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    • 专利摘要:
    SELECTIVE CATALYTIC REDUCTION SYSTEM FOR CAPTURE OF VOLATILIZED COMPOUNDS This is an apparatus and method for treating exhaust gases from diesel engines. The system consists of two functionalities, the first being a selective catalytic reduction (SCR) catalyst system and the second being a capture material that serves to capture catalyst components that have remarkable volatility under extreme exposure conditions. The SCR catalyst component is typically based on a major titanium phase, ram added minor phase catalyst components that comprise one or more of large surface area oxides, such as titanium stabilized with silica, alumina, or stabilized alumina, for example, the capture material maintains a low coverage of total fractional monolayer of oxides of the minotary phase throughout the duration of the extreme exposure. The method involves the treatment of hot exhaust streams by both the catalyst material and the capture material, the capture material being in a mixture with the catalyst material, or it can be located downstream of the same, or both, but still be kept in extreme temperatures. Therefore, volatile catalyst components such as vanadium and tungsta are removed from (...).
    公开号:BR112012014498B1
    申请号:R112012014498-7
    申请日:2010-11-12
    公开日:2020-11-17
    发明作者:David Monroe Chapman
    申请人:Tronox Llc；
    IPC主号:
    专利说明:

    BACKGROUND
    [001] The selective catalytic reduction (SCR) of nitrogen oxides produced in combustion engines, with reducing agents such as urea and ammonia, consists of an industrially significant catalytic process. Vanadium-based SCR catalysts using titania catalytic supports are approved for use in mobile road applications in Europe on Heavy Duty Diesel trucks, and these catalysts are highly active and have excellent tolerance to fuels containing sulfur. However, vanadium-based catalysts are not EPA approved for road use in the USA or Japan. This lack of approval stemming from issues related to the release of vanadium into the environment and the potential toxicity that can arise from exposure to vanadium emitted from the exhaust pipe. One possible mechanism that can potentially cause a loss of vanadium from the catalyst is the vaporization of metal oxide or hydroxide at a high temperature in the flow of hot exhaust gases.
    [002] In addition, more recent regulations on soot and NOx that will start to take effect as early as 2010 (for example, Euro VI and US 2010 regulations) may require the use of a diesel particulate filter (DPF) coupled with a SCR catalyst. In one configuration (U.S. Patent No. 7,498,010), the SCR catalyst is found downstream from the DPF. If no corrective action is taken, the accumulation of soot on the DPF will eventually block the channels for the exhaust gas flow, and may cause unacceptable elevations of pressure drop in the device. In order to avoid this situation, the soot is removed either continuously or sporadically by combustion. Since combustion is an exothermic process, it is associated with a rise in the temperature of the device that is transmitted to the exhaust gases, and the rise in temperature depends on the amount of soot collected, as well as the temperature of the upstream exhaust gas. of the DPF. These high temperature exhaust gases, which can approach 750 ° C and above, will subsequently pass directly through the SCR catalyst. Therefore, more emphasis has recently been placed on improving the thermal stability of the SCR catalyst, both for vanadium-based catalysts and for Cu-, Fe- and other metallic catalysts. In general, it is acceptable that the catalyst should be stable at temperatures up to 800 ° C for short periods of time. In order to test the durability of the catalyst formulations, it is necessary to develop tests that simulate the real exposure conditions. Ford researchers [1] have developed an accelerated aging protocol for SCR catalysts that simulate road conditions over a range of 192,000 km (120,000 miles). This test involves exposing the catalyst to a reactive gas flow that includes water (5% vol.), For a period of 64 hours at 670 ° C at a relatively high gas flow rate (hourly space velocity of gas , GHSV = 30,000 hr1). These time and temperature conditions are used as a reference point for the method of the presently described and claimed inventive concepts.
    [003] The problem of vanadium volatility at high temperatures, for example, when the SCR catalyst is located downstream of the DPF, is therefore an issue that may limit the available market for mobile vanadium and SCR catalysts it is a major consideration in the development of catalysts. Therefore, there is still a need in the art for assessing the degree of volatilization of vanadium from SCR catalysts. In addition, there is still a need in the art for a selective catalytic reduction catalyst system of deNOx that demonstrates a vanadium loss equal to zero downstream of it. An objective of the inventive concepts presently described and claimed is to address these disadvantages of the prior art. DESCRIPTION SUMMARY
    [004] The present description describes a selective catalytic reduction catalyst system for the capture of volatilized compounds, such as vanadium and tungsten compounds, and compositions and processes for the capture of volatilized compounds, such as vanadium and tungsten compounds in such a catalyst system. selective catalytic reduction, for example, in a diesel engine emission control system. Typically, the system comprises two functionalities, the first being a selective catalytic reduction (SCR) catalyst system and the second is a capture material that serves to capture the catalyst components that have remarkable volatility under extreme exposure conditions. The SCR catalyst component is typically based on a major titanium phase, with minority catalyst components added that comprise one or more of the oxides of vanadium, silicon, tungsten, molybdenum, iron, cerium, phosphorous vanadium, copper and / or manganese. Typically, the capture material comprises a major oxide phase with a large surface area, such as titania stabilized with silica, alumina, or stabilized with alumina, for example, with the capture material maintaining a low total fractional monolayer coverage of phase oxides. minority interest over the duration of the extreme exposure. The method involves the treatment of hot exhaust flows by both the catalyst material and the capture material, the capture material being in a mixture with the catalyst material, or it can be located downstream of the same, or both, however, they can still be kept in extreme temperatures. Volatile catalyst components, such as vanadium and tungsta, are removed from the vapor phase of the exhaust gas.
    [005] In one aspect of the description, it is contemplated that stable oxide supports of large surface area that include, but are not limited to, titania and alumina stabilized with silica, can be used to capture these volatile components, when said components are present in low density on the support surface of the capture bed after capture. Furthermore, with reference to certain modalities, it has been surprisingly found that when normally volatile components are present in low density on the catalyst surface before exposure to extreme conditions, they also exhibit reduced volatility in extreme conditions, in such a way that such "low density" catalysts can also be employed to reduce or eliminate the volatility of the catalyst component. Therefore, volatile components, once captured, preferably will not be substantially released again in the escape phase. Therefore, in one aspect, the system and method provide inorganic oxide supports with a large surface area and high stability that can be used in a configuration where stable supports with a large surface area are mixed, or positioned downstream from a V-based SCR catalyst material with lower stability in which the catalyst components are present in a relatively high surface density, and the stable supports with a large anterior surface area capture and remove volatile compounds from the vapor phase even at an equal temperature which is present in the catalyst material of lower stability and higher surface density from which the compounds were volatilized.
    [006] This summary is not intended to be exhaustive or to complete the summary of the description, but it is only intended to identify several notable aspects of it. Other aspects of the description not specifically noted earlier will become evident upon consideration of the previous description. BRIEF DESCRIPTION OF THE DRAWINGS
    [007] Figure 1 is a schematic representation of a modality of a selective catalytic reduction catalyst system of the currently described and claimed inventive concepts where the catalyst material is positioned upstream of the capture material.
    [008] Figure 2 is a schematic representation of another modality of a selective catalytic reduction catalyst system of the inventive concepts presently described and claimed where the catalyst material and the capture material are combined in a mixture.
    [009] Figure 3 is a graph showing the relationship between the values of Total Fractional Monolayer and the volatility of vanadium.
