Method of preparing mono- and bimetallic catalyst and processes involving oxygen and/or hydrogen

FIELD: reduction-oxidation catalysts.

SUBSTANCE: invention relates to mono- and bimetallic palladium and platinum catalysts if carbon carriers that can be used in processes involving oxygen and/or hydrogen. A method for preparing catalyst is described comprising pretreatment of carbon carrier in 3-15 M nitric acid at temperature not exceeding 80°C, impregnation of resulting carrier by nitric acid solutions of chloride-free compounds of palladium and/or platinum or palladium and at least one group I metal, drying at temperature up to 105°C, decomposition at 150-350°C, and reduction in hydrogen flow at 110-350°C. Specified preparation conditions allow one to obtain fine particles of platinum group metals 1-10 nm in size localized in pores 2-20 nm in size, concentrations of deposited palladium and/or platinum being 3 to 50 wt % or palladium and/or platinum and silver 0.1 to 1.4 wt %. Catalyst is suitable for use in processes of oxidation of alcohols into aldehydes and carboxylic acids; hydrogenation of olefin, acetylene, and diene bonds in aliphatic and carbocyclic compounds; hydrogenation of nitro compounds into amines or intermediate compounds; disproportionation of abietic and other resin acids contained in colophony and similar natural- or artificial-origin mixtures.

EFFECT: augmented assortment of redox catalysts and optimized methods of preparation thereof.

8 cl, 1 tbl, 34 ex

 

The invention relates to mono - and bimetallic palladium and platinum catalysts on carbon carriers and can be used in the chemical industry for carrying out processes involving oxygen and/or hydrogen.

In particular, the invention can be used in the chemical industry for more electrocatalysts, for example, for fuel cells, as well as for oxidation of hydrocarbons, for example, for the oxidation of aldehydes, primary and secondary alcohols. The invention can also be used in the chemical industry for hydrogenation, requiring the addition of a hydrogen on one or more unsaturated groups or fragments in the molecule organic compounds, for example for the hydrogenation of aliphatic or carbocyclic olefin, polyene, acetylene or arenovich compounds, mono - or polycyclic aromatic compounds, eminovic, nitro and carbonyl compounds. The invention can also be used in the chemical industry for carrying out processes of hydrogenation, which results in splitting of one or more carbon bonds, ties of carbon heteroatoms or relationships between heteroatoms, in particular for carrying out processes hydrodehalogenation, decarbonylation, decarboxylation, deb is milirovanie, get amines from nitro compounds or azo compounds. The invention can also be used in the chemical industry for carrying out processes of intra - and intermolecular redistribution of hydrogen, in particular for carrying out the process of disproportionation of resin acids in rosin and other natural compounds.

The invention is particularly suitable for use in the processes of oxidation, selective hydrogenation and transfer of hydrogen, requiring high dispersion of platinum and palladium. To an even greater extent the invention is suitable for use in the processes of oxidation and selective hydrogenations on highly dispersed catalysts with a high content of platinum and palladium in the catalyst or high concentrations of metal in the active layer of granules of the catalyst. The greatest advantage of using the invention can be obtained by carrying out high-temperature hydrogenation processes and transport of hydrogen in which the use of other palladium catalysts is accompanied by intensive sintering of palladium and resin formation, reducing the service life of the catalyst and reducing the quality of the product.

Known methods of preparation of palladium and platinum catalysts on carbon carriers [..Stiles. Catalyst Manufacture. Laboratory and Commercial preparations. N.Y.: Marcel Dekker, 1983; E.Auer, A.Freund, J.Pietsch, .Tacke. Carbons as supports for industrial precious metal catalysts, Appl. Catal A: General 173 (1998) 259-271]. The reference compound of palladium upon receipt of the catalyst are salts of this metal, and inorganic or organic acids, ORGANOMETALLIC compounds and complexes with organic ligands. The use of carboxylates, ORGANOMETALLIC compounds and metal complexes of palladium and platinum has the disadvantage that in this case we have to use non-aqueous solutions, which is economically disadvantageous; metalloorganicheskie derivatives are sensitive to oxygen, which leads to technological complications.

Typically, the catalysts containing palladium or platinum on a carbon carrier, obtained from the chloride of palladium or platinum. The application of chloride of palladium on carbon material from the acidic environment and recovery immediately after such application or after drying gives low activity catalysts and refers to the old practice. All other methods of preparing catalysts Pd/C palladium chloride based on the ability of these salts to hydrolysis in alkaline medium due to the easy formation of nuclei of a metal oxide and differ only by the nature of the alkaline agent, the methods of its introduction (in advance, after or simultaneously with palladium), the ratio between the alkali and palladium, the physical parameters of the process Hydra is Lisa, as well as the characteristics of the media [Adeben. Active carbon as a carrier. - Ch.5 in kN.: The media and supported catalysts. Theory and practice /Alvin B. Stiles: TRANS. from English./ Edited Ala. - M.: Chemistry, 1991]. For example, the claimed method of producing a catalyst for the hydrogenation of benzoic acid by carbon impregnation of the carrier with an aqueous solution paradichlorobenzene acid and sodium carbonate, recovering palladium formate, sodium, rinsing, and drying with subsequent impregnation with a solution of sodium carbonate and re-drying, characterized in that as the carrier using porous pyrocarbon, consisting of hollow globules the size of 50-500 nm with a specific surface area by BET 75-640 m2/g and an average interplanar distance 0,34-0,36 nm [SU 1270939, B01J 23/44, 20.07.97]; a method of producing a catalyst for hydrotreatment of terephthalic acid, characterized in that the carrier pretreated with 700-1200°With gaseous hydrocarbons to additional content pyrolytic carbon 3-50 wt.% [SU 1660282, B01J 37/03, 10.02.97]; a method of producing a catalyst for the hydrogenation of nitrobenzotrifluoride, characterized in that as the carbon media carbon material with the surface 120-660 m2/g, the volume of transient pores of 0.4-1.2 cm3/g, abrasion resistance 0,5-0,1%min, representing soot reinforced with pyrocarbon obtained by pyrolysis of gaseous hydrocarbons [SU 1188964, B01J 37/02, 20.07.97]; the preparation method of catalyst for the synthesis of 2,6-dimethylaniline, including pre-mixing an aqueous solution paradichlorobenzene acid concentration of 0.025-0.5 mol/l sodium carbonate solution of a concentration of 0.05-1.0 mol/l in a molar ratio of 1:(2-3), application of the mixture of the solution with pH=6,8-8,5 on a carbon carrier in the amount of 10-100% of the pore volume, hydrogen reduction, rinsing and drying, characterized in that the mixture of dispersed solutions in the presence of gaseous carbon dioxide and the application is carried out by passing the received aerosol through the moving layer of the device, which is a matrix formed by bent layers of carbon of a thickness of 10-1000 nm, the radius of curvature of 10-1000 nm, a true density of 1.8-2.1 g/cm3, x-ray density 2,11-2.24 g/cm3, the distribution of pore sizes, with a maximum in the area of 20-200 nm, and an additional maximum in the region of 1-20 nm; washing is carried out with distilled water in the presence of gaseous hydrogen and the process is conducted at a ratio of components responsible for the content of palladium in the catalyst 0,093 to 1.0 wt.% [SU 1713172, B01J 23/44, 27.09.95]. Known methods of preparing catalysts Pt/C which can be divided into two groups: 1) liquid-phase or gas-phase recovery inflicted H 2PtCl6, 2) deposition of platinum from a colloidal solution obtained from hexachloroplatinic acid in the presence of a reducing agent. The first method is applicable to media with a developed specific surface, and the second using graphite or soot with low specific surface. For example, there is a method of preparation of the catalyst oxidation phosphate glucose phosphate gluconic acid containing 5 wt.% Pt, including the adsorption of hexachloroplatinic acid with a concentration of 6.67 per cent of Pt(IV) on granular carbon media Norit ROX for 3 days and recovery formalin in alkaline medium (5M NaOH) at pH 12 [van Dam H.E., A.P.G. Kieboom, van Bekkum H. Appl. Catal., 1987, v.33(2), 361-372]. The claimed method of preparing a platinum catalyst on a carbon carrier for use as electrodes in fuel cells, which comprises mixing an aqueous solution of hexachloroplatinic acid with a concentration of from 5 to 100 g/l and dithionite sodium concentration from 10 to 100 g/l in the ratio from 2:1 to 1:5 at temperatures of from 20 to 80°adding hydrogen peroxide before or after the addition of dithionite sodium adsorption obtained colloidal platinum particles on the carbon soot [US 4136059, 23.01.1979]; the claimed catalyst for the synthesis of hydroxylamine containing dispersed metal platinum on carbon graphite-like nose of the body, formed by planar layers of carbon, characterized in that the catalyst contains media from the true density of 1.8-2.1 g/cm3and a pore volume of 0.2-1 cm3/g, in which layers of carbon Packed in the crystallites oriented in space in the form of a face of the polyhedron, and have the interplanar distance d002=0,340-0,350 nm, the average size of crystallite in the direction "a" La=4-18 nm, the average size of crystallite in the direction "C" Lc=3.5 to 14 nm [RF 2065326, B01J 23/42, 1996.08.20]. The method of preparation of the catalyst involves the deposition of metallic platinum on graphite-like carbon. For this to suspension media add a mixture of aqueous solutions of N2PtCl6(0.04 M), Na2CO3(1 M), NaOAc(1 M), Na2S2O4(0,02 M) and CH2O (10% aqueous solution), the mixture was incubated under stirring for 3 h and the temperature is 65°To receive the catalyst with a platinum content of 0.5 wt.%.

The disadvantage of the method of preparation of catalysts using palladium chloride or platinum is the low dispersion of the metal in the resulting catalysts, the difficulty of varying the thickness of the active layer, the necessity of very exact compliance with the terms of hydrolysis due to the sensitivity of this process to even small changes in conditions, and the need for long-term leaching of the catalyst from the CHL is reed-ions and disposal of large quantities of wastewater. In addition, it is known [US 3138560, 1967], which when added to the carbon holders of tetrachloropalladate sodium chloride or palladium most palladium immediately precipitates as a shiny film of metallic palladium, and the catalysts prepared in this way generally have a low activity.

When describing the methods of preparation of the catalysts Pd/C through alkaline hydrolysis sometimes point to the possibility of use as the source connection chloride, but other salts of palladium, in particular nitrate. From the chemistry of palladium is known that the rapid hydrolysis of its chloride and the possibility of obtaining dispersed oxide particles, and then the metal due to the ease of formation of nuclei of oxide phases in alkaline medium due to the ability of the chloride ions coordinated to two ions of palladium in the form of a bridging ligand, whereas the palladium nitrate only slowly hydrolyzed under the same conditions. Therefore, obtaining the same way and with the same characteristics of the catalyst of palladium nitrate is only possible with the introduction of additives chlorides of other elements.

