Method of production of the microporous materials with the coating made out of the rare-earth metal oxide

FIELD: chemical industry; oil-refining industry; other industries; methods of production of the catalytic microporous fine-dispersed materials.

SUBSTANCE: the invention is pertaining to the method of production of the catalytic microporous fine-dispersed material, which is used in such processes, as purification of the oil fractions, purification of the sewage disposal, the catalytic conversion of the exhaust gases exiting from the combustion engines. The method allows to produce the catalytic microporous fine-dispersed material with the coating of the rare-earth metal oxide, in which the quantity of the metal oxide deposited on it is high without the risk for efficiency of the material. At that the rare-metal oxide is deposited on the outer surfaces of the indicated material and may be within the interval of 20-70 mass % with respect to with respect to the total equivalent content of the rare-earth metal oxide and the microporous fine-dispersed material. The method provides for the combination of the quantity of the colloid dispersion of the hydrate of the rare-earth metal oxide with the compatible microporous fine-dispersed material with formation of the suspension and the thermal treatment of the indicated suspension for the rare-earth metal oxide fixation on the outer surfaces of the indicated material. At that the indicated microporous fine-dispersed material has the average size of the pores less than 20 Å, and the indicated colloid dispersion has the particle size of the particles of not less than 20 Å. The invention also presents the catalytic free-loose fine-dispersed material with the rare-earth metal oxide coating containing the ceolite fine-dispersed material, the rare-earth metal oxide. At that the indicated ceolite fine-dispersed material has the average size of the pores less than the size of the particles of the indicated rare-earth metal oxide, and more than 20 mass % of the indicated rare-earth metal oxide is on the outer surfaces the indicated ceolite fine-dispersed material with respect to the total equivalent content of the rare-earth metal oxide and the ceolite. The ceolite free-loose fine-dispersed material having the high contents of the rare-earth metal oxide has the tendency to be the very stable material.

EFFECT: the invention ensures production of the catalytic microporous fine-dispersed material with the coating of the rare-earth metal oxide without the risk for efficiency of the material and the ceolite free-loose fine-dispersed material having the high contents of the rare-earth metal oxide has the tendency to be the very stable material.

31 cl, 11 ex, 3 tbl

 

Description

The technical field to which the invention relates.

The present invention relates to a method for the catalytic fine microporous material with a coating of a metal oxide and related products.

Background of invention

Porous fine materials, bearing catalytically active elements, are known in the art. These materials are used in many processes, such as cleaning oil fractions or wastewater treatment, such as catalytic conversion of exhaust gases emanating from internal combustion engines.

The catalysts usually contain a carrier obtained by forming a porous material, such as alumina. Thus, the media can take many different forms, such as spheres, cylindrical extruded extruded profiles or profiles with multi-leaf cross-section or cross-section of various forms, such as the wheel.

Commonly used porous materials are alumina, silica, zeolites or similar. These carriers typically have a large specific surface area, for example over 20 m2/g, to provide a large surface area, which is becoming catalytically active when applied to the catalytically active ele the clients.

The various elements are usually introduced by impregnation into the porous material. For example, U.S. patent 5232889 refers to the catalyst obtained by impregnation of a porous material, preferably alumina spheres with a colloidal dispersion of deposited metal. Colloidal dispersion should have a particle size not greater than the pore size of a porous material. When colloidal dispersion penetrates into the pores of the carrier, the reaction surface areas of the carrier change the pH of the dispersion, causing the deposition of metal in a porous material. U.S. patent 6040265 also relates to the impregnation of a porous material, such as alumina or zeolites, the primary solution of the acetate of the metal, at least one secondary metal acetate and the organic agent deposition, such as soluble sugars, saccharides, polysaccharides or their derivatives, with the formation of the impregnated porous material. In addition, Canadian patent 2033291 relates to a catalyst for the conversion of nitrogen oxides at high temperature exhaust. The catalyst comprises zeolite (molar ratio SiO2/Al2O3> 20), which contains 0.5 to 10 wt.% cerium oxide. The catalyst may be obtained either by impregnation of the zeolite with an aqueous solution of nitrate, halide or sulfate cerium, or it can be obtained by implementing ion exchange. The mixture is then dried and about elewaut at 300-600° C.

The prior art also shows that other elements can form an aggregation with a porous material with obtaining catalytic material. For example, U.S. patent 5804526 refers to the adsorbent, which shows excellent adsorption ability with respect to nitrogen oxides. The adsorbent can be obtained, for example, aggregation of cerium oxide and zeolite. The content of cerium oxide in the catalyst is in the range of 10-80 wt.% in relation to the total equivalent content of zeolite and cerium oxide. The adsorbent is prepared from a mixture of crystalline particles of cerium oxide and zeolite particles dealumination zeolite ZSM-5 crystalline particles of cerium oxide are composed of polycrystalline aggregates having an average size of crystal grains of less than 500Å. In the aggregated state of the crystalline particles of cerium oxide are adjacent to the surfaces of the zeolite particles.

There are several patents that are considering the use of a catalytic coating on a porous metal or similar substrate to remove gases. U.S. patent 4900712 relates to the adsorption of one or more catalytically active oxides on alumina with high surface area. The method for the catalytic coating includes the use of colloidal method of uniformly applying legs is avannah oxides on alumina with high surface area. Colloidal dispersions get choose aqueous salt solution of the metal nitrate and turning the nitrate salt of the metal colloid of the metal oxide ion exchange resin. Colloidal dispersion of oxide suspended with alumina, where the colloidal oxide particles adsorbed on the alumina. In order to maintain the adhesion of the catalytic coating on the substrate and to maintain high surface area for the catalyst alloying oxide limit to less than about 20 wt.% in relation to the total equivalent content of alumina and alloying oxide.

U.S. patents 5431887 and 5556819 refer to filters with flame coating for use in catalytic devices for the removal of smoke flame. The filter is covered with a suspension of alumina (can be used zeolite or a mixture of both) and colloidal dispersed cerium oxide, and cerium oxide acts as a binder. Colloidal dispersion of cerium oxide is obtained using high temperatures for extended periods of time, as described in the above U.S. patent 4900712.

There is, however, a need in the way, which gives stable Svobodnoye catalytic fine microporous material with a coating of a metal oxide with different content and eliminates the disadvantages of the prior art.

Brief description of the invention

The present invention provides an effective method of obtaining a stable microporous catalytic fine material for use in the purification of a number of gaseous and particulate discharge in different areas of technology.

According to the aspect of the present invention provides a method for the catalytic fine microporous material with a coating of oxide of rare earth metal, having more than 20 wt.% oxide of rare earth metal deposited on the outer surfaces of the specified fine microporous material, relative to the total equivalent oxide content of rare earth metal and fine microporous material containing stages:

i) combining the number of colloidal dispersions hydrate of oxide of rare earth metal compatible with fine microporous material with formation of a suspension, and the amount of the colloidal dispersion is sufficient to ensure that during the heat treatment stage (ii) more than 20 wt.% oxide of rare earth metal, and the specified fine microporous material has an average pore size less than 20 Åand the specified colloidal dispersion has a particle size of not less than 20 Å with accommodation in the specified colloidal dispersion on these on uinyh surfaces specified fine microporous material;

(ii) heat treatment of the specified suspension at a temperature below about 200°C, above about 400°C or sequential combinations thereof, where specified, the suspension is subjected to heat treatment, firstly, at temperatures below about 200°C and, secondly, above approximately 400°C to fix the oxide of rare earth metal on the specified exterior surfaces specified fine microporous material with obtaining Svobodnoye fine material.

According to another aspect of the present invention preferably microporous fine material is compatible aluminosilicate. Most preferably microporous fine material is compatible zeolite.

According to another aspect of the present invention is preferably an oxide of rare earth metal selected from the group consisting of oxides of the lanthanide metals, yttrium, scandium, and mixtures thereof. Most preferably the oxide of rare earth metal is cerium oxide.

In another aspect of the present invention, the colloidal dispersion is crystalline and has a pH less than 4.2.

In another aspect of the present invention the method comprises the additional step (iii), which includes grinding the specified fine microporous material with a coating of the oxide of rare earth metal to obtain particle sizes in the range of 1-25 microns.

