Catalytic system and method for dehydrogenation of ethylbenzene to styrene

 

(57) Abstract:

Describes a catalytic system for the dehydrogenation of ethylbenzene to styrene containing chromium oxide, alkali metal oxide, silicon dioxide and aluminum oxide, characterized in that it further contains tin oxide as a carrier of alumina in Delta or theta phase or in a mixture of Delta + theta or theta + alpha or Delta + theta + alpha phases, modified with silica, and chromium expressed as Cr2O3present in an amount of from 6 to 30 wt.%, tin, expressed as tin oxide, is present in amounts of from 0.1 to 3.5 wt.%, alkali metal, expressed as M2Oh, is present in an amount of from 0.4 to 3 wt.%, the silicon dioxide is present in an amount of from 0.08 to 3 wt.%, and aluminum oxide is the rest up to 100%. Describes the method of dehydrogenation of ethylbenzene to styrene. The technical result is to simplify the process by creating a highly active catalytic system. 2 c. and 12 C.p. f-crystals, 3 ill., table 1.

The present invention relates to a catalytic system and to a method for dehydrogenation of ethylbenzene to styrene, which is used by this system.

Styrene is an important premiato the production of polystyrene (crystal General purpose polystyrene (GPPS), high impact polystyrene (hips) and expandable polystyrene (VSP)), acrylonitrilebutadienestyrene (ABS) and Acrylonitrile copolymer (SAA) the best choice of rubber (BSC).

Currently, the styrene is produced mainly in two ways:

by dehydrogenation of ethylbenzene (EB) (this method is about 90% of global production (Arr. Cat. 133, 1995, 219));

as a co-product when epoxydecane propylene with gidroperekisi ethylbenzene with catalysts based on complexes of molybdenum.

It was recently studied two alternative ways of obtaining the monomer, which in some cases were brought to industrial production:

- oxidative dehydrogenation of ethylbenzene;

- dehydrogenation of ethylbenzene with subsequent oxidation of hydrogen.

Will be considered the production of styrene only by dehydrogenation of ethylbenzene, because this method is a method of the present invention.

The reaction of dehydrogenation of ethylbenzene to styrene has various characteristics that should be taken into account in the development of technology.

First, this reaction controleer dehydrogenation increases with increasing temperature and decreasing total pressure, the reaction proceeds at constant pressure, the volume increase.

To achieve economically acceptable conversions such thermodynamics forces to carry out the reaction in the temperature range 540-630oC. because Of the low reaction rate of the dehydrogenation of ethylbenzene at these temperatures also need to work in the presence of a suitable catalyst.

Because of the rather high operating temperatures inevitably occur side effects that usually differ a higher activation energy compared with the energy of dehydrogenation. Consequently, the main product is accompanied by-products, consisting mainly of toluene, benzene, coke and light products. The function of the catalyst is to direct the reaction towards the desired product.

Another important aspect is that the reaction is strongly indeterminacy with the heat of reaction equal to 28 Kcal/mol of styrene, which corresponds to 270 Kcal/kg of the obtained styrene. Rated high heat and high thermal levels at which it should share, are factors that have a major influence on technological development. Currently marketed tehe factors through the creation of a technological system, which includes:

- the use of successive adiabatic reactors with intermediate stages of heating where the temperature ranges from 540 to 630oC when contact time is more or less tenths of a second;

- use reactors with radial flow, working in a vacuum in which the pressure is from 0.3 to 0.5 ATM;

- the use of water vapor in a joint filing with downloadable raw materials, which must be digidrirovanne.

Water is the main component fed to the reactor. Normal its molar concentration is 90%. However, the commonly used concentration of over 90% for chemical extend the life of the catalyst.

Water vapor has several functions:

- reduce the partial pressure of the products and, therefore, shift thermodynamic equilibrium in the preferred direction;

- contribute to the cleaning of the catalyst from the coke by the reaction of water gas, because there is no burning of the catalyst by air;

- supply all the heat necessary for the reaction of dehydrogenation of EB.

