A fischer-tropsch synthesis reactor, reaction system and method suitable for stable production

Abstract

The application discloses a Fischer-Tropsch synthesis reactor, a reaction system and a method suitable for stable production, and the Fischer-Tropsch synthesis reactor comprises a reactor cylinder and an inner member arranged in the reactor cylinder, and the inner member comprises a gas distributor and a catalyst activation unit; the gas distributor is arranged at the bottom of the reactor cylinder, so that the inlet gas for performing the Fischer-Tropsch synthesis reaction is uniformly distributed in the Fischer-Tropsch synthesis reactor; and the catalyst activation unit is arranged above the gas distributor and comprises a plurality of cyclone separators which are connected in series along the flow direction of the catalyst in the activation process. The application can realize continuous activation of the catalyst in the Fischer-Tropsch synthesis and stable performance of the Fischer-Tropsch synthesis reaction.

Description

Technical Field

[0001] This invention belongs to the field of Fischer-Tropsch synthesis technology, and relates to a Fischer-Tropsch synthesis reactor that integrates a catalyst activation unit, specifically to a Fischer-Tropsch synthesis reactor, reaction system and method suitable for stable production. Background Technology

[0002] my country's energy structure is characterized by abundant coal, scarce oil, and limited natural gas. Therefore, converting raw coal into high-quality liquid fuels and high-value-added chemicals has always been a focus of attention. Coal indirect liquefaction (CLD) is a process that uses coal as raw material, transforming it into clean syngas through gasification and purification, and then converting it into large-molecule hydrocarbons and alcohols via Fischer-Tropsch synthesis. It is an important pathway to achieve the rational, efficient, and clean utilization of coal.

[0003] The Fischer-Tropsch synthesis reaction is the core part of the indirect coal liquefaction process. It is the process of synthesizing hydrocarbon products from syngas (H2+CO) in the presence of metal catalysts such as iron, cobalt, and ruthenium.

[0004] For iron-based catalysts used in industrial applications of Fischer-Tropsch synthesis, due to requirements of catalyst preparation and molding processes, storage and transportation, and catalyst feeding processes, the iron is in an oxidized state when it leaves the factory. It is necessary to activate the catalyst with reducing gases such as hydrogen, carbon monoxide, and low-carbon olefins before the Fischer-Tropsch synthesis reaction to form a stable active phase for the Fischer-Tropsch synthesis reaction.

[0005] The activation reaction process is the conversion of the iron oxide component, which plays a major catalytic role, into elemental iron and iron carbide components. Existing catalyst activation methods include single-stage activation using the same gas and temperature throughout the entire process, and methods that divide the activation process into two or more stages, using different activation gases and temperatures in different stages. For example, CN112569984A describes the preparation of a supported θ-iron carbide composition by first reducing the precursor with hydrogen, then reducing it with syngas; CN112569983A describes the preparation of a supported X-iron carbide composition by first reducing the precursor with hydrogen, then passivating it with oxygen, and then reducing it with syngas.

[0006] For reaction processes that require two or more activation stages, if a single reactor is used for gas switching and replacement, it will take a long time and affect the yield. If two or more reactors are used, the investment in the equipment will be large, and there will be a problem of complicated catalyst transfer between reactors.

[0007] Furthermore, current industrial activation operations are performed in a batch-by-batch manner, meaning that the catalyst to be activated cannot be continuously fed, nor can the activated catalyst be continuously produced. Batch activation leads to empty reactor beds and insufficient utilization; it also requires frequent adjustments to parameters such as pressure and flow rate, making the operation complex and causing inconsistencies in the performance of catalysts between batches; and it also requires frequent opening and closing of some valves, reducing efficiency and increasing the likelihood of malfunctions.

[0008] In addition, due to the intermittent activation of the catalyst, the catalyst replacement in the Fischer-Tropsch synthesis reactor is also intermittent. That is, a portion of the catalyst is unloaded at intervals and then a batch of activated catalyst is added. For example, the catalyst replacement amount per batch in the current industrial Fischer-Tropsch synthesis reactor is about 10%, which lasts for 2-3 hours. The replacement process requires adjustment of process parameters to coordinate the replacement, which has a significant impact on the stability of the continuous operation of the Fischer-Tropsch synthesis unit and ultimately affects its economic efficiency.

