WO2023208083A1 - 采用生物基气相燃料的催化裂化催化剂再生方法和系统 - Google Patents

采用生物基气相燃料的催化裂化催化剂再生方法和系统 Download PDF

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WO2023208083A1
WO2023208083A1 PCT/CN2023/091025 CN2023091025W WO2023208083A1 WO 2023208083 A1 WO2023208083 A1 WO 2023208083A1 CN 2023091025 W CN2023091025 W CN 2023091025W WO 2023208083 A1 WO2023208083 A1 WO 2023208083A1
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Prior art keywords
regenerator
catalyst
gas
regeneration
oxygen
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PCT/CN2023/091025
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English (en)
French (fr)
Inventor
许友好
阳文杰
何鸣元
王新
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中国石油化工股份有限公司
中石化石油化工科学研究院有限公司
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Priority claimed from CN202210476007.5A external-priority patent/CN117000299A/zh
Priority claimed from CN202210476013.0A external-priority patent/CN117000300A/zh
Priority claimed from CN202210476023.4A external-priority patent/CN117000301A/zh
Priority claimed from CN202210474594.4A external-priority patent/CN117000295A/zh
Application filed by 中国石油化工股份有限公司, 中石化石油化工科学研究院有限公司 filed Critical 中国石油化工股份有限公司
Publication of WO2023208083A1 publication Critical patent/WO2023208083A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas

Definitions

  • the present application relates to the regeneration of carbon-containing catalytic cracking catalysts, and specifically to methods and systems for regenerating catalytic cracking catalysts using bio-based gas phase fuels.
  • Carbon emissions during heavy oil processing are mainly due to catalytic cracking coke, hydrogen production process, flue gas emissions from boilers and other equipment, and energy consumption in the process.
  • the catalytic cracking unit is the core equipment in the refinery.
  • the carbon emissions caused by the scorching of the catalytic cracking regenerator account for 24-55% of the entire plant's carbon emissions, accounting for nearly 1% of the country's total carbon dioxide emissions. It is the key to reducing carbon emissions in the petrochemical industry. focus.
  • CN102698817A discloses a catalytic cracking catalyst regeneration process method. This method uses pure oxygen regeneration, couples a steam shift reaction zone after the flue gas energy recovery system, and uses CO in the flue gas as a raw material for the steam shift reaction. In order to produce hydrogen, the carbon in the flue gas is further recycled.
  • this method only focuses on the treatment and recovery of flue gas. Incomplete regeneration of flue gas reduces energy utilization. It also involves the separation and purification of raw materials and products in the water vapor shift reaction zone, which is costly; it does not change the regeneration The source of energy that supplies energy.
  • CN113877397A discloses an incomplete regeneration method for reducing carbon dioxide emissions.
  • This process uses pure oxygen to incompletely regenerate the catalyst.
  • the carbon monoxide in the obtained flue gas is used as a chemical raw material, and the carbon dioxide is used for storage or oil displacement, thereby reducing carbon emissions.
  • this process mainly involves the post-treatment process of flue gas, and the cost is relatively high. Involving the separation of carbon monoxide, carbon dioxide, oxygen and other wastes, the separation process is complicated, incomplete regeneration does not maximize the use of chemical energy of carbon deposits, and the sequestration of enriched carbon dioxide results in a waste of resources.
  • US5565089 discloses a catalytic cracking catalyst regeneration process method. First, air Carry out coking, then recover the carbon dioxide in the flue gas, circulate it and gradually incorporate it into the oxygen-containing gas flow until the temperature in the regenerator is normal, and finally only inject oxygen and carbon dioxide to regenerate the catalyst. This process pays attention to the regeneration process air intake system and flue gas treatment, but the carbon dioxide produced for energy still all comes from fossil energy.
  • the energy of the catalytic cracking unit comes from the charring of the catalyst.
  • a large amount of chemicals such as low-carbon olefins is produced, more reaction heat is required due to the high gas yield.
  • the amount of coke is usually increased by refining the oil slurry, increasing the proportion of heavy oil in the raw oil, or by spraying combustion oil to increase the regeneration temperature. All three methods can satisfy the reaction heat balance, but they will all have a certain impact on the operation of the device.
  • the supplementary energy all comes from fossil energy, which increases the carbon dioxide emissions from fossil energy and is not conducive to improving the utilization rate of petroleum resources.
  • Optimizing the regeneration process can improve energy utilization efficiency, thereby reducing unit carbon dioxide emissions to a certain extent; recycling the emitted carbon dioxide can also reduce carbon dioxide emissions to a certain extent, but the cost is high and the process is relatively complex. complex.
  • the above ideas have not fundamentally changed the source of energy. Carbon dioxide still comes from fossil energy.
  • the purpose of this application is to provide a catalyst regeneration method and system suitable for a fluidized catalytic cracking unit.
  • the method and system introduce gas phase fuel derived from biomass into the catalyst regeneration system for combustion and energy supply to maintain the efficiency of the fluidized catalytic cracking unit. Thermal balance, thereby fundamentally reducing carbon dioxide emissions from fossil energy.
  • the present application provides a catalyst regeneration method suitable for a fluidized catalytic cracking unit.
  • the fluidized catalytic cracking unit includes a catalytic cracking reactor and a catalyst regenerator.
  • the regeneration method includes the following steps: :
  • the present application provides a catalyst regeneration system suitable for a fluidized catalytic cracking unit, including a biomass processing unit and a catalyst regeneration unit, wherein:
  • the biomass processing unit is used to process biomass to obtain gas phase fuel containing hydrogen and/or methane, and includes a gas phase fuel generator and a gas phase fuel storage tank.
  • the gas phase fuel generator is preferably selected from a biomass gasifier , a biomass anaerobic fermentation tank or a combination thereof, and has a biomass inlet and a gas phase product outlet, the gas phase fuel storage tank has an inlet and a gas phase fuel outlet, the gas phase product outlet of the gas phase fuel generator is connected to the gas phase fuel The inlet connection of the storage tank;
  • the catalyst regeneration unit is used to regenerate the ungenerated catalyst from the catalytic cracking reactor, and includes a catalyst regenerator having an ungenerated catalyst inlet, an oxygen-containing gas inlet, a gas phase fuel inlet, a regenerated flue gas outlet and regenerated catalyst outlet, and
  • the gas phase fuel outlet of the gas phase fuel storage tank is connected with the gas phase fuel inlet of the catalyst regenerator through a pipeline.
  • Biomass is cheap and easy to obtain.
  • Biomass energy is a renewable energy source.
  • the carbon comes from carbon dioxide captured by plants from the air, rather than fossil energy. Using it as an energy source can fundamentally change the energy supply of the catalytic cracking unit. sources, reduce fossil energy carbon dioxide emissions, and achieve low-carbon development of oil refining.
  • the gas phase fuel produced from biomass has a high hydrogen content, and the water vapor generated by the combustion of the hydrogen contained in it is used to age the catalyst during the catalyst regeneration process and improve the selectivity of the target low-carbon olefin product; or, When the catalyst is required to have high activity, the adverse impact of water vapor on the catalyst activity can be weakened by optimizing the regeneration process;
  • the mixture with the to-be-generated catalyst is relatively uniform, and the combustion and heat conduction processes are relatively stable.
  • oxygen-enriched regeneration can achieve low-cost separation and capture of carbon dioxide in the regeneration flue gas, which is conducive to achieving negative carbon emissions;
  • Figure 1 is a schematic diagram of a preferred embodiment of the catalyst regeneration method and system of the present application
  • FIG. 2 is a schematic diagram of another preferred embodiment of the catalyst regeneration method and system of the present application.
  • FIG. 3 is a schematic diagram of another preferred embodiment of the catalyst regeneration method and system of the present application.
  • Figure 4 is a schematic diagram of yet another preferred embodiment of the catalyst regeneration method and system of the present application.
  • any specific numerical value disclosed herein is not limited to the precise value of the numerical value, but is to be understood to also encompass values close to the precise value, such as within ⁇ 5% of the precise value. all possible values.
  • one or more new values can be obtained by any combination between the endpoint values of the range, between the endpoint value and the specific point value within the range, and between each specific point value. Numerical ranges, these new numerical ranges should also be deemed to be specifically disclosed herein.
  • upstream and downstream are based on the flow direction of the reaction materials. Towards the end. For example, when a reactant stream flows from bottom to top, “upstream” refers to a location below and “downstream” refers to a location above.
  • connection includes both the situation where the two are directly connected, and the situation where the two are connected via one or more intermediate devices.
  • any matters or matters not mentioned shall directly apply to those known in the art without any change.
  • any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby are regarded as part of the original disclosure or original record of the present invention and shall not be It is regarded as new content that has not been disclosed or expected in this article, unless those skilled in the art believe that the combination is obviously unreasonable.
  • the present application provides a catalyst regeneration method suitable for a fluidized catalytic cracking unit.
  • the fluidized catalytic cracking unit includes a catalytic cracking reactor and a catalyst regenerator.
  • the regeneration method includes the following step:
  • the biomass-derived gas phase fuel may be, for example, a gas phase fuel obtained via gasification or anaerobic fermentation of biomass.
  • the method provided by this application uses gas phase fuel derived from biomass as a supplementary energy source, and contacts and burns with oxygen-containing gas together with the to-be-generated catalyst to provide energy, which not only satisfies the heat balance of the catalytic cracking unit, but also reduces carbon emissions and also has the advantages of It is conducive to the separation and capture of carbon dioxide, becoming the source of negative carbon technology.
  • the utilization of biomass is essentially an indirect solar energy utilization process.
  • the carbon in biomass comes from carbon dioxide captured by plants from the atmosphere, rather than from fossil energy.
  • the energy consumed in the entire process also comes from solar energy. Therefore, the utilization of biomass energy is also the recycling of carbon elements and is a carbon-neutral emission process.
  • introducing biomass into the power center of the catalytic cracking unit and using biomass energy to supply the operation of the unit consumes renewable energy, and the carbon dioxide emitted does not come from fossil energy. It can fundamentally change the source of energy and realize carbon dioxide emissions. reduce emissions. Pure oxygen regeneration can also be used, so that the regenerated flue gas only contains carbon dioxide and oxygen, which reduces the cost of separation and capture and can achieve negative carbon emissions.
  • the biomass includes but is not limited to agricultural and forestry biomass, forestry biomass, aquatic plants, energy crops, livestock and poultry manure, municipal solid waste, domestic sewage and industrial organic sewage, etc.
  • the agricultural and forestry biomass includes but is not limited to straw, chaff, cotton stalks, etc.
  • the forestry biomass includes but is not limited to firewood, fast-growing forest, forestry processing residues, etc.
  • the aquatic plants include but is not limited to reeds and algae.
  • the energy economic crops include cassava, rapeseed, etc.
  • the urban solid waste includes domestic garbage, commercial service industry garbage, etc.
  • the domestic sewage and industrial organic sewage include cooling water, kitchen drainage, brewing, food and other industries discharged Organic wastewater, etc.
  • the operating temperature of the catalyst regenerator in step 4) is in the range of 550-750°C, and the average catalyst residence time is 1.0-15.0 minutes.
  • the gas phase fuel in step 2) is injected into the catalyst regenerator through a gas distributor from a position not lower than the inlet level of the catalyst to be generated.
  • the oxygen-containing gas is air or oxygen diluted by circulating flue gas.
  • the amount of gas phase fuel introduced is no more than 13% by volume of the amount of air introduced, such as 3-13% by volume, or when the oxygen-containing gas is recycled
  • flue gas dilutes oxygen the amount of gas phase fuel introduced is The amount of oxygen introduced does not exceed 44% by volume, for example 10-44% by volume.
  • the catalyst regenerator is a single-stage regenerator, and the operating conditions of the regenerator include: the operating temperature is 550-750°C, the average catalyst residence time is 1.0-15.0 minutes, and the gas surface The linear speed is 0.5-2.0m/s.
  • the method of this application is preferably carried out in It is carried out in a two-stage regenerator or a dual regenerator, and the gas phase fuel is only fed into the burning section of the two-stage regenerator or the first regenerator of the dual regenerator, and the operation in the two-stage regenerator and the dual regenerator is Conditions are appropriately optimized.
  • the catalyst regenerator is a two-stage regenerator including a charring section and a regeneration section in fluid communication, and in step 2), the gas phase fuel is sent to the charring section and/or The regeneration section is preferably only fed into the coking section.
  • step 3 oxygen-containing gas is introduced into the bottom of the coking section and the regeneration section respectively, and in step 4), the ungenerated catalyst is fed into the coking section.
  • the operating conditions of the coking section include: the operating temperature is 550-720°C, the average residence time of the catalyst is 10.0-120.0 seconds, preferably 15.0-90.0 seconds, and the apparent linear velocity of the gas is 0.5-5.0m/s , preferably 1.0-4.0m/s; and the operating conditions of the regeneration section include: the operating temperature is 600-750°C, the average residence time of the catalyst is 0.5-5.0 minutes, preferably 1.0-4.0 minutes, and the apparent linear velocity of the gas It is 0.4-2.0m/s, preferably 0.5-1.5m/s. Still further preferably, the operating temperature of the regeneration section is 10-150°C higher than the operating temperature of the coking section.
  • the operating conditions of the coking section include: 600-700°C, the average catalyst residence time is 60.0-90.0 seconds; and the operating conditions of the regeneration section include: 650-720°C, the catalyst The average residence time is 2.0-4.0 minutes, whereby the water vapor generated by the combustion of the gas-phase fuel can be used to age the catalyst during the catalyst regeneration process, thereby improving the selectivity of the catalyst to the target low-carbon olefin product while avoiding the effects of water vapor on the catalyst.
  • the gaseous phase fuel may be injected into only the burning section of the regenerator, or may be injected into both the burning section and the regeneration section of the regenerator.
  • the operating conditions of the coking section include: 550-650°C, the average catalyst residence time is 15.0-60.0 seconds; and the operating conditions of the regeneration section include: 600-680°C, the catalyst The average residence time is 1.0-3.0 minutes, which can fully weaken the adverse effect of water vapor on the catalyst activity, so that the obtained regenerated catalyst has a relatively high High catalytic cracking activity, thus suitable for fluid catalytic cracking that mainly produces fuel oil.
  • the gas phase fuel is injected only into the burnt section of the regenerator.
  • the catalyst regenerator is a dual regenerator including a first regenerator and a second regenerator in fluid communication, and in step 2), the gas phase fuel is fed into the first regenerator.
  • the regenerator and/or the second regenerator are preferably fed into the second regenerator only.
  • step 3 the oxygen-containing gas is introduced into the bottom of the first regenerator and the second regenerator respectively, and in step 4) the oxygen-containing gas is introduced into the second regenerator.
  • the raw catalyst is sent to the first regenerator.
  • the operating conditions of the first regenerator include: the operating temperature is 550-720°C, the average residence time of the catalyst is 20.0-240.0 seconds, preferably 30.0-150.0 seconds, and the apparent linear velocity of the gas is 0.5-5.0m /s, preferably 1.0-4.0m/s; and the operating conditions of the second regenerator include: operating temperature 600-750°C, average catalyst residence time 0.5-5.0 minutes, preferably 1.0-4.0 minutes, gas The apparent linear speed is 0.4-2.0m/s, preferably 0.5-1.5m/s. Still further preferably, the operating temperature of the second regenerator is 10-150°C higher than the operating temperature of the first regenerator.
  • the operating conditions of the first regenerator include: 600-700°C, the average catalyst residence time is 90.0-180.0 seconds; and the operating conditions of the second regenerator include: 650-720 °C, the average residence time of the catalyst is 2.0-4.0 minutes, whereby the water vapor generated by the combustion of the gas phase fuel can be used to age the catalyst during the catalyst regeneration process, thereby improving the selectivity of the catalyst for the target low-carbon olefin products while avoiding Water vapor has an excessive impact on the catalyst activity, making it suitable for fluid catalytic cracking processes that mainly produce chemicals such as light olefins.
  • the gaseous phase fuel may be injected into the first regenerator only, or may be injected into the first regenerator and the second regenerator simultaneously.
  • the operating conditions of the first regenerator include: 550-650°C, the average catalyst residence time is 15.0-60.0 seconds; and the operating conditions of the second regenerator include: 600-680 °C, the average residence time of the catalyst is 1.0-3.0 minutes, which can fully weaken the adverse impact of water vapor on the catalyst activity, so that the resulting regenerated catalyst has high catalytic cracking activity, and is therefore suitable for fluidized catalysis that mainly produces fuel oil. cracking.
