Ultra-thin anatase titanium dioxide, stabilised with silicon dioxide, vanadium dioxide-based catalysts and methods of obtaining thereof

FIELD: chemistry.

SUBSTANCE: invention relates to the field of selective catalytic reduction of nitrogen oxides, namely to a material of a carrier for the catalyst, used in the said process. The claimed carrier material represents particles of anatase titanium dioxide, including ≥85% by dry weight of TiO2 and ≤10% by dry weight of SiO2, with (i) SiO2 being mainly in the form, selected from the group, consisting of forms with the low molecular weight, nanoparticles and their combinations; and (ii) at least 50% of silicon atoms being in states Q3, Q2, Q1 and Q0 of the coordination environment. The invention also relates to a catalytic device for the neutralisation of Diesel exhaust, including such particles, a system for Diesel exhaust regulation, including the said catalytic device, a method in which the conversion of nitrogen oxides is catalysed in the presence of the claimed particles of anatase titanium dioxide, as well as to methods of obtaining the said particles.

EFFECT: claimed particles make it possible to increase the thermal stability of the final catalyst with the preservation or increase of the catalytic activity for the selective catalytic reduction of nitrogen oxides from mobile devices, operating on lean mixtures.

44 cl, 18 dwg, 15 tbl, 18 ex

 

The level of technology

Selective catalytic reduction (SCR) of nitrogen oxides produced during combustion processes, using reducing agents such as NH3was successful industrial technology for more than 30 years. Initially it was introduced to regulate emissions of NOx in exhaust gases from stationary power plants and other industrial enterprises. Recently, the interest in this technology has increased as a result of its applicability for the treatment of emissions from mobile sources of energy, such as marine vessels, cars, trucks and machinery. This increased interest was largely stimulated by the legislative decrees that determine the emissions from mobile sources. For example, regulations of the US EPA (Federal Agency for the environment USA), which will operate in 2010 for mobile diesel engines, establish such emission levels for NOx that is essential to effective additional treatment of the exhaust, and SCR is a dominant technological option.

Fixed units of application requirements to the catalyst is not very high. For example, stationary engines typically operate in the regime close to stable, in conditions of constant temperature and with relatively low� volumetric velocity of the gas. In addition, are not too strict requirements for the catalyst with respect to its volume. However, in cases of application for on-road mobile installations requirements catalysts are much more rigid. In this case, the engines don't work in a stationary mode or at a constant temperature, but, on the contrary, their load (and thus temperature) varies widely. In one possible configuration of the SCR catalyst is placed downstream of a diesel particulate filter (DPF), and scored regeneration DPF soot can cause the passage of high temperature pulse of hot gas through located downstream SCR catalyst. In addition, mobile versions of applications usually provide much higher volumetric gas flow speed, and requirements for the catalyst with respect to its volume are hard. For example, in early versions of applications in the SCR for heavy duty diesel engines volume of the catalyst was several times larger than the working volume of the engine! For these reasons, it has become imperative to develop improved catalysts which have higher temperature resistance and increased volume activity so that you can find cost-effective technological solutions to meet the increasingly strict but�regulatory requirements.

The technology that was used for many years in stationary applications, include catalysts based on metal oxides, in particular those that are based on TiO2as a catalyst, and with the active catalytic functionality on the basis of vanadium oxide, V2O5. Thus, applied a mixture of TiO2(80-95%), WO3(3-10%), and, optionally, with the rest of the amount attributable to SiO2(such as DT-52™ and DT-58™), as a catalyst, and the active component of vanadium oxide is usually present in an amount of from 0.1 to 3% by weight. In these catalysts, titanium dioxide initially present with a relatively high surface area anatase form. The use and limitations of the catalysts based on vanadium oxide for mobile SCR systems using urea as described in the review of "Studies in Surface Science and Catalysis" ("research in the field of surface properties and catalysis, edited by Granger, R. and Parvulescu, V. I., volume 171, Chapter 9. There are two considerations relatively high stability of the catalyst based on vanadium oxide. First, the catalysts can be used in mobile applications with the layout, where a diesel particulate filter (DPF) is placed upstream relative to SCR catalyst based on vanadium oxide. In this arrangement, Wang�yokenny the catalyst may be exposed to extreme variations in temperature, associated with the exothermic regeneration of a diesel particulate filter (DPF). The second consideration is that it is desirable that the catalyst based on vanadium oxide retained its catalytic activity at high temperatures (e.g., >550°C), to better compete with metallocene zeolite catalysts based on noble metals, which exhibit a high degree of stability and activity at high temperatures. Material DT-58™ contains 10% by weight of SiO2, 9% by weight of WO3and 81% of TiO2and has a specific surface area of about 90 m2/gram. However, it is well known that catalysts based on titanium dioxide and vanadium oxide are not particularly thermally stable. There are several opinions regarding this lack of thermal stability. First, titanium dioxide itself is prone to sintering at an elevated temperature, due to the loss of surface area. Secondly, titanium dioxide at high temperatures is also subjected to conversion to the rutile crystal form, and this form mainly appears less active carrier than the anatase form. Third, the oxide of vanadium without the carrier has a melting point of about 675°C, and thereby, even when deposited on a carrier of titanium dioxide, at elevated temperatures the slopes.�Yong to some extent to move and eventually aggregated with the formation of crystals of vanadium oxide with a low surface area (and less active).

For these reasons, the imperative is to increase thermal stability of the final catalyst, and at the same time maintaining or enhancing the catalytic activity for selective catalytic reduction of nitrogen oxides (SCR-DeNOx) from mobile engines operating on lean mixtures. The simultaneous achievement of both objectives is very challenging, since often one factor can be improved at the expense of another. For example, described the introduction of silicon dioxide and/or rare earth metals in titanium dioxide to improve stability, but further progress is required in relation to how stability and activity.

Stable amorphous silicon dioxide ultrathin anatase titanium dioxide previously used as catalysts. It is known that amorphous silicon dioxide improves the stability of the anatase phase and the preservation of the specific surface area ultrathin anatase titanium dioxide, and therefore, the amorphous silica is an additive in industrial products type DT-58™ and DT-S10™, and these materials can be used on an industrial scale in catalysis for selective catalytic control of diesel emissions, especially for DeNOx-applications.

Early patent describes the use of "silicic acid� for the stabilization of the anatase titanium dioxide for DeNOx (U.S. patent 4,725,572). However, with careful reading of the patent is that the source of silicon dioxide is actually a colloidal dispersion of the silica. A more recent U.S. patent (U.S. 6956006 B1) also describes the use of colloidal silica to give the anatase titanium dioxide of high thermal and hydrothermal stability. A recently published patent application U.S. 2007/0129241 A1) discusses DeNOx-catalysts based on vanadium oxide/titanium dioxide with enhanced stability. Used it as the source of silicon dioxide is also a colloidal silica. However, these titanocene catalysts from colloidal silica, as noted, do not have sufficient stability and acceptable activity after exposure to extremely high temperatures. Catalysts based on titanium dioxide, which minimise these disadvantages, would find wide application, and would be a top priority.

At the time, like the aforementioned material DT-58™ media is a prototype carrier material for catalysts in diesel emissions, improved carrier based on titanium dioxide would, in General, be (1) more thermally stable, thereby allowing you to place it in closer proximity to the engine, and (2) a catalytically active, those� provide the possibility of applying the filter housing to a lower value (say, 10 l to 12 l) for the maintenance of the catalyst, thereby optimizing (reducing) the size of the system of emissions control.

The present invention is directed to obtaining such improved titanocene media, modified with silica, and made of these catalysts.

Summary of the invention

The present invention describes compositions and methods for producing a stable ultra-thin anatase titanium dioxide for use, for example, as a carrier material for vandieken catalysts, preferably for use in the catalytic system of emissions control. Stabilization includes the processing of titanium dioxide soluble form of silicon dioxide with a low molecular weight and/or shape of small nanoparticles (<5 nm), such as, in a preferred embodiment, the silicate Tetra(alkyl)ammonium, such as silicate of Tetramethylammonium, or silicic acid, which is used for the effective preservation of the anatase phase prevent caking (crystal growth) in harsh thermal and hydrothermal conditions, even in the presence of vanadium oxide. New stable silica dioxides of titanium, combined with vanadium oxide, have equal or improved catalytic activity for selective catalytic reduction of NOx by �compared with currently available anadyomene catalysts on the basis of silicon dioxide-titanium dioxide.

In one of its aspects the invention provides a carrier material of the catalyst, which comprises particles of anatase titanium dioxide, comprising ≥85 percent by weight in the dry weight of TiO2and ≤10 percent by weight in the dry weight of SiO2and SiO2is mainly in the form of low molecular weight and/or in the form of small nanoparticles. The carrier material of the catalyst may further include, for example, from 3% to 10% of WO3and may have a specific surface area by BET (Brunauer-Emmett-Teller) of at least 80 m2/gram. The carrier material of the catalyst may include, for example, ≥85% by dry weight of TiO2, 3%-9% SiO2and 3%-9% dry weight WO3. SiO2may be present with a value of the partial monolayer of less than 1.0 before the carrier material of the catalyst is subjected to sintering. SiO2in the form of small nanoparticles may have a diameter of <5 nm. Form SiO2low molecular weight may have a MW <100000. SiO2may include atoms of silicon, which is mainly (i.e., >50%) are located in the States of Q3, Q2, Q1and Q0coordination sphere. SiO2may include fragmented plots that have depth mostly ≤5 nm after redistribution, according to the observations using scanning electron microscopy or transmis�ionic electron microscopy. Used TiO2(optional, may be obtained in the presence of urea.

In another aspect the invention may provide a catalyst based on vanadium oxide comprising stabilized silica titanocene the carrier material of the catalyst as described here, which includes distributed it V2O5. The catalyst based on vanadium oxide may include, for example, from 0.5% to 5% on a dry weight basis of V2O5(or, more preferably, from 1.0 to 3%). V2O5may be present with a value of the partial monolayer of less than 1.0 before sintering. The catalyst based on vanadium oxide may be subjected to sintering, for example, at temperatures ≥650°C. In yet another aspect, the invention can provide a catalytic device for neutralization of diesel exhaust, including panagiotidis the catalyst, as it is described here. In another aspect the invention may provide a system of regulation of diesel exhaust, which includes the above-described catalytic device for neutralization of diesel exhaust and diesel particulate filter, and in which the catalytic device for neutralization of diesel exhaust is placed upstream or downstream of the diesel particulate filter.

In another one of your TSA�tov the invention is a method, which catalyse the conversion of nitrogen oxides in gaseous N2that includes a stage in which the engine exhaust comprising NOx, exposed to mandioquinha catalyst described here, with the added reducing agent for the formation of N2and H2O. the Reducing agent may be, for example, NH3and/or urea. In this method, the catalyst based on vanadium oxide may include, for example, 0.5% -5% (or, more preferably, from 1.0% to 3%) on a dry weight basis of V2O5. The engine exhaust can be passed through a diesel particulate filter before or after treatment with a catalyst based on vanadium oxide.

In another one of its aspects the invention is a method of producing the material of the catalyst carrier, which includes stages, which receive the suspension comprising TiO2combine the TiO2-suspension (1) a solution of the precursor of silicon dioxide, comprising SiO2mainly in the form of low molecular weight and/or SiO2comprising small nanoparticles, and (2) WO3with the formation of a mixture of TiO2-WO3-SiO2and the solution of the precursor of silicon dioxide combined with TiO2-slurry before, after or at the time when WO3combined with TiO2-suspension, and the mixture is then TiO2-WO3-SiO2washed, and exposed to a�up to the sintering with the formation of stable silica titanocene carrier material of the catalyst. In this method, stable silicon dioxide titanocene the carrier material of the catalyst may include, for example, 86%-94% dry weight of TiO2, 3%-9% dry weight of SiO2and 3%-7% dry weight WO3and titanocene the carrier material before sintering may have a specific surface area of primarily at least 80 m2/gram. TiO2in suspension may include, for example, preformed particles of titanium hydroxide, oxyhydroxide titanium or titanium dioxide. Optional, TiO2in suspension do not get in the presence of urea. Small nanoparticles formed of SiO2in the solution of the precursor of silicon dioxide is mainly can have a diameter of <5 nm. Form SiO2low molecular weight in solution of the precursor of silicon dioxide is mainly can have MW <100000. SiO2in the solution of the precursor of silicon dioxide may include atoms of silicon, which is mainly (i.e., >50%) are located in the States of Q3, Q2, Q1and Q0coordination sphere. The solution of the precursor of silicon dioxide may include a solution of silicate of Tetra(alkyl)ammonium or silicic acid. SiO2mainly can include fragmented areas that have a depth of ≤5 nm after redistribution, according to the observations using a scanning �electronic microscopy or transmission electron microscopy. The method may further include a stage in which the mixture of TiO2-WO3-SiO2combine with V2O5with the formation of mandioquinha catalyst. Formed so panagiotidis the catalyst may include, for example, from 0.5% to 3% to 5% on a dry weight basis of V2O5. V2O5it may be present with a value of granular monolayer of less than 1.0 before sintering. Panagiotidis the catalyst may be subjected to sintering, for example, at temperatures ≥650°C.

In another aspect the invention provides a method of producing stable silica titanocene carrier material of the catalyst, which includes stages, which receive the TiO2-a suspension comprising particles of TiO2get the source of the dispersed silicon dioxide, unite TiO2-slurry with a source of particulate silicon dioxide with formation of a mixture of TiO2-SiO2and bring the pH of the mixture of TiO2-SiO2to the level of <8.5 and the temperature to <80°C, and a source of particulate silica is dissolved and periostat on particles of TiO2with the formation of stable silica titanocene carrier material of the catalyst. The method may further include the stage at which combine stable silicon dioxide titanocene �the material carrier of the catalyst with WO 3with the formation of stable silicon dioxide titnaked-tungsten material of the catalyst carrier. The method may further include the stage at which stable silicon dioxide titnaked-tungsten carrier material of the catalyst is washed, and subjected to sintering. Stable silicon dioxide titnaked-tungsten carrier material of the catalyst may include, for example, 86%-94% dry weight of TiO2, 3%-9% dry weight of SiO2and 3%-7% dry weight WO3and titanocene the carrier material before sintering may have a specific surface area of primarily at least 80 m2/gram. Particles of TiO2in TiO2-suspension may include, for example, preformed particles of titanium hydroxide, oxyhydroxide titanium or titanium dioxide. Particles of TiO2in TiO2-suspensions are not necessarily in the presence of urea. SiO2in a mixture of TiO2-SiO2after dissolution may include atoms of silicon, which is mainly (i.e., >50%) are located in the States of Q3, Q2, Q1and Q0coordination sphere. According to the method, the SiO2on particles of TiO2mainly includes fragmentary sections, which have a depth of ≤5 nm after redistribution SiO2according to observations with the help�computer scanning electron microscopy or transmission electron microscopy. The method may further include a stage in which the mixture of TiO2-WO3-SiO2combine with V2O5with the formation of mandioquinha catalyst. In this way panagiotidis the catalyst may include, for example, from 0.5% -3% on a dry weight basis of V2O5. V2O5in panagiotidou the catalyst may be present with a value of granular monolayer of less than 1.0 before sintering, and panagiotidis the catalyst may be subjected to sintering, for example, at temperatures ≥650°C.

This document discloses at least the following objects.

Object 1. The carrier material of the catalyst, including:

particles of anatase titanium dioxide, comprising ≥85% by dry weight of TiO2and ≤10% on a dry weight SiO2and SiO2is mainly in the form of low molecular weight and/or in the form of small nanoparticles.

Object 2. The carrier material of the catalyst in accordance with the Object 1, further comprising from 3% to 10% of WO3.

Object 3. The carrier material of the catalyst in accordance with the Object 2, wherein the specific surface according to BET of at least 80 m2/gram.

Object 4. The carrier material of the catalyst in accordance with the Object 1, comprising ≥85% by dry weight of TiO2, 3%-9% SiO2and 3%-9% dry weight WO3.

Object 5. Mat�Rial a catalyst in accordance with the object 1, in which SiO2is present with the value of the partial monolayer of less than 1.0 before sintering of the carrier material of the catalyst.

The object 6. The carrier material of the catalyst under item 1, in which SiO2in the form of small nanoparticles has a diameter of <5 nm.

The object 7. The carrier material of the catalyst under item 1, in which SiO2in the form of low molecular weight has a molecular weight of <100000.

The object 8. The carrier material of the catalyst under item 1, in which SiO2includes the silicon atoms, which are mainly located in the States of Q3, Q2, Q1and Q0coordination sphere.

The object 9. The carrier material of the catalyst under item 1, in which SiO2includes fragmentary sections, which have a depth essentially ≤5 nm after redistribution, according to the observations using scanning electron microscopy or transmission electron microscopy.

The object 10. The carrier material of the catalyst under item 1, in which TiO2was not obtained in the presence of urea.

The object 11. The catalyst based on vanadium oxide, including:

the carrier material of the catalyst in accordance with the Object 2 having distributed therein V2O5.

The object 12. The catalyst oxide in�Nadia in accordance with the Object 11, comprising from 0.5% to 5% on a dry weight basis of V2O5.

The object 13. The catalyst based on vanadium oxide in accordance with the Object 11 in which V2O5present it with the value of the partial monolayer of less than 1.0 before sintering.

The object 14. The catalyst based on vanadium oxide in accordance with the Object 11, which was subjected to sintering at temperatures ≥650°C.

