Catalyst for dehydrogenation of c2-c5-hydrocarbons

FIELD: organic chemistry, chemical technology, catalysts.

SUBSTANCE: invention describes a catalyst for dehydrogenation of (C2-C5)-hydrocarbons that comprises aluminum, chrome oxides, compound of modifying metal, alkaline and/or alkaline-earth metal. Catalyst comprises additionally silicon and/or boron compounds and as a modifying agent the proposed catalyst comprises at least one compound chosen from the following group: zirconium, titanium, iron, gallium, cobalt, molybdenum, manganese, tin. The catalyst is formed in the process of thermal treatment of aluminum compound of the formula Al2O3. n H2O wherein n = 0.3-1.5 and in common with compounds of abovementioned elements and shows the following composition, wt.-% (as measure for oxide): chrome oxide as measured for Cr2O3, 12-23; compound of a modifying metal from the group: Zr, Ti, Ga, Co, Sn, Mo and Mn, 0.1-1.5; silicon and/or boron compound, 0.1-10.0; alkaline and/or alkaline-earth metal compound, 0.5-3.5, and aluminum oxide, the balance. Catalyst shows the specific surface value 50-150 m2/g, the pore volume value 0.15-0.4 cm3/g and particles size 40-200 mcm. Also, invention describes a method for preparing this catalyst. Invention provides preparing the catalyst showing the enhanced strength and catalytic activity.

EFFECT: improved and valuable properties of catalyst.

12 cl, 2 tbl

 

The invention relates to methods for preparing catalysts for dehydrogenation of paraffin hydrocarbons, in particular for the dehydrogenation of C2-C5paraffins to the corresponding olefins.

Olefins are one of the most important products of organic synthesis. They are used in the production of polypropylene, synthetic rubber, high-octane gasoline antiknock additives and a variety of other industries.

One of the ways to obtain olefins is the dehydrogenation of paraffins. It is well known that from a thermodynamic point of view, the dehydrogenation of hydrocarbons, C2-C5not related to the number of effective processes. Since the reaction of dehydrogenation of indetermine, to achieve technically acceptable conversion of raw materials to the required temperature of 500-600°C. However, at these temperatures with a noticeable speed of flow and the adverse reactions of cracking and isomerization. This is because the carbon-carbon (C-C) bond is significantly less strong than the bond carbon-hydrogen (C-H). Therefore, the catalyst in the dehydrogenation process should guide the process energetically unfavorable ways, i.e. allow to carry out the process at low temperatures, and the reaction rate of cracking is possible to do the minimum. It must minimize the inevitable education certainly is about the number of normal hydrocarbons and cyclic structure. That is, the dehydrogenation catalyst should have high selectivity to the desired olefin decreasing isomerization side reactions leading to coking. The formation of coke on the catalyst requires periodic regeneration of the latter at elevated temperatures, therefore, the catalyst must be stable. Special requirements to the mechanical strength of the catalyst, because the destruction of the problems of environmental pollution.

Available literature describes many catalytic compositions based on noble metals or combined with other elements.

The known method (Patent EP N 637578, IPC C 07 C 5/333, 1995) with a catalytic system containing gallium, platinum, possibly one or more alkaline or alkaline-earth metals and the media, which consists of alumina in Delta or theta phase or in a mixed Delta+theta or theta+alpha or Delta+theta+alpha phase, modified silicon oxide.

However, compositions containing precious metals, have increased kekirawa ability at elevated temperatures. This leads to rapid coking of the catalyst and loss of activity and, as a consequence, the decrease of the lifetime.

The disadvantage of the catalyst is relatively small strength.

N is though that catalysts based on precious metals and gallium are a new generation of catalysts for dehydrogenation, most researchers concluded that effective catalysts for the dehydrogenation of C2-C5paraffins are chromium oxides supported on alumina and having high mechanical strength, although chrome compounds are harmful substance. Therefore, when creating new catalysts based on chromium compounds main task is durable fixation of chromium in the media, reducing wastewater when it is received, increased activity and stability.

Known catalyst containing the oxides of potassium, chromium, silicon, aluminum oxide (A.S. USSR N 1366200, IPC B 01 J 37/02, 23/26, 1988). The catalyst was prepared by impregnation of alumina previously calcined at 1000-1150°C, first solutions of chromium compounds and potassium, followed by drying, and then re-impregnated with a solution of silicon compounds, followed by drying and calcination.

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

There is a method of cooking alimohammadi catalyst for dehydrogenation of paraffin hydrocarbons (RF Patent N 1736034, IPC B 01 J 37/02, 23/26, 21/04, 1995), which includes the calcination of aluminum hydroxide in suspension layer with entries batch and temperature 450-800° C for 0.05 to 2.0 with further decrease in temperature to 280-400°C, peptization aluminum hydroxide nitric acid with the simultaneous introduction of chromium and potassium compounds, forming by spray drying and calcination, the calcination under these conditions expose 50-80 wt.% aluminum hydroxide, the remaining 20-50 wt.% aluminum hydroxide calcined at 950-1200°C for 2-10 hours

The catalyst is not sufficiently high activity and stability, low mechanical strength. The method of its production is complex and multi-stage. The molding of the catalyst is carried out at the stage spray drying.

