Vegetable oil and distilled fatty acid processing catalyst and a method for preparation thereof

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to catalysts exhibiting activity in hydrogenation of vegetable oils and fats and suitable for use in food processing industry, perfumery, petrochemical and petroleum processing industries. Invention describes a method for preparing granulated catalysts intended for liquid-phase hydrogenation of vegetable oils and distilled fatty acids and representing metallic palladium deposited in amount 0.5-2.0 wt % on carbon carrier, fraction 0.5-6.0 mm, having specific surface area 100-450 m2/g and pore volume 0.2-0.6 cm3/g. Hydrogenation process is conducted on fixed catalyst bed at 140-210°C, hydrogen pressure 2 to 12 atm and consumption or raw material 100 to 1500 g/h per 1 kg catalyst.

EFFECT: increased hydrogenation rate in production of technical sorts of solidified fat and increased stability of catalysts.

4 cl, 1 dwg, 3 tbl, 20 ex

 

The invention relates to the field of catalysts, in particular intended for hydrogenation of vegetable oils and fats, and can be used in the food, perfume, petrochemical and refining industries.

Known catalysts for the hydrogenation of vegetable oils and distilled fatty acids (DIC) based on transition metals Mo, W, Rh, Ir, Ru, Os, Ti, Re, Fe, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Ga, etc. (J.I.Gray and L.F.Russell, J.Am. Oil Chemists Soc., v.56 (1979), 36-44). In this series the most widely Ni-containing catalysts. However, Nickel system inferior to the activity of palladium catalysts in the presence of which requires a degree of hydrogenation of vegetable oils and JK is achieved, ceteris paribus, at lower temperatures and pressures.

The hydrogenation process with the participation of such catalysts is carried out mainly in periodic mode using a suspended catalyst or in a continuous mode with a fixed catalyst bed. In the first case the synthesis of the hydrogenated fat is carried out in a temperature range 80-250°With at atmospheric or elevated pressure by means of a flow of hydrogen into the suspension of the powder catalyst (fraction of from 1 to 20 μm) in oil or GC. This mode presents the catalysts a number of additional requirements related to the peculiarity of their perfo the operation. Powdered catalyst must be easily separated (filtered) from the reaction products and to have good properties from the point of view of reuse. In the second case, the hydrogenation is carried out at 90-250°With the column type reactor at elevated hydrogen pressure up to 30 ATM, passing the reagents from the bottom up through a fixed bed of granular catalyst (fraction of 0.5-15 mm). Catalysts in a fixed bed in addition to high efficiency (under "efficiency" refers to such process parameters as the activity and stability of catalyst while maintaining consumer properties of the product) must have high strength and low hydrodynamic resistance of the catalyst layer to the flow of the reactants.

The present invention provides a method of preparing deposited on a carbon substrate granular palladium catalyst, effective for processing vegetable oils and GC in continuous mode.

The activity and selectivity of granular Pd-containing catalysts for the hydrogenation of vegetable oils, fats and fatty acids depend on many factors, such as the content of the metal or metals of group VIII in the catalyst, the type of substrate, the method by which the metal or metals of group VIII were deposited on a substrate, as well as the distribution m is a metal or metal grains of the media.

The known method [US 4479902, SS 3/11 M, 30.10.1984], in which the continuous hydrogenation of vegetable oils is performed on Pd or Pt catalysts deposited on TiO2with the metal content of 0.1 wt.% at a temperature of 150-250°C, a hydrogen pressure from atmospheric up to 14 ATM. The media is a spherical granules or extrudates size of about 1.6 mm Feature of the proposed method is the preparation of TiO2the method of deposition, which provides a sufficiently high specific surface area (130 m2/g).

The disadvantages of these catalysts are the low reaction rate and a low degree of hydrogenation of double bonds. So, in optimal conditions, the hydrogenation of soybean oil in a flowing mode in the presence of 0.1%Pd/C leads to a product with an iodine number (IC) 97,9.

In the patent [US 5234883, B01J 21/06, 10.08.1993] for the curing of unsaturated fatty acids is proposed catalyst with a high content of palladium (0.5 to 10 wt.%; the particle size of the metal 5-50 nm), which is used as a carrier TiO2obtained by molding a primary particle size 20 nm, with the following distribution of granule sizes: <0.5 mm 29%, 0.5-1.0 mm 32%, >1 mm 39%. The peculiarity of this method is the preparation of the primary particles of the medium TiO2pyrogenic method, which provides a lower specific surface area (50 m2/g).

what dostatkom this catalyst is low catalytic activity, due to the apparently low specific surface of the carrier.

The authors of the patent [FR 2175223, SS 53/00, B01J 23/00, 19.10.1973] for the continuous method of hydrogenation of unsaturated fatty acids in order to obtain a product is below 10 or 20 offers the catalyst Pd/α-Al2O3with a palladium content of 0.5-5.0 wt.%. The carrier is molded in the form of tablets (3,2×3.2 mm) or extrudates (1,6×3.2 mm). The hydrogenation conditions: temperature 93-232°C, a hydrogen pressure of from 6.9 to 69 ATM, the ratio of hydrogen/fatty acid 1:1 to 20:1, supply of fatty acids is 0.1-2 l/h per 1 liter of the catalyst. In contrast to commonly used media γ-Al2About3that can interact with fatty acids, giving aluminum compounds that block the active centers of the metal contaminate the catalyst and the product and make it difficult for the allocation of precious metal in pure form during regeneration α-Al2About3more inert. However, the catalyst Pd/α-Al2About3shows high activity at high hydrogen pressures (>21 ATM), even in these harsh conditions is the rapid deactivation of the catalyst, which is caused by blocking of active sites for adsorption of oil contains impurities of sodium soap and polar phosphatides on the hydrophilic surface of the aluminum oxide.

The known method [SA 1157844, SS /12, B01J 23/44, 29.11.1983] continuous curing fatty acids and vegetable oils in the presence of a palladium catalyst deposited on activated carbon with a Pd content of 0.5 to 3.0 wt.% and the size of the carrier extrudates 3×5 mm hydrogenation Conditions: 80-250°C, a hydrogen pressure of 0.5 to 50 ATM. This catalyst is capable of volumetric feed rate of the distilled fatty acids 0.2 h-1derived from beef fat, reduce initial value is from 58 to 0.2 to 0.7 at a temperature of 190°and a hydrogen pressure of 25 ATM. The increase in feed rate GC to 0.6 h-1leads to an increase of the iodine number of up to 2.5 and 3.3. However, in practice, when using the catalyst for hydrogenation of real raw material efficiency is much lower. To maintain the required degree of hydrogenation is necessary to introduce additional costly purification step GC or significantly reduce feed rate GC. This catalyst, therefore, is economically disadvantageous for use in industrial scale.

