KR20190079406A - Dehydrogenation appratus and method - Google Patents

Abstract

The present invention relates to a dehydrogenation reaction apparatus and a method for improving reaction performance of a catalyst by preventing deactivation of a catalyst due to coke generation in a dehydrogenation system in which a plurality of moving bed dehydrogenation reactors are connected in series. According to the present invention, the reaction performance of the catalyst can be improved by preventing deactivation of the catalyst due to coke generation, thereby improving an overall process yield. In addition, according to the present invention, since a coke generation amount of the catalyst is reduced, a problem of increasing a coke generation amount caused by harsh operation under a hydrogen-to-hydrocarbon consumption down operation condition is solved, thereby being able to drastically increase a process yield by the hydrogen-to-hydrocarbon consumption down operation.

Description

[0001] DEHYDROGENATION APPRATUS AND METHOD [0002]

The present invention relates to a dehydrogenation apparatus and process, and more particularly to a dehydrogenation apparatus and process which can be used to convert paraffins from the corresponding olefins, for example propane to propylene or butane to butylene.

In the petrochemical industry, continuous catalytic conversion proceeds. The Moving Catalyst Dehydrogenation Process of Hydrocarbons is an important process in the production of light hydrocarbon components and is an important process in the production of ethylene and propylene. In the mobile phase catalytic dehydrogenation process, the catalyst circulates continuously between the reactor and the regenerator.

The types of reactors used in the conventional dehydrogenation process are two types of reactors: a moving bed type and a fixed bed type. Among them, a mobile phase type reactor includes a plurality of moving bed reactors connected in series do.

Patent Publication No. 2016-0022313 includes one or more reactors 25 in which the catalyst 65 is moved through a series of reactors 25 and after the catalyst 70 is discharged from the last reactor 25 Discloses a conventional dehydrogenation system in which the catalyst coke is burned in the catalyst regeneration zone 15 and the catalyst is transported back to the first reactor 25 after the regeneration step.

The dehydrogenation reaction is a strong endothermic reaction and requires a high temperature of 600 DEG C or higher in order to proceed the reaction at a satisfactory rate. The coke produced in the catalyst by the continuous reaction of the catalyst continuously increases as the dehydrogenation reaction progresses, and the catalytic activity gradually decreases. Inactivation of the catalyst can reduce the activity of the catalyst for alkane dehydrogenation and the selectivity for alkene formation. As a result, the process efficiency is deteriorated. Therefore, the catalyst that has passed through the third reactor 25, which is the last reactor, undergoes a regeneration process of removing the coke from the catalyst regenerator 75. In particular, in the case of the third reactor 25, the catalyst is irreversibly deactivated due to a sharp increase in the coke, and thus the process yield is drastically reduced.

In recent years, the reaction heat supplied to each reactor decreases, and the reactors may be connected to the reactor in four or more stages in order to reduce the load of the heater and reduce the process unit intensity by increasing the reaction selectivity. Despite the regeneration of the catalyst in the dehydrogenation process in which the mobile bed reactor is connected in multiple stages, the performance of the catalyst deteriorates with time in accordance with the catalyst dehydrogenation reaction. This is especially true when the reactor is used in three or more stages. Regeneration of the catalyst proceeds under conditions that adversely affect the properties of the catalyst. The properties of the catalyst change and the catalyst is caked, and the activity of the catalyst can be lowered in a few cycles. When the catalyst regenerator is placed at the end of the last reactor and the catalyst is discharged at the last reactor stage to regenerate, the dehydrogenation reaction proceeds under the same conditions with the same catalyst transfer rates of all the reactors. That is, the reaction rate can not be controlled according to the conditions of each reactor, so that the production of coke can not be appropriately controlled and the process operation is considerably difficult.

SUMMARY OF THE INVENTION It is an object of the present invention to overcome the problems of the prior art described above and one object of the present invention is to provide a hydrocarbon dehydrogenation apparatus having three or more reactors in which a reactant stream is continuously moved, And to provide a dehydrogenating device capable of improving the yield of the dehydrogenation process.

It is a further object of the present invention to provide a method and apparatus for controlling the feed rate of catalysts in the front-end reactors and the downstream-end reactors of the dehydrogenation reaction system, The present invention provides a dehydrogenating apparatus and method which can drastically reduce coke production amount of a catalyst during a downward operation.

