Catalyst of dehydration of c4-c5 paraffin hydrocarbons

FIELD: chemistry.

SUBSTANCE: dehydration catalyst represents aluminium oxide carrier, modified with silicon oxide, on which active component chrome oxide and promoter potassium oxide are distributed. Silicon oxide is fixed on aluminium oxide in form of silicon oxide structures Si(OSi)n(O-)4-n, where n is from 1 to 4, in which silicon in spectrum NMR MAS 29Si is characterised by presence of lines with chemical shifts from -95 to -105 ppm (line Q3) and from -107 to -124 ppm (line Q4) with ratio of integral intensities Q3/Q4 from 0.5 to 1.5, with chrome in active component being characterized in UV-Vis-spectrum of diffuse reflection by band of absorption of d-d electronic transition of octahedral Cr(III) cation with wave number from 16500 to 17000 cm-1. Catalyst has specific surface value from 10 to 250 m2/g, volume of pores not less than 0.15 cm3/g, and its composition is formed in the following ratio, wt %: chrome oxide - 8-20, potassium oxide- 0.1-5, silicon oxide - 0.1-5, aluminium oxide carrier - the remaining part.

EFFECT: claimed catalyst of paraffin hydrocarbons possesses high activity, selectivity and thermal stability.

3 cl, 2 dwg, 1 tbl, 17 ex

 

The invention relates to the field of chemical technology and catalytic chemistry, in particular to catalysts, methods of producing catalysts for dehydrogenation processes C4-C5paraffin hydrocarbons to the corresponding olefins in the presence of a catalyst containing the oxides of chromium, potassium and silicon deposited on the alumina carrier. C4-C5olefins are widely used for production of synthetic rubbers, plastics, components of motor fuels and other valuable petrochemical products. The increasing demand for branch, Rubezhnoe, Ukraine rubbers require the increase of the production capacity of isobutylene and isopentanol, which is possible through the development and use of more efficient catalytic systems.

The process of dehydrogenation of C4-C5paraffin hydrocarbons is carried out preferably in a fluidized bed reactor microspherical alimohammadi catalyst at a temperature over 500°C. Formed during the reaction of the coke deposits are burned during periodic regeneration of the catalyst at temperatures above 600°C.

Operational characteristics almuhanovich catalysts for dehydrogenation of paraffin hydrocarbons are determined by the properties of the active component of chromium oxide and characteristics of alumina is the La. Concentration, state of chromium in the active component determine the yield of olefins selectivity of the catalytic activity and thermal stability of the catalytic system. Structural stability of the catalyst is determined by the stability of the porous system and phase composition in the process of dehydrogenation. To improve properties almuhanovich catalysts suggested a large number of compositions with the compounds of silicon, obtained by drying the catalyst slurry, impregnating the finished alumina carriers with solutions of the active component, promoters and modifiers.

A known catalyst for the dehydrogenation of paraffin hydrocarbons (Copyright certificate SSSS No. 789151, IPC B01J 21/4, B01J 23/24, publ. 23.12.80), such as n-butane, isobutane, isopentane, in which the source of silicon oxide used natural aluminosilicate. The catalyst is prepared by drying the catalyst slurry. The catalyst composition, wt.%: the chromium oxide - 12,7-14,3; silica - 4-15; potassium oxide - 1,3-1,9; sodium oxide - 0,4-0,8; aluminium oxide - rest. The catalyst has high activity: the amount of isoamylenes and isoprene on missed isopentane - 46.8 wt.%; the amount of n-butylenes and butadiene missed on n-butane - 47.5 wt.%; the isobutylene on missed isobutylene - 57.6 wt.%. The disadvantage of the catalyst is low selective behaviour is ity on target olefins due to the high output of products of cracking.

A known catalyst for the dehydrogenation of C2-C5hydrocarbons (RF Patent No. 2287366, IPC B01J 23/26, B01J 37/02, C07C 5/333, publ. 28.09.99), containing oxides of aluminum, chromium, silicon compounds and/or boron, alkali or alkaline earth metal, at least one compound from the group of zirconium, titanium, iron, gallium, cobalt, molybdenum, manganese, tin. As the carrier is used as a compound of aluminium of the formula Al2O3·nH2O (n=0,3-1,5) amorphous structure in the form of microspherical powder. The catalyst is prepared by impregnation of aluminum compounds with solutions of the above elements, followed by drying and calcination at 700 to 800°C. as the source of silicon used tetraethoxysilane. The catalyst has a value of specific surface area of 50-150 m2/g, pore volume of 0.15-0.4 cm3/g, a particle size of 40-200 μm. The catalyst composition, wt.%: the chromium oxide - 12-23; the connection of reactive metal from the group of Zr, Ti, Fe, Ga, Co, Mo, Mn, Sn - 0.1 to 1.5; a compound of silicon and/or boron is 0.1 to 10; the connection of alkaline and/or alkaline earth metal - 0,5-3,5; aluminium oxide - rest. The catalyst in the reaction of dehydrogenation of isobutane is characterized by high activity - output unsaturated C4-hydrocarbon missed isobutane is 51.9 percent. The disadvantages of the catalyst are low selectivity - yield unsaturated C4the hydrocarbon is decomposed in isobutane not more 86,6%, the complexity of the technology of production, complexity of composition and playback properties.

