EQUIPMENT AND METHODS FOR DEHYDRATION REACTION USING FLUIDIZED BED TECHNOLOGY

Abstract

The invention relates to an apparatus and method for the production of propylene by dehydrogenation of propane using fluidized bed technology, in which a chlorine dispersion device and a dehydrogenation device are added downstream of a catalyst regeneration device. According to the invention, when the chlorine dispersion device and the dehydrogenation device are added downstream of the catalyst regeneration device, the affinity between the sintered catalyst metal and the support increases during catalyst regeneration, and the catalytic dispersion capacity as well as the propylene yield can be maintained at the original level.

Description

Fluidized bed dehydrogenation reactor and method

[0001] The present invention relates to a fluidized bed dehydrogenation device and method, and more particularly, to a device and method for dehydrogenating hydrocarbons using fluidized bed technology.

[0002] Conventional fluidized bed propane dehydrogenation processes typically consist of a fluidized bed dehydrogenation reactor, a gas-catalyst separation unit, and a catalyst regenerator. Propane gas and a catalyst are injected together into the bottom of the reactor and flow together toward the top, where the dehydrogenation reaction occurs. After the reaction is complete, the catalyst separated from the gas in the gas-catalyst separation unit flows into the catalyst regenerator located below. In the catalyst regenerator, air or oxygen is injected to combust and remove coke from the catalyst surface. This coke removal process is exothermic and generates a high level of heat, which the fluidized bed propane dehydrogenation process utilizes as reaction heat, thereby increasing the energy efficiency of the process.

[0003] The heat generated during the coke combustion removal process in the catalyst regenerator can cause sintering of the catalytic metals on the catalyst support surface, thereby reducing catalytic performance. The oxidized catalytic metals, combined with the oxygen injected for catalyst regeneration, move through mass transfer within the support surface. This mass transfer is enhanced at higher temperatures and higher oxygen concentrations. The catalytic metals moving across the support surface tend to aggregate into a thermodynamically more stable form. Agglomeration of the catalytic metals reduces the number of active sites where the dehydrogenation reaction actually occurs, thus reducing reaction performance. Lowering the temperature or oxygen concentration during catalyst regeneration to mitigate this sintering phenomenon can, however, reduce the coke within the catalyst, which can remain and degrade catalytic performance.

[0004] Fluidized bed technology is a technology that introduces solid particles together with a fluid (gas or liquid) and makes them move like the fluid. It fluidizes the catalyst (solid particles) for propane dehydrogenation, reacts with propane gas (gas) for a short time, and circulates the process to secure a high propylene yield. At this time, coke is produced as a byproduct on the surface of the catalyst after the propane dehydrogenation reaction. Since the coke blocks the reaction active sites and reduces performance, a regeneration process to remove the coke and restore the catalyst to its original state is essential. In particular, in the fluidized bed process with a short catalyst regeneration cycle, the design of the catalyst regenerator is a key technology. If the catalyst regeneration is not performed properly, the rapid increase in coke will irreversibly deactivate the catalyst, and as a result, the process yield will decrease rapidly.

[0005] [Prior Art Literature]

[0006] [Patent Document]

[0007] (Patent Document 1) US 10065905 B2

[0008] (Patent Document 2) US 2019 / 0225563 A1

[0009] The purpose of the present invention is to solve the problems of the prior art described above, and one purpose of the present invention is to provide a fluidized bed dehydrogenation reactor that can improve catalytic reaction performance by preventing deactivation of a catalyst in a fluidized bed dehydrogenation reactor, thereby ensuring high conversion, yield, and selectivity of the dehydrogenation reaction.

[0010] Another object of the present invention is to provide a fluidized bed hydrocarbon dehydrogenation method capable of improving the yield of the dehydrogenation process by preventing a decrease in catalytic activity due to residual coke generation in the fluidized bed dehydrogenation process of hydrocarbons.

