Untitled record

full description

invention background

This invention includes embodiments related to catalyst support materials, catalyst compositions, and methods for the manufacture and use of said catalyst support materials and catalysts. In particular, the invention includes embodiments relating to compositions and methods for the manufacture of catalyst carriers and catalysts.

5 Seal the nitrogen oxide content with nitrogen oxide-containing gas or liquid in applications

Mobile and fixed.

Some of the processes of removal of NOx formed in off-gases are known in the art as selective catalytic reduction (SCR). In this process, nitrogen oxides are reduced by ammonia (or another reducing agent).

10 Like unburned hydrocarbons present in the exhaust gas flow product) in the presence of oxygen, a nitrogen catalyst, and water. The SCR process is used in the USA, Japan, and Europe to reduce the emissions of large utility boilers and other commercial applications. Use of SCR processes to reduce emissions in mobile applications such as in large diesel engines such as those on ships, diesel locomotives, automobiles, and the like.

15th Some SCR catalysts with metal oxide such as vanadium, tungsten, molybdenum, and iron are known to eliminate NOx. However, there are one or more limitations as discussed below. Use of a tungsten-containing catalyst may be restricted due to price and availability. Molybdenum-containing catalyst systems are restricted by the relatively high volatility compared to the tungsten analogs and the relatively high SO2 oxidation accelerator compared to tungsten-containing systems.

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<p>. Oxidation of SO2 is a problem in persistent DeNOx applications due to the formation of ammonium sulfate which causes clogging and an overpressure drop in the process stomach.</p>

Accordingly, catalyst carriers and catalysts that are proportional to the reduction of nitrogen oxide content with nitrogen oxide-containing gas or liquid are still needed under various conditions. 5 There is also a need for a method to manufacture the mentioned catalyst carriers, catalysts, and a reduction method

Nitrogen oxide content of nitrogen oxide containing gas or liquid in mobile and stationary applications.

General description of the invention

The embodiments of the present invention fulfill these and other needs by providing NOx reduction catalysts, 10 methods for manufacturing NOx reduction catalysts, and methods for removing nitrogen oxide content with a liquid or gas

containing nitrogen oxide using the mentioned NOx reductase catalyst,

Accordingly, a first aspect of the invention presents a method for the fabrication of a catalyst carrier. The method includes: fusing an anatase titania slurry with (1) one or more low molecular weight silica forms, and 2) a molybdenum source to form a mixture of TiO2-MoO3-SiO2. Includes 15 low molecular weight silica forms estimated medium size silica forms Size less than 4

A nanomolar and an average molecular weight of less than 44,000, either singly or in combination of two or more of them.

A second aspect of the invention presents a method for fabricating a catalyst carrier. The method includes: (a) introducing anatase titania slurry; (b) fusing anatase titania slurry with (1) one or more 20 low molecular weight silica images, and (2) a molybdenum source to form a mixture of

TiO2-MoO3-SiO2. Low molecular weight silica images include estimated average size silica images with a size of less than 4 nM and an average molecular weight of less than 44,000, either singly or in combination of two or more of them.

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A third aspect of the invention presents a catalyst carrier. The catalyst carrier comprises from about 68% to about 44% by weight of anatase titanium dioxide; From about 0,1% to about 10% by weight MoO3; And from about 0.1% to about 10% by weight SiO2 in low molecular weight forms. Low molecular weight SiO2 images include silica images with a mean size 5 estimated with a size of less than 4 nanomolar and an average molecular weight of less than 44,000, either singly or in combination of two or more of them.

Four aspects of the invention present a method for fabricating a catalyst support material. The method includes the following: molten anatase titania with (1) a volatilization inhibitor comprising a low molecular weight silica image and (2) a primary promoter comprising molybdenum oxide to form a 10 TiO2-Mb-SiO2 mixture. The low molecular weight silica images include silica with an estimated average size of less than 4 nanomolars and an average molecular weight of less than 44,000, either singly or in combination of two or more of them.

A fifth aspect of the invention presents a method for fabricating a catalyst carrier. The method includes: a) introducing anatase titania slurry; and b) merging anatase titania slurry with 1) a volatilization inhibitor comprising 15 form of low molecular weight silica and 2) a primary promoter comprising molybdenum oxide to form a mixture of TiO2-Mb- SiO2 Low molecular weight silica images include silica images with an estimated average size of less than 4 nm and an average molecular weight of less than 44,000, either individually or in combinations of two or more of them.

<p>20 A sixth aspect of the invention presents a catalyst carrier. The catalyst support material comprises titanium dioxide anatase; a major enhancer comprising molybdenum oxide; and a volatilization inhibitor comprising a low molecular weight silica profile. Low molecular weight silica images include silica images with an estimated mean size of less than 4 nM and an average molecular weight of less than 44,000, either individually or in combination of two 25 or more of them.</p>

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A seventh aspect of the invention presents a method for reducing nitrogen oxide content from a liquid or gas containing nitrogen oxide. The method comprises contacting a gas or liquid containing nitrogen oxide with a catalyst for sufficient time to reduce the level of NOx compounds in the gas or liquid. The catalyst comprises the following: from about 68% to about 44% by weight of anatase titanium dioxide; from

5 About 0.1% to about 10% by weight of MoO3; From about 0,5% to about 3% by weight V2O5; And from about 0.1% to about 10% by weight SiO2 in low molecular weight forms. Low molecular weight silica images include silica images with an estimated average size of less than 4 nM and an average molecular weight of less than 44,000, either singly or in combination of two or more of them.

10 An eighth aspect of the invention presents another method for reducing nitrogen oxide content from a liquid or gas containing nitrogen oxide. The method involves contacting a gas or liquid containing nitrogen oxide with a catalyst for sufficient time to reduce the level of NOx in a gas or liquid containing nitrogen oxide, whereby the catalyst is manufactured by: low molecular and (2) Mo source, to form a mixture of -TiO2

15th MoO2-SiO2. Low molecular weight silica images include silica images with an estimated average size of less than 4 nM and an average molecular weight of less than 44,000, either singly or in combination of two or more of them.

A ninth aspect of the invention presents a catalyst carrier. The catalyst carrier comprises a general formula of TiO2-MoO3-SiO2, wherein the titanium dioxide is largely in the form of anatase 20 and the silicon oxide is a weighted volume, average volume less than 4 nm and an average molecular weight less than 44,000.

The attached figures, which are incorporated into and form part of this specification, are included to illustrate and provide an additional understanding of the methods and systems of the invention. In addition to the description, the figures serve to explain the principles of the invention. 25 Attributes of one model are expected to be usefully integrated into the others without further citation.

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Brief explanation of the drawings

Figure 1: Flowchart of a conventional method for manufacturing a catalyst carrier;

Figure 2: A flowchart of a method for manufacturing a catalyst carrier according to one of the embodiments of the invention;

5 Figure 3 represents a flowchart of a method for manufacturing catalysts according to one of the models of the invention; And

Figure 4: A comparative graphic representation of the performance of the NH3 slip catalyst against the conversion of NOx according to one of the embodiments of the invention.

To facilitate understanding, similar reference numbers have been used, wherever possible, to allocate similar elements common to the figures.

10 Detailed description:

In the following description, it is understood that terms such as “top,” “bottom,” “outward,” “inward,” and the like are words of convenience and are not restrictive terms. Below is a detailed reference to representative models of the invention, which are illustrated in the attached figures and examples. Referring to figures in general, it will be understood that the explanations are for the purpose of describing a specific form of

15th The invention is not intended to restrict the invention.

Where it is indicated that a particular form of the invention comprises or consists of at least one element of a group and combinations thereof, it shall be understood that the form may comprise or consist of

Any of the elements of the set, either individually or in combination with any of the other elements of the set. In addition to the above, when any variable appears more than once in any component or in

20 formula, whose definition on each appearance will be independent of its definition in every other appearance. Also, combinations of alternatives and/or variants are permitted if these combinations result in independent compounds.

Tariffs

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Unless otherwise indicated, all terms used in the present application have their natural meaning.

The terms "catalyst support material," "support particles," or "support material" have the standard meaning ascribed to them in the art.

5 The terms “active metal catalyst” or “active ingredient” refer to a catalytic component deposited on the surface of a support material that is supposed to catalyze the reduction of NOx compounds.

The terms “catalyst” and “catalytic composition” have the standard meaning ascribed to them in the art and refer to a combination of catalyst support components and titania-based catalyst support material particles.

10 Unless otherwise specified, all references to percent (%) in the present application refer to percent by weight. The terms “percentage” and “loading” refer to the loading of a component on the total catalytic composition. For example, vanadium oxide loading On the catalyst the ratio of the weight of vanadium oxide to the total weight of the catalyst, including a carrier as titania, vanadium oxide and any other portable metal oxides.

15th Molarity to molarity ratio of the number of moles of a specific component loaded to the number of moles in the total catalytic composition.

The term "phosphate" is used to refer to any compound containing a phosphorus bound to oxygen.

One embodiment of the invention includes a method for manufacturing a catalyst carrier. The method involves fusing anatase titania slurry with (1) one or more forms of low molecular weight silica and

20 2) Molybdenum source for the formation of a TiO2-MoO2-SiO2 mixture. Includes silica images with

Low molecular weight silica images have an estimated average size of less than 4 nanomolar and an average molecular weight of less than 44,000, either individually or in combination of two or more of them.

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An embodiment of the invention comprises a catalyst carrier comprising from about 68% to about 44% by weight titanium dioxide; From about 0,1% to about 10% MoO3; And from about 0.1% to about 10% by weight SiO2. SiO2 comprises one or more low molecular weight silica forms with an estimated average size of less than 4 nanomolar and an average molecular weight of 5 less than 44,000, either individually or in combination of two or more of them.

For the purpose of illustrative, but not limited to, an embodiment of the invention of methods for manufacturing a catalyst support material is compared with conventional methods. As shown in Figure 1, a conventional method for manufacturing a catalyst support material comprises step 110 introducing anatase titania slurry. Step 120 involves adjusting the pH. Step 130 includes providing all or

10 Significantly all commercially available silica is in the form of a preformed particle silica eg colloidal, fumed, etc. Step 140 involves adjusting the pH. Step 150 involves providing a tungsten.

In contrast to Figure 1, Figure 2 describes an embodiment of a method for manufacturing catalyst carriers. Figure 2 represents the flowchart of a model method for fabricating a catalyst carrier 15 by controlling the shape and distribution of silica with molybdenum. The method is not limited to arranging or

Repeat steps unless explicitly indicated. The method includes step 210 providing a titania slurry. Non-exhaustive examples of slurries of titania include brookite, anatase, rutile, monoclinic, tetrahedral rhombic like powders dispersed in water, and high pressure forms such as lα-PbO2, baddeleyite like, cotunnite, rhombic, 20 and individual cubic phases, either or in combination of two or more of them. In one embodiment, step 210 providing a slurry titania includes providing an anatase titania slurry. Non-exhaustive examples of anatase titania slurry include preformed titanium hydroxide, titanium oxy-hydroxide, orthotitanic acid, orthotitanic acid.

metatitanic acid, titanyl sulfate, sulfated titanium dioxide, sulfated titania

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titanium dioxide or titanium dioxide hydrolysate particles, organo-titanates

particles , either singly or in combination of two or more of them.

