CN111375353A

CN111375353A - Fixed bed upflow reactor and application thereof

Info

Publication number: CN111375353A
Application number: CN201811648468.6A
Authority: CN
Inventors: 周嘉文; 杨秀娜; 阮宗琳; 王昊晨; 姜阳; 崔国英; 关明华
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2018-12-30
Filing date: 2018-12-30
Publication date: 2020-07-07
Anticipated expiration: 2038-12-30
Also published as: CN111375353B

Abstract

The invention discloses a fixed bed up-flow reactor and application thereof, wherein the reactor comprises a reactor shell, and a lower sliding grid, a first catalyst bed layer, a linkage type dust filtering layer, a second catalyst bed layer and an upper sliding grid are arranged in the reactor shell along the material flowing direction; the linkage type dust filtering and accumulating layer is respectively and fixedly connected with the upper sliding grid and the lower sliding grid through supporting rods, a reaction material inlet is formed in the bottom of the reactor shell, and a reaction material outlet is formed in the top of the reactor shell; the linked dust filtering layer is arranged in the reactor, so that the movement abrasion among catalyst particles can be effectively reduced, the service life of the catalyst is prolonged, the catalyst dust is continuously removed in the reaction process, the reaction uniformity is improved, the pressure drop rise of a catalyst bed layer is greatly slowed down, and the long-period stable operation of the reactor is maintained.

Description

Fixed bed upflow reactor and application thereof

Technical Field

The invention belongs to the field of petrochemical equipment, and relates to an upflow reactor and application thereof.

Background

In the field of petrochemical industry, a hydrogenation process is an important technical means for treating distillate oil and secondary processing oil, and can effectively remove impurities such as sulfur, nitrogen, metal, colloid, carbon residue and the like in oil products and hydrogenate unsaturated hydrocarbon into saturated hydrocarbon through hydrogenation. The hydrogenation process can be classified into a fixed bed hydrogenation process, a suspension bed hydrogenation process, and a fluidized bed hydrogenation process according to the type of the reactor, wherein the fixed bed hydrogenation process is most widely applied.

According to the feeding mode of the fixed bed reactor, the method can be divided into an up-flow type fixed bed reactor, namely a down-flow type fixed bed reactor and a down-flow type fixed bed reactor, namely an up-flow type fixed bed reactor, wherein the up-flow type fixed bed reactor can treat various types of oil products, and has unique advantages in the oil product hydrogenation process, such as the residual oil of inferior oil products and coal liquefaction oil are easy to cause hydrogenation catalyst poisoning or rapid inactivation due to the blockage of catalyst pore passages because of high impurity content, and impurities can block the bed layer to cause the rapid rise of pressure drop to cause the deterioration of the working condition of the reactor, even the normal operation can not be realized, if the gas-liquid cocurrent upward movement causes the expansion of the catalyst bed layer in the up.

CN200810117101.1 proposes an upflow reactor and its application, the upflow reactor includes an initial distributor located at the bottom of the reactor and an intermediate distributor above the initial distributor, the initial distributor is composed of a conical baffle plate and a sieve plate located above the conical baffle plate; the intermediate distributor is composed of an open-pore sieve plate and a sieve plate string structure, and the upflow reactor provided by the invention aims to realize uniform distribution of gas, thereby improving the utilization rate of the catalyst. CN201110353672.7 proposes a gas-liquid distributor of an up-flow reactor and application thereof, comprising a distribution disk tower plate and a cap type gas collection distributor. CN201510697566.9 proposes an upflow distributor and an upflow reactor, and the invention aims to provide a technical scheme for uniformly distributing and uniformly mixing the fluid after passing through the upflow distributor. CN201110156274.6 discloses a residual oil hydrotreating process, which is characterized in that a feed inlet is added in front of a demetallizing agent bed layer of a residual oil hydrotreating device, residual oil and hydrogen enter the device for reaction through a raw material feed inlet of the residual oil hydrotreating device, catalytic cracking recycle oil enters the device for reaction through the added feed inlet, the residual oil hydrotreating device is filled by adopting catalyst grading, three or more types of catalysts including a protective agent, a demetallizing agent and a desulfurizing agent are sequentially adopted, and an up-flow reactor or a fixed bed reactor is adopted. The method aims to improve the impurity removal rate of residual oil hydrotreating and prolong the operation period of a residual oil hydrotreating device, and mainly optimizes the residual oil hydrotreating process flow.

In the upflow hydrogenation reactor, raw materials and hydrogen are mixed and then enter the reactor from the bottom of the reactor, and enter a catalyst bed layer through a baffle plate, a distributor and a bed layer support, a gas phase is dispersed into bubbles and moves upwards in parallel with a liquid phase continuous phase, the bed layer expands due to the flow of fluid, a small amount of catalyst particles are carried by the fluid and move upwards continuously, and the particles reach the distributor or the bed layer support of the adjacent catalyst bed layer. Because the catalyst particles with small bed support gaps cannot pass through, the particles are likely to block the distributor or the bed support, so that the fluid, especially the gas, is unevenly distributed, thereby influencing the distribution of the fluid in the reactor and generating adverse effect on the reaction process. And simultaneously, along with abrasion and pulverization among catalyst particles, a large amount of catalyst dust is generated, and the dust moves upwards along with reaction materials to block the surface of a screen mesh or a grid, so that the pressure drop of a bed layer is rapidly increased, and the start-up period of the reaction is influenced.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a fixed bed upflow reactor and application thereof, wherein a linkage type dust filtering layer is arranged in the reactor, so that the movement abrasion among catalyst particles can be effectively reduced, the service life of the catalyst is prolonged, the catalyst dust is continuously removed in the reaction process, the reaction uniformity is improved, the pressure drop rise of a catalyst bed layer is greatly slowed down, and the long-period stable operation of the reactor is maintained.

