Fischer-Tropsch synthesis catalyst, its preparation method, and device for synthesizing supported catalyst

Abstract

The present invention discloses a Fischer-Tropsch synthesis catalyst, a preparation method thereof, and a device for synthesizing a supported catalyst. The supported catalyst includes a carrier and an active component. The device for synthesizing the supported catalyst includes a turbulence device, a separation device, and a power device. The turbulence device is respectively connected to the separation device and the power device. Among them, the power device provides high-pressure gas, and the carrier and the active component are turbulently mixed in the turbulence device under the action of the high-pressure gas. After turbulent mixing, the carrier and the active component enter the separation device for gas-solid separation, and the separated solid is the supported catalyst. The present invention mixes and loads the carrier and the active component of the catalyst by means of turbulent mixing, is not limited by the form of the active component precursor, can use a non-soluble active component precursor, and can simultaneously obtain a Fischer-Tropsch synthesis catalyst with a high active component loading amount.

Description

Technical Field

[0001] The present invention relates to the field of catalysts, and in particular to a Fischer-Tropsch synthesis catalyst, a preparation method thereof, and an apparatus for synthesizing a supported catalyst. Background Art

[0002] In the 1920s, Fischer and Tropsch developed a synthetic route for synthesizing hydrocarbons from syngas as a raw material under the action of a catalyst and appropriate conditions, which is called Fischer-Tropsch synthesis (FTS). This route first prepares syngas from non-petroleum resources, and then catalytically converts syngas to liquid fuels. The most significant feature of Fischer-Tropsch synthesis is that the product distribution is relatively wide (a mixture of different alkanes and alkenes from C1 to C200).

[0003] Due to the rapid growth in the demand for aviation kerosene, the production of aviation kerosene has received increasing attention. The traditional production method of aviation kerosene is crude oil distillation, and the kerosene fraction obtained by distillation is further refined by hydrotreating and hydrocracking to obtain aviation kerosene meeting international standards. Typical jet fuel components derived from crude oil contain 20% n-alkanes, 40% iso-alkanes, 20% naphthenes, and 20% aromatics. However, this process heavily relies on petroleum resources and has high requirements for the material of equipment. Developing alternative technologies for preparing aviation kerosene has received extensive attention worldwide.

[0004] At present, the alternative technologies for aviation kerosene production are as follows: (1) Routes using unconventional oil sources, which usually include three unconventional petroleum resources: oil sands in Canada, VHO in Venezuela, and oil shale. However, the raw material sources of this method are very limited. (2) Processes for producing jet fuel from biomass, including high-temperature pyrolysis of lignin and other substances to generate bio-oil and then deoxygenation and upgrading to liquid fuels, hydrogenation processes for triglycerides and fatty acids to produce aviation kerosene, etc. However, the processes for producing jet fuel from biomass have problems such as high raw material costs, complex treatment processes, excessive investment, and poor quality of the produced bio-oil. (3) Conversion of syngas to aviation kerosene through Fischer-Tropsch synthesis. As a bridge for energy conversion, syngas can convert coal, natural gas, and biomass into clean oil products, and is considered to be one of the most promising alternative routes for producing aviation kerosene. Fischer-Tropsch synthesis fuels not only have similar properties to traditional aviation fuels, but also have low sulfur and nitrogen contents in their compositions, which can reduce pollution emissions from aeroengines. This synthetic route not only has the advantages of being green and environmentally friendly, mild reaction conditions, and high atom economy, but also has important strategic significance for adjusting China's energy structure, improving China's dependence on petroleum resources, and ensuring China's energy security.

[0005] The product distribution of Fischer-Tropsch synthesis over traditional catalysts usually follows the Anderson-Schulz Flory (ASF) distribution law, and the theoretical maximum selectivity of C8-C16 components does not exceed 40%, making it difficult to industrially produce aviation kerosene from syngas through Fischer-Tropsch synthesis. Currently, only two companies in the world, Sasol in South Africa and Shell in the Netherlands, have achieved commercial production of Fischer-Tropsch synthetic aviation kerosene. The preparation processes they use are relatively complex and the investment costs are high. The process adopted by Sasol includes using a precipitated iron catalyst to catalyze the synthesis of hydrocarbon products from syngas, and then refining the hydrocarbon products through complex processes such as hydrocracking, oligomerization, hydrorefining, aromatization, and alkylation. The yield of the final jet fuel is 60 wt%. In 2002, Sasol's semi-synthetic and fully synthetic aviation kerosene synthesized by the Fischer-Tropsch process obtained usage certification on commercial aircraft. Among them, the semi-synthetic aviation kerosene has more than 10 years of application experience in aviation. The SMDS process adopted by Shell includes the production of syngas, the synthesis of heavy-chain alkanes from syngas catalyzed by a Co-Ru / Al2O3 catalyst, and the hydroconversion of heavy-chain alkanes. The yield of jet fuel is 50 wt%.

