A fischer-tropsch synthesis system and method for continuously activating a fischer-tropsch synthesis catalyst

Abstract

The present disclosure relates to a Fischer-Tropsch synthesis system and method for continuously activating a Fischer-Tropsch synthesis catalyst, which can realize continuous activation of the catalyst, reduce the inventory of the continuous activation reactor, reduce the volume of the catalyst activation reactor, reduce the floor area, the output of the activation tail gas, and the output flow of the activated catalyst, not only can the activation tail gas recycling process in the prior art be changed into a single-pass process, thereby being able to eliminate the catalyst activation circulating gas compressor, but also can avoid the situation of local temperature rise in the Fischer-Tropsch synthesis reaction. At the same time, the internal chamber of the continuous activation reactor is divided into multiple smaller reaction zones by partition plates, which can not only further reduce catalyst wear, but also improve the activation effect of the catalyst. In addition, the activation tail gas is combined with the Fischer-Tropsch tail gas for treatment by a gas-liquid-solid separation device, which can eliminate the treatment process and device of the activation tail gas.

Description

Technical Field

[0001] This disclosure relates to the field of Fischer-Tropsch synthesis processes, and more specifically, to a Fischer-Tropsch synthesis system and method for continuously activating a Fischer-Tropsch synthesis catalyst. Background Technology

[0002] The Fischer-Tropsch synthesis reaction converts syngas into hydrocarbon products under the action of a catalyst. For the widely used Fischer-Tropsch iron-based catalysts in industry, fresh catalysts need to be pretreated to become activated catalysts with Fischer-Tropsch activity before being transferred to the Fischer-Tropsch synthesis reactor to replace the deactivated catalyst, thereby achieving efficient and stable operation of the system. The specific process flow includes: batch activation of the catalyst in a catalyst activation reactor, followed by the Fischer-Tropsch synthesis reaction in the reactor. Due to the rapid deactivation rate of the Fischer-Tropsch iron-based catalyst, when the performance of the Fischer-Tropsch synthesis reaction does not meet process requirements, a suitable amount of deactivated catalyst is first discharged, and then a suitable amount of fresh activated catalyst is intermittently added. This intermittent operation method severely affects the size of the activation reactor, catalyst wear, catalyst activity, and the operational stability within the Fischer-Tropsch reactor.

[0003] CN110511777A discloses a technology for activating catalysts using a gas-solid fluidized bed, while CN114736714A provides a Fischer-Tropsch synthesis system, its start-up method, and an online replacement method for the Fischer-Tropsch synthesis catalyst. The gas-solid activation process shortens the catalyst activation time, increases the frequency of catalyst replacement, reduces the amount of catalyst replaced in a single cycle, improves the flexibility of catalyst storage and use, effectively shortens the start-up cycle, and provides a flexible online catalyst replacement technology. However, the implementation process requires weighing the catalyst and preparing the slurry; although the catalyst replacement cycle is shortened, it is still a batch operation.

[0004] CN111286356A relates to a system for high-temperature Fischer-Tropsch synthesis to produce hydrocarbons. The Fischer-Tropsch tail gas exiting the Fischer-Tropsch synthesis reactor is mixed with a small amount of fresh reducing gas as an activating gas and then introduced into the fresh catalyst of a fluidized bed reduction reactor. This eliminates the need for fresh reducing gas and the reduction cycle compressor, offering advantages such as low consumption, high energy efficiency, high product diversity, and high resilience of the entire system. However, it requires complex treatment of the Fischer-Tropsch tail gas, and the fluidized bed reduction reactor is relatively large.

[0005] CN117942881A discloses a system and method for continuous activation and replacement of Fischer-Tropsch synthesis catalysts. The system includes a catalyst feeding tank, a first-stage gas-solid fluidized bed reactor, a second-stage gas-solid fluidized bed reactor, a third-stage gas-solid fluidized bed reactor, a circulating gas heat exchanger, a gas-liquid separator, a circulating gas compressor, and a finished activated catalyst storage tank. This system enables continuous activation of Fischer-Tropsch synthesis catalysts for industrial production. However, using a multi-stage reactor series configuration leads to a complex process flow, with varying residence times required for each activation stage, potentially resulting in poor controllability in actual operation.

[0006] In summary, due to the large catalyst throughput and long activation cycle, existing technologies require the activation of a large amount of catalyst at once, resulting in a large reactor volume and complex process flow in the catalyst activation system. In existing technologies, the catalyst activation system and the Fischer-Tropsch synthesis system operate basically independently. Summary of the Invention

[0007] The purpose of this disclosure is to provide a Fischer-Tropsch synthesis system and method for continuously activating Fischer-Tropsch catalysts, in order to solve the problems existing in the prior art, such as large reactor volume, complex process flow, large consumption of activation gas, easy catalyst wear, high investment cost, and high operating cost.

[0008] To achieve the above objectives, the first aspect of this disclosure provides a Fischer-Tropsch synthesis system for continuously activating a Fischer-Tropsch synthesis catalyst, the Fischer-Tropsch synthesis system comprising a catalyst feeding tank, a continuous activation reactor, a Fischer-Tropsch synthesis reactor, and a gas-liquid-solid separation device. The inlet of the catalyst feed tank is connected to a fresh catalyst source, and the outlet of the catalyst feed tank is connected to the catalyst inlet of the continuous activation reactor; the catalyst outlet of the continuous activation reactor is connected to the activation catalyst inlet of the Fischer-Tropsch synthesis reactor; the activation gas inlet of the continuous activation reactor is connected to an activation gas source, and the activation tail gas outlet of the continuous activation reactor and the Fischer-Tropsch tail gas outlet of the Fischer-Tropsch synthesis reactor are respectively connected to the synthesis tail gas of the gas-liquid-solid separation device. The continuous activation reactor includes a shell, partitions, a gas distributor, and a temperature control device; The internal chamber of the shell includes an integrated lower head, a dense phase section, an enlarged section, a dilute phase section, and an upper head arranged from bottom to top; the activation tail gas outlet is located at the top of the upper head, and the catalyst inlet and the catalyst outlet are located at the lower part of the dense phase section; The gas distributor is located at the lower part of the dense phase section so that the activation gas can enter the dense phase section through the gas distributor; The partition plate is arranged along the axial direction of the housing in the internal cavity of the housing, and divides the internal cavity into multiple activation reaction zones; the bottom of each of the multiple activation reaction zones is provided with an activation gas inlet, which is used to communicate with an activation gas source; The temperature control devices are respectively installed in multiple activation reaction zones to control the temperature of each zone.

[0009] Optionally, the number of activated reaction zones is four or more, preferably 12 to 24.

[0010] Optionally, the partition extends radially along the housing to the inner wall of the housing; the partition includes short partitions and long partitions spaced apart. The top of the short partition is located at 1 / 2 to 3 / 4 of the height of the dense phase section; The top of the long partition plate is located at 1 / 3 to 2 / 3 of the height of the rare phase section.

[0011] Optionally, a partition connection port is provided at the lower part of the long partition plate so that the catalyst can travel in the flow direction between two adjacent activation reaction zones.

[0012] Optionally, the ratio of the height of the lower end cap to the diameter of the dense phase section is (0.2~1):1; the ratio of the height of the dense phase section to the diameter of the dense phase section is (2~7):1; the ratio of the diameter of the dilute phase section to the diameter of the dense phase section is (1.5~6):1; and the ratio of the height of the dilute phase section to the diameter of the dilute phase section is (1.5~3):1.

[0013] Optionally, a gas-solid separation device is provided at the upper part of the dilute phase section for separating catalyst particles in the activated tail gas; the gas-solid separation device includes a cyclone separator.