The invention provides a fixed bed up-flow reactor, which comprises a reactor shell, wherein a lower sliding grid, a first catalyst bed layer, a linkage type dust filtering layer, a second catalyst bed layer and an upper sliding grid are arranged in the reactor shell along the material flowing direction; linkage type filters the laying dust layer and passes through the bracing piece respectively with last sliding grid and lower sliding grid fixed connection, reactor shell bottom sets up the reaction material entry, and reactor shell top sets up the reaction material export.

In the fixed bed upflow reactor, the support rod is a telescopic support rod, and particularly can be a spring support rod.

In the fixed bed upflow reactor, the height of the second catalyst bed layer is generally larger than or equal to that of the first catalyst bed layer, because the impact force and the catalyst buoyancy force of reaction feeding on the catalyst bed layer along the material flow direction in the reactor are gradually reduced, and under the buffer action of the linkage type filtration dust layer, the impact force and the buoyancy force of the reaction feeding on the second catalyst bed layer are rapidly reduced, the abrasion among catalyst particles is greatly reduced, and the dust generation amount is reduced, so that the height of the second catalyst bed layer is larger than or equal to that of the first catalyst bed layer, and the height ratio of the second catalyst bed layer to the first catalyst bed layer is 1: 1-50: 1, preferably 2: 1-8: 1.

In the fixed bed up-flow reactor, the lower sliding grid is positioned at the lower part of the first catalyst bed layer and is connected with the linkage type dust filtering layer through the supporting rod, and the lower sliding grid floats up and down along with the expansion/contraction of the first catalyst bed layer in the reaction process.

In the fixed bed upflow reactor, the lower sliding grid comprises a slideway and a grid plate, the slideway is of a steel structure and is fixed (fixed by welding) on the inner wall of the reactor along the axial position of the reactor, and preferably a circle is arranged along the inner wall of the reactor; the edge of the grid plate is movably lapped on the slideway, and the lapping surface of the grid plate and the slideway is sealed by a sealing component; one end of the sealing component is fixed on the outer edge of the grid plate, the other end of the sealing component is movably lapped on the surface of the slideway, so that the grid plate keeps high sealing when floating up and down on the surface of the slideway, and the leakage of materials, catalyst particles and dust is prevented, and the sealing component can be a sealing ring and/or a sealing strip; the length of the slideway is generally 10 mm-500 mm, preferably 30 mm-300 mm, and an excessively small length can easily block due to small floating space, so that the start-up period is short; the excessive length causes a large floating space of the catalyst to cause severe abrasion of the catalyst, thereby causing a problem of excessive dust of the catalyst.

In the fixed bed upflow reactor, the upper sliding grid comprises a slideway and a grid plate, the slideway is of a steel structure and is fixed (fixed by welding) on the inner wall of the reactor along the axial position of the reactor, and preferably a circle is arranged along the inner wall of the reactor; the edge of the grid plate is movably lapped on the slideway, and the lapping surface of the grid plate and the slideway is sealed by a sealing component; one end of the sealing component is fixed on the outer edge of the grid plate, the other end of the sealing component is movably lapped on the surface of the slideway, so that the grid plate keeps high sealing when floating up and down on the surface of the slideway, and the leakage of materials, catalyst particles and dust is prevented, and the sealing component can be a sealing ring and/or a sealing strip; the length of the slideway is generally 10 mm-500 mm, preferably 30 mm-300 mm, and an excessively small length can easily block due to small floating space, so that the start-up period is short; the excessive length causes a large floating space of the catalyst to cause severe abrasion of the catalyst, thereby causing a problem of excessive dust of the catalyst.

In the fixed bed up-flow reactor, the linkage type dust filtering and depositing layer comprises an upper linkage layer, a dust filtering and depositing layer and a lower linkage layer; wherein:

the upper linkage layer comprises an upper linkage layer slideway, an upper linkage layer grating and an upper linkage layer plastic elastomer, wherein the upper linkage layer grating is positioned on the upper surface of the upper linkage layer plastic elastomer, and the upper linkage layer grating is lapped on the surface of the upper linkage layer slideway; the upper linkage layer slideway is fixed on the inner wall of the reactor along the axial position of the reactor, preferably a circle of slideway is arranged along the inner wall of the reactor, and the upper linkage layer slideway is of a steel structure;

the lower linkage layer comprises a lower linkage layer slideway, a lower linkage layer grating and a lower linkage layer plastic elastomer, the lower linkage layer plastic elastomer is positioned on the lower linkage layer grating, and the lower linkage layer grating is lapped on the surface of the lower linkage layer slideway; the lower linkage layer slideway is fixed on the inner wall of the reactor along the axial position of the reactor, preferably a circle of slideway is arranged along the inner wall of the reactor, and the lower linkage layer slideway is of a steel structure;

the filter device is characterized in that a filter dust layer is arranged between the upper linkage layer and the lower linkage layer, a plurality of dust collecting baskets are arranged in the filter dust layer, membrane modules are arranged between adjacent dust collecting baskets, and inlets of the membrane modules are communicated with a hydrogen inlet pipeline.

In the fixed bed up-flow reactor, the membrane assembly is of a tube bundle structure, more than one membrane tube is arranged in the fixed bed up-flow reactor, and the membrane tube is an inorganic membrane; the hydrogen is pushed by the pressure difference between the inside and the outside of the membrane tube to permeate and diffuse through the nano/micron pore canal on the tube wall to form nano/micron bubbles, and the size of the nano/micron bubbles is generally 0.5 nm-1000 nm, preferably 50 nm-500 nm. After the membrane module disperses the hydrogen that the hydrogen inlet pipeline lets in for receiving/micron hydrogen bubble, permeate to and filter the laying dust layer and mix with reaction material and dissolve, in this process, reaction material has certain shearing action under the buoyancy effect on the one hand and between receiving/micron hydrogen bubble, can improve the hydrogen oil by a wide margin and dissolve dispersion degree, thereby improve hydrogenation reaction rate and reaction efficiency, on the other hand through receiving/micron hydrogen bubble when the infiltration diffusion erodes filtering the continuous of laying dust basket internal and external surface, can make the catalyst dust deposit inside filtering the laying dust basket more even, be favorable to preventing to filter the local pressure drop in the laying dust layer and rise, be favorable to controlling the pressure drop rate of rise and the long period pressure drop stability of filtering the laying dust layer.