[0011] One aspect of the present invention to achieve the above-described purpose is:

[0012] A fluidized bed dehydrogenation reactor in which a dehydrogenation reaction of a hydrocarbon stream is carried out using a dehydrogenation catalyst;

[0013] A catalyst regenerator for regenerating the inactivated catalyst transferred from the fluidized bed dehydrogenation reactor of the front stage;

[0014] A chlorine dispersion device connected to the rear end of the catalyst regenerator and supplying a dispersion gas mixed with chlorine and oxygen to the regenerated catalyst to disperse chlorine; and

[0015] The present invention relates to a fluidized bed dehydrogenation device including a hydrogen reduction device connected to the rear end of the above chlorine dispersion device, which supplies hydrogen reduction gas to a chlorine-dispersed catalyst to perform hydrogen reduction and then recirculates the gas to a fluidized bed dehydrogenation reactor.

[0016] The above chlorine dispersion device and hydrogen reduction device may be of the bubbling-fluidized-bed type.

[0017] A sparger or distribution plate may be installed at the bottom of the chlorine distribution device and hydrogen reduction device to ensure that the gas is well distributed over the entire catalyst and can react.

[0018] A gas mixing prevention device may be further installed between the above chlorine dispersion device and the hydrogen reduction device to prevent oxygen, which is a combustible substance, and hydrogen, which is combustible, from mixing with each other and to block hydrogen from flowing into the fluidized bed dehydrogenation reactor.

[0019] The above chlorine dispersion device and hydrogen reduction device can be configured so that gas is supplied from the bottom and discharged from the top, and the residence time is controlled by the height of the catalyst layer.

[0020] Another aspect of the present invention for achieving the above-described purpose is:

[0021] A fluidized bed hydrocarbon dehydrogenation method comprising the steps of contacting a fluidized bed comprising a catalyst with a hydrocarbon stream in a fluidized bed dehydrogenation reactor, then withdrawing an inactive catalyst from the fluidized bed, regenerating the catalyst by a catalyst regenerator, and returning the catalyst to the fluidized bed, wherein the method

[0022] A step of extracting the regenerated catalyst from the catalyst regenerator and dispersing chlorine using a dispersion gas mixed with chlorine and oxygen; and

[0023] The present invention relates to a fluidized bed hydrocarbon dehydrogenation method, characterized by including a hydrogen reduction step of supplying hydrogen reduction gas to a chlorine-dispersed catalyst to perform hydrogen reduction and then recycling the hydrogen to a fluidized bed dehydrogenation reactor.

[0024] The above chlorine dispersion step is performed at a regeneration gas space velocity of 0.1 to 50 h -1 , chlorine concentration 30 to 1000 ppm, oxygen concentration 3 to 21%, treatment time 3 to 60 minutes, temperature 550 to 750℃ can be performed within the range.

[0025] The above hydrogen reduction step is performed at a reduced gas space velocity of 0.5 to 100 h -1 , can be performed within the range of processing time 1 to 60 minutes and temperature 550 to 750℃.

[0026] The dehydrogenation reaction in the fluidized bed dehydrogenation reactor is carried out under the following conditions: catalyst ratio in the reactor 0.5 to 10%, propane gas flow rate 0.5 to 8 m / s, catalyst inlet temperature 550 to 750°C, propane gas inlet temperature 500 to 700°C, catalyst residence time 3 to 60 seconds, propane residence time 1 to 30 seconds, reaction gas space velocity 5 to 50 h. -1 It can be implemented within the scope of .

[0027] The above catalyst regeneration is performed at a regeneration gas space velocity of 0.1 to 50 h -1 , can be performed within the range of processing time 1 to 40 minutes and temperature 550 to 750℃.

[0028] According to the present invention, by adding a chlorine dispersion device and a hydrogen reduction device to the rear end of a catalyst regenerator, the bonding strength of the sintered catalyst metal and the carrier during the catalyst regeneration process increases, and the catalyst dispersion and propylene yield can be maintained at the initial level.