It is still another object of the present invention to solve the problem of increased coke production due to severe operation under the downward operating conditions of hydrogen-to-hydrocarbon ratios during the dehydrogenation process and to reduce dehydration which can increase the production amount by hydrogen- And to provide a fire extinguishing system and method.

It is a further object of the present invention to maintain a certain level of catalytic activity over many cycles and to inhibit the formation of carbon-containing deposits so that the selectivity to the desired process of activity and dehydrogenation of the catalyst, even after a number of regeneration cycles, And to provide a dehydrogenation apparatus and a method capable of preventing dehydration.

According to an aspect of the present invention,

A plurality of moving bed dehydrogenation reactors connected in series, said at least one moving bed dehydrogenation reactors being disposed between any two adjacent dehydrogenation reactors of said plurality of moving bed dehydrogenation reactors and comprising at least one combustion zone for combusting and removing coke, An interreactor catalyst regenerator for regenerating the deactivated catalyst transferred from the reactor upstream of the period catalyst regenerator and recirculating the deactivated catalyst to the first reactor; And a main catalyst disposed downstream of the last reactor and containing at least one combustion zone for burning off the coke to regenerate the deactivated catalyst transferred from the last reactor and recycle it to the reactor next to the reactor during the reaction period And a regenerator (main catalyst regenerator).

In the present invention, the moving bed dehydrogenation reactor may be a four-stage reactor, and the reaction period catalyst regenerator may be installed between the second reactor and the third reactor.

The moving bed dehydrogenation reactor may be a four-stage reactor, and the reaction period catalyst regenerator may be installed between the third reactor and the fourth reactor.

The mobile bed dehydrogenation reactor may comprise a five-stage reactor, and the reaction period catalyst regenerator may be installed between the third reactor and the fourth reactor.

The moving bed dehydrogenation reactor may be configured as a five-stage reactor, and the reaction period catalyst regenerator may be installed between the fourth reactor and the fifth reactor.

The moving bed dehydrogenation reactor may be a five-stage reactor, and the reaction period catalyst regenerator may be installed between the second reactor and the third reactor.

The reaction period catalyst regenerator includes a first catalyst breakage impurity separation drum for separating cracked or crumbled catalyst fragments from the catalyst stream; A first surge drum for accommodating a catalyst whose impurities have been removed; A first regenerative reactor comprising at least one combustion zone in which a regeneration reaction for the catalyst from the first surge drum proceeds; A first flow control hopper for controlling a feed rate of regenerated catalyst discharged from the first regeneration reactor; A first hopper for separating and supplying hydrocarbons from the regenerated catalyst stream; And a first lifting unit for supplying regenerated catalyst delivered from the first hopper to the first reactor.

The main catalyst regenerator includes a second catalyst breakage impurity separation drum for separating cracked or crushed catalyst fragments from the catalyst stream; A second surge drum for containing the impurity-removed catalyst; A second regeneration reactor comprising at least one combustion zone in which a regeneration reaction for the catalyst from the second surge drum proceeds; A second flow control hopper for controlling a feed rate of regenerated catalyst discharged from the second regeneration reactor; A second hopper for separating and supplying hydrocarbons from the regenerated catalyst stream; And a second lifting inlet for feeding the regenerated catalyst passed from the second hopper to the reactor at the next stage of the reaction period catalyst regenerator.

The dehydrogenation apparatus may further include a transfer means for transferring the deactivated catalyst from the reactor upstream of the reaction period catalyst regenerator to the first catalyst regenerator.

Another aspect of the present invention is a method for dehydrogenating hydrocarbons through a plurality of moving bed dehydrogenation reactors comprising the steps of: contacting a hydrocarbon with a dehydrogenation catalyst using a plurality of reactors connected in series to effect dehydrogenation; Between any two adjacent reactors of the mobile bed dehydrogenation reactors, a reaction period catalyst regenerator is installed, and the deactivated catalyst transferred from the reactor upstream of the reaction period catalyst regenerator is used as a combustion gas An intermediate catalyst regeneration step in which the catalyst is recycled to the first reactor after being used for combustion; And a main catalyst regeneration step of recycling the inactivated catalyst transferred from the last reactor by burning the coke deposit on the catalyst particles with a combustion gas and then recycling it to the reactor at the next stage of the reaction period catalyst regenerator To a dehydrogenation process.

