Method and system for catalytic cracking catalyst regeneration using biomass charcoal fuel

Abstract

Disclosed is a catalyst regeneration method suitable for a fluid catalytic cracking unit. The fluid catalytic cracking unit comprises a catalytic cracking reactor and a catalyst regenerator. The regeneration method includes the following steps: 1) a step of providing biomass charcoal derived from biomass; 2) a step of supplying the biomass charcoal and the used catalyst, together or separately, from the catalytic cracking reactor to the catalyst regenerator; 3) a step of introducing an oxygen-containing gas into the catalyst regenerator, wherein the oxygen content of the oxygen-containing gas is 14% to 28% by volume; and 4) a step of bringing the used catalyst into contact with the biomass charcoal and the oxygen-containing gas in the catalyst regenerator to perform coke combustion regeneration. The method provided by the present application can fundamentally change the energy source of the device, greatly reduce the carbon emissions of the catalytic cracking unit, realize the recycling of carbon, and provide energy for other processing devices.

Description

Technical Field

[0001] This application relates to the regeneration of a coked catalytic cracking catalyst, and particularly to a method and system for regenerating a catalytic cracking catalyst using biomass carbon fuel.

Background Art

[0002] Today, the development of the world's oil refining industry is facing many challenges, such as the replacement of new energy and the strengthening of energy conservation and emission reduction requirements. Flexibly adjusting the production plan, reducing carbon dioxide emissions, and mitigating climate change have become the only way for the oil refining industry to transform its economic growth model and maintain sustainable development. It is urgent to achieve carbon peak by 2030 and carbon neutrality by 2060. The "14th Five-Year Plan" has formulated a carbon peak action plan that clearly requires accelerating the promotion of green development. China's national carbon emission trading market was also officially launched in 2021. Therefore, it is particularly important to effectively reduce carbon emissions in the process of oil refining and chemical product production. The research on low-carbon catalytic cracking schemes to reduce oil and increase the production of chemical products is an important issue for future refineries. Carbon emissions in the heavy oil processing process mainly come from catalytic cracking coke combustion, exhaust gas discharged from equipment such as hydrogen production processes and boilers, and energy consumption in the process. Among them, the catalytic cracking unit is the core equipment of the refinery. The carbon emissions from coke combustion in the catalytic cracking regenerator account for 24% - 55% of the total carbon emissions of the whole factory and nearly 1% of the national carbon dioxide emissions. This is the focus of carbon emission reduction in the petrochemical industry.

[0003] CN113877397A discloses an incomplete regeneration process for reducing carbon dioxide emissions. This process uses pure oxygen to incompletely regenerate the catalyst. In the resulting exhaust gas, carbon monoxide is used as a chemical raw material, and carbon dioxide is used for storage or oil recovery, thereby reducing carbon dioxide emissions. However, this process mainly involves a costly exhaust gas post-treatment process. This process involves the separation of carbon monoxide, carbon dioxide, oxygen, and other wastes, and the separation process is also complex. Incomplete regeneration cannot maximize the chemical energy of coke, and the storage of concentrated carbon dioxide causes waste of resources.

[0004] U2)011 / 0155642A1 discloses a catalytic cracking process for reducing carbon dioxide emissions, using a regeneration technology with a coke combustion tube and a dense bed connected in series, pure oxygen, and multi-point auxiliary oxygen. It emphasizes adding a tank to the regeneration route to degas the regenerated catalyst with nitrogen, and adding a tank to the route to be regenerated to mix the regenerated catalyst and the catalyst to be regenerated and raise the temperature before regeneration. Although the coke combustion efficiency of this process is improved, the advantages of pure oxygen regeneration are lost, and the recovery of carbon dioxide is difficult. The effect of reducing carbon dioxide emissions is slight, and the cost is relatively high.

[0005] US4542114A proposes a regeneration operation method using oxygen and carbon dioxide, which is a method of recycling, collecting, and recovering carbon dioxide. However, this process is relatively complex. Since the separation of carbon dioxide uses distillation separation, the energy consumption is high, and energy loss occurs because the pressure energy of the regenerated exhaust gas is not recovered, which does not conform to the concept of low carbon and environmental protection.

[0006] The energy of the catalytic cracking unit is derived from the coke combustion of the catalyst. When a large amount of low-carbon olefins and other chemical substances are produced, the gas yield increases, so more reaction heat is required. If the amount of coke combustion is not sufficient to meet the energy consumption of the unit, usually, the coke production amount is increased by recycling the oil slurry, increasing the proportion of heavy oil in the feedstock oil, or injecting fuel oil to raise the regeneration temperature. All of these three methods can satisfy the heat balance of the reaction, but all of them have a certain impact on the operation of the unit. In addition, since the auxiliary energy is derived from fossil energy sources, it increases the carbon dioxide emissions from fossil energy sources and does not contribute to the improvement of the utilization rate of petroleum resources. By optimizing the regeneration process, the energy utilization efficiency can be improved, and thereby the carbon dioxide emissions can be reduced to a certain extent. The carbon dioxide emissions can also be reduced to a certain extent by recycling and recovering the discharged carbon dioxide, but the cost is high and the process is relatively complex. However, the above ideas do not fundamentally change the energy source, and the carbon dioxide still comes from fossil energy sources.

[0007] Therefore, it is necessary to develop a catalyst regeneration method that can fundamentally reduce the carbon dioxide emissions from fossil energy sources, meet the energy supply required by the unit while reducing carbon dioxide emissions, and realize low-carbon development. Summary of the Invention

[0008] The object of the present application is to provide a method and a system for catalyst regeneration suitable for a fluid catalytic cracking unit. This method and system introduce a solid biomass carbon fuel derived from biomass into the catalyst regeneration system for combustion to provide energy, maintain the heat balance of the fluid catalytic cracking unit, and thereby fundamentally reduce the carbon dioxide emissions from fossil energy sources.

[0009] To achieve the above object, on the one hand, the present application provides a catalyst regeneration method suitable for a fluid catalytic cracking apparatus including a catalytic cracking reactor and a catalyst regenerator. The regeneration method includes the following steps: 1) A step of providing biomass charcoal derived from biomass; 2) A step of supplying the biomass charcoal and the catalyst to be regenerated from the catalytic cracking reactor to the catalyst regenerator together or separately; 3) A step of introducing an oxygen-containing gas into the catalyst regenerator, wherein the oxygen content of the oxygen-containing gas is 14% to 28% by volume, and preferably, the oxygen-containing gas is selected from air and oxygen diluted with the regenerated exhaust gas; and 4) A step of bringing the catalyst to be regenerated into contact with the biomass charcoal and the oxygen-containing gas in the catalyst regenerator for coke combustion regeneration.

[0010] Preferably, in step 1), pyrolytic carbon black obtained from other sources, such as pyrolysis treatment of waste tires, is further provided, and in step 2), the pyrolytic carbon black and the biomass charcoal are supplied to the catalyst regenerator together or separately.

[0011] On the other hand, the present application provides a catalyst regeneration system suitable for a fluid catalytic cracking apparatus including a biomass treatment apparatus and a catalyst regeneration apparatus: The biomass treatment apparatus is used to treat biomass to obtain biomass charcoal, and includes a biomass charcoal generator, a pulverizer, and a storage tank connected in sequence. The biomass charcoal generator is provided with a biomass raw material inlet and a product outlet. The product outlet is connected to the inlet of the pulverizer, and the outlet of the pulverizer is connected to the inlet of the storage tank; The catalyst regeneration apparatus is used to regenerate the catalyst to be regenerated from the catalytic cracking reactor, and includes a catalyst regenerator having at least one solid material inlet, an oxygen-containing gas inlet, a regeneration exhaust gas outlet, and a regenerated catalyst outlet. The outlet of the storage tank is connected to the solid material inlet of the catalyst regenerator.

[0012] Preferably, after the biomass charcoal is introduced into the catalytic cracking reactor, it is supplied to the catalyst regenerator together with the catalyst to be regenerated.