Known highly active, not containing silicon oxide, the catalyst for the dehydrogenation of C3-C5paraffin hydrocarbons (RF Patent No. 2350594, IPC C07C 5/333, B01J 23/26, B01J 21/04, B01J 23/04, B01J 37/02), such as propane, isobutane, isopentane, based on the alumina carrier bemani morphology with a value of specific surface area 80-250 m2/g, pore volume of at least 0.2 cm3/g, size microcrystallites by the values of the regions of coherent scattering from 500 to 3000 Å, the interlayer water in an amount corresponding to a molar ratio of water to aluminum oxide from 0.8 to 1.2. The catalyst is prepared by impregnation of the support with solutions of precursors of chromium oxide, potassium oxide and a promoter, representing at least one of the oxides selected from the group: copper oxide, zinc oxide, manganese oxide, tin oxide, boron oxide, zirconium oxide, followed by drying and calcination at a temperature of from 600 to 900°C. the catalyst Composition, wt.%: the chromium oxide - 10-20, potassium oxide, and 0.1 - 5 promoter - 0,1-5, alumina media - the rest. The catalyst is characterized by high activity in reactions of dehydrogenation of propane, isobutane, isopentane. The yield of propylene on missed propane is 33.4%, and the yield of isobutene on missed isobutane 54.6% of output isoamylene missed isopentane - 47,5%. The disadvantages of the catalyst are low selectivity for the target olefins and low thermal stability.

The closest technical solution of the present invention is a catalyst for obtaining light olefins (U.S. Patent No. 6362385, C07C 5/333, C07C 5/373, C07C 5/327, publ. 26.03.2002) by dehydrogenation of the corresponding paraffins containing chromium oxide, tin oxide, alkali metal oxide, aluminium silicate, high temperature alumina. The catalyst was prepared by thermal decomposition of microspheric pseudoboehmite prepared by spray drying Zola aluminum hydroxide and crematoria. On the prepared aluminum oxide is applied by impregnation of the oxides of chromium, tin, alkaline metal is dried and calcined. The catalyst composition, wt.%: Cr2O3- 6-30, SnO - 0,1-3,5, alkali metal, expressed as M2O - 0,4-3, SiO2- 0,08-3, Al2O3- the rest. The catalyst is characterized by high selectivity for the target olefin. In the reaction of dehydrogenation of isobutane selectivity for isobutylene is 94 mol.%. In the reaction of dehydrogenation of propane selectivity for propylene is 89 mol. %. The disadvantages of the catalyst are low activity and lack of stability of the granules to abrasion due to the formation of coagulation contacts between the particles of their components.

The task is razlagaemogo invention is to increase activity, selectivity and thermal stability of the catalyst in the dehydrogenation of C4-C5paraffin hydrocarbons by forming on the surface of the active component oxide chromium (III) in the form of clusters in the presence of modifier silicon, arranged in the form of surface ocenography structures of Si(OSi)n(O)4-nwhere n is 1 to 4.

The task is solved by providing a catalyst for the dehydrogenation of C4-C5paraffin hydrocarbons, which represents an alumina carrier, a modified silicon oxide, which is distributed active ingredient chromium oxide and a promoter oxide of potassium. The catalyst has a value of specific surface area from 10 to 250 m2/g, pore volume of at least 0.15 cm3/year

The difference of the invention from the prototype is the following:

in the catalyst, the silicon oxide fixed on the aluminum oxide in the form ocenography structures of Si(OSi)n(O)4-nwhere n is from 1 to 4, in which the silicon NMR MAS29Si is characterized by the presence of lines with chemical shifts from -95 to -105 M. D. (line Q3and from -107 to -124 M. D. (line Q4) when the ratio of integrated intensities Q3/Q4from 0.5 to 1.5;

in the catalyst of chromium oxide (III) is placed and fixed in the form of clusters, in which chromium is characterized in UV-visible-spectrum diffuse from the agenia absorption band of the d-d electronic transition of octahedral cation Cr(III) with the wave number from up to 17000 16500 cm -1;

- alumina carrier in the catalyst contains χ-Al2O3in the amount of from 0.5 to 15 wt.%;

in the catalyst, the concentration of strong acid sites, characterized by the heat of desorption of ammonia more than 150 kJ/mol is not more than 3 µmol NH3/year

while the composition of the catalyst prepared in the following ratio, wt.%:

the chromium oxide8-20
the potassium oxide0,1-5
the silicon oxide0,1-5
alumina mediarest