The claimed catalyst [US 4791226, 13.12.1988] for the purification of terephthalic acid on active coal with a specific surface area of ≥600 m2/g, the palladium content <0.3 wt.% and the crystallite size of palladium <a 3.5 nm; the way of preparation this is about catalyst includes applying a salt of palladium, including nitrate, carbon media from the organic solvent and is based on the ability of the original palladium compounds to recover in these conditions to the metal in contact with the carbon surface. The disadvantage of this catalyst and method of its preparation is low palladium content and the necessity of using organic solvents.

Recently, platinum nitrate is widely used as bichloride of platinum precursor in the preparation of catalysts for purification of exhaust gases. For example, the famous platinum / rhodium catalyst for purification of automobile exhaust gases, the method of preparation of this catalyst includes nitrate impregnation of platinum and rhodium media with cellular structure containing oxides of aluminum and cerium, and calcining the sample at 500°C for 2 hours [D.Dou; D.J.Liu, W..Williamson, K.C.Kharas, H.J.Robota, Applied Catalysis B: Environmental 30 (2001), 11-24].

Closest to the claimed method is a method of preparation of the catalyst, including the application of palladium on granular carbon media, followed by drying, decomposition and reconstruction, characterized in that the deposition of palladium lead from aqueous palladium nitrate solution with a concentration of free nitric acid in a molar ratio to palladium(6:1)-(1:1), drying is carried out in t the ke of air at 110-130° With decomposition in a current of inert gas at 200 to 300°and recovery is carried out in hydrogen at 150-250°With original components take in quantities providing the palladium content in the finished catalyst of 1.5 to 2.5 wt.% [RF 2056939, B01/J23/44, 27.03.96]. The disadvantage of this method is that it is designed for a catalyst containing palladium, which is not optimal for most catalytic processes.

Known oxidation processes using palladium and platinum catalysts, including the oxidation of aldehydes, primary and secondary alcohols, in addition to platinum and palladium catalysts on carbon soot used in electrocatalysis in phosphoric acid fuel cell and membrane fuel cells proton exchange, where the anode is the oxidation of hydrogen or methane [R.L.Augustine. Heterogeneous Catalysis for the Synthetic Chemist.- NY: Marcel Dekker. 1996; E.Auer, A.Freund, J.Pietsch, T.Tacke, Appl. Catal. A: General 173 (1998) 259-271]. Known processes for the hydrogenation using palladium and platinum catalysts on carbon carriers, including hydrogenation with the accession of hydrogen on one or more relations or hydrogenation with splitting of one or more bonds in the molecule olefins, conjugated dienes, acetylene and other compounds with unsaturated hydrocarbon fragment, aromatic mono - and the police is symbolic connections, cyano-, nitro-, amino - and other nitrogen-containing compounds, chlorine-, bromine - and iododerma compounds, carbonyl, carboxyl and other compounds with unsaturated functional groups or having regard carbon heteroatoms [.Freifelder. Practical Catalytic Hydrogenation. NY: Wiley, 1971; P.N.Rylander. Hydrogenation methods.- London: Academic Press, 1985; R.L.Augustine. Heterogeneous Catalysis for the Synthetic Chemist. NY: Marcel Dekker, 1996]. There are also known processes of hydrogenation and disproportionation through intra - and intermolecular transfer of hydrogen using palladium catalysts [R.F. Heck, Palladium Reagents in Organic Synthesis. London: Acad. Press, 1985], including the process of disproportionation of mono - and polycyclic compounds containing olefin and diene fragments, for example, abietic and other resin acids in rosin [FR. 1425589, 1966; jap. 61-4779, 1986;. Poland 57930, 1969]. A method for the disproportionation of rosin [RF 2055848, 10.03.96] by step passing the molten resin through a catalytic system consisting of socialization - utverzhdennuyu dehydrated aluminium-containing additives in the amount of 3-10 wt.% acid-activated bentonite clay type with specific active surface 50-70 m2/g, calcined at 250-400°and the palladium catalyst is palladium charcoal in a ratio of 3:1; the method of obtaining disproportionating rosin [RF 2059680, 0.05.96] by step passing the molten resin through the catalytic system, including aluminosilicate catalyst with a specific active surface 50-70 m2/g utverzhdennuyu 1-5 wt.% aluminium-containing additive, with annealing at 400 to 450°dehydrated bentonite clay of the type promoted by silica with a specific active surface 120-300 m2/g in the amount of 1-5 wt.% on clay, and palladium charcoal in a ratio of 3:1; mode disproportionation of rosin and resin acids by heating them in the presence of a catalyst is palladium on a carbon carrier, wherein the catalyst used palladium on carbon-carbon composite with the interplanar distance d002of 0.34-0.35 nm and the size of microcrystallites La3,0-5,5 nm and Lc3,0-6,8 nm [RF 2081143, C09F 1/04, 1997]; obtaining legkoobratimy disproportionating rosin with low content of unsaponifiable substances by dissolving rosin and carrying out the reaction in solution using Pd/C catalyst at a temperature of <200°C [Tang Yaxian et al. Disproportionately rosin obtained in the process of dissolution. - Linchan huaxue yu gongye (Chem. and Ind. forest Prod.), 1996, 16, No.4, p.1-7, Rehim. 1998, P]. In industry the process of disproportionation of rosin lead in the melt on the catalyst PU (palladium charcoal) with a palladium content of 1.8-2.0 wt.%.

A disadvantage of the known processes involving oxygen and hydrogen is using palladium and platinum catalysts on carbon supports is low efficient use of the expensive component of the catalyst and low selectivity, due to sub-optimal content and condition of palladium and platinum in a known catalysts Pd/C and Pt/C and is associated with the disadvantages of the known methods of making such catalysts. A disadvantage of the known processes is the complexity of the technology, the use of solvent or hard conditions of the process, due to the need to reduce the disadvantages of the known catalysts Pd/C and Pt/C and methods of their production and raises the cost of the final product. A disadvantage of the known processes is the need to use for the same purpose of socializaton that increases the number of stages upon receipt of the catalyst, complicates the process of obtaining, increases the cost of the final product. A disadvantage of the known processes is also a difference in the used catalysts, due to differences in ways of compensating the disadvantages of the known catalysts for various processes and leads to the production of catalysts in small batches and different technological schemes instead of more cost-effective large-scale production.

In some works it is stated that the introduction of a second metal in the catalyst composition, for example metals of group VIII, as well as Ag, Au, Cu, Sn, Bi, Pb, Ti, Zr, Hg leads to improved catalytic efficiency of platinum or palladium. For example, in the reactions of oxide is Oia alcohols introduction tin or bismuth to platinum or palladium catalyst significantly reduces the rate of deactivation of the catalyst. The introduction of a second metal also leads to an increase in catalytic activity and in some cases, the selectivity of the oxidation reaction [R.L.Augustine. Heterogeneous Catalysis for the Synthetic Chemist. NY: Marcel Dekker, 1996; pp.559-569].

In the reaction of selective hydrogenation of acetylene addition to the palladium catalyst of the second metal, such as Ru, Ag, Au, Cu, Sn, Bi, Pb, Ti, Zr, Hg, increases the selectivity of the process by reducing the catalytic activity and, consequently, a better diffusion of the reactants to the active centers [R.L.Augustine. Heterogeneous Catalysis for the Synthetic Chemist. NY: Marcel Dekker, 1996; pp.387-401; E.A.Sales, R.C.Santos, S.B. de Olivera, L.B. de Olivera Santos. 'an. Assoc. Bras. Quim., 1997, # 46(2), pp.65-73]. The inventive method allows the preparation to obtain bimetallic catalysts with high efficiency in processes involving oxygen and/or hydrogen and organic substrates.

Described [RF 2056939, B01J 23/44, 27.03.96] the disproportionation of rosin on the catalyst containing 1.5 to 2.5 wt.% palladium particle size of 2.8 nm and the thickness of the active layer in the granule 10-50 μm and obtained by thermal decomposition of nitrate palladium on a carbon carrier Sibunit, which is produced by pyrolytic deposition of carbon soot technical and represents a three-dimensional matrix formed by layers of carbon with a thickness of 10-1000 nm, which preserves the structure of graphite with azimuthal destroy what stacia graphite grids, so the coherent scattering has a size of La, Lcabout 3.5 nm and the interplanar distance is d0020,345-0,355 nm, with a radius of curvature of the layers of 10-1000 nm, the true density of 1.80-2.1 g/cm3, x-ray density 2,112-2,236 g/cm3, a pore volume of 0.2-1.7 cm3/g, the pore sizes with a maximum in the area of 20-200 nm or two peaks in the area of 20-200 and 4-20 nm [US 4978649, 18.12.1990; Yu.I.Yermakov et al. New carbon material for catalysts. - React. Kinet. Catal. Lett., 1987, v.33, No.2, pp.435-440; E.M.Moroz et al. Structural and substructural parameters of carbon supports Sibunit and Altunit. - React. Kinet. Catal. Lett., 1992, v.47, No.2, pp.311-317]. The use of such a catalyst allows the process in less harsh conditions, without solvent, socializaton or the introduction of promoters, and the resulting product complies with pine rosin brands And the highest quality category by the intensity of staining and acid number, when the content of abietic acid, satisfying the accepted norms (<5%). Lack of processes using such catalyst is a restriction of intra - and intermolecular redistribution of hydrogen in the high-viscosity substrates, and the use of a catalyst containing palladium >2 wt.% does not provide higher performance (i.e. reduced utilization of active component), and the use of a catalyst containing palladium< 1.5 wt.% requires more time to achieve the same degree of conversion abietic acid (reduced performance).

The objective of the invention is to develop a high-tech method of producing mono - or bimetallic palladium and/or platinum catalyst on a carbon carrier, highly effective for use in processes involving oxygen and/or hydrogen, including those held in highly viscous environments and at high temperatures.