[0014] A second aspect of this disclosure provides a Fischer-Tropsch synthesis method with continuously activated Fischer-Tropsch synthesis catalyst, the method comprising: Fresh catalyst from the catalyst feeding tank is continuously fed into the continuous activation reactor described in the first aspect through the catalyst feed inlet, and then enters multiple activation reaction zones to contact with activation gas for activation treatment, thereby obtaining activated catalyst and activation tail gas; The activated catalyst is continuously fed into the Fischer-Tropsch synthesis reactor to carry out the Fischer-Tropsch synthesis reaction, resulting in Fischer-Tropsch tail gas, first synthetic wax, and first slag wax. The activated tail gas and the Fischer-Tropsch tail gas are then separated by a gas-liquid-solid separator to obtain carbon dioxide, light oil, heavy oil, and synthetic water.

[0015] Optionally, the method further includes separating the first slag wax using a solid-liquid separation device to obtain a second synthetic wax and solid waste; and mixing the first synthetic wax and the second synthetic wax to obtain a synthetic wax product.

[0016] Optionally, the multiple activation reaction zones in the continuous activation reactor are grouped into a first reaction zone group, a second reaction zone group, and a third reaction zone group; The Fischer-Tropsch synthesis method further includes activating the fresh catalyst sequentially through a first reaction zone, a second reaction zone, and a third reaction zone, and then introducing the activated catalyst from the third reaction zone into the Fischer-Tropsch synthesis reactor. The reaction conditions of the first reaction zone group include: temperature 150~230℃, hydrogen-carbon molar ratio of activation gas (5~30):1, and catalyst residence time 1~4h; The reaction conditions for the second reaction zone group include: temperature 200~270℃, hydrogen-carbon molar ratio of activation gas (10~50):1, and catalyst residence time 2~8h; The reaction conditions for the third reaction zone include: a temperature of 250~300℃, a hydrogen-to-carbon molar ratio of (30~200):1 for the activation gas, and a catalyst residence time of 8~16h.

[0017] Optionally, the catalyst feeding tank includes a first feeding tank and a second feeding tank; The Fischer-Tropsch synthesis method also includes: The fresh catalyst in the first feeding tank is continuously fed into the continuous activation reactor; When the amount of fresh catalyst in the first feeding tank is below the set amount, switch to the second feeding tank; When the amount of fresh catalyst in the second feeding tank is below the set amount, switch to the first feeding tank; The ratio of the set storage capacity to the storage capacity of the first feeding tank is (0.15~0.25):1; The ratio of the set storage capacity to the storage capacity of the second feeding tank is (0.15~0.25):1.

[0018] By employing the continuous activation reactor disclosed herein to activate the catalyst, continuous activation of the catalyst can be achieved, reducing the amount of catalyst stored in the continuous activation reactor and decreasing its volume. This not only reduces the floor space required but also minimizes catalyst wear. Furthermore, with a constant apparent gas velocity, the smaller diameter of the continuous activation reactor results in a lower output of activation tail gas compared to Fischer-Tropsch tail gas. This allows the existing activation tail gas recirculation process to be converted into a single-pass process, thereby eliminating the need for a catalyst activation recirculation gas compressor. Additionally, the activated catalyst can be continuously added to the Fischer-Tropsch synthesis reactor at a low flow rate, avoiding localized temperature rises within the Fischer-Tropsch synthesis reaction. This allows the activated catalyst to be added directly without premixing, eliminating the need for buffer tanks and preparation tanks for the activated catalyst, thus reducing process and system complexity.

[0019] Meanwhile, partitions are used to divide the internal chamber of the continuous activation reactor into multiple smaller reaction zones. On the one hand, this allows fresh catalyst to flow within multiple smaller reaction zones, which can further reduce catalyst wear compared to the use of larger activation zones in existing technologies. On the other hand, temperature control devices are installed in each reaction zone to control the temperature of each zone. Furthermore, in conjunction with the corresponding activation gas parameters, the catalyst activation reaction can be made more complete, thereby improving the activation effect of the catalyst.

[0020] In addition, incorporating the activation tail gas into the Fischer-Tropsch synthesis tail gas and treating it through a gas-liquid-solid separation device can eliminate the need for activation tail gas treatment steps and equipment, thereby further simplifying the system and process of the Fischer-Tropsch synthesis process.

[0021] Other features and advantages of this disclosure will be described in detail in the following detailed description section. Attached Figure Description

[0022] The accompanying drawings are provided to further illustrate the present disclosure and form part of the specification. They are used together with the following detailed description to explain the present disclosure, but do not constitute a limitation thereof. In the drawings: Figure 1 This is a schematic diagram of a Fischer-Tropsch synthesis system with a continuously activated Fischer-Tropsch synthesis catalyst disclosed herein.

[0023] Figure 2 This is a schematic diagram of a continuous activation reactor disclosed herein.

[0024] Explanation of reference numerals in the attached figures 1 Shell; 2 Lower head; 3 Dense phase section; 4 Enlarged section; 5 Dilute phase section; 6 Upper head; 7 Partition plate; 7A Long partition plate; 7B Short partition plate; 8 Gas distributor; 9 Activation tail gas outlet; 10 Catalyst inlet; 11 Catalyst outlet; 12 Partition connection port; 13 Activation gas inlet; 101 First feed tank; 102 Second feed tank; 103 Continuous activation reactor; 104 Fischer-Tropsch synthesis reactor; 105 Gas-liquid-solid separation device; 106 Tail gas decarbonization device; 107 Circulating gas compressor; 108 Oil recovery device; 109 Liquid-solid treatment device; a. Activation gas; b. Fischer-Tropsch synthesis gas; c. Activation catalyst; d. Activation tail gas; e. Fischer-Tropsch tail gas; f. Synthesis tail gas; g. First cycle gas; h. Second cycle gas; i. Decarbonization tail gas; j. Carbon dioxide; k. Light oil; l. Heavy oil; m. Synthetic water; n. First synthetic wax; o. First slag wax; p. Second slag wax; q. Second synthetic wax; r. Synthetic wax product; s. Solid waste. Detailed Implementation

[0025] The specific embodiments of this disclosure will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit this disclosure.

[0026] like Figure 1 As shown, the first aspect of this disclosure provides a Fischer-Tropsch synthesis system for continuously activating a Fischer-Tropsch synthesis catalyst. The Fischer-Tropsch synthesis system includes a catalyst feeding tank, a continuous activation reactor 103, a Fischer-Tropsch synthesis reactor 104, and a gas-liquid-solid separation device 105. The inlet of the catalyst feed tank is connected to a fresh catalyst source, and the outlet of the catalyst feed tank is connected to the catalyst inlet 10 of the continuous activation reactor 103; the catalyst outlet 11 of the continuous activation reactor 103 is connected to the activation catalyst inlet of the Fischer-Tropsch synthesis reactor 104; the activation gas inlet of the continuous activation reactor 103 is connected to an activation gas source, and the activation tail gas outlet 9 of the continuous activation reactor 103 and the Fischer-Tropsch tail gas outlet of the Fischer-Tropsch synthesis reactor 104 are respectively connected to the synthesis tail gas of the gas-liquid-solid separation device 105; The continuous activation reactor 103 includes a shell 1, a partition 7, a gas distributor 8, and a temperature control device; The internal chamber of the shell 1 includes a lower end cap 2, a dense phase section 3, an enlarged section 4, a dilute phase section 5, and an upper end cap 6, which are integrally arranged from bottom to top; the activation tail gas outlet 9 is located at the top of the upper end cap 6, and the catalyst inlet 10 and the catalyst outlet 11 are located at the lower part of the dense phase section 3. The gas distributor 8 is disposed at the lower part of the dense phase section 3 so that the activation gas can enter the dense phase section 3 through the gas distributor 8; The partition plate 7 is arranged along the axial direction of the housing 1 in the internal cavity of the housing 1 and divides the internal cavity into multiple activation reaction zones; the bottom of each of the multiple activation reaction zones is provided with an activation gas inlet 13, which is used to communicate with an activation gas source; The temperature control devices are respectively installed in multiple activation reaction zones to control the temperature of each zone.