[0006] Fischer-Tropsch synthesis catalysts are the key and core technologies in the development and research of Fischer-Tropsch synthesis chemical processes. The active components of Fischer-Tropsch synthesis catalysts are mainly Group VIII elements (transition metals). The Group VIII transition metal elements mainly refer to elements such as Fe, Co, Ni, Ru, and Rh. These transition metal elements have the following characteristics: ① They have good CO dissociation and adsorption capabilities, and their own chemical properties are relatively stable; ② They have a certain metal hydrogenation ability. Co-based catalysts can promote the production of heavy hydrocarbons to a large extent; they have good reaction activity and are not easily carbon-deposited; their water-gas shift reaction activity is relatively low, and the carbon utilization rate is high. Due to their advantages in terms of activity, selectivity, and service life, Co-based Fischer-Tropsch synthesis catalysts have become a research hotspot in the field of Fischer-Tropsch synthesis catalysts.

[0007] CN103007982A discloses a Fischer-Tropsch synthesis catalyst containing zeolite molecular sieve, which contains an active metal component selected from iron and / or cobalt, a carrier containing zeolite molecular sieve and optionally containing a heat-resistant inorganic oxide matrix. Based on the catalyst, the content of the zeolite molecular sieve is 1-60 wt%, the content of the heat-resistant inorganic oxide matrix is 0-80 wt%, and the content of the active metal component in terms of oxide is 2-50 wt%. The preparation method is: preparing a carrier containing zeolite molecular sieve and optionally containing a heat-resistant inorganic oxide matrix, and introducing an active metal component selected from iron and / or cobalt into the carrier, such as by impregnation, and then drying, calcining or not calcining to obtain the catalyst. The method for preparing the catalyst in this invention is a conventional loading technique, and the loading amount of the active component and the size and morphology of the catalyst particles are limited.

[0008] CN 111867725 A discloses the preparation of a cobalt-containing catalyst. The method adopted is to co-grind the carrier and the active component to obtain the required catalyst. The inventive method is not applicable to cobalt catalysts with molecular sieves as the carrier.

[0009] CN 110252389 A discloses a cobalt-based core-shell catalyst, its preparation method and application. The active component cobalt is added to the molecular sieve seed solution to synthesize a cobalt-based catalyst with metallic cobalt as the core and molecular sieve as the shell. The synthesis process of the inventive method is complex, and it is difficult to precisely control the content of the active component.

[0010] CN 111215125 A discloses a catalyst for Fischer-Tropsch synthesis with the target product of C5-C12 and its preparation method. The solid-phase synthesis method is adopted, and under anhydrous conditions, the active component is added to the molecular sieve synthesis process. The inventive method also has the deficiency of a complex synthesis process.

[0011] Therefore, further research on Fischer-Tropsch synthesis catalysts is still needed in the art. Summary of the Invention

[0012] The main object of the present invention is to provide a Fischer-Tropsch synthesis catalyst, its preparation method, and a device for the synthesis of supported catalysts, so as to overcome the defects in the prior art such as the complex preparation process of Fischer-Tropsch synthesis catalysts and the limited loading amount of active components.

[0013] To achieve the above object, the present invention provides a device for the synthesis of supported catalysts. The supported catalyst includes a carrier and an active component. The device for the synthesis of supported catalysts includes a turbulence device, a separation device, and a power device. The turbulence device is respectively connected to the separation device and the power device;

[0014] Among them, the power device provides high-pressure gas, and the carrier and the active component are turbulently mixed in the turbulence device under the action of the high-pressure gas; after turbulent mixing, the carrier and the active component enter the separation device for gas-solid separation, and the separated solid is the supported catalyst.

[0015] In the device for the synthesis of supported catalysts of the present invention, the separated solid is circulated into the turbulence device for turbulent mixing, and the circulation time is 30 to 120 minutes.

[0016] In the device for the synthesis of supported catalysts of the present invention, the power device is a gas compressor, and a flow rate regulating device and / or a flow rate measuring device are also provided between the power device and the turbulence device to regulate and / or measure the high-pressure gas entering the turbulence device.

[0017] The device for synthesizing a supported catalyst according to the present invention, wherein the turbulence device comprises a turbulence tube, one end of the turbulence tube is communicated with the power device, the other end is communicated with the separation device, and a suction tube is further arranged at the connection between the turbulence tube and the power device for introducing the carrier and the active component into the turbulence device.

[0018] The device for synthesizing a supported catalyst according to the present invention, wherein a tubular furnace is arranged outside the turbulence tube to heat the turbulence tube.

[0019] The device for synthesizing a supported catalyst according to the present invention, wherein the separation device comprises a solid outlet and a gas outlet, and the separation device is arranged above the suction tube so that the separated solid directly flows into the turbulence device through the suction tube.

