Catalyst recovery and regeneration system and method, and olefin preparation method

Abstract

The invention provides a catalyst recycling and regenerating system and method and an olefin preparation method. The catalyst recycling and regenerating system comprises a cyclone separator, a catalyst magnetic separation device, a molecular sieve regenerator and a catalyst mixer. By applying the technical scheme provided by the invention, the catalyst simultaneously comprises the magnetic component and the non-magnetic component, the magnetic component comprises the magnetic metal or the magnetic metal oxide, and is easy to inactivate due to high-temperature heating in the regeneration process; according to the catalyst recycling and regenerating system, the magnetic-containing component and the non-magnetic component can be separated through a magnetic separation method, the non-magnetic component is independently regenerated in the molecular sieve regenerator, the regenerated non-magnetic component is mixed with the magnetic-containing component, and recycling of the catalyst is achieved. The catalyst recycling and regenerating system can reduce the consumption of the catalyst, so that the operation cost is reduced, and the economic benefit is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of greenhouse gas treatment, and in particular to a catalyst recovery and regeneration system and method, and an olefin preparation method. Background Art

[0002] Climate change is a major global issue affecting human survival and development. With the acceleration of industrialization, carbon emissions continue to grow, placing tremendous pressure on the environment. CO2 utilization technology transforms CO2 from waste into a resource. This technology can generate sustainable revenue from CO2-derived products to offset the expensive cost of carbon capture, making it a key means of reducing CO2 emissions from high costs to low costs, or even negative costs.

[0003] Light olefins such as ethylene and propylene are important basic raw materials and platform compounds, and are among the world's most produced chemical products. Ethylene and propylene are the core of the petrochemical industry and occupy an important position in the national economy. However, the production of light olefins consumes a large amount of fossil energy and generates hundreds of millions of tons of carbon emissions each year. If renewable energy and CO2 are used as the source, hydrogen produced by renewable energy power generation (called green hydrogen) is reacted with CO2 to convert it into light olefins, and then synthesized into plastics, rubber, fibers and other materials, it is possible to fix carbon in materials for long-term use, achieving near-zero CO2 emissions from the entire process from production to use.

[0004] The catalyst commonly used in CO2 hydrogenation to olefins is a bifunctional catalyst, which contains multiple components, such as metal oxides and molecular sieves. Among them, molecular sieve catalysts rely on their large number of microporous structures with specific forms to catalyze the conversion of reactants. During the reaction, carbon deposition is easy to cause pore blockage, resulting in a decrease in catalytic performance. The traditional methanol to olefins reaction requires continuous high-temperature oxidation and regeneration of the molecular sieve catalyst to maintain catalytic activity. However, CO2 hydrogenation to olefins catalysts usually contain other components such as metal oxides. Excessive temperatures will cause sintering and deactivation, reducing the catalytic activity of the component. Therefore, the life of traditional CO2 hydrogenation to olefins catalysts is relatively short, making it difficult to achieve large-scale industrial operation. Summary of the Invention

[0005] The main purpose of the present invention is to provide a catalyst recovery and regeneration system and method, and a method for preparing olefins, so as to solve the problem in the prior art that the activity of the catalyst is easily reduced during heating and regeneration.

[0006] In order to achieve the above object, according to one aspect of the present invention, a catalyst recovery and regeneration system is provided, the catalyst recovery and regeneration system comprising:

[0007] The cyclone separator includes an inlet for the catalyst to be recovered, a gas outlet, an outlet for the damaged catalyst, and an outlet for the catalyst to be separated. The cyclone separator is used to separate the damaged catalyst from the catalyst to be regenerated. The inlet for the catalyst to be recovered is used to introduce the catalyst to be regenerated.

[0008] The catalyst magnetic separation device includes a catalyst inlet to be separated, a magnetic component collecting device and a molecular sieve outlet. The catalyst inlet to be separated is connected to the catalyst outlet to be separated. The catalyst magnetic separation device is used to separate the magnetic components and non-magnetic components in the catalyst to be regenerated by magnetic separation. The magnetic component collecting device is used to collect the magnetic components separated by magnetic separation.

[0009] A molecular sieve regenerator includes a molecular sieve inlet and a regenerated molecular sieve outlet. The molecular sieve regenerator is used to regenerate the non-magnetic components to obtain regenerated non-magnetic components. The molecular sieve inlet is connected to the molecular sieve outlet.

[0010] The catalyst mixer includes a regenerated molecular sieve inlet, a magnetic component inlet and a regenerated catalyst outlet. The catalyst mixer is used to mix the regenerated non-magnetic component and the magnetic component to obtain a regenerated catalyst. The regenerated molecular sieve inlet is connected to the regenerated molecular sieve outlet, and the magnetic component inlet is connected to the magnetic component collecting device.

[0011] Furthermore, the cyclone separator consists of 2-5 stages;

[0012] The molecular sieve regenerator includes a gas inlet for introducing an oxygen-containing gas;

[0013] The heating temperature of the molecular sieve regenerator is 600-700℃;

[0014] The catalyst recovery and regeneration system also includes a regenerated molecular sieve collecting device for collecting regenerated non-magnetic components, the regenerated molecular sieve collecting device includes a regenerated molecular sieve collecting device inlet and a regenerated molecular sieve collecting device outlet, the regenerated molecular sieve collecting device inlet is connected to the regenerated molecular sieve outlet, the regenerated molecular sieve collecting device outlet is connected to the regenerated molecular sieve inlet, and the regenerated catalyst collecting device is used to collect regenerated non-magnetic components;

[0015] The catalyst recovery and regeneration system further includes a regenerated catalyst collecting device for collecting regenerated catalyst, the regenerated catalyst collecting device including a regenerated catalyst collecting device inlet and a catalyst outlet, the regenerated catalyst collecting device inlet being connected to the regenerated catalyst outlet; preferably, the regenerated catalyst collecting device further includes a catalyst feeding port for replenishing fresh catalyst;

[0016] The catalyst recovery and regeneration system also includes a damaged catalyst collecting device for collecting damaged catalysts. The damaged catalyst collecting device includes a damaged catalyst inlet, which is connected to a damaged catalyst outlet.

