Catalyst liquid phase filling system, method and application thereof, and method for synthesizing 4-methyl-1-pentene by propylene dimerization

Abstract

The present application relates to the technical field of catalyst loading, in particular to a kind of catalyst liquid phase loading system and method and application, a kind of method for propylene dimerization to 4-methyl-1-pentene.The system provided in the present application realizes the process of catalyst loading and loading in non-oxidizing atmosphere, reduces the risk of catalyst and air contact, weakens the degree of wear of catalyst, and the loading efficiency is high, uniformity is good, improves the stability and safety of catalyst;At the same time, the method for propylene dimerization to 4-methyl-1-pentene is carried out in the system provided in the present application, can effectively improve the conversion rate of propylene, improves the running time of system.

Description

Technical Field

[0001] The present invention relates to the technical field of catalyst filling, and in particular to a catalyst liquid phase filling system, a catalyst liquid phase filling method, an application of the catalyst liquid phase filling system, and a method for synthesizing 4-methyl-1-pentene by dimerization of propylene. Background Art

[0002] For catalytic reactions with high thermal efficiency and high sensitivity to reaction temperature, it is often necessary to promptly remove the heat released by the reaction, or to promptly replenish the heat required for the reaction, in order to maintain a stable reaction temperature, reduce the probability of side reactions, and improve the selectivity of the desired product. To facilitate heat extraction or supply during the reaction, a shell-and-tube reactor is often used. The reactants react through a shell and tube filled with catalyst, and the heat extraction or supply medium passes through the tubes to remove or supply heat to achieve heat exchange.

[0003] Catalyst loading in a tubular reactor is typically done manually or by a loading machine, loading the reactor into bags or hoppers. The uniformity of the loading in each reaction tube is manually checked using a pressure drop test. Any reaction tubes with significant deviations or unevenness require the catalyst to be removed and reloaded until the uniformity or pressure drop deviation across all reaction tubes meets certain requirements. This loading method places the catalyst in an air atmosphere and is not suitable for loading catalysts that require avoidance of air contact during the loading process, such as reducing metals or catalysts that may burn, explode, or change properties upon contact with air. Existing technologies typically employ methods such as shortening the catalyst's contact time with air and employing inert gas protection for catalyst loading. Gas is often used as a transport medium to assist in catalyst loading, and efficient catalyst transport and loading requires a high linear velocity. However, high linear velocities consume a lot of energy, increase catalyst wear, and affect catalyst performance. Catalyst fines can also be transferred downstream of the reactor, reducing the reliability and safety of the process equipment.

[0004] CN202122005435.3 discloses a material loading system consisting of a first hopper, a second hopper, a conduit disposed at the bottom of the first hopper into which the second hopper can be inserted, and a delivery pipe connecting the second hopper to the material inlet of a container. This system reduces the contact time between the material and air by inserting the conduit into the second hopper. Although the structure is relatively simple, the entire system is not an oxygen-free environment during the material loading process, and there is still a risk of oxidation.

[0005] CN201521034191.X discloses a catalyst loading machine comprising a feed hopper, a storage hopper, a discharge pipe, a bracket, a first adjustment plate, and a second adjustment plate; the loading machine arranges nitrogen pipelines on the feed hopper and the discharge pipe to allow nitrogen at a certain pressure to be introduced when loading the catalyst, thereby preventing the reducing catalyst from coming into contact with air during the loading process; however, the feed hopper is not completely isolated from the air, and there is still a risk of contact with air.

[0006] Supported catalysts are generally insensitive to air. However, when loaded with reducing metals or active components that can combust or explode upon contact with air, the resulting catalyst becomes very air-sensitive. For these catalysts, achieving a safe, uniform loading process that maintains catalytic properties is extremely difficult, and mature technology is not yet available. Furthermore, the risk of catalyst contact with air persists during transfer to the catalyst loading device, leading to reduced catalyst activity and even safety risks such as combustion or explosion. Using high linear gas speeds for catalyst transport and loading consumes a lot of energy, increases catalyst wear, and affects catalyst performance. Catalyst fines are transferred downstream of the reactor, reducing the reliability and safety of the process unit. Summary of the Invention

[0007] The purpose of the present invention is to overcome the above-mentioned technical problems and provide a catalyst liquid phase filling system, a catalyst liquid phase filling method, an application of the catalyst liquid phase filling system, and a method for synthesizing 4-methyl-1-pentene by propylene dimerization. The system not only realizes liquid phase filling of the catalyst in a non-oxidizing atmosphere, but also reduces the degree of catalyst wear, thereby improving the catalytic activity of the catalyst.

[0008] To achieve the above objectives, the present invention provides, in a first aspect, a catalyst liquid-phase loading system, comprising: a connected catalyst kettle and a shell-and-tube reactor, as well as a gas pipe, a catalyst delivery pipe, a delivery liquid feed pipe, and a delivery liquid circulation pipe; the shell-and-tube reactor comprising a housing, the housing being provided with a catalyst inlet and a delivery liquid outlet, an upper tube sheet and a lower tube sheet being provided within the housing, and a plurality of tube bundles being provided between the upper tube sheet and the lower tube sheet; a guide plate connecting the catalyst inlet and the tube bundles is provided on the upper tube sheet;

[0009] Among them, the gas pipe is connected to the gas port of the catalyst kettle, so that the catalyst carrier is loaded in situ under a non-oxidizing atmosphere to obtain a catalyst; the catalyst delivery pipe is connected to the discharge port and catalyst inlet of the catalyst kettle, as well as the delivery liquid feed pipe, for loading the catalyst into the tube array under the delivery of the delivery liquid; the delivery liquid circulation pipe is connected to the delivery liquid outlet and the delivery liquid feed pipe, for recycling the delivery liquid.

[0010] Preferably, the guide plate is selected from a spiral guide plate, and the annular channel formed by the guide plate connects the catalyst inlet and the tube array.

[0011] Preferably, according to the material flow direction, the catalyst delivery pipe is provided with a discharge valve and an inlet valve in sequence.

[0012] Preferably, at least one material level meter port and a catalyst return port are provided on the top of the shell.

[0013] Preferably, the pipeline between the catalyst inlet and the inlet valve is connected to the return port of the catalyst kettle through a catalyst return pipe.

[0014] Preferably, the catalyst return port is provided with a catalyst return liquid delivery pipe connected to the downstream of the catalyst delivery pipe, and according to the material flow direction, the connection point between the catalyst delivery pipe and the catalyst return liquid delivery pipe is located before the inlet valve.

[0015] A second aspect of the present invention provides a method for loading a catalyst in liquid phase, which is performed in the system provided in the first aspect, wherein the method comprises:

[0016] In a non-oxidizing atmosphere, the catalyst carrier is in-situ loaded in a catalyst kettle to obtain a catalyst;

[0017] Under the transportation of the transport liquid, the catalyst enters the shell-and-tube reactor through the catalyst transport pipe and is filled in the shell-and-tube reactor through the guide plate. The transport liquid is circulated back to the transport liquid feed pipe through the catalyst circulation pipe.

[0018] Preferably, the method comprises the following steps:

[0019] S1. Keep the system in a non-oxidizing atmosphere, close the air inlet valve, exhaust valve, top valve, bottom valve, feed valve and return valve, and add the catalyst carrier through the feed port; repeatedly open and close the air inlet valve and exhaust valve alternately to replace the atmosphere, so that the catalyst kettle is in a non-oxidizing atmosphere;

[0020] S2. Open the top valve and bottom valve to allow the active components to enter the catalyst kettle, then close the top valve and bottom valve; adjust the air inlet valve, start the stirring blade and heating component, so that the catalyst carrier is in-situ loaded in a non-oxidizing atmosphere;

[0021] S3. When the system is provided with a liquid feed branch, the pressure of the liquid feed tank is adjusted to be greater than the pressure of the catalyst kettle, the bottom valve of the liquid feed tank and the valve of the liquid feed branch are opened, the stirring paddle is started, so that the catalyst slurry is in a mixed state, and then the bottom valve of the liquid feed tank and the valve of the liquid feed branch are closed; otherwise, S3 is ignored;

[0022] S4, the pressure of the catalyst kettle is regulated to be higher than the pressure of the catalyst conveying pipe, the conveying liquid tank bottom valve, the conveying liquid feeding valve, the discharging valve, the catalyst inlet valve and the conveying liquid discharge valve are opened, the return valve and the return material valve are kept closed, so that the catalyst is filled in the tube under the conveying of the conveying liquid, the conveying liquid is circulated back to the conveying liquid feeding pipe through the conveying liquid circulating pipe, and preferably the conveying liquid is circulated back to the conveying liquid feeding pipe after being filtered and pressurized in sequence;

