Catalyst oxygen-free filling system and method and application thereof

Abstract

The present application relates to the technical field of catalyst loading, in particular to a catalyst oxygen-free loading system, a catalyst oxygen-free loading method, application of the catalyst oxygen-free loading system and a method for preparing 4-methyl-1-pentene by propylene dimerization, wherein the catalyst oxygen-free loading system comprises a gas pipe, a catalyst conveying pipe, a conveying gas pipe and a catalyst return pipe, so that the catalyst kettle and the column tube reactor are in a non-oxidizing atmosphere, the loading and the filling process of the catalyst are realized, the risk of the catalyst contacting with air during the transfer process after loading is avoided, the safety and uniformity of the filling process are improved, and the stability and wear resistance of the catalyst are improved. Meanwhile, the process for preparing 4-methyl-1-pentene by propylene dimerization is carried out in the above system, so that the propylene conversion rate can be effectively improved.

Description

Technical Field

[0001] The present invention relates to the technical field of catalyst loading, and in particular to a catalyst oxygen-free loading system, a catalyst oxygen-free loading method, an application of the catalyst oxygen-free loading system, and a method for preparing 4-methyl-1-pentene by propylene dimerization. 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 shell-and-tube reactor is typically done manually or by a loading machine, using bags or hoppers to load the reactor. Pressure drop testing is then used to manually check the uniformity of the loading in each reaction tube. Any tubes with significant deviations or unevenness require catalyst removal and reloading until uniformity or pressure drop deviation across all reaction tubes meets certain requirements. This loading method, which exposes the catalyst to air, is not suitable for reducing metals or catalysts that require avoidance of air contact due to potential combustion, explosion, or property changes caused by contact with air. Existing techniques typically employ methods such as shortening the catalyst's contact time with air and employing inert gas protection for catalyst loading.

[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] CN202111486627.9 discloses a device and operating method for loading and unloading catalysts in a fixed bed reactor, which includes a fixed bed reactor, a catalyst feeding tank, a gas pipeline and a feed pipe. The device uses an inert gas conveying method to realize the catalyst loading and unloading of the fixed bed reactor, but does not mention the catalyst loading of the shell-and-tube reactor.

[0007] Supported catalysts are generally air-insensitive. However, when loaded with reducing metals or active components that can ignite or explode upon contact with air, the resulting catalysts become highly air-sensitive. Achieving a safe, uniform loading process that maintains catalytic properties is challenging for these catalysts. Furthermore, the risk of air contact persists during transfer of these catalysts to the catalyst loading equipment. Summary of the Invention

[0008] The purpose of the present invention is to overcome the problems that the existing catalyst transfer and loading process inevitably comes into contact with air, thereby affecting the safety of the loading process and even leading to low catalyst stability. A catalyst oxygen-free loading system, method and application thereof, and a method for preparing 4-methyl-1-pentene by propylene dimerization are provided. The system not only realizes the loading and loading of the catalyst in a non-oxidizing atmosphere, but also improves the stability and safety of the catalyst.

[0009] To achieve the above objectives, the present invention provides, in a first aspect, a catalyst anaerobic 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 gas pipe, and a catalyst return pipe; the shell-and-tube reactor comprises a shell, the shell being provided with a catalyst inlet and a delivery gas outlet, an upper tube sheet and a lower tube sheet being provided within the shell, 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;

[0010] The gas pipe is connected to the gas port of the catalyst kettle, and is used to load the catalyst carrier in a non-oxidizing atmosphere to obtain a catalyst; the catalyst delivery pipe is connected to the discharge port of the catalyst kettle, the delivery gas pipe and the catalyst inlet, and is used to deliver the catalyst by the delivery gas and load it into the tube array, and the delivery gas is discharged through the delivery gas outlet;

[0011] When the tube array is filled with catalyst, the surplus catalyst accumulated in the catalyst delivery tube and the upper tube plate is circulated back to the catalyst kettle through the catalyst return tube under the transportation of the delivery gas.

[0012] 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.

[0013] Preferably, the ratio of the width of the annular channel to the inner diameter of the shell is 0.01-1:1, preferably 0.01-0.5:1, and the ratio of the width of the annular channel to the outer diameter of the tube is greater than 1:1, preferably 1.25-20:1.

[0014] Preferably, the catalyst return port is provided with the catalyst return pipe, and the catalyst return pipe is connected to the return port of the catalyst kettle.

[0015] Preferably, the catalyst return pipe passes through the shell and extends to above the upper tube plate.

[0016] Preferably, the ratio of the vertical distance from the catalyst return tube to the upper tube plate to the height of the guide plate is 0.2-5:1, preferably 1-1.5:1.

[0017] Preferably, the catalyst return port is provided with a catalyst return blowing air pipe connected to the downstream of the catalyst delivery pipe, and the pipeline between the catalyst inlet and the inlet valve is connected to the return port of the catalyst kettle through the catalyst return pipe.

[0018] Preferably, the catalyst return blowing air pipe passes through the shell and extends to above the upper tube plate.

[0019] Preferably, the ratio of the vertical distance from the catalyst return blowing air pipe to the upper tube plate to the height of the guide plate is 0.2-5:1, preferably 1-1.5:1.

[0020] A second aspect of the present invention provides a method for loading a catalyst without oxygen, which is performed in the system provided in the first aspect, wherein the method comprises:

[0021] In a non-oxidizing atmosphere, the catalyst carrier is loaded in a catalyst kettle to obtain a catalyst;

[0022] The catalyst is transported by a transport gas, entering the shell-and-tube reactor through a catalyst transport pipe, and is loaded into the shell-and-tube reactor through a guide plate, and the transport gas is discharged through a transport gas outlet;

[0023] When the tubes are filled with the catalyst, the surplus catalyst accumulated in the catalyst delivery tube and the upper tube plate is circulated back to the catalyst kettle under the transportation of the delivery gas.

