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    • 专利摘要:
    vanadium-based denox catalysts and catalyst supports. a vanadium-based catalyst composition for nitrogen oxide reduction include a titania-based support material; vanadium deposited on the titania-based support material; a primary promoter comprising a tungsten oxide, molybdenum oxide or combinations thereof; and an amount of phosphate to achieve a range of phosphorus molecules for vanadium plus molybdenum of about 0.2: 1 or more. A zirconia, tin or manganese oxide may be added to inhibit the volatility of the solid. The results show a low so2 oxidation range of nox conversion and / or molybdenum stability.
    公开号:BR112012025536B1
    申请号:R112012025536
    申请日:2011-03-09
    公开日:2019-09-10
    发明作者:Clark Dennis；El-Shoubary Modasser；M Augustine Steve
    申请人:Cristal Usa Inc；Millennium Inorganic Chemicals Inc；
    IPC主号:
    专利说明:

    “TITANIA-BASED CATALYST SUPPORT MATERIAL, VANADIUM-BASED CATALYTIC COMPOSITION FOR THE REDUCTION OF NITROGEN OXIDES, PROCESS FOR PREPARING THE SUCH SUPPORT MATERIAL AND THE SUCH CATALYTIC COMPOSITION AND REDUCING THE LIGHT IN THE LIGHT OF LIGHTING THE LOSS OF LIGHT
    BACKGROUND
    1. FIELD OF THE INVENTION [001] The present invented and claimed inventive concept generally relates to catalysts and methods of making catalysts and, more particularly, but not by way of limitation, to catalysts and methods of making catalysts that are useful to purify the exhaust gases and waste gases from combustion processes.
    2. BACKGROUND OF THE INVENTION [002] The high temperature of combustion of fossil fuels or coal in the presence of oxygen leads to the production of unwanted nitrogen oxides (NOx). Significant research and commercial efforts have sought to prevent the production of these well-known pollutants, or to remove these materials, prior to their release into the air. In addition, federal legislation has increasingly imposed more stringent requirements to reduce the amount of nitrogen oxides released into the atmosphere.
    [003] The processes for removing NOx formed in the exhaust flue gases are well known in the art. The selective catalytic reduction (SCR) process is particularly effective. In this process, nitrogen oxides are reduced by ammonia (or another reducing agent such as unburned hydrocarbons present in the residual effluent gas) in the presence of oxygen and a catalyst to form nitrogen and water. The SCR process is widely used in the United States, Japan, and Europe to reduce emissions from large boilers and other commercial applications. Increasingly, SCR processes have been used to reduce emissions in mobile applications such as large diesel engines like those found on ships, diesel locomotives, automobiles and the like.
    [004] Effective SCR DeNOx catalysts include a variety of mixed metal oxide catalysts, including vanadium oxide supported in an anatase form of titanium dioxide (see, for example, USPatent No. 4,048,112) and titania with an oxide molybdenum, tungsten, iron, vanadium, nickel, cobalt, copper, chromium or uranium (see, for example, US Patent No. 4,085,193).
    [005] The vanadium and tungsten oxides supported on titania have been standard catalyst compositions for NOx reduction since their discovery in the 1970s. In reality, very few competing alternatives to the catalytic performance of vanadium and tungsten oxides supported on titania. Tungsten is an element
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    2/20 important in the applications of DeNOx catalysts, both mobile and immobile, to improve the conversion and selectivity of vanádia catalysts supported on titania. However, world markets have seen a sharp increase in their cost, creating an incentive to reduce the amount of tungsten used in DeNOx catalyst materials. Recent efforts have resulted in the reduction of tungsten in commercial catalysts from 8% W to 4% W by weight. However, below these levels, the catalyst's performance begins to fall below acceptable ranges.
    [006] An effective catalyst particularly for selective NOx catalytic reduction is a metal oxide catalyst comprising a titanium dioxide, divanadium pentoxide, and tungsten trioxide and / or molybdenum trioxide (U.S. Patent No. 3,279,884). Also, USPatent No. 7,491,676 teaches a method of producing an improved catalyst made of titanium dioxide, vanadium oxide and a supported metal oxide, where the vanadium-supported metal oxide has an isoelectric point less than or equal to pH of 3.75 before depositing vanadium oxide.
    [007] It is also known in the art that iron supported on titanium dioxide is a selective catalytic reducer of DeNOx (see, for example. U.S. Patent No. 4,085,193). However, the limitations for using iron are its relatively low activities and high oxidation range from sulfur dioxide to sulfur trioxide (see, for example, Canadian Patent No. 2,496,861). Another alternative being proposed is the use of transition metals supported on beta zeolites (see, for example, U.S. Patent Appl. Pub. No. 2006/0029535). The limitation of this technology is the high cost of zeolite catalysts, which can be a factor of 10 times greater than the comparable catalysts supported on titania.
    [008] Molybdenum containing catalyst systems are well documented in the prior art; however, the use of molybdenum as a commercial catalyst is hampered by two factors. The first factor is the relative volatility of hydrated metal oxide compared to tungsten counterparts leading to losses of molybdenum under commercial conditions. The second factor is the higher oxidation range of SO2 compared to systems containing tungsten. Oxidation of SO2 is a problem in immobile DeNOx applications due to the formation of ammonium sulfate which causes clogging and excessive pressure drop in the process equipment. The inventive concept. The present invented and claimed inventive concepts are directed to a catalyst containing molybdenum perfected to address these issues.
    SUMMARY OF THE INVENTION [009] The present invented and claimed inventive concepts are directed to a titania-based catalyst support material. In addition to titania, the support material includes a primary promoter comprising tungsten oxide and / or
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    3/20 molybdenum oxide and an amount of phosphorus to achieve a molar ratio of phosphorus to tungsten plus molybdenum of about 0.2: 1 or greater. In one embodiment, the primary promoter contains molybdenum oxide and an amount of phosphate to achieve a molar ratio of phosphorus to tungsten plus molybdenum of about 0.2: 1 or greater.
    [0010] When a primary molybdenum promoter is used, a volatility inhibitor can be added to further improve the performance of the catalyst. Compatible volatility inhibitors include, but are not limited to, zirconium oxide, tin oxide, manganese oxide, lanthanum oxide, cobalt oxide, niobium oxide, zinc oxide, bismuth oxide, aluminum oxide, aluminum oxide nickel, chromium oxide, iron oxide, yttrium oxide, gallium oxide, germanium oxide, indium oxide, and combinations thereof.
    [0011] A process for making a titania-based catalyst support material includes the following steps. An aqueous slurry of titania is provided and exposed to a soluble promoter compound. The soluble promoter compound can include tungsten, molybdenum, or a combination of tungsten and molybdenum. A phosphate compound is added in sufficient quantity to achieve a molar ratio of phosphorus to tungsten plus molybdenum of about 0.2: 1 or greater, and the pH is adjusted to a value allowing the deposition of the promoter and phosphate to produce a phosphate titania promoter mixture. The water is removed from the phosphated promoter - titania mixture to produce promoter - titania mixture solids which are calcined to produce a titania-based catalyst support material having a molar ratio of phosphorus to tungsten plus molybdenum of about 0, 2: 1 or greater.
    [0012] Also incorporated is a catalytic composition based on vanádia for the reduction of nitrogen oxides. The catalytic composition has a titania-based support material with vanadium deposited on the titania-based support material. The composition includes a primary promoter comprising a tungsten oxide and / or molybdenum oxide, and an amount of phosphate to achieve a molar ratio of phosphorus to tungsten plus molybdenum of about 0.2: 1 or greater. In one embodiment, a primary promoter is molybdenum oxide and phosphate is present in an amount to achieve a molar ratio of phosphorus to molybdenum of about 0.2: 1 or greater. When both phosphate and the volatility inhibitor are used with the molybdenum oxide promoter, phosphate in a molar ratio of phosphorus to molybdenum of about 0.2: 1 or greater, molybdenum retention is greatly improved and oxidation of SO2 is reduced.