[0023] S5, during the filling process, the filling height of the catalyst in the tube is measured through a material level meter; when the catalyst is accumulated on the upper tube plate, the discharging valve is closed, the conveying liquid continues to be conveyed, if the catalyst is not accumulated on the upper tube plate, the discharging valve is opened to continue filling, and if the catalyst is still accumulated on the upper tube plate, the conveying liquid discharge valve is closed;

[0024] The pressure of the conveying liquid tank is regulated to be higher than the pressure of the catalyst kettle, the return valve, the return material valve and the catalyst return conveying liquid valve are opened, the catalyst accumulated on the upper tube plate is circulated back to the catalyst kettle, preferably the catalyst accumulated on the upper tube plate is subjected to solid-liquid separation, the obtained solid phase is circulated back to the catalyst kettle, and the obtained liquid phase is returned and mixed into the conveying liquid after being filtered and pressurized in sequence;

[0025] S6, after the catalyst accumulated on the upper tube plate is returned, all the valves are closed, and the catalyst filling is completed.

[0026] The third aspect of the application provides an application of the system provided in the first aspect in a reduction state metal catalyst catalytic reaction.

[0027] The fourth aspect of the application provides a method for synthesizing 4-methyl-1-pentene by dimerization of propylene, and the method is carried out in the system provided in the first aspect, and the method comprises: propylene is introduced into the system through the reactant material inlet, contacts the catalyst filled in the tube and reacts to obtain 4-methyl-1-pentene, and the obtained 4-methyl-1-pentene is discharged through the reactant material outlet.

[0028] Compared with the prior art, the application has the following advantages:

[0029] (1) The system provided by the application realizes catalyst loading and filling process in a non-oxidizing atmosphere, reduces the risk of catalyst contact with air, weakens the degree of catalyst wear, has high filling efficiency and good uniformity, and improves the stability and safety of the catalyst;

[0030] (2) The system provided by the present invention realizes in-situ loading of the catalyst on the loading system by providing a catalyst kettle, eliminating the need for transferring the catalyst to the loading system after the catalyst preparation is completed; the reaction material components with a relatively low linear velocity are used as the transport liquid, thereby realizing liquid-phase loading of the catalyst under anaerobic conditions. After loading, the catalyst can be directly used for the reaction without cleaning, and the degree of catalyst wear during the loading process is relatively low; guide plates are provided on the upper tube sheet of the tubular reactor to form a catalyst loading channel, thereby realizing rapid and uniform loading of the catalyst under inert conditions;

[0031] (3) The method of dimerizing propylene to 4-methyl-1-pentene is carried out in the system provided by the present invention, which can effectively improve the conversion rate of propylene and increase the operating time of the system. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a schematic structural diagram of a catalyst liquid phase filling system provided by the present invention;

[0033] Figure 2 It is a structural schematic diagram of another catalyst liquid phase filling system provided by the present invention;

[0034] Figure 3 This is a top view of the local structure of a shell-and-tube reactor provided by the present invention;

[0035] Figure 4 This is a side view of a local structure of a shell-and-tube reactor provided by the present invention;

[0036] Figure 5 This is a schematic structural diagram of the catalyst liquid phase filling system provided in Comparative Example 2;

[0037] Figure 6 This is a top view of the local structure of the shell and tube reactor provided in Example 3.

[0038] Description of Reference Numerals

[0039] 1. Catalyst kettle 1-2, gas port 1-3, feeding port 1-4, discharge port

[0040] 1-5, return port 1-6, heating component 1-7, stirring paddle 1-8, dosing port

[0041] 1-9, reagent tank 1-10, top valve 1-11, bottom valve 2, gas pipe

[0042] 2-1, intake valve 3, exhaust pipe 3-1, exhaust valve 4, catalyst delivery pipe

[0043] 4-1, discharge valve 4-2, inlet valve 5, liquid delivery tank 5-1, gas phase port

[0044] 5-2, liquid phase port 5-3, gas pipe for liquid delivery tank 5-4, gas phase valve 5-5, discharge pipe for liquid delivery tank trachea

[0045] 5-6, conveying liquid tank exhaust valve 5-7, conveying liquid feed pipe 5-8, conveying liquid tank bottom valve

[0046] 5-9, conveying liquid feed branch pipe 5-10, conveying liquid feed branch valve 5-11, conveying liquid feed valve

[0047] 7. Shell and tube reactor 7-1, shell 7-2, tubes 7-3, upper tube plate

[0048] 7-4, guide plate 7-5, lower tube plate 7-8, catalyst inlet 7-9, conveying liquid outlet

[0049] 7-10, reaction material inlet 7-11, reaction material outlet 7-12, upper pipe port of tube array

[0050] 7-13, tube lower port 7-14, material level meter port 7-15, catalyst return port

[0051] 7-16, heat exchange medium outlet 7-17, heat exchange medium inlet 7-18, material level meter

[0052] 8. Conveying liquid circulation pipe 8-1, conveying liquid discharge valve 8-2, filtering equipment

[0053] 8-3, pump 11, catalyst return pipe 11-1, return valve 11-2, return valve

[0054] 12. Solid-liquid separator 13. Liquid return pipe 13-1. Liquid return valve

[0055] 15. Catalyst return liquid delivery pipe 15-1. Catalyst return liquid delivery valve DETAILED DESCRIPTION

[0056] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0057] In the present application, unless otherwise specified, the "top" of the container refers to the 0-10% position from top to bottom of the container; the "upper part" of the container refers to the 10-40% position from top to bottom of the container; the "middle part" of the container refers to the 40-60% position from top to bottom of the container; the "lower part" of the container refers to the 60-90% position from top to bottom of the container; and the "bottom" of the container refers to the 90-100% position from top to bottom of the container.

[0058] The first aspect of the present application provides a catalyst liquid loading system, as shown in the figure, which comprises a connected catalyst kettle 1 and a tube reactor 7, and a gas pipe 2, a catalyst conveying pipe 4, a conveying liquid feeding pipe 5-7 and a conveying liquid circulating pipe 8; the tube reactor 7 comprises a shell 7-1, which is provided with a catalyst inlet 7-8 and a conveying liquid outlet 7-9, and is provided with an upper tube plate 7-3 and a lower tube plate 7-5 inside, and a plurality of tube bundles 7-2 are arranged between the upper tube plate 7-3 and the lower tube plate 7-5; the upper tube plate 7-3 is provided with a flow guide plate 7-4 connecting the catalyst inlet 7-8 and the tube 7-2; Figure 1-2

[0059] The gas pipe 2 is connected to the gas port 1-2 of the catalyst kettle 1, so that the catalyst carrier is loaded in situ under a non-oxidizing gas atmosphere to obtain a catalyst; the catalyst conveying pipe 4 is connected to the discharge port 1-4 of the catalyst kettle 1 and the catalyst inlet 7-8, and the conveying liquid feeding pipe 5-7, which is used to load the catalyst in the tube 7-2 under the conveying of the conveying liquid; and the conveying liquid circulating pipe 8 is connected to the conveying liquid outlet 7-9 and the conveying liquid feeding pipe 5-7, which is used to circulate the conveying liquid back.

[0060] In the present application, unless otherwise specified, the catalyst conveying pipe 4 is connected to the discharge port 1-4 of the catalyst kettle 1 and the catalyst inlet 7-8 of the tube reactor 7, and the catalyst inlet 7-8 and the tube 7-2 are connected through the flow guide plate 7-4, which constitutes a catalyst loading channel.

[0061] In the present application, the type of the flow guide plate has a wide selection range, which can be the type of the flow guide plate in the field, including but not limited to spiral flow guide plates, arc-shaped flow guide plates, straight line-shaped flow guide plates, broken line-shaped flow guide plates, etc., and preferably spiral flow guide plates. In the present application, the use of spiral flow guide plates can reduce the degree of catalyst abrasion, and at the same time form a complete catalyst loading channel, so that the loading efficiency is higher and the uniformity is better.

[0062] In some embodiments of the present application, preferably, as shown in the figure, Figure 3-4 ​As shown, the guide plate 7-4 is selected from a spiral guide plate, and the annular channel formed by the guide plate 7-4 connects the catalyst inlet 7-8 and the tube array 7-2.