According to the method of the present invention, since the amount of coke produced at the regeneration rate condition decreases as the starting point of coke generation at the front and rear ends of the reactor is increased to two stages, the problem of increase in coke production due to harsh operation under the condition of hydrogen- The process yield can be greatly increased by downward operation of the hydrogen-to-hydrocarbon ratio.

In addition, according to the present invention, it is possible to operate the catalyst conveying speed downward compared with the conventional catalyst operating rate under the same coke producing operation condition, and thus, the main catalyst The pollution phenomenon of the causative substance can be alleviated, the life of the catalyst can be prolonged, and the phenomenon of catalyst contamination can be reduced, thereby preventing rapid increase in coke production.

In addition, according to the present invention, it is possible to improve the screen clogging of the reactor due to the catalyst breakage prevention effect due to the decrease in the number of catalyst transporting times, to improve the rate of increase of the pressure difference of the reactor, and to increase the yield of the dehydrogenation process by reducing the pressure difference.

According to the present invention, even when the catalyst regenerator is expanded to two or more stages and the catalyst containing the high concentration coke is included in the removal of the coke, the amount of heat generated in the combustion zone can be divided into two groups, It becomes possible to operate under severe operating conditions, and finally, the production amount of alkene can be remarkably increased.

According to the present invention, the activity of the catalyst for the conversion of an alkane can be adjusted and maintained to a value suitable for the process, and continuously obtains selectivity and high yield for the desired dehydrogenation process and inhibits the formation of coke Can be optimized.

1 is a schematic system configuration diagram of a dehydrogenation system according to the prior art.
2 is a schematic view showing a hydrocarbon dehydrogenating apparatus of an embodiment of the present invention.
3-7 are process diagrams illustrating a dehydrogenation process in accordance with various embodiments of the present invention.
8 is a schematic view showing a dehydrogenation apparatus of another embodiment of the present invention.

The present invention will now be described in more detail with reference to the accompanying drawings.

Although the term used in the present invention is a general term that is widely used at present, there are some terms selected arbitrarily by the applicant in a specific case. In this case, in consideration of the meaning stated or used in the description part of the invention, The meaning should be grasped. Like reference numerals designate like elements throughout the specification.

When an element is referred to herein as being "connected" or "connected" to another element, it may be directly connected or connected to the other element, but there may be other elements in between It should be understood. As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a stated feature, number, step, operation, component, part or combination thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, parts, or combinations thereof.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings are merely schematic representations of the multi-stage dehydrogenation reactor of the present invention and show only major components. Other heat exchangers, internal-heaters, moving pipes for catalyst delivery, pumps and other similar components have been omitted.

As used herein, the term "dehydrogenated hydrocarbon" is intended to include hydrocarbons wherein the molecule comprises at least two hydrogen atoms than the molecule of the hydrocarbon to be dehydrogenated. Otherwise, the term hydrocarbon is intended to include materials whose molecules are formed solely of carbon and hydrogen elements. The dehydrogenated hydrocarbons thus include in particular one or more carbon atoms in the molecule, acyclic and cyclic aliphatic hydrocarbons having carbon double bonds.

Examples of such aliphatic dehydrogenated hydrocarbons are propene, isobutene, ethylene, 1-butene, 2-butene and propylene. That is, the dehydrogenated hydrocarbons include, in particular, monounsaturated straight chain hydrocarbons (n-alkenes) or branched aliphatic hydrocarbons (e.g., isoalkenes), and also cycloalkenes. Further, the dehydrogenated hydrocarbons are also intended to include alkanepolyenes (e.g., dienes and trienes) that contain two or more carbon-carbon double bonds in the molecule. The dehydrogenated hydrocarbons are also intended to include hydrocarbon compounds obtainable from an alkylaromatic compound such as ethylbenzene or isopropylbenzene by dehydrogenation of an alkyl substituent. These are, for example, compounds such as styrene or? -Methylstyrene.