[0024] Preferably, the method comprises the following steps:

[0025] S1. Keep the system in a non-oxidizing atmosphere, close the air inlet valve, exhaust valve, return valve, top valve, bottom valve and discharge valve, open the upper head of the catalyst kettle, add the catalyst carrier; repeatedly open or close the air inlet valve and exhaust valve alternately to keep the catalyst kettle in a non-oxidizing atmosphere;

[0026] S2, opening the top valve and the bottom valve, adding the active component to the catalyst kettle, and then closing the top valve and the bottom valve; adjusting the air inlet valve so that the catalyst support and the active component are loaded in a non-oxidizing atmosphere to obtain the catalyst;

[0027] S3, opening the unloading valve, delivery gas valve, inlet valve, and delivery gas discharge valve, and closing the return valve and return valve, adjusting the air inlet valve so that the pressure of the catalyst kettle is higher than the pressure of the catalyst delivery pipe, so that the catalyst is loaded into the tube array under the delivery of the delivery gas, and the delivery gas is discharged;

[0028] S4. During the loading process, the filling height of the catalyst in the tube array is measured by a material level meter; when catalyst accumulates on the upper tube plate, the discharge valve is closed and the conveying gas continues to be purged; if there is no catalyst accumulation on the upper tube plate, the discharge valve is opened to continue loading; if there is still catalyst accumulation on the upper tube plate, the conveying gas discharge valve is closed;

[0029] When the catalyst return port is provided with a catalyst return pipe, the return valve and the return valve are opened, the delivery gas valve is adjusted so that the delivery gas pressure is higher than the pressure of the catalyst kettle, and the surplus catalyst is recycled back to the catalyst kettle; or

[0030] When the catalyst return port is provided with a catalyst return blowing air pipe, and the pipeline between the catalyst inlet and the inlet valve is connected to the return port of the catalyst kettle through the catalyst return pipe, the inlet valve is closed, the delivery gas valve is adjusted so that the pressure of the delivery gas is higher than the pressure of the catalyst kettle, the catalyst return blowing air valve, the return valve and the return valve are opened, and the surplus catalyst is recycled back to the catalyst kettle;

[0031] S5. After the excess catalyst on the upper tube sheet is purged, close all valves and the catalyst loading is completed.

[0032] The third aspect of the present invention provides a use of the system provided in the first aspect in loading a reduced metal catalyst.

[0033] A fourth aspect of the present invention provides a method for preparing 4-methyl-1-pentene by dimerization of propylene, the method being carried out in the system provided in the first aspect, the method comprising:

[0034] Propylene is contacted with a catalyst loaded in tubular form in the system and reacted to obtain 4-methyl-1-pentene; wherein the catalyst comprises: a carrier and an active component loaded on the carrier, and the active component is selected from K and / or Na.

[0035] Compared with the prior art, the present invention has the following advantages:

[0036] (1) The catalyst non-oxygen loading system provided by the application realizes the loading and filling process of the catalyst in a non-oxidizing atmosphere by setting a gas pipe, a catalyst conveying pipe, a conveying gas pipe and a catalyst return pipe, avoids the risk of the catalyst contacting air during the transfer process after loading, improves the safety and uniformity of the filling process, and improves the stability and wear resistance of the catalyst;

[0037] (2) The system provided by the application realizes efficient, rapid and uniform loading of the catalyst in a non-oxidizing environment, in particular by setting a flow guide plate on the upper tube plate of the column tube reactor to form a catalyst loading channel;

[0038] (3) The system provided by the application realizes coherent operation of loading and filling through the regulation and control of valves, thereby realizing coherent non-oxygen loading of the catalyst;

[0039] (4) The process of preparing 4-methyl-1-pentene by dimerizing propylene is carried out in the system provided by the application, which can effectively improve the propylene conversion rate, and under the premise of the same catalyst loading amount, improve the operation time of the process. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1 is a structure schematic diagram of a catalyst non-oxygen loading system provided by the application;

[0041] Figure 2 is a structure schematic diagram of another catalyst non-oxygen loading system provided by the application;

[0042] Figure 3 is a top view of a partial structure of a column tube reactor provided by the application;

[0043] Figure 4 is a side view of a partial structure of a column tube reactor provided by the application;

[0044] Figure 5 is a structure schematic diagram of a catalyst non-oxygen loading system provided by Comparative Example 2;

[0045] Figure 6 is a top view of a partial structure of a column tube reactor provided by Comparative Example 3.

[0046] BRIEF DESCRIPTION OF DRAWINGS

[0047] 1, catalyst kettle 1-1, catalyst kettle upper head 1-2, gas port 1-3, discharge port

[0048] 1-4, return port 1-5, heating equipment 1-6, stirring paddle 1-7, additive port

[0049] 1-8, reagent tank 1-9, top valve 1-10, bottom valve 2, gas line

[0050] 2-1, inlet valve 3, exhaust pipe 3-1, exhaust valve 4, catalyst delivery pipe

[0051] 4-1, discharge valve 4-2, inlet valve 5, delivery gas pipe 5-1, delivery gas valve

[0052] 7, shell-and-tube reactor 7-1, shell 7-2, tube 7-3, upper tube sheet

[0053] 7-4, baffle 7-5, lower tube sheet 7-6, upper head 7-7, lower head

[0054] 7-8, catalyst inlet 7-9, delivery gas outlet 7-10, reactant material inlet

[0055] 7-11, reactant material outlet 7-12, upper tube opening 7-13, lower tube opening

[0056] 7-14, level gauge opening 7-15, catalyst return opening 7-16, heat exchange medium outlet

[0057] 7-17, heat exchange medium inlet 7-18, level gauge 8, delivery gas circulation pipe

[0058] 8-1, delivery gas discharge valve 8-2, dust removal equipment 8-3, gas booster

[0059] 11, catalyst return pipe 11-1, return valve 11-2, material return valve 12, gas-solid separator

[0060] 13, gas phase return pipe 13-1, gas phase return valve 14, catalyst return blow gas pipe

[0061] 14-1, catalyst return blow gas valve DETAILED DESCRIPTION

[0062] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as exactly that endpoint. Any values that fall within common

[0063] In the present invention, unless otherwise specified, the "top" of a container refers to the position of 0-10% from the top to the bottom of the container; the "upper part" of a container refers to the position of 10-40% from the top to the bottom of the container; the "middle" of a container refers to the position of 40-60% from the top to the bottom of the container; the "lower part" of a container refers to the position of 60-90% from the top to the bottom of the container; and the "bottom" of a container refers to the position of 90-100% from the top to the bottom of the container.

[0064] The first aspect of the present invention provides a catalyst oxygen-free filling system, such as Figure 1-2 As shown, the system includes 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 gas pipe 5, and a catalyst return pipe 11; the shell-and-tube reactor 7 includes a shell 7-1, the shell 7-1 is provided with a catalyst inlet 7-8 and a delivery gas 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; the upper tube sheet 7-3 is provided with a guide plate 7-4 connecting the catalyst inlet 7-8 and the tube bundles 7-2;

[0065] The gas pipe 2 is connected to the gas port 1-2 of the catalyst kettle 1, and is used to load the catalyst carrier in a non-oxidizing atmosphere to obtain a catalyst; the catalyst delivery pipe 4 is connected to the feed port 1-3, the delivery gas pipe 5 and the catalyst inlet 7-8 of the catalyst kettle 1, and is used to deliver the catalyst by the delivery gas and load it into the array tube 7-2, and the delivery gas is discharged through the delivery gas outlet;

[0066] When the tube array 7 - 2 is filled with catalyst, the surplus catalyst accumulated in the catalyst delivery tube 4 and the upper tube plate 7 - 3 is circulated back to the catalyst kettle 1 through the catalyst return pipe 11 under the transportation of the delivery gas.