[0027] By employing the continuous activation reactor 103 disclosed herein to activate the catalyst, continuous activation of the catalyst can be achieved, reducing the amount of material stored in the continuous activation reactor 103 and thus reducing the volume of the catalyst activation reactor. On the one hand, this not only reduces the floor space but also reduces catalyst wear. On the other hand, with the apparent gas velocity remaining constant, the diameter of the continuous activation reactor 103 is smaller, resulting in a lower output of activation tail gas compared to Fischer-Tropsch tail gas. This allows the existing activation tail gas recirculation process to be converted into a single-pass process, thereby eliminating the need for a catalyst activation recirculation gas compressor. Furthermore, the activated catalyst can be continuously added to the Fischer-Tropsch synthesis reactor 104 at a low flow rate, avoiding localized temperature rises within the Fischer-Tropsch synthesis reaction. This allows the activated catalyst to be added directly without premixing, eliminating the need for a buffer tank and preparation tank for the activated catalyst, thereby reducing the complexity of the process and system.

[0028] Meanwhile, the internal chamber of the continuous activation reactor 103 is divided into multiple smaller reaction zones by partition 7. On the one hand, this allows the fresh catalyst to flow in multiple smaller reaction zones, which can further reduce catalyst wear compared to the use of a larger activation zone in the prior art. On the other hand, a temperature control device is set in each reaction zone to control the temperature of each zone, which can make the catalyst activation reaction more complete and improve the activation effect of the catalyst.

[0029] In addition, by incorporating the activation tail gas into the Fischer-Tropsch tail gas and treating it through the gas-liquid-solid separation device 105, the treatment process and equipment for the activation tail gas can be eliminated, thereby further simplifying the system and process of the Fischer-Tropsch synthesis process.

[0030] In a preferred embodiment, the gas distributor 8 is disposed at the connection between the lower end cap 2 and the dense phase section 3.

[0031] In one embodiment, the partition 7 of this disclosure extends radially along the housing 1 to the inner wall of the housing 1.

[0032] In one embodiment, the partition 7 includes short partitions 7B and long partitions 7A spaced apart. In this embodiment, the short partitions 7B and long partitions 7A are spaced apart, that is, a short partition 7B is placed between two adjacent long partitions 7A.

[0033] In one embodiment, the top of the short partition 7B of this disclosure is located at 1 / 2 to 3 / 4 of the height of the dense phase section 3.

[0034] In a preferred embodiment, the top of the short partition 7B of this disclosure is located at 3 / 4 of the height of the dense phase segment 3.

[0035] In one embodiment, the bottom of the short partition 7B described in this disclosure can extend through the gas distributor 8 to the top surface of the lower end cap 2, or it can be fixed to the upper surface of the gas distributor 8.

[0036] In a preferred embodiment, the bottom of the short partition 7B of this disclosure extends through the gas distributor 8 to the inner wall of the lower end cap 2.

[0037] In one embodiment, the top of the long partition plate 7A of this disclosure is located at 1 / 3 to 2 / 3 of the height of the rare phase segment 5.

[0038] In a preferred embodiment, the top of the long partition 7A of this disclosure is located at 2 / 3 of the height of the dilute phase segment 5.

[0039] In one embodiment, the bottom of the long partition plate 7A described in this disclosure can extend through the gas distributor 8 to the top surface of the lower end cap 2, or it can be fixed to the upper surface of the gas distributor 8.

[0040] In a preferred embodiment, the bottom of the long partition 7A of this disclosure extends through the gas distributor 8 to the top surface of the lower end cap 2.

[0041] In one embodiment, the activation gas inlet 13 of this disclosure is disposed at the bottom of the lower end cap 2.

[0042] In one embodiment, the number of activated reaction zones is four or more.

[0043] In a preferred embodiment, the number of activation reaction zones is 12 to 24.

[0044] In one embodiment, the number of activation gas inlets 13 described in this disclosure can be flexibly selected according to the arrangement of the partition 7. For example, the number of activation gas inlets 13 can be one or more.

[0045] In one embodiment, when the bottoms of the long partition plate 7A and the short partition plate 7B extend through the gas distributor 8 to the top surface of the lower head 2, the partition plate 7 divides the internal space of the lower head 2 into multiple regions, and each region is provided with an activation gas inlet 13; wherein, the number of regions is the same as the number of activation reaction zones, and the number of activation gas inlets 13 is the same as the number of activation reaction zones. When the bottom of the long partition plate 7A extends through the gas distributor 8 to the top surface of the lower head 2, and the bottom of the short partition plate 7B is fixed to the upper surface of the gas distributor 8, the partition plate 7 divides the internal space of the lower head 2 into multiple regions, and each region is provided with an activation gas inlet 13; wherein, the number of regions is 1 / 2 of the number of activation reaction zones, and the number of activation gas inlets 13 is 1 / 2 of the number of activation reaction zones; When the bottoms of the long partition 7A and the short partition 7B are fixed to the upper surface of the gas distributor 8, there is one activation gas inlet 13.

[0046] In a preferred embodiment, the bottoms of the long partition 7A and the short partition 7B of this disclosure extend through the gas distributor 8 to the top surface of the lower head 2 to divide the lower head 2 into multiple regions, and each region has an activation gas outlet.

[0047] In one embodiment, the catalyst inlet 10 and catalyst outlet 11 described in this disclosure are both located at the lower part of the dense phase section 3, and their height is equal to any position at the lower 1 / 4 to 1 / 2 of the short partition plate 7B.

[0048] In one embodiment, the number of catalyst inlet 10 and catalyst outlet 11 described in this disclosure can be one or more.

[0049] In a preferred embodiment, the number of catalyst inlet 10 and catalyst outlet 11 described in this disclosure is one, and the catalyst inlet 10 and catalyst outlet 11 are respectively arranged on two adjacent activation reaction zones, so that the catalyst can flow through all activation reaction zones in sequence and exit the device after reaction.

[0050] In one embodiment, a partition connection port 12 is provided at the lower part of the long partition plate 7 to allow the catalyst to travel between two adjacent activation reaction zones in the direction of catalyst flow. In this embodiment, since both the catalyst inlet 10 and the catalyst outlet 11 are open when the continuous activation reactor 103 is in use, under the action of pressure difference, the catalyst flows from the high-pressure activation reaction zone to the low-pressure activation reaction zone through the partition connection port 12, thereby enabling the catalyst to travel between two adjacent activation reaction zones in the direction of flow.

[0051] In one embodiment, the partition connection port 12 is a square opening.

[0052] In one embodiment, the dimensions of the partition connection port 12 include: a length of 1 / 6 to 1 / 3 of the diameter of the dense phase section 3 of the continuous activation reactor 103, and a width of 1 / 6 to 1 / 3 of the diameter of the dense phase section 3 of the continuous activation reactor 103.

[0053] In one embodiment, the distance between the bottom edge of the partition connection port 12 and the gas distributor 8 is 0.2 to 1 times the diameter of the dense phase section 3 of the continuous activation reactor 103.

[0054] In the above embodiment, fresh catalyst enters the activation reaction zone through the catalyst inlet 10. With the assistance of the activation gas and the gradual increase in the amount of catalyst added, the height of the catalyst in the activation reaction zone gradually increases. When the height of the catalyst in the activation reaction zone exceeds the height of the short partition plate 7B, the excess catalyst enters the adjacent activation reaction zone. As the amount of catalyst entering gradually increases, the catalyst enters the next activation reaction zone through the partition connection port 12 on the long partition plate 7A. During the continuous activation process in the continuous activation reactor 103, fresh catalyst enters the continuous activation reactor 103 through the catalyst inlet 10, and the above process is repeated so that the catalyst reacts in all activation reaction zones in sequence and then exits the device through the catalyst outlet 11. The activation gas not only plays an activation role throughout the process but also acts as a fluidizing gas to assist the flow, ensuring that the catalyst flows in an "S-shape" within the continuous activation reactor 103.

