SA515360063B1 - Catalyst support materials, catalysts, methods of making them and uses thereof - Google Patents

Abstract

Catalyst support materials, catalysts, methods of making such and uses thereof are described. Methods of making catalyst support material include combining anatase titania slurry with i) a low molecular weight form of silica; and ii) a source of Mo to form a Ti02-Mo03-Si02 mixture. Catalyst support material include from about 86% to about 94% weight anatase titanium dioxide; from about 0.1% to about 10% weight Mo03; and from about 0.1% to about 10% weight SiQ2. Low molecular weight forms of silica include forms of silica having a volume weighted median size of less than 4 nm and average molecular weight of less than 44,000, either individually or in a combination of two or more thereof. Catalyst include such catalyst support material with from about 0.1 to about 3 % weight of V205 and optionally from about 0.01% to about 2.5% weight P.

Description

— \ — Catalyst carriers and catalysts, manufacturing methods and uses

Catalyst support materials, catalysts, methods of making them and uses thereof. In particular, the invention includes embodiments relating to compositions and methods for manufacturing catalyst carriers and catalysts for the reduction of nitrogen oxide content with a nitrogen oxide containing gas or liquid in mobile and stationary applications. Some processes of NOX Al) formed in the combustion gases are known in the field Jie Selective catalytic reduction (SCR) process In this process, nitrogen oxides are reduced by ammonia (or other reducing agent Ji 0 unburned hydrocarbons present in the exhaust gas stream product) in the presence of oxygen and a catalyst for the formation of nitrogen and water. The SCR process is used in the USA; Japan» and Europe to reduce emissions of large utility boilers and other commercial applications. Increasingly, SCR processes are used to reduce emissions in Jie mobile applications in large diesel engines such as those found on ships, diesel locomotives, automobiles and the like. Yo some SCR catalysts are with vanadium oxide, tungsten, molybdenum Ji. 3i , and iron is known to eliminate *0 to 8. However, there is one or ST of limitations as discussed below. The use of a tungsten-containing catalyst may be restricted by price and availability. Molybdenum-containing catalyst systems are restricted due to their relatively high volatility compared to 0 isotopes and the relatively high oxidation accelerator 502 compared to systems containing tungsten.

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- so

. Oxidation of 502 is an issue in stationary DeNOX applications due to the formation of ammonium sulfate

Which causes obstruction and excessive pressure drop in the operation stomach.

sl However, catalyst carriers and catalysts suitable for content reduction are still required

nitrogen oxide with a nitrogen oxide-containing gas or liquid under various conditions. as

0 A method for the manufacture of said catalyst carriers and catalysts and a reduction method is also needed

“nitrogen oxide” content A gas containing nitrogen oxide or catalyst in applications

mobile and fixed.

General description of the invention

The embodiments of the present invention satisfy these and other needs by providing NOX 0 reduction catalysts, methods for manufacturing NOX reduction catalysts, and methods for removing the nitrogen oxide content with liquid or Je

It contains nitrogen oxide using the aforementioned NOX reduction catalysts,

Accordingly, a first aspect of the invention provides a method for manufacturing a catalyst support. What does the method include?

The following: Combine the anatase titania slurry with 1) one or more Molecular Weight 5108 forms

low (Y) and a molybdenum source to form a mixture of TIO2-MoO3-Si02. Yo includes low molecular weight silica forms and average size silica forms estimated at less than

nanomolar and average molecular weight less than WEE individually or in combination of two or

more of them.

A second aspect of the invention provides a method for fabricating a catalyst-bearing Sale. The method includes the following: (a) submission

anatase titania slurry: (b) the incorporation of the anatase titania slurry with 1) one or more low molecular weight Yo form silicas; 1) and a source of molybdenum to form a mixture of

.1102-1/003-2 includes low molecular weight silica forms.

Average Size Estimated Size Less Than ; Nano molar and average molecular weight less than 4,000 5, either as a picture

individually or in combination of two or more of them

A third aspect of the invention provides a catalyst carrier. The catalyst carrier includes from about IAT to about 7 94 by weight of anatase titanium dioxide : from about 0.1 7 to about 7 01 by weight 0/003 : from about 70.1 to Approximately #01 by weight 5102 in low molecular weight forms. Low molecular weight forms of 5102 include silica forms with an average size of 0 estimated at an E < nanomolar size and an average molecular weight of less than WEE 000 individually or in combination of two or more of them. A fourth aspect of the invention provides a method for manufacturing a catalyst carrier. The method includes the following: combining anatase titania slurry with 1) a volatilizer bie comprising form 51168 of low a weight and 1) a primary promoter comprising molybdenum oxide to form 0 The TIO2-Mb-SiO2 mixture includes low molecular weight silica forms 511668 with an estimated average size of less than ; nanomolar and an average molecular weight of less than 4,0005, either singly or in combination of two or more of them. A fifth aspect of the invention provides a method for manufacturing a catalyst carrier. The method includes: a) introduction of anatase titania Lda and b) incorporation of anatase titania Lda with 1) a volatilization inhibitor comprising a Vo form of silica with low Ja gg (Y5). primary promoter incorporating molybdenum oxide to form a mixture of JTIO2-Mb-Si02 containing <i) low molecular weight silica moieties an aaa average silica moiety rated <4 nm and . Less average molecular weight of WEE ee individually or in combination of two or more of them. Yo presents a sixth side of the invention Bale catalyst carrier. The catalyst support material sale includes titanium dioxide jee; A major anatase comprising molybdenum oxide and a volatilization inhibitor comprising a low molecular weight silica form. Low molecular weight images 51108 includes images 51108 with an estimated mean size of less than ; nanomolar and average molecular weight less than WEE ve individually or in combination of two or more Yo's. EAN

A seventh aspect of the invention provides a method for reducing the nitrogen oxide content of a liquid or gas containing oxide 0100960. The method involves contacting a gas or liquid containing nitrogen 56 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 870/7 to about 794 by weight of anatase titanium dioxide ; from 0 about 7009 to about 701 wt 10003: from about 70.5 to about 77 wt 5): and from about 0.1 7 to about 7 01# by weight 5102 in low molecular weight forms. Low molecular weight images 51108 includes images 51108 with an estimated mean size of less than ; nanomolar and average molecular weight less than WEE ve individually or in combination of two or more of them.

Je of a liquid or nitrogen oxide An eighth aspect of the invention provides another method for the reduction of 0 nitrogen content. The method involves contact with a gas or liquid containing . nitrogen oxide containing nitrogen in a NOX-containing gas or liquid with a catalyst for sufficient time to reduce a single oxide level) 1 with anatase titania wherein the catalyst is made by the following: slurry amalgamation, 6 1102 - Lada to form Mo or more Low Molecular Weight 5168 Forms and 7) Source 0 10002-502. Low molecular weight silica forms include silica forms with an estimated average volume of less than UE molar and an average molecular weight of less than 44.0 080, either individually or in combination of two or more of them. A ninth aspect of the invention introduces a catalyst carrier. The catalyst carrier has a general formula of 1102-1/003-5102, wherein titanium dioxide is largely in the form of anatase 0 and silicon oxide is a weighted volume, average volume less than ; Nanomolar and average molecular weight less than EE ven The enclosed figures, which are combined and form an eda of this specification, are included to illustrate and provide an additional ped for the methods and systems of the invention. In addition to the description, the figures serve to explain the principles of the invention. Attributes of one form can be expected to be usefully integrated into other forms without further Yo citation. EAN

h —_ _ Brief Explanation of Drawings JS No. 1 : Flowchart of a conventional method of manufacturing a catalyst support material: Fig. No. Jig : Y Flowchart of a method of manufacturing a catalyst support according to one of the embodiments of the invention: © Fig. ? Jig Flowchart of a method for manufacturing catalysts according to one of the models of the invention: and Figure No. 4: represents a comparative graphic representation of the performance of a sliding catalyst of NH3 versus converting NOX according to one of the models of the invention. To facilitate understanding, similar reference numbers have been used, wherever possible, to allocate similar elements common to figures. A Description 1 to explain: In the following description, it is understood that the terms el AE Jie “outward,” “inward,” and the like are words for the purpose of convenience and are not restricted terms. Led Following is a detailed reference to representative embodiments of the invention, which are illustrated in the accompanying figures and examples. With reference to figures generally, it will be understood that the illustrations are intended to describe a specific embodiment of the invention and are not intended to limit the invention. Where it is indicated that a specific embodiment of the invention includes or consists of at least one element of a group of and combinations thereof, it will be recognized that the embodiment may include or consist of any of the elements of the group, either individually or in combination with any of the other items from the set. Furthermore, when a variable appears more than once in any component or in a Yo formula, its definition at each occurrence will be independent of its definition at each other occurrence. Also, combinations of substituents and/or variants are permitted if these combinations result in independent compounds.

All terms used in the present application shall have their normal meaning unless otherwise indicated as REIN The terms 'catalyst support material' 'particles 5000014' or 'Alla' have the standard meaning ascribed to them in the field .

2 The terms 'active metal catalyst' or 'BEY active' refer to a catalytic component deposited on the surface of a carrier that is supposed to catalyze the reduction of NOx compounds The terms Sad and 'catalytic composition' have the standard meaning ascribed to them in Domain and refers to a combination of catalyst support material and catalyst support material particles based on titania.

