Regeneration and cyclic utilization method of ZMQ-1 molecular sieve catalytic cracking catalyst

Abstract

The invention relates to the field of petrochemical engineering, and discloses a regeneration and cyclic utilization method of a ZMQ-1 molecular sieve catalytic cracking catalyst, which comprises the following steps: pretreating a used ZMQ-1 molecular sieve catalyst, and continuing for 1-1.5 hours at the temperature of 250-350 DEG C by adopting nitrogen flow to remove light hydrocarbon molecules; heating the catalyst to 500-650 DEG C in the atmosphere of mixed gas flow of oxygen and nitrogen, continuously carrying out oxidation incineration for 2-3 hours, and removing deposited carbon on the surface of the catalyst; heating the oxidized and incinerated catalyst to 650-750 DEG C in a steam atmosphere for 1.5-2 hours to recover the pore structure of the catalyst; the catalyst is activated by using hydrogen or ammonia gas so as to recover the acidity and surface activity of the catalyst. The regeneration method can significantly improve the carbon deposition resistance, thermal stability and catalytic performance of the catalyst, prolongs the service life of the catalyst, has low energy consumption and a simplified operation process, and is suitable for catalyst regeneration and cyclic utilization in a catalytic cracking reaction.

Description

Technical Field

[0001] The invention relates to the technical field of petrochemical industry, in particular to a method for regenerating and recycling a ZMQ-1 molecular sieve catalytic cracking catalyst. Background Art

[0002] As an important conversion process in the oil refining process, catalytic cracking technology is widely used in the deep conversion of heavy oil, which can improve the yield of light oil products, especially in the production of gasoline and diesel. Molecular sieve catalysts, especially ZMQ-1 molecular sieve catalysts, can be used in catalytic cracking processes due to their excellent catalytic performance and stability. However, although ZMQ-1 molecular sieve catalysts have excellent catalytic activity in cracking reactions, the carbon deposition problem of the catalyst has always been the main bottleneck affecting the performance and life of the catalyst.

[0003] During the catalytic cracking process, a large amount of carbon material will accumulate on the catalyst surface. These carbon deposits will not only reduce the surface acidity and pore structure of the catalyst, thereby affecting the cracking activity of the catalyst, but may also cause the deactivation of the catalyst. In order to solve this problem, catalyst regeneration has become an indispensable part of the catalytic cracking process. Most of the existing catalyst regeneration technologies rely on high-temperature oxidation incineration and steam treatment, but these methods often have several problems. For example, high-temperature oxidation incineration may lead to excessive consumption of acid sites on the catalyst surface, and although steam treatment can restore the pore structure of the catalyst, the effect is usually limited. Traditional regeneration methods are difficult to fully restore the catalytic performance of the catalyst, especially during long-term catalytic cracking reactions, the performance of the catalyst gradually decreases, resulting in reduced conversion and selectivity of the cracking reaction.

[0004] In addition, the existing catalyst regeneration process is often too complicated, the operation process is cumbersome and the energy consumption is high, which makes it difficult to meet the requirements of modern oil refining process for high efficiency, greenness and low energy consumption. Especially when multiple redox treatments are carried out at high temperature, not only is it difficult to effectively restore the activity of the catalyst, but it also increases the consumption of the catalyst, thereby reducing the overall economic benefits of the catalytic cracking process.

[0005] Therefore, how to improve the regeneration efficiency of the catalyst, extend the service life of the catalyst, and at the same time improve the simplicity and economy of the regeneration process has become an urgent problem to be solved in catalytic cracking technology. Summary of the invention

[0006] In view of the deficiencies in the prior art, the present invention provides a method for regenerating and recycling a ZMQ-1 molecular sieve catalytic cracking catalyst, which solves the carbon deposition problem of the existing ZMQ-1 molecular sieve catalyst in the catalytic cracking process and the technical problems of low regeneration efficiency, poor stability, and complex operation.

[0007] To achieve the above objectives, the present invention is implemented by the following technical scheme: A method for regenerating and recycling a ZMQ-1 molecular sieve catalytic cracking catalyst comprises the following steps:

[0008] 1) pre-treating the used ZMQ-1 molecular sieve catalyst by using a nitrogen flow at a temperature of 250-350° C. for 1-1.5 hours to remove light hydrocarbon molecules;

[0009] 2) In an atmosphere of a mixed flow of oxygen and nitrogen, the catalyst is heated to 500-650°C for 2-3 hours for oxidation incineration to remove carbon deposits on the catalyst surface;

[0010] 3) heating the oxidatively incinerated catalyst to 650-750°C in a steam atmosphere for 1.5-2 hours to further remove carbon deposits and restore the pore structure of the catalyst;

[0011] 4) After cooling to room temperature, use hydrogen or ammonia to activate the catalyst to restore its acidity and surface activity;

[0012] 5) The regenerated catalyst is put into a catalytic cracking reactor to carry out a catalytic cracking reaction, and the activity of the catalyst is monitored in real time during the catalytic cracking process and timely regeneration is carried out.

[0013] Preferably, the oxygen concentration in the mixed gas flow of oxygen and nitrogen is 20%-30%, and the mixed gas flow rate is 30-50NL / h.

[0014] Preferably, the flow rate of the steam is 10-30NL / h.

[0015] Preferably, the flow rate of the nitrogen gas used in the pretreatment process is 50-120 NL / h, and the heating rate is 5°C / min to 10°C / min.

[0016] Preferably, the flow rate of the hydrogen or ammonia is controlled at 10-20 NL / h, and the activation treatment time is 1 hour.

[0017] Preferably, the temperature in the catalytic cracking reactor is controlled between 450-550° C., and the duration of the catalytic cracking reaction is 8-12 hours.

[0018] Preferably, a synergistic additive is used in the regeneration process, and the synergistic additive includes aluminum fluoride and a molybdenum-based compound, the addition amount of aluminum fluoride is 1%-4% of the total amount of the catalyst, and the addition amount of the molybdenum-based compound is 0.5%-1% of the total amount of the catalyst.

[0019] Preferably, during the recycling process of the catalyst, when the catalyst activity drops below 80%, midway regeneration is performed to restore the catalyst activity.

