Catalyst for processing vegetable oils and distilled fat acids and preparation method thereof

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts, particularly, to those intended for hydration of vegetable oil and fat and may be used in food, chemical and petrochemical industries. Proposed method comprises preparing granulated catalysts for liquid-phase hydration of vegetable oils and distilled fat acids by hydrogen that represent metallic palladium applied in amount of 0.5-2.0 wt % on carbon carrier of 0.5-6.0 mm-fraction with specific surface of 100-450 m2/g and volume of pores of 0.2-0.6 cm3/g. Hydration is conducted on catalyst stationary bed at 140-210°C, hydrogen pressure of 2 to 12 atm and raw stock consumption of 100 to 1500 g/(kgkt·h).

EFFECT: high hydration rate and stability of technical brands.

4 cl, 1 dwg, 3 tbl

 

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 of 80-250°C 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 associated with the nature of their operate is tion. 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°C in the reactor column type 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 of metal is and 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).

Weeks the STATCOM 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 (of 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 of 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 of 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 3/12, B01J 23/44, 29.11.1983] continuous is th 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°C. 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 in the active layer of a thickness of 10-50 μm from the outer surface of the granules. The palladium particles have a preferred size of 2-8 nm and localizes the us 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 200-300°C, and restore to the 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 granulated catalysts prepared by this method.

The disadvantages of these catalysts are ongena 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 from 40 to 400Å, 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 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 vegetable oils and distilled fatty acids, which comprises applying palladium on granular carbon media, followed by drying, decomposition and reconstruction, as the carbon material used mesoporous graphite-like material with razmara the granules 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 from 40 to 400Å, 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, 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 subsequent treatment of the deposited precursors of the metal with 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 for these supplies is Dah 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 materials can 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 on the Nove, 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°C 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 pressure drop across the layer is such that you may experience 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.

The recovery behavior is chestnykh 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 with the difference being the size of the granules;

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

The hydrogenation process is performed 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 is AI 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 kept 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 the nitrogen to hydrogen and restore the catalyst for 1 h at 150°C, followed by rise in temperature up to 250°C and holding at that temperature for 2 hours, Reduce the temperature from 250 to 40°C, 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 is described in this patent examples, 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 resulting 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 250°C for 2 hours to Reduce the temperature from 250 to 40°C, and replacing the hydrogen with nitrogen. The catalyst is washed with distilled water to a reaction with AgNO ions 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 ml of palladium nitrate solution with a concentration of palladium of 46.4 g/l (0,436 mol/l) and the concentration of free nitric acid, 175 g/l, stirred the mass for 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°C. and maintaining at this temperature for another 2 hours replace the Air is 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°C hydrogen, nitrogen, cooling the catalyst in a stream of nitrogen 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 wt.%.

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 prepared according to example 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 the carbon carrier is arch 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 (comparative).

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 content p is Ladia 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°C in a stream of nitrogen. Temperature rise to a predetermined carried out at a rate of 20°C/h If 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 by reducing the concentration of nitrogen oxides in the exhaust gas to a value of not more than 10 mg/m3. 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 PM At the Le restoration was completed in the reactor served cold hydrogen to reduce the temperature in the reactor up to 30-40°C. Then the reactor is 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°, acid number of 0.3 mg KOH/g) or GC (IC of 94.5 g I2/100 g, the title of 28.4°, acid number 195,4 mg KOH/g). Raw materials before dosing into the reactor is heated (rapeseed oil up to 60°C, GC up to 90°C), the capacity 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 is passed through a layer of rolled atora 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 a mass supported palladium in the production of summary : modified compositions obtained, and have 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 catalizzatore,0% Pd/Sib (example 19) after its use in the hydrogenation process GC within 110 hours With the involvement of the method of 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 Å, we cover almost the 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
M is the RCA Sibunit 1AR-BFASFB-4KVUSibunit 2
The origin (source)hydrocarbonscoalthe furfuralcoalhydrocarbonshydrocarbons
Appearancepellethandlepellethandlepelletpellet
Size mm1-34-53-54-63-54-6
Sbeats1)m2/g4404381200606120346
Vmicro2)cm3/g0,015 0,192mean HDI of 0.5310,2220,0100,010
Vmeso3)cm3/g0,6650,0270,4420,1440,310to 0.480
VΣ4)cm3/g0,6800,2190,9730,3660,3200,490
Vmeso/VΣ0,980,120,450,390,970,98
Dcf5), 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 the om monomolecular layer was assumed to be equal to ω=rate £ 0.162 nm 2;
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) average size of 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., °CDispersion, CO/Pd2)the cf., 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)2plating1702000,37320
50.5%Pd/SubPd(NO3)2plating170150 0,40315
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)2plating31.5 2500,17120
110.5%Pd/SubPd(NO3)2plating1702500,27326
120.5%Pd/SubH2PdCl4plating-2500,1540
131.0%Pd/SubPd(NO3)2plating1702000,39320
141.0%Pd/SubPd(NO3)2impregnation1702000,38332
150.5%Pd/AP-BPd(NO3)2plating 2500,10128
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)Dispers the awn (D) of the obtained catalysts determined by pulse method by chemisorption of CO at 20°C. The D value is 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, °CPH2kgf/cm2Reaction time, hoursThe feed rate, g/HREat a CR-TA, g/(kg)CT·h)Eat a CR-TA, g/(gPd·h)Titer, °IC, g I2/100 g
10.5%Pd/Sub170-1826159,6686137,157,2-59,3
GK150-1626-8304,330761,457,5 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
GK174-1776 20of 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/SubGK154-1576-8308, 61430,757,5-60,26,2-9,5
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/Suboil179-1896 1510.7764152,962,2-64,0
GK199-2046316,244388,657,5 to 58.2
131.0%Pd/SubGK148-1606-8125,237137,155,2-57,0
141.0%Pd/SubGK160-1686-818a 4.935035,057,5-59,0from 9.1 to 15.2
160.5%Pd/FASGK148-157615 4,834368,673,5-75,7
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 4.935035,0 57,2-59,06,5-9,0

