CN111375349A

CN111375349A - Upflow reactor and application thereof

Info

Publication number: CN111375349A
Application number: CN201811644433.5A
Authority: CN
Inventors: 杨秀娜; 阮宗琳; 王昊晨; 姜阳; 崔国英; 周嘉文; 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: CN111375349B

Abstract

The invention discloses an upflow reactor and application thereof, wherein the reactor comprises a reactor shell, and a floating type support grid, a catalyst bed layer and a floating grid interlayer are arranged in the reactor shell along the material flowing direction; the bottom of the reactor shell is provided with a reaction material inlet, and the top of the reactor shell is provided with a reaction material outlet; the floating support grid comprises a slideway, a grid plate and a sealing component; the slideway is fixed on the inner surface of the reactor along the axial position of the reactor, the grid plate is movably lapped on the lower edge of the slideway, and the grid plate and the slideway are sealed by a sealing component; 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. The upflow hydrogenation reactor can reduce the motion abrasion among catalyst particles to the maximum extent, can greatly slow down the pressure drop rise of a catalyst bed layer, and maintains the long-period stable operation of the upflow reactor.

Description

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 an upflow reactor and application thereof, wherein a floating grid interlayer and a dust deposition layer are arranged in the reactor.

The invention provides an up-flow reactor, which comprises a reactor shell, wherein a floating type support grid, a catalyst bed layer and a floating grid interlayer are arranged in the reactor shell along the material flowing direction; the bottom of the reactor shell is provided with a reaction material inlet, and the top of the reactor shell is provided with a reaction material outlet.

In the upflow reactor, N catalyst beds are arranged and are respectively a No. 1 catalyst bed, a No. 2 catalyst bed, … …, an N-1 catalyst bed and an Nth catalyst bed (N is more than or equal to 1).

In the upflow reactor, N floating grid interlayers are arranged, namely a 1 st floating grid interlayer, a 2 nd floating grid interlayer, … …, an N-1 st floating grid interlayer and an Nth floating grid interlayer (N is more than or equal to 1).

In the upflow reactor, the catalyst bed layers and the floating grid interlayers are the same in quantity and are arranged alternately, and the upflow reactor sequentially comprises a 1 st catalyst bed layer, a 1 st floating grid interlayer, a 2 nd catalyst bed layer, a 2 nd floating grid interlayer, … …, an N-1 st catalyst bed layer, an N-1 th floating grid interlayer, an Nth catalyst bed layer and an Nth floating grid interlayer along the material flowing direction.

In the upflow reactor, the height of the catalyst bed layer is sequentially increased along the feeding direction of the reactor, namely the height of the catalyst bed layer is sequentially increased from the 1 st catalyst bed layer, the 2 nd catalyst bed layer, … …, the N-1 st catalyst bed layer to the Nth catalyst bed layer; the height of the floating grid interlayer is gradually reduced along the feeding direction of the reactor, namely the height of the floating grid interlayer is reduced from the 1 st floating grid interlayer, the 2 nd floating grid interlayer, … …, the N-1 th floating grid interlayer to the Nth floating grid interlayer.

In the upflow reactor, the floating support grid comprises a slideway, a grid plate and a sealing member, wherein the grid plate is movably overlapped on the lower edge of the slideway and is sealed with the slideway by the sealing member; 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, 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. The grating plates can be parallel metal bars or johnson nets; the slideway is fixed on the inner surface of the reactor along the axial position of the reactor, preferably fixed on the inner surface of the reactor by welding, and the upper edge of the slideway is close to the No. 1 catalyst bed layer.

In the upflow reactor, the floating grid interlayer floats up and down along with the expansion/contraction of the catalyst bed layer in the using process, and the position of the floating grid interlayer is mainly related to the buoyancy of the catalyst bed layer; when the buoyancy of the catalyst bed layer is small, the position of the floating grid interlayer is close to the lower part of the reactor, and when the buoyancy of the catalyst bed layer is large, the position of the floating grid interlayer is close to the upper part of the reactor, and the floating grid interlayer floats up and down along with the catalyst bed layer, so that the abrasion of catalyst particles is reduced, and the pressure drop stability of the catalyst bed layer is ensured.