Ve Unless otherwise specified, all references to Ve (7) in the present application refer to Ve, by weight. The terms "ag ial" and "loading" refer to the loading of a component on the total catalytic composition. For example, the loading of vanadium oxide on the catalyst is the ratio of the weight of the vanadium oxide to the total weight of the catalyst, including dla assaha titania , vanadium oxide and any other carried metal oxides. Similarly, loading with respect to molar Vo refers to the 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 Li, phosphorus with oxygen. An embodiment of the invention includes a method for manufacturing a catalyst carrier. The method involves incorporating a slurry of 1) ae anatase titania with one or more Low molecular weight Forms 51108 and 100) Molybdenum source to form the 1102-1/002-5102 mixture. Low molecular weight Forms 51/168 includes low molecular weight silica forms of average size estimated at less than a nanomolar volume and average weight Less molecular than WEE, individually or in combination of two or more of them.EAN

—A— catalyst carrier comprising from about 787 to sold) One embodiment of the invention comprises from about 701 0003/1 to about 7 0.1 by weight Titanium dioxide: from about silica 5502 comprises one or more low molecular weight SiO2 moieties of about 7 0 to 7601 with an average estimated size of less than 4 nanomolar and average molecular weight, individually or in a combination of the two WEE ee is less than 0 For the purpose of illustration but not limitation, one embodiment of the invention is compared to methods for manufacturing a catalyst support material with conventional methods. As shown in Figure 1, a conventional method for manufacturing a catalyst support includes step 111 of introducing anatase titania Ld. Step 111 involves adjusting the pH. Step IY includes providing all or 0 to substantially all commercially available silica in the form of preformed 51108 particle ie colloidal, fumed, etc. Step 106060 includes the pH adjustment. The Vor step includes providing tungsten. In contrast to Figure 1, Figure 7 describes an embodiment of the invention for a method for manufacturing catalyst carriers. Figure No.? The flowchart of a model represents a method for fabricating a catalyst support VO by controlling the image and distribution of 511108 with molybdenum The method is not limited to the order or repetition of steps unless noted Asha The method includes step 701 Providing titania slurry 0 Non-exhaustive examples of titania slurries include monoclinic, brookite , anatase rutile , rhomboid Jie water-dispersed powders, and hyperbaric forms such as —PbO2 ani | Similar to ,baddeleyite, cotunnite, rhombic, 0 and cubic phases, either individually or in combination of two or more of them. In one embodiment, step 01 provisioning of the titania slurry includes the provision of anatase titania slurry. Non-exhaustive examples of anatase titania slurries include preformed titanium hydroxide, titanium pass, OXy-hydroxide in the orthotitanic acid position, titanyl sulfate, sulfated titanium dioxide, sulfated titania ‏

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hydrolysate, organo-titanates or titanium dioxide particles either individually or in combination of two or more of them. Although embodiments and examples using anatase titania slurry are described in some instances of description, it must be recognized that the embodiments of the invention are not limited to anatase titania slurry Jam, © to other forms of titania slurry either individually or in combination of two or more of them. Step 771 includes optionally adjusting the pH of the titania slurry in a range of about ? to about 7 as needed. One embodiment includes pH adjustment in a range of about ; to about 0. Another embodiment involves adjusting the pH 011 to about 4. The pH can be adjusted using, for example, but not limited to, diluted ammonium hydroxide 0, alkyl amines such as , di, or tripropyl amine , alkanolamines such as ,mono, di, and triethanolamine, either singly or in combination of two or more of them. Step 7710 includes providing at least some of the low molecular weight form of silica to the titania slurry. An embodiment comprises one or more low molecular weight silica forms with an estimated mean size of less than 4 nM NO and an average molecular weight of less than 55,0060, either individually or in combination of two or more of them. One embodiment of the invention includes a step 7460 optionally adjusting the pH of a J titania slurry with a pH of about * to about 6. The AT embodiment comprises a pH adjustment to a range of about ; To about dado Another example of adjusting the pH to about of The pH can be adjusted using Sie 0 and not limited to, dilute ammonium hydroxide, mono, Ji. alkyl amines mono, di, and triethanolamine, (fi alkanol amines ,di, or tripropylamine either) individually or in combination of two or more of them. In one embodiment, a low molecular weight silica form includes; but not limited to silicic acid (Si(OH)4) Examples of silicic acid include Si(OH)4 generated by Yo ion exchange to any of the cation forms of silica listed in the present application using a resin Exchange EMV E

“yam sabil Je) acidic ion-exchange resin ion-exchange resin ammonium silicate Example, ion exchange for 511085 alkali solutions or solutions which can be supplied either individually or in "silicic 8010" Other unrestricted examples (Chapter 7), Detailed Description, 00 Cit.) Her include a combination of two or more of these as described in ©. As described in silicon using the NMR characterization of silicic acid for © (op cit. Na) 100 m . Michel 5 Engelhardt low weight silica as an example of silicic acid although Description of some embodiments using molecular silicic In some of the descriptions, it shall be understood that the embodiments of the invention are not limited to low molecular weight, either singly or in silica and include other forms of 0 combinations of two or more of them .0 low molecular weight silica. In another embodiment, non-exhaustive examples of SWRs include an average size of less than ; nanomolar or average molecular weight less than 0,080;;; contains tetramethylammonium (i.e. tetra (alkyl) ammonium silicate) soluble produced either individually or in combination of two or tetraethylorthosilicate (TEOS) (more than one silicate. Unexpected silicas for the use of Lh forms of size less than a nanomolar or average molecular weight of less than 44,000 for the manufacture of catalyst support materials may include one or more of the following. Catalytic Unexpectedly Improved Stability and Activity Compared to Catalyst Carriers Below in Examples Susceptibility Led Colloidal As Discussed Conventional silica with materials 0 compared to initial value TAY at least +75 to greater than das , molybdenum reduce volatilization while maintaining performance equivalent to molybdenum materials or titania volatilization values of conventional anatase catalyst carriers. Catalytic carriers may show phase retention and surface area after heat treatments. and/or severe hydrothermal, even in the presence of

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-11- Low molecular weight that can be used silica Other examples of materials producing silicon, silicon halides include, but not limited to, aqueous solutions of fluoro-silicic acid solutions, other organic salts, silicon aqueous alkoxides, sodium and potassium silicate quaternary, solutions of ammonium silicate either individually or in combination of two or more of them. silicic acid Si(OH)4, H0 where 0 is no Aqueous SIX4 comprising silicon halides that are not exclusive to aqueous solutions of AY) or O either individually or in combination of two or more of them. Examples other than Br (Cl X= p methyl, ethyl, =R where Si(OR)4 include the exclusive silicon of the alkoxides isopropyl, propyl, butyl, iso-butyl, sec-butyl, tert -butyl, pentyls, hexyls,

OCtyls, nonyls, decyls, undecyls, and dodecyls 0 » either individually or in combination of two or more of them. in one of the models; Examples of other organic silicon compounds include (Jie but not limited to) hexamethyldisilazane in one embodiment; examples of fluoro silicic acid salts include -ammonium hexafluorosilicate [(NH4)2SiF6] in one Examples of quaternary ammonium silicate solutions include eg, but not eg

Exclusive Vo (((Si02) ((NRA)N where (R=H) or the alkyl Jie listed above; and 0h1,; -?; either individually or in combination of two or more of them. Non-limiting examples of aqueous solutions of sodium 6 and potassium include 1825103 25103 and MSIO3 (where M is 200 or Potassium in varying amounts with respect to “(silicon) either individually or in combination of two or more who are they.

0 An advantage of using low molecular weight silica forms with an average ana estimated volume of less than ; nanometers or an average molecular weight of less than 44,0000 could include the opportunity to interact with titania . One exception. as described below; The following modification of the silicas particle use conditions includes the pH and temperature where particle 5111685 was dissolved and re-deposited on the surface of 1118018 .

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— \ \ — in a given form; Suitable precursors for silica include highly alkaline solutions; They are referred to as water-soluble silicas according to the stack in 2 ller (op cit., Chapter). These solutions are typically transparent because particle 511085, if present, is generally smaller than visible light priv. However, depending on the silica concentration and alkalinity, small silica particles can form in these solutions.Her (op cit., p.133) estimates that for 8i02:Na20 the molar ratio of oF) the average number of silicon atoms per particle in dilute solutions is about 900; Which is a JB of 150010 silicon atoms per particle in the 4 nano Jie of the particle described above. Jie (this sald) produces silica; Although it can contain some nanoparticles above about 4 nm which are appropriate for the present invention since most of the Ve mass of silica is in the form of low molecular weight ral species. Using alkali silicates; and residual alkali ions such as Sodium to toxicity of .vanadia—based SCR catalysts in Model AT ¢ Step 7760 provides a low molecular weight form of silica that includes providing an alkaline solution of 51/6816 .tetramethylammonium

1 Embodiments of the invention include repeating step 770 providing at least a certain low weight form (al) of silica at specified intervals as needed and any number of times required “Jia but not exclusively before; During and after the step “You provide a source of molybdenum” either individually or a combination of two or more thereof. It should be realized that embodiments of the invention involve providing a group of low molecular weight silica forms that differ apart

0 some. Low molecular weight silica moieties can have a variety of properties. In addition to the above; Although embodiments of the invention have been described providing at least some forms of silica with a molecular weight of mite, it must be recognized that these embodiments of the invention are not limited to simply providing forms of low molecular weight silica and include the provision of other forms Lad

silica oe Yo; in one of the models; In addition to step 7710 of providing a specific low-weight image

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S1 Molecular silica The method includes providing other forms of silica that differ from forms of silica with a low molecular weight. Subsequently; in one of the models; The total silica contained in the sale catalyst support material is defined as the sum of a low molecular weight form of silica and other forms of alias silica over a low molecular weight form of silica | . in one of the models; Low molecular weight silica forms comprise greater than 750% of the total silica contained in the dlls of the catalyst. in a particular form; a low molecular weight form of silica comprising greater than 756 of the total silica present in the catalyst carrier including one or more low molecular weight forms having a median estimated volume of 0 less than ; nanometer or average molecular weight Wetton JB individually or in combination of two or more of them. Step You include providing at least some of the molybdenum source to the anatase titania slurry. As shown in Figure No.; The method is not limited to sequencing or repeating Step 7560. Pila Jam of the invention contains a source of Jd molybdenum 1 during or after Step 7700 of providing a low molecular weight form of silica. One embodiment includes step Yoo providing at least some 3shally molybdenum source 0 from sequentially providing a low molecular weight form of silica. Jdmolybdenum provide step 0 0 70 for a low molecular weight form of 5168. When step You provide some source of molybdenum before step YY. One embodiment involves adjusting pH 011 to a range of about 1 to about 6. The AT model involves adjusting the pH to a range from about ; to about ©. The pH can be adjusted using (Jie but not limited to) diluted ammonium hydroxide amines O8 as mono; or yo-bi or tripropylamine; alkanol amines Jie mono-or cyclo- and triethanol cond either in the form of 6m

-?1- singly or in combination of two or more of them. In the sequential AT model; The method includes step YO of providing at least some of the molybdenum source after step 700 of providing Sea low molecular weight silica and after an optional step 50 7 of pH adjustment. 0 One of the models on the method also includes Step You provide some source of molybdenum

At least and step sya 771 has a lower molecular weight of 51108 at the same time. The embodiments of the invention also include repeating the step You provide at least some source of molybdenum at desired intervals and any number of times; like; not exclusively before; cp li and after step YY from provision 51108 ; either individually or in combination of two or more catalyst support catalyst bearing ale terminators It should be recognized that methods for synthesizing Ve together Molybdenum also include the reaction product of one or more of the other material sources; And the result of one or more of the 51168 images interacting with each other »and also the result of one interaction; And the silica reaction products with one or more of the molybdenum sources or more of the other sources among the elements present.