    [0010] Figure 4 is a graph showing the relationship between the Total Fractional Monolayer values and the tungsten volatility. DETAILED DESCRIPTION
    [0011] During the investigation of vaporization of catalyst components (supported on oxide supports) during accelerated aging tests at high temperature, it was surprisingly discovered that the catalyst components exhibit varying degrees of volatility depending on the catalyst support, and the volatilities of the supported catalyst materials can be substantially different from the volatilities of the bulky oxides. In the case where the supported catalyst shows a non-negligible vaporization of the catalyst components, it is desirable to provide a means of capturing the volatilized components released in the vapor stream. One way to capture those components that are volatile at high temperature is simply to allow them to condense at a temperature below the catalyst bed downstream. However, this approach is problematic because volatile components can condense in unintended locations. Therefore, it is even more desirable to provide a means to capture volatile components even at very high sustained temperatures, such as those found in the catalyst bed. Therefore, the inventive concepts presently described and claimed refer to a treatment system for exhausting diesel engines, and its use, which comprises a catalytic selective catalytic reduction system based on vanadium (V-based SCR catalyst) and which comprises a "capture bed" either mixed in, or immediately downstream of the V-based SCR catalyst. The function of the capture bed is to capture and retain any volatile compounds even at elevated temperatures and gas flow conditions that approach those experienced in the catalytic portion of the catalyst / capture bed mixture, or in an upstream catalyst bed, such that volatile components are removed from the vapor phase of the exhaust gas.
    [0012] In an embodiment of the inventive concepts presently described and claimed, where the catalyst material and the capture bed material comprise a mixture, the v / v ratio of the catalyst material and the capture bed material may be, for example, in the range of 1:20 to 20: 1, and more preferably, for example, 1:10 to 10: 1.
    [0013] In addition, depending on the use in question, the terms "catalyst bed," "catalyst material," and "catalyst bed material" can be used interchangeably. Similarly, the terms "capture bed," capture material, "and" capture bed material "can be used interchangeably.
    [0014] Depending on the use in question, the term "substantially all" means at least 90% of the material to which it refers, or more preferably, to at least 95% of the material to which it refers, or more preferably, to at least 96% of the material to which it refers, or more preferably, at least 97% of the material to which it refers, or more preferably, at least 98% of the material to which it refers, or more preferably, at least 99% to which it refers.
    [0015] It has now been discovered that stable oxide supports with a large surface area, which include, but are not limited to, titania or alumina stabilized with silica, can be used to capture volatile components, when said components are present in low density on the support surface of the capture bed material after its capture. Furthermore, with reference to certain modalities, it has been surprisingly found that when normally volatile components are present in a low density on the catalyst surface before exposure to extreme conditions, they also exhibit reduced volatility in extreme conditions, to the extent that so that "low density" catalysts can also be used to reduce or eliminate the volatility of the catalyst component. Therefore, a main aspect of the inventive concepts presently described and claimed is to provide high stability, inorganic oxide supports with a large surface area that can be used in a configuration where stable supports with a large surface area are mixed, or positioned downstream. from a V-based SCR catalyst material with lower stability in which the catalyst components are present in a relatively high surface density, with the stable supports with a large anterior surface area capturing and removing volatile compounds from the steam even at an equal temperature that is present in the catalyst material of lower stability and higher surface density from which the compounds were volatilized.
    [0016] This configuration, shown in a schematic diagram in Figure 1, can be obtained, in an exemplifying modality by preparing wash-coated catalysts that are “divided into zones”, that is, the V-based SCR catalyst with lower stability and upper surface density is located in a position in front of the device, while inorganic oxide of high stability, high surface area and low density is located in a position facing towards the rear of the device.
    [0017] Another configuration, shown in a schematic diagram in Figure 2, can be obtained in an exemplary modality by co-extruding (or another mixing mode) of catalyst materials and capture bed materials. When the oxide of high stability and high surface area is comprised of a composition that is a good support for V-based SCR catalysts, then the capture material can be an active catalyst even if it accumulates the volatile oxides of the less catalyst stable. The titania-based materials that are suitable for use in this configuration as the highly stable supports with large surface area are those described in a recent patent application (U.S. serial number 12 / 533,414). Below, it will be noted that an example of a V-based SCR catalyst with lower stability and higher surface density is supported with 2% by weight of vanadium in the commercially available catalyst DT-52 ™ (DT-52 ™ itself is a material comprising about 10% by weight of WO3 and about 90% by weight of TiO2 (anastasium form) and has a BET surface of about 90 m2 / g). However, this catalyst is a highly active SCR catalyst under normal conditions, however, it exhibits a considerable loss of surface area after exposure to extreme conditions. Therefore, one embodiment of the inventive concepts presently described and claimed comprises a mixture of a vanadium-based DT-52 ™ catalyst material with the titania-based materials or catalysts described in the recent application (U.S. serial number 12 / 533,414). For example, the mixture can be obtained in coating applications by washing or extrusion or any other suitable method to create highly interspersed mixtures of particulate materials. In a second embodiment, the present invention comprises an alumina system with superior surface area and superior stability (or any other suitable capture bed material) positioned downstream of the vanadium-based DT-52 ™ catalyst (or any other material appropriate catalytic). For example, titania-based support materials that can be used in this document include, but are not limited to, materials comprising anastase titania particles that comprise> 85%, in dry weight, of TiO2 and <10%, in dry weight of SiO2, SiO2 being substantially in the form of low molecular weight and / or in the form of a small nanoparticle. The material can also comprise, for example, from 3% to 10% of WO3 and can have a BET surface area of at least 80 m2 / gm. The material may comprise> 85% dry weight of TiO2, 3% to 10% SiO2, and 3% -10% dry weight of WO3, for example. SiO2 may be present at a fractional monolayer value less than 1.0 before the material is sintered. The small nanoparticle form of SiO2 can comprise a diameter <5nm. The low molecular weight form of SiO2 can comprise a MW of <100,000. SiO2 can comprise silicon atoms that are substantially (for example,> 50%) in coordinating environments Q3, Q2, Q1 and Q °. SiO2 can comprise patches that are substantially <5 nm deep after redistribution as seen by a scanning electron microscope or a transmission electron microscope. Optionally, TiO2 may not be prepared in the presence of urea. The material, in a preferred embodiment, comprises silica that is substantially in a low molecular weight form and / or in the form of a small nanoparticle. This means that more than 50% of the silica is in the form of low molecular weight (PM <100,000) or in the form of a small nanoparticle (diameter <5 nm), or is a combination of both. In a more preferred version, silica comprises> 60% of low molecular weight forms and / or small nanoparticle forms. In an even more preferred version, silica comprises> 70% of low molecular weight and / or small nanoparticle forms. In an even more preferred version, silica comprises> 80%, and even more preferably,> 90%, of low molecular weight forms and / or small nanoparticle forms of silica. In addition, the low molecular weight and small nanoparticle forms of the material preferably have geometric surface areas of> 450 m2 / g.
    [0018] Alternatively, the material comprises> 85%, in dry weight, of TiO2, from 5.0% to 9.0%, in dry weight, of SiO2, and from 3.0% to 7.0%, in dry weight, WO3. More particularly, the material comprises from 87% to 89%, in dry weight, of TiO3, from 7% to 9%, in dry weight, of SiO2, and from 3% to 5%, in dry weight, of WO3. In a preferred embodiment, the material comprises about 88% (± 0.5%), in dry weight, of TiO2, about 8% (± 0.5%), in dry weight, of SiO2, and about 4 % (± 0.5%), in dry weight, of WO3. In one embodiment, the weight% of WO3 is less than the weight% of SiO2. In one embodiment, the material has a new surface area of at least 80 m2 / gm, and, more preferably, at least 100 m2 / gm. In another embodiment, the material comprises> 85%, in dry weight, of TiO2, from 3.0% to 8.0%, in dry weight, of SiO2, and from 4.0% to 9.0%, by weight dry, from WO3. More particularly, the material comprises> 87%, in dry weight, of TiO3, from 3% to 6%, in dry weight, of SiO2, and of 4% to 8%, in dry weight, of WO3. In a preferred embodiment, the material comprises about 90% (± 0.5%), in dry weight, of TiO2, about 4% (± 0.5%), in dry weight, of SiO2, and about 6 % (± 0.5%), in dry weight, of WO3. In one embodiment, the weight% of WO3 is greater than the weight% of SiO2. In one embodiment, the material has a new surface area of at least 80 m2 / gm, and, more preferably, at least 100 m2 / gm. In one embodiment, the TiO2 component of the material used here substantially comprises a surface area <400 m2 / g and a pore volume <0.40 cm3 / g.
