The method of dehydrogenation of alkyl-aromatic compounds, a method of dehydrogenation of ethyl benzene or substituted benzene and the reactor dehydrogenation of alkyl-aromatic compounds

 

Application: extraction of aromatic compounds. Essence: spend the interaction of alkylaromatic compounds, such as ethylbenzene, in the reactor with a fluidized bed with a dehydrogenation catalyst in a dehydrogenation zone with getting vinylaromatic compounds, such as styrene, and regeneration of the catalyst in place by interaction of the pair with the deactivated catalyst in the regeneration zone. The specified reactor fluidized bed is characterized by the area above the layer of the reaction zone and the regeneration zone of the catalyst, all of which are within a single housing. Technical result: effective regeneration of the catalyst in place. 3 N. and 35 C.p. f-crystals, Fig 3.

In one aspect this invention relates to a method for the dehydrogenation of alkylaromatic compounds, such as ethylbenzene, education vinylaromatic compounds, such as styrene. Additionally this invention relates to a method of regeneration of catalyst used in the process of dehydrogenation of alkylaromatic compounds. In another aspect this invention relates to a reactor with a fluidized bed, in which Pro is of such compounds, such as ethylbenzene, isopropylbenzene, diethylbenzene, p-atilola, finds application upon receipt of styrene and substituted derivatives of styrene, such as-methylsterol, divinylbenzene and p-methylsterol. Styrene and its substituted derivatives applicable as monomers for the formation of polystyrene, styrene-butadiene rubbers (SBC), Acrylonitrile-butadiene-styrene (ABS), styrene-Acrylonitrile (SAN) resins based on unsaturated complex polyester.

The fluidized bed reactor is important in many diverse catalyzed organic processes, including the processes of dehydrogenation.

The main way of production vinylaromatic compounds, such as styrene, is the direct catalytic delegationen alkylaromatic compounds, such as ethylbenzene. Patents disclosing such a process include, for example, U.S. patents 4404123, 5171914, 5510552 and 5679878. The catalyst typically contains iron oxide and optionally may contain an oxide of chromium and potassium compounds such as potassium hydroxide or potassium carbonate, as promoters. Because the process is vysokoenergichnym, the energy for the process is provided by the introduction of superheated steam into the reactor per°C and 700°C. Adverse reactions can be limited by maintaining a low partial pressure of ethylbenzene.

The use of a reactor with a fixed bed for the specified processes of dehydrogenation has some drawbacks. First, a reactor with a fixed bed, which is characterized by a fixed bed of catalytic particles, it is uniformly heated to a high temperature. When the endothermic dehydrogenation of ethylbenzene to styrene located downstream end (outlet) of the fixed catalyst layer tends to be colder than the upstream end (inlet) of the catalytic layer. As the temperature difference can reduce the conversion of ethylbenzene to below the downstream end of the reactor, the flow of the source material is typically heated to a higher temperature than is desirable. As a consequence, the catalytic layer near the entrance to the reactor may be overheated and usually breaks down faster than the catalyst further downstream. In such conditions requires a large catalytic layer to withstand a prolonged cycle. On the other hand, in the process of dehydrogenation of ethylbenzene to styrene in a fixed bed at the same time with ethylbenzo is but require a high mass ratio of steam to ethylbenzene, usually more than 1.2 to 2.0, and perhaps higher, which adversely process imposes high energy costs and greater recycling of water. The mass ratio of steam to alkylaromatic compound referred to hereafter as "the ratio of steam to oil". When the total activity of the layer falls below the point of practicality, the catalyst must be replaced. As an additional disadvantage of the reactor with fixed bed usually stop for a few weeks to replace the catalytic Converter.

Other sources, such as U.S. patents 3651146 and 4471146, reveal the process of oxidative dehydrogenation, where ethylbenzene is brought into contact with oxygen in a reactor with a fluidized bed in the presence of a catalyst for oxidative dehydrogenation, for example the mixed phosphate of the alkali earth metal and Nickel, or a composite material of an alkaline metal oxide of chromium, to obtain styrene. Normal reactor fluidized bed contains a single reaction zone, where the catalyst particles are separated and circulate. Compared to fixed bed reactors, fluidized bed provide a more isothermal temperature distribution. Isothermal catalytic layer generally causes less bredagh to replace the catalyst, when it is fully deactivated and unable to regenerate. As the catalyst is treated as a liquid, the deactivated catalyst can be unloaded from the reactor, and the active catalyst may be added to the reactor without interrupting the chemical process. The process of oxidative dehydrogenation can also be carried out while continuously moving a portion of the catalyst in the regenerator for regeneration in oxygen atmosphere and then recycling the regenerated catalyst back to the reactor for oxidative dehydrogenation.

The disadvantage is that the process of oxidative dehydrogenation with simultaneous submission of alkylaromatic compounds and oxygen can provide low outputs vinylaromatic product, because it is more difficult to regulate adverse reactions oxidation. In addition, the security issues arising in connection with the transportation and processing of mixtures of organic compounds and oxygen, are significant. As an additional disadvantage is the continuous circulation of the catalyst between the reactor process with fluidized bed and the regenerator requires sophisticated equipment and often requires catalyst particles with high with whom and with migration for the dehydrogenation of ethylbenzene to styrene in the absence of oxygen and in the presence of a catalyst for oxidative dehydrogenation, such as silicon dioxide, modified magnesium, or are able to recover the vanadium oxide on a carrier of a metal oxide.

These processes eliminate the danger of the use of mixtures of alkylaromatic compounds and oxygen, however, the service life of such catalysts is short. Therefore, the catalyst must be continuously circulated between the reactor and regenerator, where the catalyst is regenerated in an oxygen atmosphere. As noted above, the continuous recirculation of the catalyst between the reactor and regenerator requires sophisticated equipment and often requires catalyst particles with high resistance to abrasion.

The above description confirms the need for improved processes for the catalytic dehydrogenation. It would be useful, for example, to open the process of dehydrogenation of alkylaromatic compounds, such as ethylbenzene, to vinylaromatic compounds, such as styrene, which provides an efficient regeneration of the catalyst in place when economically advantageous ratio of steam to oil. It would be helpful if during the process of the deactivated catalyst could be replaced by an active catalyst without you is ogla be provided with an isothermal temperature of the layer. It would also be helpful if the process did not require oxygen, which complicates the security and procedures transportation. And finally, the process would be more desirable if they would have had all of these features and also gave a high yield of vinylaromatic connection.

In another aspect of U.S. patent 4152393 discloses a reactor consisting of a single housing that contains a reaction zone and a regeneration zone, located so specifically as a set of concentric walls and walkways that powdered solid substance can be transported with the gas stream from the regeneration zone into the reaction zone by the first and then back to the regeneration zone by the second. Gases passing through the regeneration zone is not transferred to the reaction zone, and the gases passing through the reaction zone, are not transferred to the regeneration zone. The patent States that such a reactor suitable for the ammoxidation of propylene.

