MX373345B

Catalyst support materials, catalysts, methods of making them and uses thereof

Abstract

Catalyst support materials, catalysts, methods of making and using them are described. Methods for making a catalyst support material include combining the anatase titania slurry with i) to a low molecular weight form of silica; and ii) a source of Mo to form a TiO2-MoO3-Sio2 mixture. The catalyst support material includes from about 86% to about 94% by weight of anatase titanium dioxide; from about 0.1% to about 10% by weight of Moo3 and from about 0.1% to about 10% by weight of SiO2. Low molecular weight forms of silica include forms of silica with a volume average size weight of less than 4 nm and average molecular weight of less than 44,000, either individually or in a combination of two or more of these. The catalyst includes such catalyst support materials with from about 0.1 to about 3% by weight of V2O5 and optionally from about 0.01% to about 2.5% by weight of P.

MX373345B, drawing sheet 1 — Sheet 1 of 71

Term

8.4 yearsleft in the term

Expires 18 February 2035.

10 claims: 2 independent, 8 dependent

1
5 1. Un método para hacer un material de soporte catalítico caracterizado porque comprende:a. proporcionar una lechada de anatasa titania;y b. combinar la lechada de anatasa titania con i) una forma de sílice de bajo peso molecular y ii) una fuente de Mo para 10 formar una mezcla de TÍO2- M0O3-SÍO2, en donde la forma de sílice de bajo peso molecular comprende un miembro seleccionado de un grupo que consiste en (a) formas de sílice que tienen un volumen ponderado de tamaño medio de menos de 4 nm y (b) formas de sílice que tienen un peso molecular promedio de menos de 15 44,000, y sus combinaciones y que comprenden además proporcionar una cantidad de fosfato a la lechada de anatasa titania;en donde el material de soporte catalítico comprende de 86% a 94% en peso de dióxido de anatasa titanio;de 0.1% a 10% en peso de M0O3;de 0.1% a 10% en peso de SÍO2 en una forma 20 de bajo peso molecular;y de 0.01% a 2.5% en peso de P.
2
El método de conformidad con la reivindicación 1, caracterizado porque la forma de sílice de bajo peso molecular comprende un miembro seleccionado de un grupo que consiste en IMPI INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL solución de silicato de sodio, un silicato de tetrametilamonio, alcalino, silicato de tetraalquilamonio y sus combinaciones.
3
Un material de soporte catalítico que comprende una lechada de titania anatasa con i) una forma de sílice de bajo 5 peso molecular y ii) una fuente de Mo para formar una mezcla de TÍO2-M0O3-SÍO2 en donde el material de soporte de catalítico comprende:de 86% a 94% en peso de dióxido de titanio anatasa;de 0.1% a 10% en peso de M0O3;de 0.01% a 2.5% de P;y de 0.1% 10 a 10% en peso de una forma de SÍO2 de bajo peso molecular.
4
El material de soporte catalítico de conformidad con la reivindicación 3, caracterizado porque comprende además combinar la mezcla de TÍO2-M0O3-SÍO2 con V2O5 para formar un catalizador de vanadia. 15
5
El material de soporte catalítico de conformidad con la reivindicación 4, caracterizado porque el material de soporte catalítico comprende SÍO2 que tiene un valor de monocapa fraccional de menos de 0.5 antes de que se calcine el material de soporte catalítico. 20
6
El material de soporte catalítico de conformidad con la reivindicación 4, caracterizado porque el material de soporte catalítico tiene un área de superficie BET de al menos 50 m 2 /g antes de la calcinación. IMPI INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL
7
El material de soporte catalítico de conformidad con la reivindicación 4, caracterizado porque la forma de SÍO2 de bajo peso molecular comprende más de 50% de átomos de silicio en los entornos de coordinación de Q3, Q2, Q1 y Q0. 5
8
El material de soporte catalítico de conformidad con la reivindicación 4, caracterizado porque comprende:de 0.2% a 5% en peso de SÍO2 en una forma de bajo peso molecular;de 0.2% a 5% en peso de M0O3;y en donde el de 86% a 94% en peso de dióxido de anatasa titanio comprende 10 partículas de anatasa titania.
9
El material de soporte catalítico de conformidad con la reivindicación 4, caracterizado porque la proporción molar de fósforo a molibdeno está en un intervalo de 0.2:1 a 4:1.
10
El material de soporte catalítico de conformidad con 15 la reivindicación 4, caracterizado porque el material de soporte catalítico tiene cantidades traza de tungsteno; en donde las trazas de tungsteno son menores de 1% en peso, menores de 0.5% en peso o menores de 0.1% en peso del total del material de soporte catalítico. 20 11. Un método para reducir el nivel de NOx, caracterizado porque comprende:poner en contacto un gas o líquido que contiene óxido de nitrógeno con un catalizador durante un tiempo suficiente para reducir el nivel de NOx en el gas o líquido que contiene óxido de nitrógeno con un catalizador que comprende: el material de soporte catalítico de conformidad con cualquiera de las reivindicaciones 4 a 10, y que comprende 5 además de 0.5 a 3% en peso de V2O5.

Independent claims10

418 paragraphs in 92 sections, as filed

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

CATALYTIC SUPPORT MATERIALS, CATALYSTS, METHODS FOR MAKING THEM AND USES THEREOF

field of invention

This invention includes embodiments relating to catalyst support materials and catalyst compositions and method of making and using such catalyst support materials and catalysts. Particularly, the invention includes embodiments relating to compositions and methods for making catalyst support materials and catalysts for reducing the nitrogen oxide content of a nitrogen oxide-containing gas or liquid in mobile and stationary applications.

Background of the Invention

Some processes for the removal of N0x formed in flue gases are known in the art, such as the selective catalytic reduction (SCR) process. In this process, nitrogen oxides are reduced by ammonia (or other reducing agents such as unburned hydrocarbons present in the waste gas effluent) in the presence of oxygen and a catalyst to form nitrogen and water. The SCR process is used in the United States, Japan, and Europe to reduce emissions from large utility boilers and other commercial applications. Quickly, SCR processes are

Ref. 254571

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY are being used to reduce emissions in mobile applications such as large diesel engines such as those found in ships, diesel locomotives, automobiles, and the like.

Some metal oxide SCR catalysts such as molybdenum, tungsten, vanadium and iron to remove ΝΟχ are known. However, there are one or more limitations as explained below. Tungsten-containing catalyst may be limited by price and availability. Molybdenum-containing catalyst systems are limited by the relatively higher volatility compared to tungsten counterparts and the relatively higher degree of oxidation of SO2 compared to systems containing tungsten. SO2 oxidation is a problem in DeNO applicationsx stationary due to the formation of ammonium sulfate that causes clogging and excessive pressure drop in the process equipment.

Accordingly, catalytic support materials and catalysts suitable for reducing the nitrogen oxide content of a nitrogen oxide-containing gas or liquid at various conditions are still needed. There is also a need for a method of making such catalytic support materials and catalysts and a method of reducing the nitrogen oxide content of a nitrogen oxide-containing gas or liquid in mobile and stationary applications.

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Brief Description of the Invention

Embodiments of the present invention meet these and other needs by providing NO reduction catalystsX, methods to make these NO reducing catalystsX and method for removing nitrogen oxide content from a liquid or gas containing nitrogen oxide with such N0 reducing catalystsx.

Accordingly, one aspect of the invention provides a method of making a catalyst support material. The method includes: combining a titania anatase slurry with i) one or more forms of low molecular weight silica and ii) a source of Mo to form a mixture of THIO2-M0O3-SIO2. Low molecular weight admixture in silica includes forms of silica having a volume weight average size of less than 4 nm and an average molecular weight of less than 44,000, either individually or in a combination of two or more of these.

A second aspect of the invention provides a method of making a catalyst support material. The method includes: (a) providing a titania anatase slurry; and (b) combining the titania anatase slurry with i) one or more forms of low molecular weight silica and ii) a Mo source to form a THIO2-M0O3-SIO2 mixture. Low molecular weight forms of silica include forms of silica having an average size weighted volume of

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY less than 4 nm and average molecular weight less than 44,000, either individually or in a combination of two or more of these

A third aspect of the invention provides a catalyst support material. The catalyst support material includes from about 86% to about 94% by weight of anatase titanium dioxide; from about 0.1% to about 10% by weight of M0O3; and from about 0.1% to about 10% by weight of S1O2 in low molecular weight forms. Low molecular weight forms of SIO2 include forms of silica with a volume weighted average size of less than 4 nm and average molecular weight of less than 44,000, either individually or in a combination of two or more of these.

A fourth aspect of the invention provides a method of making a catalyst support material. The method includes: combining a titania anatase slurry i) volatility inhibitor comprising a low molecular weight form of silica and ii) primary promoter comprising molybdenum oxide to form a mixture of TiO2Mb-Si02. Low molecular weight forms of silica include silica forms with a volume weighted average size of less than 4 nm and average molecular weight of less than 44,000, either individually or in a combination of two or more of these.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

A fifth aspect of the invention provides a method of making a catalyst support material. The method includes: a) providing a titania anatase slurry; and b) combining the titania anatase slurry with i) volatility inhibitor comprising a low molecular weight form of silica and ii) primary promoter comprising molybdenum oxide to form a TiO2-Mb-SiO2 mixture. Low molecular weight forms of silica include forms of silica with a volume weighted average size of less than 4 nm and average molecular weight of less than 44,000, either individually or in a combination of two or more of these.

A sixth aspect of the invention provides catalyst support material. The catalyst support material includes anatase titanium dioxide; a primary promoter comprising molybdenum oxide; and a volatility inhibitor comprising low molecular weight forms of silica. Low molecular weight forms of silica include forms of silica with a volume weighted average size of less than 4 nm and average molecular weight of less than 44,000, either individually or in a combination of two or more of these.