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 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 Å, a 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 is about 400 Å, 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 claim 2, characterized in that for the preparation of the catalyst, 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°C, decomposition in a current of inert gas at 200-300°C, the recovery is carried out in hydrogen at 150-250°C.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts for dehydrogenation of paraffin hydrocarbons and methods of producing said catalysts, as well as methods of producing olefin hydrocarbons via catalytic dehydrogenation of corresponding C3-C5 paraffin hydrocarbons and can be used in chemical and petrochemical industry. Described is a catalyst for dehydrogenation of C3-C5 paraffin hydrocarbons, which contains chromium and potassium oxides and optionally zirconium dioxide, deposited on a solid solution of formula ZnxAl2O(3+x) where x=0.025-0.25, with a defective spinel structure. Described is a method of producing the catalyst by hydrating a precursor of the solid solution, saturating with a mixture of solutions of chromic acid, potassium chromate and a zinc salt and optionally zirconyl nitrate, followed by drying and calcination in air, wherein hydration is carried out during the saturation process. A method of dehydrogenating paraffin hydrocarbons in the presence of said catalyst is also described.

EFFECT: high catalytic activity, selectivity and stability with low coke formation.

14 cl, 2 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing hydrogen using catalysts. Described is a method of producing hydrogen via direct decomposition of natural or liquefied petroleum gas (LPG), where the catalyst used is based on nickel-iron-gamma-aluminium oxide, prepared through combined adsorption of aqueous solutions of nickel and iron nitrates on gamma-aluminium oxide, carried out in 2-4 steps, where the weight ratio of nickel to iron on the catalyst surface is equal to 1:1 and total weight makes up 20-40%.

EFFECT: high output of hydrogen.

2 cl, 6 ex

FIELD: process engineering.

SUBSTANCE: invention relates to petrochemistry, particularly, to production of zeolite-based catalyst for alkylation of isobutane by olefins and may be used in oil processing. Invention covers catalyst of alkylation of isobutane by zeolite-based olefins that contains aluminium oxide and silicon dioxide at silicon dioxide-to-aluminium oxide molar ratio equal to 2.8-7.0, sodium oxide, rare-earth element, oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium at the following ratio of components, in wt %: sodium oxide - 0.26-0.8, calcium oxide - 0.8-4.2, rare earth element oxide - 12.0-20.0, oxides of platinum and/or palladium and/or rhenium and/or ruthenium - 0.02-2.0, zeolite with SiO2/Al2O3 equal to 2.8-7.0, making the rest. It covers also two versions of the method of catalyst production comprising zeolite treatment by water solutions of salts of calcium, rare earth element and ammonium at increased temperature and pressure of saturated vapors for time period required for conversion of zeolite into rare-earth calcium zeolite, its washing, drying and calcinating. In compliance with this method, first, rare-earth calcium zeolite is impregnated with unipolar water unless air escapes from zeolite pores and, then, processing is performed by impregnation with water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium taken in amount that ensures said content of metal oxide in finished catalyst. It comprises also drying, calcinating, or applying on rare-earth metal calcium zeolite of water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium in unipolar water taken in amount that ensures aforesaid content of metal oxide in finished catalyst, drying, tabletting and calcinating.