  • the gas phase fuel may be injected into the first regenerator only.
  • the char ratio in the charring section or the first regenerator is 40-70%, preferably 40-50%; and the charring ratio in the regeneration section or the second regenerator is 40-70%, preferably 40-50%.
  • the coke ratio is 30-60%, preferably 50-60%.
  • the gaseous phase fuel is obtained by gasification of biomass, and contains 12-60% hydrogen, 15-30% based on the total volume of the gaseous fuel. Oxidized carbon and 3-8% methane, with the balance carbon dioxide and/or nitrogen.
  • the step 1) further includes: gasifying the biomass in the presence of a gasification medium, the gasification temperature is 500-1500°C, the gasification medium is selected from air, oxygen /Oxygen-rich gas and water vapor.
  • the gas phase fuel is obtained from biomass through anaerobic fermentation, and contains 40-100 volume % methane based on the total volume of the gas phase fuel.
  • the step 1) further includes: subjecting the biomass to anaerobic fermentation in a closed fermentation tank, and the fermentation temperature is not higher than 60°C.
  • the biomass is pretreated before gasification or anaerobic fermentation.
  • the biomass pretreatment process is well known to those skilled in the art.
  • the pretreatment is selected from grinding. , one or more of drying, extrusion, steam explosion, acid treatment, alkali treatment and microbial pretreatment.
  • the temperature within the catalyst regenerator is controlled to not exceed 750°C by a heat extraction system including one or more internal heat collectors and/or external heat collectors.
  • the heat extraction system uses the heat extracted from the catalyst regenerator to generate high-pressure steam and exports it to other devices for energy supply.
  • the present application can use the energy generated by the regeneration system of the catalytic cracking unit to supply other operating units and become the power center of the refinery, fundamentally reducing the carbon emissions of the refinery.
  • This application introduces biomass into the power center of the catalytic cracking unit, and uses biomass energy to supply the operation of the unit.
  • the carbon dioxide emitted does not come from fossil energy, which can fundamentally change the source of energy and achieve carbon emission reduction.
  • the present application provides a catalyst regeneration system suitable for a fluidized catalytic cracking unit, including a biomass treatment unit and a catalyst regeneration unit, wherein:
  • the biomass processing unit is used to process biomass, such as gasification or anaerobic fermentation, to obtain gas phase fuel containing hydrogen and/or methane, and includes a gas phase fuel generator and a gas phase fuel storage tank.
  • the gas phase fuel generates
  • the device is preferably selected from a biomass gasifier, a biomass anaerobic fermentation tank or a combination thereof, and has a biomass inlet and a gas phase product outlet, the gas phase fuel storage tank has an inlet and a gas phase fuel outlet, the gas phase fuel generator The gas phase product outlet is connected with the inlet of the gas phase fuel storage tank;
  • the catalyst regeneration unit is used to regenerate the ungenerated catalyst from the catalytic cracking reactor, and includes a catalyst regenerator having an ungenerated catalyst inlet, an oxygen-containing gas inlet, a gas phase fuel inlet, a regenerated flue gas outlet and Regenerated catalyst out mouth, and
  • the gas phase fuel outlet of the gas phase fuel storage tank is connected with the gas phase fuel inlet of the catalyst regenerator through a pipeline.
  • the biomass processing unit further includes a biomass pre-conditioner and an optional gas phase product dryer
  • the biomass pre-conditioner is used to pre-treat the biomass
  • the pre-treatment is selected from the group consisting of: One or more of grinding, drying, extrusion, steam explosion, acid treatment, alkali treatment and microbial pretreatment
  • the gas phase product dryer is used to dry the gas phase product obtained from the biomass anaerobic fermentation tank.
  • the catalyst regenerator includes a charred section and a dense phase regeneration section, the dense phase regeneration section is located above the charred section, and the outlet of the charred section is accommodated inside the dense phase regeneration section. , so that the burning section and the dense phase regeneration section are fluidly connected;
  • the burning section is provided with:
  • a first oxygen-containing gas inlet is provided at the bottom of the coking section and is used to input oxygen-containing gas into the coking section;
  • the gas phase fuel inlet is provided above the first oxygen-containing gas inlet for inputting gas phase fuel
  • a gas distributor configured to distribute gaseous phase fuel input through the gaseous phase fuel inlet
  • the spent catalyst inlet is used to transport the spent catalyst from the catalytic cracking reactor to the inside of the coke section;
  • An optional first circulating flue gas inlet which is used to circulate a part of the flue gas discharged from the dense phase regeneration section back to the interior of the burning section;
  • the dense phase regeneration section is provided with:
  • the second oxygen-containing gas inlet is provided at the bottom of the dense phase regeneration section and is used to input oxygen-containing gas into the dense phase regeneration section;
  • An optional second gas phase fuel inlet which is provided above the second oxygen-containing gas inlet and is used to input gas phase fuel into the dense phase regeneration section;
  • an optional second gas distributor configured to distribute the gas phase fuel input through the second gas phase fuel inlet
  • the regeneration flue gas outlet is arranged at the top of the dense phase regeneration section and is used to discharge the regeneration flue gas in the dense phase regeneration section;
  • the regenerated catalyst outlet is used to return the regenerated catalyst to the catalytic cracking reactor.
  • Optional second circulation flue gas inlet which is used to discharge a portion of the flue gas discharged from the dense phase regeneration section Circulate back to the inside of the dense phase regeneration section;
  • the dense phase regeneration section is also equipped with a heat collector for delivering heat to the outside of the regenerator.
  • the catalyst regenerator includes a first regenerator and a second regenerator, the second regenerator is located downstream of the first regenerator, and the first regenerator and the second regenerator pass a catalyst
  • the transport pipe is connected to transport the catalyst material partially regenerated by the first regenerator to the second regenerator;
  • the first regenerator settings are:
  • a first oxygen-containing gas inlet which is provided at the bottom of the first regenerator and is used to input oxygen-containing gas into the first regenerator;
  • the gas phase fuel inlet is provided above the first oxygen-containing gas inlet for inputting gas phase fuel
  • a gas distributor configured to distribute gaseous phase fuel input through the gaseous phase fuel inlet
  • the to-be-generated catalyst inlet is used to transport the to-be-generated catalyst from the catalytic cracking reactor to the inside of the first regenerator;
  • a first regeneration flue gas outlet which is provided at the top of the first regenerator and is used to discharge the regeneration flue gas in the first regenerator;
  • An optional first circulating flue gas inlet which is arranged at the bottom of the first regenerator and communicates with the first regeneration flue gas outlet, is used to circulate part of the flue gas discharged from the first regenerator back to the first regeneration device,
  • the second regenerator is provided with:
  • a second oxygen-containing gas inlet which is provided at the bottom of the second regenerator and is used to input oxygen-containing gas into the second regenerator;
  • An optional second gas phase fuel inlet which is arranged above the second oxygen-containing gas inlet and is used to input gas phase fuel to the second regenerator;
  • an optional second gas distributor configured to distribute the gas phase fuel input through the second gas phase fuel inlet
  • the regenerated catalyst outlet is used to return the regenerated catalyst to the catalytic cracking reactor;
  • a second regeneration flue gas outlet is provided at the top of the second regenerator and is used to discharge the regeneration flue gas in the second regenerator;
  • An optional second circulating flue gas inlet which is provided at the bottom of the second regenerator and communicates with the first regeneration flue gas outlet or the second regeneration flue gas outlet, is used to circulate part of the flue gas back to the second regenerator.
  • the second regenerator is provided at the bottom of the second regenerator and communicates with the first regeneration flue gas outlet or the second regeneration flue gas outlet, is used to circulate part of the flue gas back to the second regenerator.
  • the catalyst regeneration system of the present application is suitable for regenerating the unspent catalyst from the catalytic cracking reaction unit 100, and includes: biomass treatment units 300 and 600 and catalyst regeneration Units 200, 400, 500, 700.
  • the catalytic cracking reactor 110 is used to perform the catalytic cracking reaction: its bottom inlet 102 is passed into a lifting medium to lift the regenerated catalyst entering through the regenerated catalyst inlet 103 ( from the regenerator); the raw oil entering from the raw oil inlet 101 contacts the catalyst to perform a catalytic cracking reaction.
  • the reacted oil and gas products are separated by the oil agent separation device 120.
  • the separated oil and gas products are collected in the gas collecting chamber 140 and then input to the product separation device 150 for separation to obtain various products.
  • the separated unfinished catalyst is stripped through the stripping section 130 of the settler and then transported to the catalyst regeneration unit through the unfinished catalyst outlet 131 for regeneration, thereby realizing recycling.
  • the catalytic cracking reactor 110 applicable to this application can be various reactors commonly used in this field, such as riser reactors, fluidized bed reactors, variable diameter reactors and combinations thereof.
  • the biomass processing unit 300 includes:
  • Biomass preprocessor 310 used to pretreat biomass
  • Biomass anaerobic fermentation tank 320 is used for anaerobic fermentation of pretreated biomass to obtain gas phase fermentation products.
  • Gas phase product dryer 330 used for drying the gas phase fermentation product obtained from the biomass anaerobic fermentation tank, and
  • the gas phase fuel storage tank 340 is used to store the gas phase product.
  • the anaerobic fermentation process of biomass can be carried out in a biomass anaerobic fermentation tank 320, such as a closed fermentation tank.
  • the fermentation substrate can be a mixed biomass raw material, and the fermentation temperature is not higher than 60°C.
  • urea, biomass carbon, etc. can be added to enhance the fermentation process.
  • the anaerobic fermentation products mainly include methane, carbon dioxide, water, etc. Since water has a negative impact on subsequent processes, drying is required. Drying can be performed in the gas phase product dryer 330 to remove moisture in the fermentation product so that the moisture content is lower than 1.0g/m 3 .
  • the dried gas phase product is stored in the gas phase fuel storage tank 340 for later use.
  • methane can account for more than 40%, such as 40-50%, can reach more than 60%, and can reach more than 75%, based on the total volume of the gas phase product.
  • the energy consumed in the anaerobic fermentation process comes from other products of the fermentation process or at least part/all comes from renewable energy sources such as solar energy, green electricity, and nuclear energy, reducing carbon emissions throughout the life cycle.
  • the biomass processing unit 600 includes:
  • Biomass preprocessor 610 used to pretreat biomass
  • Biomass gasifier 620 used to gasify pretreated biomass to obtain gas phase products
  • a gas phase fuel storage tank 630 is used to store the gas phase product.
  • the biomass can be transported to the biomass preprocessor 610, undergoes grinding, drying and other processing, and then is transported to the biomass gasifier 620.
  • the biomass gasifier 620 the biomass is gasified to obtain gas phase products, which are transported to the gas phase fuel storage tank 630 for subsequent regeneration processing, while the remaining products are led out or sent to other devices for processing.
  • the biomass material is ground or pulverized into granular materials with a particle size of 0.2-40 mm, and then dried so that the moisture content reaches less than 10%.
  • the biomass is gasified.
  • the gasification temperature can be in the range of 500-1500°C.
  • the gasification medium used in the gasification process can be selected from air, oxygen/oxygen-rich gas, water vapor, etc.
  • the energy consumed in the biomass gasification process can come from other products of the gasification process, or at least part or all of it comes from renewable energy sources such as solar energy, green electricity, and nuclear energy, reducing carbon emissions throughout the life cycle.
  • the main components of the obtained gas phase product are hydrogen, carbon monoxide, carbon dioxide and a small amount of methane gas.
  • hydrogen accounts for 12-60%
  • carbon monoxide accounts for 15-30%
  • methane accounts for 3-8%, based on the total volume of gas phase products.
  • the remaining components may be carbon dioxide and/or nitrogen.
  • FIG. 1 shows a schematic diagram of a first preferred embodiment of the catalyst regeneration method and system of the present application, in which the regeneration process is a single-stage regeneration.
  • the regeneration unit 200 includes a regenerator 210, and the regenerator 210 is provided with:
  • An oxygen-containing gas inlet 211 is used to input oxygen-containing gas into the regenerator, and the oxygen-containing gas inlet 211 is provided at the bottom of the regenerator;
  • Distribution plate 212 the distribution plate 212 is configured to distribute the oxygen-containing gas input through the oxygen-containing gas inlet 211;
  • the gas phase fuel inlet 214 is provided above the distribution plate 212 and is used to input gas phase fuel (gas phase product from the gas phase fuel storage tank 340);
  • a gas distributor 213 configured to distribute the gas phase fuel input through the gas phase fuel inlet 214;
  • the to-be-generated catalyst inlet 216 is used to transport the to-be-generated catalyst of the catalytic cracking reactor to the inside of the regenerator;
  • the regenerated catalyst outlet 217 is used to transport the regenerated catalyst to the catalytic cracking reactor.
  • the gas-phase fuel storage tank 340 is connected to the gas-phase fuel inlet 214 so that the gas-phase fuel is transported to the interior of the regenerator, burned and regenerated to regenerate the spent catalyst.
  • the distribution plate 212 and the gas distributor 213 are both arranged inside the regenerator 210 to evenly distribute the oxygen-containing gas and the gas phase fuel in the to-be-generated catalyst inside the regenerator, so that the catalyst can burn evenly during the regeneration process and avoid local overheating. .
  • the distribution plate 212 and the gas distributor 213 are both disposed at a lower portion inside the regenerator 210, so that the to-be-generated catalyst is in a fluidized state inside the regenerator during the regeneration process in the regenerator.
  • the regenerator is a dense phase bed, and the bed density of the catalyst is 300-700kg/m 3 .
  • the gaseous phase fuel is injected through the gas distributor from a position never lower than the inlet level of the catalyst to be generated.
  • the gas distributor 213 is provided at the lower part of the dense-phase bed section of the regenerator to better distribute the gaseous phase fuel evenly.
  • the conditions of the regeneration process are: the oxygen-containing gas is air, the regeneration temperature is 550-750°C, the average residence time of the catalyst is 1.0-15.0 minutes, and the apparent linear velocity of the gas is 0.7-2.0 m/s.
  • the gas phase fuel and the to-be-generated catalyst are transported to the bottom of the regenerator to contact with oxygen-containing gas for char regeneration and energy supply. Due to the injection of gas phase fuel, a large amount of heat is generated during the regeneration process. If the temperature within the regenerator is too high, the activity of the catalyst will be adversely affected. Therefore, the regeneration unit 200 is also equipped with a heat extractor 215 for extracting excess heat from the regenerator.
  • the heat exchanger can be an internal heat exchanger (arranged inside the regenerator) or/and an external heat exchanger (arranged outside the regenerator). There are one or more heat exchangers, which can absorb the excess energy generated by the regenerator. For supplying other devices.
  • the excess heat of the regeneration system can be used to generate high-pressure steam through the heat collector, and can be exported to other devices for energy supply.
  • the temperature of the regenerator bed is controlled not to exceed 750°C, for example, not to exceed 720°C.
  • the regeneration unit 200 also includes a cyclone separator 220, and the regeneration smoke The gas leaves the regenerator through the cyclone separator 220 and enters the flue gas energy recovery system 230 to recover energy.
  • the cyclone 220 may be provided inside the regenerator 210 .
  • FIG. 2 shows a schematic diagram of a second preferred embodiment of the catalyst regeneration method and system of the present application, in which the regeneration process adopts dual regenerator regeneration.
  • the regeneration unit 400 includes a first regenerator 410 and a second regenerator 420 .
  • the two regenerators are connected in series, and the second regenerator 420 is located downstream of the first regenerator 410 and is connected through a catalyst delivery pipe 417 so that the catalyst material of the first regenerator is delivered to the second regenerator.
  • the first regenerator 410 is provided with:
  • the first oxygen-containing gas inlet 411 is provided at the bottom of the first regenerator and is used to input oxygen into the first regenerator;
  • Gaseous phase fuel inlet 414 the gas phase fuel inlet is provided above the first oxygen-containing gas inlet for inputting gas phase fuel;
  • a gas distributor 416 configured to distribute gaseous phase fuel input through the gaseous phase fuel inlet
  • the to-be-generated catalyst inlet 418 (connected to the to-be-generated inclined pipe), the to-be-generated catalyst inlet is used to transport the to-be-generated catalyst of the catalytic cracking reactor to the inside of the first regenerator;
  • the first flue gas outlet 419 is located at the top of the first regenerator
  • the second regenerator 420 is provided with:
  • the second oxygen-containing gas inlet 421 is provided at the bottom of the second regenerator and is used to input oxygen into the second regenerator;
  • the regenerated catalyst outlet 439 (connected to the regeneration inclined pipe) is used to transport the regenerated catalyst to the catalytic cracking reactor;
  • the second flue gas outlet 429 is provided at the top of the second regenerator.