[0017] Furthermore, the catalyst recovery and regeneration system also includes a fluidized bed reactor for carrying out olefin synthesis reaction under the action of the catalyst. The fluidized bed reactor includes a raw material inlet, a catalyst inlet and a product outlet. The catalyst inlet is connected to the catalyst outlet, and the product outlet is connected to the catalyst inlet to be recovered.

[0018] Preferably, the catalyst recovery and regeneration system further comprises a raw material preheater for preheating the raw material. The raw material preheater comprises a preheating raw material inlet and a preheating raw material outlet, and the preheating raw material outlet is connected to the raw material inlet.

[0019] Furthermore, the raw material preheater also includes a process gas inlet and a process gas outlet, which are configured to preheat the raw material using the heat of the process gas separated by the cyclone separator, the process gas inlet is connected to the gas outlet of the cyclone separator, and the process gas outlet is connected to the gas-liquid separator, the gas phase cooler and the distillation tower arranged in sequence;

[0020] The gas-liquid separator comprises a liquid outlet, which is communicated with the liquid collecting device.

[0021] Furthermore, the catalyst recovery and regeneration system also includes a reactor heat extractor and a superheated steam generator, wherein:

[0022] The reactor heat extractor can remove the heat released by the reaction in the fluidized bed reactor;

[0023] The superheated steam generator can use the heat obtained from the reactor heat extractor to heat the circulating steam into superheated steam. The superheated steam is used for fluidized transport of solid catalyst in any one or more of the magnetic component collection device, regenerated molecular sieve collection device, catalyst mixer and regenerated catalyst collection device.

[0024] According to another aspect of the present application, a catalyst recovery and regeneration method is provided, wherein the catalyst includes a magnetic component and a non-magnetic component, the magnetic component includes any one or more of a magnetic metal and a magnetic metal oxide, and the non-magnetic component includes a molecular sieve; the method includes: passing a product system containing the catalyst into a cyclone separator for coarse separation to obtain a process gas and a catalyst to be separated; separating the catalyst to be separated by magnetic separation to obtain a magnetic component and a non-magnetic component; heating and oxidizing the non-magnetic component to obtain a regenerated non-magnetic component; mixing the regenerated non-magnetic component and the magnetic component to obtain a regenerated catalyst.

[0025] Furthermore, the catalyst is a FeCu / TiO2-SAPO34 tandem catalyst.

[0026] Furthermore, the temperature of the heating oxidation is 600-700° C., and the time is 1-30 min;

[0027] The regenerated non-magnetic component and the magnetic component are mixed in a mass ratio of (0.2-1):1.

[0028] According to another aspect of the present application, a method for preparing olefins is provided, which comprises: introducing preheated hydrogen and carbon dioxide into a fluidized bed to carry out an olefin synthesis reaction under the action of a catalyst to obtain a product system containing the catalyst; wherein the catalyst is a regenerated catalyst obtained by any of the above-mentioned catalyst recovery and regeneration methods or a regenerated catalyst obtained using any of the above-mentioned catalyst recovery and regeneration systems, the product system containing the catalyst is treated according to any of the above-mentioned catalyst recovery and regeneration methods, or is treated using any of the above-mentioned catalyst recovery and regeneration systems, and the obtained process gas is subjected to gas-liquid separation, gas phase cooling and distillation to obtain an olefin product.

[0029] Furthermore, the volume ratio of hydrogen to carbon dioxide introduced into the fluidized bed is 2 to 4;

[0030] The temperature of the olefin synthesis reaction is 300-400°C and the pressure is 1-3 MPa;

[0031] The reaction space velocity of olefin synthesis reaction is 3000~20000mL / (gcat·h);

[0032] The regenerated catalyst is placed in a regenerated catalyst collecting device. Before the olefin synthesis reaction begins, the mass ratio of the catalyst in the fluidized bed to that in the regenerated catalyst collecting device is 0.5-1.

[0033] The technical solution of the present invention is applied to a catalyst comprising both a magnetic component and a non-magnetic component, wherein the magnetic component comprises a magnetic metal or a magnetic metal oxide, which is easily deactivated due to high-temperature heating during the regeneration process. The catalyst recovery and regeneration system of the present application can separate the magnetic component and the non-magnetic component by magnetic separation, regenerate the non-magnetic component alone in a molecular sieve regenerator, and then mix it with the magnetic component after regeneration to achieve catalyst recovery and reuse. The catalyst recovery and regeneration system of the present application can reduce catalyst consumption, thereby reducing operating costs and improving economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The accompanying drawings, which constitute part of this application, are intended to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0035] Figure 1 A structural schematic diagram of a catalyst recovery and regeneration system according to an embodiment of the present invention is shown.

[0036] Among them, the above-mentioned drawings include the following figure marks: 01, raw gas mixer; 02, raw material preheater; 03, fluidized bed reactor; 04, cyclone separator; 05, gas-liquid separator; 06, gas phase cooler; 07, distillation tower; 08, liquid collecting device; 09, damaged catalyst collecting device; 10, catalyst magnetic separation device; 11, magnetic component collecting device; 12, molecular sieve regenerator; 13, regenerated molecular sieve collecting device; 14, catalyst mixer; 15, regenerated catalyst collecting device; 16, reactor heat extractor; 17, superheated steam generator. DETAILED DESCRIPTION

[0037] It should be noted that, in the absence of conflict, the embodiments and features of the embodiments in this application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0038] As analyzed in the background of this application, the prior art has the problem that the catalyst activity is easily reduced during heating and regeneration. To solve this problem, this application provides a catalyst recovery and regeneration system and method, and an olefin preparation method.

