RU2547258C1 - Catalyst for selective hydrogenation of acetylene and diene hydrocarbons in c2-c5+-hydrocarbon fractions - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: composition of the catalyst is formed in the following ratio, wt %: palladium 0.005-1, promoter 0.005-5, copromoter if necessary 0.005-5, carrier - the remaining part. The promoter on the carrier is fixed in the oxide form to the active component. Palladium particles are fixed on the carrier in the zero degree of oxidation in the electronic condition of valence orbitals of their own atoms. The catalyst is characterised by a band of an absorbing complex of carbon monoxide with palladium with the wave number of 2060-2100 cmin the infrared spectrum of absorbed carbon monoxide. As the carrier applied is a highly-porous cellular carrier, produced from a metal or aluminium oxide, characterised by the porosity not less than 85%, the average size of the pores is 0.5-6.0 mm. On the highly-porous cellular carrier placed is a layer of aluminium oxide with the formation of a secondary carrier, on which the promoter and the active component palladium are successively placed. The secondary carrier aluminium oxide is characterised by the width from 10 mcm to 500 mcm, specific surface of not less than 20 m/g, volume of the pores from 0.1 to 1.0 cm/g and is made with the pores with a diameter over 5 nm, the volume of which constitutes 50-98% of the total volume of the pores. The secondary carrier in the general composition of the catalyst constitutes not less than 5 wt %.EFFECT: improvement of thermo- and weight-exchange and diffusion characteristics with the elimination of a possibility to form local overheats of the catalyst layer and diffusion limits of the transport of initial compounds and reaction products.4 tbl, 22 ex

Description

The present invention relates to chemical technology for the production of catalysts, in particular catalysts for the selective hydrogenation of acetylene and diene hydrocarbons in C ₂ -C ₅₊ hydrocarbon fractions.

Industrial processes for the purification of C ₂ -C ₅₊ hydrocarbon fractions from acetylene and diene hydrocarbons for the subsequent polymerization of monomers are carried out in liquid, mixed gas-liquid and in gaseous media by selective hydrogenation in reactors with an irregular granular catalyst bed. The catalyst is a Group VIII metal of the periodic system dispersed on the surface of an inorganic or organic carrier. Most often, palladium supported on alumina, kieselguhr, silica gel, coal, and sepionite is used as the active metal. Moreover, the carrier has the form of granules, spheres, rings, etc. The used catalyst should have: high activity, providing a residual content of acetylene and diene compounds in the reaction products to values of ~ 0.0001% by mass; high selectivity - by hydrogenating acetylene and diene hydrocarbons to the corresponding olefin compounds, and a long inter-regeneration cycle due to the low ability to initiate the formation of oligomers that deactivate the catalyst.

Currently used in industrial processes for the selective hydrogenation of acetylene and diene hydrocarbons, granular catalysts with an irregular layer in the form of spheres, cylinders, or other geometric shapes are characterized by unsatisfactory heat and mass transfer in the catalyst layer. Poor thermal conductivity of the inorganic carrier causes the formation of local overheating in the granular layer, which leads to a change in the physical characteristics (density, viscosity) of the hydrocarbon stream with an increase in the unevenness of its distribution over the cross section of the catalyst layer and subsequent deterioration of the performance of the catalyst. The formation of local overheating with an increase in temperature from the recommended technological regulation also causes the occurrence of side reactions of deep hydrogenation of acetylene and diene hydrocarbons to alkanes and oligomerization processes, leading to a decrease in selectivity for the main component and accelerated catalyst deactivation, respectively. Large grains of the catalyst with a diameter of usually more than 2-3 mm do not provide good mass transfer of the starting components and reaction products as a result of diffusion restrictions associated with the location of the active component in the depth of the carrier granule. This leads to ineffective use of the active component and the occurrence of side reactions of deep hydrogenation of acetylenic and diene hydrocarbons to alkanes with a decrease in the activity and selectivity of the catalyst. Reducing the grain size of the catalyst to reduce the adverse effects of diffusion restrictions with increasing the availability of the active component to the reacting molecules leads to an increase in hydraulic resistance with a limited ability to increase the performance of industrial reactors.

Based on this, in addition to optimizing the chemical composition of the catalyst with varying the characteristics of the active component and the acid-base properties of the support, it is important in the development of the catalyst to select the geometric characteristics of the support, its shape and texture characteristics that provide: effective heat and mass transfer in the catalyst layer, low hydraulic resistance of the catalyst layer; causing the possibility of increasing the feed rate of hydrocarbons; optimal distribution of the active component with its high access for reacting molecules. Catalysts of block, honeycomb and tissue structures meet these requirements.

A catalyst has been proposed (UK Patent No. 1596959 "Selective hydrogehation of C2 minus fractions", IPC B01J 23/44, priority 05/30/78, publ. 03.09.81) for the selective hydrogenation of acetylene in an ethane-ethylene mixture on a block catalyst, which is a multi-channel structure based on α-Al ₂ O ₃ . The palladium content in the catalyst is 0.005-0.1% of the mass, the promoting elements Cu, Ag, Ni, Fe are 0.005-0.25% of the mass. α-Al ₂ O _{3 is} characterized by a specific surface area of at least 50 m ² / g and a macroporous structure in which at least 33% of the pores are larger than 500 Å. The use of multichannel block media can reduce diffusion difficulties for mass and heat transfer. However, the disadvantage of this catalyst is its low activity.

Also known is a catalyst for the selective hydrogenation of acetylene and diene hydrocarbons mixed with monoolefins (RU 2164814, B01J 23/40, publ. 10.04.2001). In the specified catalyst, a glass fiber silicate material with a silica content of 50-99 wt.% And a specific surface area of 0.1-200 m ² / g is used as a carrier. Elementary fibers of a glass fiber carrier have a diameter of 1-20 μm. The carrier has a woven or non-woven structure, having good characteristics of heat, mass transfer, diffuse properties, and can improve the performance of the installation for cleaning hydrocarbon systems from impurities. The catalyst has high thermal stability, but is characterized by insufficient activity.

When developing a catalyst, it is important to consider not only the composition of the active component, other components of the catalyst, its structural characteristics, but also its electronic state, electronic characteristics of the active component.

The closest analogue selected catalyst according to patent RU 2453365, B01J 21/04, "Catalyst for the selective hydrogenation of acetylene and diene hydrocarbons in C ₂ -C ₅₊ hydrocarbon fractions", publ. 06/20/2012. The catalyst is an alumina carrier on which the active component of palladium and the promoter are placed. The promoter on the support is fixed in the oxide form, the palladium particles are fixed on the support in the zero state of electronic oxidation of the valence orbitals of its atoms, in which the catalyst is characterized by an absorption band of a complex of carbon monoxide with palladium with a wave number of 2060-2100 cm ^-1 in the infrared spectrum of the adsorbed monoxide carbon, the composition of the catalyst is formed in the following ratio, wt.%:

Palladium 0.005-1,

Promoter 0.005-5,

Sopromotor, if necessary, 0.005-5,

Alumina carrier - the rest.

The technical result of the prototype is to increase the dispersion and change the electron density and geometric characteristics of the particles of the active component with a more complete interaction with the promoter. This allows you to increase the activity and selectivity of the catalyst.

However, this granular catalyst does not provide good heat and mass transfer and diffusion, which causes local overheating and inefficient transport of the starting components to the active component, respectively, and leads to a decrease in the activity and selectivity of the catalyst and the side reactions of hydrogenation of acetylene and diene hydrocarbons to alkanes and oligomerization processes.

The objective of the invention is to improve heat and mass transfer and diffusion characteristics with the exception of the possibility of forming local overheating of the catalyst layer and diffuse restrictions on the transport of the starting compounds and reaction products, respectively, thereby further increasing the activity and selectivity of the catalyst for selective hydrogenation of alkyne and diene hydrocarbons in C ₂ -C ₅₊ hydrocarbon fractions.

The problem is solved by the development of a catalyst for the selective hydrogenation of acetylene and diene hydrocarbons in C ₂ -C ₅₊ hydrocarbon fractions, with an alumina carrier on which the active component of palladium and the promoter are located. The promoter on the support is fixed in oxide form until the active component is fixed, palladium particles are fixed on the support in the zero state of electronic oxidation of the valence orbitals of its atoms, in which the catalyst is characterized by an absorption band of a complex of carbon monoxide with palladium with a wave number of 2060-2100 cm ^-1 infrared spectrum of adsorbed carbon monoxide, the composition of the catalyst is formed in the following ratio, wt.%:

Palladium 0.005-1,

Promoter 0.005-5,

Sopromotor, if necessary, 0.005-5,

The carrier is the rest.

Moreover, the alumina carrier is characterized by pores with a diameter of more than 5 nm, the volume of which is 50-98% of the total pore volume.

The difference between the invention and the prototype is the following:

- as a carrier, a highly porous cellular carrier made of metal or aluminum oxide is taken, characterized by a porosity of at least 85%, an average pore size (cells) of 0.5-6.0 mm;

- on a highly porous cellular carrier, a layer of aluminum oxide is fixed with the formation of a secondary carrier on which the promoter and the active component of palladium are sequentially placed;

- the secondary carrier alumina is characterized by a thickness of 10 μm to 500 μm, a specific surface area of at least 20 m ² / g, a pore volume of 0.1 to 1.0 cm ³ / g;

- the secondary carrier of aluminum oxide in the total composition of the catalyst is at least 5% wt.

With the specified set of restrictive and distinctive features:

- highly porous cellular carrier, characterized by a porosity of at least 85% and an average pore size (cells) of 0.5-6.0 mm, provides high mass and heat transfer, low hydraulic resistance;

- the presence of a secondary carrier with a thickness of 10 μm to 500 μm, with a specific surface area of at least 20 m ² / g, a pore volume of 0.1 to 1.0 cm ³ / g, in which pores with a diameter of more than 5 nm are 50-98% total pore volume, with a content of not less than 5% wt. provides not only the optimal distribution of palladium on the surface of the catalyst with its high dispersion, but also the absence of diffusion restrictions on the access of the reaction molecules to the active component, which leads to an increase in the activity of the catalyst and the selectivity of hydrogenation of acetylenic and diene hydrocarbons.

- the presence of a promoter in oxide form causes an increase in the dispersion of the active component with the formation of coordinatively saturated surface atoms of palladium particles in a zero oxidation state with high electron density in valence orbitals, which have high activity and selectivity in the hydrogenation reactions of acetylenic and diene hydrocarbons.

As a result of the use of a catalyst based on a highly porous support with a thin layer of a secondary alumina support in accordance with this invention, the process of hydrogenation of acetylene and diene hydrocarbons in C ₂ -C ₅₊ hydrocarbon fractions is carried out more efficiently, which is reflected in an increase in the yield of target hydrocarbons.

The catalyst was prepared as follows.

A highly porous metal support was obtained by electrochemical deposition of a metal on a metallized substrate of a reticulated mesh-cellular polyurethane foam matrix or by slip method.

Electrochemical deposition of metal on a metallized substrate of a reticulated mesh-cellular polyurethane foam matrix was carried out in three stages: deposition of an electrically conductive layer on a polyurethane foam matrix, electrochemical deposition of a metal coating on a metallized polyurethane foam matrix and removal of an organic polyurethane foam matrix by calcining at a temperature of 300--1900 ° C 8 ocloc'k.