    [0019] The modalities of the inventive concepts presently described and claimed allow the use of V-based SCR catalysts in configurations where the catalyst material and also the capture bed material, will be exposed to very high temperatures.
    [0020] It is useful to consider the parameters that serve to define the capture materials, and one of these parameters involves the psurf surface density, (atoms / nm2) of catalyst components in a support material. The catalyst and capture materials of the inventive concepts currently described and claimed are typically composed of a major phase (mass fraction greater than about 0.7) and one or more minority phases (mass fraction less than about 0.3) , and the minority phase is seen as existing on the surface of the majority phase. For example, titanium-based SCR catalysts typically contain a minority phase comprising vanadium (usually less than 5%), tungsta (usually less than 15%), and optionally silica (generally less than 15%), which have been deposited over the surface of titania (majority phase). When minority phases are present in a fraction of very low mass, they can exist in an atomically dispersed state, attached only to the support material. In contrast, when minority phases are present in a fraction of higher masses, they can start to form bonds homogeneously and, therefore, form one or more layers on the support material. In extreme cases, minority phases can actually crystallize, forming, for example, voluminous crystalline tungstat in its native monoclinic crystalline form, in an intimate mixture with the supporting titania. In this state, it is possible that the minority phases develop a more typical chemical character than that of the bulky minority oxide phase. In the particular cases of vanadium and tungsta, bulky oxides can exhibit volatility under extreme conditions of temperature, water vapor, gas flow rate and time.
    [0021] As can be seen from the chemical literature, the maximum amount of vanadium that can be maintained in a highly dispersed state in titania without the formation of vanadium crystal [2] is equal to 7.1 V atoms / nm2, and it is assumed that this density represents monolayer coverage. It is estimated that the monolayer covering of highly dispersed tungsten in titania [3] occurs in a loading of tungsten of 4.5 W / nm2, and that for silica [4] it is estimated that it occurs in a loading of silica of 6 Si atoms / nm2. These densities of complete surface or monolayer, psurf, monolayer, for the highly dispersed minority phases can be used to further define the current fractional coverage in the mass fraction, fm, i, of the minority phases (i) in the real catalyst: fm, i = psurf, i / psurf, monolayer, i
    [0022] In the case where there are multiple supported oxides (for example, silica, tungsta and vanadium) in the actual catalyst, the total fractional monolayer coverage Tfm can then be defined as the sum of fm, i for each of the supported oxides minority stage. From the above definitions, it is apparent that the combination of a large majority-phase support surface area and a small fraction of minor-phase mass results in a very low fractional coverage for component oxides. This combination is quite desirable for the capture materials of the inventive concepts currently described and claimed. Additionally, since the purpose of the inventive concepts presently described and claimed is to capture volatile oxides under conditions of extreme exposure, it is therefore highly desired that the surface area for the major phase oxide is stable and does not decrease substantially as a result of the conditions exposure. The relevant surface area to be used in this definition is that measured after the exposure of the capture materials or catalyst to the harsh conditions that simulate a lifetime exposure. Therefore, the stable surface area means that there is minimal loss in surface area from the new state (before exposure) and the aged state (after exposure). The condition of low fractional coverage is also a desirable resource of the catalyst materials themselves, so it is surprisingly discovered that component volatility is minimal under such a condition. Consequently, it is also desirable for the catalyst material to retain a noticeable surface area during exposure to difficult conditions.
    [0023] The examples and modalities refer to various materials of titania and alumina that can comprise the major phase of the catalyst support material or the capture bed material of the invention. However, the major phases of the catalyst support material and the capture bed material are not limited to these and may also comprise, alone or in combination, other titaniums, silica stabilized titanias, aluminas (which include, but are not limited to, limit to, bohemite, gamma and alpha alumina), stabilized alumines (for example, those stabilized by lanthanum or other lanthanides), amorphous silicas, silica alumines, zeolites (which include, but are not limited to, faujasite, mordenite, ZSM- 5 and Beta zeolite), and / or molecular sieves. In one embodiment, the minority phase of the capture material used in the selective catalytic reduction catalyst system of the currently described and claimed inventive concepts maintains a total fractional monolayer coverage in the majority phase equal to about 5 or less under conditions found in aging tests accelerated technology developed by Ford Co. [1] to simulate the service life (eg 192,000 km (120,000 miles)) of road exposure to an SCR catalyst that is positioned downstream of a DPF. Ford's test conditions [1] are, for example, an exposure to 670 ° C for 64 hours with a gas hourly space velocity (GHSV) of 30,000 hr 1 with 5% vol. of water. Other test conditions that can be used are 750 ° C for 4 hours and a GHSV of -100,000 hr1 and 5 vol%. of water. For example, the materials referred to here as MC-X5v1 and MC-X5v2 have a Tfm less than or equal to about 3 after these exposures. In another illustrative version of a material that does not meet the requirements for the capture material of the present invention, DT-52 ™ w / 2% by weight of V2O5 has a Tfm greater than about 3 after exposure in a relatively moderate to 670 ° C for 4 hours with a GHSV> 10,000 hr1e -5% H2O water. Preferably, the exposure conditions simulate the exposure of catalytic service life under real conditions. Likewise, the degree of aging that occurs (and therefore the final surface area and Tfm) also depends on the vanadium content. In the present description, the vanadium content of the catalysts is preferably in the range of 0.5% to 5% vanadium, and more preferably in the range of 1% to 3% vanadium. EXAMPLES
    [0024] The experimental apparatus below was designed to provide an illustration of the inventive concepts presently described and claimed. The SCR catalyst samples, which consist of catalyst components that include one or more of vanadium, tungsten and / or silica, were aged at elevated temperatures in a gas flow that maintains H2O and O2, each at 5 vol%, and NO and NH3, each at 500 ppm, with the balance consisting of N2. This gas flow is a representative mixture that approximates the gas composition under realistic conditions. The inorganic vapors generated from the catalyst samples were then captured in a “capture bed” located downstream from the catalyst, but still in the hot zone of the furnace. For the approach to be successful, volatile component vapors, in this case vanadium and tungsta oxides and hydroxides, must react quickly and quantitatively with the capture material at the high test temperatures. If this condition is met, then the quantity captured downstream is also an indirect measurement of the vapor pressure of the oxide of interest. In the following discussion, the two quantities (quantity captured and vapor pressure of the volatile component) are used interchangeably. Example 1- Mass balance.