As used herein, the term "conversion" refers to the ratio of dehydrogenated hydrocarbons to hydrocarbons fed, which is converted when the reaction gas passes through the dehydrogenation reactor once.

The term "selectivity" as used herein means the number of moles of propylene obtained per mole of converted propane, expressed as a mole percentage.

FIG. 2 is a schematic view of a dehydrogenation apparatus for a hydrocarbon according to an embodiment of the present invention, FIGS. 3 to 7 are process drawings illustrating a dehydrogenation reaction process according to various embodiments of the present invention, FIG. 1 is a schematic view showing a dehydrogenation apparatus of another embodiment of the present invention. FIG. In the figure, the dehydrogenation catalyst stream is indicated by the solid arrow and the reactant stream is indicated by the dotted arrow.

Referring to FIG. 2, a dehydrogenation apparatus of an embodiment of the present invention includes a plurality of mobile bed dehydrogenation reactors 100, 200, 300, 400, 500 connected in series: a plurality of mobile bed dehydrogenation reactors A reaction regenerator installed between the two adjacent dehydrogenation reactors and including at least one combustion zone to regenerate the deactivated catalyst transferred from the reactor upstream of the reaction period catalyst regenerator and recycle it to the first reactor, catalyst regenerator 700; And a main catalyst regenerator provided at the end of the last reactor and including at least one combustion zone for regenerating the deactivated catalyst transferred from the last reactor and then recirculating the deactivated catalyst to the reactor at the end of the reaction period catalyst regenerator, (800).

In the present invention, the dehydrogenation reactors may be composed of three or more stages, preferably four or more stages, more preferably five or more stages. 2, the dehydrogenation reactor 100 of the present invention includes a first reactor 100, a second reactor 200, a third reactor 300, a fourth reactor 400, and a fifth reactor 500 ). The first reactor 100 is supplied with a feed gas stream comprising hydrocarbon (e.g., propane) to be dehydrogenated, hydrogen or steam, and the gas stream supplied by a heater (not shown) connected to the first reactor 100 Is heated and supplied. Is supplied directly to the second reactor (200) and is dehydrogenated in the second reactor to recover the first product stream. Next, the first product stream and the vapor and the catalyst, which has been reacted in the first reactor 100, are supplied to the second reactor 200 connected to the heater to perform the dehydrogenation reaction in the second reactor 200, (200). ≪ / RTI > Next, the second product stream is supplied to a third reactor 300 connected with a heater, dehydrogenated in a third reactor 300, and the third product stream is recovered from the third reactor 300. The third product stream is supplied to the fourth reactor 400 connected to the heater and dehydrogenated in the fourth reactor 400. The fourth product stream is supplied to the fifth reactor 500 connected to the heater, Dehydrogenation reaction is performed in the reactor 500 and the fifth effluent stream from the fifth reactor 500 is recovered by a product separator (not shown). The term " product stream " generated in each stage reactor means a reaction product produced through the dehydrogenation reaction and includes hydrogen, propane, propylene, ethane, ethylene, methane, butane, butylene, butadiene, nitrogen, oxygen, water vapor, carbon monoxide or carbon dioxide Or a gas or liquid containing a dispersed solid, or a mixture thereof.

3, the mobile phase dehydrogenation reactor is composed of four-stage reactors 100 to 400, and the reaction period catalyst regenerator 700 is connected to the second reactor 200 and the third reactor 200. In this embodiment, (300). The catalyst regenerated by the catalyst regenerator 700 is injected into the first reactor 100 and the catalyst regenerated by the main catalyst regenerator 800 downstream of the fourth reactor 400 is injected into the third reactor 300 .

In another embodiment, as shown in FIG. 4, the mobile bed dehydrogenation reactor is comprised of a four-stage reactor 100-400, the reactor catalyst regenerator 700 includes a third reactor 300, (400). The catalyst regenerated by the catalyst regenerator 700 in the reaction period is injected into the first reactor 100 and the catalyst regenerated by the main catalyst regenerator 800 downstream of the fourth reactor 400 is injected into the fourth reactor 400 .

5, the mobile bed dehydrogenation reactor is composed of a five-stage reactor 100-500, and the reaction period catalyst regenerator 700 includes a third reactor 300 and a fourth reactor (400). The catalyst regenerated by the catalyst regenerator 700 is injected into the first reactor 100 and the catalyst regenerated by the main catalyst regenerator 800 downstream of the fifth reactor 500 is injected into the fourth reactor 400 .