[0029] In addition, when the process is operated within the range of reaction conditions and regeneration conditions for the dehydrogenation, catalyst regeneration, chlorine dispersion, and hydrogen reduction reactions presented in the present invention, the reaction performance of the catalyst can be improved by preventing deactivation of the catalyst due to coke generation during the dehydrogenation reaction, thereby improving the overall process yield.

[0030] Figure 1 is a schematic diagram of a fluidized bed dehydrogenation reactor according to the prior art.

[0031] Figure 2 is a schematic diagram illustrating a fluidized bed dehydrogenation device according to one embodiment of the present invention.

[0032] Figure 3 is an enlarged view of the chlorine dispersion device and hydrogen reduction device of a fluidized bed dehydrogenation device according to one embodiment of the present invention.

[0033] Figure 4 is a schematic perspective view of a sparger installed in a chlorine dispersion device and a hydrogen reduction device of a fluidized bed dehydrogenation reactor according to one embodiment of the present invention.

[0034] The present invention will be described in more detail below with reference to the accompanying drawings. Like reference numerals designate like elements throughout the specification. The drawing reference numerals represent a simplified schematic of the dehydrogenation reactor according to the present invention, with only key components depicted. Other components, such as heat exchangers, internal heaters, catalyst transfer pipes, pumps, and other similar components, are omitted.

[0035] When a component is referred to in this specification as being "connected" or "connected" to another component, it should be understood that it may be directly connected or connected to that other component, but there may also be other components present in between.

[0036] In this specification, singular expressions include plural expressions unless the context clearly dictates otherwise. It should be understood that the terms "comprise" or "have" in this specification limit the presence of a feature, number, step, operation, component, part, or combination thereof described in the specification, but do not exclude the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0037] The term “reactor” herein means a reaction device in which a reaction gas comes into contact with a catalyst on a catalyst bed.

[0038] It should be understood that the various ranges and / or numerical limitations herein include countless different ranges falling within the explicitly stated range or limitation.

[0039] FIG. 2 is a schematic diagram of a fluidized bed dehydrogenation device according to one embodiment of the present invention, and FIG. 3 is an enlarged view of a chlorine dispersion device and a hydrogen reduction device of the fluidized bed dehydrogenation device according to one embodiment of the present invention.

[0040] Referring to FIG. 2, a fluidized bed dehydrogenation device of one embodiment of the present invention includes a fluidized bed dehydrogenation reactor (100) in which a dehydrogenation reaction of a hydrocarbon stream is performed using a dehydrogenation catalyst, a catalyst regeneration unit (200) for regenerating an inactivated catalyst transferred from a fluidized bed dehydrogenation reactor in a previous stage, a chlorine dispersion unit (300) for dispersing chlorine by supplying a dispersion gas containing a mixture of chlorine and oxygen to the regenerated catalyst transferred from the catalyst regeneration unit; and a hydrogen reduction unit (400) connected to a rear end of the chlorine dispersion unit for supplying a hydrogen reduction gas to the chlorine-dispersed catalyst to perform hydrogen reduction and then recycling the hydrogen reduction to the fluidized bed dehydrogenation reactor.

[0041] To maintain consistent catalyst performance after propane dehydrogenation, it's crucial to completely remove coke from the catalyst surface during the catalyst regeneration process. Furthermore, it's crucial to minimize sintering of the catalyst metal and ensure that it's dispersed widely into small particles to ensure sufficient active sites. Furthermore, selecting an appropriate operating condition range is crucial to minimize the amount of coke generated on the catalyst while maintaining yield during the dehydrogenation process. A fluidized bed dehydrogenation reactor and regenerator design that satisfy this operating condition range is essential.

[0042] In the present invention, the fluidized bed dehydrogenation reactor (100) may be any reactor type known in the art. For example, the fluidized bed dehydrogenation reactor (100) may be a tubular reactor, a tank reactor, or a moving bed reactor.