    [0025] In this example, the use of a catalyst material comprising DT-52 ™ with 2 wt.% Vanadium (prepared by evaporating an alkaline monoethanolamine / vanadium solution) was maintained in a position upstream of a bed capture, in tests to demonstrate that the volatile components from the catalyst sample can be quantitatively captured by the downstream bed. The DT-52 ™ support is commercially available from Millennium Inorganic Chemical, Inc. (MIC), and has a composition of 90% TiO2, 10% WO3. An alumina range (Alfa Aesar, aluminum oxide, gamma, catalyst support, large surface area, bimodal) was used as the capture bed material and was additionally calcined at 800 ° C for 6 hours in air, and had an area nominal surface area of 200 m2 / g. A small amount, 0.2 g of -14 / + 24 mesh, of the alumina was placed in a reactor tube in a position downstream of the catalyst sample. The alumina capture bed was separated from an equivalent amount (0.2 g) of -14 / + 24 mesh of the catalyst sample by a small (<1 cm) plug of quartz straw. A second short quartz straw plug downstream of the alumina capture bed was used to maintain the position of the alumina. DT-52 ™ with 2% by weight vanadium was chosen as the catalyst sample in this experiment because it is known in the art that this material does not have a high degree of stability at high temperatures. To confirm this, the surface area of the vanadium doped starting DT-52 ™ was 58 m2 / g, while the surface area of the exposed and recovered material (as described below) was 12 m2 / g. Therefore, the catalyst material was subjected to a significant loss of surface area during exposure. The catalyst material and the alumina capture bed material were then exposed to 750 ° C for 1 hour with a total gas flow of 65 L / hour, and both the catalyst sample and the capture bed sample were manually retrieved for analysis. An exposure temperature of 750 ° C was chosen instead of 670 ° C, since the first causes a comparable amount of catalyst to occur in a shorter period of time, so that the test can be shortened by 64 hours to 1 to 4 hours, while still providing representative results. This gas flow represents a GHSV of -200,000 hr1, and is therefore many times greater than that used in the Ford test [1]. However, the upper flow allowed the vapor transport of volatile components to be considerably enhanced due to the law of mass action, in order to facilitate the subsequent recovery overhead and volatile component analysis. Since smaller amounts of volatile components would be transported and recovered using lower flow conditions, the present test is considered a very sensitive method for determining the component's volatility.
    [0026] After exposure, each sample was digested with concentrated aqueous HF, and analyzed by ICPES to determine tungsten and vanadium. The detection limits are 2.5 pg for each V and W per gram (ppm) of capture material (for example, alumina).
    [0027] The results, presented as an average of 4 separate tests, are given in Table 1. Table 1.

    [0028] It can be seen that the loss of V to the vapor phase is minimal, but measurable, while the loss of W is notable since the recovered capture alumina material contained approximately 0.45% by weight of W Likewise, it was observed that the mass balances for each of these are essentially equal to 100%, since the average mass balances are in a standard deviation from the theoretical value. Example 2- Demonstration of capture material stability.
    [0029] This example demonstrates that once tungsta and vanadium are present on the surface of the highly stable capture material with a large surface area (in this case, alumina range), they are not volatile under the test conditions, even at excessively high exposure temperatures. Therefore, a sample of gamma alumina (Alfa Aesar, aluminum oxide, gamma, catalyst support, large surface area, bimodal) was loaded with 47013 ppm W and 11200 ppm V (by depositing the alkaline monoethanolamine solution) and subsequently calcined at 600 ° C for 6 hours in air. This catalyst sample was positioned upstream of a downstream capture material (non-doped alumina range) as in Example 1. Separate tests demonstrated that the surface area of the alumina doped with W and V was 191 m2 / g after exposure at 750 ° C for 16 hours in an atmosphere that contained 10% H2O, which demonstrates the high stability of the material. The catalyst and capture materials were then exposed to the reagent flow at 750 ° C for 1 hour with a gas flow rate of 65 L / hour, and the spent samples were removed and analyzed. There was no measurable amount of W or V in the capture bed, so that these oxides do not exhibit volatility when supported on a highly stable alumina support with a large surface area. In summary, Examples 1 and 2 demonstrate two important findings, that is, that both V and W, when supported on a low thermal stability titania, exhibit measurable volatility at 750 ° C, but V and W do not exhibit measurable volatility at the same temperature when supported on a highly stable alumina with a large surface area. Examples 3 to 7: Evaluation of various catalyst materials based on vanadium.
    [0030] The findings described in Examples 1 and 2 presented a method of the inventive concepts presently described and claimed as a means to investigate the volatility of various catalyst components, such as V and W on a laboratory scale. Therefore, in the following examples, SCR catalysts containing tungsta and vanadium supported on various titania-based supports, were screened for the volatility of the catalyst components. The materials in these Examples contained 2% by weight of V2O5, deposited from the alkaline monoethanolamine solution, and the materials doped with V were calcined at 600 ° C for 6 hours in air to remove water and organic components. The DT-58 ™ base material is a titanium-based SCR catalyst support commercially available from MIC. DT-58 ™ comprises 81% TiO2, 9% WO3 and 10% SiO2 and has a BET surface area of about 90 to 110 m2 / g. The samples in Examples 5 and 6, labeled MC-X5v1 and MC-X5v2, are SCR catalyst supports developed as described later in reference to “Stabilized Anatase Titania” and in US Patent Application with serial number 12 / 533.414 , which is expressly incorporated herein in its entirety as a reference. The composition of the MC-X5v1 support is 90% TiOz, 4% SiO2 and 6% WO3, while the composition of the MC-X5v2 support is 88% TiO2, 8% SiO2 and 4% WO3. Table 2
    (a) = 2% by weight of V2O5 (b) = average of several tests
    [0031] First, it is desired to determine a set of conditions that would be representative of the actual exposure of a catalyst. As previously described, Ford researchers [1] developed an accelerated aging protocol for SCR catalysts that are positioned downstream of a diesel particulate filter (DPF), which simulates road exposure for 192,000 km (120,000 miles) ). The accelerated aging test involves exposing the catalyst to a flow of reagent gas that includes water (5% vol.), For a period of 64 hours at 670 ° C in a GHSV = 30,000 hr-1. These exposure conditions represent the extremely difficult conditions that would occur as a result of the high temperatures created during soot combustion during DPF regeneration, and would not normally be found in traditional SCR applications.
    [0032] Therefore, catalysts DT-58 ™ and MC-X5v1 were exposed for 64 hours at 670 ° C in an atmosphere that contained 10 vol%. of H2O, and the surface area and pore volumes of the aged catalysts were determined as shown in Table 2. The same starting catalyst materials were also used as the catalyst samples in a double bed configuration upstream of a capture bed gamma alumina downstream, and were treated at 750 ° C as described in Examples 1 and 2, above, after the exposure time was 4 hours and the reactant gas flow was 32.5 L / hour (equivalent to GHSV ~ 100,000 hr1). The gas flow rate under these conditions is still higher than in the Ford test [1], however, it is more strictly representative than that of the test.
    [0033] The results in Table 2 show that the surface areas for the catalysts exposed in the test method of the inventive concepts presently described and claimed at 750 ° C for 4 hours were slightly smaller than those for the same materials aged at 670 ° C for 64 hours. Therefore, if the surface area is used as a measurement of the extent to which the catalyst samples have been aged (and therefore the severity), then the conditions in the first test are slightly more severe than in the Ford test [1]. Therefore, it is concluded that the test of the inventive concepts presently described and claimed, when conducted at 750 ° C for 4 hours with a reagent gas flowing at 32.5 L / hour, is a good first approximation to the actual exposure of the catalyst to over 192,000 km (120,000 miles) of road use.