The closest technical solution to claimed is a method of preparation of the catalyst proposed for the disproportionation of rosin [EN 2056939, B01J 23/44, 27.03.1996 (prototype)], according to which the catalyst contains 1.5 to 2.5 wt.% palladium on a carbon carrier. While palladium is concentrated the active layer thickness of 10-50 μm from the outer surface of the granules. The palladium particles have a preferred size of 2-8 nm and localized in the pores of the support size of 3-15 nm. The catalyst was prepared by deposition of palladium on granular media from aqueous palladium nitrate solution with a concentration of free nitric acid 6:1-1:1 (molar) with respect to palladium, dried in a current of air at 110-130°C. the Decomposition of deposited palladium nitrate is carried out in a current of inert gas at 200 to 300°and restore in hydrogen at 150-250°C.

In the example in the prototype examples, the catalysts were prepared on a carbon carrier with the following characteristics: grain size 1-3 mm, specific surface area by nitrogen adsorption 400 m2/g, a bulk density of 0.6 kg/DM3total pore volume (capacity) 0.6 cm3/g, predominant pore size 4-10 nm, the ash content of 0.8 wt.%, the abrasion resistance of 0.1%/min

Catalysts prepared by this method exhibit high efficiency in the processes of intra - and intermolecular redistribution of hydrogen in the high-viscosity substrates, in particular during the disproportionation part rosin and abietic other resin acids. We have shown that when in flow mode liquid-phase process of hydrogenation of vegetable oils and JC as a stationary layer can be used pellet is rowanne catalysts, cooked this way.

The disadvantages of these catalysts are reduced performance in recalculation on weight of supported palladium and high hydrodynamic resistance in the reaction column of catalyst layer flow of the reactants.

The invention solves the problem of creating an active and stable granular catalyst for processing in a flowing mode of vegetable oils and GC.

The task is solved by a catalyst composition for the hydrogenation of vegetable oils and JC comprising crystallites of catalytically active palladium deposited on the surface of the carbon material as a carbon material is used mesoporous graphite-like material with a grain size of 0.5-6.0 mm, preferably 3.0 to 6.0 mm, a specific surface area of 100-450 m2/g, with an average size of mesopores in the range of from 40 to 400Åtotal pore volume of 0.2-0.6 cm3/g and the proportion of mesopores in the total volume of pores of not less than 0.6, in which the crystallites of palladium in the amount of the carbon material granules are distributed so that the maximum distribution of the active component was at a distance from the outer surface of the granules corresponding to 1-30% of its radius, when the content of supported palladium in the range from 0.5 to 2.0 wt.%.

The problem is solved by the method of preparation of the catalyst for processing raises the selected oils and distilled fatty acids, which includes applying a palladium on granular carbon media, followed by drying, decomposition and reconstruction, as the carbon material used mesoporous graphite-like material with a grain size of 0.5-6.0 mm, preferably 3.0 to 6.0 mm, a specific surface area of 100-450 m2/g, with an average size of mesopores in the range of from 40 to 400Åtotal pore volume of 0.2-0.6 cm3/g and the proportion of mesopores in the total volume of pores of not less than 0.6, with production of metal catalyst supported palladium content in the range from 0.5 to 2.0 wt.%.

In such catalysts in obtaining food and technical summary : modified compositions obtained implements a higher degree of utilization of the active component; however, they have an increased service life. The increase in the thickness of the active layer leads to performance degradation of the catalyst due to increased diffusion braking catalytic process in the depth of the granules.

To obtain the above-mentioned catalysts can be used are well known in the literature methods, such as impregnation of the support with solutions of various salts of palladium. However, it has been found that the best catalysts obtained by using the method of spraying an acidic salt solutions suitable palladium on carbon carrier with the subsequent processing applied predecessors metal is and hydrogen.

As precursors of the metal can be used commercially available PdCl2or Pd(NO3)2. When it was found that increasing the concentration of deposited Pd>1.5 wt.% in such catalysts, when these costs for raw materials leading to increased consumption by palladium. The decrease in the concentration of Pd<0.5 wt.% to obtain hydrogenated fat necessary quality job requires low loads on raw, which makes the use of such a catalyst ineffective.

The specified distribution of the palladium particles by the volume of the pellet carrier is implemented by applying palladium from aqueous hydrochloric acid solution of palladium chloride at a molar ratio PdCl2/HCl=1:2-1:4, or from a nitric acid solution of palladium nitrate with a concentration of free nitric acid from 0.5 to 3.0 mol/l (from 31.5 to 189 g/l). Changing the ratio of the palladium precursor is acid" in the above limits can be varied concentration profile of palladium on section granules media. At lower ratios, the formation of the colloidal solution of the hydrolysis products and the rapid spontaneous recovery of palladium upon contact of the solution with the carbon surface, at the same time when a large excess of acid is excessively deep penetration of the palladium salt in the granules of the media.

As the carbon material may act as carriers, prepared by heat treatment of plastics, as well as synthesized according to a special technology of gaseous hydrocarbons (V.A.Likholobov et al., React. Kin. Cat. Lett., v.54, 2 (1995) 381-411), namely Sibunit, catalytic filamentous carbon (KB) and various composites on their basis, for which Vmeso/Vis ≥0,6. The size of granules such carriers obtained by known technologies, as a rule, does not exceed 3 mm Catalysts prepared on their basis, during operation in the reactor column type when passing through the layer of catalyst such viscous substrates, as oil and JC have a high hydrodynamic resistance. Indeed, represented in the drawing evaluation of mathematical calculations of the values of the dynamic component of the hydraulic resistance of the catalyst layer for spherical particles on industrial alloy Ni-Al catalyst (⊘cf=11.8 mm) in the column hydrogenation under the following process parameters: consumption of rapeseed oil 2.5 t/h; the flow rate of hydrogen of 160 l/s; the pressure in the column (average): 6 ATM; temperature: 180°To show that with decreasing the grain size of the catalyst is observed exponential increase of the resistance of the catalyst layer to the flow of oil. When using a granule size of less than 3.0 mm, the ratio of the pressure drop over the layer that is, that can cause problems with pumping the feedstock through the catalyst bed. Therefore, in the present invention as carriers of catalyst applied to the conditions of hydrogenation of oils and JC offered granules are larger in size.

Restoration of surface oxides of palladium metal to carry hydrogen. When this upper limit temperature is determined by the need to reduce the sintering of the metal during recovery, the lower the need to ensure complete recovery.

These parameters provide high performance in terms of a mass supported palladium in the production of summary : modified compositions obtained low hydrodynamic resistance in the reaction column of catalyst layer flow of reagents, as well as increased stability of the catalyst (longer service life).

Distinctive features of the present invention in comparison with the prototype are

1) the low content of the active component in the catalyst;

2) using as a carrier of porous carbon material with a share of mesopores in the total pore volume (Vmeso/V) not less than 0.6 and bòthe great size of the granules;

3) the scope of the catalyst, including its use in the process of hydrogenation of vegetable oils and fats.