The problem is solved by obtaining mono - or bimetallic palladium and/or platinum catalyst on a carbon carrier by impregnation of a carbon carrier, pre-treated in an oxidizing atmosphere, the compounds of palladium and/or platinum or palladium and at least one of the metals of group I, while the media is pre-treated in nitric acid with a concentration of from 3 to 15 M at a temperature not exceeding 80°With an impregnating solution is prepared from nitric acid solutions bichloride compounds of palladium and/or platinum or palladium and at least one of the metals of group I, their drying and decomposition is carried out in a current of inert gas at a temperature not exceeding 105°and from 150 to 350°accordingly, the recovery is carried out in a stream of hydrogen at 150-350°under other conditions of application, drying, decomposition, reconstruction is possible and the ratio of initial components, providing the dispersed particles of platinum group metals with 1-10 nm in size, localized in the pores with a size of 2-20 nm, when the content of supported palladium and/or platinum from 3 to 50 wt.% or palladium and/or platinum and silver from 0.1 to 1.4%;

obtaining mono - or bimetallic palladium and/or platinum catalyst on a carbon carrier, obtained by thermal decomposition of hydrocarbons in the carbon black pellets with subsequent oxidative activation or without it, and consisting of a carbon material with a pore volume of 0.1 to 1.5 cm3/g formed by layers of carbon with a thickness of 10-1000 nm radius of curvature of 10-1000 nm, the true density by helium 1,80-2.1 g/cm3, x-ray density 2,112-2,236 g/cm3and distribution of pore sizes with highs in the field of 3-20 nm and 20-200 nm; or on a carbon carrier, obtained by the decomposition of methane or ethylene at temperatures from 600 to 700°With a catalyst containing deposited on the aluminum oxide of the metal Nickel and iron or copper, with a specific surface area by nitrogen adsorption of from 105 to 260 m2/g, the surface of mesopores from 95 to 240 m2/g, the volume of micropores from 0.01 to 0.02 cm3/g, a total pore volume from 0.31 to 0.4 cm3/g and an average pore diameter of from 6.2 to 17.5 nm.

the use of such a catalyst in processes involving oxygen, for which it is known that they are accelerated in the presence of palladium and platinum catalysts, in particular, in the selective oxidation of aldehydes to carboxylic acids, primary alcohols to aldehydes or carboxylic alcohols, secondary alcohols to ketones;

the use of such a catalyst in processes involving hydrogen, for which it is known that they are accelerated in the presence of palladium and platinum catalysts, in particular in the hydrogenation of organic compounds containing unsaturated C=C, C≡C, C=N, C≡N, N=O, C=O group or aromatic, conjugated dienes and other unsaturated fragments, for example, in the hydrogenation of olefinic bonds in aliphatic or carbocyclic compounds, the hydrogenation of acetylene and diene bonds in unsaturated aliphatic or carbocyclic hydrocarbons, in the selective hydrogenation of acetylene and diene compounds to monoenoic compounds in mixtures of acetylene and diene compounds with olefinic compounds, in particular, in the selective hydrogenation of acetylene in its mixture with ethylene or hydrogenation of abietic and other resin acids in rosin and similar mixtures of natural or synthetic origin;

the use of such a catalyst in hydrogenation processes occurring with splitting one or more of the existing in the molecule of the source of links connection, C-O, C-N, C-halogen, C-S, or N, for example in hidri the implement of nitro compounds to amines or intermediate products;

the use of such a catalyst in the processes of intra - and intermolecular hydrogen transport, in particular in the disproportionation abietic and other resin acids in rosin and similar mixtures of natural or synthetic origin.

The advantages of the proposed method for preparation of the catalyst over the known methods of obtaining mono - and bimetallic palladium and platinum catalysts on carbon carriers is achieved by the fact that it provides the required characteristics of the catalyst. While the inventive method allows the use of aqueous solutions, but excludes contamination of the catalyst of the chloride ions, without rinsing, enables the production of catalysts with different metal content, thickness of the active layer and other characteristics specified for them within the same technological scheme and with relatively simple hardware design process developments that, on the whole, minimizes energy costs, consumption of reagents used, the number and duration of individual stages of preparation and the amount to be disposed waste, thereby reducing the cost of catalyst and ensuring environmental cleanliness.

The advantages of the processes of oxidation, hydrogenation and transfer of hydrogen from teaching the events of the inventive catalyst are provided with high performance, selectivity and lifetime of the catalyst. The benefits from increased productivity of the catalyst is achieved by the fact that the process can be conducted in less severe conditions, and/or at lower catalyst loading, and/or increasing the feed rate of raw materials; the benefits from the increased selectivity of the catalyst is achieved by the fact that increases the yield of the target product and its quality and product can be used without additional purification; to benefit from a more stable operation of the catalyst is achieved by the fact that costs are reduced catalyst and restart, and continuous process can be replaced on a periodic, carrying out the process as the need for this product. The use of the catalyst does not require changes to the hardware design of these processes and changes in other conditions of their implementation, but allows such changes to obtain additional benefits from the use of the inventive catalyst in comparison with the processes known catalysts. The use of the catalyst also allows you to refuse the introduction of the promoters, but allows such an introduction to the catalyst or the raw material for additional benefits.

The metal content, the size of its particles and characteristics of selected media such to provide the catalyst nightclub is of use in any process involving oxygen and hydrogen. The optimal values of these parameters are determined for each specific process and conditions of its carrying out. Catalysts with a metal content up to 50 wt.% can be used for cooking fuel cells. Catalysts with a metal content up to 10 wt.% may be required for the oxidation and hydrogenation of substrates with very low reactivity and, if necessary, to obtain large quantities of the product with the use of small reactors. For use in most other processes benefits will be the catalyst metal content ≤4 and even ≤1.5 wt.%, because with decreasing metal content easier to provide the desired dispersion of the metal and decreases the role of diffusion factor, which increases the degree of utilization of the applied component. Catalysts with a metal content of about 0.2 wt.% may be required for processes with high speed and which is the problem of a sharp decrease in selectivity when reaching the conversion of the substrate, close to 100%. At low metal content of the catalyst is more sensitive to poisoning by impurities in the media, or served raw in most cases, it is advantageous to use catalysts containing metal ≥0.5 and even ≥1 wt.%.

Reducing the particle size of palladium and platinum catalysis is the PRS aims to increase the proportion of the productive working of metal atoms, which are the atoms on the surface of the metal crystallites (the atoms in the volume of the crystallites are not available for organic compounds and the proportion of these atoms increases with increasing particle size). The upper limit in size (10 nm) is determined by the capabilities of the method of preparation of the catalyst at the stated metal content. The lower limit in size (1 nm) is determined by the fact that smaller particles of palladium and platinum are not sufficiently strong bond with the surface of the carrier.

A strong bond with the carbon surface is necessary to make the particles resistance to sintering during the catalytic process and provides oxidative processing of carrier and method of preparation of the catalyst through thermal decomposition and reduction of nitrate, palladium and/or platinum. Additional stabilization is provided used by the media - due to the localization of the particle in its pores. The pore size, which should contain the media is determined to preserve the availability of the metal particles to molecules of organic compounds and at the same time achieved a significant stabilizing effect then compared with the localization of metal particles on a smooth surface. Optimal is the excess pore size 2-4 times compared with the size of the metal particles, the more higher of these values (4) for small particles and the lowest (2) for large particles.

A change of the mass media in the process of preparation of the catalyst caused by oxidation of its surface under the action of nitric acid, as well as reactions in the surface layer when interacting with particles of palladium and/or platinum in the process of thermal decomposition of metal nitrate and subsequent recovery. The reactions to a limited degree provides palladium and platinum is a stronger link with the media and gives the metal particles to the desired stability to the sintering. The use of media for which the weight change exceeds the specified limits, indicates instability of the carrier to thermal, oxidative and reductive treatments and causes deterioration of the properties of the catalyst.

The carrier obtained by thermal decomposition of hydrocarbons in the carbon black pellets with subsequent oxidative activation or without it, and the carrier obtained by the catalytic decomposition of methane or ethylene, satisfies the conditions specified in the porous structure and stability and, in addition, is characterized by a low content of impurities (ash content less than 1-2 wt.%) and high resistance to mechanical stress (abrasion resistance of 0.1-0.5 %/min), allowing you to further improve the properties of the catalyst.

Before using the carbon media can be subjected to the additional processing to improve its quality, for example, the oxidizing processing gas or liquid reagents for the development of functional cover surface, the recovery processing for the removal of surface functional groups, heat treatment for increasing the degree of crystallinity, washing to remove impurities, hydrothermal treatment in the presence of suitable reagents for removing pulverized carbon particles and loose fragments of carbon from the external surface of the granules, as well as other treatments. It was found that the best catalysts are obtained if the carrier is pre-treated in nitric acid.

Obtaining catalyst includes applying a nitrate, palladium and/or platinum, palladium and silver on carbon carrier, followed by drying, decomposition and reconstruction, because the positive effect is achieved by the combination of these techniques.

Using as a starting compound nitrate, palladium and/or platinum due to its advantages over other salts of palladium and platinum. Nitrates palladium and platinum has almost unlimited solubility in nitric acid solutions, which allows to obtain the catalyst even with a maximum content of palladium and/or platinum by a single impregnation of the carrier with a solution. The possibility of changes within wide limits to what ncentratio nitrate, palladium and platinum in the solution also allows you to easily vary the metal content in the catalyst and the thickness of the active layer in the granules by means of variation of the concentration and volume of the impregnating solution. Another advantage nitrate, palladium and platinum compared to other salts of palladium and platinum is that when you remove water from a carrier impregnated with a solution of nitrate of palladium and/or platinum, is volumetric filling of the pores of the support salt of palladium and/ or platinum and the particle size of the solid salt is equal to the size of the pores in which localized particles. Decomposition to oxide is a natural reduction of the volume of particles; further reducing the size of particles deposited phase occurs when the recovery of oxide to metal. The desired ratio between the particle size of palladium and/or platinum and pore size is determined by the ratio between the molar volumes of the solid nitrate of palladium and/or platinum and metallic palladium and/or platinum. Finally, when applying, drying, and especially when thermal decomposition of the nitrates of palladium and/or platinum, due to the redox interaction between the carbon carrier and applied component, the formation of bonds between atoms of the metal and the carbon surface, which ensures the stability of the metal particles to sintering at high temperature.

Application of palladium and/or platinum, palladium and silver lead from aqueous solutions, since in this case there is the possibility of creating enough you the Oka concentration of palladium and/or platinum, palladium and silver in the solution, and the process of application is the most cheap and simple technological design. Application lead by known methods, for example by irrigation medium, placed in a rotating tank, before filling solution 5-100% of the volume of internal pores of the support. Typically, the impregnation solution contains free nitric acid, which is associated with an excess of nitric acid upon receipt impregnating solution by nitric acid treatment of metallic palladium and platinum hydroxide. The final concentration of nitric acid in the impregnating solution is selected depending on the desired characteristics for the resulting catalyst, but such as to prevent the formation of the products of hydrolysis in solution and uncontrolled (spontaneous) recovery of nitrates of the metal upon contact of the solution with the carbon surface with the formation of coarse crystallites. Bimetallic catalysts prepared joint or sequential deposition precursors of metals.