[0020] The device for synthesizing a supported catalyst according to the present invention, wherein the separation device is a cyclone separator.

[0021] The device for synthesizing a supported catalyst according to the present invention, wherein an included angle is formed between the flow direction of the substance in the suction tube and the flow direction of the substance in the turbulence tube, and the included angle is greater than 0° and less than 90°.

[0022] The device for synthesizing a supported catalyst according to the present invention, wherein the power device is communicated with the turbulence device through a pipeline, and the diameter of the connection between the pipeline and the turbulence device gradually decreases.

[0023] In order to achieve the above object, the present invention also provides a preparation method of a Fischer-Tropsch synthesis catalyst, comprising the following steps:

[0024] The carrier and the active component of the Fischer-Tropsch synthesis catalyst are introduced into the turbulence device of the device for synthesizing a supported catalyst according to any one of claims 1-9. Driven by the high-pressure gas provided by the power device, the carrier and the active component are turbulently mixed in the turbulence device, and the turbulently mixed carrier and active component enter the separation device for gas-solid separation, and the separated solid is the Fischer-Tropsch synthesis catalyst.

[0025] The preparation method of the Fischer-Tropsch synthesis catalyst according to the present invention, wherein the flow rate of the high-pressure gas is 50-300 L / min, and the temperature for the carrier and the active component to be turbulently mixed is 323-673 K.

[0026] The preparation method of the Fischer-Tropsch synthesis catalyst of the present invention, wherein the separated solid is circulated back to the turbulent flow device for turbulent mixing, the Fischer-Tropsch synthesis catalyst also includes an auxiliary agent, the auxiliary agent is simultaneously introduced into the turbulent flow device together with the carrier and the active component for turbulent mixing, and the mass ratio of the carrier, the active component and the auxiliary agent is 80-100:10-40:0.1-1.

[0027] The preparation method of the Fischer-Tropsch synthesis catalyst described in the present invention, wherein the carrier is a microporous molecular sieve, a mesoporous molecular sieve or a micro-mesoporous molecular sieve, and the particle size of the carrier is 10-500 mesh; the active component is at least one of a cobalt-containing compound, an iron-containing compound, an iron element and a cobalt element; the auxiliary agent is at least one of a Group IA metal compound, a transition metal compound and a lanthanide metal compound.

[0028] The preparation method of the Fischer-Tropsch synthesis catalyst of the present invention, wherein the carrier is treated as follows before the turbulent mixing: the carrier is stirred and refluxed with an aqueous solution of ethylenediamine-tetraacetic acid, and then the obtained solid is added to an alkaline solution for reaction, filtered, dried, and calcined.

[0029] In order to achieve the above object, the present invention further provides a Fischer-Tropsch synthesis catalyst obtained by the above preparation method.

[0030] Beneficial effects of the present invention:

[0031] The present invention mixes and loads the catalyst carrier and the active component by turbulent mixing, is not limited by the form of the active component precursor, can use an insoluble active component precursor, and can obtain a Fischer-Tropsch synthesis catalyst with a higher active component loading.

[0032] The turbulent mixing method of the present invention can reduce the contact between the reactants and the channel wall, thereby minimizing blockage and scaling; in addition, the turbulent mixing method of the present invention can enable the catalyst to have a high nucleation rate, thereby making the catalyst into extremely small solid particles, thereby improving the catalytic activity of the catalyst.

[0033] The turbulent mixing of the present invention can achieve almost instantaneous mixing, and the process operation is simple and easy to industrialize. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is a schematic diagram of a device for synthesizing supported catalysts according to the present invention;

[0035] Figure 2 for Figure 1 An enlarged schematic diagram of the turbulence device section;

[0036] Figure 3Schematic diagram of the catalyst of the present invention used in the Fischer-Tropsch synthesis reaction process.

[0037] Figure 4 Transmission electron microscope (TEM) image of the catalyst obtained in Example 4 of the present invention.

[0038] Among them, the reference numerals:

[0039] 1 Power device

[0040] 2 Turbulence device

[0041] 21 Turbulence tube

[0042] 22 Tube furnace

[0043] 23 Suction tube

[0044] 3 Separation device

[0045] 31 Gas outlet

[0046] 32 Solid outlet

[0047] 41 Flow rate regulating device

[0048] 42 Flow rate measuring device Detailed implementation manners

[0049] The following provides a detailed description of the embodiments of the present invention. These embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation manners and processes are given. However, the protection scope of the present invention is not limited to the following embodiments. For the experimental methods without specific conditions noted in the following embodiments, they are usually carried out under conventional conditions.