[0043] The design criteria of a fluidized bed dehydrogenation reactor (100) to maintain coke production while maintaining a high propylene yield are as follows: a catalyst ratio in the reactor of 0.5 to 10%, a propane gas flow rate of 0.5 to 8 m / s, a catalyst inlet temperature of 550 to 750°C, a propane gas inlet temperature of 500 to 700°C, a catalyst residence time of 3 to 60 seconds, a propane residence time of 1 to 30 seconds, and a reaction gas space velocity of 5 to 50 h. -1 This is suitable. The catalytic regenerator has a regeneration gas space velocity of 0.1 to 50 h -1 , it is suitable to design within the range of processing time 1 to 40 minutes and temperature 550 to 750℃.

[0044] The catalyst regenerator (200) has a regeneration gas space velocity of 0.1 to 50 h -1 , it is suitable to design within the range of processing time 1 to 40 minutes and temperature 550 to 750℃.

[0045] In the fluidized bed dehydrogenation device of the present invention, a chlorine dispersion device (300) and a hydrogen reduction device (400) are added after the catalyst regenerator (200). The chlorine dispersion device (300) and the hydrogen reduction device (400) may be in the form of a bubbling fluidized bed. The chlorine dispersion device (300) and the hydrogen reduction device (400) may be designed so that gas is supplied to the bottom and discharged to the top, and the residence time is controlled by the height of the catalyst bed.

[0046] Referring to FIG. 3, a gas mixing prevention device (350) may be further installed between the chlorine dispersion device (300) and the hydrogen reduction device (400) to prevent oxygen, which is a combustible substance, and hydrogen, which is combustible, from mixing with each other and to block hydrogen from flowing into the fluidized bed dehydrogenation reactor (100). The residence time of the catalyst in the chlorine dispersion device can be controlled by the nitrogen flow rate of the gas mixing prevention device (loop seal) (350) that functions as a valve.

[0047] The gas mixing prevention device (350) is composed of a loop seal and is used to prevent catalyst backflow and catalyst mixing between the chlorine distribution device and the hydrogen reduction device along with the transfer of the catalyst. A different type of gas (e.g., nitrogen) must be used than that of the chlorine reduction device (300) and the hydrogen reduction device (400).

[0048] In addition, a sparger or a dispersion plate may be installed at the bottom of the chlorine dispersion device (300) and the hydrogen reduction device (400) to ensure that the gas is well dispersed over the entire catalyst and reacts. Referring to Fig. 4, the sparger (20) has a plurality of injection holes (21) for spraying a fluid on the upper surface to disperse and pass the catalyst flowing in the height direction of the reactor. The sparger (20) can prevent the catalyst from clumping and piling up through the plurality of injection holes (21) and can increase the fluid residence time of the catalyst.

[0049] In the chlorine dispersion device (300) of the present invention, oxygen and chlorine are supplied to regenerate the catalyst through an oxychlorination reaction, thereby separating the sintered catalyst metals into small particles and redispersing them. Since the metal redispersion effect is better at a temperature that is relatively 10 to 50°C higher than the temperature of the catalyst regenerator and at a high oxygen concentration (3 to 15%), it is necessary to operate the chlorine dispersion device (300) separately from the catalyst regenerator (200).

[0050] The chlorine dispersion device (300) is a device that reacts the oxidized catalyst metal in the catalyst regenerator (200) with chlorine to form metal-Cl-O. Since the metal-Cl-O has a very high bonding strength with the catalyst carrier compared to the metal-O, it prevents sintering and helps the catalyst metal to be widely dispersed into small particles. However, since the treatment of a large amount of chlorine can increase the acid site of the catalyst carrier and increase the amount of coke produced during the dehydrogenation reaction, the chlorine dispersion device (300) needs to be operated within an appropriate operating range. In the present invention, the operating range of the chlorine dispersion device (300) is a regeneration gas space velocity of 0.1 to 50 h. -1 , chlorine concentration 30~1000ppm, oxygen concentration 3~21%, treatment time 3~60 minutes, temperature 550~750℃ are appropriate.