Pre-drying of the sample with the applied compound of palladium and/or platinum, palladium and silver is held to be fixed to the surface of the carrier fine particles of metal salt and thereby provide easy control for the subsequent thermal decomposition of this salt. In the presence in the water of the salt particles retain mobility and thermolysis is the preferential growth of large particles formed of a metal oxide, what causes low dispersion of the catalyst. To accelerate the drying process should be carried out at elevated temperature, when the temperature at the end of the process above the boiling point of water.

The decomposition of the metal nitrate before recovery is necessary in order to exclude the formation of volatile hydride complexes of emmakate palladium and/or platinum. They are formed in the presence of hydrogen due to the recovery of the emitted nitrogen oxides and autocatalytic decompose on the previously formed metal particles; as a result of intensive growth of crystallites loss of dispersion of the metal and the performance of the catalyst. To reduce the duration of the decomposition process the catalyst is heated to 150°C, the upper limit on temperature is due to the need to preserve the metal oxide in a sufficiently dispersed state.

The upper boundary of the temperature recovery of the catalyst is determined by the need to limit the sintering of the metal during recovery, the lower the need to ensure complete recovery. Typically, the final temperature recovery should not be less than the temperature at which the catalyst will be used in the catalytic process.

Additional practices that contribute to making the catalyst required features : the tick size of the particles of palladium and platinum, the extent of their interaction with the carbon surface and the distribution of the granule, a well-known professionals in the field of preparation of supported catalysts and, inter alia, include the variation of the volume of the impregnating solution with respect to the pore volume of the carrier, varying the initial concentration of salt in the solution and its pH, solution temperature, and then impregnate the carrier, the duration of the impregnation stage, the speed of temperature rise during drying, thermolysis and recovery, flow rate, displacing the inert gas during drying and thermolysis, and the variation of the recovery mode by holding recovery evenly throughout the volume of the catalyst or in layers, the motion of the front recovery top or from the bottom of the column or alternately, when using pure hydrogen or a mixture of inert gas, when the recovery in static conditions or in a stream of hydrogen with different feed rate, and also when restoring applied component with varying degrees of thermal decomposition. In this case, specific values of the parameters declared as distinctive for each of the stages of preparation of the catalyst, and other conditions for this stage will depend on the terms of the conduct of the remaining stages.

The invention is illustrated by the following examples.

The following examples 1-34 characterize the catalyst, process for its production and processes. The data from examples 1-14 are summarized in the table and show that the distinguishing features of the proposed method provide the catalyst required characteristics according to the content of palladium and/or platinum, palladium and silver, the size of the metal particles. Example 15 shows that with the use of chloride of platinum precursor are less dispersed catalysts, in addition, the use of chloride predecessor of the second metal upon receipt of bimetallic catalysts (example 16), as well as the production of carbon deposited catalyst in which the catalyst is exposed to solutions containing chloride ions (example 17), gives a catalyst with a substantially different condition of palladium. Examples 18 and 19 show that nitrate production method of catalyst will ensure the required stability of the particles of palladium and media. Example 20 are shown for comparison and to show the specificity of the proposed method is that the decomposition of the nitrate, palladium oxide on the carrier gives a catalyst with a substantially different condition of palladium. Example 21 describes the oxidation process using the inventive catalyst, and examples 22-26 characterize the most common processes of hydrogenation and carrying the CA hydrogen. While the examples 22-24 belong to rapidly proceeding reactions in the gas phase, example 25 fast reaction in a three phase system. Examples 26, 29, 30 describe respectively the processes hydrogenolysis and disproportionation, which require a high temperature and for which the performance problem, selectivity, durability of the catalyst and product quality is particularly acute, and the benefits from the use of the inventive catalyst manifested to the greatest degree. The final examples 27-34 characterize in more detail one of these high-temperature processes. While examples 27, 28 are given for prototype and examples 31 and 33 for comparison with a process that uses a catalyst derived from palladium chloride and industrial catalyst PU.

In examples 1-10, 16-18 the claimed catalyst was prepared on a carbon carrier Sibunit with a grain size of 1.5-3.2 mm, specific surface area by nitrogen adsorption 410 m2/g, a bulk density of 0.57 kg/DM3with the total volume of the pore capacity of 0.65 cm3/g, predominant pore size of 3-15 nm, ash content of 0.3 wt.%, the abrasion resistance <0,1 %/min In examples 11, 12 catalyst was prepared in the carbon nanofibers obtained by the decomposition of methane at 625°With a catalyst containing, wt.%: 65 Ni, 25 Cu and 10 Al2About3with the specific surface and the sorption of nitrogen 105 m 2/g, total pore capacity 0,31 cm3/g and an average pore diameter of 11.9 nm, in examples 13-15, the catalyst was prepared in the carbon nanofibers obtained by the decomposition of methane at 625°With a catalyst containing, wt.%: 65 Ni, 25 Cu and 10 Al2O3, with a specific surface area by nitrogen adsorption of 260 m2/g, total pore capacity of 0.4 cm3/g and an average pore diameter of 6.2 nm.

The dispersion of palladium and/or platinum was determined by chemisorption WITH the pulse method and the stoichiometry of the adsorption of CO/Pt, Pd, is equal to 1/1. The particle size of the metal D is calculated from the dispersion d according to the formula: D (nm)=108/d (%); to test was used electron microscopy. Data on the distribution of the pore sizes obtained from the adsorption isotherms of nitrogen at 77 K.

Example 1. The dissolution of metallic palladium in concentrated nitric acid under heating and subsequent dilution with distilled water to a volume required, prepare a solution of palladium nitrate with a concentration of palladium 160 g/l and the concentration of free nitric acid and 210 g/l 40 ml of the prepared solution is applied to conventional irrigation on 100 g of granulated carbon media, placed in a cylindrical container, rotated enough for adequate mixing of the medium speed. The sample coated with palladium nitrate placed the Ute in a tubular reactor, give a weak stream of nitrogen (30 h-1) and increasing temperature for 2 h to 105°To provide for the removal of water and nitric acid. After drying, the overall temperature for 2 h up to 220°and left at this temperature for another 1 h after completion of thermal decomposition of deposited palladium nitrate sample is cooled to 125°and serves a mixture of nitrogen and hydrogen in a ratio of 4/1 with a bulk velocity of 25 h-1; after 1 h gradually stop the supply of inert gas and continue the recovery current of pure hydrogen with increasing temperature up to 150°C. Upon completion of the restoration of the cooled catalyst to room temperature through the cooling process, the displacement of hydrogen in nitrogen. Get the catalyst with a palladium content of 6.0 wt.%. About 1 g of the obtained catalyst is subjected to crushing in a mortar and investigate the dispersion of palladium chemisorption method, selecting the samples, 50 mg; the results show that the dispersion of palladium is within 44-48%, which corresponds to the average size of the palladium particles is 2.5 to 2.2 nm. One of the samples of crushed catalyst was examined using transmission electron microscopy results show that the palladium particles have uniform size distribution in the region of 1-5 nm, with a maximum at 2.8 nm.

Example 2. 2.5 ml of a solution of nitrate of Pallady the concentration of palladium 80 g/l and the concentration of free nitric acid 150 g/l put in a stream of air through a special nozzle, providing solution in aerosol form, per 100 g of granular carbon media, placed in a closed rotating cylindrical container. After application of the palladium sample is unloaded in the pan, the pan is placed over the heater and dry the sample in a stream of argon at 40-60°C. Dried to constant mass of the sample is placed in a tubular reactor and carry out thermal decomposition of palladium nitrate in a weak current of argon (5 h-1), raising temperature for 3 h before 215°C. the Sample is cooled to 130°and from the top of the reactor served undiluted hydrogen with a bulk velocity 5 h-1to stop the rapid absorption of a reducing gas, controlling the recovery process according to a flow rate of gas at the outlet of the reactor. At the end of the recovery raise the temperature to 170°C, kept at this temperature for 1 h, cooled catalyst and replacing hydrogen with argon. Get the catalyst with a palladium content of 0.2 wt.% and dispersion of palladium 25-30% (particle size of palladium from 4.3 to 3.6 nm).

Example 3. Adding with stirring the alkaline solution of sodium formiate the hot solution paradichlorobenzene acid get suspended metal mobiles. Svezheosazhdennoi mobile palladium washed with distilled water to a reaction of the chloride ions and dissolved in koncentrirane the Noah nitric acid, followed by dilution with water to obtain a solution of palladium nitrate with a concentration of palladium 222 g/l and the concentration of free nitric acid 75 g/L. 50 ml of this solution is applied in small portions to 100 g mixed media, after which the sample nanesennom palladium nitrate is dried in a stream of nitrogen while gradually raising the temperature to 105°and then subjected to thermal decomposition in a stream of nitrogen (10 h-1), raising temperature for 2 h to 200°With eye-catching and absorbing the nitrogen oxides by passing the gas mixture through the alkaline solution. Upon completion of thermal decomposition of deposited palladium nitrate sample is cooled to 140°To increase the supply of inert gas to 10 h-1and add in a current of inert gas, hydrogen, with a gradual increase in the rate of gas supply reductant to 10 h-1. At the end of the restore spend processing catalyst sequentially in a stream of pure hydrogen at 160°and in a current of pure nitrogen, then cooled catalyst. Get the catalyst with a palladium content of 9.9 wt.% and dispersion of palladium 33-36% (particle size of palladium 3,3-3,0 nm).

Example 4. 31 ml of palladium nitrate solution with a concentration of palladium 135 g/l and the concentration of free nitric acid 96 g/l put in the usual irrigation on 100 g mixed by rotation of a cylindrical tank carrier, the sample is coated with a palladium nitrate is placed in a tubular reactor and subjected to sample drying and thermal decomposition in a stream of nitrogen (10 h-1) and increasing temperature for 1 h -1up to 90°and then for 1 h to 105°and for 2 h to 190°C. After cooling the catalyst to 125°and give the mixture of nitrogen and hydrogen in a ratio of 1/1 at a volumetric feed rate 25 h-1. The recovery process is controlled by varying the speed of the gas mixture at the outlet of the reactor and the temperature in the catalyst layers. Upon completion of the fast hydrogen absorption increases the temperature up to 200°C for 1 h and cooled catalyst in a stream of nitrogen. Get the catalyst with a palladium content of 4 wt.% and dispersion of palladium on the results of chemisorption measurements 41-48% (particle size of palladium 2,6-2,2 nm). 1 g of the obtained catalyst was additionally examined by x-ray method; the results show that regenerate reflexes are present only from the carrier and deposited palladium is x-ray amorphous (particle size metal <3 nm).