Vo the method is also not limited to how you jig step You Source 07017/50©601070. One or more sources of molybdenum may be provided; (Jd) during or after step YY of the Jie image provision method “Silica not exclusively ion exchange according to step YOY slurry directly according to step (Yo to) either individually or in combination of the two In an embodiment, at least some of the molybdenum source in step You is provided by

00_ion exchange resin by step 757. In another embodiment at least some of source 70 in step Yoo is provided to the titania slurry directly by step Yoi source molybdenum: in one embodiment; The source of molybdenum includes molybdenum 56 or a precursor of ALE molybdenum oxide solubility” either individually or in combination of two or more of them in a given embodiment; Molybdenum oxide is supplied to the carrier for sale

titania Yo as a precursor ALE soluble Jie diammonium molybdate; ammonium heptamolybdate; para

-M1- ammonium molybdate BE ammonium phosphomolybdate hydrate in an amount that achieves a mole ratio of molybdenum to 780800000 in a range ranging from about 1 ee to about 1:01 to form a catalyst that includes vanadium. In the form of Af also; molybdenum oxide is added to a titania support in an amount achieving molybdenum vanadium© in a range of about 1:1 to about 1:01 to form a catalyst comprising a. vanadium is an example; The method also includes provision of a combination of different sources of molybdenum “either individually or in combination of two or more of them. in a particular form; A range of different sources is provided from molybdenum to anatase titania LM. After step YT of silica is provided. in one of the models; The range of different sources from molybdenum 0 to anatase titania Ld. can be provided by ion exchange resin by the YOY step. It should be recognized that one embodiment of the method involves the incorporation of a titania slurry with (V5 silica)1 One or more molybdenum sources to form TiO2-MoO3 - Lyi .Si02 in an embodiment; The method also optionally includes step 7780 to provide a quantity of 0105011846 to anatase titania Ld. 10 . The addition of phosphate to a Ue catalyst support material can feature an unexpected (fie but not limited to; lower oxidation of 502; and improved ability to reduce NOX compared to without the addition of phosphate. In the presence of 2 Phosphorus at surprisingly low levels increases the activity of the catalyst As shown in Figure YoY The method is limited to sequencing or repeating step YO Lo 0 We have not explicitly noted otherwise Examples of the invention include Step 70 of providing an amount of (Jd phosphate) during or after step YY of providing a low molecular weight form of silica. In one embodiment; the method includes step 7710 of providing at least some amount of Jd phosphate Step 760 provides at least some 38. Another embodiment includes Yo step Yo providing at least some amount of phosphate while step YY providing at least some EAN

-?1- silica In another embodiment the method involves step 7160 providing at least some amount of phosphate after step 760 providing at least some silica. in one of the models; Step 7760 involves providing an amount of 000501816_before; during; or after the Yoo step of providing molybdenum in a specific form; The method involves Step Yo of © supplying an amount of phosphate prior to Step YOu providing at least some molybdenum source. The AT form includes step 770 providing an amount of phosphate while the YO step providing at least some molybdenum resource. In the comme form at least some of the molybdenum source is in step Yoo and an amount of phosphate is provided in step 0 at the same time. The AT model includes step 7760 providing at least some of the 0 amount of phosphate after step YOu providing at least some of the .molybdenum source Be aware that the method involves repeating step 7760 From providing an amount of 8 m0105 _ by repeating commas as desired and any number of times required, such as; not exclusively before; during; and after step 7718 of providing a low molecular weight form of silica; oli (Jd, 1) and after step YOu provide at least some molybdenum source; either individually or a combination of two or more of them. The method is also not limited to how step 7760 provides an amount of phosphate An amount of phosphate may be supplied by the “Jie but not limited to” ion exchange method directly to the slurry; Wad) individually or a combination of two or more thereof. in one of the models; Step Yo provides 760 ounces of phosphate; by ion exchange resin. in a particular form; An amount of phosphate is provided to the slurry by the ion exchange resin prior to step YOu providing at least some molybdenum resource. In the Al ¢ form an amount of phosphate « is added to the titania slurry by ion exchange resin at the same time as the step You provide at least some of the EAN .molybdenum source

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Suitable phosphate-containing compounds include; But not exclusively organic phosphate compounds; organic phosphonates; “polyphosphoric acid 3004 40207 “phosphine oxides” (NH4)3HPO4 5 ((NH4)2HPO4 (NH4)H2PO4) either individually or in combination of oo two or more of them. In one embodiment, a group of different sources of phosphate .

Or phosphate can be present on the surface of the carrier. in one of the models; phosphate is added; at levels to achieve a ratio in moles of phosphorus to molybdenum of about 0.7 :1 or greater. in some embodiments; phosphate is added

0 - in an amount achieving a ratio in moles of phosphorus to molybdenum in the range from about 1 7 to about Sort free of tungsten sus : Applicant unexpectedly discovers that s Low molecular weight silica molybdenum can reduce volatility compared to conventional methods of colloidal suspension of silica or aqueous slurries of fume solids. Besides what

VO preceded; The applicant has also discovered that tungsten can be reduced or replaced; using 70A in combination with a low molecular weight form of .51/168 to control molybdenum volatility. It should be understood that embodiments of the invention include optionally reducing or substituting tungsten to certain levels as needed Jie from zero to 7 0010 typical tungsten levels.

0 in an embodiment; The sald) bearing the catalyst is largely free of the presence of tungsten. In the AT model the catalyst is largely free of tungsten. in one of the models; The catalyst support is substantially free of tungsten to an amount of less than about 71 by weight of the total catalyst support.

6 m

CT1-JW to a significant degree of “minor amounts of the corresponding substance referred to either individually or in combination of two or more tungsten Jie or iron are expressly permitted; this is not limited to a specified precise value and may include values that differs from the specified value. In one embodiment; JW substantially than " explicitly allows minor quantities of 10095480 by less than about JY 0 by less than about © 7; and less than about 0.1 7; Either individually or in combination. JW expressly allows the presence of corresponding trace amounts of the indicated material Jie tungsten but does not require the presence of the indicated material tungsten (Jie led). It should be understood that such designs can be used from a low weight silica form To reduce the volatility of molybdenum in the foregoing examples to reduce the volatility of other materials and materials such as; but Vo is not limited to “vanadium oxide” tungsten oxide; bismuth oxide; lead oxide; and the like; either singly or in combination The approximation language may be applied, according to the user in the present application throughout the specification and claims, to designate any quantitative or qualitative representation that oof varies in a permissible manner without resulting in a change in the basic function to which it relates. Accordingly, the value modified by an expression like 'less than about'

1 or "largely free of" should not be limited to the exact same value and may include values that differ from the specified value. In some examples at least; Rounding language can correspond to the precision of the instrument to measure the value. In addition to the above; 'NOX removal or reduction' may be used in combination with a term and include a varying amount of NOX removal and shall not be limited to a specific precise value and may include values that differ from the specified value.

tungsten; phosphate 00 : in other embodiments; The catalyst carrier has more than a negligible “tungsten” i.e.; The catalyst support material is not to a large extent free from the presence of tungsten. The level of tungsten can be reduced by at least 7860 compared to conventional catalyst support materials and catalyst. tungsten levels can be reduced by at least 775 compared to conventional catalyst support materials

-14- Compared with catalyst carriers 701 by at least tungsten and catalysts. Levels of conventional catalysts can be reduced. catalyst support materials phosphorus in one embodiment; The catalyst support had a molar ratio of 502 or greater. The resulting catalyst showed low oxidation of 1 10, Y ranging from about tungsten to a highly phosphate yield. in some embodiments; NOX is added without less transformation of © to about 1 rn in a range from about tungsten to phosphorus. A proportion in moles of « molybdenum; tungsten when each of (file is present as .1;: in addition to tungsten to phosphorus - at levels to achieve a ratio in moles of phosphate or greater and in some embodiments; at levels to achieve a ratio of 1:0.7 about ils molybdenum in the range from molybdenum plus tungsten to phosphorus in moles of 0

SEE to about 0.7 :1 about 1102-1/003- washing and roasting of a mixture of 71700 in one embodiment; The method also includes a Si02 step for the method of fabricating a catalyst support. The method includes the following: a) AT The invention comprises one or more embodiments of 1) with anatase titania b) and the combination of a slurry: anatase titania presenting a Vo slurry and a main promoter 1) inhibitors Volatilities comprising form of low molecular weight 51168: 1102- to form a mixture of molybdenum oxide comprising primary promoter of low molecular weight silica size silica form including form .//003- 2 Estimated average size < 4 nM and average molecular weight < 44,080) either individually or in combination of two or more of them. 0 Applicant unexpectedly discovers that volatilization inhibitors comprising Low volatility profile compared to conventional methods molybdenum of 51/108 can reduce the ad-weight capacity of the fumed solids. In addition to the above; Discover Sl) colloidal or slurry silica Suspended by molybdenum or replaced by tungsten Possibility of lowering Loaf levels Applicant

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1. In combination with volatile inhibitors comprising a low-weight form molybdenum molybdenum volatilization is used to control the susceptibility of molecular silica from it should be recognized that embodiments of the invention include the provision of a combination of volatile inhibitors that differ from each other. The combination of volatilization inhibitors can have various properties. Although embodiments of the invention are described with a volatilization inhibitor comprising © 51108 images

low molecular weight; It should be understood that these embodiments of the invention are not limited to simply providing volatile inhibitors comprising a low molecular weight form of silica and include providing other forms of volatile inhibitors as well. in one of the models; In addition to providing a volatilization inhibitor comprising a low molecular weight form of

51/168; The method furthermore provides an AT plat inhibitor that does not have a low molecular weight form of 51108. Subsequently; in one of the models; Mea) the amount of volatilization inhibitor present in a catalyst support material is defined as the sum of volatilization inhibitors that include a low molecular weight form of silica and other forms of volatilization inhibitors that do not include a low molecular weight form of silica .