In the upflow reactor, the floating grid interlayer comprises a slideway, a floatable layer and a sealing component; the floatable layer comprises a first grid pressing plate, a second grid pressing plate and a fixed interlayer between the first grid pressing plate and the second grid pressing plate, and the first grid pressing plate and the second grid pressing plate are fixedly connected through a plurality of groups of axial rib plates to form a cage-type frame structure; one end of the sealing component is fixed on the outer edge of the floatable layer, and the other end of the sealing component is movably lapped on the surface of the slideway, so that the floatable layer 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. The sealing member may be a sealing ring and/or a sealing strip. The slideway is fixed on the inner surface of the reactor along the axial position of the reactor, the lower edge of the slideway is close to the catalyst bed layer, and the floatable layer floats integrally when floating on the slideway.

In the upflow reactor, the length of the slideway is 10 mm-800 mm, preferably 50 mm-300 mm. If the length of the slide way is too small, catalyst particles are blocked due to small floating space, and the start-up period is short; the too long slide way can make the catalyst floating space grow, and cause serious wearing and tearing to the catalyst to arouse the problem such as catalyst dust is too much and the active metal of catalyst drops.

In the upflow reactor, the first grid pressing plate and the second grid pressing plate have the same or different structural forms, and can adopt parallel metal grid bars or Johnson nets; when parallel metal grid bars are adopted, the width of the grid bars is generally 20-60 mm, the width of the strip gaps among the grid bars can be determined according to the diameter of catalyst particles and the diameter of the inert material in the fixed interlayer, the width of the strip gaps is required to be smaller than the diameter of the inert material and the diameter of the catalyst particles in the fixed interlayer, the inert material and the catalyst are prevented from leaking, and the width of the strip gaps 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 upflow reactor, inert filling materials can be filled in the fixed interlayer, and the inert filling materials can be one or more of inert alumina ceramic balls, porous ceramics and porous metal materials. In the use process, the inert filling materials have proper movable spaces in the fixed interlayer, and the inert filling materials can move relatively to each other to prevent the catalyst dust from adhering and accumulating. When inert alumina ceramic balls are filled in the fixed interlayer, the diameter of the inert alumina ceramic balls is generally 3 mm-30 mm.

In the 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 upflow reactor, a dust deposition layer is arranged above the uppermost floating grid interlayer (Nth floating grid interlayer), and a certain space is reserved between the uppermost floating grid interlayer and the dust deposition layer and is used for the upward and downward floating of the uppermost floating grid interlayer.

In the upflow reactor, the dust deposition layer comprises a pressing plate, a dust deposition plate and a plurality of groups of liquid-solid separation assemblies, wherein the liquid-solid separation assemblies are arranged between the pressing plate and the dust deposition plate and are uniformly arranged on the dust deposition plate; the liquid-solid separation assembly comprises a slideway, a separation barrel and a separation cap, wherein the separation barrel is fixed on the dust deposition plate, the separation cap is positioned above the separation barrel, and the separation cap is connected with the separation barrel by a vertical rib plate; the lower part of the slideway is fixed on the dust deposition plate, the upper part of the slideway is fixed on the pressing plate, the separating cap is movably lapped on the surface of the slideway, and when the dust deposition amount on the dust deposition plate is gradually increased, the separating cap can float upwards along the slideway, so that the circulation space and the liquid-solid deposition effect of materials are kept. The material gets into from the bottom of separation barrel, takes place the baffling under the effect of separation cap, and the deposit of dust particle that smugglies in making the material smugglied falls to the dust deposit board based on the action of gravity, realizes the deposit of dust in the material.

In the upflow reactor of the present invention, the separation cylinder in the liquid-solid separation module may have any one of a cylinder, a cube, a rhombohedron, a cuboid, a polygon, etc., preferably a cylinder; the unit height of the liquid-solid separation module is generally 10-1000 mm, preferably 50-200 mm.