[0063] In some embodiments of the present invention, preferably, Figure 3-4 As shown, the ratio of the width of the annular channel to the inner diameter of the shell 7-1 is 0.01-1:1, for example, 0.01:1, 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.8:1, 1:1, and any value in the range consisting of any two values, preferably 0.01-0.5:1, and the ratio of the width of the annular channel to the outer diameter of the tube 7-2 is greater than 1:1, preferably 1.25-20:1, for example, 1.25:1, 1.5:1, 2:1, 5:1, 10:1, 15:1, 20:1, and any value in the range consisting of any two values.

[0064] In some embodiments of the present invention, preferably, Figure 3-4 As shown, the ratio of the height of the guide plate 7-4 to the equivalent diameter of the catalyst is 5-100:1, for example, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 80:1, 100:1, and at least one in the range of any two numerical values, preferably 10-50:1, and the height of the guide plate 7-4 is lower than half of the vertical distance between the upper tube plate 7-3 and the top of the shell 7-1.

[0065] In some embodiments of the present invention, preferably, the catalyst is selected from a regular shape or an irregular shape, preferably selected from a regular shape, and more preferably selected from at least one of a sphere, a cylinder and a strip.

[0066] In some embodiments of the present invention, preferably, the equivalent diameter of the catalyst is 0.1-20 mm, for example, 0.1 mm, 0.3 mm, 0.5 mm, 1 mm, 3 mm, 5 mm, 10 mm, 15 mm, 20 mm, and any value in the range consisting of any two values, preferably 0.3-5 mm.

[0067] In some embodiments of the present invention, preferably, the ratio of the inner diameter of the tube 7-2 to the equivalent diameter of the catalyst is 3-50:1, for example, 3:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 50:1, and any value in the range of any two values, preferably 5-30:1.

[0068] In the present invention, unless otherwise specified, Figure 1-2 As shown, the tube array 7-2 includes an upper tube opening 7-12 and a lower tube opening 7-13.

[0069] In the present invention, unless otherwise specified, the lower tube port 7-13 of the tube array 7-2 is provided with an intercepting pipe fitting for intercepting and supporting the catalyst so that the catalyst is loaded in the tube array. The intercepting pipe fitting includes but is not limited to a plug with a small hole, a wire plug with a small hole, a wire mesh, a porcelain ball, etc.

[0070] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the system further includes a conveying liquid tank 5 connected to the inlet end of the conveying liquid feed pipe 5-7, for injecting conveying liquid into the conveying liquid feed pipe 5-7.

[0071] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the top and bottom of the transport liquid tank 5 are respectively provided with a gas phase port 5-1 and a liquid phase port 5-2. Among them, the gas phase port 5-1 is used to inject non-oxidizing gas into the transport liquid tank 5, and the liquid phase port 5-2 is used to inject transport liquid into the transport liquid feeding pipe 5-7.

[0072] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the gas phase port 5-1 is connected to the gas pipe 5-3 of the liquid delivery tank, and the gas pipe 5-3 of the liquid delivery tank is provided with a gas phase valve 5-4.

[0073] In some embodiments of the present invention, preferably, Figure 1-2 As shown, a liquid transport tank exhaust pipe 5-5 is provided on the pipeline connecting the gas phase port 5-1 and the gas phase valve 5-4, and a liquid transport tank exhaust valve 5-6 is provided on the liquid transport tank exhaust pipe 5-5. In the present invention, the liquid transport tank is placed in a non-oxidizing atmosphere by regulating the states of the gas phase valve and the liquid transport tank exhaust valve, i.e., the open state or the closed state.

[0074] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the gas port 1-2 is provided at the top of the catalyst kettle 1, and the feed port 1-4 is provided at the bottom of the catalyst kettle 1. In the present invention, the top of the catalyst kettle refers to the upper head of the catalyst kettle.

[0075] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the gas pipe 2 is provided with an air inlet valve 2 - 1 for injecting non-oxidizing gas into the catalyst kettle 1 .

[0076] In some embodiments of the present invention, preferably, Figure 1-2As shown, an exhaust pipe 3 is provided on the pipeline connecting the gas port 1-2 and the air inlet valve 2-1, and an exhaust valve 3-1 is provided on the exhaust pipe 3. In the present invention, the catalyst kettle is placed in a non-oxidizing atmosphere by regulating the states of the air inlet valve and the exhaust valve, i.e., the open state or the closed state.

[0077] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the top of the catalyst kettle 1 is further provided with a feed port 1-3 and a dosing port 1-8, which are used to add catalyst carriers and active components into the catalyst kettle respectively.

[0078] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the dosing port 1-8 is connected to a reagent tank 1-9 provided with a top valve 1-10 and a bottom valve 1-11. In the present invention, by regulating the state of the top valve and the bottom valve, i.e., the open state or the closed state, the active component entering through the dosing port is loaded in situ with the catalyst carrier in the catalyst kettle to obtain a catalyst.

[0079] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the catalyst kettle 1 is further provided with a stirring paddle 1-7 inside and a heating component 1-6 outside. In the present invention, the heating component 1-6 can be an electric heating component or a heat medium provided by a jacket or coil.

[0080] In some embodiments of the present invention, preferably, Figure 1-2 As shown, according to the material flow direction, the delivery liquid tank bottom valve 5-8 and the delivery liquid feed valve 5-11 are sequentially provided on the delivery liquid feed pipe 5-7. In the present invention, according to the material flow direction, the delivery liquid tank bottom valve 5-8 is provided after the liquid phase port 5-2, and the delivery liquid feed valve 5-11 is provided before the catalyst inlet 7-8.

[0081] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the catalyst delivery pipe 4 is sequentially provided with a discharge valve 4-1 and an inlet valve 4-2 in the direction of material flow. The discharge valve 4-1 is used to control the transfer process of the catalyst in the catalyst kettle, and the inlet valve 4-2 is used to control the loading process of the catalyst into the shell-and-tube reactor. In the present invention, unless otherwise specified, in the direction of material flow, the discharge valve 4-1 is provided after the discharge port 1-4, and the inlet valve 4-2 is provided before the catalyst inlet 7-8.

[0082] In some embodiments of the present invention, preferably, Figure 1-2As shown, according to the material flow direction, the delivery liquid feed valve 5-11 is arranged after the discharge valve 4-1. In the present invention, by adjusting the state of the delivery liquid feed valve 5-11, that is, the closed state or the open state, the catalyst is transferred to the shell and tube reactor through the catalyst delivery pipe under the delivery of the delivery liquid and loaded into the shell and tube reactor through the guide plate.

[0083] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the catalyst inlet 7-8 is tangentially arranged on the shell 7-1 and is not lower than the upper tube plate 7-3; further preferably, the vertical distance between the catalyst inlet 7-8 and the upper tube plate 7-3 is 0-50 mm; more preferably, the catalyst inlet 7-8, the upper tube plate 7-3 and the guide plate 7-4 are all at the same height.

[0084] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the conveying liquid outlet 7-9 is radially arranged on the shell 7-1 and is not higher than the lower tube plate 7-5; further preferably, the conveying liquid outlet 7-9 is arranged below the lower tube plate 7-5.

[0085] In some embodiments of the present invention, preferably, Figure 1-2 As shown, according to the material flow direction, the conveying liquid circulation pipe 8 is sequentially provided with a conveying liquid discharge valve 8-1, a filter device 8-2 and a pump 8-3. In the present invention, the conveying liquid is circulated and reused by regulating the conveying liquid discharge valve, that is, the open state and the closed state.

[0086] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the top of the shell 7-1 is provided with at least one material level gauge port 7-14 and a catalyst return port 7-15. Furthermore, preferably, the material level gauge port 7-14 is provided with a material level gauge 7-18 for measuring the catalyst filling height in the shell and tube reactor. In the present invention, unless otherwise specified, the material level gauge ports 7-14 are evenly distributed on the upper head of the shell and tube reactor 7, preferably evenly distributed around the circumference of the upper head of the shell and tube reactor 7.

[0087] In some embodiments of the present invention, preferably, the number of the material level meter ports 7-14 is 1-20, preferably 1-5.

[0088] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the pipeline between the catalyst inlet 7 - 8 and the inlet valve 4 - 2 is connected to the return port 1 - 5 of the catalyst kettle 1 through a catalyst return pipe 11 .