Ve in an embodiment; The volatile inhibitor comprises a low molecular weight silica form greater than 0 of the total volatile inhibitor contained in the catalyst support. in a specific form; a low molecular weight form of silica comprising greater than 0 75 total volatilization inhibitor contained in the catalyst carrier sald) containing one or more low molecular weight silica forms of weighted size; the average size is less than ; nanometers or average molecular weight less than 54.0080; As for

Yo individually or in combination of two or more of them. Although embodiments of the invention are described with a primary promoter comprising molybdenum oxide “it should be understood that the embodiments of the invention are not limited to simply providing a primary promoter comprising molybdenum oxide and include the provision of other forms also.

EAN yy The catalyst carrier in one of the . catalyst support materials The embodiments of the invention also include catalyst support materials The embodiments; The catalyst carrier includes: from about 7480 to about 94 #7 wt eed #dioxide by weight: from about 7901/003 to about 7.1 and from about: anatase titania 5602 wt in low weight forms molecular. Low profiles 7 01 to about © having an estimated average volume of silica molecular weight of 5102 include one or more profiles individually or Wott cnn > greater than (MW) less from ; nanomolar and average molecular weight in combination of two or more of them as previously discussed. in a particular form; 6.77.5 Ja to 0.00 Ja catalyst optionally includes from about sald. In another embodiment the catalyst carrier includes from about 87 7 to about 94 #2 by weight Ve; From about 70.7 to about 75 by weight 003 and from about anatase titania by weight 5002 particles in low molecular weight forms. Forms #© Mea to #7 as discussed low molecular weight silica 502 include one or more of the aforementioned forms; either individually or in combination of two or more of them as previously discussed. in 77.5 particular model; The catalyst carrier optionally comprises from about 0.01 to about V0 Phosphorus. On nanoparticles having diameters smaller than SI02 the catalyst carrier (sald) in one embodiment of the catalyst carrier includes low weight forms (sald); nanometers. In another embodiment it includes 5102 in molecular form of 5:02 having a molecular weight of less than 4,0080?4. In another model as well; 5502 includes in the middle of coordinates 93; f02; silicon of 750 atoms catalytic carrier over Q0.0, and [0.50 m7/gas is at least BET in one embodiment; The catalytic support has a surface area of 1.5 times that of the catalytic support; There is 5:02 with a partial monolayer value of less than AT in the catalyst carrier calcination model.

1; anatase titania catalyst-bearing sald particles) in one embodiment; phosphorus includes a mole ratio of ; molybdenum oxide primary promoter and a volatilization inhibitor comprising 1 if to about 1:0 range from about 4 molybdenum to low Ada low silica weight Aida silica weight images include medium size images rated at less than nano molar and lower average molecular weight of silica tyr© either individually or in combination of two or more of them It should be recognized that the 00s embodiments of said catalyst carriers include volatilization inhibitors comprising one or more of The volatilization inhibitors described above; either individually or in combination of two or more of them

Cua (TI02-MoO3-Si02) on the catalyst carrier of the general formula AT medium form comprises silicon oxide and is largely anatase in the form of titanium dioxide is 0 must be of EE ne of; nanomolar and average molecular weight less than JB weighted volume with asi anatase also aware that the catalytic support includes oxide reaction product with each other; P product (anil reaction product) with each other MOO3 each other; Reaction product 5102 interaction with each other and also the product of the reaction of the oxides of the elements with each other in general. The manufacture of the catalyst is limited to the “Jig” catalyst. Fig. No. Arrangement or repetition of the steps unless otherwise expressly indicated. Combination of mixture 1102-1/003-51602 with 205/7 to form catalyst 701 The method includes a catalyst calcination step 71 The method may include an addition Optionally, step by step. vanadia -0 °C. 001 eg about vanadia catalyst: embodiments of the invention also include catalysts. in one of the models; The catalyst includes from 7 to 1.1 about oe; anatase titanium dioxide ca.

S to about 77 wt 205/. 5002 includes a low molecular weight profile that has an estimated median volume of less than ; nanomolar and lower average molecular weight of Weft, ove individually or in combination of two or more of them. in a particular form; The catalyst optionally comprises from about 0.00 to about 77.5 wt phosphorus 0 in one embodiment; The catalyst comprises from about 787 to about 7 94 by weight anatase titania particles from about 70.7 to about 75 by weight (MoO3) from about 7001 to about 7 01# by weight (SIO2) and from about 70 .5 to about 77 by weight 205/.5:02 comprises low molecular weight silica forms having an estimated mean volume of less than 4 nm and an average molecular weight of less than 60 44,008; either individually or in combination of two or more 0 in a particular embodiment; the catalyst optionally includes from about 70.09 to about 77.5 wt. AT as well; the catalyst comprises from about 1.5 7 to about 70.9 by weight 205. Usage of the catalyst: The embodiments of the invention also include methods for using catalysts to reduce the content of nitrogen oxide Yo in a nitrogen-containing liquid or gas oxide The method involves contacting a nitrogen oxide gas or liquid with a catalyst for an AIS time to reduce the level of NOX in the nitrogen oxide containing gas or liquid In one embodiment the catalyst comprises from about IAT to About 94 7 lbs n of anatase titanium dioxide; from about 0.1 7 to about 7 wt 10603 from about 70.5 to about 77 wt V205 and from about 1.1 to 0 about 7 01 wt 5102 in molecular weight forms low. Low molecular weight images of 5:02 include one or more 51108 images with an estimated average size of less than ; nanomolar and average molecular weight less than 55,0000 either individually or in combination of two or more of them. in a particular form; The catalyst optionally comprises from about 1.09 to about 77.5 wt. Phosphorus. It shall be understood that embodiments of the invention include methods for reducing the YO content of nitrogen oxide with a liquid or gas containing nitrogen oxide by Gas contact

or liquid containing nitrogen oxide with one or more embodiments of catalysts described above; either individually or in combination of two or more of them. The NOX reductants described above may be added as a structure as a monolith or extrusion in a fixed bed reactor or any reaction-regeneration unit systems; to fluidized bed systems; to systems comprising continuous delivery or oo circulation of catalysts/additives between the reaction zone and the regeneration zone; and the like. of sorts

Typical circulating bed systems are conventional mobile bed reactor and fluidized bed reactor - regeneration systems. NOX reduction catalysts may be used in an amount of at least:71 at least 77: or at least 75: in an amount of at least about 70 regeneration stock: or at least an amount of about 771 regeneration stock to reduce the nitrogen oxide content ‏

Yo method models also include contact with a gas containing nitrogen oxide in the presence of one or more reducing agents such as ammonia “hydrogen hydrocarbons, carbon monoxide and the like; either individually or in combination of two or more of them with one or more embodiments of catalysts described in the embodiments of the invention under various environmental conditions such as complete combustion and low oxygen environmental conditions. Examples of low OXygen environmental conditions include; But

Yo is not limited to partial ignition units | for partial combustion; Mixed mode, full combustion units with bad air circulation, etc. The AT model involves contact of a gas or liquid containing nitrogen oxide with a catalyst for sufficient time to reduce the level of NOX in the gas or liquid containing nitrogen oxide where the catalyst is made by:

5; anatase titania providing a slurry (0) (with a molecular weight of 51168 jaa one or more than 1) with anatase titania (b) incorporating a slurry; For mixture composition 1102-1/003-5102. Includes Molybdenum Forms and Source (Low V; Low Molecular Weight) 51/168 ld silica forms

6 m

They are "average estimated volume less than nanomolar and average molecular weight less than Weft, ove individually or in combination of two or more of them. It should be recognized that the embodiment of the invention includes methods for reducing the nitrogen oxide content © with a liquid or gas containing nitrogen 56 by contacting a gas or liquid containing nitrogen oxide with one or more catalysts made by the embodiment of the methods described above, either individually or in combination of two or more of them. addition of the NOX reduction described above in the form of a structure formed as a monolith or extrusion in a fixed bed Jolie or any conventional Jolie - regeneration systems; to fluidized bed systems; to systems involving continuous delivery or cycling of catalysts/additives between reaction zone and 0 regeneration zone, etc. Typical types of recirculating bed systems include conventional mobile bed reactor and fluidized bed reactor-regeneration systems. 77: or at least 75: at least about 701 in stock replenishment: or at least about 7718 in stock Regeneration to reduce nitrogen oxide content Method models also include gas contact containing nitrogen oxide in the presence of the reducing agent Vo ammonia Jie; hydrocarbons»; hydrogen; Carbon Monoxide; And the like with one or more of the embodiments of the catalysts described in the embodiments of the invention in various environmental conditions Jie complete combustion and conditions of low oxygen environments. Examples of low OXygen environments include; But not exclusively; on partial ignition units; particle combustion units; mixed mode » complete combustion units with poor air circulation; etc.

