CN117339494A

CN117339494A - Method, device and system for removing catalyst micropowder in ebullated bed reactor

Info

Publication number: CN117339494A
Application number: CN202311445618.4A
Authority: CN
Inventors: 李剑平; 赵玮; 张桐; 常玉龙; 杨雪晶; 江霞; 刘洪来; 汪华林
Original assignee: Sichuan University; East China University of Science and Technology
Current assignee: Sichuan University; East China University of Science and Technology
Priority date: 2023-11-01
Filing date: 2023-11-01
Publication date: 2024-01-05

Abstract

The invention belongs to the technical field of biomass energy equipment, and particularly discloses a method, a device and a system for removing catalyst micro powder in an ebullated bed reactor, aiming at solving the problem of how to reduce escape or running loss of a catalyst with the particle size of less than 0.1 mm. The method, the device and the system provided by the invention can lead the liquid-solid mixed phase product out of the ebullated bed reactor and separate the liquid-solid mixed phase product by utilizing the action of a centrifugal force field, so as to remove and collect the catalyst micro powder with the particle size below 30 mu m, realize the regeneration of the catalyst micro powder and reduce the escape or the running loss of the catalyst with the particle size below 0.1mm filled by reaction. The catalyst micro powder in the liquid-solid mixed phase product is removed, so that the catalyst micro powder can be prevented from returning to the ebullated bed reactor along with the recycled liquid phase, and the problems of wall corrosion caused by the adhesion of the catalyst micro powder to the wall surface through which the catalyst micro powder flows, reaction efficiency reduction caused by the coking of the catalyst and the like are avoided.

Description

Method, device and system for removing catalyst micropowder in ebullated bed reactor

Technical Field

The invention belongs to the technical field of biomass energy equipment, and particularly relates to a method, a device and a system for removing catalyst micro powder in an ebullated bed reactor.

Background

The ebullated bed hydrogenation reactor is a device for realizing the mixing, mass transfer and heat transfer between solid particles and gas phase and liquid phase, and is a common reactor in industry. Since the development of the reactor, the reactor is mainly used for processing high sulfur, high nitrogen, high metal (nickel and vanadium), poor heavy residual oil with high asphaltene content, coal tar or biomass oil produced by coal pyrolysis, and the like which are difficult to process in the traditional technology, and is widely applied to petrochemical industry and new energy manufacturing industry. The advantages of ebullated bed hydrogenation reactors can be summarized as follows: (1) the adaptability of the raw materials is strong; (2) the reaction rate is high; (3) the operation condition is flexible; (4) the catalyst can be replaced on line, and the product quality is relatively stable; (5) the internal temperature difference is small, so that local overheating is avoided, and the bed pressure is reduced; (6) the device has long running time.

Review the recent decades of commercial development history of ebullated bed hydrogenation reactors, and can be categorized into two major categories, the expanded bed regime and the full mixed flow ebullated bed regime, depending on the state of catalyst fluidization within the reactor. The ebullated bed hydrogenation reactor in the expanded bed state is mainly based on foreign H-Oil and LC-Fining technologies and derivative technologies thereof; the gas-liquid-solid mixed flow boiling bed type hydrogenation reactor is represented by domestic petrochemical 'STRONG' technology. The functional requirements for the separators arranged in ebullated bed hydrogenation reactors are also quite different, due to the different fluidization conditions of the catalysts inside the two types of reactors. For the ebullated bed hydrogenation reactor in the expanded bed state, after the internal catalyst bed is expanded to a certain height, the upper part of the reactor is a sedimentation zone of catalyst particles, and a gas-liquid two-phase product without solid particles is obtained, so that the requirement for a separator arranged in the reactor is to perform gas-liquid two-phase separation; for a gas-liquid-solid total mixed flow ebullated bed type hydrogenation reactor, the space from the distribution plate to the height of the material surface of the reactor is a gas-liquid-solid three-phase mixture, so that the gas-liquid-solid three-phase separation is required for the separator arranged in the reactor.

In the case of ebullated bed hydrogenation reactors in the expanded bed state, for example: U.S. patent application US20170081599A1 discloses a ebullated bed hydrogenation reactor that can control the reaction rate by a circulation channel in the center of the reactor and a circulation cup at the top to keep the heat released by the reaction at a safe level; also for example: chinese patent No. CN103102930B discloses a ebullated bed hydrogenation reactor, which can effectively improve the mass transfer efficiency of gas-liquid two phases through a circulation cup at the upper part and a circulation pipeline at the lower part in the reactor cylinder; similarly, in order to improve the mass transfer efficiency of the gas-liquid two phases, chinese patent No. CN103100356B discloses a ebullated bed hydrogenation reactor, in which a rotatable centrifugal impeller is disposed in a circulation line at the lower part of the reactor cylinder. In summary, it can be found that the ebullated bed hydrogenation reactor in the expanded bed state actively controls the flow of the gas-liquid two phases entering the reactor, indirectly controls the expansion height of the catalyst bed, realizes the separation of the gas-liquid two phases and the catalyst particles in the settling zone at the upper part of the bed, and adopts a circulating cup and a circulating channel at the upper part of the reactor cylinder body, thereby realizing the separation of the gas-liquid two phase products, and further meeting the production requirements. However, such reactors suffer from the following disadvantages: (1) low reactor space utilization. The sedimentation area of catalyst particles is needed to be reserved in the expanded bed state, so that the effective utilization space in the reactor is less; and (2) the mass transfer resistance of the catalyst is large, and the conversion rate is low. The separation of the catalyst particles in the expanded bed state is completely settled by the gravity of the catalyst, so that the granularity of the catalyst filler is larger, the mass transfer process of the catalyst is influenced, and the conversion rate is low; (3) Catalyst particles are easy to coke, and the operation period of the reactor is short. Because the gas phase and the liquid phase are separated by the circulating cup at the upper part of the reactor in the state of the expanded bed, the separation strength is smaller, the separation time is longer, and the liquid phase product is easy to coke with the fine particle catalyst in the sedimentation zone. Therefore, under the conditions of increasingly complicating and inferior oil products, the reactor in the gas-liquid-solid fully mixed flow state is the development direction of the fluidized bed hydrogenation reactor in the future.

In the aspect of the fluidized bed hydrogenation reactor in a gas-liquid-solid fully mixed flow state, the technology of petroleum and chemical industry and the derivative technology thereof are represented in China, and the fluidized bed hydrogenation reactor is mainly characterized in that a three-phase separator with a three-layer or multi-layer concentric sleeve structure is arranged at the top of the reactor, and three-phase separation is mainly realized by baffling sedimentation, for example: the Chinese patent application CN1448212A only depends on the gravity action of the catalyst particles and cannot be disturbed by external fluid, and has certain limitation on the fluidization operation. Then, in order to optimize gravity sedimentation conditions, a Z-shaped baffle structure is arranged between an inner support cylinder and an outer support cylinder on the basis of CN1448212A in the Chinese patent application CN 108114510A; the Chinese patent application CN101721960A is characterized in that the concentric inner cylinder and the outer cylinder are designed into a structure with an inverted cone at the upper part and a positive cone at the lower part; in addition, on the basis of CN1448212A, a diamond-shaped diversion cone is arranged below the three-phase separator in the Chinese patent application CN 101721961A. Said invented patent application optimizes separation condition to different extent, but its substantial separation principle still depends on baffling sedimentation, and its separation efficiency and accuracy are limited by operation condition of reactor and catalyst grain size.