[0013] Compared with the existing methods and systems for catalytic cracking catalyst regeneration, the catalyst regeneration method and system of the present application have the following advantages: (1) Biomass is inexpensive and easily available. Biomass energy is a renewable energy source, and its carbon is derived from carbon dioxide captured by plants from the atmosphere, making it a zero-carbon energy source. Compared with other treatment methods such as landfilling, the resource utilization of waste tires generates less carbon dioxide and can control the carbon dioxide generation process, which is an important part of the circular economy. By using the above resources as energy sources, the energy supply source of the catalytic cracking device can be fundamentally changed, reducing carbon dioxide emissions from fossil energy and realizing the low-carbonization of refining; (2) The preparation process of biomass charcoal is simple, and the consumed energy can be obtained from renewable energy sources such as solar energy and green electricity, so the carbon dioxide emissions can be reduced throughout the life cycle of catalytic cracking; (3) Biomass charcoal has a high calorific value and is a solid fuel. It can be combined with the regeneration process of the catalytic cracking catalyst, and the method of integrating it into the regeneration system is simple and easy to implement; (4) In a preferred embodiment, by first introducing biomass charcoal into the catalytic cracking reactor, the heavy components that are difficult to convert in the reaction raw materials can be adsorbed and transported to the catalyst regenerator, thereby improving the reactivity of the raw materials, and a part of this heavy component can be used to enhance the energy supply; (5) Carbon dioxide in the regeneration exhaust gas can be separated and captured, contributing to the achievement of negative carbon emissions; (6) The surplus heat generated in the regeneration system can be supplied to other devices.

[0014] Other features and advantages of the present application will be described in detail in the following sections of the specific embodiments.

[0015] The accompanying drawings are used to provide a further understanding of the present application and form a part of this specification. They are used to explain the present application together with the following specific embodiments, but do not constitute a limitation of the present application.

Brief Description of the Drawings

[0016]

Figure 1

Figure 2

Figure 3

Figure 4

Modes for Carrying Out the Invention

[0017] Hereinafter, specific embodiments of the present application will be described in detail in conjunction with the accompanying drawings. It should be understood that the specific embodiments described in this specification are for the purpose of exemplifying and explaining the present application, and not for limiting the present application.

[0018] As used herein, the expression "exemplary" means "serving as an example, embodiment or illustration". Any embodiment described as "exemplary" in this specification is not necessarily construed as being superior to or better than other embodiments. Although various aspects of the embodiments are shown in the drawings, unless otherwise specified, the drawings are not necessarily drawn to scale.

[0019] Any specific numerical value (including the endpoint values of a numerical range) disclosed in this specification should not be limited to the exact value of the numerical value, but should be understood to cover values close to the exact value, such as all possible values within ±5% of the exact value. Further, for the disclosed numerical range, one or more new numerical ranges can be obtained by any combination between the endpoint values of the range, between an endpoint value and a specific point value within the range, and between specific point values, and these new numerical ranges should also be regarded as specifically disclosed in this specification.

[0020] In this application, the so-called "upstream" and "downstream" are based on the flow direction of the reactants. For example, when the reactants flow from the bottom to the top, "upstream" means the lower position and "downstream" means the upper position.

[0021] It should be noted that in this application, terms such as "up", "down", "middle", "outside", "front", "rear", "left", and "right" indicate the direction or positional relationship based on the direction or positional relationship in the operating state of this application. These are for convenience in explaining this application and simplifying the explanation, and do not indicate or imply that the device or element being referred to must have a specific direction and be constructed and operated in a specific direction. Therefore, these should not be understood as limitations of this application.

[0022] It should be noted that, in this application, unless specifically specified and limited, the terms "install", "connected", "connect", and "couple" should be understood in a broad sense. For those skilled in the art, the specific meanings of the above terms in this application can be understood according to the specific circumstances. For example, in this application, the term "connected" includes both the situation where two things are directly connected and the situation where two things are connected through one or more intermediate devices. In particular, in this application, the so-called "the outlet of the storage tank is connected to the solid material inlet of the catalyst regenerator" may mean that the outlet of the storage tank is directly connected to the solid material inlet of the catalyst regenerator, or the outlet of the storage tank is directly connected to the solid material inlet of the catalyst regenerator through other devices, such as a catalytic cracking reactor and / or a mixing tank and the inclined pipe to be regenerated.

[0023] The terms used in this specification have the same meanings as generally understood by those skilled in the art, unless otherwise specified. When a term is defined in this specification and its definition is different from the meaning generally understood by those skilled in the art, the definition in this specification shall prevail.

[0024] In this application, except for what is explicitly described, matters or items not described shall be directly applied as known in the technical field without any change. Furthermore, any embodiment described in this specification can be freely combined with one or more other embodiments described in this specification, and the technical solutions or technical ideas formed thereby shall be regarded as part of the original disclosure or original record of the present invention, and shall not be regarded as new content not disclosed or anticipated in this specification, unless those skilled in the art consider the combination to be clearly unreasonable.

[0025] All patent documents and non-patent documents mentioned in this specification, including but not limited to textbooks and journal papers, are incorporated herein by reference in their entirety.

[0026] Furthermore, the technical features involved in different embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.

[0027] As described above, in the first aspect, the present application provides a catalyst regeneration method suitable for a fluid catalytic cracking unit including a catalytic cracking reactor and a catalyst regenerator, and the regeneration method includes the following steps: 1) A step of providing biomass carbon derived from biomass; 2) A step of supplying biomass carbon and the catalyst to be regenerated from the catalytic cracking reactor to the catalyst regenerator together or separately; 3) A step of introducing an oxygen-containing gas into the catalyst regenerator, wherein the oxygen content of the oxygen-containing gas is 14% to 28% by volume; and 4) A step of bringing the catalyst to be regenerated into contact with biomass carbon and the oxygen-containing gas in the catalyst regenerator for coke combustion regeneration.

[0028] The utilization of biomass is essentially an indirect solar energy utilization process. The carbon contained in biomass is not derived from fossil energy but from carbon dioxide collected by plants from the atmosphere, and the energy consumed in the whole process is also derived from solar energy. Therefore, the utilization of biomass energy is also a recycling of carbon elements and a carbon-neutral emission process. In addition, by reasonably utilizing waste tires, pollution can be reduced and carbon dioxide emissions can be reduced, which is an important part of the circular economy. In the method of the present application, biomass carbon is introduced into the power center of the catalytic cracking unit to supply the energy required for the operation of the unit. The discharged carbon dioxide is not derived from fossil energy, which can fundamentally change the energy source and achieve carbon dioxide emission reduction.

[0029] According to the present application, in a preferred embodiment, the biomass includes, but is not limited to, agricultural and forestry biomass, forestry biomass, aquatic plants, energy crops, and cash crops. Agricultural and forestry biomass includes, but is not limited to, straw, rice husks, cotton stalks, etc. Forestry biomass includes, but is not limited to, firewood, fast-growing forests, forestry processing residues, etc. Aquatic plants include, but are not limited to, reeds, algae, etc. Energy crops and cash crops include, for example, cassava, rapeseed, etc.

[0030] In a preferred embodiment, the operating temperature of the catalyst regenerator is in the range of 550°C to 750°C, and the average catalyst residence time is 1.0 minute to 15.0 minutes.

[0031] In a preferred embodiment, the particle size of the biomass charcoal is 30 microns to 1000 microns, and the weight ratio of the generated catalyst to the biomass charcoal is 30:1 to 300:1. In such a preferred embodiment, the biomass charcoal particles can be well mixed with the catalyst to be regenerated, the mixing is more uniform, and it contributes to heat conduction and more complete combustion. While supplying more energy, the mixing can prevent unburned particles and ash from entering the reactor together with the regenerated catalyst.

[0032] In a preferred embodiment, in step 2), the biomass charcoal is pre-mixed with the catalyst to be regenerated from the catalytic cracking reactor and then fed into the catalyst regenerator together. More preferably, the mixing is carried out in a mixing tank, and the mixing tank is provided in the inclined pipe for the catalyst to be regenerated for transporting the catalyst to be regenerated from the catalytic cracking reactor to the catalyst regenerator.