In another embodiment, as shown in FIG. 6, the mobile bed dehydrogenation reactor is comprised of a five-stage reactor and the reaction period catalyst regenerator 700 is disposed between the fourth reactor 400 and the fifth reactor 500 Can be installed. Here, the catalyst regenerated in the reaction period catalyst regenerator 700 is injected into the first reactor 100, and the catalyst regenerated by the main catalyst regenerator 800 in the downstream end of the fifth reactor 500 is injected into the fifth reactor 500 .

7, the mobile bed dehydrogenation reactor is composed of a five-stage reactor, and the reaction period catalyst regenerator 700 is provided between the second reactor 200 and the third reactor 300 Can be installed. The catalyst regenerated by the catalyst regenerator 700 in the reaction period is injected into the first reactor 100 and the catalyst regenerated by the main catalyst regenerator 800 downstream of the fifth reactor 500 is injected into the third reactor 300 .

In the present invention, the dehydrogenation reactor (100-500) may be any type of reactor known in the art. For example, the dehydrogenation reactor (100-500) may be a tubular reactor, a shaping reactor, or a mobile phase reactor. A feed gas stream such as propane or the like is fed to five or more dehydrogenation reactors (100-500) to catalyze dehydrogenation. In this process step, propane is partially dehydrogenated on the dehydrogenation-active catalyst in the dehydrogenation reactor to give propylene. In addition, hydrogen and small amounts of methane, ethane, ethene and C4 + hydrocarbons (n-butane, isobutane, butene) are obtained.

The reaction period catalyst regenerator 700 includes a first catalyst breakage impurity separation drum 720 for separating cracked or crumbled catalyst fragments from the catalyst stream; A first surge drum 730 to receive the impurity-removed catalyst; A first regeneration reactor (710) comprising at least one combustion zone in which a regeneration reaction for the catalyst from the first surge drum proceeds; A first flow control hopper (740) for controlling the feed rate of the regenerated catalyst discharged from the first regeneration reactor; A first hopper 750 for separating and supplying hydrocarbons from the regenerated catalyst stream; And a first lifting input portion 760 for supplying the regenerated catalyst delivered from the first hopper to the first reactor.

The main catalyst regenerator 800 includes a second catalyst breakage impurity separation drum 820 for separating cracked or crushed catalyst fragments from the catalyst stream; A second surge drum 830 to receive the impurity-removed catalyst; A second regenerative reactor (810) comprising at least one combustion zone in which a regeneration reaction for the catalyst from the second surge drum proceeds; A second flow control hopper 840 for controlling the feed rate of regenerated catalyst discharged from the second regenerating reactor; A second hopper 850 for separating and supplying hydrocarbons from the regenerated catalyst stream; And a second lifting and charging unit 860 for supplying regenerated catalyst delivered from the second hopper to the reactor at the next stage of the reaction period catalyst regenerator 700.

The dehydrogenation apparatus of the present invention may further include a transporting means for transporting the deactivated catalyst from the reactor upstream of the reaction catalyst regenerator 700 to the catalyst regenerator 700 of the reaction period. The catalyst transferring means includes a catalyst collector 310 for collecting the catalyst discharged from the reactor, a hopper 320 for converting the catalyst atmosphere into a nitrogen atmosphere in a hydrogen / hydrocarbon atmosphere, and a lifting And an input unit 330. In the dehydrogenation apparatus of the present invention, similar catalyst transfer means may be connected to the lower end of each reactor 100-500.

When the dehydrogenation apparatus shown in FIGS. 2 and 8 dehydrogenates hydrocarbons, the hydrocarbon feed gas stream flows into the first reactor 100 and reacts with the hydrocarbon feed gas stream, and then reheated by a heater (not shown) 200, and reacted. After passing through the third reactor 300, the fourth reactor 400, and the fifth reactor 500 through the same process, a separation process is performed. Also, the dehydrogenation catalyst stream is continuously transferred from the first reactor 100 to the third reactor 300 in the same manner as the hydrocarbon feed gas stream, and then transferred to the reaction period catalyst regenerator 700.

