Catalyst for dehydrogenation of c3-c5 paraffin hydrocarbons, method of producing said catalyst and method for dehydrogenation of c3-c5 paraffin hydrocarbons

FIELD: chemistry.

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

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

14 cl, 2 tbl, 12 ex

 

The invention relates to catalysts for dehydrogenation of paraffin hydrocarbons, methods for their preparation, and to methods of producing olefinic hydrocarbons by catalytic dehydrogenation of the corresponding paraffin C3-C5hydrocarbons and may find application in the chemical and petrochemical industries.

Physico-chemical characteristics of the reactions of dehydrogenation materially affect technological design process and selection of catalytic systems. Among the main determinants of technological and structural design processes dehydrogenation include:

1. The need to supply a large amount of heat in the reaction zone due to the endothermic nature of the reactions.

2. The need to create a high temperature to achieve cost-effective depths dehydrogenation.

3. Small contact time to obtain a high selectivity.

4. The need of burning coke deposits or create catalysts that are resistant to coke.

5. The need for rapid cooling of the reaction products to prevent the passage of the polymerization reaction.

Among the possible technological options dehydrogenation process, to the greatest extent allowing to solve the above problems is a method of dehydrogenation in boiling the white microspherical catalyst with catalyst circulation along the contour of the reactor the regenerator. However, this variant of the process imposes specific requirements for catalyst: he must not only possess high activity, selectivity, thermal stability, but also to have a high resistance to abrasion and at the same time, to have a low abrasive characteristics that do not result in abrasion of the equipment.

The prior art describes a wide variety of solutions aimed at creating catalytic compositions having the above properties.

Known catalyst containing the oxides of potassium, chromium, silicon aluminum oxide. The catalyst was prepared by impregnation of alumina previously calcined at 1000-1150°C, solutions of compounds chromium and potassium, followed by drying, and then re-impregnated with a solution of silicon compounds, followed by drying and calcination (SU 1366200, B0J 37/02, 23/26, 1988).

The disadvantage of the catalyst and the method is the low mechanical strength and selectivity.

Known lomography catalyst for dehydrogenation of paraffin hydrocarbons and a method thereof, which includes the calcination of aluminum hydroxide in suspension layer by the interaction of temperature 450-800°C for 0.05 to 2.0 with a further reduction in temperature to 280-400°C, peptization aluminum hydroxide nitric acid with the simultaneous introduction of chrome - and calister is asih compounds, forming by spray drying and calcination. The annealing under these conditions expose 50-80 wt.% aluminum hydroxide, the remaining 20-50 wt.% aluminum hydroxide calcined at 950-1200°C for 2-10 h Forming catalyst is carried out at the stage spray drying (EN 1736034, B01J 37/02, 23/26, 21/04, 1995).

The catalyst is not sufficiently high activity and stability, low mechanical strength. The method of its production is complex and multi-stage.

Known catalyst on the basis of Al, Cr, K and Si process for the dehydrogenation of C3-C5-paraffin hydrocarbons. The method of preparation of the catalyst involves firing at 500-700°C aluminium oxide particles in the form of microspheres, calcination at temperatures above 1000°C for several hours, impregnation of the product of firing a solution containing compounds of chromium and potassium compounds, drying the obtained product and the impregnation product drying a solution containing a silicon compound, followed by final drying and calcining at temperatures below 700°C (JP 7010350, B01J 23/26, 1995).

The disadvantage of the obtained catalyst is insufficient strength and stability, as well as the complexity and multi-stage process of receipt.

Known catalyst to obtain olefinic hydrocarbons by dehydrogenation of the following composition, wt.%: Cr2O3-10,0-30,0; ZnO - 30,0-45,0; Al2O3- the rest. As the carrier used microspherical beads on the basis of aluminium spinel. Maximum performance in the way dehydrogenation determined by the product of the conversion on selectivity, 52.4% of the original when isobutane flow rate of isobutane 400 h-1and a temperature of 590°C. However, this catalyst has an insufficient mechanical strength (EN 2178398, C07C 5/333, 1999).

Known catalyst for dehydrogenation of paraffin hydrocarbons, which contains the oxides of chromium 12-23%, the compound of alkaline and/or alkaline earth metal in the amount of 0.5-3.5% and the connection of non-metal: boron and/or silicon in an amount of 0.1-10%. The catalyst also contains at least one compound of the modifier metal (Ti, Zr, Sn, Fe, Ga, Co, Mn, Mo) in an amount of 0.5 to 1.5%. The catalyst formed by heat treatment of aluminum compounds of the formula Al2O3·nH2O, where n=0,3-1,5, x-ray amorphous structure together with other compounds. The catalyst has high activity and selectivity (EN 2148430, B01J 23/26, 2000). However, the chemical composition is complex, which creates certain difficulties when playing its properties during preparation.

A known catalyst which contains chromium oxide in quantity 12-23 wt.%, connection shelochnogo/or alkaline earth metal in an amount of 0.5-3.5 wt.%, the Zirconia in an amount of 0.1-5 wt.% and at least one oxide promoter from the group of niobium, tantalum, hafnium in an amount of 0.001-2 wt.% aluminum oxide. For the preparation of the catalyst is used as a compound of aluminum layered x-ray amorphous structure of the formula Al2O3·nH2O, where n=0.3 to 1.5, preferably with the surface of 50-250 m2/, This compound can be obtained by any known means, for example by rapid dehydration of hydrargillite. The catalyst is formed during the heat treatment of aluminum compounds in conjunction with the compounds of the above elements (RU 2200143, C07C 5/333, B01J 23/26, 37/02, 10.03.2003).

