A method and system for determining the activity of a catalytic cracking gasoline desulfurization adsorbent

Abstract

The invention discloses an activity determination method and a system for a catalytic cracking gasoline desulfurization adsorbent. The method takes a combined process of distillation and heavy gasoline adsorption desulfurization as the technical basis for a desulfurization test, directly determines the sulfur content and active weight change in gasoline as reference indicators, constructs a regeneration activity determination model corresponding to the current moment to calculate the adsorption desulfurization activity index of the desulfurization adsorbent at the next moment to characterize the reaction performance of the adsorption desulfurization, and can overcome the problems of the existing activity determination method being time-consuming and unable to timely obtain the real-time reaction state in the adsorption desulfurization system, is conducive to the real-time control system to optimize the regeneration conditions of the desulfurization adsorbent, avoids the change of the phase structure of the adsorbent during the regeneration process and causes the decrease of the adsorption desulfurization performance, and effectively improves the desulfurization stability, desulfurization effect, single-pass operation life of the adsorbent and the reuse effect of the regenerated adsorbent.

Description

Technical Field

[0001] The invention relates to the technical field of adsorption removal of trace sulfur in gasoline, and in particular to an activity determination method and a system for a catalytic cracking gasoline desulfurization adsorbent. Background Art

[0002] At present, the quality standards of automotive gasoline tend to develop in the direction of ultra-low sulfur, low olefins, and low aromatics. The production of low-sulfur or even sulfur-free gasoline has become a top priority for gasoline quality upgrades, and it has also become a severe challenge for refining companies to produce clean oil products. Adsorption desulfurization technology has the advantages of mild operating conditions, low production costs, good desulfurization effects, and the desulfurization process will not cause olefin hydrogenation saturation and cause a decrease in gasoline octane number.

[0003] Based on the selective hydrodesulfurization technology, the sulfur content in gasoline can be reduced to below 10μg / g by combining adsorbent with fixed bed process, achieving the purpose of deep desulfurization. The effect of fixed bed catalytic cracking gasoline adsorption desulfurization process is mainly based on the regeneration and optimization performance of the adsorbent. It needs to have high performance requirements such as stable sulfur capacity, long operation cycle, and small gasoline octane number loss, and at the same time, the regeneration conditions of the reaction adsorbent should be balanced and optimized. In order to ensure the deep desulfurization effect of adsorption desulfurization technology, it is necessary to measure the reaction performance of the adsorbent. However, the determination method of sample analysis and detection is generally time-consuming. The reaction time and evaluation cycle of adsorbent activity analysis using known raw materials are too long, and the real-time reaction state cannot be obtained in the adsorption desulfurization system in time, resulting in result errors that directly affect the desulfurization performance of the adsorbent. Therefore, a more accurate and feasible adsorbent activity determination method is urgently needed to optimize the regeneration conditions of the reaction adsorbent in real time to avoid the change of the phase structure of the adsorbent during the regeneration process and cause the decrease of adsorption desulfurization performance. Summary of the invention

[0004] In view of the limitations of the existing methods mentioned above, the purpose of the present invention is to provide a method and system for determining the activity of a catalytic cracking gasoline desulfurization adsorbent, which uses a combined process of distillation and heavy gasoline adsorption desulfurization as the technical basis for the desulfurization test, is used to remove trace sulfur in catalytic cracking gasoline, and uses the sulfur content and active weight change in gasoline as reference indicators. A regeneration activity determination model is established to calculate the adsorption desulfurization activity index of the desulfurization adsorbent to characterize the reaction performance of the adsorption desulfurization, and it is expected to develop a complete set of application technologies that meet the National VI gasoline quality standards, providing technical reserves and application value for the low-cost production of National VI gasoline from petroleum.

[0005] Motor gasoline is blended from catalytic cracking (FCC) gasoline, catalytic reforming gasoline, alkylation gasoline, isomerization gasoline and straight-run gasoline in different proportions. Due to the high sulfur and olefin content in catalytic cracking gasoline, 85-95% of the sulfides in my country's finished gasoline come from catalytic cracking gasoline. After the sulfides in finished gasoline are burned, the sulfur oxides generated are the main pollutants in the atmosphere. Reducing the sulfur content in catalytic cracking gasoline and developing gasoline desulfurization technology that meets gasoline quality standards are the most effective ways to reduce environmental pollution and improve oil quality.