Examples 5-7. The catalyst is prepared similarly as described in examples 1-4, when the variation of the volume of the impregnating solution (Vp-p), the concentration of palladium [Pd], and nitric acid [AK], the conditions of drying, thermal decomposition and recovery. Distinctive features of conditions and the obtained catalysts shown in the table.

Example 8. 2.4 ml of palladium nitrate solution with a concentration of palladium 25 g/l and the concentration of free nitric acid 67 is/l put in the usual irrigation 24 g mix by rotation of a cylindrical tank media the sample coated with palladium nitrate is placed in a tubular reactor and subjected to sample drying and thermal decomposition in a stream of helium (9 h-1) with increasing temperature for 0.5 h up to 90°and then for 1 h to 200°C. After cooling the catalyst to 110°and restore if space velocity 20 h-1at 110°C for 1 h and at 150°C for 0.5 hours, the recovery Process is controlled by varying the speed of the gas mixture at the outlet of the reactor and the temperature in the catalyst layers. Get the catalyst with a palladium content of 0.24 wt.% and dispersion of palladium on the results of chemisorption measurements 41-43% (particle size of palladium 2,6-2.5 nm).

Example 9. 2.4 ml of palladium nitrate solution with a concentration of palladium 25 g/l with a concentration of free nitric acid 52 g/l and 2.4 ml of silver nitrate solution with a concentration of silver 25 g/l with a concentration of free nitric acid 107 g/l put in the usual irrigation 24 g mix by rotation of a cylindrical tank carrier, the sample is coated with a palladium nitrate is placed in a tubular reactor and subjected to sample drying and thermal decomposition in a stream of helium (17 h-1) with increasing temperature for 0.5 h up to 90°and then for 1 h to 200°C. After cooling the catalyst to 110°and restore if space velocity 19 h-1 at 110°C for 1 h and at 150°C for 0.5 hours, the recovery Process is controlled by varying the speed of the gas mixture at the outlet of the reactor and the temperature in the catalyst layers. Get the catalyst with a palladium content of 0.24 wt.% and 0.25 wt.% silver dispersion of palladium on the results of chemisorption measurements 25-30% (particle size of palladium from 4.3 to 3.6 nm).

Example 10. of 9.4 ml of prepared solution of palladium nitrate with a concentration of palladium 109 g/l and the concentration of free nitric acid and 157 g/l put in the usual irrigation 24.6 g of granulated carbon media, placed in a cylindrical container, rotated enough for adequate mixing of the medium speed. The sample coated with palladium nitrate is placed in a tubular reactor, giving a current of helium (16 h-1and temperature for 0.5 h up to 90°To provide for the removal of water and nitric acid. Upon completion of the drying raise the temperature of 0.7 h to 200°and left at this temperature for another 2 hours Upon completion of thermal decomposition of deposited palladium nitrate sample is cooled to 110°and serves a mixture of hydrogen and helium in the ratio of 2/1 with a bulk velocity of 45 h-1and restore the catalyst during the 1 o'clock to Receive the catalyst with a palladium content of 4.0 wt.% and dispersion of palladium 38% (particle size PL is Tina 3,0-2,7 nm).

Example. 11. The dissolution of H2[Pt(OH)6] in concentrated nitric acid under heating to prepare a solution of platinum nitrate with a concentration of platinum 228 g/l and the concentration of free nitric acid 1100 g/l to 5.1 ml of the prepared solution is applied to conventional irrigation on 10 g of a carbon carrier, placed in a rotating cylindrical container. The sample was processed in a stream of helium (900 h-1) at step heating is maintained at 90°C for 30 min, then heated to 200°C and maintained at this temperature for 1 h, the Sample restore in a stream of hydrogen (3000 h-1) at 250°C for 1 h to Receive the catalyst with a platinum content of 10 wt.% and dispersion of platinum 18% (particle size of platinum 6,3-5,9 nm).

Example 12 (for comparison with oxidized media). The dissolution of H2[Pt(OH)6] in concentrated nitric acid under heating to prepare a solution of platinum nitrate with a concentration of platinum 228 g/l and the concentration of free nitric acid 1100 g/l 5,1 ml of the prepared solution is applied to conventional irrigation on 10 g of carbon media, pre-processed in 15 BC, HNO3(1 g media/10 ml HNO3) at room temperature for 2 h and at 80°C for 2 h and air-dried for 2 days. The sample was processed in a stream of helium (300 h-1) with openatom the heating is maintained at 90° C for 30 min, then heated to 200°C and maintained at this temperature for 1 h, the Sample restore in a stream of hydrogen (3000 h-1) at 250°C for 1 h to Receive the catalyst with a platinum content of 10 wt.% and dispersion of platinum 33% (particle size of platinum 3,5-3,1 nm).

Example 13. The dissolution of H2[Pt(OH)6] in concentrated nitric acid under heating to prepare a solution of platinum nitrate with a concentration of platinum 202 g/l and the concentration of free nitric acid 1120 g/l 5.5 ml of the prepared solution is applied to conventional irrigation on 10 g of a carbon carrier, placed in a rotating cylindrical container. Before applying the active component, the carrier was washed from the metal particles by boiling in 2 M HCl solution, then a large amount of hot water to pH˜5. The sample was processed in a stream of helium (900 h-1) at step heating is maintained at 90°C for 30 min, then heated to 250°C and maintained at this temperature for 1 h, the Sample restore in a stream of hydrogen (3000 h-1) at step heating at 150°C for 1 h and at 250°C for 1 h to Receive the catalyst with a platinum content of 10 wt.% and dispersion of platinum 46% (particle size of platinum 2.4-2.0 nm).

Example 14. The dissolution of H2[Pt(OH)6] in concentrated nitric acid at Naga is evanie prepare a solution of platinum nitrate with a concentration of platinum 526 g/l and the concentration of free nitric acid 540 g/L. 2.7 ml of the prepared solution is applied irrigation on 5 g of the catalyst prepared according to example 13 and placed in a rotating cylindrical container. The sample was processed in a stream of helium (900 h-1) at step heating is maintained at 90°C for 30 min, then heated to 250°C and maintained at this temperature for 1 h, the Sample restore in a stream of hydrogen (3000 h-1) at 150°C for 1 h and at 250°C for 1 h to Receive the catalyst with a platinum content of 30 wt.% and dispersion of platinum 27%. The catalyst was examined using transmission electron microscopy results show that the platinum particles have a uniform size distribution in the region of 2-5 nm, with a maximum of 3.7 nm.

Example 15 (for comparison with the chloride precursor). To 10 g of carbon media add 200 ml of water. To the resulting suspension media was added with stirring 102 ml H2PtCl6with the concentration of platinum 42 g/l After 1 h, add 132 ml of NaOH solution with a concentration of 40 g/l and heated to 70°C. the Suspension is maintained at this temperature for 2 h and added to 29.8 ml of 10%aqueous solution of sodium formiate and incubated for another 1 h, the Catalyst was washed thoroughly with hot distilled water until a negative reaction to chloride ions are filtered and dried at room is temperature. Get the catalyst with a platinum content of 30 wt.% and dispersion of platinum 15% (the average particle size of platinum 6,5-6,9 nm).

Example 16. 3.4 ml of the solution prepared hexachloroplatinate acid with the concentration of platinum 148 g/l put in the usual irrigation 24.4 g of the catalyst prepared according to example 10 and placed in a rotating container. The sample is placed in a tubular reactor, rinsed in a stream of helium (11 h-1) at 90°in the course of 0.7 hours

Restore the catalyst in a stream of hydrogen (20 h-1) at 200°C for 1 h to Receive the catalyst with a palladium content of 4.0 wt.% and platinum 2.0 wt.% and dispersion of metal 28% (the size of the platinum particles from 3.9 to 3.7 nm). According to electron microscopy, the number of large particles increases compared to the monometallic catalyst prepared according to example 10. The results show that the use of chloride of platinum precursor in the preparation of bimetallic catalyst causes agglomeration of the palladium particles even in pre recovered catalyst.

Example 17 (on the effect of the chloride ions). The catalyst derived from palladium nitrate in example 4 and containing x-ray amorphous palladium (particle size <3 nm) dispersion (dPd41-48%, impregnated with an aqueous solution of NaCl, at a molar ratio of NaCl/Pd=4, which corresponds to sootnoshenie settled between palladium and chloride ions, if the catalyst is prepared by the hydrolysis paradichlorobenzene acid. After impregnation the sample was heated to 90°C, washed with 2 days of water for chloride ions and restore again at 200°C. After such treatments dispersion of palladium in the catalyst dPdfalls to 25-29%, and on the radiograph appears reflex from large palladium particles larger than 10 nm (calculated from the half width of the corresponding peak). The results show that treatment with solutions containing chloride ions, causing the agglomeration of the palladium particles even in pre recovered catalyst and initially strong ties particles of palladium with a surface of the carrier.

Example 18 (resistance to sintering). The catalyst obtained in example 6 and having the average dispersion of the palladium 75%, is subjected to additional treatment in hydrogen at 200°and then at 250°C. Processing at 200°accompanied by a slight decrease in the dispersion of palladium to 68%, while the processing at 250°C to 59% (average particle size of palladium is changed from 1.45 nm to 1.6 and 1.8 nm).

Example 19 (on the stability of the carrier). to 25.0 g of carbon media Sibunit used in examples 1-7, is subjected to treatment in the conditions of example 6, which used the solution with the highest concentration of nitric acid, but without palladium nitrate. On soversheni the all treatments of the mass media is 25.3 g (weight increase of 1.2% compared to the original).

Example 20 (for comparison with the oxide carrier. The catalyst was prepared as in example 7 from the table, but as media use silica with a specific surface area of 230 m2/g and a pore volume of 1.0 cm3/, Get the catalyst with a palladium content of 1.4 wt.% and dispersion of 8% (the average particle size of >13 nm).