[0055] In one embodiment, the height of the lower end cap 2 is less than or equal to the diameter of the dense phase section 3.

[0056] In a preferred embodiment, the ratio of the height of the lower end cap 2 to the diameter of the dense phase section 3 is (0.2~1):1.

[0057] In a further preferred embodiment, the ratio of the height of the lower end cap 2 to the diameter of the dense phase section 3 is (0.3~0.7):1.

[0058] In one embodiment, the ratio of the height to the diameter of the dense phase segment 3 is (2~7):1.

[0059] In a preferred embodiment, the ratio of the height to the diameter of the dense phase segment 3 is (3~6):1.

[0060] In one embodiment, the ratio of the diameter of the dilute phase segment 5 to the diameter of the dense phase segment 3 is (1.5~6):1.

[0061] In a preferred embodiment, the ratio of the diameter of the dilute phase segment 5 to the diameter of the dense phase segment 3 is (2~5):1.

[0062] In one embodiment, the ratio of the height to the diameter of the dilute phase segment 5 is (1.5~3):1.

[0063] In a preferred embodiment, the ratio of the height to the diameter of the dilute phase segment 5 is (2~2.8):1.

[0064] In one embodiment, the diameter of the dense phase segment 3 can be flexibly set according to actual production needs, which will not be elaborated further in this application.

[0065] In one embodiment, the ratio of the height of the short partition 7B to the diameter of the dense phase section 3 is (0.5~0.8):1.

[0066] In one embodiment, the angle between the expanded section 4 of the catalyst continuous activation reactor 103 and the horizontal direction is θ, preferably 15≤θ≤60, and more preferably, the angle is greater than the stagnation angle of the catalyst.

[0067] In one embodiment, a gas-solid separation device is provided at the upper part of the dilute phase section 5 for separating catalyst particles in the activated tail gas.

[0068] In a preferred embodiment, the gas-solid separation device is a conventional choice in the art, and this application does not make any special requirements. For example, the gas-solid separation device includes a cyclone separator.

[0069] In one embodiment, the number of stages of the cyclone separator can be flexibly adjusted according to actual production needs. Preferably, the number of stages of the cyclone separator is 2.

[0070] In one embodiment, the temperature control device described in this disclosure is a conventional choice in the art, and this application does not make any special requirements. For example, the temperature control device is a heat exchanger with heat exchange tubes. In this embodiment, the heat exchange tubes of the heat exchanger with heat exchange tubes are respectively arranged inside the multiple activation reaction zones.

[0071] like Figure 2 As shown, the second aspect of this disclosure provides a Fischer-Tropsch synthesis method for continuously activating a Fischer-Tropsch synthesis catalyst, the method comprising: Fresh catalyst from the catalyst feeding tank is continuously fed into the continuous activation reactor 103 described in the first aspect through the catalyst feed inlet 10, and enters multiple activation reaction zones to contact with activation gas a for activation treatment, thereby obtaining activated catalyst c and activation tail gas d. The activated catalyst c is continuously fed into the Fischer-Tropsch synthesis reactor 104 to carry out the Fischer-Tropsch synthesis reaction, yielding Fischer-Tropsch tail gas e, first synthetic wax n, and first slag wax o; the activated tail gas and the Fischer-Tropsch tail gas are separated by a gas-liquid-solid separator 105 to yield carbon dioxide j, light oil k, heavy oil l, and synthetic water m.

[0072] Through the above technical solution, by employing a continuous activation reactor 103 and matching it with the optimal activation process, continuous activation of the catalyst can be achieved within the continuous activation reactor 103. This reduces the amount of catalyst stored in the activation reaction device, thereby reducing the size of the reaction device and the intensity of catalyst wear. Furthermore, it allows for the direct and continuous feeding of fresh activated catalyst, reducing investment and operating costs through process optimization. Moreover, since the output of activation tail gas is relatively small compared to Fischer-Tropsch tail gas, the existing activation tail gas recirculation process can be changed to a single-pass process, thus eliminating the need for a compressor. Additionally, by incorporating the activation tail gas into the Fischer-Tropsch synthesis tail gas and treating it through a gas-liquid-solid separation device 105, the treatment steps and equipment for the activation tail gas can be eliminated, further simplifying the system and process of the Fischer-Tropsch synthesis process.

[0073] In one embodiment, the method further includes treating the first slag wax o with a liquid-solid treatment device 109 to obtain a second synthetic wax q and solid waste s; and mixing the first synthetic wax n and the second synthetic wax q to obtain a synthetic wax product r.

[0074] In one embodiment, the catalyst feeding tank includes a first feeding tank 101 and a second feeding tank 102; The Fischer-Tropsch synthesis method also includes: This allows fresh catalyst from the first feeding tank 101 to continuously enter the continuous activation reactor 103; When the amount of fresh catalyst in the first feeding tank 101 is below the set amount, switch to the second feeding tank 102; When the amount of fresh catalyst in the second feeding tank 102 is below the set amount, switch to the first feeding tank 101; The ratio of the set storage capacity to the storage capacity of the first feeding tank 101 is (0.15~0.25):1; The ratio of the set storage capacity to the storage capacity of the second feeding tank 102 is (0.15~0.25):1.

[0075] In a preferred embodiment, the ratio of the set storage amount to the storage amount of the first feeding tank 101 is 0.2:1; The ratio of the set storage capacity to the storage capacity of the second feeding tank 102 is 0.2:1.

[0076] In this embodiment, switching when the first feeding tank 101 or the second feeding tank 102 drops below the set storage capacity allows fresh catalyst from the catalyst feeding tank to continuously enter the continuous activation reactor 103, enabling continuous catalyst feeding. This avoids problems such as complex operation procedures, large size of catalyst activation device, large storage capacity of catalyst activation device, large consumption of activation gas, and the need to configure activation circulation compressor, which are present in existing intermittent operation processes.

[0077] In one embodiment, a method for storing and transferring fresh catalyst in a catalyst feeding tank includes: First, the first feeding tank 101 is purged multiple times with inert gas or activated gas to ensure that the feeding tank is in an anhydrous and oxygen-free atmosphere. Then, the pressure is maintained at 0.2~0.5MPa. Preferably, it is purged with N2 3 times. Finally, the pressure of the first feeding tank 101 is maintained at 0.3MPa. The pressure of the first feeding tank 101 is increased to 2.0~5.0MPa and the temperature is increased to 120~180℃. Preferably, the tank pressure is controlled at 3.2MPa and the temperature is controlled at 150℃. Fresh catalyst is continuously transferred from the first feed tank 101 to the continuous activation reactor 103. Preferably, the fresh catalyst is transferred to the continuous activation reactor 103 by a dense phase transfer pump or by pressure differential. When the catalyst level in the first feeding tank 101 falls below the set level, it is necessary to ensure that the second feeding tank 102 contains a sufficient amount of fresh catalyst, and then switch to the second feeding tank 102 to continue adding catalyst. When the catalyst storage in the second feeding tank 102 is lower than the set storage level, it is necessary to ensure that the first feeding tank 101 has a sufficient amount of fresh catalyst and switch to the first feeding tank 101 to continue adding catalyst.

[0078] In one embodiment, each Fischer-Tropsch synthesis reactor 104 may be configured with one continuous activation reactor 103 or two continuous activation reactors 103.

[0079] In one embodiment, the type of continuous activation reactor 103 described in this disclosure includes a slurry bed reactor or a fluidized bed reactor.

[0080] In a preferred embodiment, the continuous activation reactor 103 described in this disclosure is a fluidized bed reactor.