The object 15. Catalytic device for neutralization of diesel exhaust, which includes a catalyst based on vanadium oxide in accordance with the Object 11.

The object 16. Control system of diesel exhaust, including:

catalytic device for neutralization of diesel exhaust emissions in accordance with the Object 15; and

a diesel particulate filter and a catalytic device for neutralization of diesel exhaust is placed upstream or downstream of the diesel particulate filter.

Object 17. The way in which catalyze the conversion of nitrogen oxides in gaseous N2including:

impact on diesel emissions, including NOx, the catalyst based on vanadium oxide in accordance with the Object 11, with added reducing agent for the formation of N2and H2O.

The object 18. Method in accordance with the Object 17, in which the reducing agent is a NH3and/or urea.

The object 19. Method in accordance with the Object 17 in which the catalyst based on vanadium oxide consists of 0.5% -3% on a dry weight basis of V2O5.

The object 20. Method in accordance with the Object 17, in which diesel exhaust is passed through a diesel particulate filter before or after exposure of the catalyst based on vanadium oxide.

The object 21. The method of producing the material of the catalyst carrier, comprising stages on which:

prepare a suspension containing TiO2;

combine TiO2-suspension (1) a solution of the precursor of silicon dioxide containing SiO2mainly in the form of low molecular weight and/or SiO2comprising small nanoparticles, and (2) WO3with the formation of a mixture of TiO2-WO3-SiO2; moreover, the solution of the precursor of silicon dioxide combined with TiO2-slurry before, after or at the time when WO3combined with TiO2-suspension, and

washed and subjected to sintering a mixture of TiO2-WO3-SiO2with the formation of stable silica titanocene carrier material.

The object 22. Method in accordance with the Object 21, which stabilized silica titanocene the carrier material includes

86%-94% dry weight of TiO2, 3%-9% dry weight of SiO2and 3%-7% dry weight WO3; and in which titanocene mate�ial the original carrier has a specific surface area of at least 80 m 2/g before sintering.

The object 23. Method in accordance with the Object 21, in which TiO2in the suspension comprises pre-formed particles of titanium hydroxide, oxyhydroxide titanium or titanium dioxide.

The object 24. Method in accordance with the Object 21, in which TiO2in the suspension obtained in the presence of urea.

The object 25. Method in accordance with the Object 21, in which SiO2in the form of small nanoparticles in a solution of a precursor of silicon dioxide mainly has a diameter of <5 nm.

The object 26. Method in accordance with the Object 21, in which SiO2in the form of low molecular weight in solution of the precursor of silicon dioxide mainly has MW <100000.

Object 27. Method in accordance with the Object 21, in which SiO2in the solution of the precursor of silicon dioxide includes the silicon atoms, which are mainly located in the States of Q3, Q2, Q1and Q0coordination sphere.

The object 28. Method in accordance with the Object 21 in which the solution of the precursor of silicon dioxide includes the solution of silicate of Tetra(alkyl)ammonium or silicic acid.

The object 29. Method in accordance with the Object 21, in which SiO2mainly includes fragmentary sections, which have a depth of ≤5 nm after redistribution, according to the observations using a scanning e�Tronic microscopy or transmission electron microscopy.

The object 30. Method in accordance with the Object 21, which includes a stage in which combine a mixture of TiO2-WO3-SiO2V2O5with the formation of the catalyst based on vanadium oxide.

Object 31. Method in accordance with the Object 30, in which the catalyst based on vanadium oxide consists of 0.5% -3% on a dry weight basis of V2O5.

The object 32. Method in accordance with the Object 30, in which V2O5in the catalyst based on vanadium oxide is present with the value of the partial monolayer of less than 1.0 before sintering.

The object 33. Method in accordance with the Object 30, which includes an additional stage in which the catalyst based on vanadium oxide is subjected to sintering at temperatures ≥650°C.

The object 34. A method of producing stable silica titanocene carrier material of the catalyst, comprising stages on which:

prepare TiO2-the suspension containing particles of TiO2;

prepare the source dispersed silicon dioxide;

combine TiO2-slurry with a source of particulate silica with the formation of TiO2-SiO2-mixture; and

adjusted the pH TiO2-SiO2-mixture to <8.5 and the temperature to <80°C, and a source of particulate silica is dissolved and periostat on particles of TiO2with the formation of stable dioxo�Ohm silicon titanocene carrier material of the catalyst.

The object 35. Method in accordance with the Object 34, further comprising a stage on which unite stabilized silica titanocene the carrier material of the catalyst with WO3to obtain stable silicon dioxide titnaked-tungsten material of the catalyst carrier.

The object 36. Method in accordance with the Object 35, further comprising stages, which are stabilized by the silica titnaked-tungsten carrier material of the catalyst was washed and subjected to sintering.

The object 37. Method in accordance with the Object 35, which stabilized the silicon dioxide titnaked-tungsten material of the catalyst carrier includes:

86%-94% dry weight of TiO2, 3%-9% dry weight of SiO2and 3%-7% dry weight WO3; and in which titanocene the carrier material initially has a specific surface area of at least 80 m2/g before sintering.

The object 38. Method in accordance with the Object 34 in which the particles of TiO2in TiO2-include suspension of pre-formed particles of titanium hydroxide, oxyhydroxide titanium or titanium dioxide.

The object 39. Method in accordance with the Object 34 in which the particles of TiO2in TiO2-the suspension obtained in the presence of urea.

The object 40. Method in a suitable�Wii with the Object 34, in which SiO2in TiO2-SiO2-mixture, after dilution, includes the silicon atoms, which are located mainly in the States of Q3, Q2, Q1and Q0coordination sphere.

The object 41. Method in accordance with the Object 34, in which SiO2on particles of TiO2mainly includes fragmentary sections, which have a depth of ≤5 nm after redistribution SiO2according to observations by means of scanning electron microscopy or transmission electron microscopy.

The object 42. Method in accordance with the Object 35, which includes a stage on which combine a mixture of TiO2-WO3-SiO2V2O5with the formation of the catalyst based on vanadium oxide.

The object 43. Method in accordance with the Object 42 in which the catalyst based on vanadium oxide consists of 0.5% -3% on a dry weight basis of V2O5.

The object 44. Method in accordance with the Object 42, where V2O5the catalyst based on vanadium oxide is present with the value of the partial monolayer of less than 1.0 before sintering.

The object 45. Method in accordance with the Object 42, which includes an additional stage in which the catalyst based on vanadium oxide is subjected to sintering at temperatures ≥650°C.

Other aspects of the invention will become apparent upon consideration negativezero�about description.

Brief description of the drawings

Figure 1 is a graph showing the effect of calcination temperature on the specific surface mandioquinha catalyst.

Figure 2 is a graph showing the effect of calcination temperature on the percentage of the anatase phase of titanium dioxide in vandieken catalysts.

Figure 3 is a graph showing the effect of temperature of calcination on DeNox-activity 1% bear vandieken catalysts.

Figure 4 is a graph showing the effect of temperature of calcination on DeNox-conversion of 3% bear vandieken catalysts.

Figure 5 is a graph showing the effect of temperature on DeNox-activity varied vandieken catalysts.

Figure 6 is a graph showing the effect of temperature on the specific surface of the catalyst carrier according to the present invention compared with traditional catalyst support.

Figure 7 presents the obtained transmission electron microscope (TEM) micrograph of kremnicka-wolframate-titanocene catalyst from Example 6, showing fragmentary sections of two-dimensional silicon dioxide <2 nm deep on the surface of titanium dioxide.

Figure 8 is obtained � a scanning electron microscopy micrograph of Vandyke-titanocene catalyst from Example 10, showing dispersed therein colloidal particles of silicon dioxide with a size of ~20 nm.

Figure 9 presents the obtained transmission electron microscope (TEM) micrograph of the catalyst, showing particles of colloidal silica with a size of ~20 nm on the outer surface of Vandyke-titanocene catalyst from Example 10.

Figure 10 presents the obtained transmission electron microscope (TEM) micrograph of the particles of the catalyst from Example 11, showing the crystals of anatase with a fragmented two-dimensional layer of silicon dioxide on the outer surface of the crystals. In this image the particles of silicon dioxide are not observed.

Figure 11 is obtained by using transmission electron microscopy (TEM) micrograph of the particles of the catalyst from Example 11, showing the crystals of anatase with a fragmented two-dimensional layer of silicon dioxide on the outer surface of the crystals. In this image you can see one of the remaining particle of silicon dioxide, which has a diameter of <5 nm.

Figure 12 is obtained by using transmission electron microscopy (TEM) micrograph of the particles of the catalyst from Example 12, showing a small two-dimensional fragmented parcels of silicon dioxide in the anatase Chris�Allaah.

Figure 13 is obtained by using transmission electron microscopy micrograph of craniometric fragmented sites present on the surface of catalyst particles of anatase titanium dioxide according to Example 13.

Figure 14 is obtained by using transmission electron microscopy micrograph of craniometric fragmented sites present on the surface of catalyst particles of anatase titanium dioxide according to Example 13.

Figure 15 is obtained by using transmission electron microscopy (TEM) micrograph of a catalyst before adding vanadium oxide and sintering. The image shows the edges of the crystal lattice associated with the anatase titanium dioxide; silicon dioxide is present in the form of fragmented plots with size 1-3 nm on the surface of titanium dioxide (Example 14).

Figure 16 is obtained by using transmission electron microscopy (TEM) micrograph of mandioquinha catalyst, which shows a large (>20 nm) three-dimensional inclusions of silicon dioxide (see arrows), which are poorly dispersed on the surface of titanium dioxide (for example, Example 15).

Figure 17 represents one obtained by using the transmission electron microscope� (TEM) micrograph of mandioquinha catalyst, which shows a large (>20 nm), three-dimensional inclusions of silicon dioxide (see arrows), which are poorly dispersed on the surface of titanium dioxide (for example, Example 15).

Figure 18 is a graph showing the influence of various temperatures of calcination (activation) on deNox-catalytic activity forms vanadium catalysts on a carrier of titanium dioxide.

Detailed description of the invention

The primary purpose of the present invention is to obtain stable, having a high specific surface area titanocene of carrier material in the anatase crystalline form, mainly for use as a carrier for vanadium oxide (V2O5in embodiments, the use as catalyst for the regulation of diesel exhaust. Stabilization includes the processing of titanium dioxide silicon dioxide in the form of low molecular weight and/or in the form of small nanoparticles, such as soluble silicate precursor Tetra(alkyl)ammonium (i.e., silicate of Tetramethylammonium) or tetraethylorthosilicate (TEOS). Other examples of precursors of silicon dioxide with a low molecular weight, which can be used in the present invention include, but are not limited to these, aqueous solutions of silicon halides (i.e., SiX anhydrous4where X=F, Cl, B or I), the silicon alkoxides (Si(OR)4where R=methyl, ethyl, isopropyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl, pentile, exile, octile, lonely, Cecily, undecyl and dodecyl, for example), other organosilicon compounds, such as hexamethyldisilazane, salt fortramadol acid, such as hexaferrites ammonium [(NH4)2SiF6], solutions of Quaternary ammonium silicates (for example, (NR4)n, (SiO2), where R=H, or alkali such as the ones listed above, and where n=0.1 to 2, for example), aqueous solutions of sodium silicate and potassium (Na2SiO3, K2SiO3and MSiO3in which M represents Na or K in various amounts relative to Si), silicic acid (Si(OH)4), formed by ion exchange from any of the cationic forms of silicon oxide, listed here, using acidic ion-exchange resin (for example, ion exchange of solutions of alkali metal silicates or solutions of Quaternary ammonium silicate).

The term "form of low molecular weight" of silicon dioxide has to do with the particles of silicon dioxide having a molecular weight (MW) less than about 100,000. The term "form small nanoparticles" refers to particles of silicon dioxide having a diameter <5 nm.

A focus on improving thermal/hydrothermal stability of catalysts on the basis� vanadium oxide is relatively new, as this segment of the market of mobile devices to regulate emissions is still developing. And only after the authors of the present invention conducted extensive survey of traditional catalysts, it was found that the optimization of catalysts based on vanadium oxide stipulates that (1) it is necessary to minimize the total contents of silicon dioxide, and (2) that such forms of silicon dioxide, as the soluble form of low molecular weight and/or form small nanoparticles were most effective to ensure the required stability and activity.

Materials of the catalyst carriers according to the present invention exhibit unusual preservation of the anatase phase of titanium dioxide and specific surface area after heavy thermal and/or hydrothermal treatments, even in the presence of vanadium oxide. In the compositions and methods of the present invention is used in the form of low molecular weight and/or small nanoparticles of silicon dioxide to produce exceptionally ultrathin anatase phase of titanium dioxide and stability of the specific surface area, whereas the final panagiotidis catalyst demonstrates equal or increased catalytic activity against based on vanadium oxide in selective catalytic�of Stanovlenie NOx after accelerated aging. Such compositions and methods have not previously been known in the technology.

Two key aspects of the present invention that distinguish it from the prototype, include the nature of amorphous silicon dioxide and a method, which it is injected into the titanium dioxide.

As to the amorphous nature of silica, it is first necessary to distinguish between dispersed amorphous forms of dixide silicon and dissolved or gaseous forms, which are composed of amorphous silicate monomers or clusters with very low molecular weight, which are not considered as dispersed form, or include a very small nanoparticles. The form of silicon dioxide, suitable for the present invention described herein and are referred to as "silicon dioxide with a low molecular weight and/or small (<5 nm) nanoparticles. Two sources that describe the types of amorphous silicon dioxide, are "Ullmann's Encyclopedia of Industrial Chemistry" ("encyclopedia of industrial chemistry Ullman"), fifth edition, volume A23, pp. 583-660, (1993), and "The Chemistry of Silica" ("Chemistry of silica" by R. K. Iler, 1979. For example, one form of dispersed amorphous silicon dioxide is colloidal silica, or silicasol. This type of silicon dioxide consists of dense suspensions, discrete amorphous particles of silicon dioxide, which have diameters in the range R�of Smurov between about 5 nm and 100 nm. In this size range, the particles typically scatter visible light and thus form a slurry from turbid to opaque. Typically, these particles can be analyzed by the methods of scattering of visible light by using publicly available market devices. As will be seen from the examples below, without additional modification of the colloidal silica in the dispersed form (>5 nm) is not a form of silicon dioxide, suitable for the present invention. One reason that this form of silica is undesirable (without further modification) according to the present invention, is that most of the weight of the silica particle is inside, and not available on the surface for interaction with titanocene substrate. Thus, according to the author Iler (already quoted work, p. 8), particles of amorphous silicon dioxide with a diameter of 5 nm have 1500 silicate atoms, and 37% of these silicate atoms are on the surface of the particles, whereas the particle size of 1 nm almost all silicate the atoms are on the surface. Thus, for the purposes of the present invention, it is desirable to use sources of silicon dioxide, which mainly include particles that have a diameter <5 nm, and/or which have low molecular weight, for example, have MW with�provide < 100000, and thus are available to interact with the titanium dioxide. The exception, as will be described below, is a further modification of the dispersed silicon dioxide using conditions of pH and temperature at which the dispersed silicon dioxide was dissolved, and perioadei on the surface of titanium dioxide.

It is understood that the term "mainly", where it is used in this application means that more than 50% of the discussed process or of the material have a specific characteristic or condition, to which reference is made.

For example, as noted above, in a preferred embodiment of the present invention, the carrier material of the catalyst comprises silicon dioxide, which is mainly in the form of low molecular weight and/or in the form of small nanoparticles. This means that over 50% of silicon dioxide is either in the form of low molecular weight (MW <100000), either in the form of small nanoparticles (diameter <5 nm), or a combination of both forms. In a more preferred embodiment, silicon dioxide includes >60% forms low molecular weight and/or forms of small nanoparticles. In an even more preferred embodiment, silicon dioxide includes >70% forms low molecular weight and/or forms of small nanoparticles. In an even more preferred options�ante silicon dioxide includes > 80%, and further still more preferably >90% forms low molecular weight and/or forms of small nanoparticles of silicon dioxide.

In addition, low molecular weight or small nanoparticles according to the present invention preferably have the values of specific geometric surface area of >450 m2/g.

The dispersed form of silicon dioxide (i.e., in which the diameter is >5 nm) include silica gel, precipitated silica and pyrogenic silica. While the primary particles of dense amorphous silica dispersed in these forms can be very small (e.g., 2.5 nm), primary particles irreversibly glomerida with each other with the formation of much larger secondary particles, the sizes of which can vary from hundreds of nanometers to many micrometers in diameter. It is obvious that most of the silicate atoms in these secondary particles is not close to the surface and available to interact with the titanium dioxide. Of course, these secondary particles are easy to analyze using the methods of scattering visible light, and being in suspension, the particles make it quite opaque. Disperse silicon dioxide in either of these forms, without further modification, unsuitable for the present invention.

One class exce�of rare of silicon dioxide, which is suitable for the present invention, is a highly alkaline solutions, called "soluble silicates". They are described by the author Iler (the above reference, Chapter 2). These solutions are usually transparent, as particles of silicon dioxide, if present, mostly too small to scatter visible light. However, depending on the concentration of silicon dioxide or alkalinity in these solutions can form fine particles of silicon dioxide. Author Iler (the above reference, p. 133) gives the estimate for the molar relationship "SiO2:Na2O" at 3.1 average number of fragments SiO2on the particle in dilute solutions is about 900, which is less than 1500 silicate fragments in the above particle size of 5 nm. Such a silicate precursor, even if it may contain some nanoparticles larger than about 5 nm, suitable for the present invention, since most of the mass of silicon dioxide is in the form of smaller particles with low molecular weight. However, the alkali metal silicates are the preferred form of the present invention, since the residual alkali metal ions, such as Na, are extremely effective catalytic poisons for SCR catalysts based on vanadium oxide.