[0051] Oxygen is supplied to the catalyst regenerator (200) and the chlorine dispersion device (300), and the oxygen supplied at this time remains in the catalyst in a state of being combined with the catalytic metal component (metal-O). If the metal component is oxidized in this way, the dehydrogenation reaction does not occur. Therefore, in the present invention, a reduction reaction in which hydrogen and oxygen are reacted to remove oxygen is absolutely necessary in the hydrogen reduction device (400). Therefore, the hydrogen reduction device (400) must be located at the rear end of the catalyst regenerator (200) and the chlorine dispersion device (500) when configuring the process, and reduce the oxidized catalyst before the catalyst is supplied to the fluidized bed dehydrogenation reactor (100).

[0052] The hydrogen reduction device (400) removes Cl-O from the catalyst metal in the metal-Cl-O state through hydrogen to restore it to the metal state. At this time, if the hydrogen reduction process is too short, Cl-O is not completely removed, blocking the active sites of the metal. If the hydrogen reduction process is too long, the bonding form between the catalyst metals is changed, reducing the catalyst performance. Therefore, it is necessary to operate within an appropriate operating range. The appropriate operating range of the hydrogen reduction device (400) is a reducing gas space velocity of 0.5 to 100 h. -1 , the processing time is 1 to 60 minutes, and the temperature is 550 to 750℃.

[0053] The operation of a fluidized bed hydrocarbon dehydrogenation device according to one embodiment of the present invention will be described. The dehydrogenation of propane will be described as an example.

[0054] First, propane is preheated through a propane preheater (10) and introduced into the bottom of a fluidized bed dehydrogenation reactor (100). The catalyst that has passed through the hydrogen reduction device (400) is introduced into the bottom of the fluidized bed dehydrogenation reactor (100). The dehydrogenation reaction proceeds as the propane and catalyst introduced into the bottom of the fluidized bed dehydrogenation reactor (100) flow together to the top. The gas (propylene, hydrogen, propane mixed gas) that has passed through the fluidized bed dehydrogenation reactor (100) is discharged to the top of the gas-catalyst separation device (11), and each gas is separated through a separate separation process. Next, the catalyst is separated into the bottom of the gas-catalyst separation device (11), and the coke is burned off in a catalyst regenerator (200). The catalyst regenerated by the catalyst regenerator (200) is moved to a chlorine dispersion device (300) and undergoes a process in which the sintered catalyst metal is redispersed. Finally, the catalyst that has passed through the hydrogen reduction device (400) at the bottom of the chlorine dispersion device (300) is recycled to the fluidized bed dehydrogenation reactor (100) after removing residual oxygen and chlorine from the catalyst.

[0055] Dehydrogenation is a highly endothermic reaction. The exact dehydrogenation temperature and pressure used in the dehydrogenation reaction section depend on various factors, such as the composition of the paraffinic hydrocarbon feedstock, the activity of the selected catalyst, and the hydrocarbon conversion. In the present invention, the dehydrogenation reaction is conducted under conditions of pressure ranging from 0 to 40 bars and temperature ranging from 480°C to 760°C. A suitable hydrocarbon feed is charged to the reactor and contacted with the catalyst contained therein at an LHSV ranging from 1 to 10.

[0056] In the present invention, the dehydrogenation conditions include a catalyst inlet temperature of 550 to 750°C and a propane gas inlet temperature of 550 to 750°C. The temperature required for efficient operation of the dehydrogenation process depends on the activity of the feed hydrocarbon and the catalyst used. The pressure maintained within the dehydrogenation zone can be in the range of 100 to 750 mmHg, and the pressure range is preferably 250 to 700 mmHg. The operating pressure within the dehydrogenation zone is measured at the inlet, middle section, and outlet of the zone to provide an average pressure. The reaction gas space velocity is 0.5 to 50 hr based on the total liquid hydrocarbon charged. -11 The fluidized bed dehydrogenation reactor is charged into the dehydrogenation zone at a liquid hourly space velocity of 0.5 to 8 m / s. The propane gas flow rate is 0.5 to 8 m / s, the catalyst residence time is 3 to 60 seconds, the propane residence time is 1 to 30 seconds, and the catalyst ratio in the fluidized bed dehydrogenation reactor is operated within the range of 0.5 to 10%.