[0089] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the catalyst return port 7-15 is provided with a catalyst return liquid delivery pipe 15 connected to the downstream of the catalyst delivery pipe 4, and according to the material flow direction, the connection point between the catalyst delivery pipe 4 and the catalyst return liquid delivery pipe 15 is located before the inlet valve 4-2.

[0090] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the catalyst return delivery liquid pipe 15 is provided with a catalyst return delivery liquid valve 15 - 1 .

[0091] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the catalyst return liquid delivery pipe 15 passes through the shell 7-1 and extends to the top of the upper tube plate 7-3; further preferably, the vertical distance from the catalyst return liquid delivery pipe 15 to the upper tube plate 7-3 to the height of the guide plate 7-4 is 0.2-5:1, for example, 0.2:1, 0.5:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 2:1, 3:1, 5:1, and any value in the range of any two values, preferably 1-1.5:1.

[0092] In some embodiments of the present invention, preferably, Figure 1-2 As shown, according to the material flow direction, the catalyst return pipe 11 is sequentially provided with a return valve 11 - 1 and a return material valve 11 - 2 .

[0093] In the present invention, unless otherwise specified, the delivery liquid feed pipe 5-7 may also be provided with a delivery liquid feed branch pipe before the delivery liquid feed valve 5-11, so as to provide a greater driving force for catalyst delivery. Figure 1-2 As shown, a conveying liquid feed branch pipe 5-9 is provided downstream of the conveying liquid feed pipe 5-7, and the conveying liquid feed branch pipe 5-9 is connected to the return port 1-5.

[0094] In some embodiments of the present invention, preferably, Figure 1-2 As shown, a conveying liquid feed branch pipe valve 5-10 is provided on the conveying liquid feed branch pipe 5-9.

[0095] In some embodiments of the present invention, preferably, Figure 1-2 As shown, according to the material flow direction, the connection point between the conveying liquid feed branch pipe 5-9 and the conveying liquid feed pipe 5-7 is located between the conveying liquid tank bottom valve 5-8 and the conveying liquid feed valve 5-11, and the connection point between the conveying liquid feed branch pipe 5-9 and the catalyst return pipe 11 is located between the return valve 11-2 and the return port 1-5.

[0096] In some embodiments of the present application, preferably, as shown in Figure 1-2 The solid-liquid separator 12 is further arranged on the catalyst return pipe 11, and is arranged between the return valve 11-1 and the return material valve 11-2.

[0097] In some embodiments of the present application, preferably, as shown in Figure 1-2 The liquid phase outlet of the solid-liquid separator 12 and the conveying liquid feeding pipe 5-7 are connected by a liquid phase return pipe 13, and the liquid phase return valve 13-1 is arranged on the liquid phase return pipe 13.

[0098] In some embodiments of the present application, preferably, as shown in Figure 1-2 The liquid phase return pipe 13 is connected to the conveying liquid circulating pipe 8.

[0099] In some embodiments of the present application, preferably, as shown in Figure 1-2 The liquid phase return valve 13-1 is arranged before the filtering device 8-2 in the direction of material flow.

[0100] In some embodiments of the present application, preferably, as shown in Figure 1-2 The heat exchange medium inlet 7-17 and the heat exchange medium outlet 7-16 are further arranged on the shell 7-1, and are arranged between the upper tube plate 7-3 and the lower tube plate 7-5; further preferably, the heat exchange medium inlet 7-17 is arranged below and the heat exchange medium outlet 7-16 is arranged above.

[0101] In some embodiments of the present application, preferably, as shown in Figure 1-2 The reaction material inlet 7-10 and the reaction material outlet 7-11 are further arranged on the shell 7-1. In the present application, unless otherwise specified, the reaction material inlet 7-10 can be arranged at the top of the shell 7-1 or at the bottom of the shell 7-1; similarly, the reaction material outlet 7-11 can be arranged at the top of the shell 7-1 or at the bottom of the shell 7-1. Further preferably, the reaction material inlet 7-10 and the reaction material outlet 7-11 are arranged at the top and the bottom of the shell 7-1 respectively.

[0102] The second aspect of the present application provides a catalyst liquid phase loading method, which is carried out in the system provided in the first aspect, wherein the method comprises:

[0103] The catalyst carrier is in-situ loaded in the catalyst kettle under a non-oxidizing atmosphere to obtain a catalyst.

[0104] Under the transportation of the transport liquid, the catalyst enters the shell-and-tube reactor through the catalyst transport pipe and is filled in the shell-and-tube reactor through the guide plate. The transport liquid is circulated back to the transport liquid feed pipe through the catalyst circulation pipe.

[0105] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the method includes the following steps:

[0106] S1. Keep the system in a non-oxidizing atmosphere, close the air inlet valve 2-1, the exhaust valve 3-1, the top valve 1-10, the bottom valve 1-11, the discharge valve 4-1 and the return valve 11-2, and add the catalyst carrier through the feeding port 1-3; repeatedly open and close the air inlet valve 2-1 and the exhaust valve 3-1 alternately to replace the atmosphere, so that the catalyst kettle 1 is in a non-oxidizing atmosphere;

[0107] S2, open the top valve 1-10 and the bottom valve 1-11, the active components enter the catalyst kettle 1, close the top valve 1-10 and the bottom valve 1-11; adjust the air inlet valve 2-1, start the stirring paddle 1-7 and the heating component 1-6, so that the catalyst carrier is in situ loaded in a non-oxidizing atmosphere;

[0108] S3. When the system is provided with a delivery liquid feed branch pipe 5-9, the pressure of the delivery liquid tank 5 is regulated to be greater than the pressure of the catalyst kettle 1, the delivery liquid tank bottom valve 5-8 and the delivery liquid feed branch pipe valve 5-10 are opened, and the stirring paddle 1-7 is started to make the catalyst slurry in a mixed state, and then the delivery liquid tank bottom valve 5-8 and the delivery liquid feed branch pipe valve 5-10 are closed; otherwise, S3 is ignored;

[0109] S4, regulating the pressure of the catalyst kettle 1 to be higher than the pressure of the catalyst delivery pipe 4, opening the bottom valve 5-8 of the delivery liquid tank, the delivery liquid feed valve 5-11, the discharge valve 4-1, the catalyst inlet valve 4-2, and the delivery liquid discharge valve 8-1, keeping the return valve 11-1 and the return valve 11-2 in a closed state, so that the catalyst is loaded into the tube 7-2 under the delivery of the delivery liquid, and the delivery liquid is circulated back to the delivery liquid feed pipe 5-7 through the delivery liquid circulation pipe 8. Preferably, the delivery liquid is filtered and pressurized in sequence and then circulated back to the delivery liquid feed pipe 5-7;

[0110] S5. During the loading process, the filling height of the catalyst in the tube array 7-2 is measured by the material level meter 7-18. When catalyst accumulates on the upper tube plate 7-3, the discharge valve 4-1 is closed and the conveying liquid continues to be conveyed. If there is no catalyst accumulation on the upper tube plate 7-3, the discharge valve 4-1 is opened to continue the loading. If there is still catalyst accumulation on the upper tube plate 7-3, the conveying liquid discharge valve 8-1 is closed.

[0111] The pressure of the transfer liquid tank 5 is regulated to be higher than the pressure of the catalyst kettle 1, and the return valve 11-1, the return valve 11-2 and the catalyst return transfer liquid valve 15-1 are opened to circulate the catalyst accumulated on the upper tube plate 7-3 back to the catalyst kettle 1. Preferably, the catalyst accumulated on the upper tube plate 7-3 is subjected to solid-liquid separation, and the obtained solid phase is circulated back to the catalyst kettle 1. The obtained liquid phase is filtered and pressurized in sequence, and then returned and mixed with the transfer liquid;

[0112] S6. After the catalyst accumulated on the upper tube plate 7-3 is returned clean, all valves are closed and the catalyst loading is completed.

[0113] In some embodiments of the present invention, preferably, the non-oxidizing gas in the non-oxidizing atmosphere is selected from an inert gas and / or nitrogen, preferably nitrogen, wherein the inert gas includes but is not limited to helium, argon, etc.

[0114] In some embodiments of the present invention, preferably, the nitrogen satisfies: an oxygen content ≤ 10 ppm, preferably ≤ 3 ppm; a water content ≤ 10 ppm, preferably ≤ 3 ppm.

[0115] In some embodiments of the present invention, preferably, the transport liquid is selected from at least one component of the reaction material. In the present invention, the reaction material is selected from reactants and / or products.