If the specified set of restrictive and distinctive signs of the presence in the spectrum of the NMR MAS29Si declare lines with chemical shifts from -95 to -105 M. D. (line Q3and from -107 to -124 M. D. (line Q4provided the ratio of the integral intensities of Q3/Q4from 0.5 to 1.5 indicates the formation of oligomeric structures of tetrahedra SiO4fixed on the surface of aluminum oxide (figure 1, table 1). Line Q4corresponds to a surface silicon atom connected to four tetrahedra SiO4through links Si-O-Si. Line Q3corresponding to the surface of the silicon atom, associated with three tetrahedra SiO4and one (OH-) or (AlO-) group (Sato S., Sodesawa T., Nozaki F., Shoji, H. Solid-state NMR of silica-alumina prepared by chemical vapor deposition // Journal of Molecular Catalysis. - 1991. - V. 66. - P. 343-355). The ratio of the intensity of the signals Q3/Q4and the position of the resonance signals in the NMR MAS29Si spectra indicates a high degree of coordination of silica with alumina carrier and free hydroxyl groups in the formation on the catalyst surface areas covered with amorphous aminocinnamate structures.

Forming on the surface of the alumina carrier ocenography structures of Si(OSi)n(O)4-n(where n is from 1 to 4), characterized in the synthesis of the catalyst is smaller compared to aluminum oxide by the pH of the hydrated surface, leads to an increase in the degree of oligomerization of the surface of the particles of Cr(VI) and education polychromatic particles when applying the precursor of the active component. When thermo-activation of the catalyst surface polychromatic recovered to a high-level clusters of chromium oxide (III), characterized by an absorption band in the UV-visible spectrum of from up to 17000 16500 cm-1(figure 2), indicating that the presence of the catalyst ions of chromium (III) in octahedral coordination (Weckhuysen, B. M., I. E. Wachs, Schoonheydt, R. A. Surface Chemistry and Spectroscopy of Chromium in Inorganic Oxides // Chemical Reiews. - 1996. - V. 96. - P. 3327-3349). The specified state of chromium on the catalyst surface in the presence of a modifier of silicon oxide helps to increase the activity of the catalyst in the reaction of dehydrogenation of C4-C5-paraffins.

The introduction of silicon in the catalyst and the formation of surface ocenography structures reduces the degree of interaction of chromium with the surface of the aluminum oxide, which leads to fewer embedded in the structure of the aluminum oxide chromium in phase and structural transformations of the catalyst as a result of local overheating of the catalyst and increases its thermal stability during operation (Sanfilippo D., Miracca I. Dehydrogenation of paraffins: synergies between catalyst design and reactor engineering // Catalysis Today. - 2006. - V. 111. - P. 133-139).

Lomography the catalyst for the dehydrogenation of C4-C5-paraffins characterized by a broad signal in the spectra of temperature-programmed desorption of ammonia in the area of the heats of desorption of ammonia from 80 to 160 µmol/g of Acid centers, with the heat of desorption of more than 150 µmol/g, are in a strong acid centres, active in adverse reactions cracking of hydrocarbons. The surface modification of alumina media aminocinnamate structures causes a decrease in the concentration of acid sites with the heat of desorption of ammonia over 150 KD is/mol to not more than 3 mmol/g, this increases the selectivity of the catalyst according to the target olefins (Egorova, S. R., Kataev A. N., Bekmuhamedov, E., Lamberov A. A., Gilmullin P. P., O. Nesterov N. Development of technology of production of microspherical alumina carrier for catalyst for the dehydrogenation of paraffins. (2) Effect of hydrothermal treatment on performance microspherical alumina carrier and alimohammadi catalyst dehydrogenation of isobutane // Catalysis in industry. - 2009. No. 6. - S. 48-60).

As a result, the process of dehydrogenation of C4-C5-paraffin hydrocarbons in the presence of a catalyst in accordance with this invention is more efficient, which is reflected in the increased yield of the desired hydrocarbon, the reduction of the yield of by-products, the improvement of thermal stability.

In contrast to the claimed invention in the prototype catalyst for the dehydrogenation of light paraffins is a composition consisting of aluminum oxide, silicon oxide, chromium oxide, oxide of alkali promoter and tin. Multi-component catalyst composition in the prototype determines the complicated reproducibility of catalytic properties. In the prototype as a predecessor of the media product of the spray drying pseudoboehmite granules catalysis the Torah has a low resistance to abrasion during operation in the fluidized bed. Furthermore, the processing composition pseudoboehmite with silicon oxide at a temperature of 1000°C leads to the formation of aluminosilicate structures with high surface acidity (Paukshtis E. A. Infrared spectroscopy in heterogeneous acid-base catalysis, Novosibirsk: Nauka, 1992. - 255 S.). Therefore, in the prototype catalyst has insufficient selectivity in the reaction of dehydrogenation of paraffins.