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

In the application of the 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 upflow reactor, the hydrogenation reaction conditions of the 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 upflow reactor, when the upflow reactor is used for the liquid phase hydrogenation reaction of hydrocarbon oil, raw oil and hydrogen are mixed and dissolved to obtain a material flow containing hydrogen; the resulting stream is then introduced as reaction feed from the bottom of the upflow reactor and leaves the top of the reactor after the reaction. 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%; 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.

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

1. compared with the traditional upflow reactor, the upflow reactor is internally provided with the floating grid interlayer, so that on one hand, the upflow reactor prevents catalyst particles from moving, wearing and powdering due to the fact that the catalyst sinks after liquid is fed, protects the catalyst and reduces the generation of dust, on the other hand, the floating grid interlayer can float upwards along with the gradual rise of the pressure drop of a catalyst bed layer, and the long-period operation of the reactor is ensured.

2. In the upflow reactor, a plurality of groups of catalyst bed layers and floating grid interlayers are arranged, the heights of the catalyst bed layers are sequentially increased along the feeding direction of the reactor, and the heights of the floating grid interlayers are sequentially decreased along the feeding direction of the reactor.

3. In the upflow reactor, the catalyst dust filtering layer is arranged above the pressing layer of the Nth floating grid, certain dust generated due to collision and abrasion among particles can not be avoided due to buoyancy and production fluctuation in the using process of the catalyst, and the catalyst dust filtering layer can filter and remove the catalyst dust penetrating through the interlayer of the floating grid and prevent the dust from entering other parts such as a top outlet pipeline to cause blockage.

4. In the upflow reactor, a frame formed by the first grid plate and the second grid plate in the floating grid interlayer is of an integrated fixed structure and floats up and down integrally when floating in the reactor, but inert ceramic balls or inert filling materials filled in the interlayer have a proper moving space, and the ceramic balls can move relatively to each other, so that the adhesion and accumulation of catalyst dust can be prevented.

5. In the upflow reactor, the dust deposition layer is provided with the floating separation cap, so that the dust deposition layer can be adjusted according to the amount of dust in materials, the effective interception of catalyst dust is realized, and the pressure drop of the catalyst dust deposition layer is kept stable.

Drawings

FIG. 1 is a schematic view of the structure of an upflow reactor according to the present invention.

Fig. 2 is a schematic view of a floating grid sandwich structure according to the present invention.

FIG. 3 is a schematic view of the structure of the dust deposition layer according to the present invention.

FIG. 4 is a schematic diagram of a liquid phase hydrogenation process employing an 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. 1-3, the present invention provides an upflow reactor, wherein the upflow reactor 5 comprises a reactor shell 6, a floating support grid 8, a 1 st catalyst bed layer 11, a 1 st floating grid interlayer 12, a 2 nd catalyst bed layer 13, a 2 nd floating grid interlayer 14, an nth catalyst bed layer 15, an nth floating grid interlayer 16, and a catalyst dust deposition layer 17 are arranged in the reactor shell 6 along the material flowing direction; the bottom of the reactor shell 6 is provided with a reaction material inlet 4, and the top of the reactor shell is provided with a reaction material outlet 7.

The floating support grid 8 comprises a slideway 9, a grid plate 10 and a sealing member, wherein the slideway 9 is fixed on the inner surface of the reactor along the axial position of the reactor, and the upper edge of the slideway 9 is adjacent to the No. 1 catalyst bed layer 11. The grid plate 10 is movably lapped on the lower edge of the slideway 9 and is sealed with the slideway 9 by a sealing component; one end of the sealing component is fixed on the outer edge of the grid plate 10, and the other end is movably lapped on the surface of the slideway 9, so that the grid plate 10 keeps high sealing when floating up and down on the surface of the slideway 9, and the leakage of materials, catalyst particles and dust is prevented.