To solve the above problems, researchers have begun to introduce a swirling field into the ebullated bed hydrogenation reactor to enhance separation and to define the particle size requirements of the catalyst. For example: the Chinese patent application CN109967001A discloses a three-phase separator of a biomass pyrolysis liquid ebullated bed reactor and application thereof, and mainly strengthens the separation process by introducing a swirl field, and has the advantages of compact structure, good separation effect and the like, but the particle size of catalyst particles is at least more than 0.2mm, the specific surface area of the catalyst is small, the mass transfer efficiency is low, and the use effect of the catalyst particles with small particle size cannot be achieved. Therefore, chinese patent No. CN113244860B discloses a fluidized bed hydrogenation reactor and a method for using the same, wherein the fluidized bed hydrogenation reactor is provided with a baffle plate disposed in an upper space of the reactor and a gas-liquid-solid three-phase cyclone separator connected with the baffle plate, and the gas-liquid-solid three-phase separation is enhanced by cyclone separation, baffle separation and guide vane separation methods; similarly, chinese patent No. 113083170B discloses a fluidized bed hydrogenation reactor, which enhances the separation effect by a dynamic cyclone and a guide vane through a designed autorotation gas-liquid-solid three-phase cyclone separator, and meanwhile, the particle size of catalyst particles filled in the reactor is 0.05-0.1 mm, so that the mass transfer efficiency of the catalyst can be remarkably enhanced. However, the use of the catalyst with the particle diameter of 0.05-0.1 mm inevitably leads to the problems that in the operation process of the three-phase cyclone separator, some catalyst micropowder escapes or runs away from a gas phase outlet, and the wall surface of the reactor is coked to cause the wall surface corrosion and self-coking deactivation to cause the reduction of reaction efficiency and the like.

In view of the foregoing, there is a strong need in the art to develop a process and apparatus that overcomes the above-mentioned drawbacks in order to reduce catalyst slip or run-out, and coking and deactivation behavior, and to increase the operating efficiency of ebullated bed hydrogenation reactors.

Disclosure of Invention

The invention provides a method, a device and a system for removing catalyst micro powder in a fluidized bed reactor, which aim to solve the problem of how to reduce escape or run-away of a catalyst with the particle size of less than 0.1 mm.

The technical scheme adopted for solving the technical problems is as follows: the method for removing the catalyst micropowder in the ebullated bed reactor comprises a liquid-solid mixed phase product extraction step and a micropowder removal step;

leading out the liquid-solid mixed phase product: the three-phase mixture is discharged from a gas phase outlet of the ebullated bed reactor to a part of gas phase, and is centrifugally separated in the ebullated bed reactor by a three-phase separator, and substances remained in an overflow pipe of the three-phase separator after separation are liquid-solid mixed phase products, and the liquid-solid mixed phase products are led out of the ebullated bed reactor;

and (3) removing micro powder: separating the extracted liquid-solid mixed phase product under the action of a centrifugal force field, and removing and collecting the catalyst micro powder; the particle size of the catalyst micropowder is below 30 mu m.

Further, the method comprises the following steps:

s1, loading a three-phase mixture into a fluidized bed reactor for reaction, wherein in the process that the three-phase mixture flows to the upper part of the fluidized bed reactor under the fluidization effect, large bubbles are broken under the inertia effect and continue to move upwards to be discharged from a gas phase outlet;

s2, separating the residual liquid phase substances and catalyst particles in the step S1 under the action of a centrifugal force field of a three-phase separator;

s3, the catalyst particles with large particle size in the step S2 are thrown to the side wall of the three-phase separator under the action of a centrifugal force field, move downwards along the conical section and the underflow pipe of the three-phase separator, and finally return to the ebullated bed reactor to continue to react;

the remaining material in step S3 is a liquid-solid mixed phase product, which includes catalyst particles or powder with smaller particle size and a part of liquid phase material.

Further, the particle size range of the catalyst particles is 0.04-0.1 mm;

the particle size range of the catalyst particles with large particle size is 0.07-0.1 mm;

the smaller particle size catalyst particles or powders have a particle size of less than 0.07mm.

The invention also provides a device for removing the catalyst micro powder in the ebullated bed reactor, which comprises the ebullated bed reactor;

The boiling bed reactor comprises a reactor pressure-bearing shell and a three-phase separator arranged at the upper part of an inner cavity of the reactor pressure-bearing shell;

the top of the pressure-bearing shell of the reactor is provided with a gas phase outlet, and the bottom of the pressure-bearing shell of the reactor is provided with a gas-liquid mixed phase inlet;

the three-phase separator comprises a liquid-solid mixed phase product eduction tube, and a liquid-solid outlet of the liquid-solid mixed phase product eduction tube penetrates out from the side wall of the pressure-bearing shell of the reactor;

the device is used for realizing the method for removing the catalyst micro powder in the ebullated bed reactor;

the device also comprises a liquid-solid mixed phase product circulating pipe and a secondary cyclone separator;

the liquid-solid inlet of the liquid-solid mixed phase product circulating pipe is connected with the liquid-solid outlet of the liquid-solid mixed phase product eduction pipe, and the liquid-solid outlet of the liquid-solid mixed phase product circulating pipe is connected with the side feeding port of the secondary cyclone separator.

Further, the ebullated bed reactor also comprises a gas-liquid distributor arranged at the lower part of the inner cavity of the pressure-bearing shell of the reactor;

the top center discharge hole of the secondary cyclone separator is higher than the gas-liquid distributor and is communicated with the bottom of the inner cavity of the pressure-bearing shell of the reactor through a pipeline.

Further, the three-phase separator also comprises a separator main body, an overflow pipe, a swirl guide vane, a liquid-falling type liquid phase product eduction pipe, a liquid phase product outlet pipe and a non-return cone;

The separator main body comprises a straight cylinder section, a conical cylinder section and a bottom flow pipe which are sequentially and coaxially connected from top to bottom;

the overflow pipe and the straight barrel section are coaxially arranged, the lower end of the overflow pipe extends into the inner cavity of the straight barrel section, and the upper end of the overflow pipe is higher than the upper end of the straight barrel section;

the swirl guide vane is arranged in an annular gap channel between the straight cylinder section and the overflow pipe;

the liquid-solid mixed phase product eduction tube is arranged on a tube section of the overflow tube outside the straight tube section and is communicated with the inner cavity of the overflow tube through a liquid-solid inlet of the liquid-solid mixed phase product eduction tube;

the liquid-falling type liquid-phase product eduction tube is coaxially arranged with the overflow tube, the lower end of the liquid-falling type liquid-phase product eduction tube extends into the inner cavity of the overflow tube, and the upper end of the liquid-phase product eduction tube is higher than the upper end of the overflow tube; a closed structure is arranged between the liquid-falling type liquid-phase product eduction tube and the upper end of the overflow tube;

the liquid phase product outlet pipe is arranged on a pipe section of the falling liquid type liquid phase product outlet pipe outside the overflow pipe and is communicated with the inner cavity of the falling liquid type liquid phase product outlet pipe through a liquid phase inlet of the falling liquid type liquid phase product outlet pipe, and a liquid phase outlet of the liquid phase product outlet pipe penetrates out from the side wall of the pressure-bearing shell of the reactor;

the non-return cone is arranged at the bottom flow port at the lower end of the bottom flow pipe.

Further, the axis of the liquid-solid mixed phase product eduction tube is mutually perpendicular to the axis of the overflow tube;

The axis of the liquid phase product outlet pipe is mutually perpendicular to the axis of the liquid phase product eduction pipe.

Further, the inner diameter Da of the overflow pipe is 80-90% of the inner diameter D of the straight section;

the inner diameter Do of the liquid-falling type liquid-phase product leading-out pipe is 70-90% of the inner diameter Da of the overflow pipe;

the height difference between the liquid-solid mixed phase product eduction tube and the liquid phase product outlet tube is h1, and h1 is 40-90% of the inner diameter Dn of the pressure-bearing shell of the reactor;

the fluidization height of the ebullated bed reactor is higher than the upper end of the overflow pipe, the height difference of the two is h2, and h2 is 5-20% of the inner diameter Dn of the pressure-bearing shell of the reactor.

Further, the secondary cyclone separator is a cyclone separator with a separation precision of 5-10 mu m.

The invention also provides a system for removing the catalyst micro powder in the ebullated bed reactor, which comprises at least two micro powder removing devices which are used in series in a grading way, wherein the micro powder removing devices are the devices for removing the catalyst micro powder in the ebullated bed reactor;

the liquid phase outlet of the liquid phase product outlet pipe of the micro powder removing device is connected with the gas-liquid mixed phase inlet of the micro powder removing device at the next stage through a pipeline;

the liquid level difference h3 between any two adjacent micro powder removing devices is larger than the resistance loss along the way +0.5m.

The beneficial effects of the invention are as follows:

(1) The method, the device and the system provided by the invention can lead the liquid-solid mixed phase product out of the ebullated bed reactor and separate the liquid-solid mixed phase product by utilizing the action of a centrifugal force field, so as to remove and collect the catalyst micro powder with the particle size below 30 mu m, realize the regeneration of the catalyst micro powder and reduce the escape or the running loss of the catalyst with the particle size below 0.1mm filled by reaction.