The disadvantage of this catalyst is that it has no practical application because of the scarcity and high cost of the used compounds of hafnium, niobium, tantalum. In addition, this catalyst does not solve the stability problem.

A known catalyst for the dehydrogenation of paraffin hydrocarbons containing a chromium oxide compound of alkali metal, zirconium dioxide, the promoter on the carrier - aluminum oxide precursor which is a compound of aluminium of the formula Al2O3·nH2O, where n=0,3-1,5, x-ray amorphous structure. The precursor medium is the product of thermo-chemical activation (THA), which is produced by activation of hydrargillite in the current Dymov the x gases. The catalyst contains as a promoter, at least one compound of a metal selected from the group of zinc, copper, iron in an amount of 0.03-2.0 wt.%. The catalyst preferably formed during the heat treatment of the carrier - aluminum compounds of the formula Al2O3·nH2O, where n=0,3-1,5, x-ray amorphous structure, together with compounds of chromium, zirconium, alkali metal promoter from the group of zinc, copper, iron.

For receiving the catalyst carrier, the connection of the aluminum impregnated with the catalytic components in the required quantities, dried and calcined at 700°C. During annealing, the formation of active centers of the catalyst in the form of solid solutions of chromium and chromite zinc or copper or iron is strongly related to the structure of aluminum oxide (RU 2271860, B01J 23/26, 20.03.06).

The catalyst has a high initial activity and selectivity, however, such an effect due to the supplementation of iron and copper inevitably leads to an increase in the degree of zakonomernosti catalyst. In addition, it is known that iron oxide isostructural with α-Al2O3and for this reason the presence of large amounts of iron impurities in almograve catalyst reduces its service life due to gradual education in the process of operation inactive solid solution of the active to the component α-Cr 2O3in α-Al2O3.

The closest technical solution as a catalyst and to a method for obtaining a catalyst and the method thereof disclosed in the patent RU 2350594 C07C 5/333, B01J 23/26, B01J 21/04, B01J 37/02 13.08.2007. Catalyst for dehydrogenation of paraffin hydrocarbons, contains chromium oxide in the amount of 10-20 wt.%, the potassium oxide in an amount of 0.1-5 wt.% and promoters: the oxide of copper and/or zinc oxide and/or zirconium oxide and/or manganese oxide, in amounts of from 0.1 to 5 wt.%. The method of preparation of the catalyst involves the operation of hydrothermal processing the source media. After that, the carrier having beitou morphology, impregnated with solutions of precursors of the catalytic components. The impregnated carrier is dried and calcined at 600-900°C. the Catalyst has low activity and especially selectivity. In addition, the operation of hydrothermal processing the source media significantly complicates the technology of preparation of the catalyst.

The analysis of the prior art shows that there is a problem creating a budget microspherical catalyst for dehydrogenation of paraffin C3-C5hydrocarbon olefins in a fluidized bed with high catalytic activity, selectivity and stability with low koksoobrazovaniya having low and rusunami characteristics.

The task is solved by a catalyst for the dehydrogenation of C3-C5-paraffin hydrocarbons into olefins, which contains chromium oxide deposited on the solid solution composition of ZnxAl2O(3+x)(where x=0,025-0,25) with the structure of the defective spinel.

In addition, for the synthesis of solid solutions of ZnxAl2O(3+x)as a precursor of the solid solution using aluminum compounds of the General formula: Al2O3-x(OH)x·nH2O, where x=0-0,28, n=0,03-1,8 consisting of nanostructured primary particles of 2-5 nm in size and characterized by disordered defective layered structure similar to the structure bayerite.

The catalyst contains an oxide of chromium (III) - 6-20 wt.%; the potassium oxide is 0.1 to 5 wt.%; the Zirconia - 0-3 wt.%; zinc oxide is 0.1 to 14 wt.%; alumina - rest.

The catalyst is an microspheres, with the following distribution of particle size, wt.%: less than 50 μm is less than 30; 50-80 μm - 20-30; 80-100 μm - 15-25; 100-120 μm - 15-20; 120-140 µm - 10-15; more than 140 microns less than 5.

Catalyst for dehydrogenation of paraffin hydrocarbons, C3-C5contains from 0.2 to 20 wt.% zincaluminum spinel solid solution.

The task is also solved by a method of preparation of the catalyst.

The method of producing catalyst includes a stage on which the precursor of the solid solution hydratious about icyhot mixture of solutions of chromic acid, of potassium chromate and zinc salts followed by drying and calcination in air, and hydrating carried out in the process of soaking.

In addition, as a precursor of the solid solution using aluminum compounds of the General formula: Al2O3-x(OH)x·nH2O, where x=0-0,28, n=0,03-1,8 consisting of nanostrukturirovannyh primary particles of 2-5 nm in size and characterized by disordered, defective layered structure similar to the structure bayerite obtained by centrifugal thermal activation (CTA).

As the zinc salts used nitrate, acetate, formate, sulfate, chloride of zinc.

Drying of the catalyst is carried out with the use of the heat released during hydration of the precursor of the solid solution at a temperature of 40-120°C.