[0039] According to a typical embodiment of the present application, a catalyst recovery and regeneration system is provided, such as Figure 1 As shown, the catalyst recovery and regeneration system includes: a cyclone separator 04, a catalyst magnetic separation device 10, a molecular sieve regenerator 12 and a catalyst mixer 14. The cyclone separator 04 includes an inlet for catalyst to be recovered, a gas outlet, an outlet for damaged catalyst and an outlet for catalyst to be separated. The cyclone separator 04 is used to separate the damaged catalyst and the catalyst to be regenerated in the catalyst. The inlet for catalyst to be recovered is used to introduce the catalyst that needs to be regenerated; the catalyst magnetic separation device 10 includes an inlet for catalyst to be separated, a magnetic component collecting device 11 and a molecular sieve outlet. The inlet for catalyst to be separated is connected to the outlet for catalyst to be separated. The catalyst magnetic separation device 10 is used to separate the magnetic components and non-magnetic components in the catalyst to be regenerated by a magnetic separation method. The magnetic component collecting device 11 is used to collect the magnetic components separated by magnetic separation; the molecular sieve regenerator 12 includes a molecular sieve inlet and a regenerated molecular sieve outlet. The molecular sieve regenerator 12 is used to regenerate the non-magnetic components to obtain regenerated non-magnetic components. The molecular sieve inlet is connected to the molecular sieve outlet; the catalyst mixer 14 includes an inlet for regenerated molecular sieve, an inlet for magnetic components and an outlet for regenerated catalyst. The catalyst mixer 14 is used to mix the regenerated non-magnetic components and the magnetic components to obtain a regenerated catalyst. The regenerated molecular sieve inlet is connected to the regenerated molecular sieve outlet, and the magnetic component inlet is connected to the magnetic component collecting device 11.

[0040] For catalysts that include both magnetic and non-magnetic components, where the magnetic component includes a magnetic metal or a magnetic metal oxide, which is easily deactivated due to high-temperature heating during the regeneration process, the catalyst recovery and regeneration system of the present application can separate the magnetic and non-magnetic components by magnetic separation, regenerate the non-magnetic components separately in the molecular sieve regenerator 12, and then mix them with the magnetic components after regeneration to achieve catalyst recovery and reuse. The catalyst recovery and regeneration system of the present application can reduce catalyst consumption, thereby reducing operating costs and improving economic benefits.

[0041] The above-mentioned catalysts including those containing magnetic components and non-magnetic components can be recycled and regenerated using the catalyst recovery and regeneration system of the present application. Taking FeCu / TiO2-SAPO34 catalyst as an example, since the catalyst contains a large amount of Fe, the FeCu / TiO2 part of the catalyst is coupled with the molecular sieve part by mechanical mixing, so the FeCu / TiO2 part can be separated from the molecular sieve part by magnetic separation to achieve the separate regeneration of the molecular sieve. The regenerated molecular sieve can be mixed and coupled with FeCu / TiO2 again for reaction to achieve the improvement of catalyst life. In addition, the SAPO34 molecular sieve in the catalyst is of high value. Regeneration after separation can reduce the consumption of the catalyst, thereby reducing the operating cost and improving the economic benefit.

[0042] In some embodiments of the present application, the product system containing the catalyst is introduced into the above-mentioned cyclone separator 04 to separate the catalyst and the gas in the system at the same time.

[0043] Because the catalyst will collide and wear during use, fine particles are usually produced, which is not conducive to the fluidization of the fluidized bed and the catalytic reaction. Therefore, the small particles of catalyst are discharged to facilitate the process and improve efficiency. In some embodiments of the present application, the cyclone separator 04 is composed of 2-5 stages, with the last stage connected to the outlet of the damaged catalyst, and the remaining catalyst enters the catalyst magnetic separation device 10.

[0044] In some embodiments of the present application, Figure 1 As shown, the catalyst recovery and regeneration system further includes a damaged catalyst collecting device 09 for collecting damaged catalysts. The damaged catalyst collecting device 09 includes a damaged catalyst inlet, which is connected to a damaged catalyst outlet. The damaged catalyst collected by the damaged catalyst collecting device 09 no longer participates in the reaction.

[0045] The catalyst magnetic separation device 10 can separate the magnetic metal or metal oxide portion in the catalyst from the non-magnetic component, ie, the molecular sieve portion, by means of a magnet or an electromagnet.

[0046] In some embodiments of the present application, the above-mentioned catalyst magnetic separation device 10 is a powder magnetic separation device, which can adsorb the magnetic catalyst part on the conveyor belt through a conveyor belt with a vibration function. When the conveyor belt turns to the bottom, the scraper can scrape off the adsorbed catalyst in this row or demagnetize the electromagnet to make this row of catalyst fall into the collection port below; the unadsorbed molecular sieve is conveyed to the end and falls into another molecular sieve collection port or the next level conveyor belt with the same function, finally realizing the separation of the two components. Usually, the conveyor belt consists of 2 to 6 levels.

[0047] The molecular sieve regenerator 12 can remove carbon deposits in the microporous structure of the molecular sieve by high-temperature oxidation. In some embodiments of the present application, the molecular sieve regenerator 12 includes a gas inlet for introducing an oxygen-containing gas.

[0048] In some embodiments of the present application, the heating temperature in the molecular sieve regenerator 12 is 600-700° C., which can effectively remove carbon deposits in the molecular sieve.

[0049] In some embodiments of the present application, Figure 1 As shown, the catalyst recovery and regeneration system also includes a regenerated molecular sieve collecting device 13 for collecting regenerated non-magnetic components. The regenerated molecular sieve collecting device 13 includes a regenerated molecular sieve collecting device inlet and a regenerated molecular sieve collecting device outlet. The regenerated molecular sieve collecting device inlet is connected to the regenerated molecular sieve outlet, and the regenerated molecular sieve collecting device outlet is connected to the regenerated molecular sieve inlet. The regenerated catalyst collecting device is used to collect regenerated non-magnetic components.