Metal deposition using the slip method was carried out by duplicating the reticulated mesh-cellular polyurethane foam matrix by applying metal powders to the polyurethane foam matrix with subsequent cyclic action (compression-tension). Next, the excess slip was removed by squeezing the sample to a predetermined mass. Then, the impregnated preforms were subsequently dried at a temperature of 100-120 ° C for 1-4 hours and fired at a temperature of 1200-1900 ° C for 2-8 hours.

Nickel, copper, iron, titanium, aluminum in an individual form or in combinations with each other were used as a starting material of a highly porous support.

A highly porous alumina support was obtained by the slip method, which consisted in impregnating with solutions of aluminum compounds a reticulated mesh-cellular polyurethane foam matrix by cyclic action (compression-tension). Next, the excess slip was removed by squeezing the sample to a predetermined mass. Then, the impregnated preforms were subsequently dried at a temperature of 100-120 ° C for 1-4 hours and calcined at a temperature of 1200-1700 ° C for 2-8 hours. In this case, various modifications of alumina were formed (γ-Al ₂ O ₃ , β-Al ₂ O ₃ , η-Al ₂ O ₃ , δ-Al ₂ O ₃ , θ-Al ₂ O ₃ , α-Al ₂ O ₃ ) individually or in combination with each other.

As a starting compound for the production of a highly porous carrier of α-modification of aluminum oxide, various salts, hydroxides, aluminum oxides in individual form or in combination with each other were used.

Moreover, upon receipt of a highly porous carrier of metal or aluminum oxide by the slip method to increase the sedimentation stability and adhesion strength when fixing the slip on the surface of the reticulated mesh-cellular polyurethane foam matrix, a surfactant solution can be added to the aqueous slip solution.

To form a secondary alumina layer, the surface of a highly porous metal or alumina support was impregnated with an aluminum compound. For this, a highly porous support sample was placed in the mixer chamber. Then, aqueous or organic solutions of the starting aluminum compound were dosed. The highly porous support was impregnated with aluminum compound solutions for 0.1-2 hours at a temperature of 20-80 ° C. After impregnation, the highly porous carrier was dried for 0.5-2 hours at a temperature of 30-200 ° C. In order to form a layer of aluminum oxide with a total mass fraction of more than 5% by weight of the total catalyst mass, the highly porous metal or aluminum oxide support was impregnated with an aluminum compound two or more times with drying and / or calcination after each impregnation. In this case, upon receipt of a secondary layer of aluminum oxide on the surface of highly porous cellular material to increase the sedimentation stability and adhesion strength when fixing the aluminum compound on the surface of the highly porous metal and aluminum oxide support, a surfactant solution can be added to the aqueous solution of the aluminum compound. Further, to transfer the supported aluminum compound into the oxide form, the support was calcined with the aluminum compound. The carrier coated with an aluminum compound was calcined at 250 ° C to 1200 ° C for 2-8 hours to form various modifications of aluminum oxide (γ-Al ₂ O ₃ , β-Al ₂ O ₃ , η-Al ₂ O ₃ , δ- Al ₂ O ₃ , θ-Al ₂ O ₃ , α-Al ₂ O ₃ )) individually or in combination with each other. The secondary layer of aluminum oxide is characterized by a thickness of 10 μm to 500 μm, a specific surface area of at least 20 m ² / g, a pore volume of 0.1 to 1.0 cm ³ / g, pores with a diameter of more than 5 nm, the volume of which is 50- 98% of the total pore volume with the formation of a secondary carrier. The secondary carrier of aluminum oxide in the total composition of the catalyst is at least 5% of the mass. The use of a secondary alumina layer with a thickness of more than 10 μm and less than 500 μm is due to the need for uniform distribution of palladium on the surface of the carrier and the exclusion of diffusion restrictions, respectively. The total amount of secondary support in the catalyst is not less than 5% of the mass due to the need for the deposition of palladium in a highly dispersed state.

Next, a promoter was sequentially applied to the secondary alumina carrier of the highly porous material, and then palladium by impregnating the carrier with solutions of their starting compounds with intermediate and / or final calcination and subsequent reduction.

The promoter is at least one of the metals selected from the group: copper, silver, gold, cobalt, zinc, magnesium, chromium. For impregnation, a highly porous cellular carrier with a secondary layer of alumina was placed in the mixer chamber. Then, aqueous or organic solutions of the promoter starting compound were dosed. The alumina support was impregnated with solutions of promoter compounds for 0.5-2 hours at a temperature of 20-80 ° C. After applying the promoter compound, the carrier was dried and calcined with the promoter compound to decompose the promoter compound. The carrier coated with the promoter compound was dried at temperatures from 50 ° C to 200 ° C for 1-2 hours and calcined at 250 ° C to 800 ° C for 2-8 hours to convert the promoter compound to oxide.

The initial palladium compounds were also applied onto the surface of the alumina support by impregnation methods. The alumina support was impregnated with the promoter with palladium compounds in the same way as impregnation with alumina and the promoter compound. After applying the palladium compound, the catalyst was dried at temperatures from 50 ° C to 200 ° C for 1-2 hours and calcined at 250 ° C to 800 ° C for 2-8 hours.

The catalyst may also contain an additional metal co-promoter. The co-promoter is at least one of the metals selected from the group: potassium, sodium, rhenium, bismuth, manganese, barium. The co-promoter was applied by impregnating the alumina carrier in parallel with the application of palladium and / or the promoter.

After applying the copromotor compound, the catalyst was dried at temperatures from 50 ° C to 200 ° C for 1-2 hours and calcined at 250 ° C to 800 ° C for 2-8 hours.

Palladium chloride, palladium bromide, palladium iodide, palladium nitrate, palladium sulfate, palladium sulfide, palladium acetate, palladium acetylacetonate, palladium oxalate, individually or in combination with each other, were used as a source of the initial palladium compound.

Copper sulfate, copper hydroxide, copper nitrate, copper nitrite, copper carbonate, copper chromite, copper chromate, copper dichromate, copper acetate, copper acetylacetonate, copper complexes with polyhydric alcohols (e.g. copper glycerate, etc.) were used as the starting copper compound. .) or mixtures thereof, organometallic complex compounds of copper in an individual form or in combinations with each other.

As the starting silver compound, silver sulfate, silver chromate, silver iodide, silver bromide, silver nitrate, silver acetate, silver carbonate, organometallic silver complex compounds in individual form or in combination with each other were used.

Gold bromide, gold hydroxide, gold iodide, gold sulfate, gold chloride, complex compounds with a gold-containing anion (hydrochloric acid, potassium tetrachloroauriate) in an individual form or in combination with each other were used as the initial gold compound.

As a source of the initial cobalt compound, cobalt nitrate, cobalt acetate, cobalt bromide, cobalt iodide, cobalt carbonate, cobalt hydroxide, cobalt chloride, cobalt sulfate, cobalt chromate, complex compounds with a cobalt-containing anion (for example, sodium sulfate and cobalt-cobaltate disodium) were used. n.) in an individual form or in combinations with each other.

Zinc hydroxide, zinc nitrate, zinc nitrite, zinc carbonate, zinc chromate, zinc dichromate, zinc chromite, zinc acetate, zinc oxalate, and organometallic zinc complex compounds in individual form or in combination with each other were used as the starting zinc compound.

Magnesium hydroxide, magnesium nitrate, magnesium nitrite, magnesium carbonate, magnesium phosphate, magnesium acetate, magnesium oxalate, organometallic zinc complexes in an individual form or in combination with each other were used as the starting magnesium compound.

As the initial chromium compound, chromium nitrate, chromium sulfate, chromium phosphate, chromium oxalate, chromic acid, potassium chromate, organometallic complex chromium compounds in an individual form or in combination with each other were used.

Potassium hydroxide, potassium nitrate, potassium bromide, potassium sulfate, potassium sulfate, potassium sulfate, potassium carbonate, potassium phosphate, potassium chloride, potassium oxalate, organometallic potassium complex compounds in an individual form or in combination with each other were used as the starting potassium compound.

Sodium hydroxide, sodium nitrate, sodium bromide, sodium hydrosulfate, sodium sulfate, sodium sulfate, potassium carbonate, sodium phosphate, sodium chloride, sodium oxalate, organometallic sodium complex compounds in an individual form or in combination with each other were used as the initial sodium compound.

Rhenium acid, rhenium chloride, rhenium bromide, rhenium sulfide, ammonium perrenate, rhenium (IV) oxide, rhenium (VII) oxide, organometallic rhenium complex compounds in an individual form or in combination with each other were used as the initial rhenium compound.

Bismuth nitrate, bismuth hydroxide, bismuth sulfide, bismuth dichromate, bismuth hydroxide, bismuth iodide, bismuth oxycarbonate, bismuth oxychloride, organometallic complex bismuth compounds in individual form or in combination with each other were used as the initial bismuth compound.

Manganese (II) nitrate, manganese (II) chloride, manganese (II) bromide, manganese (II) sulfate, manganese (II) carbonate, potassium permanganate, potassium permanganate, organometallic manganese (II) complex compounds in an individual form or in combinations with each other.

As the initial barium compound, barium hydroxide, barium nitrate, barium bromide, barium iodide, sodium hydrosulfuric acid, barium carbonate, barium sulfate, barium formate, organometallic complex compounds of barium in an individual form or in combination with each other were used.

Distilled water, aqueous solutions of acetic, sulfuric, nitric, perchloric and other acids, dimethylamine, trimethylamine, propylamine, butylamine, toluene, benzene, acetonitrile, methylene chloride, ammonia solutions were used as solvents for the deposition of the starting compounds of palladium, promoter, and co-promoter. chloroform, aqueous potassium iodide, acetone, hydroxyxylamine, organic esters, alcohols or mixtures thereof, and other solvents.

Hydrogen gas, carbon monoxide, methanol, alcohols, alcohol mixtures, sodium borohydride alcohol solutions, ammonia solutions, hydrogen sulfide, hydrazine, formic acid, tartaric acid, hydroxylamine, lithium aluminate, 1,2-dihydroxybenzene, diborane, ethylene diamine were used as reducing agents. ethylene diamine in combination with ethanolamine, ethylene diamine in combination with ammonia, ethanolamine in combination with ammonia, etc.

The specific surface area was determined by the method of low-temperature nitrogen adsorption (BET). Porometric volume and pore volume distribution over the diameters of secondary alumina were calculated using the desorption branch of the isotherm according to the standard Barret – Joyner – Highland procedure (S. Greg, C. Sing. Adsorption, specific surface area, porosity. M., Mir, 1984, 306 s ) The essence of the method for determining the parameters of a porous catalyst system is described in ASTMD 3663-99, “Standard Method for Studying the Surface Area and Pore Volume of Catalysts and Catalyst Carriers”.

The phase composition of the carrier and catalyst was determined by x-ray diffraction. Radiographs were taken using long-wavelength radiation CuK _α and a graphite monochromator on a diffracting beam. The range of recording angles in the scale 29 is from 5 to 95 degrees.

IR spectra were recorded at an adsorption temperature on a Shiumadzu 8300 Fourier spectrometer with a resolution of 4 cm ^-1 and a spectral accumulation number of 50. Samples were preliminarily pressed into tablets with a density of 7-17 mg / cm ² and calcined in an infrared cell at 450 ° C 1 h in vacuum to 10 ^-4 -10 ^-5 torr and cooled to 110 ° C with liquid nitrogen.

