Zirconium dioxide extrudates

FIELD: chemistry.

SUBSTANCE: invention claims methods for obtaining calcinated zirconium dioxide extrudates (variants) for application as carrier or catalyst containing zirconium and one or more other elements selected out of IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII groups of periodic element system, or lanthanides and actinides, involving the following stages: a. Obtaining formed paste by mixing and plastifying of fine dispersed zirconium dioxides and source of one or more other elements selected out of IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII groups of periodic element system, or lanthanides and actinides, and solvent, to obtain mix containing 50 to 85 wt % of solid substances, b. extrusion of formed paste to obtain zirconium dioxide extrudate containing zirconium and one or more other elements selected out of IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII groups of periodic element system, or lanthanides and actinides, and c. Drying and calcination of zirconium dioxide extrudate formed on b. stage, with fine dispersed zirconium dioxide containing under 15 wt % of zirconium dioxide other than monocline zirconium dioxide. Also invention claims calcinated zirconium dioxide extrudates obtained by the described method, and cobalt-saturated extrudate and its application in method for obtaining higher olefins in Fischer-Tropsch reaction.

EFFECT: enhanced crush durability of zirconium dioxide extrudates.

16 cl, 3 tbl, 12 ex

 

The technical field to which the invention relates

The present invention relates to the production of calcined extrudates of zirconium dioxide and their use as catalysts or catalyst carriers.

Background of invention

Zirconium dioxide is a well known material for use as a catalyst carrier or catalyst in various processes. The Zirconia can be used as various molded bodies or molded particles, including spheres, cylinders, rings (hollow cylinders) and less symmetrical forms, such as granules. The cylinders can be obtained with a number of cross-section shapes, such as three, four, star and round.

Molded particles of Zirconia can be obtained by the process of agglomeration of particles of the powder of zirconium dioxide. To achieve the enlargement of particles can be used in a number of ways, including ways of compaction pressure, sintering and spraying. Such methods are described in the Handbook Perry's Chemical Engineers Handbook, McGraw-Hill International Editions (1984), ISBN 0 07-049479-7, pages 8-61.

The seal under pressure is particularly suitable in the case of catalysts, as it can give solid particles. The seal under pressure can be carried out in a number of ways, including extrusion (where forming the second mixture ekstragiruyut using an extruder, equipped with a suitable plate matrix, obtaining particles of cylindrical type), the pressing rollers (getting less symmetric granular particles) or tableting (which gives the particles a very well defined shape).

Immediately after molding the molded particles are usually dried, and then calcined in order to create the porosity and increase the strength of the particles. Both of these characteristics are especially important in the case of catalysts.

The extrusion method is often preferred compared to the way tabletting, because the performance of the extrusion is many orders of magnitude by magnitude greater than that of tableting. In addition, tableting usually gives volumes with low porosity, which is often a constraint in catalytic applications. Extrusion is also preferred in comparison with pressing rollers, because the extrusion provides the particles with a much more narrow distribution of particle size. The combination of the sealing rolls and granulating mills in the way of pressing rollers gives a granular material which has a wide distribution of particle size, which is often undesirable in the catalytic region, as it increases the separation in a compact layer of catalytic particles.

Dosih it was impossible to ekstradiroval zirconium dioxide like other materials, such as aluminum oxide, in conventional extrusion equipment with getting strong enough media after the annealing. Due to its high temperature resistance and its acidic and basic properties of Zirconia is an interesting material media. It would therefore be desirable to obtain an extrudate of zirconium, which has sufficient strength to have industrial value.

Zirconia exists in several crystalline forms, depending on prevailing conditions. Thus, under conditions of temperature and pressure environment of zirconium dioxide exists as a stable monoclinic crystal structure. Under extreme pressure or at high temperatures, typically about 450-1000°, zirconium dioxide exists as a tetragonal crystal structure. At even higher temperatures, usually above 1500°C, is formed of a cubic crystal phase. Relative to the overall consideration of the properties of Zirconia, reference is made to Kirk-Othmer "Encyclopedia of Chemical Technology", Second Edition, Volume 22, pages 651-655.

EP-A-0510772 (Shell) considers a method of producing extrudate catalyst containing zirconium dioxide comprising grinding the mixture of zirconium dioxide and/or a precursor of zirconium dioxide and solvent, which mixture has a solids content of from 20 to 60 m is from.%, and extruding the mixture.

EP-In-0716883 (BASF) considers a method of producing catalysts or carriers, consisting essentially of monoclinic Zirconia. The method comprises the deposition of zirconium salts of ammonia, in which the solution zirconolite or circinelloides added to aqueous ammonia solution with decreasing pH from 14 to 6, and conducting drying, calcining, and tableting. The examples of the preparation of extrudates Zirconia are not given.

US-A-6034029 (BASF) discusses a method of obtaining a powder of Zirconia, which is mainly monoclinic and which has a large surface area. The examples of the preparation of extrudates Zirconia are not given.

Now it has been unexpectedly found that there was a significant increase in the strength of the extrudate, when Zirconia is used to obtain, essentially consists of monoclinic Zirconia.

Brief description of the invention

According to one aspect of the present invention provides a method of obtaining a calcined extrudate zirconium dioxide comprising the following stages:

A. obtaining the form of the paste by mixing and plastilinovaya fine zirconium dioxide with a solvent to obtain a mixture having a total solids content of from 50 to 85 wt.%,

b. extrusion fo is mousasi pasta with molding the extrudate Zirconia and

C. drying and calcining the extrudate Zirconia,

characterized in that the fine zirconium dioxide containing not more than 15 wt.% Zirconia, which is different than monoclinic Zirconia.

According to the present invention also provides calcined extrudate Zirconia obtained by the way described here.

The calcined extrudates Zirconia obtained by the method of the present invention have significantly improved crushing strength compared to extrudates Zirconia obtained from the fine Zirconia that contains more than 15 % of Zirconia, which is different than the monoclinic zirconium dioxide, for example zirconium dioxide, which is a mixture of tetragonal and monoclinic Zirconia, which contains more than 15 wt.% Zirconia, which is tetragonal zirconium dioxide, or zirconium dioxide, which consists only of tetragonal Zirconia.

Detailed description of the invention

The key distinguishing feature of the present invention is that the very fine zirconium dioxide containing not more than 15 wt.% Zirconia, which is different than the monoclinic Zirconia. Therefore, the very fine zirconium dioxide is here not contain significant amounts of Zirconia, which is different than the monoclinic zirconium dioxide, such as cubic or tetragonal zirconium dioxide. Preferably the fine Zirconia contains not more than about 10 wt.%, preferably no more than about 5 wt.% Zirconia, which is monoclinic.

Radiographic method can be used as a method of determining the relative amounts of tetragonal, monoclinic and cubic Zirconia in the sample of zirconium dioxide, as described in R. Jenkins and R.L. Snyder, Introduction to X-ray powder diffractometry (Chemical analysis, Volume 138), John Wiley & Sons, New York (1996), ISBN 0-471-51339-3.

An example of a source of fine zirconium dioxide, suitable for use here, is DAIICHI RC-100, which is commercially available from the firm DDK Daiichi Kigenso Depending Kogyo Co. Ltd., 4-4-14 Koraibashi Chuo-ku, Osaka 541-0043, Japan.

The first stage of this method is to obtain the form of the paste by mixing and stirring the fine Zirconia described above, with the solvent and optional additives to obtain a mixture having a total solids content of from 50 to 85 wt.%, preferably from 55 to 80 wt.%, more preferably from 65 to 75 wt.%.