[0009] Finally, the catalyst activation reactor currently used in industrial applications is a separate reactor with heating and heat recovery systems, independent of the Fischer-Tropsch synthesis reactor. If two or more reactors are used, the investment in the equipment will increase exponentially, and there will be a problem of complex catalyst transfer processes between reactors. Summary of the Invention

[0010] The purpose of this invention is to provide a Fischer-Tropsch synthesis reactor, reaction system, and method suitable for stable production, which integrates a catalyst activation reactor and a Fischer-Tropsch synthesis reactor to achieve continuous catalyst activation and stable Fischer-Tropsch synthesis reaction, eliminate the catalyst transfer process between reactors, and meet the requirements of multi-stage activation process for gas type and temperature changes.

[0011] To achieve one aspect of the above-mentioned objectives, the technical solution adopted by the present invention is as follows:

[0012] A Fischer-Tropsch synthesis reactor suitable for stable production includes a reactor shell and internal components disposed within the reactor shell. The internal components include a gas distributor and a catalyst activation unit. The gas distributor is disposed at the bottom of the reactor shell to ensure uniform distribution of the feed gas for the Fischer-Tropsch synthesis reaction within the reactor. The catalyst activation unit is disposed above the gas distributor and includes multiple cyclone separators connected in series along the catalyst flow direction during activation. The inlet of each cyclone separator is used to feed the catalyst to be activated and the activation gas. The outlet at the top of each cyclone separator is used to discharge the activation tail gas. The outlet at the bottom of each cyclone separator is used to discharge the separated catalyst after reaction with the activation gas and to transport the separated catalyst to the inlet of the next-stage cyclone separator connected in series. The catalyst activation unit is used to activate the catalyst within the sequentially connected cyclone separators and continuously feed the activated catalyst through the outlet of the final-stage cyclone separator into the Fischer-Tropsch synthesis reactor to catalyze the Fischer-Tropsch synthesis reaction.

[0013] According to the Fischer-Tropsch synthesis reactor of the present invention, preferably, the Fischer-Tropsch synthesis reactor further includes an inlet pipe and an outlet pipe, one end of the inlet pipe being connected to an external gas source and the other end being connected to the feed inlet of each cyclone separator to deliver activation gas to the cyclone separator; one end of the outlet pipe being connected to an external tail gas treatment unit and the other end being connected to the outlet of each cyclone separator to deliver the activation tail gas to the external tail gas treatment unit for recycling.

[0014] According to the Fischer-Tropsch synthesis reactor of the present invention, preferably, the outlet of the upper-stage cyclone separator in the series-connected cyclone separators is positioned higher than the inlet of the lower-stage cyclone separator.

[0015] According to the Fischer-Tropsch synthesis reactor of the present invention, preferably, the cyclone separator of the catalyst activation unit is arranged along the inner wall of the reactor cylinder.

[0016] According to the Fischer-Tropsch synthesis reactor of the present invention, preferably, the Fischer-Tropsch synthesis reactor is a slurry-bed Fischer-Tropsch synthesis reactor; at least some or all of the cyclone separators connected in series are located in the slurry of the slurry-bed Fischer-Tropsch synthesis reactor.

[0017] According to the Fischer-Tropsch synthesis reactor of the present invention, preferably, the Fischer-Tropsch synthesis reactor is a gas-solid fluidized bed Fischer-Tropsch reactor; preferably, at least some or all of the cyclone separators connected in series are located within the gas-solid phase bed of the gas-solid fluidized bed Fischer-Tropsch synthesis reactor.

[0018] In another aspect of achieving the above-mentioned objective, the present invention also provides a reaction system for Fischer-Tropsch synthesis, the reaction system comprising the above-described Fischer-Tropsch synthesis reactor, a gas source for supplying activation gas, and a tail gas treatment unit for treating the activation tail gas.

[0019] According to the reaction system of the present invention, in one embodiment, the gas source is one or more, the inlet pipe is one or more sets, each set of inlet pipes connected to the same gas source is connected to a set of cyclone separators, and each set of cyclone separators is connected to a set of outlet pipes, so that the activation gas from the same gas source enters the same set of cyclone separators and is sent out through the same set of outlet pipes.

[0020] Preferably, the gas source includes one or more of a hydrogen source, a CO source, a nitrogen source, an oxygen source, and a mixed gas source formed by mixing at least two of them.

[0021] According to the reaction system of the present invention, in one embodiment, the gas source includes a hydrogen source and a CO source; the gas inlet pipe includes a first set of gas inlet pipes and a second set of gas inlet pipes located downstream of the first gas inlet pipe; the gas outlet pipe includes a first set of gas outlet pipes and a second set of gas outlet pipes.

[0022] The first set of inlet pipes is connected to the hydrogen source and is used to send hydrogen as the first activation gas into the first set of cyclone separators connected to the first set of inlet pipes; the first set of outlet pipes is used to deliver the first activation tail gas from the first set of cyclone separators.