The catalyst according to the invention is prepared by impregnating alumina carrier with solutions of precursors of silicon oxide, chromium oxide, potassium oxide, taken from the calculation of the composition of the finished catalyst, wt.%:

the chromium oxide8-20
the potassium oxide0,1-5
the silicon oxide0,1-5
alumina mediarest

The alumina carrier is placed in a vacuum chamber of the mixer and Tegaserod. Then dispense the solution of a precursor of silicon oxide in an amount corresponding to the capacity of the media. The carrier impregnated with the solution is carried out for 0.5 to 2 hours. The impregnated carrier is dried at atmospheric pressure, in vacuum p and a residual pressure of 30-150 mm RT.article or in a stream of dried nitrogen within 1-12 hours and calcined in air or in a stream of dry nitrogen at a temperature of 300-600°C for 4-6 hours.

Modified silica carrier is placed in a vacuum chamber of the mixer and Tegaserod. Then dispense aqueous solutions of the precursors of chromium oxide and potassium oxide at atmospheric pressure or in vacuum at a residual pressure of about 30-150 mm RT.article in the number corresponding to the capacity of the media. The carrier impregnated with the solution is carried out for 0.5 to 2 hours. After impregnation the catalyst is dried under atmospheric pressure or in vacuum at a residual pressure of 30-150 mm RT.article within 1-12 hours and calcined in air at a temperature of 600-900°C for 4-6 hours.

As a source of chromium oxide is used chromic anhydride, potassium chromate, potassium dichromate, ammonium chromate, ammonium bichromate, chromium hydroxide, chromium nitrate, chromium acetate, chromium oxalate, chromium acetylacetonate, alcoholate chromium, ORGANOMETALLIC complex compounds of chromium and other

As a source of potassium oxide using potassium carbonate, potassium hydroxide, potassium nitrate, potassium nitrite, potassium sulfate, potassium permanganate, potassium oxalate, potassium acetate, or a mixture thereof.

As the source of silicon oxide using crumpsall, stable ions of sodium, potassium, aluminum, AMM is tion, as well as potassium silicate, sodium; organosilicon: alkoxysilane Si(OR1)n(OR2)4-nwhere R1, R2=C6H5CmH2m+1, m=1-5, preparation.

As alumina carrier used boehmite, pseudoboehmite, the connection of the aluminum x-ray amorphous structure of the formula Al2O3·nH2O, where n=0.5 to 1.5, aluminum oxide phases γ-Al2O3, δ-Al2O3, η-Al2O3χ-Al2O3θ-Al2O3, κ-Al2O3α-Al2O3or mixed phases (γ-Al2O3+ δ-Al2O3, γ-Al2O3+ η-Al2O3, γ-Al2O3+ χ-Al2O3, γ-Al2O3+ δ-Al2O3+ θ-Al2O3, γ-Al2O3+ δ-Al2O3+ χ-Al2O3+ κ-Al2O3, δ-Al2O3+ θ-Al2O3+ α-Al2O3, δ-Al2O3+ θ-Al2O3+ κ-Al2O3+ α-Al2O3).

The phase composition of the medium is determined by the method of x-ray diffraction. Taking radiographs performed using long-wave radiation CuKαand a graphite monochromator on the diffracted beam. The range of entry angles in the scale 20 is 5 to 95 deg.

Granulometric composition of the medium determined by laser diffraction. usnot method of determining the fractional composition described in method ASTM D4464-10 "Standard Test Method for Particle Size Distribution of Catalytic Material by Laser Light Scattering".

The value of specific surface area and pore volume determined by the method of low-temperature nitrogen adsorption. The essence of the method of determining the parameters of the porous system described in the method of ASTM D 3663-99 "Standard method of investigation of the surface area and pore volume of catalysts and catalysts carriers".

Entry29Si NMR spectra of the catalysts is carried out with the rotation of the samples under magic angle with a frequency of 5 kHz.29Si NMR spectra of the catalysts register in the range of -650 650 memorial plaques at the operating frequency 79,495 MHz spectral resolution 48,83 Hz.

Recording UV-visible spectra of diffuse reflection of the catalysts is carried out on the scanning dual-beam spectrophotometer, connected with integrating sphere with a diameter of 60 mm, covered inside BaSO4. As a standard, use the plate from BaSO4. To capture the spectra of the catalyst samples with a size of 40-100 μm is placed in a holder with a quartz window. Spectra recorded in the range 200-800 nm (12500-50000 cm-1) with a spectral resolution of 2 nm. UV-visible spectra of the samples of the catalyst and the chromium oxide is decomposed by a Gaussian components for determining the position and intensity of the maxima of the absorption bands.

The surface acidity of the catalysts determined by the method termoregulirovanija desorption of ammonia on the device flow type with detector, the m thermal conductivity. Stage adsorption is carried out in a stream of ammonia for 30 min at a temperature of 100°C. After adsorption perform the Stripping physically adsorbed ammonia helium at 100°C for 30 minutes followed by cooling the sample to room temperature in a stream of helium. Termoregulirovanija desorption of ammonia is carried out from room temperature to 700°C at 10 K/min Calculations data TPD of ammonia on the distribution of acid sites perform the technique (Yushchenko centuries calculation of the spectra of the acidity of the catalysts according to termoregulirovanija desorption of ammonia // Journal of physical chemistry. - 1997. - So 71, No. 4. - S. 628-632).