A method of obtaining a catalyst dehydrogenation on the basis of Al, Cr, K and Si process for the dehydrogenation of C3-C5-paraffin hydrocarbons (Japan Patent N 7010350, IPC B 01 J 23/26, 1995), which includes processing annealing at 500-700°C aluminium oxide particles in the form of microspheres, processing, roasting at a temperature of >1000°C for several hours, processing impregnation of the product of firing a solution containing compounds Cr and compounds K, processing, drying the resulting product, process, impregnation product drying a solution containing a silicon compound and followed by the post-processing drying and roasting at < 700°C.

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

The closest technical solution composition and method of preparation of the catalyst of the claimed catalyst is a catalyst for dehydrogenation of hydrocarbons (RF Patent N 1836140, IPC B 01 J 23/26, 21/06; C 07 C 5/333, 1993). The catalyst contains chromium oxide compound of alkali and/or alkaline earth metal and at least one connection of the modifying metal on the carrier is aluminum oxide as a compound modifier metal it contains the Zirconia in the following ratio, wt.%:

Oxide of chromium calculated as Cr2O325
Connection alkaline and/or alkaline earth metal, calculated as oxideof 0.7 to 4.7
The Zirconia0,9
MediaRest

For the preparation of the catalyst using a carrier - aluminum oxide in the form of tablets, impregnate the carrier with a solution containing compounds of chromium and zirconium, the impregnated product is dried in vacuum, and then conducting heat treatment at 740°C, then carry out the impregnation of the catalyst compound of the alkali or alkaline earth metal and the two-stage drying, first in vacuum, the ATEM in an atmosphere of air, the product is then subjected to heat treatment at 740°C.

The catalyst has an increased service life by reducing formation of coke, but the lack of activity at a very high content of chromium oxide (25%) and complex manufacturing process.

The present invention is to obtain a catalyst with increased strength, activity and method of its production.

The problem is solved by a catalyst for the dehydrogenation of C2-C5hydrocarbons containing oxides of aluminum, chromium, a compound modifier metal, alkaline and/or alkaline earth metal, the catalyst additionally contains compounds of silicon and/or boron in an amount of 0.1-10%, as a modifier metal contains at least one compound from the group of zirconium, titanium, iron, gallium, cobalt, molybdenum, manganese, tin, and the catalyst formed during the heat treatment of aluminum compounds of the formula Al2O3· n H2O, where n=0.3 to 1.5, in conjunction with the compounds of the above elements and has the following composition, wt.% (in terms of oxide):

Oxide of chromium calculated as Cr2O312-23
The connection of reactive metal from the group of Zr, Ti, Fe, Ga, Co, Sn, Mo, Mn0.1 to 1.5
0,1-10,0
Connection alkaline and/or alkaline earth metalof 0.5-3.5
Aluminium oxideRest

The catalyst has a value of specific surface area of 50-150 m2/g, pore volume of 0.15-0.4 cm3/g and a particle size of 40-200 microns.

The problem is solved by obtaining a catalyst for the dehydrogenation of C2-C5hydrocarbons, including impregnation of the carrier based on alumina with solutions of chromium compounds, alkaline and/or alkaline earth metal, the modifying metal, drying and annealing at 700-800°C, as the carrier is used as a compound of aluminium of the formula Al2O3· n H2O, where n=0.3 to 1.5, as a compound modifier metal used is at least one compound from the group of zirconium, titanium, iron, gallium, cobalt, molybdenum, manganese, tin, and impose additional compounds of silicon and/or boron in an amount of 0.1-10% wt. the impregnation of the carrier, followed by drying and coating with other catalyst components or in conjunction with other components of the catalyst and the catalyst after calcination has the following composition, wt.% (in terms of oxide):

Oxide of chromium calculated as Cr 2O312-23
The connection of reactive metal from the group of Zr, Ti, Fe, Ga, Co, Mo, Mn, Sn0.1 to 1.5
The compound of silicon and/or boron0,1-10,0
Connection alkaline and/or alkaline earth metalof 0.5-3.5
Aluminium oxideRest

For the preparation of the catalyst is used as a compound of aluminium of the formula Al2O3·n H2O, where n = 0,3-1,5 having amorphous or logoutresultevent structure or partially crystalline structure obtained, for example, by the rapid dehydration of hydrargillite (applies to the catalyst).

