefficiencies and costs.

[0042] According to a further aspect, there is provided a method for treating exhaust from a natural gas combustion engine, the method comprising contacting the exhaust gas with a catalytic article described herein. Preferably, the exhaust gas is obtained by combustion of natural gas, the exhaust gas containing at least 0.5 ppm sulfur dioxide. Preferably, the exhaust gas is obtained by combustion of natural gas, the exhaust gas containing 5 to 12 wt. % water. As will be appreciated, these types of exhaust gases are conventional in treating exhaust from natural gas combustion, and it is these that most clearly benefit from the improved water and sulfur tolerance of the catalytic article described herein.

[0043] Preferably, during the step of contacting the exhaust gas with the catalytic article, the temperature of the exhaust gas is less than 550° C., preferably less than 500° C. For example, the exhaust gas may have a temperature of about 450° C. These conditions are particularly common in lean-running systems. [Brief explanation of the drawings]

[0044] The invention is further described in connection with the following non-limiting figures. [Figure 1] The figure shows the percent methane conversion as a function of temperature under dry and wet conditions, where, from left to right at 50% conversion, the lines are Zn-doped (dry), Mn-doped (dry), undoped (dry), Pt-doped (dry), followed by Zn-doped (wet), Mn-doped (wet), undoped (wet), and Pt-doped (wet). [Figure 2]Figure 1 shows methane conversion (%) as a function of temperature using a 0.5 ppm SO reactant gas feed. In this figure, at 425°C, the best conversion is obtained with Mn, followed by Zn. [Example]

[0045] The invention will now be further described with reference to the following non-limiting examples.

[0046] Example 1 A catalyst composition containing 1 wt % Mn-2.85 wt % Pd on undoped alumina (SCFA 140) was prepared as follows.

[0047] 0.9 g of manganese nitrate tetrahydrate was dissolved in a minimum amount of water and added to 3.75 g of palladium nitrate, then further diluted with approximately 1 mL of water. This mixture was added dropwise to 20 g of alumina support with constant stirring, followed by rinsing. The mixture was dried in an oven for 3 hours and then calcined at 500 °C for 2 hours.

[0048] The total Pd loading in this catalyst was approximately 128 g / ft 3 The total Mn loading is approximately 45 g / ft 3 It was.

[0049] Example 2 A further catalyst composition comprising 1 wt % Zn-2.85 wt % Pd on undoped alumina (SCFA 140) was prepared as follows.

[0050] 0.9 g of zinc nitrate hexahydrate was dissolved in a minimum amount of water and added to 3.77 g of palladium nitrate, then further diluted with approximately 1 mL of water. This mixture was added dropwise to 20 g of alumina support with constant stirring, followed by rinsing. The mixture was dried in an oven for 3 hours and then calcined at 500 °C for 2 hours.

[0051] The total Pd loading in this catalyst was approximately 128 g / ft 3 The total amount of Zn supported is approximately 45 g / ft 3 It was.

[0052] -Catalyst testing Pelleted samples (0.2-0.4 g, 250-300 μm) of the catalyst compositions prepared in Examples 1 and 2 were tested for water and sulfur resistance in a synthetic catalytic activity test (SCAT) apparatus over a range of temperatures (150-450°C at a ramp rate of 10-15°C / min) at a space velocity (SV) of 45 kJ / min using the inlet gas mixture described below.

[0053] For the water resistance test, the following inlet gas mixture was used: Dry: 4000 ppm CH4, 8% O2, balance N2 Wet: 4000 ppm CH4, 8% O2, 10% H2O, balance N2

[0054] For sulfur tolerance testing, the following inlet gas mixture was used: 4000 ppm CH4, 30 ppm C3H8, 100 ppm C2H6, 1000 ppm CO, 5% CO2, 500 ppm NO, 8% O2, 10% H2O, 0.5 ppm SO2, balance N2.

[0055] Both of these examples showed improved sulfur tolerance, improved moisture tolerance and better catalytic activity compared to the undoped Pd catalyst, as shown in the figures.

[0056] Although preferred embodiments of the present disclosure have been described in detail herein, those skilled in the art will recognize that variations may be made without departing from the scope of the present disclosure or the appended claims.

Claims

1. 1. A catalytic article for the treatment of methane in exhaust gas from a natural gas combustion engine, said exhaust gas containing 5 to 12 wt. % water; a doped alumina-supported palladium catalyst, wherein the alumina-supported palladium catalyst is doped with zinc; A catalyst article having a palladium loading of 100 to 200 g / ft 3 (3.53 to 7.06 kg / m 3 ) and a zinc loading of 20 to 80 g / ft 3 (0.71 to 2.83 kg / m 3 ).

2. The catalyst article has a coating weight of 40 to 60 g / ft ３ 10. The catalyst article of claim 1 having a total Zn loading of (1.41-2.11 kg / m 3 ).

3. The catalytic article of claim 1 , wherein the doped alumina-supported palladium catalyst is provided as a washcoat on a substrate.

4. The catalyst article of claim 1 , wherein the doped alumina-supported palladium catalyst is provided as a component of an extruded substrate.

5. 5. The catalytic article of claim 3 or 4, wherein the substrate is a flow-through monolith.

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