The structure of the floating grid interlayer 1 is illustrated by taking the floating grid interlayer 1 as an example, and the floating grid interlayer 1 12 comprises a slideway 19, a floatable layer 20 and a sealing member 24; the floatable layer comprises a first grid pressing plate 21, a second grid pressing plate 22 and a fixed interlayer 23 between the first grid pressing plate 21 and the second grid pressing plate 22, and the first grid pressing plate 21 and the second grid pressing plate 22 are fixedly connected through a plurality of groups of axial rib plates to form a cage-type frame structure; inert materials, preferably inert alumina ceramic balls, can be filled in the middle fixing interlayer 23; one end of the sealing component 24 is fixed on the outer edge of the floatable layer 20, and the other end is movably overlapped on the surface of the slideway 19, so that the floatable layer 20 keeps high sealing when floating up and down on the surface of the slideway 19, and the leakage of materials, catalyst particles and dust is prevented. The sealing member 24 may be a sealing ring and/or a sealing strip. The slide way 19 is fixed on the inner surface of the reactor along the axial position of the reactor, the lower edge of the slide way is close to the No. 1 catalyst bed layer 11, and the floatable layer 20 floats integrally when floating on the slide way 19. The 1 st floating grid interlayer 12 floats up and down along with the expansion/contraction of the 1 st catalyst bed layer 11 in the using process, and the position of the interlayer is mainly related to the buoyancy of the 1 st catalyst bed layer 11; when the buoyancy of the 1 st catalyst bed layer 11 is small, the 1 st floating grid interlayer 12 is close to the lower part of the reactor, and when the buoyancy of the 1 st catalyst bed layer 11 is large, the 1 st floating grid interlayer 12 is close to the upper part of the reactor, and floats up and down along with the 1 st catalyst bed layer 11 through the 1 st floating grid interlayer 12, so that the abrasion of catalyst particles is reduced, and the pressure drop stability of the catalyst bed layer is ensured.

The dust deposition layer 17 comprises a pressing plate 25, a dust deposition plate 26 and a plurality of groups of liquid-solid separation assemblies 27, wherein the liquid-solid separation assemblies 27 are positioned between the pressing plate 25 and the dust deposition plate 26 and are uniformly arranged on the dust deposition plate 26; the liquid-solid separation assembly 27 comprises a slideway 28, a separation cylinder 29, a separation cap 30 and a vertical rib plate 31, wherein the separation cylinder 29 is fixed on the dust deposition plate 26, the separation cap 30 is positioned above the separation cylinder 29, and the separation cap 30 is connected with the separation cylinder 29 by the vertical rib plate 31; the material enters from the bottom of the separating cylinder 29, baffling is carried out under the action of the separating cap 30, and dust particles carried in the material are deposited and fall onto the dust deposition plate 26 under the action of gravity, so that the deposition of dust in the material is realized. The lower part of the slideway 28 is fixed on the dust deposition plate 26, the upper part is fixed on the pressure plate 25, the separating cap 30 is movably lapped on the slideway surface of the slideway 28, when the dust deposition amount on the dust deposition plate 26 is gradually increased, the separating cap 30 can float upwards along the slideway 28, thereby maintaining the material flowing space and the liquid-solid deposition effect.

As shown in fig. 4, the liquid phase hydrogenation process of oil is taken as an example to illustrate the specific reaction process: the hydrogen 1 and the raw oil 2 are dissolved and mixed by a hydrogen-oil mixing device 3 to form a gas-liquid mixture or a liquid-phase material with dissolved hydrogen, the gas-liquid mixture or the liquid-phase material is taken as an upflow hydrogenation reaction feed and introduced into an upflow reactor 5 through a reaction material inlet 4, and the gas-liquid mixture or the liquid-phase material sequentially passes through a floating support grid 8, a 1 st catalyst bed layer 11, a 1 st floating grid interlayer 12, a 2 nd catalyst bed layer 13, a 2 nd floating grid interlayer 14 to an Nth catalyst bed layer 15, an Nth floating grid interlayer 16, a catalyst dust deposition layer 17 and an outlet collector 18 and then leaves the reactor through a reaction material outlet 7 as an upflow hydrogenation reaction. In the normal operation process, due to the particularity of the reaction process, under the action of buoyancy, the catalyst bed layers (including the 1 st catalyst bed layer 11, the 2 nd catalyst bed layer 13 and the Nth catalyst bed layer 15) are in an expanded state after feeding and float up and down along with the fluctuation of the feeding, and the floating grid interlayers (including the 1 st floating grid interlayer 12, the 2 nd floating grid interlayer 14 and the Nth floating grid interlayer 16) float up and down along with the expansion/contraction of the catalyst bed layers, so that the abrasion of catalyst particles and the generation of dust are reduced; the material passing through the Nth floating grid interlayer 16 enters a catalyst dust deposition layer 17, and dust carried in the material is filtered, intercepted and collected step by step.