[0116] In some embodiments of the present invention, preferably, the in-situ loading conditions include: a catalyst kettle pressure of 0-10 MPa(A), preferably 0.1-5 MPa(A); a catalyst kettle temperature of 0-500°C, preferably 20-400°C; and a time of 0.1-96 hours, preferably 0.5-24 hours. In the present invention, all pressure parameters refer to absolute pressure.

[0117] In some embodiments of the present invention, preferably, the loading conditions include: a catalyst kettle pressure of 0-10 MPa(A), preferably 0.1-5 MPa(A); a catalyst kettle temperature of 0-300°C, preferably 20-200°C; a delivery liquid pressure of 0-10 MPa(A), preferably 0.1-5 MPa(A); and a delivery liquid temperature of 0-300°C, preferably 20-100°C. In the present invention, the delivery liquid pressure refers to the saturated vapor pressure of the delivery liquid at a specific temperature.

[0118] In some embodiments of the present invention, preferably, the volume ratio of the conveying liquid and the catalyst is 2-500:1, for example, 2:1, 5:1, 10:1, 30:1, 50:1, 80:1, 100:1, 200:1, 300:1, 400:1, 500:1, and any value in the range consisting of any two numerical values, preferably 5-100:1, and the flow rate of the solid-liquid mixture of the conveying liquid and the catalyst is 0.5-15 m / s, for example, 0.5 m / s, 1 m / s, 2 m / s, 3 m / s, 4 m / s, 5 m / s, 6 m / s, 10 m / s, 15 m / s, and any value in the range consisting of any two numerical values, preferably 1-6 m / s.

[0119] The third aspect of the present invention provides an application of the system provided in the first aspect in a catalytic reaction using a reduced metal catalyst, preferably in the dimerization of propylene to synthesize 4-methyl-1-pentene.

[0120] A fourth aspect of the present invention provides a method for dimerizing propylene to synthesize 4-methyl-1-pentene. The method is carried out in the system provided in the first aspect, and comprises: introducing propylene through a reaction material inlet, contacting with the catalyst loaded in the tube array and reacting, and discharging the obtained 4-methyl-1-pentene through a reaction material outlet.

[0121] According to a particularly preferred embodiment of the present invention, a catalyst liquid phase loading system comprises: a connected catalyst kettle 1 and a shell-and-tube reactor 7, as well as a gas pipe 2, a catalyst delivery pipe 4, delivery liquid feed pipes 5-7, a delivery liquid circulation pipe 8, a catalyst return pipe 11, a catalyst return port 15 and a liquid phase return pipe 13;

[0122] The shell-and-tube reactor 7 includes a shell 7-1, which is provided with a catalyst inlet 7-8, a liquid delivery outlet 7-9, at least one material level meter port 7-14, and a catalyst return port 7-15. An upper tube sheet 7-3 and a lower tube sheet 7-5 are provided in the shell 7-1, and a plurality of tube bundles 7-2 are provided between the upper tube sheet 7-3 and the lower tube sheet 7-5.

[0123] The upper tube plate 7-3 is provided with a spiral guide plate 7-4, and the annular channel formed by the spiral guide plate connects the catalyst inlet 7-8 and the tube array 7-2;

[0124] The upper head of the catalyst kettle 1 is provided with a gas port 1-2, a feeding port 1-3, a dosing port 1-8 and a return port 1-5, and the bottom of the catalyst kettle 1 is provided with a discharge port 1-4;

[0125] Among them, the gas pipe 2 is connected to the gas port 1-2, so that the catalyst carrier is in-situ loaded under a non-oxidizing atmosphere to obtain a catalyst; the catalyst delivery pipe 4 is connected to the discharge port 1-4 and the catalyst inlet 7-8, and the delivery liquid feed pipe 5-7, for loading the catalyst into the tube array 7-2 under the delivery of the delivery liquid; the delivery liquid circulation pipe 8 is connected to the delivery liquid outlet 7-9 and the delivery liquid feed pipe 5-7, for recycling the delivery liquid;

[0126] According to the material flow direction, the catalyst delivery pipe 4 is sequentially provided with a discharge valve 4-1 and an inlet valve 4-2;

[0127] The catalyst return pipe 11 connects the pipeline between the catalyst inlet 7-8 and the inlet valve 4-2, and the return port 1-5;

[0128] The catalyst return liquid delivery pipe 15 is connected to the downstream of the catalyst delivery pipe 4 and the catalyst return port 7-15;

[0129] Among them, according to the material flow direction, the catalyst return pipe 11 is sequentially provided with a return valve 11-1, a solid-liquid separator 12 and a return valve 11-2; the liquid phase outlet of the solid-liquid separator 12 and the conveying liquid feed pipe 5-7 are connected through a liquid phase return pipe 13.

[0130] The present invention will be described in detail below through examples.

[0131] In the examples and comparative examples, the nitrogen gas satisfies the following conditions: oxygen content ≤ 3 ppm, water content ≤ 3 ppm.

[0132] Example 1

[0133] Catalyst liquid phase filling system such as Figure 1 、 3 -4, the system comprises a catalyst kettle 1, a liquid transport tank 5, a shell-and-tube reactor 7, a gas pipe 2, a catalyst transport pipe 4, a liquid transport feed pipe 5-7, a liquid transport circulation pipe 8, a catalyst return pipe 11 and a catalyst return liquid transport pipe 15;

[0134] Among them, the upper head of the catalyst kettle 1 is provided with a gas port 1-2, a feeding port 1-3, a return port 1-5, and a dosing port 1-8. The gas port 1-2 is connected to the gas pipe 2, and the gas pipe 2 is provided with an air intake valve 2-1; the gas pipeline 2 between the gas port 1-2 and the air intake valve 2-1 is connected to the exhaust pipe 3, and the exhaust pipe 3 is provided with an exhaust valve 3-1; the bottom of the catalyst kettle 1 is provided with a discharge port 1-4, which is connected to the catalyst delivery pipe 4, and the catalyst delivery pipe 4 is provided with a discharge port 1-4. A discharge valve 4-1 and a catalyst inlet valve 4-2 are provided; the discharge valve 4-1 of the catalyst delivery pipe 4 is connected to a delivery liquid feed pipe 5-7, and the delivery liquid feed pipe 5-7 is sequentially provided with a delivery liquid tank bottom valve 5-8 and a delivery liquid feed valve 5-11; the addition port 1-8 of the catalyst kettle 1 is connected to a reagent tank 1-9 with valves at both ends, and the inlet end of the reagent tank 1-9 is connected to a non-oxidizing gas; a stirring paddle 1-7 is provided inside the catalyst kettle 1; and a heating component 1-6 is provided outside the catalyst kettle 1;

[0135] The top and bottom of the liquid delivery tank 5 are respectively provided with a gas phase port 5-1 and a liquid phase port 5-2; the gas phase port 5-1 is connected to a liquid delivery tank gas pipe 5-3 with a gas phase valve 5-4; a liquid delivery tank exhaust pipe 5-5 is provided on the pipeline connecting the gas phase port 5-1 and the gas phase valve 5-4, and a liquid delivery tank exhaust valve 5-6 is provided on the liquid delivery tank exhaust pipe 5-5;

[0136] The shell-and-tube reactor 7 includes a shell 7-1, which is tangentially provided with a catalyst inlet 7-8 and a liquid delivery outlet 7-9. An upper tube sheet 7-3 and a lower tube sheet 7-5 are provided in the shell 7-1, and a plurality of tube bundles 7-2 are provided between the upper tube sheet 7-3 and the lower tube sheet 7-5. A spiral guide plate 7-4 is provided on the upper tube sheet 7-3, and an annular channel formed by the spiral guide plate 7-4 connects the catalyst inlet 7-8 and the tube bundle 7-2, forming a catalyst loading channel.