The resulting catalyst has a specific surface area of 50-150 m2/g, pore volume of 0.15-0.4 cm3/year

Impregnation of the aluminum compounds of the formula Al2O3· n H2O, where N=0.3 to 1.5, is carried out in an aqueous solution of compounds of silicon and/or boron with a pH of 6.5 - 12 and at a temperature of 70-100°C, followed by drying and placement of the remaining components on capacity or impregnate both compounds boron and/or silicon, alkaline and/or alkaline earth metal, chromium, modifying metal capacity at a temperature of 20-100°C. After impregnation the catalyst is dried in vacuum.

As boron compounds, use boric acid. As with the joining of silicon using a Hydrosol of silicon, the tetraethoxysilane.

In the known solution for the preparation of the catalyst using a carrier having formed a crystalline structure (γ-Al2O3and others), which cause repeated impregnation of the active components of the catalyst. For fixing these components on the media carry out the heat treatment in several stages. Nevertheless sufficiently strong fastening of the active component on the carrier is not happening. This is reflected in the fact that during operation catalyst is the ablation of the active component.

The proposed solution is the formation of the catalyst during the heat treatment of aluminum compounds of the formula Al2O3· n H2O, where N = 0.3 to 1.5, preferably having an amorphous or logoutresultevent structure or partly crystalline structure, together with the active components of the catalyst, which leads to strong communication media with active components.

In addition, when the joint application of all components occurs simultaneous formation and modification of the carrier and the catalytic composition, which allows chemically dispersing the active components so that after heat treatment at 700 to 800°C compounds of chromium, potassium and modifying compounds are x-ray amorphous state that is allows to significantly increase the activity and selectivity of the catalyst.

The catalyst is prepared as follows.

For the preparation of the catalyst is used as a compound of aluminum with the gross formula Al2O3· n H2O (n = 0.3 to 1.5). This compound can be obtained by any known means, for example, by the rapid dehydration of hydrargillite. While the preferred x-ray amorphous structure of this compound. The particle size of aluminum compounds 40-200 microns.

Under the aluminum oxide amorphous structure refers to such x-ray analysis, which does not detect any lines, characteristic of any crystalline phase. Under semi-crystalline oxygen-containing compound of aluminum understand such analysis which detects the spectrum of the diffraction lines characteristic of crystalline phases at least one of the compounds: bayerite, hydro-argillite, boehmite, γ-, χ-, η-, δ-, θ-, κ-Al2O3.

In the proposed method, the impregnation takes place simultaneously all the components of the catalyst or from a solution, or capacity. The preferred option is the method of applying for capacity, because there is no waste water containing harmful compounds chromium.

When the impregnation of the aluminum compounds connectors boron and/or silicon from the solution at a pH of 6.5 to 12 and a temperature of 70-100°C favorable condition the conditions for uniform distribution in the structure of the aluminum compounds of boron and/or silicon, which increase thermal stability of the catalyst. Drying captures the compound obtained aluminum, modified with boron and/or silicon. It allows you to separate in time and space processes of obtaining partially modified aluminum compounds and catalyst, which is sometimes necessary in the course of preparation of the catalyst due to problems with the provision of raw materials, sale of finished catalyst, production ecology. In addition, when preparing the preformed catalyst this stage is necessary because the resulting modified connection of the aluminum is in this case the binder.

In the case of the preparation of the preformed catalyst is prepared catalyst composition of aluminum compounds and modified with boron and/or silicon, which are impregnated aluminum compounds of the formula Al2O3· n H2O in an aqueous solution of compounds of boron and/or silicon at a pH of 6.5 to 12 and a temperature of 70-100°C and compounds of alkali and/or alkaline earth metal, the modifying metal, chrome. Then this song tabletirujut or granularit any of the known methods (extrusion, molding, extrusion, sealing and the like) with a subsequent heat treatment.

The proposed method allows to significantly simplify the technology of preparation of the catalyst dehydrogenation of paraf is new compared to existing methods by eliminating multiple stages of cooking media: precipitation of aluminum hydroxide, spray drying or forming pellets, heat treatment of the medium in comparison with the known solutions.

Determination of the phase composition of the materials used in the technology of preparation of the catalyst dehydrogenation, conduct radiographic technique based on x-ray diffraction. Survey samples is carried out in CuKα-radiation using a differential discrimination of the monochromator. The interval of angles on a scale of 2θ from 10 to 75°C, the angular velocity detector 1/60°C.

Specific surface area determined by BET method, the volume of pore - water adsorption, particle size - sieve method.

The abrasion resistance is determined by the mass fraction of the loss in catalyst attrition. The method is based on the destruction of the catalyst particles in the fluidized layer and measuring the mass of particles carried by the air flow, the speed of which is stabilised.

The invention is illustrated by the following examples.