  • the gaseous phase fuel is introduced into the first regenerator 410 from the gaseous phase fuel inlet 414 through the gas distributor 416, and the to-be-generated catalyst from the catalytic cracking reactor passes through the to-be-generated inclined tube (connected to the to-be-generated catalyst outlet 131) and through
  • the to-be-generated catalyst inlet 418 enters the first regenerator, contacts the oxygen entering from the first oxygen-containing gas inlet 411, and causes a partial burning reaction (first stage regeneration) in the first regenerator; the partially regenerated catalyst is transported through the catalyst
  • the pipe 417 is transported to the second regenerator 420, and after contact with the oxygen entering from the second oxygen-containing gas inlet 421, a coke combustion reaction occurs, and complete regeneration is performed.
  • a first circulating flue gas inlet 431 is provided at the bottom of the first regenerator, and the first circulating flue gas inlet 431 is connected with the first flue gas outlet 419, so that Part of the flue gas discharged from the first regenerator enters the first regenerator through the first circulating flue gas inlet.
  • a second circulating flue gas inlet 432 is provided at the bottom of the second regenerator.
  • the second circulating flue gas inlet 432 is connected with the first flue gas outlet 419, so that the second circulating flue gas inlet 432 is discharged from the first regenerator. Part of the flue gas enters the second regenerator through the second circulating flue gas inlet.
  • the bottom of the first regenerator and the bottom of the second regenerator are connected through a catalyst delivery pipe 417 .
  • the flue gas energy recovery device 430 to recover energy; the other part of the flue gas is circulated back to the regeneration unit in two ways and transported to the first regenerator all the way.
  • the introduced oxygen is diluted; the other path is sent to the second regenerator to dilute the oxygen.
  • the flue gas from the second regenerator After the flue gas from the second regenerator is separated by the cyclone separator 423, it enters the flue gas energy recovery device 430 through the second circulating flue gas outlet 429 to recover energy, and is sent to the carbon dioxide separation system 460 to capture the carbon dioxide gas therein.
  • the regenerated catalyst is circulated back to the catalytic cracking reactor through the regenerated catalyst inlet 439 and the regeneration inclined tube (connected with the regenerated catalyst inlet 103).
  • the operating conditions of the first regenerator are: temperature 550°C-700°C, average catalyst residence time 20.0-240.0 seconds, and superficial gas linear velocity 0.5-5.0m/s.
  • the operating conditions of the second regenerator are: temperature 600°C-750°C, average catalyst residence time 0.5-5.0 minutes, apparent gas linear velocity 0.4-2.0m/s.
  • the regeneration unit 400 is also equipped with heat collectors 415, 425 for delivering heat to the outside of the first and second regenerators.
  • the heat exchanger can be an internal heat exchanger (arranged inside the regenerator) or/and an external heat exchanger (arranged outside the regenerator). There are one or more heat exchangers, from the first regenerator and the second heat exchanger.
  • the regenerator takes out the excess energy and supplies it to other devices.
  • the excess heat of the regeneration system can be used to generate high-pressure steam through the heat collector, and can be exported to other devices for energy supply.
  • the temperature of the first regenerator bed is controlled not to exceed 700°C
  • the temperature of the second regenerator bed is controlled not to exceed 750°C, for example, not more than 750°C. exceeds 720°C.
  • the gas phase products obtained from biomass contain a large amount of methane, which can account for more than 40%. For example, 40-50% can reach more than 60%, and high can reach more than 75%, based on the total volume of gas phase products.
  • the molecular formula of methane is CH4 and its hydrogen content is up to 25%. It is generally believed in the art that excess water vapor during the regeneration process is detrimental to the activity of the catalytic cracking catalyst, and a mixture with a high hydrogen content is generally not used as a supplementary fuel in the regeneration process.
  • the regeneration process adopts a pure oxygen regeneration process and uses double regenerators for regeneration, which can better protect the catalyst and avoid the influence of water vapor.
  • the water vapor can be used to age the catalyst to improve product selectivity.
  • the regeneration method performed in the regeneration system including the regeneration unit 400 includes:
  • the biomass is transported to the biomass anaerobic fermentation system for anaerobic fermentation treatment to obtain gas phase fermentation products;
  • FIG. 3 shows a schematic diagram of a third preferred embodiment of the catalyst regeneration method and system of the present application, in which the regeneration process adopts dual regenerator regeneration.
  • the regeneration unit 500 includes a first regenerator 510 and a second regenerator 520. The two regenerators are connected in series.
  • the second regenerator 520 is located downstream of the first regenerator 510 and is connected through a U-shaped catalyst delivery pipe 517, so that the first regenerator 520 is connected in series.
  • the catalyst feed from the regenerator is sent to the second regenerator.
  • the first regenerator 510 is provided with:
  • the first oxygen-containing gas inlet 511 is provided at the bottom of the first regenerator and is used to input oxygen into the first regenerator;
  • Gaseous phase fuel inlet 514 which is arranged above the first oxygen-containing gas inlet and is used to input gas phase fuel;
  • a gas distributor 516 configured to distribute gaseous phase fuel input through the gaseous phase fuel inlet
  • the to-be-generated catalyst inlet 518 (connected to the to-be-generated inclined pipe), the to-be-generated catalyst inlet is used to transport the to-be-generated catalyst of the catalytic cracking reactor to the inside of the first regenerator;
  • the first flue gas outlet 519 is located at the top of the first regenerator
  • the second regenerator 520 is provided with:
  • the second oxygen-containing oxygen-containing gas inlet 521 is provided at the bottom of the second regenerator and is used to input oxygen into the second regenerator;
  • the regenerated catalyst outlet 539 (connected to the regeneration inclined pipe) is used to transport the regenerated catalyst to the catalytic cracking reactor;
  • the second flue gas outlet 529 is provided at the top of the second regenerator.
  • the gaseous phase fuel is introduced into the first regenerator 510 from the gaseous phase fuel inlet 514 through the gas distributor 516, and the to-be-generated catalyst from the catalytic cracking reactor passes through the to-be-generated inclined tube (connected to the to-be-generated catalyst outlet 131) and
  • the to-be-generated catalyst inlet 518 enters the first regenerator, contacts with the oxygen entering from the oxygen-containing gas inlet 511 through the fluid distribution plate 512, and sends a partial burning reaction (first stage regeneration) in the first regenerator; the partially regenerated catalyst It is transported to the second regenerator 520 through the U-shaped catalyst delivery pipe 517, and after contact with oxygen entering from the oxygen-containing gas inlet 521 through the fluid distribution plate 522, a coke combustion reaction occurs, and complete regeneration is performed.
  • a first circulating flue gas inlet 533 is provided at the bottom of the first regenerator, and the first circulating flue gas inlet 533 is connected with the first flue gas outlet 519, so that the first regenerator discharges Part of the flue gas enters the first regenerator through the first circulating flue gas inlet.
  • a second circulating flue gas inlet 532 is provided at the bottom of the second regenerator.
  • the second circulating flue gas inlet 532 is connected with the first flue gas outlet 519, so that the second circulating flue gas inlet 532 is discharged from the first regenerator. Part of the flue gas enters the second regenerator through the second circulating flue gas inlet.
  • the bottom of the first regenerator and the bottom of the second regenerator are connected through the U-shaped catalyst delivery pipe 517,
  • the U-shaped catalyst delivery pipe is provided with an opening 531, which is connected with the first flue gas outlet 519, so that part of the flue gas discharged from the first regenerator enters the U-shaped catalyst delivery pipe through the opening.
  • the flue gas energy recovery device 530 to recover energy; the other part of the flue gas is circulated back to the regeneration unit in three ways, and is transported to the first regenerator all the way. Dilute the introduced oxygen; transport it all the way to the U-shaped catalyst delivery pipe to transport the semi-regenerated catalyst to the second regenerator; transport it all the way to the second regenerator to dilute the introduced oxygen.
  • the amount of oxygen and/or circulating flue gas is controlled so that the oxygen concentration in the mixed gas in the first regenerator and the second regenerator is no higher than 28%.
  • Charging is carried out in this atmosphere, which improves the charring intensity; the inlet air does not contain nitrogen, which can reduce the energy consumed in gas preheating; and the carbon dioxide concentration of the flue gas at the outlet of the regenerator is higher, which facilitates the separation and capture of carbon dioxide.
  • the flue gas from the second regenerator After the flue gas from the second regenerator is separated by the cyclone separator 523, it enters the flue gas energy recovery device 530 through the second circulating flue gas outlet 529 to recover energy, and is sent to the carbon dioxide separation system 560 to capture the carbon dioxide gas therein.
  • the regenerated catalyst is circulated back to the catalytic cracking reactor through the regenerated catalyst inlet 539 and the regeneration inclined tube (connected with the regenerated catalyst inlet 103).
  • the operating conditions of the first regenerator are: temperature 550°C-700°C, average catalyst residence time 20.0-240.0 seconds, and superficial gas linear velocity 0.5-5.0m/s.
  • the operating conditions of the second regenerator are: temperature 600°C-750°C, average catalyst residence time 0.5-5.0 minutes, apparent gas linear velocity 0.4-2.0m/s.
  • the regeneration unit 500 is also equipped with heat extractors 515, 525 for taking out excess heat from the first and second regenerators and optionally delivering the heat to the outside.
  • the heat exchanger can be an internal heat exchanger (arranged inside the regenerator) or/and an external heat exchanger (arranged outside the regenerator). There are one or more heat exchangers, and the first regenerator and the second heat exchanger are combined.
  • the excess energy produced by the regenerator is used to supply other devices.
  • the excess heat of the regeneration system can be used to generate high-pressure steam through the heat collector, and can be exported to other devices for energy supply.
  • the temperature of the first regenerator bed is controlled not to exceed 700°C; by setting the heat collector 525, the temperature of the second regenerator bed is controlled not to exceed 750°C, for example, not more than 750°C. exceeds 720°C.
  • the gas phase product obtained by biomass gasification contains a certain amount of hydrogen, for example, hydrogen accounts for 12-60%, carbon monoxide accounts for 15-30%, and methane accounts for 3-8%, based on the total volume of the gas phase product. It is generally believed in the art that excess water vapor during the regeneration process is detrimental to the activity of the catalytic cracking catalyst, so mixed gas containing hydrogen is generally not used as a supplementary fuel during the regeneration process.
  • the regeneration process adopts a pure oxygen regeneration process and uses double regenerators for regeneration, which can better protect the catalyst and avoid the influence of water vapor.
  • the water vapor can be used to age the catalyst to improve product selection. Selective.
  • the regeneration method performed in the regeneration system including the regeneration unit 500 includes:
  • FIG. 4 shows a schematic diagram of a fourth preferred embodiment of the catalyst regeneration method and system of the present application, in which the regeneration process adopts two stages of regeneration.
  • the regeneration unit 700 includes a regenerator 740.
  • the regenerator 740 includes a burning section 710 and a regeneration section 750, wherein the regeneration section 750 is in fluid communication with the burning section 710 and is located above the burning section 710; the regeneration section 750 is in fluid communication with the burning section 710 and is located above the burning section 710; Section 750 is separated from char section 710 by a fluid distribution plate 751 .
  • the regeneration section 750 and the burning section 710 are connected in series. After the material from the burning section 710 is distributed by the fluid distribution plate 751, it enters the regeneration section 750 for complete regeneration.
  • Charging section 710 is provided with:
  • Gaseous phase fuel inlet 714 the gas phase fuel inlet is provided above the first oxygen-containing gas inlet for inputting gas phase fuel;
  • a gas distributor 713 configured to distribute the gas phase fuel input through the gas phase fuel inlet
  • the spent catalyst inlet 716 is used to transport the spent catalyst of the catalytic cracking reactor to the interior of the coke section;
  • the first circulating flue gas inlet 731 is used to circulate a part of the flue gas recovered in the regeneration section back to the interior of the burning section.
  • the to-be-generated catalyst is initially charred in the charring section 710, and the gas phase fuel is partially burned.
  • the hydrothermal deactivation effect of water produced during hydrogen combustion on the catalyst can be avoided.
  • the regeneration section 750 is provided with:
  • the second oxygen-containing gas inlet 752 is provided at the bottom of the regeneration section and is used to input oxygen into the regeneration section;
  • the second circulating flue gas inlet 753 is used to circulate a part of the flue gas recovered in the regeneration section back to the interior of the regeneration section;
  • Flue gas outlet 732 which is located at the top of the regeneration section
  • the regeneration section 750 is also equipped with a heat collector 715 for delivering heat to the outside of the regenerator.
  • the gaseous phase fuel from the gaseous phase fuel storage tank 630 is input to the coking section 710 through the gas distributor 713 through the gaseous phase fuel inlet 714, and the ungenerated catalyst from the catalytic cracking reactor enters the coking section 710 through the ungenerated catalyst inlet 716. It contacts the oxygen entering through the first oxygen-containing gas inlet 711 to send a partial burning reaction in the burning section; then, after passing through the fluid distribution plate 751, it enters the regeneration section 750 for complete regeneration. At this time, pure oxygen is input through the second oxygen-containing gas inlet 752 and contacts the partially burned catalyst to further regenerate and burn the catalyst and incompletely regenerated flue gas.
  • the regenerated catalyst is separated by the cyclone separator 720, it falls back to the regeneration section, is discharged through the catalyst outlet 717, and is recycled back to the catalytic cracking reactor.
  • Part of the flue gas discharged through the flue gas outlet 732 recovers energy through the flue gas energy recovery system 730, and then is separated by the carbon dioxide separation system 760 to capture carbon dioxide; the other part of the flue gas is recycled back to the bottom of the coke section.
  • the operating conditions of the coking section are: temperature 550-720°C, average catalyst residence time 10.0-120.0 seconds, preferably 15.0-90.0 seconds, gas apparent linear velocity 0.5-5.0m /s, preferably 1.0-4.0m/s.
  • the operating conditions of the regeneration section are: temperature 600-750°C, average catalyst residence time 0.5-5.0 minutes, preferably 1.0-4.0 minutes, gas apparent linear velocity 0.4-2.0m/s , preferably 0.5-1.5m/s.
  • the catalyst is completely regenerated in the regeneration section, and the gas phase fuel derived from biomass is completely burned in the regeneration section.
  • the regeneration section is a dense-phase bed, and its catalyst density is 300-700kg/m 3 .
  • the gas input through the first oxygen-containing gas inlet 711 and the second oxygen-containing gas inlet 752 is oxygen.
  • the oxygen input through the first oxygen-containing gas inlet 711 will be mixed with the circulating flue gas after entering the burning section to form an oxidation-carbon dioxide mixed gas.
  • the amount of oxygen and/or circulating flue gas is controlled to make the oxygen concentration in the mixed gas Not more than 28% by volume.
  • the oxygen input through the second oxygen-containing gas inlet 752 will be mixed with circulating flue gas after entering the regeneration section to form an oxidation-carbon dioxide mixed gas.
  • the amount of oxygen and/or circulating flue gas is controlled so that the mixed gas Oxygen concentration is not higher than 28%.
  • Charging is carried out in this atmosphere, which improves the burning intensity; the inlet air does not contain nitrogen, which can reduce gas preheating consumption. energy consumption; and the flue gas carbon dioxide concentration at the outlet of the regenerator is higher, which facilitates the separation and capture of carbon dioxide.
  • the burning ratio in the burning section is 40-70%; the burning ratio in the regeneration section is 30-60%.
  • pure oxygen regeneration is used, and the regenerated flue gas only contains carbon dioxide and oxygen, which facilitates the separation and capture of carbon dioxide for further conversion and utilization, achieving negative carbon emissions.
  • the gas phase fuel obtained by gasification of biomass is introduced from a gas distributor.
  • the regeneration process adopts a pure oxygen regeneration process, and performs two-stage regeneration in a series-connected charring section and regeneration section. This can improve the charring intensity, achieve better regeneration effects, and at the same time weaken the Effect of water vapor on catalysts.
  • the water vapor can be used to age the catalyst to improve product selectivity.