[0137] The catalyst inlet 7-8, the upper tube plate 7-3 and the guide plate 7-4 are at the same height; the delivery liquid outlet 7-9 and the delivery liquid feed pipe 5-7 are connected through a delivery liquid circulation pipe 8; according to the direction of material flow, the delivery liquid circulation pipe 8 is sequentially provided with a delivery liquid discharge valve 8-1, a filter device 8-2 and a pump 8-3;

[0138] Among them, the pipeline between the catalyst inlet 7-8 and the inlet valve 4-2 is connected to the return port 1-5 through a catalyst return pipe 11. According to the direction of material flow, the catalyst return pipe 11 is sequentially provided with a return valve 11-1, a solid-liquid separator 12 and a return valve 11-2; the liquid phase outlet of the solid-liquid separator 12 and the conveying liquid feed pipe 5-7 are connected through a liquid phase return pipe 13, and the liquid phase return pipe 13 is provided with a liquid phase return valve 13-1;

[0139] Among them, the catalyst return port 7-15 is provided with a catalyst return liquid delivery pipe 15 connected to the downstream of the catalyst delivery pipe 4, and according to the material flow direction, the connection point between the catalyst delivery pipe 4 and the catalyst return liquid delivery pipe 15 is located before the inlet valve 4-2;

[0140] The catalyst return liquid delivery pipe 15 is provided with a catalyst return liquid delivery valve 15-1; the catalyst return liquid delivery pipe 15 passes through the shell 7-1 and extends above the upper tube plate 7-3; the vertical distance between the catalyst return liquid delivery pipe 15 and the upper tube plate 7-3 is 20 mm;

[0141] The upper end cap of the shell-and-tube reactor 7 is provided with a reaction material inlet 7-10 and two material level gauge ports 7-14. The material level gauge ports 7-14 are provided with material level gauges 7-18. The lower end cap is provided with a reaction material outlet 7-11. A heat exchange medium inlet 7-17 and a heat exchange medium outlet 7-16 are provided above the lower tube sheet 7-5 and below the upper tube sheet 7-3 on the side of the shell 7-1, respectively.

[0142] Among them, the width of the annular channel is 80mm, the inner diameter of the shell is 500mm, the inner diameter of the tube is 20mm, the outer diameter of the tube is 25mm, the vertical distance from the upper tube plate to the top of the shell is 150mm; the height of the guide plate is 20mm; the catalyst is a spherical catalyst with an equivalent diameter of 2mm.

[0143] A catalyst liquid phase loading method is carried out in the above system and comprises the following steps:

[0144] (1) Keep the above system in a nitrogen atmosphere, close the air inlet valve, exhaust valve, top valve, bottom valve, feed valve and return valve, and add the catalyst carrier through the feed port; repeatedly open and close the air inlet valve and exhaust valve alternately to keep the catalyst kettle in a nitrogen atmosphere;

[0145] (2) Open the top valve and bottom valve to allow the active components (Na / K) to enter the catalyst kettle, then close the top valve and bottom valve; adjust the air inlet valve, start the stirring blade and heating component, and allow the catalyst support to be in-situ loaded in nitrogen. The pressure of the catalyst kettle is 0.1 MPa(A); the temperature of the catalyst kettle is 250°C; and the time is 6 hours.

[0146] (3) Regulating the pressure of the catalyst kettle to be higher than the pressure of the catalyst delivery pipe, opening the bottom valve of the delivery liquid tank, the delivery liquid feed valve, the discharge valve, the catalyst inlet valve, and the delivery liquid discharge valve, keeping the return valve and the return valve in a closed state, so that the catalyst is loaded in the tubes under the delivery of the delivery liquid (propane), and the delivery liquid is filtered, pressurized, and then circulated back to the delivery liquid feed pipe;

[0147] The loading conditions include: the pressure of the catalyst kettle is 1.7 MPa(A); the temperature of the catalyst kettle is 30° C.; the pressure of the transport liquid is 1.5 MPa(A); the temperature of the transport liquid is 30° C.; the volume ratio of the transport liquid to the catalyst is 10:1, and the flow rate of the solid-liquid mixture of the transport liquid and the catalyst is 2.5 m / s;

[0148] (4) During the loading process, the filling height of the catalyst in the tube array is measured by a level meter; when catalyst accumulates on the upper tube plate, the discharge valve is closed and the conveying liquid continues to be conveyed. If there is no catalyst accumulation on the upper tube plate, the discharge valve is opened and the loading is continued. If there is still catalyst accumulation on the upper tube plate, the conveying liquid discharge valve is closed;

[0149] Regulate the pressure of the transfer liquid tank to 1.9 MPa(A), open the return valve, the material return valve and the catalyst return transfer liquid valve, separate the catalyst accumulated on the upper tube plate into solid and liquid, and recycle the obtained solid phase back to the catalyst kettle. The obtained liquid phase is filtered and pressurized in turn, and then returned and mixed with the transfer liquid;

[0150] (5) After the catalyst accumulated on the upper tube sheet is returned clean, close all valves and the catalyst loading is completed;

[0151] In order to test the filling effect of the above system, a filling test was carried out on the catalyst carrier. The filling pressure drop required was 15kPa. After the filling was completed, the single tube pressure drop was tested and the average pressure drop of the tubes was 15kPa. The deviation of the tube pressure drop was ±4%. The amount of fine powder collected by the filtration equipment was 0.5wt% of the filling amount.

[0152] A method for synthesizing 4-methyl-1-pentene by dimerization of propylene is carried out in the above-mentioned catalyst-loaded system, wherein propylene is contacted with the catalyst loaded in the tubes and reacted (temperature is 150°C, pressure is 10 MPa(A), space velocity is 0.5 h -1 ), to give 4-methyl-1-pentene.

[0153] After the reaction stabilized, the composition of the product at the reaction material outlet was analyzed, and the propylene conversion rate was 87%.

[0154] Example 2

[0155] According to the filling system of Example 1, the difference is that Figure 2 As shown,

[0156] The system further includes: a conveying liquid feed branch pipe 5-9, and a conveying liquid feed branch pipe valve 5-10 is provided on the conveying liquid feed branch pipe 5-9;

[0157] Among them, according to the material flow direction, the connection point of the delivery liquid feed branch pipe 5-9 and the delivery liquid feed pipe 5-7 is located between the delivery liquid tank bottom valve 5-8 and the delivery liquid feed valve 5-11, and the connection point of the delivery liquid feed branch pipe 5-9 and the catalyst return pipe 11 is located between the return valve 11-2 and the return port 1-5;

[0158] The filling method of Example 1 is the same as that of Example 1, except that

[0159] After step (2) and before step (3), the method further includes:

[0160] Regulate the pressure of the transfer liquid tank to be greater than the pressure of the catalyst kettle, open the bottom valve of the transfer liquid tank and the valve of the transfer liquid feed branch pipe, start the stirring paddle to make the catalyst slurry in a mixed state, and then close the bottom valve of the transfer liquid tank and the valve of the transfer liquid feed branch pipe;

[0161] In order to test the filling effect of the above system, a filling test was carried out on the catalyst carrier. The filling required a pressure drop of 15kPa. After the filling was completed, the single tube pressure drop was tested and the average pressure drop of the tubes was 15kPa. The deviation of the tube pressure drop was ±4%. The amount of fine powder collected by the filtration equipment was 0.4wt% of the filling amount.

[0162] The method for dimerization of propylene to 4-methyl-1-pentene according to Example 1 was carried out in the above catalyst-loaded system.

[0163] After the reaction stabilized, the composition of the product at the reaction material outlet was analyzed, and the propylene conversion rate was 88%.

[0164] Comparative Example 1

[0165] The filling system of Example 1 is different in that:

[0166] The system does not include a transfer liquid tank 5;

[0167] The pump 8-3 is replaced by a gas compressor, and the conveying medium is replaced by nitrogen.

[0168] The filling method of Example 1 is the same as that of Example 1, except that

[0169] The loading conditions were changed to the catalyst kettle pressure of 0.7 MPa(A) and temperature of 30°C; the conveying gas pressure of 0.5 MPa(A) and temperature of 30°C;

[0170] The volume ratio of the conveying gas to the catalyst in the gas-solid mixture is 100:1; the gas velocity of the gas-solid mixture of the conveying gas and the catalyst is 10 m / s.

[0171] In order to test the filling effect of the above system, a filling test was carried out on the catalyst carrier. The filling required a pressure drop of 15kPa. After the filling was completed, the single tube pressure drop was tested and the average pressure drop of the tubes was 15kPa. The deviation of the tube pressure drop was ±5%. The amount of fine powder collected by the filtration equipment was 0.8wt% of the filling amount.

[0172] Compared with the liquid phase loading in Example 1, the wear of the catalyst in the gas phase loading is more serious.

[0173] The method for dimerization of propylene to 4-methyl-1-pentene according to Example 1 was carried out in the above catalyst-loaded system.

[0174] After the reaction stabilized, the composition of the product at the reaction material outlet was analyzed, and the propylene conversion rate was 84%.