[0033] In a preferred embodiment, in step 2), after introducing the biomass charcoal into the catalytic cracking reactor, it is fed into the catalyst regenerator together with the catalyst to be regenerated. In this preferred embodiment, the biomass charcoal introduced into the catalytic cracking reactor can adsorb the heavy components in the reaction raw materials that are difficult to react and carry them to the catalyst regenerator, thereby improving the reactivity of the raw materials and increasing the energy supply by utilizing the heavy components.

[0034] In a preferred embodiment, the oxygen-containing gas in step 3) is selected from air and oxygen diluted with the recycled exhaust gas.

[0035] In a specific preferred embodiment, the catalyst regenerator is a single-stage regenerator, and the operating conditions of the single-stage regenerator include an operating temperature of 600°C to 750°C, an average catalyst residence time of 2.0 minutes to 15.0 minutes, and a gas superficial velocity of 0.7 m / s to 2.0 m / s.

[0036] In another preferred embodiment, the catalyst regenerator is a two-stage regenerator comprising a coke combustion section and a regeneration section that are fluidly connected. In step 2), the biomass carbon and the catalyst to be regenerated are supplied to the coke combustion section together or separately, and in step 3), the oxygen-containing gas is introduced into the bottoms of the coke combustion section and the regeneration section, respectively.

[0037] In a further preferred embodiment, the operating conditions of the coke combustion section include: an operating temperature of 580°C to 720°C, an average catalyst residence time of 1.0 second to 60.0 seconds, preferably 5.0 seconds to 50.0 seconds, and a gas superficial velocity of 0.5 m / s to 5.0 m / s, preferably 1.0 m / s to 3.0 m / s; and the operating conditions of the regeneration section include: an operating temperature of 580°C to 750°C, an average catalyst residence time of 1.0 minute to 7.0 minutes, preferably 1.0 minute to 5.0 minutes, and a gas superficial velocity of 0.4 m / s to 1.0 m / s, preferably 0.5 m / s to 0.8 m / s.

[0038] In a further preferred embodiment, the coke combustion rate in the coke combustion section is 30% to 60%, and the coke combustion rate in the regeneration section is 40% to 70%.

[0039] In a specific preferred embodiment, in step 1), pyrolytic carbon black obtained from other sources such as pyrolysis treatment of waste tires is further provided, and in step 2), the pyrolytic carbon black and the biomass carbon are supplied to the catalyst regenerator together or separately.

[0040] In certain preferred embodiments, step 1) further comprises pyrolyzing the biomass and any waste tires under the following conditions: a pyrolysis temperature of 400°C to 1000°C, a heating rate of 0.01°C / second to 200°C / second, and a pyrolysis environment including a vacuum, a nitrogen atmosphere, a carbon dioxide atmosphere, and an inert gas-diluted oxygen atmosphere, to obtain biomass charcoal and any pyrolytic carbon black. In such embodiments, the pyrolysis process can be a co-pyrolysis of the biomass and the waste tires, or separate pyrolyses to obtain biomass charcoal and pyrolytic carbon black separately.

[0041] According to the present application, the energy consumed in the preparation process of biomass charcoal and pyrolytic carbon black can be obtained, at least partially or entirely, from renewable energy sources such as solar energy, green power, and nuclear energy.

[0042] In a further preferred embodiment, the biomass and any waste tires are pretreated before the pyrolysis treatment, and the pretreatment is selected from one or more of pulverization, water washing, acid washing, and drying to remove impurities such as metal elements in the biomass and the waste tires.

[0043] In certain preferred embodiments, the temperature of the regenerator bed is controlled to be 750°C or lower, preferably 720°C or lower, by a heat extraction system including one or more internally connected or / and externally connected heat extractors connected in series. In this embodiment, the heat extracted from the regenerator by the heat extraction system can be used to generate high-pressure steam for supplying energy externally.

[0044] In a second aspect, the present application provides a catalyst regeneration system suitable for a fluid catalytic cracking unit, comprising a biomass treatment device and a catalyst regeneration device: The biomass treatment device is used for the treatment of biomass and any waste tires, such as pyrolysis treatment to obtain biomass charcoal and any pyrolytic carbon black, and is equipped with a biomass charcoal generator, a crusher, and a storage tank connected in sequence. The biomass charcoal generator is equipped with a biomass raw material inlet and a product outlet. The product outlet is connected to the inlet of the crusher, and the outlet of the crusher is connected to the inlet of the storage tank; The catalyst regeneration device is used to regenerate the catalyst to be regenerated from the catalytic cracking reactor, and is equipped with a catalyst regenerator having at least one solid material inlet, an oxygen-containing gas inlet, a regeneration exhaust gas outlet, and a regenerated catalyst outlet; and, The outlet of the storage tank is connected to the solid material inlet of the catalyst regenerator.

[0045] In a specific preferred embodiment, the biomass treatment device further comprises a pretreatment device. The pretreatment device is used for pretreating biomass and any waste tires, and the pretreatment is selected from one or more of crushing, water washing, acid washing, and drying.

[0046] In a preferred embodiment, the catalyst regeneration system of the present application further comprises an inclined pipe to be regenerated, which connects the catalytic cracking reactor and the solid material inlet of the catalyst regenerator: The outlet of the storage tank is connected to the catalytic cracking reactor such that after the solid particles from the storage tank enter the catalytic cracking reactor, they are transported through the inclined pipe to be regenerated together with the catalyst to be regenerated to the solid material inlet of the catalyst regenerator; or A mixing tank is provided in the inclined pipe to be regenerated, and the outlet of the storage tank is connected to the mixing tank such that after the solid particles from the storage tank are mixed with the catalyst to be regenerated in the mixing tank, they are transported through the inclined pipe to be regenerated to the solid material inlet of the catalyst regenerator.

[0047] In a specific preferred embodiment, the catalyst regenerator comprises a coke combustion section and a regeneration section. The outlet of the coke combustion section is in fluid connection with the regeneration section such that the material in the coke combustion section can be transported to the regeneration section, In the coke combustion section: At least one solid material inlet provided at the lower part of the coke combustion section and used to transport biomass char, any pyrolysis carbon black, and the catalyst to be regenerated from the catalytic cracking reactor into the coke combustion section; and A first oxygen-containing gas inlet is provided at the bottom of the coke combustion section and used to transport the oxygen-containing gas into the coke combustion section; In the regeneration section: A second oxygen-containing gas inlet provided at the bottom of the regeneration section and used to transport the oxygen-containing gas into the regeneration section; A regenerated catalyst outlet used to carry out the regenerated catalyst in the regenerator from the regenerator; A regenerated exhaust gas outlet provided at the top of the regeneration section and used to discharge the regenerated exhaust gas in the regeneration section; and An optional recycled exhaust gas inlet is provided for recycling a part of the exhaust gas discharged from the regeneration section back to the regeneration section.

[0048] In certain preferred embodiments, the catalyst regenerator (such as the regeneration section of the regenerator) is further provided with a heat extraction system including one or more internally connected and / or externally connected heat extractors, and is used to control the temperature of the regenerator floor so that it does not exceed 750 °C, preferably does not exceed 720 °C. The heat extraction system can also generate high-pressure steam using the heat extracted from the regenerator and supply energy externally.

[0049] The preferred embodiments of the regeneration method and regeneration system of the present application will be further described in detail below in conjunction with the accompanying drawings.

[0050] As shown in FIGS. 1, 2, 3, and 4, the catalyst regeneration system of the present application is suitable for regenerating the catalyst to be regenerated from the catalytic cracking reactor 100, and includes a biomass treatment device 300 and catalyst regeneration devices 200, 400, 500, and 600.