In the fixed bed upflow reactor, the upper linkage layer grating and the lower linkage layer grating have the same or different structural forms, and parallel metal grating bars are spliced into a Johnson net; when parallel metal grid bars are adopted, the width of the grid bars is generally 20-60 mm, the width of the strip seams among the grid bars is determined according to the diameter of catalyst particles and the diameter of inert materials in the fixed interlayer, and the width of the strip seams is required to be smaller than the diameter of the inert materials and the diameter of the catalyst particles in the fixed interlayer, so that the inert materials and the catalyst are prevented from leaking out and the catalyst is prevented from leaking in, and the width of the strip seams is generally 1-30 mm; when a Johnson screen is used, the spacing between the screen wires is generally 1mm to 10mm, so that catalyst particles are prevented from being just stuck on the screen wires.

In the fixed bed up-flow reactor, the upper linkage layer plastic elastomer and the lower linkage layer plastic elastomer are particle bodies prepared from elastic materials, wherein the particle bodies can be one or more of spherical, strip-shaped, polygonal, tooth-ball-shaped, blocky and the like, and the elastic materials can be one or more of high-temperature-resistant rubbers such as silicon rubber, borosilicate rubber, fluorosilicone rubber and the like. When the catalyst bed layer expands/contracts, the upper linkage layer plastic elastomer and the lower linkage layer plastic elastomer can simultaneously generate elastic deformation and floating, so that the catalyst bed layer can recover the original volume as soon as possible; generally, the height of the upper linkage layer plastic elastomer and the lower linkage layer plastic elastomer is 10-500 mm, preferably 50-200 mm.

In the fixed bed upflow reactor, when the bed pressure drop is increased due to the increase of the dust deposition amount in the dust deposition layer, the dust deposition basket deforms and extrudes the plastic elastomer in the radial direction, so that the material flow in the dust deposition layer is increased, the dust deposition amount of the dust deposition layer is increased, and the increase of the bed pressure drop is slowed down.

In the fixed bed upflow reactor, the outer surface of the dust collection basket is wrapped by a stainless steel wire mesh or a Johnson mesh, and an inert filling material is filled in the dust collection basket and used for intercepting and capturing catalyst dust; the inert filling material can be one or more of inert alumina ceramic balls, porous ceramics and porous metal materials, preferably inert alumina ceramic balls are filled, and further preferably inert alumina ceramic balls with the diameter of phi 3-phi 30 are filled; the shape of the dust collection basket can be any one of a cylinder, a cube, a rhombohedron, a cuboid, a polygon and the like, and is preferably a cylinder; the height of the dust collecting basket is generally 10 to 1000mm, preferably 30 to 200 mm.

In the fixed bed upflow reactor, a gland is arranged above the upper sliding grid, is a crossbeam formed by a plurality of I-shaped steel and is fixed at the upper part of the upper sliding grid; such as by welding. The gland has the function of fixing the components in the whole reactor through the self weight of the gland and preventing the components from deforming to generate the agent leakage phenomenon caused by the expansion of the catalyst bed layer.

In the fixed bed up-flow reactor, the upper part of a first catalyst bed layer is close to a linked filtration dust layer, when the first catalyst bed layer expands, a lower sliding grid, a lower spring supporting rod and a lower linkage layer act simultaneously, the lower sliding grid floats downwards, the lower spring supporting rod extends, and the lower linkage layer floats upwards; when the first catalyst bed layer contracts, the lower sliding grid and the lower linkage layer act simultaneously, the lower sliding grid floats upwards, the spring supporting rod at the lower part contracts, and the lower linkage layer floats downwards, so that the catalyst in the bed layer is quickly recovered to the original state, the abrasion among particles of the lower catalyst bed layer and the generation of catalyst dust are reduced, and the increase of the pressure drop of the lower catalyst bed layer is relieved. So that the catalyst in the bed layer can be uniformly floated along the axial direction, the local resistance can be reduced, and the pressure drop of the catalyst bed layer can be homogenized.

In the fixed bed up-flow reactor, the lower part of the second catalyst bed layer is close to the linkage type dust filtering layer, when the second catalyst bed layer expands, the upper sliding grid and the upper linkage layer act simultaneously, the upper sliding grid floats upwards, and the upper linkage layer floats downwards; when the second catalyst bed layer contracts, the upper sliding grid and the upper linkage layer act simultaneously, the upper sliding grid floats downwards, and the upper linkage layer floats upwards, so that the catalyst in the bed layer uniformly floats along the axial direction, the local resistance is reduced, and the pressure drop of the catalyst bed layer is homogenized.

In the fixed bed upflow reactor of the present invention, the catalyst bed is filled with a catalyst with catalytic function well known to those skilled in the art, the total filling height of the catalyst bed is generally determined by the optimum space velocity for the catalyst and the height-diameter ratio of the reactor, and the height of the single catalyst bed is generally 30mm to 5000mm, preferably 300mm to 2000 mm.