The specified reactor can detect high flow of slag, which is characterized by bubbles of gas flowing along the inner walls of the reactor. The flow of slag adversely reduces the contact between the reagents in the gas phase and the particles of the solid catalyst, thereby reducing the efficiency of the process. In the gas nozzles within the above-mentioned gaps, what can cause severe abrasion of the catalyst particles. U.S. patent 6048459 discloses a method of fluidization of the material powder layer, providing for picking up and lifting part of the fluid above the fluidized bed and the recirculation raised the fluid above the layer through Protocol tube, located inside the layer. Area powdery material may be distributed under fluidized bed for use, in particular for treatment of anaerobic sludge for a long time.

In one aspect this invention relates to a method for the dehydrogenation of alkylaromatic compounds over a dehydrogenation catalyst in a single reactor with a fluidized bed to education vinylaromatic compounds and regeneration of the dehydrogenation catalyst in place. The method according to the invention contains in the first stage (a) fluidization of the dehydrogenation catalyst in a single reactor with a fluidized bed containing a reaction zone and a regeneration zone, in the conditions of fluidization so that the catalyst circulates within and between the two zones; (b) interaction of alkylaromatic compounds, and possibly a couple with a dehydrogenation catalyst, m is unity, and (C) the interaction of the pair with the dehydrogenation catalyst in the regeneration zone, the interaction is carried out in the regeneration conditions sufficient to regenerate the catalyst, at least partially.

The way dehydrogenation according to this invention, which is used to obtain vinylaromatic compounds of industrial importance, such as styrene, p-methylsterol,-methylsterol and divinylbenzene, has significant advantages over previously known processes. First, the method according to this invention does not use oxygen. Therefore, the security issues associated with transported and processed mixtures of organic compounds and oxygen, which are found in some of the previously known processes, is eliminated in the method according to this invention. Secondly, in the method according to this invention the ratio of steam to oil favorably lower than the ratio used in processes with a fixed layer of the prior art. Therefore, the method according to this invention uses less water recirculation and is more energy efficient and more economical than processes of the prior art. In caches layer, is essentially isothermal. The problems associated with uneven temperatures of the layer, such as overheating and damage to the catalyst on the upstream end of the catalytic layer and the lower performance on the downstream end of the catalytic layer is essentially eliminated. In addition, reduced thermal formation of side product. As an additional advantage of the method according to this invention can be used catalytic layer is smaller compared with the size of the catalytic layer used in a fixed bed processes of the prior art, while still achieving comparable cycles of the process. As another advantage of the method according to this invention provides a continuous regeneration of the dehydrogenation catalyst in place. When implementing the method according to this invention it is not necessary to interrupt the operation of the reactor for catalyst regeneration or to transfer catalyst from the reactor fluidized bed in the regenerator. Thus, the method according to this invention is simple in implementation and design execution. Moreover, the catalyst used in the method, the finally, when the catalyst is not capable of further regeneration method according to this invention provides for the replacement of the deactivated catalyst in a continuous process of dehydrogenation. As the solid catalyst is treated as the fluid, the deactivated catalyst is simply transported from the reactor and fresh catalyst is transported into the reactor during operation. Thus, regeneration, and replacement of the catalyst can be carried out without stopping the dehydrogenation process, resulting in increased performance. Most advantageously, when the method according to this invention receives vinylaromatic compound, preferably styrene, with a high output.

In another aspect this invention relates to a reactor with a fluidized bed, which allows you to simultaneously carry out a chemical process and the regeneration of the catalyst. A reactor with a fluidized bed contains a single vertical housing, the inner space of which is divided into the area above the layer of the reaction zone and a regeneration zone. The reactor also includes an inlet device for introducing a flow of the source material for regeneration in the regeneration zone and the inlet proposal to separate zones of the reaction and regeneration, allowing at the same time, a continuous circulation and reverse mixing of the catalyst on an industrial scale between the two zones. In a preferred embodiment, one of the inlet devices for flow of the source material for the reaction or regeneration acts as a device for the separation zones of the reaction and regeneration. The reactor according to this invention also includes a discharge device, preferably in the area above the layer, to remove the waste stream containing products and any neprevyshenie reagents and starting materials for regeneration. Optionally, the reactor further comprises a device for returning the catalyst particles captured by the exhaust stream back to the reactor. Optionally there can also be an inlet fixture and outlet devices for transportation of catalyst in the reactor and out of him.

In the reactor according to this invention may occur cross-mixing of the streams of the source reagent material and material for regeneration, although, preferably, the location of the inlet holes of the materials for the reaction and regeneration essentially must divide both processes. However, although this design is and will be chemically compatible, as explained here, with the current process of dehydrogenation-regeneration.

A reactor with a fluidized bed according to this invention can be used with a variety of catalyzed organic processes, including, for example, the processes of dehydrogenation, oxidation and halogenation. Especially important dehydrogenation process, which can be used in a reactor with a fluidized bed according to this invention, contains the dehydrogenation of alkylaromatic compounds, such as ethylbenzene, to vinylaromatic compounds, such as styrene. Advantageously, the reactor fluidized bed according to this invention provides a reaction zone of a chemical process and a regeneration zone of the catalyst within a single reactor with a fluidized bed. Thus, regeneration of the catalyst can be achieved simultaneously with the desired chemical process. There is no need to transport the deactivated catalyst from the reactor with a fluidized bed according to this invention in a separate vessel for regeneration, thus the catalyst is subjected to much less stress and damage than it happens in the reactors with the transfer. In process quality by simply transporting the deactivated catalyst from the reactor and transportation of fresh catalyst to the reactor. These benefits provide the necessary improvements in the design process fluidized bed.

Fig.1 shows the side and top views of the cross-section of the first preferred variant of the reactor with a fluidized bed according to this invention, the details of which are explained next.

Fig.2 shows side and top views of the cross-section of a second preferred variant of the reactor with a fluidized bed according to this invention, the details of which are explained next.

Fig.3 represents a graph of the conversion of ethylbenzene and selectivity to styrene as a function of time of the experiment process for dehydrogenation of ethylbenzene and regeneration of the catalyst is carried out in the reactor of pulsating action.

In one aspect this invention relates to a method for the dehydrogenation of alkylaromatic compounds over a dehydrogenation catalyst in a single reactor with a fluidized bed to education vinylaromatic connection and regeneration at the site of the dehydrogenation catalyst. The method according to this invention contains (a) fluidization of the dehydrogenation catalyst in a single reactor with a fluidized bed containing a reaction zone and zones. In the second stage, which is carried out simultaneously with the first stage, the method comprises (b) interaction of alkylaromatic compounds and may couple with the dehydrogenation catalyst in the reaction zone, under conditions of reaction sufficient to obtain the corresponding vinylaromatic connection. At the third stage, which is carried out simultaneously with the first and second stages, the method comprises (C) interaction of the pair with the dehydrogenation catalyst in the regeneration zone, the interaction is carried out in the regeneration conditions sufficient to regenerate at least part of the catalyst.

In the process of fluidized bed according to this invention at any given time a portion of the catalyst is circulated in the reaction zone, while essentially all of the remaining catalyst is circulated in the regeneration zone with some mutual mixing at the boundary of two zones. During the residence time in the reaction zone, the catalyst loses its activity and become partially or completely deactivated. Decontamination, mainly, can be caused by a buildup of coke on the catalyst surface. The invention, however, should not bind or Litvinovsky catalyst, will circulate in a regeneration zone. The deactivated catalyst in the regeneration zone will be re-activated in contact with the steam. Reactivation results in partial or essentially complete recovery of catalyst activity compared to the activity of fresh unused or newly synthesized" catalyst. Since that time, in the conditions of the fluidized regenerated catalyst in the regeneration zone will be recirculated to the reaction zone, and the cycle of reaction-regeneration will be repeated again and again. The above description is given as a means to explain the cycle of reaction-regeneration and definition for words "to regenerate, at least partially, the catalyst".