    [0013] A process for making a vanadium-based catalytic composition for the reduction of nitrogen oxides includes the following steps. An aqueous slurry of titania is provided and exposed to a solution-promoting compound, where the promoter can be
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    4/20 a molybdenum, a tungsten or a combination of molybdenum and tungsten. The pH is adjusted to a value allowing the deposition of the molybdenum promoter to produce a hydrolyzed promoter - titania mixture. The water is removed from the hydrolyzed promoter - titania mixture, optionally by filtration and drying, to produce promoter - titania mixture solids. The promoter - titania mixture solids are then calcined to produce a support material, which is added to an aqueous solution of vanadium oxide to produce a suspension of the product. A phosphate compound is added in sufficient quantity to achieve a molar ratio of phosphorus to a promoter (tungsten plus molybdenum) of about 0.2: 1 or greater in the product suspension. The phosphate compound can be added during the preparation of the support, so that the hydrolyzed promoter - titania mixes before the water is removed. Optionally, phosphate can be added during the deposition of the active phase, such as directly after the addition of the aqueous vanadium oxide solution to the support material. In both cases, water is removed from the product suspension to produce solids that are calcined to form a catalytic vanadium-based composition for the reduction of nitrogen oxides, the catalytic vanadium-based composition having a proportion of phosphorus molecule for tungsten plus molybdenum of about 0.2: 1 or greater.
    [0014] In yet another embodiment, the process described above uses a molybdenum promoter and an aqueous titania slurry is exposed to a compatible volatility inhibitor in order to deposit a titania volatility inhibitor. Compatible volatility inhibitors include soluble compounds of zirconium, tin, manganese, lanthanum, cobalt, niobium, zinc, bismuth, aluminum, nickel, chromium, iron, yttrium, gallium, germanium, indium, and mixtures thereof, and work to perfect them. the molybdenum retention of the catalyst during use.
    [0015] In another modality, a method is provided for a selective reduction of nitrogen oxides with ammonia, where nitrogen oxides are present in a gas stream. Such methods involve contacting a gas or liquid with a vanadium-based catalytic composition as described above for a time sufficient to reduce the level of NOx compounds in the gas or liquid.
    [0016] Thus, using (1) technology known in the art; (2) the general description referenced above of the present disclosed and claimed inventive concept; and (3) the detailed description of the invention that follows, the advantages and novelties of the present invented and claimed inventive concept would be readily apparent to one skilled in the art.
    DETAILED DESCRIPTION OF THE INVENTION [0017] Before explaining at least one embodiment of the invention in detail, it is understood that the invention is not limited in its application to construction details,
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    5/20 experiments, exemplary data, and / or the component arrangements set out in the following description. The invention is capable of other modalities or of being practiced or carried out in various ways. Also, it should be understood that the terminology used here is for the purpose of description and should not be considered as limiting.
    [0018] In both mobile or immobile DeNOx applications, it is desirable to replace the tungsten used in the selective catalytic reduction DeNOx catalyst with a less expensive and more available alternative such as molybdenum. The use of molybdenum allows someone to use a more active component that is also half the molecular weight of tungsten. This reduces the amount of component used while maintaining the desired conversions.
    [0019] However, the use of molybdenum in a catalyst (SCR) for commercial selective catalytic reduction is hindered, in part, by the relative volatility of hydrated molybdenum oxide compared with homologous tungsten. In the presence of water and high temperature, molybdenum evaporates, leading to loss of molybdenum under commercial conditions. Thus, the use of molybdenum in SCR catalysts has been limited due to the concern that volatility will result in an eventual loss of catalyst activity and decrease the selectivity of the catalyst due to the loss of the promoter over time.
    [0020] The evaporation of molybdenum can be compensated, somewhat, by the use of higher levels of molybdenum in the catalyst material. However, catalysts containing molybdenum cause a greater oxidation range of SO2 compared to systems containing tungsten in immobile DeNOx applications. Oxidation from SO2 to SO3 is undesirable because of the propensity for SO3 to react with water and ammonia to form a solid ammonium sulfate (NH4) 2SO4. Ammonium sulfate is a solid at exhaust temperatures typical of immobile sources. Therefore, it tends to clog the process pipeline causing a pressure drop in the DeNOx equipment below the power generation equipment. Additional concerns stem from the fact that SO3 is a stronger acid relative to SO2, and its release into the atmosphere results in a greater range of acid rain formation.
    [0021] While initial research focused on the use of selected metal oxide volatility inhibitors to reduce the volatility of molybdenum, it was found that phosphate alone, added to the active catalyst phase and / or to a catalyst support, both reduce the oxidation range of SO2 and still stabilize molybdenum from sublimation. Specifically, it has been found that by adding phosphate in levels to achieve a molar ratio of phosphorus to molybdenum of about 0.2: 1 or greater, the amount of molybdenum retained in the catalyst can be doubled. In addition, with the addition of phosphorus at these levels, the oxidation bands of SO2 are suppressed with
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    6/20 no apparent change in the NOx conversion ranges at high temperatures, and the NOx conversion ranges at low temperatures are actually increased. It has also been found that phosphate has an unexpected effect in helping to preserve the titania surface area at high calcination temperatures when using both molybdenum and tungsten as a primary promoter. It is also surprising to note that the addition of phosphate suppresses the sintering of titanium dioxide under severe calcination conditions.
    [0022] This is quite surprising because previously, phosphate was considered a "poison" in DeNOx catalysts using the standard tungsten promoter, both in terms of NOx conversion and in terms of SO2 oxidation. For example, Walker et al. [1] teaches that phosphorus in lubricating oil systems in diesel vehicles presents poisoning problems for SCR catalysts. Chen et al. [2] teaches that phosphorus (P) is a weak poison for the SCR catalyst and that a phosphorus range for vanadium (P / V) of just 0.8 decreases the activity of the DeNOx catalyst by 30%. Blanco et al. [3] teaches that phosphorus will deactivate the vanadium-containing SCR catalyst and that the presence of phosphorus collapses the pore structure of the catalyst and causes accelerated sintering of the catalyst. Finally, Soria et al. [4] shows that after a vanadium-containing catalyst is exposed to phosphorus, it requires high calcination temperatures in excess of 700 ° C to regenerate activity.
    [0023] In this way, the present invented concepts disclosed and claimed provide a vanadium-based catalytic composition for the reduction of nitrogen oxides, using a titania-based support material with vanadium deposited in the titania-based support material, a primary promoter comprising a molybdenum oxide; and an amount of phosphate to achieve a molar to molybdenum ratio of about 0.2: 1 or greater.
    Definitions [0024] All terms used here are intended to have their ordinary meaning unless otherwise provided.
    [0025] The terms "catalyst support", "support particles", or "support material" are intended to have their standard meanings in the art and refer to a particular comprising TiO2 on the surface of which the catalytic metal component or oxide of metal must be deposited.
    [0026] The terms "active metal catalyst" or "active component" refer to the catalyst component deposited on the surface of the support material that catalyzes the reduction of NOx compounds.
    [0027] The terms "catalyst" and "catalytic composition" are intended to have their standard meaning in the art and refer to the combination of supported catalyst components and titanium-based catalyst support particles.
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    7/20 [0028] Unless otherwise specified, all references to percentage (%) here refer to percentage by weight. The terms "percent" and "loading" refer to the loading of a particular component in the total catalytic composition. For example, the loading of vanadium oxide in a catalyst is the ratio of the weight of vanadium oxide to the total weight of the catalyst, including the titania-based support material, vanadium oxide and any other metal oxides. Similarly, the percentage loading of molecules refers to the ratio of the number of molecules of a particular loaded component to the number of molecules in the total catalytic composition.
    [0029] The term "phosphate" is used to refer to any phosphorus-containing compound bound to an oxygen.