In another aspect of the present invention, the suspension is preferably subjected to heat treatment using the technology of spray drying, drying trays, freeze-drying, drying by removal of the solvent, spray drying in vacuum or combinations thereof.

In another aspect of the present invention, the colloidal dispersion is preferably dried to a gel and then restore in water with the formation of this colloidal dispersion used in stage (i).

According to another aspect of the present invention provides a method for the catalytic fine zeolite material with a coating of oxide of rare earth metal, having at least 1 wt.% the specified oxide of rare earth metal deposited on the outer surfaces of the specified zeolite fine material, relative to the total equivalent oxide content of rare earth metal and a zeolite containing stages:

i) combining the number of colloidal dispersions hydrate of oxide of rare earth metal with a compatible zeolite fine material with the formation of the suspension, and the amount of the colloidal dispersion is sufficient to ensure that during the heat treatment stage (ii) more than 1.0 wt.% oxide of rare earth metal, and specified the zeolite melodic rsny material has an average pore size less than 20 Å and the specified colloidal dispersion has a particle size of not less than 20 Å with accommodation in the specified colloidal dispersion on these outer surfaces specified zeolite;

(ii) heat treatment of the specified suspension at a temperature below about 200°C to fix the oxide of rare earth metal on the specified exterior surfaces specified zeolite fine material with obtaining Svobodnoye fine material.

According to another aspect of the present invention provides a method for the catalytic fine zeolite material with a coating of oxide of rare earth metal, having at least 1 wt.% the specified oxide of rare earth metal deposited on the outer surfaces of the specified zeolite fine material, relative to the total equivalent oxide content of rare earth metal and a zeolite containing stages:

i) combining the number of colloidal dispersions hydrate of oxide of rare earth metal with a compatible zeolite fine material with the formation of the suspension, and the amount of the colloidal dispersion is sufficient to ensure that during the heat treatment stage (ii) more than 1.0 wt.% oxide of rare earth metal, and the specified zeolite of melkodispersnye the second material has an average pore size less than about 20Å and the specified colloidal dispersion has a particle size of not less than approximately 20 Å with accommodation in the specified colloidal dispersion on these outer surfaces specified zeolite;

(ii) heat treatment of the specified suspension at a temperature below about 200°C, above about 400°C to below approximately 550°C or sequential combinations thereof, where specified, the suspension is subjected to heat treatment, firstly, at temperatures below about 200°C and, secondly, above approximately 400°C, but below about 550°C, to fix the oxide of rare earth metal on the specified exterior surfaces specified zeolite fine material with obtaining Svobodnoye fine material.

According to another aspect of the present invention provides a method for the catalytic fine zeolite material with a coating of cerium oxide having not less than 1 wt.% specified cerium oxide deposited on the outer surfaces of the specified zeolite fine material, relative to the total equivalent cerium content and zeolite containing stages:

i) combining the number of colloidal dispersions hydrate of cerium oxide with a compatible zeolite fine material with the formation of the suspension, and the number is about colloidal dispersion is sufficient to ensure that during the heat treatment stage (ii) more than 1.0 wt.% cerium oxide, moreover, the specified zeolite fine material has an average pore size less than about 20 Åand the specified colloidal dispersion has a particle size of not less than approximately 20Å with accommodation in the specified colloidal dispersion on these outer surfaces specified zeolite;

(ii) heat treatment of the specified suspension at a temperature below about 200°C and above approximately 400°C to below approximately 550°C or sequential combinations thereof, where specified, the suspension is subjected to heat treatment, firstly, at temperatures below about 200°C and, secondly, above approximately 400°C, but below 550°C, for fixing the obtained cerium oxide on the specified exterior surfaces specified zeolite fine material with obtaining Svobodnoye fine material.

In another aspect the present invention provides a method for the catalytic fine zeolite material with a coating of oxide of rare earth metal, having at least 1 wt.% the specified oxide of rare earth metal deposited on the outer surfaces of the specified zeolite fine material, relative to the total equivalent oxide content of rare earth metal and a zeolite containing stages:

i) combining an amount the VA colloidal dispersion of hydrate of oxide of rare earth metal with a compatible zeolite fine material, having a pH of less than about 4.2, with the formation of the suspension, and the amount of the colloidal dispersion is sufficient to ensure that during the heat treatment stage (ii) more than 1.0 wt.% oxide of rare earth metal, and the specified zeolite fine material has an average pore size less than about 20 Åand the specified colloidal dispersion has a particle size of not less than about 20 Å with accommodation in the specified colloidal dispersion on these outer surfaces specified zeolite;

(ii) heat treatment of the specified suspension at a temperature below about 200°C, above about 400°C or sequential combinations thereof, where specified, the suspension is subjected to heat treatment, firstly, at temperatures below about 200°C and, secondly, above approximately 400°C, to fix the oxide of rare earth metal on the specified exterior surfaces specified zeolite fine material with obtaining Svobodnoye fine material.

In another aspect of the present invention, the oxide of rare earth metal deposited on the outer surface is in the range of about 1.0 to 75 wt.%, preferably, in the range of about 20-70 wt.%, in relation to the total equivalent oxide content of rare earth metal and zeolite.

Another thing is the aspect of the present invention colloidal dispersion receive in a regulated interval sizes of colloidal particles of 20-50 Å , 50-70 Å or 100-150 Å.

In another aspect of the present invention obtain a colloidal dispersion having a specific particle size of about 20-50 Åcontains stages:

a) mixing a base and hydrogen peroxide solution gidrolizuacy salt of rare-earth metal with getting hydroxide solution of rare earth metal;

b) adding a strong acid to the specified hydroxide solution of rare earth metal to obtain a colloidal dispersion of hydrate of oxide of rare earth metal, in which a strong acid capable of deaggregating colloidal dispersion of hydrate of oxide of rare earth metal.

In another aspect of the present invention obtain a colloidal dispersion having a specific particle size of 50-70 Åcontains stages:

a) mixing the base with a solution gidrolizuacy salt of rare-earth metal, by means of ozonation of air through the solution, to obtain the solution of the hydroxide of the rare earth metal;

b) adding a strong acid to the specified hydroxide solution of rare earth metal to obtain a colloidal dispersion of hydrate of oxide of rare earth metal, in which a strong acid capable of deaggregating colloidal dispersion of hydrate of oxide of rare earth metal.

In another aspect of the present invention receipt of the colloidal dispersion, having a specific particle size 100-150 Åcontains stages:

a) mixing the base with a solution gidrolizuacy salts of rare earth metal, rare earth where the metal has two States of oxidation;

b) providing a slow oxidation in air solution gidrolizuacy salt of rare-earth metal with getting hydroxide solution of rare earth metal;

(C) adding a strong acid to a solution of the hydroxide of the rare earth metal to obtain a colloidal dispersion of hydrate of oxide of rare earth metal, where a strong acid capable of deaggregating colloidal dispersion of hydrate of oxide of rare earth metal.

According to another aspect of the present invention provides a zeolite Svobodnoye fine material with a coating of oxide catalytic rare earth metal containing:

zeolite fine material;

the oxide of rare earth metal;

where specified zeolite fine material has an average pore size less than 20 Å;

more than 20 wt.% the specified oxide of rare earth metal deposited on the outer surfaces of the specified zeolite fine material in relation to the total equivalent oxide content of rare earth metal and zeolite.

In another aspect of the present invention is usually men who e 30 wt.% oxide of rare earth metal (relative to the total equivalent oxide content of rare earth metal) leached into the water, when Svobodnoye zeolite fine material with a coating of oxide of rare earth metal suspended in the water.

According to another aspect of the present invention provides a method for the catalytic fine microporous material with a coating of oxide of rare earth metal having an oxide of rare earth metal deposited on the outer surfaces of the specified fine microporous material containing stages:

i) combining the number of colloidal dispersions hydrate of oxide of rare earth metal compatible with fine microporous material with formation of a suspension, and the specified fine microporous material has an average pore size less than the particle size of the specified colloidal dispersion in the specified colloidal dispersion on the outer surfaces of the specified fine microporous material;

(ii) heat treatment of the specified suspension for fixation of the oxide of rare earth metal on the outer surfaces of the microporous fine material.