Another aspect of the present invention relates to a dehydrogenation process. In the method of the present invention, in the dehydrogenation of hydrocarbons through a plurality of mobile bed dehydrogenation reactors, dehydrogenating the hydrocarbon by contacting the hydrocarbon with a dehydrogenation catalyst using a plurality of reactors connected in series, Between any two adjacent reactors of the digestion reactors, a reaction period catalyst regenerator (700) is installed, and an inactivated catalyst transferred from the reactor upstream of the reaction period catalyst regenerator is burned and regenerated by burning the catalyst coke An intermediate catalyst regeneration step in which the catalyst is recycled to the first reactor 100; And a main catalyst regeneration step of recycling the deactivated catalyst transferred from the last reactor by burning and regenerating the coke on the catalyst and recycling it to the reactor at the next stage of the reaction period catalyst regenerator 700.

The intermediate catalyst regeneration step essentially comprises the step of burning the coke deposits on the spent catalyst particles with a combustion gas (e.g., an oxygen-containing gas), optionally contacting the catalyst particles with a chlorinated gas, One or more of the steps of chlorinating the catalyst particles to redisperse the platinum or the like and drying to remove the water caused by the upstream reaction in the chlorinated catalyst may be additionally carried out.

The method of the present invention further includes a main catalyst regeneration step of regenerating the catalyst by transferring the inactivated catalyst that has terminated the reaction in the last reactor to the main catalyst regenerator connected to the last reactor. In the main catalyst regeneration step, it is essential to burn the coke deposit on the spent catalyst particles by using a combustion gas (for example, an oxygen-containing gas). The catalyst particles are contacted with chlorine gas, The catalyst may be regenerated through one or more of the following steps: chlorination of the catalyst particles to redisperse the catalyst, and drying to remove water caused by the upstream reaction in the chlorinated catalyst.

The method of the present invention further comprises adjusting the catalyst transfer rate in the dehydrogenation reactor in the front end of the catalyst before the reaction period catalyst regenerator and the catalyst transfer rate in the dehydration reactor in the catalyst reaction regenerator rear end. For example, when the dehydrogenation apparatus is composed of a four-stage dehydrogenation reactor, the first reactor 100 and the second reactor 200 or the first reactor 100 in the front stage of the reaction period catalyst regenerator 700, To the third reactor 300 can be individually adjusted differently from the catalyst transfer rates in the third reactor 300 and the fourth reactor 400 or the fourth reactor 400 in the downstream stage. In the case where the dehydrogenation apparatus is composed of a five-stage dehydrogenation reactor, the first reactor 100 and the second reactor 200 in the former stage of the reaction period catalyst regenerator 700, or the first reactor 100, 3 catalyst or the first reactor 100 to the fourth reactor 400 may be carried out in the third reactor to the fifth reactor 500 or the fourth reactor 400 or the fourth reactor 500, The fifth reactor 500, or the fifth reactor 500, as shown in FIG.

The catalyst transport speed is faster than the reactors disposed at the upstream side in the reactors located between the reaction period catalyst regenerator and the main catalyst regenerator disposed at the rear stage of the reactor. The reason for this is that as the content of olefins including propylene, which is a main component of the catalyst coke, increases toward the downstream of the reactor and the average reaction temperature tends to increase, the catalyst coke production rate increases, This is because it is necessary to prevent the reduction of the catalytic activity by the catalyst.

In the present invention, the catalyst feed rate can be adjusted differently for each reactor stage. In the present invention, a catalyst discharge regulator (not shown) is installed at the lower part of the reaction regenerator and the lower part of the main catalyst regenerator to divide the catalyst regenerator position at the front end, The feed speed can be adjusted differently. However, in the reactors disposed in front of each catalyst regenerator, the catalysts are operated at the same catalyst circulation speed.

For example, in the dehydrogenation of propane, in a series of dehydrogenation processes, the feed gas stream is preheated to 600-700 < 0 > C and dehydrogenated in the mobile bed dehydrogenation reactor to produce a product gas stream comprising propane, propylene, .