The catalyst was tested in the process of dehydrogenation of isobutane and isopentane at a temperature of dehydrogenation 530-570°C, flow rate of feed 300-400 h-1. The regeneration is carried out with air at a temperature of 650°C, maintaining the catalyst for 30 minutes Testing is carried out in a laboratory setup flow type with quartz tubular reactor in the fluidized bed of catalyst. The volume of the loaded catalyst - 100 cm3. The process is carried out cycles in the following sequence: dehydration - 15 min, purge with an inert gas to 5 minutes, the regeneration air is 30 min, purge with an inert gas to 5 minutes, then cycles again. After exposure of the catalyst at a temperature of 570°C for 2 hours to carry out the two idle cycle. On the third cycle in the reaction of dehydrogenation selected contact gas from 6 to 15 minute inclusive, in the amount of 1 l of the Contact gas is analyzed by gas chromatography. According to the results of chromatographic analysis calculate the yield of the desired olefin in missing and decomposed paraffin - activity and selectivity of the catalyst, respectively.

The specific implementation of the invention are illustrated in the following examples.

Example 1

200 g of the carrier - boehmite formula Al2O3·nH2O, where n=1, with a particle size of from 20 to 250 μm is impregnated with 86 ml of Kremenets with a concentration of SiO25.6 wt.%, stabilized ammonium ions. The impregnation is carried out for 1 hour at room temperature and atmospheric pressure. The carrier is dried in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C for 2 hours.

The catalyst is prepared by impregnation of the support with a solution of precursors of the oxides of chromium and potassium, for which the dried carrier is placed in a vacuum chamber of the mixer and dosed 82 ml of an aqueous solution containing 24,1 g of chromic anhydride and 2.3 g of potassium hydroxide. The impregnation is carried out for 1 hour at room temperature. The impregnated carrier is dried in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C for 2 hours, calcined in air at a temperature of 750°C for 4 h the owls.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 2

Catalyst carrier and the catalyst was prepared as described in example 1, but spend an additional heat treatment at 1100°C for 2 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 3

Catalyst carrier and the catalyst was prepared as described in example 1, but using pseudoboehmite formula Al2O3·nH2O, where n=1.5, soaking 90 ml of tetraethoxysilane in ethanol with a concentration of silicon is 1.1 wt.% for 0.5 hours at room temperature and atmospheric pressure. The carrier is dried in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C for 1 hour, treated at 550°C for 2 hours in a stream of dry air. Heat-treated carrier is impregnated with 172 ml of an aqueous solution containing of 34.5 g of ammonium chromate, 2.8 g of potassium carbonate for 1 hour at room temperature and atmospheric pressure. The impregnated carrier is dried at atmospheric pressure and a temperature of 80°C for 12 hours, then calcined in air at a temperature of 750°C for 4 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 4

Catalyst carrier and the catalyst was prepared as described in example 1, but using compound aluminum x-ray amorphous structure of the formula Al2O3·nH2O, where n=0,5, soaking 94 ml of an aqueous solution of metasilicate potassium concentration of SiO28.2 wt.% in for 1 hour in vacuum at a residual pressure of 100 mm RT.article and at room temperature. The carrier is dried for 12 hours at atmospheric pressure and a temperature of 80°C. the Dried carrier is impregnated with 180 ml of an aqueous solution containing a 41.9 g of ammonium bichromate and 4.2 g of potassium carbonate for 1 hour at a residual pressure of 100 mm RT.art., dried for 2 hours in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C, calcined in air at a temperature of 770°C for 4 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 5

Catalyst carrier and the catalyst was prepared as described in example 1, but using pseudoboehmite formula Al2O3·nH2O, where n=1.5, soaking 90 ml benzene solution of tetramethoxysilane with the concentration of silicon 5.0 wt.%for 1 hour at room temperature and atmospheric pressure. The carrier is dried in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C for 2 hours. The dried carrier is impregnated with 172 ml of an aqueous solution containing 37,2 g of ammonium bichromate, 6.6 g of potassium chromate for 0.5 h in vacuum at a residual pressure of 80 mm RT.article at room temperature, dried for 2 hours in vacuum at a residual pressure of 30 mm RT.article and a temperature of 85°C, calcined in air at 800°C for 5 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 6