It should be also clear that after repeated reaction and regeneration comes a time when the catalyst cannot be regenerated to a practical level even with the procedure of regeneration. When this happens, the deactivated catalyst can be replaced simply by transporting it from the reactor and transporting of fresh catalyst to the reactor, preferably at the same time. In the reactor according to this invention the Deputy of the present invention is the process of dehydrogenation. The catalyst may be transported into the reactor and out through the air nozzle or the contour of the pneumatic transfer. Alternatively, the catalyst may be removed from the reactor through driven by gravity discharge device at the bottom of the reactor, and the catalyst may be added to the reactor from the inlet fixture type standpipe at the top of the reactor.

In a preferred aspect of the present invention alkylaromatic compound is ethylbenzene or substituted derivative of benzene, and the resulting vinylaromatic compound is styrene.

Any alkylaromatic compound can be used in the method of dehydrogenation according to this invention, provided that the resulting product is vinylaromatic connection. The aromatic portion of the molecule vinylaromatic compounds may contain, for example, monocyclic aromatic ring, such as phenyl; condensed aromatic ring such as a naphthyl; or the Association of the rings, such as biphenylyl. Preferably, the aromatic part of the molecule is a monocyclic aromatic ring, more preferably phenyl. Alkyl cha the config or cyclic hydrocarbon radical, provided that it can be digidrirovanny in the method according to this invention with the formation of the vinyl part of the molecule. Non-restrictive examples of suitable alkyl parts of molecules include ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the higher homologues. Preferably, the alkyl part of the molecule is a C2-C10alkyl, more preferably C2-C5alkyl, most preferably ethyl. Alkylaromatic compound may be optionally substituted by two or more altergroup or replaced by other types of substituents, which are essentially inert in respect of the dehydrogenation process according to this invention. Examples of alkylaromatic compounds, which are advantageously used in the method according to this invention, include, without limitation, ethylbenzene, diethylbenzene, atilola, ethicial, isopropylbenzene, tert-mutilative, ethylnaphthalene, ethylbiphenyl and higher alkylated homologues. Preferably, the alkylaromatic compound is a C8-C20alkylaromatic compound, more preferably C8-C15alkylaromatic compound and most preferably ethylbenzene or theoderic pairs. Optional steam can also be introduced into the flow of the source material for the dehydrogenation. Any mass ratio of steam to alkylaromatic compound (the ratio of steam to oil) is suitable for the method according to this invention, provided that in its implementation, receive vinylaromatic connection. It should be noted that the ratio of steam to oil given on the basis of the total mass of steam introduced into the reactor from all sources, including pairs of both raw material streams for dehydrogenation and regeneration. Typically, the mass ratio of steam to oil more than about 0.2/1, preferably more than about 0.5/1. Typically, the mass ratio of steam to oil is less than about 5.0/1, preferably less than about 3.0 a/1, even more preferably less than about 1.2/1, and most preferably less than about 1.0/1. Generally, the method according to this invention is carried out at a lower respects steam to oil compared with processes of the prior art. Low ratio of steam to oil advantageously reduces the energy requirement and cost of turning water into steam and reduces the amount of water being recirculated to the reactor.

In the method according to this invention may not necessarily be what eactor, operates mainly in order to remove the product stream from the zone above the layer, which can occur undesirable thermal reactions. Any gas which is essentially inert with respect to the processes of dehydrogenation and regeneration, can be suitably used as processaudio gas, including, for example, nitrogen, argon, helium, carbon dioxide, steam, and mixtures thereof. Concentration processaudio gas in the area above the layer can be of any concentration, provided that the full process is desirable vinylaromatic connection. Typically, the concentration processaudio gas varies depending on, for example, from specific alkylaromatic compounds and specific process conditions, in particular temperature and gas velocity. Generally the concentration of processaudio gas in the area above the layer of more than about 10 volume percent and preferably more than about 20 volume percent. Generally the concentration of processaudio gas in the area above the layer is less than about 90 volume percent and preferably less than about 70 volume percent.

Optional thread(s) source material for the dehydrogenation and/or for regeneration may also contain a diluent. The diluent main is Any gas, which is essentially inert in relation to the stages of dehydrogenation and regeneration, can be suitably used as diluent, such as nitrogen, argon, helium, carbon dioxide, steam, and mixtures thereof. The concentration of the diluent in the flow of the source material or dehydrogenation, or for regeneration can be any concentration, provided that full process gives the desired vinylaromatic connection. Typically, the concentration of diluent varies depending on, for example, from a particular diluent, specific alkylaromatic compounds, the specific conditions of the dehydrogenation process or regeneration, and the particular catalyst and its properties decontamination. Typically, the concentration of diluent in the flow of the source material for the dehydrogenation or recovery of more than about 10 volume percent and preferably more than about 20 volume percent. Typically, the concentration of diluent in one of the two streams of less than about 90 volume percent, preferably less than about 70 volume percent. When a diluent is used pairs, then the ratio of steam to oil, described above, determines the concentration of vapor in the flow of the source material for sportsouth in the method according to this invention.

Any dehydrogenation catalyst, which is able to catalyze the dehydrogenation of alkylaromatic compounds to vinylaromatic compounds can be used in the method according to this invention. Non-restrictive examples of dehydrogenation catalysts which can be advantageously used include the catalysts described in the following U.S. patents: 4404123, 4503163, 4684619, 5171914, 5376613, 5510552 and 5679878 that are relevant to a variety of catalysts based on iron oxide containing, for example, one or more compounds of alkali metals, preferably sodium, potassium and cesium; alkaline earth metals, preferably calcium and/or compounds of cerium, chromium, zinc, copper and/or gallium, as well as the catalyst described in U.S. patent 3651160, which refers to the chromium oxide and the oxides of alkali metals. Preferably, the catalyst is a dehydrogenation catalyst containing iron oxide. More preferably, the catalyst contains (a) at least one oxide of iron, (b) at least one carbonate, bicarbonate, oxide or hydroxide of potassium and/or cesium, (C) an oxide, carbonate, nitrate or hydroxide of cerium, (d) optionally a hydroxide, carbonate, bicarbonate, acetate, oxalate, nitrate only binding agents, such as hydraulic cement. As additional features of the preferred catalyst may optionally contain one or more oxides selected from oxides of zinc, chromium and copper. Usually the preferred catalyst contains from 25 to 60 weight percent iron, from 13 to 48 mass% of potassium and 1 to 20 weight percent cerium, weight percents are based on the oxides. These proportions and different proportions of suitable catalyst components described in the aforementioned U.S. patents.