As used here, the term "solvent" means any liquid that is suitable for use in obtaining Faure is wusasa paste when mixed with the fine Zirconia and if present, with the cobalt precursor.

The solvent may be any suitable solvent known in the art, for example, water; alcohols such as methanol, ethanol and propanol; ketones, such as acetone; aldehydes, such as propanal, and aromatic solvents such as toluene. Preferably and most suitable diluent is water. Optional components, such as acids and bases, may be introduced into the solvent to act as agent for peptization in obtaining an extrudable paste.

Zirconium is present as Zirconia extrudate zirconium dioxide obtained according to the present invention can itself be used as the catalytically active component. If it is desired, however, the milled mixture may also contain sources of one or more other elements, used as a catalytically active component instead of or in addition to zirconium, optionally, together with one or more elements of the promoter. Accordingly, the mixture may contain a source of one or more elements selected from groups IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII of the periodic system of the elements or the lanthanides and actinides. Preferred catalytically active components are the elements of group VIII of the periodic system of elements. the particularly preferred are the sources of the elements, selected from iron, ruthenium, cobalt, rhenium, Nickel, palladium, platinum, copper and zinc. Cobalt, iron and Nickel are particularly preferred catalytically active elements, and the cobalt is the most preferred. The mixture can also predominantly contain the source element of group IVB of the periodic system of elements (the elements) are used as promoters, in particular titanium together, if desirable, an additional source of zirconium.

In obtaining extrudates Zirconia here is optional, can be used binders. Suitable binders include silica, alumina, titanium dioxide, etc.

The source of one or more elements of the above groups may be soluble or insoluble in the solvent. Typical sources include salts derived from organic acids, such as acetates, benzoate, ethanoate and propionate; halides, for example chlorides, bromides, iodides and fluorides; other salts, such as nitrates, oxides, hydroxides, carbonates and chlorates. Sources of insoluble in the solvent, are preferred. It was found that particularly preferred are the hydroxides.

In a preferred embodiment of the present invention the fine Zirconia mixed with preceding what tonikom cobalt and a solvent to form paste form, which then ekstragiruyut obtaining cobalt catalyst on the carrier Zirconia. Hence, in accordance with another aspect of the present invention provides a method of obtaining a calcined cobalt/zirconium dioxide comprising the following stages:

A. obtaining the form of the paste by mixing and stirring the fine Zirconia and cobalt precursor with a solvent to obtain a mixture having a total solids content of from 50 to 85 wt.%,

b. extruding the form of the paste forming the extrudate Zirconia/cobalt and

C. drying and calcining the extrudate Zirconia/cobalt

characterized in that the fine zirconium dioxide containing not more than 15 wt.% Zirconia, which is different than monoclinic Zirconia.

The present invention additionally provides for the calcined extrudate Zirconia/cobalt, obtained by the method of the present invention.

The precursors of cobalt, suitable for use here include any predecessor of cobalt, which leaves on the media Zirconia after calcination only cobalt oxide, so that the catalytic properties of the final product does not deteriorate. Suitable precursors of cobalt include (but not graniteware this) hydroxide cobalt, cobalt acetate, cobalt nitrate, cobalt oxide and mixtures thereof. Particularly preferred precursor of cobalt for use here is the hydroxide of cobalt.

It is preferable to include in the mixture of the main component to act as agent for peptization to obtain an extrudable paste Zirconia. The basic compound is preferably ammonia, connection, releasing ammonia, ammonium compound or an organic amine. Such basic compounds are removed during annealing and are not stored in the extrudates with the deterioration of the catalytic characteristics of the final product. The main connection is the most preferred is ammonium compound. The most suitable ammonium compound is ammonia.

The amount of basic compound included in the mixture should be sufficient for peptization of zirconium dioxide present in the mixture. The amount of basic compound present in the mixture, can be easily determined by measuring the pH of the mixture. In the process of milling the mixture should preferably have a pH in the range of from 8.0 to 11.5, preferably from 9.0 to 11.0.

To obtain the form of the paste together milled Zirconia/cobalt is preferably included in the mixture of the acid component to act as agent for peptization. Sour is the principal compound is preferably a compound of an inorganic acid or a compound of organic acid. Such acidic compounds removed during annealing and are not stored in the extrudates with the deterioration of the catalytic characteristics of the final product. The preferred inorganic acid for use here is nitric acid. The most suitable organic acid is citric acid.

To improve the flow characteristics of the mixture in the extrusion process in the mixture can be injected surfactant or polyelectrolyte. The introduction of the mixture of surfactants gives a more smooth texture of the extrudate and facilitates the cutting of the extruded product. In addition, can be improved pore formation in the calcined catalytic material, which can improve the catalytic properties of the products. Suitable surfactants include cationogenic surfactants, such as fatty amines, Quaternary ammonium compounds, aliphatic monocarboxylic acid, an ethoxylated alkylamines followed, polyvinylpyridine, sulfoxonium, sulfonamide, postname and itaniemi compounds; anionic surfactants, for example alkylated aromatic compounds, acyclic monocarboxylic acids, fatty acids, from sulphonated aromatic compounds, sulfates of alcohols, sulfates of atherosperma, sulfation is installed fats and oils, and salts of phosphonic acid; nonionic surfactants, such as polietilenglikoli, polyoxyethylene, polyoxyethylenated, polyols, polyvinyl alcohol, and acetylene glycols. The amount of surfactant is usually from 0.5 to 8 wt.%, preferably from 1 to 5 wt.%, in relation to the weight of zirconium dioxide and/or a precursor of zirconium dioxide present in the mixture. Surfactant can be introduced at any stage of mixing prior to extrusion.

In principle, it is possible to combine the components of the mixture in any order. However, it was found the advantage of obtaining a mixture in the following way. At the very least, the mixture contains zirconium dioxide and the solvent are first mixed together. If the mixture should include primary connection was established the advantage of adding a basic compound to the solvent prior to introduction of the solvent in the fine Zirconia. If desirable, may be a source of one or more elements of the aforementioned groups of the periodic system of elements. As discussed here, the preferred element is cobalt. In the case of the extrudate together milled Zirconia/cobalt fine Zirconia and cobalt precursor are mixed together and then adding dilute the I, if present, acid. Surfactant, if desired, may be introduced at any point in the process of mixing, preferably by the end of the mixing.

Typically, the mixture is mixed while grinding during the period of time from 10 to 120 min, preferably from 15 to 90 minutes during the milling process to the mixture is fed to the energy of the grinding device. For milling process using the device Simpson Muller Mixer, Type LG, commercially available from the firm Simpson Technologies Corporation, 751 Shoreline Drive, Aurora, Illinois 60504, USA. Optional process plastilinovaya machine can be used AOUSTIN, commercially available from the firm F. Aoustin & Cie, Rue de Preaux BP 32, 76161 Darnetal Cedex, France.

The milling process may be carried out in a wide temperature range, preferably from 15 to 50°C. In the supply of energy to the mixture during the milling process takes place, the growth temperature of the mixture in the milling process. The milling process is suitably carried out at ambient pressure. Can be used with any suitable commercially available grinding machine. At the end of the milling process receive form a paste.

Form a paste then ekstragiruyut using any conventional commercially available extruder. In particular, twin-screw extruder can be used on the I forcing the mixture through the holes in the Spinneret plate to obtain extrudates of catalyst required form. Strand formed by extrusion, can then be cut into suitable pieces.