Catalyst carrier and the catalyst was prepared as described in example 1, but using compound aluminum x-ray amorphous structure of the formula Al2O3·nH2O, where n=0,5, soaking 94 ml crematoria with a concentration of SiO23.3 wt.%, stable aluminium ions, for 1 hour at a temperature of 30°C and at a residual pressure of 150 mm RT.article The carrier is dried for 2 hours in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C. the Carrier is impregnated with 90 ml of an aqueous solution containing of 21.9 g of chromic anhydride, 2.2 g of potassium hydroxide for 0.5 hours at a temperature of 30°C and atmospheric pressure, dried for 12 hours at a temperature of 80°C and atmospheric pressure, calcined in air at t is mperature 780°C for 4 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 7

Catalyst carrier and the catalyst was prepared as described in example 1, but using boehmite formula Al2O3·nH2O, where n=1, soaking 86 ml benzene solution of tetramethoxysilane with the concentration of silicon 6.4 wt.% for 1 hour at room temperature and at atmospheric pressure. The carrier is dried for 2 hours in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C. the Dried carrier is impregnated with 82 ml of an aqueous solution containing from 34.1 g of chromic anhydride, 4.9 g of potassium carbonate for 1 hour at room temperature and at a residual pressure of 150 mm RT.art., dried for 2 hours in vacuum at a residual pressure of 30 mm RT.article and a temperature of 85°C, calcined in air at 800°C for 4 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 8

Catalyst carrier and the catalyst was prepared as described in example 1, but using boehmite formula Al2O3·nH2O, where n=1, soaking 86 ml of methoxytrimethylsilane in ethyl alcohol with a concentration of silicon of 2.5 wt.% during the course is 2 hours at room temperature and atmospheric pressure. The carrier is dried for 2 hours in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C, then treated at a temperature of 450°C for 2 hours in nitrogen atmosphere. The carrier impregnated with 164 ml of an aqueous solution containing a 27.4 g of ammonium bichromate, 2.8 g of potassium carbonate for 0.5 hours in vacuum at a residual pressure of 50 mm RT.article and a temperature of 30°C, dried for 12 hours at a temperature of 80°C and atmospheric pressure, calcined in air at a temperature of 740°C for 4 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 9

Catalyst carrier and the catalyst was prepared as described in example 1, but using boehmite formula Al2O3·nH2O, where n=1, soaking 86 ml crematoria with a concentration of SiO28.0 wt.%, stable sodium ion for 2 hours in vacuum at a residual pressure of 150 mm RT.article and room temperature. The carrier is dried for 2 hours in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C. the Dried carrier is impregnated with 82 ml of an aqueous solution containing the 39.6 g of chromic anhydride, 5.0 g of potassium hydroxide for 0.5 hours at atmospheric pressure and room temperature, dried for 12 hours at atmospheric pressure and a temperature of 8°C, calcined in air at 700°C for 6 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 10

Catalyst carrier and the catalyst was prepared as described in example 1, but using boehmite formula Al2O3·nH2O, where n=1, soaking 86 ml benzene solution of ethyl silicate-32 concentration of silicon 3.1 wt.% for 2 hours at room temperature and atmospheric pressure. The carrier is dried for 12 hours in a stream of dried nitrogen at a temperature of 90°C, calcined in nitrogen atmosphere at a temperature of 450°C for 5 hours. Heat-treated carrier is impregnated with 180 ml of an aqueous solution containing of 35.4 g of ammonium chromate, 2.3 g of potassium hydroxide for 0.5 hours in vacuum at a residual pressure of 80 mm RT.article and a temperature of 30°C, dried for 2 hours in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C, calcined in air at 800°C for 4 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 11

Catalyst carrier and the catalyst was prepared as described in example 1, but using boehmite formula Al2O3·nH2O, GD is n=1, soaking 86 ml of dimethoxydimethylsilane in ethyl alcohol with a concentration of silicon of 2.3 wt.% for 1 hour at room temperature and atmospheric pressure. The carrier is dried in a stream of dried nitrogen at a temperature of 90°C for 12 hours, then calcined in a stream of dried nitrogen at a temperature of 450°C for 5 hours. The calcined carrier is impregnated with 90 ml of an aqueous solution containing of 28.2 g of chromic anhydride, 2.8 g of potassium hydroxide for 1 h in vacuum at a residual pressure of 150 mm RT.article at room temperature, dried for 2 hours in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C, calcined in air at 800°C for 4 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 12

Catalyst carrier and the catalyst was prepared as described in example 1, but using boehmite formula Al2O3·nH2O, where n=1, soaking 86 ml of an aqueous solution of metasilicate potassium concentration of SiO211.1 wt.% for 0.5 hours in vacuum at a residual pressure of 150 mm RT.article and a temperature of 30°C. the Medium is dried for 2 hours in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C, calcined in a stream of dried nitrogen at a temperature of 350°C for 2 the aces. The calcined carrier is impregnated with 88 ml of an aqueous solution containing 26.7 g of chromic anhydride and 1.9 g of potassium hydroxide for 1 hour in vacuum at a residual pressure of 100 mm RT.article at room temperature, dried for 2 hours in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C, calcined in air at a temperature of 780°C for 5 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 13