(2) The catalyst micro powder in the liquid-solid mixed phase product is removed, so that the catalyst micro powder can be prevented from returning to the ebullated bed reactor along with the recycled liquid phase, and the problems of wall corrosion caused by the adhesion of the catalyst micro powder to the wall surface through which the catalyst micro powder flows, reaction efficiency reduction caused by the coking of the catalyst and the like are avoided.

(3) After the catalyst micro powder in the liquid-solid mixed phase product is removed, the obtained clean liquid phase can be reused as the raw material of the ebullated bed reactor, thereby being beneficial to realizing the recycling of resources.

(4) According to the device and the system provided by the invention, the lower end of the liquid-falling type liquid-phase product eduction tube extends into the inner cavity of the overflow tube, the upper end of the liquid-falling type liquid-phase product eduction tube is higher than the upper end of the overflow tube, and a closed structure is arranged between the liquid-falling type liquid-phase product eduction tube and the upper end of the overflow tube, so that the overflow tube and the liquid-falling type liquid-phase product eduction tube form an assembly with an annular gap overflow structure in the three-phase separator; in the use process of the device or the system, small bubbles can move towards the center of the liquid-falling type liquid-phase product eduction tube under the action of a centrifugal force field, continuously upwards move along the liquid-falling type liquid-phase product eduction tube, are discharged from the upper end of the liquid-falling type liquid-phase product eduction tube, and are finally discharged from the gas-phase outlet; meanwhile, catalyst particles or powder with smaller particle sizes and partial liquid phase substances can move upwards through an annular space between the overflow pipe and the liquid-falling type liquid phase product eduction pipe under the action of the swirling field, and are finally discharged through the liquid-solid mixed phase product eduction pipe; in addition, the liquid phase product outlet pipe is arranged on the pipe section of the liquid phase product outlet pipe outside the overflow pipe, and is communicated with the inner cavity of the liquid phase product outlet pipe through the liquid phase inlet of the liquid phase product outlet pipe, so that part of liquid phase close to the center of the liquid phase product outlet pipe moves upwards along the liquid phase product outlet pipe under the action of inner rotational flow, and is finally discharged from the liquid phase product outlet pipe; therefore, the device or the system not only can drain partial fluid separated from the main flow, prevent the partial fluid from entering the liquid-falling type liquid-phase product eduction tube along the outer wall of the liquid-falling type liquid-phase product eduction tube by bypassing the bottom of the side wall of the liquid-falling type liquid-phase product eduction tube, but also can escape from the upper end of the liquid-falling type liquid-phase product eduction tube to form a short-circuit flow, thereby realizing the regulation and control of the short-circuit flow, effectively reducing the adverse effect of the short-circuit flow and ensuring the separation precision and efficiency; moreover, because the centrifugal force to which the catalyst particles with different particle sizes are subjected is different, the catalyst in the three-phase separator is distributed in a state that the particle sizes are gradually increased outwards along the radial direction of the straight barrel section, so that the annular overflow structure is beneficial to promoting the graded distribution of the catalyst with different particle sizes, further, the catalyst particles with large particle sizes and part of smaller particle sizes are returned to the reactor, and part of the catalyst particles with smaller particle sizes and most of catalyst micro powder are led out of the reactor, thereby realizing the multi-particle separation of the catalyst and further reducing the escape or running loss of the catalyst micro powder.

(5) The lower end of the liquid-solid mixed phase product eduction tube is lower than the liquid-solid inlet of the liquid-solid mixed phase product eduction tube, so that the liquid-solid inlet of the liquid-solid mixed phase product eduction tube is communicated with the annular space between the overflow tube and the liquid-solid mixed phase product eduction tube, and the catalyst in the three-phase separator is distributed along the radial outward direction of the straight tube section in a state that the particle size is gradually increased, so that most of catalyst micro powder enters the annular space and is conveyed out of the fluidized bed reactor from the liquid-solid mixed phase product eduction tube, and finally enters the two-stage cyclone to be removed, thereby further avoiding the problems of coking corrosion of the wall surface in the fluidized bed reactor, low reaction efficiency and the like, and being beneficial to full capture of the catalyst micro powder.

Drawings

FIG. 1 is a schematic view of a partial cut-away configuration of an apparatus for removing catalyst fines in an ebullated-bed reactor according to the present invention;

FIG. 2 is a schematic view of a partial enlarged structure at the three-phase separator of FIG. 1;

FIG. 3 is a schematic diagram of the system for removing catalyst fines from an ebullated-bed reactor employed in example 1 of the present invention;

FIG. 4 is a schematic diagram of the system for removing catalyst fines from an ebullated-bed reactor employed in example 2 of the present invention;

Marked in the figure as: the reactor comprises a pressure-bearing shell 1, a straight cylinder section 2, an overflow pipe 3, a swirl-making guide vane 4, a liquid-falling type liquid phase product outlet pipe 5, a liquid-solid mixed phase product circulating pipe 6, a secondary cyclone separator 7, a liquid phase product outlet pipe 8, a conical cylinder section 9, an underflow pipe 10, a non-return cone 11, a gas-liquid distributor 12, a gas phase outlet 13, a gas-liquid mixed phase inlet 14, an air compressor 31, a first ebullated bed hydrogenation reactor 32-1, a second ebullated bed hydrogenation reactor 32-2, a liquid phase product outlet pipe 33, a circulating tank 34, a water pump 35, a first secondary cyclone 36, a first booster pump 37, a second secondary cyclone 38, a second booster pump 39, a heating furnace 41, a third ebullated bed hydrogenation reactor 42-1, a fourth ebullated bed hydrogenation reactor 42-2, a separator 43, an air cooler 44, a third secondary cyclone 45, a third booster pump 46, a fourth secondary cyclone 47, a fourth booster pump 48 and a cushion feeder 49.

Detailed Description

The invention is further described below with reference to the drawings and examples.

First, it should be noted that the term "about" as used herein means ±10%; the terms "comprising," "including," "having," and variations thereof mean "including but not limited to"; the terms "upper," "lower," "top," "bottom," "inner," "outer," and the like are used for convenience of description only and are not to be construed as limiting the invention, as the means or elements referred to must have, be constructed or operated in a particular orientation; the term "plurality" when referring to a number, generally refers to a number of three or more, for example: "plurality" generally refers to three or more; the term "light liquid" or "liquid product" refers to liquid phase materials that carry less to the catalyst, such as: the amount of catalyst carried over to 0.04mm is 1.1 μg/g or less, the amount of catalyst carried over to 0.07mm is 0.4 μg/g or less, and the amount of catalyst carried over to 0.1mm is 0.05 μg/g or less; the terms "large bubbles" and "small bubbles" are two relative concepts, "large bubbles" generally mean bubbles that are able to collapse under the influence of inertia, typically over 5mm in diameter, before a gas-liquid-solid three-phase mixture enters a gas-liquid-solid three-phase separator; "small bubbles" refers to other bubbles of the gas-liquid-solid three-phase mixture that are not "large bubbles"; the term "catalyst fines" refers to smaller particle size powders of catalyst particles that are sheared by swirling flow or collide with walls during the reaction; the expression "consisting essentially of or consisting of … …" is to be interpreted as also containing structural elements not mentioned in this sentence; the term "and/or" is merely an association relationship describing an associated object, meaning that three relationships may exist, for example: a and/or B may represent: a exists alone, A and B exist together, and B exists alone. Furthermore, the terms "first," "second," "third," "fourth," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.

The word "optionally" as used herein means "provided in some embodiments and not provided in other embodiments. Any particular embodiment of the invention may include a plurality of "optional" features unless such features conflict. All percentages and parts herein indicating the amount of a substance are by weight unless otherwise indicated.

The method for removing the catalyst micropowder in the ebullated bed reactor comprises a liquid-solid mixed phase product extraction step and a micropowder removal step;

leading out the liquid-solid mixed phase product: the three-phase mixture is discharged from a gas phase outlet 13 of the ebullated-bed reactor to the rest part after partial gas phase is discharged, is centrifugally separated in the ebullated-bed reactor by a three-phase separator, and the substances remained in an overflow pipe 3 of the three-phase separator after separation are liquid-solid mixed phase products, and are led out of the ebullated-bed reactor; the liquid-solid mixed phase product mainly comprises catalyst particles or powder with smaller particle size and partial liquid phase substances;

and (3) removing micro powder: separating the extracted liquid-solid mixed phase product under the action of a centrifugal force field, and removing and collecting the catalyst micro powder; there are a variety of ways and means for generating the centrifugal force field, for example: cyclone, stirring action, helical blades, etc.; the particle size of the catalyst micropowder is below 30 mu m.