[0175] Comparative Example 2

[0176] According to the filling system of Example 1, the difference is that Figure 5 As shown,

[0177] The catalyst kettle 1 does not contain the heating component 1-6, the stirring paddle 1-7, the dosing port 1-8, and the reagent tank 1-9 with valves at both ends connected to the dosing port 1-8;

[0178] The filling method of Example 1 is the same as that of Example 1, except that

[0179] In step (1), the catalyst is directly added to the catalyst kettle 1 through the feed port 1-3;

[0180] There is no step (2).

[0181] The method for dimerization of propylene to 4-methyl-1-pentene according to Example 1 was carried out in the above catalyst-loaded system.

[0182] After the reaction stabilized, the composition of the product at the reaction material outlet was analyzed, and the propylene conversion rate was 53%.

[0183] Compared with Comparative Example 2, Example 1 shows that the active Na / K of the loaded catalyst undergoes partial oxidation modification during the transfer process, resulting in a decrease in activity.

[0184] Comparative Example 3

[0185] According to the filling system of Example 1, the difference is that Figure 6 As shown,

[0186] The catalyst inlet is perpendicular to the shell of the shell and tube reactor, and no guide plate is provided on the upper tube plate of the shell and tube reactor;

[0187] The catalyst return port is at the same centerline height as the catalyst inlet and is opposite to the catalyst inlet.

[0188] According to the filling method of Example 1, the method is carried out in the above-mentioned system.

[0189] To test the loading efficiency of the above system, a loading test was conducted on catalyst supports. The required pressure drop was 15 kPa. After loading, the individual tube pressure drops were measured, resulting in an average pressure drop of 12 kPa across the tubes. The deviation in the tube pressure drop was ±15%, and the filtration equipment collected 0.8 wt% of the loaded fine powder. Compared to Example 1, the absence of guide plates in Comparative Example 3 resulted in a greater deviation in the tube pressure drop, increased catalyst wear, and poor loading uniformity.

[0190] The method for dimerization of propylene to 4-methyl-1-pentene according to Example 1 was carried out in the above catalyst-loaded system.

[0191] After the reaction stabilized, the composition of the product at the reaction material outlet was analyzed, and the propylene conversion rate was 80%.

[0192] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A catalyst liquid phase filling system, characterized in that: The system comprises: a connected catalyst kettle (1) and a shell-and-tube reactor (7), as well as a gas pipe (2), a catalyst delivery pipe (4), a delivery liquid feed pipe (5-7), and a delivery liquid circulation pipe (8); the shell-and-tube reactor (7) comprises a shell (7-1), the shell (7-1) is provided with a catalyst inlet (7-8) and a delivery liquid outlet (7-9), an upper tube plate (7-3) and a lower tube plate (7-5) are provided in the shell (7-1), and a plurality of tube bundles (7-2) are provided between the upper tube plate (7-3) and the lower tube plate (7-5); a guide plate (7-4) connecting the catalyst inlet (7-8) and the tube bundles (7-2) is provided on the upper tube plate (7-3); The gas pipe (2) is connected to the gas port (1-2) of the catalyst kettle (1), so that the catalyst carrier is in-situ loaded under a non-oxidizing atmosphere to obtain a catalyst; the catalyst delivery pipe (4) is connected to the discharge port (1-4) and the catalyst inlet (7-8) of the catalyst kettle (1), as well as the delivery liquid feed pipe (5-7), for loading the catalyst into the tube array (7-2) under the delivery of the delivery liquid; the delivery liquid circulation pipe (8) is connected to the delivery liquid outlet (7-9) and the delivery liquid feed pipe (5-7), for recycling the delivery liquid; The guide plate (7-4) is selected from a spiral guide plate, and the annular channel formed by the guide plate (7-4) connects the catalyst inlet (7-8) and the tube array (7-2).

2. The system according to claim 1, wherein: The ratio of the width of the annular channel to the inner diameter of the shell (7-1) is 0.01-1:1, and the ratio of the width of the annular channel to the outer diameter of the tube (7-2) is greater than 1:1; and / or, the ratio of the height of the guide plate (7-4) to the equivalent diameter of the catalyst is 5-100:1, and the height of the guide plate (7-4) is lower than half of the vertical distance between the upper tube plate (7-3) and the top of the shell (7-1); and / or, the catalyst is selected from a regular shape or an irregular shape; And / or, the equivalent diameter of the catalyst is 0.1-20 mm; And / or, the ratio of the inner diameter of the tubes (7-2) to the equivalent diameter of the catalyst is 3-50:

1.

3. The system according to claim 2, wherein: The ratio of the width of the annular channel to the inner diameter of the shell (7-1) is 0.01-0.5:1, and the ratio of the width of the annular channel to the outer diameter of the tube (7-2) is 1.25-20:1; and / or, the ratio of the height of the guide plate (7-4) to the equivalent diameter of the catalyst is 10-50:1, and the height of the guide plate (7-4) is lower than half of the vertical distance between the upper tube plate (7-3) and the top of the shell (7-1); And / or, the catalyst is selected from at least one of spherical, cylindrical and bar shapes; And / or, the equivalent diameter of the catalyst is 0.3-5 mm; And / or, the ratio of the inner diameter of the tubes (7-2) to the equivalent diameter of the catalyst is 5-30:

1.

4. The system according to claim 1, wherein: The system further comprises a delivery liquid tank (5) connected to the inlet end of the delivery liquid feed pipe (5-7); The top and bottom of the liquid delivery tank (5) are respectively provided with a gas phase port (5-1) and a liquid phase port (5-2); The gas phase port (5-1) is connected to a gas pipe (5-3) of a liquid delivery tank, and the gas pipe (5-3) of the liquid delivery tank is provided with a gas phase valve (5-4); A liquid delivery tank exhaust pipe (5-5) is provided on the pipeline connecting the gas phase port (5-1) and the gas phase valve (5-4), and a liquid delivery tank exhaust valve (5-6) is provided on the liquid delivery tank exhaust pipe (5-5).

5. The system according to claim 1, wherein: The gas port (1-2) is arranged at the top of the catalyst kettle (1), and the feed port (1-4) is arranged at the bottom of the catalyst kettle (1); And / or, the gas pipe (2) is provided with an air inlet valve (2-1); And / or, the top of the catalyst kettle (1) is further provided with a feed port (1-3) and a dosing port (1-8); And / or, a stirring paddle (1-7) is further provided inside the catalyst kettle (1), and a heating component (1-6) is provided outside the catalyst kettle (1).

6. The system according to claim 5, wherein: An exhaust pipe (3) is provided on the pipeline connecting the gas port (1-2) and the air inlet valve (2-1), and an exhaust valve (3-1) is provided on the exhaust pipe (3); And / or, the dosing port (1-8) is connected to a reagent tank (1-9) provided with a top valve (1-10) and a bottom valve (1-11).

7. The system according to claim 1, wherein: According to the material flow direction, the conveying liquid feed pipe (5-7) is provided with a conveying liquid tank bottom valve (5-8) and a conveying liquid feed valve (5-11) in sequence; And / or, according to the material flow direction, the catalyst delivery pipe (4) is sequentially provided with a discharge valve (4-1) and an inlet valve (4-2); and / or, the catalyst inlet (7-8) is tangentially arranged on the shell (7-1) and is not lower than the upper tube plate (7-3); and / or, the vertical distance between the catalyst inlet (7-8) and the upper tube plate (7-3) is 0-50 mm; and / or, the catalyst inlet (7-8), the upper tube plate (7-3) and the guide plate (7-4) are all at the same height; And / or, the conveying liquid outlet (7-9) is radially arranged on the shell (7-1) and is not higher than the lower tube plate (7-5); And / or, according to the material flow direction, the conveying liquid circulation pipe (8) is provided with a conveying liquid discharge valve (8-1), a filtering device (8-2) and a pump (8-3) in sequence.

8. The system according to claim 7, wherein: According to the material flow direction, the conveying liquid feed valve (5-11) is arranged after the discharge valve (4-1).

9. The system according to claim 7, wherein: The top of the shell (7-1) is provided with at least one material level meter port (7-14) and a catalyst return port (7-15); The material level meter port (7-14) is provided with a material level meter (7-18) for measuring the filling height of the catalyst in the tube array; Wherein, the number of the material level meter ports (7-14) is 1-20; And / or, the pipeline between the catalyst inlet (7-8) and the inlet valve (4-2) is connected to the return port (1-5) of the catalyst kettle (1) through a catalyst return pipe (11).