    [0034] Each of the catalysts listed in Table 2 has been evaluated several times and the average results are shown. The results in Table 2 demonstrate that the catalysts show variable degrees of loss of V and W. Also shown in Table 2 are the values of Total Fractional Monolayer (Tfm) for each material, where the surface area is that of the aged samples. Shown in Figures 3 and 4 are the correlations found between the amount of V and W lost from the catalyst samples and the Tfm values. The data and graphs show that when the TFm values are equal to or less than about 3, the catalyst components of vanadium and tungsta exhibit low volatility and are substantially retained in the catalyst material, while when the TFm values are greater than 3, the catalyst components exhibit much greater volatility and are lost from the catalyst material (however, they are captured in the capture material). Naturally, even with the relatively high levels of V and W that are lost from the catalyst material DT-52 ™, when these volatile oxides and hydroxides are captured in the capture bed material, for example, alumina, the TFm for this material is much less than 1 after exposure. These good correlations can be used to predict the behavior of unknown materials that can be used as catalyst and capture materials. Therefore, vanadium-based titania materials that have large aged surface areas and low amounts of added catalyst components such as SiO2 and WO3 will demonstrate little or no loss of W and V to the vapor phase under these difficult exposure conditions, and therefore , are attractive catalyst materials. These support materials will also be good capture materials in the case where less stable catalyst materials with high TFm ωmo to vanadium in DT-52 ™ are positioned upstream or in an intimate mix like the most stable materials with low TFm.
    [0035] Without adhering to the theory, it is believed that the reason for the low volatility of the minority phase components in stabilized alumina or titania (or other materials contemplated in this document) is that when the minority phase components are present in a covering low fractional (low fm), they interact in a chemically strong way with the major phase support, and, successively, this favorable interaction energy reduces the equilibrium constants involved in the vaporization of the supported components. Titânia Anastásio Stabilized.
    [0036] In preferred embodiments of the inventive concepts presently described and claimed, the material comprising the catalyst material and / or the major phase capture bed material used here is anastasian titania (for example, as described in US serial number 12 / 533,414), and the titania anastase is stabilized by a silica provides it in a low molecular weight and / or small nanoparticle form. In addition, the minority phase arranged in titania anastase preferably comprises vanadium (and, optionally, tungsta), for a selective catalytic reduction based on DeNOx vanadium from poor combustion engines (diesel).
    [0037] The current specific composition of the catalyst support material based on silica-titania or silica-titania-tungsta (major phase) and / or the capture bed material can be dictated by the requirements of the specific catalytic application. In a preferred composition, the material comprises a titania-based material stabilized with silica comprising particles containing> 90% dry weight of TiO2 and <10% by weight of SiO2. In another preferred composition, the material comprises a titania-tungst silica material stabilized with> 85% dry weight, titania, 3% to 10% dry weight, SiO2, and 3% to 10% weight dry, from WO3. Alternatively, in a mode where the application requires particularly good thermal stability, the material comprises> 85%, in dry weight, of TiO2, 5.0% to 9.0%, in dry weight, of SiO2, and 3.0 % to 7.0%, in dry weight, of WO3. More particularly, the material can comprise 87% to 89% dry weight of TiO3, 7% to 9% dry weight of SiO2 and 3% to 5% dry weight of WO3. In a preferred embodiment, the material comprises about 88% (± 0.5%), in dry weight, of TiO2, about 8% (± 0.5%), in dry weight, of SiO2, and about 4 % (± 0.5%), in dry weight, of WO3. In one embodiment, the weight% of WO3 is less than the weight% of SiO2. In one embodiment, the material has a new surface area of at least 80 m2 / gm, and, more preferably, at least 100 m2 / gm.
    [0038] In another mode where the application requires a particularly good catalytic activity or capture of volatiles, the material comprises> 85%, in dry weight, of TiO2, 3.0% to 8.0%, in dry weight, of SiO2 , and 4.0% to 9.0%, in dry weight, of WO3. More particularly, this active material comprises> 87%, in dry weight, of TiO3, 3% to 6%, in dry weight, of SiO2, and 4% to 8%, in dry weight, of WO3. In a preferred embodiment, the material comprises about 90% (± 0.5%), in dry weight, of TiO2, about 4% (± 0.5%), in dry weight, of SiO2, and about 6 % (± 0.5%), in dry weight, of WO3. In one embodiment, the weight% of WO3 is greater than the weight% of SiO2.
    [0039] In one embodiment of the inventive concepts presently described and claimed, the TiO2 component of the material used in this document substantially comprises a surface area <400 m2 / g and a pore volume <0.40 cm3 / g.
    [0040] In one embodiment, the material is produced by mixing an aqueous paste of titania and a silica component at a temperature <80 ° C and a pH <8.5. Alternatively, the aqueous titania paste and the silica component used here can be mixed at a temperature <70 ° C and a pH <7.0.
    [0041] The vanadium-based catalyst of the inventive concepts presently described and claimed can comprise the catalyst support based on stabilized silica-titania or titania-tungsta described herein by means of which an amount of vanadium oxide (V2O5) is available, V2O5 preferably comprising 0.5% to 1% to 2% to 3% to 4% to 5% of its dry weight. The vanadium-based catalyst materials of the inventive concepts presently described and claimed can be further treated by calcination (sintering) at a temperature> 650 ° C to increase their NOx catalytic activity.
    [0042] The emission system of the inventive concepts presently described and claimed can be used with a diesel particulate filter (DPF) upstream of the engine or downstream of the engine.
    [0043] Preferably, most of the silica particles in the titanium-based material stabilized with silica have diameters <5 nm, and more preferably <4 nm, and more preferably <3 nm, and, with even more preferably, <2 nm, and / or comprises low molecular weights (e.g., PM <100,000), whether or not the particles have a V2O5 deposited on them.
    [0044] When the titania-based silica material also has V2O5 deposited, V2O5 preferably comprises 0.5% to 1% to 2% to 3.0% to 4% to 5% of the dry weight of the material .
    [0045] The distribution of WO3 and SiO2 species on the surface of the titania-based material also plays a role in optimizing the DeNOx activity of vanadium-based catalysts. Therefore, when the catalysts are recently prepared, that is, when the added silica and tungsten oxides are first deposited and before treatment at high temperature, the fractional monolayer coverage is preferably equal to about 1.0 or less .
    [0046] SiO2 may be present in a fractional monolayer value less than 1.0 before the material is sintered. The small nanoparticle form of SiO2 can comprise a diameter <5nm. The low molecular weight form of SiO2 can comprise a MW of <100,000. SiO2 can comprise silicon atoms that are substantially (e.g.,> 50%) in the Q3, Q2, Q1 and Q ° coordination environments. SiO2 can comprise patches that are substantially <5 nm deep after redistribution as shown by a scanning electron microscope or a transmission electron microscope. Optionally, TiO2 may not be prepared in the presence of urea.
    [0047] In another aspect, the invention can be a vanadium-based catalyst comprising a titania-based material stabilized with silica as described in the present document comprising V2O5 disposed therein. The vanadium-based catalyst can comprise, for example, 0.5% to 1% to 2% to 3% to 4% to 5%, by dry weight, of V2O5 (or, more preferably, 1.0% to 2% to 3%). V2O5 may be present at a fractional monolayer value less than 1.0 before sintering. The vanadium-based catalyst can be sintered at> 650 ° C, for example. In another aspect, the system of the inventive concepts presently described and claimed may be a diesel selective catalytic reduction catalyst system comprising the vanadium-based catalyst and the capture bed material as described herein. In another aspect, a diesel engine exhaust treatment system may further comprise a diesel particulate filter, and the present catalytic capture bed device is positioned upstream or downstream of the diesel particulate filter. .
    [0048] In another aspect, the inventive concepts presently described and claimed comprise a method of catalyzing the conversion of nitrogen oxides into N2 gas, which comprises exposing NOx engine emissions to the vanadium-based catalyst as described in present document with a reducing agent added to produce N2 and H2O. The reducing agent can be, for example, NH3 and / or urea. In the method, the vanadium-based catalyst can comprise 0.5% to 5% (or, more preferably, 1.0% to 3%), by dry weight, of V2O5, for example. Engine emissions can be passed through a diesel particulate filter before or after being exposed to the vanadium-based catalyst where emissions are then passed through the capture bed material.