[0067] In the present invention, unless otherwise specified, the catalyst delivery pipe 4 connects the discharge port 1-3 of the catalyst kettle 1 and the catalyst inlet 7-8 of the shell-and-tube reactor 7, and the catalyst inlet 7-8 and the shell-and-tube reactor 7-2 are connected through the guide plate 7-4, forming a catalyst loading channel.

[0068] In the present invention, the guide plate has a wide range of options and can be any conventional guide plate in the art, including but not limited to spiral guide plates, curved guide plates, linear guide plates, and broken-line guide plates, with spiral guide plates being preferred. In the present invention, the use of spiral guide plates can reduce catalyst wear while forming a complete catalyst loading channel, thereby achieving higher loading efficiency and better uniformity.

[0069] In some embodiments of the present invention, preferably, 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.

[0070] In some embodiments of the present invention, preferably, 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 numerical 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, 8:1, 10:1, 15:1, 20:1, and any value in the range consisting of any two numerical values.

[0071] In some embodiments of the present invention, preferably, 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.

[0072] In some embodiments of the present invention, preferably, the catalyst is selected from a regular shape or an irregular shape, preferably at least one selected from a spherical shape, a cylindrical shape and a bar shape.

[0073] 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, 2 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.

[0074] 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, 30:1, 50:1, and any value in the range of any two values, preferably 5-20:1.

[0075] 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.

[0076] 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 wire plug with small holes, a plug with small holes, a wire mesh, a porcelain ball, etc.

[0077] 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 1-3 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 1-1 of the catalyst kettle.

[0078] 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 .

[0079] In some embodiments of the present invention, preferably, Figure 1-2 As 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.

[0080] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the top of the catalyst kettle 1 is also provided with a dosing port 1-7, and the dosing port 1-7 is connected to a reagent tank 1-8 provided with a top valve 1-9 and a bottom valve 1-10. In the present invention, by regulating the state of the top valve and the bottom valve, that is, the open state or the closed state, the active component entering through the dosing port is loaded with the catalyst carrier in the catalyst kettle to obtain a loaded catalyst.

[0081] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the catalyst kettle 1 is further provided with a stirring paddle 1-6 inside and a heating component 1-5 outside. In the present invention, the heating component 1-5 can be an electric heating component or a heat medium provided by a jacket or coil.

[0082] In some embodiments of the present invention, preferably, Figure 1-2As 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 1-3, and the inlet valve 4-2 is provided before the catalyst inlet 7-8.

[0083] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the gas delivery pipe 5 is provided with a gas delivery valve 5-1, positioned after the discharge valve 4-1, in the direction of material flow. In the present invention, by regulating the state of the gas delivery valve 5-1, i.e., the closed state or the open state, the catalyst is transferred through the catalyst delivery pipe to the shell-and-tube reactor under the transport of the delivery gas, and then loaded into the shell-and-tube reactor via the guide plate.

[0084] In the present invention, unless otherwise specified, the gas delivery pipe 5 may also be provided with a gas delivery branch pipe after the gas delivery valve 5 - 1 , so as to provide greater driving force for catalyst delivery.

[0085] 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.

[0086] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the conveying gas outlet 7-9 is tangentially arranged on the shell 7-1 and is not higher than the lower tube plate 7-5; further preferably, the conveying gas outlet 7-9 is arranged below the lower tube plate 7-5.

[0087] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the delivery gas outlets 7-9 and the delivery gas pipe 5 are connected via a delivery gas circulation pipe 8 for circulating the delivery gas back to the delivery gas pipe.

[0088] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the conveying gas circulation pipe 8 is sequentially provided with a conveying gas discharge valve 8-1, a dust removal device 8-2, and a gas booster 8-3 in the direction of material flow. In the present invention, by regulating the conveying gas discharge valve, i.e., the open state and the closed state, the conveying gas is placed in the filling process and the recycling process.

[0089] In some embodiments of the present invention, preferably, Figure 1-2 As shown, at least one material level meter port 7-14 and a catalyst return port 7-15 are provided on the top of the shell 7-1; further preferably, 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.

[0090] In the present invention, unless otherwise specified, the material level gauge ports 7-14 are evenly distributed on the upper head 7-6 of the shell-and-tube reactor 7, preferably evenly distributed on the upper head 7-6 of the shell-and-tube reactor 7 in a circumferential manner.

[0091] In some embodiments of the present invention, preferably, the number of the material level meter ports 7-14 is 1-20, preferably 1-5.

[0092] In some embodiments of the present invention, preferably, Figure 1 As shown, the catalyst return port 7-15 is provided with the catalyst return pipe 11, and the catalyst return pipe 11 is connected to the return port 1-4 of the catalyst kettle 1.

[0093] In some embodiments of the present invention, preferably, Figure 1 As shown, the catalyst return pipe 11 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 pipe 11 to the upper tube plate 7-3 and the height of the guide plate 7-4 are in a ratio of 0.2-5:1, for example, 0.2:1, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 2:1, 3:1, 5:1, and any value in the range of any two values, preferably 1-1.5:1.

[0094] In some embodiments of the present invention, preferably, Figure 2 As shown, the pipeline between the catalyst inlet 7 - 8 and the inlet valve 4 - 2 is connected to the return port 1 - 4 through the catalyst return pipe 11 .

[0095] In some embodiments of the present invention, preferably, Figure 2 As shown, when the catalyst return port 7-15 is provided with a catalyst return blowing air pipe 14 connected to the downstream of the catalyst delivery pipe 4, and the pipeline between the catalyst inlet 7-8 and the inlet valve 4-2 is connected to the return port 1-4 of the catalyst kettle 1 through the catalyst return pipe 11; further preferably, according to the material flow direction, the connection point between the catalyst delivery pipe 4 and the catalyst return blowing air pipe 14 is located before the inlet valve 4-2.

[0096] In some embodiments of the present invention, preferably, Figure 2 As shown, the catalyst return blowing air pipe 14 is provided with a catalyst return blowing air valve 14 - 1 .