The process of hydrogenation is avodat on a stationary catalyst bed at a temperature of 140-210° C, the hydrogen pressure is from 2 to 12 ATM and the flow of raw materials from 100 to 1500 g/(kg)CT·h).

Below are examples 1-20, illustrating the claimed method. Of these examples 15-18 are given for comparison and example 7 are shown as a prototype. Example 20 describes a method of testing catalysts in the reaction of hydrogenation of vegetable oils and GC.

Example 1.

In the rotating cylindrical reactor load of 50 g of carbon media brand Sibunit 1 (data on physico-chemical and textural properties of media used are shown in table 1). Here and in the following examples, the media pre-cleaned of dust by boiling in distilled water. Then unload on a sieve with mesh size of 1 mm, washed with distilled water and dried at 120°C to constant weight. 27 ml of a nitric acid aqueous solution of Pd(NO3)2(0,087 mol/l) concentration of free HNO3equal to 170 g/l, is fed into the nozzle, and the resulting mixture is sprayed at a speed of 5 ml/min into the reactor. The sample is placed in a tubular reactor and dried in a stream of nitrogen at elevated temperature for 1 h to 120°C and maintained at this temperature for another 2 hours Then increase the temperature to 250°C (at this temperature is the decomposition of Pd(NO3)2to palladium oxide). Under these conditions, the sample is incubated for 3 h, then cooled to 50°C. Replace al the t into hydrogen and restore the catalyst for 1 h at 150° With further rise of temperature up to 250°and holding at that temperature for 2 hours, Reduce the temperature from 250 to 40°and replacing the hydrogen with nitrogen. Get the catalyst Pd/Sib with a palladium content of 0.5 wt.%.

Data on the dispersion and distribution of the particles of palladium in catalysts prepared in accordance with the present patent examples, are presented in table 2.

Example 2.

The catalyst prepared according to example 1, but the granules of the carrier is brought into contact with a solution of palladium nitrate by impregnation. To do this in vinyl plastic drum load of 50 g of carbon media brand Sibunit 1, which is 1/4 of the volume of the drum. In propitiating the tube passing through the axis of the drum and having openings during rotation of the drum for 5 min dispense a solution of Pd(NO3)2and stirred the mass for 10 minutes Subsequent stages of drying, calcination and recovery of the catalyst is carried out as in example 1. Get the catalyst Pd/Sib with a palladium content of 0.5 wt.%.

Example 3.

In the rotating cylindrical reactor load of 50 g of carbon media brand Sibunit 1. Aqueous solutions of Na2CO3(0,348 mol/l; and 13.5 ml) and H2PdCl4(0,174 mol/l; 13,5 ml) with the same bulk velocity (2.5 ml/min) in a molar ratio of Na2CO3:H2PdCl4=2:1 is fed to the nozzle and the received mixture is sprayed into the reactor. The catalyst was unloaded and dried under vacuum at 75°C to constant weight. The subsequent recovery operation is carried out in a tubular reactor in a stream of hydrogen at a temperature of 250°C for 2 hours to Reduce the temperature from 250 to 40°and replacing the hydrogen with nitrogen. The catalyst is washed with distilled water to a reaction with AgNO3ions of chlorine in the wash water and dried under vacuum at 75°C to constant weight. Get the catalyst Pd/Sib with a palladium content of 0.5 wt.%.

Example 4.

The catalyst prepared according to example 1, but the recovery of hydrogen is carried out at 200°C. Receive the catalyst Pd/Sib with a palladium content of 0.5 wt.%.

Example 5.

The catalyst prepared according to example 1, but the recovery of hydrogen is carried out at 150°C. Receive the catalyst Pd/Sib with a palladium content of 0.5 wt.%.

Example 6.

The catalyst prepared according to example 1, but using 27 ml of nitric acid aqueous solution of Pd(NO3)2(0,174 mol/l) concentration of free HNOCequal to 170 g/L. Get the catalyst Pd/Sib with a palladium content of 1.0 wt.%.

Example 7 (prototype).

In vinyl plastic drum load of 50 g of carbon media brand Sibunit 1, which is 1/4 of the volume of the drum. In propitiating the tube passing through the axis of the drum and having openings during rotation of the drum 5 minutes dosed 22 m the solution of palladium nitrate with a concentration of palladium of 46.4 g/l (0,436 mol/l) and the concentration of free nitric acid, 175 g/l, mix the lot within 10 minutes the Sample is coated with a 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 the Air is replaced 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 250°C for 2 hours Displace at 120°With hydrogen, nitrogen, cooling the catalyst in a stream of nitrogen up to 40°C. Obtain a catalyst with a palladium content of 2.0 wt.%.

Example 8.

The catalyst prepared according to example 1, but using 27 ml of nitric acid aqueous solution of Pd(NO3)2(0,087 mol/l) concentration of free HNO3equal to 140 g/L. Get the catalyst Pd/Sib with a palladium content of 0.5 wt.%.

Example 9.

The catalyst prepared according to example 1, but using 27 ml of nitric acid aqueous solution of Pd(NO3)2(0,087 mol/l) concentration of free HNO3equal to 106 g/L. Get the catalyst Pd/Sib with a palladium content of 0.5 wt.%.

Example 10.

The catalyst prepared according to example 1, but using 27 ml of nitric acid aqueous solution of Pd(NO3)2(0,087 mol/l) concentration of free HNO3equal to 31.5 g/L. Get the catalyst Pd/Sib with a palladium content of 0.5 m is S.%.

Example 11.

The catalyst prepared according to example 1, but instead of carbon media brand Sibunit 1 download carbon media Sibunit 2. To preserve the ratio of the volume of the impregnating solution and the total volume of pores of the carrier used in 19.6 ml of nitric acid aqueous solution of Pd(NO3)2(0,120 mol/l) concentration of free HNO3equal to 170 g/L. Get the catalyst Pd/Sib with a palladium content of 0.5 wt.%.

Example 12.

The catalyst prepared according to example 3, but instead of carbon media brand Sibunit 1 download carbon media Sibunit 2. To preserve the ratio of the volume of the impregnating solution to the total pore volume of the carrier used to 9.8 ml of an aqueous solution of Na2CO3(to 0.480 mol/l) and 9.8 ml of H2PdCl4(0,240 mol/l), with the same volumetric rate (2 ml/min) in a molar ratio of Na2CO3:H2PdCl4=2:1 is fed to the nozzle, and the resulting mixture is sprayed into the reactor. Get the catalyst Pd/Sib with a palladium content of 0.5 wt.%.

Example 13.

The catalyst prepared according to example 11, but using in 19.6 ml of nitric acid aqueous solution of Pd(NO3)2(0,240 mol/l) concentration of free HNO3equal to 170 g/HP Recovery hydrogen is carried out at 200°C. Receive the catalyst Pd/Sib with a palladium content of 1.0 wt.%.