In the fixed bed upflow reactor, the lower part of the lower sliding grid can be also provided with a catalyst bed layer supporting grid and/or a protective agent bed layer, and when the catalyst bed layer supporting grid and the protective agent bed layer are arranged at the same time, the protective agent bed layer is positioned at the upper part of the catalyst supporting grid. The catalyst bed layer supporting grid is formed by splicing parallel metal grid bars and is used for supporting the weight of the upper catalyst bed layer. The catalyst bed support grid is well known to those skilled in the art and can be selected and changed according to actual needs. Generally, the catalyst support grid comprises a girder, grid bars and a screen, wherein two sides of the girder are fixedly lapped on a boss on the inner wall of the reactor, the grid bars are positioned on the girder and the boss, the screen is flatly paved on the upper surface of the grid bars, and the mesh number of the screen is generally 5-30 meshes, preferably 10-20 meshes. The protective agent bed layer is filled with a protective agent, the protective agent is mainly used for removing metal impurities and solid particles in raw materials, and simultaneously, substances which are easy to coke in the raw materials are properly hydrogenated, so that poisoning and coking in the catalyst are slowed down, and the service life of the main catalyst is prolonged, the protective agent can be commercially available products or can be prepared and selected according to the existing method, and the selections are well known by persons in the field; the total height ratio of the protective agent bed layer to the catalyst bed layer is 1: 1-1: 50, preferably 1: 2-1: 5.

The second aspect of the invention provides an application of the fixed bed upflow reactor, which is used for hydrocarbon oil hydrogenation reaction, and is particularly suitable for hydrocarbon oil liquid phase hydrogenation reaction.

In the application of the fixed bed upflow reactor, the hydrocarbon oil is a hydrocarbon raw material with distillation range of any fraction within 130-550 ℃, and can be selected from one or more of naphtha, reformed oil, aviation kerosene, diesel oil, wax oil, lubricating oil, residual oil, deasphalted oil, biodiesel, animal oil or vegetable oil.

In the application of the fixed bed upflow reactor, the hydrogenation reaction conditions of the fixed bed upflow reactor are as follows: the temperature is 40-360 ℃; the pressure is 0.5-20.0 MPa, preferably 1.0-8.0 MPa; the liquid hourly space velocity is 0.5-15 h^-1(ii) a The supply of hydrogen can be far more than the chemical hydrogen consumption in the hydrogenation process, and the hydrogen-oil mass ratio is generally 0.001-15%, preferably 0.01-5%.

In the application of the fixed bed upflow reactor of the invention, when the fixed bed upflow reactor is used for the liquid phase hydrogenation reaction of hydrocarbon oil, the preferred specific process is as follows:

(1) firstly, dividing hydrogen into two paths: hydrogen I and hydrogen II, wherein the hydrogen I and the raw oil are mixed and dissolved to obtain a material flow containing hydrogen; wherein the mass ratio of the hydrogen I to the hydrogen II is generally 10: 1-1: 10, preferably 5: 1-1: 1;

(2) introducing the material flow formed in the step (1) as reactor feeding from the bottom of the reactor, performing hydrogenation reaction on a first catalyst bed layer, introducing hydrogen II from a linkage type filtration dust layer, dispersing the hydrogen II into nano/micron hydrogen bubbles through an inorganic membrane tube in the linkage type filtration dust layer, mixing and dissolving the hydrogen bubbles with the reaction feeding, performing hydrogenation reaction on a second catalyst bed layer, and leaving from the top of the reactor.

The raw oil and hydrogen are mixed and dissolved, a conventional shell type hydrogen-oil mixing component can be adopted, and any one or more of components which can strengthen fluid disturbance such as an SWN type component, an SMX type component, an SMK type component, an SML type component, an SMH type component, a spiral plate sheet, a corrugated plate sheet, a rotating blade, a flat blade, a bent blade or a porous plate sheet and the like are contained in a shell; raw oil and hydrogen can also be dissolved and dispersed by utilizing a membrane tube micro-disperser, a microporous plate, a microporous material and the like, preferably the membrane tube micro-disperser is utilized, and the bubble size of pre-dispersed hydrogen is 10 nm-1000 nm, generally 50-500 nm. In the mixing and dissolving process, the mass ratio of the hydrogen to the oil is 0.001-15%, preferably 0.01-5%; the hydrogen-oil mixing and dissolving conditions are as follows: the temperature is 40-360 ℃, the pressure is 0.5-20.0 MPa, and the retention time is 0.5-30 minutes; the reactor feed mixture formed after the hydrogen and oil are mixed can be a gas phase and a liquid phase, and can also be a pure liquid phase in which the hydrogen is dissolved and dispersed.

In the method of the invention, the first catalyst bed layer and the second catalyst bed layer can be filled with catalysts of the same or different types, and are filled with catalysts with hydrogenation functions well known to persons skilled in the art, such as any one or more of hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrogenation saturation, hydroisomerization, hydrodewaxing and the like; the total packing height of the catalyst beds is determined by the optimum space velocity for the use of the respective catalyst, whereas the height of the individual catalyst beds is generally from 30mm to 5000mm, preferably from 300mm to 2000 mm.

Compared with the prior art, the fixed bed upflow reactor has the following advantages:

1. in the fixed bed up-flow reactor, the linked filtration dust layer is arranged to divide the catalyst bed layer into a first catalyst bed layer and a second catalyst bed layer, the upper linked layer and the lower linked layer in the linked filtration dust layer are respectively connected with the upper sliding grid and the lower sliding grid, and the linked filtration dust layer is linked with the upper sliding grid, the upper linked layer, the spring supporting rod at the upper part, the spring supporting rod at the lower part, the lower linked layer and the lower sliding grid together along with the feeding of the reactor and the expansion/contraction of the catalyst bed layer, so that the catalyst in the bed layer can be quickly restored to the original state, the abrasion among particles of the catalyst bed layer and the generation of catalyst dust are reduced, and the pressure drop rise of the catalyst bed layer is relieved.