0 Examples The following examples illustrate the features of the embodiments of the invention and are not intended to limit the invention ale although some parts of AEN 1-71e are formulated in the simple present tense; However, the ARG procedure has been completed and the differences (non-add) between embodiments of this invention compared to conventional techniques are demonstrated. The volatility of molybdenum was determined in the following way. 1.7 g of

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-?1'- catalyst (0.7-7, mm particle size 5102 -1102) with quartz wool in a 4 inch quartz tube; A fF inch OD fixed at both ends with open handle hinges. 7 g of VEY Alfa—Aesar) gamma alumina EVAR YOO mm particle size) was added from the opposite end of the tube to prevent cross contamination. It is also hung on a quartz glass wool 0 stopper. The tube was connected by means of hinges 38 to a flow reactor with a stopper. temperature increased to a Veo and carrier gas of formula 7010 water vapor” 7010 02; 00 ppm (NO) and 5060 ppm 013 N balance was passed over the catalyst towards the alumina layer after 2 hours; the catalyst and alumina layers were cooled. The catalyst was removed from both ends of the tube and the alumina was removed Then each 0 powder sample was dissolved with HE and analyzed separately using ICPOES (Inductively (Coupled Plasma Optical Emission Spectroscopy)_to obtain .molybdenum content & calculate .molybdenum Sublimation of the catalyst by dividing the amount of molybdenum by alumina by the molybdenum yield present in the alumina titania carrier materials The mass balance of the experiment was calculated by dividing the molybdenum yield 1 detected in the carrier materials for 1118018 and alumina after hydrothermal treatment by an amount of molybdenum measured in titania carrier before hydrothermal treatment DeNOX transformation was determined using a catalyst in powder form without further formation Reactor ?/ + inch of quartz sequestration 17 g catalyst mounted on glass wool.Feed formulation is 0 ppm Zo (NO 0 2; and 75 (H20) varying amounts of NH3 and Yo. ranges from 0 to 101 ppm; equilibrium 812. The shift of BNO 8000 780 and 4860 m in atmospheric pressure was measured and recorded as a function of partial pressure increase to ammonia in the reactor feedstream.The reactor effluent was analyzed using an infrared detector to determine NO transformation and NH3 slip.Oxidation of 502 was determined using a catalyst in powder form without further formation.Yo reactor retains quartz 1/ 4" 17g catalyst mounted on glass wool. Feeding formula is 0 5 part EAN

A" in 502 million; 02 7780; equilibrium 02. Space velocity calculated to be Y4.0 litres/gas.catalyst.hour under ambient conditions. Die 00 degree Aggie shift data recorded Example 1 One of the embodiments disclosed in the present application and/or the concept(s) of the claimed invention was prepared in the following manner: 176.7 g of anatase Lda titanium hydrolysate aqueous ZY1, F (solids); produced by Process 36 (trade name - Gl) from Inorganic Chemicals 00AM(AA(/A); to dan 01 denature heat by means of a temperature-controlled heated Gib led and the temperature was kept at 01°C throughout the preparation.The pH was adjusted to:using diluted ammonium hydroxide 0.A dilute solution (7(1) by weight (SIO2) was prepared from sodium silicate by adding 1.1 g of 18-4011 1005000 sodium silicate (¢,¥4 7 wt. Jie 2) to 58.4 g of deionized water. 01 g (base as received) ion-exchange resin for strong acid Dowex™ H 6506 and placed in a burette column. (Photo Dowex™ 6506© H ion exchange resin yo resin 100-80030096 ... was used in the following examples and is available from Dow Chemical (US “Company) Dilute silicas solution was added through Column containing ion exchange resin to slurry at a rate of ª mL/min.After complete addition the ion-exchange resin in the column was rinsed with 01 mL of deionized water added at a rate of ª mL / min to a titania slurry The pH was adjusted again to 0 using ammonium hydroxide and left to react for 0 min Ob solution was prepared by dissolving 7.14 g of ammonium heptamolybdate 00 + g of 785 phosphoric acid in 01 mL of water This solution was added to the slurry by means of an ion exchange column at a rate of © mL/min After completion of the addition the pH of the mixture was adjusted to using ammonium hydroxide diluted and the Yo was allowed to react for 10 minutes.The mixture was filtered and rinsed with 0.10 L of deionized water EAN

m \ — deionized water ; It was dried at 1#00 oF, after which it was calcined oF die at an evaporative temperature for 7 hours. The target loading of the catalytic support is 6.5 7 wt. SIO2, 0.1 7 wt. Phosphorus » and Y 7 wt. molybdenum. Before volatility studies, .1 # wt was added. 7808018 to the sample by the following © method. 01 g sample of the prepared support was slurred in 50 mL of water. To dda a fifth (p> +,¥11) [V205] vanadium pentoxide and “+”YYY) [HOCH2CH2NH2] monoethanolamine g) were added and the temperature of the mixture was raised to 1 °dade and the temperature was adjusted pH was reduced to A using ammonium 06 and the mixture was left to stir for 11 minutes. Solids were separated by filtration; Ye and then dried at 100 degrees YEP for 1 hour.” And roasting it in 1 ,an Total hours in the air. Prior to the DeNOx Test and Oxidation Measurement 502; 70.5 7808018 was added to the sample by the following method. 01 g sample of the prepared support was slurred in 0 5 mL ele to this was added quintile (a > 0146) vanadium pentoxide monoethanolamine ; Yo (, 154 g) and The temperature of the mixture was raised to 01 degrees Aggie pH was adjusted to A using hydroxide 877171001107 and the mixture was left to stir for yo min.The solids were separated by filtration;and dried at 001 rancidity for 1 hour”; and roasted at 1 degree YEP for 7 hours in air. Example Y In the second _ model of the method; the order of adding molybdenum solutions is reversed; silica Susy phosphorus solution is added molybdenum and phosphorus through an ion exchange column before the silica solution Vanadia was added as described in Example 1. Comparative Example 1 EAN

— \q —

0 anf fo, a sample of anatase titanium slurry heated with water (ZYY,Y) solids)

to 01°C by means of a heated plate with a controlled temperature and a degree maintained

heat throughout preparation. molybdenum solution was prepared by dissolving 4.14 g of

001 ammonium heptamolybdate mL of water and this solution was added directly to the slurry. The pH was adjusted to © using ammonium hydroxide and left

Mix for 10 minutes. the mixture was filtered; It was dried at 510°C, after which it was calcined at

degrees Celsius for 7 hours. The target load is 1 7 by weight Mo added

.1 of the one described in example a, vanadia

Comparative example Y

0 The sale carrier was prepared as described in comparative example 1 except for the addition of the filtrate washed with 1 liter of deionized water to remove the dissolved ions associated with ammonia Jie before drying and calcining. . aly target loading 1 7 by weight molybdenum ; vanadia is added as described in example 1

Vo?a Jd dissolved with water (277.71 solids) to anatase titanium 87.7 g sample of hot slurry was heated to a controlled temperature and the Gib degree was maintained by bla dap 0 by dissolving 1.84 g of molybdenum over heat throughout preparation. A solution has been prepared

ammonium heptamolybdate | 0 in 10 ml water. This solution was added to the slurry. After the addition is completed; The pH of the mixture was adjusted to © using dilute ammonium hydroxide solution and allowed to react for 10 minutes. A dilute 1 (7 wt.k) solution (SIO2 of sodium silicate) was prepared by adding +,A0 g of Inobond Na—Y4,¢) sodium silicate 4011 7 wt.k (SIO2) to 14.1g of deionized water

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=« As deionized water. 01 g of fraction (base as received) ion exchange resin—strong acid exchangeresin (photo) (Dowex™ 6506 H) was weighed and placed into a column burette. Diluted 5110685 solution was added through a column containing on ion exchange resin—exchange resin to slurry at a rate of 01 mL/min.The column was then rinsed with 0 5 mL of deionized water Jara at a feed of 0 mL/min. Then the pH was adjusted again to 35 © using hydroxide 80710001000 and left to react for 10 minutes.The mixture was filtered As, rinsed with Je Own Ma p deionized ¢ As, dried at +1 O 2 ¢ and then roasted at 570 an annealed for 7 h. Target loading is 0 wt 02 and 7 7 wt Mo vanadia added as described in example 1.

Ja A "b A catalyst support material was prepared as described in example fr except that the order of addition of silica; molybdenum was reversed so that silica was added before

1. For the example described a, vanadia has been added. molybdenum as follows: 1 The results of the volatility test are shown in Table 1 Table Ve aé Mo on balance Mof on Mo | On Mo, for example, Iad Takla | Catalysts before catalysts after alumina Test Test A fares EAN

“yy

JEEE I A I

JE EN EE A

I | comparator JED ¥ for JED comparator Wie 1 shows the removal of associated ions by using a washing step with 10 times the excess of deionized water 0 _The mentioned guide shows one of the advantages al models of the invention that dam to hold 70 . Example 1 shows a significant additional attenuation of molybdenum's volatility. In addition to the above; A comparison of Example 1 with Example 7 shows that the pallability of molybdenum is at least partially related to or affected by the order of addition of silica versus phosphorus ; molybdenum using an ion exchange column. represents the example? 11 repetitions of both the preparation method and the volatility test. These results demonstrate the diversity of the test; In addition to showing that the order of addition is not important for compositions containing only molybdenum and 5/168. Additionally" iterations indicate that this method is EAN

DJ

Simple preparation is effective Leaf in reducing the volatility of molybdenum with respect to

Comparative examples.

example ¢

To clarify the effect of increasing the silica content on the volatility of molybdenum, carrier materials were prepared.

© for catalyst support materials as described in Example QF except for an addendum

Upload target silica to Lovo (example JE) AT(i¢;b). vandia added

1. For the example described in Ta

Comparative example?

To illustrate the unexpected advantage of adding silica through an ion exchange column; A sale Ve catalyst support material compared with colloidal silica was prepared. was heated up

aa YAY,” from a water-soluble anatase titanium slurry AR A (solids) to Te

Roasted heat via a hot plate with a controlled temperature and the dish temperature is maintained

preparation. A molybdenum solution was prepared by dissolving 0.84 g of ammonium

heptamolybdate in yo ml water. This solution was added to the slurry. After 1 completes addition; The pH of the mixture was adjusted to © using ammonium hydroxide

diluted and left to react for 10 minutes. Diluted silica slimy dispersion (trade name -

Ludox 05-0 (ZY) Grace Davison solids) by mixing 1 g with 79 g

of deionized water; Yo ml was added to the titania slurry. It was completed

The pH was adjusted back to © with ammonium hydroxide and allowed -0 to react for Ye min. The mixture was filtered and adhd was neutralized using 5060 mL deionized water

deionized water” and dried at ca neo, after which it was calcined at reflux temperature OF

for 7 hours. The target loads are 7 065 by weight (SI02 and 7 7 by weight Mo).