In one embodiment, this heat treatment includes heating the specified suspension at a temperature sufficient to drain enough water from this suspension, with the formation of Svobodnoye the th of fine material. Preferably, this heat treatment further comprises calcining the specified Svobodnoye fine material.

In another embodiment, this heat treatment includes heating the specified suspension to dry calcined powder at one stage.

In another embodiment, the specified suspension contains nitrate ions, and the specified heat treatment is carried out at a temperature sufficient to decompose at least part of the nitrate ions to gaseous components.

In another embodiment, the method includes grinding the specified fine microporous material with a coating of oxide of rare earth metal to obtain particle sizes in the range of 1-25 microns. It should be noted that there may be used other intervals of particle sizes. In particular, the grinding can be obtained from smaller particles, for example 0.5 to 1 μm particles. The choice of particle size based on the intended use of the coated microporous fine material and the ability to work with the crushed particles.

A detailed description of the preferred options

Accordingly, the present invention relates to a new method, which receive Svobodnoye catalytic fine microporous material compatible with the coating on the sid rare earth metal. Preferably compatible microporous material is compatible aluminosilicate, such as a compatible zeolite fine material.

In the present invention, rare earth metals are defined as scandium, yttrium, and lanthanide metals.

In one embodiment of the present invention is a method of obtaining fine microporous material with a coating of oxide of rare earth metal contains stages:

i) combining the number of colloidal dispersions hydrate of oxide of rare earth metal compatible with fine microporous material with formation of a suspension, so that the amount of colloidal dispersion is sufficient to ensure that during the heat treatment stage (ii) a certain percentage content by weight of oxide of rare earth metal,

(ii) heat treatment of the specified suspension to fix the oxide of rare earth metal on the outer surfaces of the microporous fine material with obtaining Svobodnoye fine material.

Compatible microporous material is defined as material that maintains compatibility with the colloidal dispersion so that the colloidal dispersion remains intact (i.e. fine material remains essentially in dispersed form). If the colloidal dispersion of clicks is not the flakes largely before drying, then the suspension may not give education Svobodnoye powder during drying of the suspension (such as a spray drier, and the product may not be homogeneous. Accordingly, the microporous material is chosen so as not to cause any significant flocculation of colloidal particles in the dispersion, and preferably no or essentially no flocculation of colloidal particles in a dispersion. Some of the factors that determine the compatibility of microporous material and colloidal dispersions include, but are not limited to: pH microporous material and the presence insoumise salts, such as ammonium nitrate. If the pH is too high, then the colloids will form flakes. In this case, with decreasing pH colloids can dispergirujutsja in the liquid.

Preferably compatible microporous fine material is compatible silicate, and more preferably a compatible zeolite fine material. Compatible zeolite fine material, which can be used in the present invention, includes (but is not limited to) silicalite zeolites, X, Y and L zeolites, pajaziti ((Na2, Ca, Mg)29[Al58Si134O384]·240 H2O; cubic shape), β-zeolites (Nan[AlnSi64-nO128] n <7; the tetragonal form), mordenite zeolites (Na8[Al8Si40O96]·24H2O; orthorhombic form), ZSM zeolites (Nan[AlnSi96-nO192]·16H2O with n < 27; orthorhombic form) and their mixtures. Preferably the zeolites are hydrophobic, laboratornymi zeolites or mixtures thereof, which have an affinity for hydrophobic and slabovidimym organic compounds. Zeolites having a pH of less than 4.2, and are also highly preferred to maintain compatibility with the colloidal dispersion. Can be used zeolites with a higher pH, therefore, the zeolite is mixed with water and add the acid to reduce the pH to the desired pH level.

Used zeolite materials can also be characterized by the following formula:

MmM′nM″p[aAlO2•bSiO2•cTO2],

in which

M is a monovalent cation

M′ represents a divalent cation,

M″ represents a trivalent cation,

a, b, c, n, m and p are numbers that reflect the stoichiometric proportion,

c, m, n or p can also be null,

Al and Si are tetrahedrally coordinated Al atoms and Si,

T is tetrahedrally coordinated atom, the ability to replace Al or Si,

the ratio b/a of the zeolite or zeolite which such material has a value from about 5 to about 300, and the size of the micropores of the zeolite is in the range of 5-13 Å.

Preferred oxide of rare earth metal is an oxide of the lanthanide metal, yttrium, scandium, or their mixture. More preferably, the oxide of rare earth metal is cerium oxide.

Colloidal dispersion of rare earth metals used in the present invention, receive, but not limited to, those of the following salts of rare earth metals: YCl3, Y2(CO3)3, Y(C2H3O2)3Y(NO3)3, CeCl3Ce2(CO3)3Ce(C2H3O2)3Ce(ClO4)3and Ce(NO3)3. Preferably colloidal dispersion of rare earth metals are in a certain range of particle sizes from 20 to 150 Å. In the General case, the colloidal dispersion is obtained by mixing aqueous suspensions of salts of rare earth metal with an acid to obtain gidrolizuacy salt. Preferred acids are nitric acid and hydrochloric acid. Alternatively, if the source metal salt is a nitrate or chloride, this stage of mixing the nitrate or chloride salt is unnecessary. Any approach received gidrolizuacy salt, such as a metal nitrate or chloride of the metal, is hydrolyzed. Preferably it is hydrolyzed and Oka who is adding a mixture of ammonium hydroxide and hydrogen peroxide. Get the metal hydroxide and mixed with water and a strong acid to obtain a suspension. The strong acid may be, for example, nitric acid, hydrochloric acid or Perlina acid, and it is capable of deaggregating obtained insoluble hydrate of the metal. The remainder of the suspension is then mixed with water to form a colloidal dispersion of metal oxide. When a strong acid is nitric acid, the molar ratio of nitrate ions to the oxide of rare earth metal in the specified colloidal dispersion is in the range of 0.1 to 1.0, preferably 0.1 to 0.5 and most preferably 0.12 to 0.25.

In embodiments, the colloidal dispersion can be obtained in a certain range of particle sizes from 20 to 150 Å. The particle size adjust parameters of deposition and oxidation, is used to obtain a colloidal dispersion. In specific embodiments, the base and, optionally, hydrogen peroxide is added to the oxidation solution gidrolizuacy salts of rare earth metal to obtain the hydrate dispersion of rare earth metal, and depending on:

(i) carry out the reaction in hot or cold conditions

(ii) conduct the reaction with air purge;

(iii) what concentration is the solution containing the hydrate rare earth metal,

(iv) add if the basis is to their salts, or Vice versa,

the crystallite size can vary from 20 to 100Å. In other private options for more large particles, such as 100-150Å, the base added to the solution gidrolizuacy salt of rare-earth metal and allow to slowly oxidize in air.

In one embodiment, the colloidal dispersion receive in a certain interval of particle size 20-50Å. The ammonium hydroxide and hydrogen peroxide is mixed with a solution of cerium nitrate, getting hydroxide solution of cerium. Then nitric acid is added to a solution of the hydroxide of cerium (IV) and get in the colloidal dispersion 20-50 Å particles of hydrate of cerium oxide and nitrate ions. Preferably the molar ratio of nitrate ions to the cerium oxide in the specified colloidal dispersion is in the range of 0.12 to 0.25. Valid other options that can be used for any suitable gidrolizuacy salt of rare-earth metal or mixtures thereof, may be used instead of any suitable strong acid capable of deaggregating obtained insoluble hydrate of rare earth metal, such as hydrochloric acid or Perlina acid, and can be used for any suitable base, such as sodium hydroxide, potassium hydroxide, a hydroxide of tetraethylammonium. Preferably the base is the meet pH greater than 4. More preferably the base is selected from the group consisting of ammonium hydroxide and its derivatives. When the base using sodium hydroxide or potassium, sodium, and potassium are difficult to remove precipitated particles hydrate. So need some leaching of the particles.

In another embodiment, the ammonium hydroxide is mixed with a solution of cerium nitrate and the mixture is blown with air, for example, the air barbthroat through the mixture. Receive as a result of a hydroxide solution of cerium (IV) and then add nitric acid, forms a colloidal dispersion 50-70Å particles of hydrate of cerium oxide and nitrate ions. Preferably the molar ratio of nitrate ions to the cerium oxide in the specified colloidal dispersion is in the range of 0.12 to 0.25. Valid are other options that can be used for any suitable gidrolizuacy salt of rare-earth metal or mixtures thereof, any suitable strong acids and any suitable base, as described above.