The catalysts were tested in the selective hydrogenation reaction of acetylene in the ethane-ethylene fraction, methylacetylene and propadiene in the propane-propylene fraction, vinylacetylene, 1,2-butadiene, butin-1 in the butadiene fraction, butine-1 (2), α-C _5- acetylenes in the isoprene fraction and acetylene, diene hydrocarbons and unsaturated substituents in aromatic compounds in the composition of the C ₅₊ -hydrocarbon fraction in a laboratory reactor with a catalyst volume of 50 cm ³ .

The tests of the catalysts in the reaction of selective hydrogenation of acetylene of ethane-ethylene fraction were carried out in a laboratory reactor with a catalyst volume of 50 cm ³ at a temperature of 40 ° C at the inlet of the reactor, a pressure of 2.0 MPa, a gas feed rate of 2000 h ^-1 and molar the ratio of hydrogen to acetylene is 1.2: 1.0. After 12 hours of hydrogenation, hourly contact gas samples were taken and analyzed by gas chromatography. According to the results of chromatographic analysis, the conversion of acetylene, ethylene selectivity were calculated and the stability of the catalyst for 100 hours was evaluated.

The tests of the catalysts in the reaction of selective hydrogenation of methylacetylene and propadiene in the propane-propylene fraction were carried out in a laboratory reactor with a catalyst volume of 50 cm ³ at a temperature of 50 ° C at the inlet of the reactor, a pressure of 1.6 MPa, a gas feed rate of 2000 h ^-1 and a molar ratio of hydrogen to total concentration of methylacetylene and propadiene of 1.6: 1.0. After 12 hours of hydrogenation, hourly contact gas samples were taken and analyzed by gas chromatography. According to the results of chromatographic analysis, the conversion of methylacetylene and propadiene, the propylene selectivity were calculated and the stability of the catalyst for 100 hours was evaluated.

The tests of the catalysts in the reaction of selective hydrogenation of vinylacetylene, 1,2-butadiene and butine-1 in the butadiene fraction were carried out in a laboratory reactor with a catalyst volume of 50 cm ³ at a temperature of 20 ° C at the inlet of the reactor, a pressure of 0.2 MPa, a feed volumetric feed rate a liquid of 2 h ^-1 and a molar ratio of hydrogen to vinylacetylene 2.0: 1.0. After 12 hours of hydrogenation, hourly contact gas samples were taken and analyzed by gas chromatography. According to the results of chromatographic analysis, the conversion of vinylacetylene, 1,2-butadiene and butine-1, the selectivity for 1,3-butadiene were calculated and the stability of the catalyst for 100 hours was evaluated.

The tests of the catalysts in the reaction of selective hydrogenation of acetylenic compounds (butin-1, butin-2, α-C ₅ acetylenes) in the isoprene fraction were carried out in a laboratory reactor with a catalyst volume of 50 cm ³ at a temperature of 25 ° C at the reactor inlet, pressure 0.2 MPa, the volumetric feed rate of the feed through the liquid is 2 h ^-1 and the molar ratio of hydrogen to acetylenes is 2.0: 1.0. After 12 hours of hydrogenation, hourly contact gas samples were taken and analyzed by gas chromatography. According to the results of chromatographic analysis, the conversion of vinylacetylene, 1,2-butadiene and butine-1 selectivity for 1,3-butadiene was calculated and the stability of the catalyst for 100 hours was evaluated.

The tests of the catalysts in the reaction of selective hydrogenation of acetylene, diene hydrocarbons and unsaturated substituents in aromatics in the C ₅₊ hydrocarbon fraction were carried out in a laboratory reactor with a catalyst volume of 50 cm ³ at a temperature of 50 ° C at the inlet of the reactor, 4.0 MPa, volumetric feed rates for liquid 2.5 h ^-1 and a hydrogen flow rate of 500 ml / min. After 12 hours of hydrogenation, hourly contact gas samples were taken and analyzed by gas chromatography. According to the results of chromatographic analysis, the conversion of diene hydrocarbons and the growth of aromatic hydrocarbons were calculated and the stability of the catalyst for 100 hours was evaluated. The catalytic activity and stability of the catalysts were also monitored by the diene number in the catalyst. The diene indices in the studied samples were determined on the basis of the Diels-Alder reaction of diene synthesis, which consists in the addition of maleic anhydride to conjugated double bonds in boiling toluene in the presence of a catalyst - iodine, hydrolysis of unreacted anhydride, subsequent extraction and titration of the resulting maleic acid solution in maleic acid hydrochloride the presence of phenolphthalein.

The heat and mass transfer indices were evaluated during the tests of the catalysts in the corresponding hydrogenation reactions. The essence of the method was to measure the maximum difference in temperature along the axis of the cross section of the reactor, located in the center of the catalyst layer. The diameter of the cross section of the reactor was 30 mm.

The diffusion efficiency index was estimated from the calculated value of Ψ - Thiele modulus. At Ψ <0.5, the process proceeds in the kinetic region and the degree of surface utilization is close to unity; diffusion restrictions are absent. For Ψ> 2.5, the process proceeds in the region of internal diffusion, only a part of the catalyst limited by the surface layer of grain is used, diffusion restrictions are noted.

In table 1.1. initial data of catalysts for catalytic tests of hydrogenation of ethane-ethylene and propane-propylene fractions are given in table 2.1. - the results of these tests, in table 1.2. the initial data of the catalysts for catalytic tests of hydrogenation of butadiene, isoprene and C ₅₊ hydrocarbon fractions are given in table 2.2. - the results of these tests.

Examples of specific embodiments of the invention are described below.

Example 1. The catalyst is used in the reactions of selective hydrogenation of acetylene in the composition of the ethane-ethylene fraction and methylacetylene and propadiene in the composition of the propane-propylene fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular nickel support with a secondary layer of aluminum oxide with solutions of silver acetate and palladium acetate. The highly porous cellular nickel support is characterized by a porosity of 92% and an average pore diameter of 2.3 mm. The secondary alumina carrier of the γ modification has a specific surface area of 280 m ² / g, a pore volume of 0.86 cm ³ / g, mesopores with a diameter of more than 5 nm, which together comprise 50% of the total pore volume. The thickness of the alumina layer is 22 μm.

A highly porous cellular nickel carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 200 ml of a 5% aqueous solution of acetic acid containing 0.1856 g of silver acetate are dosed. The impregnation is carried out for 1 hour at a temperature of the impregnating solution of 70 ° C. After impregnating the alumina support with an aqueous solution of silver acetate, the solvent is removed at a temperature of 70 ° C. for 2 hours. Then, the alumina support impregnated with silver acetate is dried at a temperature of 120 ° C for 1 hour and calcined to convert silver to an oxide state at a temperature of 400 ° C for 3 hours.

Next, a highly porous cellular nickel carrier with a secondary layer of aluminum oxide with silver oxide in an amount of 100 g is placed in the mixer chamber, 190 ml of a 5% aqueous solution of acetic acid containing 0.0643 g of palladium acetate are metered. The impregnation is carried out for 3 hours at a temperature of the impregnating solution of 70 ° C. After the carrier is impregnated with palladium acetate, the solvent is removed at a temperature of 100 ° C. for 2 hours. Then, the carrier impregnated with palladium acetate is dried at a temperature of 120 ° C for 1 hour, calcined at a temperature of 300 ° C for 3 hours, and reduced in a hydrogen atmosphere at a temperature of 120 ° C for 3 hours.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide of the absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2065 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.4 ° C. Thiele module - 0.04.

The catalyst used has the following composition:

Pd - 0.02% of the mass;

Ag - 0.12% of the mass;

γ-Al ₂ O ₃ - 5.0% of the mass.

Highly porous cellular Nickel carrier - 94.86% of the mass.

The results of the catalytic tests of this sample are presented in table 2.1.

Example 2. The catalyst is used in the selective hydrogenation of acetylene in the composition of the ethane-ethylene fraction and methylacetylene and propadiene in the composition of the propane-propylene fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular copper support with a secondary layer of aluminum oxide with solutions of copper nitrate and palladium acetylacetonate. Sopromotor - potassium is applied to the alumina carrier by impregnation from an aqueous solution of potassium hydroxide before impregnation of the alumina carrier with an aqueous solution of copper acetate. A highly porous cellular copper support is characterized by a porosity of 85% and an average pore diameter of 0.5 mm. The secondary alumina carrier of the β-modification has a specific surface area of 200 m ² / g, a pore volume of 1.00 cm ³ / g, mesopores with a diameter of more than 5 nm, which together comprise 57% of the total pore volume. The thickness of the alumina layer is 10 μm.

A highly porous cellular copper carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 100 ml of an aqueous solution containing 0.0144 g of potassium hydroxide is dosed. The impregnation is carried out for 3 hours at a temperature of the impregnating solution of 40 ° C. After impregnating the alumina support with an aqueous potassium hydroxide solution, the solvent is removed at a temperature of 90 ° C. for 2 hours. Then, the alumina support impregnated with potassium hydroxide is dried at a temperature of 110 ° C for 2 hours and calcined at a temperature of 400 ° C for 3 hours.

Next, a highly porous cellular copper carrier with a secondary layer of aluminum oxide and potassium oxide in an amount of 100 g is placed in the mixer chamber, 160 ml of an aqueous solution containing 0.1483 g of copper nitrate are dosed. The impregnation is carried out for 0.5 hours at a temperature of the impregnating solution of 80 ° C. After impregnating the alumina support with an aqueous solution of copper nitrate, the solvent is removed at a temperature of 90 ° C. for 1 hour. Then, the alumina support impregnated with copper nitrate is dried at a temperature of 200 ° C for 1 hour and calcined to convert copper to an oxide state at a temperature of 400 ° C for 7 hours.

Next, a highly porous cellular copper carrier with a secondary layer of aluminum oxide with potassium and copper oxides in an amount of 100 g is placed in the mixer chamber, 150 ml of benzene containing 0.0574 g of palladium acetylacetonate are metered. The impregnation is carried out for 0.5 hours at a temperature of the impregnating solution of 20 ° C. After impregnating the alumina carrier with a benzene solution of palladium acetylacetonate, the solvent is removed at a temperature of 60 ° C. for 0.5 hour. Then, the alumina carrier impregnated with palladium acetylacetonate is dried at a temperature of 110 ° C for 1 hour, calcined at a temperature of 250 ° C for 8 hours, and reduced in a hydrogen atmosphere at a temperature of 600 ° C for 1 hour.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide of the absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2060 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.3 ° C. Thiele module - 0.02.

The catalyst used has the following composition:

Pd - 0.02% of the mass;

Cu - 0.04% of the mass;

K - 0.01% of the mass;

β-Al ₂ O ₃ - 5.4% of the mass.

Highly porous cellular copper carrier - 94.53% of the mass.

The results of the catalytic tests of this sample are presented in table 2.1.

Example 3. The catalyst is used in selective hydrogenation reactions of acetylene in the composition of the ethane-ethylene fraction and methylacetylene and propadiene in the composition of the propane-propylene fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular iron support with a secondary layer of alumina with solutions of hydrochloric acid and palladium chloride. Sopromotor - potassium is applied to an alumina carrier by impregnation from an aqueous solution of potassium carbonate together with impregnation of the carrier with hydrochloric acid. The highly porous cellular iron support is characterized by a porosity of 93% with an average pore diameter of 3.5 mm. The secondary alumina carrier of the δ modification has a specific surface area of 135 m ² / g, a pore volume of 0.56 cm ³ / g, mesopores with a diameter of more than 5 nm, which together account for 79% of the total pore volume. The thickness of the alumina layer is 53 μm.