�AME nature of the nanoparticles of amorphous silica in alkaline solutions was further investigated by the authors Fedeyko, etc., ("Langmuir", 2005, volume 21, pp. 5197-5206). These authors used numerous ways, including small-angle x-ray scattering (SAXS) and small-angle neutron scattering (SANS). These methods are capable of detecting the presence of the nanoparticles up to a size of from about 2 to 3 nm. The authors showed that in dilute solution when the ratio [OH]/[SiO2] is less than about 1, silicon dioxide forms small nanoparticles, while [OH]/[SiO2] more than 1 silicon dioxide is present in the form of monomers and oligomers that are too small to detect in experiments on the scattering of radiation. This latter type of particles of amorphous silicon dioxide, mostly too shallow for easy detection methods scattering of visible light and x-ray radiation, in which the present invention is called "amorphous silicon dioxide with a low molecular weight and/or small nanoparticle", and they are the preferred forms of silica for the present invention.

One useful means for characterizing the monomers and oligomers of silicon dioxide in the solution is29Si-nuclear magnetic resonance (for example, see Chapter 3 in the book "High Resolution Solid-State NMR of Silicates and Zeolites" ("Solid-state high-resolution NMR of silicates and zeolites") authors G. Engelhardt and D. Michel, 1987). The method can give information� on conventional tetrahedral coordination environment of Si atoms, does Si or not one or more adjacent nearest Si neighbors (connected by bridging oxygen atoms). The designation, which is usually used to describe this coordination is as follows: Q0is related to the Central Si atom that does not have adjacent nearest Si neighbors, i.e., Si(OH)4; Q1refers to a Central Si atom with one closest adjacent Si-neighbor, i.e., Si(OH)3(OSi)1; Q2means the Central Si atom with two adjacent nearest Si neighbors, i.e., Si(OH)2(OSi)2; Q3has to do with the Central Si atom with three adjacent nearest Si neighbors, i.e., Si(OH)1(OSi)3; and Q4refers to a Central Si atom with four adjacent nearest Si neighbors, i.e., Si(OSi)4.

Without the intention to go into any theory, it appears that for direct use (without additional processing to change the form of silicon dioxide) is desirable the use of solutions of silicates, which consist mainly of oligomers from Q0to Q3. On the other hand, solutions of silicate oligomers, which are made almost entirely of Q4particles are undesirable for the present invention. In principle, the rationale is that for the latter types of silicate oligomers the main part of the silica is fully�TEW surrounded by other silicate particles, and thus unavailable for reaction with the surface of titanium dioxide, where it is most needed for the stabilization of anatase.

One form of silicon dioxide, which is suitable for use in the present invention, is a commercially available on the market the alkali silicate solution of Tetramethylammonium. Understanding the nature of this solution can be based on an earlier study. The authors Engelhardt and Michel (above reference, p. 92) describe the research method29Si-nuclear magnetic resonance 1M solution of SiO2(approximately 6% by weight with a ratio of TMA/Si=1.0 which is roughly equivalent to the concentration of TMON (hydroxide of Tetramethylammonium) at the level of 9% by weight. In this solution, the silicon dioxide is mainly in the form of cubic octamer, which contains 8 atoms of silicon, and they have Q3-coordination. These fine particles comprise about 90% by weight of silicon dioxide. The real solution of TMA silicate (Tetramethylammonium) used in examples of the present invention, has a slightly higher concentration of silicon dioxide (9% by weight) and the lower concentration TMAN (7% by weight), and thereby the distribution of the silica particles is somewhat different from the above literary message, as shown in Table 6 below.

Another form of silicon dioxide which is suitable for the present�present invention, is a "silicic acid". This type of silicon dioxide is described in Iler (the above reference, Chapter 3). A more detailed characterization of the silicic acid was carried out using the method29Si-nuclear magnetic resonance, as described by the authors G. Engelhardt and D. Michel (above reference, p. 100). This form of silicon dioxide can be obtained by acidification of the alkaline solutions of silicates, for example, by ion exchange using acidic ion-exchange resins.

The concept of partial monolayer.

Of interest is the demonstration that the compositions and methods of the present invention differs from prototype examples, and one way to do this includes the idea of partial monosloevogo coating the surface of the substrate oxide added. In the definitions below the subscript "x" denotes discussed the added oxide, e.g., silicon dioxide.

Withx=the amount of oxide added in the calculation of the surface area for solid monosloevogo coating, g/m2;

SA=surface area of mixed oxide;

Mx=the amount of oxide added per mass of solid monosloevogo cover; g/g) mixed oxide;

Lx=the actual number of added oxide is deposited on the mixed oxide, g/g;

FMx=p�rcially monolayer oxide added on the aged mixed oxide;

TFM=partial monolayer in General on the aged mixed oxide.

Mx=Cx×SA Equation 1).

FMx=Lx/Mx(Equation 2)

TFM=Sum(FMx) (Equation 3)

First, you need the best way to assess the degree, Withx, monosloevogo cover perfectly added dispersed oxides on a substrate made of titanium oxide or similar oxides. For vanadium oxide literary value for monosloevogo coating of the carrier oxide is 7-8 V atoms/nm2that corresponds to 1100 micrograms of V2O5/m2. (See the work of the authors I. E. Wachs et al., 2003). For tungsten oxide used literary value 4.5 W-atoms/nm2(I. E. Wachs, 2006), which corresponds to 1700 micrograms WO3/m2. For silicon dioxide was obtained literary value 600 micrograms of SiO2/m2(Iler, p. 36, above link). Thus, as an example, a mixed oxide consisting of 10% by weight of SiO2(0.10 g/g), 9% by weight of WO3(0.09 g/g) and 2% by weight of V2O5(0.02 g/g) with the rest of the amount of TiO2, is measured by the uptake of N2the specific surface according to BET of 250 m2/g. the Value of TFM for this material is TFM=(1/250)×((0,10/600E-6)+(0,09/E-6)+(0,02/E-6))=0,95. This figure shows that if the added oxides SiO2, WO3and V2O 5were perfectly evenly dispersed on the surface of titanium dioxide, mixed oxide would have formed a thickness of 0.95 ml of the added oxides. As far as the silicon dioxide, the partial monoline coverage would have amounted to 0.67, or two-thirds of the surface would be covered with perfectly dispersed coating of silicon dioxide. The compositions according to the present invention, being freshly prepared (i.e., after addition of the added oxides, but to aging or sintering, usually have a value of specific surface area greater than about 100 m2/g, and the total amount of oxides added at 15% by weight or less, and thereby the partial monocline coating specifically for silicon dioxide is about to 0.80 or less.

Ways of introduction of silica for the present invention.

The coating on the surface of titanium dioxide with the use of alkali metal silicates or silicic acid, such as described above, for many years employed in the industry manufacturing practices for the production of paints and coatings. For example, see chapters 52 and 53 of an overview paper "Colloidal Silica, Fundamentals and Applications," ("Colloidal silica, fundamentals and applications"), in Surfactant Science Series, volume 131, edited by N. E. Bergna, W. O. Roberts (2006). As described in Chapter 52 works Bergna and Roberts,one approach to coating the surface of titanium dioxide coatings of silicon dioxide includes the impact on the load-bearing particles of titanium dioxide silica in alkaline conditions, with the concentration of silicon dioxide, the value of which is less than the limit of solubility for amorphous silicon dioxide. As described in Chapter 53 of the work Bergna and Roberts, another method includes the impact on the surface titanocene media monogrammable acid at low pH, when the concentration of silicon dioxide, which again is very low and below the limit of solubility. Although the ways of introduction of silicon dioxide in the above-mentioned literary references are a means for the introduction of silicon dioxide, suitable according to the present invention, there are several important differences. One difference is that for the prototype phase of titanium dioxide, which is used as the substrate, is rutile (due to its higher ability to dissipate light than the anatase), and there is no indication on how the addition of silicon dioxide by using these methods you can prevent the transformation of anatase phase to rutile. The second important difference lies in the fact that the particles titanocene of the substrate in the composition of the prototype paints and coatings, regardless of whether they are anatase or rutile represent substrates with relatively small specific surface area, and specific uptake of N2the values of specific surface area of BE generally constitute less than about 15 m 2/g. thirdly, the key difference is the degree of surface coating added an oxide such as silicon dioxide. According to the above definition of partial monosloevogo coating composition accordingly to the present invention, if they were prepared on the substrate with a low specific surface area (15 m2/g), would be a General partial monolayer of about 5 or more, and partial monocline coating specifically for silicon dioxide would be approximately ≥3. Thus, in the prior art kremniikarbidnoi coating is present over all the particles of titanium dioxide, with a thickness that exceeds the thickness of the monolayer. Indeed, kremniikarbidnoi coating is present so that completely inactivates photocatalytic activity of the surface of titanium dioxide. Finally, in a preferred embodiment of the present invention, titanium dioxide coated with silica under conditions where the added silicon dioxide far exceeds the solubility limit of several hundreds of ppm. As will be seen below, the present invention is silica, being initially besieged, not completely cover the surface of titanium dioxide, so that the desired catalytic functionality of the surface of titanium dioxide for SCR reaction is still not lost. The poet�Moo thereby to achieve the goal of the present invention, consisting in maximizing the catalytic activity of the surface, preserving at the same time, the stability of the carrier.

There is another rationale why disperse silicas are preferred forms of silica for the present invention, including the form of dispersed silicon dioxide with internal porosity and thus high pore volume. From the literature (e.g., Wachs, etc., J. Cat., volume 161, pp. 211-221 (1996)) it is well known that silicon dioxide is not a good carrier for SCR catalysts based on vanadium oxide, titanium dioxide and doped tungsten oxide titanium dioxide are good media. Therefore, for the present invention, it is desirable to minimize the magnitude of the specific surface area of silicon dioxide, which is present for adverse interaction with the vanadium oxide, at the same time, reaching maximum values of surface area TiO2-WO3to make the most active catalyst. Thus, the used amount of silicon dioxide is only sufficient for the stabilization of titanium dioxide, and its use in this form (with a molecular dispersion on the surface of titanium dioxide), which has minimal adverse impact on panagiotidis catalyst.

N�end, now described another approach to obtaining materials according to the present invention, which can be used the above particulate form of silicon dioxide. It is well known that dispersed amorphous silicon dioxide is soluble to the extent of which depends on the pH of solution and temperature, for example, see the work of the author Iler (the above reference, p. 42). When the pH value above about 9 and at temperatures above the ambient temperature of amorphous silicon dioxide will have appreciable solubility. Then this dissolved silica may be again injected into the sediment, for example, on the surface of titanium dioxide, followed by lowering the temperature and/or pH to a level that reduces the solubility of silicon dioxide. This way disperse silicas, which are thoroughly mixed with anatase titanium dioxide, can be dissolved and redistributed with the effective dispersion on the surface of titanium dioxide via hydrothermal treatment. However, this additional processing is not the preferred method of producing compositions according to the present invention, since this stage increases the processing time and cost during the preparation of the mixed oxide. Most preferred is the use of prehodnoceni of silicon dioxide and immediate processing of titanium dioxide.

Examples

The source material for titanium oxide

In one embodiment of the present invention, the slurry used sulfated titanium dioxide (see Table 1). Such suspension sulfated titanium dioxide can be obtained as an intermediate product in the manufacturing process the preparation of titanium dioxide using the sulfate method, for example, how do you get in a production plant of the company MIC in tannay, France. This suspension includes about 27% having a high specific surface area aqueous anatase titanium dioxide, TiO2. TiO2has mainly crystalline particles having dimensions less than 5 nm, and the corresponding specific surface area determined by BET absorption of N2exceeding 250 m2/g. the Slurry has a viscosity of 0.5 to 3 poises, a density of 1275 kg/m3and a low pH of about 1.5 to 2.0, which is due to the fact that the suspension contains about 6.6% by weight of SO3. However, the present invention is not limited to this suspension. Here could be used in any composition, comprising an aqueous anatase titanium dioxide. In fact, there is no need to use sulfated suspension of titanium dioxide as a starting material. Instead, it could be used�van dried precursor anatase titanium dioxide with a low content of sulfate.

Table 1
The suspension of sulfated titanium dioxide
TypeMethodUnitTechnical condition
Residue on
The residue from the calcinationTiO243 Drying, then calcining at a temperature of 1000°C% (by weight)27±1
IronTiO2.15 X-ray fluorescencemg/kg≤80
SO3G1.3 S-analyzer/moisture content at 105°C% (by weight)6.6±1
P2O5TiO2.16 X-ray fluorescence% (by weight)≤0.4
NaTiO2.47 Atomic absorption % (by weight)≤0.05
KTiO2.5 X-ray fluorescence% (by weight)≤0.01
PbTiO2.13 X-ray fluorescence% (by weight)≤0.01
Peak heightG1.2 X-ray diffractionDegrees≥1
RutileTiO2.48 X-ray diffractionIs not defined
Specific surface areaG1.1 B. E. T.m2/g≥250
* Statistical significance

However, preferred is the preparation used here, the suspension of titanium dioxide from titanium dioxide, which was obtained in the presence of urea.

In one embodiment the TiO2-the component used here, the carrier material of the catalyst mainly has a specific surface area of <400 m2/g and pore about�eat < 0,40 cm3/g.

Experimental methods: the structure and stability of catalysts based on titanium dioxide, and the changes that occur during exposure to elevated temperatures, explored a variety of ways. The methods used include x-ray diffraction analysis (XRD), transmission electron microscopy (TEM), SEM (scanning electron microscopy), spectroscopy solid-state nuclear magnetic resonance high-resolution NMR, nitric porometry (N2BET/BJH) and evaluation of catalytic activity in the reaction of NO with NH3(DeNOx)

SAR: the samples were assessed according to the composition of the crystalline phase and the crystallite size of as follows. Samples were prepared for XRD by pressing in the spherical holders PCA PW1812/00 and then analysed using a diffractometer Panalytical X Pert Pro™, equipped with a sealed Cu x-ray tube and the position sensor X-Celerator. Operating conditions of the device were set to 45 kV, 40 mA, 0,008°2θ/step and 50 seconds duration of exposure. Phase identification was performed in the mode "search-match" pilot symbols with both databases ICCD and ICSDs. For Quantitative Analysis of Phase composition by x-ray diffraction used the Rietveld method. The crystallite size measured by single peaks according to the Scherrer formula, the cat�the ROI used in the software package Panalytical High Score. The Scherrer formula is based on the fact that the crystallite size is inversely proportional to the full width at half (FWHM) of an individual peak is narrower than peaks are, the larger the crystallite size. The value of the instrumental broadening, used for calculations, borrowed from a LaB6 standard (standard reference material of NIST (National Institute of standards and technology)). In addition, to calculate the size of the grains also used full-profile method, such as Rietveld Analysis, the software package X Pert High Score Plus™.

TOPICS: samples were prepared for THE analysis by immersing copper (Cu) grids for THE fully wrapped carbon directly in the prepared powder. Then the grids were examined in a transmission electron microscope (TEM) at magnifications ranging from 50 - to 400,000-fold. The analysis was performed using THE instrument JEOL 2000FX II, operating at a voltage of 200 kV. During the process of image acquisition, special attention was paid to the characterization of the size and distribution of phases. Images were taken with a digital CCD camera Gatan MultiScan™, and converted to jpeg format.

SEM: samples were prepared for SEM analysis prepared by dispersing the powder on aluminum SEM-substrate, coated with colloidal graphite carbon. SEM analysis was performed using �of Ribera JEOL 7401 at a voltage of 2 kV without conductive coating.

Characterization of the samples by using29Si-NMR spectroscopy. A useful approach for characterizing the state of the coordination of silicon dioxide in solid samples containing silicon dioxide (for example, see the work of authors Engelhardt and Michel, 1987 (the above link), as described above, is spectroscopy of29Si-nuclear magnetic resonance with rotation under magic angle (29SIMASNMR). However, the problem with29Si-MASNMR is that the nucleus29Si are present with relative low natural content (4,7%), and therefore the method is not very sensitive. A common method of increasing the sensitivity is the approach with cross-polarization (for example, see "Colloid Chemistry of Silica" ("the Colloid chemistry of silica"), edited by N. Bergna, ACS Series, vol. 234, p. 270 (1994)). In this method, the spin polarization from the more common spin which has a large nuclear magnetic moment (in this case,1M), by double resonance is transferred to the less common spin (29Si). This method increases the sensitivity for29Si-NMR signal, when Si has an associated group (HE). It is well known that in the silicates silicon has a tetrahedral coordination, and is surrounded by four nearest-neighboring oxygen atoms, the nearest neighboring atoms to�which are either N, or Si. One would expect that the isolated silicate tetrahedron, which is planted on the surface of titanium oxide, would have at least one nearest neighboring atom N, Si-IT, and this proton could improve the sensitivity of the method for the core silicon. Of measurement29Si-HMP spectroscopy can also be performed on liquid samples that contain soluble silicates with low molecular weight, as described by the authors Engelhardt and Michel (the above link).