[0020] The present invention provides a method for regenerating and recycling a ZMQ-1 molecular sieve catalytic cracking catalyst, which has the following beneficial effects:

[0021] 1. The present invention significantly improves the carbon deposit removal rate and acid site recovery rate of the catalyst by adding aluminum fluoride and molybdenum-based compounds as synergistic additives during the catalyst regeneration process. Experimental results show that the synergistic additives can more effectively remove carbon deposits during the regeneration process and restore the acid sites and catalytic activity of the catalyst, which effectively restores the activity of the catalyst after multiple uses, thereby improving the regeneration efficiency of the catalyst.

[0022] 2. By adopting the regeneration method of the present invention, the surface acid sites of the catalyst are fully restored and the pore structure of the catalyst is optimized, which enables the catalyst to exhibit higher catalytic activity in the catalytic cracking reaction. Compared with the traditional regeneration method, the regeneration process provided by the present invention can better maintain the structural stability of the catalyst and the catalytic effect of the cracking reaction, thereby improving the product selectivity and conversion rate of the cracking reaction.

[0023] 3. The regeneration method of the present invention adopts a relatively simple process combining high-temperature steam atmosphere and oxygen atmosphere, and cooperates with synergistic additives to not only efficiently remove carbon deposits, but also effectively restore the activity of the catalyst. This regeneration method avoids the common complex steps in the traditional catalyst regeneration process, such as long-term high-temperature oxidation and multiple acid washing treatments, making the regeneration process of the present invention simpler, more convenient to operate, and saving energy and time.

[0024] 4. The synergistic additive regeneration process of the present invention can significantly improve the regeneration effect of the catalyst, reduce catalyst consumption, and reduce the generation of waste catalysts, thereby reducing resource waste and environmental pollution, which is in line with the trend of green development. In addition, by improving the regeneration efficiency and service life of the catalyst, the operating cost of the catalytic cracking process can be reduced, improving the economy and sustainability of the entire process. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is a schematic diagram of the method flow of the present invention. DETAILED DESCRIPTION

[0026] The following will be combined with the drawings in the specification of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Please refer to the attached Figure 1The present invention provides a method for regenerating and recycling a ZMQ-1 molecular sieve catalytic cracking catalyst, which restores the activity of the catalyst through an efficient and economical regeneration process and prolongs the service life of the catalyst, thereby improving the economy and stability of the catalytic cracking reaction.

[0028] like Figure 1 As shown, the regeneration and recycling method of the ZMQ-1 molecular sieve catalytic cracking catalyst of the present invention may include the following steps:

[0029] S1. Pretreatment of used ZMQ-1 molecular sieve catalyst;

[0030] S2. Oxidation and incineration of the catalyst;

[0031] S3, heating treatment of the catalyst in a steam atmosphere;

[0032] S4, activation treatment of the catalyst;

[0033] S5. Catalyst placement and real-time activity monitoring.

[0034] For step S1, in this embodiment, the pretreatment step of the ZMQ-1 molecular sieve catalyst is intended to remove light hydrocarbon molecules and other low molecular weight impurities on the catalyst surface and in the pores. Through this step, the activity decay of the catalyst during the catalytic cracking process can be effectively reduced, and the foundation for the subsequent regeneration step is laid. The pretreatment process is usually carried out at a temperature range of 250-350°C and lasts for 1-1.5 hours under the action of a nitrogen flow to ensure that the light hydrocarbon molecules attached to the surface are completely removed.

[0035] Specifically, the main purpose of the pretreatment process is to volatilize and remove light hydrocarbons and small molecules on the catalyst surface and in the pores through a combination of temperature and airflow, which usually have an adverse effect on the pore structure and activity of the catalyst. If this step is not performed, the accumulated light hydrocarbons will cause the pores of the catalyst to become blocked, further accelerating the deactivation of the catalyst. Therefore, through the effective pretreatment of this step, not only can light hydrocarbons be removed, but also the reduction in catalyst activity caused by carbon deposition can be reduced.

[0036] As an option, the pretreatment process uses nitrogen flow as an inert gas to ensure that the atmosphere does not cause oxidation or other chemical changes to the catalyst. The flow rate of the nitrogen flow is generally set between 50-120NL / h. This flow rate can ensure that the gas passes evenly through the pores and surfaces of the catalyst particles and effectively removes hydrocarbon molecules. In this process, the flow of nitrogen promotes the migration of substances on the catalyst surface and reduces the surface contamination of the catalyst.

[0037] It should be noted that the pretreatment temperature is controlled within the range of 250-350°C. Lower temperatures help volatilize light hydrocarbon molecules, while higher temperatures help improve the contact efficiency between gas molecules and the catalyst surface. The pretreatment time is usually set to 1 to 1.5 hours, and the specific time can be adjusted appropriately according to the use of the catalyst and the degree of surface contamination. In some embodiments, if there are more hydrocarbon substances on the catalyst surface, the pretreatment time can be appropriately extended to ensure that all light hydrocarbon molecules can be completely removed.

[0038] In one possible implementation, there may be some light hydrocarbons or other low molecular weight impurities partially accumulated on the surface of the catalyst, which are usually not easy to volatilize, so they need to be pretreated at a higher temperature to ensure sufficient removal. At this time, the temperature can be selected to be close to the upper limit of 350°C to improve the volatilization and desorption efficiency.

[0039] In addition, it is important to note that the gas flow direction and gas distribution should also be kept uniform during the pretreatment process. In order to ensure that every part of the catalyst is fully exposed to the nitrogen flow, the gas flow rate and distribution should be optimized according to the loading method and structure of the catalyst. For catalysts with larger particles, the gas flow rate can be appropriately increased to ensure that the gas can flow evenly through each layer of the catalyst particles.

[0040] For example, the pretreated catalyst can significantly reduce the residual amount of light hydrocarbons, thereby avoiding excessive carbon deposition during the subsequent oxidation incineration and steam regeneration process, and improving the overall regeneration efficiency of the catalyst. The pore structure of the pretreated ZMQ-1 molecular sieve catalyst is more unobstructed, and it can better adsorb and react target molecules.

[0041] In summary, step S1, as the starting link of the catalyst regeneration process of the present invention, plays a key role in removing light hydrocarbon molecules on the catalyst surface and in the pores and restoring the porosity and reaction activity of the catalyst.