In addition, the invention is intended for implementing the method of dehydrogenation of paraffin hydrocarbons, C3-C5in which used catalyst disclosed above.

The method is carried out in a fluidized bed of catalyst in catalyst circulation along the contour of the dehydrogenation reactor - reactor regeneration.

The temperature of the dehydrogenation is 520-610°C, the temperature of regeneration is 550-650°C, the volumetric feed rate of 400-800 h-1time dehydrogenation 10-30 min, the regeneration time of 5-30 min, purge time the inert gas between the stage and the dehydrogenation - regeneration - dehydration - 3-15 minutes

Product CTA performed by using a rapid centrifugal termoparnaya activation of aluminum hydroxide structure hydrargillite (gibbsite) or bayerite at elevated temperature in the insulated chamber under the action of centrifugal forces and subsequent forced cooling (EN 2237019, C01F 7/02, 27.09.2004). According to scanning electron microscopy oxygen-containing compound of aluminum General formula: Al2O3-x(OH)x·nH2O, where x=0-0,28, n=0,03-1,8 obtained by the method of centrifugal termoparnaya activation, has a particle shape close to spherical. Centrifugal thermal activation hydrargillite (gibbsite) or bayerite carried out in the installation, which is a chamber inside which rotates a solid carrier is shaped in a special way the plate. The rotation speed can be changed and determines the contact time. Under the plate there are heating elements. The temperature of the coolant regulate three thermocouples. Technical hydrate of alumina (hydro-argillite) or bayerite of the bin is served on a heated plate, abruptly heated under the action of centrifugal force moves along the surface of the fluid to the walls of the chamber, provided with a cooling jacket. When you blow the heated particles of the product Akti the purpose of cold-wall chamber in rapid cooling (quenching). The camera is equipped with holes for steam to escape and receiving bin for powder. The study of x-ray amorphous phase by the method of radial distribution of electron density with the construction of the model curves for various oxide and hydroxide phases were allowed to establish that the product CTA differs from THA product. It is especially noticeable distinction in the field of interatomic distances 4-6 A. This difference is due to the presence of a product CTA atomic bonds, characteristic for disordered/defective layered structure similar to the structure bayerite. According to NMR Al27the intensity of the lines belonging to the aluminium cations in 4, 5 and 6 coordinated state, in relation to oxygen in the product CTA differs from the similar distribution in THA product (..Isupova, Yu.Yu.Tanashev, I.V.Kharina, E.M.Moroz et al. // Chemical engineering Journal, 2005, v.107, issue 1-3, pp.163-169).

Product CTA has a high chemical activity, which speeds up subsequent hydration in pseudoboehmite at the stage of synthesis of the catalyst in the presence of water in an acidic environment.

These properties of the product contribute to obtaining a catalyst for the dehydrogenation of lower C3-C5paraffins having high catalytic activity, selectivity, stability and mechanical strength at low abrasive properties.

It was found that the in troduction is giving supplements of zinc oxide in the catalyst based on the product CTA allows you to increase the activity and selectivity of the process while reducing the yield of coke. This is explained by the formation zincaluminum defective spinel structure in the interaction product CTA (high activity) with salts of zinc.

Zinc oxide, part of the solid solution has a lower abrasion than, for example, zirconium oxide, which reduces the wear of the equipment.

In the concentration range of zinc oxide is from 0.1 to 14 wt.% is formed of non-stoichiometric spinel, which automatically becomes defective and therefore more reactive.

The catalyst is prepared by impregnation of aluminum compounds of the General formula: Al2O3-x(OH)x·nH2O, where x=0-0,28, n=0,03-1,8 consisting of nanostructured primary particles of 2-5 nm in size and characterized by disordered, defective layered structure similar to the structure bayerite obtained by centrifugal thermal activation (CTA).

When preparing an impregnating solution volume of water take approximately 30-40% more than required by capacity, taking into account the fact that an excessive amount of water consumed in the hydration product CTA in pseudoboehmite - AlOOH. The impregnation is carried out in a period of 1-4 hours at a solution temperature of 20-100°C (preferably 40-100°C) with constant stirring in a closed volume at constant partial pressure of water vapor. Additional heat for the odd exothermic reaction of hydration of the product - CTA in pseudoboehmite, is used for the subsequent drying of the catalyst. Drying of the catalyst is carried out for one hour with continuous stirring with the open propitiates.

Heat can more efficiently carry out the stage of drying, since the drying of granular materials only with heated walls of the drying device to difficult, it is necessary to significantly increase drying time or put an additional dryer.

Due to the high chemical activity of the precursor of the solid solution-product CTA at the stage of impregnation of the interaction of a solution containing salts of zinc, and the precursor of the solid solution with the formation of hydrocalumite zinc (Yai). Education Yai contributes to the formation of solid solution of ZnxAl2O(3+x)when annealed in air catalyst at temperatures of 650-800°C, preferably 750°C.

As starting substances for the preparation of the impregnating solution used chromic anhydride or solutions of chromic acid, hydroxides or carbonates of potassium chromates and/or bichromate potassium, nitrates, chlorides, acetates or sulfates of zirconium. As the zinc salts used nitrate, acetate, formate, sulfate, chloride of zinc.