The dehydrogenation catalyst used in the reactor with a fluidized bed according to this invention may be particles of any size or shape as long as the catalyst is capable of catalyzing the dehydrogenation of alkylaromatic compounds to vinylaromatic connection. Usually, the average particle size of the catalyst is more than about 20 micrometers (μm) in diameter (or cross-sectional dimension) and preferably more than about 50 microns in diameter. Usually, the average particle size of less than about 1000 microns and preferably less than about 200 microns. Preferably, the catalyst particle is smooth with rounded edges and essentially nechesina and region must be known, is there a specific catalyst sufficient abrasion resistance for use in a reactor with a fluidized bed.

If desirable, the flow of the source material for the dehydrogenation may be preheated before introduction into the reaction zone. Warming may be suitably provided by the condensation of saturated steam of high pressure or, alternatively, by burning a fuel source or off-gas process. Any temperature may be used provided that it is below the temperature at which thermal cracking of alkylaromatic compounds becomes measurable. The usual preheating temperature higher than about 150°C., preferably higher than about 250°C. and more preferably higher than about 350°C. Conventional preheating temperature lower than about 600°C. and preferably lower than about 590°C. in this way the flow of the source material for regeneration may be preheated before introduction into the regeneration zone. The normal temperature of the heated stream for regeneration is higher than about 200°C., preferably higher than about 300°C. and more preferably higher than about 400°C. the temperature of the heated stream for regeneration is usually lower than the eye of the form in the method according to this invention, is a reactor with a fluidized bed shown in Fig.1, containing a single vertical housing, the inner space of which is divided into a regeneration zone (1), the reaction zone (2) and the area above the layer (3). The regeneration zone, placed in this preferred embodiment, on the bottom of the reactor, contains the area where the catalyst is regenerated. The reaction zone located in this preferred embodiment, in the Central zone of the reactor, is an area where there is catalyzed organic chemical process, such as the dehydrogenation process described here. The area above the layer, located in the upper part of the reactor, occupies the space above the middle zone up to the top of the inner wall of the reactor. The area above the layer occupied by the gaseous reactants and products, also provides space for expansion of the fluidized bed. In the area above the layer can occur in the gas-phase thermal reactions, but the conditions of process support is preferably such that to minimize these gas-phase reactions towards catalyzed process occurring in the reaction zone.

The regeneration zone in Fig.1 includes an inlet device for introducing a flow of the source material to keep, for example, the inlet opening (4), which leads to the discharge part (10), which is a distribution plate or set of nozzles (9). The area above the layer contains an inlet device (5), containing, for example, the inlet opening and the feeding tube, for introducing a flow of the source reagent material, here the flow of the source material to dehydrogenation in reaction zone. In Fig.1 and 2, the intake device for the regeneration zone is shown in the lower part of the figure, and the intake device for the reaction zone is shown in the upper part of the figure. In practice, the inlet device of the regeneration zone may be located elsewhere, provided that it leads to a regeneration zone. Similarly, the intake device of the reaction zone may be located elsewhere as the reactants enter the reaction zone.

Preferably, the suction device (5) ends with many sprinklers or distributor (6) in the reaction zone, located more preferably at a level above the bottom of raspredeliteli (9) pair. The distributor or multiple sprinklers (6) preferably are designed to deliver flow of the source material for the reaction in any napravlenie reagent may vary, to provide variable amounts in areas of regeneration and reaction, when you need it. The larger the area, the longer is the residence time of gases and solids in this area. As described herein, the distribution device (6) provides functional distinction between the regeneration zone and the reaction zone so that the regeneration process essentially takes place in the regeneration zone, while organic process essentially takes place in the reaction zone, although still allowed back mixing of solids and gases. Distributors of gas and many sprinklers can be manufactured, for example, from a gas-permeable sintered metal or, more preferably, the gas distributors and spreaders can be equipped with nozzles for dispersing gas. The area above the layer also contains an exhaust device (7), such as the outlet for the waste stream containing neprevyshenie alkylaromatic compound, vapour, optional procissi gas and/or diluent and products, including vinylaromatic connection. The discharge device (7) can be attached to the cyclone (shown in Fig.1 below the outlet 7) for collecting particles catalyti fluidized bed via the input device (8), located at any point along the reactor, but preferably as shown in Fig.1, in the regeneration zone. The discharge device (7) can be optionally attached to a separating unit (not shown in Fig.1), containing, for example, devices for condensation and distillation unit for the separation neprevyshenie alkylaromatic compounds and reaction products. Neprevyshenie reagents can be recycled back into the reaction zone through the inlet (5). In addition to the specified reactor may contain means for measuring the temperature of the catalytic layer and, optionally, means for heating the reactor (not shown). The reaction zone and the regeneration zone may also contain reflective walls (not shown), which function to reduce the formation of bubbles and their size, thereby facilitating contact between the gaseous flow of the source material and the catalyst.

In another preferred embodiment of the present invention a reactor with a fluidized bed further comprises one or more devices to improve the circulation of solids and heat transfer. In a preferred embodiment, the device for laying the Foundation for the Rennie reflective walls. Alternatively, a device for improving circulation of solids contains one or more suction pipes made from any heating or cooling elements. The embodiment of the invention, containing a lot of suction pipe shown in Fig.2 (parts 1-10 Fig.2 identical parts 1-10 Fig.1). The suction pipe (11) can each contain, for example, concentric cylinders, open at both ends, or a beam or set of heating pipes or any other design that promotiom blowing catalyst. Usually the suction pipe vertically suspended, passing through the reaction zone and regeneration to the place near the top of the reaction zone. The flow of the source material for the dehydrogenation fed through the inlet opening (5) in many sprinklers (6) and down to the inner cylinder of the suction pipe (11) in the reaction zone. Under the influence of the conditions of fluidization of the catalyst particles will fall into the inner circumference of the suction pipe and be carried to the top of the suction pipe. At the top of the catalyst particles will flow through the output part of the inner cylinder and down through the annular gap between the two cylinders back into the regeneration zone.

In addition to indicated the Ana) for transportation of the catalyst in the reactor and out, respectively.

In another embodiment, a reactor with a fluidized bed of the reaction zone and the regeneration can be placed in reverse order, so that the reaction zone is at the bottom of the reactor, while the regeneration zone is in the middle part of the reactor. (Fig.1, where the reaction zone is at (1), the regeneration zone is at (2) and inlets in them adapted accordingly.)

The reactor according to this invention can be used in catalytic processes, where the flow of the source reagent material chemically compatible with the flow of the source material for regeneration. The unique reactor according to this invention provides a continuous flow of catalyst particles between the reaction and regeneration within a single reactor with a fluidized bed. Thus, catalyzed organic process of interest, and regeneration of the catalyst can be carried out simultaneously without transferring catalyst from the reactor in a separate regenerator. The reactor according to this invention does not contain complex concentric walls or winding paths, through which move the particles of the catalyst. Thus, for installations industrial scale reactor according to this invention will not costevective, can be any operating temperature, provided that the process is formed vinylaromatic connection. Operating temperature dehydrogenation will vary depending on the specific catalyst and specific alkylaromatic compounds. For the preferred catalyst containing iron oxide, the temperature of the dehydrogenation is usually higher than about 550°C. and preferably higher than about 570°C. Typically, the temperature of the dehydrogenation of lower than about 650°C. and preferably lower than about 610°C. Below about 550°C. the conversion of alkylaromatic compounds can be too low, whereas above 650°C can occur thermal cracking of alkylaromatic compounds and vinylaromatic product. In this invention the temperature measured on the layer of catalyst in fluidized form.