[0023] The second set of inlet pipes is connected to the hydrogen source and the CO source, and is used to send the mixture of hydrogen and CO as the second activation gas into the second set of cyclone separators connected to the second set of inlet pipes; the second set of outlet pipes is used to deliver the second activation tail gas from the second set of cyclone separators.

[0024] The exhaust gas treatment unit includes a first exhaust gas treatment unit and a second exhaust gas treatment unit; wherein, the first exhaust gas treatment unit is used to remove water from the first activated exhaust gas and to circulate the treated first activated exhaust gas as the first activated gas into the first set of intake pipes.

[0025] The second exhaust gas treatment unit is used to remove water, carbon dioxide and organic matter from the second activated exhaust gas, and to circulate part of the treated second activated exhaust gas into the second set of intake pipes as second activation gas, and part as venting gas.

[0026] To achieve another aspect of the above-mentioned objective, the present invention also provides a method for Fischer-Tropsch synthesis using the above-mentioned reaction system, wherein, during the Fischer-Tropsch reaction, a catalyst to be activated is continuously fed into the catalyst activation unit, and the activated catalyst is continuously replenished into the Fischer-Tropsch synthesis reactor using the catalyst activation unit, while the catalyst is continuously discharged from the Fischer-Tropsch synthesis reactor to maintain a stable total amount of catalyst in the Fischer-Tropsch synthesis reactor.

[0027] Compared with the prior art, the present invention has the following advantages:

[0028] 1) The catalyst activation of the present invention is continuous, which can reduce the equipment volume of the catalyst activation unit. As a result, it is advantageous to integrate it into the Fischer-Tropsch synthesis reactor. Compared with the current two-unit system of catalyst activation reactor and Fischer-Tropsch synthesis reactor, which usually results in large investment and complicated operation, this device combines the two into one reactor, eliminating the need to build a separate activation reactor.

[0029] 2) This invention solves the problem of intermittent activation process in existing gas-solid fluidized bed reactors, realizes continuous catalyst feeding and discharging, eliminates idle time such as cooling and waiting in intermittent activation reactors, and improves reaction stability and efficiency;

[0030] 3) The catalyst activation unit of the present invention consists of multiple cyclone separators connected in series, which allows for the grouping of different numbers of cyclone separators to receive gas, meeting the complex needs of different types of gas intake. The operation is flexible, such as dividing it into three sections (or three groups), with hydrogen entering the upper section of the cyclone separator, oxygen-containing gas entering the middle section, and a mixture of hydrogen and CO entering the lower section; or dividing it into two sections, with hydrogen entering the upper section and a mixture of hydrogen and CO entering the lower section; or all sections being one section, with hydrogen or a mixture of hydrogen and CO entering all sections.

[0031] 4) After activation, the catalyst of this invention is continuously fed into the Fischer-Tropsch synthesis reactor, which can simultaneously solve the problem that the catalyst in the Fischer-Tropsch synthesis reactor cannot be continuously and automatically replaced. It also solves the problems of operation complexity and unstable operation caused by intermittent replacement in the existing Fischer-Tropsch synthesis unit, thereby improving the reaction performance of the Fischer-Tropsch synthesis unit.

[0032] 5) This invention integrates catalyst activation within the Fischer-Tropsch reactor, which utilizes the exothermic Fischer-Tropsch reaction to provide heat for catalyst activation, thus contributing to energy conservation and emission reduction, and alleviating the operational pressure on the dedicated heat transfer device installed within the Fischer-Tropsch synthesis reactor. Attached Figure Description

[0033] Figure 1 This is a schematic diagram of one embodiment of the Fischer-Tropsch synthesis reactor of the present invention. Detailed Implementation

[0034] The present invention will be further described below with reference to the embodiments and accompanying drawings. However, the present invention is not limited to the listed embodiments, but should also include equivalent improvements and modifications to the technical solutions defined in the appended claims of the present invention.

[0035] like Figure 1 As shown, the Fischer-Tropsch synthesis reactor of the present invention includes a reactor body 1 and internal components disposed within the reactor body. The internal components include a gas distributor 2 and a catalyst activation unit. The gas distributor 2 is disposed at the bottom of the reactor body 1 to ensure uniform distribution of the feed gas for the Fischer-Tropsch synthesis reaction within the reactor. The catalyst activation unit is disposed above the gas distributor 2 and includes multiple cyclone separators 3 connected in series along the flow direction of the catalyst during activation. The inlet of each cyclone separator 3 is used to feed the catalyst to be activated and the activation gas. The outlet at the top of each cyclone separator 3 is used to discharge the activation tail gas. The outlet at the bottom of each cyclone separator 3 is used to discharge the separated catalyst after reaction with the activation gas and to transport the separated catalyst to the inlet of the next-stage cyclone separator 3 connected in series. The catalyst activation unit is used to activate the catalyst within the sequentially connected cyclone separators 3 and continuously feed the activated catalyst through the outlet of the final-stage cyclone separator 3 into the Fischer-Tropsch synthesis reactor to catalyze the Fischer-Tropsch synthesis reaction.