Nitric porometry: samples were evaluated for nitrogen injection using analyzers Micromeretics TriStar™. The samples were subjected to degassing overnight at 150°C in a stream of nitrogen. Then they were cooled to room temperature to measure the adsorption capacity. Curves of adsorption/desorption were measured at the temperature of liquid nitrogen. Specific surface area was determined using BET method, and pore volumes were measured using the BJH method (Barrett-Joyner-Halenda) on the adsorption branch.

The vanadium oxide was added by impregnating or alkaline solution (e.g., monoethanolamine) or acid solution (e.g., oxalic acid). Then the impregnated material was subjected to aging at high temperature in the hydrothermal treatment conditions (750°C for 16 hours in 10% H2O) (Il� at a temperature of 600°C-900°C for 6 hours in air atmosphere), to ensure accelerated aging. It is desirable to have 100% anatase with a high specific surface area (associated with very small crystallites and crystalline tungsten oxide after treatment with aging.

Examples 1-3: benchmarking of industrial materials

The following three examples, the authors present invention has sought to test the efficacy of several industrial prototype materials that are used in SCR devices, namely DT-52™ (Example 1), DT-58™ (Example 2) and DT-S10™ (Example 3). The properties of these three materials are listed in Table 2. It can be seen that DT-52™ contains no added tungsten oxide but not silicon dioxide), DT-S10™ contains added silica (but not tungsten oxide), and DT-58™ contains both added tungsten oxide and silicon dioxide.

Table 2
The target properties of industrial materials
Material
PropertyUnitDT-52DT-58DT-S10
WO3per cent by weight10.09.00.0
SiO2per cent by weight0.010.010.0
TiO2per cent by weightThe remaining amount (90)The rest of the number (81)the remaining amount (90)
Specific surface aream2/g90110110
Crystalline phaseAnataseAnataseAnatase

For each of Examples 1-3, the base materials were used in the same condition as they were purchased, and the vanadium oxide was placed on them in the following way. Preparing a solution of monoethanolamine (MEA) in demineralized water, which had a concentration of 0.4 M (24.4 g/l MEA). To this solution was added to 10.9 g/l V2O5, (0.06 M). To obtain a catalyst with the final content of vanadium oxide at 1% on �Yeosu approximately 13.7 g of the above solution was mixed with 15.8 g titanocene media (loss on ignition=5% by weight), and the mixture was heated in a rotary evaporator under vacuum at a temperature of 75°C until complete drying. Then the obtained product was calcined in a static muffle furnace at a temperature of 600°C, 700°C or 800°C. similarly, the catalysts were obtained with a finite content of vanadium oxide (3% by weight when using of 41.2 g of the solution "MEA/vanadium oxide and 15.8 g of titanium oxide.

Then carried out the assessment of porosity by N2, phase composition and size of the crystals by x-ray diffraction, and DeNOx activity of the above materials (the results are shown in Table 3). In respect of DeNOx-activity, 0.1 g of sample from each sample of catalyst coated with a vanadium oxide was pelletized, and sorted to size -20/+40 mesh, and was placed in the reactor to determine the conversion of NO in the presence of NH3. The current thread, which contained 5% O2, 1000 ppm of NH3, 1000 ppm NO and 3% H2O, is passed over the catalyst with a space velocity of 650 l/g of catalyst per hour.

Visual overview Table 3 confirms the trends described in the literature, and that these higher levels of vanadium oxide and higher temperatures are associated with loss of specific surface area, the transformation of anatase phase to rutile, the crystallization of tungsten oxide and increase the size of the crystals (sintering). However BMR�Torrevieja individual materials distinguishes them from each other. As examples, the data for samples with 3% by weight of vanadium oxide plotted on Figures 1 (specific surface area according to BET) and Figure 2 (% anatase phase), which are indicators of thermal stability of the catalysts.

From these Tables 1 and 2 and Figures 1 and 2 can be clearly seen that the material DT-S10™ (with silicon dioxide) has the highest thermal stability, followed by DT-58™ (with silicon dioxide and tungsten oxide), and followed by DT-52™ (tungsten oxide). If the only requirement for a good media mandioquinha catalyst was thermal stability, a clear advantage would be for DT-S10™.

The next two figures (Figures 3 and 4) shows the degree of DeNOx conversion at 325°C for materials with a content of 1% and 3% vanadium oxide, respectively. You can clearly see that the sample only with silicon dioxide (DT-S10™) has the lowest degree of conversion for most temperatures of aging; there is only the sample with 3% vanadium oxide, subjected to aging at a temperature of 800°C, which has activity equal to the activity of the material DT-58™.

Thus, based on the characteristics of these industrial designs, there is a clear need to develop a catalyst with improved stability and with increased activity.

Examples 4-5. N�'sfor next examples show the characteristics of two additional industrial prototype materials (MIC DT-60™ and Taus Corporation ITAC 115GS™) compared with DT-58™. Samples of these materials were analyzed to determine the composition using x-ray fluorescence analysis, with the results shown in Table 4.

Table 4
The compositions of materials
Oxide, % by weightDT58MIC DT60Taus
TiO280.58484.2
WO39.15.35.2
SiO29.810.310.2
SiO30.40.20.2

The results show that the samples of the DT-60™ and Taus™ contain nominally about 10% by weight of SiO2and about 5% by weight of WO3. All three types of materials contained 0.9 percent by weight of V2O5caused by deposition from MEA solution as in Examples 1-3. The products then were subjected to aging at 80°C for 6 hours in air in a static muffle furnace, and the products were analyzed using N2-WET method. To determine DeNOx-activity, (microreactor), a sample weighing 0.1 g of each sample of catalyst comprising vanadium oxide, pelletized, and sorted to size -20/+40 mesh, and was placed in the reactor to determine the conversion of NO in the presence of NH3. The current thread, which contained 5% O2, 1000 ppm of NH3, 1000 ppm NO and 3% H2O, is passed over the catalyst with a space velocity of 650 l/g of catalyst per hour.

Table 5 below shows a comparison of the stability of the specific surface area of samples.

Table 5
The values of specific surface area of industrial designs
SampleSpecific surface area (m2/g)
DT58™45.9
DT60™53.3
Taus™51.5

Data show that the samples with lower content of tungsten oxide have a slightly higher stability than the DT-58™. However, the DeNOx activity of the catalysts, as shown in Figure 5, showing�t, what activity for samples DT-60™ and Taus™ is lower than the activity for sample DT-58™. Thus, as for examples 1-3, Examples 4 and 5 demonstrate the need for higher stability and activity for new materials according to the present invention.

Example 6: stabilization of the surface of silicon dioxide

As noted here in different places, the present invention is directed to a very stable ultra-thin titanium dioxide using the minimum amount of the addition of silicon dioxide. As noted above, particulate silica (e.g., colloidal, pyrogenic and precipitated) are not ideal sources of silica for use in vanadium catalysts on titanocene the media because most of the silica is not available for interaction with the surface of titanium dioxide. The purpose of the present invention was to find another form of silicon dioxide, which could be used for more effective stabilization of the surface of titanium dioxide, but which would have a minimal adverse effect on the catalytic activity of vanadium oxide deposited on the carrier surface of titanium dioxide.

Considered the use of silicon dioxide in the form of low molecular weight and/or IU�fir nanoparticles than in dispersed form, which is present in the above-described traditional amorphous silica. The form of silicon dioxide with the lowest molecular weight in aqueous solution is silicic acid, Si(OH)4. However, this chemical has a very low solubility in water, and therefore limited the concentration level of several hundred parts per million (ppm). (The discussion of the chemical aspects of aqueous silica in water can be found, for example, in the work of the author Iler (the above link) and Brinker, C. J. and Scherer, G. W., 1990, Chapter 3).

Owing to the low solubility of Si(OH)4the authors of the present invention conducted experiments with solutions of silicates of the Tetra(alkyl)ammonium (including but not limited to such, Tetramethylammonium, TMA). These reagents contain silica in the form of low molecular weight (see the work of authors Engelhardt and Michel, the above link). In addition, silica in these solutions clearly present at high concentrations (for example, 9% by weight of SiO2). Thus, the authors present invention investigated whether or not molecular particles in these solutions to be small enough to selectively react with the surface of titanium dioxide, at the same time without creating a separate zone to associate with the vanadium oxide, which could reduce to�talities activity.

29Si-NMR spectroscopy of liquid sample soluble silicate.

To determine the nature of the silicate particles in commercially available on the market solution of TMA silicate, a commercial source TMA-silicate used in these examples, a solution of TMA silicate from Alfa, 9% SiO2), was evaluated using29Si-HMP spectroscopy using a device with an operating frequency of 400 MHz on databases Spectral Data Services, Inc. Table 6 shows the results.

Table 6
Q-forms of TMA silicate solutions and solid samples of titanium dioxide
DescriptionQ0Q1Q2Q3About4
TMA-silicate from Alfa (liquid)417392316
Example 6 (solid)04165030
Example 14 (t�erdy) 11534446

You can see that the TMA-silicate solution contains mainly particles of silicon dioxide with the order of binding of Q3or below. However, there is a certain amount of silicon dioxide with the order of binding of Q4so not all of the silicon dioxide contained in the solution in perfect shape (with the order of binding of Q3or below). However, as will be shown here, the authors present invention newly found that sources of soluble silica, such as silicates of the Tetra(alkyl)ammonium, can be used to obtain extremely stable (anatase phase, high specific surface area) of the catalysts based on vanadium oxide, which exhibit excellent catalytic activity for selective catalytic reduction in reactions with NOx.

Increased stability through new processing silicon dioxide

The above Examples 1-5 identify the characteristics of stability and catalytic activity of industrial materials containing vanadium oxide and subjected to processing in conditions of accelerated aging. Example 6 demonstrates the improvement in thermal stability that can be achieved with use�Itanium new method of processing the silica according to the present invention. The suspension produced in industry sulfated hydrogel of titanium dioxide was diluted to a content of TiO2Of 21.6% by weight. Of 112.5 g of this suspension was placed in a round bottom flask, which was equipped with a mechanical stirrer drive. This slurry was heated to a temperature of 60°C using the heating jacket with temperature regulation, and it was kept at this temperature during the entire cooking cycle. To this suspension was added to 33.3 g of silicate of Tetramethylammonium (TMA product-SiO2(Alfa-Aesar, 9% SiO2, the ratio of TMA/SiO2=0,5). This mixture is left to react for 20 minutes. Then brought the pH to 6.0 by addition of a concentrated solution of NH4OH (29%). Then added of 3.07 g of ammonium paratungstate (APT), and the final pH was adjusted to 6.5 by addition of another portion of concentrated solution of NH4OH. This mixture is left to react for an additional 30 minutes and then filtered, the precipitate washed with demineralized (DI) water and dried. The final nominal composition of this product, calculated as oxides, was 81% by weight of TiO2, 10% by weight of SiO2and 9% by weight of WO3. Then it was divided into portions which were subjected to calcination within the temperature range from 600°C to 900°C for 6 hours in air using stationsomewhere furnace. Industrial design DT-58™ with the same composition was also subjected to aging in identical conditions. Both samples were evaluated for the preservation of specific surface area using the BET method, with the data shown in Figure 6.

The data in Figure 6 clearly show that, while the compositions of the two products are nominally the same, the sample prepared with the use of a new form of silicon dioxide with a low molecular weight and/or small nanoparticle according to the present invention, has a much higher thermal stability (largely retains specific surface area) than the prototype material (DT-58™).

Characterization of the solid samples method29Si MASNMR spectroscopy. The following analysis TMA-SiO2-material according to the invention and a traditional material (DT-58™) shows that the silica present in the materials according to the present invention, has a very different morphological characteristics. Two samples in its "fresh" state (before adding vanadium oxide, but after calcination at 500°C) were analyzed using the Spectral Data Services, Inc., using29Si MASNMR spectroscopy device with an operating frequency of 270 MHz. An attempt was made to conduct an experiment on DT-58™ cu�SS-polarization, but after 1 hour the signal was not received, and in these conditions, would show an intense signal, if near the core of Si attended any (OH)-group, as would be expected for silicon dioxide uniformly dispersed on the surface of titanium dioxide. Therefore, this sample was tested for 4 hours using only MASNMR method. Was obtained a weak signal with a chemical shift -111 M. D. regarding tetramethylsilane. This signal is consistent with Si at Q4-coordination environment, or Si(OSi)4. Therefore, both observations (no signal cross polarization and the presence of Q4signal) in the NMR experiment are consistent with dispersed silica, where the bulk Si is inside particles of silicon dioxide, and on the surface of silicon dioxide there are numerous Si(Oh) groups.

A sample of the new catalyst was tested under nominally the same NMR conditions, and this sample also contained 10% by weight of SiO2however , the source of silica was TMA-SiO2that contains silicon dioxide in the form of low molecular weight and/or small nanoparticle. In this case, the observed intense signal in the experiment with1H-29Si-Kpocc-polarization, which shows that there are hydroxyl groups associated with Si. This supports the idea that this is the silicon dioxide�, which effectively dispersed on the surface of titanium dioxide according to the present invention. In addition, the spectrum has been deployed on four peaks, with the following relative intensities: -110 M. D., 30%; -100 M. D., 50%; -90, M. D., 16%; and -82 M. D. (4%), and these peaks were attributed to the coordination of Q4, Q3, Q2and Q1accordingly, as shown in Table 6. In addition, it can be seen that about 70% of silicon dioxide are in such a coordination environment (Q3, Q2and Q1), the hydroxyl groups are the closest neighboring groups, and it further reinforces the view that silica effectively dispersed on the surface of titanium dioxide. Thus, the authors of the present invention conclude that the use of a precursor of silicon dioxide with a low molecular weight and/or in the form of small nanoparticles, such as TMA-SiO2or other compositions described herein results in silicon dioxide, which effectively dispersed on the surface of titanium dioxide. In particular, the preferred coordination environment of silicon atoms on titanocene medium according to the present invention are mainly (at least 50%) the condition Q3, Q2, Q1and Q0coordination, as defined using29Si CP-MASNMR. The key�the first manifestation of this difference in the nature of silicon dioxide is that well-dispersed silicon dioxide is much more effective in calculating the masses, regarding the stabilization of titanium dioxide. Therefore, for the stabilization of titanium dioxide requires a smaller amount of silica when the silica is well dispersed on the surface of titanium dioxide.

To further assess the nature kremniikarbidnoi coating on the new sample was subjected to THE analysis, as shown in Figure 7, which demonstrates that silica is present in the form of isolated fragmentary sections on the surface of anatase titanium dioxide. Fragmentary sections showing a two-dimensional character in the sense that their length is generally less than 5 nm, while the depth (the distance measured from the surface of titanium dioxide) in the typical case is less than 2 nm.

Example 7: the Advantage of a composition of TiO2:SiO2:WO3with a ratio of 90:4:6 in terms of stability and activity.

The following example according to the invention shows a good stability and activity of the materials obtained by the methods according to the present invention. The suspension produced in industry hydrogel sulfated titanium dioxide was diluted to a content of TiO2Of 21.6% by weight. Of 208.3 g of the suspension was placed in a round bottom flask, which was equipped�and agitator with mechanical drive. This slurry was heated to a temperature of 60°C using the heating jacket with temperature regulation, and it was kept at this temperature during the entire cooking cycle. (In one embodiment of the invention used herein, a suspension of titanium oxide and craniometry component was mixed at a temperature of <80°C and at pH <8,5. In the alternative, used here, a suspension of titanium dioxide and craniometry component was mixed at a temperature <70°C and at pH <7.0) was. Then added 3.4 g of ammonium paratungstate (APT, 88% of WO3) and left to react for 30 minutes. To this mixture was added to 22.2 g of silicate of Tetramethylammonium in Example 6, and the mixture is left to react for 10 minutes. Then adjusted the pH to 6.5 by adding concentrated solution of NH4OH (29%). This mixture is left to react for an additional 20 minutes, and then filtered, the residue washed with demineralised (DI) water and dried at 105°C, and then caliciviral at 500°C for 6 hours. The final nominal composition of this product, calculated as oxides, was 90% by weight of TiO2, 4% by weight of SiO2and 6% by weight of WO3. This powder besieged the vanadium oxide from the MEA solution, as in the above Examples 1-3 to final content was 2% by ve�at V 2O5, based on the total oxide. A portion of the dried powder was heated to a temperature of 750°C and kept at this temperature for 16 hours in an air atmosphere containing 10% by weight of H2O.

Example 8: the Advantage of a composition of TiO2:SiO2:WO3with a ratio of 90:5:5 in terms of stability and activity. This example additionally shows a good stability and activity of the materials obtained by the methods according to the present invention. The suspension produced in industry hydrogel sulfated titanium dioxide was diluted to a content of TiO2Of 21.6% by weight. Of 208.3 g of the suspension was placed in a round bottom flask, which was equipped with a mechanical stirrer drive. This slurry was heated to a temperature of 60°C using the heating jacket with temperature regulation, and it was kept at this temperature during the entire cooking cycle. Then added 2.8 g of ammonium paratungstate (APT, 88% of WO3) and left to react for 30 minutes. To this mixture was added of 27.8 g of silicate of Tetramethylammonium (TMA-SiO29% of SiO2), and the mixture is left to react for 10 minutes. Then adjusted the pH to 6.5 by adding concentrated solution of NH4OH (29%). This mixture is left to react for an additional 20 minutes, and then �was railtravel, was the precipitate washed with demineralized (DI) water and dried at 105°C, and then caliciviral at 500°C for 6 hours. The final nominal composition of this product, calculated as oxides, was 90% by weight of TiO2, 5% by weight of SiO2and 5% by weight of WO3. This powder besieged the vanadium oxide from the MEA solution, as in the above Examples 1-3 to final content was 2% by weight of V2O5in the calculation of the total oxide. A portion of the dried powder was heated to a temperature of 750°C and kept at this temperature for 16 hours in an air atmosphere containing 10% by weight of H2O.