In the regeneration zone, the catalyst is in contact with steam and re-activated. The temperature of the regeneration zone can also be changed up until the catalyst is at least partially regenerated. Usually the regeneration temperature below the temperature of thermal cracking of alkylaromatic reagent and vinylaromatic product. For the preferred catalyst, the content is. Usually the regeneration temperature is lower than about 650°C. and preferably lower than about 610°C. as the catalyst is continuously circulated between the reaction and regeneration and the temperatures of the two zones support with closely similar values, a fluidized bed is essentially isothermal throughout both zones.

The process can be conducted at any workplace total pressures ranging from below atmospheric to above atmospheric is provided that is formed vinylaromatic product. If the total pressure in the reactor is too high, the equilibrium of the dehydrogenation process may move back in the direction of alkylaromatic compounds. On the other hand, you need adequate steam pressure to slow the coking of the catalyst. Preferably, the process is carried out in vacuum, in order to maximize the output vinylaromatic product. When the mass relations of steam to oil described herein previously, the pressure below atmospheric sufficient to regenerate the catalyst at least partially. Preferably, the total pressure in the reactor is higher than about 1 psi (6.9 kPa). More preferably, the total pressure in the reactor is higher than about 3 pounds per square duistere, the total pressure is less than about 44 pounds per square inch (303,4 kPa). Most preferably the total pressure below atmospheric in the range between about 3 psig (20.7 kPa) and about 13 pounds per square inch (90,6 kPa). Pressure over the area above the layer and areas of the reaction and regeneration may vary depending on factors, such as the weight and buoyancy of the catalyst and frictional effects. Typically, the pressure is slightly higher at the bottom of the reactor than at the top.

The volume flow rate of the source material for the dehydrogenation will depend on the specific alkylaromatic compounds and catalyst formed concrete vinylaromatic product, the dimensions of the reaction zone (e.g., diameter and height) and shape and mass of catalyst particles. It is desirable to rapidly remove the reagent and products from the zone above the layer in order to reduce thermal cracking and other undesirable side reactions. In addition, the gas flow should be sufficient to cause fluidization of the catalytic layer. Typically, the volume flow rate of the source material for the dehydrogenation varies from the minimum speed required to achieve fluidization of the catalyst particles to the speed of authoritie happens when the catalyst particles not linked to each other, when the particles move like a fluid when the pressure drop in the layer essentially constant along the layer. Pneumatic transfer occurs when a significant number of catalyst particles is captured gas stream and is taken out of the reactor. Preferably, the volume flow rate of the source material for degidrirovanie varies from minimum speed ozonation to minimum speed turbulent flow. Bubbling occurs when gas bubbles can be seen in the fluidized bed, but there is a small reverse mixing of gas and solids. Turbulent flow occurs when and significant bubbling, and substantial back mixing of gas and solids. More preferably, the flow rate should be high enough to cause the opposite mix.

As the main guide measured under operating conditions hourly space velocity of gas (COG), calculated as the total flow rate of the source material for the dehydrogenation, including the costs of alkylaromatic compounds and, optionally, steam, processaudio gas and/or diluent, more than about 60 ml of Oia, more than about 120 h-1and more preferably more than 720 h-1. Typically, CASH stream to the dehydrogenation of less than about 12000 h-1preferably less than about 3600 h-1and more preferably less than 1800 h-1measured as the total flow rate at the operating conditions of the process.

As the main guide measured at operating conditions, the gas retention time in the reaction zone, calculated as the height of the reaction zone, multiplied by the void fraction of the reaction zone divided by the gas flow rate per unit flow amount of the raw material streams for recycling and reactions, more than about 0.3 seconds (s). "Void fraction of the reaction zone is a portion of the reaction zone, which is empty. "The gas flow rate per unit cross section of the stream is the flow of gas through the empty reactor. Preferably, measured under the operating conditions of the gas retention time in the reaction zone more than about 1, more preferably more than about 2 C. As a rule, measured under the operating conditions of the gas retention time in the reaction zone is less than about 60, preferably less than about 30 and more preferably less than about 5 C.

Watch the volumetric rate of gas flow source material for regeneration through the zone regenerative fluid. In addition, the volume flow rate of the source material for regeneration can vary from the minimum speed required to achieve fluidization of the catalyst particles to a speed below the minimum speed necessary to achieve the pneumatic transfer of catalyst particles. Preferably, the volume flow rate of the source material for regeneration varies from minimum speed ozonation to minimum speed turbulent flow. Usually measured at the operating conditions hourly space velocity of gas (COG), calculated as the total flux of the source material for regeneration, more than about 60 ml just starting material per ml catalyst per hour (h-1). Preferably, CASH stream for regeneration of more than about 120 h-1and more preferably more than about 360 h-1. Usually measured as the total flow at operating conditions, hourly volumetric rate of gas flow for regeneration of less than about 12000 h-1preferably less than about 3600 h-1and more preferably less than 720 h-1.

In the recovery area, measured at operating conditions, the gas retention time was calculated as the height of the zone of regeneration, annagh materials for regeneration and reaction more than about 0.3 C. "Void fraction zone of regeneration" is part of the regeneration zone, which is empty. Preferably, the residence time of gas in the regeneration zone more than about 1, and more preferably more than about 5 C. As a rule, measured under the operating conditions the residence time of gas in the regeneration zone is less than about 60, preferably less than about 30 and more preferably less than about 10 C.

When alkylaromatic compound and, optionally, steam is brought into contact with the dehydrogenation catalyst thus, as described above, receive vinylaromatic connection. Ethylbenzene becomes predominantly styrene. Atitool turns into p-methylsterol (p-vinyltoluene). Tert-mutilative converted into tert-butalbiral. Isopropylbenzene (cumen) becomes-methylsterol, and diethylbenzene becomes divinylbenzene. During dehydrogenation produces hydrogen. Other products produced with lower outputs include benzene and toluene.

The conversion of alkylaromatic compounds in the process according to this invention may vary depending on the specific composition of the source material, a catalyst composition as molar percentage of alkylaromatic compounds which turned in all products. In the specified process is the conversion of alkylaromatic compounds are usually more than about 30 mol. percent, preferably more than about 50 mol. percent and more preferably more than about 70 mol. percent.

In this way the selectivity to products will vary depending on the specific composition of the source material, the catalyst composition, process conditions and conditions of the fluidized bed. For the purposes of this invention, "selectivity" is defined as the molar percentage turned alkylaromatic compound, which forms a specific product, preferably vinylaromatic connection. In the process according to this invention, the selectivity to vinylaromatic connection, preferably the styrene or substituted derivative of styrene, usually more than about 60 mol. percent, preferably more than about 75 mol. percent and more preferably more than about 90 mol. percent.

The invention will be further clarified by consideration of the following examples, which are intended only to clarify the application of the invention. Other embodiments of the invention will be apparent to special the ü. Measuring the selectivity adjusted to account for the deviation from 100 percent organic material balance.