[0006] Most of the existing production of clean motor gasoline uses catalytic hydrodesulfurization technology, which can reduce the sulfur content in catalytic cracking gasoline to below 50μg / g. This technology saturates some olefins in gasoline while reducing the sulfur content in gasoline. Since olefins contribute greatly to the octane number of gasoline, it causes an increase in the loss of gasoline octane number and greatly increases the refining production cost. At the same time, it is difficult to completely remove benzothiophene sulfides in gasoline. The adsorption desulfurization technology has low production costs, good desulfurization effects, and will not cause olefin hydrogenation saturation and cause a decrease in gasoline octane number during the desulfurization process. However, it still needs to be further improved and perfected in terms of desulfurization activity regeneration, adsorption selectivity, and service life.

[0007] The preliminary experimental research of this application is based on selective hydrodesulfurization, using a combination of adsorbent and fixed bed process, using catalytic cracking gasoline with sulfur content that meets the National IV standard as raw material, and conducting research on the adsorption and removal of trace sulfur in catalytic cracking gasoline by adsorbent. The results show that the modified Y molecular sieve has good adsorption and desulfurization performance and excellent regeneration performance, and can effectively remove sulfides in catalytic cracking gasoline to achieve the purpose of deep desulfurization. The octane number loss of gasoline after desulfurization is small, which meets the National V clean gasoline quality standard.

[0008] Furthermore, in order to develop a complete set of technical processes that meet the National VI gasoline quality standards and apply them, the research team of this application proposed a combined process of distillation and heavy gasoline adsorption desulfurization to achieve deep desulfurization while reducing production costs and obtaining higher application value. However, in order to achieve the deep desulfurization standards of high desulfurization accuracy (sulfur content reduced to below 10μg / g) and low gasoline octane loss (octane loss less than 0.5 units), how to accurately determine the optimal distillation temperature for light gasoline 3 with a sulfur content of less than 10μg / g and the optimal operating conditions for gasoline fractionation and continuous distillation production, and further optimize the operating conditions of the fixed bed adsorption desulfurization process and the regeneration conditions of the reaction adsorbent, are technical research difficulties that need to be solved urgently.

[0009] In order to give full play to the best desulfurization performance of the reactive adsorbent, the reduction and regeneration process conditions of the adsorbent need to be further optimized to meet the requirements of industrial application. Optimizing the regeneration conditions of the reactive adsorbent can avoid the change of the phase structure of the adsorbent during the regeneration process, which may cause the desulfurization performance to decrease, and make the adsorbent have excellent regeneration cycle performance.

[0010] The desulfurization adsorbent mainly plays the role of sulfur reaction and storage. The sulfur in hydrocarbon oil is stored on the adsorbent through reaction, and then the sulfur stored in the adsorbent is removed through regeneration reaction to restore the desulfurization activity of the adsorbent. Studies have found that when the adsorbent cannot meet the process conditions for a long time during the reaction process, the active components with desulfurization activity on the adsorbent will react with the aluminum source and silicon source in the carrier, and cannot be converted into active components again during the regeneration process, causing the adsorbent activity to continue to decline, shortening its service life, and making it difficult to achieve the recycling of the adsorbent.

[0011] In order to characterize the regeneration activity of the desulfurization adsorbent, the current experimental research mainly uses XRD spectra to characterize the crystal structure of the adsorbent before and after regeneration, uses pressure pump detection to analyze the changes in the specific surface area, pore volume and pore size of the adsorbent, or uses EDS spectrometer to analyze the content ratio of each element in the fresh, deactivated and regenerated adsorbent to indirectly reflect the desulfurization activity and regeneration performance of the adsorbent. However, the research method cannot directly analyze in real time after sampling, and the analysis and determination of the active component content of the adsorbent is slow and the cycle is long. Most of the existing methods for determining sulfur capacity or desulfurization activity use hydrogen sulfide gas of known concentration as the sulfidation medium to calculate the penetration sulfur capacity of the desulfurizer, or use catalytic gasoline with known sulfur content as raw material, and analyze the activity of the adsorbent by analyzing the desulfurization rate of the product at different time periods. However, the net reaction time and evaluation cycle are too long, and it is still impossible to achieve real-time measurement and regulation on the complete production line, making it difficult to achieve industrial application.