[0081] In one embodiment, the amount of continuous activation reactor 103 described in this disclosure can be flexibly selected according to the number of continuous activation reactors 103 and actual usage needs. For example, the amount of continuous activation reactor 103 is 1~3t.

[0082] In this embodiment, the activation treatment is carried out using the continuous activation reactor 103 described in this disclosure. Since the process is continuous, compared with the prior art process of using batch activation, the ratio of the amount of the continuous activation reactor 103 of this disclosure to the amount of activation equipment in the prior art is (1 / 3 to 1 / 20):1. Therefore, with a smaller amount of equipment, the size of the activation reaction device can be greatly reduced, and the phenomenon of severe catalyst wear caused by scale-up effect can be significantly reduced.

[0083] In one embodiment, the operating pressure of the continuous activation reactor 103 described in this disclosure is 1.0~5.0 MPa, preferably 2.5~3.5 MPa; the reaction temperature is 120~300℃, preferably 180~270℃; and the apparent gas velocity is 0.1~1.0 m / s, preferably 0.3~0.6 m / s. In this embodiment, by using the continuous activation reactor 103 in conjunction with the above-mentioned operating reaction conditions, continuous activation of the catalyst can be achieved within the activation reactor. Because the amount of catalyst stored in the activation reactor is reduced, the structural size of the activation reactor is significantly reduced, avoiding reactor scale-up effects and significantly reducing catalyst wear. Here, apparent gas velocity is a conventional technical term in the art, characterizing the linear velocity of the gas, i.e., the volumetric flow rate of the gas entering the reactor at the operating temperature and pressure divided by the cross-sectional area of ​​the reactor.

[0084] In one embodiment, the molar hydrogen-to-carbon ratio in the continuous activation reactor 103 of this disclosure is (5-200):1, preferably (20-80):1. In this embodiment, the hydrogen-to-carbon ratio is the ratio of hydrogen to CO in the gaseous feedstock, and the molar hydrogen-to-carbon ratio is the molar ratio of hydrogen to CO in the gaseous feedstock. Using operating conditions with a suitable hydrogen-to-carbon ratio can improve the activation effect of fresh catalyst.

[0085] In one embodiment, the multiple activation reaction zones in the continuous activation reactor 103 are arranged into a first reaction zone group, a second reaction zone group, and a third reaction zone group; wherein, the multiple activation reaction zones are arranged sequentially according to the flow direction of the catalyst to form the first reaction zone group, the multiple activation reaction zones to form the second reaction zone group, and the multiple activation reaction zones to form the third reaction zone group.

[0086] The Fischer-Tropsch synthesis method further includes activating the fresh catalyst sequentially through a first reaction zone, a second reaction zone, and a third reaction zone, and then introducing the activated catalyst from the third reaction zone into the Fischer-Tropsch synthesis reactor 104. The reaction conditions of the first reaction zone group include: temperature 150~230℃, hydrogen-carbon molar ratio of activation gas (5~30):1, and catalyst residence time 1~4h; The reaction conditions for the second reaction zone group include: temperature 200~270℃, hydrogen-carbon molar ratio of activation gas (10~50):1, and catalyst residence time 2~8h; The reaction conditions for the third reaction zone include: a temperature of 250~300℃, a hydrogen-to-carbon molar ratio of (30~200):1 for the activation gas, and a catalyst residence time of 8~16h.

[0087] In a preferred embodiment, the reaction conditions of the first reaction zone group include: temperature 170~200℃, hydrogen-carbon molar ratio of activation gas of (10~20):1, and catalyst residence time of 2~3h; The reaction conditions for the second reaction zone group include: temperature 220~250℃, hydrogen-carbon molar ratio of activation gas (20~30):1, and catalyst residence time 4~6h; The reaction conditions for the third reaction zone include: a temperature of 260~280℃, a hydrogen-to-carbon molar ratio of (40~60):1 for the activation gas, and a catalyst residence time of 8~12h.

[0088] In a further preferred embodiment, the reaction conditions of the first reaction zone group include: a temperature of 180°C, an activation gas hydrogen-carbon molar ratio of 10:1, and a catalyst residence time of 1 hour. The reaction conditions for the second reaction zone group include: temperature 220℃, hydrogen-carbon molar ratio of activation gas 20:1, and catalyst residence time 4h; The reaction conditions for the third reaction zone include: a temperature of 270°C, an activation gas hydrogen-to-carbon molar ratio of 50:1, and a catalyst residence time of 8 hours.

[0089] In one embodiment, each reaction zone group contains at least one activated reaction zone.

[0090] In one embodiment, the flow rate of the activated catalyst can be flexibly adjusted according to actual usage. For example, the flow rate of the activated catalyst described in this disclosure is 50~100 kg / h, preferably 70~90 kg / h. In this embodiment, the activated catalyst obtained from the continuous activation reactor 103 is a continuous low-flow stream, which can be directly added to the Fischer-Tropsch synthesis reactor 104 without premixing the catalyst slurry, thus avoiding localized temperature hotspots. This eliminates the need for an activated catalyst buffer tank and a preparation tank, enabling continuous feeding of fresh activated catalyst. Continuous operation of the Fischer-Tropsch synthesis system is achieved through continuous feeding of fresh catalyst and continuous discharge of deactivated catalyst.

[0091] In one embodiment, the method further includes contacting Fischer-Tropsch syngas b and activated catalyst c in Fischer-Tropsch synthesis reactor 104 to carry out Fischer-Tropsch synthesis reaction.

[0092] In one embodiment, the Fischer-Tropsch synthesis reaction is carried out at a temperature of 250-300°C and a pressure of 2.5-3.0 MPa.

[0093] In one embodiment, the apparent gas velocity inside the Fischer-Tropsch synthesis reactor 104 is 0.1~0.6 m / s, and the hydrogen-to-carbon ratio at the inlet of the Fischer-Tropsch synthesis reactor 104 is 2~5.

[0094] In a preferred embodiment, to further improve the reaction efficiency of the Fischer-Tropsch synthesis reaction, the apparent gas velocity and the hydrogen-to-carbon ratio at the inlet can be optimized. For example, the apparent gas velocity inside the Fischer-Tropsch synthesis reactor 104 can be any one or any two of 0.2 m / s, 0.3 m / s, 0.4 m / s, and 0.5 m / s; the hydrogen-to-carbon ratio at the inlet of the Fischer-Tropsch synthesis reactor 104 can be any one or any two of 2.5, 3.0, 3.5, 4.0, and 4.5.

[0095] In one embodiment, both the fresh catalyst and the activated catalyst described in this disclosure are conventional Fischer-Tropsch iron-based catalysts in the art, and this application does not make any special requirements.

[0096] In one embodiment, the bulk density of the catalyst in the Fischer-Tropsch synthesis reactor 104 is 0.6~1.5 g / cm³. 3 The average diameter of the particles is 60~120μm, and more specifically, the volume fraction of catalyst particles with an average diameter of less than 20μm is <10%.

[0097] In one embodiment, a first slag wax is continuously discharged from the lower part of the Fischer-Tropsch synthesis reactor 104.

[0098] In one embodiment, the product yield within the Fischer-Tropsch synthesis reactor 104 is kept stable by adding an activating catalyst and evacuating the deactivated catalyst.

[0099] In one embodiment, a first synthetic wax n is continuously discharged from the middle of the Fischer-Tropsch synthesis reactor 104.

[0100] In one embodiment, Fischer-Tropsch tail gas e is continuously discharged from the top of the Fischer-Tropsch synthesis reactor 104, and activation tail gas d is discharged from the top of the continuous activation reactor 103. The Fischer-Tropsch tail gas e and the activation tail gas d are then mixed to form synthesis tail gas f. In this embodiment, since the amount of activation tail gas d is smaller than that of Fischer-Tropsch tail gas e, mixing the two has almost no effect on the composition of the gas phase; therefore, they can be mixed. The flow rate ratio of activation tail gas d to Fischer-Tropsch tail gas e is (0.01~0.05):1. Because the amount of activation gas used is small, the circulating operation can be changed to a single-pass flow, eliminating the need for a catalyst activation circulating gas compressor, optimizing the process flow, and reducing investment and operating costs.