[0097] In some embodiments of the present invention, preferably, Figure 2 As shown, the catalyst return blowing air pipe 14 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 blowing air pipe 14 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, 1.2:1, 1.5:1, 2:1, 3:1, 5:1, and any value in the range of any two values, preferably 1-1.5:1.

[0098] 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 .

[0099] In some embodiments of the present invention, preferably, Figure 1-2 As shown, a gas-solid separator 12 is further provided on the catalyst return pipe 11, and the gas-solid separator 12 is provided between the return valve 11-1 and the return valve 11-2.

[0100] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the gas phase outlet of the gas-solid separator 12 and the gas delivery pipe 5 are connected through a gas phase return pipe 13 , and a gas phase return valve 13 - 1 is provided on the gas phase return pipe 13 .

[0101] In the present invention, unless otherwise specified, the gas phase outlet of the gas-solid separator 12 and the conveying gas pipe 5 are connected through the gas phase return pipe 13, which means that the gas phase of the gas-solid separator is circulated back to the conveying gas pipe through the gas phase return pipe, and the gas phase is pressurized to the pressure of the conveying gas before the catalyst is conveyed.

[0102] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the gas phase return pipe 13 is connected to the conveying gas circulation pipe 8; further preferably, according to the material flow direction, the gas phase return valve 13-1 is arranged before the dust removal equipment 8-2.

[0103] In some embodiments of the present invention, preferably, Figure 1-2As shown, the shell 7-1 is further 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.

[0104] In the present invention, unless otherwise specified, the heat exchange medium inlet 7-17 can be located at the top or at the bottom; the heat exchange medium outlet 7-16 can be located at the top or at the bottom. Figure 1-2 As shown, the heat exchange medium inlet 7-17 is arranged at the bottom, and the heat exchange medium outlet 7-16 is arranged at the top.

[0105] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the top and bottom of the shell 7-1 are respectively provided with a reaction material inlet 7-10 and a reaction material outlet 7-11. That is, the reaction material inlet 7-10 can be provided at the top of the shell 7-1 or at the bottom of the shell 7-1; the reaction material outlet 7-11 can be provided at the top of the shell 7-1 or at the bottom of the shell 7-1. Preferably, as Figure 1-2 As shown, the reaction material inlet 7-10 is arranged at the top of the shell 7-1, and the reaction material outlet 7-11 is arranged at the bottom of the shell 7-1.

[0106] A second aspect of the present invention provides a method for anaerobic loading of a catalyst, which is performed in the system provided in the first aspect, wherein the method comprises:

[0107] In a non-oxidizing atmosphere, the catalyst carrier is loaded in a catalyst kettle to obtain a catalyst;

[0108] The catalyst is transported by a transport gas, entering the shell-and-tube reactor through a catalyst transport pipe, and is loaded into the shell-and-tube reactor through a guide plate, and the transport gas is discharged through a transport gas outlet;

[0109] When the tube array is filled with the catalyst, the surplus catalyst accumulated in the catalyst delivery tube and the upper tube plate is circulated back to the catalyst kettle under the transportation of the delivery gas.

[0110] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the method includes the following steps:

[0111] S1. Keep the system in a non-oxidizing atmosphere, close the air inlet valve 2-1, the exhaust valve 3-1, the return valve 11-2, the top valve 1-9, the bottom valve 1-10 and the discharge valve 4-1, open the upper head 1-1 of the catalyst kettle 1, add the catalyst carrier; repeatedly open or close the air inlet valve 2-1 and the exhaust valve 3-1 alternately, so that the catalyst kettle 1 is in a non-oxidizing atmosphere;

[0112] S2, opening the top valve 1-9 and the bottom valve 1-10, adding the active component to the catalyst kettle 1, and then closing the top valve 1-9 and the bottom valve 1-10; adjusting the air inlet valve 2-1 so that the catalyst support and the active component are loaded in a non-oxidizing atmosphere to obtain the catalyst;

[0113] S3. Open the unloading valve 4-1, the delivery gas valve 5-1, the inlet valve 4-2, and the delivery gas discharge valve 8-1, and close the return valve 11-1 and the return valve 11-2. Adjust the inlet valve 2-1 so that the pressure of the catalyst kettle 1 is higher than the pressure of the catalyst delivery pipe 4, so that the catalyst is loaded into the tube array 7-2 under the delivery of the delivery gas, and the delivery gas is discharged;

[0114] S4. 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 the catalyst accumulates on the upper tube plate 7-3, the unloading valve 4-1 is closed and the conveying gas continues to be purged. If there is no catalyst accumulation on the upper tube plate 7-3, the unloading valve 4-1 is opened to continue loading. If there is still catalyst accumulation on the upper tube plate 7-3, the conveying gas discharge valve 8-1 is closed.

[0115] When the catalyst return port 7-15 is provided with a catalyst return pipe 11, the return valve 11-1 and the return valve 11-2 are opened, and the delivery gas valve 5-1 is adjusted so that the delivery gas pressure is higher than the pressure of the catalyst kettle 1, and the surplus catalyst is recycled back to the catalyst kettle 1; or

[0116] When the catalyst return port 7-15 is provided with a catalyst return blowing air pipe 14, and the pipeline between the catalyst inlet 7-8 and the inlet valve 4-2 is connected to the return port 1-4 of the catalyst kettle 1 through the catalyst return pipe 11, the inlet valve 4-2 is closed, the delivery gas valve 5-1 is adjusted so that the pressure of the delivery gas is higher than the pressure of the catalyst kettle, the catalyst return blowing air valve 14-1, the return valve 11-1 and the return valve 11-2 are opened, and the surplus catalyst is recycled back to the catalyst kettle 1;

[0117] S5. After the excess catalyst on the upper tube plate 7-3 is purged, all valves are closed and the catalyst loading is completed.

[0118] In the present invention, repeatedly opening or closing the intake valve 2-1 and the exhaust valve 3-1 alternately means opening the intake valve 2-1 to inflate for a period of time, then closing the intake valve 2-1 and opening the exhaust valve 3-1 to exhaust; then closing the exhaust valve 3-1 and opening the intake valve 2-1 to inflate again; and repeating the above operation.

[0119] In some embodiments of the present invention, preferably, Figure 1-2As shown, the method further includes: step S3, after the conveying gas is discharged through the conveying gas outlet 7-9, it is successively dust-removed and pressurized, and then circulated back to the conveying gas pipe 5.