In another embodiment, the ammonium hydroxide is mixed with solution of nitrate of cerium, where the mixture is slowly oxidized in the air, for example, when leaving at room temperature for a few days with getting hydroxide solution of cerium (IV). Then to the solution was added nitric acid and is obtained colloidal dispersion 100-150 Å particles of hydrate of cerium oxide and nitrate ions. Preferably the molar ratio of nitrate ions to the cerium oxide in the specified colloidal dispersion is in the range of 0.12 to 0.25. Valid are other options that can be used for any suitable gidrolizuacy salt of rare-earth metal or mixtures thereof, any suitable strong acids and any suitable base, as described above.

Salts of trivalent and/or tetravalent cerium can be turned into colloids cerium (IV) is relatively easy. In another embodiment, the dispersion is produced by mixing the aqueous suspension of cerium carbonate with nitric acid. The resulting cerium nitrate hydrolyzed and oxidized by adding a mixture of ammonium hydroxide and hydrogen peroxide. Get the cerium hydroxide and mixed with water and nitric acid to obtain cerium colloidal dispersion which contains particles of hydrate of cerium oxide and nitrate ions. Cerium colloidal dispersion is then added to a compatible zeolite with formation of a suspension which is subjected to heat treatment at a temperature as described above, obtaining Svobodnoye fine material.

In General, a suspension of colloidal dispersions hydrate of oxide of rare earth metal and a compatible microporous fine material which is relatively stable. It is established that the suspension is stable to coagulation and chemical changes, such as chemical reaction, dissolution, change of pH and conductivity changes.

Microporous fine material has an average pore size that is less than the average particle size of the colloidal dispersion, so that the colloidal dispersion may be placed on outer surfaces of the material. Preferably the material has an average pore size less than about 20Åand the colloidal dispersion has an average particle size of not less than about 20Å. More preferably, the material has an average pore size less than about 10Å.

Preferably more than 20 wt.% oxide of rare earth metal (relative to the total equivalent content microporous fine material and oxide of rare earth metal) deposited on the outer surface of the microporous fine material. The high content of oxide of rare earth metal deposited on the outer surface, is provided preferably in the range of from about 20 to about 70 wt.% in relation to the total equivalent oxide content of rare earth metal and fine microporous material. Svobodnoye fine material, i.e. fine microporous material having high the th content of the oxide of rare earth metal, is unexpectedly quite stable.

Stability Svobodnoye fine material to determine leachability fine microporous material with a coating of oxide of rare earth metal; low BaselCement equivalent occasion a stable of fine material. BaselCement is determined by the amount of the oxide of rare earth metal that is dissolved (leached) in water, when fine microporous material with a coating of oxide of rare earth metal suspended in the water.

Microporous fine material with a coating of oxide of rare earth metal may be subjected to heat treatment at various temperatures and combinations of temperatures while maintaining its stability. In private variants, fine microporous material with a coating of oxide of rare earth metal is subjected to heat treatment at temperatures below about 200 °C and suspendredraw in the water, suddenly, very little oxide of rare earth metal leached. Because the material was processed at such low temperatures, it was expected that the oxide of rare earth metal is completely dissolved in the water. It was found, however, that is usually less than 30 wt.% oxide of rare earth metal (relative to the total equivalent content is aniu oxide of rare earth metal) is leached in water, that shows that the fine material is quite stable under heat treatment at temperatures below about 200°C. When fine microporous material with a coating of oxide of rare earth metal thermoablative at temperatures above approximately 400°C and suspended in the water, it was found that typically less than 0.1 wt.% oxide of rare earth metal (relative to the total equivalent oxide content of rare earth metal) is leached in water. These results are valid for both high and low content. In contrast to the approach of the prototype this approach works well with a range of content, including high content (more than about 20 wt.% oxide of rare earth metal) using a range of temperatures up to approximately 900°C, including subsequent temperature without compromising the high surface area or catalytic activity of the material.

In a preferred embodiment, the resulting suspension according to the method of the present invention may be subjected to heat treatment at temperatures below about 200°C, above about 400°C or sequential combinations, where the suspension process, first, at temperatures below about 200°C and, secondly, above approximately 400°C. Preferably, the suspension is subjected to termoobrabotka a temperature below about 200° C and then at a temperature above approximately 400°C. More preferably, the suspension is subjected to heat treatment at a temperature of from about 85°C to about 105°C and then at a temperature above approximately 400°C, where the suspension is heated at a rate of 100°C/h until a temperature above approximately 400°C. At this point the temperature of the stand at least 1 hour Worst results are for fine microporous material with a coating of oxide of rare earth metal, if it is subjected to heat treatment only at a temperature of between about 200°C and about 400°within a commercially reasonable period of time, usually 5 hours Although it is possible to heat the fine microporous material with a coating of oxide of rare earth metal at a temperature between about 200°C and about 400°C for several weeks, however, there are similar results, it is not feasible to obtain a fine microporous material with a coating of oxide of rare earth metal.

With no regard to any particular theory it is believed that when the colloidal dispersion of a hydrate of oxide of rare earth metal is mixed with a compatible microporous material with formation of a suspension, the counterions strong acids, use is th in obtaining colloidal dispersions (for example, nitrate ions)migrate into the pores of the microporous material and the oxide of rare earth metal is fixed on the outer surfaces of the microporous material, so that the oxide of rare earth metal is no longer water-dispersible. It is considered that, when the stage of drying is carried out at low temperatures, i.e. below about 200°C, this increases the fixation of the oxide of rare earth metal on the outer surfaces of the microporous microporous material and fine material with a coating of oxide of rare earth metal is insoluble in water. If, however, the stage of drying is between about 200°C and about 400°C within a commercially reasonable period of time, usually 5 hours, it is considered that the counterions are released from the pores of the microporous material and are able to recombine with the component of the oxide of rare earth metal with the re-formation of water-dispersible oxide of rare earth metal. In total this will worsen fine microporous material with a coating of oxide of rare earth metal, if it dissolves in water. In other words, the oxide of rare earth metal will vydeliajutsia in the water, reducing fine microporous material with a coating of oxide of rare earth metal. With continued heating above approximately 400°C before alagaesia, what counterions decompose into gaseous components, which are released from the pores of the microporous fine material with a coating of oxide of rare earth metal, so that the material is insoluble in water.

Accordingly, in one embodiment, the suspension is subjected to heat treatment for fixing the oxide of rare earth metal on the outer surfaces of the microporous material. Phase locking the heat treatment may include a stage of drying and/or stage of calcination.

At the stage of drying, the suspension is preferably heated at a temperature and for a period of time sufficient to obtain a dry powder (i.e. removal of at least part and preferably all or essentially all of the water from the suspension). Preferably the solution is dried (e.g., spray drying) at a temperature below about 200°C. In most cases, the stage includes drying or spray drying, drying on trays, drying, freezing, drying to remove the solvent, spray drying in vacuum, or combinations thereof.

At the stage of annealing, the suspension or the dried powder is preferably heated at a temperature and for a period of time sufficient to remove or decompose at least part of the counterions and more preferably all or essentially all anti the ones obtained from the dried microporous material. During the above process, the remaining water (if the suspension has not already been subjected to the initial process of low-temperature drying) is removed and at least part of the counterions is decomposed and more preferably all or essentially all counterions decompose into gaseous components. Preferably the solution is spray dried and calcined in one technological stage, such as spray drying in the kiln. However, the heat treatment may be carried out in two stages, such as initial stage of drying (for example, through spray drying), followed by a stage of calcination.

In another embodiment, the preferred rare earth metal used in the above method, is cerium, and preferred compatible microporous material is compatible zeolite fine material. You can have more than 1 wt.% in relation to the total equivalent content of zeolite and cerium oxide, cerium oxide, deposited on the outer surface of the zeolite fine material. The high content of cerium oxide, deposited on the outer surface, is provided typically in the range of from about 20 to about 70 wt.% in relation to the total equivalent content of cerium oxide and zeolite. Zeolite fine material having a high content of the W oxide of cerium, is unexpectedly quite persistent. When zeolite fine material with a coating of cerium oxide is subjected to heat treatment at temperatures below about 200°C and suspended in water, leached unexpectedly very little cerium oxide. Found that typically less than 30 wt.% cerium oxide (relative to the total equivalent of the content of the cerium oxide) is leached in water, which shows that the fine material is quite stable even when heat treatment at temperatures below about 200°C. When zeolite fine material with a coating of cerium oxide is suspended in water, it was found that typically less than 0.1 wt.% cerium oxide (relative to the total equivalent of the content of the cerium oxide) is leached in water.