Add vanadia as described in Example 1

comparative example;

EAN py sale ionic; Jalil) was prepared through a silica column to demonstrate the unexpected advantage of adding a chimney. silica was heated compared using a catalyst support material as a catalyst carrier (grade Te solids) to ART A) aqueous anatase titanium slurry 1 g enthalpy by means of a temperature-controlled hot plate And the temperature was maintained throughout the ammonium of 0.84 g by melting the molybdenum preparation. A solution of © ml water was prepared. This solution was added to the slurry and after Yo in heptamolybdate ammonium completed the addition; The pH of the mixture was adjusted to © using a solution of fume silica minutes. A slurry was prepared from diluted 01 and allowed to react for 60 ml and add Yo g to +, YO by adding Evonik from Aerosil 200 - (trade name) again to 0 using pH This titania slurry was adjusted to a 0 min. 01 slurry and allowed to react for ammonium hydroxide and deionized water. The mixture was filtered and rinsed with 5060 mL of deionized water °C for 76 h.oF m., after which it was roasted at Veo dried at .molybdenum idl 7, 1 wt 5102; 7 0.5 target loadings 1. as described in example was added. vanadia 0 o example together through an ion exchange column; Molybdenum and silica were modified to illustrate the effect of adding the preparation in the following way. Dissolved with water (6,7 77 solids) anatase titanium was A 76.7 g sample of denaturant slurry was heated via a hot plate at a controlled temperature and kept at 10 dan to 0 ammonium to © using the pH solution heat throughout preparation. silicate by weight 5102) of 7 1) diluted H. A dilute solution of 06 wt 7 k (Y4,¢) sodium silicate Inobond 18-4011 g was prepared from 1.17 g by adding 7.148 g of . deionized water £46 g of water (1022

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dio" ammonium heptamolybdate to solution 55168 . 01 part (base as received) ail) ion-exchange resin of strong acid (Dowex™ 6506 H-form) was weighed and applied In a burette column A solution of 511685 and molybdenum diluted through a column containing ion exchange resin was added to the slurry at a rate of © ml/min The pH was adjusted back to © with ammonium hydroxide and allowed to react for 10 min. The mixture was filtered, rinsed with 10 L of deionized water ¢ and dried at Veo C; then calcined at −1°C for 1 hour. target 6.5 7 wt. 76.7 g sample of anatase titanium slurry dissolved in water (6.7 77 solids) was heated to dan Te cryogenic heat by means of a hot plate at a controlled temperature The temperature was maintained at 0°C throughout the preparation. The molybdenum was incorporated into the mortar to achieve a 0.5 7 wt loading of molybdenum by the addition of 1.97 g ammonium heptamolybdate. The pH was adjusted to © using dilute ammonium hydroxide. A dilute solution (m by weight (SIO2) of sodium silicate was prepared by adding 1.1 g of Inobond Na-401.1 (Y4,¢) sodium silicate 7 wt.as EAE) (SIO2 g of deionized water | 71 g (base as received) of strong mea! ion-exchange resin (H 6506" 001/6*7a-photo) was placed in a burette column. Silica solution was added and molybdenum diluted through a column containing Yo ion exchange resin to slurry at a rate of © ml/min.PH adjusted once EAN

Another solution was added to © using ammonium hydroxide and left to react for 10 minutes. The mixture was filtered and rinsed with 0.1 L of deionized water; It was dried at TPE No. and then roasted at EGR 01 die annealed for 1 hours. Target uploads are 6.5 7 by weight 5702; and 1 7 by weight molybdenum ; in which veo 7 wt molybdenum was added directly to the slurry and 0,5 wt 7 was added with silica solution through an ion exchange column. 7808018 was added as described in Example 1. JE 1b A catalyst support material was prepared as described in Example + 0 except that 0.1 wt 7 molybdenum was added directly to the slurry 0.10 7 wt was added with the silica solution through an ion exchange column for a total of 1 7 wt of molybdenum added to the carrier. 7808018 added as described in Example 3 Example 1c Vo catalyst support material is prepared as described in Example + except that 1,5 7 wt. of molybdenum is added directly to the slurry and 7 wt. with a silica solution through an ion exchange column for a total of 1 7 wt. of molybdenum added to the carrier. 7808018 was added as described in Example 3 0 Example A to show that phosphorus has no effect on reducing the volatility of molybdenum The following carriers were prepared.

A +1 YEA A g sample of anatase titanium slurry dissolved in water (7717.9 solids) was heated to dan Te on a Gob hot plate at a controlled temperature and the temperature was maintained throughout preparation. pH is set to ; using diluted ammonium 06 solution. A phosphorus 3 solution was prepared; molybdenum by dissolving © 7.18 g of ammonium heptamolybdate + 0.00 g of D78 phosphoric acid in 10 ml of water. 01 g of fraction (base as received) ion exchange resin—(eal exchangeresin strong H) 6506 “001/6”*7a-photo) was weighed and placed in a burette column. solution of phosphorus molybdenum through a column containing ion-exchange resin to slurry at a rate of ª mL/min.The pH was adjusted back to 0 with ammonium hydroxide and allowed to react for 10 minutes.The mixture was filtered, rinsed with 0.1 liter of deionized water, dried at Veo C, and then calcined at OF die for 1 hours Target loadings are 6.11 7 wt© and 7 wt of molybdenum 0 vanadia added as described in example 1 Ja/Ab YEA A g sample was heated Anatase titanium slurry dissolved in water (7717.9 solids) to dan Te celsius by means of a hot plate at a controlled temperature and the temperature was maintained throughout preparation.pH was adjusted to ¢ using ammonium hydroxide | diluted 0. A phosphor solution was prepared us 3; molybdenum by dissolving 1 g of heptamolybdate 80100001007 and +00 g of D78 phosphoric acid in 10 ml of water. A solution of phosphorus 3 molybdenum was added directly to the slurry at a rate of ©[Je] min. The se PH was further adjusted to 4 with ammonium 06 and left to react for 10 minutes. The mixture was filtered and rinsed with 0.1 L of Yo deionized water; It was dried at 016°C and then calcined at EAN

Only toad hours. Target loadings are 0.15 7 wt© and 1 7 wt molybdenum. Volatility test results are shown for examples; 7- And comparative examples? And the; in the schedule? Here: Yds CEE — A — — 8

5 oo mils suggests the example; Increasing the content of silica with Aad improves retention of molybdenum. Comparative examples? And the; Neither the fumed silica nor the colloid added to the catalyst carrier preparation had any measured effect on the volatility of molybdenum in contrast to that indicated by the improvement achieved by the addition of 511168 through an ion exchange column. Examples 150 show that molybdenum can be added in any combination of addition directly and through an ion exchange column in combination with silica while retaining efficacy in reducing the volatility of molybdenum. Examples IY and Lapp demonstrate some apparent reduction of molybdenum volatility induced by the addition of phosphorus and molybdenum -through ion exchange versus direct addition to the slurry, however this improvement is not to the same degree as that induced by 5102 and molybdenum alone . at the end; Compare example fr with SIO2 (added only) and example phosphorus (1 added only) EAN

With the examples (Si 150) co and phosphorus (both added to the carrier preparation) it is suggested that the improvement in molybdenum retention induced by a combination of phosphorus 5 Si is additive. Example A © A catalyst carrier has been prepared; As described in Example 7 except that 177 g of 7/85 phosphoric acid was added to achieve a loading of 0.710 7 by weight of phosphorus oA JE. A catalyst support material was prepared in accordance with as described in example 1 except that 1.97 g of 785 sail phosphoric acid was added loading 0 7 075 by weight of phosphorus 70.9 of vanadia was added in each da in accordance with to that described in Example 1. The performance of the catalysts prepared in the examples A YoY is compared given in Fig. 4. Although it appears that the addition of 0.11 7 wt. of phosphorus initially reduces both the total conversion of NOX and that at 01 sj ppm slip” since phosphorus increases to 1 7 0.7 by weight and 7 Yo by weight, the maximum NOX conversion and NOX conversion at 01 ppm slip increase as well. Such results are unexpected as it is generally accepted in the art that phosphorus is a NOX-converting poison. And the; Although some disclosures peg that phosphorus can be added to levels where NOX conversion levels are not compromised (eg JE see US Patent 700001874497” (Kato etal) prior art has not disclosed 0 Or it is suggested that phosphorus could actually increase NOX conversion as shown above. The data from the figure helps in the formation of a are listed in the tables below. The NOX conversion is calculated at 10 ppm 'GYR' as the measured value while the 01 ppm trendline cuts through 58 slides as a result of the increase in the partial pressure of ammonia in the reactor. '' is specified as maximum

and *NOX conversion" as the maximum conversion value when the partial pressure of ammonia is increased from 0 to 00 ppm. The oxidation of ce I — — shows a comparison of the results from Example TY to those from Examples (0 7 IY B JA Grant that © as stated in the prior art; (mids add) phosphorus to the catalytic carrier 502 from oxidation. According to the aforementioned" and the Load data surprisingly show that the total conversion of aly NQX is at 01 ppm of 201000018. _Sliction increases. Laie is increased. Loading is increased.

LO You wt for reactor tests carried out at Zw, Yo Nv, Ve of phosphorus for reactor tests phosphorus wt of 7 +,Y + however; It appears to undergo a maximum when carried out at +55°C. Examples A and Lapp show that further increases in effectiveness in non-slip 0 ammonia can be 01 ppm of NOX and that the degree of conversion of silica and presence to the carrier; phosphorus 3 molybdenum is affected By the method in which it is added either through an ion exchange column (IV) or directly to the slurry (LAB).

=” ¢ — example ja A catalyst carrier was prepared as described in example “a except that 0.07 g of 785 phosphoric acid was added to achieve Vo + 7 wt. from loading phosphorus . example 8b© A catalyst carrier was prepared as described in Example A except that 177 g was added

from 785 phosphoric acid _ to achieve 0.01 7 wt. from loading phosphorus 4g Ji. A catalyst support was prepared as described in Example A except that 0.01 g of 785 phosphoric acid was added _ To achieve Ye, + 7 in wt from downloading .phosphorus

24 JE Yo A catalyst support was prepared as described in Example A except that 1,597 g phosphorus was added by weight from loading 7 0,40 _ to achieve phosphoric acid 785 from 1. as described in Example vanadia in each case; 70,9 A01 example added

Vo to determine whether the efficacy of phosphorus in increasing the conversion of ysNOX and reducing the oxidation of 502 is limited when added in a carrier formulation; Then the catalyst preparation was modified to combine small amounts of phosphoric acid with vanadium pentoxide. 71 g of a sample of the support prepared as described in Example 1 was slurryed in Je Oa water.