Although some embodiments and examples using anatase titania slurry are described in some descriptions, it should be recognized that embodiments of the invention are not limited to anatase titania slurry 5 and include other forms of titania slurry, either singly or in combination of two or more

who are they. Step 220 includes optionally adjusting the pH of the titania slurry in the range of about 3 to about 8 as needed. One embodiment involves adjusting the pH in a range of about 4 to about 5. Another embodiment involves adjusting the pH to about 4. The pH can be adjusted using an example, but not limited to,

Di, or tripropyl amine, , as alkyl amines, dilute 10 ammonium hydroxide either singly or mono, di, and triethanolamine, either as alkanol amines

In combination of two or more of them. Step 230 involves providing at least some of the low molecular weight form of silica to the slurry of titania. An embodiment includes one or more low molecular weight silica images with an estimated average size of less than 4 nM 15 and an average molecular weight of less than 44,000, either individually or in combination of two or more of them.

One embodiment of the invention comprises a step of 240 optionally adjusting the pH of the titania slurry to a pH of about 3 to about 8. Another embodiment comprises adjusting the pH to a range of about 4 to about 5. Another embodiment includes a modification of the pH to a range of about 4 to about 5. pH to about 4. The pH can be adjusted using, for example, 20, but not limited to, dilute ammonium hydroxide, alkyl amines such as, mono

mono, di, and triethanolamine, as alkanol amines, di, or tripropyl amine

either , either singly or in combination with two or more of them.

In one embodiment, a low molecular weight silica form includes, but is not limited to, (4)silicic acid (Si(OH). Examples of silicic acid include 4(Si)OH generated by ion exchange 25 for any of the cationic forms of the listed silica In the current application using exchange resin

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eg) acidic ion-exchange resin

For example, the ion exchange of solutions of alkaline silicas or solutions of quaternary ammonium silicate). Other unbound examples include “silicic acid” which may be provided either singly or in combination of two or more of them as described in op cit. (Her, Chapter 3), detailed description

5 of silicic acid using silicon NMR characterization, as described in G.

.) op cit. p. (100) D. Michel and Engelhardt

Although some embodiments using silicic acid as an example of low molecular weight silica are described in some descriptions, it should be recognized that embodiments of the invention are not limited to silicic acid and include other forms of low molecular weight silica, either singly or in combination of two or more of them.

In another embodiment, non-exhaustive examples of low molecular weight silica images with an estimated mean size of less than 4 nm or an average molecular weight of less than 44,000 include

tetramethylammonium i.e. tetra (alkyl) ammonium silicate produced soluble

silicate) and tetraethylorthosilicate (TEOS), either singly or in combination of two or 15 more of them.

Unexpected advantages of using low-molecular-weight silica images with an estimated average size of less than 4 nM or an average molecular weight of less than 44,000 to manufacture catalyst support materials may include one or more of the following. Catalyst carriers may have unexpected improved stability and activity compared to catalyst support

20 Conventional materials with colloidal silica as discussed below in the examples. The volatility of molybdenum can be reduced by at least 50% to greater than 60% compared to the initial or conventional molybdenum volatility values ​​while equivalent performance can be maintained to conventional catalyst carriers. Catalytic carriers may exhibit titania anatase phase retention and surface area after intense heat and/or hydrothermal treatments, even in the presence of vanadia.

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Other examples of low molecular weight silica producing materials that can be used include, but are not limited to, aqueous solutions of silicon, silicon halides alkoxides, other organic silicon compounds, fluoro-silicic acid salts, quaternary ammonium silicate solutions, sodium and potassium silicate solutions. aqueous, 5 and 4(silicic acid Si(OH), either singly or in combination of two or more of them.

Non-exhaustive examples of aqueous solutions of silicon halides include anhydrous SIX4, where

Br, CI, X = F, or I, either singly or in combination of two or more of them. The examples are not

Exclusive silicon alkoxides include 4(Si(OR), where methyl, ethyl, =R

isopropyl, propyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyls, hexyls, either singly or in combination with, octyls, nonyls, decyls, undecyls, and dodecyls 10

two or more of them. In one embodiment, examples of other organosilicon compounds include such, but not limited to, hexamethyldisilazane. In one embodiment, examples of salts of fluoro-silicic acid include [ammonium hexafluorosilicate [(NH4)2SiF6]. In one embodiment, examples of quaternary ammonium silicate solutions include an example, but not an example

15th Blocking, (NR4)n(SiO2), where R=H, or an alkyl as listed above, and 0.1=n-2, either singly or in combination of two or more of them. Unrestricted examples of solutions of sodium silicate The hydrated potassium includes K2SiO3, Na2SiO3, and MSiO3 (where M is Sodium or Potassium in varying amounts relative to silicon), either singly or in combination of two or more of them.

20 One advantage of using low molecular weight silica images with an estimated average size of less than 4 nm or an average molecular weight of less than 44,000 could include the opportunity for interaction with titania. One exception, as described below, involves the following adjustment of the silicas usage conditions to pH and temperature where the silicas particle was dissolved and re-depositioned on the surface of the titania.

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In a particular embodiment, suitable silica-producing materials include highly alkaline solutions, referred to as water-soluble silicas as described in Iler (op cit., Chapter 2). These solutions are typically transparent because the silica particle, if present , are generally too small to scatter visible light. However, depending on the silica concentration and alkalinity, small particles of silica can form in these solutions. (133.Her (op cit., p) It is estimated that for SiO2:

Na2O has a molar ratio of 3.1, the average number of silicon atoms per particle in dilute solutions is about 400, which is less than 1,500 silicon atoms per particle in 4 nm of the particle described above. Such a silica-producing material, although it can contain some nanometer particles above about 4 nm, is suitable for the present invention because most of the mass of silica is in the form of smaller, lower molecular weight species. Use of alkali silicates, and residual alkali ions such as Sodium can poison the vanadia-based SCR catalysts.

In another embodiment, step 230 provides a low molecular weight form of silica comprising providing an alkaline solution of tetramethylammonium silicate.

15th Examples of the invention include repeating step 230 providing at least a specific low-molecular-weight profile of silica at certain intervals as needed and at any number of times required such as, but not limited to, before, during, and after step 250, to provide a source of molybdenum, Either individually or a combination of two or more of them. It should be understood that embodiments of the invention include providing a set of low molecular weight silica images that differ from each other.

20 some. Low molecular weight silica photogroup can have diverse properties.

Furthermore, although embodiments of the invention have been described providing at least some low molecular weight silica images, it should be recognized that such invention embodiments are not limited to providing only low molecular weight silica images and include providing Other photos too

25 of silica, in one embodiment, in addition to step 230 of providing a specific low-weight profile

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For molecular silica, the method involves providing other forms of silica also that differ from forms of low molecular weight silica. Thus, in one embodiment, the total silica contained in a catalyst support material is defined as the sum of a low molecular weight form of silica and other forms of silica that differ from a low molecular weight form of silica

. silica 5

In one embodiment, the low molecular weight silica images comprise greater than 50% of the total silica contained in the catalyst carrier. In a given embodiment, a low-molecular-weight image of silica comprising &gt;50% of the total silica contained in the catalyst carrier includes one or more low-molecular-weight images having an estimated mean size of 10 &lt;4 nm or a lower average molecular weight of 44,000, either individually or in combination with

two or more of them.

Step 250 includes providing at least some of the molybdenum source to the anatase titania slurry. As shown in Figure 2, the method is not limited to sequential ordering or repetition of step 250. Examples of the invention include step 250 of providing a 15 molybdenum source before, during, or after step 230 of providing a low molecular weight image of

. silica

One embodiment includes step 250 providing at least some of the molybdenum source and step 230 of providing a low-molecular-weight image of sequentially silica. In a sequential model, the method includes step 250 providing at least some source of molybdenum before providing step 20 230 of a low molecular weight form of silica. When step 250 provides some source

molybdenum Prior to step 230, one embodiment involves adjusting the pH to a range of about 1 to about 8. Another embodiment involves adjusting the pH to a range of about 4 to about 5. The pH can be adjusted using such , but not limited to, dilute ammonium hydroxide, alkyl amines such as mono, 25-dimethylamine, or tripropylamine, alkanol amines such as mono, or di-, and triethanolamine, either as

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singly or in combination of two or more of them. In another sequential embodiment, the method includes step 250 of providing at least some of the molybdenum source after step 230 of providing a low molecular weight form of silica and after an optional step 240 of pH adjustment

. pH

5 One embodiment of the method also involves providing at least some molybdenum source and step 230 providing at least some molybdenum source and step 230 low molecular weight forms of silica at the same time.

The embodiments of the invention also include repeating step 250 of providing at least some molybdenum source at desired intervals and at any number of times, such as, but not limited to, before, during, and after step 230 of providing silica, either individually or in combination. of two or more

<p>10 Of which. It should be recognized that methods for manufacturing a catalyst support material also include the product of the reaction of one or more molybdenum sources with each other, the product of one or more silica forms with each other, and also the product of one or more molybdenum sources With one or more silica sources, and other reaction products among the elements present.</p>

<p>15th The method is also not limited to how step 250 provides a source of molybdenum. One or more sources of molybdenum may be supplied, before, during or after step 230 of the silica image provisioning method, such as, but not limited to, ion exchange according to Step 252, to the slurry directly according to Step 254, to. Either individually or a combination of two or more of them. In one embodiment, at least some of the molybdenum source is provided in step 250 by</p>

<p>20 Ion exchange resin by step 252. In another embodiment, at least some of the molybdenum source in step 250 is supplied to the titania slurry directly by step 254. molybdenum source: In one embodiment, the molybdenum source includes molybdenum oxide or a soluble molybdenum oxide precursor. , either individually or in combination with two or more of them. In a particular embodiment, molybdenum oxide is provided to a carrier</p>

<p>25 titania as soluble precursor as ammonium dimolybdate, ammonium hepta molybdate, bar</p>

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Ammonium molybdate ammonium phosphomolybdate tartrate in an amount to achieve a mole ratio of molybdenum to vanadium in a range ranging 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 in an amount that achieves a mole ratio of molybdenum to

5 vanadium in a range from about 1:1 to about 10:1 to form a catalyst comprising vanadium. In one embodiment, the method also includes providing a combination of different sources of molybdenum, either singly or in combination of two or more of them. In a particular embodiment, a combination of different sources from molybdenum to anatase titania is provided after step 230 of providing silica. In one embodiment, a combination of different sources can be provided from

10 molybdenum slurry to anatase titania by ion exchange resin by step 252. It should be recognized that one embodiment of the method involves fusing a slurry of titania with (1) silica and (2) one or more molybdenum sources to form a TiO2-MoO3 mixture

.SiO2

In one embodiment, the method also includes step 280 optionally to provide an amount of phosphate to

15th Malt anatase titania. Addition of phosphate to a catalyst support material can have unexpected advantages such as, but not limited to, reduced oxidation of SO2 and an improved ability to reduce NOx compared to without phosphate addition. In the presence of SiO2, phosphorus at surprisingly low levels increases the activity of the catalyst.