A highly porous cellular iron carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 1000 ml of a 5% aqueous solution containing 0.0105 g of hydrochloric acid and 0.0223 g of potassium carbonate are dosed. The impregnation is carried out for 1 hour at a temperature of the impregnating solution of 80 ° C. After impregnating the alumina support with an aqueous solution of hydrochloric acid and potassium carbonate, the solvent is removed at a temperature of 80 ° C. for 0.5 hour. Then, the alumina carrier impregnated with hydrochloric acid and potassium carbonate is dried at a temperature of 110 ° C for 2 hours and calcined at a temperature of 500 ° C for 8 hours to convert the starting compounds of gold and potassium into their oxide forms.

Next, a highly porous cellular copper carrier with a secondary layer of alumina, gold and potassium oxide in an amount of 100 g is placed in the mixer chamber, 150 ml of a 3% hydrochloric acid solution containing 0.0840 g of palladium chloride are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 20 ° C. After impregnating the alumina support with an aqueous solution of palladium chloride, the solvent is removed at a temperature of 80 ° C. for 1 hour. Then, the alumina carrier impregnated with palladium chloride is dried at a temperature of 200 ° C for 1 hour, calcined at a temperature of 450 ° C for 3 hours, and reduced for 3 hours in ethanol.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide of the absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2098 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.7 ° C. Thiele module - 0.06.

The catalyst used has the following composition:

Pd - 0.05% of the mass;

Au - 0.005% of the mass;

K - 0.005% of the mass;

β-Al ₂ O ₃ - 6.0% of the mass.

Highly porous cellular iron carrier - 93.94% of the mass.

The results of the catalytic tests of this sample are presented in table 2.1.

Example 4. The catalyst is used in selective hydrogenation reactions of acetylene in the composition of the ethane-ethylene fraction and methylacetylene and propadiene in the composition of the propane-propylene fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular aluminum support with a secondary layer of aluminum oxide with solutions of zinc nitrate and palladium acetate. Sopromotor - sodium is applied to an alumina carrier by impregnation from an aqueous solution of sodium hydroxide after application of zinc nitrate. A highly porous cellular aluminum support is characterized by a porosity of 90% with an average pore diameter of 5.1 mm. The secondary alumina support of the α-modification has a specific surface area of 20 m ² / g, pore volume of 0.1 cm ³ / g, mesopores with a diameter of more than 5 nm, which together comprise 98% of the total pore volume. The thickness of the alumina layer is 124 μm.

A highly porous cellular aluminum carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 80 ml of an aqueous solution containing 1.3730 g of zinc nitrate are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 20 ° C. After the carrier was impregnated with an aqueous solution of zinc nitrate, the solvent was removed at a temperature of 80 ° C for 0.5 hours. Then, the alumina support impregnated with zinc nitrate is dried at a temperature of 110 ° C for 1 hour and calcined at a temperature of 250 ° C for 3 hours to convert zinc nitrate to zinc oxide.

Next, a highly porous cellular aluminum carrier with a secondary layer of aluminum oxide with zinc oxide in an amount of 100 g is placed in the mixer chamber, 100 ml of an aqueous solution containing 0.1739 g of sodium hydroxide is dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 50 ° C. After the carrier was impregnated with an aqueous solution of sodium hydroxide, the solvent was removed at a temperature of 70 ° C for 1 hour. Then, the carrier impregnated with sodium hydroxide is dried at a temperature of 200 ° C for 2 hours and calcined at a temperature of 400 ° C for 3 hours.

Next, a highly porous cellular aluminum carrier with a secondary layer of aluminum oxide with zinc and potassium oxides in an amount of 100 g is placed in the mixer chamber, 140 ml of a 5% aqueous solution of acetic acid containing 0.1268 g of palladium acetate are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 40 ° C. After the carrier is impregnated with palladium acetate, the solvent is removed at a temperature of 80 ° C. for 0.5 hours. Then, the alumina carrier impregnated with palladium acetate is dried at a temperature of 200 ° C for 2 hours, calcined at a temperature of 300 ° C for 2 hours, and reduced in a hydrogen atmosphere at a temperature of 300 ° C for 6 hours.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2063 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.5 ° C. Thiele module - 0.12.

The catalyst used has the following composition:

Pd - 0.06% of the mass;

Zn - 0.30% of the mass;

Na - 0.10% of the mass;

α-Al ₂ O ₃ - 5.5% of the mass.

Highly porous cellular aluminum carrier - 94.04% of the mass.

The results of the catalytic tests of this sample are presented in table 2.1.

Example 5. The catalyst is used in the selective hydrogenation reactions of acetylene in the composition of the ethane-ethylene fraction and methylacetylene and propadiene in the composition of the propane-propylene fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular alumina support with a secondary layer of alumina with solutions of magnesium nitrate, palladium acetylacetonate and sodium carbonate. The highly porous cellular alumina support of the α modification is characterized by a porosity of 95% with an average pore diameter of 2.5 mm. The secondary alumina carrier of the γ modification has a specific surface area of 183 m ² / g, a pore volume of 0.89 cm ³ / g, mesopores with a diameter of more than 5 nm, which together comprise 75% of the total pore volume. The thickness of the alumina layer is 26 μm.

A highly porous cellular alumina carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 90 ml of an aqueous solution containing 0.2671 g of magnesium nitrate is dosed. Impregnation is carried out for 1 hour at a temperature of the impregnating solution of 70 ° C. After impregnating the alumina support with an aqueous solution of magnesium nitrate, the solvent is removed at a temperature of 80 ° C. for 2 hours. Then, the alumina support impregnated with magnesium nitrate is dried at a temperature of 110 ° C for 1 hour and calcined to convert magnesium to an oxide state at a temperature of 200 ° C for 8 hours.

Next, a highly porous cellular alumina carrier with a secondary layer of alumina with magnesium oxide in an amount of 100 g is placed in the mixer chamber, 60 ml of benzene containing 0.0143 g of palladium acetylacetonate are metered. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 60 ° C. After impregnating the alumina support with a benzene solution of palladium acetylacetonate, the solvent is removed at a temperature of 70 ° C. for 0.5 hour. Then, the alumina carrier impregnated with palladium acetylacetonate is dried at a temperature of 50 ° C for 1 hour and calcined at a temperature of 250 ° C for 8 hours.

Next, a highly porous cellular alumina carrier with a secondary layer of alumina with magnesium and palladium oxides in an amount of 100 g is placed in the mixer chamber, 110 ml of an aqueous solution containing 1.0087 g of sodium carbonate are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 20 ° C. After impregnating the alumina support with an aqueous solution of sodium carbonate, the solvent is removed at a temperature of 80 ° C. for 0.5 hours. Then, the alumina support impregnated with a solution of sodium carbonate is dried at a temperature of 200 ° C for 1 hour, calcined at a temperature of 800 ° C for 2 hours, and reduced in a hydrogen atmosphere at a temperature of 500 ° C for 4 hours.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2100 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.3 ° C. Thiele module - 0.04.

The catalyst has the following composition:

Pd - 0.005% of the mass;

Mg - 0.025% of the mass;

Na - 0.10% of the mass;

γ-Al ₂ O ₃ - 6.7% of the mass.

The highly porous cellular alumina of the α modification is 93.17% of the mass.

The results of the catalytic tests of this sample are presented in table 2.1.

Example 6. The catalyst is used in the selective hydrogenation of acetylene in the composition of the ethane-ethylene fraction and methylacetylene and propadiene in the composition of the propane-propylene fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular alumina support with a secondary layer of alumina with solutions of chromium nitrate and palladium nitrate. Sopromotor - bismuth is applied to the carrier by impregnation of an aqueous solution of bismuth nitrate together with impregnation of the carrier with chromium nitrate. The highly porous cellular alumina support of the α modification is characterized by a porosity of 93% with an average pore diameter of 6.0 mm. The secondary alumina carrier of the θ modification has a specific surface area of 80 m ² / g, a pore volume of 0.35 cm ³ / g, mesopores with a diameter of more than 5 nm, which together comprise 83% of the total pore volume. The thickness of the alumina layer is 500 μm.

A highly porous cellular alumina carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 80 ml of an aqueous solution containing 0.7696 g of chromium nitrate and 0.4642 g of bismuth nitrate are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 20 ° C. After impregnating the alumina support with an aqueous solution of chromium and bismuth nitrates, the solvent is removed at a temperature of 70 ° C for 3 hours. Then, the alumina support impregnated with chromium and bismuth nitrates is dried at a temperature of 120 ° C for 2 hours and calcined at a temperature of 300 ° C for 3 hours.

Next, a highly porous cellular alumina carrier with a secondary layer of alumina with chromium and bismuth oxides in an amount of 100 g is placed in a mixer chamber, 90 ml of a 5% aqueous nitric acid solution containing 0.1088 g of palladium nitrate is dosed. The impregnation is carried out for 1.5 hours at a temperature of the impregnating solution of 80 ° C. After impregnating the alumina support with an aqueous solution of palladium nitrate, the solvent is removed at a temperature of 100 ° C. for 2 hours. Then, the alumina support impregnated with palladium nitrate is dried at a temperature of 110 ° C for 1 hour, calcined at a temperature of 800 ° C for 3 hours, and reduced for 2 hours in an alcoholic solution of sodium borohydride.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2094 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.9 ° C. Thiele module - 0.45.

The catalyst has the following composition:

Pd - 0.05% of the mass;

Cr - 0.10% of the mass;

Bi - 0.20% of the mass;

θ-Al ₂ O ₃ - 6.9% of the mass.

The highly porous cellular alumina of the α modification is 92.95% of the mass.

The results of the catalytic tests of this sample are presented in table 2.1.

Example 7. The catalyst is used in the selective hydrogenation reactions of acetylene in the composition of the ethane-ethylene fraction and methylacetylene and propadiene in the composition of the propane-propylene fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular alumina support with a secondary layer of alumina with solutions of cobalt nitrate, ammonium perrenate and palladium sulfate. Sopromotor - rhenium is applied to the alumina carrier by impregnation from an aqueous solution of ammonium perrenate together with the impregnation of the alumina carrier with cobalt nitrate. The highly porous cellular alumina support of the α modification is characterized by a porosity of 94% with an average pore diameter of 3.1 mm. The secondary alumina carrier of the δ modification has a specific surface area of 120 m ² / g, a pore volume of 0.48 cm ³ / g, mesopores with a diameter of more than 5 nm, which together account for 71% of the total pore volume. The thickness of the alumina layer is 28 μm.

A highly porous cellular alumina carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 80 ml of an aqueous solution containing 0.7398 g of cobalt nitrate and 0.2882 g of ammonium perrenate are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 50 ° C. After the carrier is impregnated with an aqueous solution of cobalt nitrate and ammonium perrenate, the solvent is removed at a temperature of 80 ° C for 2 hours. Then the carrier impregnated with cobalt nitrate and ammonium perrenate is dried at a temperature of 200 ° C for 2 hours and calcined at a temperature of 300 ° C for 2 hours.

Next, a highly porous cellular alumina carrier with a secondary layer of alumina with cobalt and rhenium oxides in an amount of 100 g is placed in the mixer chamber, 70 ml of a 2% aqueous solution of sulfuric acid containing 0.0676 g of palladium sulfate are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 70 ° C. After impregnating the alumina support with an aqueous solution of palladium sulfate, the solvent is removed at a temperature of 80 ° C. for 2 hours. Then, the alumina support impregnated with palladium sulfate is dried at a temperature of 110 ° C for 1 hour, calcined at a temperature of 400 ° C for 3 hours, and reduced in a hydrogen atmosphere at 300 ° C for 3 hours.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide of the absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2073 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.3 ° C. Thiele module - 0.03.