[0042] For step S2, in this embodiment, the oxidation incineration treatment step of the catalyst is intended to remove carbon deposits on the catalyst surface and in the pores. These carbon deposits are mainly composed of hydrocarbon molecules, aromatic hydrocarbons, asphaltene and other substances that are not completely cracked during the catalytic cracking reaction, which will accumulate on the catalyst surface and affect the reaction activity and pore structure of the catalyst. Through oxidation incineration treatment, these carbon deposits can be effectively removed and the surface activity of the catalyst can be restored, providing the required catalytic performance for the subsequent catalytic cracking reaction.

[0043] Specifically, in this step, the catalyst needs to be heated in a mixed atmosphere of oxygen and nitrogen. The mixing ratio of oxygen and nitrogen has an important influence on the efficiency of oxidative incineration. In some embodiments, the volume fraction of oxygen in the mixed gas can be set between 5% and 30%. This concentration range can ensure sufficient oxidation of carbon deposits while avoiding excessive oxygen causing over-oxidation of the catalyst or damage to its active components. Nitrogen acts as an inert gas to dilute the oxygen concentration and protect the catalyst surface from excessive oxidation.

[0044] In this embodiment, the catalyst is heated to a temperature range of 500-650° C. under the action of a mixed flow of oxygen and nitrogen. Within this temperature range, carbon deposits undergo an oxidation reaction under the action of oxygen to generate products such as CO2 and water vapor.

[0045] This reaction can effectively remove carbon deposits on the catalyst surface and in the pores, and restore the surface cleanliness of the catalyst. It should be noted that too low a temperature may result in a slow oxidation reaction rate and poor treatment effect; while too high a temperature may cause oxidative degradation of the catalyst, resulting in damage to its structure and performance. Therefore, in this step, the heating temperature of the catalyst is generally controlled between 500-650°C and maintained at this temperature for 2-3 hours to ensure that the carbon deposits are fully oxidized without damaging the catalyst.

[0046] In some embodiments, the mixed gas flow of oxygen and nitrogen can be further optimized by adjusting the flow rate and ratio. Generally, the flow rate of oxygen can be set at 50-150NL / h, and the flow rate of nitrogen can be set at 100-200NL / h. This gas flow rate can ensure that the gas flows evenly in the catalyst bed, ensure that oxygen can fully contact the catalyst surface, and promote the oxidation process of carbon deposits. At the same time, the uniformity of the gas flow also helps to avoid the occurrence of local overheating, thereby ensuring that the active area on the catalyst surface is evenly treated.

[0047] It should be noted that the temperature control during the oxidation incineration process needs to be appropriately adjusted according to the use of the catalyst. For example, for catalysts that have been used for a long time, the carbon accumulation on the surface may be serious, and the temperature may need to be slightly increased (close to 650°C) to enhance the oxidation effect. For catalysts with lighter carbon accumulation on the surface, the overall structure of the catalyst can be protected by controlling the oxidation temperature at a lower temperature (such as 500°C).

[0048] For example, after the oxidative incineration treatment, the carbon deposits on the surface of the catalyst are almost completely removed, and the pore structure of the catalyst is restored. At this time, the reaction activity of the catalyst is effectively restored, and better catalytic performance can be provided for subsequent steam regeneration and catalytic cracking reactions. Especially for highly active catalysts, the effect after oxidative incineration is usually manifested as higher reaction efficiency and longer service life than untreated catalysts.

[0049] In summary, the oxidation incineration step in this embodiment plays a key role in the catalyst regeneration process. By controlling the temperature and time in a mixed atmosphere of oxygen and nitrogen, the carbon deposits on the catalyst surface can be effectively removed, and the reaction activity and pore structure of the catalyst can be restored.

[0050] Regarding step S3, during the regeneration process of the catalyst, after the carbon deposits are removed by the oxidation incineration step, the pore structure of the catalyst surface may be damaged, especially the combustion process of the carbon deposits at high temperature may cause partial destruction of the catalyst surface and its pores. Therefore, in order to further restore the pore structure and surface activity of the catalyst, a heating treatment step under a steam atmosphere is introduced in this embodiment.

[0051] In the heating treatment step under steam atmosphere, the catalyst needs to be heated to a temperature range of 650-750°C under the action of steam flow. This treatment can not only further remove the residual trace carbon deposits, but also promote the recovery of the pore structure of the catalyst. Steam reacts with the carbon deposits on the surface of the catalyst at high temperature to generate water vapor and carbon dioxide, which helps to remove the residual carbonaceous substances from the pores and surface of the catalyst. In addition, the water molecules in the steam atmosphere can also reactivate the catalyst surface to a certain extent, restoring its acidity and catalytic activity.

[0052] Specifically, in this embodiment, the catalyst is heated to 650-750° C. in a steam atmosphere and maintained at this temperature for 1.5-2 hours. Within this temperature range, the steam reacts with the residual carbon deposits that may exist on the surface of the catalyst to generate water vapor and carbon dioxide.

[0053] In addition, steam can also react with metal oxides on the catalyst surface, causing certain metal components to recover activity, thereby further enhancing the performance of the catalyst. It should be noted that if the steam heating temperature is too low, carbon deposits may not be fully removed; while if the temperature is too high, the catalyst surface or pore structure may be further damaged, so the temperature range should be strictly controlled.

[0054] In some embodiments, the flow rate of the steam gas flow also affects the effect of this step. Generally speaking, the steam flow rate can be controlled at 100-300 NL / h to ensure that the steam can fully contact every part of the catalyst. For catalysts in larger reactors, the steam flow rate can be adjusted to ensure uniform gas distribution and avoid excessive or low local steam flow rates, thereby ensuring the overall recovery effect of the catalyst.

[0055] It should be understood that in this step, the source of steam can be high-purity water vapor or steam that has been treated in a certain way. Since the role of steam is not limited to removing carbon deposits, but can also restore the surface acidity of the catalyst and has a certain "activation" effect, the use of high-purity steam flow helps to better restore the catalytic activity of the catalyst.

[0056] In some embodiments, an appropriate amount of reducing gas (such as hydrogen) can be introduced and mixed with steam to further improve the activity of the catalyst, especially in certain catalysts containing metal components, where hydrogen can help the reduction reaction of the metal, thereby restoring its catalytic activity. Exemplarily, the hydrogen concentration in the reducing atmosphere can be controlled in the range of 1%-5% to avoid excessive reduction and damage to the catalyst structure.

[0057] In general, the steam atmosphere heating step plays an important role in restoring the pore structure of the catalyst and improving the catalytic activity. Through steam treatment, the residual carbon deposits after oxidative incineration can be further removed, while improving the surface properties of the catalyst, providing a more efficient and stable catalyst for catalytic cracking reactions. Especially for catalysts that have been used for a long time, the steam treatment step significantly improves the regeneration efficiency and service life of the catalyst.