The catalyst transfer rate in the conventional dehydrogenation reactor is determined by one catalyst regulator (not shown) at the lower part of the catalyst regenerator, so that the reaction can be carried out under the same conditions as the catalyst transfer rates of all the reactors. On the other hand, in the present invention, the catalyst conveying speeds of the shear reactors (the first reactor to the second reactor or the first reactor to the third reactor) and the downstream reactors (the third reactor to the fifth reactor or the fourth reactor to the fifth reactor) Can be regulated by a catalyst regenerator and a catalyst discharge rate regulator installed in the lower part of the main catalyst regenerator, respectively, so that the catalyst feed rate can be controlled differently for each reactor end. The production amount can be increased when the ratio of hydrogen to the hydrocarbon in the starting gas mixture is low. However, in the conventional system, the production amount of coke increases and it is difficult to operate the hydrogen-to-hydrocarbon ratio downward. However, in the present invention, the amount of coke produced can be controlled during the dehydrogenation process operation by controlling the catalyst transfer rate in each reactor, thereby increasing the production amount. The molar ratio of hydrogen to hydrocarbons in the starting gas mixture used in the dehydrogenation process according to the present invention can be adjusted down to 0.5 or less. In this way, the reaction yield can be improved by 5% to 10% and the reaction selectivity can be improved by 2 to 5% by lowering the ratio of hydrogen and hydrocarbon.

The dehydrogenation process of the present invention can be applied to the dehydrogenation of alkane hydrocarbons such as ethane, propane, isobutane, n-butane, pentane, hexane, heptane and octane. While the foregoing has specifically described the dehydrogenation reaction of propane for the production of propylene, as is understood by those of ordinary skill in the art through the disclosure herein, the disclosure is directed to an alkane containing two or more carbon atoms, For example, it can be used in a dehydrogenation reaction to convert ethane, n-butane, isobutane and pentane to the corresponding olefins.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. This will be obvious. Accordingly, the true scope of protection of the present invention should be defined in the appended claims and their equivalents.

100, 200, 300, 400, 500: dehydrogenation reactor
110, 210, 310, 410, 510: a catalyst collector
120, 220, 320, 420, 520: hopper
130, 230, 330, 430, 530:
700: reaction period catalyst regenerator (interreactor catalyst regenerator)
800: main catalyst regenerator
710: First regeneration reactor 810: First regeneration reactor
720: first catalyst debris separation drum 820: second catalyst debris separation drum
730: first surge drum 830: second surge drum
740: first flow control hopper 840: second flow control hopper
750: first hopper 850: second hopper
760: first lifting input portion 860: second lifting input portion
10: Separate blower 20: Dust collector

Claims (18)