[0101] In one embodiment, the synthesis tail gas f is passed into a gas-liquid-solid separation device 105 to obtain oil, first circulating tail gas g, and second circulating tail gas h.

[0102] In one embodiment, the first cycle tail gas g is treated by the tail gas decarbonization device 106 to obtain carbon dioxide j and decarbonized tail gas i. The tail gas after mixing the second cycle tail gas h and the decarbonized tail gas i is pressurized by the recycle gas compressor 107 and then mixed with Fischer-Tropsch synthesis gas b.

[0103] In one embodiment, the oil is separated by an oil recovery device 108 to obtain light oil k, heavy oil l, synthetic water m, and second residue wax p.

[0104] In one embodiment, the first slag wax o and the second slag wax p are mixed and then separated by a liquid-solid treatment device 109 to obtain a second synthetic wax q and solid waste s; the second synthetic wax q and the first synthetic wax n are mixed to form a synthetic wax product r.

[0105] In one embodiment, the liquid-solid treatment device 109 is a conventional choice in the art, and this application does not make any special requirements. For example, the liquid-solid treatment device 109 is a magnetic separator.

[0106] In one embodiment, the solid waste s includes a deactivated catalyst, wherein the mass of the deactivated catalyst is consistent with the total amount of activated catalyst entering the Fischer-Tropsch synthesis reactor 104.

[0107] In one implementation, such as Figure 2 As shown, the Fischer-Tropsch synthesis method with continuously activated Fischer-Tropsch catalyst includes: Fresh catalyst from the first feeding tank 101 is continuously fed into the continuous activation reactor 103; when the amount of fresh catalyst in the first feeding tank 101 drops below 20% by volume, the process switches to the second feeding tank 102; when the amount of fresh catalyst in the second feeding tank 102 drops below 20% by volume, the process switches back to the first feeding tank 101. Fresh catalyst is fed into the dilute phase section 5 of the continuous activation reactor 103 through the catalyst inlet 10, and then enters each activation reaction zone under the action of gravity and partition plates 7. Activation gas is fed into the lower head 2 through the activation gas inlet 13, and then distributed by the gas distributor 8 before entering each activation reaction zone. The reaction temperature of each activation reaction zone is adjusted by the temperature control device, and the fresh catalyst is activated by contacting the activation gas in each activation reaction zone to obtain activated catalyst and activated tail gas. The Fischer-Tropsch synthesis gas b and the activated catalyst c are brought into contact in the Fischer-Tropsch synthesis reactor 104 to carry out the Fischer-Tropsch synthesis reaction; the reaction temperature of the Fischer-Tropsch synthesis reaction is 250~300℃, the reaction pressure is 2.5~3.0MPa, the apparent gas velocity inside the Fischer-Tropsch synthesis reactor 104 is 0.1~0.6m / s, and the hydrogen-to-carbon ratio at the inlet of the Fischer-Tropsch synthesis reactor 104 is 2~5; The activated tail gas d enters the cyclone separator upwards for separation, and then mixes with the Fischer-Tropsch tail gas e at the activated tail gas outlet 9 to form the synthesis tail gas f. The synthesis tail gas f is passed into the gas-liquid-solid separation device 105 to obtain oil, the first cycle tail gas g, and the second cycle tail gas h. The first cycle tail gas g is treated by the tail gas decarbonization device 106 to obtain carbon dioxide j and decarbonized tail gas i. The tail gas after mixing the second cycle tail gas h and the decarbonized tail gas i is pressurized by the circulating gas compressor 107 and then mixed with the Fischer-Tropsch synthesis gas b. The oil is separated by the oil recovery device 108 to obtain light oil k, heavy oil l, synthetic water m, and the second residue wax p. The first residue wax o and the second residue wax p are mixed and then separated by the liquid-solid treatment device 109 to obtain the second synthetic wax q and solid waste s. The second synthetic wax q and the first synthetic wax n are mixed to form the synthetic wax product r.

[0108] The present disclosure will be further illustrated by the following examples, but the present disclosure is not limited thereto.

[0109] Example 1 use Figure 1 The continuous activation reactor 103 shown is used for catalyst activation. The diameter of the dense phase section 3 of the continuous activation reactor 103 is 1.2m, the height-to-diameter ratio of the dense phase section 3 is 5, the included angle of the expansion section 4 is 45°, the length-to-diameter ratio of the dilute phase section 5 is 3, and the reactor is divided into 24 sections by long and short partitions, with the short partitions extending 2.5m upwards from the distributor. The area where the fresh catalyst inlet 10 is located is designated as the first activation reaction zone, and the zones are labeled according to the catalyst flow direction, sequentially as the second, third...twentieth activation reaction zones. Among them, the first to eighth activation reaction zones are the first reaction zone group, the ninth to fourteenth activation reaction zones are the second reaction zone group, and the fifteenth to twenty-fourth activation reaction zones are the third reaction zone group. like Figure 2 The Fischer-Tropsch synthesis method for continuously activated Fischer-Tropsch catalysts includes: The 6 tons of fresh catalyst in the first feeding tank 101 is heated to 160°C and transferred to the continuous activation reactor 103 at a mass flow rate of 80 kg / h. Fresh catalyst is introduced into each activation reaction zone of the continuous activation reactor 103 through the catalyst feed inlet 10 to contact with the activation gas for activation treatment, resulting in activated catalyst and activation tail gas; wherein, the continuous activation reactor 103 operates at a pressure of 3.2 MPa, and the apparent gas velocity in each activation reaction zone is 0.4 m / s; the reaction conditions in each activation reaction zone include: The temperature of the first activation reaction zone is 180℃, the hydrogen-to-carbon ratio is 10:1, and the residence time of the catalyst is 1 hour. The temperature of the second activation reaction zone is 190℃, the hydrogen-to-carbon ratio is 10:1, and the residence time of the catalyst is 1 hour. The temperature of the third activation reaction zone is 200℃, the hydrogen-to-carbon ratio is 10:1, and the residence time of the catalyst is 1h. The temperature of the fourth activation reaction zone is 210℃, the hydrogen-to-carbon ratio is 10:1, and the residence time of the catalyst is 1h. The temperature of the activation reaction zones 05-08 is 220℃, the hydrogen-to-carbon ratio is 10:1, and the residence time of the catalyst is 4h. The temperature of the 09th activation reaction zone is 230℃, the hydrogen-to-carbon ratio is 20:1, and the residence time of the catalyst is 4h. The temperature of the 10th activation reaction zone is 240℃, the hydrogen-to-carbon ratio is 20:1, and the residence time of the catalyst is 4h. The temperature of the 11th activation reaction zone is 250℃, the hydrogen-to-carbon ratio is 20:1, and the residence time of the catalyst is 4h. The temperature of the 12th activation reaction zone is 255℃, the hydrogen-to-carbon ratio is 30:1, and the residence time of the catalyst is 4h. The temperature of the 13th activation reaction zone is 260℃, the hydrogen-to-carbon ratio is 30:1, and the residence time of the catalyst is 4h. The temperature of the 14th activation reaction zone is 265℃, the hydrogen-to-carbon ratio is 30:1, and the residence time of the catalyst is 4h. The temperature of the 15th to 24th activation reaction zones is 270℃, the hydrogen-to-carbon ratio is 50:1, and the residence time of the catalyst is 8h. Fischer-Tropsch synthesis gas (b) and activated catalyst (c) are brought into contact in Fischer-Tropsch synthesis reactor 104 to carry out a Fischer-Tropsch synthesis reaction. The reaction temperature is 270°C, the reaction pressure is 2.85 MPa, the apparent gas velocity inside Fischer-Tropsch synthesis reactor 104 is 0.3 m / s, the hydrogen-to-carbon ratio at the inlet of Fischer-Tropsch synthesis reactor 104 is 3.8, the catalyst stockpile is 48 t, the activated catalyst is added at a mass flow rate of 80 kg / h, and the bed temperature rise is 0.3°C. Deactivated catalyst slurry is continuously discharged from Fischer-Tropsch synthesis reactor 104 at a mass flow rate of 1000 kg / h (catalyst solids content 8%), while the liquid level is maintained by controlling the amount of synthetic wax discharged from the internal filter of Fischer-Tropsch synthesis reactor 104.