Example 1

A reactor with a fluidized bed [4.25 inches (10,63 cm) inner diameter, 20 inches (50 cm) height] design, as shown in Fig.1. The reactor contains a single vertical case, functionally divided into three zones: zone (1) regeneration of the catalyst at the bottom of the reactor zone (3) above the layer at the top of the reactor and (2) reactions in the middle part between the regeneration zone and the area above the layer. The first inlet (4) at the bottom of the reactor leads to the discharge area (10) where is the distributor (9) gas. Specified the first inlet is used to distribute the flow of source material for regeneration in the regeneration zone. The second inlet opening (5) located in the area above the layer, used for the introduction of flow of the source material to dehydrogenation zone (2) reaction. A second inlet connected to the intake pipe, which ends in many sprinklers (6) in the reaction zone at a height of 3 inches (7.5 cm) above the bottom of the distribution plate (9). Many sprinklers in six rows of tubes of sintered metal [Inconel, 1/4 inch VD (6.3 mm is s holes in the spray horizontally placed. The outlet opening (7) is located in the area above the layer for removal of the product stream. Solids captured product stream is collected in the cyclone (located below the outlet 7) and then returns to the reactor through the third inlet hole (8) in the zone of regeneration. Exhaust gases are collected downstream from the cyclone. The reactor is also equipped with electric resistance for heating the reactor and two internal thermocouples (K type) for measuring the temperature of the fluidized bed in the reaction zones and regeneration.

The reactor used for the dehydrogenation of ethylbenzene in the presence of a catalyst dehydrogenation to styrene with simultaneous and continuous regenerierung dehydrogenation catalyst. The dehydrogenation catalyst (2370 g) having an average particle diameter of 300 μm and containing 28.7 percent of iron oxide (Fe2O3), 14.3 percent of cerium oxide (CE2About3), 7.6 percent of copper oxide (CuO), 31.6% of potassium carbonate (K2CO3), 0.6 percent of oxide of chromium (CR2O3), 9.5 percent of zinc oxide (ZnO) and 7.6 percent of cement by weight, loaded into the reactor. The flow of the source material for the reaction contains a mixture of ethylbenzene and PA is the first chromatograph Carle, equipped with a parallel row of five columns (2.7 percent Carbowax1540 on Porasil C; 3% Carbowax1540 on Porasil C; 27 percent Bis(ITS)AND on ChromosorbPAW; PorapakQ and two columns H molecular sieves). Liquid products are analyzed by gas chromatograph HP 5890 equipped with a column DB-5 (J&W as an internal standard for gas analysis using nitrogen, while for fluid analysis as an internal standard using heptane. Sampling is carried out for six hours, taking four or more samples every 30 min for the last few hours. Results presented here for the conversion of ethylbenzene and selectivity to styrene are average of four or more of the samples.

In the above-described reactor water when the feed speed 4.3 cm3/min at room temperature, heated to 600°C and is added through the inlet opening (4) in the discharge region (10) and through the distribution plate (9) in the zone (1) regeneration at the bottom of the reactor. Liquid ethylbenzene in the feed speed of 2.5 cm3/min and nitrogen gas at a feed speed 1088 cm3/min at room temperature mix is abrasyvatelej (6). Feed speed correspond to the mass of the entire steam to oil 2/1 with surface speed of 1.86 m/min in the recovery area, and 237 m/min in the reaction zone. The residence time of gas in the regeneration zone of 1.46, the gas retention time in the reaction zone 0,67 C. the Temperature and pressure in the reactor support at 600°C and 15.5 pounds per square inch (106,9 kPa), respectively. The products obtained via the outlet port (7) analyze, as described above. The conversion of ethylbenzene is 74,0 mol. percent. The selectivity to styrene is 86,0 mol. percent. Other products contain benzene and toluene. The material balance is calculated for 95 weight percent organic source material.

Example 2

Using the reactor and the catalyst of example 1, the water in the feed speed 2,17 cm3/min heated to 600°C and add to the distribution plate in the regeneration zone. Liquid ethylbenzene in the feed speed 2,52 cm3/min and liquid water at feed speed 2,17 cm3/min at room temperature, heated to 500°C and add through the reaction zone to the set of spreaders. Specified feedrate correspond to the mass of the entire steam to oil 2/1 with surface speed of 156 m/min in the recovery area, and 339,. is the temperature and pressure in the reactor support at 600°C and 15.5 pounds per square inch (106,9 kPa), respectively. The conversion of ethylbenzene is 85 mol. percent. The selectivity to styrene is 69 mol. percent. The material balance is calculated for 96 weight percent of the organic source material.

In example 1, the nitrogen added as processaudio gas to the stream of ethylbenzene, but no couple do not add to the stream of ethylbenzene. In contrast, in example 2, no processaudio gas is not added to the stream of ethylbenzene and steam flow is distributed between the source material for the dehydrogenation and source material for regeneration. When example 2 is compared with example 1, it is obvious that the conversion of ethylbenzene above in example 2, due to longer periods of stay in the layer, and the selectivity to styrene is lower due to increased free-radical cracking in the region above the layer.

Example 3

Using the reactor and the catalyst of example 1, the water in the feed speed 4.3 cm3/min heated to 600°C and add to the distribution plate in the regeneration zone. Liquid ethylbenzene in the feed speed 2,49 cm3/min at room temperature, heated to 500°C and add through the reaction zone to the 2/1 with surface speed of 309 m/min in the recovery area, and 417 m/min in the reaction zone. The residence time of gas in the regeneration zone 1,47, the gas retention time in the reaction zone 0,63 C. the Temperature and pressure in the reactor support at 600°C and 15.5 pounds per square inch (106,9 kPa), respectively. The conversion of ethylbenzene is 85 mol. percent. The selectivity to styrene is 72 mol. percent. The material balance is calculated to 98 mass% of the organic source material.

The process conditions of example 3 are closely similar to the conditions of example 2, except as noted. In example 2, half of the couple is taken to the recovery area, and half of all steam delivered into the reaction zone. In contrast, in example 3, the steam is taken to the recovery area. When example 3 is compared with example 2, it is obvious that the conversion of ethylbenzene and selectivity for styrene are comparable. There is a small difference, which depends on the introduction of steam.

Example 4

Example 2 is repeated at the close of such process conditions except that maintain a constant pressure of about 5 psig (34,5 kPa). The catalyst used in example 4, has a chemical composition identical to the catalyst of the previous examples, however, the number of used catalyst 1355 g, and the catalyst has an average; karasti supply of liquid ethylbenzene and water in the reaction zone 2,52 cm3/min and 1.45 cm3/min, respectively; the mass ratio of steam to oil 2/1; surface flow velocity in the regeneration zone 123 cm/min; surface flow velocity in the reaction zone 200 cm/min and a temperature of 600°C. the Conversion of ethylbenzene is 49 mol. percent. The selectivity to styrene is 88 mol. percent. The material balance is estimated to 93 weight percent of the organic source material.

Comparison of examples 2 and 4 shows that a significantly higher selectivity to styrene can be achieved when the reactor with a fluidized bed under vacuum. Lower the partial pressure of ethylbenzene reduces the total transformation.