The catalyst used has the following composition:

Pd - 0.03% of the mass;

Co - 0.15% of the mass;

Re - 0.20% of the mass;

δ-Al ₂ O ₃ - 7.2% of the mass.

The highly porous cellular alumina of the α modification is 92.42% by weight.

The results of the catalytic tests of this sample are presented in table 2.1.

Example 8. The catalyst is used in selective hydrogenation reactions of acetylene in the ethane-ethylene fraction and methylacetylene and propadiene in the propane-propylene fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular alumina support with a secondary layer of alumina with solutions of cobalt nitrate and palladium nitrate. Sopromotor - manganese is applied to the alumina carrier by impregnation from an aqueous solution of manganese nitrate together with the impregnation of the alumina carrier with palladium nitrate. As the carrier, a system is used that has the same texture characteristics as the carrier in example 7.

A highly porous cellular alumina carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 60 ml of an aqueous solution containing 0.7398 g of cobalt nitrate are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 70 ° C. After the alumina carrier is impregnated with an aqueous solution of cobalt nitrate, the solvent is removed at a temperature of 90 ° C. for 2 hours. Then, the alumina support impregnated with cobalt nitrate is dried at a temperature of 50 ° C for 2 hours and calcined at a temperature of 400 ° C for 2 hours.

Next, a highly porous cellular alumina carrier with a secondary layer of alumina with cobalt oxide in an amount of 100 g is placed in the mixer chamber, 70 ml of a 5% aqueous nitric acid solution containing 0.0653 g of palladium nitrate and 1.0436 manganese nitrate are dosed. The impregnation is carried out for 0.5 hours at a temperature of the impregnating solution of 80 ° C. After impregnating the alumina support with palladium and manganese nitrates, the solvent is removed at a temperature of 80 ° C. for 2 hours. Then, the alumina support impregnated with palladium and manganese nitrates is dried at a temperature of 120 ° C for 1 hour, calcined at a temperature of 250 ° C for 4 hours, and reduced in a hydrogen atmosphere at 200 ° C for 3 hours.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide of the absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2079 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.2 ° C. Thiele module - 0.03.

The catalyst used has the following composition:

Pd - 0.03% of the mass;

Co - 0.15% of the mass;

Mn - 0.20% of the mass;

δ-Al ₂ O ₃ - 7.2% of the mass.

The highly porous cellular alumina of the α modification is 92.42% by weight.

The results of the catalytic tests of this sample are presented in table 2.1.

Example 9. The catalyst is used in the selective hydrogenation reactions of acetylene in the composition of the ethane-ethylene fraction and methylacetylene and propadiene in the composition of the propane-propylene fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular alumina support with a secondary layer of alumina with solutions of silver nitrate and palladium nitrate. As the carrier, a system is used that has the same texture characteristics as the carrier in example 7.

A highly porous cellular alumina carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 80 ml of an aqueous solution containing 0.2361 g of silver nitrate are dosed. The impregnation is carried out for 1 hour at a temperature of the impregnating solution of 60 ° C. After the carrier was impregnated with an aqueous solution of silver nitrate, the solvent was removed at a temperature of 80 ° C. for 2 hours. Then, the carrier impregnated with silver nitrate is dried at a temperature of 110 ° C for 2 hours and calcined at a temperature of 800 ° C for 3 hours.

Next, a highly porous cellular alumina carrier with a secondary layer of aluminum oxide with silver oxide in an amount of 100 g is placed in the mixer chamber, 80 ml of an aqueous solution containing 0.0653 g of palladium nitrate are dosed. The impregnation is carried out for 3 hours at a temperature of the impregnating solution of 50 ° C. After impregnating the alumina support with an aqueous solution of palladium nitrate, the solvent is removed at a temperature of 80 ° C. for 1 hour. Then, the alumina support impregnated with palladium nitrate is dried at a temperature of 200 ° C for 1 hour and calcined at a temperature of 550 ° C for 3 hours and reduced in a hydrogen atmosphere at 200 ° C for 3 hours.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2097 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.1 ° C. Thiele module - 0.03.

The catalyst used has the following composition:

Pd - 0.03% of the mass;

Ag - 0.15% of the mass;

δ-Al ₂ O ₃ - 7.2% of the mass.

The highly porous cellular alumina of the α modification is 92.62% of the mass.

The results of the catalytic tests of this sample are presented in table 2.1.

Example 10. The catalyst is used in the selective hydrogenation reactions of acetylene in the composition of the ethane-ethylene fraction and methylacetylene and propadiene in the composition of the propane-propylene fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular alumina support with a secondary layer of alumina with solutions of copper nitrate and palladium nitrate. As the carrier, a system is used that has the same texture characteristics as the carrier in example 7.

A highly porous cellular alumina carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 60 ml of an aqueous solution containing 0.5648 g of copper nitrate are dosed. The impregnation is carried out for 1 hour at a temperature of the impregnating solution of 60 ° C. After the carrier was impregnated with an aqueous solution of copper nitrate, the solvent was removed at a temperature of 80 ° C for 2 hours. Then, the alumina carrier impregnated with copper nitrate is dried at a temperature of 110 ° C for 2 hours.

Next, a highly porous cellular alumina carrier with a secondary layer of alumina with copper oxide in an amount of 100 g is placed in the mixer chamber, 60 ml of an aqueous solution containing 0.0653 g of palladium nitrate are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 80 ° C. After the carrier was impregnated with an aqueous solution of palladium nitrate, the solvent was removed at a temperature of 80 ° C for 1 hour. Then, the carrier impregnated with palladium nitrate is dried at a temperature of 110 ° C for 1 hour, calcined at a temperature of 200 ° C for 3 hours, and reduced in a hydrogen atmosphere at 200 ° C for 3 hours.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2085 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.2 ° C. Thiele module - 0.03.

The catalyst used has the following composition:

Pd - 0.03% of the mass;

Cu - 0.15% of the mass;

δ-Al ₂ O ₃ - 7.2% of the mass.

The highly porous cellular alumina of the α modification is 92.62% of the mass.

The results of the catalytic tests of this sample are presented in table 2.1.

Example 11 (prototype). The catalyst is used in selective hydrogenation reactions of acetylene in the composition of the ethane-ethylene fraction and methylacetylene and propadiene in the composition of the propane-propylene fraction.

The catalyst is prepared by sequentially impregnating the alumina support with solutions of copper nitrate and palladium nitrate. The carrier δ-Al ₂ O ₃ has a specific surface area of 125 m ² / g, a pore volume of 0.51 cm ³ / g, mesopores with a diameter of more than 5 nm, which make up 65% of the total pore volume.

An alumina carrier in an amount of 100 g is placed in a mixer chamber, 60 ml of an aqueous solution containing 0.5648 g of copper nitrate are dosed. The impregnation is carried out for 1 hour at a temperature of the impregnating solution of 60 ° C. After the carrier was impregnated with an aqueous solution of copper nitrate, the solvent was removed at a temperature of 80 ° C for 2 hours. Then, the alumina carrier impregnated with copper nitrate is dried at a temperature of 110 ° C for 2 hours.

Next, an alumina carrier with copper oxide in an amount of 100 g is placed in the mixer chamber, 60 ml of an aqueous solution containing 0.0653 g of palladium nitrate are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 80 ° C. After the carrier was impregnated with an aqueous solution of palladium nitrate, the solvent was removed at a temperature of 80 ° C for 1 hour. Then, the carrier impregnated with palladium nitrate is dried at a temperature of 110 ° C for 1 hour, calcined at a temperature of 200 ° C for 3 hours, and reduced in a hydrogen atmosphere at 200 ° C for 3 hours.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2083 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 2.4 ° C. Thiele module - 2.81.

The catalyst used has the following composition:

Pd - 0.03% of the mass;

Cu - 0.15% of the mass;

δ-Al ₂ O ₃ - 99; 82% of the mass.

The results of the catalytic tests of this sample are presented in table 2.1.

Example 12. The catalyst is used in selective hydrogenation reactions: vinylacetylene, 1,2-butadiene, butine-1 in the composition of the butadiene fraction; butyn-1 (2), α-C ₅ acetylenes in the isoprene fraction; acetylene, diene hydrocarbons and unsaturated substituents in aromatic compounds in the C ₅₊ hydrocarbon fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular zinc support with a secondary layer of aluminum oxide with solutions of copper acetate and palladium sulfate. The highly porous cellular zinc support is characterized by a porosity of 91% with an average pore diameter of 2.8 mm. The secondary alumina carrier of the δ modification has a specific surface area of 119 m ² / g, a pore volume of 0.49 cm ³ / g, mesopores with a diameter of more than 5 nm, which together comprise 78% of the total pore volume. The thickness of the alumina layer is 46 μm.

A highly porous cellular zinc carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 90 ml of an aqueous solution containing 3.1194 g of copper acetate is dosed. The impregnation is carried out for 0.5 hours at a temperature of the impregnating solution of 70 ° C. After the carrier was impregnated with an aqueous solution of copper acetate, the solvent was removed at a temperature of 110 ° C. for 2.5 hours. Then the carrier impregnated with copper acetate is dried at a temperature of 180 ° C for - 2 hours and calcined to convert copper to an oxide state at a temperature of 550 ° C for 4.5 hours.

Next, a highly porous cellular zinc carrier with a secondary layer of aluminum oxide with copper oxide in an amount of 100 g is placed in the mixer chamber, 80 ml of a 2% aqueous solution of sulfuric acid containing 2.2528 g of palladium sulfate are dosed. The impregnation is carried out for 0.5 hours at a temperature of the impregnating solution of 20 ° C. After impregnating the alumina support with palladium nitrate, the solvent is removed at a temperature of 80 ° C. for 1 hour. Then, the carrier impregnated with palladium sulfate is dried at a temperature of 120 ° C for 2 hours, calcined at a temperature of 650 ° C for 7 hours, and reduced in a hydrogen atmosphere at 300 ° C for 4 hours.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide of the absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2062 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.3 ° C. Thiele module - 0.05.

The catalyst used has the following composition:

Pd - 1.0% of the mass;

Cu - 1.0% of the mass;

δ-Al ₂ O ₃ - 6.3% of the mass.

Highly porous cellular zinc carrier - 91.7% of the mass.

The results of the catalytic tests of this sample are presented in table 2.2.

Example 13. The catalyst is used in selective hydrogenation reactions: vinylacetylene, 1,2-butadiene, butine-1 in the composition of the butadiene fraction; butyn-1 (2), α-C ₅ acetylenes in the isoprene fraction; acetylene, diene hydrocarbons and unsaturated substituents in aromatic compounds in the C ₅₊ hydrocarbon fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular titanium support with a secondary layer of aluminum oxide with solutions of silver acetate and palladium acetylacetonate. A highly porous cellular titanium support is characterized by a porosity of 93% with an average pore diameter of 1.5 mm. The secondary alumina carrier of γ modification has a specific surface area of 185 m ² / g, pore volume of 0.78 cm ³ / g, mesopores with a diameter of more than 5 nm, which together comprise 57% of the total pore volume. The thickness of the alumina layer is 21 μm.