Example 21. 0.12 g of the catalyst obtained in the conditions of example 13 and 100 ml of an aqueous glucose solution containing 16 g of glucose, are placed in a reactor with a volume of 250 ml, equipped with a thermometer, a pH electrode, a device for supplying oxygen and a bubbler. The oxidation is carried out at atmospheric pressure, 50°C and pH 10. The resulting acid is neutralized with 10% NaOH solution. During the reaction take samples, the solution is filtered, and then analyzed by ion chromatography. Conversion after 120 min of reaction is 62%, the selectivity of 90% and an activity of 400 g of gluconic acid per g of Pt per hour.

Example 22. 5 g of the catalyst obtained in the conditions of example 5 from table and containing 1 wt.% palladium is placed in a cylindrical reactor, rinsed with an inert gas and without heating to give a current of hydrogen mixed with 1 vol.% hexene-1. Chromatographic analysis of the gas mixture after exiting the reactor shows a 99.9% conversion of the initial olefin, when its turning on 93% in hexane and 7% in the mixture of CIS - and TRANS-hexene with internal C=C of the link is I.

Example 23. 200 mg of the catalyst obtained in the conditions of example 8 containing 0.24 wt.% palladium is placed in a static reactor circulating installation volume of 0.7 l, recover the in situ hydrogen at 325°C for 0.5 h and rinsed initial reaction mixture containing 1.4% of acetylene, 67.7% of ethylene, 11.8% of hydrogen and 19.1% argon. The reaction is carried out at a temperature of 20°C, the pressure of 0.45 MPa and speed of circulation ˜40 ml/sec. Changes in the concentration during the reaction is monitored chromatographically. Analysis of the mixture after 13 min shows that the catalyst provides >99% conversion of acetylene. The catalyst activity is 4.7·10-3mol/l min g Pd, the selectivity of 54%.

Example 24. Acetylene hydrogenation catalyst obtained in example 9 and containing 0.24 wt.% palladium and 0.25 wt.% silver, carried out at the same catalyst loading, the same raw materials and in the same reactor as example 23. The catalyst activity was 1.1·10-3mol/l min g Pd, selectivity for acetylene 70%. Analysis of the mixture through 29 min shows that the catalyst provides >99% conversion of acetylene. Comparison with example 23 shows that the introduction of silver, it is possible to increase the selectivity of the hydrogenation of acetylene.

Example 25. 10 g of the catalyst obtained in the conditions of example 7 from the table and containing 1.4 wt.% palladium is placed in Qili the shape of the reactor, purge with an inert gas, restore in hydrogen and 95°served With controlled irrigation nitrobenzene in a stream of hydrogen. Chromatographic analysis of the liquid products at the exit of the reactor shows complete conversion of the nitrobenzene, when selectivity anilino >98%.

Example 26. 1 g of the catalyst prepared according to example 7 of table and containing 1.4 wt.% palladium is loaded into a tubular reactor. Purge the system with nitrogen, then with hydrogen. In control panel, set the temperature to 250°and include the heating of the reactor. When reaching into the reactor set temperature start supply of furfural with speed 0,086 cm3/min) at a molar ratio of furfural and hydrogen 1.0:0.7 to. The duration of the experiment is 6 hours with gazohromatograficheskim analysis of products in 1 hour. For 6 hours of average catalyst conversion to furfural is 64%, with a relative yield of furan 69%.

Example 27 (prototype, example 1 in the description of the patent of the Russian Federation 2056939). In the rotating drum is placed 50 g of granulated carbon media, in which the free pore volume is 0.7 cm3/g and more than 95% of the pores have a size less than 10 nm and the distribution curve of the pore size according to the adsorption data (1A) has a sharp maximum at 4-5 nm. When spin is applied by irrigation 22 ml nor the rata palladium concentration of palladium of 46.4 g/l and the concentration of free nitric acid, 106 g/l (molar ratio Pd/nitric acid = 1:3,8). The sample coated with palladium nitrate is placed in a tubular reactor and dried in a stream of air at elevated temperature for 1 h to 120°and maintaining at this temperature for another 2 hours to Replace the air with nitrogen and increase the temperature to 250°C. At this temperature, carry out the decomposition in a stream of nitrogen for 5 h and cooled to 120°C. Replace the nitrogen to hydrogen and regenerate the catalyst at 150°C for 2 hours Displace at 120°With hydrogen, nitrogen, cool the catalyst in a stream of nitrogen up to 40°C. Obtain a catalyst with a palladium content of 2.0 wt.%. With 95% of palladium particles have a size of from 2 to 8 nm (data transmission electron microscopy). 1.5 g of the obtained catalyst is placed in a slowly rotating holder and stand under an inert atmosphere at 195-200°C for a certain time in the melt resinous pine rosin with the original content of abietic acid 53%. The catalyst provides a reduction in the content of abietic acid in 1 HR to 16%, over 1.5 h to 10%, after 2 h up to 5%.

Example 28 (prototype, example 12 in the description of the patent of the Russian Federation 2056939). The holder is placed 1.5 g of the catalyst obtained as in example 27, but with a palladium content of 1 wt.%, the particle size of palladium 2-8 nm and the active layer thickness of 20 μm, and carry out the disproportionation of rosin in the same conditions. The content of the abietic acid is 20% after 1 h, 15% after 1.5 h and 8% after 2 hours

Example 29. Disproportionation of rosin is carried out in the same conditions, but with 1.5 g of the catalyst obtained in example 5 from the table and containing 1 wt.% palladium. The content of abietic acid after 1 h is reduced to 15% and after 2 h to 4.5%. Comparison with examples 27 and 28 shows that the catalyst obtained by the present method and containing 1 wt.% palladium, outperforms the catalyst with the same content of palladium received in the prototype, and provides a reduction in the content of abietic acid to the accepted norms for the same time as the catalysts obtained by the prototype and contains 2 times more palladium.

Example 30. Disproportionation of rosin is carried out in the same conditions, but when loading of 1.5 g of the catalyst obtained in example 4 and containing 4 wt.% palladium. The content of abietic acid is reduced to 9% after 1 h, up to 4% after 1.5 h and 3% after 2 hours Compared with example 29 shows that the proposed method can improve the performance of the catalyst by increasing the palladium content.

Example 31 (for comparison with the catalyst obtained through the hydrolysis of palladium chloride). The catalyst prepared according to example 7 of the table, but at 210-220°C, after which the granular catalyst is separated, add fresh rosin and repeat catalitic the ski test in the same conditions. Spend a few cycles with the replacement of the rosin and the duration of each cycle is 2 hours Upon completion of the first cycle of the residual content of abietic acid is 1.5%, after the fifth of 2.3%, after the 10th of 2.5%. At the same time preparing the catalyst on the same media, but through the hydrolysis of palladium chloride with sodium carbonate under the conditions of example 1 from [SU 1713172, 22.08.89], and test it by the same method. Upon completion of the first cycle of the residual content of abietic acid at 0.0%, after the fifth 1%, after the 10th of 2.5%. The example shows that the activity of the inventive catalyst in successive cycles does not significantly reduced, whereas the catalyst obtained from palladium chloride, rapidly loses activity.

Example 32. In the industrial reactor, used for the disproportionation of rosin, download 1.7 tons of catalyst containing 1.4 wt.% palladium and obtained analogously to example 7 from the table, but in batches of 200 kg, and carry out the disproportionation of rosin at 175-185°and a feed rate of the raw material of 0.6 h-1. In the first 1000 hours of operation, the catalyst provides a rosin, which does not require additional vacuum distillation and has an acid number 168-165 mg KOH/g at a residual content of abietic acid of 0.1-1.3 wt.%.

Example 33 (for comparison with the process on an industrial catalyst). Disproportion is of the rosin is carried out in industrial conditions on the catalyst PU with a palladium content of 1.8 wt.%, at the same catalyst loading, the same raw materials and in the same reactor as example 32. To meet product quality requirements, the process of disproportionation in this case, you have to spend at 230-260°and applying rosin <0.2 h-1; the active work of the catalyst does not exceed 800 hours, when the acid number of the product declining by the end of this period, from 160 to 153 mg KOH/g and the content of abietic acid, increasing from 2%to 5%.

Example 34. The disproportionation process described in example 32, continue over 3700 hours with a gradual temperature increase by the end of this period up to 215°to ensure that the residual content of abietic acid in the product at the same level; acid number remains at 163-165 mg KOH/g resin. After this time the reactor is transferred to the cyclic operation mode, with periodic output mode is "hot" circulation "cold" simple over a longer period of time sufficient to cure the resin. After 12 cycles and the total time of active work 4466 h the process of disproportionation with this catalyst requires the same temperature regime as using freshly loaded catalyst PU. The example gives further evidence for greater productivity, selectivity and stability-high volt the inventive catalyst before the previously used catalyst and shows the possibility in this case of periodic process, when rosin is subjected to disproportionation as necessary.

As can be seen from the examples and tables, the present invention allows to obtain a high-tech way catalyst with high dispersibility and the stability of the particles of palladium and/or platinum for baking when modified in a fairly wide range of metal content that provides the catalyst for improved performance, selectivity and stability in the processes of oxidation, hydrogenation and transfer of hydrogen and a catalytic process for greater efficiency, allowing, thus, the present invention find wide application in the chemical industry.

RoomVp-pmlMetal[metal], g/l[AK], g/lDrying conditionsThe conditions of thermal decompositionConditions recoveryMe, wt.%DPd,Ptnm
140Pd160210N2that 105°N2, 220°, 3 hH2/Not(1/4), N2, 125-150°6,02,5-2,2
22,5Pd80150Ar2, 40-60°H2, 130-170°0,24.3-3,6
350Pd22275N2that 105°N2, 200°, 2 hoursH2/N2(>1/1), H2, 140-160°9,93,3-3,0
431Pd13596N2, 90-105°N2, 190°, 2 hoursH2/N2(1/1), N2,125-200°4,02,6-2,2
57Pd144100N2, 90-105°N2, 200°, 3 hH2/N2, 125-200°13,5-3,3
620Pd51250N2, 90-105°N2, 200°, 3 hH2, 125-150°11,6-1,3
720Pd5180N2, 90-105°N2, 200°, 3 hH2/N2, 125-200°1,42,8-2,6
82,4Pd2567Not, 90°No, 200°1 hH20,242,6-2,5
92,4Pd2567Not, 90°No, 200°1 hH2, 110-150°0,24a 4.3-3,6
2,4Ag251070,24
109,4Pd109157Not, 90°No, 200°S, 0,7 hH2/Not (2/1), 110-150°4,03,0-2,7
1151Pt2281100Not, 90°No, 250°1 hH2, 250°106,3-5,9
12*51Pt2281100Not, 90°No, 250°1 hH2, 250°103,5-3,1
1355Pt2021120Not, 90°No, 250°1 hH2, 150-250°102,4-2,0
1427Pt526540Not, 90°No, 250°1 h H2, 150-250°304,7-2,6
* carrier pre-processed in 15 M HNO3for 2 h at 80°

1. Method of preparation of mono - or bimetallic catalyst for processes involving oxygen and/or hydrogen, comprising the impregnated carbon media compounds of palladium and/or platinum or palladium and at least one of the metals of group I, characterized in that the medium is pre-treated in nitric acid with a concentration of from 3 to 15 M at a temperature not exceeding 80°With an impregnating solution is prepared from nitric acid solutions bichloride compounds of palladium and/or platinum or palladium and at least one of the metals of group I, their drying and decomposition carried out in a current of inert gas at a temperature not exceeding 105°and from 150 to 350°accordingly, the recovery is carried out in a stream of hydrogen at 110-350°under other conditions of application, drying, decomposition, recovery, and the ratio of initial components, providing the dispersed particles of platinum group metals 1-10 nm in size, localized in the pore size of 2-20 nm, when the content of supported palladium and/or platinum from 3 to 50 wt.% or palladium and/or platinum and silver from 0.1 to 1.4 wt.%.