Example 14.

The catalyst is prepared by a PR is a measure of 13, but granules of the carrier is brought into contact with a solution of palladium nitrate impregnated according to the method described in example 2. Get the catalyst Pd/Sib with a palladium content of 1.0 wt.%.

Example 15 (comparative).

The catalyst is prepared as in example 1, but instead of carbon media brand Sibunit 1 download active carbon AR-b as an impregnating solution used was 8.8 ml of a nitric acid aqueous solution of Pd(NO3)2(0,267 mol/l) concentration of free HNO3equal to 170 g/L. Get the catalyst Pd/AP-B with a palladium content of 0.5 wt.%.

Example 16 (comparative).

The catalyst prepared according to example 1, but instead of carbon media brand Sibunit 1 download carbon carrier FAS. As an impregnating solution using 39 ml of nitric acid aqueous solution of Pd(NO3)2(to 0.060 mol/l) concentration of free HNO3equal to 170 g/L. Get the catalyst Pd/FAS with a palladium content of 0.5 wt.%.

Example 17 (comparative).

The catalyst prepared according to example 1, but instead of carbon media brand Sibunit 1 download active charcoal FB-4. As an impregnating solution used to 14.6 ml nitric acid aqueous solution of Pd(NO3)2(0,161 mol/l) concentration of free HNO3equal to 170 g/L. Get the catalyst Pd/FB-4 with a palladium content of 0.5 wt.%.

Example 18 (compare the capacity).

The catalyst prepared according to example 1, but instead of carbon media brand Sibunit 1 download carbon material CEF. As an impregnating solution used to 12.8 ml of a nitric acid aqueous solution of Pd(NO3)2(0,184 mol/l) concentration of free HNO3equal to 170 g/L. Get the catalyst Pd/CEF with a palladium content of 0.5 wt.%.

Example 19.

In a lined vinyl plastic drum load 70 kg carbon media brand Sibunit 2, which is 1/4 of the volume of the drum. In propitiating pipeline passing through the axis of the drum and having openings for 5 min served 27,4 l of a solution of Pd(NO3)2(0,243 mol/l) concentration of free HNO3equal to 147 g/L. due to the rotation of the drum causes intense mixing for 15-20 min, the resulting solution is evenly distributed over the surface of the media.

8 servings impregnated carrier fed into the reactor for carrying out drying and calcining in a stream of nitrogen, followed by reduction in hydrogen flow.

Drying and calcining of the catalyst is carried out at a temperature of 250°in a stream of nitrogen. Temperature rise to a predetermined exercise speed 20°C/o'clock When the set temperature is reached, the catalyst is kept in a stream of nitrogen ˜ 10 o'clock the decomposition of palladium nitrate is considered complete when the red eye reduction is Sri concentration of nitrogen oxides in the exhaust gas to a value of not more than 10 mg/m 3. Then the catalyst bed is cooled in nitrogen to 40-50°C.

For recovery in the reactor for 2 hours and serve with cold hydrogen. Then produce heating of the catalyst within 5-7 h hot hydrogen to a temperature of 200°C and maintained at this temperature 5-8 hours After recovery is completed in the reactor served cold hydrogen to reduce the temperature in the reactor up to 30-40°C. Then the reactor was rinsed with nitrogen for 15-30 minutes Before unloading, to avoid ignition of the catalyst, palladium Passepartout by adding nitrogen from the air with a gradual transition only on the air. When unloading receive 566 kg of catalyst Pd/Sib with a palladium content of 1.0 wt.%.

Example 20.

In a tubular reactor made of stainless steel (internal ⊘=25 mm) load a portion of the catalyst mass 14, the Reactor is hermetically connected to the system. The system is rinsed with nitrogen, then with hydrogen to increase the hydrogen pressure in the system to work. In control panel, set the desired temperature of the reaction and include heating furnace. The capacity to download raw rapeseed oil (IC 110,9 g I2/100 g, the title of 10.2°, an acid number of 0.3 mg KOH/g) or GC (IC of 94.5 g I2/100 g, the title 28,4°, acid number 195,4 mg KOH/g). Raw materials before dosing into the reactor is heated (rapeseed oil - 60°, JC up to 90° (C), the container is here rinsed with nitrogen and establish working pressure of hydrogen.

The hydrogenation process is carried out in continuous mode in a stationary catalyst bed at a temperature of 140-210°C, the hydrogen pressure is from 2 to 12 ATM and the flow of raw materials from 100 to 1500 g/(kg)CT·h). When this mixing of hydrogen with oil or GC is carried out in a special way at the bottom of the reactor. The resulting mixture passed through the catalyst bed from the bottom up. Sampling for quality analysis of the product produced every 2-3 hours

Determination of the titer of the obtained hydrogenated fat performed by standard methods (Bezzubov, L.P. Chemistry of fats. M: Food promyshlennosti. 1976, s). The iodine number is determined by titration of a sample of the product solution of sodium bromide and bromine in methyl alcohol according to the method of the Kaufman Guide to research methods, chemical control and accounting of production in the oil industry. Leningrad. 1982, vol. 1, s).

Analytical quality data hydrogenated fat, is obtained in this way on the catalysts prepared in accordance with the above examples, are presented in table 3.

The test results show that the catalysts prepared according to the invention, in addition to low hydrodynamic resistance in the reaction column of catalyst layer flow of reagents provide high performance in terms of weight caused the CSOs palladium in the production of summary : modified compositions obtained and also have a high stability. From the data of chemical analysis it follows that for catalysts prepared in accordance with examples 1, 11, 13, 19, under the influence of the reaction medium, there was no reduction of the content of palladium. According to XRD, not detected by sintering particles of the active component in the catalyst of 1.0% Pd/Sib (example 19) after its use in the hydrogenation process GC within 110 hours involving method electron microscopy high resolution is not found sintering of fine particles of palladium in the catalyst after his trial in the reactions of hydrogenation of rapeseed oil for 100 h and GK for 184 hours Sredneoblastnye the size of the Pd particles in the source and in the exhaust catalysts was 4.4, the 4.3 and 4.8 nm, respectively.

As can be seen from the examples, drawings and tables, the present invention allows to obtain catalysts having a high rate of hydrogenation of the feedstock in the production of technical grades summary : modified compositions obtained and characterized by an increased stability.

According to the recommendations of IUPAC porous body is classified according to the predominant pore size in the microporous (pores up to 2 nm), mesoporous (2-50 nm) and macroporous (>50 nm). That is, in the claims, indicating the size of the mesopores in the range of from 40 to 400 Åwe covered the practice is Cesky entire range of pore sizes for mesoporous carbons. In this regard, the proposed Supplement table 1 one line comment (below red).