A plurality of moving bed dehydrogenation reactors connected in series, said at least one moving bed dehydrogenation reactors being disposed between any two adjacent dehydrogenation reactors of said plurality of moving bed dehydrogenation reactors and comprising at least one combustion zone for combusting and removing coke, An interreactor catalyst regenerator for regenerating the deactivated catalyst transferred from the reactor upstream of the period catalyst regenerator and recirculating the deactivated catalyst to the first reactor; And a main catalyst disposed downstream of the last reactor and containing at least one combustion zone for burning off the coke to regenerate the deactivated catalyst transferred from the last reactor and recycle it to the reactor next to the reactor during the reaction period And a main catalyst regenerator. 2. The dehydrogenation apparatus of claim 1, wherein the mobile bed dehydrogenation reactor is comprised of a four-stage reactor, and the reaction period catalyst regenerator is installed between the second reactor and the third reactor. The dehydrogenation apparatus of claim 1, wherein the mobile bed dehydrogenation reactor is comprised of a four-stage reactor, and the reaction period catalyst regenerator is installed between the third reactor and the fourth reactor. The dehydrogenation apparatus of claim 1, wherein the mobile bed dehydrogenation reactor is comprised of a five-stage reactor, and the reaction period catalyst regenerator is installed between the third reactor and the fourth reactor. The dehydrogenation apparatus of claim 1, wherein the mobile bed dehydrogenation reactor is comprised of a five-stage reactor, and the reaction period catalyst regenerator is installed between the fourth reactor and the fifth reactor. The dehydrogenation apparatus of claim 1, wherein the mobile bed dehydrogenation reactor is comprised of a five-stage reactor, and the reaction period catalyst regenerator is installed between the second reactor and the third reactor. The process of claim 1, wherein the reaction period catalyst regenerator comprises: a first catalyst breakage impurity separation drum for separating cracked or crumbled catalyst fragments from the catalyst stream; A first surge drum for accommodating a catalyst whose impurities have been removed; A first regeneration reactor including a combustion zone in which a regeneration reaction for the catalyst from the first surge drum proceeds; A first flow control hopper for controlling a feed rate of regenerated catalyst discharged from the first regeneration reactor; A first hopper for separating and supplying hydrocarbons from the regenerated catalyst stream; And a first lifting inlet for supplying regenerated catalyst delivered from the first hopper to the first reactor. 8. The dehydrogenation apparatus of claim 7, wherein the first regenerative reactor further comprises at least one of a chlorination zone and a drying zone in addition to the combustion zone. 2. The apparatus of claim 1, wherein the main catalyst regenerator comprises: a second catalyst breakage impurity separation drum for separating crushed or crushed catalyst fragments from the catalyst stream; A second surge drum for containing the impurity-removed catalyst; A second regenerative reactor including a combustion zone in which a regeneration reaction for the catalyst from the second surge drum proceeds; A second flow control hopper for controlling the feed rate of the regenerated catalyst discharged from the first regeneration reactor; A second hopper for separating and supplying hydrocarbons from the regenerated catalyst stream; And a second lifting inlet for supplying the regenerated catalyst delivered from the second hopper to a reactor downstream of the interreactor catalyst regenerator. 10. The dehydrogenation apparatus of claim 9, wherein the second regeneration reactor further comprises at least one of a chlorination zone and a drying zone in addition to the combustion zone. The dehydrogenation apparatus of claim 1, wherein the dehydrogenation apparatus further comprises transport means for transporting the deactivated catalyst from the reactor upstream of the reaction period catalyst regenerator to the first catalyst regenerator. The apparatus according to claim 1, wherein the catalyst transferring means comprises: a catalyst collector for collecting the catalyst discharged from the reactor; a hopper for converting the catalyst atmosphere into a nitrogen atmosphere in a hydrogen / hydrocarbon atmosphere; Wherein the dehydrogenation unit is configured as a dehydrogenation unit. A process for dehydrogenating hydrocarbons through a plurality of mobile bed dehydrogenation reactors comprising the steps of contacting the hydrocarbon with a dehydrogenation catalyst using a plurality of reactors connected in series and dehydrogenating the dehydrogenation reaction, , An inactivated catalyst transferred from the reactor in front of the reaction period catalyst regenerator is regenerated by burning the coke deposits on the catalyst particles with a combustion gas An intermediate catalyst regeneration step wherein the intermediate catalyst is recycled to the first reactor; And a main catalyst regeneration step of recycling the inactivated catalyst transferred from the last reactor by burning the coke deposit on the catalyst particles with a combustion gas and then recycling it to the reactor at the next stage of the reaction period catalyst regenerator ≪ / RTI > 14. The method of claim 13, wherein the intermediate catalyst regeneration step further comprises: chlorinating the catalyst particles after the combustion step, in addition to burning the coke deposit on the spent catalyst particles with a combustion gas; And drying the chlorinated catalyst to form regenerated catalyst particles. ≪ RTI ID = 0.0 > 11. < / RTI > 14. The method of claim 13, wherein the regenerating the primary catalyst further comprises: chlorinating the catalyst particles in addition to burning the coke deposit on the spent catalyst particles using a combustion gas; And drying the chlorinated catalyst to form regenerated catalyst particles. ≪ RTI ID = 0.0 > 11. < / RTI > 14. The method of claim 13, further comprising adjusting the catalyst transport rate in the dehydrogenation reactors at the front end of the reactor prior to the reaction period catalyst regenerator and the catalyst transport rate in the dehydration reactors at the rear end of the reaction period catalyst regenerator differently . 14. The dehydrogenation process according to claim 13, wherein the dehydrogenation reaction is carried out under a hydrogen / hydrocarbon ratio of 0.5 or less. 18. The method according to any one of claims 13 to 17,
Wherein the process is used for the dehydrogenation of alkane hydrocarbons selected from the group consisting of ethane, propane, isobutane, n-butane, pentane, hexane, heptane and octane.

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