A highly porous cellular titanium carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 200 ml of an aqueous solution containing 7.7315 g of silver acetate are dosed. The impregnation is carried out for 3 hours at a temperature of the impregnating solution of 30 ° C. After the carrier was impregnated with an aqueous solution of silver acetate, the solvent was removed at a temperature of 90 ° C. for 2 hours. Then the carrier impregnated with silver acetate, dried at a temperature of 180 ° C for 2 hours and calcined at a temperature of 400 ° C for 4 hours.

Next, a highly porous cellular titanium carrier with a secondary layer of aluminum oxide with silver oxide in an amount of 100 g is placed in the mixer chamber, 80 ml of methylene chloride containing 0.2868 g of palladium acetylacetonate are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 20 ° C. After the carrier was impregnated with palladium acetylacetonate, the solvent was removed at a temperature of 30 ° C for 0.5 hours. Then, the carrier impregnated with palladium acetylacetonate is dried at a temperature of 60 ° C for 1 hour, calcined at a temperature of 250 ° C for 8 hours, and reduced for 3 hours in an alcoholic solution of sodium borohydride.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide of the absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2074 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.4 ° C. Thiele module - 0.04.

The catalyst used has the following composition:

Pd - 0.1% of the mass;

Ag - 5.0% of the mass;

γ-Al ₂ O ₃ - 5.6% of the mass.

Highly porous cellular titanium carrier - 89.3% of the mass.

The results of the catalytic tests of this sample are presented in table 2.2.

Example 14. The catalyst is used in selective hydrogenation reactions: vinylacetylene, 1,2-butadiene, butine-1 in the composition of the butadiene fraction; butyn-1 (2), α-C ₅ acetylenes in the isoprene fraction; acetylene, diene hydrocarbons and unsaturated substituents in aromatic compounds in the C ₅₊ hydrocarbon fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular alumina support with a secondary layer of alumina with solutions of sodium tetrachloroauriate and palladium acetylacetonate. The highly porous cellular alumina support of the α modification is characterized by a porosity of 95% with an average pore diameter of 2.6 mm. The secondary alumina carrier of the α-modification has a specific surface area of 25 m ² / g, a pore volume of 0.30 cm ³ / g, mesopores with a diameter of more than 5 nm, which together account for 94% of the total pore volume. The thickness of the alumina layer is 58 μm.

A highly porous cellular alumina carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 90 ml of an aqueous solution containing 2.5140 g of sodium tetrachloroauriate is dosed. The impregnation is carried out for 4 hours at a temperature of the impregnating solution of 60 ° C. After the carrier was impregnated with sodium tetrachloroauriate, the solvent was removed at a temperature of 80 ° C. for 2 hours. Then, the carrier impregnated with sodium tetrachloroauriate is dried at a temperature of 150 ° C for 4 hours and calcined to convert gold to an oxide state at a temperature of 500 ° C for 4 hours.

Then, a highly porous cellular alumina carrier with a secondary layer of aluminum oxide with gold oxide in an amount of 100 g is placed in the mixer chamber, 90 ml of a 5% aqueous hydrochloric acid solution containing 0.5864 g of palladium chloride are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 60 ° C. After the carrier is impregnated with palladium chloride, the solvent is removed at a temperature of 90 ° C. for 1 hour. Then, the carrier impregnated with palladium acetate is dried at a temperature of 160 ° C for 1 hour, calcined at a temperature of 700 ° C for 2 hours and reduced in a hydrogen atmosphere at 400 ° C for 5 hours.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2097 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.6 ° C. Thiele module - 0.06.

The catalyst used has the following composition:

Pd - 0.35% of the mass;

Au - 2.5% of the mass;

α-Al ₂ O ₃ - 5.6 wt%.

Highly porous cellular alumina of α-modification - 91.55% of the mass.

The results of the catalytic tests of this sample are presented in table 2.2.

Example 15. The catalyst is used in selective hydrogenation reactions: vinylacetylene, 1,2-butadiene, butine-1 in the composition of the butadiene fraction; butyn-1 (2), α-C ₅ acetylenes in the isoprene fraction; acetylene, diene hydrocarbons and unsaturated substituents in aromatic compounds in the C ₅₊ hydrocarbon fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular alumina support with a secondary layer of alumina with solutions of zinc acetate and palladium acetate. Sopromotor - sodium is applied to the alumina carrier by impregnation from an aqueous solution of sodium carbonate before impregnation of the alumina carrier with an aqueous solution of zinc acetate. The highly porous cellular alumina support of the α modification is characterized by a porosity of 91% with an average pore diameter of 4.7 mm. The secondary alumina carrier of the θ modification has a specific surface area of 69 m ² / g, a pore volume of 0.44 cm ³ / g, mesopores with a diameter of more than 5 nm, which together account for 81% of the total pore volume. The thickness of the alumina layer is 237 μm.

A highly porous cellular alumina carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 250 ml of an aqueous solution containing 50.4348 g of sodium carbonate are dosed. The impregnation is carried out for 4 hours at a temperature of the impregnating solution of 30 ° C. After the carrier is impregnated with an aqueous solution of sodium carbonate, the solvent is removed at a temperature of 40 ° C. for 4 hours. Then, the alumina support impregnated with sodium carbonate is dried at a temperature of 50 ° C for 2 hours and calcined at a temperature of 500 ° C for 5 hours.

Next, a highly porous cellular alumina carrier with a secondary layer of aluminum oxide and sodium oxide in an amount of 100 g is placed in the mixer chamber, 85 ml of an aqueous solution containing 1.5238 g of zinc acetate are metered. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 60 ° C. After the carrier was impregnated with an aqueous solution of zinc acetate, the solvent was removed at a temperature of 80 ° C. for 1 hour. Then, the carrier impregnated with zinc acetate is dried at a temperature of 200 ° C for 2 hours and calcined to convert zinc to an oxide state at a temperature of 350 ° C for 5 hours.

Next, a highly porous cellular alumina carrier with a secondary layer of aluminum oxide with sodium and zinc oxides in an amount of 100 g is placed in the mixer chamber, 80 ml of a 5% aqueous solution of acetic acid containing 1.0566 g of palladium acetate are dosed. The impregnation is carried out for 0.5 hours at a temperature of the impregnating solution of 30 ° C. After the carrier was impregnated with an aqueous solution of palladium acetate, the solvent was removed at a temperature of 80 ° C for 2 hours. Then, the carrier impregnated with palladium acetate is dried at a temperature of 180 ° C for 2.5 hours, calcined at a temperature of 550 ° C for 6 hours and reduced for 2 hours in a hydrogen atmosphere at a temperature of 400 ° C.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide of the absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2062 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.4 ° C. Thiele module - 0.26.

The catalyst has the following composition:

Pd - 0.5% of the mass;

Zn - 0.5% of the mass;

Na - 5.0% of the mass;

α-Al ₂ O ₃ - 6.9% of the mass.

Highly porous cellular alumina of α-modification - 87.1% of the mass.

The results of the catalytic tests of this sample are presented in table 2.2.

Example 16. The catalyst is used in selective hydrogenation reactions: vinylacetylene, 1,2-butadiene, butine-1 in the composition of the butadiene fraction; butyn-1 (2), α-C ₅ acetylenes in the isoprene fraction; acetylene, diene hydrocarbons and unsaturated substituents in aromatic compounds in the C ₅₊ hydrocarbon fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular alumina support with a secondary alumina layer using solutions of chromic acid and palladium acetylacetonate. The highly porous cellular alumina support of the α modification is characterized by a porosity of 93% with an average pore diameter of 4.1 mm. The secondary alumina carrier of the θ-modification has a specific surface area of 67 m ² / g, a pore volume of 0.40 cm ³ / g, mesopores with a diameter of more than 5 nm, which together account for 88% of the total pore volume. The thickness of the alumina layer is 68 μm.

A highly porous cellular alumina carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 60 ml of an aqueous solution containing 1.3615 g of chromic acid are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 60 ° C. After the carrier is impregnated with a chromium compound, the solvent is removed at a temperature of 90 ° C. for 4 hours. Then, the alumina support impregnated with chromic acid is dried at a temperature of 200 ° C for 2 hours and calcined at a temperature of 500 ° C for 6 hours.

Next, a highly porous cellular alumina carrier with a secondary layer of alumina with chromium oxide in an amount of 100 g is placed in the mixer chamber, 80 ml of toluene containing 1.4340 g of palladium acetylaceton are dosed. The impregnation is carried out for 3 hours at a temperature of the impregnating solution of 55 ° C. After the carrier was impregnated with palladium acetylacetonate, the solvent was removed at 60 ° C. for 3 hours. Then, the carrier impregnated with palladium acetylacetonate is dried at a temperature of 100 ° C for 2 hours, calcined at a temperature of 400 ° C for 2 hours and reduced for 4 hours in an alcoholic solution of sodium borohydride.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2094 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.8 ° C. Thiele module - 0.07.

The catalyst has the following composition:

Pd - 0.5% of the mass;

Cr - 0.6% of the mass;

α-Al ₂ O ₃ - 6.5% of the mass.

The highly porous cellular alumina of the α modification is 92.4% of the mass.

The results of the catalytic tests of this sample are presented in table 2.2.

Example 17. The catalyst is used in selective hydrogenation reactions: vinylacetylene, 1,2-butadiene, butine-1 in the composition of the butadiene fraction; butyn-1 (2), α-C ₅ acetylenes in the isoprene fraction; acetylene, diene hydrocarbons and unsaturated substituents in aromatic compounds in the C ₅₊ hydrocarbon fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular alumina support with a secondary layer of alumina with solutions of magnesium acetate and palladium dihydroxodiammine. Sopromotor - barium is applied to the alumina carrier by impregnation from an aqueous solution of barium nitrate together with the impregnation of the alumina carrier with cobalt nitrate. The highly porous cellular alumina support of the α modification is characterized by a porosity of 94% with an average pore diameter of 2.4 mm. The secondary alumina carrier of the γ modification has a specific surface area of 169 m ² / g, a pore volume of 0.75 cm ³ / g, mesopores with a diameter of more than 5 nm, which together account for 51% of the total pore volume. The thickness of the alumina layer is 49 μm.

A highly porous cellular alumina carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 70 ml of an aqueous solution containing 6.2554 g of magnesium acetate and 0.5023 g of barium nitrate are dosed. The impregnation is carried out for 3 hours at a temperature of the impregnating solution of 20 ° C. After the carrier is impregnated with an aqueous solution of magnesium acetate and barium nitrate, the solvent is removed at a temperature of 90 ° C. for 3 hours. Then the carrier, impregnated with magnesium acetate and barium nitrate, dried at a temperature of 150 ° C for 1 hour and calcined at a temperature of 600 ° C for 5 hours.

Next, an alumina carrier with magnesium and barium oxides in an amount of 100 g is placed in the mixer chamber, 70 ml of an aqueous solution containing 0.5772 g of palladium dihydroxodiamine is dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 20 ° C. After the carrier was impregnated with an aqueous solution of palladium dihydroxodiamine, the solvent was removed at a temperature of 60 ° C for 3 hours. Then the carrier, impregnated with palladium dihydroxodiamine, is dried at a temperature of 140 ° C for 1 hour, calcined at a temperature of 500 ° C for 3 hours and reduced in a hydrogen atmosphere at 250 ° C for 4 hours.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide of the absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2090 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.6 ° C. Thiele module - 0.06.

The catalyst used has the following composition:

Pd - 0.35% of the mass;

Mg - 0.70% of the mass;

Ba - 0.30% of the mass;

γ-Al ₂ O ₃ - 8.5% of the mass.