[0050] The present invention discloses a device for the synthesis of supported catalysts. The present invention does not particularly limit the supported catalysts. For example, the supported catalysts include carriers and active components. Figure 1 Schematic diagram of the device for the synthesis of supported catalysts of the present invention, as Figure 1 shown, the device for the synthesis of supported catalysts includes a turbulence device 2, a separation device 3, and a power device 1. The turbulence device 2 is respectively connected to the separation device 3 and the power device 1;

[0051] Among them, the power device 1 provides high-pressure gas, and the carrier and the active component are turbulently mixed in the turbulence device 2 under the action of the high-pressure gas; the turbulently mixed carrier and active component enter the separation device 3 for gas-solid separation, and the separated solid is the supported catalyst.

[0052] The device for synthesizing the supported catalyst of the present invention can make the carrier and the active component of the catalyst undergo turbulent mixing in the turbulent device 2, so that the carrier and the active component can collide at high speed and be fully mixed, promoting the uniform entry of the active component into the carrier and obtaining a supported catalyst with a uniform distribution of the active component. In addition, the catalyst with a higher loading amount of the active component can be obtained by using the method of the present invention.

[0053] In one embodiment, the power device 1 of the present invention is a gas compressor, which compresses the gas into high-pressure gas and then inputs it into the turbulent device 2. The present invention does not particularly limit the pressure of the high-pressure gas, for example, it is greater than 1.01×10 5 Pa and can be adjusted as needed; the present invention does not particularly limit the type of gas, for example, it is air. In another embodiment, the power device 1 of the present invention is connected to the turbulent device 2 through a pipeline, and a flow rate regulating device 41 and / or a flow rate measuring device 42 are also provided on the pipeline between the two. The flow rate regulating device 41 is used to regulate the flow rate of the high-pressure gas entering the turbulent device 2, and the flow rate regulating device 41 is, for example, a flow valve; the flow rate measuring device 42 is used to measure the amount of the high-pressure gas entering the turbulent device 2, and the flow rate measuring device 42 is, for example, a meter.

[0054] The turbulent device 2 of the present invention is mainly a device that can make the carrier and the active component undergo turbulent mixing under the driving action of high-pressure gas. In one embodiment, the turbulent device 2 of the present invention is as Figure 2 shown, including a turbulent pipe 21. One end of the turbulent pipe 21 is connected to the power device 1, and the other end is connected to the separation device 3. For example, one end of the turbulent pipe 21 is connected to the power device 1 through a pipeline, and the other end is connected to the separation device 3 through a pipeline. A suction pipe 23 is also provided at the connection between the turbulent pipe 21 and the power device 1 of the present invention. For example, a tee pipe structure is formed at this connection, and the high-pressure gas enters the turbulent pipe 21 through the pipeline between the turbulent pipe 21 and the power device 1, and the carrier and the active component enter the turbulent device 2 through the suction pipe 23. Under the driving action of the high-pressure gas, the carrier and the active component undergo turbulent mixing in the turbulent device 2.

[0055] In another embodiment, the included angle between the flow direction of the substance in the suction pipe 23 and the flow direction of the substance in the turbulent pipe 21 of the present invention is greater than 0° and less than 90°; in other words, the suction pipe 23 is connected to the turbulent pipe 21 in an oblique direction.

[0056] In yet another embodiment, the pipeline connecting the turbulent tube 21 of the present invention to the power device 1 is the first pipeline. The diameter of the connection between the first pipeline and the turbulent tube 21 gradually decreases, presenting a nozzle shape. This can further increase the flow rate of the high-pressure gas, causing the carrier and active components entering the device to undergo turbulent mixing under the drive of the high-pressure gas. In one embodiment, the connection between the first pipeline and the turbulent tube 21 is the location where the suction pipe 23 is provided. In this way, the carrier and active components that have just entered the device can be pushed by the high-speed and high-pressure gas.

[0057] In still another embodiment, a tube furnace 22 is provided outside the turbulent tube 21 of the present invention to heat the turbulent tube 21. The temperature at which the carrier and active components undergo turbulent mixing significantly affects the diffusion of the active components in the carrier. Especially when the temperature reaches the melting temperature of the active components, the diffusion effect of the active components in the carrier is better. Therefore, by providing the tube furnace 22, the present invention can further promote the diffusion of the active components in the carrier.

[0058] In one embodiment, the turbulent device 2 of the present invention is connected to the separation device 3 through a second pipeline. The separation device 3 includes a solid outlet 32 and a gas outlet 31. The solid outlet 32 is, for example, provided at the lower part of the separation device 3, and the gas outlet 31 is, for example, provided at the upper part of the separation device 3. The carrier and active components after turbulent mixing enter the separation device 3 for gas-solid separation. The separated solid (i.e., the carrier and active components after turbulent mixing) flows out through the solid outlet 32, and the separated gas flows out from the gas outlet 31, which is the tail gas.