Research methods

Phase composition of the solid solution and the catalyst was determined by the method of Ren is generatora analysis (XRF) and derivatographic (DTA). XRD was carried out on the apparatus HZG-4c in the field angles from 10 to 80 degrees in 2θ with a computer recording the results. DTA was carried out on the machine NETZSCH STA 449C with a heating rate of 10 deg/min

The composition of the solid solution of ZnxAl2O(3+x)expected change parameter cubic alumina phase in the catalyst with respect to the parameter γ-Al2O3phase. Calculation of the lattice parameter was performed on a line (422) in the field 66,6 is 67.2 degrees to 29. The dependence of the lattice parameter of the solid solution, calcined at 750°C on the content of zinc oxide, are given in table 1.

Table 1.
The change of lattice parameters of the solid solutions of ZnxAl2O(3+x)from the content of the zinc oxide
PhaseThe content of ZnO wt.%The lattice parameter, a, nm
γ-Al2O300.7916
ZnxAl2O(3+x)20.7932
-"-30.7939
-"- 40.7941
-"-60.7950
-"-80.7957
ZnAl2O444.30.8085

The table shows that the lattice parameter increases with increase in the content of zinc oxide. View the data in graphical coordinates shows that the change in lattice parameter of the solid solution is well described by Vegard rule. This change parameter indicates the formation of a solid solution based on the structure of spinel with a deficit of cations of zinc, vacancies in positions in the crystal lattice are related to the cations of zinc create a defective structure. Components caused by defective media have a high catalytic activity (Molchanov V.V., Buyanov R.A., Gaudin VV // Kinetics and catalysis, 1998, CH, No. 3, s-471).

Specific surface area and porous structure of the original products CTA and catalysts was determined on the machine company Quantachrome Corporation on adsorption and desorption of nitrogen. To calculate the magnitude of the specific surface area BET, pore size and distribution of pore sizes was performed with the program "Gas Sorpsion Reprt Autosob for Windows for AS-3 and AS-6" Version 1.23.

Fractional composition of the catalyst was determined by laser scattering instrument Shimadzu SALD 2101.

Chemical analysis of the catalyst was performed by atomic absorption apparatus Saturn.

The catalytic activity of the resulting catalysts in the process of dehydrogenation of C3-C5-paraffin hydrocarbons to olefinic hydrocarbons was evaluated by the activity of the dehydrogenation reaction of isobutane in the fluidized layer of the above-described catalyst. Temperature dehydrogenation of 560-580°C, the temperature of the regeneration - 560-650°C, the volumetric feed rate of 400 h-1time dehydrogenation 10 min, the regeneration time of 5-30 min, purge time the inert gas between stages of dehydrogenation - regeneration-dehydration - 3-15 minutes

The invention is illustrated by the following examples.

Example 1.

As a precursor of the solid solution used product CTA with the following characteristics: specific surface area of 230 m2/g, a particle size of 2-5 nm, loss on ignition at 800°C 15.9 wt.%, vaccum 0.3 cm3/year

To prepare 100 kg of catalyst composition: Cr2O3- 12 wt.%, K2O - 1.5 wt.%, ZrO2to 1.0 wt.%) and ZnO - 3.0 wt.%; 98.1 kg of the precursor was placed in a mixer with a Z-shaped blades and was added impregnating solution. For preparation of the impregnating solution into the container PR is stirring covered CrO 3=15.8 kg, KOH=1.8 kg, and was added to 19.9 liters of distilled water. In a separate container were dissolving 3 kg ZnO and 2.9 kg Zr(CO3)2in 9,54 l HNO3(concentration 629 g/l). Next, the contents of the second container was poured into the first container, and the resulting impregnation solution was poured into the mixer.

Impregnation was performed under continuous stirring at the closed lid of the mixer to raise the temperature of the impregnating solution to 90-120°C by passing an endothermic reaction, the hydration product of the CTA. Then he opened the lid of the mixer and were dried at a temperature of 120-40°C due to the heat released during hydration. Drying led to the formation of the granular mass. The dried catalyst the catalyst was progulivali at a temperature of 650-800°C for 1 hour.

Example 2-11. Preparation of precursor and catalyst was carried out similarly to example 1. The difference lies in the fact that the obtained catalyst samples differ in the content of chromium oxide and promoting additives of oxides of zinc, zirconium and potassium oxide.

Data on chemical composition and catalytic properties of the samples are shown in table 2.

The catalysts used for the dehydrogenation of C3-C5-paraffin hydrocarbons to olefinic hydrocarbons in a fluidized bed. The temperature of the dehydrogenation 560 and 580°C, the temperature of the regeneration catalysis the Torah 560 and 650°C, the volumetric feed rate of 400 h-1time dehydrogenation 10 min, the regeneration time of 5-30 minutes, the Catalyst is circulated in a circle dehydrogenation - regeneration - dehydrogenation. While purging with an inert gas between stages of dehydrogenation - regeneration - dehydrogenation was 3-15 minutes

46.8
Table 2.
The influence of the content of additives of zinc oxide and zirconium oxide on the catalytic characteristics of microspherical CrO3-K2O/Al2O3catalytic Converter.
ExampleContent, wt.%The reaction temperature, °C
560580
Cr2O3ZnOZrO2K2OEAPBPCEAPBPC
No. 112.03.01.0 1,550.995.11.256.991.52.2
No. 212.0000,147.390.81.255.088.72.1
No. 312.02.001,551.393.61.257.889.92.2
No. 412.03.001,550.893.81.257.990.02.2
No. 58.001.01,593.21.051.1at 88.12.0
No. 68.03.001,550.294.20.856.689.91.6
No. 712.04.001,551.593.91.157.390.11.8
No. 812.06.001,551.794.51.157.491.11.8
No. 912.08.001,551.4 94.41.157.590.91.6
No. 106.014.001,549.894.10.655.189.01.4
No. 1120,00,13,0546,190,01,050,8and 88.81,3
No. 12 (prototype)204.90448.388.0
EAP - out of isobutylene on missed isobutane (activity);
BP - out of isobutylene to spread out isobutane (select the activity);
C - formation of coke.