The extrudates may be in the form of cylinders, including a hollow cylinder, or may have a form that is multipartite or twisted multipartite in cross-section, or may take any other shape known in the art. Usually the extrudates have a nominal diameter of from 0.5 to 6 mm, preferably from 0.8 to 4 mm, especially 1 to 3 mm.

After the extrusion, the extrudates are dried, for example at a temperature of from 100 to 300°during the period of time from 30 min to 3 h before annealing. The calcination is suitably carried out in air at temperatures up to 1000°C, preferably in the range from 300 to 1000°S, more preferably in the range from 300 to 800°With, especially in the range from 400 to 600°C. the Calcination of the extrudates is usually carried out for a period of time up to 5 h, preferably from 30 minutes to 4 hours

The surface area of the catalyst is zirconium dioxide is preferably in the range from 40 to 300 m2/g, more preferably from 50 to 100 m2/g as measured by BET method of nitrogen adsorption, as described in J. Amer. Soc., 60 (1938), 309.

Just received the extrudates may be subjected to a stage of deposition, where the sources of one or more catalytically active elements or promoters element is deposited in the extrudates. The sources can be any of the elements in the groups of the periodic system of elements, as discussed earlier. In those cases, when the initial mixture contains a source of this element, the deposition of another source of this element can be increased content item in the extrudates.

The deposition source of catalytically active element or viewing item on the extrudates may be carried out by any method known in the art.

The preferred deposition technology is impregnation. The impregnation can be carried out with the contacting of the catalyst with the compound of the desired element in the presence of a fluid, preferably in the form of a solution of the compound element. Suitable liquids for use in the impregnation include both organic and inorganic liquid, and water is the most suitable and the preferred liquid. Suitable connections are desirable item include both organic and inorganic compounds with a preference for compounds that are soluble in the selected solvent. It should be noted that the introduction of acids or bases can facilitate solubility of suitable compounds of the desired element. Preferably the compounds are inorganic compounds. The most preferred ablauts the aqueous solutions of nitrates and hydroxides of the desired element. Especially preferred are nitrate compounds desirable feature because they can be used as a melt, thus giving a high concentration of the desired element in the liquid.

The extrudates are most suited in contact with the connection to the desired element when immersed in the liquid. Preferably the catalyst is immersed in a sufficient volume of liquid in order to accurately fill the pore volume in the extrudates.

If the impregnation is carried out in one stage, the extrudates are in contact simultaneously with the connection of each of the desired elements in the presence of a fluid. Preferably the catalyst is immersed in an aqueous solution of nitrates or hydroxides of the desired elements. If the impregnation is carried out with the use of multiple stages, the extrudates are contacted on the first stage with a compound of one of the desired elements in the presence of a fluid, and at a later stage with the connection of another desirable element in the presence of a fluid. The liquid in stages may be the same or different, are most suited to the same.

After impregnation on a single stage or after each impregnation with multistage impregnation, the extrudates are dried. The conditions under which the extrudates are dried, are as described above. Preferably one or each drying extraditability, the calcination conditions are as described above.

The catalytically active element may be present in the product in quantities from 1 to 100 parts by weight, preferably from 10 to 50 parts by weight, per 100 parts by weight of Zirconia. The promoter, if present, may be present in amounts of from 0.1 to 60 parts by weight, preferably from 1 to 10 parts by weight, per 100 parts by weight of Zirconia.

In a preferred embodiment of the present invention, the extrudate Zirconia impregnated with a cobalt precursor, which is then dried and calcined education calcined extrudate Zirconia impregnated with cobalt. Hence, according to another aspect of the present invention provides a method of obtaining a calcined extrudate Zirconia impregnated with cobalt, which comprises the following stages:

A. obtaining the form of the paste by mixing and plastilinovaya fine zirconium dioxide with a solvent to obtain a mixture having a total solids content of from 50 to 85 wt.%,

b. extruding the form of the paste forming the extrudate Zirconia,

C. the impregnated extrudate Zirconia liquid precursor of cobalt with the formation of the extrudate Zirconia impregnated with cobalt, and

d. drying and calcination of the extrudate Zirconia, propiano what about the cobalt,

characterized in that the fine zirconium dioxide containing not more than 15 wt.% Zirconia, other than monoclinic Zirconia.

The present invention also relates to the calcined extrudate Zirconia impregnated with cobalt, obtained by the way described here.

The liquid precursors of cobalt, suitable for impregnating the extrudate Zirconia, include aqueous solutions of cobalt hydroxide, cobalt acetate, cobalt nitrate, and mixtures thereof. Preferred liquid cobalt precursor is an aqueous solution of cobalt nitrate. Other preferred liquid cobalt precursor is an aqueous solution of cobalt hydroxide in ammonia.

The calcined extrudates zirconium dioxide obtained according to the present invention show a significant improvement in strength as compared with the calcined extrudates Zirconia, which are obtained from the fine Zirconia that contains more than 15 wt.% Zirconia, other than monoclinic Zirconia. For practical applications it is preferable that the strength of the calcined extrudate was more than 100 N/cm, as determined by the standard test method for tensile radial crush strength of extruded catalyst particles (ASTM D6175-98).

At the same BP is me, having a high crushing strength, calcined extrudates zirconium dioxide obtained according to the present invention, also have a high pore volume, preferably 0.3 ml/g or more as determined by the introduction of mercury using the method described in the work of H.L. Ritter and L.C. Drake, In. Eng. Chem., Anal. Ed., 17 (1945), 782.

The calcined extrudates Zirconia obtained here, also have a high surface area, preferably 50 m2/g or more as determined by nitrogen adsorption according to BET method described in J.Amer.Chem.Soc., 60 (1938) 309.

Hence, in accordance with another aspect of the present invention offers a calcined extrudate zirconium dioxide having the following characteristics:

(a) a pore volume of 0.3 ml/g or more;

(b) the strength of the radial crush strength of 100 N/cm or more and

(C) surface area of 50 m2/g or more.

The extrudates zirconium dioxide obtained according to the present invention can be applied to any process which may be used or required catalyst comprising zirconium dioxide. The extrudates Zirconia can be suitably used, for example, as carriers of catalysts that are typically used in hydrocarbon synthesis reactions, such reactions Fischer-Tropsch processes of hydroconversion like Hydra is demetallization, the hydrocracking and hydrodesulfurization heavy hydrocarbon oils, hydrogenation hydrogenosomes components or hydrocarbon fractions, such as kerosene and various types of cyclic oils, epoxydecane connection with the olefinic unsaturation of the corresponding alkanols, exhaust gas cleaning, in particular in denoxing nitrogen-containing oxygenates, in the isomerization of olefins or paraffins, the dimerization of olefins and dehydration of alcohols to olefins.

The extrudates Zirconia, in particular, are also used as carriers of catalysts in reactions of the type Fischer-Tropsch aimed at obtaining (long-chain) hydrocarbons from carbon monoxide and hydrogen.

Hence, in accordance with another aspect of the present invention provides for the use of calcined extrudate Zirconia, as obtained here, as a catalyst carrier in the preparation of hydrocarbons in the interaction of carbon monoxide and hydrogen under the reaction conditions of the Fischer-Tropsch process.

Especially preferred for use in such reactions are extrudates of zirconium dioxide obtained according to the present invention, containing the elements, optionally, with one or more promoters that are activated after recovery. Especially used is in the Fischer-Tropsch synthesis are extrudates Zirconia, received in accordance with the method of the present invention containing iron, Nickel or cobalt as the catalytically active component. Cobalt is particularly preferred.