2. In the fixed bed up-flow reactor, the linkage type filtering dust-deposition layer is arranged at the position between the catalyst bed layers, so that on one hand, the impact force of reaction feeding on the second catalyst bed layer is buffered and rapidly reduced, the abrasion between catalyst particles of the second catalyst bed layer is greatly reduced, the dust generation amount is greatly reduced, the pressure drop of the second catalyst bed layer is controlled to a lower level, and a small amount of dust generated by the first catalyst bed layer is filtered and deposited through the linkage type filtering dust-deposition layer, so that the pressure drop of the first catalyst bed layer can be effectively controlled.

3. In the fixed bed upflow reactor, a dust deposition basket is arranged in a linked filtering dust deposition layer, a membrane component is arranged around the dust deposition basket, an inorganic membrane tube disperses hydrogen into nano/micron hydrogen bubbles and then permeates into the filtering dust deposition layer to be mixed and dissolved with reaction materials, in the process, on one hand, the reaction materials have a certain shearing action with the nano/micron hydrogen bubbles under the action of buoyancy, the dissolving and dispersing degree of gas-liquid two-phase materials (such as hydrogen and oil) can be greatly improved, so that the reaction rate and the reaction efficiency are improved, on the other hand, the catalyst dust in the filtering dust deposition basket can be more uniformly deposited by continuously scouring the inner surface and the outer surface of the filtering dust deposition basket when a large amount of nano/micron hydrogen bubbles are permeated and dispersed, and the local pressure drop in the filtering dust deposition basket is favorably prevented from rising, the pressure drop increasing speed of the dust collecting layer and the long-period pressure drop stability can be controlled.

4. In the fixed bed upflow reactor, the filtering dust accumulation layer is a fixed layer and does not float, the inert filling materials filled in the fixed bed upflow reactor have a proper moving space, the inert filling materials can move relatively, the adhesion and local accumulation of catalyst dust can be prevented, and meanwhile, the scouring of hydrogen bubbles and the linked floating of the upper/lower linkage layers can improve the rolling speed of all fillers in the filtering dust accumulation layer, so that the dust accumulation in the filtering dust accumulation layer is more uniform.

Drawings

FIG. 1 is a schematic diagram of a fixed bed upflow reactor according to the present invention.

FIG. 2 is a schematic view of a linkage type dust collecting filter layer according to the present invention.

FIG. 3 is a schematic view showing the arrangement of the filter dust and the inorganic membrane tubes in the filter dust layer according to the present invention.

FIG. 4 is a flow diagram of a hydrogenation process employing a fixed bed upflow reactor of the present invention.

Detailed Description

The invention is described in detail below with reference to the figures and examples, but the invention is not limited thereby.

In the description of the present invention, it should be noted that the terms "upper", "lower", "inner", "outer", "top", "bottom", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.

In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "provided", "disposed", "connected", "mounted", and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.

As shown in fig. 1-4, the present invention provides a hydrogenation reactor 5, where the hydrogenation reactor 5 includes a reactor shell 6, and a lower sliding grid 8, a first catalyst bed 10, a linked filtration dust-collecting layer 12, a second catalyst bed 13, an upper sliding grid 15, and a gland 17 are arranged in the reactor shell 6 along a material flowing direction; the linkage type dust filtering layer 12 is fixedly connected with the lower sliding grid 8 through a support rod 11 and is fixedly connected with the upper sliding grid 15 through a support rod 14, and the support rod 11 and the support rod 14 are telescopic support rods and can be spring support rods specifically; the bottom of the reactor shell 6 is provided with a reaction material inlet 4, and the top of the reactor shell 6 is provided with a reaction material outlet 7.

The lower sliding grid 8 comprises a slideway 9 and grid plates, the slideway 9 is of a steel structure, and is fixed (fixed by welding) on the inner wall of the reactor along the axial position of the reactor, and preferably a circle is arranged along the inner wall of the reactor; the edge of the grating plate is movably lapped on the slideway 9, and the lapping surface of the grating plate and the slideway 9 is sealed by a sealing component; one end of the sealing component is fixed on the outer edge of the grid plate, the other end of the sealing component is movably lapped on the surface of the slideway, so that the grid plate keeps high sealing when floating up and down on the surface of the slideway, and the leakage of materials, catalyst particles and dust is prevented, and the sealing component can be a sealing ring and/or a sealing strip; the length of the slideway is generally from 10mm to 500mm, preferably from 30mm to 300 mm.

The upper sliding grid 15 comprises grid plates and a slideway 16, the slideway 16 is of a steel structure, is fixed (fixed by welding) on the inner wall of the reactor along the axial position of the reactor, and is preferably arranged for a circle along the inner wall of the reactor; the edge of the grid plate is movably lapped on the slideway 16, and the lapping surface of the grid plate and the slideway 16 is sealed by a sealing component; one end of the sealing component is fixed on the outer edge of the grid plate, the other end of the sealing component is movably lapped on the surface of the slideway, so that the grid plate keeps high sealing when floating up and down on the surface of the slideway, and the leakage of materials, catalyst particles and dust is prevented, and the sealing component can be a sealing ring and/or a sealing strip; the length of the slideway is generally from 10mm to 500mm, preferably from 30mm to 300 mm.