[0058] For step S4, during the regeneration process of the catalyst, after the heating treatment in the steam atmosphere, the pore structure and surface carbon accumulation of the catalyst are improved, but the acidity and surface activity of the catalyst may not have recovered to the optimal state, so further activation treatment is required. The purpose of the activation process is to restore the overall performance of the catalyst by adjusting the acidity and surface activity of the catalyst surface to ensure that it can exert the maximum catalytic efficiency in the catalytic cracking reaction.

[0059] In this embodiment, the activation treatment of the catalyst is carried out by exposing the catalyst to a hydrogen or ammonia atmosphere at room temperature. The introduction of hydrogen and ammonia can effectively restore the acidic centers and surface active sites of the catalyst through reduction or protonation reactions, thereby improving the activity of the catalyst.

[0060] In one possible implementation, the activation temperature range of the catalyst in a hydrogen or ammonia atmosphere is 300-500°C, and the activation time is controlled to 1-2 hours. Specifically, the flow rate and concentration of the hydrogen or ammonia gas flow have a significant effect on the catalyst activation effect. In some embodiments, the flow rate of hydrogen can be set to 100-300NL / h, and the flow rate of ammonia can generally be set to 50-200NL / h to ensure that the catalyst surface is fully treated. The concentration of hydrogen is generally 80%-100%, and the concentration of ammonia is generally 10%-30%.

[0061] It should be noted that when hydrogen is used as a reducing gas, hydrogen molecules react with metal oxides on the catalyst surface, which can effectively reduce the metal components on the catalyst surface and restore its catalytic activity. This reaction can effectively remove oxides on the catalyst surface, promote metal activation, and thus restore the cracking activity of the catalyst.

[0062] In another embodiment, the introduction of ammonia can further adjust the acid sites of the catalyst through protonation reaction. Ammonia reacts with acidic oxygen atoms on the surface of the catalyst to generate amino groups or nitrogen hydrogen groups, which can effectively increase the acidity of the catalyst and make it have stronger catalytic performance in the cracking reaction. This process not only restores the acid sites of the catalyst, but also helps to eliminate certain surface impurities and improve the overall reaction activity of the catalyst.

[0063] In some embodiments, in order to further improve the activation effect, an alternating atmosphere can be used, that is, hydrogen and ammonia are used alternately within a certain period of time to achieve the dual effects of reduction and protonation. The time interval between alternating hydrogen and ammonia is generally 30-60 minutes, and the treatment time of each atmosphere is 1 hour. The specific duration can be adjusted according to the type and requirements of the catalyst.

[0064] It is important to understand that the temperature and time parameters for hydrogen and ammonia activation treatments vary depending on the type of catalyst, service life, and activity requirements. In order to avoid excessive reduction or acidic adjustments to the catalyst structure, it is generally recommended to strictly control the range of temperature and gas flow. Specifically, the temperature for hydrogen activation is usually set between 300-450°C, while the temperature for ammonia activation can be appropriately lower, usually 300-400°C, to ensure optimal restoration of the catalyst surface properties.

[0065] For example, some high-strength ZMQ-1 molecular sieve catalysts may require a lower activation temperature (such as 300-350° C.), while for some catalysts that are more resistant to high temperatures, a higher activation temperature (such as 450-500° C.) may be selected. Therefore, the activation step in the present invention has strong flexibility and can be adjusted according to actual conditions to achieve the best activation effect on the catalyst.

[0066] In summary, the hydrogen or ammonia activation treatment in step S4 is crucial for restoring the acidic centers and metal active sites of the catalyst.

[0067] For step S5, after the regeneration process of the catalyst is completed, step S5 is to put the regenerated catalyst into the catalytic cracking reactor to continue to participate in the catalytic cracking reaction. This step not only involves the actual use of the catalyst, but also requires real-time monitoring of the activity of the catalyst and timely midway regeneration during the catalytic cracking process. Through dynamic monitoring of the catalyst activity, it is possible to effectively ensure that the catalyst always maintains high performance in the cracking reaction, and take necessary regeneration measures in time, thereby extending the service life of the catalyst and improving the overall reaction efficiency.

[0068] In this embodiment, the regenerated catalyst is first introduced into a catalytic cracking reactor and a catalytic cracking reaction is carried out under conventional cracking reaction conditions. The operating temperature of the catalytic cracking reaction is generally 500-650°C, and the common reaction pressure range is 1-3MPa. During this process, the catalyst will contact the reaction gas (such as crude oil) in the cracking reactor, and the catalytic cracking reaction will occur on the acidic center and surface active site of the catalyst.

[0069] It should be noted that in actual operation, the activity of the catalyst will gradually decrease during the cracking process due to the formation of carbon deposits and the consumption of catalyst acid sites during the reaction. Therefore, it is very important to monitor the activity of the catalyst in real time and perform timely regeneration when necessary. In order to achieve real-time monitoring of the catalyst activity, the present invention adopts a monitoring system based on the reaction temperature, reaction gas composition and catalyst activity changes.

[0070] In some embodiments, the activity monitoring of the catalyst can be performed by measuring the composition changes of the reaction gas. For example, the generation rate of the target product in the reaction gas, especially the changes of light hydrocarbon products (such as methane, ethylene, propylene, etc.) can be monitored by an online analyzer, which can indirectly reflect the activity state of the catalyst. When the activity of the catalyst shows a downward trend, it can be discovered in time through the monitoring system.

[0071] In one possible implementation, the catalyst activity can be evaluated by real-time detection of changes in the gas composition in the reactor. Specifically, the concentration of light hydrocarbon molecules (such as C1-C4 olefins) in the reaction gas is closely related to the surface activity of the catalyst. As the catalytic cracking reaction proceeds, if the concentration of light hydrocarbon products is found to decrease significantly, it may indicate that the catalyst activity has decreased and regeneration is required.

[0072] Specifically, the activity monitoring of the catalyst can also be carried out with the help of monitoring the carbon accumulation on the catalyst surface during the catalytic reaction. For example, by online monitoring of the amount of carbon accumulation on the catalyst surface, combined with the relationship between carbon accumulation and catalyst performance, the activity level of the catalyst can also be reflected. For the monitoring of carbon accumulation, the change of the catalyst surface temperature under a high-temperature atmosphere can be monitored. When the catalyst surface temperature rises abnormally, it indicates that the carbon accumulation on the catalyst surface has reached a certain level and the catalyst activity has decreased. At this time, the system will trigger the mid-term regeneration program.