[0050] The catalyst mixer 14 is used to mix the magnetic components separated by the catalyst magnetic separation device 10 and the regenerated non-magnetic components regenerated by the molecular sieve regenerator 12 to prepare a regenerated catalyst.

[0051] In some embodiments of the present application, Figure 1 As shown, the catalyst recovery and regeneration system also includes a regenerated catalyst collecting device 15 for collecting regenerated catalyst. The regenerated catalyst collecting device 15 includes a regenerated catalyst collecting device inlet and a catalyst outlet. The regenerated catalyst collecting device inlet is connected to the regenerated catalyst outlet. Preferably, the regenerated catalyst collecting device 15 also includes a catalyst feeding port for replenishing fresh catalyst.

[0052] The regenerated catalyst prepared by the catalyst mixer 14 can be recycled and used in the catalytic reaction again. Therefore, the catalyst recovery and regeneration system of the present application may also include a catalyst application device. In some typical embodiments of the present application, in order to further improve the efficiency of the catalyst recovery and regeneration system, such as Figure 1As shown, the catalyst recovery and regeneration system also includes a fluidized bed reactor 03, which is used to carry out olefin synthesis reaction under the action of the catalyst. The fluidized bed reactor includes a raw material inlet, a catalyst inlet and a product outlet. The catalyst inlet is connected to the catalyst outlet, and the product outlet is connected to the inlet of the catalyst to be recovered.

[0053] In some embodiments of the present application, Figure 1 As shown, the catalyst recovery and regeneration system further includes a raw material preheater 02 for preheating the raw material. The raw material preheater 02 includes a preheating raw material inlet and a preheating raw material outlet, and the preheating raw material outlet is connected to the raw material inlet.

[0054] In some embodiments of the present application, Figure 1 As shown, the catalyst recovery and regeneration system also includes a raw gas mixer 01, which is used to mix raw gas (such as hydrogen and carbon dioxide). The raw gas mixer 01 is connected to the raw material preheater 02. After the raw gas is evenly mixed in the raw gas mixer 01, it is passed into the raw material preheater 02 for preheating. The preheated gas enters the fluidized bed reactor 03 for reaction.

[0055] In some embodiments of the present application, the raw material preheater 02 further includes a process gas inlet and a process gas outlet, and is configured to preheat the raw material using the heat of the process gas separated by the cyclone separator 04. The process gas inlet is connected to the gas outlet of the cyclone separator 04, and the process gas outlet is connected to the gas-liquid separator 05, the gas phase cooler 06, and the distillation tower 07, which are arranged in sequence. In the cyclone separator 04, the process gas is separated from the damaged catalyst and the catalyst to be separated. The catalyst to be separated enters the catalyst magnetic separation device 10, the molecular sieve regenerator 12, the catalyst mixer 14, etc. for regeneration; the process gas is separated and purified by the gas-liquid separator 05, the gas phase cooler 06, and the distillation tower 07. Among them, the gas-liquid separator 05 can separate the water, methanol and other components that are easily liquefied at room temperature in the process gas from other gaseous components; the gas phase cooler 06 deep-colds and liquefies the gas phase, and further separates the components by the distillation tower 07.

[0056] In some embodiments of the present application, Figure 1 As shown, the gas-liquid separator 05 includes a liquid outlet, which is connected to a liquid collecting device 08 , which is used to collect the liquid phase components separated from the gas-liquid separator 05 .

[0057] Since some reactions carried out in the fluidized bed reactor 03 are exothermic reactions, such as the reaction of preparing olefins using hydrogen and carbon dioxide as raw materials, in order to fully utilize the heat in the system, reduce energy consumption, and further reduce the cost of the catalyst recovery and regeneration system, the heat generated in the reaction can also be utilized. In some embodiments of the present application, such as Figure 1As shown, the catalyst recovery and regeneration system also includes a reactor heat exchanger 16 and a superheated steam generator 17, wherein the reactor heat exchanger 16 can remove the heat released by the reaction in the fluidized bed reactor 03; the superheated steam generator 17 can use the heat obtained from the reactor heat exchanger 16 to heat the circulating steam into superheated steam, and the superheated steam is used for fluidized transportation of solid catalyst in any one or more devices among the magnetic component collection device 11, the regenerated molecular sieve collection device 13, the catalyst mixer 14 and the regenerated catalyst collection device 15.

[0058] In some embodiments of the present application, Figure 1 The catalyst recovery and regeneration system shown is used to prepare olefins. During operation, there are mainly three parts of material flow, the first part is the reaction material, the second part is the catalyst, and the third part is steam.

[0059] The flow of reactants is mainly to obtain the final product after the reaction and separation of the reactants. The flow process of the reactants mainly includes: hydrogen and carbon dioxide enter the raw material mixer 01 for mixing; after uniform mixing, they are passed into the raw material preheater 02 to exchange heat with the high-temperature process gas after the reaction to increase the temperature; after heat exchange, they are passed into the fluidized bed reactor 03 for olefin synthesis reaction; the process gas obtained after the reaction is discharged from the product outlet of the fluidized bed reactor 03 and enters the cyclone separator 04; after cyclone separation, the gas phase is passed into the raw material preheater 02 to exchange heat with fresh raw material gas to reduce the temperature; the cooled process gas enters the gas-liquid separator 05 to separate water, methanol and other easily liquefied components at room temperature from other gas phase components; the separated gas phase is passed into the gas phase cooler 06 for deep-cold liquefaction of the gas phase; the liquid after deep-cold liquefaction is passed into the distillation tower 07 to separate the components, among which ethylene, propylene and butene are the main olefin products; the liquid phase after gas-liquid separation enters the liquid collecting device 08, and then the liquid is treated as waste liquid.