The extrudates Zirconia obtained here can be restored by contact with a hydrogen-containing gas at elevated temperature and pressure. Typically, the recovery involves the treatment of the catalyst at a temperature in the range from 100 to 450°and at a pressure of from 1 to 200 bar (abs.) within 1-200 hours In recovery can be used pure hydrogen, but it is generally preferable to use a mixture of hydrogen and inert gas such as nitrogen. The relative amount of hydrogen present in the mixture may be in the range from 0.1 to 100 vol.%.

In accordance with a preferred option for recovering the catalyst is brought to the desired level of temperature and pressure in a nitrogen atmosphere. Then the catalyst is in contact with a gas mixture containing only a small amount of gaseous hydrogen, the rest is nitrogen gas. In the process of restoring the relative amount of gaseous hydrogen in the gas mixture is gradually increased to 50% vol. or even up to 100%vol.

Then the catalyst may be contacted with a mixture of carbon monoxide and hydrogen at povyshen the x temperature and pressure. Usually the reaction is carried out at a temperature in the range from 125 to 350°C, preferably from 175 to 250°S, more preferably from 200 to 250°With, especially from 205 to 240°C. the Pressure of the reaction is usually in the range of from 5 to 100 bar (abs.), more preferably from 20 to 100 bar, especially from 40 to 70 bar (abs).

Hydrogen and carbon monoxide is usually served in a process at a molar ratio in the range from 0.7 to 2.5, preferably in the range from 1 to 2. Low molar ratios of hydrogen to carbon monoxide increase the C5+ selectivity of the catalysts, i.e. the selectivity of the formation of C5+ hydrocarbons. Neprevyshenie hydrogen and carbon monoxide can be recycled again to contact with the catalyst. With this arrangement, the molar ratio of hydrogen to carbon monoxide in the gas is really in contact with the catalyst, can be significantly lower than that of the injected gas, for example in the range from 0.4 to 1.1.

Hourly space velocity gas(GHSV)(CPSG)) may vary within wide ranges and is typically in the range from 100 to 10000, preferably 100-5000, more preferably from 500 to 3500, even more preferably from 800 to 1600 nl/l/h Term CPSG is well known in the art and refers to the flow rate of gas per hour, i.e. to the volume of the synthesized gas nl (i.e. when the standard rate is the temperature 0° C and a standard pressure of 1 bar (100000 PA)), which is in contact in 1 h with 1 l of catalyst particles. In the case of a fixed catalyst layer CPSG usually expressed per 1 liter of the catalytic layer, i.e. including the empty space between particles.

A method of producing hydrocarbons can be carried out using a range of reactor types and modes of reaction, for example a regime with a fixed layer or the mode of boiling. Mode fixed bed is preferred. It should be noted that the size and shape of catalyst particles may vary depending on the mode of action for which they are intended. Specialist in the art is able to choose the size and shape, the most suitable for this mode of reaction.

In addition, it should be clear that the specialist in the art can select the most suitable conditions for a particular reactor design, reaction and process flow. For example, the preferred hourly space velocity of the gas may depend on the type of reaction used. Thus, if it is desirable that the method of synthesis of hydrocarbons was carried out in fixed bed, preferably hourly spatial velocity of the gas is chosen in the range from 500 to 2500 nl/l/h

The products of such reactions Fischer-Tropsch process are compounds which Yu hydrocarbons, including paraffins, olefins and oxygenates, such as alcohols and aldehydes. The extrudates together milled Zirconia/cobalt and extrudates Zirconia impregnated with cobalt, are particularly suitable here for more olefins, particularly C11-C14 olefins, in particular, in combination with the preferred system of the conditions of the Fischer-Tropsch process. C11-C14 olefins, in particular, are used as precursors spirits of some detergents.

Hence, in accordance with another aspect of the present invention provides a method of obtaining a higher olefins having from 11 to 14 carbon atoms, including the interaction of hydrogen and carbon monoxide in the reaction conditions of the Fischer-Tropsch process in the presence as catalyst calcined extrudate Zirconia/cobalt or calcined extrudate Zirconia impregnated with cobalt.

In order to maximize C11-C14 carbon fraction in the stream of hydrocarbon product while still maintaining a high C5+ exit (not less than 85 %), it is preferable to conduct the reaction of the Fischer-Tropsch process under such conditions that the average alpha value of the used catalyst lies within the range of 0.87 and 0.92, preferably from 0.9 and 0.92, especially 0.91. The alpha value is known in engineering as ASF-alpha value (indicator Anderson-XUL is a-Flory growth of the chain). As used here, the average alpha value is the value ASF-ratio of the probability of chain growth, which best describes the measured distribution of hydrocarbons between C20 and S, i.e. the value defined by the statistical regression of the measured data using the method of the so-called "least squares regression", well known to the person skilled in the art. The alpha value in the range preferred for use here, and as shown above, provides approximately twice the C11-C14 fraction than the value in the interval 0,95-0,96, while still having relatively high C5+ output.

In order to maximize olefinic unsaturation C11-C14 carbon fraction, the preferred system of the conditions of the Fischer-Tropsch process is the following: the interaction of hydrogen and carbon monoxide in a molar ratio of from 1.1:1 to 0.4:1 at a temperature average layer in the range from 200 to 250°C, preferably 205-240°C, a pressure in the range from 20 to 100 bar, preferably from 40 to 70 bar, and CPSG from 100 to 5000 h-1preferably from 500 to 3500 h-1.

In addition, in order to maximize C11-C14 fraction, preferably the catalyst has an average particle diameter of 2.2 mm or less, preferably in the range from 1 to 2 mm.

The number of catalytic the ski active cobalt on the media Zirconia is preferably in the range of 3 to 300 parts by weight of on 100 parts by weight of the material of the carrier Zirconia, more preferably from 10 to 80 parts by weight, especially from 20 to 60 parts by weight of

The preferred reaction product of the reaction of the Fischer-Tropsch process, described here, contains 20-60 wt.% C11-C14 olefins relative to the total weight of C11-C14 carbon fractions. Also preferably the reaction product of a Fischer-Tropsch contains 85 % or more of hydrocarbons having 5 carbon atoms or more, relative to the total weight of hydrocarbons in the reaction product.

The present invention will be now illustrated by the following examples.

Examples

In the following examples, the term loss by burning (or "LOI") shall mean the quantity of moisture present in the sample, as measured by the weight loss of the sample after treatment at 550°in a furnace for 2 hours

Example 1

The calcined extrudate Zirconia

The calcined extrudate Zirconia according to the present invention was prepared as follows. 7060 g of powder of zirconium oxide trademarks DAIICHI RC-100 (commercially available from the company DKK Daiichi Kigenso Depending Kogyo Co., Ltd., with losses due to burning of 1.9 %) is mixed with 2654 g of water, 416 g of ammonia solution (containing 25 wt.% ammonium hydroxide), 69 g of the polyelectrolyte SUPERFLOC N100 (commercially available from the company Cytec Industries B.V., Botlekweg 175, 3197 KA, Botlek-Rotterdam, The Netherlands) and 139 g of poly is innovage alcohol trademark MOWIOL 8-88 (commercially available from Kuraray company Specialties Europea, GmbH, c/j Clariant Benelux N.V., Diemerhof 36, 1112 XN Diemen, The Netherlands).