[0051] As shown in FIGS. 1, 2, 3 and 4, in the catalytic cracking reactor 100, the catalytic cracking reactor 110 is used to carry out the catalytic cracking reaction: At the bottom inlet 102 of the catalytic cracking reactor 110, a lifting medium for lifting the regenerated catalyst entering from the regenerated catalyst inlet 103 (from the regenerator) is supplied, and the feedstock oil entering from the feedstock oil inlet 101 contacts the catalyst to carry out the catalytic cracking reaction. The oil and the gas products of the reaction are separated by the oil-catalyst separator 120. After the separated oil and gas products are collected by the gas collection chamber 140, they are supplied to the product separator 150 for separation, and various products are obtained. The separated catalyst to be regenerated is transported to the regenerator for regeneration through the stripping section 130 of the settler, the discharge port 131 of the catalyst to be regenerated, and the inclined pipe of the catalyst to be regenerated, and recycling is realized by regeneration. The catalytic cracking reactor 110 used in the present application can be various reactors commonly used in the art, such as riser reactors, fluidized bed reactors, variable diameter reactors, and combinations thereof.

[0052] As shown in the figure, the biomass treatment apparatus 300 for treating biomass and any waste tires, particularly for pyrolysis treatment, comprises: A pretreatment unit 310 for pretreating biomass and any waste tires; A biomass charcoal generator 320 used to treat the pretreated biomass and any waste tires, particularly to obtain biomass charcoal and any pyrolytic carbon black by pyrolysis; A product separator 330 for separating products from the biomass charcoal generator 320 to obtain biomass charcoal and any pyrolytic carbon black; A crusher 340 used to crush biomass charcoal and any pyrolytic carbon black to obtain particles of biomass charcoal and any pyrolytic carbon black having a certain particle size distribution; A storage tank 350 used to store particles of biomass charcoal and any pyrolytic carbon black.

[0053] In the pre-processor 310, the pre-treatment process of biomass and any waste tires can be selected from one or more of crushing, pulverizing, melting, water washing, acid washing, and drying to remove metal elements in the biomass and any waste tires and prevent catalyst poisoning.

[0054] In a preferred embodiment, in the biomass carbon generator 320, the biomass and any waste tires are pyrolyzed, and the operating conditions include a temperature of 400°C to 1000°C, a heating rate of 0.01°C / second to 200°C / second, and a pyrolysis environment including vacuum, nitrogen atmosphere, carbon dioxide atmosphere, and oxygen atmosphere diluted with an inert gas.

[0055] In such a preferred embodiment, the pyrolysis process produces other pyrolysis products in addition to biomass carbon and any pyrolytic carbon black. The pyrolysis products can be separated in the product separator 330, and the obtained biomass carbon and any pyrolytic carbon black are transported to the pulverizer 340, and the remaining pyrolysis products are removed for treatment or sent to other devices.

[0056] According to the present application, in a specific embodiment, the obtained biomass carbon and any pyrolytic carbon black can be pulverized by the pulverizer 340 so that the particle size of the biomass carbon and any pyrolytic carbon black is distributed between 30 microns and 1000 microns. Then, the granular biomass carbon and any pyrolytic carbon black are introduced into the regenerator together with the catalyst to be regenerated for regeneration.

[0057] To facilitate the transportation of the granular biomass carbon and any pyrolytic carbon black, the granular biomass carbon and any pyrolytic carbon black may be stored in the storage tank 350.

[0058] Figure 1 is a schematic diagram of the first preferred embodiment of the catalyst regeneration method and system of the present application, and the regeneration process is single-stage regeneration.

[0059] As shown in FIG. 1, the catalyst regeneration apparatus 200 includes a regenerator 210, and the regenerator 210 is provided with: An inlet 216 for the catalyst to be regenerated, which is used to transport the catalyst to be regenerated from the catalytic cracking reactor into the regenerator; An oxygen-containing gas inlet 211, which is used to transport the oxygen-containing gas into the regenerator, and An outlet 218 for the regenerated catalyst, which is used to carry out the regenerated catalyst in the regenerator from the regenerator.

[0060] The regeneration apparatus 200 is further provided with a heat extractor 215 for transferring heat to the outside of the regenerator.

[0061] The storage tank 350 is fluidly connected to the regenerator 210, and the biomass charcoal and any pyrolytic carbon black particles in the storage tank are transported to the regenerator 210.

[0062] During the regeneration operation, the biomass charcoal and any pyrolytic carbon black in the storage tank 350 are directly introduced into the regenerator 210 through the inlet 214, and are brought into contact with the catalyst to be regenerated and the oxygen-containing gas entering through the oxygen-containing gas inlet 211 in the regenerator 210 for regeneration. After being separated by the cyclone separator 220, the regenerated catalyst falls into the regenerator, is discharged from the catalyst discharge port 218, and is circulated back to the catalytic cracking reactor. The discharged exhaust gas is recovered as energy through the exhaust gas energy recovery system 230.

[0063] FIG. 2 is a schematic diagram of a second preferred embodiment of the catalyst regeneration method and system of the present application, and the regeneration process is single-stage regeneration.

[0064] As shown in FIG. 2, a mixing tank 360 is provided in the inclined pipe to be regenerated, and the storage tank 350 is connected to the mixing tank 360, so that the biomass charcoal and any pyrolytic carbon black particles in the storage tank 350 are transported to the mixing tank, pre-mixed with the generated catalyst, and then transported to the regenerator 410.

[0065] During the regeneration operation, the biomass charcoal and any pyrolytic carbon black in the storage tank 350 are transported to the mixing tank 360, mixed with the catalyst to be regenerated, and then introduced into the regenerator 410, where the catalyst to be regenerated is brought into contact with the oxygen-containing gas entering from the oxygen-containing gas inlet 411 for regeneration. After being separated by the cyclone separator 420, the regenerated catalyst returns to the regenerator, is discharged from the catalyst outlet 418, and is circulated back to the catalytic cracking reactor. The exhausted exhaust gas is recovered as energy through the exhaust gas energy recovery system 430.

[0066] In one embodiment, the ratio of the catalyst to be regenerated to the introduced biomass charcoal and any pyrolytic carbon black is 30:1 to 300:1 (weight ratio), the operating temperature of the regenerator is 600°C to 750°C, the average catalyst residence time is 2.0 minutes to 15.0 minutes, and the gas superficial velocity is 0.7 m / s to 2.0 m / s.

[0067] To inject biomass charcoal and any pyrolytic carbon black, a large amount of heat is generated during the regeneration process. If the temperature in the regenerator is too high, it will have an adverse effect on the activity of the catalyst. Therefore, the regeneration apparatuses 200 and 400 are also provided with heat extractors 215 and 415 for removing excess heat from the regenerator. The heat extractor can be an internal heat extractor (disposed inside the regenerator) or / and an external heat extractor (disposed outside the regenerator), and there can be one or more heat extractors. The surplus heat of the regeneration system can be used to generate high-pressure steam through the heat extractor and carried out to other devices for energy supply. In a specific embodiment, by providing the heat extractor, the temperature of the regenerator floor is controlled not to exceed 750°C, for example, not to exceed 720°C.

[0068] Figure 3 is a schematic diagram of a third preferred embodiment of the catalyst regeneration method and system of the present application, and the regeneration process is a two-stage regeneration method.

[0069] As shown in Figure 3, the catalyst regeneration apparatus 500 includes: It may be in the form of a coke combustion tube, equipped with a coke combustion section 550, and in the coke combustion section: An inlet 516 for the catalyst to be regenerated, used to transport the catalyst to be regenerated from the catalytic cracking reactor into the coking section; A first oxygen-containing gas inlet 511, used to transport oxygen to the coke combustion section; There is a regeneration section 510, and the outlet of the coke combustion section 550 is in fluid connection with the regeneration section 510 so that the substances in the coke combustion section can be transported to the regeneration section. The regeneration section is provided with: A second oxygen-containing gas inlet 514, used to transport the second oxygen into the regeneration section; A regenerated catalyst outlet 518, used to transport the regenerated catalyst in the regeneration section to the outside of the regeneration section; A heat extractor 515 is provided, which is configured to extract excess heat from the regeneration section.