  • the regeneration unit 700 is also equipped with a heat sink 715 for delivering heat to the outside of the regenerator.
  • the heat exchanger can be an internal heat exchanger (arranged inside the regenerator body) or/and an external heat exchanger (arranged outside the regenerator body). There are one or more heat exchangers, which can absorb the excess heat generated by the regenerator. The energy is used to power other devices. The excess heat of the regeneration system can be used to generate high-pressure steam through the heat collector, and can be exported to other devices for energy supply.
  • the temperature of the regenerator bed is controlled not to exceed 750°C, for example, not to exceed 720°C.
  • the heat collector 715 is configured in the regeneration section to take out the heat of the bed in the regeneration section and transport it to the outside of the regenerator, and to control the temperature of the bed in the regeneration section.
  • the temperature of the bed in the regeneration section is controlled via the heat collector to not exceed 750°C, preferably not to exceed 720°C.
  • the regeneration unit 700 also includes a cyclone separator 720.
  • the regenerated flue gas leaves the regenerator through the cyclone separator 720 and enters the flue gas energy recovery system 730 to recover energy.
  • the cyclone 720 may be disposed inside the regenerator 740 .
  • Catalysts suitable for the catalyst regeneration method and system of the present application may be catalysts commonly used in various catalytic cracking processes, and are not particularly limited by the present application.
  • the catalyst includes zeolite, inorganic oxide and optional clay. Each component accounts for the total weight of the catalyst: zeolite 1-50 wt%, inorganic oxide 5-99 wt% % by weight, 0% by weight - 70% by weight of clay.
  • Zeolite is the active component, selected from Medium pore zeolite and/or optional large pore zeolite, the medium pore zeolite accounts for 10% to 100% by weight of the total weight of the zeolite, and the large pore zeolite accounts for 0% to 90% by weight of the total weight of the zeolite; the medium pore zeolite is selected from ZSM One or more of the series of zeolites and/or ZRP zeolite, the above zeolite can be modified with non-metals such as phosphorus and/or transition metals such as iron, cobalt, nickel; large pore zeolite is selected from hydrogen Y, rare earth Y, rare earth One or more of hydrogen Y, ultra-stable Y, etc.
  • Catalyst a is commercially available catalyst ASC-2, and its properties are listed in Table 4;
  • Catalyst b is a TCC catalyst, which is used after aging. Aging conditions: 800°C, water vapor aging for 15 hours. The preparation process of catalyst b is as follows:
  • step (3) Add the phosphorus- and iron-containing MFI mesoporous molecular sieve (dry basis: 2 kg) prepared in step (1) to the mixed slurry obtained in step (2), stir evenly, spray-dry and shape, and use ammonium dihydrogen phosphate to form The solution (phosphorus content is 1% by weight) is washed to remove free Na + and dried to obtain the catalytic conversion catalyst c sample.
  • the dry basis composition of catalyst c includes: 2 wt% MFI mesoporous molecular sieve containing phosphorus and iron, 36 wt% pseudo-boehmite and 8 wt% aluminum sol, the balance is kaolin clay.
  • the device shown in Figure 1 is used to conduct the test.
  • the specific preparation process of the gas phase fuel is as follows:
  • the biomass is washed or pickled in the pretreatment unit, and then pretreated by crushing and grinding.
  • the pretreated biomass is fermented in an anaerobic fermentation device at a fermentation temperature of 37°C. After the fermentation product is dehydrated by a drying device, a gas phase product is obtained, with methane accounting for more than 40% (based on the volume of the gas phase product), which is stored in a storage tank for later use.
  • Raw material A is used as the reaction raw material, and the catalytic conversion catalyst a is used as the catalyst.
  • the green catalyst is regenerated according to the method of this application.
  • the to-be-generated catalyst from the to-be-generated inclined tube comes into contact with the gas phase fuel and air introduced from the gas distributor at the bottom of the regenerator, and a coke combustion reaction occurs.
  • the excess energy generated by the regeneration system is used for external energy supply through the heat extraction system.
  • the operating temperature of the regenerator is 685°C, the average residence time of the catalyst is 5 minutes, and the apparent linear velocity of the gas is 1.0m/s.
  • the regenerated catalyst enters the reactor and contacts the feed oil for catalytic cracking reaction. Excess energy is used to supply other devices through the heat extraction system.
  • the regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in Table 6.
  • the test was carried out with reference to Example 1, except that instead of using a biomass processing unit, diesel was injected into the regenerator as fuel oil, and the fuel oil was used as a supplementary source of energy.
  • the regenerator burning temperature is 685°C.
  • the average residence time of the catalyst is 5 minutes, and the gas surface
  • the line speed is 1.0m/s.
  • the regenerated catalyst enters the reactor and contacts the feed oil for catalytic cracking reaction.
  • the regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in Table 6.
  • the carbon dioxide emission index refers to the amount of fossil energy carbon dioxide emitted for every 1 MJ of energy generated by the regeneration system.
  • the calculation method refers to the "Guidelines for Accounting and Reporting of Greenhouse Gas Emissions of China Petrochemical Enterprises (Trial)" (the same below);
  • the carbon dioxide produced by biomass methane-rich gas comes from the carbon dioxide existing in the atmosphere and is a neutral carbon emission process.
  • the device shown in Figure 2 is used for testing, in which a flue gas energy recovery system 430 and a carbon dioxide separation system 460 are provided.
  • the reactor 110 is a conventional riser reactor.
  • the biomass is washed or pickled in the pretreatment unit, and then pretreated by crushing and grinding.
  • the pretreated biomass is fermented in an anaerobic fermentation device at a fermentation temperature of 37°C. After the fermentation product is dehydrated by a drying device, a gas phase product is obtained, with methane accounting for more than 40% (based on the volume of the gas phase product), which is stored in a storage tank for later use.
  • Raw material B is used as the reaction raw material, and the catalytic conversion catalyst b is used as the catalyst.
  • the green catalyst is regenerated according to the method of this application.
  • the gas phase fuel is introduced into the first regenerator through the gas distributor, and undergoes a combustion reaction together with the to-be-generated catalyst that enters the first regenerator through the to-be-generated inclined tube, and a partial burning reaction occurs in the first regenerator (first stage regeneration);
  • the partially regenerated catalyst is transported to the second regenerator through the catalyst delivery pipe for coke combustion reaction and complete regeneration.
  • part of the flue gas from the regenerator cyclone separation system returns to the first regenerator and the second regenerator, and the oxygen content is controlled not to exceed 28%.
  • the excess energy generated by the regeneration system is used for external energy supply through the heat collector.
  • the operating temperature of the first regenerator is 650°C
  • the average residence time of the catalyst in the first regenerator is 120 seconds
  • the apparent linear velocity of the gas is 1.5m/s.
  • the operating temperature of the second regenerator is 670°C
  • the average residence time of the catalyst in the second regenerator is 3.0 minutes
  • the apparent linear velocity of the gas is 1.0 m/s.
  • Example 7 The test was carried out with reference to Example 2. The only difference is that diesel is used as the fuel oil, which is injected into the waiting pipeline to premix with the waiting catalyst and then enters the regenerator as a supplementary energy source. The regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in Table 7.
  • the carbon dioxide emission index refers to the amount of carbon dioxide emitted from fossil energy for every 1 MJ of energy produced by the regeneration system; the carbon dioxide produced by the gas phase fuel comes from the carbon dioxide existing in the atmosphere and is a neutral carbon emission process.
  • the device shown in Figure 3 is used for testing, in which a flue gas energy recovery system 530 and a carbon dioxide separation system 560 are provided.
  • the reactor 110 is a conventional riser reactor.
  • the biomass processing unit 600 includes: a biomass preprocessor 610, a biomass gasifier 620, and a gas phase fuel storage tank 630.
  • the operating conditions of the biomass gasifier 620 are a temperature of 950°C
  • the gasification medium is water vapor
  • the volume fractions of hydrogen, carbon monoxide, and methane in the obtained gas phase product are 50%, 25%, and 7% respectively, based on the volume of the gas phase product. .
  • Raw material C serves as the reaction raw material
  • the catalytic conversion catalyst C serves as the catalyst.
  • pure oxygen gas is introduced into the first regenerator and the second regenerator respectively, and the gas phase fuel from the gas phase fuel storage tank 630 is introduced from the gas distributor of the first regenerator, and the gas phase fuel from the gas phase fuel storage tank 630 is introduced into the first regenerator and the second regenerator.
  • a combustion reaction occurs together with the to-be-generated catalyst in the inclined tube.
  • part of the flue gas coming out of the regenerator cyclone separation system 520 returns to the bottom of the first regenerator and the second regenerator, and the oxygen content is controlled not to exceed 28%.
  • the excess energy generated by the regeneration system is used for external energy supply through the heat collector.
  • the operating temperature of the first regenerator is 630°C, the average residence time of the catalyst in the first regenerator is 40 seconds, and the apparent linear velocity of the gas is 1.0 m/s.
  • the operating temperature of the second regenerator is 665°C, the average residence time of the catalyst in the second regenerator is 1.5 minutes, and the apparent linear velocity of the gas is 1.0 m/s.
  • the regenerated catalyst enters the reactor and contacts the feed oil for catalytic cracking reaction. Regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in Table 8.
  • Example 8 The test was carried out with reference to Example 3. The only difference is that diesel is used as fuel oil, which is injected into the waiting pipeline to premix with the waiting catalyst and then enters the regenerator as a supplementary energy source. Regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in Table 8.
  • the carbon dioxide emission index refers to the amount of carbon dioxide emitted from fossil energy for every 1 MJ of energy produced by the regeneration system; the carbon dioxide produced by the gas phase fuel comes from the carbon dioxide existing in the atmosphere and is a neutral carbon emission process.
  • the device shown in Figure 4 is used for regeneration, in which a flue gas energy recovery system 730 and a carbon dioxide separation system 760 are provided.
  • the reactor 110 is a conventional riser reactor.
  • the biomass processing unit 600 includes: a biomass preprocessor 610, a biomass gasifier 620, and a gas phase fuel storage tank 630.
  • the operating conditions of the biomass gasifier 620 are a temperature of 950°C
  • the gasification medium is water vapor
  • the volume fractions of hydrogen, carbon monoxide, and methane in the obtained gas phase product are 50%, 25%, and 7% respectively, based on the volume of the gas phase product. .
  • Raw material B is used as the reaction raw material, and the catalytic conversion catalyst b is used as the catalyst. Regenerate the catalyst to be produced according to the method of this application. Pure oxygen gas is introduced into the coking section and the regeneration section respectively.
  • the gas phase fuel from the gas phase fuel storage tank 630 is introduced from the gas distributor at the bottom of the coking section.
  • the raw catalyst undergoes a combustion reaction together, and at the same time, part of the flue gas coming out of the regenerator cyclone separation system 720 returns to the bottom of the burning section and the regeneration section, and the oxygen content is controlled not to exceed 28%.
  • the excess energy generated by the regeneration system is used for external energy supply through the heat collector.
  • the operating temperature of the coking section is 630°C, the average residence time of the catalyst in the coking section is 40 seconds, and the apparent linear velocity of the gas is 1.2m/s.
  • the operating temperature of the dense phase regeneration section is 670°C, the average residence time of the catalyst in the dense phase regeneration section is 1.5 minutes, and the apparent linear velocity of the gas is 0.8m/s.
  • the regenerated catalyst enters the reactor and contacts the feed oil for catalytic cracking reaction. Regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in Table 9.
  • Example 9 The test was carried out with reference to Example 4. The only difference is that diesel is used as the fuel oil, which is injected into the waiting pipeline to premix with the waiting catalyst and then enters the regenerator as a supplementary energy source. Regeneration conditions, reaction conditions, and carbon dioxide emissions are shown in Table 9.
  • the carbon dioxide emission index refers to the amount of carbon dioxide emitted from fossil energy for every 1 MJ of energy produced by the regeneration system; the carbon dioxide produced by the gas phase fuel comes from the carbon dioxide existing in the atmosphere and is a neutral carbon emission process.