Example 1. The compound of aluminium of the formula Al2O3· n H2O (n = 0,7) amorphous structure in the form of microspherical powder with a particle size of from 100 to 200 μm in a quantity of 25 kg load in propitiating with heating and stirring. There is poured a solution containing 5 kg of chromic anhydride, 460 g of potassium alkalis, 570 g of oxynitride zirconium and 150 g of tetraethoxysilane.

The impregnation is carried out at a temperature of 20°C for 1 hour. This was followed by drying in vacuum. The dried catalyst was calcined at 700°C 6 hours in a furnace of the fluidized bed. The composition of the obtained catalyst are presented in table. N 1, and its physico-chemical and catalytic properties in the table. N 2.

Examples 2 to 5. The catalyst is prepared analogously to example 1, different temperature impregnation, the structure of the aluminum compounds and the composition of the input modifying elements. Data on temperature, the structure of the aluminium compound and the modifying additives are given in table. N 1. And properties of the obtained catalysts is given in tab. N 2.

Example 6. In a reactor with a stirrer and heated pour 80 l of demineralized water, load 270 g of boric acid and heated to 70°C, then download 27 kg aluminum compounds of the formula Al2O3· n H2O (n = 0.5) is in the form of microspherical powder amorphous structure. Bring the pH of the slurry to 6.5 mineral acid. The process is conducted at 85°C for 2 hours, then the precipitate is filtered off, dried in a chamber dryer at a temperature of 100°C to remove free moisture. After drying, the partially modified connection of the aluminum impregnated in the apparatus with heating and stirring, which serves a solution containing 250 g of potassium alkali and 180 g of cesium hydroxide, and 120 g of manganese hydroxide and 130 hydroxide zirconium and 5 kg of chromium trioxide. The impregnation is carried out at 60°C for 1 hour, followed by drying in a vacuum and calcining at 750°C for 6 hours. The resulting catalyst has the properties and composition shown in table. NN 1 and 2.

Examples 7 and 8. The catalyst is prepared analogously to example 6, different temperature impregnation and the pH of the suspension, the composition of the used catalyst components. All data are presented in table. NN 1 and 2.

Example 9. In a reactor with a stirrer and heated pour 18 l of water, then load 30 g silicates and 3 kg melkoporistaja aluminum compounds Al2O3· 0,9 H2O having logoutresultevent structure and a particle size of predominantly 40 microns. Bring the pH of the suspension to 7.2 nitric acid. Process connection aluminium silicon conducted for 2 hours at 85°C. Then the precipitate is filtered off and dried at 110°C in a chamber dryer. After drying, the resulting powder was impregnated with 85°C with a solution containing 900 g of chromic anhydride and 25 g of lithium nitrate, 28 g of barium nitrate and 68 g of oxynitride zirconium. Moreover, the impregnation takes place simultaneously with obtaining a pasty mass of catalyst, which is then formed into pellets, dried at 110°C and annealed at 730°C. Receive the catalyst with the properties shown in table. NN 1 and 2.

Prima is 10 (the prototype). 1200 g of aluminum oxide in the form of tablets impregnated with a solution containing 532,8 g of chromium trioxide and 28.0 g of oxoacetate zirconium (respectively 52 wt.% zirconium dioxide). After impregnation, the product is dried for 3 hours at a temperature of 140°C and for 16 hours at a temperature of 110°C in an atmosphere of air, then calicivirus for 2 hours at a temperature of 740°C in an atmosphere of air. Then carry out the impregnation of the catalyst with potassium acetate and the two-stage drying during the first 3 hours at a temperature of 140°C in vacuum, and then for 16 hours at a temperature of 110°C in an atmosphere of air. Then the product calicivirus for 2 hours at a temperature of 740°C in an atmosphere of air. Get the catalyst on the media of the following composition: 72.1 wt.% Al2O3; 25 wt.% Cr2O3; 0.9 wt.% ZrO2and 2 wt.% K2O and the properties are shown in table. N 2.

As seen from the examples, the catalyst of the proposed structure has high mechanical strength, allowing not to harm the environment, and the catalyst has a high activity and selectivity in the process of dehydrogenation of hydrocarbons.

1. Catalyst for dehydrogenation of C2-C5hydrocarbons containing oxides of aluminum, chromium, a compound modifier m is metal, alkaline and/or alkaline earth metal, wherein the catalyst additionally contains compounds of silicon and/or boron in an amount of 0.1 - 10 wt.%, as the modifying metal contains at least one compound from the group of zirconium, titanium, iron, gallium, cobalt, molybdenum, manganese, tin, and the catalyst formed during the heat treatment of aluminum compounds of the formula Al2O3·n H2O, where n = 0.3 to 1.5, in conjunction with the compounds of the above elements, and has the following composition, wt.% (in terms of oxide):

Oxide of chromium calculated as Cr2O312 - 23
The connection of the modifying metal
from the group of Zr, Ti, Fe, Ga, Co, Sn, Mo, Mn0.1 to 1.5
The compound of silicon and/or boron0,1 - 10,0
Connection alkaline and/or alkaline earth metalof 0.5 - 3.5
Aluminium oxideRest

2. The catalyst according to claim 1, characterized in that the compound of aluminium of the formula Al2O3·n H2O, where n = 0.3 to 1.5, is amorphous or poorly crystalsound structure or a partially crystalline structure.