A seventh aspect of the invention provides a method of reducing the nitrogen oxide content of a liquid or gas containing nitrogen oxide. The method

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY includes contacting the gas or liquid containing nitrogen oxide with a catalyst for a time sufficient to reduce the level of N0 compoundsx in gas or liquid. The catalyst includes: from about 86% to about 94% by weight of anatase titanium dioxide; from about 0.1% to about 10% by weight of M0O3; from about 0.5% to about 3% by weight of V2O5; and from about 0.1% to about 10% by weight of S1O2 in low molecular weight forms. Low molecular weight forms of silica include forms of silica with a volume weighted average size of less than 4 nm and average molecular weight of less than 44,000, either individually or in a combination of two or more of these.

An eighth aspect of the invention provides another method of reducing the nitrogen oxide content of a liquid or gas containing nitrogen oxide. The method includes contacting the gas or liquid containing nitrogen oxide with a catalyst for a time sufficient to reduce the level of NOX in the gas or liquid containing nitrogen oxide where the catalyst is made by: the combination of a slurry of anatase titania i) one or more forms of low molecular weight silica and ii) a source of Mo, to form a mixture of TIO2-M0O3-SIO2. Low molecular weight forms of silica include forms of silica with an average size weighted volume of less than 4 nm and weight

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY molecular average of less than 44,000, either individually or in a combination of two or more of these.

A ninth aspect of the invention provides a catalyst support material. The catalytic support material comprises a general formula of THIO2-M0O3-SIO2, wherein the titanium dioxide is substantially in an anatase form and the silicon oxide has a volume average size weight less than 4 nm and an average molecular weight less than 44,000.

The figures, which are incorporated in and constitute a part of this description, are included to illustrate and provide a further understanding of the methods and systems of the invention. Together with the description, the figures serve to explain the principles of the invention. It is contemplated that features of one modality may be beneficially incorporated into other modalities without further recitation.

Brief Description of the Figures

FIG. 1 is a flow chart of a conventional method for making a catalyst support material;

FIG. 2 is a flow chart of a method of making a catalyst support material in accordance with one embodiment of the invention;

FIG. 3 is a flow chart of a method of making catalysts in accordance with one embodiment of the invention; Y

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

FIG. 4 is a graphical comparative representation of exhaust catalyst performance of NH3 slip versus NO conversionX according to one embodiment of the invention.

For ease of understanding, identical reference numerals have been used wherever possible to designate identical elements that are common throughout the figures.

Detailed description of the invention

In the following description, terms such as top, bottom, out, in, and the like are understood to be words of convenience, and are not construed as limiting terms. Reference will now be made in detail to illustrative embodiments of the invention, which are illustrated in the accompanying figures and examples. Referring generally to the figures, it will be understood that the illustrations are for the purpose of describing a particular embodiment of the invention and are not intended to limit the invention as such.

Whenever it is said that a particular embodiment of the invention comprises or consists of at least one element of a group and combinations thereof, it is understood that the embodiment may comprise or consist of any of the elements of the group, either individually or in combination with any of the other elements in that group. Also,

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY when a variable appears more than once in any constituent or in the formula, its definition in each occurrence is independent of its definition in each occurrence. Also, combinations of substituents and/or variables are permissible only if such combinations result in stable compounds.

Definitions

All terms used herein are intended to have their ordinary meaning unless otherwise provided.

The terms catalyst support, support particles, or support material are intended to have the standard meaning in the art.

The terms active metal catalyst or active component refer to the catalytic component deposited on the surface of the support material putative to catalyze the reduction of N0 compounds.x.

The terms catalyst and catalyst composition are intended to have their standard meaning in the art and refer to the combination of the supported catalyst components and the titania-based catalyst support particles.

Unless otherwise specified, all references to percent (%) herein refer to percent by weight. The terms percentage and charge are

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY refer to the loading of a particular component in the total catalytic composition. For example, the vanadium oxide loading on a catalyst is the ratio of the vanadium oxide by weight to the total weight of the catalyst, including the titania-based support material, the vanadium oxide, and any other supported metal oxides. Similarly, mole percent loading refers to the ratio of the number of moles of a particular component loaded to the number of moles in the total catalyst composition.

The term phosphate is used to refer to any compound that contains phosphorus bound to oxygen.

An embodiment of the invention includes a method of making a catalyst support material. The method includes combining a titania anatase slurry with i) one or more forms of low molecular weight silica and ii) a source of Mo to form a mixture of THIO2-M0O3-SIO2. Low molecular weight forms of silica include forms of silica with a volume weighted average size of less than 4 nm and average molecular weight of less than 44,000, either individually or in a combination of two or more of these.

One embodiment of the invention includes a catalyst support material comprising from about 86% to about 94% by weight of titanium dioxide; from about 0.1% to about 10% M0O3; and from about 0.1% to about 10% by weight of SÍO2.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

S1O2 includes one or more forms of low molecular weight silica with a volume weight average size of less than 4 nm and weight average molecular weight of less than 44,000, either individually or in a combination of two or more of these.

For illustration and not limitation, an embodiment of the invention for methods of making a catalytic support material is compared with conventional methods. As described in FIG. 1, a conventional method for making a catalyst support material includes Step 110 to provide a titania anatase slurry. Step 120 includes adjusting the pH. Step 130 includes providing all or substantially all of the silica as commercially available preferred silica particles, such as colloidal, fumed, etc. Step 140 includes adjusting the pH. Step 150 includes providing tungsten.

In contrast to FIG. 1, FIG. 2 describes an embodiment of the invention for a method of making catalytic support materials. FIG. 2 is a flow chart of one embodiment of a method for making a catalytic support material by controlling the shape and distribution of silica with molybdenum. The method is not limited by the order or frequency of the steps, unless expressly indicated. The method includes Step 210 which provides a titania slurry. Non-limiting examples of titania slurries include rutile, anatase, brookite, monoclinics,

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY Tetragonal orthorhombic phases as powders dispersed in water, and high-pressure forms, such as la-PbO2-type, badeleyite-type, cotunite-type, orthorhombic OI, and cubic phases, either individually or in a combination of two or more of these. In one embodiment, Step 210 providing a titania slurry comprises providing an anatase titania slurry. Non-limiting examples of anatase titania slurry include titanium hydroxide, titanium oxyhydroxide, other titanic acid, metatitanic acid, titanyl sulfate, sulfated titanium dioxide, sulfated titania hydrolyzate, organo-titanates or titanium dioxide particles, either individually or in a combination of two or more of these.

Although some embodiments and examples have been described with anatase titania slurry in some of the descriptions, it should be understood that the embodiments of the invention are either restricted to anatase titania slurry and include other forms of titania slurry, either individually or in a combination of two or more of these.

Step 220 optionally comprises adjusting the pH of the titania slurry to a range of about 3 to about 6 as needed. One embodiment includes adjusting the pH to a range of from about 4 to about 5. Another embodiment includes adjusting the pH to about 4. The pH can be adjusted with such as, but

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY without limitation, diluted ammonium hydroxide, alkylamines such as mono, di, or tripropylamines, alkanolamines such as mono, di, and triethanolamine, either individually or in a combination of two or more of these.

Step 230 comprises providing at least some low molecular weight form of silica to the titania slurry. One embodiment includes one or more forms of low molecular weight silica with a volume weight average size of less than 4 nm and average molecular weight of less than 44,000, either individually or in a combination of two or more of these. One embodiment of the invention includes Step 240 of optionally adjusting the pH of the titania slurry to a pH of about 3 to about 6. Another embodiment includes adjusting the pH to a range of from about 4 to about 5. Another embodiment includes adjusting the pH at about 4. The pH can be adjusted such as with, but not limited to, dilute aluminum hydroxide, alkylamines such as mono, di, and tripropylamine, alkanolamines such as mono, di, and triethanolamine, either individually or in a combination of two or more of these.

Silica

In one embodiment, low molecular weight forms of silica include but are not limited to silicic acid (Si(OH)4). Examples of silicic acid include Si(OH)4 generated by ion exchange in any of the ways

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cationic silica compounds listed herein using an acidic ion exchange resin (for example, ion exchange of alkaline silicate solutions or quaternary ammonium silicate solutions). Other non-limiting examples of silicic acid that may be provided either individually or in a combination of two or more of these include as described in Iler (or p cit., Chapter 3), a detailed characterization of silicic acid using the characterization of nuclear magnetic resonance with Si, as described in G. Engelhardt and D. Michel (op cit. p. 100).

Although some embodiments have been described with silicic acid as an example of low molecular weight silica in some of the descriptions, it is to be understood that embodiments of the invention are not restricted to silicic acid and include other forms of low molecular weight silica. molecular weight, either individually or in a combination of two or more of these.

In another embodiment, non-limiting examples of low molecular weight forms of silica with a volume weight average size of less than 4 nm or average molecular weight of less than 44,000 include the soluble precursor of tetra(alkyl)ammonium silicate, es say tetramethylammonium silicate) and tetraethylorthosilicate (TEOS), either individually or in a combination of two or more of these.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Unexpected advantages of using low molecular weight forms of silica with a volume weight average size of less than 4 nm or average molecular weight of less than 44,000 to make catalytic support materials may include one or more of the following. Catalytic support materials can unexpectedly improve stability and activity, compared to conventional catalytic support materials with colloidal silica as explained above in the examples. Molybdenum volatility can be reduced by at least 50% or greater than 80% compared to baseline or conventional molybdenum volatilities while maintaining equivalent performance with conventional catalyst support materials. Catalytic support materials can exhibit retention of the titania anatase phase and surface area after various thermal and/or hydrothermal treatments, even in the presence of vanadia.