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Abstract

公开了一种适用于流化催化裂化装置的催化剂再生方法，所述流化催化裂化装置包括催化裂化反应器和催化剂再生器，所述再生方法包括如下步骤：1)提供生物质来源的包含氢气和/或甲烷的气相燃料；2)将所述气相燃料不经分离纯化直接送入催化剂再生器；3)将含氧气体引入所述催化剂再生器，其中所述含氧气体的氧气含量为14-28体积％；以及4)将来自催化裂化反应器的待生催化剂送入催化剂再生器，在其中与所述气相燃料和含氧气体接触，进行烧焦再生。通过本申请方法在催化剂再生过程引入了源于生物质的气相燃料供能，替代化石燃料，从根本上改变了催化裂化装置的能量来源，可以大幅减少催化裂化单元的碳排放，实现对碳元素的循环利用，还可以为其它工艺单元提供能量。

Description

采用生物基气相燃料的催化裂化催化剂再生方法和系统 技术领域
本申请涉及含炭催化裂化催化剂的再生，具体涉及采用生物基气相燃料的催化裂化催化剂再生方法和系统。
背景技术
当今，全球炼油工业的发展面临新能源替代、节能减排要求趋严等诸多挑战。灵活调整裂化生产方案、减少二氧化碳排放、减缓气候变化已经成为炼油工业转变经济增长方式、保持可持续发展的必由之路。2030年实现碳达峰和2060年实现碳中和具有紧迫性。“十四五”规划制定了碳达峰行动方案，明确要求加快推动绿色发展，中国全国碳排放权交易市场也已于2021年正式启动。因此，石油炼制与化工生产过程中有效减少碳排放显得尤为重要，减油增化的低碳化催化裂化方案的研究是炼厂未来的重要任务。重油加工过程中的碳排放主要是催化裂化烧焦、制氢过程、锅炉等设备的烟气排放以及工艺过程的能耗。其中催化裂化装置是炼厂中的核心设备，催化裂化再生器烧焦导致的碳排放占全厂碳排放的24-55％，占全国二氧化碳排放总量近1％，是石油化工行业碳减排重点。
CN102698817A公开了一种催化裂化催化剂再生工艺方法，该方法采用纯氧再生，在烟气能量回收系统后耦合了水蒸气变换反应区，将烟气中的CO用作水蒸气变换反应的原料，用于产氢，将烟气中的碳进一步回收利用。但该方法只关注了烟气的处理与回收，不完全再生烟道气降低了能量的利用率，还涉及到水蒸气变换反应区的原料和产物的分离纯化，成本较高；也未改变再生供能的能量来源。
CN113877397A公开了一种降低二氧化碳排放的非完全再生方法，该工艺采用纯氧气对催化剂进行不完全再生，得到的烟气中的一氧化碳用作化工原料，二氧化碳用于封存或驱油，从而降低碳排放。但该工艺主要涉及到烟气的后处理过程，成本较高。涉及到一氧化碳、二氧化碳、氧气和其它废弃的分离，分离过程复杂，不完全再生也未最大化利用积碳的化学能，将富集的二氧化碳封存造成了资源的浪费。
US5565089公开了一种催化裂化催化剂再生工艺方法，首先用空气 进行烧焦，然后回收烟气中的二氧化碳，将其循环并逐渐并入含氧气体流直至再生器中温度正常，最后只注入氧气和二氧化碳进行催化剂的再生。该工艺关注了再生过程进气系统和烟气处理，但供能产生的二氧化碳仍然全部来自于化石能源。
催化裂化装置的能量来源于催化剂的烧焦，当多产低碳烯烃等化学品时，由于气体产率高，因此需要更多的反应热。当烧焦量不足以满足装置的能耗时，通常通过回炼油浆、增加原料油中重油比例等方法提高生焦量，或者采用喷燃烧油的方式提高再生温度。这三种方式均可以满足反应热平衡，但都会对装置运行产生一定影响。且补充的能量均来自于化石能源，增加了源于化石能源的二氧化碳排放量，也不利于提高石油资源利用率。对再生过程的优化可以提高能量利用效率，从而在一定程度上降低单位二氧化碳排放量；对排放的二氧化碳进行回收利用，也能在一定程度上降低二氧化碳的排放量，但成本偏高，且流程较为复杂。但上述思路并没从根本上改变能量的来源，二氧化碳仍然来源于化石能源。
因此，有必要开发一种可以从根本上减少源于化石能源的二氧化碳排放的催化剂再生方法，在满足装置所需能量供应的基础上减少二氧化碳的排放，实现低碳化发展。
发明内容
本申请的目的是提供一种适用于流化催化裂化装置的催化剂再生方法和系统，所述方法和系统将源于生物质的气相燃料引入催化剂再生系统燃烧供能，维持流化催化裂化装置的热平衡，从而在根本上减少源于化石能源的二氧化碳排放。
为了实现上述目的，一方面，本申请提供了一种适用于流化催化裂化装置的催化剂再生方法，所述流化催化裂化装置包括催化裂化反应器和催化剂再生器，所述再生方法包括如下步骤：
1)提供生物质来源的包含氢气和/或甲烷的气相燃料；
2)将所述气相燃料不经分离纯化直接送入催化剂再生器；
3)将含氧气体引入所述催化剂再生器，其中所述含氧气体的氧气含量为14-28体积％；以及
4)将来自催化裂化反应器的待生催化剂送入催化剂再生器，在其 中与所述气相燃料和含氧气体接触，进行烧焦再生。
另一方面，本申请提供了一种适用于流化催化裂化装置的催化剂再生系统，包括生物质处理单元和催化剂再生单元，其中：
所述生物质处理单元用于对生物质进行处理得到包含氢气和/或甲烷的气相燃料，并且包括气相燃料发生器和气相燃料储罐，所述气相燃料发生器优选选自生物质气化器、生物质厌氧发酵罐或者它们的组合，并且具有生物质入口和气相产物出口，所述气相燃料储罐具有入口和气相燃料出口，所述气相燃料发生器的气相产物出口与所述气相燃料储罐的入口连通；
所述催化剂再生单元用于对来自催化裂化反应器的待生催化剂进行再生，并且包括催化剂再生器，所述催化剂再生器具有待生催化剂入口、含氧气体入口、气相燃料入口、再生烟气出口和再生催化剂出口，以及
所述气相燃料储罐的气相燃料出口通过管道与所述催化剂再生器的气相燃料入口连通。
与现有的催化裂化催化剂再生方法和系统相比，本申请的催化剂再生方法和系统的主要优点在于以下几个方面：
(1)生物质廉价易得，生物质能属于可再生能源，碳来源于植物从空气中捕集的二氧化碳，而非化石能源，将其作为能量来源，可以从根本上改变催化裂化装置能量供应的来源，减少化石能源二氧化碳的排放，实现炼油的低碳化发展。
(2)生物质制得的气相燃料无需经过复杂的分离纯化，可直接利用，降低了利用成本；
(3)生物质制得的气相燃料具有较高的氢含量，利用其中所含的氢燃烧产生的水蒸汽在催化剂再生过程中对催化剂进行老化，提高目标低碳烯烃产物选择性；或者，在需要催化剂具有高活性时，可以通过再生过程的优化来削弱水蒸汽对催化剂活性的不利影响；
(4)以气相燃料作为燃烧介质，与待生催化剂之间混合较为均匀，燃烧和热量传导过程较为稳定。
(5)采用富氧再生时可实现对再生烟气中二氧化碳低成本分离捕集，有利于实现负碳排放；
(6)再生系统产生的多余热量可用于供应其它装置，使得催化裂 化装置逐步发展成为炼化一体化企业的动力中心。
本申请的其他特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
附图是用来提供对本申请的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本申请，但并不构成对本申请的限制。在附图中：
图1为本申请的催化剂再生方法和系统的一种优选实施方式的示意图；
图2为本申请的催化剂再生方法和系统的另一种优选实施方式的示意图；
图3为本申请的催化剂再生方法和系统的又一种优选实施方式的示意图；以及
图4为本申请的催化剂再生方法和系统的再一种优选实施方式的示意图。
优选实施方式
以下结合附图对本申请的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本申请，并不用于限制本申请。
在本文中，表述“示例性”意为“用作例子、实施例或说明性”。本文中作为“示例性”所说明的任何实施方式不必解释为优于或好于其它实施方式。尽管在附图中示出了实施方式的各种方面，但是除非特别指出，不必按比例绘制附图。
在本文中所披露的任何具体数值(包括数值范围的端点)都不限于该数值的精确值，而应当理解为还涵盖了接近该精确值的值，例如在该精确值±5％范围内的所有可能的数值。并且，对于所披露的数值范围而言，在该范围的端点值之间、端点值与范围内的具体点值之间，以及各具体点值之间可以任意组合而得到一个或多个新的数值范围，这些新的数值范围也应被视为在本文中具体公开。
在本申请中，所谓“上游”和“下游”均是基于反应物料的流动方 向而言的。例如，当反应物流自下而上流动时，“上游”表示位于下方的位置，而“下游”表示位于上方的位置。
在本申请中，需要说明的是，术语“上”、“下”、“内”、“外”、“前”、“后”、“左”、“右”等指示的方位或位置关系为基于本申请工作状态下的方位或位置关系，仅是为了便于描述本申请和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本申请的限制。
在本申请中，需要说明的是，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”和“连通”应作广义理解。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本申请中的具体含义。例如，在本申请中，术语“连通”既包括两者直接连通的情形，也包括两者经由一个或多个中间设备连通的情形。
除非另有说明，本文所用的术语具有与本领域技术人员通常所理解的相同的含义，如果术语在本文中有定义，且其定义与本领域的通常理解不同，则以本文的定义为准。
本申请中，除了明确说明的内容之外，未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。而且，本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合，由此形成的技术方案或技术思想均视为本发明原始公开或原始记载的一部分，而不应被视为是本文未曾披露或预期过的新内容，除非本领域技术人员认为该结合明显不合理。
在本文中提及的所有专利和非专利文献，包括但不限于教科书和期刊文章等，均通过引用方式全文并入本文。
此外，下面所描述的本申请不同实施方式中涉及的技术特征只要彼此之间未构成冲突就可以相互结合。
如上所述，在第一方面，本申请提供了一种适用于流化催化裂化装置的催化剂再生方法，所述流化催化裂化装置包括催化裂化反应器和催化剂再生器，所述再生方法包括如下步骤：
1)提供生物质来源的包含氢气和/或甲烷的气相燃料；
2)将所述气相燃料不经分离纯化直接送入催化剂再生器；
3)将含氧气体引入所述催化剂再生器，其中所述含氧气体的氧气含量为14-28体积％；以及
4)将来自催化裂化反应器的待生催化剂送入催化剂再生器，在其中与所述气相燃料和含氧气体接触，进行烧焦再生，
根据本申请，所述生物质来源的气相燃料可以是，例如，经由生物质通过气化或者厌氧发酵得到的气相燃料。
本申请提供的方法，采用生物质来源的气相燃料作为补充能量来源，与待生催化剂一起与含氧气体接触燃烧供能，既满足了催化裂化装置的热量平衡，又降低了碳排放，也有利于对二氧化碳进行分离和捕集，成为负碳技术的策源地。生物质的利用从本质上讲是一种间接的太阳能利用过程，生物质之中的碳来自于植物从大气中捕获的二氧化碳，而不是来自于化石能源，整个过程消耗的能量也来自于太阳能。因此，生物质能的利用也是对碳元素的循环利用，是碳的中性排放过程。同时，将生物质引入催化裂化装置的动力中心，以生物质能供应装置的运行，消耗的就是可再生能源，排放的二氧化碳也并非来自于化石能源，可以从根本上改变能量的来源，实现碳减排。还可采用纯氧再生，使得再生烟气只有二氧化碳和氧气，降低了分离捕集成本，可实现负碳排放。
根据本申请，在优选实施方式中，所述生物质包括但不限于农林生物质、林业生物质、水生植物、能源经济作物、畜禽粪便、城市固体废物、生活污水和工业有机污水等。所述农林生物质包括但不限于秸秆、谷壳、棉杆等，所述林业生物质包括但不限于柴薪、速生林、林业加工残留物等，所述水生植物包括但不限于芦苇、水藻等，所述能源经济作物包括木薯、油菜等，所述城市固体废物包括生活垃圾、商业服务业垃圾等，所述生活污水和工业有机污水包括冷却水、厨房排水、酿酒、食品等行业排放的有机污水等。
在优选的实施方式中，步骤4)中所述催化剂再生器的操作温度在550-750℃范围内，且催化剂平均停留时间为1.0-15.0分钟。
在优选的实施方式中，步骤2)中所述气相燃料通过气体分布器从不低于待生催化剂入口水平高度的位置注入催化剂再生器。
在某些优选的实施方式中，所述含氧气体为空气或者循环烟气稀释的氧气。进一步优选地，当所述含氧气体为空气时，所引入的气相燃料的量为所引入的空气量的不超过13体积％，例如3-13体积％，或者当所述含氧气体为循环烟气稀释的氧气时，所引入的气相燃料的量为所 引入的氧气量的不超过44体积％，例如10-44体积％。
在某些优选的实施方式中，所述催化剂再生器为单段再生器，所述再生器的操作条件包括：操作温度为550-750℃，催化剂平均停留时间为1.0-15.0分钟，气体表观线速度为0.5-2.0m/s。
由于生物质制得的气相燃料具有较高的氢含量，因此在催化剂再生器中燃烧时会产生较大量的水蒸汽，为了避免该水蒸汽对催化剂的活性造成不利影响，本申请的方法优选在两段再生器或双再生器中进行，所述气相燃料仅送入两段再生器的烧焦段中或者双再生器的第一再生器中，并且对两段再生器和双再生器中的操作条件进行适当优化。
在某些特别优选的实施方式中，所述催化剂再生器为包括流体连通的烧焦段和再生段的两段再生器，并且在步骤2)中，将所述气相燃料送入烧焦段和/或再生段，优选仅送入烧焦段，在步骤3)中将含氧气体分别引入烧焦段和再生段的底部，且在步骤4)中将待生催化剂送入烧焦段。进一步优选地，所述烧焦段的操作条件包括：操作温度为550-720℃，催化剂平均停留时间为10.0-120.0秒，优选为15.0-90.0秒，气体表观线速度为0.5-5.0m/s，优选为1.0-4.0m/s；且所述再生段的操作条件包括：操作温度为600-750℃，催化剂平均停留时间为0.5-5.0分钟，优选为1.0-4.0分钟，气体表观线速度为0.4-2.0m/s，优选为0.5-1.5m/s。更进一步优选地，所述再生段的操作温度比所述烧焦段的操作温度高10-150℃。
在某些进一步优选的实施方式中，所述烧焦段的操作条件包括：600-700℃，催化剂平均停留时间为60.0-90.0秒；且所述再生段的操作条件包括：650-720℃，催化剂平均停留时间为2.0-4.0分钟，由此可以利用所述气相燃料燃烧产生的水蒸汽在催化剂再生过程中对催化剂进行老化，从而提高催化剂对于目标低碳烯烃产物的选择性，同时避免水蒸汽对催化剂活性的过度影响，从而适用于以生产低碳烯烃等化学品为主的流化催化裂化过程。在此类优选实施方式中，所述气相燃料可以仅注入再生器的烧焦段，也可同时注入再生器的烧焦段和再生段。
在另一些进一步优选的实施方式中，所述烧焦段的操作条件包括：550-650℃，催化剂平均停留时间为15.0-60.0秒；且所述再生段的操作条件包括：600-680℃，催化剂平均停留时间为1.0-3.0分钟，由此可以充分削弱水蒸汽对催化剂活性的不利影响，使所得再生催化剂具有较 高的催化裂化活性，从而适用于生产燃料油为主的流化催化裂化。在此类优选实施方式中，所述气相燃料仅注入再生器的烧焦段。
在另一些特别优选的实施方式中，所述催化剂再生器为包括流体连通的第一再生器和第二再生器的双再生器，并且在步骤2)中，将所述气相燃料送入第一再生器和/或第二再生器，优选仅送入第二再生器，在步骤3)中将含氧气体分别引入第一再生器和第二再生器的底部，且在步骤4)中将待生催化剂送入第一再生器。进一步优选地，所述第一再生器的操作条件包括：操作温度为550-720℃，催化剂平均停留时间为20.0-240.0秒，优选为30.0-150.0秒，气体表观线速度为0.5-5.0m/s，优选为1.0-4.0m/s；且所述第二再生器的操作条件包括：操作温度为600-750℃，催化剂平均停留时间为0.5-5.0分钟，优选为1.0-4.0分钟，气体表观线速度为0.4-2.0m/s，优选为0.5-1.5m/s。更进一步优选地，所述第二再生器的操作温度比所述第一再生器的操作温度高10-150℃。