(+,Yo¢) monoethanolamine g) +,Yo') vanadium To this Ye pentroxide was added to achieve the target 7205 loading of YEP Te temperature of the mixture to an gm) and then raised

EAN

4 . Phosphorus was added to the slurry by introducing vo FY g of TAS solution H3PQ4 to achieve a target loading of 708.05 in addition to the 7.15 already present on the carrier. The pH 011 was adjusted to A with ammonium hydroxide and the mixture © was left to stir for Vo min. Solids were separated by filtration methods; and dried at 100 degrees YEP for 7 hours; As roasted at YEP YEG 001 for 7 hours in air. Example 10b The catalyst was prepared in the same manner as described in Example 01 except that 0.076 g of 7/85 phosphoric acid was added to achieve the target loading of +7, wt 0 phosphorus plus 20,00 already on the carrier. The reactor performance from Examples 4 and 10 is shown in the table; Below. Schedule ; Example of a total NOX load. (Jy sa] at 01 |maximum NOX conversion |oxidation 5m ppm slip 502 6m

BE

directly to the carrier phosphorus ; molybdenum The table shows that when adding and passing phosphorus increases initially with NOX loading (Examples 19 - 23), the maximum conversion is as expected; oxidation of phosphorus by weight decreases from 0.7 7 loading. Examples show that the addition of B01 and B01 phosphorus repeatedly with increasing loading 2 separate steps i.e. during the preparation of the carrier with the addition of more during 3 phosphorus © to the optimum with Decreases at NOX preparation of the catalyst are also effective in increasing the conversion of JA and da 01. Show that there are some differences Comparison of examples phosphorus Adding more and/or phosphorus depending on how it was added NOX phenomenon in the transformation of A. molybdenum

Yo 11 metal phosphorus and oxidation quenching 502 are only affected by NOX to determine whether the conversion improvement is the same as silica or other elements are able to induce the same improvements; Sulfur tested and method; Ny example 0 dissolved in water (7717.9 solids) anatase titanium g sample of YE9,0 slurry the substrate was heated via a hot plate at a controlled temperature In it, the degree of Sha was kept to the degree of ammonium to; Using temperature pH solution throughout preparation. The pH was adjusted g (base as received) of the diluted 01 ion exchange resin. A portion of 056 images) was weighed and placed in a column —Dowex™ 6506 H)_strong acid ion-exchange resin Y. ammonium heptamolybdate burette. A solution was prepared by dissolving 7.14 g of ml water; 01 g) in NHI (SaQ) ammonium sulfate and 15 g of supernatant min. after [de © aly] complete solution were added to the slurry by means of an ion exchange column at a rate of

EAN

add; The pH of the mixture was adjusted to ; using diluted ammonium 056 solution and left to react for 10 minutes. A dilute solution of 1 (7 wt 2) of sodium silicate was prepared by adding 1.1 g of 18-4011 1005000 sodium Y4, ¢) silicate 7 wt k (SIO2 to 48, 4 g of deionized water © A dilute 511085 solution was added through a column containing ion-exchange resin to the slurry at a rate of 2 [Se] min. After completion of the addition ahd Ion exchange resin in column using 01 mL of deionized water added at a rate of ©[de] min to titania slurry pH was adjusted further to ;using ammonium hydroxide and allowed to react for y min. The mixture was filtered and rinsed 0 with 0.1 L of deionized water; dried at 10°C; then calcined at 0°C for 0 hours. Target loadings of v0 7 wt (SiO2 7.717 5 Y 7 wt molybdenum) 70.9 vanadia was added as described in Example 1. Example 111b The catalytic support was prepared as described in Example 11a except that Add 0.156 0 g of Y4,¢) sodium s ilicate 1005000 Na-4011 7 by weight as 5102) was replaced by perammonium sulfate in a molybdenum solution. The target loadings are 6.8 7 by weight 5102 and 7 7 by weight Mo 70.9 vanadia added as described in Example 1 Example 11c The catalytic support was prepared as described in Example 11 except that Addition of 1.00 Yo g of 7/85 phosphoric acid and 0.75 g of ammonium sulfate was added to the molybdenum solution. Target loads of this product were 0.15 7 wt phosphorus « 870.09 » 0.5 7 wt 5102; and ZY by weight Mo 0.9 7 a; vanadia of described in Example 1. The reactor test results are shown in Table © below. Table © : 6 pm

Rate Example NOX Conversion. At 01 | Maximum NOX Conversion |Jaen Oxidation ppm Slip 502 — The — ARR oh) Bala ASA Khem 015 0 902 H M 7 © Rala AVY 17 YV, ¢ the SANE The results of Example 11a surprisingly show that 5 added is in the same molar ratio while 6 (+7 phosphorus) also effectively reduces the oxidation of 502. Addition of 5 in the manner described in Example 11 also seems to improve the conversion of NOX. It should be understood that the addition of sulfur is not limited to a particular sequential order; nor a certain amount of ©; and image as ion exchange unless otherwise expressly stated. It is also surprising that silica has a favorable effect on reducing the oxidation of 502 and increasing the conversion of NOX when adding silica with molybdenum at molar equivalent to 1.15 7 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 a to increase the conversion of NOx while reducing the oxidation of 502 . The z AR JE data show that the incorporation of sulfur with phosphorus has a detrimental effect on the conversion of NOX while also being effective in reducing the oxidation of 02. Example 11a A 01.5 g sample of a dissolved anatase titanium slurry is heated with water (6.7 77 solids) Yo to Te melt temperature via a hot plate with a temperature controlled led; 6 m was retained

AG ¢ —

temperature throughout preparation. pH is set to ; using lotion

Diluted ammonium hydroxide. A dilute solution (1) #7 wt. (S102) was prepared from

sodium silicate Inobond Na-4011 g of 1.8 0 by adding sodium silicate

(79.4 7 by weight as SIO2) to 14.9 g of deionized water.

460g fraction (base as received) ion exchange resin resin 100-8003006

of a strong acid Dowex™ 650CH H (photo) and then placed in a column burette.

Diluted 511085 solution was added through a column containing ion exchange resin – ion

exchange resin to slurry at a rate of © ml/min.

The pH 3 was further adjusted to ¢ using ammonium hydroxide 0 and left to react for 10 minutes.

A second solution was prepared by dissolving 7.77 g of 01 ammonium heptamolybdate

ml water. This solution was added to the slurry by means of an ion exchange column at a rate of © ml/

a minute. After the addition is completed; The ion-exchange resin was rinsed into the column

Using 10 mL of deionized water added at a rate of [Je minVo] to the slurry of titania .

The pH of the mixture was adjusted to ¢ using an ammonium hydroxide solution.

diluted and left to react for 10 minutes. The mixture was filtered and rinsed with 0.1 L of water

deionized water; It was dried at ca No and then calcined at + OF

degrees Celsius for 7 hours. Target loads were 0.5 7 wt. SI02 and; 7 wt.Mo 1

Example 71b

The catalytic support was prepared as described in Example VY except that 0,0 was added

g of 785 phosphoric acid into a molybdenum solution. Target downloads

EAN

h —_ _ of this carrier Vo + 7 wt 0.9 » phosphorus 7 wt Si02 f; 7 wt. molybdenum Example 11c The catalytic support was prepared as described in Example DY except that VAY 8 g of 785 phosphoric acid was added to the molybdenum solution. What were the target loads of this carrier? 7 wt. 0.5 “phosphorus 2 wt#5102”; And the; 7 wt. molybdenum NY JEL 3,77 except that IVY was added Catalytic carrier was prepared as described in Example 0 Target loadings were . molybdenum to a solution of phosphoric acid 785 g of wt. 5102”; And the; 7 wt. 2 # 0.5 “phosphorus wt. 7 0.1 of this carrier.

AVY JE

1,44 Except that IVY was added the catalytic support was prepared as described in Example Vo . molybdenum to a solution of phosphoric acid 7785 g of wt 7 0,5 “phosphorus wt 7 7,0 Target loadings of this carrier were as described in example vanadia 1, was added 9 and?; 7 wt. 0/a. In each case; 2 3 A) and then perform a DeNOx accelerated transformation selection in the following manner. The catalyst was then evaluated as a powder without further formation. A 0.0 rum Ax rum" quartz reactor held 1 g of catalyst mounted on glass wool. The feed composition was 0001 ppm of (NO 0275 75 120. EME

The partial pressure is increased 13 not sequentially from 700 ppm to 9000 ppm and then finally to 10 ppm so that the remainder is N2 . The conversion of NO was not measured after achieving steady state at each concentration of NH3 while the reactor temperature day was kept at Fou ° C and the pressure was in barometric. The output of the © flow reactor was analyzed with an infrared detector to determine the NO conversion. The results of the NOX conversion test and the 502 oxidation test are shown in the following table led1. Table T Jt (total loading |NOX conversion. at 01 ppm sal] phosphorus million slip 502 0 np at 6 1 part 0 mo at gal blood at Million of in Le day NH3 Million: NH3 EAN

A —_ _ 4 7 loading of molybdenum catalysts shows similar trends as observed. The oxidation rate of 502 generally leads to reduction with increasing phosphorus loading; The conversion of NOX at Yo. dap Celsius passes surprisingly at the maximum of Alla with an increase of phosphorus . The use of the term 'metal' as a catalyst component should be understood to have the same meaning as the corresponding metal oxide © as a catalyst component unless otherwise indicated. For example; 'molybdenum' as an oxidant 'has the same meaning as '1/0003 as an oxidizer.' The approximation language may be applied, according to the user in the present application in the rest of the specification and the claims, to designate any quantitative or qualitative representation that would vary in a permissible manner without resulting in a change in the basic function to which it relates. ; the value modified by an expression such as "about" or numerical range values are not limited to a specified exact value of 0 and can include values that differ from the specified value. In some examples J) can correspond to the approximation language to the precision of a value-measuring instrument. In addition to the above; NOX removal or reduction can be used in combination with the expression and includes varying the amount of NOK removal and is not limited to a specific exact value and can include values that differ from a specified value. It will be apparent to those skilled in the art that various modifications and various changes in the method and system can be made from the present invention without departing from the spirit or scope of the invention. Subsequently; A currently disclosed concept and/or protected innovation is intended to include modifications and variations within the scope of the supplementary claims and their equivalents. While currently disclosed and/or innovative protected concepts are described in detail with respect to a specific number of aspects; It should be understood that currently disclosed and/or innovative 0 protected concepts are not limited to those aspects that have been disclosed. rather; Wa's disclosed concepts and/or protected creation may be modified to include any number of variations; the changes; substitutions; or equivalent arrangements not described therein but which correspond to the scope of the ga protectors. additionally; While various examples of currently disclosed and/or Wa and/or protected innovative concepts are described; We should be aware that aspects of the invention disclosed protected innovative concepts can include only some of the embodiments described. Accordingly, currently disclosed concepts and/or protected creation should not be considered restricted by the description as limited only by the scope of the enclosed claims. © Wily Ibid.