The method can remove and collect catalyst micropowder with the particle size below 30 mu m, realize regeneration of the catalyst micropowder, reduce escape or running loss of catalyst with the particle size below 0.1mm, and the catalyst with the particle size below 0.1mm refers to catalyst particles filled during reaction; in addition, the catalyst micro powder in the liquid-solid mixed phase product is removed, so that the catalyst micro powder can be prevented from returning to the ebullated bed reactor along with the recycled liquid phase, and the problems of wall corrosion caused by the adhesion of the catalyst micro powder coking on the wall surface through which the catalyst micro powder flows, low reaction efficiency caused by the coking of the catalyst and the like are avoided; in addition, after the catalyst micro powder in the liquid-solid mixed phase product is removed, the obtained clean liquid phase can be reused as the raw material of the ebullated bed reactor, thereby being beneficial to realizing the recycling of resources.

Specifically, the method further comprises the following steps:

s1, loading a three-phase mixture into a fluidized bed reactor for reaction, wherein in the process that the three-phase mixture flows to the upper part of the fluidized bed reactor under the fluidization effect, large bubbles are broken under the inertia effect and continue to move upwards to be discharged from a gas phase outlet 13;

S3, the catalyst particles with large particle size in the step S2 are thrown to the side wall of the three-phase separator under the action of a centrifugal force field and move downwards along the conical section 9 and the underflow pipe 10 of the three-phase separator, and finally return to the ebullated bed reactor for continuous reaction;

wherein the remaining substances in the step S3 are liquid-solid mixed phase products.

Specifically, the particle size range of the catalyst particles is 0.04-0.1 mm; the particle size range of the catalyst particles with large particle size is 0.07-0.1 mm; the smaller particle size catalyst particles or powders have a particle size of less than 0.07mm. The particle size of the catalyst particles which can be added in the method, the device and the system provided by the invention is between 0.04 and 0.1mm, and the catalyst particles are basically not adversely affected by the catalyst micropowder, and compared with the existing ebullated bed hydrogenation reactor, the particle size of the catalyst which can be added is smaller, the specific surface area is larger, and the reaction rate is higher.

As shown in fig. 1, the device for removing the catalyst micro powder in the ebullated-bed reactor comprises the ebullated-bed reactor;

the ebullated bed reactor comprises a reactor pressure-bearing shell 1 and a three-phase separator arranged at the upper part of the inner cavity of the reactor pressure-bearing shell 1;

the top of the pressure-bearing shell 1 of the reactor is provided with a gas phase outlet 13, and the bottom of the pressure-bearing shell is provided with a gas-liquid mixed phase inlet 14;

The three-phase separator comprises a liquid-solid mixed phase product eduction tube, and a liquid-solid outlet of the liquid-solid mixed phase product eduction tube penetrates out from the side wall of the pressure-bearing shell 1 of the reactor;

the device also comprises a liquid-solid mixed phase product circulating pipe 6 and a secondary cyclone separator 7;

the liquid-solid inlet of the liquid-solid mixed phase product circulating pipe 6 is connected with the liquid-solid outlet of the liquid-solid mixed phase product eduction pipe, and the liquid-solid outlet of the liquid-solid mixed phase product circulating pipe 6 is connected with the side feed inlet of the secondary cyclone separator 7.

The device can lead the liquid-solid mixed phase product out of the fluidized bed reactor through a liquid-solid mixed phase product lead-out pipe and a liquid-solid mixed phase product circulating pipe 6, and apply centrifugal force field action to the liquid-solid mixed phase product through a secondary cyclone separator 7, so that the catalyst micro powder in the liquid-solid mixed phase product is removed from a bottom flow port of the secondary cyclone separator 7 and collected; the clean liquid phase obtained after the catalyst micropowder is removed can be stored or sent into an ebullated bed reactor to continuously participate in the reaction. The secondary cyclone 7 may be various, preferably a tangential feed cyclone, and more preferably a cyclone having a separation accuracy of 5 to 10 μm.

As also shown in fig. 1, in a preferred embodiment of the present invention, optionally, the ebullated bed reactor further comprises a gas-liquid distributor 12 disposed at the lower portion of the interior cavity of the pressure-bearing housing 1 of the reactor; the top center discharge hole of the secondary cyclone separator 7 is higher than the gas-liquid distributor 12 and is communicated with the bottom of the inner cavity of the reactor pressure-bearing shell 1 through a pipeline. In this way, the liquid-solid mixed phase product discharged outside can be ensured to have enough kinetic energy to enter the secondary cyclone 7, and the obtained clean liquid phase is ensured to have enough kinetic energy to enter the ebullated bed reactor, so that the energy consumption is reduced.

As further shown in fig. 1, in a preferred embodiment of the present invention, optionally, the three-phase separator further comprises a separator body, an overflow pipe 3, a swirl imparting vane 4, a liquid-falling liquid phase product lead-out pipe 5, a liquid phase product outlet pipe 8, and a non-return cone 11;

the separator main body comprises a straight cylinder section 2, a cone cylinder section 9 and an underflow pipe 10 which are coaxially connected in sequence from top to bottom;

the overflow pipe 3 is coaxially arranged with the straight barrel section 2, the lower end of the overflow pipe extends into the inner cavity of the straight barrel section 2, and the upper end of the overflow pipe is higher than the upper end of the straight barrel section 2;

the swirl guide vane 4 is arranged in an annular gap channel between the straight cylinder section 2 and the overflow pipe 3; the swirl guide vane 4 is mainly used for spirally guiding a gas-liquid-solid three-phase mixture entering from the upper end of the annular gap channel, providing required centrifugal force for phase separation, and realizing acceleration and steering movement of fluid and catalyst particles; the swirl guide vanes 4 are generally arranged on the inner wall surface of the straight barrel section 2 and/or the outer wall surface of the overflow pipe 3 at a certain inclination angle, and the swirl guide vanes 4 are generally arranged in two or more blocks and distributed in an annular array in an annular gap channel around the axis of the straight barrel section 2; the structure of the swirl guide vane 4 can be various, and is preferably a spiral blade so as to realize better swirl guiding effect;

The liquid-solid mixed phase product eduction tube is arranged on the tube section of the overflow tube 3 outside the straight tube section 2 and is communicated with the inner cavity of the overflow tube 3 through the liquid-solid inlet thereof;

the liquid-falling type liquid-phase product eduction tube 5 is coaxially arranged with the overflow tube 3, the lower end of the liquid-phase product eduction tube extends into the inner cavity of the overflow tube 3, and the upper end of the liquid-phase product eduction tube is higher than the upper end of the overflow tube 3; a closed structure is arranged between the liquid-falling type liquid-phase product eduction tube 5 and the upper end of the overflow tube 3; the sealing structure can be a structure part integrated with the overflow pipe 3 and/or the liquid-falling type liquid-phase product eduction pipe 5, and can also be a sealing piece arranged between the overflow pipe 3 and the liquid-falling type liquid-phase product eduction pipe 5; so, can make overflow pipe 3 and liquid-falling type liquid phase product eduction tube 5 form the assembly with annular space overflow structure in the three-phase separator, and this annular space overflow structure has annular space that the upper end is closed and communicates with liquid-solid mixed phase product eduction tube, and discharge the small bubble and guide the vertical overflow channel of the light liquid outside;

the liquid phase product outlet pipe 8 is arranged on a pipe section of the falling liquid type liquid phase product eduction pipe 5 outside the overflow pipe 3, and is communicated with the inner cavity of the falling liquid type liquid phase product eduction pipe 5 through a liquid phase inlet thereof, and a liquid phase outlet of the liquid phase product outlet pipe 8 penetrates out from the side wall of the pressure-bearing shell 1 of the reactor; in the working process, the liquid phase product outlet pipe 8, the liquid phase product outlet pipe 5 and the overflow pipe 3 together enable part of liquid phase (light liquid) close to the center of the liquid phase product outlet pipe 5 to move upwards along the liquid phase product outlet pipe 5 under the action of internal rotational flow, and finally the liquid phase product is discharged from the liquid phase product outlet pipe 8;

The non-return cone 11 is arranged at a bottom flow port at the lower end of the bottom flow pipe 10, and a gap for discharging large-particle-diameter catalyst particles, liquid phase and other substances is reserved between the non-return cone and the bottom flow port; the non-return cone 11 is mainly used for preventing three-phase mixture and substances such as large-particle-size catalyst particles and liquid phase discharged from a bottom flow port at the lower end of the bottom flow pipe 10 from entering a three-phase separator from the bottom flow port at the lower end of the bottom flow pipe 10; the non-return cone 11 is generally arranged at the bottom flow port through a connecting bracket, and the structure of the non-return cone can be various, and is preferably a spindle-shaped structure; the back taper 11 is further preferably a spindle-shaped structure having an upper taper angle of 15 to 150 ° and a lower taper angle larger than the upper taper angle.