在某些进一步优选的实施方式中所述第一再生器的操作条件包括：600-700℃，催化剂平均停留时间为90.0-180.0秒；且所述第二再生器的操作条件包括：650-720℃，催化剂平均停留时间为2.0-4.0分钟，由此可以利用所述气相燃料燃烧产生的水蒸汽在催化剂再生过程中对催化剂进行老化，从而提高催化剂对于目标低碳烯烃产物的选择性，同时避免水蒸汽对催化剂活性的过度影响，从而适用于以生产低碳烯烃等化学品为主的流化催化裂化过程。在此类优选实施方式中，所述气相燃料可以仅注入第一再生器，也可同时注入第一再生器和第二再生器。
在另一些进一步优选的实施方式中所述第一再生器的操作条件包括：550-650℃，催化剂平均停留时间为15.0-60.0秒；且所述第二再生器的操作条件包括：600-680℃，催化剂平均停留时间为1.0-3.0分钟，由此可以充分削弱水蒸汽对催化剂活性的不利影响，使所得再生催化剂具有较高的催化裂化活性，从而适用于生产燃料油为主的流化催化裂化。在此类优选实施方式中，所述气相燃料可以仅注入第一再生器。
在某些更进一步优选的实施方式中，所述烧焦段或者第一再生器中的烧焦比例为40-70％，优选40-50％；且所述再生段或者第二再生器中的烧焦比例为30-60％，优选50-60％。
在某些优选的实施方式中，所述气相燃料经由生物质通过气化得到，并且以该气相燃料的总体积计，包含12-60％的氢气，15-30％的一 氧化碳和3-8％的甲烷，其余为二氧化碳和/或氮气。
在进一步优选的实施方式中，所述步骤1)进一步包括：在气化介质的存在下使所述生物质气化，气化温度为500-1500℃，所述气化介质选自空气、氧气/富氧气体和水蒸汽。
在另一些优选的实施方式中，所述气相燃料经由生物质通过厌氧发酵得到，并且以该气相燃料的总体积计，包含40-100体积％的甲烷。
在进一步优选的实施方式中，所述步骤1)进一步包括：使所述生物质在密闭发酵罐中进行厌氧发酵，发酵温度不高于60℃。
在某些更进一步优选的实施方式中，所述生物质在气化或者厌氧发酵之前经过预处理，生物质预处理过程是本领域技术人员所熟知的，优选地所述预处理选自研磨、干燥、挤压、蒸汽爆破、酸处理、碱处理和微生物预处理中的一种或几种。
在某些优选实施方式中，通过包括一个或多个内取热器或/和外取热器的取热系统控制所述催化剂再生器内的温度不超过750℃。进一步优选地，所述取热系统将自所述催化剂再生器取出的热量用于发生高压蒸汽，外输到其它装置用于供能。在此类优选实施方式中，本申请可将催化裂化装置的再生系统产生的能量用于供应其它的操作单元，成为炼厂的动力中心，从根本上降低炼厂的碳排放。本申请将生物质引入催化裂化装置的动力中心，以生物质能供应装置的运行，排放的二氧化碳也并非来自于化石能源，可以从根本上改变能量的来源，实现碳减排。
在第二方面，本申请提供了一种适用于流化催化裂化装置的催化剂再生系统，包括生物质处理单元和催化剂再生单元，其中：
所述生物质处理单元用于对生物质进行处理，例如气化或者厌氧发酵，得到包含氢气和/或甲烷的气相燃料，并且包括气相燃料发生器和气相燃料储罐，所述气相燃料发生器优选选自生物质气化器、生物质厌氧发酵罐或者它们的组合，并且具有生物质入口和气相产物出口，所述气相燃料储罐具有入口和气相燃料出口，所述气相燃料发生器的气相产物出口与所述气相燃料储罐的入口连通；
所述催化剂再生单元用于对来自催化裂化反应器的待生催化剂进行再生，并且包括催化剂再生器，所述催化剂再生器具有待生催化剂入口、含氧气体入口、气相燃料入口、再生烟气出口和再生催化剂出 口，以及
所述气相燃料储罐的气相燃料出口通过管道与所述催化剂再生器的气相燃料入口连通。
在优选的实施方式中，所述生物质处理单元进一步包括生物质预处理器和任选的气相产物干燥器，所述生物质预处理器用于对生物质进行预处理，所述预处理选自研磨、干燥、挤压、蒸汽爆破、酸处理、碱处理和微生物预处理中的一种或几种，所述气相产物干燥器用于对生物质厌氧发酵罐得到的气相产物进行干燥处理。
在某些优选的实施方式中，所述催化剂再生器包括烧焦段和密相再生段，所述密相再生段位于烧焦段的上方，且所述烧焦段的出口容纳在密相再生段的内部，使得烧焦段与密相再生段流体相通；
所述烧焦段设置有：
第一含氧气体入口，其设置在烧焦段的底部，用于向所述烧焦段输入含氧气体；
所述气相燃料入口，其设置在所述第一含氧气体入口的上方，用于输入气相燃料；
气体分布器，其配置为分配经所述气相燃料入口输入的气相燃料；
所述待生催化剂入口，其用于将来自催化裂化反应器的待生催化剂输送至所述烧焦段内部；和
任选的第一循环烟气入口，其用于将密相再生段排出的一部分烟气循环回所述烧焦段内部；
所述密相再生段设置有：
第二含氧气体入口，其设置在密相再生段的底部，用于向密相再生段输入含氧气体；
任选的第二气相燃料入口，其设置在所述第二含氧气体入口的上方，用于向密相再生段输入气相燃料；
任选的第二气体分布器，其配置为分配经所述第二气相燃料入口输入的气相燃料；
所述再生烟气出口，其设置在密相再生段的顶部，用于将密相再生段内的再生烟气排出；
所述再生催化剂出口，用于将再生催化剂返回催化裂化反应器；和
任选的第二循环烟气入口，其用于将密相再生段排出的一部分烟气 循环回所述密相再生段内部；
任选地，所述密相再生段还配置有取热器，用于向所述再生器的外部输送热量。
在另一些优选的实施方式中，所述催化剂再生器包括第一再生器和第二再生器，第二再生器位于第一再生器的下游，所述第一再生器和第二再生器通过催化剂输送管连接，将经第一再生器部分再生的催化剂物料输送到第二再生器；
第一再生器设置有：
第一含氧气体入口，其设置在第一再生器的底部，用于向所述第一再生器输入含氧气体；
所述气相燃料入口，其设置在所述第一含氧气体入口的上方，用于输入气相燃料；
气体分布器，其配置为分配经所述气相燃料入口输入的气相燃料；
所述待生催化剂入口，用于将来自催化裂化反应器的待生催化剂输送至所述第一再生器内部；
第一再生烟气出口，其设置在第一再生器的顶部，用于将第一再生器内的再生烟气排出；和
任选的第一循环烟气入口，其设置在第一再生器的底部并与所述第一再生烟气出口连通，用于将第一再生器排出的部分烟气循环回所述第一再生器，
所述第二再生器设置有：
第二含氧气体入口，其设置在第二再生器的底部，用于向第二再生器输入含氧气体；
任选的第二气相燃料入口，其设置在所述第二含氧气体入口的上方，用于向第二再生器输入气相燃料；
任选的第二气体分布器，其配置为分配经所述第二气相燃料入口输入的气相燃料；
所述再生催化剂出口，用于将再生催化剂返回催化裂化反应器；
第二再生烟气出口，其设置在第二再生器的顶部，用于将第二再生器内的再生烟气排出；和
任选的第二循环烟气入口，其设置在第二再生器的底部并与所述第一再生烟气出口或第二再生烟气出口连通，用于将部分烟气循环回所 述第二再生器。
下面结合附图对本申请的再生方法和系统的优选实施方式做进一步的具体说明。
如图1，图2，图3和图4所示，本申请的催化剂再生系统适用于对来自催化裂化反应单元100的待生催化剂进行再生，并且包括：生物质处理单元300和600以及催化剂再生单元200，400，500，700。
如图1至图4所示，在催化裂化反应系统100中，催化裂化反应器110用于进行催化裂化反应：其底部入口102通入提升介质，以提升经由再生催化剂入口103进入的再生催化剂(来自再生器)；从原料油入口101进入的原料油与催化剂接触进行催化裂化反应。反应的油气产物经油剂分离装置120进行分离，分离的油气产物经集气室140聚集之后输入到产物分离装置150进行分离，得到各种产品。分离出的待生催化剂经过沉降器的汽提段130汽提后经待生催化剂出口131输送到催化剂再生单元中进行再生，从而实现循环使用。本申请适用的催化裂化反应器110可以是本领域常用的各种反应器，例如提升管反应器，流化床反应器，变径反应器及其组合等。
如图1-2所示，生物质处理单元300包括：
生物质预处理器310，用于对生物质进行预处理，
生物质厌氧发酵罐320，用于对经过预处理的生物质进行厌氧发酵处理得到气相发酵产物，
气相产物干燥器330，用于对生物质厌氧发酵罐得到的气相发酵产物进行干燥处理，和
气相燃料储罐340，用于储存所述气相产物。
如图所示，生物质的厌氧发酵过程可以在生物质厌氧发酵罐320例如密闭发酵罐中进行，发酵底物可以为混合生物质原料，发酵温度不高于60℃。根据本申请，在一种更优选的实施方式中，可添加尿素、生物质炭等增强发酵过程。
根据本申请，厌氧发酵产物中主要有甲烷、二氧化碳、水等，由于水对于后续过程有不利影响，需要进行干燥处理。干燥可以在气相产物干燥器330中进行，脱除发酵产物中的水分，使得含水量低于1.0g/m3。
干燥之后，将干燥后的气相产物储存在气相燃料储罐340中用于后 续过程。干燥后的气相产物中，甲烷可以占40％以上，例如40-50％，可以达到60％以上，高的可以达到75％以上，基于气相产物的总体积。
根据本申请，所述的厌氧发酵过程消耗的能量来源于发酵过程的其它产物或者至少部分/全部来自于太阳能、绿电、核能等可再生能源，减少全生命周期碳排放。
如图3-4所示，生物质处理单元600包括：
生物质预处理器610，用于对生物质进行预处理，
生物质气化器620，用于对经过预处理的生物质进行气化处理得到气相产物，和
气相燃料储罐630，用于储存所述气相产物。
如图所示，生物质可以输送到生物质预处理器610中，经过研磨、干燥等处理，后输送到生物质气化器620。在生物质气化器620中，生物质经气化得到气相产物，输送至气相燃料储罐630用于后继的再生处理过程，而其余产物引出或送入其它装置进行处理。在一种具体实施方式中，将生物质材料研磨或粉碎成粒度为0.2-40mm的颗粒材料，而后进行干燥，使其含水量达到10％以下。
之后，对生物质进行气化处理。气化温度可以在500-1500℃范围内。气化处理过程中使用的气化介质可以选自空气、氧气/富氧气体、水蒸汽等。根据本申请，生物质气化处理过程消耗的能量可以来源于气化过程的其它产物，或至少部分/全部来自于太阳能、绿电、核能等可再生能源，减少全生命周期碳排放。
根据本申请，所得气相产物的主要成分为氢气、一氧化碳、二氧化碳和少量的甲烷气体。一般而言，氢气占12-60％，一氧化碳15-30％，甲烷占3-8％，基于气相产物的总体积。其余组分可以为二氧化碳和/或氮气。
图1示出了本申请的催化剂再生方法和系统的第一种优选实施方式的示意图，其中再生过程为单段再生。如图1所示，该再生单元200包括再生器210，在所述再生器210上设置有：
用于向所述再生器输入含氧气体的含氧气体入口211，所述含氧气体入口211设置在再生器的底部；
分布板212，所述分布板212经配置为分配经所述含氧气体入口211输入的含氧气体；
气相燃料入口214，所述气相燃料入口214设置在所述分布板212的上方，用于输入气相燃料(来自气相燃料储罐340的气相产物)；
气体分布器213，所述气体分布器213经配置为分配经所述气相燃料入口214输入的气相燃料；
待生催化剂入口216，所述待生催化剂入口216用于将催化裂化反应器的待生催化剂输送至所述再生器内部；
再生催化剂出口217，所述再生催化剂出口217用于将再生催化剂输送至催化裂化反应器。
气相燃料储罐340与气相燃料入口214相连通，使得气相燃料输送至所述再生器内部，燃烧并使待生催化剂再生。
分布板212和气体分布器213均设置在再生器210的内部，以将含氧气体以及气相燃料在再生器内部的待生催化剂中均匀分布，使得催化剂可以在再生过程中燃烧均匀，避免局部过热。通常，分布板212和气体分布器213均设置在再生器210内部的下部，以使得待生催化剂在再生器内再生过程中在再生器内部处于流态化状态。
所述再生器为密相床，催化剂的床层密度为300-700kg/m3。气相燃料通过气体分布器从不低于待生催化剂入口水平高度位置注入。在此实施方式中，气体分布器213设置在再生器的密相床段的下部，以更好地均匀分配气相燃料。
在一种具体实施方式中，再生过程的条件：含氧气体为空气，再生温度为550-750℃，催化剂平均停留时间为1.0-15.0分钟，气体表观线速度为0.7-2.0m/s。
气相燃料和待生催化剂一起输送到再生器底部与含氧气体接触进行烧焦再生和供能。由于气相燃料的注入，再生过程中会产生大量的热量。如果再生器内的温度过高，会不利地影响催化剂的活性。因此，再生单元200还配置有取热器215，用于自所述再生器取出多余的热量。取热器可以是内取热器(设置在再生器的内部)或/和外取热器(设置在再生器的外部)，取热器为一个或多个，可以将再生器产生的多余能量用于供应其它装置。通过取热器可以将再生系统的多余热量用于发生高压蒸汽，外输到其它装置用于供能。在一种具体实施方式中，通过设置取热器，控制再生器床层温度不超过750℃，例如不超过720℃。
如图1所示，再生单元200还包括设置在旋风分离器220，再生烟 气经旋风分离器220离开再生器，进入烟气能量回收系统230回收能量。旋风分离器220可以设置在再生器210的内部。
图2示出了本申请的催化剂再生方法和系统的第二种优选实施方式的示意图，其中再生过程采用双再生器再生。所述再生单元400包括第一再生器410和第二再生器420。所述两个再生器串联，第二再生器420位于第一再生器410的下游，通过催化剂输送管417连接，使得第一再生器的催化剂物料输送到第二再生器。
第一再生器410设置有：
第一含氧气体入口411，所述第一含氧气体入口设置在第一再生器的底部，用于向所述第一再生器输入氧气；
气相燃料入口414，所述气相燃料入口设置在所述第一含氧气体入口的上方，用于输入气相燃料；
气体分布器416，所述气体分布器经配置为分配经所述气相燃料入口输入的气相燃料；和
待生催化剂入口418(与待生斜管相连接)，所述待生催化剂入口用于将催化裂化反应器的待生催化剂输送至所述第一再生器内部；
第一烟气出口419，其设置在第一再生器的顶部；
所述第二再生器420设置有：
第二含氧气体入口421，其设置在第二再生器的底部，用于向第二再生器输入氧气；
再生催化剂出口439(与再生斜管相连接)，用于将再生催化剂输送至催化裂化反应器；和
第二烟气出口429，其设置在第二再生器的顶部。
进行再生操作时，气相燃料自气相燃料入口414经气体分布器416引入第一再生器410，来自催化裂化反应器的待生催化剂经待生斜管(与待生催化剂出口131相连通)并经待生催化剂入口418进入第一再生器，与由第一含氧气体入口411进入的氧气接触，在第一再生器内发送部分烧焦反应(第一段再生)；部分再生的催化剂经过催化剂输送管417输送至第二再生器420，与由第二含氧气体入口421进入的氧气接触后发生焦炭燃烧反应，进行完全再生。
在一种具体实施方式中，第一再生器的底部设置有第一循环烟气入口431，所述第一循环烟气入口431与第一烟气出口419相连通，使得 第一再生器排出的部分烟气通过所述第一循环烟气入口进入所述第一再生器。
在一种具体实施方式中，第二再生器的底部设置有第二循环烟气入口432，所述第二循环烟气入口432与第一烟气出口419相连通，使得第一再生器排出的部分烟气通过所述第二循环烟气入口进入所述第二再生器。
在一种具体实施方式中，第一再生器的底部和第二再生器的底部通过催化剂输送管417相连接。
由此，第一再生器产生的烟气经过旋风分离器413分离后，一部分进入烟气能量回收装置430回收能量；另一部分烟气分两路循环回再生单元，一路输送至第一再生器，稀释引入的氧气；另一路输送至第二再生器，稀释氧气。
第二再生器的烟气经旋风分离器423分离后，通过第二循环烟气出口429进入烟气能量回收装置430回收能量，并输送至二氧化碳分离系统460捕集其中的二氧化碳气体。再生后的催化剂经再生催化剂入口439经过再生斜管(与再生催化剂入口103相连通)循环回催化裂化反应器。
在一种具体实施方式中，第一再生器操作条件为：温度550℃-700℃，催化剂平均停留时间20.0-240.0秒，气体表观线速度为0.5-5.0m/s。第二再生器操作条件为：温度600℃-750℃，催化剂平均停留时间为0.5-5.0分钟，气体表观线速0.4-2.0m/s。
由于气相燃料的注入，再生过程中会产生大量的热量。如果再生器内的温度过高，会不利地影响催化剂的活性。因此，再生单元400同样还配置有取热器415，425，用于向所述第一再生器和第二再生器的外部输送热量。取热器可以为内取热器(设置在再生器的内部)或/和外取热器(设置在再生器的外部)，取热器为一个或多个，自第一再生器和第二再生器取出多余的能量用于供应其它装置。通过取热器可以将再生系统的多余热量用于发生高压蒸汽，外输到其它装置用于供能。在一种具体实施方式中，通过设置取热器415，控制第一再生器床层温度不超过700℃，通过设置取热器425，控制第二再生器床层温度不超过750℃，例如不超过720℃。