[0120] In some embodiments of the present invention, preferably, Figure 1-2 As shown, the method further includes: performing gas-solid separation on the surplus catalyst, recycling the obtained solid phase back to the catalyst kettle 1, and returning the obtained gas phase after dust removal and pressurization to be mixed with the conveying gas.

[0121] In some embodiments of the present invention, preferably, the non-oxidizing gas and the transport gas in the non-oxidizing atmosphere are independently selected from inert gas and / or nitrogen, preferably nitrogen, wherein the inert gas includes but is not limited to helium, argon, etc.

[0122] 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.

[0123] In some embodiments of the present invention, preferably, the loading conditions include: the pressure of the catalyst kettle is 0-10 MPa(A), preferably 0.1-5 MPa(A); the temperature of the catalyst kettle is 0-500°C, preferably 20-400°C; and the time is 0.1-96h, preferably 0.5-24h.

[0124] In some embodiments of the present invention, preferably, the loading conditions include: the pressure of the catalyst kettle is 0-10MPa(A), preferably 0.1-5MPa(A); the temperature of the catalyst kettle is 0-300℃, preferably 20-200℃; the pressure of the conveying gas is 0-10MPa(A), preferably 0.1-5MPa(A); the temperature of the conveying gas is 0-300℃, preferably 20-200℃.

[0125] In some embodiments of the present invention, preferably, the volume ratio of the conveying gas to the catalyst in the gas-solid conveying mixture is 2-1000:1, for example, 2:1, 5:1, 10:1, 30:1, 50:1, 80:1, 100:1, 500:1, 800:1, 1000:1, and any value in a range consisting of any two values, preferably 10-500:1; further preferably, the gas velocity of the gas-solid mixture is 5-25 m / s, for example, 5 m / s, 8 m / s, 10 m / s, 12 m / s, 15 m / s, 20 m / s, 25 m / s, and any value in a range consisting of any two values, preferably 5-15 m / s. Wherein, the gas-solid conveying mixture includes the conveying gas and the catalyst.

[0126] The third aspect of the present invention provides a use of the system provided in the first aspect in loading a reduced metal catalyst.

[0127] A fourth aspect of the present invention provides a method for preparing 4-methyl-1-pentene by dimerization of propylene, which is carried out in the system provided in the first aspect and comprises:

[0128] Propylene is contacted with a catalyst loaded in tubular form in the system and reacted to obtain 4-methyl-1-pentene; wherein the catalyst comprises: a carrier and an active component loaded on the carrier, and the active component is selected from K and / or Na.

[0129] The present invention will be described in detail below through examples.

[0130] In the examples and comparative examples, the nitrogen gas satisfies the following conditions: oxygen content ≤ 3 ppm, water content ≤ 3 ppm.

[0131] Example 1

[0132] Catalyst oxygen-free loading system such as Figure 1 、 3 -4, the system includes a catalyst kettle 1, a shell-and-tube reactor 7, a gas pipe 2, an exhaust pipe 3, a catalyst delivery pipe 4, a delivery gas pipe 5, a delivery gas circulation pipe 8, a catalyst return pipe 11 and a gas phase return pipe 13;

[0133] Among them, the upper head 1-1 of the catalyst kettle 1 is provided with a gas port 1-2, a return port 1-4, and a dosing port 1-7. 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 valve 3-1 is provided on the exhaust pipe 3; the bottom of the catalyst kettle 1 is provided with a discharge port 1-3, and the discharge port 1-3 is connected to the catalyst delivery pipe 4, and the catalyst delivery pipe 4 is sequentially provided with a discharge valve 4-1 and an inlet valve 4-2; the discharge valve 4-1 of the catalyst delivery pipe 4 is connected to the delivery gas pipe 5, and the delivery gas pipe 5 is provided with a delivery gas valve 5-1; the dosing port 1-7 of the catalyst kettle 1 is connected to the outlet end of the reagent tank 1-8 with valves at both ends, and the inlet end of the reagent tank is connected to the non-oxidizing gas; the catalyst kettle 1 is provided with a stirring paddle 1-6 and a heating device 1-5;

[0134] The shell-and-tube reactor 7 includes a shell 7-1, which is tangentially provided with a catalyst inlet 7-8 and a conveying gas 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.

[0135] Among them, the catalyst inlet 7-8, the upper tube plate 7-3 and the guide plate 7-4 are at the same height; the conveying gas outlet 7-9 and the conveying gas pipe 5 are connected through the conveying gas circulation pipe 8; according to the direction of material flow, the conveying gas circulation pipe 8 is sequentially provided with a conveying gas discharge valve 8-1, a dust removal device 8-2 and a gas booster 8-3;

[0136] The catalyst return pipe 11 connects the catalyst return port 7-15 and the return port 1-4, and the catalyst return pipe 11 passes through the shell 7-1 and extends to the top of the upper tube plate 7-3. According to the direction of material flow, the catalyst return pipe 11 is sequentially provided with a return valve 11-1, a gas-solid separator 12 and a return valve 11-2.

[0137] Among them, the gas phase return pipe 13 provided with a gas phase return valve 13-1 is connected to the gas phase outlet of the gas-solid separator 12 and the conveying gas circulation pipe 8, and the gas phase return valve 13-1 is arranged before the dust removal equipment 8-2;

[0138] Among them, the upper head 7-6 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 inlet gauge port 7-14 is provided with a material level gauge 7-18, and the lower head 7-7 is provided with a reaction material outlet 7-11; the heat exchange medium inlet 7-17 and heat exchange medium outlet 7-16 are respectively provided above the lower tube plate 7-5 and below the upper tube plate 7-3 on the side of the shell 7-1;

[0139] The width of the annular channel is 80 mm, the inner diameter of the shell is 500 mm, the outer diameter of the tubes is 25 mm, the inner diameter of the tubes is 20 mm, the vertical distance from the upper tube sheet to the top of the shell is 150 mm; the height of the guide plate is 20 mm; and the vertical distance from the catalyst return pipe to the upper tube sheet is 20 mm.

[0140] The catalyst is a supported Na / K spherical catalyst for preparing 4-methyl-1-pentene by propylene dimerization, and has an equivalent diameter of 2 mm.