[0059] Among them, the flow routes of the active components and the carrier of the present invention are as Figure 1 shown by the dashed arrows in the figure. The high-pressure gas generated by the power device 1 provides power for the cyclic flow and collision of solids such as the carrier and active components. Its flow is a one-way non-cyclic flow, as Figure 1 shown by the solid arrows.

[0060] In another embodiment, the separation device 3 of the present invention is a cyclone separator. In yet another embodiment, the separation device 3 of the present invention is provided above the suction pipe 23 (the second pipeline is a bent pipeline) so that the separated solid directly flows into the turbulent device 2 through the suction pipe 23 under the action of gravity. For example, the separation device 3 of the present invention is provided directly above the suction pipe 23, and the solid outlet 32 of the separation device 3 is correspondingly arranged with the suction pipe 23 so that the solid output from the solid outlet 32 is recycled back into the turbulent device 2 for continuous turbulent mixing. In still another embodiment, the cycle time of the present invention is 30 - 120 min, that is, after the carrier and active components of the catalyst are cyclically mixed in the device for synthesizing the supported catalyst for 30 - 120 min, the reaction is stopped, and the solid output from the solid outlet 32 is collected to obtain the supported catalyst.

[0061] By controlling the time and number of cycles of the active component and the carrier circulation, the present invention can achieve the control of the degree of penetration of the active component into the carrier. The longer the time of turbulent mixing of the active component and the carrier, the more collisions between solid particles, and the more sufficient the penetration of the active component in the catalyst carrier.

[0062] The present invention is described above by taking the turbulent mixing of the catalyst carrier and the active component as an example, but the present invention is not limited thereto. The turbulent mixing may include other components of the catalyst, such as promoters.

[0063] The present invention does not particularly limit the size of the device for synthesizing the supported catalyst, which can be adjusted as needed. In one embodiment, the length of the turbulent tube 21 is 100 - 2000 mm, and the inner diameter is 8 - 30 mm.

[0064] The following will detail the operating steps of the device for synthesizing the supported catalyst of the present invention.

[0065] First, start the power device 1, adjust the flow rate regulating device 41, control the gas flow rate at 50 - 300 L / min, and control the temperature of the turbulent tube 21 at 323 - 673 K. Add a mixture of 10 - 200 g of the catalyst carrier, the active component, and the promoter into the suction tube 23 of the turbulent tube 21. The mass ratio of the carrier to the active component and the promoter is 80 - 100:10 - 40:0.1 - 1. The catalyst carrier, the active component, and the promoter are driven by the gas into the turbulent tube 21 and perform turbulent mixing in the turbulent tube 21. In one embodiment, the active component, the promoter, and the carrier are in a circulating flow, as Figure 1 shown by the dotted arrow, fully mixed and colliding at high speed, promoting the uniform entry of the active ingredient into the carrier. In addition, the content of the active component in the catalyst of the present invention can be accurately controlled by the ratio of the carrier, the active component, and the promoter in the feedstock.

[0066] After circulating for 30 - 120 min, collect the solid product at the solid outlet 32 at the bottom of the separation device 3. The obtained solid product is subjected to post-treatment of the catalyst, such as drying, calcination, etc., to obtain the final Fischer - Tropsch synthesis catalyst.

[0067] Among them, the temperature of the turbulent tube 21 is heated by the tubular furnace 22 outside the tube to achieve the set turbulent temperature; the turbulent velocity is controlled by the flow rate regulating device 41, and the specific velocity is calculated from the diameter of the turbulent tube 21 and the air volume flow rate; the outlet of the turbulent tube 21 is in contact with the atmosphere, so the turbulent pressure can be approximated as atmospheric pressure.

[0068] The present invention also provides a method for preparing a Fischer - Tropsch synthesis catalyst, using the above - mentioned device for synthesizing the supported catalyst, including the following steps:

[0069] The carrier and active components of the Fischer-Tropsch synthesis catalyst are introduced into the turbulent device 2 of the above-mentioned device for supported catalyst synthesis. Driven by the high-pressure gas provided by the power device 1, the carrier and the active components are turbulently mixed in the turbulent device 2. The carrier and the active components after turbulent mixing enter the separation device 3 for gas-solid separation, and the separated solid is the Fischer-Tropsch synthesis catalyst.

[0070] According to the Bernoulli equation, in the process of fluid flow, the tube diameter and gas flow rate are the main parameters that can adjust the Reynolds number after the gas material is fixed. When the Reynolds number reaches a certain value, the flow of the fluid reaches a turbulent state. In the turbulence tube of the present invention, the gas flow state in the turbulence tube can be controlled by adjusting the tube diameter and gas velocity of the turbulence tube. Generally speaking, the greater the gas velocity, the greater the Reynolds number in the turbulence tube, and the greater the degree of turbulence. The turbulence tube of the present invention can suck solid powder into the airflow, thereby increasing the apparent density of the airflow, and then reducing the gas velocity that forms turbulence.