The three-phase separator with the structure is characterized in that the lower end of the liquid-falling type liquid-phase product eduction tube 5 extends into the inner cavity of the overflow tube 3, the upper end of the liquid-falling type liquid-phase product eduction tube 5 is higher than the upper end of the overflow tube 3, and a closed structure is arranged between the liquid-falling type liquid-phase product eduction tube 5 and the upper end of the overflow tube 3, so that an assembly with an annular gap overflow structure is formed in the three-phase separator by the overflow tube 3 and the liquid-falling type liquid-phase product eduction tube 5; in the use process, small bubbles can move towards the center of the liquid-falling type liquid-phase product eduction tube 5 under the action of a centrifugal force field, continuously upwards move along the liquid-falling type liquid-phase product eduction tube 5, are discharged from the upper end of the liquid-falling type liquid-phase product eduction tube 5, and are finally discharged from the gas-phase outlet 13; meanwhile, catalyst particles or powder with smaller particle sizes and partial liquid phase substances can move upwards through an annular space between the overflow pipe 3 and the liquid-falling type liquid phase product eduction pipe 5 under the action of the swirling field, and are finally discharged through the liquid-solid mixed phase product eduction pipe; in addition, the liquid phase product outlet pipe 8 is arranged on a pipe section of the falling liquid type liquid phase product outlet pipe 5 outside the overflow pipe 3, and is communicated with the inner cavity of the falling liquid type liquid phase product outlet pipe 5 through the liquid phase inlet, so that part of liquid phase close to the center of the falling liquid type liquid phase product outlet pipe 5 can move upwards along the falling liquid type liquid phase product outlet pipe 5 under the action of internal rotational flow, and is finally discharged from the liquid phase product outlet pipe 8; therefore, not only can partial fluid separated from the main flow be drained, but also the partial fluid is prevented from entering the liquid-falling type liquid-phase product eduction tube 5 along the outer wall of the liquid-falling type liquid-phase product eduction tube 5 by bypassing the bottom of the side wall of the liquid-falling type liquid-phase product eduction tube 5, and the upper end of the liquid-falling type liquid-phase product eduction tube 5 escapes to form a short-circuit flow, so that the regulation and control of the short-circuit flow are realized, the adverse effect of the short-circuit flow can be effectively reduced, and the separation precision and efficiency are ensured; moreover, because the centrifugal force to which the catalyst particles with different particle sizes are subjected is different, the catalyst in the three-phase separator is distributed in a state that the particle sizes are gradually increased along the radial direction of the straight barrel section 2, so that the annular overflow structure is favorable for promoting the graded distribution of the catalyst with different particle sizes, further, the catalyst particles with large particle sizes and part of smaller particle sizes are returned to the reactor, and part of the catalyst particles with smaller particle sizes and most of catalyst micro powder are led out of the reactor, thereby realizing the multi-particle separation of the catalyst, and further reducing the escape or running loss of the catalyst micro powder.

As also shown in fig. 1, in a preferred embodiment of the invention, optionally, the axis of the liquid-solid mixed phase product delivery pipe is perpendicular to the axis of the overflow pipe 3; so that the liquid-solid mixed phase product in the annular space between the overflow pipe 3 and the liquid-falling type liquid phase product eduction pipe 5 is smoothly led outwards, and the amount of catalyst particles or micro powder carried out is reduced; simultaneously, the axis of the liquid-phase product outlet pipe 8 is mutually perpendicular to the axis of the liquid-phase product eduction tube 5, so that the liquid-phase product eduction tube 5 is beneficial to smoothly and outwards guiding and discharging the liquid-phase product, and the amount of catalyst particles or micro powder carried out is reduced.

Referring again to fig. 2, in a preferred embodiment of the invention, the inner diameter Da of the overflow pipe 3 is optionally 80-90% of the inner diameter D of the straight section 2; therefore, the three-phase mixture entering the three-phase separator can be ensured to generate enough centrifugal force under the guide effect of the swirl guide vanes 4 in the annular space channel, and the drainage quantity during annular space overflow is ensured; the inner diameter Da of the overflow pipe 3 is preferably 85% of the inner diameter D of the straight section 1.

Considering that the inclination angle of the swirl vane 4 is the main influencing factor for generating centrifugal force, the tangential velocity of the fluid is determined; the inclination angle of the rotary making guide vane 4 is represented by an included angle between a tangent line of the ventral surface of the rotary making guide vane 4 and the axis of the straight cylinder section 1; the inclination angle is smaller than 45 degrees, so that the axial speed of the fluid is increased, the tangential speed is reduced, and the basic centrifugal force condition required by the separation of the catalyst particles can not be met; the inclination angle is larger than 65 degrees, so that the axial speed of the fluid is reduced, the tangential speed is increased, the separation condition of catalyst particles is achieved, but the integral pressure drop of the reactor is increased, and the energy consumption is increased; therefore, the swirl guide vanes 4 are preferably provided at an inclination angle of 45 to 65 °. The pitch angle of the swirl vane 4 is further preferably 50 °, 55 °, 60 °.

Considering that the gas content and the catalyst particle ratio are about 30-40% and the liquid phase ratio is about 60-70% at the lower part of the inner cavity of the straight barrel section 2 in the working process, the gas phase ratio is reduced in the upward fluidization process, the catalyst particles are collected, the liquid phase ratio is increased, and the liquid speed in the liquid-falling liquid-phase product eduction tube 5 is required to be reduced in order to prevent the liquid phase from flowing upward at the same speed to carry the catalyst particles away, so that the inner diameter Do of the liquid-falling liquid-phase product eduction tube 5 is limited to be 70-90% of the inner diameter Da of the overflow tube 3 and is larger than the highest ratio of the liquid phase, so that the purpose of reducing the real liquid speed of the liquid phase is achieved, and the probability of carrying the catalyst particles or micro powder by the liquid phase is effectively reduced.

In addition to the above, the inner diameter Do of the liquid-falling liquid phase product delivery pipe 5 is preferably set to 85% of the inner diameter Da of the overflow pipe 3; in this way, the true liquid velocity in the liquid-falling liquid phase product lead-out pipe 5 can be reduced from 6.9mm/s to 5.2mm/s or less, resulting in 0.04mm of catalyst being carried over in an amount of 0.9 μg/g or less, resulting in 0.08mm of catalyst being carried over in an amount of 0.4 μg/g or less, resulting in 0.1mm of catalyst being carried over in an amount of 0.

In some preferred embodiments of the present invention, the falling liquid type liquid phase product lead-out pipe 5 may be configured to have a lower end higher than the liquid-solid inlet of the liquid-solid mixed phase product lead-out pipe, may be configured to have a lower end lower than the liquid-solid inlet of the liquid-solid mixed phase product lead-out pipe and higher than the lower end of the overflow pipe 3, may be configured to have a lower end equal to the lower end of the overflow pipe 3 in height, and may be configured to have a lower end lower than the lower end of the overflow pipe 3 and higher than the lower end of the straight tube section 2; therefore, the adjusting effect on the flow field and the drainage effect on the short-circuit flow can be effectively improved. It is further preferable to make the lower end of the liquid-falling type liquid phase product extraction pipe 5 lower than the liquid-solid inlet of the liquid-solid mixed phase product extraction pipe so as to promote the effects of the above adjustment and drainage.