Other examples of low molecular weight silica precursors that can be used include, but are not limited to, aqueous solutions of silicon halides, silicon alkoxides, other organic silicon compounds, fluoro-silicic acid salts, quaternary ammonium silicate solutions. , and solutions of potassium silicate, and silicic acid (Si(OH)4), either individually or in a combination of two or more of these.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Non-limiting examples of aqueous solutions of silicon halides include SiX4 anhydrous, where X= F, Cl, Br, or I, either individually or in a combination of two or more of these. Non-limiting examples of silicon alkoxides include Si(OR)4, where R=methyl, ethyl, isopropyl, propyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyls, hexyls, octyls, nonyls, decyls, undecyls, and dodecyls, either individually or in a combination of two or more of these. In one embodiment, examples of other organic silicon compounds include such as, but not limited to, hexamethyldisilazane. In one embodiment, examples of fluoro-silicic acid salts include ammonium hexaf fluorosilicate [(NH4) 2SiFg] . In one embodiment, examples of quaternary ammonium silicate solutions include such as, but not limited to, (NR4)n, (SÍO2) , where R=H, or alkyl as listed above, and n=0.1-2, either individually or in a combination of two or more of these. Non-limiting examples of aqueous potassium sodium silicate solutions include Na2SiO3, K2SIO3, and MS1O3 (wherein M is Na or K in varying amounts in proportion to Si), either individually or in a combination of two or more of these. .

An advantage of using low molecular weight forms of silica with a volume weighted average size of less than 4 nm or average molecular weight of less than

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

44,000 may include opportunity and availability for interaction with Titania. An exception, as described below, involves subsequent modification of the silica particles using pH and temperature conditions where the silica particles have dissolved, and re-precipitation on the titania surface.

In a particular embodiment, suitable silica precursors include highly alkaline solutions, referred to as water-soluble silicates as described in Iler (qp cit., Chapter 10 2). These solutions are typically clear since silica particles, if present, are generally too small to scatter visible light. However, depending on the concentration and alkalinity of the silica, small silica particles may form in these solutions. Iler (op cit., p.133) estimate that for a SiO2:Na2O molar ratio of 3.1, the average number of silicon atoms per particle in dilute solutions is about 900, which is less than the 1500 atoms of silicon per particle in the 4 nm particle described above. Such a silicate precursor, although it may contain some nanoparticles above about 4 nm, is suitable for the present invention because most of the bulk of the silicon is in the form of smaller, low molecular weight species.

When using alkali silicates, the alkali ions

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Residuals such as Na can poison vanadia-based SCR catalysts.

In another embodiment, Step 230 providing low molecular weight silica comprises providing an alkaline solution of tetramethylammonium silicate.

Embodiments of the invention include repeating Step 230 providing at least some form of low molecular weight silica at desired intervals and as many times as desired, such as, but not limited to, before, during and after Step 250, providing a Mo source, either individually or a combination of two or more of these.

It should be appreciated that embodiments of the invention include providing a plurality of forms of low molecular weight silica that differ from each other. The plurality of forms of low molecular weight silica can have various characteristics.

Furthermore, although the embodiments of the invention have been described as providing at least some forms of low molecular weight silica, it should be understood that the embodiments of the invention are not restricted to only providing the low molecular weight forms of silica. low molecular weight and further include providing other forms of silica.

In one embodiment, in addition to Step 230 of providing some form of low molecular weight silica, the method further includes providing other forms of silica that differ from

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY forms of low molecular weight silica. Thus, in one embodiment, the total silica present in the catalyst support material is defined as the sum of the low molecular weight of the silica and other forms of silica that differ from the low molecular weight form of silica.

In one embodiment, the low molecular weight forms of silica comprise greater than 50% of the total silica present in the catalyst support material. In a particular embodiment, the low molecular weight form of silica comprising greater than 50% of the total silica present in the catalyst support material includes one or more low molecular weight forms with a volume average size weight of less than 4 nm or average molecular weight of less than 44,000, either individually or in a combination of two or more of these.

Step 250 comprises providing at least some source of Mo to the anatase titania slurry. As shown in FIG. 2, the method is not limited by the sequential order or frequency of Step 250. Embodiments of the invention include Step 250 of providing an Mo source before, during, or after Step 230 of providing a low weight form of silica. molecular.

One embodiment includes Step 250 providing at least some Mo source and Step 230 providing the low molecular weight silica form sequentially. In a sequential mode, the method includes Step 250 of

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provide at least some Mo source before providing Step 230 a low molecular weight form of silica. When Step 250 provides some source of Mo prior to Step 230, one embodiment includes adjusting the pH to a range from about 1 to about 6. Another embodiment includes adjusting the pH to a range from about 4 to about 5. The pH can be adjusted such as with, but not limited to, dilute aluminum hydroxide, alkylamines such as mono, di, or tripropylamine, alkanolamines such as mono, di, and triethanolamine, either individually or in a combination of two or more of these. In another sequential embodiment, the method includes Step 250 of providing at least some Mo source after Step 230 of providing the low molecular weight form of silica and after optional Step 240 of adjusting the pH.

An embodiment of the method also includes providing Step 250 of at least some source of Mo and Step 230 of a low molecular weight form of silica simultaneously.

Embodiments of the invention also include repeating Step 250 of providing at least some Mo source at desired intervals and as many times as desired, such as, but not limited to, before, during, and after Step 230 of providing silica, either individually or a combination of two or more of these.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

It should be appreciated that methods of making a catalytic support material also include the reaction product of one or more Mo sources with each other, the reaction product of one or more forms of silica with each other, and also the product of the reaction of one or more sources of Mo with the one or more sources of silica, and other reaction products between the elements present.

The method is also not limited by how the Mo is provided in the source of Step 250. One or more Mo sources may be provided before, during, or after Step 230 of providing the silica form by a method such as, but not limited to a, ion exchange via Step 252, to slurry directly via Step 254, etc. either individually or a combination of two or more of these. In one embodiment, at least some of the Mo sources are provided in Step 250 by ion exchange resin via Step 252. In another embodiment, at least some of the Mo sources are provided in Step 250 to the slurry. of titania directly through Step 254.

mo source

In one embodiment, the Mo source includes molybdenum oxide and the soluble molybdenum oxide precursor, either individually or in a combination of two or more of these. In a particular embodiment, molybdenum oxide is provided to the titania support material as a precursor.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY soluble such as ammonium dimolybdate, ammonium heptamolybdate, ammonium parammolybdate tetrahydrate, ammonium fosafomolybdate in an amount to obtain a molar ratio of molybdenum to vanadium in a range from about 0.5:1 to about 20:1 to form a catalyst comprising vanadium. In yet another embodiment, molybdenum oxide is added to the titania support material in an amount to obtain a molybdenum to vanadium ratio in a range of from about 1:1 to about 10:1 to form a catalyst comprising vanadium.

In one embodiment, the method further includes providing a plurality of different Mo sources, either individually or in a combination of two or more of these. In a particular embodiment, a plurality of different Mo sources are provided to the anatase titania slurry after Step 230 of providing silica. In one embodiment, the plurality of different Mo sources can be provided to the anatase titania slurry by ion exchange resin via Step 252.

It should be appreciated that one embodiment of the method includes combining a titania slurry with i) silica and ii) one or more Mo sources to form a TIO2-M0O3SiO mixture.2.

In one embodiment, the method further comprises Step 260 of optionally providing an amount of

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY phosphate to anatase titania grout. The addition of phosphate to a catalyst support material can have unexpected advantages, such as, but not limited to, reduced oxidation of SO2 and improved ability to reduce NOx compared without the addition of phosphate. In the presence of SIO2, low levels of phosphorus surprisingly increase the activity of the catalyst.

As shown in FIG. 2, the method is not limited by the sequential order or frequency of Step 260 unless expressly stated otherwise. Embodiments of the invention include Step 26 or 0 of providing an amount of phosphate before, during, or after Step 230 of providing a low molecular weight form of silica.

In one embodiment, the method includes Step 260 of providing at least some phosphate before Step 230 of providing at least some silica. Another embodiment includes Step 260 of providing an amount of phosphate during Step 230 of providing at least some silica. In another embodiment, the method includes Step 260 of providing at least some phosphate after Step 230 of providing at least some silica.

In one embodiment, Step 260 comprises providing an amount of phosphate before, during, or after Step 250 of providing Mo. In one embodiment

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In particular, the method includes Step 260 of providing an amount of phosphate prior to Step 250 of providing at least some source of Mo. Another embodiment includes Step 260 of providing an amount of phosphate during Step 250 of providing at least some Mo source. In a particular embodiment, at least some of the Mo source in Step 250 and an amount of phosphate in Step 260 are provided simultaneously. Another embodiment includes Step 260 of providing at least some phosphate after Step 250 of providing at least some Mo source.

It should be appreciated that the method includes repeating Step 260 of providing an amount of phosphate at desired frequency intervals and as many times as desired, such as, but not limited to, before, during, and after Step 230 of providing an amount of phosphate. of low molecular weight silica, and before, during, and after Step 2 50 providing at least some source of Mo, either individually or a combination of two or more of these.

The method is also not limited by how the amount of phosphate Step 260 is provided. The amount of phosphate can be provided by a method such as, but not limited to, ion exchange in the slurry directly, etc., either individually or a combination of two or more of these. In one embodiment, the amount of phosphate from step 260 is

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY provided by ion exchange resin. In a particular embodiment, the amount of phosphate is provided to the ion exchange resin slurry before Step 250 of providing at least some source of Mo. In another embodiment, the amount of phosphate is added to the titania resin slurry. ion exchange simultaneously with Step 250 to provide at least some of the Mo source.

Suitable phosphate-containing compounds include, but are not limited to, organic phosphates, organic phosphonates, phosphine oxides, H4P2O7, H3PO4, polyphosphoric acid, (NH4)H2PO4, (ΝΗ4)2ΗΡΟ4, and (NH4)3PO4 either individually or in a combination of two or more of these. In one embodiment, a plurality of different phosphate sources are provided. Furthermore, the phosphate may be present within the support material, or the phosphate may be present on the surface of the support material.

In one embodiment, the phosphate is added at levels to obtain a phosphorus to molybdenum ratio of about 0.2:1 or greater. In some embodiments, the phosphate is added in an amount to obtain a phosphorous to molybdenum ratio in the range of about 0.2:1 to about 4:1.

Substantially Free of Tungsten

Applicant has unexpectedly discovered that the low molecular weight form of silica can reduce the

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY volatility of Mo compared with conventional methods of colloidal silica suspension or aqueous slurry of smoked solids. Furthermore, the applicant has also discovered that the level of tungsten can be reduced or replaced with Mo by using Mo in combination with the low molecular weight form of silica to control the volatility of Mo. It should be appreciated that embodiments of the invention optionally include reducing or replacing tungsten to desired levels such as none to 100% of typical tungsten levels.