As shown in Figure 2, the method is not limited to sequential ordering or repeating step 280

20 Unless we note otherwise expressly. Examples of the invention include step 280 providing an amount of phosphate before, during, or after step 230 providing a low molecular weight form of phosphate.

. silica

In one embodiment, the method involves step 280 providing at least some amount of phosphate before step 230 providing at least some silica. Another model includes

25 .Step 280 provides at least some amount of phosphate during step 230 of saving at least some

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silica . In another embodiment, the method involves step 280 providing at least some amount of phosphate after step 230 providing at least some amount of phosphate. silica

In one embodiment, step 280 includes provision of a quantity of phosphate before, during, or after step 250 of provision of molybdenum. In a particular embodiment, the method includes step 280 of

5 Provide at least some source of phosphate prior to step 250 from providing at least some molybdenum. Another embodiment involves step 280 of providing an amount of phosphate during step 250 of providing at least some source of molybdenum. In a particular embodiment, at least some of the molybdenum source is in step 250 and an amount of phosphate is supplied in step 280 at the same time. Another model involves step 280 of providing at least some of the

10 . Provide at least some amount of phosphate after step 250 from a source

.molybdenum

It should be understood that the method involves repeating step 280 providing an amount of phosphate by repeating intervals as desired and as many times as desired such as, but not limited to, before, during, and after step 230 of providing a low molecular weight form of, silica

15th and before, during, and after step 250 of providing at least some molybdenum source, either individually or in combination of two or more of them.

The method is also not limited to how step 280 provides an amount of phosphate. A quantity of phosphate may be supplied by a method such as, but not limited to, direct ion exchange to the slurry, etc., either singly or in combination of two or more of them. In one form, it provides

20 Step 280 Quantity of phosphate, by ion exchange resin. In a particular embodiment, an amount of phosphate is supplied to the slurry by ion exchange resin prior to step 250 providing at least some molybdenum source. In another embodiment, an amount of phosphate is added to the titania slurry by ion exchange resin at the same time as step 250 providing at least some of the molybdenum source.

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Suitable compounds containing phosphate include, but are not limited to, organic phosphates, organic phosphonates, polyphosphoric acid, H3PO4, H4P2O7, phosphine oxides, NH4)2HPO4, (NH4)H2PO4, and NH4)3HPO4), either as Single or in combination of 5 or more of them. In one form, a set of different sources are provided from

phosphate. In addition to the above, phosphate can be present inside the carrier, or phosphate can be present on the surface of the carrier.

In one embodiment, phosphate is added, at levels to achieve a mole ratio of phosphorus to molybdenum of about 0.2:1 or greater. In some embodiments, phosphate 10 is added in an amount to achieve a molar ratio of phosphorus to molybdenum in a range of about

0.2:1 to about 4:1.

Significantly Free of tungsten: The applicant unexpectedly discovered that low molecular weight silica can reduce molybdenum volatility compared to conventional methods of a colloidal silica suspension or aqueous slurry of fumed solids. In addition to the above 15, the applicant also discovered that the level of the tungsten can be reduced or replaced, using

molybdenum in combination with a low molecular weight form of silica to control molybdenum volatility. It should be understood that embodiments of the invention optionally include a reduction or replacement of the tungsten to certain levels as needed such as from zero to 100% of the typical tungsten levels.

20 In one embodiment, the catalyst carrier is largely free from the presence of tungsten. In another embodiment, the catalyst is largely free of tungsten. In one embodiment, the catalyst carrier is largely free from the presence of tungsten to an amount of less than about 1% by weight of the total catalyst carrier.

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“Significantly free” expressly permits trace amounts of the corresponding substance to be indicated either singly or in combination of two or more, such as tungsten or iron, and is not limited to a specific exact value and may include values ​​that differ from the specified. In one embodiment, "substantially free" expressly permits trace amounts of tungsten by less than about 5%, by less than about 0.5%, and by less than about 0.1%, either individually or in combination .

“Significantly free” expressly permits corresponding trace amounts of a substance referred to as tungsten but does not require the presence of the indicated substance, such as tungsten.

It should be realized that such designs of a low-weight silica form can be used to reduce the volatility of molybdenum in the previous examples to reduce the volatility of other materials and materials such as, but not limited to, vanadium oxide, tungsten oxide, bismuth oxide, lead oxide, and the like. , either individually or in combination with two or more of them.

The approximation language may, according to the user in the present application, be applied to the rest of the specification and claims, to designate any quantitative or qualitative representation that will vary in a permissible manner without entailing

A change in the primary function to which it relates. Therefore, the adjusted value with an expression like "less than about"

15th or “significantly free” should not be limited to a specified exact value and may include values ​​other than the specified value. In at least some examples, the approximation language can correspond to

to the accuracy of the instrument for measuring value. Further, “NOx removal or reduction” may be used in combination with the term and includes a varying amount of NOx removal and should not be limited to a specified exact value and may include values ​​that differ from the specified value.

20 phosphate and tungsten: In other embodiments, the catalyst carrier has more than a trace of tungsten, that is, the catalyst carrier is not significantly free from the presence of tungsten. The level of tungsten can be reduced by at least 60% compared to conventional catalyst support materials and catalyst. Levels of tungsten can be reduced by at least 35% compared to conventional catalyst support materials.

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And the museum is gone. Levels of tungsten can be reduced by at least 10% compared to conventional catalyst support materials and catalysts.

In one embodiment, the catalyst carrier material had a mole ratio of phosphorus to tungsten of about 0.2:1 or greater, the resulting catalyst showed low oxidation of SO2

5 without much lower transformation of NOx. In some embodiments, phosphate is added in an amount to achieve a molar ratio of phosphorus to tungsten in a range of about 0.2:1 to about 4:1. Similarly, when both tungsten and molybdenum are present, phosphate is added in levels to achieve a molar ratio from phosphorus to tungsten plus molybdenum of about 0.2:1 or greater, and in some embodiments, at levels to achieve a ratio

10 The mol from phosphorus to tungsten plus molybdenum in a range that ranges from about 0.2:1 to about 4:1.

In one embodiment, the method also includes step 270 washing and roasting a mixture of -TiO2-MoO3

.SiO2

The invention includes another embodiment of a method for manufacturing a catalyst support material. The method includes: a) 15 introducing anatase titania slurry; b) fusing anatase titania slurry with 1) one or more of the

volatile inhibitors comprising a form of low molecular weight silica; 2) and a main booster

TiO2- to form a mixture of molybdenum oxide comprising the primary promoter

MoO3-SiO2. Low molecular weight silica images include silica images with an estimated average size of less than 4 nM and an average molecular weight of less than 44,000, either as

20 singly or in combination of two or more of them.

The applicant unexpectedly discovered that volatilization inhibitors comprising a low molecular weight form of silica could reduce the volatility of molybdenum compared to conventional methods of a colloidal silica suspension or aqueous slurry of fumed solids. In addition to the above, the applicant also discovered the possibility of lowering tungsten levels or replacing it with molybdenum by

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Use of molybdenum in combination with volatilization inhibitors comprising a low molecular weight form of silica to control the volatility of molybdenum.

It should be understood that the embodiments of the invention include the provision of a group of volatilizers that differ from each other. The group of volatilizers can have diverse properties.

5 Although embodiments of the invention have been described with a volatilization inhibitor comprising low molecular weight silica forms, it should be recognized that such invention embodiments are not limited to merely providing volatilities inhibitors comprising a low molecular weight form of silica and include providing Others are also volatilizers.

In one embodiment, in addition to providing a volatile inhibitor comprising a low molecular weight form of

10 silica, the method furthermore includes providing another volatilization inhibitor that does not comprise a low molecular weight form of silica. Thus, in one embodiment, the total amount of volatilization inhibitor present in the catalyst support material is defined as the sum of the volatilities inhibitors comprising the low molecular weight form of silica and other forms of the volatility inhibitors not including the low molecular weight form of silica.

15th In one embodiment, the volatilization inhibitor comprises a low molecular weight form of silica with greater than 50% of the total volatilization inhibitor contained in the catalyst carrier. In a specific embodiment, a low molecular weight silica form comprising greater than 50% of the total volatilization inhibitor contained in the catalyst carrier that includes one or more low molecular weight silica forms with a weighted size, average size less than 4 nm or average Molecular weight less than 44,000, either

20 individually or in combination with two or more of them.

Although embodiments of the invention have been described with a primary promoter comprising molybdenum oxide, it should be recognized that embodiments of the invention are not limited to simply providing a primary promoter comprising molybdenum oxide and include the provision of other images as well.

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catalyst carrier

The embodiments of the invention also include catalyst support materials. In one embodiment, the catalyst carrier includes: from about 68% to about 44% by weight anatase titania dioxide; It is about 0.1% to about 10% MoO3 by weight; And from about 0.1% to about 10% by weight SiO2 in low molecular weight forms. Low molecular weight forms of SiO2 include one or more silica forms having an estimated mean size of less than 4 nanomolar and mean molecular weight (MW) greater than &gt; 44,000, either individually or in combination of two or more of them as previously discussed In a particular embodiment, the catalytic carrier material optionally comprises from about 0.01 to about 2,5% P.

10

15

In another embodiment, the catalyst carrier comprises from about 68% to about 44% by weight anatase titania particles, from about 0.2% to about 5 wt% MoO3, and from about 0.2% to about 5 wt% SiO2 in forms with Low molecular weight. Pictures include

low molecular weight SiO2 on one or more forms of silica as previously discussed, either singly or in combination of two or more of them as previously discussed. In a given embodiment, the catalyst carrier optionally comprises from about 0.01 to about 2,5%

.Phosphorus

In one embodiment of the catalyst carrier, SiO2 comprises nanometric particles with diameters less than 4 nm. In another embodiment, the SiO2 in the catalytic carrier comprises low-molecular-weight forms of SiO2 having a molecular weight of less than 44,000. In another embodiment as well, SiO2 comprises in

20 The catalytic carrier contains more than 50% of the silicon atoms in the Q3, Q2, Q1 and Q0 coordinates.

In one embodiment, the catalytic carrier has a BET surface area of ​​at least 50 m2/gas. In another embodiment of the catalytic carrier, SiO2 is present with a partial monolayer value of less than 0.5 before the catalyst carrier is calcined.