The raw oil used in the examples of the present invention and the comparative examples is a normal line from an atmospheric and vacuum apparatus of a certain plant, and specific properties are shown in Table 1. The protecting agent/catalyst used in the hydrogenation reaction of the examples and the comparative examples is FBN-03B01/FH-40A which smooths the research institute of petrochemical engineering.

TABLE 1 Properties of the raw materials

Example 1

By adopting the upflow reactor, raw oil and hydrogen are mixed by adopting a conventional static mixer (the model is SV 2.3/25-6.4-500), then the mixture is taken as the reactor feed and introduced into the upflow reactor (the diameter of the reactor is 100 mm), and a floating support grid, a 1 st catalyst bed layer 300mm, a 1 st floating grid interlayer 100mm, a 2 nd catalyst bed layer 500mm and a 2 nd floating grid interlayer 80mm are sequentially filled in the reactor along the material flowing direction; in the floating support grid, the length of the slideway is 60 mm; in the 1 st floating grid interlayer, the first grid pressing plate and the second grid pressing plate are in the same structural form, and adopt parallel metal grid bars, the width of the grid bars is generally 40mm, and the width of the gaps between the grid bars is 2 mm; filling phi 3-6 inert alumina ceramic balls in the fixed interlayer; the No. 2 floating grid interlayer is completely the same as the No. 1 floating grid interlayer; in the filling process, all bed layers are tightly filled; wherein, no stainless steel wire net is filled between each bed layer, and the reaction result is shown in table 1.

Example 2

By adopting the upflow reactor, raw oil and hydrogen are mixed by adopting an inorganic membrane tube disperser, firstly, the hydrogen is dispersed into microbubbles with the size of 50nm and then permeates out of the tube, the microbubbles and liquid introduced into the shell form a reactor feeding mixture, and then the mixture is introduced into the upflow reactor as the reactor feeding (the diameter of the reactor is 150 mm); a floating support grid, a 1 st catalyst bed layer 400mm, a 1 st floating grid interlayer 100mm, a 2 nd catalyst bed layer 600mm, a 2 nd floating grid interlayer 80mm and a catalyst dust deposition layer 120mm are sequentially filled in the reactor along the material flowing direction; in the floating support grid, the length of the slideway is 80 mm; in the 1 st floating grid interlayer, the first grid pressing plate and the second grid pressing plate are identical in structural form, parallel metal grid bars are adopted, the width of each grid bar is 40mm, and the width of a gap between the grid bars is 2 mm; filling phi 3-6 inert alumina ceramic balls in the fixed interlayer; the No. 2 floating grid interlayer is completely the same as the No. 1 floating grid interlayer; the separating cylinder in the liquid-solid separating component is cylindrical in shape, and the height of the unit is 50 mm. In the filling process, all bed layers are tightly filled; wherein, no stainless steel wire net is filled between every two beds. The reaction results are shown in Table 1.

Example 3

The upflow reactor is adopted, raw oil and hydrogen are mixed by a conventional static mixer (the model is SV 2.3/25-6.4-500), then the mixture is used as a feed to be introduced into the upflow reactor (the diameter of the reactor is DN300 × 1070 mm), a floating support grid, a first catalyst bed layer of 400mm, a first floating grid interlayer of 120mm, a second catalyst bed layer of 600mm, a second floating grid interlayer of 100mm and a catalyst dust deposition layer of 150mm are sequentially filled in the reactor along the material flowing direction, the length of a slideway in the floating support grid is 80mm, a first grid pressing plate and a second grid pressing plate in a floating grid interlayer are identical in structural form and adopt parallel metal grid bars, the width of the grid bars is generally 40mm, the width of a slot between the grid bars is 2mm, phi 3-6 inert alumina ceramic balls are filled in a fixed interlayer, the floating grid interlayer of the No. 2 is completely identical to that of the floating grid pressing plate of the No. 1, a separation cylinder in a liquid-solid separation assembly, the height of the unit is 70mm, the unit is compacted between the unit, and no stainless steel wire mesh is filled in the bed layers, and no reaction results are found in the process.