In one embodiment, the catalyst support material is substantially free from the presence of tungsten. In another embodiment, the catalyst is substantially free of tungsten. In one embodiment, the catalyst support material is substantially free from the presence of tungsten in an amount of less than about 1% by weight of the total catalyst support material.

Substantially Free expressly allows for the presence of trace amounts of the respective substance referred to as the substance either individually or in a combination of two or more, such as tungsten or iron, and is not limited to a precise specified value and may include values that differ from the specified value. In one embodiment, substantially free expressly permits the presence of trace amounts of tungsten at less than about 1%, at less than

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY approximately 0.5%, and less than approximately 0.1%, either individually or in a combination. Substantially free expressly allows for the presence of respective trace amounts of a referred substance such as tungsten but does not require the presence of the referred substance, such as tungsten.

It should be understood that the designs in the form of low weight silica to reduce the volatility of Mo in the examples above can be used to reduce the volatility of other metals and substances, such as, but not limited to, tungsten oxide, vanadium oxide. , bismuth oxide, lead oxide, and the like, either individually or in a combination of two or more of these.

Like language, as used herein throughout the description and claims, may be applied to modify any quantitative or qualitative representation that could permissibly vary without resulting in a change in the basic function to which it refers. Accordingly, a value modified by a term such as less than about or substantially free of will not be limited to a precise specified value and may include values that differ from the specified value. In at least some of the instances, similar language may correspond to the precision of an instrument for measuring value. Also, remove or reduce

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

ΝΟχ can be used in combination with a term and includes a variable amount of NO removalX and will not be limited to a precise specified value and may include values that differ from a specified value.

Phosphate and Tungsten

In other embodiments, the catalyst support material has more than a trace presence of tungsten, ie, the catalyst support material is not substantially free of the presence of tungsten. The level of tungsten can be reduced by at least 80% compared to catalyst and catalyst support materials. Tungsten levels can be reduced by at least 35% compared to conventional catalyst and catalyst support materials. Tungsten levels can be reduced by at least 10% compared to conventional catalyst and catalyst support materials.

In one embodiment, the catalyst support material has a phosphorus to tungsten ratio of about 0.2:1 or greater, the resulting catalyst exhibiting reduced SO2 oxidation without significantly lower N0 conversion.x. In some embodiments, the phosphate is added in an amount to obtain a phosphorous to tungsten ratio in a range of from about 0.2:1 to about 4:1. Similarly, when both tungsten and molybdenum are present, the

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY Phosphate is added at levels to obtain a ratio of phosphorus to tungsten plus molybdenum of approximately 0.2:1 or greater, and in some embodiments, at levels to obtain a ratio of phosphorus to tungsten plus molybdenum in the range of about 0.2:1 to about 4:1.

In one embodiment, the method further comprises Step 270 of washing and calculating the THIO2-M0O3-SIO2 mixture.

The invention includes another embodiment of a method of making a catalyst support material. The method includes: a) providing a titania anatase slurry; and b) combining the titania anatase slurry with i) one or more volatility inhibitors comprising a low molecular weight form of silica; and ii) primary promoter comprising molybdenum oxide to form a THIO2M0O3-SIO2 mixture. Low molecular weight forms of silica include forms of silica with a volume weighted average size of less than 4 nm and average molecular weight of less than 44,000, either individually or in a combination of two or more of these.

Applicant has unexpectedly discovered that volatility inhibitors comprising a low molecular weight form of silica can reduce Mo volatility compared to conventional methods of suspending colloidal silica or aqueous slurry of fumed solids. In addition, the applicant has also discovered that the levels of

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Tungsten can be reduced or replaced with Mo by using Mo in combination with volatility inhibitors comprising a low molecular weight form of silica to control Mo volatility.

It should be appreciated that embodiments of the invention include providing a plurality of volatility inhibitors that differ from each other. The plurality of volatility inhibitors can have various characteristics.

Although embodiments of the invention have been described with a volatility inhibitor comprising low molecular weight forms of silica, it is to be understood that embodiments of the invention are not restricted to only providing volatility inhibitors including a low molecular weight silica form and further include other forms of volatility inhibitors.

In one embodiment, in addition to providing the volatility inhibitor that comprises a low molecular weight form of silica, the method further includes providing another volatility inhibitor that does not include a low molecular weight form of silica. Thus, in one embodiment, the total amount of volatility inhibitor present in the catalyst support material is defined as the sum of the volatility inhibitors comprising

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY a form of low molecular weight silica and other forms of volatility inhibitors that do not include a form of low molecular weight silica.

In one embodiment, the volatility inhibitor comprising a low molecular weight form of silica comprises greater than 50% of the total volatility inhibitor present in the catalyst support material. In a particular embodiment, the low molecular weight silica form comprises greater than 50% of the total volatility inhibitor present in the catalyst support material includes one or more low molecular weight silica forms with a volume weighted average size of less than 4 nm or an average molecular weight of less than 44,000, either individually or in a combination of two or more of these.

Although the embodiments of the invention have been described with the primary promoter comprising molybdenum oxide, it should be understood that the embodiments of the invention are not restricted to only providing the primary promoter including molybdenum oxide and further include providing other forms of understanding that the embodiments of the invention are not restricted to only providing primary promoters.

Catalytic Support Material

Embodiments of the invention also include catalytic support materials. In one mode, the

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY catalyst support material includes: from about 86% to about 94% by weight of titania anatase dioxide; from about 0.1% to about 10% of Mo03% in weigh; and from about 0.1% to about 10% by weight of SiO2 in low molecular weight forms. The low molecular weight forms of SiO2 include one or more forms of silica with a volume weighted average size of less than 4 nm and an average molecular weight (MW) of <44,000, either individually or in a combination of two or more of these as explained above. In a particular embodiment, the catalyst support material optionally comprises from about 0.01 to about 2.5% P.

In another embodiment, the catalytic support material comprises from about 86% to about 94% by weight of titania anatase particles, from about 0.2% to about 5% by weight of M0O3, and from about 0.2% to about 5% by weight. of SiO2 in low molecular weight forms. The low molecular weight forms of SiO2 they include one or more forms of silica as explained above, either individually or in a combination of two or more of these as explained above. In a particular embodiment, the catalyst support material optionally comprises from about 0.01 to about 2.5% P.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

In one embodiment of the catalytic support material, SiO2 comprises nanoparticles with diameters of less than 4 nm. In another embodiment, SiO2 in the catalytic support material comprises an SiO2 low molecular weight with a molecular weight of less than 44.00 0. In yet another embodiment, SiO2 in the catalytic support material comprises more than 50% silicon atoms in Q coordination environments3, Q2, Q1 and Q°.

In one embodiment, the catalyst support material has a BET surface area of at least 50 m/g. In another embodiment of the supported catalyst, SÍO2 is present at a fractional monolayer value of less than 0.5 prior to calcining the catalyst support material.

In one embodiment, the catalyst support material includes titania anatase particles, a primary promoter comprising molybdenum oxide; a phosphorus to molybdenum ratio in a range of from about 0:1 to about 4:1, and a volatility inhibitor comprising low molecular weight forms of silica. Low molecular weight forms of silica include forms of silica with a volume weighted average size of less than 4 nm and average molecular weight of less than 44,000, either individually or in a combination of two or more of these. It should be appreciated that embodiments of such catalytic support materials comprising inhibitors of

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volatility inhibitors include one or more volatility inhibitors described above, either individually or in a combination of two or more of these.

Another embodiment of the catalytic support material includes a general formula of THIO2-M0O3-SIO2, wherein the titanium dioxide is substantially in an anatase form and the silicon oxide has a volume average size weight less than 4 nm and a weight average molecular weight of less than 44,000.

It should be appreciated that the catalytic support material includes the reaction product of anatase titanium oxide with each other, the reaction product of M0O3 with each other, the reaction product of P with each other, the reaction product of S1O2 with each other and also the product of the reaction of oxides of the elements with each other in general.

Methods to Make a Catalyst

With reference to FIG. 3, an embodiment of the invention for making a catalyst is described below. FIG. 3 is a flow chart of one embodiment of a method of making a catalyst and is limited by the order or frequency of steps unless expressly stated otherwise.

The method includes Step 310 of combining the THIO2-M0O3-SIO2 mixture with V2O5 to form a catalyst of

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY Vanadia. The method may optionally further comprise Step 320 calcining the vanadia catalyst, such as around 600°C.

Catalyst

Embodiments of the invention also include catalysts. In one embodiment, the catalyst includes from about 86% to about 94% by weight of anatase titanium dioxide; from about 0.1% to about 10% by weight of M0O3, from about 0.1% to about 10% by weight of S1O2, and from about 0.5% to about 3% by weight of V2Os. SÍO2 includes a low molecular weight form with a volume average size weight of less than 4 nm and average molecular weight of less than 44,000, either individually or in a combination of two or more of these. In a particular embodiment, the catalyst optionally comprises from about 0.01 to about 2.5% by weight of P.

In one embodiment, the catalyst includes from about 86% to about 94% by weight of titania anatase particles, from about 0.2% to about 5% by weight of M0O3, from about 0.1% to about 10% by weight of SÍO2, and from about 0.5% to about 3% by weight of V2O5. S1O2 includes a low molecular weight form of silica with an average size weighted volume of less than 4 nm and molecular weight

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY average less than 44,000, either individually or in a combination of two or more of these. In a particular embodiment, the catalyst optionally comprises from about 0.01% to about 2.5% by weight of P.

In another embodiment, the catalyst comprises from about 0.3% to about 1.5% by weight of V2O5. In yet another embodiment, the catalyst comprises from about 0.5% to about 0.9% by weight of V2O5.