Catalyst carrier and the catalyst was prepared as described in example 1, but using boehmite formula Al2O3·nH2O, where n=1, soaking 86 ml of trimethoxyoctylsilane in ethyl alcohol with a concentration of silicon of 5.2 wt.% in the course of 1.5 hours at a temperature of 20°C and atmospheric pressure. The impregnated carrier is dried for 12 hours in a stream of dried nitrogen at a temperature of 90°C, calcined in a stream of dried nitrogen at 400°C for 5 hours. The carrier impregnated with 180 ml of an aqueous solution containing of 52.9 g of ammonium chromate, 4.8 g of potassium carbonate for 1 h in vacuum at a residual pressure of 100 mm RT.article at room temperature, dried for 2 hours in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C, calcined in air at 800°C for 4 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 14

Catalyst carrier and the catalyst was prepared as described in example 1, but using boehmite formula Al2O3·nH2O, where n=1, soaking 86 ml Kremenets SiO22.0 wt.%, stabilized ammonium ions, for 1 hour in vacuum at a residual pressure of 100 mm RT.article and a temperature of 20°C. the Impregnated carrier is dried for 2 hours in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C, calcined in air at a temperature of 300°C for 5 hours. The carrier impregnated in two phases 180 ml of an aqueous solution containing a 43.4 g of ammonium chromate, 3.7 g of potassium carbonate, dried for 2 hours in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C, calcined in air at a temperature of 750°C for 6 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 15

Catalyst carrier and the catalyst was prepared as described in example 1, but using boehmite formula Al2O3·nH2O, where n=1, soaking 86 ml crematoria with a concentration of SiO25.0 wt.%, stable aluminium ions, for 0.5 hours PR is atmospheric pressure and room temperature. The dried carrier is calcined in air at 400°C for 4 hours. Heat-treated carrier is impregnated with 90 ml of an aqueous solution containing 27.7 G. of chromic anhydride, 2.1 g of potassium hydroxide for 1 hour at atmospheric pressure and a temperature of 30°C, dried for 2 hours in vacuum at a residual pressure of 30 mm RT.article and a temperature of 80°C, calcined in air at 800°C for 2 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 16 (comparison)

Microspheric pseudonimity media with a particle size of 5 are 300 μm, obtained by spray drying the Sol of hydrated aluminum oxide and silicon oxide containing 1.2 wt.% SiO2, subjected to heat treatment at a temperature of 450°C for 1 hour and then at 1030°C for 4 hours in a stream of dry air. The calcined carrier within 2 hours impregnate at atmospheric pressure and a temperature of 85°C 68 ml of an aqueous solution containing 48.6 G. of chromic anhydride, and 4.40 g of potassium hydroxide, 3.0 g of tin oxalate. The impregnated carrier was incubated for one hour at room temperature, then dried for 15 hours at atmospheric pressure and a temperature of 90°C, calcined in a stream of dry air at a temperature of 750°C in accordance with the s 4 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

Example 17 (comparison)

Catalyst carrier and the catalyst was prepared as described in example 16, but perform additional processing at a temperature of 1100°C for 2 hours.

Composition and properties of the catalysts and the results of catalytic tests in the reactions of dehydrogenation of isobutane and isopentane are shown in table 1.

As seen from the above examples, the proposed catalyst of superior activity, selectivity and thermal stability in the reactions of dehydrogenation of C4-C5paraffin hydrocarbons, the catalysts of the prototype.

Higher dehydrating activity of the catalyst samples compared with the catalysts of the prototype due to the fixation on the surface of the catalyst active phase of chromium oxide (III) in the form of high-level clusters, in which ions of chromium (III) are present in octahedral coordination and are characterized by an absorption band in the UV-visible spectrum of from up to 17000 16500 cm-1. The formation of a highly active clusters of chromium oxide (III) is provided through the distribution on the surface of the alumina carrier amorphous ocenography structures of Si(OSi)n(O)4-n(where n is from 1 to 4), in which the silicon in the specification of the tre NMR MAS 29Si is characterized by the presence of lines with chemical shifts from -95 to -105 M. D. (line Q3and from -107 to -124 M. D. (line Q4). As the ratio of the intensity of the signals Q3/Q4and position of the resonance signals in the NMR MAS29Si spectra, with predominantly formed specific aminocinnamate patterns with a greater degree of coordination of silica with alumina carrier and free hydroxyl groups.