[0057] Dehydrogenation can be performed using any suitable dehydrogenation catalyst. Typically, a Group VIII noble metal catalyst selected from the group consisting of platinum, palladium, iridium, rhodium, osmium, ruthenium, or mixtures thereof can be used. The dehydrogenation catalyst comprises a Group VIII noble metal component, an alkali metal component, and a porous inorganic support material. An example of a preferred porous support material is an alumina support, the particles of which are usually spherical and have a diameter of 40 to 140 μm.

[0058] Another aspect of the present invention relates to a fluidized bed hydrocarbon dehydrogenation method. The method of the present invention comprises the steps of: contacting hydrocarbon with a dehydrogenation catalyst using a fluidized bed dehydrogenation reactor (100) to perform a dehydrogenation reaction; removing inactivated catalyst transferred from a previous fluidized bed dehydrogenation reactor by burning coke; regenerating the catalyst by redispersing the main component of the catalyst with chlorine (Cl2); and reducing the chlorine-dispersed catalyst with hydrogen using a hydrogen reducing gas and recycling it to the fluidized bed dehydrogenation reactor.

[0059] The dehydrogenation reaction in the fluidized bed dehydrogenation reactor (100) is carried out at a catalyst ratio of 0.5 to 10% in the reactor, a propane gas flow rate of 0.5 to 8 m / s, a catalyst inlet temperature of 550 to 750°C, a propane gas inlet temperature of 500 to 700°C, a catalyst residence time of 3 to 60 seconds, a propane residence time of 1 to 30 seconds, and a reaction gas space velocity of 5 to 50 h. -1 It is implemented within the scope of .

[0060] In the present invention, catalyst regeneration in the catalyst regenerator (200) is performed at a regeneration gas space velocity of 0.1 to 50 h -1 , processing time is 1 to 40 minutes, and temperature is within the range of 550 to 750℃.

[0061] In the present invention, the chlorine dispersion step is performed at a regeneration gas space velocity of 0.1 to 50 h -1, chlorine concentration 30 to 1000 ppm, oxygen concentration 3 to 21%, treatment time 3 to 60 minutes, temperature 550 to 750℃ can be performed within the range.

[0062] The above hydrogen reduction step is performed at a reduced gas space velocity of 0.5 to 100 h -1 , processing time is 1 to 60 minutes, and temperature is within the range of 550 to 750℃.

[0063] In the above catalyst regeneration step, regenerated catalyst particles can be obtained through a step of burning coke deposits on spent catalyst particles using a combustion gas (e.g., oxygen-containing gas); a step of contacting the catalyst particles with a halogenating gas and halogenating the catalyst particles to redisperse the catalytically active component; and a step of drying the halogenated catalyst to remove moisture resulting from the upstream reaction.

[0064] Hereinafter, preferred examples are presented to aid in understanding the present invention. However, the following examples are provided solely to facilitate a better understanding of the present invention and are not intended to limit the scope of the present invention.

[0065] Example

[0066] Example 1 and Comparative Example 1

[0067] In order to compare the performance difference between the fluidized bed dehydrogenation reactor of the present invention and the prior art, the performance was compared according to the presence or absence of a chlorine dispersion device and a hydrogen reduction device when operated under the same reaction and regeneration conditions.

[0068] In Example 1, the experiment was conducted using a fluidized bed hydrocarbon dehydrogenation reactor equipped with a chlorine dispersion device and a hydrogen reduction device as shown in FIG. 2, and in Comparative Example 1, the experiment was conducted using a fluidized bed hydrocarbon dehydrogenation reactor as shown in FIG. 1 without a chlorine dispersion device and a hydrogen reduction device.