The linkage type dust filtering and accumulating layer 12 comprises an upper linkage layer 21, a dust filtering and accumulating layer 20 and a lower linkage layer 19; wherein: the upper linkage layer 21 comprises an upper linkage layer slideway 28, an upper linkage layer grating 29 and an upper linkage layer plastic elastomer 27, wherein the upper linkage layer grating 29 is positioned on the upper linkage layer plastic elastomer 27, and the upper linkage layer grating 29 is lapped on the surface of the upper linkage layer slideway 28; the lower linkage layer 19 comprises a lower linkage layer slideway 23, a lower linkage layer grid 22 and a lower linkage layer plastic elastomer 24, wherein the lower linkage layer plastic elastomer 24 is positioned on the lower linkage layer grid 22, and the lower linkage layer grid 22 is lapped on the surface of the lower linkage layer slideway 23; the upper linkage layer grating 29 and the lower linkage layer grating 22 have the same or different structural forms and are formed by splicing parallel metal grating bars or Johnson nets, the upper linkage layer plastic elastomer 27 and the lower linkage layer plastic elastomer 24 are particle bodies prepared from elastic materials, the particle bodies can be one or more of shapes of spheres, strips, polygons, tooth balls, blocks and the like, and the elastic materials can be one or more of high-temperature-resistant rubbers such as silicon rubber, borosilicate rubber, fluorosilicone rubber and the like. A dust filtering layer 20 is arranged between the upper linkage layer 21 and the lower linkage layer 19, a plurality of dust collecting baskets 25 are arranged in the dust filtering layer 20, the outer surfaces of the dust collecting baskets 25 are wrapped by stainless steel wire meshes or Johnson nets, and inert filling materials are filled in the dust filtering baskets 25 and used for intercepting and trapping catalyst dust; a membrane module 26 is arranged between adjacent dust-deposition baskets 25, the inlet of the membrane module 26 is communicated with a hydrogen inlet pipeline, the membrane module 26 is in a tube bundle structure, more than one membrane tube is arranged in the membrane module 26, and the membrane tubes are inorganic membranes; the hydrogen is pushed by the pressure difference between the inside and the outside of the membrane tube to permeate and diffuse through the nano/micron pore channels on the tube wall to form nano/micron bubbles. A gland 17 is arranged above the upper sliding grid 16, and the gland 17 is a girder formed by a plurality of I-shaped steel and is fixed at the upper part of the upper sliding grid 16; such as by welding. The gland 17 serves to fix the components in the entire reactor by its own weight, and to prevent the components from being deformed by the expansion of the catalyst bed to cause the agent leakage.

The raw oil used in the examples and comparative examples of the present invention is reformate from a continuous reformer of a certain plant, and the reformate is introduced into the upflow hydrogenation reactor of the present invention to perform a hydrodeolefination reaction, wherein the specific composition of the raw oil is shown in table 1. The protecting agent/catalyst used in the hydrogenation reaction of the examples and the comparative examples is FBN-03B01/FHDO-18 of the compliant petrochemical research institute.

TABLE 1 raw oil composition

Example 1

By adopting the upflow reactor, raw oil and hydrogen I are mixed by adopting a conventional static mixer (the model is SV 2.3/25-6.4-500), then the mixture is taken as reactor feed and introduced into the upflow reactor (the diameter of the reactor is 100 mm), and hydrogen II is introduced into a hydrogen inlet in a linkage type filtering dust layer, wherein the mass ratio of the hydrogen I to the hydrogen II is 5: 1; the reactor is internally provided with a lower sliding grid of 100mm, a first catalyst bed layer of 600mm, a linkage type dust filtering layer of 260mm, a second catalyst bed layer of 800mm and an upper sliding grid of 80mm in sequence along the material flowing direction; the lower sliding grid comprises a slideway and a grid plate, and the length of the slideway is 100 mm; the upper sliding grid comprises a slideway and a grid plate, and the length of the slideway is 80 mm; the linkage type dust filtering layer comprises an upper linkage layer, a dust filtering layer and a lower linkage layer; the upper linkage layer comprises an upper linkage layer slideway, an upper linkage layer grating and an upper linkage layer plastic elastomer; the lower linkage layer comprises a lower linkage layer slideway, a lower linkage layer grating and a lower linkage layer plastic elastomer; a dust filtering layer is arranged between the upper linkage layer and the lower linkage layer, dust collecting baskets are arranged in the dust filtering layer, membrane modules are arranged between adjacent dust collecting baskets, and inlets of the membrane modules are communicated with a hydrogen inlet pipeline; the membrane component is of a tube bundle structure, the interior of the membrane component comprises 12 inorganic membrane tubes, and hydrogen is pushed by the pressure difference between the inside and the outside of the membrane tubes to permeate and diffuse through nano/micron pore channels on the tube wall to form hydrogen bubbles of 50nm, and then permeates to a filtration dust layer to be mixed and dissolved with reaction materials; the upper linkage layer grating and the lower linkage layer grating are identical in structural form, and Johnson nets with the mesh wire spacing of 2mm are adopted; the upper linkage layer plastic elastomer and the lower linkage layer plastic elastomer are strip-shaped bodies prepared from borosilicate rubber materials, the height of the upper linkage layer plastic elastomer layer is 80mm, and the height of the lower linkage layer plastic elastomer layer is 60 mm; the outer surface of the dust collection basket is wrapped by a Johnson net, inert alumina ceramic balls with the diameter of 3-6 are filled in the dust collection basket, the shape of the dust collection basket is cylindrical, and the height of the dust collection basket is 120 mm. The gland is a crossbeam formed by a plurality of I-shaped steel bars and is fixed at the upper part of the upper sliding grid; in the filling process, all bed layers are tightly filled; the results are shown in Table 2.