Preferably, the suspension is spray dried at a temperature below about 200°C. In most cases, stage heat treatment includes either spray drying, drying on trays, drying, freezing, drying to remove the solvent, spray drying in vacuum, or combinations thereof.

Zeolite fine material has an average pore size that is less than the average particle size of the colloidal dispersion of hydrate of cerium oxide, so that the colloidal dispersion may be placed on outer surfaces of the zeolite. Preferably CE is lit has an average pore size which is less than 20 Åand a colloidal dispersion of cerium oxide has a particle size of not less than 20 Å.

In a preferred embodiment, the above method introduces an additional stage (iii) grinding the fine material with the provision of the particle size in the range of 1-25 microns.

Catalytic fine microporous materials with a coating of oxide of rare earth metal can be used in several different applications. In one aspect of the invention the microporous fine materials with a coating of oxide of rare earth metal can be introduced into tissue paper covering traditional tobacco rod, to reduce the allocation of the side streams of smoke. In particular, the fine material can be used as filler in the manufacture of tissue paper impregnated in tissue paper or applied as a coating (coating) or layer (s) on the outer and/or inner surface of the tissue paper. Alternatively, the treated paper can be used as a multi-layer wrapper; i.e. the treated paper may be applied as the outer wrapper on top cigarettes with traditional tissue paper.

In another aspect of the invention the fine material can be used for catalysis of the exhaust gas is the combustion of the fuel, such as automobile exhaust gases. Modern automotive engine gives a lot of pollutants due to incomplete combustion of hydrocarbon fuels. Exhaust gas mixtures usually contain CO, unburned hydrocarbons and several thousand hours/million NOx. Catalytic converters, which reduce the three by-product of combustion, called ternary catalysts. Other applications include the coating on the inner walls of self-cleaning ovens, catalytic cracking, thermal sprayed coating and wear resistant seal.

A catalyst such as cerium oxide, has the ability to provide oxygen for complete oxidation of hydrocarbons and CO during periods when the engine is on a strong course. When the engine is in a weak move, the cerium is oxidized to CE4+that stores oxygen. When you begin a rich fuel cycle, cerium able to reversibly change the degree of oxidation with CE4+on CE3+providing oxygen for chemical reactions (for example, converting CO in the CO2). For the catalyst, which must be able to work effectively at high temperatures that exist in the exhaust pipe, it must have sufficient surface area to ensure a sufficient number of active sites for katal the political reactions. Microporous fine materials with a coating of cerium oxide obtained in accordance with the present invention provide a high catalytic surface area for implementing sufficient catalysis agents of pollution. In addition, the cerium oxide stabilized microporous fine materials ensuring durability oxide to high temperatures in the exhaust pipe.

The following examples are provided to further illustrate various aspects of the present invention. These examples are intended to be illustrative only and are not intended to limit the scope of the present invention.

EXAMPLES

Colloidal dispersion of cerium oxide

Example 1

The cerium carbonate (50 g, 99.9 % of purity)containing 69,3 wt.% equivalent cerium oxide, suspended in distilled water (0.1 l) and dissolved by addition of nitric acid (38,4 ml, 16 M). Received neutral solution is boiled for a few minutes, filtered to remove traces of undissolved solids and dilute to 1 liter of water to form a solution of cerium nitrate. A mixture containing ammonium hydroxide (40 ml, 18 M), hydrogen peroxide (20 ml, "100 by volume) and water (160ml), add with stirring to received and supported at 75 °C solution of cerium nitrate. The obtained insoluble dark-is it complex peroxide cerium (IV) is rapidly changing in color, and after adding a mixture of ammonium hydroxide/hydrogen peroxide get pale cream precipitate of the hydroxide of cerium (IV)having a pH of 7.0.

The precipitate centrifuged and washed twice by stirring with excess distilled water to 1 L. the Selected residue is mixed with distilled water (750 ml) and nitric acid (12.5 ml, 16 M) to obtain the molar ratio of nitric acid:the cerium oxide 1. The resulting suspension is heated at a temperature of about 70°C for 15 min to deaggregate hydroxide of cerium (IV) and get the air suspension. the pH of the conditioned slurry is less than 1.

After cooling, the suspension is centrifuged and the residue was dispersed in distilled water (150 ml) to obtain a translucent greenish colloidal solution.

Example 2

1 kg of hydrate of cerium oxide (IV) (obtained from the company Rhone Poulenc) (approximately 72% of cerium oxide with a ratio of nitrate:cerium oxide 0,24) is placed in a crucible (layer depth 3.0 cm) and heated for 1 h in a muffle furnace at 320°in the air. The obtained dry powder dispersible cerium compound (0,78 kg) has a crystallite size 59 Åand the ratio of nitrate:cerium is 0.14.

100 g of the heat-treated powder of the cerium compound is dispersed with stirring in hot demineralised water with the education colloidal dispersion with a concentration of 450 g/l equivalent cerium oxide.

Example 3

1.22 kg of gel dispersible cerium oxide (obtained from the company's Advanced Materials Resources, Inc., Toronto, Canada and manufactured as described in example 1) is mixed for 30 min with 5.5 l of demineralized water. The obtained colloidal dispersion contains 200 g/l of cerium oxide. The colloidal dispersion has a density of 1.15 g/ml and a pH of 1.8.

Mixed suspensions of colloidal dispersion of a cerium oxide - zeolite

Example 4A

0,536 kg of zeolite powder (trade mark Zeolyst™ CBV 400 received from the company Zeolyst International, Pennsylvania, USA; pH 3-5) is added with stirring to 2.0 l of colloidal dispersion of cerium oxide (180 g/l of equivalent cerium oxide), obtained as described in example 3. Thixotropic mixture (density of 1.30 g/ml, pH 3.8)containing nominally 44 wt.% cerium oxide (relative to the total equivalent content of cerium oxide and zeolite) and 56 wt.% zeolite (relative to the total equivalent content of cerium oxide and zeolite), spray dried (inlet temperature 180°C and outlet temperature 105° (C) obtaining Svobodnoye powder gel.

Example 4B

45 g of the zeolite powder (trade mark Zeolyst™ CBV 400 received from the company Zeolyst International; pH 3-5) is added with stirring to 0.5 l of colloidal dispersion of cerium oxide (100 g/l of equivalent cerium oxide), obtained as described in example 3. Thixotropic is MES (density 1.20 g/ml, the pH of 2.8), containing nominally 72 wt.% cerium oxide (relative to the total equivalent content of cerium oxide and zeolite) and 28 wt.% zeolite (relative to the total equivalent content of cerium oxide and zeolite), spray dried (inlet temperature 180°C and outlet temperature 105° (C) obtaining Svobodnoye powder gel.

Example 5

0,59 kg of zeolite powder (trade mark Zeolyst™ CBV 600 received from the company Zeolyst International; pH 3-5) is added with stirring to 2.0 l of colloidal dispersion of cerium oxide (180 g/l of equivalent cerium oxide), obtained as described in example 3. Thixotropic mixture (density : 1.28 g/ml, pH 3,3), containing nominally 44 wt.% cerium oxide (relative to the total equivalent content of cerium oxide and zeolite) and 56 wt.% zeolite (relative to the total equivalent content of cerium oxide and zeolite), spray dried (inlet temperature 180°C and outlet temperature 105° (C) obtaining Svobodnoye powder gel.

Example 6

0,36 kg of zeolite powder (trade mark Zeolyst™ CBV 300 received from the company Zeolyst International; pH 5-7) is added with stirring to 0,50 l colloidal dispersion of cerium oxide (180 g/l of equivalent cerium oxide), obtained as described in example 3. Thixotropic mixture (density : 1.28 g/ml, pH 3,7)containing nominally 33 wt.% cerium oxide (as far as the structure equivalent to the total content of cerium oxide and zeolite) and 67% of the mass. zeolite (relative to the total equivalent content of cerium oxide and zeolite), spray dried (inlet temperature 180°C and outlet temperature 105° (C) obtaining Svobodnoye powder gel.