Example 5

Example 4 is repeated at the close of such process conditions except that the temperature of the reactor constant support rather at 590°C than at 600°C. the process Conditions are the following: the speed of water flow in the regeneration zone 2.9 cm3/min; feed rate of liquid ethylbenzene and water in the reaction zone 2,52 cm3/min and 1.45 cm3/min, respectively; the mass ratio of steam to oil 2/1; surface flow velocity in the zone d is (a). The conversion of ethylbenzene is 50 mol. percent. The selectivity to styrene is 94. percent. The material balance is calculated to 99 mass% of the organic source material. Comparison of examples 4 and 5 shows that work under vacuum at a temperature lower than 600°C, provides a further increase in the selectivity to styrene.

Example 6

Example 4 is repeated at the close of such process conditions except that the temperature of the reactor support rather constant at 580°C than at 600°C. the process Conditions are the following: the speed of water flow in the regeneration zone of 2.83 cm3/min; feed rate of liquid ethylbenzene and water in the reaction zone 2,52 cm3/min and 1.45 cm3/min, respectively; the mass ratio of steam to oil 2/1; surface flow velocity in the regeneration zone 121 cm/min; surface flow velocity in the reaction zone 197 cm/min and a pressure of 5 psig (34,5 kPa). The conversion of ethylbenzene is 44 mol. percent. The selectivity to styrene is 95 mol. percent. The material balance is calculated for 100 mass% of the organic source material. Comparison of examples 4, 5 and 6 shows that work under vacuum conditions at a temperature nigri closely similar process conditions except that the mass ratio of steam to oil 1/1 instead of 2/1. Other process conditions are the following: the speed of water flow in the regeneration zone 1.45 cm3/min; feed rate of liquid ethylbenzene and water in the reaction zone 2,52 cm3/min and 0.73 cm3/min, respectively; the surface flow velocity in the regeneration zone 61,5 cm/min; surface flow velocity in the reaction zone to 107.6 cm/min, a pressure of 5 psig (34,5 kPa) and a temperature of 600°C. the Conversion of ethylbenzene is 49 mol. percent. The selectivity to styrene is 89 mol. percent. The material balance is calculated to 98 mass% of the organic source material.

Comparison of examples 4 and 5 with example 7 shows that the decrease of the ratio of steam to oil from 2/1 to 1/1, does not affect the conversion of ethylbenzene and selectivity to styrene.

Example 8

Example 4 is repeated at the close of such process conditions, except for the size of the catalyst particles and relationships steam to oil. For example 8 catalyst (1570) has an average particle diameter of 82 μm, and the ratio of steam to oil is 0.5/1. Other process conditions are the following: the speed of water flow in the regeneration zone 0.8 cm3/min; feed rate of liquid ethylbenzene and water in the reaction zone of 5.48 cm3/min and 0.54 cm3/min, respectively; surface e 5 pounds per square inch (34,5 kPa) and a temperature of 600°C. the Conversion of ethylbenzene is 54 mol. percent. The selectivity to styrene is 95 mol. percent. The material balance is calculated for 100 mass% of the organic source material.

Comparison of examples 4 and 7 with example 8 shows that a high selectivity to styrene can be achieved with relationships steam to oil 0.5/1. In addition, the reduction in the average diameter of the catalyst particles from 220 mm to 82 μm results in an increase in the conversion of ethylbenzene. Most likely, this result is a consequence of the improvement of mass transfer, as smaller catalyst particles tend to reduce the equilibrium diameters of bubbles in the reactor with a fluidized bed.

Example 9

The reactor pulsating action is used to study the dehydrogenation of ethylbenzene to styrene as a function of time. In pulsed mode in the reactor re-implement the circulation through the stage of dehydrogenation and then the stage of catalyst regeneration. Experiments in reactors pulsating actions show that such results can be expected in the reactor with a fluidized bed.

The dehydrogenation catalyst having the size of the Oia (CE2About3), 7.8 percent of copper oxide (CuO), 36.0 percent potassium carbonate (Caso3), 0.6 percent of oxide of chromium (CR2About3and 4.7 percent of cement by weight, loaded into the reactor with continuous flow and fixed bed [stainless steel 304, inventory 40, 1 inch (2.5 cm) VD36 inches (90 cm) in length]. The catalyst layer is 7 inches (17.5 cm) length of the reactor. The space above the layer of ceramic filled saddle-shaped nozzles, the Burleigh (1/4 inch, 0.6 cm). Below the layer is a metal spacer. The reaction temperature is measured in the pocket of a thermocouple embedded in the catalyst bed. Impulse dehydrogenation is carried out by passing ethylbenzene, pre-heated to 550°C. over the catalyst for 2 minutes the flow Rate of liquid ethylbenzene, measured at a temperature and ambient pressure (taken as 23°C and 1 ATM), is equal to 1.16 ml/min. at the same time the water is pre-heated to 550°C, is passed over the catalyst during the same 2-minute period. The rate of water flow adjust to ensure that the mass ratio of steam to oil 0,30/1. The total pressure support of 5.0 psig (34,5 kPa). After that, the flow of ethylbenzene stop and spend the impulse regenera process conditions. The flow rate of liquid water during the pulse regeneration, measured at 24°C and 1 ATM is equal to 1 ml/min. After regeneration repeat pulse dehydrogenation by re-introducing a stream of ethylbenzene for 2 min, as described previously, with a continuous flow of water vapor. After 2 min the flow of ethylbenzene again stop, while the steam continues to the regeneration cycle for 2 min Cycles of dehydrogenation-regeneration repeat during the whole time of experience 200 hours Product stream is continuously passed through the condenser, share and analyze with conventional methods.

The results of the process in pulsed mode shown in Fig.3, which graphically represents the conversion of ethylbenzene and selectivity for styrene as a function of time experience at constant temperature (550°C) and pressure (5 psig, to 34.5 kPa). Unexpectedly, it was found that the conversion of ethylbenzene is slightly increasing over time. The selectivity for styrene remains constant at a value of more than 95 mol. percent throughout the experience. The results from the reactor pulsating actions show that the dehydrogenation catalyst can be subjected to circulation through the stages of dehydrogenation-regeneration in reacto anicely experiment 1.

The process of example 9 is repeated in the same reactor with continuous flow and fixed bed under similar process conditions, except that the dehydration is conducted rather in continuous mode than in pulsed mode. Thus, there is only one cycle of dehydrogenation and there is no cycle of regeneration of the catalyst. It was found that in these conditions, the catalyst gradually deactivated with a concomitant decrease in conversion of ethylbenzene. When the catalyst is deactivated, the process temperature increases to maintain a constant conversion of ethylbenzene. When the ratio of steam to oil 0,3/1 temperature should increase with the speed of 0.45°C / min, to support the transformation. When comparative experiment 1 compared with experiment 9, determines that the service life of the catalyst is achieved in the reactor pulsating action, significantly extended at constant temperature and pressure, whereas without regeneration of the catalyst is rapidly deactivated and requires elevated temperatures to provide a permanent transformation. The results from the reactor pulsating actions show that the dehydrogenation catalyst can be subjected to circulation through the stages of dehydrogenation of regenera the promotion.