Referring again to fig. 2, in a preferred embodiment of the present invention, the height difference between the liquid-solid mixed phase product outlet pipe and the liquid phase product outlet pipe 8 is optionally h1, h1 being 40 to 90% of the inner diameter Dn of the pressure-bearing shell 1 of the reactor. In this way, the required fluidization velocity in the ebullated bed reactor can be reduced, and the energy consumption can be reduced. Preferably, h1 is 40%, 50% or 60% of the inner diameter Dn of the pressure-bearing shell 1 of the reactor, most preferably 40%, where the required fluidization velocity in the ebullated-bed reactor is minimal and the energy consumption is minimal.

Referring again to FIG. 2, in a preferred embodiment of the present invention, optionally, the fluidized height of the ebullated bed reactor is higher than the upper end of the overflow pipe 3, and the difference in height between the two is h2, h2 being 5 to 20% of the inner diameter Dn of the pressure-bearing housing 1 of the reactor; in this way, the energy required for the fluidization height can be reduced, and the pressure drop in the three-phase separator is lower; preferably, h2 is 5%, 10% and 15% of the inner diameter Dn of the pressure-bearing shell 1 of the reactor; optimally, h2 is 5% of the inner diameter Dn of the pressure-bearing shell 1 of the reactor, and at this time, the energy required for reaching the fluidization height is minimum and the pressure drop in the three-phase separator is minimum.

As shown in fig. 3 or fig. 4, the system for removing catalyst micropowder in the ebullated-bed reactor comprises at least two micropowder removing devices which are used in series in a grading manner, wherein the micropowder removing devices are the devices for removing catalyst micropowder in the ebullated-bed reactor; the liquid phase outlet of the liquid phase product outlet pipe 8 of the micro powder removing device is connected with the gas-liquid mixed phase inlet 14 of the micro powder removing device at the next stage through a pipeline; the liquid level difference h3 between any two adjacent micro powder removing devices is larger than the along-path resistance loss which is the sum of the loss of a pipeline connecting the two micro powder removing devices and the mechanical energy lost by lifting the liquid level required by the micro powder removing device at the next stage, wherein the loss of the along-path resistance is larger than +0.5m.

The system works in the process: the gas-liquid-solid three-phase mixture moves to the upper space of the ebullated bed reactor under the fluidization effect, and after reaching the fluidized liquid level of the reactor, the large bubbles break under the inertia effect and continue to move upwards to be discharged from the gas phase outlet 13; the rest mixture enters from a channel formed by a straight section 2 of the three-phase separator and an overflow pipe 3, and a swirling flow field is formed under the action of a swirling guide vane 4; the density difference of the liquid phase and the solid phase is large, and the catalyst particles with large particle size move towards the side wall of the three-phase separator and move downwards along the wall surface under the action of centrifugal force, and return to the reactor from the bottom flow port to continue the reaction; the purer liquid phase is converged near the axis of the three-phase separator, namely, the center of the liquid-falling type liquid phase product eduction tube 5, and is continuously discharged upwards from the liquid phase product outlet tube 8 to enter the next-stage device for reaction; catalyst particles or powder or catalyst cokes and partial liquid phase with smaller particle diameters move upwards from an overflow pipe 3, enter an annular space between a liquid-falling type liquid phase product eduction pipe 5 and the overflow pipe 3, are educed into a secondary cyclone 7 from a liquid-solid mixed phase product eduction pipe and a liquid-solid mixed phase product circulating pipe 6, and realize the removal and trapping of catalyst micro powder through the secondary cyclone 7, so that the catalyst micro powder is prevented from escaping or escaping from a gas phase outlet 13, the liquid phase product at the separation part of the secondary cyclone 7 can be recycled at the same level, the catalyst micro powder easy to coke is removed, and the utilization rate of resources is improved.

The method, the device and the system are provided for solving the problems of easy escape, easy running loss, easy coking, wall corrosion and the like of catalyst particles or powder in the fluidized bed hydrogenation reactor in the prior art after extensive and intensive researches by the inventor; the catalyst micro powder which is easy to coke can be removed from the reactor through the annular space between the overflow pipe 3 and the liquid-falling type liquid phase product eduction pipe 5 and the liquid-solid mixed phase product circulating pipe 6, and the catalyst micro powder is captured by the secondary cyclone 7.

Example 1

The system provided by the invention is applied to 4000L/h ebullated bed hydrogenation reactor cold die test.

1) The test equipment comprises the following components and process flows:

as shown in fig. 3, the system for removing the catalyst fines in the ebullated bed reactor employed in this example comprises an air compressor 31, a first ebullated bed hydrogenation reactor 32-1, a second ebullated bed hydrogenation reactor 32-2, a liquid product delivery pipe 33, a recycle tank 34, a water pump 35, a first secondary cyclone 36, a first booster pump 37, a second secondary cyclone 38, and a second booster pump 39;

The air outlet of the air compressor 31 and the water outlet of the water pump 35 are respectively connected with the gas-liquid mixed phase inlet 14 of the first ebullated bed hydrogenation reactor 32-1 through pipelines;

the liquid-solid mixed phase product eduction tube of the first ebullated bed hydrogenation reactor 32-1 is connected with the lateral tangential feed inlet of the first secondary cyclone 36 through the liquid-solid mixed phase product circulating tube 6 thereof, and the top center discharge port of the first secondary cyclone 36 is communicated with the bottom of the inner cavity of the first ebullated bed hydrogenation reactor 32-1 or the gas-liquid mixed phase inlet 14 through the first booster pump 37; the liquid phase product outlet pipe 8 of the first ebullated bed hydrogenation reactor 32-1 is communicated with the gas-liquid mixed phase inlet 14 of the second ebullated bed hydrogenation reactor 32-2 through the liquid phase product delivery pipe 33;

the liquid-solid mixed phase product eduction tube of the second ebullated bed hydrogenation reactor 32-2 is connected with the side tangential feed inlet of the second secondary cyclone 38 through the liquid-solid mixed phase product circulation tube 6 thereof, and the top center discharge port of the second secondary cyclone 38 is communicated with the bottom of the inner cavity of the second ebullated bed hydrogenation reactor 32-2 or the gas-liquid mixed phase inlet 14 through the second booster pump 39; the liquid-phase product outlet pipe 8 of the second ebullated-bed hydrogenation reactor 32-2 is connected with the liquid inlet of the circulation tank 34 through a pipeline;

The liquid outlet of the circulating tank 34 is connected with the water inlet of the water pump 35 through a pipeline.

Referring to fig. 3, the process flow of this test is: after the water is pressurized by the water pump 35, the water and the air compressed by the air compressor 31 are fed into the first ebullated bed hydrogenation reactor 32-1 through the gas-liquid mixed phase inlet 14 at the bottom; the catalyst particles in the first ebullated bed hydrogenation reactor 32-1 reach a fluidized state under the force of air and water; separating the gas-liquid-solid three-phase mixture in the first fluidized bed hydrogenation reactor 32-1 through a three-phase separator, discharging the obtained gas phase (and air) from a gas phase outlet 13 of the first fluidized bed hydrogenation reactor 32-1, discharging the obtained liquid-solid mixed phase product from a liquid-solid mixed phase product eduction pipe of the first fluidized bed hydrogenation reactor, removing solid by a first secondary cyclone 36, pressurizing by a first booster pump 37, entering the first stage device to participate in the reaction again, discharging the obtained liquid phase product from a liquid phase product eduction pipe 33, continuously reacting through a second fluidized bed hydrogenation reactor 32-2 connected in series in two stages to jointly realize the deep purification and high-efficiency reaction of the liquid phase product, discharging the gas phase (and air) obtained by the second fluidized bed hydrogenation reactor 32-2, and delivering the obtained liquid phase product into a circulation tank 34 for recycling; where h3 represents the liquid level difference between the first ebullated-bed hydrogenation reactor 32-1 and the second ebullated-bed hydrogenation reactor 32-2.

2) Major structural dimensions of ebullated bed hydrogenation reactor

The main structural dimensions of the ebullated-bed hydrogenation reactor are shown in Table 1 below, and the first ebullated-bed hydrogenation reactor 32-1 and the second ebullated-bed hydrogenation reactor 32-2 are identical in size and structure.