[0069] In Example 1 and Comparative Example 1, the performance of each device was compared by measuring the propylene yield after repeating the reaction and regeneration for 10 times based on the propylene yield of the first cycle. The propylene yield was measured using a GC (Gas chromatography) analyzer by collecting gas from the sampling port at the rear end of the reactor. At this time, the dehydrogenation reaction conditions were a catalyst ratio of 8%, a propane gas flow rate of 5 m / s, a catalyst inlet temperature of 700°C, a propane gas inlet temperature of 500°C, a catalyst residence time of 60 seconds, a propane residence time of 20 seconds, and a reaction gas space velocity of 30 h. -1 and the catalyst regeneration condition was 5h of regeneration gas space velocity. -1 , the treatment time was 30 minutes, and the regeneration temperature was fixed at 700℃, and the evaluation was conducted.

[0070] Condition Comparative Example 1 Example 1 Propylene yield (%) in the first cycle 4545 Propylene yield after 10 reaction-regeneration repetitions (%) 4045 Catalyst metal dispersion after the first cycle (%) 6060 Catalyst metal dispersion after 10 reaction-regeneration repetitions (%) 5060

[0071] As confirmed through the results in Table 1 above, in Comparative Example 1 and Example 1 applying the technology of the present invention, the propylene yield was 45% and the catalyst metal dispersion was 60% in the first cycle, which were the same. However, after 10 repetitions of reaction and regeneration, in Comparative Example 1, the yield was 40% and the catalyst metal dispersion was 50%, which was a result of the sintering phenomenon of the catalyst metal, confirming that the yield decreased. On the other hand, when a chlorine dispersion device and a hydrogen reduction device were added in Example 1, the performance and properties from the first cycle were maintained, with a yield of 45% and a catalyst metal dispersion of 60%.

[0072]

[0073] Example 2 and Comparative Examples 2-3

[0074] Performance was compared within the appropriate reaction and regeneration conditions suggested in the present invention, and beyond those ranges. When both a chlorine dispersion device and a hydrogen reduction device were applied and all other conditions were maintained constant, the reaction conditions were compared under conditions where the catalyst ratio was changed, and the regeneration conditions were compared under conditions where the regeneration time was changed.

[0075] Except that the catalyst regeneration ratio and catalyst regeneration time were changed as shown in Table 2 below, the same procedure as Example 1 was followed. After repeating the reaction-regeneration, the yield and catalyst metal dispersion were measured, and the results are shown in Table 2 below.

[0076] Example 2 Comparative Example 2 Comparative Example 3 Conditions Catalyst ratio 8%, regeneration time 30 minutes Catalyst ratio 0.2%, regeneration time 30 minutes Catalyst ratio 8%, regeneration time 100 minutes First cycle Propylene yield (%) 453445 Propylene yield after 10 reaction-regeneration repetitions (%) 453442 First cycle Catalyst metal dispersion (%) 606060 Catalyst metal dispersion after 10 reaction-regeneration repetitions (%) 606055

[0077] As confirmed through the results in Table 2 above, when the catalyst ratio among the reaction conditions decreases, the yield is maintained after 10 reaction-regeneration repetitions, but the overall yield decreases, and when the regeneration time among the regeneration conditions increases, the initial cycle yield remains the same, but the sintering phenomenon increases, reducing the catalyst metal dispersion and decreasing the yield after 10 reaction-regeneration repetitions.

[0078] Although the preferred embodiments of the present invention have been described in detail above, it should be understood that the present invention is not limited to the disclosed embodiments, but is intended to include various modifications and equivalent arrangements included within the scope of the appended claims.

[0079]

[0080] [Explanation of symbols]

[0081] 10: Propane preheater

[0082] 11: Gas-catalytic separation device

[0083] 20: Spazer

[0084] 21: Injection hole

[0085] 100: Fluidized bed dehydrogenation reactor

[0086] 200: Catalytic Regenerator

[0087] 300: Chlorine Dispersion Device

[0088] 350: Gas mixing prevention device

[0089] 400: Hydrogen reduction device

Claims

1. A fluidized bed dehydrogenation reactor in which a dehydrogenation reaction of a hydrocarbon stream is performed using a dehydrogenation catalyst; A catalyst regenerator for regenerating the inactivated catalyst transferred from the fluidized bed dehydrogenation reactor of the front stage; A chlorine dispersion device connected to the rear end of the catalyst regenerator and supplying a dispersion gas mixed with chlorine and oxygen to the regenerated catalyst to disperse chlorine; and A fluidized bed dehydrogenation device including a hydrogen reduction device connected to the rear end of the above chlorine dispersion device, which supplies hydrogen reduction gas to the chlorine-dispersed catalyst to perform hydrogen reduction and then recirculates the hydrogen to the fluidized bed dehydrogenation reactor.