[0141] A catalyst oxygen-free loading method is carried out in the above system and comprises the following steps:

[0142] (1) Before loading the catalyst, install a wire mesh at the bottom of the tube; seal the loading system well, and expel the air in the system by repeatedly inflating and exhausting to maintain a nitrogen atmosphere;

[0143] (2) Keep the valves on the pipeline connected to the catalyst kettle in a closed state (i.e., close the inlet valve, exhaust valve, return valve, top valve, bottom valve and discharge valve), open the upper head of the catalyst kettle, add the catalyst carrier into the catalyst kettle; repeatedly fill the gas pipe with nitrogen and exhaust the gas through the exhaust pipe to create a nitrogen atmosphere in the catalyst kettle;

[0144] (3) The active component (Na / K) is transferred to a reagent tank in a nitrogen atmosphere, the inlet end of the reagent tank is connected to nitrogen, and the outlet end is connected to the catalyst kettle addition port; the valves at both ends of the reagent tank are opened, and the active component is pressed into the catalyst kettle by nitrogen; the stirring paddle and electric heating are turned on, and the catalyst kettle air inlet valve is adjusted to ensure the temperature and pressure required for catalyst loading, and the catalyst loading is carried out; wherein, the loading conditions include: 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;

[0145] (4) Adjust the air inlet valve so that the pressure of the catalyst kettle is higher than the pressure of the catalyst delivery pipe, open the discharge valve, delivery air valve, inlet valve, and delivery air discharge valve, and keep the return valve and return valve in a closed state, so that the catalyst enters the catalyst delivery pipe from the bottom of the catalyst kettle, enters the annular channel on the upper tube plate through the catalyst inlet, and then enters the tube array under nitrogen delivery, and is intercepted in the tube array. The delivery gas is then used to circulate the catalyst after dust removal and pressurization in the delivery gas circulation pipe;

[0146] The loading conditions include: the pressure of the catalyst kettle is 0.7 MPa(A), the temperature of the catalyst kettle is 30°C; the pressure of the conveying gas is 0.5 MPa(A), the temperature of the conveying gas is 30°C; the volume ratio of the conveying gas to the catalyst in the gas-solid conveying mixture is 100:1, and the gas velocity of the gas-solid conveying mixture is 10 m / s;

[0147] (5) During the loading process, the catalyst loading height is measured by a level gauge; when catalyst is accumulated on the upper tube plate, the discharge valve is closed and the conveying gas is continued to be purged. 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, it means that the tubes are fully loaded with catalyst, and the conveying gas discharge valve is closed;

[0148] Increase the pressure of the conveying gas to be higher than the pressure of the catalyst kettle, open the return valve and the return valve, adjust the conveying gas valve, and blow the excess catalyst accumulated in the catalyst conveying pipe and on the upper tube plate to the gas-solid separator through the catalyst return pipe for gas-solid separation. The catalyst is returned to the catalyst kettle through the return port of the catalyst kettle, and the gas is recycled after dust removal and pressurization through the gas phase return pipe;

[0149] After the catalyst on the upper tube plate is blown clean, close all valves and the catalyst loading is completed.

[0150] After the catalyst was loaded, the above system was used to catalyze the dimerization of propylene to prepare 4-methyl-1-pentene at a reaction temperature of 150 °C, a reaction pressure of 10 MPa (A), and a space velocity of 0.5 h -1 After the reaction stabilized, the composition of the reaction material outlet was analyzed and the propylene conversion rate was 84%.

[0151] A filling test was carried out using catalyst carriers to test the filling effect of this filling system. After the filling was completed, the single tube pressure drop was tested and the average pressure drop of the tubes was 15kPa, the maximum pressure drop was 15.7kPa, the minimum pressure drop was 14.4kPa, and the deviation of the tube pressure drop was less than ±5%. The amount of fine powder collected by the dust removal equipment was 0.8% of the filling amount.

[0152] Example 2

[0153] According to the system provided in Example 1, the difference is that Figure 2 As shown, that is,

[0154] When the catalyst return port 7-15 is provided with a catalyst return blowing air pipe 14 connected to the downstream of the catalyst delivery pipe 4, according to the material flow direction, the connection point between the catalyst delivery pipe 4 and the catalyst return blowing air pipe 14 is located before the inlet valve 4-2, and the pipeline between the catalyst inlet 7-8 and the inlet valve 4-2 is connected to the return port 1-4 through the catalyst return pipe 11;

[0155] The vertical distance from the catalyst return blowing pipe to the upper tube plate is 20 mm.

[0156] According to the method provided in Example 1, the method is carried out in the above system, except that,

[0157] In step (5), the pressure of the conveying gas is increased to be higher than the pressure of the catalyst kettle, the catalyst return blowing valve, the return valve and the return valve are opened, the inlet valve is closed, the conveying gas valve is adjusted, and the excess catalyst accumulated on the catalyst conveying pipe and the upper tube plate is blown to the gas-solid separator through the catalyst return pipe for gas-solid separation. The catalyst is returned to the catalyst kettle through the return port of the catalyst kettle, and the gas is recycled after dust removal and pressurization through the gas phase return pipe.

[0158] After the catalyst was loaded, the above system was used to catalyze the dimerization of propylene to prepare 4-methyl-1-pentene at a reaction temperature of 150 °C, a reaction pressure of 10 MPa (A), and a space velocity of 0.5 h -1 After the reaction stabilized, the composition of the reaction material outlet was analyzed and the propylene conversion rate was 84%.

[0159] A filling test was carried out using catalyst carriers to test the filling effect of this filling system. After the filling was completed, the single tube pressure drop was tested and the average pressure drop of the tubes was 15kPa, the maximum pressure drop was 15.5kPa, and the minimum pressure drop was 14.3kPa. The deviation of the tube pressure drop was less than ±5%, and the amount of fine powder collected by the dust removal equipment was 0.8% of the filling amount.

[0160] Comparative Example 1

[0161] The catalyst oxygen-free loading system involved in this comparative example only includes a shell and tube reactor 7, a shell 7-1, a shell and tube 7-2, an upper tube plate 7-3, a lower tube plate 7-5, an upper head 7-6, a lower head 7-7, a reaction material inlet 7-10, a reaction material outlet 7-11, a heat exchange medium outlet 7-16, and a heat exchange medium inlet 7-17 with the same dimensions as those in Example 1.

[0162] In an air atmosphere, the catalyst pre-loaded with active metals is loaded into a shell-and-tube reactor using a bag filling method.

[0163] The pressure drop test method of Example 1 was used to test the pressure drop of a single tube after one loading. The pressure drop of 67% of the tubes was 15±5% kPa. The catalyst in the tubes whose pressure drop did not meet 15±5% kPa was unloaded and then loaded a second time. After the loading was completed, the pressure drop of a single tube was tested. The pressure drop of 80% of the tubes was 15±5% kPa. The previous step was repeated. After the fourth loading was completed, the pressure drop of all tubes was 15±5% kPa, and the loading was completed.