[0070] A fluid distribution plate 551 may be provided at the outlet of the coke combustion section 550, and after the material in the coke combustion section passes through the fluid distribution plate 551, it may be arranged inside the regeneration section 510 so that it can be transported to the regeneration section for subsequent regeneration.

[0071] In a preferred embodiment, the mixing tank 360 can be provided in the pipeline to be regenerated so that the particles of biomass charcoal and any pyrolytic carbon black are pre-mixed with the catalyst to be regenerated in a certain ratio in the mixing tank to be regenerated and then transported to the regenerator to be contacted with oxygen for coke combustion regeneration.

[0072] During the regeneration operation, the biomass charcoal and any pyrolytic carbon black in the storage tank 350 are mixed with the catalyst to be regenerated in the mixing tank 360, and then introduced into the coke combustion section 550, where they come into contact with pure oxygen entering through the first oxygen-containing gas inlet 511 to perform partial coke combustion. After that, the partially coke-combusted catalyst enters the regeneration section 510 through the fluid distribution plate 551 for complete regeneration. At this time, pure oxygen is supplied from the oxygen-containing gas inlet 514 and comes into contact with the partially coke-combusted catalyst, so that the catalyst and the incomplete regeneration exhaust gas are further regenerated and combusted. The regenerated catalyst is separated by the cyclone separator 520, then returned to the regeneration section, discharged from the catalyst outlet 518, and circulated back to the catalytic cracking reactor. A part of the discharged exhaust gas is recovered as energy by the exhaust gas energy recovery system 530, separated by the carbon dioxide separation system 540 to achieve the collection of carbon dioxide; the other part of the exhaust gas is circulated back to the bottom of the regeneration section to control the oxygen content in the regeneration section.

[0073] In a specific embodiment, the gas supplied through the first oxygen-containing gas inlet 511 and the second oxygen-containing gas inlet 514 is oxygen. The oxygen supplied through the second oxygen-containing gas inlet 514 is mixed with the recycled exhaust gas from the pipeline 517, etc. after entering the regeneration section to form an oxygen-carbon dioxide mixed gas. The amount of oxygen and / or the amount of recycled exhaust gas is controlled so that the oxygen concentration in the mixed gas is 28% or less. Coke combustion is carried out in this atmosphere to improve the coke combustion intensity; the suction gas does not contain nitrogen, reducing the energy consumed by gas preheating; the carbon dioxide concentration of the exhaust gas at the outlet of the regeneration section is high, which is favorable for the separation and collection of carbon dioxide.

[0074] In a specific embodiment, the operating conditions of the coke combustion section are: operating temperature 580°C to 720°C; average catalyst residence time 10.0 seconds to 60.0 seconds; and gas superficial velocity 0.5 m / s to 5.0 m / s.

[0075] In a specific embodiment, the operating conditions of the regeneration section are: an operating temperature of 580°C to 750°C; an average catalyst residence time of 1.0 minute to 7.0 minutes; and a gas superficial linear velocity of 0.4 m / s to 1.0 m / s.

[0076] In a specific embodiment, the coke combustion ratio in the coke combustion section is 30% to 60%, and the coke combustion ratio in the regeneration section is 40% to 70%. The present application can use pure oxygen regeneration, and the regeneration exhaust gas contains only carbon dioxide and oxygen, which is convenient for separating and collecting carbon dioxide for further conversion and utilization, thereby achieving negative carbon emissions.

[0077] To inject biomass carbon and any pyrolytic carbon black, a large amount of heat is generated during the regeneration process. If the temperature in the regeneration section is too high, it will have an adverse effect on the activity of the catalyst. Therefore, the regeneration device 500 is also provided with a heat extractor 515 for removing excess heat from the regeneration section. The heat extractor can be an internal heat extractor (disposed inside the regeneration section) or / and an external heat extractor (disposed outside the regeneration section). There can be one or more heat extractors, and the surplus energy generated by the regeneration section is used to supply other devices. The surplus heat of the regeneration system can be carried out to other devices for energy supply after being used to generate high-pressure steam through the heat extractor. In a specific embodiment, by providing the heat extractor, the temperature of the floor of the regeneration section is controlled not to exceed 750°C, for example, not to exceed 720°C.

[0078] FIG. 4 is a schematic diagram of a fourth preferred embodiment of the catalyst regeneration method and system of the present application, and the regeneration process is single-stage regeneration.

[0079] During the regeneration operation, the biomass charcoal and any pyrolytic carbon black particles in the storage tank 350 are mixed with the regenerated catalyst and then introduced into the reactor 110. After contacting the feedstock, they enter the regeneration system 600 together with the catalyst to be regenerated. The catalyst to be regenerated in the regenerator 610 contacts the oxygen-containing gas entering from the oxygen-containing gas inlet 611 for regeneration. The regenerated catalyst is discharged from the catalyst outlet 616 and circulated back to the catalytic cracking reactor. The discharged exhaust gas is recovered as energy through the exhaust gas energy recovery system 620.

[0080] By injecting biomass charcoal and any pyrolytic carbon black, components difficult to convert in the feedstock oil can be adsorbed in the reactor, thereby improving the reactivity of the feedstock oil and enhancing the energy supply by utilizing the difficult-to-react parts.

[0081] Furthermore, a large amount of heat is generated during the regeneration process. If the temperature in the regenerator is too high, it will have an adverse effect on the activity of the catalyst. Therefore, the regeneration device 600 is also provided with a heat extractor 613 for removing excess heat from the regenerator. The heat extractor can be an internal heat extractor (disposed inside the regenerator) or / and an external heat extractor (disposed outside the regenerator). There can be one or more heat extractors. The surplus heat of the regeneration system can be used to generate high-pressure steam through the heat extractor and then carried to other devices for energy supply. In a specific embodiment, by providing the heat extractor, the temperature of the regenerator bed is controlled not to exceed 750°C, for example, not to exceed 720°C.

[0082] The catalyst suitable for the method and system of catalyst regeneration of the present application can be a catalyst conventionally used in various catalytic cracking processes, and the present application has no particular limitations. In some specific embodiments, the catalyst includes zeolite, inorganic oxide, and any clay, and each component, based on the total weight of the catalyst: zeolite accounts for 1% to 50% by weight; inorganic oxide accounts for 5% to 99% by weight; and clay accounts for 0% to 70% by weight. Here, the zeolite is the active component and is selected from medium-pore zeolite and / or any large-pore zeolite. The medium-pore zeolite accounts for 10% to 100% of the total weight of the zeolite, and the large-pore zeolite accounts for 0% to 90% of the total weight of the zeolite. The medium-pore zeolite is selected from one or more of the ZSM series zeolites and / or ZRP zeolites, and the above zeolite can be modified with non-metals such as phosphorus and / or transition metals such as iron, cobalt, nickel, etc. The large-pore zeolite is one or more selected from hydrogen Y, rare earth Y, rare earth hydrogen Y, ultrastable Y, etc.

Example

[0083] The present application will be further described below with reference to examples, but the present application is not limited thereby.

[0084] The characteristics of feedstocks A and B used in the following examples and comparative examples are shown in Table 1 and Table 2 respectively.

[0085]

Table 1

[0086]

Table 2

[0087] The preparation method of catalyst a is as follows: (1) Dissolve 20 g of NH 4 Cl in 1000 g of water, and add the crystallized product ZRP-1 molecular sieve (manufactured by Qilu Petrochemical Company Catalyst Factory, SiO2 / Al 2 O 3 = 30, rare earth content RE 2 O 3 = 2.0 wt%) 100 g (dry basis) was added, exchanged at 90 °C for 0.5 h, filtered to obtain a filter cake. 4.0 g of H 3 PO 4 (concentration 85%) and 4.5 g of Fe(NO 3 ) 3 were added, mixed with the filter cake, impregnated and dried, then calcined at 550 °C for 2 h to obtain an MFI mesoporous molecular sieve containing phosphorus and iron. The elemental analysis chemical composition of the obtained molecular sieve was: 0.1Na 2 O·5.1Al 2 O 3 ·2.4P 2 O 5 ·1.5Fe 2 O 3 ·3.8RE 2 O 3 ·88.1SiO 2 is as follows.