[0073] For example, the real-time activity monitoring system of the catalyst may be provided with an automatic alarm and adjustment mechanism. Once the catalyst activity is detected to be lower than the set minimum standard, the system will automatically start the mid-cycle regeneration program and automatically adjust the regeneration conditions (such as temperature, atmosphere flow, etc.) according to parameters such as the carbon deposition degree and activity level of the catalyst.

[0074] For timely recovery of the catalyst during the regeneration process, in some embodiments, the time and temperature of the regeneration process will be flexibly adjusted according to the activity recovery of the catalyst. Specifically, when the catalyst activity recovers to a predetermined level, the system will automatically stop the regeneration process and return the catalyst to the reactor to continue participating in the cracking reaction.

[0075] It is understood that during the catalytic cracking reaction, the activity of the catalyst is not only affected by the reaction temperature, reaction pressure and the properties of the feed oil, but also by factors such as the carbon accumulation on the catalyst surface, acid sites and pore structure. Therefore, the accuracy and sensitivity of the real-time monitoring system and the ability to start the regeneration program at the right time are crucial to ensure the stability of the catalytic cracking reaction and the service life of the catalyst.

[0076] It should be emphasized that the mid-cycle regeneration and activity monitoring system of the present invention can greatly improve the stability of the catalytic cracking process and reduce the risk of premature catalyst deactivation due to carbon deposition, thereby extending the service life of the catalyst, reducing downtime and improving production efficiency.

[0077] In summary, by monitoring the activity of the regenerated catalyst in real time during the catalytic cracking process and performing mid-course regeneration as needed, the present invention provides an effective catalyst recycling method, so that the catalytic cracking reaction can be carried out more efficiently and stably.

[0078] As a preferred embodiment of the present invention, a synergistic additive is used in the catalyst regeneration process to improve the regeneration efficiency of the catalyst and extend its service life. The synergistic additive includes aluminum fluoride and a molybdenum-based compound. Aluminum fluoride and molybdenum-based compounds play an important role in enhancing catalyst activity, improving pore structure, and inhibiting carbon deposition during the catalyst regeneration process.

[0079] In this embodiment, the amount of aluminum fluoride added is 1%-4% of the total amount of the catalyst, and the amount of the molybdenum-based compound added is 0.5%-1% of the total amount of the catalyst. The selection of the addition amount has been optimized and can significantly improve the regeneration effect of the catalyst without affecting other properties of the catalyst.

[0080] Specifically, during the regeneration process, aluminum fluoride, as a strong acidic compound, can effectively enhance the acid sites of the catalyst and promote the cracking reaction. The addition of aluminum fluoride can not only improve the conversion rate of catalytic cracking, but also inhibit the accumulation of carbon deposits, thereby extending the service life of the catalyst. The appropriate addition of aluminum fluoride helps to adjust the acid distribution of the catalyst and optimize its reaction performance.

[0081] The introduction of molybdenum-based compounds (such as ammonium hexamolybdate or molybdate) has a unique synergistic effect. Molybdenum-based compounds can effectively improve the catalyst's ability to resist carbon deposition and inhibit carbon deposition during cracking. This is because molybdenum-based compounds have strong oxidizing ability, which can promote the oxidative decomposition of carbon deposits and reduce carbon deposition on the catalyst surface. In addition, molybdenum-based compounds can also improve the pore structure of the catalyst and enhance the cyclic stability of the catalyst.

[0082] In a preferred embodiment, aluminum fluoride and the molybdenum-based compound work in a synergistic manner during the regeneration process of the catalyst. Specifically, aluminum fluoride improves the cracking ability of the catalyst by improving the acidity of the catalyst, while the molybdenum-based compound improves the anti-coking performance of the catalyst to avoid excessive coking under high temperature reaction conditions, thereby maintaining the long-term stability of the catalyst.

[0083] For example, the specific steps of the catalyst regeneration process are as follows: first, the catalyst is pretreated with a nitrogen flow to remove light hydrocarbon molecules; then, the catalyst is heated to 500-650°C by a mixed flow of nitrogen and oxygen for oxidative incineration to remove carbon deposits; then, with the assistance of aluminum fluoride and molybdenum-based compounds, the catalyst enters a steam atmosphere and is heated again to 650-750°C to further restore the pore structure of the catalyst and remove excess carbon deposits; finally, hydrogen or ammonia is used for activation treatment to restore the acidity and surface activity of the catalyst.

[0084] It should be noted that the synergistic effect of aluminum fluoride and the platinum-based compound is the key to this embodiment. Aluminum fluoride can increase the acid site density of the catalyst, thereby enhancing its catalytic cracking reaction ability, while the platinum-based compound inhibits the formation of carbon deposits by providing a strong oxidizing effect. The combination of the two can effectively improve the regeneration effect of the catalyst, so that the catalyst maintains a high activity and stability during multiple cycles.

[0085] In one possible implementation, aluminum fluoride and the platinum-based compound can be added to the catalyst by an impregnation method. In this method, the catalyst is first mixed with an aluminum fluoride solution, dried, and then a platinum-based compound solution is added and dried again, so that the aluminum fluoride and the platinum-based compound are evenly distributed on the catalyst surface.

[0086] It should be noted that the addition amount of aluminum fluoride and molybdenum-based compounds has an important influence on the performance of the catalyst. Excessive aluminum fluoride may cause the catalyst to be too acidic, thereby affecting the selectivity of the catalytic cracking reaction; while excessive addition of molybdenum-based compounds may cause changes in the pore structure of the catalyst, thereby affecting its overall performance. Therefore, the addition amount of aluminum fluoride and molybdenum-based compounds should be strictly controlled within the range of 1%-4% and 0.5%-1% to ensure the excellent performance of the catalyst.

[0087] In summary, the preferred embodiment can improve the acid sites and pore structure of the catalyst through the synergistic effect of adding aluminum fluoride and molybdenum-based compounds, and can also significantly improve the catalyst's ability to resist carbon deposition, enhance the catalyst's long-term stability, and thus improve the overall efficiency and economy of the catalytic cracking reaction.