Example 7

Various amounts of cerium colloidal dispersion obtained as described in example 3 is mixed with different weight zeolite powder (trade mark Zeolyst™ CBV 720 received from the company Zeolyst International; pH 3-5). A mixture of cerium colloidal dispersion and zeolite powder gives suspensions, covering various compositions shown in table 1.

td align="center"> 200
Table 1
Sample original mixThe cerium oxide (wt.%)1The amount of cerium colloidal dispersion

(l)
Weight zeolite (g)Total

(l)
The density of the slurry (g/ml)pH
1330,753500,921,333,3
2441,003001,151,273,1
3541,252501,401,243,0
4641,501,601,222,9
5721,00901,0251,202,8

1wt.% in relation to the total equivalent content of cerium oxide and zeolite.

The spray drying the mixed samples colloidal dispersion of a cerium oxide - zeolite

Example 8

All samples obtained from example 7, easily pass through a 150 μm sieve. There are a small number of random material (< 1 %). Samples of the initial mixture is left to stand for 24 h at 22°C before spray drying. Sample 1 shows no obvious deposition. Samples 2-5 show the deposition; however, the sediment is easily re-suspendered when shaken or mild stirring.

The spray drying of large quantities of samples is performed with the use of spray dryers Mobile Minor (rated evaporation capacity 5 kg of water per hour). The feed rate of the spray dryer is 1.7 l/h, inlet temperature is 220°C, and the outlet temperature is 109-116°C. the mixture is stirred when spraying. Table 2 shows the results of spray drying.

Table 2
The sample source with whom thou The sample mass to power the spray drying (kg)theoretical yield of powder gel (kg)The actual output of powder gel (kg)% extract
1162,568,364,095
21,2100,4000,4141021
31,2140,3670,4351181
41,6200,4390,43599
51,0650,2680,23587
The average % recovery100

1These outputs are greater than 100 % as a result of successive reactions without rinsing spray dryers.

The powders of the gel, as shown in table 2, are spherical and Svobodnoye. Powder gel explore thermogravimetric analysis to determine the preferred heat treatment temperature and then subjected to heat treatment at 500°C (powder gel is heated at a rate of 100°C/h, until it reaches a temperature of 500°C, when the withstand temperature of not less than 1 h), when the observed weight loss and/or selection NOsub> x. Quantitative evaluation of the above spray dried powders gel cerium oxide-zeolite are shown in table 3.

Table 3
Sample original mixwt.% cerium oxide1The density of the produced fluid (g/ml)
1330,55
2440,56
3540,68
4640,80
5720,94

1wt.% in relation to the total equivalent content of cerium oxide and zeolite.

Since the density of cerium oxide is much more than the density of the zeolite, the results of the experiments shown in table 3, confirm that the cerium oxide is a powder gel cerium oxide-zeolite; when the wt.% cerium oxide increases, the density increases.

Nevydelujeme powders gel cerium oxide-zeolite

Example 9

10.0 g of powder gel cerium oxide-zeolite (trade mark Zeolyst™ CBV 720 received from the company Zeolyst International; pH 3-5), obtained as described in example 8 (in addition to heat treatment at 500°C), and containing 4.4 g of cerium oxide (44 wt.% cerium oxide), added to 100 ml of water and heated PR is 70° C for about 10 minutes This solution is then centrifuged and to the resulting clear supernatant (the liquid from leaching) add ammonium hydroxide guarding any cerium oxide dissolved in the supernatant. Only 0.35 g of cerium oxide was found in fluids from leaching.

Example 10

10.0 g of powder gel cerium oxide-zeolite (trade mark Zeolyst™ CBV 600 received from the company Zeolyst International; pH 3-5), obtained as in example 5 (except heat treatment at 500°C), and containing 6.5 g of cerium oxide (65 wt.% cerium oxide), add 50 ml of water and heated at 70°C for about 10 minutes Determine the conductivity and find that it is 10 x 10-3Cm.

Example 11

10.0 g of powder gel cerium oxide-zeolite (trade mark Zeolyst™ CBV 600 received from the company Zeolyst International; pH 3-5), obtained as in example 5 (except heat treatment at 500°C), and containing 4.4 g of cerium oxide (44 wt.% cerium oxide), add 50 ml of water and heated at 70°C for about 10 minutes Determine the conductivity and find that it is 6,4x10-3Cm.

Increased conductivity means more leaching of oxide of cerium, thus, examples 10 and 11 show that with increase in the content of cerium oxide conductivity increases proportionate is about, that means more leaching of cerium oxide. Although leaching increases with higher content, it was found that the samples heat treated at temperatures below about 200°C, usually have less than 30 wt.% cerium oxide (relative to the total equivalent of the content of the cerium oxide), Vasilchenko in the water.

These examples show the wide range of percentage content of zeolites with a coating of cerium oxide. Experiments show increased correlation between high final densities of zeolites with a coating of cerium oxide and high content of cerium oxide. Unexpectedly, the stability of these coated zeolites, even without heat treatment of zeolites with a coating of cerium oxide above 500°C is quite high, as shown in examples 9 and 11.

Although the preferred variants of the invention are described in detail here, specialists in the art should understand what can be done with their changes without departing from the essence of the invention or scope of the attached claims.

1. The method for the catalytic fine microporous material with a coating of oxide of rare earth metal having an oxide of rare earth metal deposited on the outer surfaces of the specified fine microporous material containing study the

i) combining the number of colloidal dispersions hydrate of oxide of rare earth metal compatible with fine microporous material with formation of a suspension, and the specified fine microporous material has an average pore size less than the particle size of the specified colloidal dispersion, with accommodation in the specified colloidal dispersion on the outer surfaces of the specified fine microporous material;

(ii) heat treatment of the specified suspension for fixation of the oxide of rare earth metal on the outer surfaces of the microporous fine material.

2. The method according to claim 1, in which the specified heat treatment includes heating the specified suspension at a temperature sufficient to remove enough water from this suspension, with the formation of Svobodnoye fine material.

3. The method according to claim 2, in which the specified heat treatment further includes igniting the specified Svobodnoye fine material.

4. The method according to claim 1, in which the specified heat treatment includes heating the specified suspension to dry calcined powder at one stage.

5. The method according to claim 1, in which the specified suspension contains nitrate ions and the specified heat treatment is carried out at a temperature, PT is accurate to decompose at least part of the nitrate ions to gaseous components.

6. The method according to claim 3, in which the specified suspension contains nitrate ions and the specified annealing is carried out at a temperature sufficient to decompose at least part of the nitrate ions to gaseous components.

7. The method according to claim 1, wherein said method further comprises grinding fine microporous material with a coating of oxide of rare earth metal with the provision of particle sizes in the range of 1-25 microns.

8. The method for the catalytic fine microporous material with a coating of oxide of rare earth metal, having more than 20 wt.% the specified oxide of rare earth metal deposited on the outer surfaces of the specified fine microporous material, relative to the total equivalent oxide content of rare earth metal and fine microporous material containing stage

i) combining the number of colloidal dispersions hydrate of oxide of rare earth metal compatible with fine microporous material with formation of a suspension, and the amount of the colloidal dispersion is sufficient to ensure that during the heat treatment stage (ii) more than 20 wt.% oxide of rare earth metal, and the specified fine microporous material has an average pore size less than the 20 Å the colloidal dispersion has a particle size of not less than 20 Åwith placement of the specified colloidal dispersion on these outer surfaces specified fine microporous material;

(ii) heat treatment of the specified suspension at a temperature below about 200°From above about 400°or sequential combinations thereof, where specified, the suspension is subjected to heat treatment, firstly, at temperatures below about 200°and, secondly, above approximately 400°to fix the oxide of rare earth metal on the specified exterior surfaces specified fine microporous material with obtaining Svobodnoye fine material.

9. The method according to claim 1 or 8, in which the specified fine microporous material is compatible aluminosilicate.

10. The method according to claim 9, in which the specified fine microporous material is compatible zeolite fine material.