[0110] The activated tail gas d enters the cyclone separator upwards for separation, and then mixes with the Fischer-Tropsch tail gas e at the activated tail gas outlet 9 to form the synthesis tail gas f. The synthesis tail gas f is passed into the gas-liquid-solid separation device 105 to obtain oil, the first cycle tail gas g, and the second cycle tail gas h. The first cycle tail gas g is treated by the tail gas decarbonization device 106 to obtain carbon dioxide j and decarbonized tail gas i. The tail gas after mixing the second cycle tail gas h and the decarbonized tail gas i is pressurized by the circulating gas compressor 107 and then mixed with the Fischer-Tropsch synthesis gas b. The oil is separated by the oil recovery device 108 to obtain light oil k, heavy oil l, synthetic water m, and the second residue wax p. The first residue wax o and the second residue wax p are mixed and then separated by the liquid-solid treatment device 109 to obtain the second synthetic wax q and solid waste s. The second synthetic wax q and the first synthetic wax n are mixed to form the synthetic wax product r.

[0111] During implementation, no significant temperature rise was observed within reactor 104 of the Fischer-Tropsch synthesis reactor. After stable operation, the overall catalyst performance is as follows: CO conversion rate 97.6%, CO2 selectivity 14.6%, CH4 selectivity 2.2%, and gas consumption per ton of oil / gas production 5072 Nm³. 3 The catalyst solids content in the synthetic wax product was measured to be 12 ppm.

[0112] Example 2 The Fischer-Tropsch synthesis method using the continuously activated Fischer-Tropsch catalyst is the same as in Example 1, except that the flow rate of the activated catalyst is 82 kg / h.

[0113] During implementation, no significant temperature rise was observed within reactor 104 of the Fischer-Tropsch synthesis reactor. After stable operation, the overall catalyst performance is as follows: CO conversion rate 97.8%, CO2 selectivity 14.3%, CH4 selectivity 2.3%, and gas consumption per ton of oil / gas production 5026 Nm³. 3 The catalyst solids content in the synthetic wax product was measured to be 11 ppm.

[0114] Example 3 The Fischer-Tropsch synthesis method for continuously activated Fischer-Tropsch catalyst is the same as in Example 1, except that the conditions for all activation reaction zones are the same, including: temperature 275°C, hydrogen-carbon molar ratio of activation gas 50:1, and residence time of catalyst in each activation reaction zone 1 h.

[0115] During implementation, no significant temperature rise was observed within reactor 104 of the Fischer-Tropsch synthesis reactor. After stable operation, the overall catalyst performance is as follows: CO conversion rate 97.5%, CO2 selectivity 14.8%, CH4 selectivity 2.2%, and gas consumption per ton of oil / m³ is 5089 Nm³. 3 The catalyst solids content in the synthetic wax product was measured to be 14 ppm.

[0116] Example 4 The Fischer-Tropsch synthesis method using the continuously activated Fischer-Tropsch synthesis catalyst is the same as in Example 1, except that each Fischer-Tropsch synthesis reactor 104 is equipped with a continuous activation reactor 103 with a capacity of 2.5t.

[0117] During implementation, no significant temperature rise was observed within reactor 104 of the Fischer-Tropsch synthesis reactor. After stable operation, the overall catalyst performance is as follows: CO conversion rate 97.2%, CO2 selectivity 15.1%, CH4 selectivity 2.5%, and gas consumption per ton of oil / gas production 5122 Nm³. 3 The catalyst solids content in the synthetic wax product was measured to be 19 ppm.

[0118] Example 5 The Fischer-Tropsch synthesis method for continuously activated Fischer-Tropsch catalyst is the same as in Example 1, except that the reactor is divided into 8 zones by long and short partitions, wherein the 1st to 3rd activation reaction zones are the first reaction zone group, the 4th to 6th activation reaction zones are the second reaction zone group, and the 7th to 8th activation reaction zones are the third reaction zone group. The temperature of the first activation reaction zone is 200℃, the hydrogen-to-carbon ratio is 10:1, and the residence time of the catalyst is 1h. The temperature of the second activation reaction zone is 210℃, the hydrogen-to-carbon ratio is 10:1, and the residence time of the catalyst is 1h. The temperature of the third activation reaction zone is 220℃, the hydrogen-to-carbon ratio is 10:1, and the residence time of the catalyst is 4h. The temperature of the fourth activation reaction zone is 255℃, the hydrogen-to-carbon ratio is 30:1, and the residence time of the catalyst is 4h. The temperature of the 05 activation reaction zone is 260℃, the hydrogen-to-carbon ratio is 30:1, and the residence time of the catalyst is 4h. The temperature of the 06th activation reaction zone is 265℃, the hydrogen-to-carbon ratio is 30:1, and the residence time of the catalyst is 4h. The temperature of the activation reaction zone 07-08 is 270℃, the hydrogen-to-carbon ratio is 50:1, and the residence time of the catalyst is 8h.

[0119] During implementation, no significant temperature rise was observed within reactor 104 of the Fischer-Tropsch synthesis reactor. After stable operation, the overall catalyst performance is as follows: CO conversion rate 97.3%, CO2 selectivity 14.9%, CH4 selectivity 2.4%, and gas consumption per ton of oil / m³ is 5108 Nm³. 3 The catalyst solids content in the synthetic wax product was measured to be 11 ppm.

[0120] Example 6 The Fischer-Tropsch synthesis method for continuously activated Fischer-Tropsch catalyst is the same as in Example 1, except that the hydrogen-to-carbon ratio of the activation gas entering each activation reaction zone is 20:1.

[0121] During implementation, no significant temperature rise was observed within reactor 104 of the Fischer-Tropsch synthesis reactor. After stable operation, the overall catalyst performance is as follows: CO conversion rate 96.9%, CO2 selectivity 15.3%, CH4 selectivity 2.4%, and gas consumption per ton of oil / gas consumption 5176 Nm³. 3 The catalyst solids content in the synthetic wax product was measured to be 17 ppm.

[0122] Comparative Example 1 A traditional slurry-bed activation reactor with a reactor cylinder diameter of 4.5m was used. One conventional Fischer-Tropsch catalyst slurry-bed activation reactor was employed to activate 12t of catalyst over a 3-day activation cycle. Since the activation tail gas volume was 21% of the Fischer-Tropsch tail gas volume, it was circulated through an activation circulation compressor to ensure stable operation. After catalyst activation in the slurry-bed activation reactor, 75t of slurry (8% solids content, i.e., 6t of deactivated catalyst) was discharged from Fischer-Tropsch synthesis reactor 104 in a single operation. Subsequently, 12t of fresh activated catalyst particles were transferred to two Fischer-Tropsch synthesis reactors within 0.5 hours. During the process, a large amount of deactivated catalyst was first discharged from Fischer-Tropsch synthesis reactor 104, followed by a short-term transfer of a large amount of fresh activated catalyst. The liquid level and temperature fluctuations within the reactor were significant, with the bed temperature rising by 3.6℃.