[0088] In general, the present invention solves the problem of catalyst activity reduction due to carbon deposition and pore blockage in catalytic cracking reaction through a multi-step process including pretreatment, oxidative incineration, steam regeneration, activation treatment, real-time monitoring and mid-stage regeneration. The present invention also introduces aluminum fluoride and molybdenum-based compounds as synergistic additives to further enhance the catalyst's anti-carbon deposition ability and acidity control performance, and realizes efficient regeneration and recycling of the catalyst.

[0089] In order to better understand the present invention, the above method is described in detail below in conjunction with specific embodiments.

[0090] Example 1: Standard regeneration process

[0091] In this embodiment, the ZMQ-1 molecular sieve catalyst is regenerated through conventional pretreatment, oxidative incineration and steam atmosphere heating steps. The specific operation is as follows:

[0092] S1: The catalyst was heated to 300°C in a nitrogen flow for 1 hour to remove light hydrocarbons. The nitrogen flow rate was 1000 Nm 3 / h, nitrogen flow rate is 10m / s.

[0093] S2: In a mixed flow of oxygen and nitrogen, the catalyst is heated to 550°C for 2 hours for oxidative incineration. The oxygen flow rate is 500 Nm 3 / h, nitrogen flow rate is 500Nm 3 / h, the mixing ratio of oxygen and nitrogen is 1:1.

[0094] S3: The catalyst is heated to 700°C in a steam atmosphere and maintained for 1.5 hours to restore its pore structure. The steam flow rate is 300 Nm 3 / h, the mass fraction of steam is 100%.

[0095] S4: After cooling to room temperature, use hydrogen to activate and restore the acid sites. The hydrogen flow rate is 200Nm 3 / h, the temperature is 500℃ and the duration is 2 hours.

[0096] S5: The regenerated catalyst is put into the cracking reactor and regenerated in the middle at an appropriate time according to the real-time monitoring data.

[0097] Example 2: Synergistic additives to improve regeneration process

[0098] This embodiment uses synergistic additives (aluminum fluoride and molybdenum-based compounds) to improve the catalyst's ability to resist carbon deposition and acidity. The specific operation is as follows:

[0099] S1: The catalyst was heated to 250°C in nitrogen for 1 hour to remove light hydrocarbons. The nitrogen flow rate was 800 Nm 3 / h.

[0100] S2: The catalyst is heated to 600°C in a mixed flow of oxygen and nitrogen for 2.5 hours for oxidation and incineration to remove carbon deposits. The oxygen flow rate is 400Nm 3 / h, nitrogen flow rate is 400Nm 3 / h, the mixing ratio of oxygen and nitrogen is 1:1.

[0101] S3: Aluminum fluoride and molybdenum-based compounds were added as synergistic additives, with the amount of aluminum fluoride added being 3% of the total catalyst and the amount of molybdenum-based compounds added being 0.8% of the total catalyst. The catalyst was then heated to 750°C in a steam atmosphere for 1.5 hours to restore the pore structure of the catalyst. The steam flow rate was 250 Nm 3 / h, the steam quality fraction is 100%.

[0102] S4: After the catalyst is cooled to room temperature, it is activated with ammonia to restore the acid sites. The ammonia flow rate is 150Nm 3 / h, the temperature is 550℃ and the duration is 1 hour.

[0103] S5: Put into the reactor for cracking reaction, monitor the catalyst activity in real time, and regenerate it in time.

[0104] Example 3: Catalyst regeneration at lower temperatures

[0105] This embodiment uses a relatively low temperature to regenerate the catalyst to avoid structural damage to the catalyst caused by excessively high temperatures, and is particularly suitable for certain special catalyst systems. The specific operation is as follows:

[0106] S1: The catalyst was heated to 280°C in a nitrogen flow for 1.5 hours to remove light hydrocarbons. The nitrogen flow rate was 1000 Nm 3 / h.

[0107] S2: The catalyst is heated to 500°C in a mixed flow of oxygen and nitrogen for 2 hours for oxidation and incineration to remove carbon deposits. The oxygen flow rate is 350Nm 3 / h, nitrogen flow rate is 650Nm 3 / h, the mixing ratio of oxygen to nitrogen is 1:2.

[0108] S3: The catalyst was heated to 650 °C in a steam atmosphere for 1 hour to restore the pore structure. The steam flow rate was 300 Nm 3 / h, the steam quality fraction is 100%.

[0109] S4: After cooling to room temperature, hydrogen is used for activation treatment to restore the acid sites of the catalyst. The hydrogen flow rate is 200Nm 3 / h, the temperature is 480℃ and the duration is 2 hours.

[0110] S5: Putting the catalyst into the reactor for catalytic cracking, and regenerating the catalyst midway according to the activity of the catalyst.

[0111] Example 4: High temperature steam atmosphere regeneration

[0112] This embodiment strengthens the pore recovery ability of the catalyst by regenerating in a high-temperature steam atmosphere. It is applicable to situations where the catalyst has been severely carbonized or structurally damaged. The specific operation is as follows:

[0113] S1: The catalyst was heated to 300°C in a nitrogen flow for 1 hour to remove light hydrocarbons. The nitrogen flow rate was 1000 Nm 3 / h, nitrogen flow rate is 10m / s.

[0114] S2: The catalyst is heated to 600°C in a mixed flow of oxygen and nitrogen for 2 hours for oxidative incineration. The oxygen flow rate is 500Nm 3 / h, nitrogen flow rate is 500Nm 3 / h, the mixing ratio of oxygen and nitrogen is 1:1.

[0115] S3: The catalyst is then heated to 800°C in a high-temperature steam atmosphere for 2 hours to completely remove carbon deposits and restore the pore structure. The steam flow rate is 350Nm 3 / h, the steam quality fraction is 100%.

[0116] S4: After the catalyst is cooled to room temperature, hydrogen is used for activation to restore acidity. The hydrogen flow rate is 250Nm 3 / h, the temperature is 550℃ and the duration is 2 hours.

[0117] S5: Carry out catalytic cracking reaction and carry out mid-process regeneration at an appropriate time according to the activity of the catalyst.

[0118] Example 5: Low temperature pretreatment and high temperature oxidation incineration regeneration

[0119] This embodiment combines low-temperature pretreatment with high-temperature oxidation incineration to effectively remove light hydrocarbons and carbon deposits on the catalyst and optimize its regeneration effect. The specific operation is as follows:

[0120] S1: The catalyst was heated to 270°C in a nitrogen flow for 1 hour to remove light hydrocarbon molecules. The nitrogen flow rate was 1000 Nm 3 / h.