[0036] In this invention, activation gas refers to the gas required during the catalyst activation process; activation tail gas refers to the activation gas discharged from the cyclone separator after contacting and reacting with the catalyst.

[0037] In this invention, the cyclone separator can be a commonly used cyclone separator for gas-solid separation. Although cyclone separators are often used for gas-solid separation, the applicant has found that since there is also sufficient contact between gas and solid materials in the cyclone separator, when it is cleverly used for catalyst activation, selecting a suitable gas source and setting it in the Fischer-Tropsch reactor to ensure a suitable temperature not only facilitates the separation of gas and solid after activation, but also helps to achieve a good catalyst activation effect.

[0038] In addition, those skilled in the art will understand that the Fischer-Tropsch synthesis reactor may also include its commonly used internal components, such as heat transfer components for removing the exothermic reaction of the Fischer-Tropsch synthesis reaction, and gas-solid separation components located below the top gas phase outlet for reducing catalyst entrainment, which are well known in the art and will not be described in detail here.

[0039] For material transport, the Fischer-Tropsch synthesis reactor also includes an inlet pipe and an outlet pipe. One end of the inlet pipe is connected to an external gas source, and the other end is connected to the feed inlet of each cyclone separator to transport activation gas to the cyclone separator. One end of the outlet pipe is connected to an external tail gas treatment unit, and the other end is connected to the outlet of each cyclone separator to transport the activation tail gas to the external tail gas treatment unit for recycling, such as removing at least one of water, CO2, and organic alkanes from the activation tail gas.

[0040] In one embodiment, the outlet of the upper-stage cyclone separator in the series-connected cyclone separators is positioned higher than the inlet of the lower-stage cyclone separator, so as to facilitate the conveying of solid materials by means of gravity, thereby avoiding the need to set up a separate solid material conveying mechanism.

[0041] In one embodiment, the cyclone separators of the catalyst activation unit are arranged along the inner wall of the reactor cylinder, for example, fixed to the inner wall of the reactor. Those skilled in the art will understand that the number of cyclone separators during activation can be set according to the time required for catalyst activation, the residence time of material in a single cyclone separator, and different activation conditions. It is understood that different activation conditions can affect the required activation time; inert gas can even be introduced into some of the upstream, midstream, or downstream cyclone separators to adjust the number of effective cyclone separators (those with inert gas can be considered ineffective cyclone separators). In one embodiment, the number of cyclone separators in the catalyst activation unit is at least two or three, such as 6-30, 8-20, 5-10, or 15-25.

[0042] The Fischer-Tropsch synthesis reactor can be a slurry-bed Fischer-Tropsch synthesis reactor or a gas-solid fluidized bed Fischer-Tropsch reactor. In one embodiment, the Fischer-Tropsch synthesis reactor is a slurry-bed Fischer-Tropsch synthesis reactor, which is well known in the art, such as the slurry-bed reactor disclosed in CN102698662B. The Fischer-Tropsch synthesis reactor of the present invention can be based on an existing slurry-bed Fischer-Tropsch synthesis reactor, with some internal components added or removed as needed, and a built-in catalyst activation unit is used to continuously replenish the activated catalyst into the reactor. During the reaction, the cyclone separator of the catalyst activation unit can be at least partially or entirely located in the slurry of the slurry-bed Fischer-Tropsch synthesis reactor, which is beneficial to the good dispersion of the catalyst and the utilization of the heat of the Fischer-Tropsch reaction.

[0043] In one embodiment, the Fischer-Tropsch synthesis reactor is a gas-solid fluidized bed Fischer-Tropsch synthesis reactor, which is well known in the art. For example, see the gas-solid fluidized bed Fischer-Tropsch synthesis reactor disclosed in CN111286356B. The Fischer-Tropsch synthesis reactor of the present invention can be based on an existing gas-solid fluidized bed Fischer-Tropsch synthesis reactor, with some internal components added or removed as needed, and a built-in catalyst activation unit is used to continuously replenish the activated catalyst into the reactor. During the reaction, the cyclone separator of the catalyst activation unit can be located at least partially or entirely within the gas-solid phase bed of the gas-solid fluidized bed Fischer-Tropsch synthesis reactor, which is beneficial for good catalyst dispersion and utilization of the heat of the Fischer-Tropsch reaction.