As can be seen from the table 2 examples, supplementation of zinc oxide and the formation of solid solutions of ZnxAl2O(3+x)increases the yield of isobutylene and selectivity of the dehydrogenation reaction. Especially most clearly the promoting effect of supplementation of zinc oxide is observed at low concentrations of chromium oxide. The positive effect of promotion by zinc oxide is observed in a wide range of concentrations of zinc oxide in the catalyst and the solid solution. However, if the same content of chromium oxide yield of isobutylene and selectivity practically do not change with increasing ZnO content from 2.0 to 8.0 wt.%, the output of coke with increasing content of zinc oxide is gradually reduced.

1. Catalyst for dehydrogenation of paraffin hydrocarbons With3-C5, characterized in that it contains in its composition of the oxides of chromium and potassium, and optionally zirconium dioxide, deposited on the solid solution composition of ZnxAl2O(3+x)where x=0,025-0,25, with the structure of the defective spinel.

2. The catalyst according to claim 1, characterized in that to obtain the precursor of the solid solution used in the connection of aluminum General formula:
Al2O3(OH)x·nH2O, where x=0-0,28, n=0,03-1,8, with the standing of nanostructured primary particles of 2-5 nm in size and characterized by disordered defective layered structure, close to the structure bayerite obtained by centrifugal thermal activation.

3. The catalyst according to claim 1, characterized in that it contains in its composition in terms of oxides:
oxide chromium (III) 6-20 wt.%
the potassium oxide is 0.1-5 wt.%
the Zirconia 0-3 wt.%
zinc oxide of 0.1 to 14 wt.%
alumina rest

4. The catalyst according to claim 1, characterized in that the content zincaluminum spinel solid solution is from 0.2 to 20 wt.%.

5. The catalyst according to claim 1, characterized in that it represents the microspheres, with the following distribution of particle size, wt.%:

less than 50 micronsless than 30
50-80 microns20-30
80-100 microns15-25
100-120 microns15-20
120-140 microns10-15
more than 140 micronsless than 5

6. The method of preparation of the catalyst according to any one of claims 1 to 5, characterized in that the precursor of the solid solution hydratious, impregnated with a mixture of solutions of chromic acid, potassium chromate and zinc salts followed by drying and calcination in air, and g is tretirovanie carried out in the process of soaking.

7. The method of preparation of the catalyst according to claim 6, characterized in that the mixture of the solutions used for impregnation of the precursor of the solid solution further comprises a nitrate Zirconia.

8. The method of preparation of the catalyst according to claim 6 or 7, characterized in that as the zinc salts used nitrate, acetate, formate, sulfate, chloride of zinc.

9. The method of preparation of the catalyst according to claim 6, characterized in that as the precursor of the solid solution is used as a compound of aluminum General formula: Al2O3(OH)x·nH2O, where x=0-0,28, n=0,03-1,8 consisting of nanostructured primary particles of 2-5 nm in size and characterized by disordered defective layered structure similar to the structure bayerite obtained by centrifugal thermal activation.

10. The method of preparation of the catalyst according to claim 6, characterized in that the drying is carried out with the use of the heat released during hydration of the precursor of the solid solution at a temperature of 40-120°C.

11. The method of preparation of the catalyst according to claim 6 characterized in that the calcination carried out in air at a temperature of 650-800°C.

12. The method of dehydrogenation of paraffin hydrocarbons With3-C5, characterized in that in its implementation using the catalyst according to any one of claims 1 to 5.

13. The method according to item 12, characterized in that h is about his conduct in the fluidized bed of catalyst in catalyst circulation along the contour of the dehydrogenation reactor - the reactor regeneration.

14. The method according to item 12, characterized in that the temperature of the dehydrogenation is 520-610°C, the temperature of the regeneration of the catalyst is 550-650°C, the volumetric feed rate of 400-800 h-1time dehydrogenation 10-30 min, the regeneration time of 5-30 min, purge time the inert gas between stages of dehydrogenation - regeneration - dehydration - 3-15 minutes



 

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54 cl

FIELD: chemistry.