To establish a baseline dataset for comparison, 4 different samples from the DT-58™ besieged the vanadium oxide to 2% by weight of the content, as described above, and subjected to hydrothermal aging in the same conditions. The results for these four samples are then averaged.

The materials of Examples 7 and 8, along with the reference DT-58™ materials were analysed by x-ray diffraction, nitrogen injection and DeNOx-activity, with the results shown below in Table 7. To evaluate materials for DeNOx applications, a 0.1 g sample of each example catalyst coated with a vanadium oxide and subjected to aging was granulated and sorted to size 20/+40 mesh, and was placed in the reactor to determine the NO in the presence of NH 3. The current thread, which contained 5% O2, 500 ppm NH3/ 500 ppm NO and 10% H2O, is passed over the catalyst with a space velocity of 650 l/g of catalyst per hour. For each of the materials of Examples 7 and 8 was carried out according to two tests DeNOx. On four benchmark 0M-58™ materials conducted a total of 10 trials. The results described in two ways. First, it describes the degree of conversion of NO. The second method involves the calculation of the "speed" of the reaction. As is well known to specialists with the usual qualifications, SCR-reaction mostly appeared to be of first order in NO and zero order at NH3and under these conditions the reaction rate is proportional to the value of-ln(1-x) where "x" represents the percentage of conversion (% conversion/100). The reaction rate represents the best of the comparison method the samples at high degrees of conversion. Data were calculated basic statistical parameters, and the variance analysis showed that the materials according to the present invention gave significantly different (P for the null hypothesis <0.05) and higher activity than the reference samples.

Table 7
Characterization of the samples by XRD, nitrogen injection and DeNOx-activity
DT-58*Example 7Example 8
Phase according to RAMIAnatase, %95.4100.0100.0
Rutile,%2.30.00.0
% WO32.30.00.0
Crystal size according to XRD (angstroms for conversion in nm divided by 10)Anatase391233333
Rutile8900
WO349800
Distribution, pore size (PSD) according to the nitrogen injectionSpecific surface area by BET (m2/g34.947.530.6
Pore volume according to BJH (cm3/g)0.250.290.24
The degree of conversion of NO, %250°C19.426.731.5
350°C64.072.678.8
450°C73.180.282.4
Reaction speed NO, %250°C0.220.310.38
350°C1.041.301.57
450°C1.341.621.75
*Average for 4 samples

Table 7 clearly shows that the samples obtained according to the present invention (Examples 7 and 8), retain much of the anatase phase, prevent crystallization of tungsten oxide and inhibit the growth of crystals (i.e., exhibit m�nsee sintering), than the base materials. In addition, the materials according to the present invention retain a higher specific surface area and pore volume than that shown, reference materials. Finally, the materials obtained according to the present invention, exhibit higher catalytic activity for SCR reaction.

The following two examples (9 and 10) demonstrated a dramatic difference in the stability and activity between the catalysts prepared with dispersed (colloidal) silica, with a relatively relevant to the invention materials.

Example 9. The new material according to the present invention was prepared in the following way: a suspension produced in industry hydrogel sulfated titanium dioxide (comprising 27% of TiO2, 7% of sulfate and H2O) was diluted with water to obtain a dispersion with a content of TiO221,7% by weight. Of 207.7 g of this dispersion was heated with stirring for 20 minutes to a temperature of 60°C, and then added 2.3 g of ammonium paratungstate (APT, 88% of WO3) at low pH value. APT was left to react for 20 minutes. Then added 44,4 g soluble form of silicon dioxide with low molecular weight in the form of silicate of Tetramethylammonium (TMA) (Alfa-Aesar, 9% by weight of SiO2) and left to react for an additional 20 minutes. Then �adjust the pH value to about 6.5 by adding concentrated solution of NH 4OH (this stage could be carried out before adding the WO3). Then the suspension was filtered, washed precipitate to remove ammonium sulfate and then dried and caliciviral at 500°C for 6 hours in air. The nominal composition of this base material was 8% by weight of SiO2, 4% by weight of WO3and 88% TiO2(TiO2:SiO2:WO3=88:8:4).

Example 10. A comparative sample was obtained using traditional dispersion of colloidal silica in the following way: a suspension produced in industry sulfated hydrogel of titanium dioxide (27% TiO2) diluted with water to obtain a dispersion with a content of TiO2Of 21.6% by weight. 203,7 g of this dispersion was heated with stirring to a temperature of 60°C, and then added 2.3 g of ammonium paratungstate (APT - 88% WO3). APT was left to react for 20 minutes. Then added 13.3 g of dispersion of colloidal silica AS-30 (W. R. Grace - 30% by weight of SiO2), and left to react for an additional 20 minutes. As will be clear to a person with ordinary skills in this field of technology, this form of colloidal silica stabilized by ions of NH4+and not ions of Na+because the latter are catalytic poison for the SCR reaction. Then adjusted the pH of the mixture to 6.5 by adding to�centered solution of NH 4OH. Then the suspension was filtered, the residue washed and dried, and caliciviral at 500°C for 6 hours in air. The nominal composition of this base material was 8% by weight of SiO2, 4% by weight of WO3and 88% TiO2. Thus, the materials of both Example 9 and Example 10 nominally have the same overall composition (88:8:4-TiO2:SiO2:WO3), calculated as oxides.

To these two basic materials, including titanium dioxide, silicon dioxide and tungsten are added to vanadium oxide up to the task content of 2% by weight of V2O5. The vanadium oxide was added by impregnating alkaline MEA solution. Then the impregnated material was subjected to aging at high temperature in the hydrothermal treatment conditions (750°C for 16 hours in 10% H2O) to provide accelerated aging. Subjected to aging, the samples were evaluated using x-ray diffraction analysis, and the observed diffraction pattern was analyzed by Rietveld analysis. To evaluate the materials of Example 9 and Example 10 for DeNOx applications, a sample weighing 0.1 g of each sample of catalyst comprising vanadium oxide and subjected to aging, was pelletized, and sorted to size -20/+40 mesh, and was placed in the reactor to determine the conversion of NO in the presence of NH3. The current thread, which contained 5% O2, 500 mln NH 3, 500 ppm NO and 10% H2O, is passed over the catalyst with a space velocity of 650 l/g of catalyst per hour. Data on the extent and rate of conversion of NO is given as described above.

Table 8
Characterized samples
DT-58*Example 9Example 10
Phase according to RAMIAnatase, %95.4100.091.2
Rutile, %2.30.06.1
% WO32.30.02.7
Crystal size according to XRD (angstroms for conversion in nm divided by 10)Anatase3912001863
Rutile890not measured
WO34980268
The distribution of the pore sizes (PSD) according to the nitrogen injectionSpecific surface area by BET (m2/g34.954.28.1
The pore volume according to BJH (cm3/g)0.250.260.04
The degree of conversion of NO, %250°C19.420.18.4
350°C64.064.634.0
450°C73.170.833.2
Reaction speed NO, %250°C0.220.220.09
350°C1.041.040.42
450°C1.34 1.230.40
* Average for 4 samples

The results in Table 8 again show a marked advantage in terms of stability of the anatase phase (and resistance to sintering), provide materials according to the present invention, an advantage in maintaining the specific surface area relevant to the invention the materials, and the advantage in terms of activity associated with the present invention (Example 9), relative to the sample obtained with the use of colloidal silicon dioxide (Example 10).

The catalyst is coated with a vanadium oxide and subjected to aging in Example 10 was evaluated using SEM (Fig. 8) and THE microscope (Fig. 9). The images clearly show the presence of particles dispersed colloidal silica having diameters of about 20 nm, covering the underlying particles of vanadium oxide is anatase titanium dioxide with a diameter of ~100-200 nm.

Example 11. This example demonstrates another embodiment of the present invention, and it comprises dissolving a dispersion of silicon dioxide with subsequent precipitation of a surface coating of silicon dioxide on titanium dioxide by hydrothermal treatment at a-level for professional�m pH value. The suspension produced in industry hydrogel sulfated titanium dioxide was diluted to a content of TiO2Of 21.6% by weight. 833,3 g of this suspension was placed in a round bottom flask, which was equipped with a mechanical stirrer drive. This slurry was heated to a temperature of 60°C using the heating jacket with temperature regulation, and it was kept at this temperature during the entire cooking cycle. Then added 13.6 g of ammonium paratungstate (APT, 88% of WO3), and left to react for 20 minutes. Then adjusted the pH to 6.0 by addition of a concentrated solution of NH4OH (29%). To this mixture was added 80 g of a dispersion of fumed silica (Cabot M-S, 10% SiO2in demineralised water), and the mixture is left to react for 20 minutes. Then adjusted the pH to 9.0 by addition of a concentrated solution of NH4OH (29%), and this slurry was heated to reflux for 6 hours. Then it is slowly cooled for precipitation of soluble silica, filtered, the residue washed with demineralised water and dried at 105°C, and then caliciviral at 500°C for 6 hours. The final nominal composition of this product, calculated as oxides, was 90% by weight of TiO2, 4% by weight of SiO2and 6% by weight of WO3(9:4:6). In these conditions, the partial monocline coating of silicon dioxide on the titanium dioxide was significantly below 1.0. This powder besieged the vanadium oxide from the MEA solution, as in the above Examples 1-3 to final content was 2% by weight of V2O5, based on the total oxides. A portion of the dried powder was heated to a temperature of 750°C and kept at this temperature for 16 hours in an air atmosphere containing 10% by weight of H2O.

The material of the catalyst of Example 11 was analysed by x-ray diffraction, nitrogen injection and DeNOx-activity, and THEMES. To evaluate the material for DeNOx applications, a sample weighing 0.1 g of each sample of catalyst comprising vanadium oxide and subjected to aging, was pelletized, and sorted to size -20/+40 mesh, and was placed in the reactor to determine the conversion of NO in the presence of NH3. The current thread, which contained 5% O2, 500 ppm NH3, 500 ppm NO and 10% H2O, is passed over the catalyst with a space velocity of 650 l/g of catalyst per hour. The results are shown in Table 9.

Table 9
Characterization of the samples
DT-58*�reamer 11
Phase according to RAMIAnatase, %95.4100.0
Rutile, %2.30.0
% WO32.30.0
Crystal size according to XRD (angstroms for conversion in nm divided by 10)Anatase391309
Rutile890
WO34980
The distribution of the pore sizes (PSD) the consent of the nitrogen injectionSpecific surface area by BET (m2/g)34.930.3
Pore volume according to BJH (cm3/g)0.250.21
The degree of conversion of NO, %250°C19.430.6
350°C 64.077.6
450°C73.183.5
Reaction speed NO, %250°C0.220.36
350°C1.041.50
450°C1.341.80
* Average for 4 samples

THE assays, as shown in Figures 10 and 11 show that, while there are few residual spherical particles of silicon dioxide, which were not completely dissolved and perioadei, they typically have a size less than 5 nm. For the most part, the fumed silica was largely dissolved and perioade on the surface of anatase in the form of coarse coating, where it is most effective for modifying the surface characteristics of the underlying titanium dioxide.

These results demonstrate a pronounced advantage in terms of stability of the anatase phase (and resistance to sintering), provide materials according to the present invention, an advantage in maintaining the specific surface area�knosti, relevant to the invention the materials, and the advantage in terms of activity associated with the present invention, when silica, initially in a dispersed form, dissolve and redistribute in the form of nanoparticles to create a uniform coating on the surface of titanium dioxide.

Example 12. This example is another demonstration of the preemptive effect of the redistribution of silica during hydrothermal treatment, only in this case the original source is colloidal silica. The suspension produced in industry sulfated hydrogel of titanium dioxide was diluted to a content of TiO2Of 21.6% by weight. Of 208.3 g of the suspension was placed in a round bottom flask, which was equipped with a mechanical stirrer drive. This slurry was heated to a temperature of 60°C using the heating jacket with temperature regulation, and it was kept at this temperature during the entire cooking cycle. To this mixture was added 6.7 g of dispersion of colloidal silica AS-30 (W. R. Grace - 30% by weight of SiO2), and the mixture is left to react for 30 minutes. Then added 3.4 g of ammonium paratungstate (APT, 88% of WO3) and left to react for 10 minutes. Then adjusted the pH to 6.5 by adding concentrated solution of NH4OH (29%). �ATEM the pH adjusted to 9.0 by the addition of concentrated solution of NH 4OH (29%), and this slurry was heated to reflux for 6 hours. Then it was filtered, the residue washed with demineralised water and dried at 105°C, and then caliciviral at 500°C for 6 hours. The final nominal composition of this product, calculated as oxides, was 90% by weight of TiO2, 4% by weight of SiO2and 6% by weight of WO3(90:4:6). In these circumstances, fragmentary monocline coating of silicon dioxide on the titanium dioxide was significantly below 1.0. This powder besieged the vanadium oxide from the MEA solution, as in the above Examples 1-3 to final content was 2% by weight of V2O5, based on the total oxides. A portion of the dried powder was heated to a temperature of 750°C and kept at this temperature for 16 hours in an air atmosphere containing 10% by weight of H2O.

The material of the catalyst of Example 12 was analysed by x-ray diffraction, nitrogen injection and DeNOx-activity, and THEMES. To evaluate the material for DeNOx applications, a sample weighing 0.1 g of each sample of catalyst comprising vanadium oxide and subjected to aging, was pelletized, and sorted to size 20/+40 mesh, and was placed in the reactor to determine the conversion of NO in the presence of NH3. The current thread, which contained 5% O2, 500 ppm NH3, 500 ppm NO and 10% H2O, prop�Scully over the catalyst with a space velocity of 650 l/g of catalyst per hour.

The results shown below in Table 10, compared with production of colloidal silica (but without hydrothermal treatment, Example 10). Analyses of x-ray diffraction and N2-BET showed that the material of Example 12 has an improved stability of the anatase phase and resistance to sintering, whereas the results concerning the catalytic activity show that the material of Example 12 also has an increased catalytic activity directly associated with hydrothermal redistribution of silicon dioxide.

Table 10
Characterization of the samples
Example 12Example 10
Phase according to RAMIAnatase, %91.691.2
Rutile, %6.66.1
% WO31.82.7
Crystal size according to XRD (angstroms for conversion in nm divided by 10)Anatase 5621863
Rutile40Not measured
WO3694268
The distribution of the pore sizes (PSD) according to the nitrogen injectionSpecific surface area by BET (m2/g)23.38.1
The pore volume according to BJH (cm3/g)0.150.04
The degree of conversion of NO, %250°C31.08.4
350°C76.434.0
450°C79.933.2
Reaction speed NO, %250°C0.370.09
350°C1.400.42
450°C1.600.40
* Average for 4 samples

THE image of the material from Example 12 are shown below in Figure 12. The analysis shows that, while there are few residual spherical particles of silicon dioxide, which were not completely dissolved and perioadei (with a size of approximately 10 nm or less), mostly colloidal silica was largely dissolved and perioade on the surface of anatase in the form of coarse, fragmented coverage where it is most effective for modifying the surface characteristics of titanium dioxide.

Example 13: silicic acid. This example presents another variant implementation of the present invention, in which silicon dioxide with a low molecular weight is a silicic acid formed by ion exchange with the sodium silicate. First, a dilute solution (3% by weight of SiO2) of sodium silicate was prepared by adding 569 g of demineralized (DI) water to 71 g of sodium silicate Philadelphia Quartz "N", 28,7% by weight of SiO2. Weighed 650,7 g serving (taken directly from the supply) strongly acidic ion-exchange resin (Dowex 650C in the protonated form). Separately, a slurry produced in industry hydrogel sulfated titanium dioxide was diluted to a content of TiO2Of 21.6% by weight. 1666,7 g of this suspension on�Esteli in a round bottom flask, which was equipped with a mechanical stirrer drive. This slurry was heated to a temperature of 60°C using the heating jacket with temperature regulation, and it was kept at this temperature during the entire cooking cycle. Then to diluted sodium silicate solution under vigorous stirring was added ion-exchange resin, and monitoring the pH. Once the control of the pH showed that the ion-exchange reaction has come to an end (pH<3,0), the resin was filtered, and to the suspension of titanium dioxide added 533 g of silicic acid. This mixture is left to react for 20 minutes. Then added to 27.3 g of ammonium paratungstate (APT, 88% of WO3) and left to react for 20 minutes. Then adjusted the pH to 6.5 by adding concentrated solution of NH4OH (29%). The mixture is then filtered, the residue washed with demineralised water and dried at 105°C, and then caliciviral at 500°C for 6 hours. The final nominal composition of this product, calculated as oxides, was 90% by weight of TiO2, 4% by weight of SiO2and 6% by weight of WO3(90:4:6). This powder besieged the vanadium oxide from the MEA solution, as in the above Examples 1-3 to final content was 2% by weight of V2O5, based on the total oxides. A portion of the dried powder was heated up to t�of mperature 750°C and kept at this temperature for 16 hours in air atmosphere, which contained 10% by weight of H2O. to evaluate the materials of Example 13 for DeNOx applications, a sample weighing 0.1 g of each sample of catalyst comprising vanadium oxide and subjected to aging, was pelletized, and sorted to size -20/+40 mesh, and was placed in the reactor to determine the conversion of NO in the presence of NH3. The current thread, which contained 5% O2, 500 ppm NH3, 500 ppm N0and 10% H2O, is passed over the catalyst with a space velocity of 650 l/g of catalyst per hour. Subjected to aging, the samples were then evaluated by x-ray diffraction, nitrogen injection and DeNOx-activity, and compared with DT-58™, as shown in Table 11.