3. The catalyst according to claim 1, characterized in that it has led the inu specific surface area of 50 150 m2/g and a pore volume of 0.15 - 0.4 cm3/year

4. The catalyst according to claim 1, characterized in that it has a particle size of 40 to 200 microns.

5. A method of producing a catalyst for the dehydrogenation of C2-C5hydrocarbons, including impregnation of the carrier based on alumina with solutions of chromium compounds, alkaline and/or alkaline earth metal, the modifying metal, drying and calcination at 700 - 800°C, characterized in that as the carrier is used as a compound of aluminium of the formula Al2O3·n H2O, where n = 0.3 to 1.5, as a compound modifier metal used is at least one compound from the group of zirconium, titanium, iron, gallium, cobalt, molybdenum, manganese, tin, and impose additional compounds of silicon and/or boron in an amount of 0.1 - 10 wt.% impregnation of the carrier, followed by drying and coating with other catalyst components or in conjunction with other components of the catalyst and the catalyst after calcination has the following composition, wt.% (in terms of oxide):

Oxide of chromium calculated as Cr2O312 - 23
The connection of the modifying metal
from the group of Zr, Ti, Fe, Ga, Co, Mo, Mn, Sn0.1 to 1.5
The compound of silicon and/or the ora 0,1 - 10,0
Connection alkaline and/or alkaline earth metalof 0.5 - 3.5
Aluminium oxideRest

6. The method according to claim 5, characterized in that the catalyst has a specific surface area of 50 to 150 m2/g, pore volume of 0.15 - 0.4 cm3/year

7. The method according to claim 5, characterized in that the compound of aluminium of the formula Al2O3·n H2O, where n = 0.3 to 1.5, is amorphous or poorly crystalsound structure or partly crystalline structure, obtained by the rapid dehydration of hydrargillite.

8. The method according to claim 5, characterized in that the impregnation of the aluminum compounds of the formula Al2O3·n H2O, where n = 0.3 to 1.5, is carried out in an aqueous solution of compounds of silicon and/or boron with a pH of 6.5 - 12 and at a temperature of 70 - 100°C, followed by drying and placement of the remaining components of the capacity.

9. The method according to claim 5, characterized in that the compound of aluminium of the formula Al2O3·n H2O, where n = 0,3 - 1,5, impregnate both compounds boron and/or silicon, alkaline and/or alkaline earth metal, chromium, modifying metal capacity at a temperature of 20 to 100°C.

10. The method according to claim 5, characterized in that after impregnation the catalyst is dried in vacuum.

11. The method according to claim 5, characterized in that the boron compounds used in the comfort of boric acid.

12. The method according to claim 5, characterized in that compounds of silicon using a Hydrosol of silicon, tetraethoxysilane.



 

Same patents:

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention provides catalytic composition for dehydration of alkylaromatic hydrocarbons optionally combined with ethane comprising: carrier consisting of alumina in δ phase or in θ phase, or in mixed δ+θ or θ+α, or δ+θ+α phase, modified with silicon oxide and having surface area less than 150 m2/g as measured by BET method; 0.1-35% gallium in the form of Ca2O3; 0.01-5% manganese in the form of Mn2O3; 0-100 ppm platinum; and 0.05-4% alkali or alkali-earth metal oxide, all percentages being based on the total weight of composition. Other variants of composition are also covered by invention. Methods of preparing such catalytic composition (options) envisage use of alumina-based carrier in the form of particles corresponding to group A of the Geldart Classification. Process of dehydration of alkylaromatic hydrocarbons optionally combined with ethane comprises: (i) dehydration of hydrocarbon stream optionally mixed with inert gas in fluidized-bed reactor in presence of catalytic composition consisted of alumina-supported and silica-modified gallium and manganese at temperature within a range of 400 to 700°C, total pressure within a range of 0.1 to 3 atmospheres, and gas hourly space velocity from 50 to 10000 h-1; and (ii) regeneration and heating of catalyst caused by catalytic oxidation of fuel in fluidized-bed reactor at temperature above 400°C.

EFFECT: increased activity of catalytic composition and prolonged lifetime thereof.

22 cl, 2 tbl, 16 ex

FIELD: petroleum chemistry, organic chemistry, chemical technology.