By using the optimized catalyst mainly based oxide, W is the styrene over 90% of the weight.

Despite these characteristics, these technologies have drawbacks, which mainly relate to the following aspects:

- the use of huge quantities of superheated steam (molar ratio of H2O/EB = 9,0-9,8) at temperatures above 700oC, which makes necessary the application of a furnace overheating and, therefore, leads to a high cost of capital;

- the aging of the catalyst, which requires replacement after approximately 18-36 months of work; to replace the catalyst, you want to stop the installation and to cease production on the time required to replace it; you can extend the lifetime of the catalyst by increasing the ratio of H2O/EB, but it additionally leads to the risk of energy balance;

recovery (return) energy is not quite optimized: existing technology actually Recuperat only malochuvstwitiona vapor and not Recuperat latent heat;

- carrying out the reaction in vacuum (average absolute pressure of 0.4 ATM) and, therefore, highly diluted phase in EB: partial pressure of EB is the average of 0.04 ATM.

In the patent RU 1366200 A1 discloses a catalyst for the In U.S. patent 4038215 A disclosed method of dehydrogenation of ethylbenzene, performed at a temperature of 350-700oC, average hourly rate of gas flow of 0.1-10 h-1and including the regeneration of the catalyst by burning the coke at a temperature of 550-650oC.

Unexpectedly found that when using a specific catalyst system, consisting mainly of Cr2O3supported on alumina modified silicon dioxide, to which was added tin oxide, technology dehydrogenation of ethylbenzene is significantly improved.

The catalytic system of the present invention for the dehydrogenation of ethylbenzene to styrene contains chromium oxide, tin oxide, at least one oxide of an alkali metal (M2O) and aluminum oxide as a carrier, in the Delta or theta phase or in a mixture of Delta + theta or theta + alpha or Delta + theta + alpha phases, modified with silica, and differs in that:

- chromium expressed as Cr2O3present in an amount of from 6 to 30% weight. preferably from 13 to 25 wt%.;

- tin, expressed as tin oxide, is present in amounts of from 0.1 to 3.5 wt%, preferably from 0.2 to 2.8 wt%.;

- alkali metal, expressed as M2O, is present in an amount of from 0.4 to 3 wt%, is luminia is the rest up to 100%.

Alkali metal, preferably potassium, is used to soften the acidity of the carrier of aluminum oxide.

As for the surface area of the carrier, preferably it is less than 150 m2/g when determining the method of Brunauer-Emmett-teller (BET method).

The method for the catalytic system described above, essentially consists in the dispersion of the chromium compounds, alkali metal and tin on a medium consisting of aluminum oxide (in the Delta or theta phase or in a mixture of Delta + theta or theta + alpha or Delta + theta + alpha phases) and silicon dioxide.

Some methods of dispersion of chromium oxide, potassium oxide and tin oxide (ferrous and/or tetravalent) on the media listed below, but it should be understood that the invention is not limited.

This dispersion treatment may consist of a carrier impregnated with a solution containing precursors of the oxides of chromium, potassium and tin, with subsequent drying and calcination, or by ion absorption, followed by liquid separation, drying and calcination of the solid. Among the above methods is preferred impregnation, according to the.

As for tin, it can be added to the catalytic system using other methods, which are listed below:

by adding tin to the media before dispersing the precursors of the oxides of chromium and potassium;

treatment of solid substances containing chromium oxide and potassium oxide by ion exchange, impregnation, and others, with a solution containing a compound of tin;

- deposition of tin on the media through the "deposition from the vapor phase using volatile compounds deposited compounds before the addition of precursors of chromium oxide and potassium oxide;

- deposition of tin on a solid substance containing aluminum oxide, chromium oxide and potassium oxide, by deposition from the vapor phase using volatile compounds deposited compounds.