生物质得到的气相产物中含有大量的甲烷，甲烷可以占40％以上， 例如40-50％，可以达到60％以上，高的可以达到75％以上，基于气相产物的总体积。甲烷的分子式为CH4，氢含量高达25％。本领域通常认为，再生过程中过量的水蒸气对于催化裂化催化剂的活性是不利的，一般不使用氢含量高的混合气作为再生过程的补充燃料。在图2所示的优选实施方式中，再生过程采用纯氧再生工艺，并采用双再生器再生，可以更好地保护催化剂，避免水蒸气的影响。在某些进一步优选的实施方式中，通过进一步优化第一和第二再生器的操作条件，可以利用所述水蒸气对催化剂进行老化，以提高产物选择性。
在某些具体实施方式中，在包含该再生单元400的再生系统中进行的再生方法包括：
1)将生物质经过预处理后输送至生物质厌氧发酵系统中进行厌氧发酵处理，得到气相发酵产物；
2)将所述气相发酵产物经过干燥处理，将干燥后的气相燃料储存在气相燃料储罐中；
3)将所述气相燃料输送至所述第一再生器的内部，与来自催化裂化反应器的待生催化剂和氧气接触，使所述待生催化剂部分烧焦；
4)来自第一再生器的物料进入第二再生器，经第二含氧气体入口向第二再生器注入氧气，使催化剂完全再生。
图3示出了本申请的催化剂再生方法和系统的第三种优选实施方式的示意图，其中再生过程采用双再生器再生。再生单元500包括第一再生器510和第二再生器520，所述两个再生器串联，第二再生器520位于第一再生器510的下游，通过U型催化剂输送管517连接，使得第一再生器的催化剂物料输送到第二再生器。
第一再生器510设置有：
第一含氧气体入口511，所述第一含氧气体入口设置在第一再生器的底部，用于向所述第一再生器输入氧气；
气相燃料入口514，所述气相燃料入口设置在所述第一含氧气体入口的上方，用于输入气相燃料；
气体分布器516，所述气体分布器经配置为分配经所述气相燃料入口输入的气相燃料；和
待生催化剂入口518(与待生斜管相连接)，所述待生催化剂入口用于将催化裂化反应器的待生催化剂输送至所述第一再生器内部；
第一烟气出口519，其设置在第一再生器的顶部；
所述第二再生器520设置有：
第二含氧含氧气体入口521，其设置在第二再生器的底部，用于向第二再生器输入氧气；
再生催化剂出口539(与再生斜管相连接)，用于将再生催化剂输送至催化裂化反应器；和
第二烟气出口529，其设置在第二再生器的顶部。
进行再生操作时，气相燃料自气相燃料入口514经气体分布器516引入第一再生器510，来自催化裂化反应器的待生催化剂经待生斜管(与待生催化剂出口131相连通)并经待生催化剂入口518进入第一再生器，与由含氧气体入口511经流体分配板512进入的氧气接触，在第一再生器内发送部分烧焦反应(第一段再生)；部分再生的催化剂经过U型催化剂输送管517输送至第二再生器520，与由含氧气体入口521经流体分配板522进入的氧气接触后发生焦炭燃烧反应，进行完全再生。
在一种具体实施方式中，第一再生器的底部设置有第一循环烟气入口533，所述第一循环烟气入口533与第一烟气出口519相连通，使得第一再生器排出的部分烟气通过所述第一循环烟气入口进入所述第一再生器。
在一种具体实施方式中，第二再生器的底部设置有第二循环烟气入口532，所述第二循环烟气入口532与第一烟气出口519相连通，使得第一再生器排出的部分烟气通过所述第二循环烟气入口进入所述第二再生器。
在一种具体实施方式中，第一再生器的底部和第二再生器的底部通过所述U型催化剂输送管517相连接，
U型催化剂输送管设置有开口531，所述开口与第一烟气出口519相连通，使得第一再生器排出的部分烟气通过所述开口进入所述U型催化剂输送管。
由此，第一再生器产生的烟气经过旋风分离器513分离后，一部分进入烟气能量回收装置530回收能量；另一部分烟气分三路循环回再生单元，一路输送至第一再生器，稀释引入的氧气；一路输送至U型催化剂输送管用于将半再生催化剂输送至第二再生器；最后一路输送 至第二再生器，稀释引入的氧气。控制氧气和/或循环烟气的量，使得第一再生器和第二再生器中混合气中氧气浓度不高于28％。在该气氛下进行烧焦，提高了烧焦强度；进气不含氮气，可减少气体预热消耗的能量；且再生器出口烟气二氧化碳浓度更高，便于二氧化碳的分离和捕集。
第二再生器的烟气经旋风分离器523分离后，通过第二循环烟气出口529进入烟气能量回收装置530回收能量，并输送至二氧化碳分离系统560捕集其中的二氧化碳气体。再生后的催化剂经再生催化剂入口539经过再生斜管(与再生催化剂入口103相连通)循环回催化裂化反应器。
在一种具体实施方式中，第一再生器操作条件为：温度550℃-700℃，催化剂平均停留时间20.0-240.0秒，气体表观线速度为0.5-5.0m/s。第二再生器操作条件为：温度600℃-750℃，催化剂平均停留时间为0.5-5.0分钟，气体表观线速0.4-2.0m/s。
由于气相燃料的注入，再生过程中会产生大量的热量。如果再生器内的温度过高，会不利地影响催化剂的活性。因此，再生单元500同样还配置有取热器515，525，用于自所述第一再生器和第二再生器取出多余的热量，并任选向外部输送热量。取热器可以为内取热器(设置在再生器的内部)或/和外取热器(设置在再生器的外部)，取热器为一个或多个，将第一再生器和第二再生器产生的多余能量用于供应其它装置。通过取热器可以将再生系统的多余热量用于发生高压蒸汽，外输到其它装置用于供能。在一种具体实施方式中，通过设置取热器515，控制第一再生器床层温度不超过700℃；通过设置取热器525，控制第二再生器床层温度不超过750℃，例如不超过720℃。
生物质气化得到的气相产物中含有一定量的氢气，例如，氢气占12-60％，一氧化碳15-30％，甲烷占3-8％，基于气相产物的总体积。本领域通常认为，再生过程中过量的水蒸气对于催化裂化催化剂的活性是不利的，因而一般不使用含有氢气的混合气作为再生过程的补充燃料。在图3所示的优选实施方式中，再生过程采用纯氧再生工艺，并采用双再生器再生，可以更好地保护催化剂，避免水蒸气的影响。在某些进一步优选的实施方式中，通过进一步优化第一和第二再生器的操作条件，可以利用所述水蒸气对催化剂进行老化，以提高产物选 择性。
在某些具体实施方式中，在包含该再生单元500的再生系统中进行的再生方法包括：
1)将生物质经过预处理后输送至气化装置中进行气化处理，得到气相产物；
2)将所述气相产物输送至所述第一再生器的内部，与来自催化裂化反应器的待生催化剂和氧气接触，使所述待生催化剂部分烧焦；
3)来自第一再生器的物料进入第二再生器，向第二再生器注入氧气，使催化剂完全再生。
图4示出了本申请的催化剂再生方法和系统的第四种优选实施方式的示意图，其中再生过程采用两段再生。如图所示，再生单元700包括再生器740，所述再生器740包括烧焦段710和再生段750，其中，再生段750与烧焦段710流体相通，且位于烧焦段710的上方；所述再生段750与烧焦段710以流体分配板751相间隔。由此，再生段750与烧焦段710以串联方式连接在一起。来自烧焦段710的物料经流体分配板751分配之后，进入到再生段750中进行完全再生。
烧焦段710设置有：
用于向所述烧焦段输入氧气的第一含氧气体入口711，所述第一含氧气体入口设置在烧焦段的底部；
气相燃料入口714，所述气相燃料入口设置在所述第一含氧气体入口的上方，用于输入气相燃料；
气体分布器713，所述气体分布器经配置为分配经所述气相燃料入口输入的气相燃料；
待生催化剂入口716，所述待生催化剂入口用于将催化裂化反应器的待生催化剂输送至所述烧焦段内部；和
第一循环烟气入口731，所述第一循环烟气入口用于将再生段回收的一部分烟气循环回所述烧焦段内部。
由此，在烧焦段710内使待生催化剂初步烧焦，且使气相燃料部分燃烧。可以避免氢气燃烧过程中产生的水对催化剂的水热失活影响。
所述再生段750设置有：
第二含氧气体入口752，其设置在再生段的底部，用于向再生段输入氧气；
第二循环烟气入口753，所述第二循环烟气入口用于将再生段回收的一部分烟气循环回所述再生段内部；和
烟气出口732，其设置在再生段的顶部；
其中，所述再生段750还配置有取热器715，用于向所述再生器的外部输送热量。
进行再生操作时，通过气相燃料入口714经气体分布器713向烧焦段710输入来自气相燃料储罐630的气相燃料，来自催化裂化反应器的待生催化剂经待生催化剂入口716进入烧焦段710，与经第一含氧气体入口711进入的氧气接触，在烧焦段内发送部分烧焦反应；之后，经流体分配板751之后，进入再生段750进行完全再生。此时，通过第二含氧气体入口752输入纯氧气，与部分烧焦的催化剂接触，使催化剂和不完全再生烟气进一步再生、燃烧。再生催化剂经旋风分离器720分离之后，回落到再生段，并经催化剂出口717排出，并循环回催化裂化反应器。经烟气出口732排出的烟气，一部分经烟气能量回收系统730回收能量，接着经二氧化碳分离系统760分离，实现二氧化碳的捕集；另一部分烟气循环回生焦段的底部。
在一种具体实施方式中，所述烧焦段的操作条件为：温度550-720℃，催化剂平均停留时间为10.0-120.0秒，优选为15.0-90.0秒，气体表观线速度为0.5-5.0m/s，优选为1.0-4.0m/s。
在一种具体实施方式中，再生段的操作条件为：温度600-750℃，催化剂平均停留时间为0.5-5.0分钟，优选为1.0-4.0分钟，气体表观线速度为0.4-2.0m/s，优选为0.5-1.5m/s。催化剂在再生段中完全再生，源于生物质的气相燃料在再生段中燃烧完全。在一种具体实施方式中，再生段为密相床，其催化剂密度为300-700kg/m3。
在一种具体实施方式中，经由第一含氧气体入口711和第二含氧气体入口752输入的气体均为氧气。不过，经由第一含氧气体入口711输入的氧气，进入到烧焦段之后会与循环烟气混合，形成氧化-二氧化碳混合气，控制氧气和/或循环烟气的量，使得混合气中氧气浓度不超过28体积％。同样地，经由第二含氧气体入口752输入的氧气，进入到再生段之后会与循环烟气等混合，形成氧化-二氧化碳混合气，控制氧气和/或循环烟气的量，使得混合气中氧气浓度不高于28％。在该气氛下进行烧焦，提高了烧焦强度；进气不含氮气，可减少气体预热消 耗的能量；且再生器出口烟气二氧化碳浓度更高，便于二氧化碳的分离和捕集。
在一种具体实施方式中，烧焦段中的烧焦比例为40-70％；再生段的烧焦比例为30-60％。在一种具体实施方式中，采用纯氧再生，再生烟气中只包含二氧化碳和氧气，便于分离捕集二氧化碳进行进一步转化利用，实现负碳排放。根据本申请，所述的生物质气化得到的气相燃料从气体分布器引入。
在图4所示的优选实施方式中，再生过程采用纯氧再生工艺，并在串联的烧焦段和再生段中进行两段再生，这样可以提高烧焦强度，再生效果更好，同时还可以削弱水蒸气对催化剂的影响。在某些进一步优选的实施方式中，通过进一步优化烧焦段和再生段的操作条件，可以利用所述水蒸气对催化剂进行老化，以提高产物选择性。
由于气相燃料的注入，再生过程中会产生大量的热量。如果再生器内的温度过高，会不利地影响催化剂的活性。因此，再生单元700还配置有取热器715，用于向所述再生器的外部输送热量。取热器可以为内取热器(设置在再生器本体的内部)或/和外取热器(设置在再生器本体的外部)，取热器为一个或多个，将再生器产生的多余能量用于供应其它装置。通过取热器可以将再生系统的多余热量用于发生高压蒸汽，外输到其它装置用于供能。在一种具体实施方式中，通过设置取热器，控制再生器床层温度不超过750℃，例如不超过720℃。在本申请中，取热器715经配置在再生段，用于取出再生段床层的热量输送至再生器的外部，并控制再生段床层的温度。
在一种具体实施方式中，经由所述取热器控制再生段床层的温度不超过750℃，优选不超过720℃。
如图4所示，再生单元700还包括设置在旋风分离器720，再生烟气经旋风分离器720离开再生器，进入烟气能量回收系统730回收能量。旋风分离器720可以设置在再生器740的内部。
适用于本申请的催化剂再生方法和系统的催化剂可以是各种催化裂化过程中常规采用的催化剂，本申请没有特别的限制。在某些具体实施方式中，所述催化剂包括沸石、无机氧化物和任选的黏土，各组分分别占催化剂总重量为：沸石1重量％-50重量％，无机氧化物5重量％-99重量％，粘土0重量％-70重量％。其中沸石为活性组分，选自 中孔沸石和/或任选的大孔沸石，中孔沸石占沸石总重量的10重量％-100重量％，大孔沸石占沸石总重量的0重量-90重量％；中孔沸石选自ZSM系列沸石中的一种或多种和/或ZRP沸石，可对上述沸石用磷等非金属和/或铁、钴、镍等过渡金属改性；大孔沸石选自氢Y、稀土Y、稀土氢Y、超稳Y等中的一种或几种。
实施例
下面将通过实施例来进一步说明本申请，但是本申请并不因此而受到任何限制。
以下实施例和对比例所使用的原料油A和B性质分别列于表1和表2，原料C组成列于表3。
表1原料油A的性质
表2原料油B的性质

表3原料C的组成
催化剂a为市售催化剂ASC-2，性质列于表4；
表4催化剂a的性质
催化剂b为TCC催化剂，老化后使用，老化条件：800℃下，水蒸汽老化15小时。催化剂b的制备过程如下：
用4300克脱阳离子水将969克多水高岭土(中国高岭土公司产物，固含量73％)打浆，再加入781克拟薄水铝石(山东淄博铝石厂产物，固含量64％)和144毫升盐酸(浓度30％，比重1.56)搅拌均匀，在60℃静置老化1小时，保持pH为2-4，降至常温，再加入预先准备好的5000克含化学水的高硅铝比中孔择形ZSM-5沸石浆液，搅拌均匀，喷雾干燥，洗去游离Na+，得催化剂。性质列于表5。
表5催化剂b的性质
催化剂c的制备过程如下：
(1)将20克NH4Cl溶于1000克水中，向此溶液中加入100克(干基)晶化产品ZRP-1分子筛(齐鲁石化公司催化剂厂生产，SiO2/Al2O3＝30，稀土含量RE2O3＝2.0重量％)，在90℃交换0.5小时后，过滤得滤饼；加入4.0克H3PO4(浓度85％)与4.5克Fe(NO3)3溶于90克水中，与滤饼混合浸渍烘干；然后在550℃温度下焙烧处理2小时得到含磷和铁的MFI中孔分子筛。所得分子筛的元素分析化学组成为：0.1Na2O·5.1Al2O3·2.4P2O5·1.5Fe2O3·3.8RE2O3·88.1SiO2。
(2)用250千克脱阳离子水将75.4千克多水高岭土(苏州瓷土公 司工业产品，固含量71.6重量％)打浆，再加入54.8千克拟薄水铝石(由东铝厂工业产品，固含量63重量％)，用盐酸将其pH调至2-4，搅拌均匀，在60-70℃下静置老化1小时，保持pH为2-4，将温度降至60℃以下，加入41.5千克铝溶胶(齐鲁石化公司催化剂厂产品，Al2O3含量为21.7重量％)，搅拌40分钟，得到混合浆液。
(3)将步骤(1)制备的含磷和铁的MFI中孔分子筛(干基为2千克)加入到步骤(2)得到的混合浆液中，搅拌均匀，喷雾干燥成型，用磷酸二氢铵溶液(磷含量为1重量％)洗涤，洗去游离Na+，干燥即得催化转化催化剂c样品。以催化剂c的干基总重量为基准，该催化剂c的干基组成包括：2重量％含磷和铁的MFI中孔分子筛、36重量％拟薄水铝石和8重量％铝溶胶，余量为高岭土。
实施例1
采用图1所示的装置进行试验，其中气相燃料的具体制备过程如下：
生物质在预处理单元中经过水洗或酸洗后、再经粉碎研磨等预处理，预处理后的生物质在厌氧发酵装置中进行发酵，发酵温度为37℃。发酵产物经过干燥装置脱除水分后，得到气相产物，甲烷占40％以上(基于气相产物的体积)，储存在储罐中备用。
以原料A作为反应原料，催化转化催化剂a为催化剂。按照本申请的方法对待生催化剂进行再生。来自于待生斜管的待生催化剂与从再生器底部的气体分布器引入的气相燃料及空气接触，发生焦炭燃烧反应。再生系统产生的多余能量通过取热系统用于对外供能。再生器的操作温度为685℃，催化剂的平均停留时间为5分钟，气体表观线速为1.0m/s。再生后的催化剂进入反应器，与原料油接触进行催化裂化反应。多余能量通过取热系统用于供应其它装置。再生条件、反应条件、二氧化碳排放情况如表6所示。
对比例1
参照实施例1进行试验，不同之处在于不采用生物质处理单元，而是将柴油作为燃料油喷入到再生器中，以燃料油作为能量的补充来源。再生器烧焦温度为685℃。催化剂的平均停留时间为5分钟，气体表观 线速为1.0m/s。再生后的催化剂进入反应器，与原料油接触进行催化裂化反应。再生条件、反应条件、二氧化碳排放情况如表6所示。