SUBSTANCE: invention relates to a method for continuous, heterogeneously catalysed partial dehydrogenation of at least one dehydrogenated (C2-C4)-hydrocarbon in gas phase, comprising a procedure where at least one initial gas stream is continuously fed into a reaction space surrounded by jacket which touches the reaction space and has at least one opening for inlet of at least one initial gas stream in the reaction space and at least a second opening for outlet of at least one stream of the formed gas from the reaction space, said initial gas stream containing at least one dehydrogenated hydrocarbon; in the reaction space at least one dehydrogenated hydrocarbon passes through at least one layer of catalyst lying in the reaction space to obtain a gaseous product which contains at least one dehydrogenated hydrocarbon which does not react with the dehydrogenated hydrocarbon; and using an oxidative or a non-oxidative method, molecular hydrogen and/or water vapour are partially dehydrogenated to form at least one dehydrogenated hydrocarbon; at least one stream of the formed gas is continuously removed from the reaction space; the method is characterised by that the surface of the jacket on the side in touch with the reaction space is made from steel S, partially in a layer of thickness d equal to at least 1 mm, said steel having the following composition: from 18 to 30 wt % Cr (chromium), from 9 to 36 wt % Ni (nickel), from 1 to 3 wt % Si (silicon), from 0.1 to 0.3 wt % N (nitrogen), from ≥ 0 to 0.15 wt % C (carbon), from ≥ 0 to 4 wt % Mn (manganese), from ≥ 0 to 4 wt % Al (aluminium), from ≥ 0 to 0.05 wt % P (phosphorus), from ≥ 0 to 0.05 S (sulphur) and from ≥ 0 to 0.1 wt % one or more rare-earth metals, and in the rest Fe and impurities due to the synthesis process, where the percentages are associated with total weight, respectively. The invention also relates to a jacket in which the disclosed method is realised.

EFFECT: use of the present invention enables to reduce catalysed thermal decomposition of dehydrogenated hydrocarbon and/or a hydrocarbon capable of being dehydrogenated.

30 cl, 1 ex

FIELD: process engineering.

SUBSTANCE: invention relates to chemical and petrochemical industries and may be used for heterogeneous-catalytic reactions, in particular, dehydration of paraffin hydrocarbons. Proposed catalyst comprises aluminium oxide the precursor of which is the product of thermochemical activation of hydrargillite, chromium oxide, alkaline metal oxide, and is formed in thermochemical activation of hydrargillite together with compounds of chromium and alkaline metal. Note here that catalyst comprises oxides of iron, calcium and magnesium in weight ratio Fe:Ca:Mg (in terms of oxides) equal to 0.3:1.0:0.1, formed in thermochemical activation from compounds of iron, calcium and magnesium in the following ratio of components in wt % (in terms of oxides): chromium oxide (in terms of Cr2O3) - 10.0-16.0, alkaline metal oxide - 1.2-2.0, sum of oxides of iron, calcium and magnesium - 0.05-1.5, aluminium oxide making the rest. Invention covers also method of using described catalyst for dehydration of paraffin hydrocarbons wherein mix of said catalyst with fluoaluminic catalyst "ИМ"-2201 of the following composition (in wt %) is used: chromium oxide - 13.0-14.3; alkaline metal oxide - 2.8-3.3; silicon oxide - 9.5-10.5; sum of oxides of iron, calcium and magnesium - 1.2, aluminium oxide making the rest in ratio of 1:9 to 1:1, respectively.

EFFECT: higher strength and selectivity, high yield of olefins.

2 cl, 3 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for synthesis of branched olefins, said method involving dehydrogenation of an isoparaffin composition containing 0.5% or less quaternary aliphatic carbon atoms on a suitable catalyst. Said isoparaffin composition is obtained via hydroisomerisation a paraffin composition and contains paraffin containing 7-18 carbon atoms. Said paraffins, at least some of their molecules, are branched, where content of branched paraffins in the isoparaffin composition is equal to at least 50% of the weight of the isoparaffin composition. The average number of branches per paraffin molecule is between 0.5 and 2.5 and the branches include methyl and optional ethyl branches. Said branched olefins contain 0.5% or less quaternary aliphatic carbon atoms. Said paraffin composition is obtained using Fischer-Tropsch method. The invention also relates to methods of producing a branched alkyl aromatic hydrocarbon and branched alkylaryl sulphonates including the method described above.

EFFECT: high versatility and cost effectiveness of the method.

7 cl, 19 ex

FIELD: process engineering.

SUBSTANCE: invention relates to perfected system of layer of catalyst for dehydration in olefins production using traditional processing technologies. Catalyst layer system comprises dehydration catalyst including the following separate components bonded together a) active component selected from metal oxide of group VI and substrate selected from aluminium oxide, alumina, aluminium oxide monohydrate, aluminium oxide trihydrate, aluminium oxide-silicon oxide, aluminium apha-oxide; b) first inert material with high density and heat capacity, not capable of heat release in cyclic nonoxidising dehydration, and c) secondary component containing heat generating material and carrier suitable for application of heat release inert material thereon. Note here that said secondary material is catalytically inert to dehydration and side reactions and generates heat when subjected to reduction or regeneration. Method of adiabatic nonoxidising dehydration comprising: preparation of above described system, conduction of cyclic process, forcing raw material flow of aliphatic hydrocarbon into catalyst layer system for dehydration, dehydration of said flow, blowing through by steam and regeneration of catalyst layer.

EFFECT: reduced temperature difference over layer.

7 cl, 8 ex, 3 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to organic synthesis and specifically to synthesis of olefin and diene hydrocarbons through dehydrogenation of paraffin hydrocarbons. The invention describes a method for synthesis of C3-C5 olefins through dehydrogenation of paraffin hydrocarbons in the presence of a catalyst which contains chromium oxide, an alkali metal oxide, oxides of transition metals and a support. The raw material of the process is a mixture of C1-C5 paraffin hydrocarbons, where the said mixture may contain two to seven components.

EFFECT: higher overall conversion of C3-C5 paraffins to olefins, higher overall olefin selectivity of the process.

5 cl, 5 ex, 5 tbl

FIELD: chemistry.

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

EFFECT: high output of hydrogen.