Radiographic analysis Daiichi powder, using the quantification of Rietveld, shows that it contains 92,09 % monoclinic Zirconia, 7.9 % of tetragonal Zirconia and 0.006 % cubic Zirconia; all numbers are relative accuracy ± 10 %. X-ray diffractometer used for these measurements is diffractometer Philips PW 1800, with the following characteristics: x-ray tube; copper anode; voltage 40 kV; current 55 mA; zone differences: auto; reception area: clean; vertical colerne areas in primary and diffeyrobson beam; graphite monochromator in diffeyrobson beam; logged interval 10-90 2 theta; a step size of 0.025 2 theta; time accounts/stage 5; the standard sample holder with a diameter of 20 mm and a depth of 1.5 mm

This mixture is kneaded in the mixer type, SIMPSON LG (supplied by the firm of Simpson Technologies Corporation) for 15 minutes the mixture is Then passed through kneading machine AOUSTIN continuous size 2 inches × 17 inches (commercially available from the firm F. Aoustin & Cie 11, Rue de Preaux BP 32, 76161 Darnetal Cedex, France) at 200 rpm the paste thus Obtained is measured LOI 32,81 % and a pH of 10.3. Pasta ekstragiruyut of 2.25 inch BONNOT extruder (commercially available from the company The Bonnot Company, 1520 Corporate Woods Pkwy., Unionton, Ohio 44685, school is) using 2.5 mm three-brained Spinneret plate and 1.5 mm cylindrical Spinneret plate. The extrudates are dried at 120°C for 1 h followed by calcination in a rotary kiln at a temperature of 550 product°C for 2 h, the surface Area of the final extrudate is 88 m2/g pore Volume is 0,326 ml/g tensile radial crush strength of the final extrudate is determined using standard test method ASTM D6175-98. The results are presented in table 1 below.

Example 2 (comparative example)

Repeat the procedure of example 1 except that the powder of zirconium dioxide used in example 1 is replaced by a mixture of 80 % Daiichi HC-100 and 20 % of a powder of Zirconia brand SERP HC 15 (commercially available from the firm Societe Europeenne des Produits Refractaires, Les Miroires, 18 Rue D'alsace, 92400 Courbevoie, France). SERP NA 15 contains of 98.3 wt.% tetragonal Zirconia and 1.7 wt.% monoclinic zirconium dioxide (as analyzed by x-ray method using the same diffractometer and the same parameters as described in example 1 above) and has a LOI is 24.4 %. In order to achieve the same LOI extruded paste as in example 1, the amount of injected water is reduced. The paste thus obtained is measured LOI 32,87 % and a pH of 10.2. Extrusion, drying and calcination is conducted in the same manner as in example 1. The strength of the radial crush strength of the final extrudate is measured ACC is accordance with standard test method ASTM D6175-98. The results are presented in table 1 below.

Example 3 (comparative example)

Repeat the procedure of example 1 except that the powder of zirconium dioxide used in example 1 is replaced by a mixture of 50 % Daiichi HC-100 and 50 % of a powder of Zirconia brand SERP HC 15 (as used in example 2). In order to achieve the same LOI extruded paste as in example 1, the amount of injected water is reduced. The paste thus obtained is measured LOI 31,89 % and a pH of 9.8. Extrusion, drying and calcination is conducted in the same manner as in example 1. The strength of the radial crush strength of the final extrudate is measured in accordance with standard test method ASTM D6175-98. The results are presented in table 1 below.

Example 4 (comparative example)

Repeat the procedure of example 1 except that the powder of zirconium dioxide used in example 1 is replaced by a powder of Zirconia SERP HC 15 (as used in example 2). In order to achieve the same LOI extruded paste as in example 1, the amount of injected water is reduced. The paste thus obtained is measured LOI 31,89 % and a pH of 9.8. Extrusion, drying and calcination is conducted in the same manner as in example 1. The strength of the radial crush strength of the final extrudate is measured in accordance with standard test method ASTM D6175-98. Result is you presented in table 1 below.

Example 5 (comparative example)

Repeat the procedure of example 1 except that the powder of zirconium dioxide used in example 1 is replaced by a powder of Zirconia SERP HC 15 (as used in example 2), which was calcined at 400°before the introduction of the extrudable mixture. The powder consists of a mixture of tetragonal (98,3 %) and monoclinic (1,7 %) Zirconia (as analyzed by x-ray method using the same diffractometer and the same parameters as described in example 1 above) and has a LOI is 24.4 %. In order to achieve the same LOI extruded paste as in example 1, the amount of injected water is reduced. The paste thus obtained is measured LOI 33,75 % and a pH of 9.8. Extrusion, drying and calcination is conducted in the same manner as in example 1. The strength of the radial crush strength of the final extrudate is measured in accordance with standard test method ASTM D6175-98. The results are presented in table 1 below.

Example 6 (comparative example)

Repeat the procedure of example 1 except that the powder of zirconium dioxide used in example 1 is replaced by a powder of Zirconia MEL XZO 880/1 (commercially available from the firm MEL Chemicals, Clifton Junction, P.O. Box 6, Swinton, M27 8LS, Manchester, UK). This powder consists of 100 % tetragonal Zirconia (how about analizirovalo radiographic method using the same diffractometer and the same parameters, as described in example 1 above) and has a LOI of 1.9 %. In order to achieve the same LOI extruded paste as in example 1, the amount of injected water is reduced. The paste thus obtained is measured LOI 48.5 % and a pH of 9.3. Extrusion, drying and calcination is conducted in the same manner as in example 1 (except that the use of 2.5 mm cylindrical Spinneret plate). The strength of the radial crush strength of the final extrudate is measured in accordance with standard test method ASTM D6175-98. The results are presented in table 1 below.

Table 1
Tensile radial crush strength, N/cm
ExampleWt.% monoclinic Zirconia in the original powder2.5 mm three-brained1.5 mm cylindrical
192,09208154
2 (comparative)7410667
3 (comparative)46,93225
4 (comparative)1,7< 20< 20
5 (comparative)1,7<20< 20
6 (against the tion) 020 N/cmnot measured

The data in table 1 clearly show that the calcined extrudates zirconium dioxide, which is obtained by using a powder of Zirconia, which essentially consists of monoclinic Zirconia (for example, 92,09 %)have significantly higher crushing strength than the extrudates obtained using tetragonal Zirconia or a mixture of monoclinic and tetragonal Zirconia.

Example 7

The calcined extrudate Zirconia obtained without the introduction of either acid or base

264 g of powder of zirconium oxide trademarks DAIICHI RC-100 (as used in example 1) with LOI of 5.3 % is mixed with 90 g of 5 wt.% an aqueous solution of polyvinyl alcohol (trademark MOWIOL 18 - 88). This mixture is blended for 2 min in a Sigma (Z-blade) musicalnoe machine type LUK 0,5 supplied by the company Werner &Pfleiderer, Stuttgart, Germany. The mixture is injected 2.5 g SUPERFLOC N100 and the mixing continued for 5 minutes Then added to the mixture of 5 g of water and mixing continued for 30 minutes thus Obtained paste is measured LOI 31.5 % and a pH of 8.4.

This pasta ekstragiruyut using a 1-inch screw pin extruder (supplied by the company The Bonnot Company)using a 1.6 mm trendline the Spinneret plate. The extrudates are dried at 120°C for 1 h followed by annealing in a stationary furnace at a temperature of 550 product°C for 2 h pore Volume of the final extrudates is 0,312 ml/g and a surface area of 55 m2/, tensile radial crush strength of the final extrudates is 233 N/a see

This example shows that there is no need to use acid or base in the production method of the present invention. Therefore, in cases where the acid or base lead to harmful effects on the catalyst, the use of acid or base in receiving the extrudate can be avoided.