EFFECT: increase in catalyst activity to 100 wt %, in isooctane selectivity to 75,7 wt % and in yield of target alkyl benzene by 10-15 wt %.

14 cl, 10 ex, 2 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to petrochemistry, particularly, to production of zeolite-based catalyst for alkylation of isobutane by olefins and may be used in oil processing. Invention covers catalyst of alkylation of isobutane by zeolite-based olefins that contains aluminium oxide and silicon dioxide at silicon dioxide-to-aluminium oxide molar ratio equal to 2.8-7.0, sodium oxide, rare-earth element, oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium at the following ratio of components, in wt %: sodium oxide - 0.26-0.8, calcium oxide - 0.8-4.2, rare earth element oxide - 12.0-20.0,oxides of platinum and/or or palladium and/or molybdenum and/or nickel and/or cobalt - 0.02-2.0, zeolite with SiO2/Al2O3 equal to 2.8-7.0, making the rest. It covers also two versions of the method of catalyst production comprising zeolite treatment by water solutions of salts of calcium, rare earth element and ammonium at increased temperature and pressure of saturated vapors for time period required for conversion of zeolite into rare-earth calcium zeolite, its washing, drying and calcinating. In compliance with this method, first, rare-earth calcium zeolite is impregnated with unipolar water unless air escapes from zeolite pores and, then, processing is performed by impregnation with water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or molybdenum and/or nickel and/ or cobalt taken in amount that ensures said content of metal oxide in finished catalyst. It comprises also drying, calcinating, or applying on rare-earth metal calcium zeolite of water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or molybdenum and/or nickel and/or cobalt. The process includes two stages: first, cold impregnation at not over 30°C, and, second, at, at least, 70°C, and finally drying, tabletting and calcinating.

EFFECT: increase in catalyst activity approximating to 100 wt %, isotope selectivity approximating to 73.5 wt %, yield of target alkyl benzene by 10-15 wt %.

16 cl, 10 ex, 2 tbl

FIELD: petrochemistry.

SUBSTANCE: invention relates to hydrocarbons cracking catalysts; the method describes modification of zeolitealuminumsilica-base catalyst for hydrocarbons cracking by means of soaking of the catalyst in the organisticmetallosiloxane solution amid cavitation processing with the intensively of the interval rate of injection 0.2-0.5 W/m followed by maturing at the ambient temperature, solvent distilling and high-temperature processing.

EFFECT: cracking catalyst which has high cracking intensity and selectivity was received.

3 cl, 9 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the method of production of purification catalysts of internal combustion engines exhaust gases; the method of preparation of purification catalysts of internal combustion engines exhaust gases is described herein, the method is characterized by application of cordierite carriers of the cellular structure, formation of the inert layer of aluminum and silicon hydrate on the carrier by means of processing with the caustic soda water solution at the ambient temperature followed by soaking the carrier in the reactor with the inert layer with the cerium salt water solutions and precursor that is represented by perchlorate palladium (II) received directly during the solution of perchlorate palladium (II) in the water in the presence of perchloric acid; thereafter the reduction of palladium by means of hydrogen on the surface of the catalyst is conducted in the above reactor at the atmospheric pressure and ambient temperature.

EFFECT: precipitation and facilitation of the catalysts preparation technology.

1 dwg, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to petrochemical and chemical industry, particularly a method of preparing moulded catalysts for conversion of methane into aromatic hydrocarbons and hydrogen in nonoxidative conditions. The invention describes a catalyst for a nonoxidative methane conversion process, containing high-silica zeolite H-ZSM-5, a binding additive - calcium form of montmorillonite, modifying elements - molybdenum and cobalt, where content of the binding additive in the catalyst is not more than 40.0 wt %, while content of molybdenum and cobalt is not more than 3.0 wt % and 1.0 wt %, respectively. Described is a method of preparing a catalyst, involving modification of zeolite with promoting elements through successive wetness impregnation of zeolite H-ZSM-5 with molybdenum and cobalt salt solutions, followed by calcination, and then mixing the zeolite modified with metals with a binding additive suspension in a given proportion to obtain a moulding mass and moulding said mass into granules in a moulding device. The invention also describes a method for nonoxidative conversion of methane in the presence of the catalyst described above.