11. The method according to claim 10, in which the specified suspension is subjected to heat treatment, firstly, at temperatures below about 200°and, secondly, above approximately 400°C.

12. The method according to claim 11, in which the oxide of rare earth metal selected from the group consisting of oxides of the lanthanide metals, yttrium, scandium, and mixtures thereof.

13. The method according to item 12, in which the om oxide of rare earth metal is cerium oxide,

14. The method according to claim 10, in which the specified colloidal dispersion has a pH less than 4.2 and the specified colloidal dispersion is crystalline.

15. The method of claim 8, wherein said method comprises the additional step (iii), which includes grinding the specified fine microporous material with a coating of oxide of rare earth metal to obtain particle sizes in the range of 1-25 microns.

16. The method according to claim 10, in which the specified colloidal dispersion of hydrate of oxide of rare earth metal is obtained on the basis of salts of rare earth metal selected from the group consisting of nitrate of rare earth metal chloride rare earth metal, rare earth acetate metal perchlorate rare earth metal and mixtures thereof.

17. The method according to claim 10, wherein said zeolite is mixed with water and add the acid to achieve a pH of less than 4.2.

18. The method according to claim 10, wherein said zeolite is mixed with water and reach a pH of less than 4.2.

19. The method according to claim 10, in which the specified colloidal dispersion receive in a regulated interval sizes of colloidal particles of 20-50 Å, 50-70 Å or 100-150 Å.

20. The method according to claim 19, in which receiving the said colloidal dispersion having a certain specified particle size 20-50 Åcontains stage

a) mixing a base and hydrogen peroxide with R is the target gidrolizuacy salt of rare-earth metal with getting hydroxide solution of rare earth metal;

b) adding a strong acid to a solution of the hydroxide of the rare earth metal to obtain a colloidal dispersion of hydrate of oxide of rare earth metal, in which a strong acid capable of deaggregating colloidal dispersion of hydrate of oxide of rare earth metal.

21. The method according to claim 19, in which receiving the said colloidal dispersion having a certain specified particle size of 50-70 Åcontains stage

a) mixing the base with a solution gidrolizuacy salt of rare-earth metal, by ozonation of air through the solution to obtain a solution of the hydroxide of the rare earth metal;

b) adding a strong acid to a solution of the hydroxide of the rare earth metal to obtain a colloidal dispersion of hydrate of oxide of rare earth metal, in which a strong acid capable of deaggregating colloidal dispersion of hydrate of oxide of rare earth metal.

22. The method according to claim 19, in which receiving the said colloidal dispersion having a certain specified particle size 100-150 Åcontains stage

a) mixing the base with a solution gidrolizuacy salts of rare earth metal, rare earth where the metal has two oxidation States;

b) providing a slow oxidation in air solution gidrolizuacy salt of rare-earth metal is getting hydroxide solution of rare earth metal;

c) adding a strong acid to a solution of the hydroxide of the rare earth metal to obtain a colloidal dispersion of hydrate of oxide of rare earth metal, in which a strong acid capable of deaggregating colloidal dispersion of hydrate of oxide of rare earth metal.

23. The method according to claim 10, in which the specified colloidal dispersion of a hydrate of oxide of rare earth metal is colloidal dispersion of hydrate of cerium oxide obtained on the basis of cerium salt selected from the group consisting of cerium nitrate, cerium chloride, cerium acetate, cerium perchlorate and mixtures thereof.

24. The method according to claim 10, wherein said oxide of rare earth metal deposited on the outer surface is in the range of 20-70 wt.% in relation to the total equivalent oxide content of rare earth metal and zeolite.

25. The method according to paragraph 24, in which the specified oxide of rare earth metal is cerium oxide.

26. The method according to claim 10, in which the zeolite is selected from the group consisting of silicalite zeolites, poasito, X, Y and L zeolites, β-zeolites, mordenite zeolites and ZSM zeolites and mixtures thereof.

27. Catalytic Svobodnoye fine material with a coating of oxide of rare earth metal containing

zeolite fine material

the oxide of rare earth metal,

where MC is connected zeolite fine material, having an average pore size less than the particle size of the specified oxide of rare earth metal, and

more than 20 wt.% the specified oxide of rare earth metal is on the outside of a specified zeolite fine material in relation to the total equivalent oxide content of rare earth metal and zeolite.

28. Svobodnoye fine material according to item 27, where specified, the average pore size is 20 Å.

29. Svobodnoye fine material according to item 27, in which the oxide of rare earth metal selected from the group consisting of oxides of the lanthanide metals, yttrium, scandium, and mixtures thereof.

30. Svobodnoye fine material according to clause 29, in which the oxide of rare earth metal is cerium oxide.

31. Svobodnoye fine material according to item 27, wherein said oxide of rare earth metal deposited on the outer surface is in the range of 20-70 wt.% in relation to the total equivalent oxide content of rare earth metal and zeolite.



 

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1 tbl, 10 ex

FIELD: petrochemical processes.

SUBSTANCE: catalyst, containing high-silica zeolite of the H-ZSM-5 type having silica modulus SiO2/Al2O3 = 20 to 160 in amount 60.0-90.0%, contains (i) as modifying component at least one oxide of element selected from group: boron, phosphorus, magnesium, calcium, or combination thereof in amount 0.1-10.0 wt %; and (ii) binding agent: alumina. Catalyst is formed in the course of mechanochemical and high-temperature treatments. Described is also a catalyst preparation process comprising impregnation of decationized high-silica zeolite with compounds of modifying elements, dry mixing with binder (aluminum compound), followed by mechanochemical treatment of catalyst paste, shaping, drying, and h-temperature calcination. Conversion of methanol into olefin hydrocarbons is carried out in presence of above-defined catalyst at 300-550°C, methanol supply space velocity 1.0-5.0 h-1, and pressure 0.1-1.5 mPa.

EFFECT: increased yield of olefin hydrocarbons.

3 cl, 1 tbl, 15 ex

FIELD: oxide catalyst preparation methods.

SUBSTANCE: invention relates to preparation of oxide-structure catalysts and provides a method for preparing oxide catalyst characterized by mixing two or more salt precursors of catalyst components followed by melting resulting mixture to achieve homogenous melt, cooling this melt to room temperature and subsequent decomposition of salts and calcination, wherein salt precursors of catalyst components are selected from d-metal nitrates (Ce and Y nitrates), melting of mixture is effected at 90 to 170°C in presence of ammonium nitrate used at ratio (2-10):1 to metal nitrate mixture, and decomposition of the melt into oxides is performed under effect of microwave emission. In a preferred embodiment of invention, microwave emission is used for 0.5-5 min at working frequency 2.45 GHz and power 600-1900 W. A method of preparing oxide catalysts involving introduction of oxide structure carrier into resulting melt at continuous stirring is also described.

EFFECT: enabled preparation of oxide catalysts and spinel-structure catalysts characterized by high degree of uniformity, lack of harmful impurities in catalyst composition, high-developed surface, and high heat resistance.

8 cl, 2 tbl

FIELD: petroleum processing and catalysts.

SUBSTANCE: method consists in performing ion exchanges by rare-earth and ammonium cations on zeolite NaY, two-step ultrastabilization of zeolite in water steam medium, mixing zeolite with matrix components to form composition, and spray drying of resulting composition followed by calcination and preparation of catalyst. In the first stage, ultrastabilization of zeolite is conducted at 550-650°C and partial water steam pressure within a range 0.1 to 1.0 atm. In the second stage, ultrastabilization is performed after spray drying by calcination of composition at 650-750°C and partial water steam pressure within a range 0.05 to 0.3 atm.

EFFECT: increased lattice module of zeolite and relative crystallinity resulting in increased catalytic activity.

6 cl, 1 tbl, 9 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention provides rare-earth element carboxylate composition used as a part of catalytic system for polymerization of conjugated dienes and containing rare-earth element carboxylate and organic solvent, which composition is characterized by additionally containing oxyalkylenated C1-C20-alcohol with molecular mass 90 to 100000 or mixture of such oxyalkylenated alcohols. Described is also preparation of liquid rare-earth element carboxylate composition as well as conjugated diene polymerization process in presence of catalytic system to give polymer with high content of 1,4-cis units.