表6实施例1和对比例1的操作条件和结果
以处理100g原料为基准。
二氧化碳排放指标指的是再生系统烧焦每产生1MJ能量所排放的源于化石能源二氧化碳的量，计算方法参考《中国石油化工企业温室气体排放核算方法与报告指南(试行)》(下同)；生物质富甲烷气产生的二氧化碳来自于大气中存在的二氧化碳，是中性的碳排放过程。
从表6的数据可以观察到，实施例采用生物质气相燃料作为补充能量的来源时，再生系统产生同等的能量时，排放的二氧化碳的量较之对比例显著降低，还能将更多的能量输送至其它装置，这有利于从根本上减少二氧化碳的排放量。
实施例2
采用图2所示的装置进行试验，其中设有烟气能量回收系统430和二氧化碳分离系统460，反应器110为常规提升管反应器。
气相燃料的具体制备过程如下：
生物质在预处理单元中经过水洗或酸洗后、再经粉碎研磨等预处理，预处理后的生物质在厌氧发酵装置中进行发酵，发酵温度为37℃。发酵产物经过干燥装置脱除水分后，得到气相产物，甲烷占40％以上(基于气相产物的体积)，储存在储罐中备用。
原料B作为反应原料，催化转化催化剂b为催化剂。按照本申请的方法对待生催化剂进行再生。气相燃料经气体分布器引入第一再生器，与经待生斜管进入第一再生器的待生催化剂一起发生燃烧反应，在第一再生器内发生部分烧焦反应(第一段再生)；部分再生的催化剂经过催化剂输送管输送至第二再生器发生焦炭燃烧反应，进行完全再生。同时从再生器旋风分离系统出来的烟气部分返回第一再生器和第二再生器，控制氧气含量不超过28％。再生系统产生的多余能量通过取热器用于对外供能。
第一再生器的操作温度为650℃，催化剂在第一再生器中的平均停留时间为120秒，气体表观线速度为1.5m/s。第二再生器的操作温度为670℃，催化剂在第二再生器中的平均停留时间为3.0分钟，气体表观线速度为1.0m/s。再生后的催化剂进入反应器，与原料油接触进行催化裂化反应。再生条件、反应条件、二氧化碳排放情况如表7所示。
对比例2
参照实施例2进行试验，区别仅在于采用柴油作为燃料油，注入待生管线中与待生催化剂预混后进入再生器，作为补充能量来源。再生条件、反应条件、二氧化碳排放情况如表7所示。
表7实施例2和对比例2的操作条件和结果
以处理100g原料为基准。
二氧化碳排放指标指的是再生系统烧焦每产生1MJ能量所排放的源于化石能源二氧化碳的量；气相燃料产生的二氧化碳来自于大气中存在的二氧化碳，是中性的碳排放过程。
从表7的数据可以观察到，实施例采用生物质气化得到的气相燃料作为补充能量的来源时，再生系统产生同等的能量时，排放的二氧化 碳的量较之对比例显著降低，这有利于从根本上减少二氧化碳的排放量；另一方面，实施例2中丙烯的产率也有一定的提升，表明再生催化剂对丙烯的选择性提高。
实施例3
采用图3所示的装置进行试验，其中设有烟气能量回收系统530和二氧化碳分离系统560，反应器110为常规的提升管反应器。
生物质处理单元600包括：生物质预处理器610，生物质气化器620，和气相燃料储罐630。生物质气化器620的运行条件为温度950℃，气化介质为水蒸气，得到的气相产物中氢气、一氧化碳和甲烷的体积分数分别为50％，25％，7％，基于气相产物的体积。
原料C作为反应原料，催化转化催化剂c为催化剂。按照本申请的方法对待生催化剂进行再生，在第一再生器和第二再生器分别通入纯氧气体，从第一再生器的气体分布器引入来自气相燃料储罐630的气相燃料，与来自于斜管的待生催化剂一起发生燃烧反应，同时从再生器旋风分离系统520出来的烟气部分返回第一再生器和第二再生器的底部，控制氧气含量不超过28％。再生系统产生的多余能量通过取热器用于对外供能。
第一再生器的操作温度为630℃，催化剂在第一再生器中的平均停留时间为40秒，气体表观线速度为1.0m/s。第二再生器的操作温度为665℃，催化剂在第二再生器中的平均停留时间为1.5分钟，气体表观线速度为1.0m/s。再生后的催化剂进入反应器，与原料油接触进行催化裂化反应。再生条件、反应条件、二氧化碳排放情况如表8所示。
对比例3
参照实施例3进行试验，区别仅在于采用柴油作为燃料油，注入待生管线中与待生催化剂预混后进入再生器，作为补充能量来源。再生条件、反应条件、二氧化碳排放情况如表8所示。
表8实施例3和对比例3的操作条件和结果

以处理100g原料为基准。
二氧化碳排放指标指的是再生系统烧焦每产生1MJ能量所排放的源于化石能源二氧化碳的量；气相燃料产生的二氧化碳来自于大气中存在的二氧化碳，是中性的碳排放过程。
从表8的数据可以观察到，实施例采用气相燃料作为补充能量的来源时，再生系统产生同等的能量时，排放的二氧化碳的量较之对比例显著降低，这有利于从根本上减少二氧化碳的排放量。
实施例4
采用图4所示的装置进行再生，其中设有烟气能量回收系统730和二氧化碳分离系统760，反应器110为常规的提升管反应器。
生物质处理单元600包括：生物质预处理器610，生物质气化器620，和气相燃料储罐630。生物质气化器620的运行条件为温度950℃，气化介质为水蒸气，得到的气相产物中氢气、一氧化碳和甲烷的体积分数分别为50％，25％，7％，基于气相产物的体积。
原料B作为反应原料，催化转化催化剂b为催化剂。按照本申请的方法对待生催化剂进行再生，在烧焦段和再生段分别通入纯氧气体，从烧焦段底部的气体分布器引入来自气相燃料储罐630的气相燃料，与来自于斜管的待生催化剂一起发生燃烧反应，同时从再生器旋风分离系统720出来的烟气部分返回烧焦段和再生段的底部，控制氧气含量不超过28％。再生系统产生的多余能量通过取热器用于对外供能。
烧焦段的操作温度为630℃，催化剂在烧焦段中的平均停留时间为40秒，气体表观线速为1.2m/s。密相再生段的操作温度为670℃，催化剂在密相再生段的平均停留时间为1.5分钟，气体表观线速为0.8m/s。再生后的催化剂进入反应器，与原料油接触进行催化裂化反应。再生条件、反应条件、二氧化碳排放情况如表9所示。
对比例4
参照实施例4进行试验，区别仅在于采用柴油作为燃料油，注入待生管线中与待生催化剂预混后进入再生器，作为补充能量来源。再生条件、反应条件、二氧化碳排放情况如表9所示。
表9实施例4和对比例4的操作条件和结果

以处理100g原料为基准。
二氧化碳排放指标指的是再生系统烧焦每产生1MJ能量所排放的源于化石能源二氧化碳的量；气相燃料产生的二氧化碳来自于大气中存在的二氧化碳，是中性的碳排放过程。
从表9的数据可以观察到，实施例采用生物质气化得到的气相燃料作为补充能量的来源时，再生系统产生同等的能量时，排放的二氧化碳的量较之对比例显著降低，这有利于从根本上减少二氧化碳的排放量。
以上详细描述了本申请的优选实施方式，但是，本申请并不限于上述实施方式中的具体细节，在本申请的技术构思范围内，可以对本申请的技术方案进行多种简单变型，这些简单变型均属于本申请的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本申请对各种可能的组合方式不再另行说明。
此外，本申请的各种不同的实施方式之间也可以进行任意组合，只要其不违背本申请的思想，其同样应当视为本申请所公开的内容。

Claims (13)

  1. 适用于流化催化裂化装置的催化剂再生方法，所述流化催化裂化装置包括催化裂化反应器和催化剂再生器，所述再生方法包括如下步骤：
    1)提供生物质来源的，例如经由生物质通过气化或者厌氧发酵得到的，包含氢气和/或甲烷的气相燃料；
    2)将所述气相燃料不经分离纯化直接送入催化剂再生器；
    3)将含氧气体引入所述催化剂再生器，其中所述含氧气体的氧气含量为14-28体积％；以及
    4)将来自催化裂化反应器的待生催化剂送入催化剂再生器，在其中与所述气相燃料和含氧气体接触，进行烧焦再生，
    优选地，所述催化剂再生器的操作温度在550-750℃范围内，且催化剂平均停留时间为1.0-15.0分钟。
  2. 按照权利要求1所述的方法，其中所述气相燃料通过气体分布器从不低于待生催化剂入口水平高度的位置注入催化剂再生器，且所述含氧气体为空气或者循环烟气稀释的氧气；
    优选地，当所述含氧气体为空气时，所引入的气相燃料的量为所引入的空气量的不超过13体积％，优选3-13体积％，或者当所述含氧气体为循环烟气稀释的氧气时，所引入的气相燃料的量为所引入的氧气量的不超过44体积，优选10-44体积％。
  3. 按照权利要求1或2所述的方法，其中所述催化剂再生器为单段再生器，所述再生器的操作条件包括：操作温度为550-750℃，催化剂平均停留时间为1.0-15.0分钟，气体表观线速度为0.5-2.0m/s。
  4. 按照权利要求1或2所述的方法，其中所述催化剂再生器为包括流体连通的烧焦段和再生段的两段再生器，并且在步骤2)中，将所述气相燃料送入烧焦段和/或再生段，优选仅送入烧焦段，在步骤3)中将含氧气体分别引入烧焦段和再生段的底部，且在步骤4)中将待生催化剂送入烧焦段，
    优选地，所述烧焦段的操作条件包括：操作温度为550-720℃，催化剂平均停留时间为10.0-120.0秒，优选为15.0-90.0秒，气体表观线速度为0.5-5.0m/s，优选为1.0-4.0m/s；并且
    所述再生段的操作条件包括：操作温度为600-750℃，催化剂平均停留时间为0.5-5.0分钟，优选为1.0-4.0分钟，气体表观线速度为0.4-2.0m/s，优选为0.5-1.5m/s；
    进一步优选地，所述再生段的操作温度比所述烧焦段的操作温度高10-150℃。
  5. 按照权利要求1或2所述的方法，其中所述催化剂再生器为包括流体连通的第一再生器和第二再生器的双再生器，并且在步骤2)中，将所述气相燃料送入第一再生器和/或第二再生器，优选仅送入第一再生器，在步骤3)中将含氧气体分别引入第一再生器和第二再生器的底部，且在步骤4)中将待生催化剂送入第一再生器，
    优选地，所述第一再生器的操作条件包括：操作温度为550-720℃，催化剂平均停留时间为20.0-240.0秒，优选为30.0-150.0秒，气体表观线速度为0.5-5.0m/s，优选为1.0-4.0m/s；并且
    所述第二再生器的操作条件包括：操作温度为600-750℃，催化剂平均停留时间为0.5-5.0分钟，优选为1.0-4.0分钟，气体表观线速度为0.4-2.0m/s，优选为0.5-1.5m/s；
    进一步优选地，所述第二再生器的操作温度比所述第一再生器的操作温度高10-150℃。
  6. 按照权利要求4或5所述的方法，其中所述烧焦段或者第一再生器中的烧焦比例为40-70％，优选40-50％；且所述再生段或者第二再生器中的烧焦比例为30-60％，优选50-60％。
  7. 按照权利要求1-6中任一项所述的方法，其中所述气相燃料经由生物质通过气化得到，并且以该气相燃料的总体积计，包含12-60％的氢气，15-30％的一氧化碳和3-8％的甲烷，其余为二氧化碳和/或氮气；或者
    所述气相燃料经由生物质通过厌氧发酵得到，并且以该气相燃料的总体积计，包含40-100体积％的甲烷。
  8. 按照权利要求1-7中任一项所述的方法，其中步骤1)进一步包括：
    在气化介质的存在下使所述生物质气化，气化温度为500-1500℃，所述气化介质选自空气、氧气/富氧气体、水蒸汽；或者
    使所述生物质在密闭发酵罐中进行厌氧发酵，发酵温度不高于60 ℃。
  9. 按照权利要求8所述的方法，其中所述生物质在气化或者厌氧发酵之前经过预处理，所述预处理选自研磨、干燥、挤压、蒸汽爆破、酸处理、碱处理和微生物预处理中的一种或几种。
  10. 一种适用于流化催化裂化装置的催化剂再生系统，包括生物质处理单元和催化剂再生单元，其中：
    所述生物质处理单元用于对生物质进行处理，例如进行气化或者厌氧发酵，得到包含氢气和/或甲烷的气相燃料，并且包括气相燃料发生器和气相燃料储罐，所述气相燃料发生器优选选自生物质气化器、生物质厌氧发酵罐或者它们的组合，并且具有生物质入口和气相产物出口，所述气相燃料储罐具有入口和气相燃料出口，所述气相燃料发生器的气相产物出口与所述气相燃料储罐的入口连通；
    所述催化剂再生单元用于对来自催化裂化反应器的待生催化剂进行再生，并且包括催化剂再生器，所述催化剂再生器具有待生催化剂入口、含氧气体入口、气相燃料入口、再生烟气出口和再生催化剂出口，以及
    所述气相燃料储罐的气相燃料出口通过管道与所述催化剂再生器的气相燃料入口连通。
  11. 根据权利要求10所述的催化剂再生系统，其中所述生物质处理单元进一步包括生物质预处理器和任选的气相产物干燥器，所述生物质预处理器用于对生物质进行预处理，所述预处理选自研磨、干燥、挤压、蒸汽爆破、酸处理、碱处理和微生物预处理中的一种或几种，所述气相产物干燥器用于对生物质厌氧发酵罐得到的气相产物进行干燥处理。
  12. 根据权利要求10或11所述的催化剂再生系统，其中所述催化剂再生器包括烧焦段和密相再生段，所述密相再生段位于烧焦段的上方，且所述烧焦段的出口容纳在密相再生段的内部，使得烧焦段与密相再生段流体相通；
    所述烧焦段设置有：
    第一含氧气体入口，其设置在烧焦段的底部，用于向所述烧焦段输入含氧气体；
    所述气相燃料入口，其设置在所述第一含氧气体入口的上方，用 于输入气相燃料；
    气体分布器，其配置为分配经所述气相燃料入口输入的气相燃料；
    所述待生催化剂入口，其用于将来自催化裂化反应器的待生催化剂输送至所述烧焦段内部；和
    任选的第一循环烟气入口，其用于将密相再生段排出的一部分烟气循环回所述烧焦段内部；
    所述密相再生段设置有：
    第二含氧气体入口，其设置在密相再生段的底部，用于向密相再生段输入含氧气体；
    任选的第二气相燃料入口，其设置在所述第二含氧气体入口的上方，用于向密相再生段输入气相燃料；
    任选的第二气体分布器，其配置为分配经所述第二气相燃料入口输入的气相燃料；
    所述再生烟气出口，其设置在密相再生段的顶部，用于将密相再生段内的再生烟气排出；
    所述再生催化剂出口，用于将再生催化剂返回催化裂化反应器；和
    任选的第二循环烟气入口，其用于将密相再生段排出的一部分烟气循环回所述密相再生段内部；
    任选地，所述密相再生段还配置有取热器，用于向所述再生器的外部输送热量。
  13. 根据权利要求10或11所述的催化剂再生系统，其中所述催化剂再生器包括第一再生器和第二再生器，第二再生器位于第一再生器的下游，所述第一再生器和第二再生器通过催化剂输送管连接，将经第一再生器部分再生的催化剂物料输送到第二再生器；
    第一再生器设置有：
    第一含氧气体入口，其设置在第一再生器的底部，用于向所述第一再生器输入含氧气体；
    所述气相燃料入口，其设置在所述第一含氧气体入口的上方，用于输入气相燃料；
    气体分布器，其配置为分配经所述气相燃料入口输入的气相燃料；
    所述待生催化剂入口，用于将来自催化裂化反应器的待生催化剂 输送至所述第一再生器内部；
    第一再生烟气出口，其设置在第一再生器的顶部，用于将第一再生器内的再生烟气排出；和
    任选的第一循环烟气入口，其设置在第一再生器的底部并与所述第一再生烟气出口连通，用于将第一再生器排出的部分烟气循环回所述第一再生器，
    所述第二再生器设置有：
    第二含氧气体入口，其设置在第二再生器的底部，用于向第二再生器输入含氧气体；
    任选的第二气相燃料入口，其设置在所述第二含氧气体入口的上方，用于向第二再生器输入气相燃料；
    任选的第二气体分布器，其配置为分配经所述第二气相燃料入口输入的气相燃料；
    所述再生催化剂出口，用于将再生催化剂返回催化裂化反应器；
    第二再生烟气出口，其设置在第二再生器的顶部，用于将第二再生器内的再生烟气排出；和
    任选的第二循环烟气入口，其设置在第二再生器的底部并与所述第一再生烟气出口和/或第二再生烟气出口连通，用于将部分烟气循环回所述第二再生器。
PCT/CN2023/091025 2022-04-29 2023-04-27 采用生物基气相燃料的催化裂化催化剂再生方法和系统 WO2023208083A1 (zh)

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