2. A fluidized bed dehydrogenation device according to claim 1, characterized in that the chlorine dispersion device and the hydrogen reduction device are of the bubbling-fluidized-bed type.

3. A fluidized bed dehydrogenation device characterized in that, in paragraph 1, a sparger or a distribution plate is installed at the bottom of the chlorine distribution device and the hydrogen reduction device to enable gas to be well distributed over the entire catalyst and react.

4. A fluidized bed dehydrogenation device characterized in that, in the first paragraph, a gas mixing prevention device is further installed between the chlorine dispersion device and the hydrogen reduction device to prevent oxygen, which is a combustible material, and hydrogen, which is combustible, from mixing with each other and to block hydrogen from flowing into the fluidized bed dehydrogenation reactor.

5. A fluidized bed dehydrogenation device according to claim 1, characterized in that the chlorine dispersion device and the hydrogen reduction device are designed so that gas is supplied from the bottom and discharged from the top, and the residence time is controlled by the height of the catalyst layer.

6. A fluidized bed hydrocarbon dehydrogenation method comprising the step of contacting a fluidized bed comprising a catalyst with a hydrocarbon stream in a fluidized bed dehydrogenation reactor, then taking out an inactive catalyst from the fluidized bed, regenerating the catalyst by a catalyst regenerator, and returning the catalyst to the fluidized bed, wherein the method comprises: A step of extracting the regenerated catalyst from the catalyst regenerator and dispersing chlorine using a dispersion gas mixed with chlorine and oxygen; and A fluidized bed hydrocarbon dehydrogenation method characterized by including a hydrogen reduction step of removing oxygen by supplying hydrogen reduction gas to a chlorine-dispersed catalyst.

7. In the 6th paragraph, the chlorine dispersion step is performed at a regeneration gas space velocity of 0.1 to 50 h -1 A fluidized bed hydrocarbon dehydrogenation method characterized in that it is performed within the range of chlorine concentration 30 to 1000 ppm, oxygen concentration 3 to 21%, treatment time 3 to 60 minutes, and temperature 550 to 750°C.

8. In the 6th paragraph, the hydrogen reduction step is performed at a reduced gas space velocity of 0.5 to 100 h -1 A fluidized bed hydrocarbon dehydrogenation method characterized in that it is performed within the range of 1 to 60 minutes for a processing time and 550 to 750°C for a temperature.

9. In paragraph 6, the dehydrogenation reaction in the fluidized bed dehydrogenation reactor is carried out at a catalyst ratio of 0.5 to 10% in the reactor, a propane gas flow rate of 0.5 to 8 m / s, a catalyst inlet temperature of 550 to 750°C, a propane gas inlet temperature of 500 to 700°C, a catalyst residence time of 3 to 60 seconds, a propane residence time of 1 to 30 seconds, and a reaction gas space velocity of 5 to 50 h. -1 A fluidized bed hydrocarbon dehydrogenation method characterized in that it is carried out within the scope of .

10. In the 6th paragraph, the catalyst regeneration is performed at a regeneration gas space velocity of 0.1 to 50 h -1 A fluidized bed hydrocarbon dehydrogenation method characterized in that it is performed within the range of 1 to 40 minutes for a processing time and 550 to 750°C for a temperature.

11. A fluidized bed hydrocarbon dehydrogenation method, characterized in that, in paragraph 6, a Group VIII noble metal catalyst selected from the group consisting of platinum, palladium, iridium, rhodium, osmium, ruthenium, or a mixture thereof is used as the dehydrogenation catalyst.

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