Table 1
The main characteristics of granular porous carbon materials
MarkSibunit 1AR-BFASFB-4KVUSibunit 2
The origin (source)hydrocarbonscoalthe furfuralcoalhydrocarbonshydrocarbons
Appearancepellethandlepellethandlepelletpellet
Size mm1-34-53-54-63-54-6
Sbeats1)m2/g4404381200606120346
Vmicro2)cm3/g0,0150,192mean HDI of 0.5310,2220,0100,010
Vmeso3)cm3/g 0,6650,0270,4420,1440,310to 0.480
VΣ4)cm3/g0,6800,2190,9730,3660,3200,490
Vmeso/VΣ0,980,120,450,390,970,98
Dcf5)that Å55,241,0251,570,0130, 8mm74,1
1)Sbeats(m2/g) specific surface area by BET. The surface area was calculated from plot isotherms, where R/R0=0,05-0,20; size of area of the nitrogen molecule in the completed monomolecular layer was assumed to be equal to ω=rate £ 0.162 nm2;
2)Vmicro(cm3/g) micropore volume. Calculated using the comparative method in areas of the isotherm corresponding to the region between the filling of micropores and the beginning of the capillary condensation; the value of Vmicrocorresponds to the volume of ultramicro and Supermicro, i.e. the volume of micropores smaller than 20 Å;
3)Vmeso(cm3/g) = V-Vmicro;
4)V(cm3/g) pore volume of less than 5000 Å. Calculated from nitrogen adsorption at P/P0=0,98;
5)Dcp(Å) - the average size of the mesopores, calculated on the desorption curve of adsorption of nitrogen.

Table 2
The composition and properties of the catalysts.
No.CatalystPredecessor PdMethod of applying Pd[C]g/l1)Treset.that °Dispersion, CO/Pd2)Δcf., mkm,3)
10.5%Pd/SubPd(NO3)2plating1702500,29302
20.5%Pd/SubPd(NO3)2impregnation1702500,25370
30.5%Pd/SubH2PdCl4plating-2500,2338
40.5%Pd/SubPd(NO3)2plating1702000,37 320
50.5%Pd/SubPd(NO3)2plating1701500,40315
61.0%Pd/SubPd(NO3)2plating1702500,22380
72.0%Pd/SubPd(NO3)2impregnation1752500,20415
80.5%Pd/SubPd(NO3)2plating1402500,27268
90.5%Pd/SubPd(NO3)2plating1062500,22195
100.5%Pd/SubPd(NO3)2plating31.52500,17120
110.5%Pd/SubPd(NO3)2plating1702500,27326
120.5%Pd/SubH2PdCl4plating-2500,154
131.0%Pd/SubPd(NO3)2plating1702000,39320
141.0%Pd/SubPd(NO3)2impregnation1702000,38332
150.5%Pd/AP-BPd(NO3)2plating1702500,10128
160.5%Pd/FASPd(NO3)2plating1702500,0720
170.5%Pd/FB-4Pd(NO3)2plating1702500,0817
180.5%Pd/CEFPd(NO3)2plating1702500,48272
191.0%Pd/SubPd(NO3)2impregnation1472000,34342
1)The concentration of free nitric acid.
2)The dispersion (D) of the obtained catalysts determining what and pulse method by chemisorption of CO at 20° C. the Value of D calculated on the basis of the stoichiometry of CO/Pds=1:1 (mol/mol).
3)Electron microprobe granules of the catalyst is carried out by scanning slice granules in diameter using a MAR-3. Δcf- the arithmetic mean of the parameter a, which characterizes the thickness of the active layer in μm at 1/2 peak height distribution of the metal in the surface layer of the granules.

Table 3
Feature summary : modified compositions obtained obtained on palladium catalysts in accordance with example 20
# exampleThe composition of the catalystRaw materialsT °PH2kgf/cm2Reaction time, hoursThe feed rate, g/HREat a CR-TA, g/(kg)CT·h)Eat a CR-TA, g/(gPd·h)The title °IC, g I2/100 g
10.5%Pd/Suboil170-1826159,6686137,157,2-59,3
GK150-1626-8 304,330761,457,5 is 60.56,0-9,1
20.5%Pd/SubGK145-1606154,330761,4to 57.0-60.0 sec
30.5%Pd/Suboil179-183610110,9779155,759,2 is 60.5
GK174-177620of 5.438677,158,0-60,0
GK214-2246226.244388,656,5-58,0
40.5%Pd/SubGK155-1626-8305,539378,657,0-61,0
50.5%Pd/SubGK144-1606-8915,640080,0to 57.0-60.0 sec
72.0%Pd/SubGK154-1576-8 308,661430,757,5-60,26,2-9,5
80.5%Pd/SubGK149-1606154,330761,4of 57.5-60.0 sec
90.5%Pd/SubGK148-1626-8155,237174,3to 57.0-60.0 sec
100.5%Pd/SubGK144-1606-8156,546492,957,0-59,0
120.5%Pd/Suboil179-18961510.7764152,962,2-64,0
GK199-2046316,244388,657,5 to 58.2
131.0%Pd/SubGK148-1606-8125,237137,155,2-57,0
141.0%Pd/SubGK10-168 6-818a 4.935035,057,5-59,0from 9.1 to 15.2
160.5%Pd/FASGK148-1576154,834368,673,5-75,7
180.5%Pd/CEFGK155-1636166,143687,157,2-59,3
191.0%Pd/SubGK161-1966-10159a 4.935035,057,0-59,06,1-15,2
GK160-1716-8304,632932,957,0-59,0of 8.0 to 12.2
GK172-19610129a 4.935035,057,2-59,06,5-9,0

1. The catalyst for the processing of vegetable oils and distilled fatty acids, comprising crystallites of catalytically active palladium deposited on the surface of the carbon material, characterized in that the carbon material used IU opacity graphite-like material with a grain size of 0.5-6.0 mm, with a specific surface area of 100-450 m2/g, with an average size of mesopores in the range of from 40 to 400, the total pore volume of 0.2-0.6 cm3/g and the proportion of mesopores in the total volume of pores of not less than 0.6, in which the crystallites of palladium in the amount of the carbon material granules are distributed so that the maxima of the distribution of the active component are located at a distance from the outer surface of the granules corresponding to 1-30% of its radius, when the content of supported palladium in the range from 0.5 to 2.0 wt.%.

2. The method of preparation of the catalyst according to claim 1 for processing vegetable oils and distilled fatty acids, including the application of palladium on granular carbon media, followed by drying, decomposition and reconstruction, characterized in that the carbon material used mesoporous graphite-like material with a grain size of 0.5-6.0 mm, a specific surface area of 100-450 m2/g, with an average size of mesopores in the range of from 40 to 400, the total pore volume of 0.2-0.6 cm2/g and the proportion of mesopores in the total volume of pores of not less than 0.6, with production of metal catalyst supported palladium content in the range from 0.5 to 2.0 wt.%.