[0060] The flow of catalyst is mainly for the recovery, regeneration and reuse of catalyst, which is as follows: cyclone separator 04 is composed of multiple stages, and the catalyst separated in the last stage falls into the damaged catalyst collection device 09, and the remaining catalyst falls into the catalyst magnetic separation device 10. The catalyst magnetic separation device 10 can separate the ferromagnetic metal oxide part of the catalyst from the molecular sieve part, wherein the metal or metal oxide catalyst is sent to the magnetic component collection device 11; the molecular sieve catalyst after magnetic separation is sent to the molecular sieve regenerator 12 for regeneration, and the regeneration process is high-temperature oxidation to remove carbon deposits in the microporous structure of the molecular sieve; the regenerated catalyst is sent to the regenerated molecular sieve collection device 13; the catalysts in the magnetic component collection device 11 and the regenerated molecular sieve collection device 13 are sent to the catalyst mixer 14 in a certain proportion for mixing to obtain a carbon dioxide hydrogenation to olefin bifunctional catalyst that can be used for the reaction; the mixed catalyst is sent to the regenerated catalyst collection device 15, and the regenerated catalyst is then sent to the fluidized bed reactor 03 for synthesis reaction according to the reaction requirements.

[0061] Steam flow is primarily used to cool the reactor and transport catalyst materials. Specifically, during the reaction process, fluidized bed reactor 03 generates a large amount of heat, which needs to be removed promptly to ensure reaction stability. This heat is circulated through reactor heat extractor 16. The circulating steam is heated to superheated steam in superheated steam generator 17. This superheated steam is used to fluidize and transport the solid catalyst within magnetic component collection device 11, regenerated molecular sieve collection device 13, catalyst mixer 14, and regenerated catalyst collection device 15.

[0062] According to another typical embodiment of the present application, a catalyst recovery and regeneration method is provided, wherein the catalyst includes a magnetic component and a non-magnetic component, the magnetic component includes any one or more of a magnetic metal and a magnetic metal oxide, and the non-magnetic component includes a molecular sieve; the method includes: passing a product system containing the catalyst into a cyclone separator for coarse separation to obtain a process gas and a catalyst to be separated; separating the catalyst to be separated by magnetic separation to obtain a magnetic component and a non-magnetic component; heating and oxidizing the non-magnetic component to obtain a regenerated non-magnetic component; mixing the regenerated non-magnetic component and the magnetic component to obtain a regenerated catalyst.

[0063] For catalysts containing both magnetic and non-magnetic components, the catalyst recovery and regeneration method of the present application separates the magnetic and non-magnetic components through magnetic separation, regenerates the non-magnetic component through thermal oxidation, and then remixes it with the magnetic component after regeneration to achieve catalyst recovery and reuse. The catalyst recovery and regeneration method of the present application can reduce catalyst consumption, thereby reducing operating costs and improving economic benefits.

[0064] The above-mentioned catalysts including magnetic components and non-magnetic components can be recycled and regenerated using the catalyst recovery and regeneration method of the present application. Taking FeCu / TiO2-SAPO34 catalyst as an example, since the catalyst contains a large amount of Fe, the FeCu / TiO2 part of the catalyst is coupled with the molecular sieve part by mechanical mixing, so the FeCu / TiO2 part can be separated from the molecular sieve part by magnetic separation to achieve the separate regeneration of the molecular sieve. The regenerated molecular sieve can be mixed and coupled with FeCu / TiO2 again for reaction to achieve the improvement of catalyst life, and the SAPO34 molecular sieve in the catalyst is of high value. Regeneration after separation can reduce the consumption of the catalyst, thereby reducing operating costs and improving economic benefits.

[0065] The magnetic components and non-magnetic components in the catalyst are separated by a magnetic separation method so that the non-magnetic components can be subjected to a high-temperature decarbonization treatment alone. In some embodiments of the present application, a powder magnetic separation device is used for magnetic separation, and the magnetic components are adsorbed on the conveyor belt by a conveyor belt with a vibration function. When the conveyor belt turns to the bottom, the adsorbed catalyst in this row can be scraped off by a scraper or the electromagnet can be demagnetized to make this row of catalyst fall into the collection port below. The molecular sieve that is not adsorbed is transported to the end and falls into another molecular sieve collection port or a conveyor belt with the same function at the next level, ultimately achieving the separation of the two components. The conveyor belt consists of 2 to 6 levels, and the magnetic field strength is 15000 to 20000Gs (Gauss).

[0066] In some embodiments of the present application, the temperature of the above-mentioned heating oxidation is 600-700°C, which is effective for removing carbon deposits in molecular sieves. For example, the temperature of the heating oxidation can be 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 68°C, 690°C, 700°C, etc., or other values ​​within the above range. In some embodiments of the present application, the heating oxidation time is 1-30 minutes.

[0067] In some embodiments of the present application, the regenerated non-magnetic component and the magnetic component are mixed in a ratio of (0.2-1:1), and the mixed catalyst has a better catalytic effect. The regenerated catalyst obtained after mixing can be reused in the reaction and can be recycled again after the reaction is completed. This cycle increases the utilization rate of the catalyst and thus reduces the catalyst cost in the olefin production process.

[0068] According to another typical embodiment of the present application, a method for preparing olefins is provided, the method comprising:

[0069] Preheated hydrogen and carbon dioxide are introduced into a fluidized bed to carry out an olefin synthesis reaction under the action of a catalyst to obtain a product system containing the catalyst; wherein the catalyst includes a regenerated catalyst obtained by any of the above-mentioned catalyst recovery and regeneration methods; the product system containing the catalyst is treated according to any of the above-mentioned catalyst recovery and regeneration methods, or is treated using any of the above-mentioned catalyst recovery and regeneration systems, and the obtained process gas is subjected to gas-liquid separation, gas-phase cooling and distillation to obtain an olefin product.

[0070] In the above-mentioned method for preparing olefins, since the above-mentioned catalyst including magnetic components and non-magnetic components is used and is treated according to any of the above-mentioned catalyst recovery and regeneration methods, or is treated using any of the above-mentioned catalyst recovery and regeneration systems, the activity and recovery efficiency of the catalyst can be significantly improved, thereby significantly reducing the cost investment of the catalyst and the preparation cost of olefins, and having excellent economic value and environmental value.