Table 1:4000L/h ebullated bed hydrogenation reactor cold mould device structural dimension

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3) Effect of the invention

The 4000L/h ebullated bed hydrogenation reactor cold mold apparatus was tested using water and air and the test results are shown in Table 2 below.

Table 2:4000L/h ebullated bed hydrogenation reactor cold die apparatus test results

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From the test results, the inside of the ebullated bed hydrogenation reactor reached a fully mixed flow state, and the catalyst was fluidized uniformly, and had not failed during continuous operation for 90 hours, with 0.04mm catalyst carry-over control of 0.7 μg/g or less, 0.7mm catalyst carry-over control of 0.2 μg/g or less, and 0.1mm catalyst carry-over control of 0. In addition, in the running process of filling the catalysts with different particle sizes into the device, no short-circuit flow occurs at the bottom of the liquid-falling type liquid-phase product eduction tube 5, and the short-circuit flow rate is zero.

Example 2

The system provided by the invention is applied to a 30 ten thousand tons/year biomass pyrolysis liquid hydrodeoxygenation process.

1) The test equipment comprises the following components and process flows:

As shown in fig. 4, the system for removing the catalyst fines in the ebullated bed reactor employed in this example comprises a heating furnace 41, a third ebullated bed hydrogenation reactor 42-1, a fourth ebullated bed hydrogenation reactor 42-2, a separator 43, an air cooler 44, a third secondary cyclone 45, a third booster pump 46, a fourth secondary cyclone 47, a fourth booster pump 48, and a cyclone bed feeder 49;

the gas outlet of the heating furnace 41 is respectively connected with the gas-liquid mixed phase inlets 14 of the third ebullated bed hydrogenation reactor 42-1 and the fourth ebullated bed hydrogenation reactor 42-2 through pipelines;

the liquid-solid mixed phase product eduction tube of the third ebullated bed hydrogenation reactor 42-1 is connected with the lateral tangential feed inlet of the third secondary cyclone 45 through the liquid-solid mixed phase product circulating tube 6 thereof, and the top center discharge port of the third secondary cyclone 45 is communicated with the bottom of the inner cavity of the third ebullated bed hydrogenation reactor 42-1 or the gas-liquid mixed phase inlet 14 through the third booster pump 46; the gas phase outlet 13 of the third ebullated bed hydrogenation reactor 42-1 is connected to the gas inlet of the separator 43 through an air cooler 44; the liquid-phase product outlet pipe 8 of the third ebullated bed hydrogenation reactor 42-1 is communicated with the gas-liquid mixed phase inlet 14 of the fourth ebullated bed hydrogenation reactor 42-2 through a pipeline;

The liquid-solid mixed phase product eduction tube of the fourth ebullated bed hydrogenation reactor 42-2 is connected with the side tangential feed inlet of the fourth secondary cyclone 47 through the liquid-solid mixed phase product circulation tube 6 thereof, and the top center discharge port of the fourth secondary cyclone 47 is communicated with the bottom of the inner cavity of the fourth ebullated bed hydrogenation reactor 42-2 or the gas-liquid mixed phase inlet 14 through the fourth booster pump 48; the gas phase outlet 13 of the fourth ebullated bed hydrogenation reactor 42-2 is connected to the gas inlet of the separator 43 through an air cooler 44; the liquid-phase product outlet pipe 8 of the fourth ebullated-bed hydrogenation reactor 42-2 is communicated with the liquid inlet of the separator 53 through a pipeline;

the cyclone cushion feeder 49 is provided at the lower portion of the third ebullated bed hydrogenation reactor 42-1 and is located at the upper side of the gas-liquid distributor 12 of the third ebullated bed hydrogenation reactor 42-1.

Referring to fig. 4, the process flow of this embodiment is as follows: the biomass pyrolysis liquid and the hydrogen donor were fed from the cyclone cushion feeder 49 into the third ebullated bed hydrogenation reactor 42-1 at a mass ratio of 7:1. The hydrogen enters from the gas-liquid mixed phase inlet 14 at the bottom of the third ebullated bed hydrogenation reactor 42-1 after being heated by the heating furnace 41, and is mixed with biomass pyrolysis liquid to reach a fluidization state under the action of the gas-liquid distributor 12; separating the gas-liquid-solid three-phase mixture in the third ebullated bed hydrogenation reactor 42-1 by a three-phase separator, discharging the obtained hydrogen from a gas phase outlet 13, cooling by an air cooler 44, purifying by a subsequent process, discharging the obtained liquid-solid mixed-phase product from a liquid-solid mixed-phase eduction pipe and a liquid-solid mixed-phase product circulation pipe 6, removing solids by a third secondary cyclone 45 of the third ebullated bed hydrogenation reactor 42-1, pressurizing by a third booster pump 46, entering the present-stage reactor to participate in the reaction again, and discharging the catalyst micro powder separated by the third secondary cyclone 45 from a bottom flow port thereof; the obtained liquid phase product is discharged from a liquid phase product outlet pipe 8, and then continuously reacts through a second-stage series-connected fourth ebullated bed hydrogenation reactor 42-2, so that the deep purification and the high-efficiency reaction of the liquid phase product are realized together, and the liquid phase obtained by the fourth ebullated bed hydrogenation reactor 42-2 is discharged from the liquid phase product outlet pipe 8 and then enters a separator 43 for separation; where h3 represents the liquid level difference between the third ebullated bed hydrogenation reactor 42-1 and the fourth ebullated bed hydrogenation reactor 42-2.

2) Major structural dimensions of ebullated bed hydrogenation reactor

The main structural dimensions of the ebullated bed hydrogenation reactor are shown in Table 3 below, and the dimensions of the third ebullated bed hydrogenation reactor 42-1 and the fourth ebullated bed hydrogenation reactor 42-2 are completely identical.

Table 3: structural size of 30 ten thousand tons/year biomass pyrolysis liquid hydrodeoxygenation ebullated bed hydrogenation reactor device

3) Effect of the invention

The test process of the 30 ten thousand ton/year ebullated bed hydrogenation cold die device was carried out by using biomass pyrolysis liquid, and the test results are shown in the following table 4.

Table 4:30 ten thousand tons/year of hydrodeoxygenation test results of biomass pyrolysis liquid

Project	Operating condition one	Operating condition two	Operating condition III
				Liquid phase	Biomass pyrolysis liquid	Biomass pyrolysis liquid	Biomass pyrolysis liquid
Reaction temperature (. Degree. C.)	400	400	400
				Pressure (MPa)	15	15	15
Hydrogen to oil ratio (v/v)	700	500	500
				Catalyst particle size (μm)	40	70	100
Catalyst loading (m) ³ )	2.4	2.4	2.4
				Circulating oil quantity (ten thousand t/a)	150	150	150
CatalystCarry-over amount (μg/g)	1.1	0.4	0.05
				Coking corrosion conditions in the reactor	No coking and no corrosion	No coking and no corrosion	No coking and no corrosion

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From the test results, the third ebullated bed hydrogenation reactor 42-1 and the fourth ebullated bed hydrogenation reactor 42-2 were all in a mixed flow state, and the catalyst was fluidized uniformly, and had not failed in the continuous operation for 1000 hours, with 0.04mm catalyst carry-over control of 1.1. Mu.g/g or less, 0.07mm catalyst carry-over control of 0.4. Mu.g/g or less, and 0.1mm catalyst carry-over control of 0.05. Mu.g/g or less. In addition, in the running process of filling the catalysts with different particle sizes into the device, no short-circuit flow occurs at the bottom of the liquid-falling type liquid-phase product eduction tube 5, and the short-circuit flow rate is zero.

Comparative example

Listed in this comparative example are the partial conditions and results of the boiling bed hydrogenation reactor disclosed in chinese patent CN113244860B and the apparatus for catalyst fines removal in the boiling bed reactor provided by the present invention during the apathy test.

(1) The treated materials are water, air and alumina carrier particles.

(2) Other interference factors do not exist in the test process, and the air tightness of the device and the running condition of the detection table are checked before the test.

(3) The process environment conditions were consistent as set forth in table 5 below.

Table 5: comparison of test parameters

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As can be seen from the comparison, the device provided by the invention is superior to the Chinese patent CN113244860B in the aspects of treatment capacity, operation pressure, minimum catalyst particle size, continuous operation time, catalyst carrying-out amount and short-circuit flow rate, in particular to the aspects of minimum catalyst particle size and short-circuit flow regulation; the minimum catalyst particle diameter which can be filled in the device can reach 40 mu m, no catalyst particles are carried out, short-circuit flow is eliminated, and the separation precision and the reaction rate are ensured.