[0164] The above system was used to catalyze the dimerization of propylene to prepare 4-methyl-1-pentene at a reaction temperature of 150°C, a reaction pressure of 10 MPa, and a space velocity of 0.5 h -1 After the reaction stabilized, the composition of the material at the reactor outlet was analyzed and the propylene conversion rate was 12%.

[0165] Compared with Example 1, Comparative Example 1 shows that when the catalyst is loaded in an air atmosphere, the catalyst is severely deactivated.

[0166] Comparative Example 2

[0167] According to the system provided in Example 1, the difference is that Figure 5 As shown, that is,

[0168] The catalyst kettle 1 is not provided with a dosing port 1-7, a reagent tank 1-8 with valves at both ends, a stirring paddle 1-6 and a heating device 1-5; the catalyst kettle cannot be loaded with catalyst and is only a container for containing the catalyst.

[0169] According to the method provided in Example 1, the method is carried out in the above-mentioned system, except that steps (2)-(3) are omitted. That is, when the catalyst is loaded, the catalyst pre-loaded with active metals in other equipment is first transferred to the catalyst kettle, and then nitrogen replacement is performed before the catalyst loading is started.

[0170] After the catalyst was loaded, the above system was used to catalyze the dimerization of propylene to prepare 4-methyl-1-pentene at a reaction temperature of 150 °C, a reaction pressure of 10 MPa, and a space velocity of 0.5 h -1 After the reaction stabilized, the composition of the reaction material outlet was analyzed and the propylene conversion rate was 67%.

[0171] Compared with Example 1, Comparative Example 2 shows that the active Na / K of the loaded catalyst is partially oxidized during the transfer process, resulting in a decrease in activity.

[0172] Comparative Example 3

[0173] According to the system provided in Example 1, the difference is that Figure 6 As shown, that is,

[0174] The catalyst inlet of this comparative example is perpendicular to the shell of the tubular reactor, and no guide plate is provided on the upper tube plate of the tubular reactor;

[0175] The catalyst return port is on the same center line as the catalyst inlet and is opposite to the catalyst inlet.

[0176] According to the method provided in Example 1, the method is carried out in the above system.

[0177] A loading test was conducted using catalyst carriers to test the loading effect of the loading system. After the loading was completed, there was still catalyst residue on the upper tube plate.

[0178] Using the pressure drop test method of Example 1, the single tube pressure drop was tested after filling, and the average pressure drop of the tubes was 11 kPa, the maximum pressure drop was 13 kPa, the minimum pressure drop was 9 kPa, the pressure drop deviation was ±18%, and the amount of fine powder collected by the dust removal equipment was 1% of the filling amount.

[0179] Compared with Example 1, when the guide plate is not provided in Comparative Example 3, the catalyst wear is aggravated and the filling uniformity is poor.

[0180] Compared with Comparative Examples 1-3, Examples 1-2 adopt the catalyst oxygen-free loading system provided by the present invention, which enables the catalyst to be loaded and loaded in a non-oxidizing atmosphere, avoids the risk of the loaded catalyst coming into contact with air during the transfer process, improves the safety and uniformity of the loading process, and improves the stability and wear resistance of the catalyst. At the same time, the process of preparing 4-methyl-1-pentene by propylene dimerization is carried out in the above-mentioned loading system, which can effectively improve the propylene conversion rate and, under the premise of the same catalyst loading amount, increase the process operation time.

[0181] The preferred embodiments of the present invention are 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 the contents disclosed by the present invention and fall within the scope of protection of the present invention.

Claims

1. A catalyst oxygen-free 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 gas pipe (5), and a catalyst return pipe (11); the shell-and-tube reactor (7) comprises a shell (7-1), the shell (7-1) being provided with a catalyst inlet (7-8) and a delivery gas outlet (7-9); an upper tube plate (7-3) and a lower tube plate (7-5) being provided in the shell (7-1), and a plurality of tube bundles (7-2) being 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 and is used for loading the catalyst carrier in a non-oxidizing atmosphere to obtain a catalyst; the catalyst delivery pipe (4) is connected to the feed port (1-3), the delivery gas pipe (5) and the catalyst inlet (7-8) of the catalyst kettle (1) and is used for delivering the catalyst by the delivery gas and loading it into the tube array (7-2); the delivery gas is discharged through the delivery gas outlet (7-9); When the tube array (7-2) is filled with catalyst, the excess catalyst accumulated in the catalyst delivery tube (4) and the upper tube plate (7-3) is circulated back to the catalyst kettle (1) through the catalyst return tube (11) under the transportation of the delivery gas.

2. The system according to claim 1, wherein: 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).

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 0.01-1:1, 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 catalyst has an equivalent diameter of 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.

4. The system according to claim 3, 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 5-20:

1.

5. The system according to any one of claims 1 to 4, wherein: The gas port (1-2) is arranged at the top of the catalyst kettle (1), and the feed port (1-3) is arranged at the bottom of the catalyst kettle (1); The gas pipe (2) is provided with an air inlet valve (2-1) for injecting non-oxidizing gas into the catalyst kettle (1); 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); The top of the catalyst kettle (1) is further provided with a dosing port (1-7), and the dosing port (1-7) is connected to a reagent tank (1-8) provided with a top valve (1-9) and a bottom valve (1-10); The catalyst kettle (1) is further provided with a stirring paddle (1-6) inside, and a heating component (1-5) is provided outside the catalyst kettle (1).

6. The system according to claim 5, wherein: According to the material flow direction, the catalyst delivery pipe (4) is provided with a discharge valve (4-1) and an inlet valve (4-2) in sequence; Wherein, according to the material flow direction, a delivery air valve (5-1) is provided on the delivery air pipe (5), and the delivery air valve (5-1) is provided after the discharge valve (4-1); 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 gas outlet (7-9) is tangentially arranged on the shell and is not higher than the lower tube plate (7-5); and / or, the delivery gas outlet (7-9) and the delivery gas pipe (5) are connected via a delivery gas circulation pipe (8); Wherein, according to the material flow direction, the conveying gas circulation pipe (8) is provided with a conveying gas discharge valve (8-1), a dust removal device (8-2) and a gas booster (8-3) in sequence.

7. The system according to claim 6, 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.

8. The system according to claim 7, wherein: The number of the material level meter ports (7-14) is 1-5.

9. The system according to claim 7, wherein: The catalyst return port (7-15) is provided with the catalyst return pipe (11), and the catalyst return pipe (11) is connected to the return port (1-4) of the catalyst kettle (1); or, The catalyst return port (7-15) is provided with a catalyst return blowing air pipe (14) connected to the downstream of the catalyst delivery pipe (4), and the pipeline between the catalyst inlet (7-8) and the inlet valve (4-2) is connected to the return port (1-4) of the catalyst kettle (1) through the catalyst return pipe (11).