3. The method according to claim 2, characterized in that the catalyst is prepared using one of the following precursors of metals: H2PdCl4or Pd(NO3)2.

4. The method according to P2, characterized in that for the preparation of a catalyst using a nitric acid solution of palladium nitrate with a concentration of free nitric acid from 0.5 to 3.0 mol/l, the drying is carried out in a current of air or inert gas at 110-130°With decomposition in a current of inert gas at 200 to 300°C, the recovery is carried out in hydrogen at 150-250°C.



 

Same patents:

FIELD: hydrogen production processes.

SUBSTANCE: invention relates to catalysts for hydrolysis of hydride compounds to produce pure hydrogen for being supplied to power installations, including fuel cells. Invention provides catalyst for production of hydrogen from aqueous or water-alkali solutions of hydride compounds containing platinum group metal deposited on complex lithium-cobalt oxide and, additionally, modifying agent selected from series: titanium dioxide, carbon material, oxide of metal belonging to aluminum, magnesium, titanium, silicon, and vanadium subgroups. According to second variant, catalyst contains no platinum group metal. Described are also catalyst preparation method (variants) and hydrogen generation process, which is conducted at temperature no higher than 60°C both in continuous and in periodic mode. As hydrogen source, sodium borohydride, potassium borohydride, and ammine-borane can be used.

EFFECT: increased catalyst activity at environmental temperatures (from -20 to 60°C), prolonged time of stable operation of catalytic system, and reduced or suppressed platinum metals in composition of catalyst.

14 cl, 1 tbl, 20 ex

FIELD: catalytic gas treatment.

SUBSTANCE: invention proposes catalyst for treating hydrogen-rich gas mixtures to remove carbon monoxide via methanation of carbon monoxide, said catalyst containing nickel-cerium oxide system. Catalyst is prepared by reaction of nickel compounds with cerium compound. Methanation of carbon monoxide is conducted at temperature not below 20°C and pressure not below 0.1 atm in presence of above-indicated catalyst.

EFFECT: enhanced removal of carbon monoxide to level below 10 ppm.

8 cl, 5 tbl, 9 ex

FIELD: gas treatment catalysts.

SUBSTANCE: invention relates to a method for preparing catalyst and to catalyst supported by block ceramic and metallic carrier having honeycomb structure for treating internal combustion engine exhaust gases. Preparation of catalyst comprises preliminary calcination of inert honeycomb block carrier followed by simultaneously depositing at 550-800°C, on its surface, intermediate coating of modified alumina and active phase consisting of one or several platinum group metals from water-alcohol suspension including aluminum hydroxide (boehmite, AlOOH), cerium nitrate, and one or several inorganic salts of platinum group metals. Coated material is then dried and subjected to heat treatment and reduction. According to invention, aforesaid suspension contains boehmite and cerium nitrate at 1:2 ratio and further contains reducing disaccharide so that suspension has following composition, wt %: AlOOH 18-20, Ce(NO3)3·6H2O 36-40, one or several platinum group metal salts (e.g., H2PtCl6, PdCl3, or RhCl3 calculated as metals) 1.5-1.8, reducing disaccharide 5-6, and water/alcohol (between 5:1 and 10:1) the rest. Thus obtained catalyst for treating internal combustion engine exhaust gases is characterized by: specific surface area of coating 80-100 m2/g, Al2O3 content 2.5-6.5%, CeO2 content 2.5-6.5%, active phase (calculated for platinum group metals) 0.2-0.4%, and block carrier to 100%.

EFFECT: simplified technology due to reduced number of technological stages and shortened process time, and enabled preparation of high-activity catalyst.

6 cl, 1 tbl, 8 ex

Ruthenium catalysts // 2322293

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to novel ruthenium catalysts, method for preparation thereof, and to employment thereof for catalytic hydrogenation of mono- and oligosaccharides in production of corresponding sugar alcohols. Ruthenium hydrogenation catalyst contains ruthenium supported by amorphous silica-based carrier, content of ruthenium being 0.2 to 7% of the weight of carrier, while carrier contains at least 90% silica and less than 10% of crystalline silicon dioxide phases. Catalyst is prepared by single or multiple treatment of carrier material with halogen-free solution of low-molecular weight ruthenium compound and subsequent drying of treated material at temperature not lower than 200°C immediately followed by reduction of dried material with hydrogen at 100 to 350°C. Herein disclosed is also a process for liquid-phase production of sugar alcohols (excepting sorbitol) via catalytic hydrogenation of corresponding mono- and oligosaccharides in presence of proposed catalysts.

EFFECT: increased activity and selectivity of catalysts.

16 cl, 4 tbl, 7 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention relates to the area of production of olefin hydrocarbons via catalytic dehydrogenation of corresponding C3-C5-paraffin hydrocarbons and can be applied in chemical and petrochemical industries. C3-C5-Paraffin hydrocarbon dehydrogenation catalyst is described containing chromium oxide, alkaline metal oxide, transition metals, and carrier, said carrier being nanostructured oxygen-containing aluminum compound of general formula: Al2O3-x(OH)x*nH2O, wherein x=0-0.28 and n=0.03-1.8, consisting of nanostructured primary particles 2-5 nm in size and characterized by disordered/imperfect layered structure similar to byerlyte structure. Method of preparing this catalyst as well as process of dehydrogenating C3-C5-paraffin hydrocarbons into olefins are also described, the latter being conducted in fluidized bed of described catalyst, which is recycled within the circuit: dehydrogenation reactor - regeneration reactor.

EFFECT: increased mechanical strength at high catalytic activity and stability.

20 cl, 1 dwg, 2 tbl, 10 ex

FIELD: alternative fuels.

SUBSTANCE: invention relates to catalysts and process of steam conversion of hydrocarbons to produce synthesis gas. Proposed catalyst for steam conversion of hydrocarbons contains nickel oxide (4.0-9.2%) and magnesium oxide (4.0-6.5%) supported by porous metallic nickel (balancing amount). Carrier has specific surface area 0.10-0.20 m2/g, total pore volume 0.07-0.12 cm3/g, predominant pore radius 1-30 μm, and porosity at least 40%. Described are also catalyst preparation method and generation of synthesis gas via steam conversion of hydrocarbons.

EFFECT: increased heat conductivity of catalyst resulting in stable activity in synthesis gas generation process.

8 cl, 1 tbl, 5 ex

FIELD: alternative fuels.

SUBSTANCE: invention relates to autothermal conversion of hydrocarbon fuel to produce synthesis gas, which can be used in chemical production, for burning at catalytic heat plants, and in hydrogen power engineering. Proposed catalyst contains, as active components, cobalt oxide, manganese oxide, and barium oxide, and, as carrier, refractory reinforced metalporous carrier. Catalyst is prepared by impregnation of carrier with barium and manganese salt solution at Ba/Mn =5:4 followed by drying, calcination, impregnation with cobalt salt solution, drying, and calcination. Invention further describes generation of synthesis gas via autothermal conversion of hydrocarbon fuel performed utilizing above-described catalyst.