[0071] The controlled conditions in the preparation of the Fischer-Tropsch synthesis catalyst of the present invention are similar to the operating conditions of the above-mentioned device and will not be described in detail here. For example, the flow rate of high-pressure gas is 50-300 L / min, and the temperature of turbulent mixing of the carrier and the active component is 323-673K.

[0072] The Fischer-Tropsch synthesis catalyst of the present invention comprises an active component, a carrier and an auxiliary agent. The auxiliary agent, the carrier and the active component are simultaneously introduced into the turbulent device 2 for turbulent mixing. The mass ratio of the carrier, the active component and the auxiliary agent is 80-100:10-40:0.1-1.

[0073] In one embodiment, the carrier of the present invention is a microporous molecular sieve, a mesoporous molecular sieve or a micro-mesoporous molecular sieve, and the particle size of the carrier is 10-500 mesh; the active component is at least one of a cobalt-containing compound, an iron-containing compound, an iron element and a cobalt element; and the auxiliary agent is at least one of a Group IA metal compound, a transition metal compound and a lanthanide metal compound.

[0074] In one embodiment, the carrier of the present invention is treated as follows before turbulent mixing: the carrier is stirred and refluxed with an aqueous solution of ethylenediamine-tetraacetic acid, and then the resulting solid is added to an alkaline solution for reaction, filtered, dried, and calcined.

[0075] Further, the treatment steps of the carrier of the present invention before turbulent mixing are described in detail as follows: 5-100g of the carrier and 50-2000ml of ethylenediamine-tetraacetic acid aqueous solution are added to a flask, the mixture is refluxed and stirred at 293-373K for 4-8 hours, filtered and dried to obtain a solid powder. Then, 5-100g of the solid powder is added to an alkaline solution for reaction, filtered and dried, and finally the carrier is calcined at 823-1023K for standby use.

[0076] The present invention does not particularly limit the alkaline solution. For example, it is a sodium hydroxide solution, and the amount of the sodium hydroxide solution is 500 - 1500 ml, and the concentration is 0.2 - 1 mol / L.

[0077] The carrier of the present invention can adopt commercial grade molecular sieve, or the existing molecular sieve can be modified with micro-mesopores to obtain micro-mesoporous molecular sieve, and the present invention does not make a particular limitation.

[0078] Thus, the Fischer-Tropsch synthesis catalyst that can be obtained by the above preparation method of the present invention has a controllable active component content, can reach a relatively high level, and the active components are evenly distributed on the carrier, and the obtained catalyst has relatively high catalytic activity.

[0079] Figure 3 It is a schematic diagram of the process of the catalyst of the present invention used in the Fischer-Tropsch synthesis reaction. Under the catalytic action of the Fischer-Tropsch synthesis catalyst of the present invention, syngas undergoes hydrocracking and isomerization reactions to obtain C5-11 hydrocarbons.

[0080] The technical solution of the present invention will be further described in detail through specific examples below.

[0081] Example 1: Synthesis of cobalt-supported catalyst

[0082] (1) Preparation of the carrier

[0083] Take 50 g of NaY molecular sieve and 500 ml of ethylenediamine-tetraacetic acid aqueous solution and add them to a flask. The mixture is refluxed and then stirred at 293 K for 4 hours. Then, the solid product is filtered, dried, and treated with NaOH, that is, 50 g of the dried solid powder is added to an aqueous NaOH solution (1000 ml, 0.5 mol / L) for reaction and then filtered and dried. Finally, the carrier is calcined at 923 K for standby.

[0084] (2) Synthesis of the catalyst

[0085] Mix the carrier prepared in step 1 with cobalt nitrate, ruthenium nitrate, and lanthanum nitrate in a mass ratio of 80:20:0.3:0.5. Take 50 g of the mixed solid and put it into the suction pipe of the turbulent flow tube of the above device. Turn on the power device, adjust the flow valve, and control the air flow rate at 200 L / min. The length of the turbulent flow tube is 600 mm, the inner diameter is 12 mm, and the turbulent flow temperature is set at 573 K. After circulating for 60 min, collect the solid powder product at the bottom of the separation device.

[0086] (3) Post-treatment of the catalyst

[0087] The solid powder product obtained in Step 2 is first dried in an oven at 353 K for 48 h, and then calcined in a muffle furnace. The calcination temperature is 823 K, the calcination time is 12 h, and the heating and cooling rates are controlled at 10 K / min.

[0088] Example 2: Continuous production of cobalt-supported catalyst

[0089] (1) Preparation of the support

[0090] Treat 1000 g of the mesoporous NaY catalyst support according to the method of Example 1 and set aside.