    [0030] SCR catalysts containing commercial vanadium typically use a titania-based support material. Titania is the preferred metal oxide support, although other metal oxides can be used as the support, examples of which include alumina, silica, silica alumina, zirconium, magnesium oxide, hafnium oxide, lanthanum oxide, and the like . Such titania-based support materials and their methods of manufacture and use are known in the art to those skilled in the art. Titania can include titanium dioxide anatase and / or rutile titanium dioxide.
    [0031] Vanádia or vanadium pentoxide (V2O5), the active material, is deposited in or incorporated with the titanium dioxide support. Vanádia typically ranges from 0.5 to 5 percent by weight depending on the application. Tungsten oxide or molybdenum oxide is added as a promoter to achieve additional catalytic activity and improve catalyst selectivity. When the promoter is a molybdenum oxide, molybdenum oxide is typically added to the titania support material in an amount to achieve a molybdenum to vanadium molecule ratio of about 0.5: 1 to about 20: 1 in a final catalyst. Often molybdenum oxide is added to a titania support material in an amount to achieve a molybdenum to vanadium molecule ratio of about 1: 1 to about 10: 1 in the final catalyst.
    [0032] Previous vanadium catalyst compositions used molybdenum oxide promoters, but failed to combine sufficient amounts of phosphorus to stabilize the sublimation molybdenum. The vanadium-based catalytic composition of the present invented and claimed inventive concept uses phosphate added to the active catalyst phase and / or to the catalyst support to both reduce the oxidation range of SO2 and to stabilize the sublimation molybdenum. Phosphate is generally added at levels to achieve a molar ratio of phosphorus to molybdenum of about 0.2: 1 or greater. In some embodiments, phosphate is added in an amount to achieve
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    8/20 a molar ratio of phosphorus to molybdenum is in the range of about 0.2: 1 to about 4: 1.
    [0033] While testing molybdenum pair stabilization, it was discovered that when phosphate was added to a vanadium-based catalytic composition promoted by tungsten, at levels to achieve a molar ratio of phosphorus to tungsten of about 0.2: 1 or greater, the resulting catalyst shown decreased the oxidation of SO2 without a low conversion of NOx significantly. In some embodiments, phosphate is added in an amount to achieve a molar ratio of phosphorus to tungsten in a range of about 0.2: 1 to about 4: 1. Similarly, when both tungsten and molybdenum promoters are present, phosphate is added at levels to achieve a molar ratio of phosphorus to tungsten plus molybdenum of about 0.2: 1 or greater, and in some embodiments, at levels to achieve a molar ratio of phosphorus to tungsten plus molybdenum in a range of about 0.2: 1 to about 4: 1.
    [0034] Suitable phosphate-containing compounds include, but are not limited to, organic phosphates, organic phosphonates, phosphine oxides, H4P2O7, H3PO4, polyphosphoric acid, (NH4) H2PO4, (NH4) 2HPO4, (NH4) 3PO4. The phosphate may be present within the support material, or it may be present on the surface of the support material.
    [0035] In certain embodiments, the volatility inhibitor is also added to the vanadium-based catalytic composition. The volatility inhibitor can be a tin oxide, a manganese oxide, lanthanum oxide, zirconium oxide, bismuth oxide, zinc oxide, niobium oxide, cobalt oxide, aluminum oxide, nickel oxide, chromium oxide , iron oxide, yttrium oxide, gallium oxide, germanium oxide, indium oxide, and combinations thereof. The volatility inhibitor can be added in sufficient quantities to achieve a molar ratio of volatility inhibitor to molybdenum in the range of about 0.05: 1 to about 5: 1. When both phosphate and the volatility inhibitor are used with a molybdenum oxide promoter, phosphate in a molar ratio of phosphorus to molybdenum pair of about 0.2: 1 or greater, molybdenum retention is greatly improved and oxidation of SO2 is reduced significantly. The combination of phosphate and synoxically selected metal oxide volatility inhibitors provides the best combination of molybdenum stability and low SO2 oxidation bands.
    [0036] In one embodiment, the volatility inhibitor is a tin oxide present in an amount to achieve a molar ratio of tin to molybdenum in the range of about 0.1: 1 to about 2: 1. In another embodiment, the volatility inhibitor is a zirconium oxide present in an amount to reach the molar ratio of zirconium to molybdenum in the range of about 0.1: 1 to about 1.5: 1.
    [0037] Others have used promoters of molybdenum, manganese and tin, but have not discovered or recognized the synergistic effect of phosphate in its formulation. For example, U.S. Patent No. 4,966,882 discloses a catalyst composition having at least
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    9/20 minus a V, Cu, Fe, and Mn with at least one oxide of Mo, W, and Sn where the second group is added through vapor deposition to give a catalyst with improved resistance to poisons. The vapor deposition step generally requires a high level of Mo volatility, rather than decreased Mo volatility, in order to prepare a catalyst to be effective. Also, U.S. Patent No. 4,929,586 discloses a titania support formed with a specific pore volume including the components Mo, Sn, and Mn. Again, however, there was no attempt to combine P in the formulations to improve the stability of Mo and the performance of the catalyst.
    [0038] The catalyst composition disclosed in US Patent No. 5,198,403 teaches the formation of a catalyst combining: A) TiO2, B1) at least one of W, Si, B, Al, P, Zr, Ba, Y, La and Ce, and B2) at least one V, Nb, Mo, Fe and Cu. The catalyst is formed pre-kneading A with B1, and then kneading B2 to form a homogeneous mass, extruding, drying and calcining. Again, the inventors failed to recognize the effect of P stability on Mo volatility or the impact it has on reducing SO2 oxidation and sintering the surface area, probably due to the very low concentrations of phosphorus used. There was also no recognition of improvements due to the use of a volatility inhibitor such as tin or manganese.
    [0039] In another embodiment, a process is provided to make the vanadium based catalytic compositions described above for the reduction of nitrogen oxides. The process includes the following steps. An aqueous titania slurry, sometimes referred to as a hydrolyzed titania gel, is provided and exposed to a soluble promoter compound, where the promoter comprises a molybdenum and / or a tungsten. The pH is adjusted to a value allowing the deposition of the promoter to produce the hydrolyzed promoter - titania mixture. The water is removed from the hydrolyzed promoter - titania mixture, optionally by filtration and drying, to produce promoter - titania mixture solids. The promoter - titania mixture solids are then calcined to produce a support material, which is added to an aqueous solution of vanadium oxide to produce a suspension of the product. The phosphate compound is added in sufficient quantity to achieve a molar ratio of phosphorus to tungsten plus molybdenum of about 0.2: 1 or greater in the product suspension. The phosphate compound can be added during the preparation of the support, so that the hydrolyzed promoter - titania mixes before the water is removed. Optionally, phosphate can be added during the deposition of the active phase, such as directly after the addition of the aqueous vanadium oxide solution to the support material. In both cases, water is removed from the product suspension to produce solids that are calcined to form a catalytic vanadium-based composition for reducing nitrogen oxides, to
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    10/20 vanadium-based catalytic composition having a ratio of phosphorus to tungsten plus molybdenum molecule of about 0.2: 1 or greater.
    [0040] Methods for preparing a hydrolyzed titania gel are well known to those skilled in the art, as are methods for the addition of tungsten promoter. The molybdenum promoter is prepared as an aqueous salt solution such as ammonia molybdate. Other compatible molybdenum-containing salts include, but are not limited to, molybdenum tetrabromide, molybdenum hydroxide, molybdic acid, molybdenum oxychloride, molybdenum sulfite. When molybdenum is used as a promoter, the molybdenum salt solution is mixed with the hydrolyzed titania colloidal solution and the pH is adjusted to fall within a range of about 2 to about 10.