EFFECT: enabled catalyst exhibiting high heat conductivity, high activity in production of synthesis gas, and resistance to coking and deactivation with sulfur compounds present in diesel fuel and gasoline.

6 cl, 1 tbl, 3 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides isodewaxing catalyst for petroleum fractions containing supported platinum and modifiers wherein supporting carrier is fine powdered high-purity alumina mixed with zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40 at following proportions of components, wt %: platinum 0.15-0.60, alumina 58.61-89.43, zeolite 5-40, tungsten oxide (modifier) 1-4, and indium oxide (modifier) 0.24-0.97. Preparation of catalyst comprises preparing carrier using method of competitive impregnation from common solution of platinum-hydrochloric, acetic, and hydrochloric acids followed by drying and calcinations, wherein carrier is prepared by gelation of fine powdered high-purity alumina with the aid of 3-15% nitric acid solution followed by consecutive addition of silicotungstenic acid solution and indium chloride solution, and then zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40.

EFFECT: increased yield of isoparaffin hydrocarbons.

7 cl, 2 tbl, 7 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to a method for preparing spherical supported metal catalysts with metal content from 10 to 70%, to spherical metal catalyst, to a process of hydrogenation of aromatic compounds wherein the latter are hydrogenised using spherical metal catalyst, and to a process of hydrogenation of aromatic compounds wherein the latter are hydrogenised using spherical supported metal catalyst.

EFFECT: increased activity and selectivity of catalyst having high porosity and uniform pore size distribution.

13 cl, 5 tbl, 12 ex

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

FIELD: alternative fuels.

SUBSTANCE: invention relates to autothermal conversion of hydrocarbon fuel to produce synthesis gas, which can be used in chemical production, for burning at catalytic heat plants, and in hydrogen power engineering. Proposed catalyst contains, as active components, cobalt oxide, manganese oxide, and barium oxide, and, as carrier, refractory reinforced metalporous carrier. Catalyst is prepared by impregnation of carrier with barium and manganese salt solution at Ba/Mn =5:4 followed by drying, calcination, impregnation with cobalt salt solution, drying, and calcination. Invention further describes generation of synthesis gas via autothermal conversion of hydrocarbon fuel performed utilizing above-described catalyst.

EFFECT: enabled catalyst exhibiting high heat conductivity, high activity in production of synthesis gas, and resistance to coking and deactivation with sulfur compounds present in diesel fuel and gasoline.

6 cl, 1 tbl, 3 ex

FIELD: oil and fat industry and technology.

SUBSTANCE: invention relates to an improved method for hydrogenation of vegetable oils and distilled fatty acids. Method involves the hydrogenation reaction that is carried out on a catalyst stationary layer representing crystallites of active palladium applied on surface of carbonic material wherein mesoporous graphite-like material is used as carbonic material with granules size 0.5-6.0 mm but preferably 3.0-6.0 mm, specific surface 100-450 m2/g, average size of mesopores in the range from 40 to 400 Å, total volume of pores 0.2-0.6 cm3/g and part of mesopores in the total volume of pores 0.6, not less. Palladium crystallites in volume of carbonic material are distributed by so manner that the distribution maximum values of active component are in distance from external granule surface corresponding to 1-30% of its radius and in the content of applied palladium in the range from 0.5 to 2.0 wt.-%. Invention provides the high hydrogenation rate of raw in production of technical sorts of hydrogenated fats and high stability of product.

EFFECT: improved method of hydrogenation.

2 cl, 1 dwg, 3 tbl, 16 ex

FIELD: inorganic synthesis catalysts.

SUBSTANCE: invention relates to catalytic elements including ceramic contact of regular honeycomb structure for heterogeneous high-temperature reactions, e.g. ammonia conversion, and can be used in production of nitric acid, hydrocyanic acid, and hydroxylamine sulfate. Described is catalytic element for heterogeneous high-temperature reactions comprising two-step catalytic system consisting of ceramic contact of regular honeycomb structure made in the form of at least one bed constituted by (i) separate prisms with honeycomb canals connected by side faces with gap and (ii) platinoid grids, ratio of diameter of unit honeycomb canal to diameter of wire, from which platinoid grids are made, being below 20.

EFFECT: increased degree of conversion and degree of trapping of platinum, and prolonged lifetime of grids.

5 cl, 6 ex

FIELD: disproportionation reaction catalysts.

SUBSTANCE: invention relates to Fischer-Tropsch catalyst containing cobalt and zinc, to a method for preparation thereof, and to Fischer-Tropsch process. Catalyst according to invention containing co-precipitated cobalt and zinc particles, which are characterized by volume-average size below 150 μm and particle size distribution wherein at least 90% of the catalyst particle volume is occupied by particles having size between 0.4 and 2.5 times that of the average particle size and wherein zinc/cobalt atomic ratio within a range of 40 to 0.1. Catalyst is prepared by introducing acid solution containing zinc and cobalt ions at summary concentration 0.1 to 5 mole/L and alkali solution to reactor containing aqueous medium wherein acid solution and alkali solution come into contact with each other in aqueous medium at pH 4-9 (deviating by at most 0.2 pH units) at stirring with a speed determined by supplied power between 1 and 300 kW/L aqueous medium and temperature from 15 to 75°C. Resulting cobalt and zinc-including precipitate separated from aqueous medium, dried, and further treated to produce desired catalyst. Employment of catalyst in Fischer-Tropsch process is likewise described.

EFFECT: enhanced strength and separation properties suitable for Fischer-Tropsch process.

13 cl, 2 dwg, 1 tbl, 5 ex

FIELD: exhaust gas afterburning means.

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

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

27 cl, 2 dwg, 7 tbl, 6 ex

FIELD: chemical industry; methods of manufacture of the building structures.

SUBSTANCE: the invention is pertaining to the field of the chemical industry, in particular, to production of the nitric acid, nitric fertilizers, the cyanhydric acid, the nitrites and nitrates and to other productions of chemical products, where the flow sheet of production provides for the catalytic conversion of ammonia up to the nitrogen oxides with usage of the platinoid mesh catalytic agents. The platinoid mesh catalytic agent formed in the form of the catalytic package produced out of the layer-by-layer stacked wire catalytic meshes and weaved out of the wires with the diameter of 0.06-0.1 mm consisting of the alloys of platinum with rhodium, palladium, ruthenium and other metals of the platinum group differs that the catalytic package consists of two different in the geometry of the braiding types of the meshes sequentially alternating in the height of the package. At that the geometry of the braiding of the first type of the catalytic meshes is characterized by the number of the wires interlacing per 1 cm2 in the interval of 1024-450, and the geometry of the braiding of the second type of the catalytic meshes is characterized by the number of the wires interlacing per 1 cm2 in the interval of 400-200. The technical result of the invention is the increased conversion of ammonia and the decreased share of the platinoids included in the mesh catalytic agent production processes providing for the catalytic conversion of ammonia in the flow sheet of the chemical goods production.