Example 8

The calcined extrudate Zirconia impregnated with cobalt

Repeat the procedure of example 1 except that the paste ekstragiruyut using 1.0 mm three-brained Spinneret plate. The extrudates are dried at 120°C for 1 h followed by calcination in a rotary kiln at a temperature of 550 product°C for 2 hours this procedure is repeated and mix the two products. The final product has a surface area of 60.5 m2/g as measured by BET method of nitrogen adsorption, as described in J. Amer. Soc., 60 (1938), 309, pore volume 0,352 ml/g, as measured by the method of introducing mercury, described in the work of H.L. Ritter and L.C. Drake, In. Eng. Chem., Anal. Ed., 17 (1945), 782, and the strength radial the second crushing 154 N/cm, as measured by the same test method as that used in example 1.

10250 g of the obtained extrudate is heated to 60°and impregnate with 6938 g of molten solution of cobalt nitrate having a temperature of 60°during the period of time of 2 min, during which the average temperature of the impregnating mass is about 60°C. the Impregnated extrudates are dried at 120°and calcined in a rotary kiln at a temperature of product 445°C. the Final extrudates have a binder content of 11.45 wt.% (as determined by x-ray fluorescence), the surface area of 48 m2/g (as measured by the BET method of nitrogen adsorption, as described in J. Amer. Soc., 60 (1938), 309), and the strength of the radial crushing 188 N/cm, as measured by the same test method as that used in example 1.

Example 9

The calcined extrudate together milled Zirconia/cobalt

18749 g of powder of zirconium oxide DAIICHI RC-100 is mixed with 8091 g of cobalt hydroxide. Dry powders are mixed in a mixing roll mill Simpson. To this mixture add 5729 g 5 %aqueous solution of polyvinyl alcohol (MOWIOL 18-88), 210,5 g of solid polyvinyl alcohol (MOWIOL 18-88), 255 g of citric acid and 2802 g of water. This mixture is kneaded for 36 min in a mixing roll mill Simpson. Then add 505 g SUPERFLOC N100 and shmesani is continued for another 5 minutes Thus obtained paste is measured LOI of 31.8 % and pH of 7.8. Specified pasta ekstragiruyut with the use of 2.25 inch BONNOT extruder, using 1.0 mm beated the Spinneret plate. The extrudates are dried at 120°C for 4 h followed by annealing in a stationary furnace at a temperature of 550 product°C for 1 h This procedure is repeated and the two products are mixed. The final product has the strength of 113 N/a see

Example 10

The extrudates obtained in accordance with examples 8 and 9 into active catalysts for Fischer-Tropsch recovery and then treated under the reaction conditions of the Fischer-Tropsch process as follows.

Micropolicy reactor comprising catalyst particles in the form of a fixed layer, is heated to a temperature of 280°and presoviet a continuous stream of gaseous nitrogen pressure of 1 bar (abs). The catalyst is restored at the place within 24 h of a gas mixture of nitrogen and hydrogen. In the process of restoring the relative amount of hydrogen in the mixture is gradually increased from 0 to 100 vol.%. The water concentration in the exhaust gas is maintained below 3000 parts by weight of/million

After repair carry out the preparation of hydrocarbons with the introduction of the mixture of hydrogen and carbon monoxide at a ratio of N2:WITH a 1.1:1. CPSG, the temperature of the reaction (expressed as weighted average t is mperature layer) and the pressure set in accordance with table 2. Volumetric productivity (STY), expressed in grams of hydrocarbon product per 1 l of catalyst particles (including the voids between particles) per hour; the selectivity to hydrocarbons containing 5 or more carbon atoms (C5+ selectivity), expressed in wt.% from the mass of the hydrocarbon product; the selectivity to hydrocarbons containing 11 to 14 carbon atoms (C11-C14 selectivity), expressed in wt.% from the mass of the hydrocarbon product, and the selectivity to hydrocarbons containing 15-20 carbon atoms (C15-C20 selectivity), expressed in wt.% from the mass of the hydrocarbon product is determined after 40 h of work. The results are presented in table 2 below.

Table 2
The catalyst of example 8The catalyst of example 9
Temperature, °231227
Pressure, bar (abs).5152
CPSG, nl/(l.h)12001200
Volumetric productivity (STY), g/(l.h)148151
C5+ selectivity, wt.%8887
C11-C14 selectivity, wt.%99
C15-C20 CE is aktivnosti, wt.%1313

The results presented in table 2, show that/Zr catalysts obtained according to the present invention can be successfully used as catalysts in the synthesis of hydrocarbons by the Fischer-Tropsch process.

Example 11

In the following example, the catalyst obtained in accordance with example 8 above, compared with the other two catalysts (catalysts a and b)with different chemical compositions and different ways of obtaining. Catalyst a is a cobalt catalyst on a carrier of silica with zirconium dioxide as an element, a promoter, and is obtained in accordance with example 11 of EP-A-428223. The catalyst is a cobalt catalyst on a carrier of titanium dioxide having manganese as an element, a promoter, obtained in accordance with the General methods as described in WO 99/34917 using 110,5 g of powder of titanium dioxide (trade mark P25, commercially available from the company Degussa), 51,4 g of commercially available soosazhdenie MnCo(OH)xc ratio Mn:Co (at.%/at.%) 5,6. This mixture is compacted by mixing for 30 minutes the Mixture is molded by using a Bonnot extruder. The extrudates (1.7 mm beated) dried at 120°C for 2 h and calcined at 550°C for 2 h the resulting extrudates content is at 20 wt.% With, 1 wt.% Mn and a 71.1 wt.% TiO2.

Three catalyst is transformed into active catalysts for Fischer-Tropsch recovery in the same manner as in example 10 above.

After repair carry out the preparation of hydrocarbons with the introduction of the mixture of hydrogen and carbon monoxide at a ratio of N2:WITH a 1.1:1. CPSG, the temperature of the reaction (expressed as weighted average bed temperature) and the pressure set in accordance with table 3. Volumetric productivity (STY), expressed in grams of hydrocarbon product per 1 l of catalyst particles (including the voids between particles) per hour; the selectivity to hydrocarbons containing 5 or more carbon atoms (C5+ selectivity), expressed in wt.% from the mass of the hydrocarbon product; the selectivity to hydrocarbons containing 11 to 14 carbon atoms (C11-C14 selectivity), expressed in wt.% from the mass of the hydrocarbon product, and olefinic unsaturated C11-C14 hydrocarbon product, expressed in wt.% C11-C14 hydrocarbon product, determined after 120 h of operation. The results are presented in table 3 below.

Table 3
The catalyst of example 8Catalyst A (comparative)Catalyst B (comparative)
The nutritional H2:1,11,11,1
The helium gas supply, vol.%151515
Temperature, °221221222
Pressure, bar (abs.)606058
CPSG, nl/(l.h)120012001200
Volumetric productivity (STY), g/(l.h)152115170
C5+ selectivity, wt.%817387
C11-C14 selectivity, wt.%the 11.69,39,2
Olefinic unsaturation C11-C14, wt.%311919
C20-S alpha0,910,930,94

The results presented in table 3, show that the catalyst of example 8 obtained according to the present invention provides significantly improved output C11-C14 olefins compared to cobalt catalysts based on other types of media (such as silicon dioxide and titanium dioxide) and obtained using different methods.