2 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention describes catalyst components containing Ti, Mg, Cl and an optional OR1 group, in which R1 denotes a C1-C20 hydrocarbon group in such an amount that molar ratio OR1/Ti is less than 0.5, characterised by the following properties: BET specific surface area less than 80 m2/g; total porosity (Pt) measured using a mercury method in the range of 0.70-1.50 cm3/g; the difference (Pt-Pf) is greater than 0.1, where PT denotes total porosity and PF denotes porosity due to pores with radius less than or equal to 1 mcm; the amount of Ti in the catalyst component is less than 10 wt %, based on total weight of the catalyst component. Described is a method of producing said components, involving a first step (a) where a compound MgCl2.m(RIIIOH)tH2O, in which 0.3≤m≤1.7, t ranges from 0.01 to 0.6 and RIII denotes an alkyl, cycloalkyl or aryl radical, having 1-12 carbon atoms, reacts with a titanium compound of formula Ti(ORII)nXy-n, in which n lies between 0 and 0.5, y is titanium valence, X denotes a halogen and RIV denotes an alkyl radical having 1-8 carbon atoms; and a second step (b) in which a solid product obtained from step (a) undergoes thermal treatment at temperature higher than 100°C. Described also is a method for (co)polymerisation of ethylene in the presence of a catalyst system containing a product of reaction of solid catalyst components described above and an aluminium alkyl compound.

EFFECT: catalyst components exhibit high morphological stability under conditions for low-molecular polymerisation of ethylene, while maintaining high activity.

10 cl, 4 tbl, 16 ex

FIELD: process engineering.

SUBSTANCE: invention relates to catalyst of heavy hydrocarbon desulfurisation, method of its production and method of desulfurisation of heavy hydrocarbons. Proposed catalyst includes calcined mix produced by calcinating formed particle made by grinding the mix containing molybdenum trioxide, nickel compound and inorganic oxide material. Proposed method of producing said catalyst comprises grinding inorganic oxide material, molybdenum trioxide and nickel compound to produce mix to be formed in particle and calcined to obtain aforesaid mix. Method of desulfurisation of heavy hydrocarbon initial stock comprises interaction of the latter with aforesaid catalyst.

EFFECT: purified product with higher stability.

11 cl, 10 tbl, 6 ex, 2 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to activation of metal oxide catalysts. Proposed method uses oxides of VIII-group metals as catalysts and consists in that salts of VIII-group metals and magnesium nitrate are used as initial material and decomposed by thermal decomposition of precursor water solution. Prior to calcination, the latter is subjected to effects of super high frequency fields with circular polarisation at 2.45 GHz fir 5-40 s. Thereafter, said solution is calcinated at 600-650°C for 30 min.

EFFECT: higher yield of nanotubes.

4 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to a composition of a catalytic cracking composition, a method of obtaining said composition and a method for catalytic cracking hydrocarbon starting material and use thereof. Described is a composition of a catalytic cracking catalyst containing at least one zeolite having activity on catalytic cracking in catalytic cracking conditions, and aluminium oxide obtained from aluminium sulphate in an amount which is sufficient for binding particles and forming a dispersion catalyst composition, characterised by Davison index less than 30, where said catalyst composition is obtained using a method involving: a) formation of a homogeneous or essentially homogeneous aqueous suspension containing particles of at least one zeolite, having activity on catalytic cracking in catalytic cracking conditions, at least one matrix material selected from a group consisting of aluminium oxide, silicon dioxide, silicon dioxide-aluminium oxide, transition metal oxides selected from groups 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 in accordance with new denominations in the periodic table, rare-earth metal oxides, alkali-earth metal oxides and mixtures thereof, and aluminium sulphate in an amount which is sufficient to obtain at least 5 wt % aluminium oxide in the end catalyst composition; b) grinding the suspension; c) spray drying the suspension to form particles; d) calcining the spray dried particles at temperature ranging from approximately 150°C to approximately 600°C for a period of time ranging from approximately 2 hours to approximately 10 minutes; e) re-suspension of the calcined particles in aqueous solution of a base at pH ranging from approximately 7 to approximately 13 for a period of time ranging from 1 minute to approximately 3 hours and at temperature ranging from approximately 1°C to approximately 100°C; and f) extracting and drying the obtained particles in order to obtain the end catalyst composition containing at least 5 wt % aluminium oxide obtained from aluminium sulphate. The invention describes a method of obtaining the composition and use thereof in a method for catalytic cracking hydrocarbon starting material.

EFFECT: improved operational characteristics of the composition, reduced formation of coke product and achieving high degree of conversion when cracking still residue.

21 cl, 6 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a composition for use as a catalyst for hydrodesulphurisation of distillate, a method of preparing said composition and a method of obtaining distillate. Described is a method of preparing a composition for use as a catalyst for hydrodesulphurisation of distillate, involving: combined grinding of inorganic substance, molybdenum trioxide particles having size ranging from 0.2 to 150 mcm and a nickel compound to form a mixture; moulding said mixture into particles; and calcining said particles to form a calcined mixture, where said calcination is carried out while controlling temperature conditions such that calcination temperature ranges from approximately 600°C (1112°F) to approximately 760°C (1400°F) for a calcination period of time which is sufficient for obtaining said calcined mixture, having such pore size distribution that at least 70% of total pore volume of said calcined mixture is due to pores of said calcined mixture, having diameter ranging from 70 Å to 150 Å, and where said calcined mixture has molybdenum content ranging from 7 wt % to 22 wt %, where the weight percentages are based on molybdenum in metal form and total weight of the calcined mixture, and content of group VIII metal ranging from 3 wt % to 12 wt %, where the weight percentages are based on group VIII metal in its elementary form and total weight of the calcined mixture. Described is a catalytic composition containing a calcined mixture obtained by calcining a mixture containing an inorganic oxide, molybdenum trioxide particles having the size given above, a group VIII meta with content given above. Described is a method of obtaining distillate with ultralow content of sulphur, involving contact of starting material at suitable desulphation conditions with the composition described above.