[0044] The present invention also provides a reaction system for Fischer-Tropsch synthesis, the reaction system comprising the Fischer-Tropsch synthesis reactor described above, a gas source for supplying activation gas, and a tail gas treatment unit for treating the activation tail gas. Of course, those skilled in the art will understand that it may also include other necessary equipment units of the Fischer-Tropsch synthesis system, such as a synthesis gas supply unit for supplying the synthesis gas required for Fischer-Tropsch synthesis.

[0045] In this invention, the gas source can be one or more, including hydrogen, CO, nitrogen, oxygen, or a mixture thereof, or any gas source required for activating the catalyst. The inlet pipe group can also be configured with multiple inlet pipes for different types of gas as needed for the activation process. Each inlet pipe is connected to the same gas source and is connected to a set of cyclone separators (which can be one or more cyclone separators). Each set of cyclone separators can be connected to a set of outlet pipes.

[0046] In one embodiment, the gas source includes a hydrogen source and a CO source, the inlet pipe includes a first set of inlet pipes and a second set of inlet pipes located downstream of the first inlet pipe, and the outlet pipe includes a first set of outlet pipes and a second set of outlet pipes; the first set of inlet pipes is connected to the hydrogen source and is used to send hydrogen as the first activation gas into a first set of cyclone separators connected to the first set of inlet pipes; the first set of outlet pipes is used to transport the first activation tail gas from the first set of cyclone separators; the second set of inlet pipes is connected to the hydrogen source and the CO source and is used to send a mixture of hydrogen and CO as the second activation gas into a second set of cyclone separators connected to the second set of inlet pipes; the second set of outlet pipes is used to transport the second activation tail gas from the second set of cyclone separators. For example, see CN112569984A, where the activation gases for the catalyst are hydrogen and a mixture of hydrogen and CO, and the activation process can also be implemented in this invention. In this embodiment, the H2 / CO molar ratio of the second activation gas is 1:1-800:1, such as 50:1, 100:1, 200:1 or 600:1; the reaction temperature of the first cyclone separator is 180-300°C, such as 200, 240, 240 or 280°C, and the pressure is 2-3.5 MPa, such as 2.5, 2.8, 3.0 or 3.2 MPa; the reaction temperature of the second cyclone separator is 200-300°C, such as 240, 240 or 280°C, and the pressure is 2-3.5 MPa, such as 2.5, 2.8, 3.0 or 3.2 MPa.

[0047] In one embodiment, the exhaust gas treatment unit includes a first exhaust gas treatment unit and a second exhaust gas treatment unit; wherein, the first exhaust gas treatment unit is used to remove water from the first activated exhaust gas and circulate the treated first activated exhaust gas as the first activation gas into the first set of intake pipes; the second exhaust gas treatment unit is used to remove water, carbon dioxide and organic matter from the second activated exhaust gas and circulate a portion of the treated second activated exhaust gas as the second activation gas into the second set of intake pipes and a portion as venting gas.

[0048] In one embodiment, the gas source includes a hydrogen source, a CO source, and an oxygen source; the inlet pipe includes a first set of inlet pipes, a second set of inlet pipes downstream of the first set of inlet pipes, and a third set of inlet pipes downstream of the second set of inlet pipes; the outlet pipe includes a first set of outlet pipes, a second set of outlet pipes, and a third set; the first set of inlet pipes is connected to the hydrogen source and is used to deliver hydrogen as a first activation gas into a first set of cyclone separators connected to the first set of inlet pipes; the first set of outlet pipes is used to deliver gas from the first set of cyclone separators. The first set of activation tail gas; the second set of inlet pipes is connected to the oxygen source, used to send the oxygen-containing gas into the second set of cyclone separators corresponding to the second set of inlet pipes; the second set of outlet pipes is used to transport the second activation tail gas from the second set of cyclone separators; the third set of inlet pipes is connected to the hydrogen source and the CO source, used to send the mixture of hydrogen and CO as the third activation gas into the third set of cyclone separators corresponding to the second set of inlet pipes; the third set of outlet pipes is used to transport the third activation tail gas from the third set of cyclone separators. For example, see CN112569983, where the activation gases for the catalyst are hydrogen, oxygen-containing gas, and a mixture of hydrogen and CO, and the activation process can also be implemented in this invention.