    [0049] As noted earlier, the stabilization of the titania-based material with silica preferably involves the treatment of titania with silica in the form of low molecular weight and / or in the form of small nanoparticle, such as tetra silicate (alkyl) ammonium (for example, tetramethylammonium silicate) or tetraethylorthosilicate (TEOS). Other examples of low molecular weight silica precursors and / or small nanoparticles that can be used in the present invention include, but are not limited to, aqueous solutions of silicon halides (i.e., anhydrous SX4, where X = F, Cl, Br, or I), silicon alkoxides (ie Si (OR) 4, where R = methyl, ethyl, isopropyl, propyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentis, hexis, octis, nonis, decis, undecis, and dodecis, for example), other silicon-based organic compounds, such as hexamethyldisilazane, fluoro-silyl acid salts, such as ammonium hexafluorosilicate [(NH ^ SiFβ], quaternary ammonium silicate solutions (eg example, (NR4) n, (SiO2), where R = H, or alquis, like those listed above, and when n = 0.1 to 2, for example), aqueous solutions of sodium and potassium silicate (NasSiCh, K2SÍO3 , and MSÍO3, where M is Na or K in varying amounts due to Si), silicic acid (Si (OH) 4) generated by ion exchange of any of the cationic forms of silica listed here that use an acidic ion exchange resin (for example, ion exchange of alkaline silicate solutions or quaternary ammonium silicate solutions). In preferred embodiments, the titania used in this document was not prepared in the presence of urea.
    [0050] The catalyst support material and / or the capture bed material can be produced by providing an aqueous paste comprising TIO2, combining the aqueous paste of TiO2 with (1) a precursor solution of silica comprising SiO2 substantially in the form of low molecular weight and / or SiO2 comprising small nanoparticles and with (2) WO3 to form a mixture of TiO2-WO3-SiO2, the precursor solution of silica being combined with the aqueous paste of TiO2 before , after, or during WO3 is combined with the aqueous TiO2 slurry, and then washing and sintering the TiO2-WO3-SiO2 mixture to form a silica-stabilized titania-based support material. In the method, the support material based on titania stabilized with silica can comprise, for example, 86% to 94%, in dry weight, of TiO2, 3% to 9%, in dry weight, of SiO2, and 3% to 7%, in dry weight, of WO3, and the titania-based support material may comprise primarily a surface area of at least 80 m2 / gm before sintering. The TIO 2 of the aqueous paste can comprise, for example, preformed particles of titanium hydroxide, titanium oxy hydroxide or titanium dioxide. Optionally, the TiO2 of the aqueous paste is not produced in the presence of urea.
    [0051] The silica precursor solution may comprise a solution of tetra (alkyl) ammonium silicate or silicic acid. SiO2 can substantially comprise patches that are <5 nm deep after redistribution as seen by a scanning electron microscope or a transmission electron microscope. The method may further comprise combining the mixture of TiO2-WO3-SiO2 with V2O5 to form a vanadium-based catalyst. The vanadium-based catalyst thus formed may comprise, for example, 0.5% to 1% to 2% to 3% to 4% to 5%, by dry weight, of V2O5. The V2O5 of this can be present in a fractional monolayer value less than 1.0 before sintering. The vanadium-based catalyst can be sintered at> 650 ° C, for example.
    [0052] Alternatively, the titania material stabilized with silica can be produced by providing an aqueous paste of TiO2 comprising particles of TiO2, providing a source of silica particulate, combining the aqueous paste of TiO2 with the source particulate silica to form a mixture of THO2-SiO2, and by adjusting the mixture of TiO2-SiO2 to a pH <8.5 and a temperature <80 ° C, the source of the particulate silica is dissolved and re -precipitated in the TiO2 particles to form the titanium-based material stabilized with silica. The method may further comprise the step of combining the titanium-based material stabilized with silica with WO3 to form a titanium-based material stabilized with silica and tungsten. The method can also comprise washing and sintering the titania-based material stabilized with silica and tungsten. The titanium-based material stabilized with silica and tungsten may comprise, for example, 86% to 94%, in dry weight, of TiO2, 3% to 9%, in dry weight, of SiO2, and 3% to 7%, in dry weight, of WO3, and the titania-based material can primarily comprise a surface area of at least 80 m2 / gm before sintering. The TiO2 particles of the aqueous TiO2 paste may comprise, for example, preformed particles of titanium hydroxide, titanium oxy hydroxide or titanium dioxide. The SiO2 of the TiO2-SiO2 mixture, after dissolving, can comprise silicon atoms that are substantially (e.g.,> 50%) in Q3, Q2, Q1 and Q ° coordination environments. The SiO2 in the TiO2 particles of the method can substantially comprise patches that are <5 nm deep after redistribution of the SiO2 as seen by a scanning electron microscope or a transmission electron microscope. The method may further comprise combining the mixture of TiO2-WO3-SiO2 with V2O5 to form a vanadium-based catalyst. In the method, the vanadium-based catalyst can comprise, for example, 0.5% to 1% to 2% to 3%, by dry weight, of V2O5. The vanadium-based catalyst V2O5 can be present at a fractional monolayer value less than 1.0 prior to sintering, and the vanadium-based catalyst can be sintered at> 650 ° C.
    [0053] As contemplated in this document, in one embodiment, the inventive concepts presently described and claimed comprise a catalytic system of selective catalytic reduction to treat an exhaust gas from diesel engines containing nitrogen oxides and diesel soot particles. The system comprises a catalyst material and a capture material. The catalyst material comprises a major phase which can comprise a titania-based support material, and a minority phase which comprises a catalyst component which comprises at least one vanadium oxide, silicon, tungsten, molybdenum, iron, cerium, phosphorus, copper or manganese. The capture material comprises the majority phase to capture a minority phase that comprises volatile oxides or hydroxides that originate from the catalyst material, whereas the minority phase of the capture material maintains total fractional monolayer coverage in the majority phase of the catalyst material. catch equal to about 5 or less. The capture material is positioned in a mixture with the catalyst material, or is located downstream of the catalyst material or is positioned in a mixture with the catalyst material and is located downstream of the catalyst material. The minority phase of the capture material in this modality can maintain a total fractional monolayer coverage of 5 or less in the majority phase of the capture material when exposed to conditions of 750 ° C for 4 hours at an hourly space gas speed of 100,000 hr1e 5 % by vol. of water. The minor phase catalyst components of the catalyst material can maintain a total fractional monolayer value of 5 or less in the major phase after exposure to conditions of 750 ° C for 4 hours at an hourly space gas velocity of 100,000 hr1 and 5% vol . of water. Preferably, the capture material is capable of removing substantially all of the volatile oxides and hydroxides that originate from the catalyst material. The majority phase of the capture material can comprise primarily at least aluminas, stabilized aluminas, silicas, silica-aluminins, amorphous silicas, titanias, titanias stabilized with silica, zeolites or molecular sieves or combinations thereof. When the majority phase is a stabilized alumina, the stabilized alumina can be stabilized by lanthanum or other lanthanides. The majority phase of the capture material and the majority phase of the catalyst material may comprise titania stabilized with silica.