Claims (1)

J- Claims 1- A method for manufacturing a catalyst support material that includes the following: a. Providing anatase titania slurry: f b. Combine the anatase titania slurry with 1) low molecular weight form of silica; “” molybdenum_source to form a mixture of MoO2-Si02 -1102; where © a low molecular weight form of silica comprises a selected member of the group consisting of silica forms with an average aaa estimated size less than ; nanomolar and average molecular weight less than 45,000 and combinations thereof.”- The method according to the claim oO) which also includes supplying an amount of phosphate 0 to anatase titania slurry. *- The method according to the oF claim, as it also includes providing phosphite after providing 1) low molecular weight form of silica; (V and a molybdenum source. +- method according to claim Cuno) involves providing a molybdenum source or a low molecular weight form of silica to slurry titania 2081856_by means of ion exchange resin .lon exchange resin 5- The method (according to the claim Cua) includes providing a low molecular weight form of 0_ silica and a molybdenum source to a sequential anatase titania slurry. 7- The method according to claim 0 (which includes providing a low molecular weight form of silica to a slurry, Ji anatase titania, providing a source of molybdenum. 6m — \g “- method according to claim Cuno) involves providing (V) a low molecular weight form of (VSL) and a molybdenum source to anatase titania slurry 4 at the same time. 4- Method according to claim Gua ) a low molecular weight form of silica© includes a selected member of the group consisting of sodium silicate solution; alkaline solution; tetra alkyl ammonium silicate «tetramethylammonium silicate» and combinations thereof. 4- The method according to claim 11 where A low molecular weight form of silica A has an estimated average size of less than 2 nm.-0 Method with claim 0 also includes the incorporation of a mixture of TiO2-M0O3- 2 with V205 to form a catalyst Vanadia 1808018. sala-11 1 catalyst support material containing 837 # to 7 54 by weight of anatase titanium dioxide: from 70.1 to 7 01 by weight: 0003 / and from 70. 1 to 0 by weight of 5002 in low molecular weight form: where low molecular weight is estimated to be less than nanomolar and average molecular weight is less than 0044.00; and combinations thereof. Y.-1 The catalyst support of claim 91 wherein the catalyst support includes a 02 having a partial monolayer value of less than 1.5 prior to the calcination of the catalyst support. 1- The catalyst carrier according to claim 91 where the catalyst carrier has a BET surface area of at least 0 5 m7/gas before calcining. EAN _— \g sald) — catalyst carrier pursuant to claim 01 wherein it also includes from 70.09 to 0/Y,0 phosphorus. phosphorus 0 — catalyst carrier according to claim 01 wherein it includes an image Low molecular weight of 0.502 on nanoparticles having a diameter of less than ; nanometers. 7- The catalyst carrier of claim 1 wherein a low molecular weight form of 02 includes 5102 having a molecular weight greater than 0,000 2¢. -1#0 catalyst carrier (OY) in which a low molecular weight profile of 5:02 comprises greater than 750 silicon atoms in Ql and 02 coordinate environments; and 93 and 0©. —V A The catalyst carrier of claim 11 includes the following: 0 70.7 to 75 by weight 5602 in low molecular weight form: 17 7 to 75 by weight 2:3 and 7.0 01 to 77.5 phosphorus: where it contains from 787 to 794 by weight of anatase titanium dioxide on anatase titania particles. 4- The catalyst carrier material according to the claim VY, as it also includes from 70.1 to IV ./205 wt 0 catalyst carrier according to claim 99 where it also includes from 70.7 to sald) - 0 ./205 wt 28 Yo 1?- catalyst carrier according to claim Fe as it also includes from 70.5 to 4 by weight V205 -” sale = YY catalyst carrier comprising the following: primary promoter =) = e ; anatase titanium dioxide _ comprising molybdenum oxide: and a volatilization inhibitor comprising low molecular weight silica forms: where a low molecular weight form of silica comprising a selected member of a group consisting of silica forms with an average estimated size of less than 2 nm and an average molecular weight of less than (EE, ven and combinations thereof. sold) — YY catalyst bearing pursuant to claim YY Comprising a ratio in moles of phosphorus to molybdenum in the range from 0.7:1 to 1:4.Ye; ?- catalyst carrier according to claim (YY where sald is the carrier The catalyst is substantially free of tungsten .—Yo catalyst carrier according to claim Gua (YY catalyst support Sole Vo includes tungsten. 7?-sald) catalyst carrier according to of claim YY where it also includes 7205 to form the vanadia catalyst. sold) -77 - 0 bearing the catalyst according to claim 77; comprising a ratio in moles of molybdenum to vanadium in d Z from 1 see to 1:01 .sald) YA bearing the catalyst according to the claim (YY) comprising a ratio in moles of molybdenum to vanadium in the range from Y v0 to EEA Yo 4- The method of manufacturing a catalyst carrier sale includes the following: — g a) provide anatase titania slurry; 5 b) combine anatase titania slurry with: 1) a volatile inhibitor comprising low molecular weight silica forms: “) main promoter comprising molybdenum oxide to form a mixture TI02-M0oO3-Si02 0 wherein a low molecular weight form of silica comprises a member selected from a group of silica forms with an average size estimated to be less than nanomolar and an average molecular weight less than 6 5); and combinations thereof. #©0 Method according to claim YA where it also includes providing an amount of phosphite to 0 slurry anatase titania 430-1 (according to claim oF where it also includes providing phosphite before providing 1) volatilization inhibitor and 7) the main promoter. Yo?©- method of claim 79 comprising the provision of a primary promoter or volatilization inhibitor to anatase titania slurry by means of ion exchange resin.”7- Method of claim 74; It includes providing a volatilization inhibitor and a main promoter to the anatase titania slurry sequentially. 70; vo — method according to the claim. YS as it includes providing 1) volatilization inhibitor and 7) main promoter to the anatase titania slurry at the same time. 6 pm ©- the method according to the claim (YA wherein the supply of the volatilization inhibitor includes a member selected from degen) consisting of “sodium silicate” alkali solution; Tetra alkyl ammonium silicate « tetramethylammonium silicate and combinations thereof. YY © Method pursuant to Claim 749; It also includes combining a mixture of -1102-1/002 2 with 205/7 to form a vanadia catalyst. YA — method according to claim (FY) wherein the vanadia catalyst comprises from 70.1 to IV by weight V205 Va 4 ?- method comprising: contact of gas or liquid containing oxide 71009860 with A catalyst for sufficient time to reduce the level of NOX in a gas or liquid containing nitrogen oxide using a catalyst comprising: from AT # to 94 # by weight of anatase titanium dioxide: from 70.1 to 701 wt Vo of sMOO3 from 70.5 to 27 wt 205/: from 750.1 to 201 wt from 5602 in ua 3) 3 wt LW; where the low molecular weight profile of 502 includes a molar member and an average molecular weight of less than 0044.00; and combinations thereof. -4160 0 Method according to claim oF wherein the catalyst furthermore comprises from 70.01 to 727.5 by weight phosphorus. 6 pm h — gm step 111 i : SE —— step Yr. i 1 step 6 masa bn tashassadsutz #[ step to. yee k7 _ 7 g th, TY. | Te. | ™ \ : HH © _\ 0 A | | LT | ssa + w ogle AE | : a mata oo oe LF 1 : , J ver vei | . Jit Re as 7 A — g 1b" ri step: Hy Hy ‎: 0 , 0 0 0 * 1 a " a 1 y step ! + SS | {LR EAVES q — gms ci 8 1 : FUN x 3 : i § s ¥ i a 3 7 x : 2 lbit_bit yth x a l a : E: 3 3 3 TE o 8 i 3 l l a i a e e ; { : § b " 8 8 § : i § £ 8 3 i 3 3 1 3 SR NE The: a. i 7 8 0 LPNS MG AAM ERA I ron AT NA RE even an a eS ENR ae SR eae A A RR wag and right iT Fes 8 0 § ; : La SH ESE Latat sak alaaa aa araa i § 5 g H A 7 § 3 SPSS JUIN: SUE SUSI a tay es tu x a 2 7 : i § i TE & oo # {i SERS Son J aga te #assrb su tan sa lam SR Ah A Wa A E L iF P ! arms oie i Foal maf wa an og 0 7 h w ja ma r rd : i rns, vo & pe & ds fen Eee BIR dig EC INCHES a 4 * x Ew 34 « IY ¥ Hamsin ji EY 1 tAVE The validity period of this patent is twenty years from the date of filing the application, provided that the annual financial fee is paid for the patent and that it is not invalid or forfeited for violating any of the provisions of the patent system, layout designs of integrated circuits, plant varieties, and industrial designs, or its executive regulations issued by King Abdulaziz City for Science and Technology; Saudi Patent Office P.O. Box TAT Riyadh 57??11 ¢ Kingdom of Saudi Arabia Email: Patents @kacst.edu.sa