The description of the various embodiments of the present invention has been presented for purposes of illustration only and is not intended to be exhaustive or limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein was chosen to best explain the principles of the embodiments, the practical application, or the technological advancement, or to enable others skilled in the art to understand the embodiments disclosed herein, as compared to commercially available technology.

Various embodiments of the invention may be presented herein in a range format. It should be understood that the description of the range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention. Accordingly, the description of a range should be considered to specifically disclose all possible sub-ranges and individual values within the range. For example, descriptions such as ranges from 1 to 6 should be considered to specifically disclose subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual values within the range, e.g., 1, 2, 3, 4, 5, 6, independent of the width of the range.

It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination or in any other described embodiment of the invention where appropriate. Certain features described in the context of various embodiments are not to be considered essential features of those embodiments unless the embodiments are not functional without those features.

All publications, patents, and patent applications mentioned herein are incorporated herein by reference in their entirety to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated herein by reference. Furthermore, citation or identification of any reference herein shall not be construed as an admission that such reference is available as prior art to the present invention. To the extent that section titles are used, section titles should not be construed as necessarily limiting.

Claims

1. A method for removing catalyst fines in a ebullated bed reactor, characterized by: comprises a liquid-solid mixed phase product extraction step and a micro powder removal step;

leading out the liquid-solid mixed phase product: the three-phase mixture is discharged from a gas phase outlet (13) of the ebullated-bed reactor to the rest part after partial gas phase is discharged, the mixture is centrifugally separated in the ebullated-bed reactor by a three-phase separator, substances remained in an overflow pipe (3) of the three-phase separator after separation are liquid-solid mixed phase products, and the liquid-solid mixed phase products are led out of the ebullated-bed reactor;

2. The method for removing catalyst fines in an ebullated bed reactor according to claim 1, further comprising the steps of:

s1, loading a three-phase mixture into a fluidized bed reactor for reaction, wherein in the process that the three-phase mixture flows to the upper part of the fluidized bed reactor under the fluidization effect, large bubbles are broken under the inertia effect and continue to move upwards to be discharged from a gas phase outlet (13);

s3, the catalyst particles with large particle size in the step S2 are thrown to the side wall of the three-phase separator under the action of a centrifugal force field and move downwards along a conical section (9) and a bottom flow pipe (10) of the three-phase separator, and finally return to the ebullated bed reactor to continue to react;

3. The method for removing catalyst fines in an ebullated bed reactor according to claim 2, wherein: the particle size range of the catalyst particles is 0.04-0.1 mm;

4. The device for removing the catalyst micro powder in the ebullated bed reactor comprises the ebullated bed reactor;

the boiling bed reactor comprises a reactor pressure-bearing shell (1) and a three-phase separator arranged at the upper part of the inner cavity of the reactor pressure-bearing shell (1);

the top of the pressure-bearing shell (1) of the reactor is provided with a gas phase outlet (13), and the bottom of the pressure-bearing shell is provided with a gas-liquid mixed phase inlet (14);

the three-phase separator comprises a liquid-solid mixed phase product eduction tube, and a liquid-solid outlet of the liquid-solid mixed phase product eduction tube penetrates out from the side wall of the pressure-bearing shell (1) of the reactor;

the method is characterized in that: the apparatus for carrying out the method for removing catalyst fines in an ebullated bed reactor according to claim 1 or 2 or 3;

the device also comprises a liquid-solid mixed phase product circulating pipe (6) and a secondary cyclone separator (7);

the liquid-solid inlet of the liquid-solid mixed phase product circulating pipe (6) is connected with the liquid-solid outlet of the liquid-solid mixed phase product eduction pipe, and the liquid-solid outlet of the liquid-solid mixed phase product circulating pipe (6) is connected with the side feeding port of the secondary cyclone separator (7).

5. The apparatus for removing catalyst fines from an ebullated bed reactor according to claim 4, wherein: the boiling bed reactor also comprises a gas-liquid distributor (12) arranged at the lower part of the inner cavity of the pressure-bearing shell (1) of the reactor;

The top center discharge hole of the secondary cyclone separator (7) is higher than the gas-liquid distributor (12) and is communicated with the bottom of the inner cavity of the pressure-bearing shell (1) of the reactor through a pipeline.

6. The apparatus for removing fine catalyst particles from an ebullated bed reactor according to claim 4 or 5, wherein: the three-phase separator also comprises a separator main body, an overflow pipe (3), a swirl guide vane (4), a liquid-falling type liquid-phase product eduction pipe (5), a liquid-phase product outlet pipe (8) and a non-return cone (11);

the separator main body comprises a straight cylinder section (2), a cone cylinder section (9) and a bottom flow pipe (10) which are coaxially connected in sequence from top to bottom;

the overflow pipe (3) and the straight barrel section (2) are coaxially arranged, the lower end of the overflow pipe extends into the inner cavity of the straight barrel section (2), and the upper end of the overflow pipe is higher than the upper end of the straight barrel section (2);

the swirl guide vane (4) is arranged in an annular gap channel between the straight cylinder section (2) and the overflow pipe (3);

the liquid-solid mixed phase product eduction tube is arranged on a tube section of the overflow tube (3) positioned outside the straight tube section (2) and is communicated with the inner cavity of the overflow tube (3) through a liquid-solid inlet thereof;

the liquid-falling type liquid-phase product eduction tube (5) is coaxially arranged with the overflow tube (3), the lower end of the liquid-falling type liquid-phase product eduction tube extends into the inner cavity of the overflow tube (3), and the upper end of the liquid-phase product eduction tube is higher than the upper end of the overflow tube (3); a closed structure is arranged between the liquid-falling type liquid-phase product eduction tube (5) and the upper end of the overflow tube (3);

The liquid-phase product outlet pipe (8) is arranged on a pipe section of the falling liquid-type liquid-phase product outlet pipe (5) positioned outside the overflow pipe (3), is communicated with the inner cavity of the falling liquid-type liquid-phase product outlet pipe (5) through a liquid-phase inlet of the falling liquid-phase product outlet pipe, and a liquid-phase outlet of the liquid-phase product outlet pipe (8) penetrates out from the side wall of the pressure-bearing shell (1) of the reactor;

the non-return cone (11) is arranged at a bottom flow port at the lower end of the bottom flow pipe (10).

7. The apparatus for removal of catalyst fines from an ebullated bed reactor according to claim 6, wherein: the axis of the liquid-solid mixed phase product eduction tube is mutually perpendicular to the axis of the overflow tube (3);

the axis of the liquid-phase product outlet pipe (8) is mutually perpendicular to the axis of the liquid-phase product eduction pipe (5).

8. The apparatus for removal of catalyst fines from an ebullated bed reactor according to claim 7, wherein: the inner diameter Da of the overflow pipe (3) is 80-90% of the inner diameter D of the straight section (2);

the inner diameter Do of the liquid-falling type liquid-phase product eduction tube (5) is 70-90% of the inner diameter Da of the overflow tube (3);

the height difference between the liquid-solid mixed phase product eduction tube and the liquid phase product outlet tube (8) is h1, and h1 is 40-90% of the inner diameter Dn of the pressure-bearing shell (1) of the reactor;

The fluidization height of the ebullated bed reactor is higher than the upper end of the overflow pipe (3), the height difference of the two is h2, and h2 is 5-20% of the inner diameter Dn of the pressure-bearing shell (1) of the reactor.

9. The apparatus for removal of catalyst fines from an ebullated bed reactor according to claim 8, wherein: the secondary cyclone separator (7) is a cyclone separator with the separation precision of 5-10 mu m.

10. The system for removing catalyst micropowder in ebullated bed reactor comprises at least two micropowder removing devices which are used in series in a grading manner, and is characterized in that: the micro powder removing device is a device for removing catalyst micro powder in the ebullated bed reactor according to any one of claims 4 to 9;

the liquid phase outlet of the liquid phase product outlet pipe (8) of the micro powder removing device is connected with the gas-liquid mixed phase inlet (14) of the micro powder removing device at the next stage through a pipeline;