EFFECT: enabled preparation of stable composition suitable for preparation of stereospecific diene polymerization catalyst.

5 cl, 23 ex

FIELD: hydrocarbon conversion processes and catalysts.

SUBSTANCE: invention, in particular, relates to selectively upgrading paraffin feedstock via isomerization. Catalyst comprises support and sulfated oxide or hydroxide of at least one of the elements of group IVB deposited thereon; a first component selected from group consisting of consisting of lutetium, ytterbium, thulium, erbium, holmium, and combinations thereof; and a second component comprising at least one platinum-group metal component. Catalyst preparation process comprises sulfating oxide or hydroxide of at least one of the elements of group IVB to form sulfated support; depositing the first component onto prepared support; and further depositing the second component. Invention also relates to hydrocarbon conversion process in presence of above-defined catalyst.

EFFECT: improved catalyst characteristics and stability in naphta isomerization process to increase content of isoparaffins.

13 cl, 2 dwg, 1 tbl

FIELD: chemical industry; materials and the methods for the catalyst carrier manufacture.

SUBSTANCE: the invention is pertaining to the new mixed oxides produced from ceric oxide and zirconium oxide, which can used as the catalyzers or the catalyzers carriers for purification of the combustion engine exhaust gases. The mixed oxide possesses the polyphase cubical form of the crystallization and oxygenous capacity of at least 260/ micromoles of O2 /g of the sample and the speed of the oxygen extraction of more than 1.0 mg-O2/m2-minute, which are measured after combustion within 4 hours at the temperature of 1000°C. The invention also presents the substrate with the cover containing the indicated mixed oxide. The method of production of the polycrystallic particles of the indicated mixed ceric-zirconium oxide includes the following stages: i) production of the solution of the mixed salt which are containing, at least, one salt of cerium and, at least, one salt of zirconium in the concentration, sufficient for formation of the polycrystallic particles of the corresponding dry product on the basis of the mixed oxide. At that the indicated particles have the cerium-oxide component and zirconium-oxide component, in which these components are distributed inside the subcrystalline structure of the particles in such a manner, that each crystallite in the particle consists of a set of the adjacent one to another domains, in which the atomic ratios of Ce:Zr which are inherited by the adjacent to each other domains, are characterized by the degree of the non-uniformity with respect to each other and determined by means of the method of the X-ray dissipation the small angles and expressed by the normalized intensity of the dissipation I(Q) within the limits from approximately 47 up to approximately 119 at vector of dissipation Q, equal to 0.10 A-1; ii) treatment of the solution of the mixed salt produced in compliance with the stage (i),with the help of the base with formation of sediment; iii) treatment of the sediment produced in compliance with the stage (ii),using the oxidative agent in amount, sufficient for oxidizing Ce+3 up to Ce+4; iv) washing and drying of the residue produced in compliance with the stage (iii); and v) calcination of the dry sediment produced in compliance with the stage (iv),as the result there are produced polycrystallic particles of the oxide of ceric and zirconium in the form of the mixed oxide with the above indicated characteristics. The technical result is the produced mixed oxide possesses both the high oxygenous capacitance, and the heightened speed of the oxygen return in the conditions of the high temperatures.

EFFECT: the invention ensures production of the mixed oxide manufactured from ceric oxide and zirconium oxide and possessing the high oxygenous capacitance and the heightened speed of the oxygen return in the conditions of the high temperatures.

68 cl, 21 ex, 2 dwg

FIELD: reduction-oxidation catalysts.

SUBSTANCE: invention relates to catalysts for deep oxidation of carbon monoxide that can be used to treat industrial emission gases and motor transport exhaust gases. Aluminum-based oxidation catalyst contains 1.3-5.1% of rare-earth and/or alkali-earth element and represents ultradisperse powder.

EFFECT: increased catalytic activity.

4 ex

FIELD: technical chemistry; catalyst carriers for various heterogeneous processes in chemical industry.

SUBSTANCE: proposed carrier has metal base made from chromium and aluminum alloy and/or metallic chromium and coat made from chromium of aluminum oxides or oxides of chromium, aluminum, rare-earth elements or mixture of them. Method of preparation of carrier includes forming of metal powder containing aluminum and other powder-like components and calcination of carrier at solid phase sintering point; used as additional component of metal powder is powder-like chromium; mixture thus obtained is subjected to mechanical activation and is placed in mold accessible for water vapor, after which it is subjected to hydro-thermal treatment and molded product is withdrawn from mold, dried and calcined at respective temperature; then additional layer of aluminum and rare-earth elements oxides or mixture of solutions and suspensions is applied on calcined product followed by drying and calcination.

EFFECT: increased specific surface; enhanced heat resistance of carrier.

8 cl, 1 tbl, 5 ex

FIELD: oxidation catalysts.

SUBSTANCE: invention relates to catalysts for deep oxidation of carbon monoxide and can be used to treat industrial enterprise mission gases and motor car exhaust. Catalyst of invention is intermetallide of general formula Al3M, where M is Ca or V.

EFFECT: increased catalytic activity.

2 ex

FIELD: polymerization catalysts.

SUBSTANCE: catalyst preparation involves interaction of rare-earth element compound, conjugated diene, and diisobutylaluminum hydride followed by ageing of reaction mixture for 10-30 min, adding tetraisobutyl-dialumoxane and alkylaluminum hydroxide at molar ratio 1:(2-20):(3-12):(6-12):(1.5-3), respectively, and ageing resulting mixture for 10-15 h. Diene utilized is in the process is pyperilene or isoprene and rare-earth element compound is rare-earth element carboxylate or alcoholate. Catalyst can, in particular, find use in production of cis-1,4-polydienes.

EFFECT: achieved preparation of high-efficiency catalyst enabling production of highly stereospecific polybutadiene or butadiene/isoprene or butadiene/pyperilene copolymers at narrower molecular mass distribution.

4 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: catalyst consists of complex [Sm(NO3)5][C5H5NH]2 constituted by samarium nitrate, pyridine, and nitric acid taken in molar ratio 10:20:20, respectively.

EFFECT: achieved accessibility of catalyst.

1 tbl, 2 ex

FIELD: chemical industry; petrochemical industry; gaseous industry; oil-producing industry; oil-processing industry; installation for purification of the hydrocarbon raw from methanol.

SUBSTANCE: the invention is pertaining to the technology of purification of the hydrocarbon raw from methanol and may be used in gaseous, petroleum, petrochemical and chemical industries. The installation includes the assembly of the preliminary separation of the raw connected with the block of the adsorbing purification, the pipeline links and the shut-off-adjusting fittings. The assembly of the preliminary separation includes: the block of the preheating of the raw consisting of the heat exchangers (1) and (2), the rectifying column (3) with the connecting pipes for feeding of the liquid hydrocarbon raw (4), withdrawal of the methanol with the light fraction of hydrocarbons (5) and the withdrawal of the hydrocarbon tailings (6) with the bottom heating, the cooler (10) and container(11). The block of the raw preheating is connected to the connecting pipe (4) of the raw feeding into the rectifying column (3), and the connecting pipe (5) for the raw withdrawal in series through the raw preheating block, the cooler (10) and the container (11) directly connected with the block of adsorbing purification. In the other version the block of the raw preheating is connected to the connecting pipe (4) of feeding of the liquid hydrocarbon raw into the rectifying column (3), and the connecting pipe (5) of withdrawal through the heat exchanger (1) and the cooler (10) is connected to the connecting pipe (23) of the inlet into the extraction column. The connecting pipe (25) of withdrawal of the methanol with the light fraction of hydrocarbons out of the extraction column (20) is connected to the inlet connection pipe (28) of the separator (21), and the connecting pipe (26) of withdrawal of the water-methanol mixture is connected with the intermediate container (22). The connecting pipe (29) of withdrawal of the methanol with the light hydrocarbons from the separator (21) is connected to the block of the adsorbing purification. The connecting pipe (29) of withdrawal of the water-methanol mixture of the separator (21) is connected to the intermediate vessel (22), which outlet is connected to the feeding line of the extracting liquid into the extraction column (20). The invention reduces the operational costs, increases the lifetime of zeolite.

EFFECT: the invention ensures reduction of the operational costs, the increased lifetime of zeolite.

2 cl, 2 dwg, 2 ex

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