[0071] In some embodiments of the present application, the catalyst is loaded into the fluidized bed reactor 03 and the regenerated catalyst collecting device 15 before the reaction starts. During loading, the mass ratio of the catalyst in the fluidized bed reactor 03 and the regenerated catalyst collecting device 15 is 0.5 to 1. After the operation starts, the efficient olefin preparation process can be entered, and the catalyst can be continuously recycled and regenerated.

[0072] In some embodiments of the present application, the catalyst inventory within fluidized bed reactor 03 can be controlled by the amount of steam entering regenerated catalyst collection device 15. When it is necessary to reduce the inventory within fluidized bed reactor 03, the superheated steam flow rate is reduced, thereby reducing the amount of catalyst entering fluidized bed reactor 03 from regenerated catalyst collection device 15. When the feed gas flow rate remains unchanged, the amount of catalyst carried out of the fluidized bed by the reaction gas remains essentially unchanged, thereby reducing the catalyst inventory within fluidized bed reactor 03. If it is necessary to increase the inventory within fluidized bed reactor 03, the superheated steam flow rate can be increased. Similarly, a similar method can be used to control the inventory of solids within magnetic component collection device 11, regenerated molecular sieve collection device 13, and catalyst mixer 14.

[0073] In some embodiments of the present application, nitrogen, rather than hydrogen and carbon dioxide, is first flushed into the fluidized bed reactor 03 before the reaction begins. The nitrogen flow rate is equal to the sum of the H2 and CO2 flows during a normal reaction. Nitrogen is also introduced into the regenerated catalyst collection device 15. The flow of nitrogen fluidizes the catalyst within the fluidized bed. Subsequently, the nitrogen in the fluidized bed reactor 03 is replaced with H2 and CO2 feed gases, and the nitrogen in the regenerated catalyst collection device 15 is replaced with high-temperature steam to initiate normal system operation.

[0074] The reaction conditions of the fluidized bed reactor 03 can be determined by the reaction conditions required by the catalyst. In some embodiments of the present application, the temperature of the olefin synthesis reaction is 300-400° C. and the pressure is 1-3 MPa.

[0075] In some embodiments of the present application, in order to further improve the production efficiency and selectivity of olefins, the volume ratio of hydrogen to carbon dioxide introduced into the fluidized bed is 2-4.

[0076] The space velocity in the reaction can be determined according to the flow rate required for the fluidization state of the fluidized bed reactor 03. In some embodiments of the present application, the reaction space velocity of the olefin synthesis reaction is 3000 to 20000 mL / (gcat·h).

[0077] The following examples and comparative examples will further illustrate the beneficial effects that can be achieved by the present application.

[0078] Example 1

[0079] Use Figure 1 The catalyst recovery and regeneration system shown in the figure is used to produce olefins. The catalyst used is FeCu / TiO2-SAPO-34, where the FeCu / TiO2 portion can convert CO2 into methanol and hydrocarbons, and the SAPO-34 portion can further convert methanol and hydrocarbons into light olefins. The mass ratio of FeCu / TiO2 to SAPO-34 is 2:1. The specific process flow is as follows:

[0080] 1) Before the reaction begins, the catalyst is loaded into the fluidized bed reactor 03 and the regenerated catalyst collecting device 15. During loading, the mass ratio of the catalyst in the fluidized bed reactor 03 and the regenerated catalyst collecting device 15 is 1:1.

[0081] 2) Before the system reaction begins, H2 and CO2 should be replaced with N2. The N2 flow rate should be the same as the sum of the H2 and CO2 flows during normal reaction. N2 should also be introduced into the regenerated catalyst collection device 15. The flow of N2 fluidizes the catalyst in the fluidized bed. Subsequently, the N2 in the fluidized bed reactor 03 is replaced with H2 and CO2 feed gases in a ratio of 3:1. The N2 in the regenerated catalyst collection device 15 is replaced with high-temperature steam to initiate normal system operation.

[0082] 3) The reaction temperature of fluidized bed reactor 03 is 350°C, the pressure is 3 MPa, the volume ratio of H2 to CO2 is 3:1, and the reaction space velocity is 6000 mL / (gcat·h).

[0083] 4) The cyclone separator 04 is composed of 4 stages in series. The solid separated in the last stage is discharged to the damaged catalyst collection device 09. The catalyst in the damaged catalyst collection device 09 no longer participates in the reaction. The separated catalyst to be regenerated enters the catalyst magnetic separation device 10 for magnetic separation. The process gas enters the raw material preheater, exchanges heat with the fresh raw material, and the cooled process gas is sequentially passed through the gas-liquid separator for gas-liquid separation, the gas phase cooler for gas phase cooling, and the distillation tower for distillation to obtain olefin products.

[0084] 5) Catalyst magnetic separation device 10 uses a powder magnetic separation device to separate the ferromagnetic catalyst portion from the molecular sieve portion, and the ferromagnetic catalyst portion falls into a magnetic component collection device 11 and a molecular sieve regenerator 12, respectively. The components entering the magnetic component collection device 11 are not further processed and are directly transported by steam to the catalyst mixer 14.

[0085] 6) Air is introduced into the molecular sieve regenerator 12 and heated to maintain 620°C for 5 minutes, so that the carbon deposits on the molecular sieve catalyst react with oxygen to generate CO2, thereby eliminating the carbon deposits. The regenerated molecular sieve falls into the regenerated molecular sieve collection device 13, and the regenerated molecular sieve in the regenerated molecular sieve collection device 13 is transported to the catalyst mixer 14 by steam.

[0086] 7) The catalyst mixer 14 mixes the regenerated catalyst from the regenerated molecular sieve collecting device 13 with the ferromagnetic catalyst portion from the magnetic component collecting device 11 in a mass ratio of 1:2 to obtain a regenerated catalyst, and transports the mixture to the regenerated catalyst collecting device 15 via steam.