[0091] (2) Continuous synthesis of the catalyst

[0092] Mix the catalyst support with cobalt nitrate, ruthenium nitrate, and lanthanum nitrate in a mass ratio of 80:20:0.3:0.5. Take 50 g of the mixed solid and put it into the suction pipe of the turbulent tube. Turn on the air compressor and adjust the flow valve to control the air flow at 200 L / min. The length of the turbulent tube is 600 mm, the inner diameter is 12 mm, and the turbulent temperature is set at 573 K.

[0093] After circulating for 60 min, continue to add the mixed solid at a rate of 10 g / min, and collect part of the solid product at the bottom of the cyclone separator. Among them, the mass ratio of the collected solid product to the circulating material is 1:19, that is, 5% of the solid in the cyclone separator is continuously taken out as the product, and the remaining 95% of the solid continues to circulate.

[0094] After the addition of the mixed solid is completed, continue to circulate for 40 min, then take out all the solid products to obtain a light red dry powder, and turn off the air compressor.

[0095] (3) Post-treatment of the catalyst

[0096] The solid powder product obtained in Step 2 is first dried in an oven at 353 K for 48 h, and then calcined in a muffle furnace. The calcination temperature is 823 K, the calcination time is 12 h, and the heating and cooling rates are controlled at 10 K / min. Compare the mass of the recovered solid with that of the raw material solid, and the recovery rate of the recovered solid is 78.5%.

[0097] Calculated according to the feeding ratio, the mass content of cobalt metal in the obtained catalyst is 15%. According to the X-ray fluorescence analysis (XRF) method, the actual mass content of cobalt metal in the catalyst obtained in this example is 17.3%. Since the recovery rate of the recovered solid is 78.5%, it shows that in the lost solid, the loss amounts of nitrate and the carrier are close, and both are lost in the form of ultrafine powder in the tail gas of the cyclone separator. Therefore, although the method of the present invention will cause a small amount of loss of the carrier and the active component, and the content of the active component in the obtained catalyst fluctuates within a small range, this loss is within an acceptable range, and the content of the active component in the catalyst also fluctuates within an acceptable range.

[0098] Example 3: Synthesis of Iron-Supported Catalyst

[0099] (1) Preparation of Support

[0100] Take 50 g of NaY molecular sieve and 500 ml of ethylenediamine-tetraacetic acid aqueous solution and add them to a flask. The mixture is refluxed and then stirred at 293 K for 4 hours. Then, the solid product is filtered, dried, and treated with NaOH, that is, 50 g of the dried solid powder is added to an NaOH aqueous solution (1000 ml, 0.5 mol / L) for reaction and then filtered and dried. Finally, the support is calcined at 923 K for standby.

[0101] (2) Synthesis of Catalyst

[0102] Mix the support prepared in step 1 with iron nitrate, lanthanum nitrate, and cerium nitrate in a mass ratio of 80:20:0.3:0.5. Take 50 g of the mixed solid and put it into the suction pipe of the turbulent tube. Turn on the air compressor and adjust the flow valve to control the air flow at 200 L / min. After circulating for 60 min, collect the solid powder product at the bottom of the cyclone separator.

[0103] (3) Post-Treatment of Catalyst

[0104] The solid powder product obtained in step 2 is first dried in an oven at 353 K for 48 h, and then calcined in a muffle furnace. The calcination temperature is 823 K, the calcination time is 12 h, and the heating and cooling rates are controlled at 10 K / min.

[0105] Example 4: Continuous Production of Iron-Supported Catalyst

[0106] (1) Preparation of Support

[0107] Treat 1000 g of mesoporous NaY catalyst support according to the method of Example 1 for standby.

[0108] (2) Continuous Synthesis of Catalyst

[0109] The catalyst support was mixed with iron nitrate, lanthanum nitrate, and cerium nitrate at a mass ratio of 80:20:0.3:0.5. The operating experimental conditions were the same as those in Example 2. After synthesis, a grass-green dry powder was obtained, and the recovery rate of the solid was 79.8%.

[0110] The catalyst obtained in this example, which is NaY supported with iron nitrate, lanthanum nitrate, and cerium nitrate, was analyzed by transmission electron microscopy (TEM). The transmission electron micrograph is as shown in Figure 4 , as can be seen from Figure 4 It can be seen that for the supported catalyst prepared by the continuous method of the present invention, the active metals are uniformly distributed on the catalyst support.

[0111] Example 5: Continuous production of iron-supported catalysts with different loadings

[0112] (1) Preparation of the support

[0113] According to the method of Example 1, 3000 g of the mesoporous NaY catalyst support was treated and divided into 3 portions for standby, namely Samples 1, 2, and 3.

[0114] (2) Continuous synthesis of the catalyst

[0115] The catalyst support was mixed with the mixed solid of iron nitrate, lanthanum nitrate, and cerium nitrate at a mass ratio of 80:20:0.3:0.5. The operating experimental conditions were the same as those in Example 4. The amounts of the mixed solid used and the amounts of the active metals fed are shown in Table 1. After preparation, the metal content of the catalyst was tested by X-ray fluorescence analysis (XRF), and the test results are shown in Table 1 below.