EFFECT: high efficiency of the nonoxidative methane conversion process owing to high activity and stability of the catalyst.

4 cl, 7 ex, 1 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to catalytic filters for cleaning diesel engine exhaust gases. Proposed filter comprises inlet and outlet and axial length coated by first catalyst comprising platinum group metals on carrier materials and differs from known designs in that said carrier materials are selected from the group including aluminium oxide, silicon dioxide, titanium dioxide, zirconium dioxide, cerium dioxide and mixes thereof, or mixed oxides. Note here that first catalyst additionally comprises at least one zeolite to accumulate hydrocarbons starting from filter inlet. Note also that section of said filter length is coated by second catalyst that contains no zeolite. Invention covers the method of fabricating said filter wherein both catalyst are applied on said filter as suspension coat. Besides it covers application of said filter for decreasing the content of carbon, hydrocarbon and ash particles in diesel engine exhaust gases.

EFFECT: improved conversion of hydrocarbons into carbon oxide.

10 cl, 2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing ethylene on modified aluminium oxide catalysts during dehydration of ethanol. Described is a catalyst for producing ethylene during dehydration of ethanol, containing aluminium oxide and chlorine in amount of 1.0-4.0 wt %. Described is a method of producing the catalyst by saturating aluminium oxide with hydrochloric acid, followed by drying and calcination, thereby obtaining a catalyst containing aluminium oxide and chlorine in amount of 1.0-4.0 wt % with specific surface of 150-300 m2/g and pore size distribution of 3-30 nm. Described is a method of producing ethylene via dehydration of ethanol using the catalyst described above at 350-400°C and contact time of 0.3-1 s.

EFFECT: high activity and selectivity of producing ethylene from ethanol.

11 cl, 10 ex, 3 tbl

FIELD: technological processes.

SUBSTANCE: present invention relates to a catalyst for hydrocarbon production from synthesis gas, to method of its production, method of such catalyst regeneration and method of hydrocarbon production with application of such catalyst. A catalyst is described to produce hydrocarbon from synthesis gas, in which metal cobalt or metal cobalt and cobalt oxides; and zirconium oxides are applied onto a catalyst substrate, which mainly consists of a silicon dioxide. This catalyst is characterised by the fact that content of admixtures in the catalyst makes less or is equal to 15 wt %. Versions of the method are described to produce such catalyst, where the catalyst is produced by simultaneous or separate application of cobalt and zirconium compounds onto a catalyst substrate by impregnation method, impregnation method by moisture capacity, by method of deposition or method of ion exchange and performance of restoration treatment or baking and restoration treatment. Versions are described to regenerate such catalyst, where the catalyst with reduced activity is treated with a regenerating gas, containing hydrogen, or regenerating gas is supplied into a reactor, or regenerating gas is supplied into any part of the outer circulation system, and the catalyst and the regenerating gas contact with each other. Versions of the method to produce hydrocarbon from synthesis gas with application of such catalyst are described, where the method is carried out with performance of reaction in a liquid phase using a reactor with a layer of suspended residue or a layer of suspended residue with an external circulation system.

EFFECT: production of catalyst having high activity, durable service life and high resistance to water without loss of strength and wear resistance.

31 cl, 3 tbl, 2 dwg, 21 ex

FIELD: chemistry.

SUBSTANCE: this invention relates to the catalyst used for alkylation of aromatic compounds by monoolefinic aromatic compounds, in particular to the catalyst used for the selective hydrogenization of diolefin and acetylene into olefins; this method describes the catalyst for the selective hydrogenization of diolefin and acetylene containing nondense medium containing gamma-aluminum oxide or theta-aluminum oxide with the volume of micropores less than 10% of the volume of the pores and the specific service 150 m2/g and the palladium on the medium in the amount of 50 - 5000 ppm.

EFFECT: catalyst has the minimal resistance to diffusion through the large pores and minimizes hydrogenization of olefines into paraffins.

9 cl

FIELD: engines and pumps.

SUBSTANCE: catalyst for cleaning of waste gases of internal combustion engines contains honeycomb element consisting of plain and corrugated metal sheets with inlet end surface and outlet end surface for waste gases; at that, metal sheets are provided with holes for reduction of their heat capacity, and catalyst mass is applied to metal sheets; at that, holes of metal sheets are filled with catalyst mass, and surface area of all the holes is 5 to 80% of the surface area of metal sheets. Also, use of catalyst for cleaning of waste gases of internal combustion engine is described.