Among the above methods, the joint carrier impregnated with a solution containing the precursors of the active components (chromium oxide, potassium oxide and tin oxide), and deposition by deposition from the vapor phase" tin are preferred.

The precursor of the oxide of the divalent and/or tetravalent tin, which can be used are as neorganicheskiye salt, poorly soluble in water, can be used after setting the pH value of the solution, which affects their solubility.

ORGANOMETALLIC derivatives are used to add to the catalytic system in accordance with the above described method by selection of organic solvents in which they are dissolved.

The catalytic system according to the invention can be used in any dehydrogenation of ethylbenzene using a fixed, fluidized or moveable.

The method of dehydrogenation of ethylbenzene to styrene, which is a yet another object of the present invention is:

a) interaction in the reactor operating at a temperature of from 450 to 700oC, at a pressure of from 0.1 to 3 ATM and the average gas flow rate (GHSV) of from 100 to 10000 h-1(normal liters of hydrocarbon per hour liter of catalyst), ethyl benzene with a catalytic system described above, preferably diluted with an inert product when the weight concentration of the catalytic system is from 5 to 50%;

b) regeneration of the catalytic system in the regenerator operating at temperatures above 400oC, by burning the coke on eticheski inert material, such as, for example, aluminum oxide, possibly modified with oxides of alkali metal and/or silicon dioxide, etc.

The method preferably is carried out in a system with a fluidized bed consisting of a reactor in which the reaction of dehydrogenation, and regenerator, in which the regenerated catalyst by burning the coke deposited during the reaction phase.

In the system of the reactor-regenerator the catalyst in the fluidized state is continuously circulated between the reactor and regenerator, which gives the possibility to carry out the process continuously, and the heat required for the reaction is removed from the regenerated catalyst, which reaches the reactor at a temperature that is above average reaction temperature.

The supported catalyst in the reactor in a fluidized state with a gaseous reagent (ethyl benzene), which flows into the catalyst bed from the bottom through a special distribution system.

It is also advisable together with ethylbenzene to submit an inert gas (nitrogen, methane, hydrogen, water and other) at a volume ratio of inert gas/ethylbenzene preferably from 1 to 6, more preferably from 2 to 4.

Chodawu system Department of the powder components; then it can be directed into the heat exchanger for pre-heating load and then in section separation, where there are formed styrene, whereas the unreacted raw material (load) is recycled to the stage of dehydrogenation, and non-condensable products are separated and can be used in the regenerator as a fuel gas.

The catalyst in the fluidized state is moved in the reactor countercurrent with respect to the gas phase. The gas enters the catalyst bed from the top through a distribution device that distributes on the surface layer, and exits the reactor from below, passing by gravity into the desorption zone, in another part of the reactor with a diameter less than the diameter of the reaction zone or equal to, where is the displacement of interparticle gas and desorption vnutrisutochnogo gas by introducing bottom-nitrogen or methane, in order superseded or desorbed gas was again admitted to the reactor, avoiding loss of reactants or products.

The catalyst, which is still in a fluid state, and then pneumatically fed to the regenerator.

A reactor with a fluidized bed preferably works:

- the a, from 450 to 650oC depending on the desired reaction;

- at a pressure which is atmospheric or slightly above;

- when the rate of gas supply from 100 to 1000 h-1(norm. liters of benzene and inert gas per hour and per liter of catalyst), more preferably from 150 to 200;

when the residence time of the catalyst in the zone of the fluidized bed of from 5 to 30 minutes, more preferably from 10 to 15 minutes, and in the area of desorption from 0.2 to 10 minutes.

Pneumatic transport system, connecting the reactor and the regenerator consists of a transport pipeline with at least one zone in which the catalyst moves downward, preferably maintaining an intermediate state between the minimum fluidization and minimum bubble formation by introducing a suitable amount of gas at the appropriate heights, and the zone in which the catalyst moves up until it reaches the upper part of the catalytic layer of the regenerator, due to the introduction of gas at the base, which greatly reduces the density of the emulsion.