10. The system according to claim 9, wherein: The catalyst return pipe (11) 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 tube (11) to the upper tube plate (7-3) to the height of the guide plate (7-4) is 0.2-5:

1.

11. The system according to claim 10, wherein: The ratio of the vertical distance between the catalyst return tube (11) and the upper tube plate (7-3) to the height of the guide plate (7-4) is 1-1.5:

1.

12. The system according to claim 9, wherein: According to the material flow direction, the connection point between the catalyst delivery pipe (4) and the catalyst return blowing air pipe (14) is located before the inlet valve (4-2); Wherein, a catalyst return blowing air valve (14-1) is provided on the catalyst return blowing air pipe (14).

13. The system according to claim 12, wherein: The catalyst return blowing air pipe (14) 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 blowing air pipe (14) to the upper tube plate (7-3) to the height of the guide plate (7-4) is 0.2-5:

1.

14. The system according to claim 13, wherein: The ratio of the vertical distance between the catalyst return blowing air pipe (14) and the upper tube plate (7-3) to the height of the guide plate (7-4) is 1-1.5:

1.

15. The system according to claim 12, 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; Wherein, a gas-solid separator (12) is further provided on the catalyst return pipe (11), and the gas-solid separator (12) is provided between the return valve (11-1) and the return valve (11-2); The gas phase outlet of the gas-solid separator (12) and the gas delivery pipe (5) are connected via a gas phase return pipe (13), and a gas phase return valve (13-1) is provided on the gas phase return pipe (13); Wherein, the gas phase return pipe (13) is connected to the transport gas circulation pipe (8); Wherein, according to the material flow direction, the gas phase return valve (13-1) is arranged before the dust removal equipment (8-2).

16. The system according to claim 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 anaerobic loading 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 loaded in a catalyst kettle to obtain a catalyst; The catalyst is transported by a transport gas, entering the shell-and-tube reactor through a catalyst transport pipe, and is loaded into the shell-and-tube reactor through a guide plate, and the transport gas is discharged through a transport gas outlet; When the tube array is filled with the catalyst, the surplus catalyst accumulated in the catalyst delivery tube and the upper tube plate is circulated back to the catalyst kettle under the transportation of the delivery gas.

18. A catalyst anaerobic loading method, characterized in that: The method is performed in the system of claim 15, wherein the method comprises the following steps: S1. Keep the system in a non-oxidizing atmosphere, close the air inlet valve, exhaust valve, return valve, top valve, bottom valve and discharge valve, open the upper head of the catalyst kettle, add the catalyst carrier; repeatedly open or close the air inlet valve and exhaust valve alternately to keep the catalyst kettle in a non-oxidizing atmosphere; S2, opening the top valve and the bottom valve, adding the active component to the catalyst kettle, and then closing the top valve and the bottom valve; adjusting the air inlet valve so that the catalyst support and the active component are loaded in a non-oxidizing atmosphere to obtain the catalyst; S3, opening the unloading valve, delivery gas valve, inlet valve, and delivery gas discharge valve, and closing the return valve and return valve, adjusting the air inlet valve so that the pressure of the catalyst kettle is higher than the pressure of the catalyst delivery pipe, so that the catalyst is loaded into the tube array under the delivery of the delivery gas, and the delivery gas is discharged; S4. During the loading process, the filling height of the catalyst in the tube array is measured by a material level meter; when catalyst accumulates on the upper tube plate, the discharge valve is closed and the conveying gas continues to be purged; if there is no catalyst accumulation on the upper tube plate, the discharge valve is opened to continue loading; if there is still catalyst accumulation on the upper tube plate, the conveying gas discharge valve is closed; When the catalyst return port is provided with a catalyst return pipe, the return valve and the return valve are opened, the delivery gas valve is adjusted so that the delivery gas pressure is higher than the pressure of the catalyst kettle, and the surplus catalyst is recycled back to the catalyst kettle; or When the catalyst return port is provided with a catalyst return blowing air pipe, and the pipeline between the catalyst inlet and the inlet valve is connected to the return port of the catalyst kettle through the catalyst return pipe, the inlet valve is closed, the delivery gas valve is adjusted so that the pressure of the delivery gas is higher than the pressure of the catalyst kettle, the catalyst return blowing air valve, the return valve and the return valve are opened, and the surplus catalyst is recycled back to the catalyst kettle; S5. After the excess catalyst on the upper tube sheet is purged, close all valves and the catalyst loading is completed.

19. The method according to claim 18, wherein The method further comprises: step S3, after the conveying gas is discharged through the conveying gas outlet, it is sequentially subjected to dust removal and pressurization, and then recycled back to the conveying gas pipe; The method further comprises: step S4, separating the surplus catalyst into gas and solid, recycling the obtained solid phase back to the catalyst kettle, and returning the obtained gas phase after dust removal and pressurization to be mixed with the conveying gas.

20. The method according to claim 17 or 18, wherein The non-oxidizing gas and the transport gas in the non-oxidizing atmosphere are each independently selected from nitrogen; The nitrogen gas satisfies the following conditions: oxygen content ≤ 10 ppm; water content ≤ 10 ppm.

21. The method according to claim 20, wherein The nitrogen satisfies: oxygen content ≤ 3 ppm; water content ≤ 3 ppm.

22. The method according to claim 17 or 18, wherein The 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 conveying gas is 0-10 MPa(A); and the temperature of the conveying gas is 0-300°C.

23. The method according to claim 22, wherein The 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; and 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 conveying gas is 0.1-5 MPa(A); and the temperature of the conveying gas is 20-200°C.

24. The method according to claim 22, wherein The volume ratio of the transport gas to the catalyst is 2-1000:1; And / or, the gas velocity of the gas-solid conveying mixture of the conveying gas and the catalyst is 5-25 m / s.

25. The method according to claim 24, wherein The volume ratio of the transport gas to the catalyst is 10-500:1; And / or, the gas velocity of the gas-solid conveying mixture of the conveying gas and the catalyst is 5-15 m / s.

26. Use of the system according to any one of claims 1 to 16 in loading reduced metal catalysts.

27. A method for preparing 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 the method comprises: Propylene is contacted with a catalyst loaded in tubular form in the system and reacted to obtain 4-methyl-1-pentene; wherein the catalyst comprises: a carrier and an active component loaded on the carrier, and the active component is selected from K and / or Na.

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