Catalyst Usage

Embodiments of the invention also include methods of using the catalysts to reduce the nitrogen oxide content of a liquid or gas containing nitrogen oxide. One method includes contacting the nitrogen oxide gas or liquid with a catalyst for a time sufficient to reduce the level of ΝΟχ in the nitrogen oxide-containing gas or liquid. In one embodiment, the catalyst includes from about 86% to about 94% by weight anatase titanium dioxide, from about 0.1% to about 10% by weight M0O3, from about 0.5% to about 3% by weight V2O5, and from about 0.1 to about 10% by weight of S1O2 in low molecular weight forms. Low molecular weight forms of S1O2 include one or more forms of silica with a volume weighted average size of less than 4 nm and average molecular weight of less than 44,000, either individually

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY or in a combination of two or more of these. In a particular embodiment, the catalyst optionally comprises from about 0.01 to about 2.5% by weight of P.

Embodiments of the invention are to be appreciated including methods for reducing the nitrogen oxide content of a nitrogen oxide-containing liquid or gas by contacting the nitrogen oxide-containing gas or liquid with one or more embodiments of the catalysts described above. , either individually or in a combination of two or more of these.

N0 reduction additivesx described above can be added as a formed structure such as a monolith or an extrudate in a fixed bed reactor or any conventional reactor-generator system, for fluidized bed systems, for systems that involve continuously transporting or circulating catalysts/additives between the zone reaction and regeneration zone, and the like. Typical circulating bed systems are moving bed and fluidized bed reactor-generator systems. NOx reduction catalysts can be used in an amount of at least 1%; at least 2%; at least 5%, in an amount of at least 10% of the regenerator's inventory; or in an amount of at least about 20% of the regenerator inventory to reduce nitrogen oxide content.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Embodiments of the method also include contacting the nitrogen oxide-containing gas in the presence of one or more reducing agents such as ammonia, hydrocarbons, hydrogen, carbon monoxide, and the like, either individually or in a combination of two. or more of these, with one or more embodiments of the catalysts described in the embodiments of the invention at various environmental conditions such as ambient conditions of complete incineration and under oxygen. Examples of the low oxygen ambient condition include, but are not limited to, fully incinerated units, partial incinerated units, mixed mode, complete combustion units with poor air circulation, etc.

Another embodiment includes contacting a nitrogen oxide-containing gas or liquid with a catalyst for a time sufficient to reduce the N0 level.x in the gas or liquid containing nitrogen oxide, where the catalyst is made by:

(a) provision of a titania anatase slurry; and (b) combining the titania anatase slurry with i) one or more low molecular weight forms of silica and ii) a Mo source, to form a THIO2-M0O3-SIO2 mixture. Low molecular weight forms of silica include forms of silica with a volume weighted average size of less than 4 nm and average molecular weight of less than 44,000, either individually or in a combination of two or more of these.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

It should be appreciated that the embodiment of the invention includes methods for reducing the nitrogen oxide content of a nitrogen oxide-containing liquid or gas by contacting the nitrogen oxide-containing gas or liquid with one or more catalysts made by the embodiments of the methods described above, either individually or in a combination of two or more of these.

N0 reducing additivesx described above can be added as a formed structure, such as a monolith or an extrudate in a fixed bed reactor or any conventional reactor-generator system, for fluidized bed systems, for systems that involve continuously transporting or circulating catalysts/additives between the reaction zone and the regeneration zone, and the like. Typical circulating bed systems are moving bed and fluidized bed reactor-generator systems. NO reduction catalystsX they can be used in an amount of at least 1%; at least 2%; at least 5%; in an amount of at least 10% of the regenerator's 20 inventory; or in an amount of at least about 20% of the regenerator inventory to reduce nitrogen oxide content.

Embodiments of the methods also include contacting the nitrogen oxide-containing gas in the presence of reducing agent, such as ammonia,

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY hydrocarbons, hydrogen, carbon monoxide and the like with one or more modalities of the catalysts described in the modalities of the invention at various environmental conditions such as environmental conditions of complete combustion and low oxygen. Examples of low oxygen ambient conditions include, but are not limited to, full combustion units, partial combustion units, mixed mode, complete combustion units with poor air circulation, etc.

examples

The following examples illustrate the features of embodiments of the invention and are not intended to limit the invention thereto. Although portions of Examples 1-12e are written in the present tense, the examples were conducted and illustrate the non-limiting difference(s) between embodiments of this invention compared to conventional techniques.

The volatility of molybdenum was determined in the following way. 0.2 g of the catalyst (0.7-1.2 mm particle size TIO2-SiOa) is supported by quartz wool in a 0.95 cm (3/8) OD quartz tube 22.86 cm (9) long adapted in both ends with open ball joints. Added 0.2 g of 255 m2/g gamma alumina (Alpha-Aesar 0.7-1.4 mm particle size) from the opposite end of the tube to prevent

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY cross contamination. It was also suspended in a quartz glass wool connector. The tube was attached via the ball joint to a connecting flow reactor. The temperature was raised to 700°C and a carrier gas of the composition 10% steam, 10% O2, 500 ppm NO, 500 ppm NH3, balance N2 was passed over the catalyst into the bed of alumina. After 2 hours, the catalyst and alumina beds were cooled. The catalyst was removed from one end of the tube and the alumina was removed from the other end to avoid cross-contamination. Each powder sample was then dissolved with HF and analyzed separately with Inductively Coupled Plasma Optical Emission Spectroscopy (ICPOES) for Mo content. The molybdenum sublimated from the catalyst is calculated by dividing the amount of Mo by the alumina by the sum of the molybdenum present in the titania and alumina supports. The mass balance for the experiment was calculated by dividing the sum of Mo detected on the titania and alumina supports after hydrothermal treatment by the amount of Mo measured on the titania support before hydrothermal treatment.

The DeNOx conversion was determined using a catalyst in the powder form without further molding. A 0.9525 cm (3/8) quartz reactor carries 0.2 g of catalyst supported on glass wool. The feed composition is 1000 ppm NO, 5% O2, 5% H2O,

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY variable quantities of NH3 0 to 1200 ppm, and N balance2. NO conversion was measured at 250, 350, and 450°C at atmospheric pressure and recorded as a function of increasing ammonia partial pressure in the reactor feed. The reactor effluent was analyzed with an infrared detector to determine the conversion of NO and the escape of NH3.

The oxidation of SO2 was determined with a catalyst in powder form without further molding. A 0.9525 cm (3/8) quartz reactor carries 0.2 g of catalyst supported on glass wool. The fed composition is 500 ppm S02, 2 0% O2, and N balance2. The space velocity is 29.5 1/g.cat-hr calculated at ambient conditions. Conversion data was recorded at 550°C.

Example 1

An embodiment of the currently described and/or claimed inventive concept(s) was prepared as follows. A 370.7g sample of titanium anatase hydrolyzate slurry (26.3% solids), produced by the sulfate process (Trade name - G1 from Millennium Inorganic Chemicals), was heated to 60°C via a temperature-controlled hot plate, and the temperature was maintained at 60°C throughout the preparation. The pH was adjusted to 4 with dilute aluminum hydroxide. A diluted solution (1%

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY by weight of SÍO2) sodium silicate was prepared by adding 1.7 g of Inobond Na-4011 sodium silicate (29.4% by weight as SÍO2) to 48.4 g of deionized water. A 20 g portion (as received base) of Dowex™ 650C form H strong acid ion exchange resin was weighed and placed in a buret column. (Dowex™ 650C form H ion exchange resin was used in the following examples and is available from The Dow Chemical Company, US). The diluted silicate solution was added through the column with the ion exchange resin to the slurry at a flow rate of 5 ml/min. After the addition was complete, the ion exchange resin in the column was rinsed with 10 ml of deionized water added at a flow rate of 5 ml/min in the titania slurry. The pH was adjusted back to 4 with ammonium hydroxide and allowed to react for 20 min. A second solution was prepared by dissolving 3.68 g ammonium heptamolybdate and 0.55 g 85% phosphoric acid in 20 mL water. This solution is added to the slurry via the ion exchange column at a flow rate of 5 ml/min, and after the addition is complete, the pH of the mixture is adjusted to 4 with dilute aluminum hydroxide and allowed to react for 10 min. The mixture was filtered, rinsed with 1.0 liters of deionized water, dried at 105°C, and then calcined at 530°C for 6 hrs. The target loading for the catalyst support is 0.5 wt% SIO2, 0.15 wt% P, and 2 wt% Mo.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Before the volatility studies, 1.3 wt% vanadia was added to the sample via the following method. A 20 g sample of the prepared support was added to 50 ml of water. To this, vanadium pentoxide [V2O5] (0.266 g) and monoethanolamine [HOCH2CH2NH2] (0.222 g) were added and the temperature of the mixture was raised to 60°C. The pH was adjusted to 8 with ammonium hydroxide and the mixture was allowed to stir for 15 min. The solids were filtered off, dried at 100°C for 6 hours, and calcined at 600°C for 6 hours with air.

Before the DeNO testx and SO2 oxidation measurement, 0.9% vanadia was added to the sample via the following method. A 20 g sample of the prepared support was added to 50 ml of water. To this, vanadium pentoxide (0.184g) and monoethanolamine (0.154g) were added and the temperature of the mixture was raised to 60°C. The pH was adjusted to 8 with ammonium hydroxide and the mixture was allowed to stir for 15 min. The solids were filtered off, dried at 100°C for 6 hours, and calcined at 600°C for 6 hours in air.

Example 2

In a second embodiment of the method of the method, the order of addition of the silica and molybdenum and phosphorus solutions was reversed such that the molybdenum and phosphorous solution were added via an ion exchange column before the silica solution. Vanadia is added as described in Example 1.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Comparative Example 1

A 440.0 g sample of the anatase titanium hydrolyzate slurry (23.2% solids) was heated to 60°C via a temperature controlled hot plate and the temperature was maintained throughout the preparation. A molybdenum solution was prepared by dissolving 4.64 g of ammonium heptamolybdate in 100 mL of water and adding this solution directly to the slurry. The pH was adjusted to 5 with ammonium hydroxide and allowed to mix for 10 min. The mixture was filtered, dried at 105°C, and then calcined at 530°C for 6 hrs. The target loading is 2 wt% Mo. Vanadia is added as described in Example 1.