[0049] In one embodiment, the gas source is a hydrogen source, and all the inlet pipes are connected to the hydrogen source; or the gas source is a hydrogen source and a CO source, and all the inlet pipes are connected to both the hydrogen source and the CO source, so as to introduce a mixture of hydrogen and CO as the activation gas. For example, see CN110511777A, where the catalyst is activated in a fluidized bed using a mixture of hydrogen and CO, and the activation process can also be implemented in this invention; in addition, CN107406775A discloses a Fischer-Tropsch method using a reduction-activated cobalt catalyst, in which a catalyst composition is pretreated for 1-50 hours with a hydrogen-containing gas stream containing less than 10% carbon monoxide by volume of carbon monoxide and hydrogen to form a reduction-activated catalyst, and the activation process can also be implemented in this invention.

[0050] As can be seen, the catalyst activation unit of the present invention can be flexibly adjusted according to different activation processes, by introducing the same activation gas for all processes or introducing different gases separately to adapt to different activation requirements. Of course, those skilled in the art will understand that if more gas sources are required, the present invention can also be applied by adjusting the connection between the inlet pipe and the gas source.

[0051] In addition, those skilled in the art will understand that the valves on each intake pipe can be adjusted to regulate the intake volume and the proportion of gases from different gas sources within the same intake pipe.

[0052] In the method of the present invention, when the catalyst is transferred between cyclone separators or when the catalyst is fed into the inlet of the cyclone separator, the catalyst can be smoothly transferred and fed by the entraining effect of the activation gas. In addition, the temperature inside the cyclone separator can be adjusted by the inlet temperature of the activation gas, which can be affected by the initial inlet temperature and / or the length of the inlet pipe or the heat exchange area inside the reactor shell. Furthermore, the activated catalyst can be smoothly discharged by controlling the pressure difference between the cyclone separator and the Fischer-Tropsch synthesis reactor.

[0053] When performing Fischer-Tropsch synthesis using the above reaction system, the catalyst to be activated is continuously fed into the catalyst activation unit, and the activated catalyst is continuously replenished into the Fischer-Tropsch synthesis reactor using the catalyst activation unit. At the same time, the catalyst is continuously discharged from the Fischer-Tropsch synthesis reactor to maintain the stability of the total amount of catalyst in the Fischer-Tropsch synthesis reactor.

[0054] The present invention will be further illustrated below with reference to examples and comparative examples, wherein the catalyst to be activated is a catalyst prepared according to step (1) of Example 1 of CN112569982A with an average particle size of 70-80 micrometers.

[0055] Example 1

[0056] A slurry-bed Fischer-Tropsch synthesis reactor was used, in which the first group of cyclone separators in the catalyst activation unit consisted of 5 units. The activation conditions were: reaction temperature 260℃, reaction pressure 3.0MPa, activation gas was hydrogen, and gas hourly space velocity was 8000 Nm3 / (t·h).

[0057] The second group of cyclone separators has 5 units. The activation conditions are: reaction temperature 260℃, reaction pressure 3.0MPa, activation gas is a mixture of hydrogen and carbon monoxide with a hydrogen-to-carbon ratio of 50:1, and gas hourly space velocity of 8000 Nm3 / (t·h).

[0058] The output rate of fresh activated catalyst is 8 kg / h;

[0059] The Fischer-Tropsch reaction conditions were: reaction temperature 270℃, reaction pressure 3.0 MPa, hydrogen-to-carbon ratio of the syngas entering the tower 4:1, and gas hourly space velocity 15000 Nm3 / (t·h). The detection results of the Fischer-Tropsch reaction products are shown in Table 1.

[0060] Example 2

[0061] A slurry-bed Fischer-Tropsch synthesis reactor was adopted, in which the first group of cyclone separators in the catalyst activation unit consisted of 10 units. The activation conditions were: reaction temperature 260℃, reaction pressure 3.0MPa, activation gas was hydrogen, and gas hourly space velocity was 8000 Nm3 / (t·h).

[0062] The second group of cyclone separators consists of 15 units. The activation conditions are: reaction temperature 260℃, reaction pressure 3.0MPa, activation gas is a mixture of hydrogen and CO with a hydrogen-to-carbon ratio of 50:1, and gas hourly space velocity of 8000 Nm3 / (t·h).

[0063] The output rate of fresh catalyst is 100 kg / h;

[0064] The Fischer-Tropsch reaction conditions were: reaction temperature 270℃, reaction pressure 3.0 MPa, hydrogen-to-carbon ratio of the inlet gas 4:1, and gas hourly space velocity 15000 Nm³ / (t·h). The detection results of the Fischer-Tropsch reaction products are shown in Table 1.