2. The method according to claim 1, characterized in that the use of plastics technology : turning & the command carrier, obtained by thermal decomposition of hydrocarbons in the carbon black pellets with subsequent oxidative activation or without it, and consisting of a carbon material with a pore volume of 0.2-1.7 cm/g formed by layers of carbon with a thickness of 10-1000 nm radius of curvature of 10-1000 nm, the true density by helium 1,80-2.1 g/cm3, x-ray density 2,112-2,236 g/cm3and distribution of pore sizes with highs in the field of 3-20 and 20-200 nm.

3. The method according to claim 1, characterized in that the carbon carrier, obtained by the decomposition of methane or ethylene at temperatures from 600 to 700°With a catalyst containing deposited on the aluminum oxide of Nickel metal and iron or Nickel and copper and consisting of a carbon material with a specific surface area by nitrogen adsorption of from 105 to 260 m2/g, the surface of mesopores from 95 to 240 m2/g, the volume of micropores from 0.01 to 0.02 cm3/g, a total pore volume from 0.31 to 0.4 cm3/g and an average pore diameter of from 6.2 to 17.5 nm.

4. Processes involving oxygen, hydrogen and organic compounds with the use of mono - or bimetallic catalyst prepared by impregnation of a carbon carrier, wherein using the catalyst prepared according to any one of claims 1 to 3.

5. The process according to claim 4, characterized in that the process consists in the oxidation of alcohols to aldehyde is in and carboxylic acids.

6. The process according to claim 4, characterized in that the process is the hydrogenation of olefins, acetylene and diene bonds in aliphatic and carbocyclic compounds.

7. The process according to claim 4, characterized in that the process is the hydrogenation of nitro compounds to amines or intermediates.

8. The process according to claim 4, characterized in that the process is in the disproportionation abietic and other resin acids in rosin and similar mixtures of natural or synthetic origin.



 

Same patents:

FIELD: chemical industry; non-ferrous metallurgy industry; other industries; methods of production of the catalyst for oxidization of the vanadium oxide particles in the gaseous phase with the definite size distribution.

SUBSTANCE: the invention is pertaining to the method of production of the catalyst for oxidization in the gaseous phase of the vanadium oxide particles with the definite size distribution. The invention describes the method of production of the catalyst for oxidization in the gaseous phase, at which on the fluidized inert carrier they deposit the suspension of TiO2 and V2O5 particles, in which, at least, 90 volumetric % of the particles of V2O5 have the diameter of 20 microns or less and, at least, 95 volumetric % of the particles of V2O5 have the diameter of 30 microns or less. The technical result of the invention is that the certain particle-size distribution allows to achieve the high efficiency of the coating.

EFFECT: the invention allows to achieve the high efficiency of the coating.

6 cl, 2 ex

FIELD: waste water treatment.

SUBSTANCE: method comprising deposition of active components onto polymer carrier followed by washing with modifying solution and drying of resulting catalyst is characterized by that above-mentioned polymer carrier is a super-crosslinked polystyrene preliminarily washed with acetone and dried, deposition of active components onto polymer carrier is accomplished by impregnating it for 8-10 min with complex solution of platinum group metal chloride and/or gold-hydrochloric acid sodium salt in concentration 0.57-64.5 g/L in complex organo-alcohol-water solvent containing, in particular, tetrahydrofurane, methanol, and water, whereupon catalyst id dried to constant weight and then optionally washed with modifying solution of sodium carbonate, 2.76-136.74 g/L, and with distilled water to neutral pH = 6.8-7.2. Catalyst allows deep oxidation of phenol compounds at high degree of conversion.

EFFECT: enhanced phenol oxidation activity of catalyst, simplified catalyst preparation technology needing utilization of lesser amounts of expensive chemicals.

3 cl, 3 tbl, 18 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for deep processing of hydrocarbon stock and can be employed in petroleum processing and petrochemical industries. Particularly, invention provides catalyst for diesel fraction hydrodesulfurization process, which contains, as active component, oxygen-containing molybdenum and cobalt and/or nickel complex compound at Mo/(Co+Ni) atomic ratio 1.5-2.5 and is characterized by specific surface 100-190 m2/g, pore volume 0.3-0.5 cm3/g, prevailing pore radius 80-120 Å. Catalyst support is constituted by alumina or alumina supplemented with silica or montmorillonite. Described are also catalyst preparation procedure and diesel fraction hydrodesulfurization process.

EFFECT: increased catalytic activity and resistance of catalyst against deactivation in presence of diesel fuel hydrocarbon components and sulfur compound of thiophene and its derivatives series.

8 cl, 1 tbl, 7 ex

FIELD: oxidation catalysts.

SUBSTANCE: invention concerns preparation of heterogeneous phthalocyanine catalyst for use in liquid-phase oxidation of sulfur-containing compounds and provides a method, which involves preparing nonwoven polypropylene carrier by treating it with boiling alkaline solution of sodium peroxycarbonate, 3.2-4.6 g/L, at pH 9-10 followed by treatment cobalt phthalocyanine-disulfonate, 3.2-4.6 g/L, and final treatment, which consists in washing preliminarily treated carrier with sodium hydroxide solution in concentration 0.1-0.5 g/L.

EFFECT: increased catalytic activity up to 92% and simplified catalyst preparation procedure.

2 cl, 1 tbl, 5 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for production of low-sulfur motor fuels and methods for preparing such catalysts. Hydrodesulfurization catalyst according to invention is characterized by pore volume 0.3-0.7 mL/g, specific surface 200-350 m2/g, and average pore diameter 9-13 nm and containing following components, wt %: cobalt compounds (calculated as CoO) 2.5-7.5, molybdenum compounds (as MoO3), citric acid 15-35, boron compounds (as B2O3) 0.5-3.0, aluminum oxide - the rest, cobalt, molybdenum, citric acid, and boron optionally being part of complex compound having different stoichiometry. Catalyst is prepared by impregnating catalyst support with impregnation solution obtained by dissolving, in water or aqueous solution, following compounds: citric acid, ammonium paramolybdate (NH4)6Mo7O24·4H2O, at least one cobalt compound, and at least boron compound, addition order and component dissolution conditions being such as to provide formation of complex compounds, whereas concentration of components in solution is selected such that catalyst obtained after drying would contain components in above-indicated concentrations.

EFFECT: maximized activity of desired reactions ensuring production of diesel fuels with sulfur level below 50 ppm.

9 cl, 8 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: proposed catalyst is composed of 12.0-25.0% MoO3, 3.3-6.5% CoO, 0.5-1.0% P2O5, and Al2O3 to the balance. Catalyst preparation comprises one- or two-step impregnation of support with solution obtained by mixing solutions of ammonium paramolybdate, cobalt nitrate, phosphoric and citric acids taken at ratios P/Mo = 0.06-0.15 and citric acid monohydrate/Co = 1±0.1, or mixing solutions of ammonium paramolybdate and phosphoric acid at ratio P/Mo 0.06-0.15 and cobalt acetate followed by drying and calcination stages. Diesel fraction hydrodesulfurization process is carried out in presence of above-defined catalyst at 340-360°C and H2-to-feedstock ratio = 500.

EFFECT: intensified diesel fraction desulfurization.

7 cl, 2 tbl, 13 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: invention relates to catalysts for extensive hydrofining of hydrocarbon stock, in particular diesel fractions, to remove sulfur compounds. Catalyst of invention, intended for diesel fraction desulfurization processes, comprises active component, selected from oxides of group VIII and VIB metals and phosphorus, dispersed on alumina support, said alumina support containing 5-15% of montmorillonite, so that total composition of catalyst is as follows, wt %: molybdenum oxide MoO3 14.0-29.0, cobalt oxide CoO and/or nickel oxide 3-8, phosphorus 0.1-0.5, and support - the balance, molar ratio Mo/Co and/or Mo/Ni being 1.3-2.6 and P/Mo 0.08-0.1. Preparation of catalyst support consists in precipitation of aluminum hydroxide and addition of montmorillonite with moisture content 55-70% to water dispersion of aluminum hydroxide in amount such as to ensure 5-15% of montmorillonite in finished product, after which resulting mixture is extruded and extrudate is calcined at 500-600°C to give support characterized by specific surface 200-300 m2/g, pore volume 0.5-0.9 cm3/g, and prevailing pore radius 80-120 Å. Catalyst preparation comprises impregnation of calcined support with complex solution of group VIII and VIB metal salts and phosphorus followed by heat treatment in air or nitrogen flow at temperature not exceeding 200°C, impregnation solution notably containing molybdenum oxide and cobalt and/or nickel carbonate at Mo/Co and/or Mo/Ni molar ratio 1.3-2.6 stabilized with orthophosphoric acid and citric acid to P/Mo molar ratio between 0.008 and 0.1 at medium pH between 1.3 and 3.5. Described is also diesel fraction hydrodesulfurization process involving passage of diesel fraction through bed of above-defined catalyst.

EFFECT: intensified diesel fraction desulfurization.