[0088] (2) 75.4 kg of halloysite (industrial product of Suzhou Kaolin Company, solid content 71.6 wt%) was slurried with 250 kg of decantation water, then 54.8 kg of pseudo-boehmite (industrial product of Yudong Aluminum Factory, solid content 63 wt%) was added. The pH value was adjusted to 2 - 4 with hydrochloric acid, and the mixture was stirred uniformly. The mixture was allowed to stand and age at 60 °C - 70 °C for 1 h while maintaining the pH value at 2 - 4. The temperature was lowered below 60 °C, and 41.5 kg of aluminum sol (product of Qilu Petrochemical Company Catalyst Factory, Al 2 O 3 content 21.7 wt%) was added. The mixture was stirred for 40 min to obtain a mixed slurry.

[0089] (3) The MFI mesoporous molecular sieve containing phosphorus and iron (2 kg on a dry basis) prepared in step (1), and DASY zeolite (an industrial product of Qilu Petrochemical Company Catalyst Plant, unit cell constant 2.445 nm - 2.448 nm, 22.5 kg on a dry basis) were added to the mixed slurry obtained in step (2), stirred uniformly, spray-dried and formed, and washed with ammonium dihydrogen phosphate solution (phosphorus content 1 wt%) to remove free Na + and dried to obtain a sample of the catalytic conversion catalyst a. Based on the total dry basis weight of catalyst a, the dry basis composition of catalyst a is: 2 wt% MFI mesoporous molecular sieve containing phosphorus and iron, 18 wt% DASY zeolite, 32 wt% pseudo-boehmite, and 7 wt% aluminum sol, and the balance kaolin. The properties of catalyst a are shown in Table 3.

[0090]

Table 3

[0091] Catalyst b is TCC, and its preparation process was as follows: 969 g of halloysite (a product of China Kaolin Company, solid content 73%) was slurried with 4300 g of deionized water, then 781 g of pseudo-boehmite (a product of Shandong Zibo Bauxite Factory, solid content 64%) and hydrochloric acid (concentration 30%, specific gravity 1.56) were added and stirred uniformly. The mixture was allowed to stand and age at 60 °C for 1 hour while maintaining the pH at 2 - 4, then cooled to room temperature, and 5000 g of a high-silicon - aluminum ratio mesoporous shape-selective ZSM-5 zeolite slurry containing chemically prepared water was added and stirred uniformly, spray-dried, and the free Na + was washed and removed to obtain the catalyst. This catalyst was used after aging, and the aging conditions were steam aging at 800 °C for 15 hours, and the properties are shown in Table 4.

[0092]

Table 4

[0093] The preparation process of catalyst c is as follows: (1) Dissolve 20 g of NH 4 Cl in 1000 g of water, and add 100 g (dry basis) of the crystallized product ZRP-1 molecular sieve (manufactured by Qilu Petrochemical Company Catalyst Plant, SiO 2 / Al 2 O 3 = 30, rare earth content RE 2 O 3 = 2.0 wt%) to the solution. Exchange at 90 °C for 0.5 hour, and filter to obtain a filter cake. 4.0 g of H 3 PO 4 (concentration 85%) and 4.5 g of Fe(NO 3 ) 3 are added, mixed with the filter cake, impregnated and dried, and then calcined at 550 °C for 2 hours to obtain an MFI mesoporous molecular sieve containing phosphorus and iron. The elemental analysis chemical composition of the obtained molecular sieve is: 0.1Na 2 O·5.1Al 2 O 3 ·2.4P 2 O 5 ·1.5Fe 2 O 3 ·3.8RE 2 O 3 ·88.1SiO 2 .

[0094] (2) After slurrying 75.4 kg of halloysite (industrial product of Suzhou Kaolin Company, solid content 71.6 wt%) with 250 kg of deionized water, 54.8 kg of pseudo-boehmite (industrial product of Yudong Aluminum Factory, solid content 63 wt%) was added. Adjust the pH value to 2 - 4 with hydrochloric acid, and stir the mixture uniformly. Let the mixture stand and age at 60 °C - 70 °C for 1 hour, maintaining the pH value at 2 - 4. Lower the temperature below 60 °C, and add 41.5 kg of aluminum sol (product of Qilu Petrochemical Company Catalyst Plant, Al 2 O 3 content 21.7 wt%). Stir the mixture for 40 minutes to obtain a mixed slurry.

[0095] (3) The MFI mesoporous molecular sieve containing phosphorus and iron (2 kg on a dry basis) prepared in step (1) was added to the mixed slurry obtained in step (2), stirred uniformly, spray-dried and formed, and washed with an ammonium dihydrogen phosphate solution (phosphorus content 1 wt%) to remove free Na + and dried to obtain a sample of the catalytic conversion catalyst c. Based on the total dry basis weight of the catalyst c, the dry basis composition of the catalyst c is: 2 wt% MFI mesoporous molecular sieve containing phosphorus and iron, 36 wt% pseudo-boehmite, and 8 wt% aluminum sol, and the balance kaolin.

[0096] Example 1 The apparatus shown in FIG. 1 was used in the experiment, and the specific preparation process of the biomass carbon was as follows: The biomass was pretreated by washing with water or acid in a pretreatment system, and then pulverized and dried. The moisture content of the raw material was controlled to be less than 25%. The pretreated biomass was pyrolyzed in a biomass carbon generator at a pyrolysis temperature of 600 °C. The atmosphere was a nitrogen-carbon dioxide mixed gas containing 5% oxygen, and the heating rate was 5 °C / min. The obtained biomass carbon was pulverized into particles with a particle size of 30 to 80 microns by a pulverizer and then stored in a storage tank for use.

[0097] Raw material A was used as the reaction raw material, and catalytic conversion catalyst a was used as the catalyst. According to the method of the present application, the catalyst to be regenerated was regenerated. Here, air was introduced into the regenerator, and biomass carbon with a particle size of 30 to 80 microns was introduced to cause a combustion reaction with the catalyst to be regenerated. The ratio of the catalyst to be regenerated in circulation to the biomass carbon was 137:1 (by weight). The operating temperature of the regenerator was 680 °C, the average residence time of the catalyst and the biomass carbon was 14 minutes, and the gas superficial velocity was 0.8 m / s. The regenerated catalyst entered the reactor, contacted with the feedstock oil to carry out a catalytic cracking reaction, and the excess energy was supplied to other devices through a heat extraction system. The regeneration conditions, reaction conditions and carbon dioxide emissions are shown in Table 5.

[0098] Comparative Example 1 The experiment was conducted with reference to Example 1, except that diesel was directly injected into the regenerator as fuel oil without using a biomass treatment device, and the fuel oil was used as an auxiliary energy source. Air was introduced into the regenerator, the operating temperature of the regeneration reactor was 680 °C, the average catalyst residence time was 14 minutes, and the gas superficial velocity was 0.8 m / s. The regenerated catalyst entered the reactor and contacted the feedstock oil to carry out a catalytic cracking reaction. The surplus energy was supplied to other devices through a heat extraction system. The regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in Table 5.

[0099]

Table 5

[0100] From the data in Table 5, it can be seen that when biomass charcoal is used as an auxiliary energy source in Example 1, when the regeneration system produces the same amount of energy, the carbon dioxide emissions are significantly reduced compared to Comparative Example 1, contributing to a fundamental reduction in carbon dioxide emissions.

[0101] Example 2 The device shown in Figure 2 was used in the experiment. Here, the structure of the catalytic cracking reactor can refer to reactor 302 in Figure 4 of CN111718230A.

[0102] The specific preparation process of biomass charcoal was as follows: The biomass was pretreated by washing with water or acid, followed by pulverization and drying. The moisture content of the raw material was controlled to be less than 25%. The pretreated biomass was pyrolyzed at a pyrolysis temperature of 600 °C. The atmosphere was a nitrogen-carbon dioxide mixed gas containing 5% oxygen, and the heating rate was 5 °C / min. The obtained biomass charcoal was pulverized into particles with a particle size of 50 to 150 microns and then stored in a storage tank for use.