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In one embodiment, the catalyst carrier includes particles of anatase titania, a major promoter

phosphorus ratio in moles of ; molybdenum containing the primary promoter . oxide

to molybdenum in a range from about 0:1 to about 4:1, and a volatilization inhibitor comprising low molecular weight silica images. Includes low molecular weight silica images

5 Silica images have an estimated average size of less than 4 nM and an average molecular weight of less than 44,000, either singly or in combination of two or more of them. It should be recognized that such catalyst carriers embodiments include volatilizers comprising one or more of the above described volatilizers, either individually or in combination of two or more of them.

Another embodiment includes the catalyst carrier of the general formula TiO2-MoO3-SiO2, where 10 is largely titanium dioxide in the anatase form and silicon oxide is medium

Weight less than 4 nanomolars and average molecular weight less than 44,000. It should also be realized that the catalytic carrier includes the product of the reaction of titanium anatase with each other, the product of the reaction of MoO3 with each other, the product of the reaction of P with each other, the product of the reaction of S1O2 with each other and also the product of the reaction of the oxides of the elements with each other as a

15th General.

Method of manufacturing the catalyst: Referring to Figure 3, the following describes one of the examples of the invention for the manufacture of a catalyst. Figure 3 represents the flowchart of one of the models of the catalyst manufacturing method and is limited to the arrangement or repetition of the steps unless explicitly indicated otherwise.

The method involves step 310 fusing a mixture of TiO2-MoO3-SiO2 with V2O5 to form a 20-vanadia catalyst. The method may furthermore optionally comprise a 320 step catalytic roasting

vanadia, eg about 800 °C.

Catalyst: Examples of the invention also include catalysts. In one embodiment, the catalyst comprises from about 68% to about 44% by weight of anatase titanium dioxide; From about 0.1% to about 10 wt% MoO3, from about 0.1% to about 10 wt% SiO2, and from about 0.1% to about 10 wt% SiO2

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0.5% to about 3% by weight V2O5. SiO2 comprises a low molecular weight form having an estimated average size of less than 4 nanomolars and an average molecular weight of less than 44,000, either individually or in combination of two or more of them. In a given embodiment, the catalyst optionally comprises from about 0.01 to about 2.5 wt% phosphorus.

5 In one embodiment, the catalyst comprises from about 68% to about 44% by weight anatase titania particles, from about 0.2% to about 5 wt% MoO3, from about 0.1% to about 10 wt% SiO2, and from about 0, 5% to about 3% by weight V2O5. SiO2 comprises low molecular weight silica images having an estimated average size of less than 4 nanomolar and an average molecular weight of less than 44,000, either individually or in combination of two or more of them.

<p>10 In a given embodiment, the catalyst optionally comprises from about 0.01% to about 2.5 wt%</p>

.phosphorus

In another embodiment, the catalyst comprises from about 0.3% to about 1,5 wt% V2O5. In another embodiment as well, the catalyst comprises from about 0.5% to about 0,4% by weight V2O5.

Use of a catalyst: Examples of the invention also include methods for using catalysts to reduce the content of a catalyst

<p>15th nitrogen oxide in a liquid or gas containing nitrogen oxide . The method comprises contacting nitrogen oxide gas or liquid with a catalyst for sufficient time to reduce the level of NOx in a gas or liquid containing nitrogen oxide. In one embodiment, the catalyst comprises from about 68% to about 44% by weight of anatase titanium dioxide, from about 0.1% to about 10% by weight MoO3, from about 0.5% to about 3% by weight V2O5, and from about 0.1 to</p>

<p>20 About 10% by weight SiO2&lt; in low molecular weight images. Low molecular weight forms of SiO2 comprise one or more silica forms with an estimated 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 them. In a given embodiment, the catalyst optionally comprises from about 0.01 to about 2.5 wt.% Phosphorus. It should be understood that the models of the invention include methods of reduction</p>

25 Nitrogen oxide content of a liquid or gas containing nitrogen oxide by gas contact

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or a liquid containing nitrogen oxide with one or more of the catalyst models described above, either singly or in combination of two or more of them. The NOx reducing additives described above may be added in the form of a formed structure such as a monolith or extrusion in a fixed bed reactor or any reaction-regeneration unit systems, to fluidized bed systems, to systems comprising continuous conduction or

<p>5 Circulation of catalysts/additives between reaction zone and regeneration zone, etc. Typical types of circulating bed systems are conventional mobile bed reactor and fluidized bed reactor-regeneration systems. NOx reduction catalyst can be used with an amount of at least 1%; at least 2%; or at least 5%; in an amount of at least about 10% of the renewal stock; or in an amount of at least about 20% of the regeneration stock to reduce the nitrogen oxide content</p>

<p>10 Methods also include the contact of a gas containing nitrogen oxide in the presence of one or more reducing agents such as ammonia, hydrocarbons, hydrogen, carbon monoxide, and the like, either singly or in combination of two or more of them, with one or more More than the catalyst models described in the invention models in various environmental conditions such as complete combustion and low oxygen environmental conditions. Examples of environmental conditions include low oxygen, but</p>

<p>15th Not limited to partial combustion units, partial combustion units, mixed mode, complete combustion units with bad air circulation, etc.</p>

Another embodiment involves contacting a gas or liquid containing nitrogen oxide with a catalyst for sufficient time to reduce the level of NOx in a gas or liquid containing nitrogen oxide, whereby the catalyst is manufactured by:

<p>20 (a) provide anatase titania slurry; and</p>

<p>(b) Fusing an anatase titania slurry with 1) one or more low molecular weight silica forms, 2) and a Molybdenum source, to form a mixture of Ti02-Mo03-SiO2. Low molecular weight silica forms include low molecular weight silica forms</p>

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An estimated mean size of less than 4 nanomolars and an average molecular weight of less than 44,000, either singly or in combination of two or more of them. It should be understood that an embodiment of the invention comprises methods for reducing nitrogen oxide content with a liquid or gas containing nitrogen oxide by contacting a gas or liquid containing nitrogen oxide with one or more of the

<p>5 . Catalysts made by embodiments of the methods described above, either singly or in combination with</p>

two or more of them.

The NOx reducing additives described above may be added in the form of a formed structure such as a monolith or extrusion product in a fixed bed reactor or any conventional reactor-regeneration systems, to fluidized bed systems, to systems comprising continuous or cycling of catalysts/additives between a zone Interaction and area

<p>10 renewal, and the like. Typical types of circulating bed systems include conventional mobile bed reactor and fluidized bed reactor-regeneration systems. NOx reduction catalyst can be used with an amount of at least 1%; at least 2%; or at least 5%; in an amount of at least about 10% of the renewal stock; or in an amount of at least about 20% of the regeneration stock to reduce nitrogen oxide content</p>

Examples of methods also include contacting a gas containing nitrogen oxide in the presence of an agent

<p>15th Reduce such as ammonia, hydrocarbons, hydrogen, carbon monoxide, and the like with</p>

One or more catalyst models described in the embodiments of the invention under various environmental conditions such as complete combustion and low oxygen environment conditions. Examples of low oxygen environments include, but are not limited to, partial combustion units, partial combustion units, mixed mode, complete combustion units with poor air circulation, etc.

20 Examples

The following examples illustrate the features of invention models and are not intended to limit the invention to them. Although some parts of the examples 1-12 AH have been formulated in the simple present tense, the examples procedure has been completed and shows the unrestricted differences between the models of this invention compared to the traditional techniques. The volatility of molybdenum was determined by the following method. 0.2 g of . loaded

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Catalyst (0.7-1.2 mm TiO2-SiO2 particle size) by quartz wool in a 4-inch, 3/6-inch OD quartz tube fixed at both ends with open handle hinges. 0.2 g of 255 m2/g added. 1.4-0.7 Alfa-Aesar (gamma alumina (mm particle size) from the opposite end of the tube to prevent cross-contamination. Also attached to a wool stopper

<p>5 Quartz glass. The tube was connected by ball joints to a plug flow reactor. The temperature was increased to 700 °C and the carrier gas of the composition was 10% water vapor, 10% O2, 500 ppm NO, and 500 ppm NH3, the N2 balance was passed over the catalyst into the alumina layer. After 2 hours, the catalyst was cooled down and the alumina layers were applied. The catalyst was removed from one end of the tube and alumina was removed from the other end to prevent cross-contamination. Then each sample was thawed</p>

<p>10 Powder using HF and analyzed separately using ICPOES (Inductively</p>

For Coupled Plasma Optical Emission Spectroscopy content

molybdenum. The sublimated molybdenum of the catalyst was calculated by dividing the amount of molybdenum by alumina by the molybdenum yield present in the titania and alumina bearing materials. The mass balance of the experiment was calculated by dividing the molybdenum yield 15 detected in titania and alumina bearing materials after hydrothermal treatment by the amount of molybdenum measured in titania carrier before hydrothermal treatment.

DeNOx transformation was determined using a catalyst in powder form without additional formation. A 3/6 inch quartz reactor retains 0.2 g of catalyst borne on glass wool. The feed composition is 1,000 ppm O2, 5% NO, and 5% H2O, varying amounts of NH3 and 20 range from 0 to 1,200 ppm, and N2 balance. The NO shift was measured at 250, 350, and 450 m

at atmospheric pressure and was recorded as a function of the increasing partial pressure of ammonia in the reactor feed stream. The reactor effluent was analyzed using an infrared detector to determine NO shift and slippage

.NH3

The oxidation of SO2 was determined using a catalyst in powder form without additional formation. A 25 quartz 3/6" reactor retains 0.2 g of a glass wool-mounted catalyst. Nutrition formula is 500 parts

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In pM SO2, and 20% O2, N2 balance. The space velocity was calculated to be 24.5 L/gas.catalyst.hr under ambient conditions. Transformation data was recorded at 550 °C.

example 1

5 An embodiment disclosed in the present application and/or the concept(s) of the invention to be protected was prepared in the following manner. A 370,7 g sample of anatase slurry was heated

Water-soluble titanium hydrolysate (28,3% solids), produced by the sulfate process (trade name - Gl from Millennium Inorganic Chemicals), to 80°C via a temperature-controlled hot plate, and the temperature maintained Heat at 80 °C over the course of the preparation pH adjusted to 4 using ammonium

<p>10 dilute hydroxide. A dilute solution (1 wt% SiO2) of sodium silicate was prepared by adding 1.7 g of 24,4–4011 (wt% sodium silicate Inobond Na as SiO2) to 46.4 g of deionized water. 20 g (base as received) Dowex™ 650CH™ strong acid ion-exchange resin was placed in a burette column. (Image of Dowex™ 650C H exchange resin was used.</p>

<p>15th The ion-exchange resin is shown in the following examples and is available from Dow Chemical US, Company). The dilute silicas solution was added through a column containing ion-exchange resin to the slurry at a rate of 5 ml/min. After complete addition, the ion- ion-exchange resin was rinsed off. exchange resin in the column with 10 mL of deionized water added at a rate of 5 mL/min to the titania slurry.</p>

<p>20 pH again to 4 with ammonium hydroxide and left to react for</p>

20 Accurate. A second solution was prepared by dissolving 3.86 g of ammonium heptamolybdate and 0.55 g of 65% phosphoric acid in 20 ml water. This solution was added to the slurry via an ion exchange column at a rate of 5 ml/min, and after the addition was completed the pH of the mixture was adjusted to 4 with dilute ammonium hydroxide and

25 Leave it to react for 10 minutes. The mixture was filtered and rinsed with 1.0 L of deionized water

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deionized water, dried at 105°C, and then calcined at 530°C for 8 hours. The target loading of the catalytic carrier is 0.5 wt% SiO2, 0.15 wt% Phosphorus, and 2 wt% molybdenum.