[0087] 8) The regenerated catalyst collecting device 15 is provided with a catalyst feeding port, and the amount of fresh catalyst added is the same as the mass entering the damaged catalyst collecting device 09.

[0088] The recovery rate of the catalyst was 99%, and the attenuation rate of the light olefin yield over 7 days was 0.06%.

[0089] Example 2

[0090] The difference from Example 1 is that in step 6), the heating temperature of the molecular sieve regenerator 12 is 600°C.

[0091] The recovery rate of the catalyst was 99%, and the attenuation rate of the light olefin yield over 7 days was 0.06%.

[0092] Example 3

[0093] The difference from Example 1 is that in step 6), the heating temperature of the molecular sieve regenerator 12 is 700°C.

[0094] The recovery rate of the catalyst was 99%, and the decay rate of the light olefin yield over 7 days was 0.10%.

[0095] Example 4

[0096] The difference from Example 1 is that in step 6), the heating temperature of the molecular sieve regenerator 12 is 800°C.

[0097] The recovery rate of the catalyst was 99%, and the decay rate of the light olefin yield over 7 days was 0.15%.

[0098] Example 5

[0099] The difference from Example 1 is that in step 6), the heating temperature of the molecular sieve regenerator 12 is 550°C.

[0100] The recovery rate of the catalyst was 99%, and the decay rate of the light olefin yield over 7 days was 0.30%.

[0101] Comparative Example 1

[0102] The catalyst used is the same as that in Example 1. The difference from Example 1 lies in the process flow, which is as follows:

[0103] 1) Before the reaction begins, the catalyst is loaded into the fluidized bed reactor and the regenerated catalyst collection device. During loading, the mass ratio of the catalyst in the fluidized bed reactor to the regenerated catalyst collection device is 1:1.

[0104] 2) Before the system reaction begins, H2 and CO2 should be replaced with N2. The N2 flow rate should be the same as the sum of the H2 and CO2 flows during normal reaction. N2 should also be introduced into the regenerated catalyst collection device to fluidize the catalyst in the fluidized bed. Subsequently, the N2 in the fluidized bed reactor should be replaced with H2 and CO2 feed gases in a ratio of 3:1. The N2 in the regenerated catalyst collection device should be replaced with high-temperature steam to initiate normal system operation.

[0105] 3) The reaction temperature of the fluidized bed reactor is 350°C, the pressure is 3 MPa, the volume ratio of H2 to CO2 is 3:1, and the reaction space velocity is 6000 mL / (gcat·h).

[0106] 4) The cyclone separator is composed of 4 stages in series. The solid separated in the last stage is discharged to the damaged catalyst collection device. The catalyst in the damaged catalyst collection device no longer participates in the reaction. The separated catalyst to be regenerated enters the molecular sieve regenerator for regeneration. The process gas enters the raw material preheater, exchanges heat with the fresh raw material, and the cooled process gas is sequentially passed through the gas-liquid separator for gas-liquid separation, the gas phase cooler for gas phase cooling, and the distillation tower for distillation to obtain olefin products.

[0107] 5) Air is introduced into the molecular sieve regenerator and heated to maintain 620°C for 5 minutes, so that the carbon deposits on the catalyst to be regenerated react with oxygen to generate CO2, thereby eliminating the carbon deposits. The regenerated catalyst falls into the regenerated catalyst collection device.

[0108] 6) The regenerated catalyst collection device is provided with a catalyst feeding port, and the amount of fresh catalyst added is the same as the mass entering the worn catalyst collection device.

[0109] The recovery rate of the catalyst was 99%, and the decay rate of the light olefin yield over 7 days was 17.2%.

[0110] From the above description, it can be seen that the above-mentioned embodiments of the present invention achieve the following technical effects: for a catalyst comprising both a magnetic component and a non-magnetic component, wherein the magnetic component comprises a magnetic metal or a magnetic metal oxide, which is easily deactivated due to high-temperature heating during the regeneration process, the catalyst recovery and regeneration system of the present application can separate the magnetic component and the non-magnetic component by magnetic separation, regenerate the non-magnetic component alone in the molecular sieve regenerator 12, and then mix it with the magnetic component after regeneration to achieve catalyst recovery and reuse. The catalyst recovery and regeneration system of the present application can reduce the consumption of the catalyst, thereby reducing operating costs and improving economic benefits.

[0111] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A catalyst recovery and regeneration system, characterized in that: The catalyst recovery and regeneration system comprises: A cyclone separator (04), the cyclone separator (04) comprising an inlet for catalyst to be recovered, a gas outlet, an outlet for damaged catalyst and an outlet for catalyst to be separated, the cyclone separator (04) being used to separate damaged catalyst from catalyst to be regenerated in the catalyst, the inlet for catalyst to be recovered being used to introduce the catalyst to be regenerated; A catalyst magnetic separation device (10), the catalyst magnetic separation device (10) comprising an inlet for a catalyst to be separated, a magnetic component collecting device (11) and a molecular sieve outlet, the inlet for the catalyst to be separated being connected to the outlet for the catalyst to be separated, the catalyst magnetic separation device (10) being used to separate magnetic components and non-magnetic components in the catalyst to be regenerated by magnetic separation, and the magnetic component collecting device (11) being used to collect the magnetic components separated by magnetic separation; A molecular sieve regenerator (12), the molecular sieve regenerator (12) comprising a molecular sieve inlet and a regenerated molecular sieve outlet, the molecular sieve regenerator (12) being used to regenerate the non-magnetic component to obtain a regenerated non-magnetic component, the molecular sieve inlet being in communication with the molecular sieve outlet; A catalyst mixer (14), comprising a regenerated molecular sieve inlet, a magnetic component inlet and a regenerated catalyst outlet, the catalyst mixer (14) is used to mix the regenerated non-magnetic component and the magnetic component to obtain a regenerated catalyst, the regenerated molecular sieve inlet is connected to the regenerated molecular sieve outlet, and the magnetic component inlet is connected to the magnetic component collecting device (11).