Comparative Example 2

A support was prepared as described in Comparative Example 1 but with the exception that the filtrate was washed with 1 liter of deionized water to remove concurrent soluble ions such as ammonia before drying and calcination. The target loading is 2 wt% Mo. Vanadia is added as described in Example 1.

Example 3a

A 183.3 g sample of the anatase titanium hydrolyzate slurry (26.6% solids) was heated to 60°C via a temperature controlled hot plate and the temperature was maintained throughout the preparation. A molybdenum solution was prepared by dissolving 1.84 g of

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY ammonium heptamolybdate in 20 ml of water. This solution is added to the grout. After the addition is complete, the pH of the mixture is adjusted to 5 with dilute aluminum hydroxide solution and allowed to react for 10 min. A dilute (1 wt% SIO2) solution of sodium silicate was prepared by adding 0.85 g of Inobond Na-4011 sodium silicate (29.4 wt% as S1O2) to 24.1 g of deionized water. A 10 g portion (as received base) of strong acid ion exchange resin (Dowex™ 650C form H) was weighed and placed in a burette column. The diluted silicate solution was added through the column with the ion exchange resin to the slurry at a flow rate of 10 ml/min. The column was then rinsed with 10 ml of deionized water at a flow rate of 10 ml/min. The pH was adjusted back to 5 with ammonium hydroxide and allowed to react for 20 min. The mixture was filtered, rinsed with 500 ml of DI water, dried at 105°C, and then calcined at 530°C for 6 hrs. The target loading is 0.5 wt% S1O2, and 2 wt% Mo. Vanadia is added as described in Example 1.

Example 3b

A catalyst support was prepared as described in Example 3a except that the order of addition of the molybdenum and silica was reversed such that the silica was added before the molybdenum. Vanadia is added as described in Example 1.

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The volatility test results are shown in Table 1 below:

Table 1

<td>Example</td><td>Mo in Catalysts before Test (g></td><td>Mo in catalysts after test (g)</td><td>Mo in alumina (g)</td><td>Mass balance</td><td>Mo held</td><td>Mo loss</td>

<td>Example 1</td><td> 1.91</td><td> 1.82</td><td> 0.07</td><td> 99.0%</td><td> 96.3%</td><td> 3.7%</td>

<td>Example 2</td><td> 1.98</td><td> 1.84</td><td> 0.12</td><td> 99.0%</td><td> 93.9%</td><td> 6.1%</td>

<td>Comparative Example 1</td><td> 2.07</td><td> 1.44</td><td> 0.61</td><td> 99.0%</td><td> 70.2%</td><td> 29.5%</td>

<td>Comparative Example 2</td><td> 1.98</td><td> 1.76</td><td> 0.33</td><td> 105.6%</td><td> 84.2%</td><td> 15.8%</td>

<td>Example 3a</td><td> 1.82</td><td> 1.86</td><td> 0.16</td><td> 111.0%</td><td> 92.1%</td><td> 7.9%</td>

<td>Example 3a</td><td> 1.98</td><td> 1.82</td><td> 0.12</td><td> 98.0%</td><td> 93.8%</td><td> 6.2%</td>

<td>Example 3a</td><td> 1.99</td><td> 1.89</td><td> 0.11</td><td> 100.5%</td><td> 94.5%</td><td> 5.5%</td>

<td>Example 3a</td><td> 1.96</td><td> 1.86</td><td> 0.13</td><td> 101.5%</td><td> 93.5%</td><td> 6.5%</td>

<td>Example 3a</td><td> 1.96</td><td> 1.83</td><td> 0.15</td><td> 102.1%</td><td> 92.4%</td><td> 7.6%</td>

<td>Example 3a</td><td> 2.05</td><td> 1.93</td><td> 0.13</td><td> 100.5%</td><td> 93.7%</td><td> 6.3%</td>

<td>Example 3b</td><td> 1.92</td><td> 1.79</td><td> 0.13</td><td> 100.0%</td><td> 93.2%</td><td> 6.8%</td>

<td>Example 3b</td><td> 1.97</td><td> 1.88</td><td> 0.12</td><td> 101.5%</td><td> 94.3%</td><td> 6.0%</td>

<td>Example 3b</td><td> 1.90</td><td> 1.79</td><td> 0.16</td><td> 102.6%</td><td> 91.8%</td><td> 8.2%</td>

<td>Example 3b</td><td> 1.96</td><td> 1.93</td><td> 0.13</td><td> 105.1%</td><td> 93.7%</td><td> 6.3%</td>

<td>Example 3b</td><td> 1.96</td><td> 1.82</td><td> 0.16</td><td> 101.5%</td><td> 91.9%</td><td> 8.1%</td>

<td>Example 3 Average</td><td></td><td></td><td></td><td> 102.2%</td><td> 93.1%</td><td> 6.9%</td>

Comparative Example 2 relative to Example

Comparative 1 shows the advantages of removing concurrent ions using a wash step with a 10-fold excess of deionized water. Such evidence demonstrates an advantage of an embodiment of the invention that includes retention of molybdenum. Example 1 shows a significant additional attenuation of molybdenum volatility. Furthermore, the comparison of Example 1 with Example 2 shows that the volatility of molybdenum is at least partially

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY related to or influenced by the order in which silica is added versus molybdenum and phosphorus is added using an ion exchange column. Example 3 represents 11 replicates of both the preparation method and the volatility test. These results show the variability of the test, as well as demonstrating that the order of addition is not important for compositions that include only molybdenum and silica. Additionally, replications demonstrate that this simple preparation method is also effective in reducing Mo volatility relative to Comparative Examples.

Example 4

In order to show the effect of increasing silica content on molybdenum volatility, catalyst supports were prepared as described in Example 3b with the exception that the target silica loading was increased to 0.75% (Example 4a). and 1.0% (Example 4b). Vanadia is added as described in Example 1.

Comparative Example 3

In order to show the unexpected benefits of adding silica through the ion exchange column, a comparable catalyst support was prepared using colloidal silica. 182.0 g of titanium anatase hydrolyzate slurry (26.8% solids) were heated to 60°C via a temperature-controlled hot plate and the

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY temperature was maintained throughout the preparation. A molybdenum solution was prepared by dissolving 1.84 g of ammonium heptamolybdate in 20 mL of water. This solution is added to the grout. After the addition is complete, the pH of the mixture is adjusted to 5 with dilute aluminum hydroxide and allowed to react for 10 min. A colloidal dispersion of silica (Trade name - Ludox AS-30 from Grace Davison (30% solids)) was diluted by mixing 1 g with 29 deionized water, and 25 mL added to the titania slurry. The pH was adjusted back to 5 with ammonium hydroxide and allowed to react for 20 min. The mixture was filtered, rinsed with 500 ml of DI water, dried at 105°C, and then calcined at 530°C for 6 hrs. The target loadings are 0.5 wt% S1O2, and 2 wt% Mo. Vanadia is added as described in Example 1.

Comparative Example 4

In order to show the unexpected advantage of adding silica through the ion exchange column, a comparable support was prepared using fumed silica. Titanium anatase hydrolyzate slurry 182.0 g (26.8% solids) was heated to 60°C via a temperature controlled hot plate and the temperature was maintained throughout the preparation. A molybdenum solution was prepared by dissolving 1.84 g of ammonium heptamolybdate in 20 ml of water. This solution is added to the

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY slurry and, after completing the addition, the pH of the mixture is adjusted to 5 with a diluted aluminum hydroxide solution and allowed to react for 10 min. A fumed silica slurry (Trade name - Aerosil 200 from Evonik) was prepared by adding 0.25 g to 25 ml and adding this to the titania slurry. The pH was adjusted back to 5 with ammonium hydroxide and allowed to react for 20 min. The mixture was filtered, rinsed with 500 ml of DI water, dried at 105°C, and then calcined at 530°C for 6 hrs. Target loadings are 0.5 wt% SÍO2, and 2 wt% Mo. Vanadia is added as described in Example 1.

Example 5

In order to show the effect of adding silica and molybdenum together through the ion exchange column, the preparation was modified as follows.

A 370.7 g sample of titanium anatase hydrolyzate slurry (26.3% solids) was heated to 60°C via a temperature controlled hot plate and the temperature was maintained throughout the preparation. The pH was adjusted to 5 with dilute aluminum hydroxide solution. A dilute solution (1% by weight SÍO2) of sodium silicate was prepared by adding 1.7g of sodium silicate (Inobond Na-4011 29.4% by weight as SÍO2) to 48.4g of deionized water. 3.68 g of ammonium heptamolybdate was added to the silica solution. A portion of 20 g (as base received) of resin of

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY strong acid ion exchange (Dowex™ 650C form H) was weighed and placed in a burette column. The diluted molybdenum silicate solution was added through a column with the ion exchange resin to the slurry at a flow rate of 5 ml/min. The pH was adjusted back to 5 with ammonium hydroxide and allowed to react for 20 min. The mixture was filtered, rinsed with 1.0 liters of deionized water, dried at 105°C, and then calcined at 530°C for 6 hrs. The target loadings are 0.5 wt% S1O2 and 2 wt% Mo. Vanadia is added according to the method described in Example 1.

Example 6a

To show that molybdenum and silica can be added in a number of ways that are effective in reducing Mo volatility, the preparation method was varied as follows.

A 370.7 g sample of the anatase titanium hydrolyzate slurry (26.3% solids) was heated to 60°C via a temperature controlled hot plate and the temperature was maintained throughout the preparation. Molybdenum was combined with the slurry to obtain a Mo loading of 0.5% by weight by the addition of 0.92 g of ammonium heptamolybdate. The pH was adjusted to 5 with dilute aluminum hydroxide. A dilute solution (1 wt% SÍO2) of sodium silicate was prepared by adding 1.7 g of Inobond Na-4011 sodium silicate (29.4 wt% as S1O2) to 48.4 g of

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY deionized water. 2.76 g of ammonium heptamolybdate were added to the silica solution for a target proportion of 1.5% Mo and in order to make a total Mo loading of the support of 2% by weight. A 20 g portion (as base received) of strong acid ion exchange resin (Dowex™ 650C form H) was weighed and placed in a burette column. The diluted molybdenum silicate solution was added through a column with the ion exchange resin to the slurry at a flow rate of 5 ml/min. The pH was adjusted back to 5 with ammonium hydroxide and allowed to react for 20 min. The mixture was filtered, rinsed with 1.0 liters of deionized water, dried at 105°C, and then calcined at 530°C for 6 hrs. Target loadings are 0.5 wt% SiO2, and 2 wt% Mo, where 0.5 wt% Mo was added in the slurry directly and 1.5 wt% was added in the silica solution through the ion exchange column. Vanadia is added as described in Example 1.