[0012] In order to solve the above technical problems and achieve the purpose, according to one aspect of the present disclosure, the present application proposes a method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent, the method specifically comprising the following steps:

[0013] S100, determining the residual activity weight m of the active component in the adsorbent to be removed corresponding to the current time t res ;

[0014] S200, mixing the adsorbent to be removed with a reducing gas for reduction treatment to obtain a reduced adsorbent, and determining the reduced sulfur content S of the reduced adsorbent at the current time t Red (t);

[0015] S300, mixing the adsorbent to be removed with the regeneration gas for regeneration treatment to obtain a regenerated adsorbent, and determining the weight M of the regenerated adsorbent generated at the current time trePro (t);

[0016] S400, subjecting the reducing adsorbent and the sulfide-containing gasoline raw material to hydrodesulfurization adsorption treatment, and determining the weight M of the desulfurized liquid phase product generated at the current time t Pro (t) and the actual sulfur content S in the gasoline feedstock Pro (t);

[0017] S500, according to the residual active weight m res and the reduced sulfur content S Red (t), calculate the remaining sulfur content S of the reducing adsorbent corresponding to the next moment (t+1) after step S400 Ads (t+1), the calculation formula is: ; Wherein, N(S) is the relative atomic mass of sulfur, N(Act) is the relative molecular mass of the active component in the adsorbent to be removed, and n is the atomic ratio of non-sulfur elements to sulfur elements in the active component;

[0018] S600, according to the weight M of the desulfurized liquid phase product corresponding to the current time t Pro (t) and the regenerated adsorbent weight M rePro (t), combined with the actual sulfur content S Pro (t) and the residual sulfur content S Ads (t+1), a regeneration activity determination model is established within a certain catalytic reaction time period, and the adsorption desulfurization activity index δ corresponding to the adsorbent to be removed at the next time (t+1) is calculated. Act (t+1).

[0019] Further, in step S100, the method described in the present application uses one of X-ray diffraction, X-ray fluorescence spectroscopy or inductively coupled plasma spectroscopy to determine the residual active weight m of the active component in the adsorbent to be removed at the current time t res .

[0020] Furthermore, the method described in the present application adopts one of the oxygen bomb method, the coulometric method, the microcoulometry method, the ultraviolet fluorescence method, the electrical detection method or the infrared absorption method to measure the sulfur content. In step S200, the reduced sulfur content S in the reduced adsorbent at the current time t is calculated based on the weight of the reduced adsorbent and the sulfur element. Red (t); or, in step S400, the actual sulfur content S in the gasoline raw material at the current time t is calculated based on the weight of the sulfide-containing gasoline raw material and the sulfur element. Pro (t).

[0021] Furthermore, in step S400, the reducing adsorbent and the sulfide-containing gasoline feedstock are subjected to hydrodesulfurization adsorption treatment, and the hydrodesulfurization adsorption treatment method comprises: under the hydrogen state, the active components in the reducing adsorbent convert the sulfide in the gasoline feedstock into sulfur-containing intermediates, and the sulfide-containing gasoline feedstock is desulfurized and converted into a desulfurized liquid product.

[0022] Further, in step S600, according to the weight M of the desulfurized liquid product corresponding to the current time t Pro (t) and the regenerated adsorbent weight M rePro (t), combined with the actual sulfur content S Pro (t) and the residual sulfur content S Ads (t+1), a regeneration activity determination model is established within a certain catalytic reaction time period, and the adsorption desulfurization activity index δ corresponding to the adsorbent to be removed at the next time (t+1) is calculated. Act The specific method of (t+1) is:

[0023] S601, inputting the weight M of the desulfurized liquid phase product corresponding to the current time t within a certain catalytic reaction time period Pro (t) and the regenerated adsorbent weight M rePro (t), establish a regeneration activity determination model, and output the unit regeneration activity capacity Cap corresponding to the adsorbent to be removed at the next time (t+1) unit (t+1), its dimensionless calculation formula is:

[0024]

[0025]

[0026]