10. The system according to claim 9, wherein: The number of the material level meter ports (7-14) is 1-5; And / or, the catalyst return port (7-15) is provided with a catalyst return liquid delivery pipe (15) connected to the downstream of the catalyst delivery pipe (4), and according to the material flow direction, the connection point between the catalyst delivery pipe (4) and the catalyst return liquid delivery pipe (15) is located before the inlet valve (4-2).

11. The system according to claim 10, wherein: The catalyst return liquid delivery pipe (15) is provided with a catalyst return liquid delivery valve (15-1); and / or, the catalyst return liquid delivery pipe (15) passes through the shell (7-1) and extends to above the upper tube plate (7-3); And / or, the ratio of the vertical distance from the catalyst return liquid delivery pipe (15) to the upper tube plate (7-3) to the height of the guide plate (7-4) is 0.2-5:

1.

12. The system according to claim 11, wherein The ratio of the vertical distance between the catalyst return liquid delivery pipe (15) and the upper tube plate (7-3) to the height of the guide plate (7-4) is 1-1.5:

1.

13. The system according to claim 9, wherein: According to the material flow direction, the catalyst return pipe (11) is provided with a return valve (11-1) and a return material valve (11-2) in sequence; And / or, a conveying liquid feed branch pipe (5-9) is provided downstream of the conveying liquid feed pipe (5-7), and the conveying liquid feed branch pipe (5-9) is connected to the return port (1-5).

14. The system according to claim 13, wherein: The delivery liquid feed branch pipe (5-9) is provided with a delivery liquid feed branch pipe valve (5-10); and / or, according to the material flow direction, the connection point between the delivery liquid feed branch pipe (5-9) and the delivery liquid feed pipe (5-7) is located between the delivery liquid tank bottom valve (5-8) and the delivery liquid feed valve (5-11), and the connection point between the delivery liquid feed branch pipe (5-9) and the catalyst return pipe (11) is located between the return valve (11-2) and the return port (1-5); And / or, a solid-liquid separator (12) is further provided on the catalyst return pipe (11), and the solid-liquid separator (12) is provided between the return valve (11-1) and the return valve (11-2).

15. The system according to claim 14, wherein: The liquid phase outlet of the solid-liquid separator (12) and the conveying liquid feed pipe (5-7) are connected via a liquid phase return pipe (13), and a liquid phase return valve (13-1) is provided on the liquid phase return pipe (13); Wherein, the liquid phase return pipe (13) is connected to the delivery liquid circulation pipe (8); Wherein, according to the material flow direction, the liquid phase return valve (13-1) is arranged before the filtering device (8-2).

16. The system according to any one of claims 1 to 15, wherein: The shell (7-1) is also provided with a heat exchange medium inlet (7-17) and a heat exchange medium outlet (7-16), and the heat exchange medium inlet (7-17) and the heat exchange medium outlet (7-16) are arranged between the upper tube plate (7-3) and the lower tube plate (7-5); And / or, the shell (7-1) is further provided with a reaction material inlet (7-10) and a reaction material outlet (7-11).

17. A catalyst liquid phase filling method, characterized in that: The method is performed in the system according to any one of claims 1 to 16, wherein the method comprises: In a non-oxidizing atmosphere, the catalyst carrier is in-situ loaded in a catalyst kettle to obtain a catalyst; Under the transportation of the transport liquid, the catalyst enters the shell-and-tube reactor through the catalyst transport pipe and is filled in the shell-and-tube reactor through the guide plate. The transport liquid is circulated back to the transport liquid feed pipe through the catalyst circulation pipe.

18. The method according to claim 17, wherein The method comprises the following steps: S1. Keep the system in a non-oxidizing atmosphere, close the air inlet valve, exhaust valve, top valve, bottom valve, feed valve and return valve, and add the catalyst carrier through the feed port; repeatedly open and close the air inlet valve and exhaust valve alternately to replace the atmosphere, so that the catalyst kettle is in a non-oxidizing atmosphere; S2. Open the top valve and bottom valve to allow the active components to enter the catalyst kettle, then close the top valve and bottom valve; adjust the air inlet valve, start the stirring blade and heating component, so that the catalyst carrier is in-situ loaded in a non-oxidizing atmosphere; S3. When the system is provided with a liquid feed branch, the pressure of the liquid feed tank is adjusted to be greater than the pressure of the catalyst kettle, the bottom valve of the liquid feed tank and the valve of the liquid feed branch are opened, the stirring paddle is started, so that the catalyst slurry is in a mixed state, and then the bottom valve of the liquid feed tank and the valve of the liquid feed branch are closed; otherwise, S3 is ignored; S4. Regulating the pressure of the catalyst kettle to be higher than the pressure of the catalyst delivery pipe, opening the bottom valve of the delivery liquid tank, the delivery liquid feed valve, the discharge valve, the inlet valve, and the delivery liquid discharge valve, keeping the return valve and the return valve in a closed state, so that the catalyst is loaded into the tube array under the delivery of the delivery liquid, and the delivery liquid is circulated back to the delivery liquid feed pipe through the delivery liquid circulation pipe, wherein the delivery liquid is sequentially filtered and pressurized and then circulated back to the delivery liquid feed pipe; S5. During the loading process, the filling height of the catalyst in the tube array is measured by the material level meter; when catalyst accumulates on the upper tube plate, the discharge valve is closed and the conveying liquid continues to be conveyed. If there is no catalyst accumulation on the upper tube plate, the discharge valve is opened and the filling is continued. If catalyst still accumulates on the upper tube plate, the conveying liquid discharge valve, discharge valve and inlet valve are closed; The pressure of the transfer liquid tank is regulated to be higher than the pressure of the catalyst kettle, and the return valve, the material return valve and the catalyst return transfer liquid valve are opened to circulate the catalyst accumulated on the upper tube plate back to the catalyst kettle, wherein the catalyst accumulated on the upper tube plate is subjected to solid-liquid separation, the obtained solid phase is circulated back to the catalyst kettle, and the obtained liquid phase is filtered and pressurized in sequence, and then returned and mixed with the transfer liquid; S6. After the catalyst accumulated on the upper tube sheet has been returned clean, close all valves and the catalyst loading is completed.

19. The method according to claim 17, wherein The non-oxidizing gas in the non-oxidizing atmosphere is selected from nitrogen; Wherein, the nitrogen satisfies: oxygen content ≤ 10ppm; water content ≤ 10ppm; And / or, the transport liquid is selected from at least one component in the reaction material.

20. The method according to claim 19, wherein the nitrogen satisfies: an oxygen content ≤ 3 ppm; a water content ≤ 3 ppm.

21. The method according to any one of claims 17 to 20, wherein: The in-situ loading conditions include: the pressure of the catalyst kettle is 0-10 MPa(A); the temperature of the catalyst kettle is 0-500°C; and the time is 0.1-96h; And / or, the loading conditions include: the pressure of the catalyst kettle is 0-10 MPa(A); the temperature of the catalyst kettle is 0-300°C; the pressure of the transport liquid is 0-10 MPa(A); the temperature of the transport liquid is 0-300°C; And / or, the volume ratio of the transport liquid to the catalyst is 2-500:1, and the flow rate of the solid-liquid mixture of the transport liquid and the catalyst is 0.5-15 m / s.

22. The method according to claim 21, wherein The in-situ loading conditions include: the pressure of the catalyst kettle is 0.1-5 MPa (A); the temperature of the catalyst kettle is 20-400 ° C; the time is 0.5-24h; And / or, the loading conditions include: the pressure of the catalyst kettle is 0.1-5 MPa(A); the temperature of the catalyst kettle is 20-200°C; the pressure of the transport liquid is 0.1-5 MPa(A); the temperature of the transport liquid is 20-100°C; And / or, the volume ratio of the transport liquid to the catalyst is 5-100:1, and the flow rate of the solid-liquid mixture of the transport liquid and the catalyst is 1-6 m / s.

23. Use of the system according to any one of claims 1 to 16 in a catalytic reaction using a reduced metal catalyst.

24. A method for synthesizing 4-methyl-1-pentene by dimerization of propylene, characterized in that: The method is carried out in the system according to any one of claims 1 to 16, and comprises: introducing propylene through a reaction material inlet, contacting with the catalyst loaded in the tubes and reacting, and discharging the obtained 4-methyl-1-pentene through a reaction material outlet.

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