Example 6b

A catalyst support was prepared as described in Example 6a with the exception that 1.0 wt% Mo was added in the slurry directly and 1.0 wt% was added with the silica solution through the exchange column. ion for a total of 2% by weight Mo added to the support. Vanadia is added as described in Example 1.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Example 6c

A supported catalyst was prepared as described in Example 6a except that 1.5 wt% Mo was added in the slurry directly and 0.5 wt% was added with the silica solution via the exchange column. ion for a total of 2% by weight of Mo added to the support. Vanadia is added as described in Example 1.

Example 7a

To show the effect that phosphorus has on reducing the volatility of molybdenum, the following supports were prepared.

A 348.8 g sample of the anatase titanium hydrolyzate slurry (27.9% solids) was heated to 60°C via a temperature controlled hot plate and the temperature was maintained throughout the preparation. The pH was adjusted to 4 with dilute aluminum hydroxide solution. A molybdenum-phosphorus solution was prepared by dissolving 3.68 g ammonium heptamolybdate and 0.55 g 85% phosphoric acid in 20 mL water. A 10 g portion (as received base) of strong acid ion exchange resin (Dowex™ 650C form H) was weighed and placed in a burette column. The molybdenum and phosphorus solution was added through the column with the ion exchange resin to the slurry at a flow rate of 5 ml/min. The pH was adjusted back to 4

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY with ammonium hydroxide and left to react for 20 min. The mixture was filtered, rinsed with 1.0 liters of deionized water, dried at 105°C, and then calcined at 530°C for 6 hrs. Target loadings are 0.15 wt% P and 2 wt% Mo. Vanadia is added as described in Example 1.

Example 7b

A 348.8g sample of the anatase titanium hydrolyzate slurry (27.9% solids) was heated to 60°C via a temperature controlled hot plate and the temperature was maintained throughout the preparation. The pH was adjusted to 4 with dilute aluminum hydroxide. A solution of molybdenum and phosphorus was prepared by dissolving 3.68 g of ammonium heptamolybdate and 0.55 g of 85% phosphoric acid in 20 ml of water. The molybdenum and phosphorous solution was added directly to the slurry at a flow rate of 5 ml/min. The pH was adjusted back to 4 with ammonium hydroxide and allowed to react for 20 min. The mixture was filtered, rinsed with 1.0 liters of deionized water, dried at 105°C, and then calcined at 530°C for 6 hrs. The target loadings are 0.15 wt% P and 2 wt% Mo.

The volatility test results for Examples 4-7 and Comparative Examples 3 and 4 are shown in Table 2 below:

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Table 2

<td>Example</td><td>Mo in Catalysts before Test (% by weight)</td><td>Mo in catalysts after test {% by weight)</td><td>Mo in alumina (wt%)</td><td>Mass balance</td><td>MO retained</td><td>Mo loss</td>

<td>Example 4a</td><td> 1.86</td><td> 1.80</td><td> 0.11</td><td> 102.7%</td><td> 94.2%</td><td> 5.8%</td>

<td>Example 4b</td><td> 1.89</td><td> .1.84</td><td> 0.10</td><td> 102.4%</td><td> 95.1%</td><td> 4.9%</td>

<td>Comparative Example 3</td><td> 2.00</td><td> 1.75</td><td> 0.364</td><td> 104.5%</td><td> 83.7%</td><td> 16.3%</td>

<td>Comparative Example 4</td><td> 1.97</td><td> 1.81</td><td> 0.32</td><td> 108.1%</td><td> 85.0%</td><td> 15.0%</td>

<td>Example 5</td><td> 1.81</td><td> 1.59</td><td> 0.05</td><td> 90.6%</td><td> 96.9%</td><td> 3.1%</td>

<td>Example 6b</td><td> 1.91</td><td> '1.92</td><td> 0.06</td><td> 103.6%</td><td> 97.0%</td><td> 3.0%</td>

<td>Example 6c</td><td> 1.90</td><td> 1.90</td><td> 0.08</td><td> 104.2%</td><td> 96.0%</td><td> 4.0%</td>

<td>Example 6d</td><td> 1.93</td><td> 1.82</td><td> 0.09</td><td> 99.1%</td><td> 95.2%</td><td> 4.8%</td>

<td>Example 7a</td><td> 1.90</td><td> 1.68</td><td> 0.23</td><td> 100.5%</td><td> 88.0%</td><td> 12.0%</td>

<td>Example 7b</td><td> 1.97</td><td> 1.79</td><td> 0.19</td><td> 100.4%</td><td> 90.4%</td><td> 9.6%</td>

The results of Example 4 suggest that increasing the silica content of the support improves Mo retention. Comparative Examples 3 and 4 show that neither colloidal silica nor fuming added to the catalyst support preparation has any measurable effect on the volatility of molybdenum in contrast to that shown by the improvement gained by adding silica through the ion exchange column. Examples 5 and 6 show that molybdenum can be added in any combination directly and through the ion exchange column in combination with silica while maintaining effectiveness.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY reduction of Mo volatility. Examples 7a and 7b show some evident reduction of Mo volatility induced by the addition of P and Mo via ion exchange as opposed to direct addition to the slurry, but this enhancement is not to the same degree as that induced by SiOs and Mo alone. Finally, the comparison of Examples 3a and 3b (S1O2 added only) and Example 7 (P added only) with Examples 1, 5, and 6 (Si and P both added in the support preparation) suggests that the improvement in the Mo retention induced by the combination of Si and P is additive.

Example 8a

A catalyst support was prepared as described in Example 2 except that 0.73 g of 85% phosphoric acid was added to obtain a P loading of 0.20 wt%.

Example 8b

A catalyst support was prepared as described in Example 2 except that 0.92 g of 85% phosphoric acid was added to obtain a 0.25 wt% P loading. 0.9% vanadia was added in each case as described in Example 1.

The performance of the catalysts prepared in Examples 2, 3a, 8a, and 8b is compared in Figure 4. A

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY Although the addition of 0.15% by weight of P initially seems to reduce both, the total conversion of NOX and that at an escape of 10 ppm, according to P, the maximum conversion of N0 increases to 0.2% by weight and 0.25% by weight.x and the conversion of N0x at a leak of 10 ppm it increases as well. Such results are unexpected as it is commonly accepted in the art that P acts as a poison for the conversion of N0x. And, although certain descriptions claim that P can be added to levels at which the conversion of N0x not committed eg see, US20100183492, Kato et al), the prior art does not describe or suggest that P actually increases NO conversionX as shown above.

The data in Figure 4 helps generate the values listed in the following tables. The conversion of NOX at a 10 ppm leak the measured value is calculated as the trend line crosses the 10 ppm ammonia leak at the rise in ammonia partial pressure in the reactor. The maximum conversion of N0x is determined as the maximum value of conversion as the partial pressure of the ammonia increases from 0 to 1200 ppm.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Table 3

<td>Example</td><td>phosphorous load</td><td colspan="2">N0 conversionxat 10 ppm exhaust</td><td colspan="2">Maximum conversion of N0x</td><td>SO oxidation2</td>

Comparing the Example Results

3a with those of Examples 1, 2, 7a, 7b, 8a, and 8b show that, as reported in the prior art, the addition of phosphorus to the catalyst support reduces SO2 oxidation. As mentioned previously, our data also surprisingly shows the total conversion of NOX and that at a leak of 10 ppm ammonia increases as the phosphorus load increases from 0.15 to 0.25% by weight for the reactor tests done at 350C. However, it appears to pass through a maximum at about 0.20 wt% P for reactor tests performed at 450°C. Examples 7a and 7b show that the activity also increases in the absence of silica and that the degree of conversion of N0x at 10 ppm ammonia escape can be influenced by the way the

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY which molybdenum and phosphorus are added to the support, either through the ion exchange column (7a) or directly to the slurry (7b).

Example 9a

A catalyst support prepared as described in Example 3a except that 0.56 g of 85% phosphoric acid is added to obtain a P loading of 0.15 wt%.

Example 9b

A catalyst support prepared as described in Example 3a except that 0.73 g of 85% phosphoric acid is added to obtain a P loading of 0.20 wt%.

Example 9c

A catalyst support is prepared as described in Example 3a except that 1.10 g of 85% phosphoric acid is added to obtain a P loading of 0.30 wt%.

Example 9d

A catalyst support is prepared as described in Example 3a except that 1.47 g of 85% phosphoric acid is added to obtain a P loading of 0.40 wt%. In each case, 0.9% vanadia is added as described in Example 1.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Example 10a

To determine if the efficacy of phosphorus in increasing the conversion of N0x and SO2 oxidation reduction is limited to when added in the support preparation, the catalyst preparation was modified to combine small amounts of phosphoric acid with vanadium pentoxide.

A 20 g sample of the support prepared as described in Example 1 was poured into 50 ml of water. To this, vanadium pentoxide (0.184g) and monoethanolamine (0.154g) were added and the temperature of the mixture was raised to 60°C to obtain a target V2O5 loading of 0.9%. Phosphorus is added to the slurry by introducing 0.037 g of 85% H3PO4 solution to obtain a target loading of 0.05% in addition to the 0.15% already present in the support. The pH was adjusted to 8 with ammonium hydroxide and the mixture was allowed to stir for 15 minutes. The solids were filtered off, dried at 100°C for 6 hrs, and calcined at 600°C for 6 hrs in air.