9 cl, 3 tbl, 19 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for deep hydrofining of hydrocarbon feedstock, in particular diesel fractions, to remove sulfur compounds. Invention, in particular, provides catalyst for hydrodesulfurization of diesel fractions including active component selected from group VIII and VIB metal oxides dispersed on alumina carrier, which is, in particular, composed of aluminum oxides, 85-95%, and H form or cation-substituted form of zeolite ZSM-5, mordenite, zeolite BEA, or zeolite Y, 5-15%. Active component is selected from oxides of molybdenum and cobalt and/or nickel. Carrier preparation method comprises precipitation of aluminum hydroxide, incorporation of zeolite in H form or cation-substituted form in amount 5-15% (based on final product) and peptizing agent into aluminum hydroxide powder, extrusion of resulting mixture, drying, and calcination at 450-600°C. Preparation of catalyst includes impregnation of above-defined carrier with complex solution of group VIII and VI metal salts in air or nitrogen flow at temperature not higher than 200°C. Diesel fraction hydrodesulfurization process is also described.

EFFECT: enhanced purification of diesel fractions.

10 cl, 2 tbl, 14 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to a method of preparing ethylene oxide production catalyst containing silver deposited on alumina carrier originally having sodium and silicate ions on its surface. Carrier is preliminarily treated with aqueous solution of lithium salt at temperature below 100°C, after which at least 25% sodium ions are removed and replaced with up to 10 mln-1 lithium ions. Carrier is dried and then silver and promoters are precipitated on the pretreated and dried carrier.

EFFECT: achieved stability of catalyst.

7 cl, 11 tbl, 17 ex

FIELD: gas treatment catalysts.

SUBSTANCE: invention concerns environmental protection area and aims at neutralizing toxic components of emission gases and, more specifically, related to a method of preparing catalyst for oxidative treatment of gases polluted by hydrocarbons and carbon monoxide. Invention provides catalyst supported by stainless steel containing 0.05-0.15 wt % ruthenium or ruthenium in the same quantity combined with platinum or palladium in quantity not exceeding 0.05 wt %. Catalyst preparation method is also described.

EFFECT: increased degree of removal of hydrocarbons, increased strength of catalyst, and reduced price of catalyst.

2 cl, 2 tbl

FIELD: chemical engineering.

SUBSTANCE: catalytic composition material comprises a mixture composed of acetylene hydrocarbon with aromatic substituent or potential oligomer that represent a hydrogen source and carrier and metal of VIII group that represents a heterogeneous catalyzer. The mass ratio of the hydrogen source and catalyzer ranges from 5:1 to 1000:1. The method comprises filling the system with hydrogen in the course of the contacting of acetylene hydrocarbon with the heterogeneous catalyzer in heated tank at a temperature of 50-200°C and hydrogen pressure of 5-1 atm and extracting hydrogen from the system when completely hydrated hydrocarbon in the first stage is in a contact with the same catalyzer at a temperature 200-350°C and pressure 0.5-5 atm.

EFFECT: increased rate of extracting.

10 cl, 2 dwg, 2 tbl, 8 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to novel catalysts that can be used, in particular, for selective hydrogenation of polyunsaturated hydrocarbons, deep oxidation of carbon monoxide, organic and organohalogene compounds, sulfur dioxide oxidation, selective chlorination and oxychlorination of hydrocarbons, nitrogen oxide reduction, and reuse of gaseous and liquid wastes. Catalytic system represents geometrically structured one including microfibers of high-silica fibrous carrier 5-20 μm in diameter, which is characterized by existence in IR spectrum of hydroxyl group spectral band having wave number ν=3620-3650 cm-1 and half-width 65-75 cm-1, by having specific surface SAr=0.5-30 m2/g as measured via BET method involving thermal desorption of argon, and at least one active element. In addition, carrier has specific surface value measured by alkali titration method SNa=5-150 m2/g at SNa/SAr ratio (5-50):1. Active element is of the nature capable of forming charged metallic or bimetallic clusters with specific bands in the region of 34000-42000 cm-1 and ratio of integral intensity of band 34000-42000 cm-1 (corresponding to charged metallic or bimetallic clusters) to integral intensity of band with maximum at 48000 cm-1, corresponding, respectively, either to metallic or to bimetallic particles, at least 1.0.

EFFECT: increased catalytic activity, increased resistance of catalyst to deactivation and elevated selectivity thereof in heterogeneous reactions.

4 cl, 6 ex

FIELD: methods of storage of hydrogen in catalytic systems functioning on basis of cyclic hydrogenation/de-hydrogenation reactions of condensed and poly-nuclear aromatic compounds; hydrogen generators; hydrogen engines or plants.

SUBSTANCE: proposed catalytic composite material contains organic substrate as hydrogen source which is liable to hydrogenation/dehydrogenation reactions. Material contains heterogeneous catalyst including carbon or oxide carrier at high specific surface and metal of VIII (platinum) group applied on this surface at mass ratio of substrate and catalyst from 10:1 to 1000:1. Organic substrate contains the following aromatic hydrocarbons: condensed, poly-cyclic, poly-unsaturated, aromatic oligomers and polymers: biphenyl or its functional derivative, or terphenyl, or naphthalene, or anthracene, or functional derivative of one or other, polystyrene or its copolymer, polyacetylene or polycumulene. Proposed method consists in charging the composite material with hydrogen at high pressure and separation of hydrogen from it at low-pressure heating. Charging is carried out at contact of organic substrate and heterogeneous catalyst at temperature of from 50 to 180°C and hydrogen pressure of from 1 to 100 atm; separation of hydrogen is carried out at contact of hydrogenated of organic substrate with the same catalyst at temperature of from 200 to 350°C at atmospheric pressure.

EFFECT: enhanced efficiency.

9 cl, 2 dwg, 2 tbl, 7 ex

FIELD: production of hydrogen and carbon oxide referred to as synthesis gas by selective catalytic oxidation of hydrocarbon raw material in presence of oxygen-containing gases.

SUBSTANCE: proposed method includes bringing the starting material in contact with catalyst at hourly volume rate of gas within 10,000-10000000 h-1; mixture contains organic material and oxygen or oxygen-containing gas in the amount ensuring ratio of oxygen to carbon no less than 0.3; electric current is passed through at least part of catalyst. Used as catalysts are complex composites including metallic carriers.

EFFECT: possibility of quick and safe ignition of catalyst; increased degree of conversion and selectivity under conditions of change of load in wide range.

24 cl, 7 ex

FIELD: heterogeneous catalysts.

SUBSTANCE: catalytic system comprises (i) high-silica fibrous carrier characterized by 29Si MNR spectrum, in which lines with chemical shifts -100±3 ppm (line Q3) and -110±3 ppm (line Q4) are present at ratio of integral intensities Q3/Q4 from 0.7 to 1.2; IR spectrum, in which absorption bands of hydroxyl groups with wave number ν=3620-3650 cm-1 and half-width 65-75 cm-1 are present; which carrier has specific surface SAr=0.5-30 m2/g as measured by BET method from thermal desorption of argon, surface area SNa=10-250 m2/g as measured by alkali titration method, at SNa/SAr ratio 5 to 30; and (ii) at least one active element. The system represents geometrically structured one constituted by microfibers with diameter 5-20 μm and additionally has active centers characterized in IR spectra of adsorbed ammonia by presence of an absorption band with wave numbers ν=1410-1440 cm-1.

EFFECT: increased catalytic activity, resistance to deactivation, and selectivity.

3 cl, 7 ex

FIELD: methods of production a synthesis gas.

SUBSTANCE: the invention is pertaining to the process of production of hydrogen and carbon oxide, which mixture is used to be called a synthesis gas, by a selective catalytic oxidation of the hydrocarbonaceous (organic) raw material in presence of the oxygen-containing gases. The method of production of the synthesis gas includes a contacting with a catalyst at a gas hourly volumetric speed equal to 10000-10000000 h-1, a mixture containing organic raw material and oxygen or an oxygen-containing gas in amounts ensuring the ratio of oxygen and carbon of no less than 0.3. At that the process is conducted at a linear speed of the gas mixture of no less than 2.2 · 10-11 · (T1 + 273)4 / (500-T2) nanometer / s, where: T1 - a maximum temperature of the catalyst, T2 - a temperature of the gas mixture fed to the contacting. The linear speed of the gas mixture is, preferably, in the interval of 0.2-7 m\s. The temperature of the gas mixture fed to the contacting is within the interval of 100-450°C. The maximum temperature of the catalyst is within the interval of 650-1500°C. The technical effect is a safe realization of the process.

EFFECT: the invention ensures a safe realization of the process.

10 cl, 5 ex

FIELD: alternate fuel manufacture catalysts.

SUBSTANCE: invention relates to generation of synthesis gas employed in large-scale chemical processes such as synthesis of ammonia, methanol, higher alcohols and aldehydes, in Fischer-Tropsch process, and the like, as reducing gas in ferrous and nonferrous metallurgy, metalworking, and on gas emission detoxification plants. Synthesis gas is obtained via catalytic conversion of mixture containing hydrocarbon or hydrocarbon mixture and oxygen-containing component. Catalyst is a complex composite containing mixed oxide, simple oxide, transition and/or precious element. Catalyst comprises metal-based carrier representing either layered ceramics-metal material containing nonporous or low-porosity oxide coating, ratio of thickness of metallic base to that of above-mentioned oxide coating ranging from 10:1 to 1:5, or ceramics-metal material containing nonporous or low-porosity oxide coating and high-porosity oxide layer, ratio of thickness of metallic base to that of nonporous or low-porosity oxide coating ranging from 10:1 to 1:5 and ratio of metallic base thickness to that of high-porosity oxide layer from 1:10 to 1:5. Catalyst is prepared by applying active components onto carrier followed by drying and calcination.

EFFECT: increased heat resistance and efficiency of catalyst at short contact thereof with reaction mixture.

13 cl, 2 tbl, 17 ex

The invention relates to a method of liquid-phase catalytic dechlorination of highly toxic compounds polychromatically

The invention relates to a method of producing glyphosate-oxidation reaction catalyzed by a noble metal

FIELD: electronic industry, possible use for manufacturing hydrocarbon storage materials.

SUBSTANCE: short multi-wall carbon nanotubes are composed of concentrically positioned layers of nanotubes with average diameter ranging from 2 to 15 nanometers, median diameter ranging from 6 to 8 nanometers and natural length ranging from 100 to 500 nanometers. Nanotubes may comprise 2-15 coaxial layers of one-walled nanotubes. Each short multi-wall carbon nanotube has one semi-spherical end and on conical end, where semi-spherical end may be selectively opened by oxidizing, leaving conical end untouched. Short multi-wall carbon nanotubes in accordance to invention in form of powder sample are fit for field emission of electrons, starting at approximately 2 V/micrometer.

EFFECT: resulting short multi-wall carbon nanotubes are more homogeneous length and diameter-wise and have improved emission properties compared to known ones.

5 cl, 6 dwg, 2 ex

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