Table 11
Characterization of the samples
DT-58*Example 13
Phase according to RAMIAnatase, %95.4100.0
Rutile, %2.30.0
% WO32.30.0
Rastermaster according to the PCA (angstroms to recount in nm divided by 10)Anatase391286
Rutile890
WO34980
The distribution of the pore sizes (PSD) according to the nitrogen injectionSpecific surface area by BET (m2/g)34.940.8
The pore volume according to BJH (cm3/g)0.250.27
The degree of conversion of NO, %250°C19.429.6
350°C64.076.7
450°C73.183.0
* Average for 4 samples

You can clearly see, the material obtained according to the present invention has a higher thermal stability of the anatase phase, the best preservation of the specific surface area (resistance to agglomeration) � higher DeNOx-activity, compared to the DT-58™. Conducted THE analysis of the material from Example 13 and the results are outlined in Figures 13 and 14 show that the silicon dioxide is present in the form of two-dimensional fragmented plots well distributed on the surface of titanium dioxide. There's a bit of a rare three-dimensional particles, identified as silicon dioxide present on some of the images, but they are, for the most part, have a size of less than about 5 nm.

Example 14. This example presents another variant implementation of the present invention, in which silicon dioxide with a low molecular weight is in the form of silicic acid formed by ion exchange with the sodium silicate. First, a dilute solution (3% by weight of SiO2) of sodium silicate was prepared by adding to 59.7 g of demineralized (DI) water to 7.0 g of sodium silicate Philadelphia Quartz "N", 28,7% by weight of SiO2. Weighed 13.5 g portion (taken directly from the supply) strongly acidic ion-exchange resin (Dowex 650C in the protonated form) and made in flow-through column. Separately, a slurry produced in industry hydrogel sulfated titanium dioxide was diluted to a content of TiO2Of 21.6% by weight. Of 208.3 g of the suspension was placed in a round bottom flask, which was equipped with a mechanical stirrer drive. This slurry was heated to a temperature of 60°C using a heating� shirts with temperature control, and kept at this temperature during the entire cooking cycle. Then, with 66.7 g of diluted sodium silicate solution passed through the column to remove sodium. This mixture is left to react for 20 minutes. Then added 3.4 g of ammonium paratungstate (APT, 88% of WO3) and left to react for 20 minutes. Then adjusted the pH to 6.5 by adding concentrated solution of NH4OH (29%). The mixture is then filtered, the residue washed with demineralised water and dried at 105°C, and then caliciviral at 500°C for 6 hours. The final nominal composition of this product, calculated as oxides, was 90% by weight of TiO2, 4% by weight of SiO2and 6% by weight of WO3(90:4:6). This composition, before adding vanadium oxide had a specific surface area by the method of N2-BET 221 m2/g, and thus the silicon dioxide is present to the magnitude of the partial monosloevogo coating of 0.30, significantly below 1 monolayer. This sample was evaluated using THE. Prepared identical to sample, except that tungsten oxide added to the silica, and this sample was analyzed by29Si CP-MASNMR spectroscopy. The results of NMR studies, shown in Table 6, demonstrate that most of the silica present in the sample, has� the coordinate Q 3or less, as would be expected for silicon dioxide, distributed in two-dimensional fragmented areas on the surface of titanium oxide. THE image presented in Figure 15, indicates that silica is present as a granular coating with size 1-3 nm on the surface of the crystallite anatase titanium dioxide, and it was impossible to see distinct three-dimensional particles of silicon dioxide larger than 5 nm in diameter.

This powder besieged the vanadium oxide from the MEA solution, as in the above Examples 1-3 to final content was 2% by weight of V2O5, based on the total oxides. A portion of the dried powder was heated to a temperature of 750°C and kept at this temperature for 16 hours in an air atmosphere containing 10% by weight of H2O. to evaluate the materials of Example 14 for DeNOx applications, a sample weighing 0.1 g of each sample of catalyst comprising vanadium oxide and subjected to aging, was pelletized, and sorted to size -20/+40 mesh, and was placed in the reactor to determine the conversion of NO in the presence of NH3. The current thread, which contained 5% O2, 500 ppm NH3, 500 ppm NO and 10% H2O, is passed over the catalyst with a space velocity of 650 l/g of catalyst per hour. Subjected to aging, the samples were then evaluated by x-ray diffraction, nitrogen injection and DeNOx, and compared with DT-58, as shown in Table 12.

Table 12
Characterization of the samples
DT-58™Example 14
Phase according to RAMIAnatase, %95.4100.0
Rutile, %2.30.0
% WO32.301.0
Crystal size according to XRD (angstroms for conversion in nm divided by 10)Anatase391336
Rutile890
WO34980
The distribution of the pore sizes (PSD) according to the nitrogen injectionSpecific surface area by BET(m2/g)34.9 31.9
The pore volume according to BJH (cm3/g)0.250.25
The degree of conversion of NO, %250°C0.220.41
350°C1.131.67
450°C1.431.99

You can clearly see that the material obtained according to the present invention has a higher thermal stability of the anatase phase, the best preservation of the specific surface area (resistance to agglomeration) and higher DeNOx-activity, compared to the DT-58™.

Example 15. This example was designed to show that a variety of prototype materials different from the materials according to the present invention. In particular, it provides a link to the U.S. Patent 4221768, columns 3, 4 (line 3), Example 1, and patent document US 2007/0129241 (paragraph 0026). In this example, the dispersed colloidal silicon dioxide is injected into the titanium dioxide during the deposition of titanium dioxide. First, 1169 g of water poured into a glass beaker with a capacity of 4 l, and he was placed in an ice bath for cooling. Then the chilled water slowly with stirring was added 330 g of a solution of TiOCl2(25,9% TiO 2) so that the solution temperature did not increase above 30°C, to obtain a 5.7% solution of TiO2. Then 544,6 g of this solution are introduced into a glass beaker of 1 liter, and vigorously stirred. To this mixture is slowly added 4.33 g of colloidal silica Ludox AS-30 (W. R. Grace - 30% SiO2). Then to this suspension was added a concentrated solution of NH4OH (29%) until the pH reached 7. The suspension with the precipitated residue was subjected to aging for 2 hours. Then it was filtered, the residue washed with demineralised water and then dried at 105°C. the nominal composition of this powder, calculated as oxides, was 4% by weight of SiO2and 96% by weight of TiO2. Then 27 grams of dried powder (84,5% solids) was suspended in 100 g of demineralized (DI) water, heated to a temperature of 60°C, and then added 1.7 g APT, and left to react for 20 minutes. Then the pH was brought to 7.0, and the final mixture was filtered, and the precipitate was dried at 105°C, and then caliciviral at 500°C for 6 hours. The final nominal composition of this product, calculated as oxides, was 90% by weight of TiO2, 4% by weight of SiO2and 6% by weight of WO3. This powder besieged the vanadium oxide from MEA solution as in Examples 1-3 to final content was 2% by weight of V2O5, based on the total oxide�. A portion of the dried powder was heated to a temperature of 750°C and kept at this temperature for 16 hours in an air atmosphere containing 10% by weight of H2O. to evaluate the materials of Example 15 for DeNOx applications, a sample weighing 0.1 g of each sample of catalyst comprising vanadium oxide and subjected to aging, was pelletized, and sorted to size -20/+40 mesh, and was placed in the reactor to determine the conversion of NO in the presence of NH3. The current thread, which contained 5% O2, 500 ppm NH3, 500 ppm NO and 10% H2O, is passed over the catalyst with a space velocity of 650 l/g of catalyst per hour. Subjected to aging, the samples were then evaluated by x-ray diffraction, nitrogen injection and DeNOx-activity, and SO, and compared with DT-58™, as shown in Table 13 and Figure 16.

Table 13
Characterization of the samples
DT-58*Example 15
Phase according to RAMIAnatase, %95.490.0
Rutile, %2.39.0/td>
% WO32.31.0
Crystal size according to XRD (angstroms for conversion in nm divided by 10)Anatase391935
Rutile891567
WO3498190
The distribution of the pore sizes (PSD) according to the nitrogen injectionSpecific surface area by BET (m2/g)34.910.2
The pore volume according to BJH (cm3/g)0.250.07
The degree of conversion of NO, %250°C19.413.2
350°C64.046.3
450°C73.157.9
* Average for 4 samples

The results clearly �have, what is the comparative material of Example 15 (not formed from silicon dioxide with a low molecular weight and/or small nanoparticle) clearly has a lower stability and activity than the reference samples DT-58™. In addition, THE analysis (Fig. 16) shows that the silicon dioxide is present in the form of large three-dimensional inclusions (e.g. size >20 nm up to 50 nm or more).

Example 16. This embodiment is similar to the prototype variants of execution, where silicon dioxide is introduced in dissolved form during deposition (for example, see patent document 4221768, column 3, line 36), with the exception that in this example, use the TMA-silicate according to the present invention, as shown in Examples 7, 8 and 9. This example produces a material in which silicon dioxide is again introduced during the deposition of titanium dioxide. However, in this case, the TMA-silicate is used as a source of silicon dioxide, and a solution of titrisoft used as a source of titanium dioxide. First, in a beaker of 1 liter made of 990 g of a solution of titrisoft (10.1% of TiO2, ~29% H2SO4). In a separate glass of 26.5 g of TMA-silicate (9% by weight of SiO2the company Alfa Aesar) was diluted with 350 ml of demineralized water. In the third vessel with a spout for the continuous removal of the suspension with the precipitated residue was added 150 g of hot water, and the contents of this� vessel was stirred. A solution of titrisoft was injected into the vessel No. 3 with flow rate 20 ml/min, and a solution of TMA-silicate is also pumped into the vessel No. 3 with a flow rate of 10 ml/min. in addition, the vessel No. 3 also injected a concentrated solution of NH4OH (29%) to maintain the pH during the deposition of oxides at the level of 6.0. The flow of decantate from vessel No. 3 was collected in another glass. Specialists with ordinary skills in this area of technology will be clear that the vessel No. 3 is a flow reactor with continuous stirring. Once the deposition of oxides was completed, then the precipitate was filtered, washed with demineralised water and then dried at 105°C. the nominal composition of this powder, calculated as oxides, was 2.5 per cent by weight SiO2That 97.5% by weight of TiO2.

Then 51,2 g of the dried powder (73% solids) was suspended in 122 g of demineralized water, heated to a temperature of 60°C, and then added 1.8 g of APT, and left to react for 20 minutes. Then the pH was brought to 6.5, and left to react for 20 minutes. The resulting mixture was filtered, and the precipitate was dried at 105°C, and then caliciviral at 500°C for 6 hours. The final nominal composition of this product, calculated as oxides, was 93,5% by weight of TiO2And 2.5% by weight of SiO2and 4% by weight of WO3(93,5:2,5:4). At this�t powder besieged the vanadium oxide from the MEA solution, as in Examples 1-3 to final content was 2% by weight of V2O5, based on the total oxides. A portion of the dried powder was heated to a temperature of 750°C and kept at this temperature for 16 hours in an air atmosphere containing 10% by weight of H2O. to evaluate the materials of Example 16 for DeNOx applications, a sample weighing 0.1 g of each sample of catalyst comprising vanadium oxide and subjected to aging, was pelletized, and sorted to size -20/+40 mesh, and was placed in the reactor to determine the conversion of NO in the presence of NH3. The current thread, which contained 5% O2, 500 ppm NH3, 500 ppm NO and 10% H2O, is passed over the catalyst with a space velocity of 650 l/g of catalyst per hour. Subjected to aging, the samples were then evaluated by x-ray diffraction, nitrogen injection and DeNOx-activity, and compared with DT-58™, as shown in Table 14.

The results clearly show that the material obtained under conditions in which silicon dioxide with a low molecular weight and/or in the form of small nanoparticles is introduced during the deposition of titanium dioxide, has a lower stability of the anatase phase, less resistance to sintering and lower DeNOx-activity than the base materials. In Fig. 17 shows the obtained transmission electron microscope (TEM) micrograph mandioquinha catalyst�, which shows a large (>20 nm) three-dimensional inclusions of silicon dioxide, which are poorly dispersed on the surface of titanium dioxide.

Table 14
Characterization of the samples
DT-58*Example 16
Phase according to RAMIAnatase, %95.482.3
Rutile, %2.314.8
% WO32.32.9
Crystal size according to XRD (angstroms for conversion in nm divided by 10)Anatase3911456
Rutile891994
WO3498353
The distribution of the pore sizes (PSD) the consent of the nitrogen injectionSpecific�I surface area by BET (m 2/g)34.912.0
The pore volume according to BJH (cm3/g)0.250.05
The degree of conversion of NO, %250°C19.412.2
350°C64.050.0
450°C73.155.8
* Average for 4 samples

Example 17. This embodiment is similar to Example 16, except that the final composition before adding vanadium oxide is a 90:4:6 weight percent TiO2, SiO2, WO3. This example produces a material in which silicon dioxide is again introduced during the deposition of titanium dioxide. First, in a beaker of 1 liter made 891 g of a solution of titrisoft (10.1% of TiO2, ~29% H2SO4). In a separate glass of 44.4 g of TMA-silicate (9% by weight of SiO2, firm Alfa Aesar) was diluted with 400 ml of demineralized water. In the third vessel with a spout for the continuous removal of the suspension with the precipitated residue was added 150 g of hot water, and the contents of the vessel was stirred. A solution of titrisoft pumped � vessel No. 3 with flow rate 20 ml/min, and a solution of TMA-silicate is also pumped into the vessel No. 3 with a flow rate of 10 ml/min. in addition, the vessel No. 3 also injected a concentrated solution of NH4OH (29%) to maintain the pH during the deposition of oxides at the level of 6.0. The flow of decantate from vessel No. 3 was collected in another glass. Specialists with ordinary skills in this area of technology will be known that the vessel No. 3 is a flow reactor with continuous stirring. Once the deposition of oxides was completed, then the precipitate was filtered, washed with demineralised water and then dried at 105°C. the nominal composition of this powder, calculated as oxides, was 4.3 percent by weight SiO2Or 96.7% by weight of TiO2.

Then all of the dried powder was suspended in ~150 g of demineralized water, heated to a temperature of 60°C, and then added 6.8 g APT, and left to react for 20 minutes. Then the pH was brought to 6.5, and left to react for 20 minutes. The resulting mixture was filtered, and the precipitate was dried at 105°C, and then caliciviral at 500°C for 6 hours. The final nominal composition of this product, calculated as oxides, was 90% by weight of TiO2, 4% by weight of SiO2and 6% by weight of WO3. This powder besieged the vanadium oxide from MEA solution as in Examples 1-3 to final content was 2% p� weight V 2O5, based on the total oxides. A portion of the dried powder was heated to a temperature of 750°C and kept at this temperature for 16 hours in an air atmosphere containing 10% by weight of H2O. to evaluate the materials of Example 17 for DeNOx applications, a sample weighing 0.1 g of each sample of catalyst comprising vanadium oxide and subjected to aging, was pelletized, and sorted to size -20/+40 mesh, and was placed in the reactor to determine the conversion of NO in the presence of NH3. The current thread, which contained 5% O2, 500 ppm NH3, 500 ppm NO and 10% H2O, is passed over the catalyst with a space velocity of 650 l/g of catalyst per hour. Subjected to aging, the samples were then evaluated by x-ray diffraction, nitrogen injection and DeNOx-activity, and compared with DT-58™, as shown in Table 15.

Table 15
Characterization of the samples
DT-58*Example 17
Phase according to RAMIAnatase, %95.494.5
Rutile, % 2.33.9
% WO32.31.6
Crystal size according to XRD (angstroms for conversion in nm divided by 10)Anatase391748
Rutile89795
WO3498180
The distribution of the pore sizes (PSD) according to the nitrogen injectionSpecific surface area by BET (m2/g)34.918.2
The pore volume according to BJH (cm3/g)0.250.09
The degree of conversion of NO, %250°C19.416.2
350°C64.058.4
450°C73.167.0
* Average for 4 samples

The results clearly show that the material obtained when soluble silica is introduced during the deposition of titanium dioxide, has a lower stability of the anatase phase, less resistance to sintering and lower DeNOx-activity than the base materials.

Example 18. This embodiment demonstrates the effect of temperature of calcination on deNOx-catalytic activity of the materials according to the present invention. Reference catalysts based on DT-58™, having a content of 2% by weight of V2O5described in Example 8, were used as reference sample. The composition of TiO2:SiO2:WO3in the ratio of 90:4:6 according to the present invention, obtained as in Example 13 (in periodic mode) and Example 14 (in continuous mode), struck V2O5to content of 2% by weight, as described in these Examples. The composition of TiO2:SiO2:WO3in a ratio of 88:8:4 according to the present invention, obtained as in Example 9, also struck V2O5to content of 2% by weight, as described here. These are then exposed to a high temperature (calcination) ranging from 500°C to 850°C, and the degree of deNOx-catalytic activity was measured as in Example 17. Outcome data were approximated by a regression to a polynomial function, and with�losowanie curves shown in Fig. 18. Fig. 18 demonstrates that to obtain maximal activity for vandieken catalytic materials according to the present invention, particularly the activity that is greater than the activity of the reference DT-58, catalytic materials based on vanadium oxide must first be exposed to elevated temperatures, i.e., temperatures of above 650°C.