Prior to the volatility studies, 1,3 wt% vanadia was added to the sample by the . method

<p>5 next. A 20 g sample of the prepared carrier was sintered in 50 mL of water. To this, a fifth (0.288 [V2O5] vanadium pentoxide g) was added</p>

and 0.222 ([HOCH2CH2NH2] monoethanolamine g) and the mixture was heated to 80 °C, the pH was adjusted to 6 with ammonium hydroxide and the mixture was left to stir for 15 min. The solids were separated by filtration,

<p>10 It was dried at 100°C for 8 hours, and roasted at 800°C for 8 hours in air.</p>

Before the DeNOx test and the measurement of SO2 oxidation, 0,4% vanadia was added to the sample by the following method. A 20 g sample of the prepared carrier was sintered in 50 mL water. To this, a fifth (0.164 g) vanadium pentoxide was added.

<p>15th and 0.154 g (monoethanolamine) and the temperature of the mixture was raised to 80 °C. The pH was adjusted to 6 with ammonium hydroxide and the mixture was left to stir for 15 min. The solids were separated by filtration, and dried at 100 °C for 15 min. 8 hours, and roasted at 800 °C for 8 hours in air.</p>

Example 2

<p>20 In the second embodiment of the method, the order of addition of silica, molybdenum and phosphorus solutions was reversed so that molybdenum and phosphorus solutions were added through an ion exchange column before the silica solution. vanadia was added as described in Example 1.</p>

Comparative example 1

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A 440.0 g sample of a water-soluble anatase titanium slurry (23.2% solids) was heated to 80 °C via a temperature-controlled hot plate and the temperature was maintained throughout the preparation. The molybdenum solution was prepared by dissolving 4.84 g of ammonium heptamolybdate in 100 ml of water and this solution was added directly to the

<p>5 Malt. The pH was adjusted to 5 with ammonium hydroxide and left to mix for 10 minutes. The mixture was filtered, dried at 105 °C, and then calcined at 530 °C for 8 h. The target loading is 2% by weight Mo. vanadia was added as described in Example 1.</p>

Comparative example 2

<p>10 A carrier was prepared as described in Comparative Example 1 except that the washed filtrate was added with 1 liter of deionized water to remove associated dissolved ions such as ammonia prior to drying and calcining.</p>

Target loading is 2% wt molybdenum, vanadia was added as described in Example 1.

15

Example 3a

A 63.3 g sample of a water-soluble anatase titanium slurry (28.8% solids) was heated to 80 °C via a temperature-controlled hot plate and the temperature was maintained throughout the preparation. The molybdenum solution was prepared by Dissolved 1.64 g of

20 ammonium heptamolybdate in 20 mL of water. This solution was added to the slurry. After addition was completed, the pH of the mixture was adjusted to 5 using dilute ammonium hydroxide solution and left to react for 10 minutes. A dilute solution (1 wt% SiO2) of sodium silicate was prepared by adding 0.65 g of Inobond Na 4011 (24,4 wt% sodium silicate) to 24.1 g of deionized water.

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deionized water. 10 g of a portion (base as received) of strong acid ion exchange resin (Dowex™ 650C H) was weighed and placed in a burette column. The dilute silicas solution was added through a column containing ion exchange resin resin to the slurry at a rate of 10 mL/min The column was then rinsed with 5 10 mL deionized water at a feed rate of 10 mL/min The pH was adjusted

pH again to 5 with ammonium hydroxide and left to react for 20 min. The mixture was filtered, rinsed with 500 ml deionized water, dried at 105 °C, and then calcined at 530 °C for 8 h. The target loading is 0.5 wt% SiO2, and 2 wt% Mo. vanadia was added as described in Example 1.

10 example 3b

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

The volatility test results are presented in Table 1 below:

15th Table 1

<tr><td><p>Mo . lost</p></td><td><p>Mo</p><p>detained</p></td><td><p>balance</p><p>Bloc</p></td><td><p>Mo on alumina</p></td><td><p>Mo on</p><p>The catalyst bled after the test</p></td><td><p>Mo on</p><p>Al-Muhafaf Azat before</p><p>the test</p></td><td><p>Example</p></td></tr><tr><td></td><td></td><td></td><td><p>g</p></td><td><p>g</p></td><td><p>g</p></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td><p>٪3,70</p></td><td><p>٪48,30</p></td><td><p>٪44,00</p></td><td><p>0،07</p></td><td><p>1,62</p></td><td><p>1,41</p></td><td><p>example 1</p></td></tr><tr><td><p>٪8,10</p></td><td><p>٪43،4</p></td><td><p>٪44,00</p></td><td><p>0,12</p></td><td><p>1,64</p></td><td><p>1,46</p></td><td><p>Example 2</p></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr>

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<tr><td><p>٪24,50</p></td><td><p>٪70،2</p></td><td><p>٪44,00</p></td><td><p>0,81</p></td><td><p>1,44</p></td><td><p>2,07</p></td><td><p>Comparative 1</p></td></tr><tr><td><p>٪15,60</p></td><td><p>٪64,20</p></td><td><p>٪105,80</p></td><td><p>0,33</p></td><td><p>1,78</p></td><td><p>1,46</p></td><td><p>comparative example</p></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td><p>2</p></td></tr><tr><td><p>٪7,40</p></td><td><p>٪42,10</p></td><td><p>٪111,00</p></td><td><p>0,18</p></td><td><p>1,68</p></td><td><p>1,62</p></td><td><p>Example 3a</p></td></tr><tr><td><p>٪8,20</p></td><td><p>٪43,60</p></td><td><p>٪46,00</p></td><td><p>0,12</p></td><td><p>1,62</p></td><td><p>1,46</p></td><td><p>Example 3a</p></td></tr><tr><td><p>٪5,50</p></td><td><p>٪44,50</p></td><td><p>٪100,50</p></td><td><p>0,11</p></td><td><p>1,64</p></td><td><p>1,44</p></td><td><p>Example 3a</p></td></tr><tr><td><p>٪8,50</p></td><td><p>٪43,50</p></td><td><p>٪101,50</p></td><td><p>0,13</p></td><td><p>1,68</p></td><td><p>1,48</p></td><td><p>Example 3a</p></td></tr><tr><td><p>٪7,80</p></td><td><p>٪42,40</p></td><td><p>٪102,10</p></td><td><p>0,15</p></td><td><p>1,63</p></td><td><p>1,44</p></td><td><p>Example 3a</p></td></tr><tr><td><p>٪8,30</p></td><td><p>٪43,70</p></td><td><p>٪100,50</p></td><td><p>0,13</p></td><td><p>1,43</p></td><td><p>2,05</p></td><td><p>Example 3a</p></td></tr><tr><td><p>٪8,60</p></td><td><p>٪43،2</p></td><td><p>٪100,00</p></td><td><p>0,13</p></td><td><p>1,74</p></td><td><p>1,42</p></td><td><p>example 3b</p></td></tr><tr><td><p>٪8,00</p></td><td><p>٪44,00</p></td><td><p>٪101,50</p></td><td><p>0،12</p></td><td><p>1,66</p></td><td><p>1,47</p></td><td><p>example 3b</p></td></tr><tr><td><p>٪6,20</p></td><td><p>٪41,60</p></td><td><p>٪102,80</p></td><td><p>0,18</p></td><td><p>1,74</p></td><td><p>1,4</p></td><td><p>example 3b</p></td></tr><tr><td><p>٪8,30</p></td><td><p>٪43,70</p></td><td><p>٪105,10</p></td><td><p>0،13</p></td><td><p>1,43</p></td><td><p>1,46</p></td><td><p>example 3b</p></td></tr><tr><td><p>٪6,10</p></td><td><p>٪41،4</p></td><td><p>٪101,50</p></td><td><p>0,18</p></td><td><p>1,62</p></td><td><p>1,45</p></td><td><p>example 3b</p></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td><p>٪8,40</p></td><td><p>٪43,10</p></td><td><p>٪102,20</p></td><td></td><td></td><td></td><td><p>Example 3</p></td></tr>

The comparative amplitude 2 for comparative example 1 shows the advantages of removing associated ions by using a washing step with 10 times the excess of deionized water. The aforementioned evidence illustrates a feature of an embodiment of the invention that includes molybdenum retention. Example 1 shows a significant additional attenuation of molybdenum's volatility. Further to the above, comparison of Example 1 with Example 2 shows that the volatility of molybdenum is at least partially related to or influenced by the order of addition of silica versus molybdenum and phosphorus using the ion exchange column. Example 3 represents 11 iterations for both the preparation method and the volatility test. These results demonstrate the diversity of the assay, as well as the insignificance of the order of addition for formulations comprising only molybdenum and silica. Additionally, iterations show that this method

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Simple to prepare are also effective in reducing the volatility of molybdenum relative to the comparative examples.

example 4

To illustrate the effect of increasing the silica content on the volatility of molybdenum, 5 catalyst support materials were prepared as described in Example 3b except for increasing the addition of the target silica loading to 0.75% (Example 4a) and 1.0% (Example 4b). vanadia as described in Example 1.

Comparative example 3

To illustrate the unexpected advantage of adding silica through an ion exchange column, a catalyst support material was prepared compared to using colloidal silica. has been heated

162.0 g of a water-soluble anatase titanium slurry (28.6% solids) to 80°C via a temperature-controlled hot plate and the temperature maintained throughout the preparation. The molybdenum solution was prepared by dissolving 1, 64 g of ammonium heptamolybdate in 20 mL of water.This solution was added to the slurry.After complete

15th In addition, the pH of the mixture was adjusted to 5 with dilute ammonium hydroxide and left to react for 10 minutes. A colloidal dispersion of silica (trade name Ludox AS-30-Grace Davison AS-30 solids) was diluted by mixing 1 g with 24 g of deionized water, and 25 ml was added to the titania slurry. The pH was adjusted. pH again to 5 with ammonium hydroxide and left

20 To react for 20 minutes. The mixture was filtered, rinsed with 500 ml deionized water, dried at 105 °C, and then calcined at 530 °C for 8 h. The target loadings are 0.5 wt% (SiO2), and 2 wt% Mo. vanadia was added as described in Example 1.