The increase in selectivity for the target olefins samples of the catalyst of this invention in the process of dehydrogenation compared with the catalysts of the prototype due to the change of the acid characteristics of the surface of the alumina carrier when modifying aminocinnamate structures, accompanied by a decrease in the concentration of the strongest acid sites with the energy of desorption of ammonia more than 150 kJ/mol, catalyze undesirable reactions of cracking of hydrocarbons, to a minimum amount - no more than 3 µmol/g

Improving thermal stability of a sample of the catalyst of this invention compared with the catalyst of the prototype is caused by the decrease in the number of chromium atoms embedded in the structure of the alumina carrier in phase and structural transformations caused by high temperatures during regeneration, due to the Nigeria the degree of interaction of chromium with the surface of the carrier in the presence of specific ocenography structures.

td align="center"> 92,3 1,0
Table 1
# exampleThe catalyst composition, wt.%Sbeatsm2/gVpcm3/gNC. K. C., µmol/gδ(Q3), M. D.δ(Q4), M. D.I(Q3)/I(Q4)υ(4A2g4T2g), cm2The dehydrogenation
Cr2O3K2OAl2O3SiO2IsobutaneIsopentane
EAP %BP, %EAP %BP, %
General.including χ-Al2O3
12 34567891011121314151617
19,51,0of 87.002,5690,220,5-102-1180,621685054,394,747,886,7
29,51,0of 87.002,5420,180-96-1100,941692046,440,584,3
310,01,187,94,51,0830,231,2-104-1220,521691052,192,345,685,9
411,51,383,7103,51240,212,6-103-1150,751680053,691,547,086,5
513,31,780,51,54,5780,22 0,8-101-1110,841677054,1a 94.2to 47.285,7
68,10,9to 89.50,21,5720,210,3-105-1210,541688051,793,247,5to 85.2
712,51,680,913,55,01470,242,9-99-1100,871673053,990,847,184,5
88,788,44,31,9860,211,3-104-1180,581687050,792,446,285,0
914.4V2,080,32,43,3910,202,0-102-1140,781681053,493,747,384,8
109,21,087,27,02,61050,182,3-101-1170,6616840 51,1for 91.345,385,7
1111,01,286,101,7670,210,4-105-1190,561689053,894,547,586,3
1210,20,884,20,64,8960,240,8-98-1100,911675054,694,547,985,6
1312,91,681,8of 5.43,7112 0,231,8-102-1150,771679052,590,446,485,7
1411,21,386,62,40,91040,210,7-106-1230,511693053,494,647,586,5

Continuation of table 1
1234567891011121314 151617
1510,80,986,13,72,2830,231,3-103-1190,591682054,093,946,385,7
16 (comparison)19,01,976,92,5SiO2=1,2 SnO=1,01020,3210,2-101-1090,861722051,792,6of 40.3to 85.2
17 (comparison)19,01,976,92,5SiO2=1,2 SnO=1,0 670,164,3-95-1081,21743031,387,428,781,0
EP - out on olefin missed paraffin, %;
BP - outlet olefin laid out on paraffin, %;
Nc.to.C.EdesNH3- concentration of acid sites with the heat of desorption of ammonia more than 150 kJ/mol, mmol/g;
δ(Q3) and δ(Q4), M. D. - position signal ocenography structures Q3and Q4on29Si NMR spectrum in ppm;
I(Q3)/I(Q4- ratio of the intensities of the signals ocenography structures Q3and Q4on29Si NMR spectra;
υ(4A2g4T2g), cm-1is the wave number of the electronic transition4A2g4T2gin octahedral cation Cr(III), cm-1

1. The catalyst for the dehydrogenation of C4-C5paraffin hydrocarbons, which are aluminum the oxide carrier, modified silicon oxide, which is distributed active component chromium oxide promoter is potassium oxide, wherein the silicon oxide fixed on the aluminum oxide in the form ocenography structures of Si(OSi)n(O)4-nwhere n is from 1 to 4, in which the silicon NMR MAS29Si is characterized by the presence of lines with chemical shifts from -95 to -105 M. D. (line Q3and from -107 to -124 M. D. (line Q4) when the ratio of integrated intensities Q3/Q4from 0.5 to 1.5, in which the chromium is in the active component, characterized in UV-visible spectrum of diffuse reflection absorption band of the d-d electronic transition of octahedral cation Cr(III) with the wave number from up to 17000 16500 cm-1with a value of specific surface area from 10 to 250 m2/g, pore volume of at least 0.15 cm3/g, the catalyst composition is prepared in the following ratio, wt.%:

the chromium oxide8-20
the potassium oxide0,1-5
the silicon oxide0,1-5
alumina mediarest

2. The catalyst p. 1, characterized in that the alumina carrier contains χ-Al2 O3in the amount of from 0.5 to 15 wt.%.

3. The catalyst p. 1, characterized in that the concentration of strong acid sites, characterized by the heat of desorption of ammonia more than 150 kJ/mol is not more than 3 µmol NH3/,



 

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21 cl, 2 dwg, 3 tbl, 12 ex

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20 cl, 26 dwg, 2 tbl, 4 ex

FIELD: chemistry.

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17 cl, 10 dwg, 1 tbl, 4 ex

FIELD: chemistry.

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EFFECT: method makes it possible to increase mechanic strength and the specific surface of the catalyst, increase the volume speed of gas to be purified with the higher activity of the catalyst and increase its service term.

4 cl, 5 ex

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