EFFECT: obtaining distillate with ultralow content of sulphur, having sulphur concentration less than 50 wt ppm.

14 cl, 4 tbl, 11 ex, 1 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to producing applied metal oxides. Conversion of transition metal applied on carrier into appropriate transition metal oxide applied onto carrier comprises heating transition metal nitrate to decompose it in atmosphere of gas mix containing nitrous oxide and inert gas wherein oxygen content in said mix varies from 0.001 to 15 vol. %. Invention covers also method of reducing metal oxide applied onto carrier produced as described above that comprises heating metal oxide applied onto carrier in the flow of reducing gas to reduce at least a portion of metal oxide.

EFFECT: produced or reduced applied metal oxides with higher catalyst activity.

11 cl, 4 tbl, 3 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to materials with composite particles on a substrate. Described is material with composite particles on a substrate, containing: composite particles, which are formed from oxidised nickel and X, where X denotes at least one of elements selected from a group consisting of palladium, platinum, ruthenium, gold, silver and copper; and a substrate on which composite particles are deposited, where the material with composite particles on a substrate has a layer on which composite particles are localised. Described is a method of producing said material, in which composite particles formed from oxidised nickel and X, where X is an element given above, are deposited on a substrate, comprising: a first step where a mixture is obtained at temperature of at least 60°C by mixing an aqueous suspension, having a substrate on which an oxide of at least one basic metal is deposited, said metal selected from a group consisting of alkali metal, alkali-earth metals and rare-earth metals, and acidic aqueous solution of a soluble metal salt containing nickel and X, and a second step for thermal treatment of a precursor contained in said mixture. Described is a method of producing a carboxylic ester, where: an aldehyde and an alcohol react in the presence of oxygen using material containing the described composite particles on a substrate as a catalyst.

EFFECT: obtaining material with composite particles on a substrate, which has catalytic activity in carboxylic ester synthesis reactions.

16 cl, 1 tbl, 4 dwg, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of preparing a catalyst for Fischer-Tropsch synthesis, involving the following steps a)-d): a) pretreatment of aluminium oxide or silicon dioxide in spherical form through saturation in an aqueous solution with pH 7 or lower, which is selected from a group consisting of aqueous nitric acid solution, aqueous acetic acid solution, aqueous sulphuric acid solution, aqueous hydrochloric acid solution, ion-exchange water and distilled water; b) saturating the treated aluminium oxide or silicon dioxide in a zirconium solution whose volume is twice or more higher than the volume of aluminium oxide or silicon dioxide in order to deposit the treated aluminium oxide or silicon dioxide; c) annealing the aluminium oxide or silicon dioxide on which zirconium has been deposited to obtain a carrier in which zirconium in form of an oxide is selectively deposited near the outer surface of the metal carrier; d) depositing onto the carrier one or more types of metals selected from a group consisting of cobalt and ruthenium in amount ranging from 3 to 50 wt % in terms of the catalyst, where 75 wt % or more of the total amount of zirconium oxide is deposited on 1/5 or less portion of a radial area running from the outer surface of the catalyst to its centre. The invention also relates to a catalyst obtained using said method and a method of producing hydrocarbons via Fischer-Tropsch synthesis using said catalyst.

EFFECT: catalyst obtained using said method has improved catalyst performance.

4 cl, 2 tbl, 3 ex

FIELD: process engineering.

SUBSTANCE: this invention relates to reductive isomerisation catalyst, dewaxing of mineral oil, method of producing base oil and lubrication base oil. Invention covers reductive isomerisation catalyst. Reductive isomerisation comprises molecular sieve treated by ionic exchange or its calcinated material produced by ionic exchange of molecular sieve containing cationic fragments and using water as the primary solvent, and at least one metal selected from the group consisting of metals belonging to group VIII-X of periodic system, molybdenum and tungsten applied onto molecular sieve treated by ionic exchange, or onto its calcinated material. Dewaxing comprises converting portion of or all normal paraffins into isoparaffins whereat mineral oil containing normal paraffins is brought in contact with abode described reductive isomerisation catalyst in the presence of hydrogen. Invention covers also method of producing lubricant base oil and/or fuel base oil implemented by bringing base oil containing normal paraffins in contact isomerisation catalyst in the presence of hydrogen. Invention covers also method of producing lubricant base oil containing normal paraffins, including 10 or more carbon atoms by bringing it in contact with above describe reductive isomerisation catalyst in the presence of hydrogen in conversion of normal paraffins making in fact 100%.

EFFECT: catalyst with high isomerisation activity and sufficiently low cracking activity at high yield.

22 cl, 8 tbl, 4 ex, 11 dwg

FIELD: chemistry.

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

EFFECT: high output of hydrogen.

2 cl, 6 ex

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