Example 12

The use of calcined the CSOs of the solid catalyst, containing zirconium dioxide, in the reaction of hydrogen sulfide with 2-methyl-1-pentanol to the corresponding mercaptan and then to the appropriate tiefer

The extrudate Zirconia is obtained using the method described in example 7, except that the use of 1 mm beated the Spinneret plate. Drying and calcination are the same as described in example 7. The surface area of the catalyst is measured using the above-described method of determining the surface area BET is to 57.7 m2/, Measured skeletal density Zirconia is 5,41 g/ml, and measured bulk density is to 1.15 g/ml Measured pore volume is 0,316 ml/g moisture content of the extrudates determine if the exposure of the extrudates at a temperature of 450°C for 2 h Reduced mass when the heat treatment is 1.03 %. Select 244 g of extrudates and then impregnated with sulfuric acid. Selected extrudates Zirconia impregnated with 300 ml of 1 M sulfuric acid at four stages in 75 ml After each stage impregnation, the extrudates are dried in vacuum at temperature of up to 150°With using baths with silicone oil. The content of sulfate in the catalyst is zirconium dioxide is determined by extraction of the catalyst is acetic acid, having a pH of 2. The content of sulfate in extractelement by titration with sodium hydroxide. A certain content of sulfuric acid in the dried extrudates is 7.7 wt.%. After annealing for 2 h at a temperature of 450°With the content of sulfate drops to 3.4 wt.%.

The obtained calcined solid acid catalyst used in the reaction of hydrogen sulfide with 2-methyl-1-pentanol to the corresponding mercaptan and then to the appropriate tiefer. A cylindrical reactor with a diameter of 4 cm is filled with catalyst. The height of the catalytic layer is approximately 10 cm Flow of 12.5 nl/h of nitrogen containing 500 OBC per million of hydrogen sulfide is passed upward through the catalyst layer together with a flow of 9 ml/min liquid containing most of the hydrocarbons, such as hydrocarbons, are available from the company Shell under the trade name SHELLSOL A 100. The conversion of hydrogen sulfide at ambient temperature is from 80 to 90 %. The transformation remains at the same level for a period of time exceeding one month. What transformation does not reach 100 %due to inefficient transfer of hydrogen sulfide from the gas phase into the liquid stream. In addition to the reaction of isopentane with hydrogen sulfide takes place the formation of oligomers.

The examples show that the extrudates Zirconia of the present invention have excellent crushing strength and are suitable for use in image quality is as catalysts or carriers of catalysts in a wide range of chemical processes.

1. A method of obtaining a calcined extrudate Zirconia for use as a carrier or catalyst containing zirconium and one or more other elements selected from groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII of the periodic system of the elements or the lanthanides and actinides, including the following stages:

a. obtain the form of paste by mixing and plastilinovaya fine zirconium dioxide and a source of one or more other elements selected from groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII of the Periodic system of the elements or the lanthanides and actinides, with the solvent to obtain a mixture having a solids content of from 50 to 85 wt.%,

b. extruding the form of the paste to form extrudate Zirconia containing zirconium and one or more other elements selected from groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII of the Periodic system of the elements or the lanthanides and actinides, and

C. drying and calcination of the extrudate Zirconia formed at the stage b,

characterized in that the fine zirconium dioxide containing not more than 15 wt.% Zirconia, which is different than monoclinic Zirconia.

2. The method according to claim 1, in which one or more other elements selected from elements of group VIII of the Periodic system of elements.

3. Spasibo claim 2, in which one or more other elements selected from cobalt, iron and Nickel.

4. The method according to claim 3, in which one or more other elements are cobalt.

5. The method according to claim 4, in which the source of cobalt is selected from cobalt hydroxide, cobalt acetate, cobalt nitrate, cobalt oxide and mixtures thereof.

6. The method according to any one of claims 1 to 5, in which the very fine zirconium oxide contains not more than 10 wt.% Zirconia, which is different than monoclinic Zirconia.

7. The calcined extrudate Zirconia obtained by the method according to any one of claims 1 to 6.

8. The calcined extrudate Zirconia/cobalt, obtained by the method according to any of claims 4-6.

9. A method of obtaining a calcined extrudate Zirconia for use as a carrier or catalyst containing zirconium, which has been impregnated with one or more elements selected from groups IB, IIB, IIIB, IVB, VB, VIB, VIIB, and VIII of the Periodic system of the elements or the lanthanides and actinides, which includes the following stages:

a. obtain the form of paste by mixing and plastilinovaya fine zirconium dioxide with a solvent to obtain a mixture having a total solids content of from 50 to 85 wt.%,

b. extruding the form of the paste to form extrudate Zirconia,

c. por the tiles extrudate Zirconia connection with one or more other elements, selected from groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII of the Periodic system of the elements or the lanthanides and actinides, in the presence of a fluid with the formation of the extrudate Zirconia impregnated with one or more other elements selected from groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII of the Periodic system of the elements or the lanthanides and actinides, and

d. drying and calcination of the extrudate Zirconia formed on the stage,

characterized in that the fine zirconium dioxide containing not more than 15 wt.% Zirconia, which is different than monoclinic Zirconia.

10. The method according to claim 9, in which one or more other elements selected from elements of group VIII of the periodic system of elements.

11. The method according to claim 9 or 10, in which one or more other elements selected from cobalt, iron and Nickel.

12. The method according to claim 11, in which one or more other elements are cobalt.

13. The method according to item 12, in which the liquid cobalt precursor selected from aqueous cobalt salt selected from cobalt nitrate, cobalt acetate, cobalt hydroxide, and mixtures thereof.

14. The calcined extrudate Zirconia obtained by the method according to any of PP-13.

15. The calcined extrudate Zirconia impregnated with cobalt, obtained by the method according to item 12 or 13.

16. The method of obtaining high is their olefins, having from 11 to 14 carbon atoms, including the interaction of hydrogen and carbon monoxide in the reaction conditions of the Fischer-Tropsch process in the presence as catalyst calcined extrudate Zirconia/cobalt of claim 8 or calcined extrudate Zirconia impregnated with cobalt, item 15.



 

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2 cl, 1 tbl

FIELD: technological processes.

SUBSTANCE: subject of invention is method of catalytically active lamellar silicates production with single or multiple layers, in particular, clays with interlaminar struts from A1 and/or Ti, for purification of spent gases. At that at the stage of interlaminar struts formation, metal solution is added into lamellar silicate and the received mixture at the stage of drying/calcination is heated with formation of struts supporting intermediate layer out of metal atoms. After that catalytically active salt of transition metal is added in the dry form to the received dry substance. Finally the prepared dry mixture is heated up to the temperature of higher than 300°C, as a result catalytically active transition metal atoms are introduced into immediate layer, and at the same time dry mixture calcination takes place. As metal solution, solutions of aluminium, titanium, iron, copper and chrome are used. As catalytically active salt of metal, in particular, nitrate or sulphate of copper, titanium or lanthanum are used.

EFFECT: method allows to relatively quickly obtain catalytically active lamellar silicates without exhausts.

15 cl, 1 ex, 1 tbl, 1 dwg

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: method of improving selectivity of highly selective epoxidation catalyst on support containing silver in amount at most 0.19 g per 1 m2 of the support surface area comprises bringing catalyst or catalyst precursor containing silver in cationic form into contact with oxygen-containing raw material at catalyst temperature above 250°C over a period of time more than 150 h, after which catalyst temperature is lowered to at most 250°C. Olefin epoxidation process comprises bringing above-described supported catalyst or catalyst precursor into contact with oxygen-containing raw material at catalyst temperature above 250°C over a period of time more than 150 h, after which catalyst temperature is lowered to at most 250°C and catalyst is brought into contact with raw material containing olefin and oxygen.