Example 2

By adopting the upflow reactor, raw oil and hydrogen I are mixed by adopting a conventional static mixer (the model is SV 2.3/25-6.4-500), then the mixture is taken as reactor feed and introduced into the upflow reactor (the diameter of the reactor is 100 mm), and hydrogen II is introduced into a hydrogen inlet in a linkage type filtering dust layer, wherein the mass ratio of the hydrogen I to the hydrogen II is 3: 1; the reactor is internally provided with a lower sliding grid of 100mm, a first catalyst bed layer of 500mm, a linkage type dust filtering layer of 200mm, a second catalyst bed layer of 600mm, an upper sliding grid of 80mm and a gland of 100mm in sequence along the material flowing direction; the lower sliding grid comprises a slideway and a grid plate, and the length of the slideway is 100 mm; the upper sliding grid comprises a slideway and a grid plate, and the length of the slideway is 80 mm; the linkage type dust filtering layer comprises an upper linkage layer, a dust filtering layer and a lower linkage layer; the upper linkage layer comprises an upper linkage layer slideway, an upper linkage layer grating and an upper linkage layer plastic elastomer; the lower linkage layer comprises a lower linkage layer slideway, a lower linkage layer grating and a lower linkage layer plastic elastomer; a dust filtering layer is arranged between the upper linkage layer and the lower linkage layer, dust collecting baskets are arranged in the dust filtering layer, membrane modules are arranged between adjacent dust collecting baskets, and inlets of the membrane modules are communicated with a hydrogen inlet pipeline; the membrane component is of a tube bundle structure, the interior of the membrane component comprises 12 inorganic membrane tubes, and hydrogen is pushed by the pressure difference between the inside and the outside of the membrane tubes to permeate and diffuse through nano/micron pore channels on the tube wall to form hydrogen bubbles of 50nm, and then permeates to a filtration dust layer to be mixed and dissolved with reaction materials;

the upper linkage layer grating and the lower linkage layer grating are identical in structural form, and Johnson nets with the mesh wire spacing of 2mm are adopted; the upper linkage layer plastic elastomer layer and the lower linkage layer plastic elastomer are strip-shaped bodies prepared from borosilicate rubber materials, the height of the upper linkage layer plastic elastomer is 60mm, and the height of the lower linkage layer plastic elastomer is 80 mm; the outer surface of the dust collection basket is wrapped by a Johnson net, inert alumina ceramic balls with the diameter of 3-6 are filled in the dust collection basket, the shape of the dust collection basket is cylindrical, and the height of the dust collection basket is 60 mm. The gland is a crossbeam formed by a plurality of I-shaped steel bars and is fixed at the upper part of the upper sliding grid; in the filling process, all bed layers are tightly filled; the results are shown in Table 2.

TABLE 2 measurement results

Note: the superficial flow rate refers to a value obtained by dividing the feed flow rate of a liquid by the cross-sectional area of the reactor by the average flow rate of the fluid passing through the column calculated as empty column, without considering the arrangement of any members in the reactor.

As is well known to those skilled in the art, the conventional upflow hydrogenation process employs a conventional hydrogenation reactor, and in order to ensure the reaction effect and long-term operation, the height-diameter ratio of the catalyst has certain requirements, so that the diameter of the reactor is not suitable to be too large or too small, which influences the apparent flow velocity of the liquid in the upflow reactor, if the apparent flow velocity of the liquid is larger, the impact force on the catalyst bed layer and the protective agent bed layer is large, so that the abrasion of the catalyst is serious, the dust generated by the abrasion of the catalyst is easy to block the grid slots, the pressure drop rising rate of the bed layer of the reactor is high, otherwise, if the apparent flow velocity of the liquid is small, the impact force on the catalyst bed layer and the protective agent bed layer is small, so that the abrasion of the catalyst is small, the layer-to-layer lifting of the reactor bed is slow, and therefore, the method for measuring the using effect of the upflow reactor in the embodiment and the comparative example comprises the following steps: under the condition of the same treatment capacity, a conventional upflow reactor is compared with the upflow reactor of the invention, and the pressure drop ascending rate of the bed layer of the reactor is tested by changing the apparent flow rate of liquid in the comparison process. When a certain operation time is reached, the lower the pressure drop of the catalyst bed is, the better the use effect is. In order to reduce errors brought by experiments, the liquid apparent flow velocity in the experiment process adopts a method of measuring for many times to calculate an average value.

It can be seen from the pressure drop increase rate of the reactor in the present embodiment and the comparative example that, after the upflow reactor and the upflow reaction method of the present invention are adopted, the pressure drop increase rate of the reactor is relatively slow, that is, the pressure drop increase of the reactor is effectively controlled, so that the operation time of the device is greatly prolonged.

Claims

1. A fixed bed up-flow reactor comprises a reactor shell, wherein a lower sliding grid, a first catalyst bed layer, a linkage type dust filtering layer, a second catalyst bed layer and an upper sliding grid are arranged in the reactor shell along the material flowing direction; the linkage type dust filtering and accumulating layer is respectively and fixedly connected with the upper sliding grid and the lower sliding grid through supporting rods, a reaction material inlet is formed in the bottom of the reactor shell, and a reaction material outlet is formed in the top of the reactor shell;

the linkage type dust filtering and accumulating layer comprises an upper linkage layer, a dust filtering and accumulating layer and a lower linkage layer;

the upper linkage layer comprises an upper linkage layer slideway, an upper linkage layer grating and an upper linkage layer plastic elastomer, the upper linkage layer slideway is fixed on the inner wall of the reactor along the axial position of the reactor, the upper linkage layer grating is positioned on the upper surface of the upper linkage layer plastic elastomer, and the upper linkage layer grating is lapped on the surface of the upper linkage layer slideway;

the lower linkage layer comprises a lower linkage layer slideway, a lower linkage layer grating and a lower linkage layer plastic elastomer, the lower linkage layer slideway is fixed on the inner wall of the reactor along the axial position of the reactor, the lower linkage layer plastic elastomer is positioned on the lower linkage layer grating, and the lower linkage layer grating is lapped on the surface of the lower linkage layer slideway;

2. A fixed bed upflow reactor as in claim 1, wherein: the bracing piece is scalable bracing piece, specifically is the spring support pole.