SUBSTANCE: method involves contacting the parent raw flow in the flow-type reactor with oxygen-free gas flow at increased temperature with a catalyst comprising a precious metal of VII group of the periodic system of elements. The industrial isomerization platinum-containing catalyst SI-1 or industrial hydrogenation catalyst "palladium on active aluminum oxide in sulfured form" is used as a catalyst. Contact of the parent raw with catalyst is carried out by its feeding in inert gas flow, for example, nitrogen at the volume rate 1-2 h-1 at temperature 320-370°C in the presence of the additive representing a solution of hydroquinone or p-benzoquinone in isopropyl alcohol and taken in the concentration 0.01-0.5 mole/l wherein the additive is fed to the parent raw flow in the amount 5-30 vol.%. Invention provides carrying out the highly selective isomerization and cyclization of light petroleum fractions in on industrial Pt- and/or Pd-containing catalysts with the high yield of the end products no containing aromatic compounds and not requiring the presence of hydrogen or hydrogen-containing gas for its realization and regeneration of the catalyst.

EFFECT: improved method for isomerization.

4 cl, 2 tbl, 2 ex

FIELD: chemistry of aromatic compounds, chemical technology.

SUBSTANCE: process involves the following stages: feeding (C2-C5)-alkane, for example, ethane and (C2-C5)-alkyl-substituted aromatic compound, for example, ethylbenzene into dehydrogenation reactor for the simultaneous dehydrogenation to (C2-C5)-alkene, for example, to ethylene, and (C2-C5)-alkenyl-substituted aromatic compound, for example, styrene; separation of the outlet dehydrogenation flow for extraction of gaseous flow containing alkene, hydrogen and alkane, and for extraction of aromatic compounds with the high effectiveness by cooling and compression; feeding a gaseous flow and (C6-C12)-aromatic compound into the alkylation reactor for preparing the corresponding (C2-C5)-alkyl-substituted aromatic compound that is recirculated into the dehydrogenation reactor; feeding the blowing flow from the alkylation unit containing alkane and hydrogen for the separation stage by using cryogenic separator for extraction of alkane that is recirculated into the dehydrogenation reactor, and hydrogen that is extracted with the purity value 99%. Invention provides the development of economic and highly effective process for preparing alkenyl-substituted aromatic compounds.

EFFECT: improved preparing method.

61 cl, 2 tbl, 2 dwg, 2 ex

FIELD: petroleum chemistry, chemical technology.

SUBSTANCE: invention relates to dehydrogenation of isoamylenes to isoprene on iron oxide self-regenerating catalysts. Method involves addition of piperylenes in the concentration up to 4 wt.-% representing a by-side product in manufacturing process of isoprene by the indicated method to the parent isoamylenes before their dehydrogenation. Method provides enhancing selectivity of method for isoamylenes dehydrogenation to isoprene in the presence of iron oxide self-regenerating catalysts.

EFFECT: improved preparing method.

1 tbl, 6 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention concerns catalysts for dehydrogenation of C2-C5-alkanes into corresponding olefin hydrocarbons. Alumina-supported catalyst of invention contains 10-20% chromium oxide, 1-2% alkali metal compound, 0.5-2% zirconium oxide, and 0.03-2% promoter oxide selected from zinc, copper, and iron. Precursor of alumina support is aluminum oxide hydrate of formula Al2O3·nH2O, where n varies from 0.3 to 1.5.

EFFECT: increased mechanical strength and stability in paraffin dehydrogenation process.

9 cl, 1 dwg, 3 tbl, 7 ex

FIELD: petrochemical processes.

SUBSTANCE: 1,3-butadiene is obtained via catalytic dehydrogenation of n-butylenes at 580-640°C and essentially atmospheric pressure while diluting butylenes with water steam at molar ratio 1:(10-12) and supplying butylenes at space velocity 500-750 h-1. Catalyst is composed of, wt %: K2O 10-20, rare-earth elements (on conversion to CeO2) 2-6, CaO and/or MgO 5-10. MoO3 0.5-5, Co2O3 0.01-0.1, V2O5 0.01-0.1, and F2O3 the balance. Once steady condition is attained, dehydrogenation is carried out continuously during all service period of catalyst.

EFFECT: increased yield of 1,3-butadiene and process efficiency.

2 ex

FIELD: petrochemical processes.

SUBSTANCE: simultaneous dehydrogenation of mixture containing alkyl and alkylaromatic hydrocarbons is followed by separating thus obtained dehydrogenated alkyl hydrocarbon and recycling it to alkylation unit. Dehydrogenation reactor-regenerator employs C2-C5-alkyl hydrocarbon as catalyst-transportation carrying medium.

EFFECT: increased process flexibility and extended choice of catalysts.