Claims

1. The method of dehydrogenation of alkyl-aromatic compounds over a dehydrogenation catalyst to the formation of vinyl-aromatic compounds and regeneration of the dehydrogenation catalyst in place, providing for (a) fluidization of the dehydrogenation catalyst in a single reactor with a fluidized bed containing a reaction zone and a regeneration zone under conditions of fluidization, so carry out the circulation of the catalyst within and between the two zones; (b) the interaction flow of the source material for the dehydrogenation containing the alkyl-aromatic compound, and possibly couples with a dehydrogenation catalyst in the reaction zone, under conditions of reaction sufficient to obtain the corresponding vinyl aromatic compounds, and (C) the interaction flow of the source material for regeneration, containing pairs, with a dehydrogenation catalyst in the regeneration zone, the regeneration conditions sufficient to regenerate the catalyst, at least partially.

2. The method according to p. 1, where the alkyl-aromatic compound is C8-C20the alkyl-aromatic compound.

3. The method according to p. 2, where the alkyl-aromatic compound is the of cumene, of diethylbenzene and ethyltoluene.

5. The method according to p. 1, where the reactor fluidized bed further comprises a zone above the layer, and procissi gas add to the zone above the layer.

6. The method according to p. 1, where the mass ratio of only a couple to the alkyl-aromatic compound is more than about 0.2/1 and less than about 5.0/1.

7. The method according to p. 1, where the mass ratio of only a couple to the alkyl-aromatic compound is more than about 0.2/1 and less than about 1.2/1.

8. The method according to p. 1 wherein the diluting gas is fed with a stream of the source material for the dehydrogenation, or served with a stream of the source material for regeneration, or served with both threads.

9. The method according to p. 8, wherein the dilution gas selected from nitrogen, argon, helium, carbon dioxide, steam, and mixtures thereof.

10. The method according to p. 8, where the solvent is more than about 10 vol.% to less than about 90 vol.% flow of the source material for the dehydrogenation or for regeneration or both threads independently.

11. The method according to p. 1, where the flow of the source material for the dehydrogenation pre-heated to a temperature of more than about 150°C. and less than about 600°C.

12. The method according to p. 1, where the flow of the source material for the regeneration of pre-heated to a temperature of more than about 200°C and IU is less than about 650°C.

14. The method according to p. 1, where the total pressure in the reactor more than about 1 psi (6.9 kPa) and less than about 73 pounds per square inch (503,3 kPa).

15. The method according to p. 1, where the process is carried out at the time the bulk gas velocity, calculated as the total flux of the source material for the dehydrogenation, more than 60-1and less than about 12000 h-1measured at the operating conditions of the process.

16. The method according to p. 1, where the process is carried out at time of stay of the entire gas stream in the reaction zone is more than about 0.3 and less than about 60 seconds, measured at the operating conditions of the process.

17. The method according to p. 1, where the process is carried out at the time the bulk gas velocity, calculated as the total flow rate of the source material for regeneration, more than about 60 h-1and less than about 12000 h-1measured at the operating conditions of the process.

18. The method according to p. 1, where the process is carried out at residence time of gas in the regeneration zone more than about 0.3 and less than about 60 seconds, measured at the operating conditions of the process.

19. The method according to p. 1, where the dehydrogenation catalyst contains iron oxide.

20. The method according to p. 19, where the dehydrogenation catalyst further comprises at least one or more compounds selected is on p. 19, where the dehydrogenation catalyst contains (a) at least one oxide of iron, (b) at least one carbonate, bicarbonate, oxide or hydroxide of potassium and/or cesium, (C) an oxide, carbonate, nitrate or hydroxide of cerium, (d) may, hydroxide, carbonate, bicarbonate, acetate, oxalate, nitrate or sodium sulfate, (e) may, carbonate, sulfate or calcium hydroxide, (f) may be one or more compounds of zinc, chromium and copper, and (g) may cement.

22. The method according to p. 1, where the conversion of alkyl-aromatic compound is more than about 30 mol.%.

23. The method according to p. 1, where the selectivity for vinyl-aromatic compound is more than about 60 mol.%.

24. The method according to p. 1 wherein the vinyl aromatic compound is styrene or a substituted derivative of styrene.

25. The method according to p. 24, where the substituted styrene is selected from divinylbenzene,-methylstyrene and vinyltoluene.

26. The method according to p. 1, where the average particle size of the catalyst dehydrogenation more than about 20 microns and less than about 1000 microns.

27. The method according to p. 1, where the reactor fluidized bed contains a single vertical building, covering an area of over layer, a reaction zone and a regeneration zone; an inlet device for introducing pokhodnogo material of the reagent in the reaction zone, one of these inlet devices in the zones of the reaction or regeneration is able to separate two zones, allowing at the same time the circulation of catalyst particles between the two zones; and further comprises a discharge device for the exhaust flow, and possibly the intake device for return to the reactor catalyst, captured exhaust stream, and possibly the inlet and outlet devices for transportation of catalyst in the reactor and out of him.

28. The method according to p. 27, where the device for separating zones of reaction and regeneration contains many sprinklers or distributor.

29. The method of dehydrogenation of ethyl benzene or substituted benzene over a dehydrogenation catalyst to the formation of styrene or substituted styrene and regeneration of the dehydrogenation catalyst in place, providing for (a) fluidization of the dehydrogenation catalyst in a single reactor with a fluidized bed containing a reaction zone and a regeneration zone, in the conditions of fluidization, so carry out the circulation of the catalyst within and between the two zones; (b) interaction of the benzene or substituted benzene and possibly a couple, and possibly diluting gas with katalizatorov when the mass ratio of steam to ethylbenzene more than about 0.2/1 and less than about 3.0 a/1, a temperature of more than about 570°C. and less than about 610°C and a total pressure in the reactor more than about 3 psig (41 kPa) and less than about 44 pounds per square inch (302 kPa), and (C) interaction of the dehydrogenation catalyst in the regeneration zone, with the flow of the source material for regeneration containing steam and possibly a diluent, at a temperature of more than about 570°C. and less than about 610°C. to regenerate the catalyst, at least partially.

30. A reactor with a fluidized bed for the dehydrogenation of alkyl-aromatic hydrocarbons with a catalyst regeneration in place, containing a single vertical building, covering an area of over layer, a reaction zone and a regeneration zone; an inlet device for introducing a flow of the source material for regeneration in a regeneration zone and an inlet device for introducing a flow of the source material of the reagent in the reaction zone, and one of the inlet devices capable of separating the reaction zone and regeneration, allowing at the same time the circulation of catalyst particles between the two zones; and further comprises a discharge device for the exhaust flow, and possibly intake device for return to the reactor cattle introducing a flow of starting material reagent contains many sprinklers or distributor.

32. A reactor with a fluidized bed by p. 30, where the device for introducing a flow of the source material for regeneration contains many sprinklers or distributor.

33. A reactor with a fluidized bed by p. 30, where the device for separating zones of reaction and regeneration chosen from the set of sprinklers or distributor.

34. A reactor with a fluidized bed by p. 30, optionally containing a device for improving circulation of solids.

35. A reactor with a fluidized bed by p. 34, where the fixture to improve the circulation of solids contains the suction pipe may contain inner reflective walls.

36. A reactor with a fluidized bed by p. 34, where the fixture to improve the circulation of solids contains the suction pipe, made of a heating or cooling elements.

37. A reactor with a fluidized bed by p. 34, optionally containing an inlet fixture and outlet devices for transportation of catalyst in the reactor and out of him.

38. A reactor with a fluidized bed by p. 34, optionally containing at least one device for metering the

 

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