    [0041] If a volatility inhibitor is used, an aqueous solution of a salt containing the volatility inhibitor is prepared and added to the colloidal titania solution hydrolyzed with the molybdenum salt solution. Any soluble salt of zirconium, tin, manganese, lanthanum, cobalt, niobium, zinc, aluminum, nickel, chromium, iron, yttrium, gallium, germanium, indium, and / or bismuth can be added to reduce the volatility of molybdenum during use of the resulting catalyst. For example, compatible tin salts include, but are not limited to, tin sulfate, tin acetate, tin chloride, tin nitrate, tin bromide, tin tartrate. Compatible zirconium salts include, but are not limited to, zirconium sulfate, zirconium nitrate and zirconium chloride. Compatible manganese salts include, but are not limited to, manganese sultate, manganese nitrate, manganese chloride, manganese lactate, manganese metaphosphate, manganese dithionate. The mixture is stirred and the pH is adjusted to fall within a range of about 2 to about 10.
    [0042] Optionally, at this point the pH is further adjusted to about 7 and the phosphate compound is added to the sludge. Compatible phosphate compounds include, but are not limited to, organic phosphates, organic phosphonates, phosphine oxides, H4P2O7, H3PO4, polyphosphoric acid, (NH4) H2PO4, (NH4) 2HPO4, and (NH4FPO4. The sludge is dehydrated by means known in the art such as centrifugation, filtration, and the like. The mixture is then dried and calcined, again using procedures and equipment well known to those skilled in the art. Temperatures are typically around 500 ° C, but can be in the range of 250 ° C to about 650 ° C.
    [0043] The active vanadium phase is deposited on the prepared support and pasting it in 200 ml of water. To this, a vanadium pentoxide V2O5 and a solvent such as monoethanolamine (C2ONH5) were added and the temperature of the mixture is raised to a range of about 30 to about 90 ° C. Other compatible solvents include amines, alcohols, carboxylic acids, ketones, mono, di, and tri-alcohol amines. The water is then evaporated from the mixture, and the solid is collected, dried and calcined at 600 ° C. The calcination temperatures are
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    11/20 typically around 600 ° C, but can range from 300 ° C to about 700 ° C.
    [0044] Optionally the phosphate can be added during the deposition of the active phase instead of during the preparation of the support. This is accompanied by an increase in pH to about 9 and adding a phosphate compound such as H4P2O7 after the addition of vanadium. Again, the solvent is removed by evaporation. The solids are dried and calcined at about 600 ° C, as described above.
    [0045] The combined addition of P with stabilizers of zirconium oxides, tin oxide and manganese oxide during the preparation of the catalyst has been found to synergistically reduce the volatility Mo of the catalyst during use. The combined addition of P with other Mo stabilizers was found to reduce the amount of oxidation of SO2, but without reducing the conversion of NOx.
    [0046] Another improvement in catalyst performance can be achieved by adding several other transitions or groups of metal. The metal can be added as a soluble salt during both the support preparation steps and during the deposition of the active vanadium oxide phase. Non-limiting examples of compatible transition or main group metals include lanthanum, cobalt, zinc, copper, niobium, silver, bismuth, aluminum, nickel, chromium, iron, yttrium, gallium, germanium, indium, and combinations thereof.
    [0047] In order to further illustrate the present invented and claimed concepts, the following examples are given. However, it should be understood that the examples are for the purpose of illustration only and are not to be construed as limiting the scope or the invention.
    Example 1 [0048] The catalysts were prepared in two stages. The first stage prepared the support and the second applied the active phase. The first step in preparing the support was to make two solutions of metal salts. A solution was 1.47 g of tin sulfate (SnSO4) in 100 ml of water. The second solution containing molybdenum was made by dissolving 4.74 g of ammonia molybdate [(NH4) 6Mo7O244H2O] in 100 ml of water. The solutions were added to an aqueous titania gel slurry (440 g of 27.7% hydrolyzed titania produced at the Cristal Global titania facility located in Thann, France). Alternatively, calcined titania powder such as that of Cristal Global DT51 ™ can be used as the starting material for titanium dioxide. In both cases, the last 120 g powder is pasted in 320 g of deionized water. The mud was mixed for 10 minutes. At this point, the pH was further adjusted to 7 and the phosphate compound was added (1.57 g H4P2O7) to the sludge. The mixing continued for another 15 minutes and the mixture was then filtered and dried at 100 ° C for 6 hours and calcined in air at 500 ° C for 6 hours.
    [0049] The active phase was deposited by taking 10 g of the prepared support and
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    12/20 pasting it in 20 ml of water. To this, 0.133 g of vanadium pentoxide (V2O5) and 0.267 g of monoethanolamine (C2ONH5) were added and the temperature of the mixture was raised to 60 ° C. The mixture was left to stir for 10 minutes. The water was then evaporated from the mixture, and the solid was collected, dried at 100 ° C for 6 hours, and calcined at 600 ° C for 6 hours in air. Unless otherwise indicated, all catalysts were prepared with nominal vanadium fillings of 1.3 wt% (0.57 mol%).
    [0050] An alternative to the above preparation method, phosphate can be added during the deposition of the active phase instead of during the preparation of the support. This could be done by raising the pH to 9 and adding the phosphate compound (for example, 0.109 g of H4P2O7) after adding vanadium. Again, the solvent water is removed by evaporation. The solid is dried at 100 ° C and calcined at 600 ° C as described above.
    [0051] The conversion of DeNOx was determined using a catalyst in powder form with no other shape. A 3/8 ”quartz reactor holds 0.1 g of catalyst supported on a glass wool. The feed gas composition was 500 ppm NO, 500 ppm NH3, 5% O2, 5% H2O, and N2 balance. The conversion of NO was measured at 250 ° C, 350 ° C, and 450 ° C at atmospheric pressure. The effluent reactor was analyzed with an infrared detector to determine NO conversion and NH3 selectivity.
    [0052] The oxidation of SO2 was determined with a catalyst in powder form without other format. A 3/8 ”quartz reactor held 0.2 g of catalyst supported on a glass wool. The composition of the feed gas was 500 ppm SO2, 20% O2, and the balance N2. The space velocity was 29.5 L / (g cat) (hr) calculated under ambient conditions. Data conversion was recorded at 500 ° C, 525 ° C, and 550 ° C, and reported for both 525 ° C and 550 ° C readers or for the 550 ° C reader only.
    [0053] Mo's volatility was first determined by hydrothermally treating the calcined catalyst sample in a muffle furnace at 70 ° C for 16 hours while exposing it to a 10% flow of water vapor in the air. The final Mo loaded was determined after digesting the sample and using an ICP-OES (inductively coupled plasma optical emission spectroscope) to measure the concentration.
    [0054] The results of our studies are contained in Table I below.
    Table 1. Effect of Phosphate and Volatility Inhibitors on Catalyst Performance
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    Primary Prosecutor Volatility Inhibitor NO x conversion (%) Oxidation of SO 2 (%) Example No. Support Elemento Loading (mol%) Then Carrying(mol%) Loading PO4(mol%) Mo loading after 700 ° CTreatment(mol%) Mo retention (%) 250 °Ç 350 °Ç 450 ° C 525 ° C 500 ° C 1-1 DTW5 W 1.74 AT AT 8.4 43.9 63.0 12.20 17.54DTW5 W 1.74 1.15 AT AT 14.2 40.7 52.3 8.34 9.72 1-2 G1 Mo 1.67 0.52 31% 10.0 52.3 66.7 13.37, 21.28DT51 Mo 1.67 0.70 42% 12.8 63.2 70.9 12.04 18.04 1-3 G1 MO 1.67 1.15 1.22 73% 17.9 58.1 63.8 11.68 14.82DT51 Mo 1.67 2.53 1.20 72% 21.0 61.5 61.2 7.08 10.13 1-4 G1 Mo 1.67 Sn 0.430.79 48% 9.5 54.1 65.2 13.07 18.87G1 Mo 1.67 Sn 0.220.62 37% 9.3 42.0 58.0 13.44 18.73G1 Mo 1.67 Sn 0.22 2.53 1.43 86% 16.9 35.9 41.6 8.24 11.37 1-5 G1 Mo 1.67 Mn 0.420.76 46% 9.6 59.9 72.3 G1 Mo 1.67 Mn 0.220.45 27% 9.2 53.9 64.2 G1 Mo 1.67 Mn 0.22 2.53 1.00 60% 1-6 G1 Mo 0.93 Mn 0.42 1.15 10.93 101%37.8 G1 Mo 0.93 Sn 0.43 1.15 0.89 96%37.78.83 15.80
    [0055] Test 1-1 is a conventional W-containing catalyst commercially available from the Cristal Global facility located in Thann, France, under the trademark of DTW5 ™. The results of test 1-1 show that P can reduce the oxidation of SO2 in a catalyst containing W. It should also be noted that the reduction in oxidation of SO2 does not come at the cost of a significant loss in the conversion of NOx at 350 ° C.