[0065] Example 3

[0066] A slurry-bed Fischer-Tropsch synthesis reactor was used, in which the first group of cyclone separators in the catalyst activation unit consisted of 20 units. The activation conditions were: reaction temperature 260℃, reaction pressure 3.0MPa, activation gas was hydrogen, and gas hourly space velocity was 8000 Nm3 / (t·h).

[0067] The second group of cyclone separators has 20 units. The activation conditions are: reaction temperature 260℃, reaction pressure 3.0MPa, activation gas is a mixture of hydrogen and CO with a hydrogen-to-carbon ratio of 50:1, and gas hourly space velocity of 8000 Nm3 / (t·h).

[0068] The output rate of fresh catalyst is 200 kg / h;

[0069] The Fischer-Tropsch reaction conditions were: reaction temperature 270℃, reaction pressure 3.0 MPa, hydrogen-to-carbon ratio of the syngas entering the tower 4:1, and gas hourly space velocity 15000 Nm3 / (t·h). The detection results of the Fischer-Tropsch reaction products are shown in Table 1.

[0070] Example 4

[0071] A slurry-bed Fischer-Tropsch synthesis reactor was used, in which the catalyst activation unit included 15 cyclone separators in series. The activation conditions were: reaction temperature 260℃, reaction pressure 3.0MPa, activation gas was a mixture of hydrogen and CO with a hydrogen-to-carbon ratio of 50:1, and gas hourly space velocity of 8000 Nm3 / (t·h).

[0072] The output rate of the activated catalyst is 20 kg / h;

[0073] The Fischer-Tropsch reaction conditions were: reaction temperature 270℃, reaction pressure 3.0 MPa, hydrogen-to-carbon ratio of the syngas entering the tower 4:1, and gas hourly space velocity 15000 Nm3 / (t·h). The detection results of the Fischer-Tropsch reaction products are shown in Table 1.

[0074] Comparative Example 1

[0075] The online updating system described in patent application CN110511777A from the Beijing Low Carbon Clean Energy Research Institute was used to activate the catalyst, and the activated catalyst was then transferred to the Fischer-Tropsch synthesis reaction. Activation conditions: reaction temperature 260℃, reaction pressure 3.0 MPa, activation gas was a mixture of hydrogen and CO with a hydrogen-to-carbon ratio of 50:1, and gas hourly space velocity (GHSV) 8000 Nm³ / (t·h).

[0076] The Fischer-Tropsch reaction conditions were as follows: catalyst replacement rate of 480 kg / day, reaction temperature of 270℃, reaction pressure of 3.0 MPa, hydrogen-to-carbon ratio of the syngas entering the tower of 4:1, and gas hourly space velocity of 15000 Nm3 / (t·h). The detection results of the Fischer-Tropsch reaction products are shown in Table 1.

[0077] Both the example and the comparative examples ran stably for one month, and were verified by C. 3+ The monthly average oil and gas consumption per ton of oil was used to investigate the impact of the activation and replacement methods of this invention on the long-term stability of the unit, and compared with the existing batch activation method. The results are shown in Table 1.

[0078] Table 1

[0079] Example 1 5398 Example 2 5401 Example 3 5412 Example 4 5410 Comparative Example 1 5600

[0080] As shown in the table, the continuous activation and replacement process significantly reduces the gas consumption per ton of oil in the Fischer-Tropsch synthesis reactor due to the stable and continuous operation of the unit, thus significantly improving the unit's efficiency.

[0081] All devices or components involved in this invention can be existing processing facilities, devices, or components with corresponding functions in the art, and will not be described in detail. Unless otherwise specified, all matters are understood or known to those skilled in the art based on their prior knowledge, and will not be described in detail. To highlight the concept of this invention, many necessary equipment for industrial applications, such as pumps, valves, and control components, are omitted from the figures.

[0082] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is impossible to exhaustively list all embodiments here. All obvious variations or modifications derived from the technical solutions of the present invention are within the spirit and scope of the present invention.

Claims

1. A Fischer-Tropsch synthesis reactor suitable for stable production, comprising a reactor shell and internal components disposed within the reactor shell, characterized in that, The internal components include a gas distributor and a catalyst activation unit: the gas distributor is located at the bottom of the reactor body to ensure uniform distribution of the feed gas for the Fischer-Tropsch synthesis reaction within the reactor; the catalyst activation unit is located above the gas distributor and includes multiple cyclone separators connected in series along the catalyst flow direction during activation; the inlet of each cyclone separator is used to feed the catalyst to be activated and the activation gas, the outlet at the top of each cyclone separator is used to discharge the activation tail gas, and the outlet at the bottom of each cyclone separator is used to discharge the separated catalyst after reacting with the activation gas and to transport the separated catalyst to the inlet of the next-stage cyclone separator connected in series; the catalyst activation unit is used to activate the catalyst in the cyclone separators connected in series and to continuously feed the activated catalyst into the Fischer-Tropsch synthesis reactor through the outlet of the final-stage cyclone separator to catalyze the Fischer-Tropsch synthesis reaction.