2. The catalyst recovery and regeneration system according to claim 1, characterized in that: The cyclone separator (04) consists of 2-5 stages; The molecular sieve regenerator (12) comprises a gas inlet for introducing an oxygen-containing gas; The heating temperature of the molecular sieve regenerator (12) is 600-700°C; The catalyst recovery and regeneration system further comprises a regenerated molecular sieve collecting device (13) for collecting the regenerated non-magnetic components, the regenerated molecular sieve collecting device (13) comprises a regenerated molecular sieve collecting device inlet and a regenerated molecular sieve collecting device outlet, the regenerated molecular sieve collecting device inlet is connected to the regenerated molecular sieve outlet, the regenerated molecular sieve collecting device outlet is connected to the regenerated molecular sieve inlet, and the regenerated catalyst collecting device is used to collect the regenerated non-magnetic components; The catalyst recovery and regeneration system further comprises a regenerated catalyst collecting device (15) for collecting the regenerated catalyst, wherein the regenerated catalyst collecting device (15) comprises a regenerated catalyst collecting device inlet and a catalyst outlet, wherein the regenerated catalyst collecting device inlet is connected to the regenerated catalyst outlet; preferably, the regenerated catalyst collecting device (15) further comprises a catalyst feeding port for replenishing fresh catalyst; The catalyst recovery and regeneration system further comprises a damaged catalyst collecting device (09) for collecting the damaged catalyst. The damaged catalyst collecting device (09) comprises a damaged catalyst inlet, and the damaged catalyst inlet is connected to the damaged catalyst outlet.

3. The catalyst recovery and regeneration system according to claim 2, characterized in that: The catalyst recovery and regeneration system further comprises a fluidized bed reactor (03) for carrying out an olefin synthesis reaction under the action of the catalyst, wherein the fluidized bed reactor comprises a raw material inlet, a catalyst inlet and a product outlet, wherein the catalyst inlet is connected to the catalyst outlet, and the product outlet is connected to the catalyst inlet to be recovered. Preferably, the catalyst recovery and regeneration system further comprises a raw material preheater (02) for preheating the raw material, wherein the raw material preheater (02) comprises a preheating raw material inlet and a preheating raw material outlet, and the preheating raw material outlet is connected to the raw material inlet.

4. The catalyst recovery and regeneration system according to claim 3, characterized in that: The raw material preheater (02) further comprises a process gas inlet and a process gas outlet, and is configured to utilize the heat of the process gas separated by the cyclone separator (04) to preheat the raw material, the process gas inlet is connected to the gas outlet of the cyclone separator (04), and the process gas outlet is connected to the gas-liquid separator (05), the gas phase cooler (06) and the distillation tower (07) which are arranged in sequence; The gas-liquid separator (05) comprises a liquid outlet, and the liquid outlet is connected to the liquid collecting device (08).

5. The catalyst recovery and regeneration system according to claim 3, characterized in that: The catalyst recovery and regeneration system further comprises a reactor heat extractor (16) and a superheated steam generator (17), wherein: The reactor heat extractor (16) is capable of removing heat released by the reaction in the fluidized bed reactor (03); The superheated steam generator (17) can utilize the heat obtained from the reactor heat extractor (16) to heat the circulating steam into superheated steam, and the superheated steam is used for fluidized transport of solid catalyst in any one or more of the magnetic component collection device (11), the regenerated molecular sieve collection device (13), the catalyst mixer (14) and the regenerated catalyst collection device (15).

6. A catalyst recovery and regeneration method, characterized in that: The catalyst comprises a magnetic component and a non-magnetic component, wherein the magnetic component comprises any one or more of a magnetic metal and a magnetic metal oxide, and the non-magnetic component comprises a molecular sieve; and the method comprises: Passing the product system containing the catalyst into a cyclone separator for rough separation to obtain a process gas and a catalyst to be separated; Separating the catalyst to be separated by magnetic separation to obtain a magnetic component and a non-magnetic component; The non-magnetic component is subjected to heating and oxidation treatment to obtain a regenerated non-magnetic component; The regenerated non-magnetic component and the magnetic component are mixed to obtain a regenerated catalyst.

7. The catalyst recovery and regeneration method according to claim 6, characterized in that: The catalyst is a FeCu / TiO2-SAPO34 tandem catalyst.

8. The catalyst recovery and regeneration method according to claim 6, characterized in that: The temperature of the heating oxidation is 600-700°C and the time is 1-30 minutes; The regenerated non-magnetic component and the magnetic component are mixed in a mass ratio of (0.2-1):

1.

9. A method for preparing olefins, characterized in that: The preparation method comprises: Preheated hydrogen and carbon dioxide are introduced into a fluidized bed to carry out an olefin synthesis reaction under the action of a catalyst to obtain a product system containing the catalyst; wherein the catalyst comprises a regenerated catalyst obtained by the catalyst recovery and regeneration method according to any one of claims 6 to 8 or a regenerated catalyst obtained by using the catalyst recovery and regeneration system according to any one of claims 1 to 5; the product system containing the catalyst is treated according to the catalyst recovery and regeneration method according to any one of claims 6 to 8, or is treated by using the catalyst recovery and regeneration system according to any one of claims 1 to 5, and the obtained process gas is subjected to gas-liquid separation, gas phase cooling and distillation to obtain an olefin product.

10. The method for preparing olefins according to claim 9, characterized in that: The volume ratio of hydrogen and carbon dioxide introduced into the fluidized bed is 2 to 4; The temperature of the olefin synthesis reaction is 300-400°C and the pressure is 1-3MPa; The reaction space velocity of the olefin synthesis reaction is 3000 to 20000 mL / (gcat·h); The regenerated catalyst is placed in a regenerated catalyst collecting device. Before the olefin synthesis reaction starts, the mass ratio of the catalyst in the fluidized bed to that in the regenerated catalyst collecting device is 0.5-1.

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