[0116] Table 1 Feed amounts and actual measured amounts of the active components of the catalyst

[0117] sample mixed solid mass designed iron content actual iron content solid recovery rate 1 10 3％ 3.5％ 79.0％ 2 50 15％ 16.6％ 78.1％ 3 100 30％ 32.2％ 80.5％

[0118] As shown in Table 1, by using the catalyst preparation method of the present invention, under different metal loading conditions, the difference between the theoretical value and the actual value of the content of the active components of the catalyst is not large and is within an acceptable range.

[0119] Of course, the present invention can also have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and deformations according to the present invention, but these corresponding changes and deformations should all fall within the protection scope of the claims of the present invention.

Claims

1. An apparatus for the synthesis of a supported catalyst, characterized in that, The supported catalyst comprises a carrier and an active component, and the device for synthesizing the supported catalyst comprises a turbulent device, a separation device and a power device, wherein the turbulent device is connected to the separation device and the power device respectively; Wherein, the power device provides high-pressure gas, and the carrier and the active component are turbulently mixed in the turbulent device under the action of the high-pressure gas; the carrier and the active component after turbulent mixing enter the separation device for gas-solid separation, and the separated solid is the supported catalyst; The turbulence device comprises a turbulence tube, one end of which is connected to the power device, and the other end of which is connected to the separation device. A suction pipe is also provided at the connection between the turbulence tube and the power device to allow the carrier and the active component to pass into the turbulence device; a tubular furnace is provided outside the turbulence tube to heat the turbulence tube; The flow direction of the material in the suction pipe and the flow direction of the material in the turbulent flow pipe form an angle greater than 0° and less than 90°; The power device is connected to the turbulence device through a pipeline, and the diameter of the connection between the pipeline and the turbulence device gradually decreases.

2. The device for synthesizing a supported catalyst according to claim 1, characterized in that, The separated solid is circulated into the turbulent flow device for turbulent mixing, and the circulation time is 30 to 120 minutes.

3. The device for synthesizing the supported catalyst according to claim 1, characterized in that, The power device is a gas compressor, and a flow regulating device and / or a flow metering device is also provided between the power device and the turbulence device to regulate and / or meter the high-pressure gas entering the turbulence device.

4. The apparatus for synthesizing a supported catalyst according to claim 1, characterized in that, The separation device comprises a solid outlet and a gas outlet, and the separation device is arranged on the upper part of the suction pipe so that the separated solids directly flow into the turbulent flow device through the suction pipe.

5. The device for synthesizing the supported catalyst according to claim 4, characterized in that, The separation device is a cyclone separator.

6. A method for preparing a Fischer-Tropsch synthesis catalyst, characterized in that, The steps include: The carrier and active components of the Fischer-Tropsch synthesis catalyst are introduced into the turbulent device of the device for supported catalyst synthesis according to any one of claims 1 to 5. Driven by the high-pressure gas provided by the power device, the carrier and the active components are turbulently mixed in the turbulent device. After turbulent mixing, the carrier and the active components enter the separation device for gas-solid separation, and the separated solid is the Fischer-Tropsch synthesis catalyst.

7. The preparation method of the Fischer-Tropsch synthesis catalyst according to claim 6, characterized in that, The flow rate of the high-pressure gas is 50-300 L / min, and the temperature of turbulent mixing of the carrier and the active component is 323-673K.

8. The preparation method of the Fischer-Tropsch synthesis catalyst according to claim 6, characterized in that, The solid obtained by separation is circulated back to the turbulent device for turbulent mixing. The Fischer-Tropsch synthesis catalyst also includes an auxiliary agent. The auxiliary agent, the carrier and the active component are simultaneously introduced into the turbulent device for turbulent mixing. The mass ratio of the carrier, the active component and the auxiliary agent is 80-100:10-40:0.1-1.

9. The preparation method of the Fischer-Tropsch synthesis catalyst according to claim 8, wherein, The carrier is a microporous molecular sieve, a mesoporous molecular sieve or a micro-mesoporous molecular sieve, and the particle size of the carrier is 10-500 meshes; the active component is at least one of a cobalt-containing compound, an iron-containing compound, an iron element and a cobalt element; the auxiliary agent is at least one of a Group IA metal compound, a transition metal compound and a lanthanide metal compound.

10. The preparation method of the Fischer-Tropsch synthesis catalyst according to claim 6, characterized in that, Before the carrier undergoes the turbulent mixing, the following treatment is carried out: the carrier is stirred and refluxed with an aqueous solution of ethylenediamine-tetraacetic acid, and then the obtained solid is added to an alkaline solution for reaction, filtered, dried, and calcined.

11. A Fischer-Tropsch synthesis catalyst obtained by the preparation method according to any one of claims 6-10.

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