Comparative example 4

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To illustrate the unexpected advantage of adding silica through an ion exchange column, a catalyst support material was prepared compared to using fumed silica. 162.0 g of a water-soluble anatase titanium slurry (28.6% solids) was heated to 80 °C via a temperature-controlled hot plate and the temperature was maintained throughout

5 preparation. The molybdenum solution was prepared by dissolving 1.64 g of ammonium heptamolybdate in 20 ml water. This solution was added to the slurry and after addition was completed, the pH of the mixture was adjusted to 5 with dilute ammonium hydroxide solution and left to react for 10 minutes. A slurry was prepared from fumed silica (trade name - 200 Aerosil from Evonik) by adding 0.25 g to 25 ml and adding

10 This is for titania. The pH was adjusted back to 5 with ammonium hydroxide and left to react for 20 min.

The mixture was filtered, rinsed with 500 ml deionized water, dried at 105 °C, and then calcined at 530 °C for 8 h. The target loadings are 0.5% by weight SiO2, and 2% by weight molybdenum. . has been added

15th vanadia as described in Example 1.

example 5

To demonstrate the effect of adding silica and molybdenum together through an ion exchange column, the preparation was modified in the following manner.

A 370.7 g sample of a water-soluble anatase titanium slurry (28.3% solids) was heated from 20 to 80 °C via a temperature-controlled hot plate and kept at a temperature of 370,7 g.

Heat throughout preparation. The pH was adjusted to 5 using dilute ammonium hydroxide solution. 3 A dilute solution (1 wt% SiO2) of sodium silicate was prepared by adding 1.7 g of 24,4–4011 (wt% sodium silicate Inobond Na as iO22) to 46.4 g of deionized water. 3 86gm of

٤٨١٤

-٣٤-

ammonium heptamolybdate to a silica solution. A 20 g portion (basic as received) strong acid ion-exchange resin (Dowex™ 650C H-form) was weighed and placed in a burette column. A dilute silicas and molybdenum solution was added through a column containing ion exchange resin to slurry at a rate of 5 ml/min. Adjusted

5 pH again to 5 with ammonium hydroxide and left to react for 20 min. The mixture was filtered, rinsed with 1.0 L of deionized water, dried at 105 °C, and then calcined at 530 °C for 8 h. The target loadings are 0.5% by weight SiO2. and 2% by weight. molybdenum vanadia was added according to the method described in Example 1.

10 Example 8a

To show that molybdenum and silica can be added in a number of effective ways in reducing molybdenum's volatility, the method of preparation has been changed in the following manner.

A 370.7 g sample of a water-soluble anatase titanium slurry (28.3% solids) was heated to 80 °C via a temperature-controlled hot plate and kept at a temperature of 370,7 g.

15th Heat throughout preparation. molybdenum was incorporated into the slurry to achieve 0,5 wt% loading

molybdenum by adding 0.42 g of ammonium hepta molybdate. The pH was adjusted to 5 using dilute ammonium hydroxide. The dilute solution (1 wt% SiO2) of sodium silicate was prepared by adding 1.7 g of 401.1-Inobond Na (24,4 wt% sodium silicate) to 46.4 g of deionized water.

To the ammonium heptamolybdate solution was added 2,78 g. deionized water 20

silica to a target ratio of 1,5% molybdenum and to make a total molybdenum loading of a 2 wt% carrier. A 20 g portion (base as received) of strong acid ion-exchange resin (Dowex™ 650C H-photo) was weighed and placed in a burette column. The dilute silica and molybdenum solution was added through a column containing

25 Ion exchange resin to the slurry at a rate of 5 ml/min. The pH was adjusted once

٤٨١٤

-٣٥-

further to 5 with ammonium hydroxide and left to react for 20 minutes. The mixture was filtered, rinsed with 1.0 L of deionized water, dried at 105 °C, and then calcined at 530 °C for 8 h.

The target loadings are 0.5% by weight SiO2, and 2% by weight molybdenum, which were carried out

5 In which 0.5 wt% molybdenum was added directly to the slurry and 1.5 wt% silica solution was added through an ion exchange column. vanadia was added as described in Example 1.

Example 8b

A catalyst support material was prepared as described in Example 8a10 except that 1.0 wt% molybdenum was added directly to the slurry and 1.0 wt% silica solution was added through an ion exchange column for a total of 2 wt% of

molybdenum added to the carrier. vanadia was added as described in Example 1.

example 8c

15th A catalyst support material was prepared as described in Example 8a except that 1,5 wt% molybdenum was added directly to the slurry and 0.5 wt% silica solution was added through an ion exchange column for a total of 2 wt% of molybdenum

molybdenum added to the carrier. vanadia was added as described in Example 1.

20 Example 7a

To show that phosphorus has no effect on reducing the volatility of molybdenum, the following carriers were prepared.

٤٨١٤

-٣٦-

A 346.6 g sample of a water-soluble anatase titanium slurry (27.4% solids) was heated to 80 °C via a temperature-controlled hot plate and the temperature was maintained throughout the preparation. The pH was adjusted to 4 using a dilute ammonium hydroxide solution.The solution of molybdenum and phosphorus was prepared by dissolving

65% phosphoric acid and 0.55 g of ammonium heptamolybdate 5 3.86 g of ammonium heptamolybdate

in 20 ml water. 10 g of a portion (as received base) of strong acid ion exchange resin (Dowex™ 650C H-photo) was weighed and placed in a burette column. The molybdenum and phosphorus solution was added through a column containing ion exchange resin. exchange resin to the slurry at a rate of 5 ml/min

10 The pH was again reduced to 4 with ammonium hydroxide and left to react for 20 minutes.

The mixture was filtered, rinsed with 1.0 L of deionized water, dried at 105 °C, and then calcined at 530 °C for 8 h. The target loadings are 0.15 wt% P and 2 wt% molybdenum. 15 vanadia were added as described in Example 1.

Example 7b

A 346.6 g sample of a water-soluble anatase titanium slurry (27.4% solids) was heated to 80 °C via a temperature-controlled hot plate and the temperature was maintained throughout the preparation. The pH was adjusted to 4 With dilute ammonium 20 hydroxide, a solution of molybdenum and phosphorus was prepared by dissolving

65% phosphoric acid and 0.55 g of ammonium heptamolybdate 3.86 g of ammonium heptamolybdate

in 20 ml water. The molybdenum and phosphorus solution was added directly to the slurry at a rate of 5 ml/min. The pH was adjusted back to 4 with ammonium hydroxide and left to react for 20 min. The mixture was filtered, rinsed with 1.0 L of 25 deionized water, dried at 105 C, and then calcined at

٤٨١٤

-٣٧-

530 °C for 8 hours. Target loadings are 0.15% by weight P and 2% by weight

The results of the volatility test for examples 4-7 and comparative examples 3 and 4 are shown in. molybdenum

Table 2 is as follows:

Table 2

<tr><td><p>Mo . lost</p></td><td><p>Mo</p></td><td><p>balance</p></td><td><p>Mo on</p></td><td colspan="2"><p>Mo on</p></td><td><p>Mo on</p></td><td><p>Example</p></td></tr><tr><td></td><td><p>detained</p></td><td><p>_The٪_cutNS_NSThe_NSWeight</p></td><td><p>alⁿu^gm^WLi^NSna^٪</p></td><td colspan="2"><p>_The٪_NS NS_NSThe_NSAnd_fizzZen_NS</p></td><td><p>The^٪NS ^NSNS^TheNS^Andfizz^ZenAccept</p></td><td></td></tr><tr><td><p>٪5,6</p></td><td><p>٪44,20</p></td><td><p>102,7</p></td><td><p>0,11</p></td><td colspan="2"><p>1,6</p></td><td><p>1,68</p></td><td><p>Example 4a</p></td></tr><tr><td><p>٪4,4</p></td><td><p>٪45,10</p></td><td><p>102_٪,₀4</p></td><td><p>0,1</p></td><td colspan="2"><p>1,64</p></td><td><p>1,64</p></td><td><p>Example 4b</p></td></tr><tr><td><p>٪18,30</p></td><td><p>٪63,70</p></td><td><p>104_٪,₀5</p></td><td><p>0,34</p></td><td colspan="2"><p>1,75</p></td><td><p>2</p></td><td><p>Comparative example 3</p></td></tr><tr><td><p>٪15,00</p></td><td><p>٪65,00</p></td><td><p>106_٪,₀1</p></td><td><p>0,32</p></td><td colspan="2"><p>1,61</p></td><td><p>1,47</p></td><td><p>Comparative example 4</p></td></tr><tr><td><p>٪3,1</p></td><td><p>٪48,40</p></td><td><p>40,_٪6₀0</p></td><td><p>0,05</p></td><td colspan="2"><p>1,54</p></td><td><p>1,61</p></td><td><p>Example 5</p></td></tr><tr><td><p>٪3,0</p></td><td><p>٪47,00</p></td><td><p>103,_٪8</p></td><td><p>0,08</p></td><td><p>0,42</p></td><td></td><td><p>1,41</p></td><td><p>Example 8b</p></td></tr><tr><td><p>٪4,0</p></td><td><p>٪48,00</p></td><td><p>104_٪,₀2</p></td><td><p>0,06</p></td><td><p>0,4</p></td><td></td><td><p>1,4</p></td><td><p>Example 6c</p></td></tr><tr><td><p>٪4,6</p></td><td><p>٪45,20</p></td><td><p>44,_٪1₀0</p></td><td><p>0,04</p></td><td><p>0,62</p></td><td></td><td><p>1,43</p></td><td><p>Example 8 d</p></td></tr><tr><td><p>٪12,0</p></td><td><p>٪66,00</p></td><td><p>100,_٪5</p></td><td><p>0,23</p></td><td colspan="2"><p>1,86</p></td><td><p>1,4</p></td><td><p>Example 7a</p></td></tr><tr><td><p>٪4,8</p></td><td><p>٪40,40</p></td><td><p>100_٪,₀5</p></td><td><p>0,14</p></td><td colspan="2"><p>1,74</p></td><td><p>1,47</p></td><td><p>Example 7b</p></td></tr>

5 The results of example 4 suggest that increasing the content of silica by₀The_٪The carrier material improves the retention of molybdenum. Comparative Examples 3 and 4 show that neither fumigated nor colloidal silica added to the catalyst carrier preparation had any measured effect on the volatility of molybdenum in contrast to that shown by the improvement achieved by adding silica through an ion exchange column. . Examples 5 and 8 show that molybdenum can be added in any

10 Combination by addition directly and via an ion exchange column in combination with silica while efficiency is maintained in reducing the volatility of molybdenum. Examples 7a and 7b show some apparent reduction in the volatility of molybdenum induced by addition of phosphorus and molybdenum through ion exchange versus direct addition to the slurry, but this improvement is not to the same extent as that induced by SiO2 and molybdenum alone. in a

15th Finally, compare Example 3a and 3b (SiO2 added only) and Example 7 (phosphorus added only)

٤٨١٤

-٣٨-

With examples 1,5, and 8 (Si and phosphorus both added to the carrier preparation) it is suggested that the improvement in molybdenum retention induced by the combination of Si and phosphorus is an additive.