2. The Fischer-Tropsch synthesis reactor according to claim 1, characterized in that, The Fischer-Tropsch synthesis reactor also includes an inlet pipe and an outlet pipe. One end of the inlet pipe is connected to an external gas source, and the other end is connected to the feed inlet of each cyclone separator to deliver activation gas to the cyclone separator. One end of the outlet pipe is connected to an external tail gas treatment unit, and the other end is connected to the outlet of each cyclone separator to deliver the activation tail gas to the external tail gas treatment unit for recycling.

3. The Fischer-Tropsch synthesis reactor according to claim 1 or 2, characterized in that, In a series-connected cyclone separator, the outlet of the previous stage cyclone separator is positioned higher than the inlet of the next stage cyclone separator.

4. The Fischer-Tropsch synthesis reactor according to claim 3, characterized in that, The cyclone separator of the catalyst activation unit is arranged along the inner wall of the reactor cylinder.

5. The Fischer-Tropsch synthesis reactor according to any one of claims 1-2 and 4, characterized in that, The Fischer-Tropsch synthesis reactor is a slurry-bed Fischer-Tropsch synthesis reactor; at least a portion of the cyclone separators connected in series are located within the slurry of the slurry-bed Fischer-Tropsch synthesis reactor.

6. The Fischer-Tropsch synthesis reactor according to any one of claims 1-2 and 4, characterized in that, The Fischer-Tropsch synthesis reactor is a gas-solid fluidized bed Fischer-Tropsch reactor; at least a portion of the cyclone separators connected in series are located within the gas-solid phase bed of the gas-solid fluidized bed Fischer-Tropsch synthesis reactor.

7. A reaction system for Fischer-Tropsch synthesis, characterized in that, The reaction system includes a Fischer-Tropsch synthesis reactor according to any one of claims 1-6, a gas source for supplying activation gas, and a tail gas treatment unit for treating the activation tail gas.

8. The reaction system according to claim 7, characterized in that, The Fischer-Tropsch synthesis reactor further includes an inlet pipe and an outlet pipe; the gas source is one or more types, the inlet pipe is one or more sets, each set of inlet pipes connected to the same gas source is connected to a set of cyclone separators, and each set of cyclone separators is connected to a set of outlet pipes, so that the activation gas from the same gas source enters the same set of cyclone separators and is sent out through the same set of outlet pipes.

9. The reaction system according to claim 8, characterized in that, The gas source includes one or more of the following: hydrogen, CO, nitrogen, and oxygen.

10. The reaction system according to claim 8, characterized in that, The gas source includes a hydrogen source and a CO source; the inlet pipe includes a first set of inlet pipes and a second set of inlet pipes located downstream of the first inlet pipe; the outlet pipe includes a first set of outlet pipes and a second set of outlet pipes. The first set of inlet pipes is connected to the hydrogen source and is used to send hydrogen as the first activation gas into the first set of cyclone separators connected to the first set of inlet pipes; the first set of outlet pipes is used to deliver the first activation tail gas from the first set of cyclone separators. The second set of inlet pipes is connected to the hydrogen source and the CO source, and is used to send the mixture of hydrogen and CO as the second activation gas into the second set of cyclone separators connected to the second set of inlet pipes; the second set of outlet pipes is used to deliver the second activation tail gas from the second set of cyclone separators. The exhaust gas treatment unit includes a first exhaust gas treatment unit and a second exhaust gas treatment unit; wherein, the first exhaust gas treatment unit is used to remove water from the first activated exhaust gas and to circulate the treated first activated exhaust gas as the first activated gas into the first set of intake pipes. The second exhaust gas treatment unit is used to remove water, carbon dioxide and organic matter from the second activated exhaust gas, and to circulate part of the treated second activated exhaust gas into the second set of intake pipes as second activation gas, and part as venting gas.

11. A method for Fischer-Tropsch synthesis using the reaction system according to any one of claims 7-10, wherein, During the Fischer-Tropsch reaction, the catalyst to be activated is continuously fed into the catalyst activation unit, and the activated catalyst is continuously replenished into the Fischer-Tropsch synthesis reactor using the catalyst activation unit. At the same time, the catalyst is continuously discharged from the Fischer-Tropsch synthesis reactor to maintain a stable total amount of catalyst in the Fischer-Tropsch synthesis reactor.

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