EFFECT: increased selectivity of catalyst.

12 cl, 3 tbl, 12 ex

FIELD: carbon materials.

SUBSTANCE: invention relates to porous carbon materials and, more specifically, to carbon catalyst supports and sorbents. Preparation of catalyst support is accomplished by mixing carbon material with gaseous hydrocarbons at 750-1200°C until mass of carbon material increases by 2-2.5 times, after which resulting compacted material is oxidized, said initial carbon material being preliminarily demetallized carbon nanofibers.

EFFECT: increased sorption capacity of material.

1 tbl, 6 ex

FIELD: carbon materials.

SUBSTANCE: invention relates to porous carbon materials and, more specifically, to carbon catalyst supports and sorbents. Preparation of catalyst support is accomplished by treating carbon black with hydrocarbon gas at heating and stirring until mass of carbon material increases by 2-2.5 times, after which resulting compacted material is oxidized, said hydrocarbon gas being gas originated from liquid hydrocarbon electrocracking and said treatment being carried out at 400-650°C.

EFFECT: simplified technology.

1 tbl, 6 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: catalyst containing platinum, rhenium, antimony, and chlorine on alumina are prepared by impregnation of carrier with aqueous solution of compounds of indicated elements, antimony being deposited as first or second component. Once antimony or platinum-antimony combination, or rhenium-antimony combination deposited, catalyst is dried at 130°C and then calcined in air flow at 500°C. Reduction of catalyst is performed at 300-600°C and pressure 0.1-4.0 MPa for 4 to 49 h. After deposition of antimony or two elements (platinum-antimony or rhenium-antimony) and drying-calcination procedures, second and third or only third element are deposited followed by drying and calcination. Final reduction of catalyst is accomplished in pilot plant reactor within circulating hydrogen medium at pressure 0.3-4.0 MPa and temperature up to 600°C for a period of time 12 to 48 h.

EFFECT: enhanced aromatization and isomerization activities of catalyst and also its stability.

2 cl, 1 tbl, 8 ex

FIELD: exhaust gas afterburning means.

SUBSTANCE: invention relates to catalytic neutralizer for treating internal combustion engine exhausted gases. Proposed catalyst is composed of catalytically active coating on inert ceramic or metallic honeycomb structure, wherein coating contains at least one platinum group metal selected from series including platinum, palladium, rhodium, and iridium on fine-grain supporting oxide material, said supporting oxide material representing essentially nonporous silica-based material including aggregates of essentially spherical primary particles 7 to 60 nm in diameter, while pH of 4% water dispersion of indicated material is below 6.

EFFECT: increased catalyst activity and imparted sufficient resistance to aggressive sulfur-containing components.

27 cl, 2 dwg, 7 tbl, 6 ex

FIELD: petroleum processing and catalysts.

SUBSTANCE: invention relates to catalyst for steam cracking of hydrocarbons, which catalyst contains KMgPO4 as catalyst component. Catalyst is prepared by dissolving KMgPO4 precursor in water and impregnating a support with resulting aqueous solution of KMgPO4 precursor or mixing KMgPO4 powder or its precursor with a metal oxide followed by caking resulting mixture. Described is also a light olefin production involving steam cracking of hydrocarbons.

EFFECT: increased yield of olefins, reduced amount of coke deposited on catalyst, and stabilized catalyst activity.

21 cl, 4 tbl, 14 cl

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention provides copper and silica-based catalyst containing 22.5-53.0% copper. Catalyst is prepared by reductive thermal decomposition of copper silicate in hydrogen flow at 380-450°C. catalyst is used in dihydroxyalkane production processes carried out at 180-200°C.

EFFECT: increased activity and selectivity of catalyst.

3 cl, 1 tbl, 8 ex

FIELD: gas treatment processes and catalysts.

SUBSTANCE: invention relates to catalyst for selectively oxidizing hydrogen sulfide to sulfur in industrial gases containing 0.5-3.0 vol % hydrogen sulfide and can be used at enterprises of gas-processing, petrochemical, and other industrial fields, in particular to treat Claus process emission gases, low sulfur natural and associated gases, chemical and associated petroleum gases, and chemical plant outbursts. Catalyst for selective oxidation of hydrogen sulfide into elementary sulfur comprises iron oxide and modifying agent, said modifying agent containing oxygen-containing phosphorus compounds. Catalyst is formed in heat treatment of α-iron oxide and orthophosphoric acid and is composed of F2O3, 83-89%, and P2O5, 11-17%. Catalyst preparation method comprises mixing oxygen-containing iron compounds with modifying agent compounds, extrusion, drying, and heat treatment. α-Iron oxide used as oxygen-containing iron compound is characterized by specific surface below 10 m2/g, while 95% of α-iron oxide have particle size less than 40 μm. Orthophosphoric acid is added to α-iron oxide, resulting mixture is stirred, dried, and subjected to treatment at 300-700°C. Hydrogen sulfide is selectively oxidized to elemental sulfur via passage of gas mixture over above-defined catalyst at 200-300°C followed by separation of resultant sulfur, O2/H2S ratio in oxidation process ranging from 0.6 to 1.0 and volume flow rate of gas mixture varying between 900 and 6000 h-1.

EFFECT: increased yield of elemental sulfur.

9 cl, 5 tbl, 9 ex

FIELD: technological processes; chemistry.

SUBSTANCE: method of composition preparation is described, which includes: (a) adulteration of the following: 1) liquid, 2) zinc-containing compound, 3) silica-containing material, 4) alumina and 5) promoter for preparation of its mixture; where specified liquid is selected from the group that consists of water, ethanol, acetone and combination of any two and more specified compounds, and where specified promoter contains metal selected from the group that contains nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony, vanadium, gold, platinum, ruthenium, iridium, chrome, palladium, titanium, zirconium, rhodium, rhenium, and also combination of any two or more of them; (b) drying of specified mixture for preparation of dried mixture; (c) baking of specified dried mixture for preparation of baked mixture; (d) reduction of specified baked mixture with suitable reducing agent under suitable conditions for preparation of composition that contains promoter with lower valency; and (e) regeneration of specified composition. Method of composition preparation (version) is also described, which includes introduction of two promoters, as well as compositions prepared by specified methods. Method of sulfur removal from carbohydrate flow is described, which includes the following: (a) contact of specified carbohydrate flow with composition that has been prepared by the method according to any of previous points, in desulfurisation zone under conditions, under which at least partially desulfurised carbohydrate flow and sulfurised composition are formed; (b) isolation of specified at least partially desulfurised carbohydrate flow from specified sulfurised composition with preparation of isolated desulfurised carbohydrate flow and isolated sulfurised composition; (c) regeneration of at least part of specified isolated sulfurised composition in zone of regeneration to remove at least part of sulfur contained in it and/or on it with preparation of regenerated composition; (d) reduction of specified regenerated composition in reduction zone to prepare reduced composition, which contains such amount of promoter with lower valency that influences sulfur removal from sulfur-containing carbohydrate flow during contact with it; (e) return of at least part of reduced composition to desulfurisation zone. Cracked gasoline or diesel fuel prepared as a result of above mentioned method application is described.

EFFECT: preparation of compositions with sufficient abrasion resistance.

18 cl, 3 tbl, 7 ex

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