Highly porous cellular alumina of α-modification - 90.15% of the mass.

The results of the catalytic tests of this sample are presented in table 2.2.

Example 18. The catalyst is used in selective hydrogenation reactions: vinylacetylene, 1,2-butadiene, butine-1 in the composition of the butadiene fraction; butyn-1 (2), α-C ₅ acetylenes in the isoprene fraction; acetylene, diene hydrocarbons and unsaturated substituents in aromatic compounds in the C ₅₊ hydrocarbon fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular alumina support with a secondary layer of alumina with solutions of cobalt acetate and palladium acetylacetonate. The highly porous cellular alumina support of the α modification is characterized by a porosity of 88% with an average pore diameter of 3.9 mm. The secondary alumina carrier of the η modification has a specific surface area of 143 m ² / g, a pore volume of 0.74 cm ³ / g, mesopores with a diameter of more than 5 nm, which together account for 63% of the total pore volume. The thickness of the alumina layer is 118 μm.

A highly porous cellular alumina carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 90 ml of an aqueous solution containing 1.0551 g of cobalt acetate is dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 40 ° C. After the carrier is impregnated with a cobalt compound, the solvent is removed at a temperature of 80 ° C. for 1 hour. Then the carrier impregnated with cobalt acetate is dried at a temperature of 200 ° C for 2 hours and calcined at a temperature of 400 ° C for 5 hours.

Next, a highly porous cellular alumina carrier with a secondary layer of alumina with cobalt oxide in an amount of 100 g is placed in the mixer chamber, 50 ml of toluene containing 0.8604 g of palladium acetylacetonate are dosed. The impregnation is carried out for 1 hour at a temperature of the impregnating solution of 35 ° C. After the carrier was impregnated with palladium acetylacetonate, the solvent was removed at a temperature of 70 ° C. for 1 hour. Then, the carrier impregnated with palladium acetylacetonate is dried at a temperature of 150 ° C for 1 hour, calcined at a temperature of 300 ° C for 3 hours, and reduced for 2 hours in an alcoholic solution of sodium borohydride.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide of the absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2078 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.5 ° C. Thiele Module - 0.13.

The catalyst used has the following composition:

Pd - 0.30% of the mass;

Co - 0.25% of the mass;

η-Al ₂ O ₃ - 10.3% of the mass.

Highly porous cellular alumina of α-modification - 89.15% of the mass.

The results of the catalytic tests of this sample are presented in table 2.2.

Example 19. The catalyst is used in selective hydrogenation reactions: vinylacetylene, 1,2-butadiene, butine-1 in the composition of the butadiene fraction; butyn-1 (2), α-C ₅ acetylenes in the isoprene fraction; acetylene, diene hydrocarbons and unsaturated substituents in aromatic compounds in the C ₅₊ hydrocarbon fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular alumina support with a secondary layer of alumina with solutions of cobalt sulfate and palladium nitrate. The highly porous cellular alumina support of the α modification is characterized by a porosity of 95% with an average pore diameter of 3.4 mm. The secondary alumina carrier of the δ modification has a specific surface area of 118 m ² / g, a pore volume of 0.51 cm ³ / g, mesopores with a diameter of more than 5 nm, which together comprise 75% of the total pore volume. The thickness of the alumina layer is 37 μm.

A highly porous cellular alumina carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 80 ml of a 2% aqueous solution of sulfuric acid containing 2.8588 g of cobalt sulfate are dosed. The impregnation is carried out for 1 hour at a temperature of the impregnating solution of 60 ° C. After the carrier was impregnated with an aqueous solution of cobalt sulfate, the solvent was removed at a temperature of 80 ° C for 2 hours. Then, the alumina support impregnated with cobalt sulfate is dried at a temperature of 110 ° C for 2 hours and calcined at a temperature of 600 ° C for 5 hours.

Next, a highly porous cellular alumina carrier with a secondary layer of alumina with cobalt oxide in an amount of 100 g is placed in the mixer chamber, 80 ml of an aqueous solution containing 0.6529 g of palladium nitrate are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 80 ° C. After the carrier was impregnated with an aqueous solution of palladium nitrate, the solvent was removed at a temperature of 80 ° C for 1 hour. Then, the alumina support impregnated with palladium nitrate is dried at a temperature of 120 ° C for 2 hours, calcined at a temperature of 300 ° C for 4 hours and reduced in a hydrogen atmosphere at 300 ° C for 4 hours.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2085 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.3 ° C. Thiele module - 0.11.

The catalyst used has the following composition:

Pd - 0.30% of the mass;

Co - 0.60% of the mass;

δ-Al ₂ O ₃ - 7.2% of the mass.

Highly porous cellular alumina of α-modification - 91.9% of the mass.

The results of the catalytic tests of this sample are presented in table 2.2.

Example 20. The catalyst is used in selective hydrogenation reactions: vinylacetylene, 1,2-butadiene, butine-1 in the composition of the butadiene fraction; butyn-1 (2), α-C ₅ acetylenes in the isoprene fraction; acetylene, diene hydrocarbons and unsaturated substituents in aromatic compounds in the C ₅₊ hydrocarbon fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular alumina support with a secondary layer of alumina with solutions of silver sulfate and palladium nitrate. As the carrier, a system is used that has the same texture characteristics as the carrier in example 19.

A highly porous cellular alumina carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 80 ml of a 2% aqueous solution of sulfuric acid containing 1.7324 g of silver sulfate are dosed. The impregnation is carried out for 1 hour at a temperature of the impregnating solution of 60 ° C. After the carrier was impregnated with an aqueous solution of silver sulfate, the solvent was removed at a temperature of 80 ° C for 2 hours. Then the carrier impregnated with silver sulfate, dried at a temperature of 110 ° C for 2 hours and calcined at a temperature of 600 ° C for 5 hours.

Next, a highly porous cellular alumina carrier with a secondary layer of alumina with silver oxide in an amount of 100 g is placed in the mixer chamber, 80 ml of an aqueous solution containing 0.6529 g of palladium nitrate are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 80 ° C. After the carrier was impregnated with an aqueous solution of palladium nitrate, the solvent was removed at a temperature of 80 ° C for 1 hour. Then, the carrier impregnated with palladium nitrate is dried at a temperature of 120 ° C for 2 hours, calcined at a temperature of 300 ° C for 4 hours and reduced in a hydrogen atmosphere at 300 ° C for 4 hours.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2093 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.2 ° C. Thiele module - 0.11.

The catalyst used has the following composition:

Pd - 0.30% of the mass;

Ag - 0.60% of the mass;

δ-Al ₂ O ₃ - 7.2% of the mass.

Highly porous cellular alumina of α-modification - 91.9% of the mass.

The results of the catalytic tests of this sample are presented in table 2.2.

Example 21. The catalyst is used in selective hydrogenation reactions: vinylacetylene, 1,2-butadiene, butine-1 in the composition of the butadiene fraction; butyn-1 (2), α-C ₅ acetylenes in the isoprene fraction; acetylene, diene hydrocarbons and unsaturated substituents in aromatic compounds in the C ₅₊ hydrocarbon fraction.

The catalyst is prepared by sequentially impregnating a highly porous cellular alumina support with a secondary layer of alumina with solutions of copper sulfate and palladium nitrate. As the carrier, a system is used that has the same texture characteristics as the carrier in Example 19.

A highly porous cellular alumina carrier with a secondary layer of alumina in an amount of 100 g is placed in the mixer chamber, 80 ml of a 2% aqueous solution of acetic acid containing 2.3408 g of copper sulfate are dosed. Impregnation is carried out for 1 hour at a temperature of the impregnating solution of 70 ° C. After the carrier was impregnated with an aqueous solution of copper acetate, the solvent was removed at a temperature of 80 ° C for 2 hours. Then the carrier impregnated with copper acetate is dried at a temperature of 110 ° C for 3 hours and calcined at a temperature of 500 ° C for 3 hours.

Next, a highly porous cellular alumina carrier with a secondary layer of alumina with copper oxide in an amount of 100 g is placed in the mixer chamber, 80 ml of an aqueous solution containing 0.6529 g of palladium nitrate are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 80 ° C. After the carrier was impregnated with an aqueous solution of palladium nitrate, the solvent was removed at a temperature of 80 ° C for 1 hour. Then the carrier impregnated with palladium nitrate is dried at a temperature of 120 ° C for 2 hours, calcined at a temperature of 300 ° C for 4 hours. and restore in a hydrogen atmosphere at 300 ° C for 4 hours.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2099 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 0.3 ° C. Thiele module - 0.11.

The catalyst used has the following composition:

Pd - 0.30% of the mass;

Cu - 0.60% of the mass;

δ-Al ₂ O ₃ - 7.2% of the mass.

Highly porous cellular alumina of α-modification - 91.9% of the mass.

The results of the catalytic tests of this sample are presented in table 2.2.

Example 22 (prototype). The catalyst is used in selective hydrogenation reactions: vinylacetylene, 1,2-butadiene, butine-1 as part of the butadiene fraction; butyn-1 (2), α-C ₅ acetylenes in the isoprene fraction; acetylene, diene hydrocarbons and unsaturated substituents in aromatic compounds in the C ₅₊ hydrocarbon fraction.

The catalyst is prepared by sequentially impregnating the alumina support with solutions of copper sulfate and palladium nitrate. The carrier δ-Al ₂ O ₃ has a specific surface area of 127 m ² / g, a pore volume of 0.44 cm ³ / g, mesopores with a diameter of more than 5 nm, which make up 83% of the total pore volume. The diameter and length of the carrier granules is 3-4 mm.

An alumina carrier in an amount of 100 g is placed in a mixer chamber, 80 ml of a 2% aqueous solution of acetic acid containing 2.3408 g of copper sulfate are dosed. Impregnation is carried out for 1 hour at a temperature of the impregnating solution of 70 ° C. After the carrier was impregnated with an aqueous solution of copper acetate, the solvent was removed at a temperature of 80 ° C for 2 hours. Then the carrier impregnated with copper acetate is dried at a temperature of 110 ° C for 3 hours and calcined at a temperature of 500 ° C for 3 hours.

Next, an alumina carrier with copper oxide in an amount of 100 g is placed in the mixer chamber, 80 ml of an aqueous solution containing 0.6529 g of palladium nitrate are dosed. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 80 ° C. After the carrier was impregnated with an aqueous solution of palladium nitrate, the solvent was removed at a temperature of 80 ° C for 1 hour. Then, the carrier impregnated with palladium nitrate is dried at a temperature of 120 ° C for 2 hours, calcined at a temperature of 300 ° C for 4 hours and reduced in a hydrogen atmosphere at 300 ° C for 4 hours.

The finished catalyst is characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide of the absorption band of the complex of carbon monoxide with palladium in the oxidation state of zero with a wave number of 2089 cm ^-1 .

The temperature difference across the diagonal cross section of the catalyst layer is 2.5 ° C. Thiele Module - 3.13.

The catalyst used has the following composition:

Pd - 0.30% of the mass;

Cu - 0.60% of the mass;

δ-Al ₂ O ₃ - 99.1% of the mass.

The results of the catalytic tests of this sample are presented in table 2.2.

As can be seen from the above examples, the proposed catalyst surpasses the comparison catalysts in activity and selectivity in the hydrogenation reactions of acetylene and diene compounds in C ₂ -C ₅₊ hydrocarbon fractions.