Applicability

The present invention is directed, in one embodiment, the implementation, the composition comprising anatase titanium dioxide, wherein the titanium dioxide is stable silicon dioxide, made in the form of low molecular weight and/or in the form of small nanoparticles. In addition, the invention is directed to the use of these kremnicka-titanocene compositions as carriers of catalysts, in particular in combination with added tungsten oxide and vanadium oxide, based on the vanadium oxide selective catalytic reduction DeNOx engine (diesel), working on lean-burn. In addition, the invention is directed to methods of obtaining these stabilized silica titanocene or titnaked-wolframates media, and catalysts based on vanadium oxide that include stabilized silica titanocene or titnaked-tungsten�sidnie media and methods of obtaining vandieken catalysts and catalytic devices comprising these catalysts based on vanadium oxide.

Real concrete composition kremnicka-titanocene or kremnicka-titanox-wolframscience a catalyst depends on the requirements for specific applications of catalysts. In one preferred compositions of the invention comprise a stabilized silica catalyst carrier based on titanium dioxide, which comprises particles that include ≥90% by dry weight of TiO2and ≤10% on a dry weight SiO2. In another preferred compositions of the invention comprise a stabilized silica catalyst carrier based on titanium dioxide and tungsten oxide with ≥85% by dry weight of titanium dioxide, 3%-10% on a dry weight SiO2and 3%-10% on a dry weight WO3. Alternatively, in one embodiment, where the conditions of application require a particularly good thermal stability, the catalyst carrier includes ≥85% by dry weight of TiO2, 5,0%-9,0% on a dry weight SiO2, and 3.0%-7,0% on a dry weight WO3. More specifically, this stable catalyst carrier includes 87%-89% on a dry weight TiO2, 7%-9% dry weight of SiO2and 3%-5% on a dry weight WO3. In one preferred embodiment, the ISP�assign the catalyst carrier comprises about 88% (±0,5%) on a dry weight TiO 2about 8% (±0,5%) on a dry weight SiO2and about 4% (±0,5%) on a dry weight WO3. In one embodiment, the number of WO3in weight percent is less than the amount of SiO2in weight percent. In one embodiment, the catalyst carrier in the freshly prepared state has a specific surface area of at least 80 m2/gram, and more preferably at least 100 m2/gram.

In yet another embodiment, where the conditions of application require a particularly good catalytic activity, the catalyst carrier includes ≥85% by dry weight of TiO2, 3,0%-8,0% on a dry weight SiO2, and 4.0%-9,0% on a dry weight WO3. More specifically, the carrier of the active catalyst includes ≥87% on a dry weight TiO2That 3%-6% on a dry weight SiO2and 4%-8% on a dry weight WO3. In one preferred embodiment, the catalyst comprises about 90% (±0,5%) on a dry weight TiO2approximately 4% (±0,5%) on a dry weight SiO2and about 6% (±0,5%) on a dry weight WO3. In one embodiment, the number of WO3in weight percent is greater than the number of SiO2in weight percent. In one embodiment, the catalyst carrier in the freshly prepared state has a specific surface area of at least 80 m2/gram, and more preferred�Stateline at least 100 m 2/gram.

In one embodiment the TiO2-the component used here, the carrier material of the catalyst mainly has a specific surface area of <400 m2/g, and pore volume <0,40 cm3/g.

In one embodiment, the slurry of titanium dioxide and craniometry component used here is mixed at a temperature of <80°C and at pH<8,5. An alternative, used here, the suspension of titanium dioxide and a component of silicon dioxide may be mixed at a temperature <70°C and at pH<7,0.

In yet another embodiment of the invention is a catalyst based on vanadium oxide, including the new one described here-stabilized silica catalyst carrier based on titanium dioxide or titanium dioxide and tungsten oxide, which is deposited some amount of vanadium oxide (V2O5). In panagiotidou catalyst V2O5preferably about 0.5% to 3% to 5% of its dry weight. The invention is additionally directed to a catalytic device for neutralization of exhaust of the diesel engine, which is described here contain catalysts based on vanadium oxide. Materials of catalysts based on vanadium oxide according to the invention can be further processed� by calcining (sintering) at temperatures ≥650°C to improve deNOx-catalytic activity.

In addition, these new catalytic devices may be used upstream or downstream of a diesel particulate filter (DPF) in the system of regulation of diesel exhaust. In the system with the layout of the upstream catalytic device is located between the engine and the DPF, and the system layout downstream DPF is located between the engine and the catalytic device.

The term "kremnicka-titanocene media", wherever it is used here, it is assumed having the same meaning as "stable silica-based media of titanium dioxide", and the term "kremnicka-titanox-voltametry media is expected to have the same meaning as "stable silica-based media of titanium dioxide and tungsten oxide".

The majority of the particles of silicon dioxide in the carrier particles on the basis of stabilized titanium dioxide preferably has a diameter <5 nm, and more preferably <4 nm, and more preferably <3 nm, and still more preferably <2 nm, and/or has a low molecular weight (e.g., MW <100000, whether or not particles have deposited on them V2O5).

Where the particles kremnicka-titanocene media contain V2O5V2O5mostly is about� of 0.5% -3% by dry weight of carrier material.

The distribution of particle WO3and SiO2on the surface of the carrier on the basis of titanium dioxide also plays an important role in the optimization of DeNOx-activity catalysts based on vanadium oxide. Thus, when the catalysts are fresh, i.e., when the added silicon dioxide and tungsten oxide is deposited first, and to high temperature treatment, partial monocline coating should be about 1.0 or less.

As noted above, stabilization of the carrier material based on titanium dioxide silicon dioxide includes the processing of titanium dioxide silicon dioxide in the form of low molecular weight and/or in the form of small nanoparticles, such as silicate Tetra(alkyl)ammonium (for example, silicate of Tetramethylammonium) or tetraethylorthosilicate (TEOS). Other examples of precursors of silicon dioxide with a low molecular weight and/or in the form of small nanoparticles, which can be used in the present invention include, but are not limited to these, aqueous solutions of silicon halides (i.e., SiX anhydrous4where X=F, Cl, Br or I), alkoxides of silicon (i.e., Si(OR)4where R=methyl, ethyl, isopropyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl, pentile, exile, octile, lonely, Cecily, undecyl and dodecyl, for example), other organosilicon compounds such as hexamethyldisilane�EN, salt fortramadol acid, such as hexaferrites ammonium [(NH4)2SiF6], solutions of Quaternary ammonium silicates (for example, (NR4)n, (SiO2), where R=H, or alkali such as the ones listed above, and where n=0.1 to 2, for example), aqueous solutions of sodium silicate and potassium (Na2SiO3, K2SiO3and MSiO3in which M represents Na or K in various amounts relative to Si), silicic acid (Si(OH)4), formed by ion exchange from any of the cationic forms of silica listed here, using acidic ion-exchange resin (for example, ion exchange of solutions of alkali metal silicates or solutions of Quaternary ammonium silicate). In preferred embodiments, the implementation used here, the titanium dioxide was obtained in the presence of urea.

Although the present invention and its advantages have been described in detail, it should be clear that various changes, substitutions and modifications can be made without going beyond the nature and scope of the invention defined by the attached patent claims. Moreover, the scope of the present application is not intended to be limited to specific variants of execution of the method, products, material compositions, means, methods and stages that are listed in the description. �AK will be easily understandable to a person with ordinary skills in this field of technology from the description of the present invention, methods, articles of manufacture, material compositions, means, methods or stages, existing now or developed later, which perform essentially the same function or achieve substantially the same result as the corresponding options described here can be applied according to the present invention. Accordingly, the attached patent claims are assumed to be inclusive within their scope such processes, products manufacturing, material compositions, means, methods, or stage.

Each of the references, patents or publications cited here, thus explicitly incorporated here by reference in its entirety.

Cited literature sources

1. Granger, R. and Parvulescu, V. I., editors, "Studies in Surface Science and Catalysis" ("research in the field of surface phenomena and catalysis), vol. 171, Chapter 9 (2007).

2. Ullmann. "Encyclopedia of Industrial Chemistry" ("encyclopedia of industrial chemistry", fifth edition, volume A23, pp. 583-660 (1993).

3. Iler, R. K. The Chemistry of Silica" ("Chemistry of silica") (1979).

4. Fedeyko et al., "Langmuir, vol. 21, pp. 5179-5206 (2005).

5. Engelhardt G. and D. Michel. "High Resolution Solid-State NMR of Silicates and Zeolites" ("Solid-state high-resolution NMR of silicates and zeolites", John Wiley and Sons, new York (1987).

6. Wachs, I. et al., "Catalysis Today", vol 78, p. 17 (2003).

7. Wachs, I. et al., "Catalysis Today", vol 116, with�R. 162-168 (2008).

8. Bergna, H. E. and W. O. Roberts, editors, "Colloidal Silica, Fundamentals and Applications," ("Colloidal silica, fundamentals and applications"), Surfactant Science Series, volume 131, publisher CRC Press, Taylor & Francis (2006).

9. Wachs et al., "J. Catalysis, vol. 161, pp. 211-221 (1996).

10. Bergna, H., editor, "The Colloid Chemistry of Silica" ("the Colloid chemistry of silica"), ACS Series, volume 234 (1994).

11. Brinker, C. J. and G. W. Scherer. "Sol-Gel Science," Chapter 3 (1990).

1. Particles of anatase titanium dioxide as a material for a catalyst for the selective reduction of nitrogen oxides comprising ≥85% by dry weight of TiO2and ≤10% on a dry weight SiO2and (i) SiO2is mainly in the form selected from the group consisting of forms of low molecular weight, nanoparticles, and combinations thereof; and (ii) at least 50% of silicon atoms SiO2located in the States of Q3, Q2, Q1and Q0coordination sphere.

2. Particles of anatase titanium dioxide according to claim 1, further comprising from 3% to 10% of WO3.

3. Particles of anatase titanium dioxide according to claim 2, in which the specific surface according to BET of at least 80 m2/g.

4. Particles of anatase titanium dioxide according to claim 2, including ≥85% by dry weight of TiO2, 3%-9% dry weight of SiO2and 3%-9% dry weight WO3.

5. Particles of anatase titanium dioxide according to claim 1, in which SiO2is present with Zn�the increase of the partial monolayer of less than 1.0 before sintering of particles of anatase titanium dioxide.

6. Particles of anatase titanium dioxide according to claim 1, in which SiO2in the form of nanoparticles has a diameter of <5 nm.

7. Particles of anatase titanium dioxide according to claim 1, in which SiO2in the form of low molecular weight has a molecular weight of <100000.

8. Particles of anatase titanium dioxide according to claim 1, in which SiO2includes fragmentary sections, which have a depth of, essentially, ≤5 nm after redistribution, according to the observations using scanning electron microscopy or transmission electron microscopy.

9. Particles of anatase titanium dioxide according to claim 1, in which TiO2was not obtained in the presence of urea.

10. Particles of anatase titanium dioxide according to claim 2, further having distributed them V2O5.

11. Particles of anatase titanium dioxide according to claim 10, comprising from 0.5% to 5% on a dry weight basis of V2O5.

12. Particles of anatase titanium dioxide according to claim 10, in which V2O5present them with the value of the partial monolayer of less than 1.0 before sintering.

13. Particles of anatase titanium dioxide according to claim 10, which were subjected to sintering at temperatures ≥650°C.

14. Catalytic device for neutralization of diesel exhaust comprising particles of anatase titanium dioxide according to claim 10.

15. Control system of diesel exhaust, including:
catalytic �disorder for neutralization of diesel exhaust according to claim 14; and
a diesel particulate filter and a catalytic device for neutralization of diesel exhaust is placed upstream or downstream of the diesel particulate filter.

16. The way in which catalyze the conversion of nitrogen oxides in gaseous N2including:
impact on diesel emissions, including NOx, particles of anatase titanium dioxide according to claim 10 with added reducing agent for the formation of N2and H2O.

17. A method according to claim 16, wherein the reducing agent is a substance selected from the group consisting of NH3, urea and combinations thereof.

18. A method according to claim 16, in which the particles of the anatase titanium dioxide of claim 10 include a 0.5% -3% on a dry weight basis of V2O5.

19. A method according to claim 16, in which diesel exhaust is passed through a diesel particulate filter before or after exposure of the particles of the anatase titanium dioxide according to claim 10.

20. A method of producing particles according to claim 2, which includes stages, at which:
prepare a suspension containing TiO2;
combine TiO2-suspension (1) a solution of the precursor of silicon dioxide containing SiO2mainly in the form selected from the group consisting of forms of low molecular weight, nanoparticles and combinations thereof, and (2) WO3with the formation of a mixture of TiO2-WO3-SiO2; wherein a solution of precursor dioxide �Rennie unite with ΤiO 2-slurry before, after or at the time when WO3combined with TiO2-suspension, and
washed and subjected to sintering a mixture of TiO2-WO3-SiO2with the formation of stable silica titanocene carrier material.

21. A method according to claim 20, in which stable silicon dioxide titanocene the carrier material includes
86%-94% dry weight of TiO2, 3%-9% dry weight of SiO2and 3%-7% dry weight WO3; and in which titanocene the carrier material initially has a specific surface area of at least 80 m2/g before sintering.

22. A method according to claim 20, in which ΤiO2in suspension comprises a material selected from the group consisting of pre-formed particles of titanium hydroxide, oxyhydroxide titanium, titanium dioxide, and combinations thereof.

23. A method according to claim 20, in which TiO2in the suspension obtained in the presence of urea.

24. A method according to claim 20, in which SiO2in the form of nanoparticles in a solution of a precursor of silicon dioxide mainly has a diameter of <5 nm.

25. A method according to claim 20, in which SiO2in the form of low molecular weight in solution of the precursor of silicon dioxide mainly has MW <100000.

26. A method according to claim 20, in which SiO2in the solution of the precursor of silicon dioxide includes the silicon atoms, which is mainly used to measure� are located in the States of Q 3, Q2, Q1and Q0coordination sphere.

27. A method according to claim 20, in which the solution of the precursor of silicon dioxide comprises a substance selected from the group consisting of a solution of silicate of Tetra(alkyl)ammonium, silicic acid, and combinations thereof.

28. A method according to claim 20, in which SiO2mainly includes fragmentary sections, which have a depth of ≤5 nm after redistribution, according to the observations using scanning electron microscopy or transmission electron microscopy.

29. A method according to claim 20, comprising a stage in which combine a mixture of TiO2-WO3-SiO2V2O5with the formation of the catalyst based on vanadium oxide.

30. A method according to claim 29 in which the catalyst based on vanadium oxide consists of 0.5% -3% on a dry weight basis of V2O5.

31. A method according to claim 29, where V2O5in the catalyst based on vanadium oxide is present with the value of the partial monolayer of less than 1.0 before sintering.

32. A method according to claim 29, comprising the additional step, in which the catalyst based on vanadium oxide is subjected to sintering at temperatures ≥650°C.

33. A method of producing particles according to claim 1, which includes stages, at which:
prepare TiO2-the suspension containing particles of TiO2;
prepare the source dispersed silicon dioxide;
combine TiO2-susp�SIU source of particulate silicon dioxide with the formation of TiO 2-SiO2- mixture; and
adjusted pH value of TiO2-SiO2- mixture to <8.5 and the temperature to <80°C, and the source of the dispersed silica is dissolved and periostat on particles of TiO2with the formation of stable silica titanocene carrier material of the catalyst.

34. A method according to claim 33, further comprising a stage on which unite stabilized silica titanocene the carrier material of the catalyst with WO3to obtain stable silicon dioxide titnaked-tungsten material of the catalyst carrier.

35. A method according to claim 34, further comprising stages, which are stabilized by the silica titnaked-tungsten carrier material of the catalyst was washed and subjected to sintering.

36. A method according to claim 34, which stabilized the silicon dioxide titnaked-tungsten material of the catalyst carrier includes:
86%-94% dry weight of TiO2, 3%-9% dry weight of SiO2and 3%-7% dry weight WO3; and in which titanocene the carrier material initially has a specific surface area of at least 80 m2/g before sintering.

37. A method according to claim 33, in which the particles of TiO2in TiO2-suspensions include a material selected from the group consisting of pre-formed particles g�of droxide titanium, oxyhydroxide titanium, titanium dioxide, and combinations thereof.

38. A method according to claim 33, in which the particles of TiO2in TiO2-the suspension obtained in the presence of urea.

39. A method according to claim 33, in which SiO2in TiO2-SiO2- mixture after dilution includes the silicon atoms, which are located mainly in the States of Q3, Q2, Q1and Q0coordination sphere.

40. A method according to claim 33, in which SiO2on particles of TiO2mainly includes fragmentary sections, which have a depth of ≤5 nm after redistribution SiO2according to the observations using scanning electron microscopy or transmission electron microscopy.

41. A method according to claim 34, comprising a stage on which combine a mixture of TiO2-WO3-SiO2V2O5with the formation of the catalyst based on vanadium oxide.

42. A method according to claim 41, in which the catalyst based on vanadium oxide consists of 0.5% -3% on a dry weight basis of V2O5.

43. A method according to claim 41, where V2O5the catalyst based on vanadium oxide is present with the value of the partial monolayer of less than 1.0 before sintering.