EFFECT: the invention ensures the increased conversion of ammonia and the decreased share of the platinoids included in the mesh catalytic agent production processes providing for the catalytic conversion of ammonia in the flow sheet of the chemical goods production.

3 ex

FIELD: composition and structure of composite metal semiconductor meso-porous materials; titanium-dioxide-based catalyst for photo-chemical reactions.

SUBSTANCE: proposed catalyst is meso-porous titanium-dioxide-based material containing crystalline phase of anatase in the amount no less than 30 mass-% and nickel in the amount no less than 2 mass-%; material has porous structure at average diameter of pores from 2 to 16 nm and specific surface no less than 70 m2/g; as catalyst of photo-chemical reaction of liberation of hydrogen from aqua-alcohol mixtures, it ensures quantum reaction yield from 0.09 to 0.13. Method of production of such catalyst includes introduction of precursor - titanium tetraalkoxyde and template of organic nature, holding reagent mixture till final molding of three-dimensional structure from it at successive stages of forming sol, then gel, separation of reaction product and treatment of this product till removal of template; process is carried out in aqua-alcohol solvent containing no more than 7 mass-% of water; at least one of ligands is introduced into solvent as template; ligand is selected from group of macro-cyclic compounds containing no less than four atoms of oxygen and/or from complexes of said macro-cyclic compounds with ions of metals selected from alkaline or alkaline-earth metals or F-metals containing lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum and cerium; mixture is stirred before forming of sol maintaining its temperature not above 35°C till final molding of three-dimensional structure from reagent mixture; mixture is held in open reservoir at the same temperature at free access of water vapor; after removal of template from three-dimensional structure, mixture is first treated with nickel salt solution during period of time sufficient for withdrawal of nickel ions from solution by pores of structure, after which is it kept in hydrogen-containing medium during period of time sufficient for reduction of nickel ions in pores of structure to metallic nickel.

EFFECT: enhanced sorption and photo-catalytic parameters; reproducibility of catalyst properties.

7 cl, 68 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for liquid-phase catalytic alkylation of aromatic amines. Method involves alkylation reaction of aromatic amines in the presence of hydrogen and lower alcohols at temperature 50-70°C on a heterogeneous catalyst. The distinctive specificity of method represents alkylation of amine with formaldehyde solution in reactor with reaction zone filled with catalyst consisting of aluminum oxide-base block high-porous cellular carrier with porosity value 7-95%, not less, and palladium as an active component with the mass content = 1.3-2%. As a rule, in the alkylation process catalyst prepared by impregnation of block high-porous cellular carrier with palladium salts treated preliminary in the constant magnetic field is used. Usually, in the case of alkylation of aniline and for preferential synthesis of monomethylaniline the molar ratio aniline to formaldehyde solution = 1.6:(1.1-1.6) is used. Proposed method as compared with the nearest analog in the case of alkylation of aniline provides preparing monomethylaniline mainly, to decrease the content of palladium as an active component in catalyst and to decrease the reaction pressure and hydraulic resistance of catalytic layer also. Invention can be used in producing antiknock additives to motor fuels (gasolines).

EFFECT: improved alkylation method.

3 cl, 4 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention relates to a method for preparing catalyst and to catalyst no honeycomb-structure block ceramic and metallic carrier. Preparation procedure includes preliminarily calcining inert honeycomb block carrier and simultaneously applying onto its surface intermediate coating composed of modified alumina and active phase of one or several platinum group metals from water-alcohol suspension containing, wt %: boehmite 15-30, aluminum nitrate 1-2, cerium nitrate 4-8, 25% ammonium hydroxide solution 10-20, one or several precipitate group metal salts (calculated as metals) 0.020-0.052, water-to-alcohol weight ratio being 1:5 to 1:10; drying; and reduction. Thus prepared catalyst has following characteristics: specific coating area 100-200 m2/g, Al2O3 content 5-13%, CeO2 content 0.5-1,3%, active phase (on conversion to platinum group metals) 0.12-0.26%.

EFFECT: simplified technology due to reduced number of stages, accelerated operation, and high-efficiency catalyst.

5 cl, 1 tbl, 10 ex

FIELD: catalyst preparation methods.

SUBSTANCE: method involves preparing porous carrier and forming catalyst layer by impregnation of carrier with aqueous solution of transition group metal salts followed by drying and calcination. Porous catalyst carrier is a porous substrate of organic polymer material: polyurethane or polypropylene, which is dipped into aqueous suspension of powdered metal selected from metals having magnetic susceptibility χ from 3.6·106 to 150·106 Gs·e/g: iron, cobalt, chromium, nickel, or alloys thereof, or vanadium and polyvinylacetate glue as binder until leaving of air from substrate is completed, after which carrier blank is dried at ambient temperature and then fired at 750°C in vacuum oven and caked at 900-1300°C. Caked blank is molded and then subjected to rolling of outside surface to produce carrier having variable-density structure with density maximum located on emitting area. Formation of catalyst layer is achieved by multiple impregnations of the carrier with aqueous solution of acetates or sulfates of transition group metals: iron, cobalt, chromium, nickel, or alloys thereof in alternative order with dryings at ambient temperature and calcinations to produced catalyst bed 50-80 μm in thickness. In another embodiment of invention, formation of catalyst layer on carrier is accomplished by placing carrier in oven followed by forcing transition group metal carbonate vapors into oven for 60-120 min while gradually raising oven temperature to 850°C until layer of catalyst is grown up to its thickness 50-80 μm.

EFFECT: improved quality of catalyst and reduced its hydrodynamic resistance.

8 cl, 1 tbl, 3 ex

FIELD: heterogeneous catalysis, catalytic micro-reactors, possibly manufacture of carriers of stainless steel with developed porous structure of surface designed for securing catalyst.

SUBSTANCE: method comprises steps of anode electrochemical etching of stainless steel in solution of iron chloride with concentration no more than 200g/l at electric current density 21 - 50 A/dm2. Method according to second variant of invention comprises steps of anode electrochemical etching of stainless steel in solution of sodium chloride with concentration no more than 200g/l at electric current density 11 - 25 A/dm2 while adding sulfuric acid to sodium chloride solution. Metallic carrier of stainless steel for catalyst includes on its surfaces drop-shaped etched depressions. Upper edge of depression has round shape with diameter 0.05 - 0.4 mm; mean volume of depressions is 4 x 10-4 cm3; surface density of depressions is in range 250 - 350 depressions per cm2.

EFFECT: improved surface structure of catalyst carrier.

6 cl, 4 ex, 1 dwg

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