    [0054] In another embodiment, the inventive concepts presently described and claimed comprise a diesel engine exhaust treatment system comprising a selective catalytic reduction catalyst system and a diesel particulate filter to treat the exhaust gas of engines diesel containing nitrogen oxides and diesel soot particles. The catalyst system comprises a catalyst material and a capture material. The catalyst material comprises a major phase which can comprise a titania-based support material, and a minority phase which comprises a catalyst component which comprises at least one vanadium oxide, silicon, tungsten, molybdenum, iron, cerium, phosphorus, copper or manganese. The capture material can comprise a majority phase to capture a minority phase that comprises volatile oxides or hydroxides that originate from the catalyst material, the minority phase of the capture material maintaining a total fractional monolayer coverage in the majority phase of the material of capture equal to about 5 or less. The capture material can be positioned in a mixture with the catalyst material, or it can be located downstream of the catalyst material, or it can be positioned in a mixture with the catalyst material and located downstream of the catalyst material. The selective catalytic reduction catalyst system can be positioned upstream or downstream of the diesel particulate filter. The minority phase of the capture material in this modality can maintain a total fractional monolayer coverage equal to 5 or less in the majority phase of the capture material when exposed to conditions of 750 ° C for 4 hours at an hourly space gas speed of 100,000 hr1e 5% by vol. of water. The minor phase catalyst components of the catalyst material can maintain a total fractional monolayer value of 5 or less in the major phase after exposure to conditions of 750 ° C for 4 hours at an hourly space gas velocity of 100,000 hr1 and 5% in vol. of water. Preferably, the capture material is capable of removing substantially all of the volatile oxides and hydroxides that originate from the catalyst material. The majority phase of the capture material can comprise primarily at least aluminas, stabilized aluminas, silicas, silica-aluminins, amorphous silicas, titanias, titanias stabilized with silica, zeolites or molecular sieves or combinations thereof. When the majority phase is a stabilized alumina, the stabilized alumina can be stabilized by lanthanum or other lanthanides. The majority phase of the capture material and the majority phase of the catalyst material may comprise titania stabilized with silica.
    [0055] In another embodiment, the inventive concepts presently described and claimed comprise a method of treating exhaust gas from diesel engines which comprises the steps of providing a selective catalytic reduction catalyst system, with or without a diesel particulate filter, and exposing the exhaust gas from diesel engines to the selective catalytic reduction catalyst system, the capture material removing substantially all volatile oxides and hydroxides that originate from the exhaust gas catalyst material of diesel engines. In this method, the selective catalytic reduction catalyst system comprises a catalyst material and a capture material. The catalyst material comprises a major phase which can comprise a titania-based support material, and a minority phase which comprises a catalyst component which comprises at least one vanadium oxide, silicon, tungsten, molybdenum, iron, cerium, phosphorus, copper or manganese. The capture material comprises a majority phase to capture a minority phase that comprises volatile oxides or hydroxides that originate from the catalyst material, the minority phase of the capture material maintaining a total fractional monolayer coverage in the majority phase of the catalyst material. catch equal to about 5 or less. The capture material is positioned in a mixture with the catalyst material, or is located downstream of the catalyst material or is positioned in a mixture with the catalyst material and is located downstream of the catalyst material.
    [0056] The minority phase of the capture material in this modality can maintain a total fractional monolayer coverage equal to 5 or less in the majority phase of the capture material when exposed to conditions of 750 ° C for 4 hours at an hourly space velocity of gas 100,000 hr1 and 5% vol. of water. The minor phase catalyst components of the catalyst material can maintain a total fractional monolayer value of 5 or less in the major phase after exposure to conditions of 750 ° C for 4 hours at an hourly space gas velocity of 100,000 hr1 and 5% in vol. of water. Preferably, the capture material is capable of removing substantially all of the volatile oxides and hydroxides that originate from the catalyst material. The majority phase of the capture material can comprise primarily at least aluminas, stabilized aluminas, silicas, silica-aluminins, amorphous silicas, titanias, titanias stabilized with silica, zeolites or molecular sieves or combinations thereof. When the majority phase is a stabilized alumina, the stabilized alumina can be stabilized by lanthanum or other lanthanides. The majority phase of the capture material and the majority phase of the catalyst material may comprise titania stabilized with silica
    [0057] Although the inventive concepts presently described and claimed are described according to certain preferred modalities and examples, so that aspects of these can be better understood and evaluated, it is not intended to limit the inventive concepts presently described and claimed to those modalities and particular examples. Therefore, the present examples, which include preferred embodiments, serve to illustrate the practice of this invention, it being understood that those particulars shown serve as examples and for purposes of illustrative discussion of the preferred embodiments of the inventive concepts presently described and claimed only, and they are presented to provide what is believed to be the most useful and readily understood description of formulation procedures, as well as principles and conceptual aspects of the inventive concepts presently described and claimed.
    [0058] Therefore, although the inventive concepts presently described and claimed and their advantages have been described in detail, it must be understood that several changes, substitutions and changes can be made without departing from the spirit and scope of the inventive concepts presently described and claimed as defined by the appended claims. Furthermore, it is not intended that the scope of this application be limited to the particular modalities of the machines, processes, manufacturing items, material compositions, means, methods and steps described in the specification. As an individual skilled in the art will readily assess from this description, machines, processes, items of manufacture, compositions of matter, medium, methods, or stages, presently existing or later developed that perform substantially the same function or achieve substantially the same result of the corresponding modalities described in this document can be used according to the inventive concepts presently described and claimed. Consequently, it is intended that the appended claims include in their scope such machines, processes, manufacturing items, compositions of matter, means, methods, or stages.
    [0059] Each of the patents, published patent applications, references and articles cited in this document are expressly incorporated herein in their entirety for reference. REFERENCES CITED 1. G. Cavataio, et al., Society of Automotive Engineers 2007-01-1575, 455 (2007). 2. Weckhuysen, BM, and Keller, DE, “Chemistry, Spectroscopy and the Role of Supported Vanadium Oxides in Heterogeneous Catalysis”, Catalysis Today 78: 25-46, 2003. 3. Wachs, IE, Kim, T., Ross, EI, “Catalysis Science of the solid Acidity of Model Supported Tungsten Oxide Catalysts”, Catalysis Today 116: 162-168, 2006. 4. Iler, RK The Chemistry of Silica: Solubility, Polymerization, Colloid and Surface Properties, and Biochemistry, John Wiley & Sons, New York, ISBN 0-471- 02404-x: 31, 1979.
    权利要求:
    Claims (20)
    [0001]
    1. Catalytic selective catalytic reduction system to treat diesel exhaust gases that contain nitrogen oxides and diesel soot particles, FEATURED by the fact that it comprises: a catalyst material comprising: a major phase comprising a support material for titania base, and a minority phase comprising a catalyst component comprising at least one vanadium, silicon, tungsten, molybdenum, iron, cerium, phosphorus, copper or manganese oxide; and a capture material comprising a major phase to capture a minority phase comprising hydroxides or volatile oxides that originate from the catalyst material, where the minority phase of the capture material maintains full fractional monolayer coverage in the major phase of the capture material of about 5 or less; and wherein the capture material is positioned in a mixture with the catalyst material, or is located downstream of the catalyst material.
    [0002]
    2. Catalytic selective catalytic reduction system, according to claim 1, CHARACTERIZED by the fact that the minority phase of the capture material maintains the total fractional monolayer coverage of 5 or less in the majority phase of the capture material when exposed to conditions 750 ° C for 4 hours at an hourly gas space velocity of 100,000 hr1 and 5% vol. of water.
    [0003]
    3. Catalyst selective catalytic reduction system, according to claim 1, CHARACTERIZED by the fact that the minor phase catalyst components of the catalyst material maintain a total fractional monolayer value of 5 or less in the major phase after exposure to conditions of 750 ° C for 4 hours at an hourly gas space velocity of 100,000 hr1 and 5% vol. of water.
    [0004]
    4. Catalyst selective catalytic reduction system, according to claim 1, CHARACTERIZED by the fact that the capture material is capable of removing substantially all the volatile hydroxides and oxides that originate from the catalyst material.
    [0005]
    5. Catalytic selective catalytic reduction system, according to claim 1, CHARACTERIZED by the fact that the majority phase of the capture material comprises primarily at least one among aluminas, stabilized aluminas, silicas, silica-aluminas, amorphous silicas, titanias, titanias stabilized with silica, zeolites or molecular sieves or combinations thereof.