Comparative example 1

Compared with the embodiment 1, the difference lies in that the floating support grid, the floating grid interlayer and the catalyst dust deposition layer are not arranged in the reactor, but the conventional catalyst filling mode is adopted, but the catalyst bed layer is divided into two layers, each bed layer is fixed by the fixed grid, and the ceramic ball layers are respectively filled above and below the catalyst.

Mixing raw oil and hydrogen by using a conventional static mixer (the model is SV 2.3/25-6.4-500), and introducing the mixture serving as reactor feed into a conventional upflow reactor; the diameter of the reactor is 150 mm; a catalyst supporting grid, a phi 13mm alumina ceramic ball layer 60mm, a phi 3-phi 6mm alumina ceramic ball layer 60mm, a catalyst bed layer 300mm, a phi 3-phi 6mm alumina ceramic ball layer 60mm, a phi 13mm alumina ceramic ball layer 60mm, a catalyst supporting grid, a phi 13mm alumina ceramic ball layer 60mm, a phi 3-phi 6mm alumina ceramic ball layer 60mm, a catalyst bed layer 300mm, a phi 3-phi 6mm alumina ceramic ball layer 60mm, a phi 13mm alumina ceramic ball layer 60mm and a catalyst gland grid are sequentially filled in the reactor along the material flowing direction; in the filling process, all bed layers are tightly filled; wherein, stainless steel wire net is not filled between each bed layer. The reaction results are shown in Table 1.

TABLE 2 results of the reaction

Note: the liquid superficial velocity refers to a value obtained by dividing the feed flow rate of the liquid by the cross-sectional area of the reactor by the average flow velocity of the fluid passing through the column calculated as empty column, regardless of the arrangement of any members in the reactor.

As is well known to those skilled in the art, when an up-flow hydrogenation reaction is carried out by using a conventional hydrogenation reactor, in order to ensure the reaction effect and long-period operation, the catalyst height-diameter ratio is required to a certain extent, the diameter of the reactor is not too large or too small, which affects 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 rising 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 rising rate of the reactor is relatively slow, and the operation time of the apparatus is greatly prolonged, which shows that the present invention can effectively prevent the catalyst from moving, wearing and pulverizing caused by the catalyst sinking after the liquid is fed into the reactor, protect the catalyst and reduce the generation of dust, and the floating grid interlayer is arranged between the catalyst bed layers to fix the catalyst bed layers in a segmented manner and control the pressure drop in a segmented manner, so as to realize the homogenization of the catalyst dust along the axial direction of the reactor, slow down the rising of the pressure drop and ensure.

Claims

1. An upflow reactor, which comprises a reactor shell, wherein a floating type supporting grid, a catalyst bed layer and a floating grid interlayer are arranged in the reactor shell along the material flowing direction; the bottom of the reactor shell is provided with a reaction material inlet, and the top of the reactor shell is provided with a reaction material outlet;

the floating support grid comprises a slideway, a grid plate and a sealing component; the slideway is fixed on the inner surface of the reactor along the axial position of the reactor, the grid plate is movably lapped on the lower edge of the slideway, and the grid plate and the slideway are sealed by a sealing component; 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;

the floating grid interlayer comprises a slideway, a floatable layer and a sealing component; the floatable layer comprises a first grid pressing plate, a second grid pressing plate and a fixed interlayer between the first grid pressing plate and the second grid pressing plate, and the first grid pressing plate and the second grid pressing plate are fixedly connected through a plurality of groups of axial rib plates to form a cage-type frame structure; one end of the sealing component is fixed on the outer edge of the floatable layer, and the other end of the sealing component is movably lapped on the surface of the slideway.