[0123] During implementation, a significant temperature rise was observed within reactor 104 of the Fischer-Tropsch synthesis reactor. After stable operation, the overall catalyst performance is as follows: CO conversion rate 94.7%, CO2 selectivity 17.8%, CH4 selectivity 3.4%, and gas consumption per ton of oil / gas consumption 5486 Nm³. 3 The catalyst solids content in the synthetic wax product was measured to be 48 ppm.

[0124] A comparison of the data from Examples 1-6 with Comparative Example 1 shows that the system and method of this disclosure achieve continuous catalyst activation. The catalyst content in the continuous activation reactor is relatively small, thus reducing the reactor volume. Therefore, the production of activation tail gas is less than that of Fischer-Tropsch tail gas, eliminating the need for a recirculating compressor. Furthermore, there is no significant temperature rise within the Fischer-Tropsch synthesis reactor, indicating good catalyst performance and improved Fischer-Tropsch synthesis reaction efficiency. A comparison of the data from Examples 1, 3, and 6 shows that independent control of the parameters of each internal chamber in the continuous activation reactor enhances catalyst activation, thereby increasing CO conversion while reducing the selectivity of CO2 and CH4. A comparison of the data from Examples 1 and 5 shows that having 12-24 activation reaction zones increases CO conversion while reducing the selectivity of CO2 and CH4.

[0125] The preferred embodiments of the present disclosure have been described in detail above with reference to the accompanying drawings. However, the present disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

[0126] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, this disclosure will not describe the various possible combinations separately.

[0127] Furthermore, various different embodiments of this disclosure can be combined in any way, as long as they do not violate the spirit of this disclosure, they should also be regarded as the content disclosed in this disclosure.

Claims

1. A Fischer-Tropsch synthesis system with continuously activated Fischer-Tropsch catalyst, characterized in that, The Fischer-Tropsch synthesis system includes a catalyst feeder, a continuous activation reactor (103), a Fischer-Tropsch synthesis reactor (104), and a gas-liquid-solid separation unit (105). The inlet of the catalyst feed tank is connected to a fresh catalyst source, and the outlet of the catalyst feed tank is connected to the catalyst inlet (10) of the continuous activation reactor (103); the catalyst outlet (11) of the continuous activation reactor (103) is connected to the activation catalyst inlet of the Fischer-Tropsch synthesis reactor (104); the activation gas inlet of the continuous activation reactor (103) is connected to an activation gas source, and the activation tail gas outlet (9) of the continuous activation reactor (103) and the Fischer-Tropsch tail gas outlet of the Fischer-Tropsch synthesis reactor (104) are respectively connected to the synthesis tail gas of the gas-liquid-solid separation device (105); The continuous activation reactor (103) includes a shell (1), partitions (7), a gas distributor (8), and a temperature control device; The internal chamber of the shell (1) includes a lower end cap (2), a dense phase section (3), an enlarged section (4), a dilute phase section (5), and an upper end cap (6) that are integrally arranged from bottom to top. The activated tail gas outlet (9) is located at the top of the upper end cap (6), and the catalyst inlet (10) and the catalyst outlet (11) are located at the bottom of the dense phase section (3). The gas distributor (8) is located at the lower part of the dense phase section (3) so that the activation gas can enter the dense phase section (3) through the gas distributor (8); the partition plate (7) is arranged along the axial direction of the housing (1) in the internal cavity of the housing (1) and divides the internal cavity into multiple activation reaction zones; the bottom of each of the multiple activation reaction zones is provided with an activation gas inlet (13), which is used to communicate with the activation gas source; The temperature control devices are respectively installed in multiple activation reaction zones to control the temperature of each zone.

2. The Fischer-Tropsch synthesis system according to claim 1, characterized in that, The number of activated reaction zones is four or more, preferably 12 to 24.

3. The Fischer-Tropsch synthesis system according to claim 1, characterized in that, The partition plate (7) extends radially along the housing (1) to the inner wall of the housing (1); The partition (7) includes short partitions (7B) and long partitions (7A) spaced apart. The top of the short partition (7B) is located at 1 / 2 to 3 / 4 of the height of the dense phase section (3); The top of the long partition (7A) is located at 1 / 3 to 2 / 3 of the height of the rare phase segment (5).

4. The Fischer-Tropsch synthesis system according to claim 3, characterized in that, A partition connection port (12) is provided at the lower part of the long partition plate (7A) so that the catalyst can travel in the flow direction between two adjacent activation reaction zones.

5. The Fischer-Tropsch synthesis system according to claim 1, characterized in that, The ratio of the height of the lower end cap (2) to the diameter of the dense phase section (3) is (0.2~1):1; The ratio of the height of the dense phase segment (3) to the diameter of the dense phase segment (3) is (2~7):1; The ratio of the diameter of the dilute phase segment (5) to the diameter of the dense phase segment (3) is (1.5~6):1; The ratio of the height of the dilute phase segment (5) to the diameter of the dilute phase segment (5) is (1.5~3):

1.

6. The Fischer-Tropsch synthesis system according to claim 1, characterized in that, A gas-solid separation device is provided at the upper part of the dilute phase section (5) for separating catalyst particles in the activated tail gas; The gas-solid separation device includes a cyclone separator.

7. A method for Fischer-Tropsch synthesis using a continuously activated Fischer-Tropsch catalyst, characterized in that, The Fischer-Tropsch synthesis method includes: Fresh catalyst in the catalyst feeding tank is continuously fed into the continuous activation reactor (103) according to any one of claims 1 to 6 through the catalyst feed inlet (10), and enters multiple activation reaction zones to contact with activation gas for activation treatment, thereby obtaining activated catalyst and activated tail gas; The activated catalyst is continuously fed into the Fischer-Tropsch synthesis reactor (104) to carry out the Fischer-Tropsch synthesis reaction, and Fischer-Tropsch tail gas, first synthetic wax and first slag wax are obtained; the activated tail gas and the Fischer-Tropsch tail gas are separated by a gas-liquid-solid separator (105) to obtain carbon dioxide, light oil, heavy oil and synthetic water.

8. The Fischer-Tropsch synthesis method according to claim 7, characterized in that, The method further includes separating the first slag wax using a solid-liquid separation device to obtain a second synthetic wax and solid waste; and mixing the first synthetic wax and the second synthetic wax to obtain a synthetic wax product.

9. The Fischer-Tropsch synthesis method according to claim 7, characterized in that, The multiple activation reaction zones in the continuous activation reactor (103) are divided into a first reaction zone group, a second reaction zone group, and a third reaction zone group; The Fischer-Tropsch synthesis method further includes activating the fresh catalyst sequentially through a first reaction zone, a second reaction zone, and a third reaction zone, and then introducing the activated catalyst from the third reaction zone into the Fischer-Tropsch synthesis reactor (104). The reaction conditions of the first reaction zone group include: temperature 150~230℃, hydrogen-carbon molar ratio of activation gas (5~30):1, and catalyst residence time 1~4h; The reaction conditions for the second reaction zone group include: temperature 200~270℃, hydrogen-carbon molar ratio of activation gas (10~50):1, and catalyst residence time 2~8h; The reaction conditions for the third reaction zone include: a temperature of 250~300℃, a hydrogen-to-carbon molar ratio of (30~200):1 for the activation gas, and a catalyst residence time of 8~16h.

10. The Fischer-Tropsch synthesis method according to claim 7, characterized in that, The catalyst feeding tank includes a first feeding tank (101) and a second feeding tank (102); The Fischer-Tropsch synthesis method also includes: The fresh catalyst in the first feeding tank (101) is continuously fed into the continuous activation reactor (103); When the amount of fresh catalyst in the first feeding tank (101) is below the set amount, switch to the second feeding tank (102). When the amount of fresh catalyst in the second feeding tank (102) is below the set amount, switch to the first feeding tank (101). The ratio of the set storage capacity to the storage capacity of the first feeding tank (101) is (0.15~0.25):1; The ratio of the set storage capacity to the storage capacity of the second feeding tank (102) is (0.15~0.25):1.

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