[0103] Raw material B was used as the reaction raw material, and catalytic conversion catalyst b was used as the catalyst. According to the method of the present application, biomass charcoal with a particle size of 50 to 150 microns was introduced into the mixing tank to be regenerated, and was mixed with the catalyst to be regenerated at a ratio of 76:1 (by weight) with respect to the biomass charcoal of the circulating catalyst to be regenerated, and the catalyst to be regenerated was regenerated. The catalyst to be regenerated mixed with the biomass charcoal was transported to a regenerator and contacted with air containing oxygen to cause a coke combustion reaction. The surplus energy generated by the regeneration device was utilized for external energy supply through a heat extraction system. The operating temperature of the regenerator was 680°C, the average residence time of the catalyst and biomass charcoal in the coke combustion section was 14 minutes, and the gas superficial velocity was 0.8 m / s. The regenerated catalyst entered the reactor and contacted with the feedstock oil to carry out a catalytic cracking reaction. The regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in Table 6.

[0104] Comparative Example 2 An experiment was conducted with reference to Example 2, except that a biomass treatment device was not used, diesel was directly injected into the regenerator as the fuel oil, and the fuel oil was used as an auxiliary energy source. The regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in Table 6.

[0105]

Table 6

[0106] From the data in Table 6, it can be seen that when Example 2 uses biomass charcoal as an auxiliary energy source, when the regeneration system produces the same amount of energy, the carbon dioxide emissions are significantly reduced compared to Comparative Example 2, contributing to a fundamental reduction in carbon dioxide emissions.

[0107] Example 3 The apparatus shown in Figure 3 was used for the experiment. Here, the structure of the catalytic cracking reactor can be referred to the reactor 302 in Figure 4 of CN111718230A.

[0108] The specific preparation process of the biomass charcoal was as follows: The biomass was pretreated by washing with water or acid washing, followed by processes such as grinding and drying. The moisture content of the raw material was controlled to be less than 25%. The pretreated biomass was pyrolyzed at a pyrolysis temperature of 600 °C. The atmosphere was a nitrogen-carbon dioxide mixed gas containing 5% oxygen, and the heating rate was 5 °C / min. The obtained biomass charcoal was ground into particles with a particle size of 50 to 120 microns, and then stored in a storage tank in preparation for use.

[0109] C was used as the reaction raw material 5 -C 8 Olefin was used (C 5 Olefin: C 6 Olefin: C 7 Olefin: C 8 The molar ratio of olefins was 1:1:1:1), and catalytic cracking catalyst c was used as the catalyst. According to the method of the present application, the catalyst to be regenerated was regenerated, pure oxygen gas was introduced into the coke combustion section, the biomass charcoal with a particle size of 50 to 120 microns and the catalyst to be regenerated were mixed in a mixing tank, and the ratio of the catalyst to be regenerated to the biomass charcoal was mixed at 184:1 (by weight). For the combustion reaction, they were introduced together into the coke combustion section; next, pure oxygen gas was continuously introduced into the regenerator to continue the regeneration of the catalyst. At the same time, a part of the exhaust gas discharged from the cyclone separation system of the regenerator was circulated to the regenerator to dilute the introduced pure oxygen gas and control the oxygen content to be 28% or less. The surplus energy generated in the regeneration device was utilized for external energy supply through a heat extraction device.

[0110] The temperature in the middle part of the coke combustion section was 650 °C, the average residence time of the catalyst and biomass charcoal in the coke combustion section was 10 seconds, and the gas superficial velocity was 1.25 m / s; the temperature of the high-density phase bed of the regenerator was 685 °C, the average residence time of the catalyst and biomass charcoal in the high-density phase bed of the regenerator was 1.75 minutes, and the gas superficial velocity was 0.5 m / s. The regenerated catalyst entered the reactor and contacted with the feedstock oil to carry out a catalytic cracking reaction. The regeneration conditions, reaction conditions and carbon dioxide emissions are shown in Table 7.

[0111] Comparative Example 3 An experiment was conducted with reference to Example 3, except that diesel was directly injected into the bottom of the coke combustion section without using a biomass treatment device, and diesel was used as a fuel oil and as an auxiliary energy source. The temperature in the middle part of the coke combustion section was 650 °C, the average residence time of the catalyst and biomass charcoal in the coke combustion section was 10 seconds, and the gas superficial velocity was 1.25 m / s; the temperature of the high-density phase bed of the regenerator was 685 °C, the average residence time of the catalyst and biomass charcoal in the high-density phase bed of the regenerator was 1.75 minutes, and the gas superficial velocity was 0.5 m / s. The regenerated catalyst entered the reactor and contacted the feedstock oil to carry out a catalytic cracking reaction. The regeneration conditions, reaction conditions, carbon dioxide emissions, and carried-out energy are shown in Table 7.

[0112]

Table 7

[0113] From the data in Table 7, it can be seen that when using light feedstock as the cracking feedstock, the coke precipitation amount is small, and it is far from meeting the energy demand of the device. When Example 3 uses biomass charcoal as an auxiliary energy source, when the regeneration system produces the same amount of energy, the carbon dioxide emissions are significantly reduced compared to Comparative Example 3, contributing to a fundamental reduction in carbon dioxide emissions.

[0114] Example 4 The device shown in Figure 4 was used in the experiment. The specific preparation process of the biomass charcoal was as follows: The biomass was pretreated by washing with water or acid in the pretreatment system, and then pulverized and dried. The moisture content of the raw material was controlled to be less than 25%. The pretreated biomass was pyrolyzed at a pyrolysis temperature of 600 °C in a biomass charcoal generator. The atmosphere was a nitrogen-carbon dioxide mixed gas containing 5% oxygen, and the heating rate was 5 °C / min. The obtained biomass charcoal was pulverized into particles with a particle size of 50 microns to 200 microns by a pulverizer, and then stored in a storage tank for use.

[0115] Raw material A was used as the reaction raw material, and catalytic conversion catalyst a was used as the catalyst. According to the method of the present application, biomass charcoal with a particle size of 50 microns to 200 microns was introduced into the reactor together with the regenerated catalyst and brought into contact with the raw material oil, and the ratio of the catalyst to be regenerated in the circulating biomass charcoal was set to 137:1 (by weight). The catalyst to be regenerated and the biomass charcoal after the reaction were introduced into the regenerator. The operating temperature of the regenerator was 670 °C, the average residence time of the catalyst and the biomass charcoal was 15 minutes, and the gas superficial velocity was 1.5 m / s. The regenerated catalyst was mixed with the biomass and entered the reactor to contact with the raw material oil to carry out a catalytic cracking reaction. The surplus energy was supplied to other devices through the heat extraction system. The regeneration conditions, reaction conditions and carbon dioxide emissions are shown in Table 8.

[0116] Comparative Example 4 An experiment was conducted with reference to Example 4, except that a biomass treatment device was not used, diesel was directly injected into the regenerator as the fuel oil, and the fuel oil was used as the auxiliary energy source. Air was introduced into the regenerator, the operating temperature of the regenerator was 670 °C, the average residence time of the catalyst was 15 minutes, and the gas superficial velocity was 1.5 m / s. The regenerated catalyst entered the reactor and contacted with the raw material oil to carry out a catalytic cracking reaction. The surplus energy was supplied to other devices through the heat extraction system. The regeneration conditions, reaction conditions and carbon dioxide emissions are shown in Table 8.

[0117]

Table 8

[0118] From the data in Table 8, when Example 4 uses biomass charcoal as the auxiliary energy source and the regeneration system produces the same amount of energy, it can be seen that the carbon dioxide emissions are significantly reduced compared with Comparative Example 4, contributing to the fundamental reduction of carbon dioxide emissions. At the same time, the yields of liquefied gas and propylene in the product are improved, and the yield of slurry oil is decreased, indicating that the reactivity of the raw material is improved.