2. An upflow reactor as in claim 1, in which: n catalyst beds are arranged and are respectively a 1 st catalyst bed, a 2 nd catalyst bed, … …, an N-1 st catalyst bed and an Nth catalyst bed (N is more than or equal to 1); the floating grid interlayers are provided with N floating grid interlayers which are respectively a 1 st floating grid interlayer, a 2 nd floating grid interlayer, … …, an N-1 th floating grid interlayer and an Nth floating grid interlayer (N is more than or equal to 1).

3. An upflow reactor as in claim 2, in which: the catalyst bed layers and the floating grid interlayers are the same in quantity and are alternately arranged, and the catalyst bed layers and the floating grid interlayers sequentially comprise a 1 st catalyst bed layer, a 1 st floating grid interlayer, a 2 nd catalyst bed layer, a 2 nd floating grid interlayer, … …, an N-1 st catalyst bed layer, an N-1 th floating grid interlayer, an Nth catalyst bed layer and an Nth floating grid interlayer along the material flowing direction.

4. An upflow reactor as in claim 2, in which: the heights of the catalyst beds are sequentially increased along the feeding direction of the reactor, namely, the heights of the catalyst beds are sequentially increased from the 1 st catalyst bed, the 2 nd catalyst bed, … …, the N-1 st catalyst bed to the Nth catalyst bed; the height of the floating grid interlayer is gradually reduced along the feeding direction of the reactor, namely the height of the floating grid interlayer is reduced from the 1 st floating grid interlayer, the 2 nd floating grid interlayer, … …, the N-1 th floating grid interlayer to the Nth floating grid interlayer.

5. An upflow reactor as in claim 1, in which: the grating plates are parallel metal grating bars or Johnson nets.

6. An upflow reactor as in claim 1, in which: the first grid pressing plate and the second grid pressing plate are identical or different in structural form, and parallel metal grid bars or Johnson nets are adopted.

7. An upflow reactor as in claim 1, in which: inert filling materials are filled in the fixed interlayer, and the inert filling materials are one or more of inert alumina ceramic balls, porous ceramics and porous metal materials.

8. An upflow reactor as in claim 1, in which: a dust deposition layer is arranged above the uppermost floating grid interlayer, and a certain space is reserved between the uppermost floating grid interlayer and the dust deposition layer and is used for up-and-down floating of the uppermost floating grid interlayer.

9. An upflow reactor as in claim 8, in which: the dust deposition layer comprises a pressing plate, a dust deposition plate and a plurality of groups of liquid-solid separation assemblies, wherein the liquid-solid separation assemblies are arranged between the pressing plate and the dust deposition plate and are uniformly arranged on the dust deposition plate; the liquid-solid separation assembly comprises a slideway, a separation barrel and a separation cap, wherein the separation barrel is fixed on the dust deposition plate, the separation cap is positioned above the separation barrel, and the separation cap is connected with the separation barrel by a vertical rib plate; the lower part of the slideway is fixed on the dust deposition plate, the upper part of the slideway is fixed on the pressing plate, and the separation cap is movably lapped on the surface of the slideway.

10. An upflow reactor as in claim 9, in which: the shape of the separation cylinder in the liquid-solid separation assembly is any one of a cylinder, a cube, a rhombohedron, a cuboid, a polygon and the like, and is preferably a cylinder; the unit height of the liquid-solid separation assembly is 10-1000 mm, preferably 50-200 mm.

11. Use of an upflow reactor as in any of claims 1 to 10 for the hydrogenation of hydrocarbon oils.

12. Use according to claim 11, characterized in that: the hydrocarbon oil is a hydrocarbon raw material with distillation range of any fraction within 130-550 ℃, and is 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.

13. Use according to claim 11, 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%.

14. Use according to claim 11, characterized in that: when the method is used for the liquid-phase hydrogenation reaction of hydrocarbon oil, firstly, raw oil and hydrogen are mixed and dissolved to obtain a material flow containing hydrogen; the resulting stream is then introduced as reaction feed from the bottom of the upflow reactor and leaves the top of the reactor after the reaction.

15. Use according to claim 11, characterized in that: in the mixing and dissolving process, the mass ratio of the hydrogen to the oil is 0.001-15%; 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.