EFFECT: reduction of heat capacity and heat conductivity of catalyst.

12 cl, 7 dwg

FIELD: process engineering.

SUBSTANCE: invention covers the method of producing cellular element 6 with radial annular part 9 with flow passages 10, made up of, at least, one metal layer (1, 13, 14). Said metal layer is secured in, at least, one point 16, to outer tubular casing (7). Every said metal layer (1, 13, 14) has sections (2, 3) superimposed by layer accordion folding. Note here that said metal layer features alternating, mainly, flat 2 and shaped 3 sections. Besides, invention covers cellular element (6) with radial annular section (9) with flow passages (10) made up of, at least, one metal layer (1, 13, 14), which in, at least, one attachment point (16) is secured to outer tubular casing (7), wherein each metal layer (1, 13, 14) has section (2, 3) superimposed by metal layer accordion folding. Note here that metal layer features alternating, mainly, flat (2) and shaped (3) sections.

EFFECT: low material input, longer life.

22 cl, 11 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to catalyst systems and use thereof in Fischer-Tropsch synthesis. Described is a catalyst system which contains a Fischer-Tropsch synthesis catalyst or a catalyst precursor and a porous body, where the said porous body has size between 1 and 50 mm, preferably 1-30 mm, and the catalyst system has internal porosity between 50 and 95%. Described also is a method which involves the following steps: (i) feeding synthesis gas into a reactor; and (ii) bringing the synthesis gas into contact with a non-stationary catalyst for catalytic conversion of the synthesis gas at high temperature in order to obtain usually gaseous, usually liquid and optionally usually solid hydrocarbons from the synthesis gas; where the catalyst on step (ii) lies in a set of porous substrates having size of 1-50 mm, preferably 1-30 mm, thus forming a catalyst system, and where the said catalyst system has external porosity in the reactor in situ between 5 and 60%, and internal porosity of the catalyst system lies in the range of 50-95%.

EFFECT: use of the disclosed catalyst system provides a trade-off, where it is much easier to separate such catalyst systems from products in a suspension reactor (which lowers expenses), although they may be in suspended state and can therefore still move inside the reaction vessel; this ensures more uniform mass transfer and heat transfer during catalysis, but without immobilisation of the catalyst.

FIELD: process engineering.

SUBSTANCE: invention relates to application on coat made from suspension that contains catalytic components in liquid carrier in the form of solid substances and/or in dissolved form. Proposed catalytic coat is applied on ceramic cellular elements wherein parallel flow channels run from their inlet to outlet. Said channels are separated by walls with open-pore structure. Suspension comprises catalyst containing suspended solid substances in liquid carrier. Note here that said flow channels are closed in turn on inlet and outlet of cellular element. Suspension is forced through cellular element to open in turn closed flow channels.

EFFECT: increased amount of active catalyst at comparable velocity head after coat application.

9 cl, 3 ex, 5 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts designed for hydrogenating triglycerides of plant oil and fat and can be used in food, perfumery, petrochemical and oil-refining industry. Described is a catalyst which contains 0.1-2.0 wt % catalytically active palladium which is deposited on the surface of carbonaceous material. The specific surface area of the catalytically active palladium on the surface of the carbonaceous material is equal to 5-20 m2/g. Over 90% of the palladium is in the surface layer of the carbonaceous material whose thickness is not greater than 25% of the diametre of particles of the carbonaceous material which has particle size distribution of 50-250 mcm.

EFFECT: high activity (efficiency) and reduced formation of trans-isomers when producing hydrogenated fat for food purposes.

2 cl, 3 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts, particularly designed for hydrogenating triglycerides of plant oil and fat and can be used in food, perfumery, petrochemical and oil-refining industry. The invention describes a catalyst for hydrogenating unsaturated hydrocarbons, preferably plant oil and fat, which contains catalytically active palladium in amount of 0.1-5.0 wt % deposited on the surface of a solid support in form of active aluminium oxide with average mesopore size between 20 and 500 nm, on the surface of which there is a 3-30 nm layer of pyrocarbon. The invention describes a method of preparing the catalyst by depositing 0.1-5.0 wt % catalytically active palladium onto the surface of an active aluminium oxide support with average mesopore size between 20 and 500 nm, on whose surface there is a 3-30 nm layer of pyrocarbon, followed by drying, decomposition and reduction of palladium. Described also is a method of hydrogenating unsaturated hydrocarbons using the said catalyst.

EFFECT: high efficiency at given quality of hydrogenated fat (content of trans-isomers and iodine number).