Example 6a

5 A catalyst support was prepared, as described in Example 2 except that 0.73 g of 65% phosphoric acid was added to achieve a 0.20 wt% loading of phosphorus.

example 6b

A catalyst support material was prepared as described in Example 2 except that 0.42 g of 65% phosphoric acid was added to achieve a 0.25 wt% loading of phosphorus. 0,4% of vanadia was added in each case as described in

Example 1.

The performance of the prepared catalysts in Examples 2, 3a, 6a, and 6b is compared in Figure 4. Although it appears that the addition of 0.15 wt% phosphorus primarily reduces both the total NOx conversion and that at 10 ppm slip, Since the phosphorus increases to 0.2% 15 wt% and 0.25% wt% the maximum NOx conversion and NOx conversion at 10 ppm slip increase as well. Such results are unexpected as it is generally accepted in the field that phosphorus is a toxin for NOx conversion. And, although some disclosures claim that phosphorus can be added to levels where NOx conversion levels are not compromised (eg, see US Patent 2010100163442, Kato et al.), prior art has not disclosed

20 or it is suggested that phosphorus can actually increase NOx conversion as described above. The data from Figure 4 helps to form the values ​​listed in the tables below. The “NOx conversion at 10 ppm slip” is calculated as the measured value while the trend line cuts a 10 ppm ammonia slip due to the increase in the partial pressure of ammonia in the reactor. "Maximum ." is specified

٤٨١٤

-٣٩-

NOx conversion as the maximum conversion value when the partial pressure of ammonia is increased from 0 to 1,200 ppm.

Table 3

<tr><td><p>oxidation</p><p>SO2</p></td><td colspan="2"><p>Max conversion of NOx</p></td><td colspan="2"><p>NOx conversion at 10 ppm slip</p></td><td><p>download</p><p>phosphorus</p></td><td><p>Example</p></td></tr><tr><td><p>at 55</p></td><td><p>at 45 pm</p></td><td><p>at 35 pm</p></td><td><p>at 45 pm</p></td><td><p>at 35 pm</p></td><td></td><td></td></tr><tr><td><p>%NS</p></td><td><p>٪</p></td><td><p>٪</p></td><td><p>٪</p></td><td><p>٪</p></td><td><p>٪</p></td><td></td></tr><tr><td><p>10</p></td><td><p>47,8</p></td><td><p>47،5</p></td><td><p>77,4</p></td><td><p>42,5</p></td><td><p>0,15</p></td><td><p>1</p></td></tr><tr><td><p>10,5</p></td><td><p>48,1</p></td><td><p>72,4</p></td><td><p>83,7</p></td><td><p>34,3</p></td><td><p>0,15</p></td><td><p>2</p></td></tr><tr><td><p>15,4</p></td><td><p>47,4</p></td><td><p>75,6</p></td><td><p>56,4</p></td><td><p>50,4</p></td><td><p>0</p></td><td><p>3a</p></td></tr><tr><td><p>12,4</p></td><td><p>44,4</p></td><td><p>62,1</p></td><td><p>64,6</p></td><td><p>86,7</p></td><td><p>0,15</p></td><td><p>7a</p></td></tr><tr><td><p>4,7</p></td><td><p>100</p></td><td><p>68,1</p></td><td><p>45</p></td><td><p>72,7</p></td><td><p>0,15</p></td><td><p>7b</p></td></tr><tr><td><p>11,3</p></td><td><p>100</p></td><td><p>61,7</p></td><td><p>45,4</p></td><td><p>73,2</p></td><td><p>0,2</p></td><td><p>6 a</p></td></tr><tr><td><p>6,2</p></td><td><p>68,5</p></td><td><p>40,8</p></td><td><p>53,3</p></td><td><p>61,3</p></td><td><p>0,25</p></td><td><p>6b</p></td></tr>

Comparing the results from Example 3a to those from Examples 1, 2, 7a, 7b, 6a, and 6b shows that,

5 As mentioned in the previous art, adding phosphorus to the SO2 catalytic carrier reduces the oxidation. According to the above, the data also surprisingly demonstrates that the total NQX conversion and that at 10 ppm ammonia slip increases when the phosphorus loading is increased from 0.15 to 0.25 wt% for the reactor tests carried out at 350.

However, it appears to pass a maximum at 0.20 wt% of phosphorus for the 10 reactor tests carried out at 450°C. Examples 7a and 7b show that further increases in potency in the absence of silica and that the degree of NOx conversion at 10 ppm ammonia slip can be affected by the manner in which molybdenum and phosphorus are added to the carrier, either through the ion exchange column (7a) or directly to Malta (7b).

٤٨١٤

-٤٠-

Example 4a

A catalyst support was prepared as described in Example 3a except that 0.58 g of 65% phosphoric acid was added to achieve 0.15 wt% phosphorus loading.

example 4b

5 A catalyst support was prepared as described in Example 3a except that 0.73 g of 65% phosphoric acid was added to achieve 0.20 wt% phosphorus loading.

example 4c

A catalyst support was prepared as described in Example 3a except that 1.10 g of 65% phosphoric acid was added to achieve 0.30 wt% phosphorus loading.

10 example 4d

A catalyst support was prepared as described in Example 3a except that 1.47 g of 65% phosphoric acid was added to achieve 0,40 wt% phosphorus loading.

In each case, 0,4% vanadia was added as described in Example 1.

Example 10a

15th To determine whether the efficacy of phosphorus in increasing NOx conversion and decreasing SO2 oxidation is limited when added in the carrier preparation, the catalyst was modified to combine small amounts of phosphoric acid with vanadium pentoxide.

A 20 g sample of the carrier prepared as described in Example 1 was converted to a slurry in 50 mL water.

20 To this, pentoxide (0.164 g vanadium) and 0.154 g (monoethanolamine) were added and the temperature of the mixture was raised to 80 °C to achieve the target V2O5 loading of

٤٨١٤

-٤١-

0,4%. The phosphorus was added to the slurry by introducing 0.037 g of 65% H3PQ4 solution to achieve a target loading of 0.05% in addition to the 0.15% already present on the carrier.

The pH was adjusted to 6 with ammonium hydroxide and mixture 5 was left to stir for 15 min. The solids were separated by filtration methods, dried at 100 °C for 8 h, and calcined at 800 °C for 8 h in air.

Example 10b

The catalyst was prepared in the same manner as described in Example 10a except that 0.074 g of 65% phosphoric acid was added to achieve a target loading of 0.1% by weight phosphorus 10 in addition to the 0.15% already present on the carrier.

The reactor performance from Examples 4 and 10 is illustrated in Table 4 below.

Table 4

<tr><td><p>oxidation</p><p>SO2</p></td><td colspan="2"><p>Max conversion of NOx</p></td><td colspan="2"><p>NOx conversion at 10 ppm slip</p></td><td><p>Total download</p><p>phosphorus</p></td><td><p>Example</p></td></tr><tr><td><p>at 55</p></td><td><p>at 45</p></td><td><p>at 35</p></td><td><p>at 45</p></td><td><p>at 35</p></td><td></td><td></td></tr><tr><td><p>٪</p></td><td><p>٪</p></td><td><p>٪</p></td><td><p>٪</p></td><td><p>٪</p></td><td><p>٪</p></td><td></td></tr><tr><td><p>P6M,W2E1</p></td><td><p>100</p></td><td><p>75,5</p></td><td><p>67,4</p></td><td><p>81,5</p></td><td><p>0,15</p></td><td><p>4A</p></td></tr><tr><td><p>11,7</p></td><td><p>100</p></td><td><p>62,4</p></td><td><p>80,5</p></td><td><p>81,5</p></td><td><p>0,2</p></td><td><p>4b</p></td></tr><tr><td><p>10,4</p></td><td><p>44,4</p></td><td><p>76,5</p></td><td><p>54,6</p></td><td><p>54,6</p></td><td><p>0,3</p></td><td><p>4 c</p></td></tr><tr><td><p>10,1</p></td><td><p>40,5</p></td><td><p>84,8</p></td><td><p>52,2</p></td><td><p>41,1</p></td><td><p>0,4</p></td><td><p>4 d</p></td></tr><tr><td><p>11</p></td><td><p>44,3</p></td><td><p>74,4</p></td><td><p>62,8</p></td><td><p>70,7</p></td><td><p>0,2</p></td><td><p>10 a</p></td></tr>

٤٨١٤

-٤٢-

<tr><td><p>7,3</p></td><td><p>100</p></td><td><p>84,5</p></td><td><p>50</p></td><td><p>53</p></td><td><p>0,25</p></td><td><p>10b</p></td></tr>

The table shows that when molybdenum and phosphorus are added directly to the carrier (Examples 4A - 4D), the maximum NOx conversion increases initially with phosphorus loading and crosses an optimal limit at about 0.2 wt% of phosphorus loading. As expected, the oxidation of SO2 decreases precipitously. Recurring with increased phosphorus loading. Examples 10a and 10b show that adding 5 phosphorus in two separate steps, ie during the preparation of the carrier with more added during the preparation of the catalyst, is also effective in optimizing NOx conversion with decreases when more phosphorus is added. Comparing Examples 6a, 4a, and 10a shows that there are some apparent differences in the NOx conversion depending on how the phosphorus was added and/or

. molybdenum

10

Example 11

To determine whether improving NOx conversion and quenching SO2 oxidation is only affected by phosphorus or other elements are able to induce the same improvements, sulfur and silica were tested in the same way,

15th Example 11a

A 344.5 g sample of a water-soluble anatase titanium slurry (27.4% solids) was heated to 80 °C via a temperature-controlled hot plate and the temperature was maintained throughout the preparation. The pH was adjusted to 4 Using dilute ammonium hydroxide solution A 20 g portion (base as received) of strong acid 20 ion-exchange resin (Dowex™ 650C H-image) was weighed and placed in a burette column. A solution was prepared by dissolving 3.86 g of ammonium heptamolybdate and 0.84 g of above g ammonium sulfate (NHi^SaQ) in 20 ml water, and the solution was added to the slurry via an ion exchange column at a rate of 5 ml/min. completion

٤٨١٤

-٤٣-

In addition, the pH of the mixture was adjusted to 4 using dilute ammonium hydroxide solution and left to react for 10 minutes. A dilute solution (1 wt% .) was prepared

sodium Inobond Na-4011 by adding 1.7 g of sodium silicate (SiO2 .)