[0027] Wherein, assuming that the catalytic reaction cycle of the adsorbent to be removed is T, the certain catalytic reaction time period starts from the previous catalytic reaction cycle (t-T+1) at the next moment (t+1) and calculates the unit regeneration activity capacity Cap corresponding to the next moment (t+1) unit (t+1), meanD(t) is the average capacity of regeneration activity corresponding to the current time t calculated from the previous catalytic reaction cycle (tT) at the current time t, meanD(i) is the average capacity of regeneration activity corresponding to time i; Desulf(t+1) is the real-time capacity of regeneration activity corresponding to the adsorbent to be removed at the next time (t+1), Desulf(i) is the real-time capacity of regeneration activity corresponding to time i, and i is a variable;

[0028] S602, according to the unit regeneration activity capacity Cap corresponding to the adsorbent to be removed at the next time (t+1), unit (t+1), calculate the adsorption desulfurization activity index δ corresponding to the adsorbent to be removed at the next time (t+1) Act (t+1), its dimensionless calculation formula is:

[0029]

[0030] Among them, the adsorption desulfurization activity index δ Act (t+1) is used to characterize the regeneration rate of the adsorbent to be removed at the next moment (t+1).

[0031] Furthermore, after step S600, the method further comprises: according to the adsorption desulfurization activity index δ corresponding to the next moment (t+1), Act (t+1) Determine whether it is lower than the desulfurization threshold. If so, control step S200 to input reducing gas for reduction treatment, and control step S300 to stop inputting regeneration gas.

[0032] Furthermore, the reducing gas includes hydrogen, and the regenerating gas includes nitrogen and oxygen.

[0033] Furthermore, the present application also proposes an activity measurement system for a catalytic cracking gasoline desulfurization adsorbent, characterized in that it comprises at least: a processor, a memory, a data acquisition module and a control module, wherein the data acquisition module comprises a detection sensor, a chemical measuring instrument and a wireless transmission unit, and is used for data sampling to obtain the residual activity weight, desulfurized liquid product weight, reduced sulfur content and actual sulfur content corresponding to the system at the current moment, and store them in the memory; the wireless transmission unit is used for wireless communication connection, and transmits the data in the memory to the processor in real time for modeling operation, obtains a regeneration activity measurement model, calculates and outputs the adsorption desulfurization activity index corresponding to the next moment, and transmits it synchronously to the control module of the system;

[0034] The processor executes the computer program to run in the following units of the system:

[0035] The active component weight collection unit is used to collect in real time the residual active weight of the active component in the adsorbent to be removed corresponding to the current time t, as well as the weight of the regenerated adsorbent generated after the regeneration treatment and the weight of the desulfurized liquid product generated after the hydrodesulfurization adsorption treatment;

[0036] Sulfur content determination unit, used to collect the reduced sulfur content of the reduced adsorbent and the actual sulfur content in the gasoline raw material in real time;

[0037] A residual sulfur content calculation unit, used to calculate the residual sulfur content of the reducing adsorbent corresponding to the next moment according to the residual active weight and the reduced sulfur content corresponding to the current moment;

[0038] A regeneration activity determination model establishment unit is used to establish a regeneration activity determination model within a certain catalytic reaction time period according to the weight of the desulfurization liquid phase product and the weight of the regenerated adsorbent corresponding to the current moment, combined with the actual sulfur content and the residual sulfur content, to calculate the adsorption desulfurization activity index corresponding to the adsorbent to be removed at the next moment;

[0039] The regeneration reduction reaction control unit is used to determine whether the adsorption desulfurization activity index corresponding to the next moment is lower than the desulfurization threshold. If so, the control module responds, the control system inputs reducing gas for reduction treatment, and the control system stops inputting regeneration gas.