    [0056] Test 1-2 shows the results of a catalyst made using Mo in comparable loads using commercial G1 ™ or DT51 ™ supports as starting materials, the supports available commercially from the Titan Global Cristal facility located in Thann, France. This can be seen from the results that the NOx conversions are highly measurable and the oxidation ranges of SO2 are comparable for the promoted catalyst Mo to W at the same molar loads. One can see that the disadvantage of using a Mo catalyst without the present inventive concepts disclosed is that about two thirds of the promoter is lost during hydrothermal ripening.
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    14/20 [0057] The amount of Mo retained is doubled by adding phosphate to the formulation according to the recipe (Test 1-3). In addition, SO2 oxidation ranges are suppressed, NOx conversion is increased to 250 ° C, and there is no apparent change in NOx conversion at high temperatures.
    [0058] Mo volatility is also suppressed by the addition of either Sn or Mn oxides (tests 1-4 and 1-5, respectively). Both examples show that the Mo retention is comparable to the higher loads of the secondary metal oxide. However, in the lower charges investigated, Mn does not seem to suppress Mo's volatility, whereas Sn does. The addition of phosphate improves the stability of Mo in both examples. However, again, in the case of Mn, the improvement is no better than that for phosphate alone, whereas for Sn, it seems to have a combined effect of two components leading to a higher Mo retention than seen for both Sn and for phosphate alone. It is also seen in Test 1-4 that phosphate has the added advantage of suppressing oxidation of SO2 as well.
    [0059] Test 1-6 shows that in certain compositions the volatility of Mo under these conditions can be eliminated virtually. In this case the loading of Mo was nominally 1 wt% (measured as 0.93 mol%).
    Example 2 [0060] Phosphate also has an unexpected effect of helping to preserve the titania surface area under a severe increase in calcination, as shown in Table 2 below. The surface area measurements for Test 2-1 show that the addition of phosphate to a tungsten catalyst with 0.55 mol% V2O5 increases the surface area by almost 15 m 2 / g after calcination at 600 ° Ç. Test 2-2a showed the expected result of decreasing the surface area since the gravity of the calcination increased from 600 ° C to 700 ° C in 50 ° C increments. Test 2-2b shows that phosphate helps to limit these losses. The surface area and pore volume measurements for Tests 2-3 through 2-6 show that this same behavior is observed when Mo replaces W as the primary promoter. The differences between the examples are the increase in Mo and V2O5 loads.
    Table 2. Effect of phosphate on the Surface Area of the BET Catalyst and Volume of
    Pore
    Primary Prosecutor ExampleO Stat Loading of V 2 O 5 (mol%) Element Loading(mol%) LoadingPO4 (mol%) Calcination Time(Ç) BET (m 2 / g) PV cm 3 / g 2-1 392 0.40 W 1.74 0.00 600 59.14 0.25396 0.40 W 1.74 0.37 600 73.33 0.262-2a 394 0.57 W 1.74 0.00 600 56.84 0.25
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    394 0.57 W 1.74 0.00 650 49.67 0.23394 0.57 W 1.74 0.00 700 37.63 0.19 2-2b 395 0.57 W 1.74 0.52 600 74.92 0.26395 0.57 Mo 1.74 0.52 650 71.96 0.24395 0.57 Mo 1.74 0.52 700 45.62 0.212-3a 321 0.40 Mo 0.42 0.00 600 59.51 0.25 2-3b 323 0.40 Mo 0.42 0.37 600 69.06 0.262-4a 320 0.40 Mo 0.83 0.00 600 57.39 0.25346 0.40 Mo 0.83 0.00 600 58.68 0.26346 0.40 Mo 0.83 0.00 650 43.45 0.20346 0.40 Mo 0.83 0.00 700 35.50 0.18 2-4b 335 0.40 Mo 0.83 0.37 600 68.08 0.25335 0.40 Mo 0.83 0.37 650 56.19 0.24335 0.40 Mo 0.83 0.37 700 43.76 0.202-5 347 0.57 Mo 0.83 0.00 600 60.78 0.26347 0.57 Mo 0.83 0.52 600 79.18 0.252-6a 404 0.57 Mo 1.25 0.00 600 55.10 0.25404 0.57 Mo 1.25 0.00 650 40.97 0.20 2-6b 406 0.57 Mo 1.25 0.52 600 68.29 0.26406 0.57 Mo 1.25 0.52 650 55.63 0.25
    Example 3 [0061] Additional tests were performed by varying the loading of molybdenum, phosphorus and tin. The testing procedures followed those described in Example 1 and the results are shown in Table 3 below. We found that there is a need for a balance in shipments to optimize the system. For example, at high Sn / Mo ranges plus Sn will deactivate the catalyst, while at low ranges plus Sn will increase activity. We found the best balance between NOx conversion, Mo retention and low oxidation of SO2 in intermediate loads of all three components.
    Table 3. Effects of variation of Mo, P and Sn
    NOx conversion (%) testAt the. Mo(mol%) P(mol%) Sn(mol%) Mo after 700 ° CHT (mol%) MoWithheld 250 ° C 350 ° C 450 ° C Oxidation of SO2 at 550 ° C (%) 3rd 1.67 2.58 0.86 1.42 85% 13.6 37.6 42.8 10.441.67 1.29 0.86 1.36 82% 14.6 47.6 52.5 13.85
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    1.67 2.58 0.43 1.23 74% 11.8 42.1 50.0 13.431.67 1.29 0.43 0.74 45% 10.5 53.6 67.4 20.61 3b 3.33 2.58 0.43 1.68 50% 18.3 53.4 55.4 14.143.33 2.58 0.86 1.56 47% 25.5 56.0 58.1 13.573.33 1.29 0.86 1.26 38% 19.4 66.9 71.1 14.233.33 1.29 0.43 0.93 28% 20.9 54.6 60.5 16.33 3c 2.50 1.94 0.65 1.83 73% 18.9 52.4 60.4 10.652.50 1.94 0.65 2.00 80% 17.4 53.9 56.4 11.45
    [0062] As can be seen from Test Nos. 3a and 3b in Table 3, Sn and P both increase the retention of Mo and Sn and P also both decrease the oxidation of SO2 (Tests 3a). Sn appears to decrease the conversion of NOx to low loads of Mo (Test 3a), and also appears to increase the conversion of NOx in both low and high loads. All tests show that Mo increases NOx conversion and SO2 oxidation. Thus, it is important to balance P, Sn with Mo loads to optimize NOx conversion, Mo retention, and minimize SO2 oxidation as in Test No. 3c.
    Example 4 [0063] Additional tests were performed using the procedures in Example 1 to determine the effect of the order of addition of Mo, P and SN on the conversion of NOx. As can be seen the results show in Table 4, the order of addition it is important, contradicting the teaching in the prior art.