The regenerator preferably has dimensions comparable to the dimensions of the reactor; these sizes due to the need to save the switchgear disperses the catalyst, coming out of the reactor, on the surface of the catalytic layer. Regeneration occurs within a layer by burning the coke deposited on the catalyst, and heating the catalyst in burning methane or fuel gas or by-products of the main reaction with air or oxygen or any other gas that supports combustion, at a higher temperature than the average temperature of the reactor.

Before feeding into the reactor and the regenerated catalyst is subjected to recovery at temperatures from 650 to 680oC and during the time from 0.2 to 10 minutes, to restore hexavalent chromium, and then desorbed products of combustion and recovery.

Gas and solids in the regenerator also move countercurrent: air is supplied to the bottom of the catalytic layer, whereas the fuel gas is introduced at appropriate heights along the layer.

The gas leaving the regenerator and consisting of nitrogen and combustion products may pass through a cyclone or other systems located in the upper part of the device for separating the captured powder, and then, after exiting the regenerator, it can be directed into the heat exchanger for preheating air for their devices to reduce the content of the powder to a few tenths of a mg on N3gas.

Because combustion occurs catalytically at a temperature of less than 700oC, the content of carbon monoxide and oxides of nitrogen in the discharged gases is such that further purification is not required.

Preferably, the regenerator is operated at atmospheric pressure or slightly above, when the rate of gas supply from 100 to 1000 h-1and residence time of the solid components from 5 to 60 minutes, more preferably from 20 to 40 minutes.

The regenerated catalyst is transported to the reactor in the same way as depleted catalyst is transported to the regenerator.

Designed system the reactor-regenerator allows you to maintain constant operating parameters and characteristics during the whole process of installation time.

Periodically from the system paged aliquot of catalyst and replaced with an equal aliquot of fresh catalyst without any termination.

The advantages of the system the reactor-regenerator fluidized bed can be summarized as follows:

- the heat is directly transferred to the reaction with the regenerated catalyst: oroweat the formation of high point, which could result in reduced selectivity;

process using fluidized bed makes it possible to recirculate hydrogen;

all other operations are carried out in a continuous way and no need to modify the operating parameters during operation of the installation;

- the system can operate in a wide range from the point of view of this production capacity relative to design capacity;

- reaction and regeneration are carried out in physically separate areas and may not be any mixing of streams of hydrocarbon streams containing oxygen;

the process is carried out at atmospheric or slightly higher pressure, so there is no possibility of external seepages of air into the reaction zone;

- there is no need for special treatment to reduce the allocation of gaseous pollutants;

- molar concentration of inert products and ethylbenzene in the download is much smaller than in industrial technology.

In Fig. 1 shows a possible application of the system described above the reactor-regenerator.

Download (ethylbenzene (1)), evaporated in (M) and mixed with an inert gas (11), into the reactor (from A reactor through line (4) after passing through the cyclones (F), the heat exchanger (S1), where inert product-ethylbenzene pre-heated, and through the separator (H).

The liquid phase (13) is fed to the distillation, while the non-condensable products are served partially (12) in the regenerator (as fuel) and partial (14) for separation.

The regenerated catalyst (5) reaches, by introducing a gas (3), the upper part of the catalyst layer, and exits the reactor (A), acting in desorber (B) where it comes into contact with desorbers gas (2). The catalyst then enters into the transport pipeline (6), in which he served in the regenerator (D) and in the upper part of the catalyst layer.

In this case, shows one pipe (6) gas inlet along the transport pipeline. Transport pipeline in this application differs in that it has a U-shaped connection between the downward and upward parts. The catalyst is lowered along the regenerator (D), is the reducing agent (E), then in desorber (G) and, finally, in the transport pipe (5) and enters the reactor. Through suitable switchgear (figure not shown) also comes regenerating air (8), fuel gas (12), regenerating gas (9) and desarrollado heat of air (8), used for regeneration, through heat exchanger (S2and, finally, proceed to the separator (L), in which water is separated from the combustion products (15).