A higher conversion of acetylene and diene compounds of the catalyst samples of this invention compared to the prototype catalysts is due to the interaction of palladium with a promoter on the surface of the secondary alumina layer and an increase in the number of surface atoms (dispersion) of the active component capable of participating in hydrogenation reactions of acetylene and diene compounds with good heat - and mass transfer.

The increase in the selectivity of hydrogenation of acetylenic and diene hydrocarbons to the corresponding compounds of the catalyst samples of the present invention compared to the prototype is due to the formation of palladium-promoter bimetallic particles with donation of the electrons of the promoter atoms to the valence orbitals of the palladium atoms while ensuring the absence of diffusion restrictions on the access of the reaction molecules to the active component due to the selected media type. This leads to the formation of surface palladium atoms in the zero oxidation state, characterized by the presence in the infrared spectrum of the adsorbed carbon monoxide of the absorption band of the complex of carbon monoxide (CO) with palladium in the zero oxidation state (Pd ⁰ ) with a wave number of 2060-2100 cm ^-1 providing good access to it reaction molecules. As the examples show, the shift of this absorption band to the region of vibrational frequencies with a wave number of 2060–2100 cm ^{–1 is} accompanied by an increase in the activity and selectivity of hydrogenation of acetylene and diene hydrocarbons as a result of an increase in the electron density on the valence orbitals of the surface atoms of palladium particles during the formation of bimetallic palladium promoter particles .

It is the presence of a secondary carrier with a specific surface area of at least 20 m ² / g, pore volume from 0.1 to 1.0 cm ³ / g, in which pores with a diameter of more than 5 nm comprise 50-98% of the total pore volume from 10 μm to 500 μm, provides an optimal distribution of palladium on the surface of the catalyst with its high dispersion, the absence of diffusion restrictions of the reaction molecules to the active component, which leads to an increase in the activity of the catalyst in the activity and selectivity of hydrogenation of acetylenic and diene hydrocarbons.

The presence of a highly porous cellular carrier, characterized by a porosity of at least 85% and an average pore size (cells) of 0.5-6.0 mm, provides high mass and heat transfer, low hydraulic resistance, which also contributes to an increase in the activity and selectivity of hydrogenation of acetylenic and diene hydrocarbons .

Table 1.1 The initial data of the catalyst for catalytic testing of hydrogenation of ethane-ethylene and propane-propylene fractions No. p / p The composition of the catalyst, mass% HPLC Characteristics Characteristics of the secondary carrier or carrier for prototype pr 11 Absorption band of CO with Pd ⁰ , cm ^-1 ΔT *, ° C Ψ * VPYAM Secondary carrier Pd Promoter Sopromotor Porosity,% The average pore diameter, mm Layer thickness, microns The specific surface of the carrier, m ² / g Pore volume, cm ³ / g The pore composition is more than 5 nm,% of the total volume one Ni γ-Al ₂ O ₃ 5,0 0.02 Ag 0.12 - - 92 2,3 22 280 0.86 fifty 2065 0.4 0.04 2 Cu β-Al ₂ O ₃ 5,4 0.02 Cu 0.04 K 0.01 85 0.5 10 200 1.00 57 2060 0.3 0.02 3 Fe δ-Al ₂ O ₃ 6.0 0.05 Au 0.005 K 0.005 93 3,5 53 135 0.56 79 2098 0.7 0.06 four Al α-Al ₂ O ₃ 5.5 0.06 Zn 0.30 Na 0.10 90 5.1 124 twenty 0.10 98 2063 0.5 0.12 5 α-Al ₂ O ₃ γ-Al ₂ O ₃ 6.7 0.005 Mg 0,025 Na 0.10 95 2,5 26 183 0.89 75 2100 0.3 0.04 6 α-Al ₂ O ₃ θ-Al ₂ O ₃ 6.9 0.05 Cr 0.10 Bi 0.20 93 6.0 500 80 0.35 83 2094 0.9 0.45 7 α-Al ₂ O ₃ δ-Al ₂ O ₃ 7.2 0,03 Co 0.15 Re 0.20 94 3,1 28 120 0.48 71 2073 0.3 0,03 8 α-Al ₂ O ₃ δ-Al ₂ O ₃ 7.2 0,03 Co 0.15 Mn 0.20 94 3,1 28 120 0.48 71 2079 0.2 0,03 9 α-Al ₂ O ₃ δ-Al ₂ O ₃ 7.2 0,03 Ag 0.15 - - 94 3,1 28 120 0.48 71 2097 0.1 0,03 10 α-Al ₂ O ₃ δ-Al ₂ O ₃ 7.2 0.05 Cu 0.15 - - 94 3,1 28 120 0.48 71 2085 0.2 0,03 eleven - - - 0.05 Cu 0.15 - - - - - 125 0.51 65 2083 2,4 2.81 Note: VPYAM - highly porous cellular material; ΔT is the temperature gradient over the cross section of the catalyst layer, Ψ ^* - Thiele module; sample No. 11 - the prototype is synthesized using a granular alumina carrier δ-modification, which is a cylinder with a diameter of 3-4 mm; 3-4 mm long.

Table 2.1 The results of catalytic tests for the hydrogenation of ethane-ethylene and propane-propylene fractions No. p / p Hydrogenation of ethane-ethylene fraction Hydrogenation of propane-propylene fraction Acetylene conversion,% Ethylene selectivity,% The conversion of methylacetylene and propadiene,% Propylene selectivity,% one one hundred 70.3 one hundred 69.7 2 98.4 67.1 98.6 65.5 3 one hundred 63,2 one hundred 66.8 four one hundred 56.1 one hundred 58.8 5 99.1 58.3 98.7 53.1 6 one hundred 61.1 one hundred 56.8 7 one hundred 71.9 one hundred 77.6 8 one hundred 68.3 one hundred 72,4 9 one hundred 68.1 one hundred 71.8 10 one hundred 49.9 96.7 54.9 eleven 93,4 29.1 91.5 24.5

Table 1.2 Initial data of the catalyst for catalytic hydrogenation of butadiene, isoprene and C ₅₊ hydrocarbon fractions No. p / p The composition of the catalyst, wt% HPLC Characteristics Characteristics of the secondary carrier or carrier for prototype pr 22 Absorption band of CO with Pd ⁰ , cm ^-1 ΔT *, ° C Ψ * VPYAM Secondary carrier Pd Promoter Sopromotor Porosity,% The average pore diameter, mm Layer thickness, microns The specific surface of the carrier, m ² / g Pore volume, cm ³ / g The pore composition is more than 5 nm,% of the total volume 12 Zn δ-Al ₂ O ₃ 6.3 1,0 Cu 1,0 - - 91 2,8 46 119 049 78 2062 0.3 0.05 13 Ti γ-Al ₂ O ₃ 6.5 0.1 Ag 5,0 - - 93 1,5 21 185 0 78 57 2074 0.4 0.04 fourteen α-Al ₂ O ₃ α-Al ₂ O ₃ 5,6 0.35 Au 2,5 - - 95 2.6 58 25 0.30 94 2097 0.6 0.06 fifteen α-Al ₂ O ₃ θ-Al ₂ O ₃ 6.9 0.6 Zn 0.5 Na 5,0 91 4.7 237 69 0 44 81 2062 0.4 0.26 16 α-Al ₂ O ₃ θ-Al ₂ O ₃ 6.5 0.5 Cr 0.6 - - 93 4.1 68 67 0 40 88 2094 0.8 0,07 17 α-Al ₂ O ₃ γ-Al ₂ O ₃ 8.5 0.35 Mg 0.7 Ba 0.3 94 2,4 49 169 0.75 51 2090 0.6 0.06 1S α-Al ₂ O ₃ η-Al ₂ O ₃ 10.3 0.3 With 0.25 - - 88 3.9 118 143 0.74 63 2078 0.5 0.13 19 α-Al ₂ O ₃ δ-Al ₂ O ₃ 7.2 0.3 With 0.6 - - 95 3.4 37 118 051 75 2085 0.3 0.11 twenty α-Al ₂ O ₃ δ-Al ₂ O ₃ 7D 0.3 Ag 0.6 - - 95 3.4 37 118 051 75 2093 0.2 0.11 21 α-Al ₂ O ₃ δ-Al ₂ O ₃ 7.2 0.3 Cu 0.6 - - 95 3.4 37 118 051 75 2099 0.3 0.11 22 - - - 0.5 - - - - - - - 127 044 83 2089 2,5 3.13 Note: VPYAM - highly porous cellular material; ΔT is the temperature gradient over the cross section of the catalyst layer, Ψ - Thiele module; sample No. 22 - the prototype is synthesized using a granular alumina carrier δ-modification, which is a cylinder with a diameter of 3-4 mm; 3-4 mm long.

Table 2.2 The results of catalytic tests for the hydrogenation of butadiene, isoprene and C ₅₊ hydrocarbon fractions No. p / p Hydrogenation of the butadiene fraction Isoprene fraction hydrogenation Hydrogenation of a C ₅₊ hydrocarbon fraction K ₁ ,% S ₁ ,% K ₂ ,% S ₂ ,% K ₃ % 12 one hundred 58.3 one hundred 60.1 one hundred 13 98.3 65,4 99,2 67.5 98.3 fourteen 97.8 68.7 98.7 71.3 99.1 fifteen one hundred 71.8 one hundred 71.7 one hundred 16 one hundred 67.1 one hundred 65.1 one hundred 17 one hundred 73.3 one hundred 72.8 one hundred eighteen one hundred 76.9 one hundred 77.5 one hundred 19 one hundred 78,2 one hundred 77.3 one hundred twenty one hundred 66.1 one hundred 62,2 one hundred 21 one hundred 62.1 one hundred 60.3 one hundred 22 91.7 24.8 92.3 34.6 92.8 Note: To ₁ is the conversion of vinylacetylene, 1,2-butadiene and 1-butine,%; S ₁ - selectivity for 1,3-butadiene,%; K ₂ - conversion of butyn-1 (2), α-C ₅ -acetylenes,%; S ₂ - selectivity for isoprene,%; To ₃ - the conversion of acetylene, diene hydrocarbons and unsaturated substituents in aromatic compounds,%.

Claims (1)

A catalyst for the selective hydrogenation of acetylene and diene hydrocarbons in C ₂ -C ₅₊ hydrocarbon fractions, with an alumina support on which the active component of palladium and the promoter are placed, the promoter on the support is fixed in oxide form to the active component, the palladium particles are supported on the support to zero degree electron oxidation of the valence orbitals of its atoms, in which the catalyst is characterized by an absorption band of a complex of carbon monoxide with palladium with a wave number of 2060-2100 cm ^-1 in infrared a clear spectrum of adsorbed carbon monoxide, the composition of the catalyst is formed in the following ratio, wt.%:
Palladium 0.005-1,
Promoter 0.005-5,
Sopromotor, if necessary, 0.005-5,
The carrier is the rest,
wherein the alumina carrier is made with pores with a diameter of more than 5 nm, the volume of which is 50-98% of the total pore volume, characterized in that the carrier is a highly porous cellular carrier made of metal or aluminum oxide, characterized by a porosity of at least 85%, an average pore size 0.5-6.0 mm, on a highly porous cellular support, an alumina layer is placed with the formation of a secondary support on which the promoter and active component palladium are sequentially placed, the secondary support is alumina izuetsya thickness from 10 microns to 500 microns, a specific surface area of at least 20 m ² / g, pore volume from 0.1 to 1.0 cm ³ / g, a secondary carrier alumina catalyst in the total composition is at least 5 wt%.