36 cl

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to production of olefin or diolefin hydrocarbons via dehydrogenation of corresponding paraffinic C3-C5-hydrocarbons carried out in presence of catalyst comprising chromium oxide and alkali metal deposited on composite material including alumina and aluminum wherein percentage of pores larger than 0.1 μm is 10.0-88.5% based on the total volume of open pores equal to 0.10-0.88 cm3/g. Preparation of catalyst involves treatment of carrier with chromium compound solution and solution of modifying metal, preferably sodium or sodium and cerium. Carrier is prepared by from product resulting from thermochemical activation of amorphous hydrargillite depicted by formula Al2O3·nH2O, where 0.25<n<2.0, added to homogenous mass in amount 1.0 to 99.0% using, as additional material, powdered aluminum metal, which is partly oxidized in hydrothermal treatment and calcination stages. Hydrocarbon dehydrogenation process in presence of the above-defined catalyst is also described.

EFFECT: increased activity and selectivity of catalyst.

3 cl, 2 dwg, 4 tbl, 7 ex

The invention relates to catalysts used in the dehydrogenation of hydrocarbons, and to methods of using catalysts

FIELD: petroleum processing catalysts.

SUBSTANCE: catalyst designed for using in petroleum fraction hydrofining, which contains oxides of cobalt, molybdenum, phosphorus, lanthanum, boron, and aluminum, is prepared by mixing aluminum hydroxide with boric acid solution and nitric acid solution of lanthanum carbonate followed by drying, calcination, impregnation of resulting carrier with cobalt nitrate and ammonium paramolybdate solution in nitric acid at pH 2.0-3.5 and 40-80°C in presence of phosphoric acid followed by drying and calcination at elevated temperature.

EFFECT: enabled production of hydrogenate with reduced content of sulfur compounds.

2 ex

FIELD: engineering of Fischer-Tropsch catalysts, technology for producing these and method for producing hydrocarbons using said catalyst.

SUBSTANCE: catalyst includes cobalt in amount ranging from 5 to 20 percents of mass of whole catalyst on argil substrate. Aforementioned substrate has specific surface area ranging from 5 to 50 m2/g. Catalyst is produced by thermal processing of argil particles at temperature ranging from 700 to 1300°C during period of time from 1 to 15 hours and by saturating thermally processed particles with cobalt. Method for producing hydrocarbon is realized accordingly to Fischer-Tropsch method in presence of proposed catalyst.

EFFECT: possible achievement of high selectivity relatively to C5+ at low values of diffusion resistance inside particles.

3 cl, 9 ex, 9 dwg

FIELD: structural chemistry and novel catalysts.

SUBSTANCE: invention provides composition including solid phase of aluminum trihydroxide, which has measurable bands in x-ray pattern between 2Θ=18.15° and 2Θ=18.50°, between 2Θ=36.1° and 2Θ=36.85°, between 2Θ=39.45° and 2Θ=40.30°, and between 2Θ=51.48° and 2Θ=52.59°, and has no measurable bands between 2Θ=20.15° and 2Θ=20.65°. Process of preparing catalyst precursor composition comprises moistening starting material containing silicon dioxide-aluminum oxide and amorphous aluminum oxide by bringing it into contact with chelating agent in liquid carrier and a metal compound; ageing moistened starting material; drying aged starting material; and calcining dried material. Catalyst includes carrier prepared from catalyst composition or catalyst precursor and catalytically active amount of one or several metals, metal compounds, or combinations thereof. Catalyst preparation process comprises preparing catalyst carrier from starting material containing silicon dioxide-aluminum oxide and amorphous aluminum oxide by bringing it into contact with chelating agent and catalytically active amount of one or several metals, metal compounds, or combinations thereof in liquid carrier, ageing starting material; drying and calcinations. Method of regenerating used material involves additional stage of removing material deposited on catalyst during preceding use, while other stages are carried out the same way as in catalyst preparation process. Catalyst is suitable for treating hydrocarbon feedstock.

EFFECT: improved activity and regeneration of catalyst.

41 cl, 3 dwg, 8 tbl, 10 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to methods for preparing catalyst precursors and group VIII metal-based catalysts on carrier, and to a process of producing hydrocarbons from synthesis gas using catalyst of invention. Preparation of precursor of group VIII metal-based catalyst comprises: (i) imposing mechanical energy to mixture containing refractory oxide, combining catalyst precursor with water to form paste comprising at least 60 wt % of solids, wherein ratio of size of particles present in system in the end of stage (i) to that in the beginning of stage (i) ranges from 0.02 to 0.5; (ii) mixing above prepared paste with water to form suspension containing no more than 55% solids; (iii) formation and drying of suspension from stage (ii); and (iv) calcination. Described are also method of preparing group VIII metal-based catalyst using catalyst precursor involving reduction reaction and process for production of hydrocarbons by bringing carbon monoxide into contact with hydrogen are elevated temperature and pressure in presence of above-prepared catalyst.

EFFECT: increased catalytic activity and selectivity.

12 cl, 1 tbl, 3 ex

FIELD: reduction-oxidation catalysts.