[0119] Although the preferred embodiments of the present application have been described in detail above, the present application is not limited to the specific contents in the above embodiments. Within the scope of the technical idea of the present application, various simple modifications can be made to the technical solution of the present application, and all these simple modifications fall within the protection scope of the present application.

[0120] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate way without contradiction. To avoid unnecessary repetition, various possible combinations will not be described further in the present application.

[0121] In addition, each embodiment of the present application can be arbitrarily combined as long as it does not conflict with the concept of the present application, and they should also be regarded as the content disclosed in the present application.

Claims

1. A catalyst regeneration method suitable for a fluid catalytic cracking unit equipped with a catalytic cracking reactor and a catalyst regenerator, the regeneration method comprising the following steps: 1) providing biomass charcoal derived from biomass; 2) supplying the biomass charcoal and the catalyst to be regenerated from the catalytic cracking reactor to the catalyst regenerator together or separately; 3) introducing an oxygen-containing gas into the catalyst regenerator, wherein the oxygen content of the oxygen-containing gas is 14% to 28% by volume, and preferably the oxygen-containing gas is selected from air and oxygen diluted with recycled exhaust gas; and 4) contacting the catalyst to be regenerated with the biomass charcoal and the oxygen-containing gas in the catalyst regenerator for coke combustion regeneration; Preferably, the operating temperature of the catalyst regenerator is in the range of 550°C to 750°C, and the average catalyst residence time is 1.0 minute to 15.0 minutes. A catalyst regeneration method.

2. The method according to claim 1, wherein the particle size of the biomass charcoal is 30 microns to 1000 microns, and the weight ratio of the catalyst to be produced to the biomass charcoal is 30:1 to 300:

1.

3. In step 2), the biomass charcoal is pre-mixed with the catalyst to be regenerated from the catalytic cracking reactor and then supplied to the catalyst regenerator together; Preferably, the mixing is carried out in a mixing tank, and the mixing tank is provided in an inclined pipe for the catalyst to be regenerated for transporting the catalyst to be regenerated from the catalytic cracking reactor to the catalyst regenerator. The method according to claim 1 or 2.

4. The method according to claim 1 or 2, wherein in step 2), the biomass charcoal is introduced into the catalytic cracking reactor and then supplied to the catalyst regenerator together with the catalyst to be regenerated.

5. The catalyst regenerator is a single-stage regenerator, and the operating conditions of the single-stage regenerator include an operating temperature of 600°C to 750°C, an average catalyst residence time of 2.0 minutes to 15.0 minutes, and a gas superficial velocity of 0.7 m / s to 2.0 m / s. The method according to any one of claims 1 to 4.

6. The catalyst regenerator is a two-stage regenerator comprising a coke combustion section and a regeneration section that are fluidly connected. In step 2), the biomass carbon and the catalyst to be regenerated are supplied to the coke combustion section together or separately. In step 3), the oxygen-containing gas is introduced into the bottoms of the coke combustion section and the regeneration section respectively. Preferably, the operating conditions of the coke combustion section are: an operating temperature of 580°C to 720°C, an average catalyst residence time of 1.0 second to 60.0 seconds, preferably 5.0 seconds to 50.0 seconds, and a gas superficial velocity of 0.5 m / s to 5.0 m / s, preferably 1.0 m / s to 3.0 m / s. Also, the operating conditions of the regeneration section are: an operating temperature of 580°C to 750°C, an average catalyst residence time of 1.0 minute to 7.0 minutes, preferably 1.0 minute to 5.0 minutes, and a gas superficial velocity of 0.4 m / s to 1.0 m / s, preferably 0.5 m / s to 0.8 m / s. The method according to any one of claims 1 to 4.

7. The method according to claim 6, wherein the coke combustion rate in the coke combustion section is 30% to 60%, and the coke combustion rate in the regeneration section is 40% to 70%.

8. In step 1), pyrolytic carbon black obtained from other sources such as pyrolysis treatment of waste tires is further provided. In step 2), the pyrolytic carbon black and the biomass carbon are supplied to the catalyst regenerator together or separately. The method according to any one of claims 1 to 7.

9. Step 1) further comprises pyrolyzing the biomass and any waste tires under the following conditions to obtain the biomass carbon and any pyrolytic carbon black: a pyrolysis temperature of 400°C to 1000°C, a heating rate of 0.01°C / second to 200°C / second, and a pyrolysis environment including a vacuum, a nitrogen atmosphere, a carbon dioxide atmosphere, and an oxygen atmosphere diluted with an inert gas. The method according to any one of claims 1 to 8.

10. The biomass and any of the waste tires are pretreated before the pyrolysis treatment. The pretreatment is selected from one or more of pulverization, water washing, acid washing, and drying to remove impurities such as metal elements in the biomass. The method according to claim 9.

11. A catalyst regeneration system suitable for a fluid catalytic cracking unit, comprising a biomass treatment device and a catalyst regeneration device: The biomass processing device is used for processing the biomass and any of the waste tires, such as pyrolysis treatment to obtain biomass charcoal and optional pyrolytic carbon black, and is provided with a biomass charcoal generator, a crusher, and a storage tank connected in sequence. The biomass charcoal generator is provided with a biomass raw material inlet and a product outlet. The product outlet is connected to the inlet of the crusher, and the outlet of the crusher is connected to the inlet of the storage tank; The catalyst regeneration device is used for regenerating the catalyst to be regenerated from the catalytic cracking reactor, and is provided with a catalyst regenerator having at least one solid material inlet, an oxygen-containing gas inlet, a regeneration exhaust gas outlet, and a regenerated catalyst outlet. A catalyst regeneration system in which the outlet of the storage tank is connected to the solid material inlet of the catalyst regenerator.

12. The biomass processing device further comprises a pretreatment device, which is used for pretreating the biomass, and the pretreatment is selected from one or more of grinding, washing with water, washing with acid, and drying. The catalyst regeneration system according to claim 11.

13. The catalytic cracking reactor is further provided with an inclined pipe for the catalyst to be regenerated, which connects the catalytic cracking reactor and the solid material inlet of the catalyst regenerator. The outlet of the storage tank is connected to the catalytic cracking reactor, so that after the solid particles from the storage tank enter the catalytic cracking reactor, they are transported together with the catalyst to be regenerated through the inclined pipe for the catalyst to be regenerated to the solid material inlet of the catalyst regenerator, or A mixing tank is provided in the inclined pipe for the catalyst to be regenerated, and the outlet of the storage tank is connected to the mixing tank, so that the solid particles from the storage tank are mixed with the catalyst to be regenerated in the mixing tank and then transported through the inclined pipe for the catalyst to be regenerated to the solid material inlet of the catalyst regenerator. The regeneration system according to claim 11 or 12.

14. The catalyst regenerator comprises a coke combustion section and a regeneration section, and the outlet of the coke combustion section is in fluid connection with the regeneration section so that the materials in the coke combustion section can be transported to the regeneration section. In the coke combustion section: At least one solid material inlet provided at the lower part of the coke combustion section and used for transporting the biomass charcoal and the catalyst to be regenerated from the catalytic cracking reactor into the interior of the coke combustion section; and A first oxygen-containing gas inlet is provided at the bottom of the coke combustion section and is used to transport the oxygen-containing gas into the coke combustion section; In the regeneration section: A second oxygen-containing gas inlet provided at the bottom of the regeneration section and used to transport the oxygen-containing gas into the regeneration section; A regenerated catalyst outlet used to carry out the regenerated catalyst in the regenerator from the regenerator; A regeneration exhaust gas outlet provided at the top of the regeneration section and used to discharge the regeneration exhaust gas in the regeneration section; and An optional recycled exhaust gas inlet for recycling a part of the exhaust gas discharged from the regeneration section to the regeneration section is provided. Optionally, in the regeneration section, a heat extractor for controlling the temperature of the regenerator and transferring excess heat outside the regenerator is further provided. The catalyst regeneration system according to any one of claims 11 to 13.

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