[0121] S2: The catalyst is heated to 650°C in a mixed flow of oxygen and nitrogen for 3 hours for oxidation and incineration to completely remove carbon deposits. The oxygen flow rate is 450Nm 3 / h, nitrogen flow rate is 550Nm 3 / h, the mixing ratio of oxygen and nitrogen is 1:1.

[0122] S3: The catalyst was heated to 700 °C in a steam atmosphere for 2 hours to restore the pore structure. The steam flow rate was 300 Nm 3 / h, the steam quality fraction is 100%.

[0123] S4: After the catalyst is cooled to room temperature, hydrogen is used for activation treatment to restore the acid sites of the catalyst. The hydrogen flow rate is 250Nm 3 / h, the temperature is 500℃ and the duration is 2 hours.

[0124] S5: Put the regenerated catalyst into the cracking reactor, monitor the activity of the catalyst in real time, and perform mid-process regeneration at an appropriate time.

[0125] Test experiment 1:

[0126] Purpose: To compare the catalyst regeneration effects in different embodiments and verify the effects of various treatment processes on catalyst activity recovery, carbon deposit removal and catalytic performance recovery.

[0127] Experimental setup:

[0128] Experimental Materials:

[0129] ZMQ-1 molecular sieve catalyst was used and the used catalyst samples were used as experimental objects.

[0130] The synergistic additives included aluminum fluoride (Al F3) and molybdenum-based compounds (MoO3), which were added in different proportions in the experiments.

[0131] Required gases include nitrogen (N2), oxygen (O2), steam (H2O steam) and hydrogen (H2).

[0132] Embodiment design:

[0133] Example 1 (standard regeneration process): no synergistic additive, conventional oxidative incineration and steam recovery.

[0134] Example 2 (synergistic additive regeneration process): addition of aluminum fluoride (3%) and molybdenum-based compounds (0.8%), conventional oxidative incineration and steam recovery.

[0135] Example 3 (Low-temperature regeneration process): Conventional oxidative incineration and low-temperature (500-550°C) steam recovery.

[0136] Example 4 (high temperature steam atmosphere regeneration process): high temperature (750-800°C) steam recovery is used without additives.

[0137] Example 5 (combined process of low-temperature pretreatment and high-temperature oxidative incineration): After low-temperature pretreatment (250-350°C), high-temperature (650-700°C) oxidative incineration is carried out.

[0138] Experimental equipment:

[0139] Catalytic cracking reactor: An experimental device used for catalytic cracking reactions.

[0140] Thermogravimetric Analyzer (TGA): used to determine the amount of carbon deposits on the catalyst.

[0141] X-ray photoelectron spectroscopy (XPS): Analyze the elemental composition of the catalyst surface.

[0142] Gas chromatograph: used to test the distribution of catalytic cracking products.

[0143] Experimental steps:

[0144] 1. Catalyst preparation:

[0145] The used ZMQ-1 molecular sieve catalyst was taken out from the catalytic cracking reactor.

[0146] The catalyst is initially cleaned to remove large particles from the surface.

[0147] 2. Preprocessing:

[0148] The catalyst is placed in a nitrogen stream and heated at 250-350°C for 1-1.5 hours to remove light hydrocarbon molecules. This step prevents the catalyst from being contaminated and helps expose more active surfaces.

[0149] 3. Oxidation incineration:

[0150] The catalyst is heated to 500-650°C in an atmosphere of a mixed flow of oxygen and nitrogen for 2-3 hours to remove carbon deposits on the catalyst surface.

[0151] The oxygen flow rate should be maintained at 50-100L / h to ensure complete combustion of carbon on the catalyst surface.

[0152] 4. Steam atmosphere recovery:

[0153] The oxidatively incinerated catalyst is placed in a steam atmosphere and heated to 650-750°C for 1.5-2 hours. This process helps to restore the pore structure of the catalyst.

[0154] The steam flow rate used is 50-100L / h, and the humidity of the steam is controlled at 90%-100%.

[0155] 5. Catalyst characterization:

[0156] After each round of catalytic cracking reaction, the catalyst was subjected to thermogravimetric analysis (TGA) to monitor the removal of carbon deposits.

[0157] X-ray photoelectron spectroscopy (XPS) was used to test the changes in elements on the catalyst surface and confirm the recovery of active sites on the catalyst surface.

[0158] 6. Catalytic cracking reaction:

[0159] In the catalytic cracking reaction, the activity of each group of catalysts is evaluated by indicators such as conversion rate and product distribution. The main focus is on the conversion rate of the cracking reaction and the selectivity of light hydrocarbon products.

[0160] 7. Mid-cycle regeneration and activity monitoring:

[0161] After a certain period of reaction, the catalyst is regenerated according to the change in activity to ensure that the activity of the catalyst is maintained in each round of reaction.

[0162] The experimental results are shown in the following table:

[0163]

[0164] The following conclusions can be drawn from the experimental results:

[0165] 1. The role of synergistic additives:

[0166] In Example 2, the synergistic additives of aluminum fluoride (3%) and molybdenum-based compounds (0.8%) were added, showing obvious advantages. The carbon deposit removal rate (92.3%) and catalytic activity recovery rate (84.5%) were higher than all other control examples. This shows that the addition of aluminum fluoride and molybdenum-based compounds plays an important role in improving the carbon deposit removal efficiency of the catalyst and restoring the catalytic activity. The addition of aluminum fluoride helps to improve the stability of the acidic sites of the catalyst and reduce the formation of carbon deposits during the cracking process, while the molybdenum-based compounds can promote the formation of metal oxides on the catalyst surface under high temperature conditions, further enhancing the catalyst's ability to resist carbon deposits.

[0167] Through XPS analysis, the acid site recovery rate of Example 2 is 80.5%, which is much higher than that of other examples, especially Example 3 and Example 1. This shows that the synergistic additive effectively improves the recovery of active sites on the catalyst surface and enhances the catalytic performance of the catalyst in the cracking reaction.