    Table 4. Effect on the Order of Addition
    NOx conversion (%) testAt the. Addition Order Mo mol% P mol% Snmol% 250 ° C 350 ° C 450 ° C 4th 1) 3% Mo 2) 0.96% Sn3) 0.75% P 2.50 1.94 0.65 13.9 58.8 64.9 4b 1) 3% Mo 2) 0.75% P 3)0.96% 2.50 1.94 0.65 16.0 55.7 55.0 4c 1) 0.96% Sn 2) 0.75 P 3)3% Mo 2.50 1.94 0.65 12.6 54.2 61.3 4d 1) 0.96% Sn 2) 3% Mo 3)0.75% P 2.50 1.94 0.65 12.8 51.2 57.9 4e 1) 0.75% P 2) 0.96% Sn3) 3% Mo 2.50 1.94 0.65 13.3 47.8 49.1 4f 1) 0.75% P 2) 3% Mo 3)0.96% Sn 2.50 1.94 0.65 19.1 47.2 49.1
    [0064] Adding Mo first gives the biggest NOx conversion. Adding Sn
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    17/20 first may result in a slightly lower conversion of NOx; however, the results are extremely close and may be with natural experimental variability. Adding P first clearly results in the lowest conversion of NOx. It appears to be less important to which element is added by 2 ° or 3 °.
    [0065] The importance of adding Mo before P was an unexpected result and contradicts the teachings of U.S. Patent No. 5,198,403, for Brand et al. which states that P should be added before Mo. Brand et al. it also does not show the potential of P to reduce NOx conversion as demonstrated here. This is due to the very low P loading in the examples for which the reactor tests reported by Brand et al. and that you may not have allowed them to see these effects. This argument is further supported below by example 6.
    Example 5 [0066] The effect of the other transition metals on NOx conversion and Mo retention was examined. Specifically, lanthanum, cobalt, zinc, zirconium, bismuth, silver, niobium and copper were tested using the general catalyst preparation procedures described in the previous examples. Lanthanum was added as LaCb7H2O; cobalt was added as Co (NO3) 26H2O; zinc was added as ZnSOa7H2O; zirconium was added as Zr (SOá) 24H2O; bismuth was added as a bismuth citrate; silver was added as AgNOs; niobium was added as Nb (HC2Oá) 56H2O, and copper was added as CuSOá5H2O. each salt was first dissolved in 50 ml of water and added after the Mo solution and before adding the phosphorus (when added). Example 5a contains the results for four metals without any additional phosphorus. Example 5b includes the effects of the transition metal and phosphorus volatility inhibitors.
    [0067] The transition metals are listed in Table 5 below in order to decrease the effectiveness as inhibitors of Mo volatility. The results show that the transition metal affects the amount of Mo retained as well as the conversion of NOx. Of the eight metals tested, Mo stabilization improved according to Cu <Nb <Ag <Bi <Zr <Zn <Co <La, but the conversion of NOx improved according to: Ag <La <Bi <Zr <Zn <Nb <Co <Cu. The different orders show that the effect on the retention of Mo cannot be interfered with the conversion of relative NOx, which is another surprising result.
    [0068] The results in Table 5 clearly show that the retention of Mo does not improve the parallel in the performance of the catalyst. NOx conversion is best for the Cu and Co modified catalyst and the poorest when the promoters are Ag and La; while Mo retention is better for La and Zr and poorer for Cu and Ag. Thus, a person can assume that a material that improves NOx conversion necessarily also improves Mo retention, still distinguishing those present
    Petition 870180138974, of 10/08/2018, p. 31/40
    18/20 invented and claimed prior art inventive concepts that focus on catalyst performance in terms of NOxX conversion alone.
    Table 5. Effect of Transition Metals on Mo Retention and Conversion of
    NOx
    Example Mo(mol%) P(mol%) District Attorney Loading ofPromoter (mol%) Mo after 700HT (mol%) Retained Mo NOx conversion at 350 ° C (%) 5th 1.67 0 There 0.40 1.63 98% 49.41.67 0 Zr 0.44 1.54 93% 54.91.67 0 Ag 0.44 0.74 45% 53.51.67 0 Ass 0.43 0.66 40% 62.2 5b 0.97 1.24 There 0.50 0.91 94% 33.21.2 1.24 Co 0.53 0.92 90% 40.41.2 1.24 Zn 0.53 0.92 90% 35.11.2 1.24 Zr 0.52 0.91 89% 34.31.7 1.24 Bi 0.55 0.93 87% 34.00.95 1.24 Ag 0.49 0.82 86% 31.40.99 1.24 Nb 0.51 0.84 85% 37.81.04 1.24 Ass 0.54 0.74 71% 43.0
    Example 6 [0069] The purpose of this example is to show that the combined phosphomolybdates show little effectiveness due to the fact that P charged relative to Mo is low. In Example 6a and 6c, the catalyst is prepared as described in the previous examples. However, in example 6b, ammonium phosphomolybdate is used as the source for both Mo and P.
    [0070] The 1:12 P to Mo range in the compound identified below is comparable to the compounds used by Brand et al. in U.S. Patent No. 5,198,403, and thus confirms our claim that they did not see an effect from their phosphorus shipments. In addition, this confirms that a molar ratio of P: Mo of 0.2 to 1 is a low limit for which the addition of phosphorus produces desirable results.
    [0071] In each of the 6a-6c test examples reported in Table 6, Mo was the primary promoter and was loaded at a level of 1.25 mol%. Note that the combined phosphorus molybdenum compound of Example 6b, (NH4) 3PO412MoO33H2 O, does not significantly affect the oxidation of SO2 or the retention of Mo relative to tests where phosphorus is not added to the system (Example 6a). However, when P and Mo are added as two separate compounds, (NH4) 6Mo7O244H2O and H4P2O7 as in
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    Example 6c, one has an extra degree of freedom to vary the loads regardless of achieving the desired effects.
    Table 6. Results with Low P / Mo Ranges
    NOx conversion (%) Oxidation SO2 Example No. Source ofMo P source LoadingPO4(mol%) Mo after 700 ° CHT (mol%) MoRet.(%) 250 ° C 350 ° C 450 ° C 525 ° C 550 ° C 6th (NH4) 6MO7O244H2O AT 0 0.51 41% 10.1 46.2 60.6 14.85 24.45 6b (NH4) 3PO412MoO33H2O 0.10 0.57 46% 3.4 43.2 70.1 13.65 19.42 6c (NH4) 6MO7O244H2O H4P2O7 1.12 1.22 97% 11.6 45.3 55.0 9.58 12.58
    Example 7 [0072] This following example demonstrates the effect of Zr on the retention of Mo. This is industrially important because Zr is less expensive and more commonly (and more easily) used in catalyst systems compared to Sn. In the following tests, the Zr loads were increased from 0 mol% to 0.25 mol%. It is clear from this example that loading 0.08 mol% Zr (Test 7b) improves Mo retention, but not for the 100% target we want. However, loads of 0.16 and 0.25 mol%, Tests 7c and 7d, respectively, increase Mo retention to approximately 100%. It is also apparent from the comparison of NOx conversion results from Test 7 for those containing Zr, that this retention is gained at a small cost of NOx conversion. Additionally, the presence of Zr does not affect the oxidation ranges of SO2.
    [0073] Thus, Zr shows a better performance compared to Sn and Mn in terms of Mo retention. Also, the range of volatility inhibitor for Mo loading can be reduced to as low as about 0.05 to 1 with favorable results.
    Table 7. Results Using a Zr Volatility Inhibitor
    NOx conversion (%) SO2 Ox'n (%) testAt the. Mo(mol%) Zr(mol%) Mo loading after 700 ° C HT treatment (mol%) MoRet(%) 250 ° C 350 ° C 450 ° C 525 ° C 550 ° C
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    7th 1.25 0 0.51 41 10.1 46.2 60.6 14.85 24.45 7b 1.25 0.08 1.01 81 6.6 36.5 53.8 14.96 21.40 7c 1.25 0.16 1.21 97 7.7 37.2 54.2 15.20 20.89 7d 1.25 0.25 1.20 96 6.0 38.9 59.4 15.13 22.27
    [0074] From the examples and descriptions above, it is clear that the present inventive processes, methodologies, devices and compositions are well adapted to realize the objects and to achieve the advantages mentioned here, as well as those inherent in the present disclosure provided. While the present preferred embodiments of the invention have been described for the purpose of this disclosure, it will be understood that numerous changes can be made that will quickly suggest themselves to those skilled in the art and that are carried out in the spirit of the invented and claimed inventive concepts described herein.