Below, along with comparative examples 1, 4 and 5, we present a few examples, which should not be construed as limiting the present invention.

Example 1 (comparative)

Microspheroidal pseudoboehmite appended silicon dioxide (1.2% of the weight. ), with a particle diameter of from 5 to 300 μm, obtained by spray drying Zola hydrated alumina and silica Ludox.

Sample pseudoboehmite subjected to heat treatment consisting in the first calcination at 450oC for one hour, followed by another annealing at 1030oC for 4 hours in a stream of dry air.

The product obtained has a specific surface area of 100 m2/g, a porosity of 0.34 cm3/g and, in essence, consists of a transition alumina, Delta and theta phases containing a small amount of alpha-aluminum oxide (see range of x-ray diffraction in Fig. 2).

Using the initial wetness soaks 200 g of this alumina using 68 cm3aq is a temperature of 85oC. the Impregnated product is left alone for 1 hour at room temperature and then dried at 90oC for 15 hours. The dried product at the end of the trigger in a stream of dry air at 750oC for 4 hours.

Get a composition of the following weight composition:

20% Cr2O3, 1,89% K2O, 1,25% SiO2, Al2O3up to 100%.

This song experience in the reaction of dehydrogenation of ethylbenzene to styrene by mixing it with microspheroidal alpha-aluminum oxide (with an average particle diameter of 50 μm) in a weight ratio of 1:3 (catalyst/alpha-alumina) and at a temperature in the range of from 550 to 600oC. alpha-alumina modify the oxide of potassium (1% weight. in the form of K2O) by impregnation using the technique of "wet impregnation" aqueous solution of potassium carbonate, followed by drying and calcination at 750oC for 4 hours.

Characteristics of the catalyst and the conditions under which they are derived, are presented in table 1.

Example 2

Microspheroidal alumina (200 g) obtained by the method of example 1, are impregnated by the method described above and at the same temperature, using 68 cm3water water Paradise.

The impregnated product is treated as described in example 1, to obtain the catalyst having the following weight composition:

20% Cr2O3, 1,89% K2O, 1.4% of SnO, 1,22% SiO2, Al2O3up to 100%.

Characteristics of the catalyst in the reaction of dehydrogenation of ethylbenzene obtained for the catalyst, diluted in the same proportions as in example 1, are presented in table 1.

Example 3

A sample of the same catalyst obtained by the method of example 2, diluted with the same alpha-aluminum oxide, which was used in example 1 in a weight ratio of 1: 7 (catalyst/alpha-alumina), and experience in the reaction of dehydrogenation of ethylbenzene.

Characteristics of the catalyst are presented in table 1.

Example 4 (comparative)

Sample pseudoboehmite (1000 g), obtained in accordance with the procedure described in example 1 is subjected to heat treatment, which consists in first calcination at 450oC for 1 hour followed by another annealing at 1000oC for 4 hours in a stream of dry air. The calcined product has a surface area of 130 m2/g, porosity of 0.49 cm3/g and consists of transient oxides of aluminum deltanine", impregnated with 150 g of the obtained aluminum oxide with 74 cm3an aqueous solution containing 66,8 g CrO3(99.8% of the weight.) and are 5.36 g of potassium carbonate (45% wt./weight. KOH), and incubated at the same temperature as in example 1. The impregnated product is left alone for one hour at room temperature and then dried at 90oC for 15 hours. The dried product is activated in a stream of dry air at 750oC for 4 hours. Get a composition of the following weight composition:

25% Cr2O3, 1% K2O, 1,18% SiO2, Al2O3up to 100%.

The composition is diluted with alpha-alumina in a weight ratio of 1:7 (catalyst/alpha-alumina) and experience in the reaction of dehydrogenation of ethylbenzene. The obtained characteristics are presented in table 1.