3. A fixed bed upflow reactor as in claim 1, wherein: the height of the second catalyst bed layer is larger than or equal to that of the first catalyst bed layer, and the height ratio of the second catalyst bed layer to the first catalyst bed layer is 1: 1-50: 1, preferably 2: 1-8: 1.

4. A fixed bed upflow reactor as in claim 1, wherein: the lower sliding grid comprises a slideway and a grid plate, the slideway is fixed on the inner wall of the reactor along the axial position of the reactor, the edge of the grid plate is movably lapped on the slideway, and the lapping surface of the grid plate and the slideway is sealed by a sealing component.

5. A fixed bed upflow reactor as in claim 5, in which: one end of the sealing component is fixed on the outer edge of the grid plate, and the other end of the sealing component is movably lapped on the surface of the slideway.

6. A fixed bed upflow reactor as in claim 5, in which: the slide way is arranged along the inner wall of the reactor for a circle, and the length of the slide way is 10 mm-500 mm, preferably 30 mm-300 mm. .

7. A fixed bed upflow reactor as in claim 1, wherein: the upper sliding grid comprises a slideway and a grid plate, the slideway is fixed on the inner wall of the reactor along the axial position of the reactor, the edge of the grid plate is movably lapped on the slideway, and the lapping surface of the grid plate and the slideway is sealed by a sealing component.

8. A fixed bed upflow reactor as in claim 7, wherein: one end of the sealing component is fixed on the outer edge of the grid plate, and the other end of the sealing component is movably lapped on the surface of the slideway.

9. A fixed bed upflow reactor as in claim 8, wherein: the slide way is arranged along the inner wall of the reactor for a circle, and the length of the slide way is 10 mm-500 mm, preferably 30 mm-300 mm. .

10. A fixed bed upflow reactor as in claim 1, wherein: the upper linkage layer slide way is fixed on the inner wall of the reactor along the axial position of the reactor for a circle, and the upper linkage layer slide way is of a steel structure.

11. A fixed bed upflow reactor as in claim 1, wherein: the lower linkage layer slide way is fixed on the inner wall of the reactor along the axial position of the reactor for a circle, and the lower linkage layer slide way is of a steel structure.

12. A fixed bed upflow reactor as in claim 1, wherein: the membrane module is of a tube bundle structure, more than one membrane tube is arranged in the membrane module, and the membrane tubes are inorganic membranes.

13. A fixed bed upflow reactor as in claim 1, wherein: the upper linkage layer grating and the lower linkage layer grating are identical or different in structural form and are spliced by parallel metal grating bars or Johnson nets.

14. A fixed bed upflow reactor as in claim 1, wherein: the upper linkage layer plastic elastomer and the lower linkage layer plastic elastomer are particle bodies prepared from elastic materials, wherein the particle bodies are one or more of spherical, strip-shaped, polygonal, tooth-ball-shaped and blocky, and the elastic materials are high-temperature-resistant rubbers, specifically one or more of silicone rubber, borosilicate rubber and fluorosilicone rubber.

15. A fixed bed upflow reactor as in claim 1, wherein: the height of the upper linkage layer plastic elastomer and the height of the lower linkage layer plastic elastomer are 10-500 mm, and preferably 50-200 mm.

16. A fixed bed upflow reactor as in claim 1, wherein: the outer surface of the dust collection basket is wrapped by a stainless steel wire mesh or a Johnson mesh, and an inert filling material is filled in the dust collection basket, wherein the inert filling material is one or more of inert alumina ceramic balls, porous ceramic particles and porous metal materials, preferably the inert alumina ceramic balls are filled, and further preferably the inert alumina ceramic balls with the diameter of phi 3-phi 30 are filled; the dust collection basket is in any one shape of a cylinder, a cube, a rhombohedron, a cuboid and a polygonal body, and is preferably in a cylinder shape; the height of the dust-collecting basket is 10-1000 mm, preferably 30-200 mm.

17. A fixed bed upflow reactor as in claim 1, wherein: a gland is arranged above the upper sliding grid and is a crossbeam formed by a plurality of I-shaped steel bars and is fixed at the upper part of the upper sliding grid.

18. A fixed bed upflow reactor as in claim 1, wherein: and when the catalyst bed layer supporting grid and the protective agent bed layer are arranged at the same time, the protective agent bed layer is positioned at the upper part of the catalyst supporting grid.

19. Use of a fixed-bed upflow reactor as in any one of claims 1 to 18 in a hydrocarbon oil hydrogenation reaction.

20. Use according to claim 19, characterized in that: the hydrocarbon oil is a hydrocarbon raw material with distillation range of any fraction within 130-550 ℃, and is selected from one or more of naphtha, reformed oil, aviation kerosene, diesel oil, wax oil, lubricating oil, residual oil, deasphalted oil, biodiesel, animal oil or vegetable oil.

21. Use according to claim 19, characterized in that: the hydrogenation reaction conditions are as follows: the temperature is 40-360 ℃; the pressure is 0.5-20.0 MPa, preferably 1.0-8.0 MPa; the liquid hourly space velocity is 0.5-15 h^-1(ii) a The mass ratio of hydrogen to oil is 0.001-15%, preferably 0.01-5%.

22. Use according to claim 19, characterized in that: when the method is used for the liquid-phase hydrogenation reaction of the hydrocarbon oil, the specific process is as follows:

(1) firstly, dividing hydrogen into two paths: hydrogen I and hydrogen II, wherein the hydrogen I and the raw oil are mixed and dissolved to obtain a material flow containing hydrogen;

23. Use according to claim 22, characterized in that: in the mixing and dissolving process, the mass ratio of the hydrogen to the oil is 0.001-15%, preferably 0.01-5%; the hydrogen-oil mixing and dissolving conditions are as follows: 40-360 ℃, 0.5-20.0 MPa and 0.5-30 minutes of retention time.