7 cl, 3 ex, 2 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to micro channel reactors and catalysts that comprises a layer of metal aluminide. Micro channel reactor consists of complex micro channel constricted by one micro channel wall and aluminide coat applied on the surface of one micro channel wall. Note here that complex micro channel represents an inner micro channel deferring in one or several following characteristics: one continuous micro channel with turn section, turn angle of 45°, length of 20 cm or more, height and width of 2 mm or less; one micro channel is divided into two sub channels arranged in parallel; complex micro channel makes on of adjacent micro channels with the length of common adjacent section of 1 cm whereon several connecting holes are made on common micro channel wall. Note here that total area of said holes does not exceed 20% of that of micro channel wall whereon said holes are located, while area of each hole does not exceed 1.0 mm2. Complex micro channel represents one of five parallel 1 cm-long micro channels. Open ends of said channels communicated with common collector. One size of said collector is thrice the minimum length and width of parallel micro channels. Aluminide layer provides for chemical stability. Besides aluminide increases in metal diffusion from reactor walls to make solid and homogeneous coat for all inner surfaces even in complex-shape channels.

EFFECT: accurate control over chemical processes in complex micro channels, stable operation.

17 cl, 14 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to a combustion catalyst for combustion and removal of carbon-bearing material, to a method of preparing said catalyst, to a catalyst support and preparation method thereof. The method of preparing the carbon-bearing material combustion catalyst involves steps for mixing, drying and burning. At the mixing step, zeolite, except sodalite, and an alkali metal source and/or alkali-earth metal source are mixed in a polar solvent such as water or another in a defined ratio. At the drying step after mixing, the liquid mixture is heated with evaporation of water in order to obtain a solid substance. At the burning step, the substance is burnt at temperature of 600°C or higher to obtain a carbon-bearing material combustion catalyst. The invention describes a method of preparing a support for the carbon-bearing material combustion catalyst on a ceramic substrate, whereby the catalyst support is designed for combustion of carbon-bearing material contained in exhaust gas of an internal combustion engine, involving attaching the combustion catalyst made using the described method onto a ceramic substrate and a catalyst support made using this method.

EFFECT: stable combustion and removal of carbon-bearing material at low temperature for a long period of time.

17 cl, 6 ex, 2 av ex, 19 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for combustion of carbon-bearing material contained in exhaust gas of an internal combustion engine, to a method of preparing said catalyst, as well as a support for said catalyst and method of preparing said support. The invention describes a method of preparing a carbon-bearing material combustion catalyst which is attached to a ceramic substrate, involving mixing aluminium silicate having atomic equivalent ratio Si/Al≥1 and an alkali and/or alkali-earth metal source in a polar solvent such as water or another, drying the liquid mixture to obtain a solid substance and burning it at temperature of 600°C or higher. The aluminium silicate is sodalite. Alternatively, the carbon-bearing material combustion catalyst is prepared through a sequence of steps for mixing, drying and burning, whereby the method involves burning sodalite at temperature of 600°C or higher. A catalyst prepared using the method given above is described. Described also is a method of preparing a catalyst support involving a step for attaching the combustion catalyst to a ceramic substrate, and a catalyst support made using said method.

EFFECT: stable combustion and removal of carbon-bearing material at low temperature for a long period of time.

26 cl, 3 ex, 1 av ex, 27 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts for low-temperature oxidation of carbon monoxide (CO), a method of producing said catalysts and a method of oxidising CO in order to protect the environment from CO pollution. The catalyst for oxidising carbon monoxide is a Pd/C-K composition, where: C is a mesoporous carbon material obtained via carbonisation of rice husks, K is kaolin which contains aluminium, silicon, titanium, iron and calcium oxides. The catalyst is made by saturating a nanocomposite carbon-containing support with an alcohol solution containing palladium nitrate with palladium content 2-5%,said support having the following texture characteristics: SBET=450-470 m2/g, Vpor=0.5-0.6 cm3/g, dpor=3.3-3.5 nm. The carbon-containing support is made through carbonisation of rice husks in a reactor with a copper-chromium catalyst fluidised-bed at temperature 450-470°C, through activation thereof with KCO3 at temperature 850-900°C and then mixing with kaolin in weight ratio 2/3-1/1 and with water and then moulding. Carbon monoxide is oxidised in the presence or absence of water in a reaction mixture and the catalyst described above.

EFFECT: complete oxidation of carbon monoxide CO at room temperature and suitable moisture content.

9 cl, 7 dwg, 7 ex

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