Example 5 (comparative)

An aliquot of the same catalyst obtained in accordance with the procedure described in example 4 is mixed with the alpha-alumina used in example 1 in a weight ratio of 1:3 (catalyst/alpha-alumina). A mixture of experience in the reaction of dehydrogenation of ethylbenzene. The obtained parameters are presented in example 1.

Example 6

Impregnated with 150 g of the author of the solution, in which is dissolved the following products: 68,4 g CrO3(99,8%), 5.49 g of potassium carbonate (45% solution of KOH weight./weight.) and 5.35 g SnC2O4(99.9% of the weight./weight.). Drying and activation is carried out according to the method described in example 1. Get a composition of the following weight composition:

25% Cr2O3, 1% K2O, 1,68% SnO, Al2O3up to 100%.

Characteristics of the catalyst in the dehydrogenation of ethylbenzene obtained for the composition, diluted alpha-alumina in a weight ratio of 1:7 (catalyst/alpha-aluminum oxide), are presented in table 1.

Example 7

A sample of the catalyst obtained by the method of example 6 and diluted with the same alpha-alumina and in the same proportion as in example 1, have by filing ethylbenzene, diluted gaseous stream consisting of 8% vol. H272% of about. N and ethylbenzene (up to 100%) to test the influence of hydrogen loading.

The obtained characteristics are presented in table 1.

Example 8

The same catalyst used in example 7 are mixed with alpha-alumina of example 1 in the same proportion and experience by submitting ethylbenzene, diluted stream, consisting in addition of ethylbenzene from 37%. Dorada in the download.

The obtained characteristics are presented in table 1.

Testing of catalyst

The products obtained in examples 1-8, experience in the fluidized bed, using a quartz reactor which contains the catalyst in the amount of 50-100 cm3and which is equipped with a distribution device with a calibrated porosity, also made of quartz, and has an area for pre-heating of ethylbenzene, mixed with the inert product.

Extender, also made of quartz, is placed in the head part of the rector. It reduces the speed of the exit stream, providing the fall of small particles back into the catalyst bed. The temperature in the expander support level 200oC by placing it in an electrically heated furnace to avoid condensation of styrene, unreacted ethylbenzene and non-condensable by-products formed during the flow of the main reaction. The catalytic cycle, which is carried out in such a way as to mimic the behavior of an industrial reactor consists of a reaction phase, which serves ethylbenzene with an inert product within 10 minutes, the phases of deformirovaniya a duration of 15 minutes, where PR is giving 45 minutes serves regenerating gas, consisting of air, phase flushing with nitrogen for a duration of 10 minutes of the recovery phase, where over 4 minutes served regenerating gas consisting of methane, for recovery of hexavalent chromium, which is formed at the stage of regeneration, phase nitrogen leaching duration of 20 minutes, followed by reaction phase with a duration of 10 minutes.

In accordance with the requirements of the industrial way of dehydrogenation fluidized bed, the regeneration should be carried out at temperatures which are higher than the reaction temperature in the catalytic tests the regeneration and restoration is carried out at 660oC, whereas the reaction is carried out in the temperature range of 550-600oC.

The total gas flow rate, expressed as normal liters of benzene plus normal liters of inert product (gas phase), supported 6005 N/h/l catalyst layer.

In the first catalytic test, each catalyst prior to the reaction of dehydrogenation restore the already described method.

Ethylbenzene and nitrogen and/or hydrogen or any inert gaseous product is metered into the reactor by volume. For ativan the che use pre-calibrated rotameters.

Before the introduction of the catalytic layer ethylbenzene used together with an inert product is fed into the evaporator, operating at a temperature of 200oC and installed under the furnace in which the reactor. The evaporator is hermetically connected to the reactor. Evaporated and inert products before introduction into the catalytic layer is heated in a special pre-heating zone.