44. A method according to claim 41, comprising the additional step, in which the catalyst based on vanadium oxide is subjected to sintering at temperatures ≥650°C.



 

Same patents:

FIELD: metallurgy.

SUBSTANCE: electrode coating contains the following components, wt %: ferrochrome - 58.0-60.0, ferroboron - 14.0-16.0, marble - 5.0-7.0, ferrosilicon - 3.5-4.5, fluorspar - 3.5-4.5, ferromanganese - 1.5-3.5, graphite - 5.5-6.5, potash - 0.5-1.5 and nanopowder of titanium carbonitride - 1.5-3.0. The electrode coating can be applied to metal rods from steel grade Sv-08A.

EFFECT: composition of the coating allows obtaining electrode paste with high plasticity, and electrodes with such coating provide for obtainment of deposited metal with hardness of up to 66 HRC, increased wear resistance and continued operating stability of reworked parts.

4 dwg, 1 tbl

FIELD: physics, robotics.

SUBSTANCE: invention relates to military robotics and can be used for proportional increase in force of combatant and at cargo handling. This exoskeleton comprises carcass system, drives, electronic control system and power supply battery. Said carcass system consists of black-reinforced plastic panel following the trunk rear shape and articulated leverage of reinforced-black tubes. Note here that carcass leverage drives are made of solid aerogel composed of carbon nanotubes with admixture of rubber shaped to 40-120 mm diameter cylinders with conical sharpening on ends. Said drives are attached to the levers by clamping of conical ends with the help of synthetic fabric bands impregnated with epoxy resin and tied by steel rivets.

EFFECT: electric power saving, increase in force and self-contained operation time, maximised combat efficiency.

2 dwg

FIELD: chemistry.

SUBSTANCE: uniform, continuous and dense layer of pyrolytic carbon has width of carbon coating, close to monolayer coating, equal 0.4-0.5 nm, density of precipitated carbon coating, equal ρC = 2.0-2.1 g/cm3, specific surface SBET = 90-200 m2/g, cumulative volume of pores ΣVpore≤0.4 cm3/g, average size of pores DBET≤10 nm, most probable size of pores DBJH = 5-7 nm with absence of micro pores. Invention also relates to method of production of such mesoporous composite material.

EFFECT: claimed mesoporous composite material has high-quality thin carbon coating, which totally and uniformly covers external surface and walls of pores of said material.

4 cl, 3 dwg, 3 tbl, 10 ex

FIELD: power industry.

SUBSTANCE: solar element includes cathode and anode, each having external and internal flexible layers, at that these cathode and anode are located such that their internal layers are opposite each other with clearance filled by the electrolyte, at that the external layer of the cathode is made out of transparent polymer material, and its internal layer is made out of carbon nanotubes, the external layer of the anode is made out of conducting material, and its internal layer is made out of nanoparticles of solid state material, dye-sensitised.

EFFECT: simplified process of solar elements manufacturing, reduced price, and increased flexibility.

11 cl, 1 dwg

FIELD: biotechnologies.

SUBSTANCE: object is positioned on porous substrate, fixed to the substrate surface and scanned by probe microscopy method. Substrate with through pores of smaller size than the diameter of a study object is used, and an object is fixated by laminar flow of liquid or gas supplied to the substrate from the side of scanning, with clamping force exerted by the flow on an object within 10-12-10-3 N range.

EFFECT: possible study of structures and mechanical properties of organic and inorganic objects, enhanced information content of nano and micro object studies by probe microscopy.

7 ex

FIELD: physics.

SUBSTANCE: invention relates to magnetophotonics. A method of amplifying the magneto-optic Kerr effect by forming a magnetic photonic crystal with a periodically structured magnetic surface, wherein the surface morphology of the magnetic photonic crystal is determined by the level of the section of the densest face-centred cubic arrangement of microspheres in the <111> plane within a layer of a colloidal crystal.

EFFECT: amplifying meridian magneto-optic effect.

10 cl, 5 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a novel salt nanosize weakly crystalline modification 4-methyl-N-[3-(4-methylimidazol-1-yl)-5-(trifluoromethyl)phenyl]-3-[(4-pyridin-3-ylpyrimidin-2-yl)amino]benzamide (nilotinib) hydrochloride monohydrate. Nilotinib is used as an anti leucaemia cytostatic drug during therapy of cancerous diseases. The nanosize weakly crystalline modification is characterised by the following set of interplanar distances (d, E) and respective intensities (Iot, %) 14.70-27.8%; 12.94-19.4%; 11.43-22.2%; 7.474-26.4; 6.480-25.0%; 6.217-26.4%; 6.040-52.8%; 5.134-19.4%; 4.824-16.7%; 4.489-25.0%; 4.367-25.0%; 4.156-30.6%; 4.092-30.6%; 3.738-30.6%; 3.656-34.7%; 3.528-41.7%; 3.468-44.4%; 3.165-52.8%; 3.053-36.1%; 2.999-100%; 2.869-22.2%; 2.823-69.4%; 2.653-33.3%; 2.524-22.2%; 2.383-22.2%; 2.348-22.2%; 2.203-20.8%; 2.151-22.2%; 2.020-19.4%; 1.932-22.2%; 1.849-26.4%; 1.841-25.0%; 1.763-22.2%, three endothermic effects equal to (97.3±0.4) J/g at temperature of (92.6±0.5)°C, (54.5±0.4) J/g at temperature of (173.7±0.5)°C, (215.6±0.4) J/g at temperature of (273.4±0.5)°C, particle size of less than 150 nm, specific surface area of more than 30 m2/g and powder density in free filling of less than 0.024 g/cm3. A method of producing the modification includes preparing an aqueous solution of 4-methyl-N-[3-(4-methylimidazol-1-yl)-5-(trifluoromethyl)phenyl]-3-[(4-pyridin-3-ylpyrimidin-2-yl)amino]benzamide hydrochloride monohydrate at 25-100°C, which is then frozen at a rate of not less than 60 degrees/minute, followed by removing the solvent by freeze-drying for 22-27 hours. The invention also relates to a pharmaceutical composition.

EFFECT: disclosed modification is 15-20 times more soluble than the existing modification A, which means it can be absorbed into the body over a shorter period and has high activity.

3 cl, 8 dwg, 1 tbl, 5 ex

FIELD: measurement equipment.

SUBSTANCE: method may be used in scanning probing microscopy for determination of electric voltage, modulus of elasticity, hardness, viscosity, plasticity of piezoelectric materials, components of micro and nanoelectromechanical systems, as well as biomicroelectromechanical devices. Nanoindentation of the material is done with a stiff indentor with continuous speed. Simultaneously they measure change of electric voltage and contact force as the indentor is pressed into the material, for instance, piezoelectric. Measurements are made at least for two temperatures of the material.

EFFECT: expansion of functional capabilities of material properties detection by nanoindentation, possibility to determine load value that results in phase transition.

2 cl, 5 dwg

FIELD: nanotechnology.

SUBSTANCE: distinctive feature of the proposed method is the use of biopag-D and the microcapsule shells of sodium carboxymethyl cellulose, as well as the use of a precipitator - 1,2-dichloroethane in the preparation of nanocapsules by physico-chemical precipitation method by nonsolvent.

EFFECT: simplifying and speeding up the process of obtaining the microcapsules and increase in the yield by weight.

3 ex

FIELD: chemistry.

SUBSTANCE: invention provides a method of encapsulating a medicinal preparation via a nonsolvent deposition method, characterised by that the core of the nanocapsule used is fenbendazole, the envelope used is pectin, which is deposited from a suspension in benzene by adding tetrachloromethane as the nonsolvent at 25°C.

EFFECT: simpler and faster process of producing microcapsules, reduced losses when producing microcapsules.

6 ex

FIELD: engines and pumps.

SUBSTANCE: invention relates to a manufacturing method of a honeycomb ceramic unit for a catalytic neutraliser of exhaust gases, according to which to the ceramic unit from the main material there applied is a binding layer containing sodium silicate Na2O(SiO2)n or potassium silicate K2O(SiO2)n, or their mixture, above which there formed is at least one substrate layer for application of a catalyst, which contains a nanodispersed oxide of aluminium hydroxide (boehmite); for that purpose, a suspension layer is applied onto the second workpiece, which contains nanodispersed oxide of aluminium hydroxide; the workpiece with the applied suspension layer is dried; after that, the workpiece of the honeycomb ceramic unit with the applied substrate material is roasted, and therefore, a honeycomb ceramic unit for a catalytic neutraliser of exhaust gases is obtained. In addition, an application method of substrate onto the honeycomb ceramic unit for the catalytic neutraliser of exhaust gases, which applies this technology, is proposed.

EFFECT: improvement of passage of a gas flow through pores and channels of a substrate; increase and optimisation of a catalytic neutralisation process of substances in exhaust gases of diesel engines.

17 cl, 24 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of preparing oxide-polymetallic catalysts, containing metals of platinum group, for oxidative-vapour conversion of hydrocarbons with obtaining carbon oxide and hydrogen. Method includes processing NiO and CO3O4 with solutions of nitrates Al, Ce, Zr and compounds of palladium Pd(NH3)4Cl2, platinum H2[PtCl6]·6H2O and rhodium H3[RhCl6], with the following drying; coking obtained material in methane flow at 550°C, obtaining paste from said material, pseudoboehmite and tetraisopropoxylane, filling foam-nichrome pores with suspension from obtained material, removal of water at 80°C, calcinations for 3 hours in argon atmosphere at 1300°C, removal of carbon with water vapours at 600°C for 3 hours.

EFFECT: creation of highly efficient heterogeneous catalyst.

4 cl, 7 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to extraction of metals from a stream rich in hydrocarbons and carbon-containing residues using a treatment area. The method includes the following steps: feeding said stream for primary treatment, which is carried out in one or more steps, where said stream is treated in the presence of a diluent in a mechanical treatment apparatus at temperature of 80-180°C, preferably 100-160°C, and is divided into a liquid phase and a solid phase to obtain a purified product, primary consisting of liquids, and a condensed residue (oil cake); optionally drying the separated condensed residue to remove therefrom a hydrocarbon component with a boiling point lower than 300-350°C; feeding the condensed residue, optionally dried, for secondary heat treatment, which includes: flameless pyrolysis of the condensed residue, carried out at 400-800°C; oxidising the pyrolysis residue, carried out in an oxidative medium and at 400-800°C, preferably 500-700°C, to obtain a product primarily consisting of sulphides/inorganic oxides of metals; selectively extracting metal components from the product obtained at secondary heat treatment step.

EFFECT: extracting and recycling the active component of an operating catalyst.

21 cl, 5 dwg, 8 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: in claimed method aluminium oxide is processed in hydrothermal conditions. Hydrothermal processing is carried out at temperature 120-300°C for 0.5-10 h in autoclave after pouring catalyst with water, with weigh ratio aluminium oxide/water 0.5-50, formed product is cooled to room temperature and dried at temperature 110-200°C, after which catalyst calcinations is performed at 550-600°C. Invention also relates to method of obtaining isobutylene by skeletal isomerisation of n-butylenes with application of catalyst, thereof obtained.

EFFECT: increase of content of active centres of skeletal isomeration of n-butylenes.

3 cl, 1 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention refers to a catalyst for hydrocarbon material hydroprocessing. The presented catalyst comprises an amorphous alumina-based carrier, phosphorus, at least one dialkyl(C1-C4)succinate, acetic acid and a functional group with a hydrogenation/dehydrogenation ability containing at least one group VIB element and at least one group VIII element specified in cobalt and/or nickel. The Raman spectrum of the above catalyst has characteristic bands of at least one Keggin heteropolyanionwithin the range of 990 and/or 974 cm-1, characteristic bands of said succinate and a principal characteristic band of acetic acid within 896 cm-1. The invention also refers to a method for producing this catalyst and to the catalyst produced by this method, as well as to a method for hydrocarbon material hydroprocessing in the presence of this catalyst.

EFFECT: presented catalyst possesses overactivity shown in hydroprocessing by the synergetic action of a combination of acetic acid and dimethylsuccinate.

24 cl, 2 dwg, 5 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an ammonia synthesis catalyst. Said catalyst is a supported metal catalyst which is deposited on a mayenite-type compound, containing conduction electrons in concentration of 1015 cm-3 or higher and serving as a support for the ammonia synthesis catalyst. The invention also relates to a method of producing said catalyst and an ammonia synthesis method using said catalyst.

EFFECT: disclosed catalyst enables synthesis of ammonia with high efficiency in mild conditions.

7 cl, 1 dwg, 4 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of preparing applied catalysts by a method of the pulse surface thermal synthesis of an active component from precursors, representing oxidants and reducing agents interacting at an increased temperature, which are either in different compounds or in one, applied on a carrier from their solutions, melts or suspensions with the following drying. The claimed method includes moving the carrier with the precursors of the active component applied on it through a high-temperature zone with the temperature not lower than 200°C at the speed, ensuring the growth of its temperature by not less than 10°C per minute.

EFFECT: method makes it possible to obtain catalysts with high activity, and ensures easy and reliable adjustability of the production process.

4 cl, 1 tbl, 6 ex

FIELD: oil-and-gas industry.

SUBSTANCE: catalyst for steam conversion of hydrocarbons is a multilayered composition comprising the layers consistently located on the metal carrier: buffer, consisting of the oxide selected from the group TiO2, SiO2, ZrO2, Al2O3 or their combination, interphase composition, wt %: BaO - 1, La2O3 - 1,5, Al2O3 up to 100, catalytic active composition, wt %: 1 - BaO, 1.5 - La2O3, 5 - Rh, Al2O3 up to 100. The method of preparation of the steam conversion catalyst includes consecutive application on the metal carrier of buffer layer, interphase layer and catalytic active layer. The layers are applied by fine drop dispersion with the subsequent heat treatment of the respective solutions and suspensions. The method of steam conversion of hydrocarbons is performed using the catalyst of steam conversion according to the reaction: CH4+H2O=CO+3H2+226 KJ/mol at the molar ratio H2O/C, equal to 2.4-2.6, temperature 600-900°C, pressure 140,000-774,000 Pa and time of contact of steam-gas mix with the catalyst 0.02-0.12 s.

EFFECT: obtaining of the catalyst for conversion of hydrocarbons with hyperactivity, stability and resistance to coke production under operating conditions at high temperatures.

7 cl, 4 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a catalyst based on pentasil-type crystalline aluminosilicate, the method including steps of: (a) treating a hydrate of aluminium oxide with an acid-containing aqueous agent, (b) mixing the hydrate of aluminium oxide treated with an acid-containing aqueous agent from step (a) with H-zeolite with mean diameter of primary crystallites ranging from 0.01 mcm to less than 0.1 mcm, (c) moulding the mixture obtained at step (b) by extrusion and (d) calcining the mixture obtained at step (c), wherein at least 95 vol. % of particles of the hydrate of aluminium oxide (with respect to the mean diameter) is less than or equal to 100 mcm. The invention also relates to a catalyst and use of the catalyst to convert methanol into olefins.

EFFECT: obtaining catalysts with a longer service life, selectivity and activity.

17 cl, 2 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: described is catalyst for single-stage manufacturing of components for jet and Diesel fuels from oil and fat raw material, containing platinum or palladium, fixed on the surface of porous carrier, represented by borate-containing aluminium oxide, with the following component ratio, wt %: Pt or Pd 0,10-0.50; B2O3 5-25; Al2O3 - the remaining part. Catalyst can be prepared by granulation of mixture of aluminium oxide hydrate of pseudoboehmite structure with orthoboric acid with the following drying of granules at 120°C and annealing at 550-700°C for 16 h. Granules are soaked with solutions of hexachloroplatinic acid or palladium chloride, subjected to drying at 120°C and annealing at 500°C. Method of single-stage manufacturing of components for jet and Diesel fuels with improved low-temperature properties from oil and fat raw material in presence of claimed catalyst includes passing mixture of hydrogen and oil and fat raw material through immobile layer of catalyst at temperature 380°C, pressure 4.0 MPa, mass rate of raw material supply 1 h-1 and with volume ratio hydrogen:raw material, equal 1300.

EFFECT: increased efficiency of single-stage manufacturing of components for jet and Diesel fuels with improved low-temperature properties from oil and fat raw material due to simplification of catalyst composition, method of its preparation and reduction of catalyst cost.

3 cl, 4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: method of obtaining platinum-containing catalysts on nanocarbon carriers includes processing of nanocarbon component with chloroplatinic acid with the following reduction of the latter with ethyleneglycol in alkaline medium, with carbon nanoparticles being preliminarily subjected to functionalisation by boiling in concentrated nitric acid, washed after that with distillated water to neutral pH, dried in vacuum at temperature 40°C; after which carbon nanoparticels are placed in flask, which contains distillated water and chloroplatinic acid, ethyleneglycol and twice-normal solution of NaOH are added to pH ≈ 12-14, mixture is mixed in ultrasonic bath, then heated to 140-150°C with continuous mixing of said mixture in argon flow. After that, polyetheneglycol with molecular weight MM ~ 40000 is added, after that, mixture is cooled to room temperature, placed in centrifuge and washed with distillated water to neutral pH with the following drying in vacuum at 40°C to constant weight.

EFFECT: obtaining catalyst with more monodispersive and regulated distribution of platinum nanoparticels by size, which leads to economy of electric power and work labour saving and to reduction of price of obtained catalysts.

3 dwg, 1 ex

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