    Cited References
    1. A.P. Walker, P.G. Blakeman, I. Ilkenhans, B. Mangusson, AC McDonald, P. Kleijwegt, F. Stunnerberg, & M. Sanchez, “The Development and Demonstration Field of Highly Durable SCR Catalyst Systems”, SAE 2004-01-1289, Detroit , 2004, teaches that P in lubricating oil systems in diesel vehicles present poisoning problems for SCR catalysts.
    2. J.P. Chen, M.A. Buzanowski, R.T. Yang, J.E.Cichanowicz, “Deactivation of Vanadium Catalysts in the Selective Catalytic Reduction Process”, J. Air Waste Manage. Assoc., Vol. 40, p. 1403, 1990), teaches that P is a weak poison for the SCR catalyst with a P / V range added to a range of just 0.8 decreases the catalytic activity of DeNOx by 30%.
    3. J. Blanco, P. Avila, C. Barthelemey, A. Bahamonde, JA Ordriozola, JF Gacia de La Banda, H. Heinemann, “Influence of P on Catalysts Containing V for the Removal of NOx, teaches that P will disable a SCR catalyst containing V they also teach that the presence of P collapses the pore structure of the catalyst and causes accelerated sintering of the catalyst.
    4. J. Soria, J.C. Conesa, M. Lopez-Granados, J.L.G. Fierro, J.F. Garcia de La Banda, H. Heinemann, “Calcination Effect of V-O-Ti-P Catalysts”, p. 2717 in “New Frontiers in Catalysts”, L. Guzci, F. Solymosi, P. Tetenyi, Eds, Elsevier, 1993, shows that after the catalyst containing V is exposed to P it requires high calcination temperatures of 700 ° C to regenerate activity.
    权利要求:
    Claims (28)
    [1]
    1. Titanium-based catalyst support material, CHARACTERIZED by the fact that it comprises titania, a primary promoter comprising molybdenum oxide, an amount of phosphate to achieve a molar ratio of phosphorus to molybdenum of 0.2: 1 or greater, an inhibitor of volatility selected from the group consisting of zirconium oxide, tin oxide, and combinations of these, in which the volatility inhibitor is deposited on titania by exposing an aqueous titania slurry to a soluble zirconium salt, titania salt or combinations of these.
    [2]
    2. Titanium-based catalyst support material according to claim 1, CHARACTERIZED by the fact that phosphate is present in an amount to achieve a molar ratio of phosphorus to molybdenum in the range of 0.2: 1 to 4: 1.
    [3]
    3. Vanadium-based catalytic composition for the reduction of nitrogen oxides, CHARACTERIZED by the fact that it comprises the titanium-based catalyst support material, as defined in claim 1, and vanádia deposited on the titania-based support material .
    [4]
    4. Vanadium-based catalytic composition for the reduction of nitrogen oxides, according to claim 3, CHARACTERIZED by the fact that it comprises the titania-based catalyst support material, as defined in claim 2, and vanadium deposited on the support material based on titania.
    [5]
    5. Titanium-based catalyst support material according to claim 1, CHARACTERIZED by the fact that the catalytic composition is essentially free of tungsten.
    [6]
    6. Catalytic composition based on vanádia, according to claim 4, CHARACTERIZED by the fact that the catalytic composition is essentially free of tungsten.
    [7]
    7. Titanium-based catalyst support material according to claim 1, CHARACTERIZED by the fact that the volatility inhibitor is present in an amount to achieve a molar ratio of the volatility inhibitor to molybdenum in the range of 0.05: 1 to 5: 1.
    [8]
    8. Vanadium-based catalytic composition, according to claim 4, CHARACTERIZED by the fact that the volatility inhibitor is present in an amount to reach a molar ratio of the volatility inhibitor to molybdenum in the range of 0.05: 1 to 5 :1.
    [9]
    9. Titanium-based catalyst support material according to claim 7, CHARACTERIZED by the fact that it additionally comprises a main or transition group metal selected from the group consisting of lanthanum, cobalt, zinc, copper, niobium, silver , bismuth, aluminum, nickel, chromium, iron, yttrium, gallium, germanium,
    Petition 870190021026, of 02/28/2019, p. 10/14
    2/5 indium, and combinations thereof, and optionally in which the main or transition group metal is selected from the group consisting of lanthanum, cobalt, zinc and combinations thereof.
    [10]
    10. Titanium-based catalyst support material according to claim
    9, CHARACTERIZED by the fact that the volatility inhibitor is zirconium oxide or in which molybdenum, phosphate and tin are present in 2.50 mol%, 1.94 mol% and 0.65 mol%, respectively, in applications where the material of support is combined with vanadium to produce a catalytic composition based on vanadium for the reduction of nitrogen oxides.
    [11]
    11. Titanium-based catalyst support material according to claim
    10, CHARACTERIZED by the fact that phosphate is present in an amount to reach a molar ratio of phosphorus to molybdenum in the range of 0.2: 1 to 4: 1; and where the primary promoter comprises molybdenum which is present in an amount to achieve a molybdenum to vanadium molar ratio in the range of 0.5: 1 to 20: 1, and where the catalyst material additionally comprises a volatility inhibitor selected from the group consisting of zirconium oxide, tin oxide, and combinations thereof, the volatility inhibitor present in an amount to achieve a molar ratio of volatility inhibitor to molybdenum in the range of 0.05: 1 to 5: 1 and, optionally, wherein the titania-based catalyst support material additionally comprises a major or transition group metal selected from the group consisting of lanthanum, cobalt, zinc and combinations thereof.
    [12]
    12. Vanadium-based catalytic composition according to claim 4, CHARACTERIZED by the fact that the primary promoter comprises a molybdenum oxide present in an amount to reach a molybdenum to vanadium molar ratio of 0.5: 1 to 20 : 1 or where molybdenum is present in an amount to reach a molybdenum to vanadium molar ratio in the range of 1: 1 to 10: 1.
    [13]
    13. Vanadium-based catalytic composition according to claim 8, CHARACTERIZED by the fact that the volatility inhibitor is selected from the group consisting of zirconium oxide, tin oxide, or a combination thereof, or in which the inhibitor of volatility is zirconium oxide, or in which molybdenum, phosphate and tin are present in 2.50 mol%, 1.94 mol% and 0.65 mol%, respectively, or in which the volatility inhibitor is selected from the group consisting of of zirconium oxide, tin oxide, or a combination thereof, the vanadium-based catalytic composition further comprising a metal of the main or transition group selected from the group consisting of lanthanum, cobalt, zinc and combinations thereof.
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    [14]
    14. Titanium-based catalyst support material according to any one of claims 1, 2, 5, 7, 9, 10 and 11, CHARACTERIZED by the fact that molybdenum oxide and phosphate are added to titania and molybdenum oxide is added before the phosphate.
    [15]
    15. Vanadium-based catalytic composition according to any of claims 3, 4, 6, 8, 12 and 13, CHARACTERIZED by the fact that molybdenum oxide and phosphate are added to titania and molybdenum oxide is added before the phosphate.
    [16]
    16. Titanium-based catalyst support material according to any one of claims 1, 2, 5, 7, 9, 10, 11 and 14, CHARACTERIZED by the fact that molybdenum oxide is on the surface of the support material titania-based catalyst.
    [17]
    17. Vanadium-based catalytic composition according to any one of claims 3, 4, 6, 8, 12, 13 and 15, CHARACTERIZED by the fact that molybdenum oxide is on the surface of the catalyst-based support material titania.