The stream exiting the reactor during the reaction phase and deformirovaniya, cooled in a trap immersed in liquid nitrogen, in which unreacted ethylbenzene, styrene and condensation by-products are condensed. The stream exiting the traps sent to vakuumirovaniya bag, which produce hydrogen, inert product and light C1-C3-hydrocarbons formed by cracking reactions.

Liquid fraction is weighed and analyzed by gas chromatography using a gas chromatograph hp 5890 equipped with a capillary column CP WAX 10. Dosing of the components is performed using the internal standard method.

The gas separated in the bag, analyzed by gas chromatography using a gas HRO what etzikom for estimation of material balance. Coke deposited on the catalyst is burned with air, and leaving the reactor stream is collected in vakuumirovaniya bag of the same type, which is used when carrying out the reaction phase.

The gas is analyzed by gas chromatography for dosing the concentration of CO2and measure its volume to determine the amount of coke formed by carrying out the reaction phase.

The received data is recorded in a personal computer to calculate the material balance conversion and selectivity to different products.

1. Catalytic system for the dehydrogenation of ethylbenzene to styrene containing chromium oxide, alkali metal oxide, silicon dioxide and aluminum oxide, characterized in that it further contains tin oxide as a carrier, alumina in Delta or theta phase or in a mixture of Delta + theta or theta + alpha or Delta + theta + alpha phases, modified with silica, and chromium expressed as Cr2O3present in an amount of from 6 to 30 wt.%, tin, expressed as tin oxide, is present in amounts of from 0.1 to 3.5 wt.%, alkali metal, expressed as M2O, is present in an amount of from 0.4 to 3 wt.%, silicon dioxide presence, trichomania the fact that chromium expressed as Cr2O3present in an amount of from 13 to 25 wt.%, tin expressed as SnO, is present in amounts of from 0.2 to 2.8 wt.%, alkali metal, expressed as M2O, is present in an amount of from 0.5 to 2.5 wt.%.

3. The catalytic system under item 1 or 2, characterized in that the alkali metal is potassium.

4. The catalytic system under item 1 or 2, characterized in that the carrier has a surface area less than 150 m2/,

5. The method of dehydrogenation of ethylbenzene to styrene, comprising the interaction of ethylbenzene with the catalyst system in the reactor and the regeneration of the catalyst by burning the coke, characterized in that the catalytic system used catalytic system according to any one of paragraphs.1 - 4, reactor support pressure from 0.1 to 3 ATM, and the hourly average gas flow rate from 100 to 10000 h-1and regeneration is carried out in the regenerator at temperatures above 400oC.

6. The method according to p. 5, characterized in that the catalytic system is diluted with an inert product when the weight concentration of the catalytic system is from 5 to 50%.

7. The method according to p. 6, characterized in that the inert product is and silicon dioxide.

8. The method according to p. 5, characterized in that together with ethylbenzene serves inert gas.

9. The method according to p. 8, characterized in that the volume ratio of inert gas/ethylbenzene is from 1 to 6.

10. The method according to p. 9, characterized in that the volume ratio of inert gas/ethylbenzene is from 2 to 4.

11. The method according to p. 5, characterized in that the reactor and the regenerator are the reactor and the regenerator fluidized bed.

12. The method according to p. 11, characterized in that the dehydrogenation is carried out at a temperature of from 450 to 650oC, atmospheric pressure or slightly above, when the speed of the feed gas (GHSV) of from 100 to 1000 h-1and residence time of the catalyst in the zone of the fluidized bed of from 5 to 30 minutes

13. The method according to p. 12, characterized in that the gas flow rate ranges from 150 to 200 h-1, and the residence time of the catalyst varies from 10 to 15 minutes

14. The method according to p. 11, wherein the regeneration is carried out using air or oxygen or other support combustion gas at a temperature that is above average reactor temperature, at atmospheric pressure or slightly below, the residence time of the solid components from 5 to 60 min and feed rate g

 

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