    [0006]
    6. Catalytic selective catalytic reduction system, according to claim 5, CHARACTERIZED by the fact that the majority phase of the capture material comprises primarily stabilized alumines which are stabilized by lanthanum or other lanthanides.
    [0007]
    7. Catalyst selective catalytic reduction system, according to claim 1, CHARACTERIZED by the fact that the majority phase of the capture material and the majority phase of the catalyst material comprise titania stabilized with silica.
    [0008]
    8. Exhaust treatment system for diesel engine, FEATURED by the fact that it comprises: a catalytic catalytic reduction system to treat diesel exhaust gases containing nitrogen oxides and diesel soot particles, comprising: a material catalyst comprising: a major phase comprising a titania-based support material, and a minority phase comprising a catalyst component comprising at least one vanadium, silicon, tungsten, molybdenum, iron, cerium, phosphorus, copper or manganese; and a capture material comprising a major phase to capture a minority phase comprising hydroxides or volatile oxides that originate from the catalyst material, where the minority phase of the capture material maintains full fractional monolayer coverage in the major phase of the capture material of about 5 or less; and wherein the capture material is positioned in a mixture with the catalyst material, or is located downstream of the catalyst material; and a diesel particulate filter, and in which the selective catalytic reduction catalyst system is positioned upstream or downstream of the diesel particulate filter.
    [0009]
    9. Exhaust treatment system for diesel engine, according to claim 8, CHARACTERIZED by the fact that the minority phase of the capture material of the catalytic selective reduction catalyst system maintains the total fractional monolayer coverage in the majority phase of the material capture rate of 5 or less when exposed to conditions of 750 ° C for 4 hours at an hourly space gas velocity of 100,000 hr1 and 5% vol. of water.
    [0010]
    10. Diesel engine exhaust treatment system, according to claim 8, CHARACTERIZED by the fact that the minor phase catalyst components of the catalytic selective catalytic reduction system maintain a total fractional monolayer value of 5 or minor in the majority phase after exposure to 750 ° C conditions for 4 hours at an hourly gas space velocity of 100,000 hr1 and 5% vol. of water.
    [0011]
    11. Exhaust treatment system for diesel engine, according to claim 8, CHARACTERIZED by the fact that the capture material of the catalytic selective catalytic reduction system is capable of removing substantially all the volatile hydroxides and oxides that originate from from the catalyst material.
    [0012]
    12. Exhaust treatment system for diesel engine, according to claim 8, CHARACTERIZED by the fact that the majority phase of the capture material of the catalytic selective catalytic reduction system comprises primarily at least one among aluminas, stabilized aluminas, silicas , silica-alumina, amorphous silica, titanium, titanium stabilized with silica, zeolites or molecular sieves or combinations thereof.
    [0013]
    13. Exhaust treatment system for diesel engine according to claim 12, CHARACTERIZED by the fact that the majority phase of the capture material comprises primarily stabilized alumines which are stabilized by lanthanum or other lanthanides.
    [0014]
    14. Exhaust treatment system for diesel engine, according to claim 8, CHARACTERIZED by the fact that the majority phase of the capture material and the majority phase of the catalyst material of the catalytic reduction catalyst system comprise titania stabilized with silica .
    [0015]
    15. Diesel exhaust gas treatment method, CHARACTERIZED by the fact that it comprises: providing a selective catalytic reduction catalyst system comprising: a catalyst material comprising: a major phase comprising a titania-based support material, and a minority phase comprising a catalyst component comprising at least one vanadium, silicon, tungsten, molybdenum, iron, cerium, phosphorus, copper or manganese oxide; and a capture material that comprises a majority phase to capture a minority phase that comprises volatile hydroxides or oxides that originate from the catalyst material, the minority phase of the capture material maintaining total fractional monolayer coverage in the majority phase. capture material of about 5 or less; and wherein the capture material is positioned in a mixture with the catalyst material, or is located downstream of the catalyst material; and exposing the diesel exhaust gas to the selective catalytic reduction catalyst system, in which the capture material substantially removes all volatile hydroxides and oxides that originate from the diesel exhaust gas catalyst material.
    [0016]
    16. Method, according to claim 15, CHARACTERIZED by the fact that the minority phase of the capture material of the selective catalytic reduction catalyst system maintains the total fractional monolayer coverage in the majority phase of the capture material of 5 or less when exposed at 750 ° C for 4 hours at an hourly gas space velocity of 100,000 hr 1 and 5% vol. of water.
    [0017]
    17. Method, according to claim 15, CHARACTERIZED by the fact that the minor phase catalyst components of the catalytic selective catalytic reduction system maintain a total fractional monolayer value of 5 or less in the major phase after exposure to conditions of 750 ° C for 4 hours at an hourly gas space velocity of 100,000 hr1 and 5% vol. of water.
    [0018]
    18. Method, according to claim 15, CHARACTERIZED by the fact that the majority phase of the capture material of the catalytic selective reduction catalyst system comprises primarily at least one among aluminas, stabilized aluminas, silicas, silica-aluminas, amorphous silicas, titanias, titanias stabilized with silica, zeolites or molecular sieves or combinations thereof.
    [0019]
    19. Method according to claim 18, CHARACTERIZED by the fact that the majority phase of the capture material comprises primarily stabilized alumines which are stabilized by lanthanum or other lanthanides.
    [0020]
    20. Method according to claim 15, CHARACTERIZED by the fact that the majority phase of the capture material and the majority phase of the catalyst material of the selective catalytic reduction catalyst system comprise titania stabilized with silica
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    同族专利:
    公开号 | 公开日
    MX2012006736A|2012-07-03|
    KR20120095419A|2012-08-28|
    DK2513438T3|2021-03-15|
    EP2513438B1|2021-01-13|
    US8481452B2|2013-07-09|
    EP2513438A2|2012-10-24|
    MY163013A|2017-07-31|
    KR101729357B1|2017-04-21|
    PL2513438T3|2021-08-02|
    US20110138789A1|2011-06-16|
    JP2013513478A|2013-04-22|
    SI2513438T1|2021-06-30|
    EP2513438A4|2014-10-01|
    AU2010337327A1|2012-06-28|
    BR112012014498A2|2016-08-16|
    US8481453B2|2013-07-09|
    ZA201203984B|2013-08-28|
    SG181118A1|2012-07-30|
    JP2016093810A|2016-05-26|
    MX343637B|2016-11-15|
    AU2010337327B2|2016-03-24|
    RU2012122525A|2014-01-27|
    RU2600208C2|2016-10-20|
    CA2782242C|2014-09-09|
    CN102869862B|2015-07-08|
    JP6234422B2|2017-11-22|
    JP5848256B2|2016-01-27|
    WO2011081727A3|2011-09-09|
    UA110930C2|2016-03-10|
    CA2782242A1|2011-07-07|
    ES2856183T3|2021-09-27|
    US20120058031A1|2012-03-08|
    CN102869862A|2013-01-09|
    WO2011081727A2|2011-07-07|
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    法律状态:
    2017-12-26| B25D| Requested change of name of applicant approved|Owner name: CRISTAL USA INC. (US) |
    2019-01-08| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2019-11-05| B25A| Requested transfer of rights approved|Owner name: TRONOX LLC (US) |
    2020-07-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-17| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 17/11/2020, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/638,166|US8481452B2|2009-12-15|2009-12-15|Capture of volatilized vanadium and tungsten compounds in a selective catalytic reduction system|
    US12/638,166|2009-12-15|
    PCT/US2010/056485|WO2011081727A2|2009-12-15|2010-11-12|Selective catalytic reduction system for capture of volatilized compounds|
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