SUBSTANCE: invention relates to catalytic chemistry and, in particular, to preparation of deep-oxidation supported palladium catalysts, suitable, for example, in afterburning of motor car exhaust. Preparation involves depositing palladium from aqueous solution of palladium precursors followed by drying and calcination. Precursors are selected from nitrite anionic or cationic palladium complexes [Pd(NO2-)(H2O)3]Anx or [Pd(NO2-)n(H2O)m](Kat)y, wherein An are anions of acids containing no chloride ions, Kat is proton or alkali metal cation, n=3-4, m=0-1, x=1-2, and y=1-2. Nitrite ions are introduced into impregnating solution in the form of nitrous acid salts or are created in situ by reducing nitrate ions or passing air containing nitrogen oxides through impregnating solution. Ratio [Pd]/[NO2-] in impregnating solution is selected within a range 1:1 to 1:4.

EFFECT: eliminated chlorine-containing emissions, increased stability of chlorine-free impregnating solutions, reduced their acidity and corrosiveness, and increased catalytic activity in deep oxidation reactions.

2 cl, 1 tbl, 16 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: catalyst includes Cu and Mg compounds deposited on alumina as carrier and has copper compounds, expressed as Cu, from 2 to 8%, Mg/Cu atomic ratio ranging from 1.2 to 2.5, wherein concentration of copper atoms is higher in the interior of catalyst particle than on the surface (layer 20-30 Å thick) thereof and concentration of magnesium atoms prevails on the surface of catalyst particle, while specific surface of catalyst ranged from 30 to 130 m2/g. Oxychlorination of ethylene is carried out under fluidized bed conditions using air and/or oxygen as oxidants in presence of above-defined catalyst. Catalyst is prepared by impregnating alumina with aqueous Cu and Mg solutions acidified with hydrochloric acid solution or other strong acids using volume of solution equal or lesser than porosity of alumina.

EFFECT: increased activity of catalyst at high temperatures and avoided adhesion of catalyst particles and loss of active components.

8 cl, 2 tbl, 5 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to synthesis of C5-C100-hydrocarbons from CO and H2, which catalyst contains carrier based on alumina prepared from gibbsite-structure aluminum hydroxide and cobalt in concentration of 15 to 50%. Carrier is prepared by mixing dry cobalt compound with dry gibbsite-structure aluminum hydroxide at cobalt-to aluminum molar ratio between 1:1 and 1:30, followed by calcination, impregnation (in two or more steps) with aqueous cobalt salt solution, and heat treatment. Invention also discloses process of producing C5-C100-hydrocarbons using above catalyst.

EFFECT: increased selectivity of catalyst regarding production of high-molecular hydrocarbons at reduced yield of methane.

7 cl, 1 tbl, 10 ex

FIELD: gas treatment catalysts.

SUBSTANCE: invention provides catalyst consisted of inert carrier and catalytic coating containing platinum, rhodium, and oxide substrate, wherein catalytic coating includes: (i) at least one first substrate material selected from group consisted of first active aluminum oxide enriched with cerium oxide; mixed oxide, which is cerium oxide/zirconium dioxide; and zirconium dioxide component; provided that catalytic component in at least one first substrate material is first portion of the total quantity of catalyst platinum, wherein concentration of the first portion of the total quantity of catalyst platinum lies within a range of 0.01 to 5.0% of the total mass of catalyst-containing materials; and (ii) a second substrate material containing second portion of total quantity of platinum and rhodium as catalytic component, said second substrate material being second active aluminum oxide, wherein concentration of platinum plus rhodium on the second substrate material lies within a range of 0.5 to 20% of the total mass of the second substrate material. Method for preparing above catalyst is also provided.

EFFECT: increased catalytic activity and reduced catalyst preparation expenses.

17 cl, 3 dwg, 5 tbl, 3 ex

FIELD: catalyst preparation methods.

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

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

5 cl, 1 tbl, 10 ex

FIELD: catalyst preparation methods.

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

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

8 cl, 1 tbl, 3 ex

FIELD: technical chemistry; catalyst carriers for various heterogeneous processes in chemical industry.

SUBSTANCE: proposed carrier has metal base made from chromium and aluminum alloy and/or metallic chromium and coat made from chromium of aluminum oxides or oxides of chromium, aluminum, rare-earth elements or mixture of them. Method of preparation of carrier includes forming of metal powder containing aluminum and other powder-like components and calcination of carrier at solid phase sintering point; used as additional component of metal powder is powder-like chromium; mixture thus obtained is subjected to mechanical activation and is placed in mold accessible for water vapor, after which it is subjected to hydro-thermal treatment and molded product is withdrawn from mold, dried and calcined at respective temperature; then additional layer of aluminum and rare-earth elements oxides or mixture of solutions and suspensions is applied on calcined product followed by drying and calcination.

EFFECT: increased specific surface; enhanced heat resistance of carrier.

8 cl, 1 tbl, 5 ex

Up!