[0168] 2. The role of high temperature steam atmosphere regeneration process:

[0169] Example 4 uses a high-temperature steam atmosphere (750-800°C) to regenerate the catalyst, and the carbon deposit removal rate is 90.2%, which shows an improvement compared to the standard regeneration process (85.5%). However, the catalytic activity recovery rate is only 80.2%, which is significantly lower than that of Example 2, and the acid site recovery rate is 74.7%. This result shows that although the high-temperature steam atmosphere can effectively remove carbon deposits on the surface of the catalyst, the single steam atmosphere cannot effectively restore the active sites and pore structure of the catalyst. Therefore, although the high-temperature steam atmosphere regeneration method is helpful for the removal of carbon deposits, it cannot completely restore the acid sites and pore characteristics of the catalyst, and the catalytic performance is difficult to reach the optimal state.

[0170] 3. Disadvantages of low temperature regeneration process:

[0171] Example 3 uses a low-temperature (500-550°C) regeneration process, and the carbon deposit removal rate is 76.3%, the lowest among all the examples. This shows that under low-temperature regeneration conditions, the removal efficiency of carbon deposits on the catalyst surface is poor. Although low-temperature regeneration may cause less damage to the catalyst surface structure, due to the low temperature, the removal effect of carbon deposits is limited, resulting in a catalyst activity recovery rate of only 72.4%. This result further confirms that low-temperature regeneration is insufficient to restore catalyst activity, and the effect of removing carbon deposits is not as good as other high-temperature treatment processes.

[0172] 4. The role of the combined process of low-temperature pretreatment and high-temperature oxidation incineration:

[0173] Example 5 uses a low-temperature pretreatment (250-350°C) combined with a high-temperature oxidation incineration (650-700°C) process, with a catalyst carbon deposit removal rate of 88.7% and an acid site recovery rate of 72.8%. Although this process has improved in terms of carbon deposit removal and catalytic activity recovery, the effect is still insufficient compared to Example 2. Experiments show that low-temperature pretreatment helps to remove light hydrocarbon molecules, but cannot completely remove heavy carbon deposits on the catalyst surface. Although the high-temperature oxidation incineration process can remove most of the carbon deposits, it does not have a significant regeneration effect of the synergistic additive in terms of acid site recovery. Therefore, although this combined process can restore part of the activity of the catalyst, it fails to achieve the effect of the synergistic additive regeneration process in the present invention.

[0174] 5. Comparative analysis of standard regeneration processes:

[0175] Example 1 is a standard comparative experiment, and the conventional oxidation incineration (500-650°C) and steam recovery (650-750°C) methods are used to regenerate the catalyst. The carbon removal rate is 85.5%, and the catalytic activity recovery rate is 78.9%, showing a medium effect. This result shows that although the standard regeneration process can achieve the regeneration of the catalyst, due to the lack of the synergistic additive, the recovery effect of the acid sites on the catalyst surface is poor, which limits the regeneration effect of the catalyst and the catalytic performance of the cracking reaction.

[0176] The combined use of these two synergistic additives can effectively improve the catalyst's carbon deposit removal rate, acid site recovery rate and catalytic activity recovery rate, so that the regenerated catalyst can maintain high catalytic performance and a long service life. Experimental data show that the synergistic additive not only improves the catalyst's carbon deposit removal efficiency, but also effectively restores the catalyst's surface acid sites and pore structure, which is the innovation of the present invention.

[0177] Compared with the traditional regeneration process, the synergistic additive regeneration process provided by the present invention significantly improves the regeneration effect of the catalyst, especially in the catalyst activity recovery and carbon deposit removal, showing more significant advantages. Therefore, the regeneration process of the present invention has a high practical application value, especially in the field of catalytic cracking, and can significantly improve the regeneration efficiency and service life of the catalyst.

[0178] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for regenerating and recycling a ZMQ-1 molecular sieve catalytic cracking catalyst, characterized in that: The following steps are involved: 1) pre-treating the used ZMQ-1 molecular sieve catalyst by using a nitrogen flow at a temperature of 250-350° C. for 1-1.5 hours to remove light hydrocarbon molecules; 2) In an atmosphere of a mixed flow of oxygen and nitrogen, the catalyst is heated to 500-650°C for 2-3 hours for oxidation incineration to remove carbon deposits on the catalyst surface; 3) heating the oxidatively incinerated catalyst to 650-750°C in a steam atmosphere for 1.5-2 hours to further remove carbon deposits and restore the pore structure of the catalyst; 4) After cooling to room temperature, use hydrogen or ammonia to activate the catalyst to restore its acidity and surface activity; 5) The regenerated catalyst is put into a catalytic cracking reactor to carry out a catalytic cracking reaction, and the activity of the catalyst is monitored in real time during the catalytic cracking process and timely regeneration is carried out.

2. The regeneration and recycling method of the ZMQ-1 molecular sieve catalytic cracking catalyst according to claim 1, characterized in that: The oxygen concentration in the mixed air flow of oxygen and nitrogen is 20%-30%, and the mixed air flow velocity is 30-50NL / h.

3. The regeneration and recycling method of the ZMQ-1 molecular sieve catalytic cracking catalyst according to claim 1, characterized in that: The flow rate of the steam is 10-30 NL / h.

4. The regeneration and recycling method of the ZMQ-1 molecular sieve catalytic cracking catalyst according to claim 1, characterized in that: The nitrogen flow rate used in the pretreatment process is 50-120 NL / h, and the heating rate is 5°C / min to 10°C / min.

5. The regeneration and recycling method of the ZMQ-1 molecular sieve catalytic cracking catalyst according to claim 1, characterized in that: The flow rate of the hydrogen or ammonia is controlled at 10-20 NL / h, and the activation treatment time is 1 hour.

6. The regeneration and recycling method of the ZMQ-1 molecular sieve catalytic cracking catalyst according to claim 1, characterized in that: The temperature in the catalytic cracking reactor is controlled between 450-550° C., and the duration of the catalytic cracking reaction is 8-12 hours.

7. The method for regenerating and recycling the ZMQ-1 molecular sieve catalytic cracking catalyst according to claim 1, characterized in that: The regeneration process uses synergistic additives, which include aluminum fluoride and molybdenum-based compounds. The amount of aluminum fluoride added is 1%-4% of the total amount of the catalyst, and the amount of the molybdenum-based compound added is 0.5%-1% of the total amount of the catalyst.

8. The method for regenerating and recycling the ZMQ-1 molecular sieve catalytic cracking catalyst according to claim 1, characterized in that: During the recycling process of the catalyst, when the catalyst activity drops below 80%, midway regeneration is performed to restore the catalyst activity.

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