(24,4 wt% silicate as SiO2) to 46.4 g of deionized water 5. A dilute silica solution was added through a column containing ion-exchange resin

exchange resin to the slurry at a rate of 5 ml/min. After the addition was completed, the column ion exchange resin was rinsed off with 10 mL of deionized water added at a rate of 5 mL/min to the titania slurry. The pH was adjusted back to 4 with ammonium hydroxide and left to react for 20 min. The mixture was filtered and rinsed

10 using 1.0 L of deionized water, dried at 105°C, and then roasted at

530 °C for 8 hours. The target loadings are 0.5 wt% S, 0.17 wt% SiO2, and 2 wt% molybdenum. 0,4% vanadia was added as described in Example 1.

Example 11b

The catalytic carrier was prepared as described in Example 11a except that 1.08 15 g of 24.4-4011 (sodium silicate Inobond Na (wt% as SiO2) was added and replaced with perammonium sulfate in molybdenum solution. The target loadings are 0.6 wt% SiO2 and 2 wt% 0,4%.Mo vanadia was added as described in Example 1.

Example 11c

The catalytic carrier was prepared as described in Example 11a except that 0.55 . was added

ammonium sulfate and 0.35 g of above 65% phosphoric acid was added 20 g of

into molybdenum solution. The target loadings of this product were 0.15% by weight

0.5, 8% 0.09, phosphorus wt% SiO2, and 2 wt% SiO2, and 2% wt% 0,4%.Mo vanadia was added as described in Example 1. The test results of the reactor are shown in Table 5 below. Table 5:

٤٨١٤

-٤٤-

<tr><td><p>oxidation</p><p>SO2</p></td><td colspan="2"><p>Max conversion of NOx</p></td><td colspan="2"><p>NOx conversion at 10 ppm slip</p></td><td><p>the average</p><p>and download</p></td><td><p>Example</p></td></tr><tr><td><p>at 55</p></td><td><p>at 45 pm</p></td><td><p>at 35 pm</p></td><td><p>at 45 pm</p></td><td><p>at 35 pm</p></td><td></td><td></td></tr><tr><td><p>_٪NS</p></td><td><p>٪</p></td><td><p>٪</p></td><td><p>٪</p></td><td><p>٪</p></td><td></td><td></td></tr><tr><td><p>13,1</p></td><td><p>100</p></td><td><p>63,2</p></td><td><p>44,6</p></td><td><p>87,7</p></td><td><p>S% 0.17</p></td><td><p>11a</p></td></tr><tr><td><p>10,4</p></td><td><p>100</p></td><td><p>64,4</p></td><td><p>65,6</p></td><td><p>71,2</p></td><td><p>٪0,31</p><p>SiO2</p></td><td><p>11b</p></td></tr><tr><td><p>11,4</p></td><td><p>61,3</p></td><td><p>85,2</p></td><td><p>27,4</p></td><td><p>23,7</p></td><td><p>0.15% P and</p><p>S %0.04</p></td><td><p>11 c</p></td></tr>

The results of Example 11a surprisingly show that the added S is at the same molarity while 0.15% phosphorus also effectively reduces the oxidation of SO2. Adding S in the manner described in Example 11a also appears to improve the NOx transformation.

It should be understood that the addition of sulfur is not limited to a particular sequential order, nor to a certain quantity, and form such as ion exchange unless expressly stated otherwise. It is also surprising that silica has a favorable effect on reducing SO2 oxidation and increasing NOx conversion when silica is added with molybdenum at molarity equivalent to 0.15 wt% phosphorus and through an ion exchange column.

Example data 11a and 11b show that phosphorus is not the only element that can be used 10 to increase the conversion of NOx while reducing SO2 oxidation. Example 11c data show that combining sulfur with phosphorus has a detrimental effect on NOx conversion while also being effective in reducing oxidative stress.

.SO2

Example 12a

A 331.5 g sample of a water-soluble anatase titanium slurry (28.3% solids) was heated from 15 to 80 °C via a temperature-controlled hot plate, and the

٤٨١٤

-٤٥-

temperature throughout preparation. The pH was adjusted to 4 using dilute ammonium hydroxide solution. A dilute solution (1 wt% SiO2) was prepared from

sodium silicate Inobond Na-4011 by adding 1.5 g of sodium silicate

(24.4% by weight as SiO2) to 144.4 g of deionized water.

5 Weigh a 40 g portion (base as received) of strong acid ion-exchange resin (Dowex™ 650C H-photo) and put into a burette column.

The dilute silica solution was added through a column containing ion exchange resin to the slurry at a rate of 5 ml/min.

The pH was adjusted back to 4 with ammonium hydroxide and 10 was left to react for 20 min.

A second solution was prepared by dissolving 7.38 g of ammonium heptamolybdate in 20 ml water. This solution was added to the slurry via an ion exchange column at a rate of 5 ml/min. After addition was completed, the ion-exchange resin was rinsed off the column with 20 mL deionized water added at a rate of 5 mL/min.

15th to titania .

The pH of the mixture was adjusted to 4 using dilute ammonium hydroxide solution and left to react for 10 min. The mixture was filtered, rinsed with 1.0 L of deionized water, dried at 105 °C, and then calcined at 530 °C for 8 h. Target loadings were 1.5 wt% SiO2 and 4% wt SiO2

.Mo 20

Example 12b

The catalytic carrier was prepared as described in Example 12a except that 0.58 g of 65% phosphoric acid was added to the molybdenum solution. Targeted uploads

٤٨١٤

-٤٦-

Of this carrier 0.15 wt%, 1,5 wt% phosphorus, 4% wt% SiO2, phosphorus

.molybdenum

Example 12 c

The catalytic carrier was prepared as described in Example 12a except that 1,12 . was added

5 g of 65% phosphoric acid to molybdenum solution. The target loadings of this carrier were 0.3 wt%, 1.5 wt% phosphorus, 1.5 wt% SiO2, and 4% wt% SiO2.

.molybdenum

Example 12 d

10 The catalytic carrier was prepared as described in Example 12a except that 3.72 g of 65% phosphoric acid was added to the molybdenum solution. The target loadings of this carrier were 1,0 wt%, 1,5 wt% phosphorus, 1.5 wt% SiO2, and 4% wt% SiO2.

.molybdenum

Example 12 AH

15th The catalytic carrier was prepared as described in Example 12a except that 7.44 g of 65% phosphoric acid was added to the molybdenum solution.

The target loadings of this carrier were 2.0 wt%, 1.5 wt% phosphorus, 1.5 wt% SiO2 and 4% wt% Mo. In each case, 0.4 vanadia was added as described in Example 1.

20 DeNOx accelerated transform selection was performed in the following manner. The catalyst was evaluated as a powder without further formation. A 6/3" quartz reactor accommodates 0.1 g of a glass wool-borne catalyst. The feed composition was 1,000 ppm of H2O 5%, O2%, 5%, NO.

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The partial pressure of NH3 was sequentially increased from 700 ppm to 400 ppm and then finally to 1200 ppm with the remainder being N2.

The NO conversion was not measured after achieving the steady state at each NH3 concentration while the reactor temperature was kept at 350°C and the pressure was atmospheric. product has been analyzed

5 Flush the reactor with an infrared detector to determine the NO conversion.

The results of the NOx conversion test and the SO2 oxidation test are shown in Table 8 below.

Table 8

<tr><td><p>oxidation</p><p>So2</p></td><td colspan="3"><p>NOx conversion at 10 ppm slip</p></td><td><p>Total download</p><p>phosphorus</p></td><td><p>Example</p></td></tr><tr><td><p>at 55</p><p>Celsius</p></td><td><p>1200 parts in</p><p>the million</p><p>NH3</p></td><td><p>400 parts</p><p>in a million</p></td><td><p>700ppm</p><p>NH3</p></td><td></td><td></td></tr><tr><td><p>٪</p></td><td><p>٪</p></td><td><p>٪</p></td><td><p>٪</p></td><td><p>٪</p></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td><p>11,1</p></td><td><p>84,8</p></td><td><p>67,6</p></td><td><p>56,4</p></td><td><p>4,04</p></td><td><p>12a</p></td></tr><tr><td><p>4,1</p></td><td><p>76,6</p></td><td><p>75,4</p></td><td><p>58,4</p></td><td><p>0,15</p></td><td><p>12b</p></td></tr><tr><td><p>10,7</p></td><td><p>64,6</p></td><td><p>76,7</p></td><td><p>85,6</p></td><td><p>0,3</p></td><td><p>12 c</p></td></tr>

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<tr><td><p>5,1</p></td><td><p>62,6</p></td><td><p>77,2</p></td><td><p>87,1</p></td><td><p>1,04</p></td><td><p>12 d</p></td></tr><tr><td><p>4,4</p></td><td><p>72,6</p></td><td><p>57,4</p></td><td><p>44,3</p></td><td><p>0,20</p></td><td><p>12 AH</p></td></tr>

4% of molybdenum catalyst loading showed similar trends as observed. The rate of SO2 oxidation in general leads to a reduction with increasing phosphorus loading, and the conversion of NOx at 350 °C surprisingly goes through the most extreme state with increasing phosphorus.

The use of the term "metal" as a catalyst component should be understood as having the same meaning as metal oxide

5 Views as a catalyst unless otherwise noted. For example, "molybdenum as an oxidizer" has the same meaning as "MoO3 as an oxidizer." Rounding language can be applied, according to the user in the current application

In all other specifications and claims, to designate any quantitative or qualitative representation of

would,

It varies in a permissible manner without entailing a change in the basic function to which it relates. Therefore, a value adjusted with an expression such as “about” or numerical range values ​​are not limited to a specific exact value

10 It can include values ​​that are different from the specified value. In at least some examples,

The language of the approximation corresponds to the accuracy of a tool for measuring value. In addition to the above, it is possible to use “slash or ”

"NOx reduction" in combination with the expression, and includes a quantitative variation of the NOK offset and is not limited to a specified exact value and may include values ​​that differ from a specified value.

It will become clear to those experienced in the field that a variety of modifications and changes can be made in a

15th The method and system of the current invention without departing from the spirit or field of the invention. Thus, a currently disclosed and/or patented concept is intended to include modifications and variations that are within the scope of the appended claims and their equivalents.

While currently disclosed and/or protected concepts have been described in detail with respect to a specified number of aspects, it should be recognized that currently disclosed and/or innovative concepts

20 The protection is not limited to those aspects that have been disclosed. Rather, concepts currently disclosed and/or protected may be modified to include any number of variations, changes, substitutions, or equivalent arrangements not described therein but which correspond to the domain of elements

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protection. Additionally, while various embodiments of currently disclosed and/or protected inventive concepts have been described, it should be recognized that aspects of the currently disclosed and/or protected innovative concepts may include some of the embodiments described Just. Accordingly, currently disclosed and/or protected innovative concepts should not be considered to be restricted by description

<p>5 The former are restricted only to the scope of the attached protection elements.</p>

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