Example 10b

A catalyst was prepared in the same way as described in Example 10a except that 0.074 g of 85% phosphoric acid is added to obtain a target loading of 0.1 wt% P in addition to the 0.15% already present in the catalyst. support.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

The operation of the reactor of 9 and 10 is shown in Table 4 below.

Table 4

<td>Example</td><td>Total phosphorus load</td><td colspan="2">NOx conversion to 10 ppm exhaust</td><td colspan="2">Maximum conversion of NOX</td><td>SO oxidation2</td>

This table shows that when molybdenum and phosphorus are added directly to the support (Examples 9a 9d) the Maximum Conversion of N0x initially increases with P loading and passes through at an optimum of about 0.2 wt% P loading. As expected, oxidation of S02 monotonically it decreases with increasing P load. Examples 10a and 10b show that adding phosphorus in two separate steps, that is during support preparation with further addition during catalyst preparation, is also effective in increasing NO conversion.X to an optimum with reductions when too much P is added. Comparison of Examples 8a, 9a, and 10a shows that there are some noticeable differences in NO conversionX depending on how the phosphorous and/or molybdenum are added.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Example 11

To demonstrate whether enhancement of NOx conversion and suppression of SO oxidation2 effected only by P or other elements capable of inducing the same improvements, sulfur and silica were tested in the same way.

lias example

A 349.5 g sample of titanium anatase hydrolyzate slurry (27.9% solids) was heated to 60°C via a temperature controlled hot plate and the temperature was maintained throughout the preparation. The pH was adjusted to 4 with dilute aluminum hydroxide solution. A 20 g portion (as received base) of strong acid ion exchange resin (Dowex™ 650C form H) was weighed and placed in a burette column. A solution was prepared by dissolving 3.68 g ammonium heptamolybdate and 0.69 g ammonium persulfate ((NH4)2yes2O8) in 20 ml of water, and the solution is added to the slurry via the ion exchange column at a flow rate of 5 ml/min. After the addition is complete, the pH of the mixture is adjusted to 4 with dilute aluminum hydroxide solution and allowed to react for 10 min. A dilute solution (1% by weight SiO2) of sodium silicate was prepared by the addition of 1.7 g of Inobond Na-4011 sodium silicate (29.4% by weight as SiO2) to 48.4 g of deionized water. The diluted silicate solution

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY was added through the column with the ion exchange resin to the slurry at a flow rate of 5 ml/min. After the addition was complete, the ion exchange resin in the column was rinsed with 10 ml of deionized water added at a flow rate of 5 ml/min in the titania slurry. The pH was adjusted back to 4 with ammonium hydroxide and allowed to react for 20 min. The mixture was filtered, rinsed with 1.0 liters of deionized water, dried at 105°C, and then calcined at 530°C for 6 hrs. Target loadings are 0.5 wt% SiCh, 0.17 wt% S, and 2 wt% Mo. 0.9% vanadia is added as described in Example 1.

Example 11b

The catalyst support was prepared as described in Example lia with the exception that 1.06 g of Inobond Na-4011 sodium silicate (29.4 wt% as SIO2) was substituted with ammonium persulfate in the molybdenum solution. Target loadings are 0.8 wt% SiO2 and 2 wt% Mo. 0.9% vanadia is added as described in Example 1.

Example 11c

The catalyst support was prepared as described in Example lia except that 0.55 g of 85% phosphoric acid and 0.35 g of ammonium persulfate were added to the molybdenum solution. The target loadings for this product are 0.15 wt% P, 0.09 wt% S, 0.5 wt%

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY weight of S1O2, and 2% by weight of Mo. 0.9% of vanadia is added as described in Example 1.

The results of the reactor test are shown in Table 5 below.

Table 5

<td>Example</td><td>Modifier and Charge</td><td colspan="2">N0 conversionxat 10 ppm exhaust</td><td colspan="2">Maximum conversion of NOX</td><td>SO oxidation2</td>

The results of Example lia surprisingly show that S added in the same molar ratio as 0.15% P also effectively reduces SO2 oxidation. The addition of S in the manner described in Example lia also appears to enhance the conversion of N0x. It should be appreciated that the addition of sulfur is not restricted to a particular order, amount and sequential manner, as is ion exchange unless expressly stated otherwise. It is also surprising that silica has a favorable effect in reducing SO2 oxidation and increasing N0 conversion.x when the silica is added with molybdenum at a molar equivalent at 0.15% by weight of P and through the ion exchange column. The data in Example lia and 11b show that P is not the only

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY element that can be used to increase the conversion of NOXwhile reducing SO2 oxidation. The data from Example 11c show that the combination of sulfur with phosphorus has a deleterious effect on the conversion of NOX while still effective in reducing SO2 oxidation.

Example 12a

A 331.5 g sample of the anatase titanium hydrolyzate slurry (26.3% solids) was heated to 60°C via a temperature-controlled hot plate, and the temperature was maintained throughout the preparation. The pH was adjusted to 4 with dilute aluminum hydroxide solution. A dilute (1 wt% SIO2) solution of sodium silicate was prepared by adding 5.1 g of Inobond Na-4011 sodium silicate (29.4 wt% as S1O2) to 144.9 g of deionized water. A 40 g portion (as received base) of strong acid ion exchange resin (Dowex™ 650C form H) was weighed and placed in a burette column. The diluted silicate solution was added through a column with the ion exchange resin to the slurry at a flow rate of 5 ml/min. The pH was adjusted back to 4 with ammonium hydroxide and allowed to react for 20 min. A second solution was prepared by dissolving 7.36 g of ammonium heptamolybdate in 20 ml of water. This solution is added to the slurry via the ion exchange column at a flow rate of 5 ml/min. After the addition is complete, the

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY ion exchange resin in the column was rinsed with 20 ml of deionized water added at a flow rate of 5 ml/min in the titania slurry. The pH of the mixture was adjusted to 4 with a diluted aluminum hydroxide solution and allowed to react for 10 min. The mixture was filtered, rinsed with 1.0 liters of deionized water, dried at 105°C, and then calcined at 530°C for 6 hrs. Target loadings are 1.5 wt% SiO2 and 4% by weight of Mo.

Example 12b

The catalyst support was prepared as described in Example 12a except that 0.56 g of 85% phosphoric acid was added to the molybdenum solution. The target loadings of this support are 0.15 wt% P, 1.5 wt% SiO2, and 4% by weight of Mo.

Example 12c

The catalyst support was prepared as described in Example 12a except that 1.12 g of 85% phosphoric acid was added to the molybdenum solution. The target loadings of this support are 0.3 wt% P, 1.5 wt% SiO2, and 4% by weight of Mo.

Example 12d

The catalyst support was prepared as described in Example 12a except that 3.72 g of

85% phosphoric acid was added to the solution.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY molybdenum. The target loadings of this support are 1.0 wt% P, 1.5 wt% SÍO2, and 4 wt% Mo.

Example 12e

The catalyst support was prepared as described in Example 12a except that 7.44 g of 85% phosphoric acid was added to the molybdenum solution. The target loadings of this support are 2.0 wt% P, 1.5 wt% SÍO2 and 4 wt% Mo. In each case, 0.9 vanadia are added as described in Example 1.

A DeNO conversion testx accelerated was done in the following way. The catalyst was evaluated as a powder without further casting. A 0.9525 cm (3/8) quartz reactor carries 0.1 g of the catalyst supported on glass wool. The feed composition is 1000 ppm NO, 5% O2, 5% H2O. The partial pressure of NH3 is successively increased from 700 ppm to 900 ppm and then finally to 1200 ppm with the balance being N.2. NO conversion was measured after reaching steady state in each NH3 configuration while the reactor temperature was maintained at 350°C and the pressure was atmospheric. The reactor effluent was analyzed with an infrared detector for NO conversion. The results of the N0 conversion testx and SO2 oxidation test are shown in the following Table

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Table 6

<td>Example</td><td>Total Phosphorus Load</td><td colspan="3">N0 conversionxat 350C</td><td>SO2 oxidation</td>

Catalysts loaded with 4% Mo show trends similar to those that have been observed. The degree of oxidation of SO2 generally decreases with increasing phosphorous loads, and the conversion of N0x at 350 °C it surprisingly experiences a maximum with increasing phosphorus.

The use of the term metal as a catalyst component should be understood as having the same meaning as the respective metal oxide as a catalyst component unless otherwise indicated. For example, Mo as an oxidant means the same thing as s M0O3 as an oxidant.

Approximate wording, as used herein throughout the description and claims, may be applied to modify any quantitative or qualitative representation that could permissibly vary without resulting in a change in the basic function to which it refers. Therefore, a value modified by a term such as approximately or the intervals

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY numbers are not limited to a precise specified value and may include values that differ from the specified value. In at least some instances, the approximate wording may correspond to the precision of an instrument for measuring value. Also, remove or reduce NOx can be used in combination with a term, and includes a variable amount of N0 removal.x and will not be limited to a precise specified value and may include values that differ from a specified value.

It will be apparent to one skilled in the art that various modifications and variations may be made to the method and system of the present invention without departing from the spirit or scope of the invention. Thus, the currently described and/or claimed inventive concept(s) are intended to include modifications and variations that are within the scope of the appended claims and their equivalents.

Although the currently disclosed concept(s) and/or claimed inventions have been described in detail in connection with only a limited number of aspects, it is to be understood that the currently disclosed concept(s) and/or or claimed inventions are not limited to such disclosed aspects. Rather, the currently described and/or claimed inventive concept(s) may be modified to incorporate any

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY number of variations, alterations, substitutions, equivalent provisions so far not described but in accordance with the scope of the claims.

Additionally, although various embodiments of the currently disclosed and/or claimed inventive concept(s) have been described, it is understood that aspects of the currently disclosed and/or claimed inventive concept(s) claimed may include only some of the described embodiments. Accordingly, the currently disclosed and/or claimed inventive concept(s) shall not be viewed as limited by the above description but only by the scope of the appended claims.

It is stated that in relation to this date, the best method known by the applicant to carry out the aforementioned invention is the one that is clear from the present description of the invention.

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61693245	United States of America	–	2012-08-24
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