    [18]
    18. Process for making a vanadium-based catalytic composition for the reduction of nitrogen oxides as defined in any of claims 3, 4, 6, 8, 12, 13, 15 and 17, CHARACTERIZED by the fact that it comprises the following phases:
    (a) providing an aqueous titania slurry and exposing the aqueous titania sludge to a soluble salt selected from the group consisting of soluble tin compounds, soluble zirconia compounds, and mixtures thereof;
    (b) exposing the aqueous titania sludge to a soluble molybdenum promoting compound, and adjusting the pH to a value to produce a hydrolyzed promoter - titania mixture;
    (c) removing water from the hydrolyzed promoter - titania mixture from step (b) to produce promoter - titania mixture solids, and calcining the promoter - titania mixture solids to produce a support material;
    (d) providing an aqueous oxide solution;
    (e) adding the support material from step (c) to the vanadium oxide solution to produce a product suspension;
    (f) adding both in step (b) and in step (e), a phosphate compound in sufficient quantity to achieve a molar ratio of phosphorus to molybdenum of 0.2: 1 or greater in the product suspension; and (g) removing water from the product suspension of step (f) to produce solid products, and calcining the solid products to produce a vanadium-based catalytic composition for the reduction of nitrogen oxides, the vanadium-based catalytic composition having a molar ratio of phosphorus to molybdenum from 0.2: 1 to 4: 1.
    [19]
    19. Process for making a titania-based catalyst support material as defined in any one of claims 1, 2, 5, 7, 9, 10, 11, 14 and 16, CHARACTERIZED by the fact that it comprises the following steps:
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    4/5 (a) providing an aqueous titania slurry and exposing the aqueous titania sludge to a soluble salt selected from the group consisting of soluble tin compounds, soluble zirconia compounds, and mixtures thereof;
    (b) exposing the aqueous titania slurry to a soluble molybdenum promoting compound, and to a phosphate compound in sufficient quantity to achieve a molar ratio of phosphorus to molybdenum of 0.2: 1 or greater, adjusting the pH to a value to produce a promoter - phosphate titania mixture; and (c) removing the water from the phosphated promoter - titania mixture from step (b) to produce the promoter - titania mixture solids, and calcining the promoter - titania mixture solids to produce a titania-based catalyst support material having a molar ratio of phosphorus to molybdenum of 0.2: 1 or greater.
    [20]
    20. Process according to claim 19, CHARACTERIZED by the fact that the phosphate compound is added to the product suspension in step (d), after the addition of the soluble molybdenum promoter and before removing the water in step (c) .
    [21]
    21. Process according to claim 18, CHARACTERIZED by the fact that the soluble phosphate compound is added in sufficient quantity to achieve a molar ratio of phosphorus to promoter in the product suspension, as defined in claim 18, in the range of 0 , 2: 1 to 4: 1.
    [22]
    22. Process according to claim 19 or 20, characterized by the fact that the soluble phosphate compound is added in sufficient quantity to achieve a molar ratio of phosphorus to promoter in the titania-based catalyst support material, as defined in claim 19, in the range of 0.2: 1 to 4: 1.
    [23]
    23. Process according to claim 18, CHARACTERIZED by the fact that the phosphate compound is added in sufficient quantity to achieve a molar ratio of phosphorus to molybdenum in the suspension of the product in the range of 0.2: 1 to 4: 1 or, where the phosphate compound is added to the product suspension in step (e), after the addition of soluble molybdenum and before the removal of water in step (g) or, where the soluble promoter compound is added in sufficient quantity to achieve a molybdenum to vanadium molar ratio in the range of 0.5: 1 to 20: 1 in the vanadium based catalytic composition or, in which the soluble promoter compound is added in sufficient quantity to achieve a molybdenum to vanadium molar ratio in the range from 1: 1 to 10: 1 in the catalytic composition based on vanádia.
    [24]
    24. Process according to claim 18, CHARACTERIZED by the fact that it additionally comprises the addition of a metal of the main or transition group in step (b) or in step (e), the metal of the selected main or transition group of the group consisting of lanthanum, cobalt, zinc, copper, niobium, silver, bismuth, aluminum, nickel, chromium, iron, yttrium, gallium, germanium, indium and their combinations.
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    [25]
    25. Process according to claim 19, CHARACTERIZED by the fact that it further comprises the addition of a metal from the main or transition group in step (b), the metal from the main or transition group selected from the group consisting of lanthanum, cobalt, zinc, copper, niobium, silver, bismuth, aluminum, nickel, chromium, iron, yttrium, gallium, germanium, indium and their combinations.
    [26]
    26. Process according to claim 18, CHARACTERIZED by the fact that the soluble volatility inhibitor is added as an aqueous solution, or, in which the volatility inhibitor is present in an amount to achieve a volatility inhibitor molar ratio for molybdenum in the range of 0.05: 1 to 5: 1 in the vanadium based catalytic composition or in the titania based catalyst support material.
    [27]
    27. Process according to claim 19, CHARACTERIZED by the fact that the soluble volatility inhibitor is added as an aqueous solution, or, in which the volatility inhibitor is present in an amount to achieve a volatility inhibitor molar ratio for molybdenum in the range of 0.05: 1 to 5: 1 in the vanadium based catalytic composition or in the titania based catalyst support material.
    [28]
    28. Method for reducing NOx compounds in a gas or liquid, CHARACTERIZED by the fact that it comprises contacting the gas or liquid with a vanadium-based catalytic composition as defined in any of claims 3, 4, 6, 8, 12 , 13, 15 and 17 for a time sufficient to reduce the level of NOx compounds in said gas or liquid, where the vanadium-based catalytic composition comprises a titania-based support material; vanádia deposited in the support material based on titania; primary molybdenum oxide promoter, and an amount of phosphate to achieve a molar ratio of phosphorus to molybdenum of 0.2: 1 or greater;
    wherein the vanadium-based catalytic composition further comprises a volatility inhibitor selected from the group consisting of zirconium oxide, tin oxide, and combinations thereof, the volatility inhibitor present in an amount to achieve an inhibitor molar ratio volatility for molybdenum in a range of 0.05: 1 to 5: 1.
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    同族专利:
    公开号 | 公开日
    KR101711240B1|2017-02-28|
    AU2011241040A1|2012-10-25|
    EP2558200A2|2013-02-20|
    MX2012011778A|2012-12-17|
    US20110250114A1|2011-10-13|
    ZA201207969B|2014-01-29|
    WO2011129929A2|2011-10-20|
    US20150298057A1|2015-10-22|
    WO2011129929A3|2012-01-26|
    MX363357B|2019-03-21|
    TW201201906A|2012-01-16|
    CA2795092A1|2011-10-20|
    KR20130057431A|2013-05-31|
    CN103025427A|2013-04-03|
    CN103025427B|2015-03-18|
    BR112012025536A2|2016-06-21|
    SG184464A1|2012-11-29|
    TWI423846B|2014-01-21|
    SG10201502831PA|2015-05-28|
    AU2011241040B2|2015-09-17|
    CA2795092C|2016-02-02|
    EP2558200A4|2014-01-15|
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    法律状态:
    2017-11-28| B25D| Requested change of name of applicant approved|Owner name: CRISTAL USA INC. (US) |
    2018-07-10| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2018-12-04| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2019-08-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-09-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/03/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/03/2011, OBSERVADAS AS CONDICOES LEGAIS |
    2019-11-26| B25A| Requested transfer of rights approved|Owner name: TRONOX LLC (US) |
    2022-01-04| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 11A ANUIDADE. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/759,392|US20110250114A1|2010-04-13|2010-04-13|Vanadia-Based DeNOx Catalysts and Catalyst Supports|
    PCT/US2011/027650|WO2011129929A2|2010-04-13|2011-03-09|Vanadia-based denox catalysts and catalyst supports|
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