[0040] As described above, the activity determination method and system of a catalytic cracking gasoline desulfurization adsorbent described in the present invention have at least the following beneficial effects: (1) The combined process of catalytic cracking gasoline distillation and heavy gasoline adsorption desulfurization is simpler than the conventional process, reduces costs and effectively removes sulfides in catalytic cracking gasoline, reducing the sulfur content to below 10 μg / g, thereby achieving the purpose of deep desulfurization; (2) By directly measuring the activity weight of the desulfurization adsorbent before the reduction reaction and the sulfur content of the reaction product generated after the regeneration-reduction reaction, the reaction parameters of the regeneration-reduction reaction and the desulfurization adsorption reaction at the current moment are collected in real time to construct a regeneration activity determination model, which can overcome the problems of the existing activity determination method being time-consuming and unable to obtain the real-time reaction status in the adsorption desulfurization system in a timely manner, and is conducive to the real-time control system to optimize the regeneration conditions of the desulfurization adsorbent, and avoid the change of the phase structure of the adsorbent during the regeneration process. The desulfurization performance of the adsorbent is reduced, and the desulfurization stability, desulfurization effect, single-pass operation life and reuse effect of the regenerated adsorbent are effectively improved; (3) The regeneration activity measurement model is used to calculate the adsorption desulfurization activity index of the adsorbent to be removed at the next moment within a certain catalytic reaction time period, without the need to repeatedly measure the relative activity of the fresh adsorbent in the same catalytic reaction, thereby simplifying and systematizing the measurement and analysis process; (4) The reaction delay error and measurement error existing in the relative activity measurement of the adsorbent to be tested and the fresh adsorbent are effectively reduced, which is conducive to accurately determining the optimal distillation temperature for light gasoline 3 with a sulfur content of less than 10μg / g and the optimal operating conditions for gasoline fractionation and continuous distillation production, and is helpful to realize real-time measurement and online regulation of the regeneration conditions of the desulfurization adsorbent on the complete production line, so as to achieve a dynamic balance between the optimal adsorption desulfurization process conditions and the adsorbent regeneration cycle performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] The above and other features of the present disclosure will become more apparent by describing in detail the embodiments shown in the accompanying drawings. The same reference numerals in the accompanying drawings of the present disclosure represent the same or similar elements. Obviously, the accompanying drawings described below are only some embodiments of the present disclosure. For those skilled in the art, other accompanying drawings can be obtained based on these accompanying drawings without creative work. In the accompanying drawings:

[0042] Figure 1 Shown is a flow chart of a method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent in one embodiment;

[0043] Figure 2 The figure shows a structural block diagram of an activity measurement system of a catalytic cracking gasoline desulfurization adsorbent in one embodiment;

[0044] Figure 3 The figure is a schematic process block diagram of a method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent in one embodiment;

[0045] Figure 4 The figure shows a method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent and a schematic diagram of product quality indicators of the desulfurization adsorbent in one embodiment;

[0046] Figure 5 The figure shows a combined process flow diagram of a method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent in one embodiment;

[0047] Figure 6 The figure shows a schematic diagram of the combined system modules of a method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent in one embodiment;

[0048] Figure 7 The figure shows a comparison of the test results of the desulfurization performance of an adsorbent in an activity measurement system for a catalytic cracking gasoline desulfurization adsorbent in one embodiment;

[0049] Figure 8 The figure shows a comparison chart of adsorption desulfurization activity indexes of multiple regeneration-reduction tests of a reactive adsorbent in an activity measurement system for a catalytic cracking gasoline desulfurization adsorbent in one embodiment;

[0050] Fig. 9 The figure shows a comparison chart of the sulfur content of products of a catalytic cracking gasoline desulfurization adsorbent activity determination method in one embodiment of a reaction adsorbent multiple regeneration-reduction test;

[0051] Fig.10 The figure shows a comparison of desulfurization rates of multiple regeneration-reduction tests of a reactive adsorbent in one embodiment of a method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent.

[0052] Among them, the numbers are respectively represented as follows: 1, FCC gasoline; 2, distillation fractionation tower; 3, light gasoline; 4, heavy gasoline; 5, preheater; 6, first fixed bed reactor; 7, physical adsorption desulfurization product; 8, first high-pressure separator; 9, tail gas; 10, liquid product after first separation; 11, heating furnace; 12, second fixed bed reactor; 13, second high-pressure separator; 14, tail gas; 15, liquid product after second separation; 16, hydrogen; 17, regeneration gas. DETAILED DESCRIPTION

[0053] The following will be combined with the embodiments and drawings to clearly and completely describe the concept, specific structure and technical effects of the present disclosure, so as to fully understand the purpose, scheme and effect of the present disclosure. It should be noted that the embodiments and features in the embodiments of the present application can be combined with each other without conflict.

[0054] like Figure 1 The flowchart of the method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent described in the present application is shown below. Figure 1 A method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent according to an embodiment of the present disclosure is described below.

[0055] The present disclosure provides a method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent, the method specifically comprising the following steps:

[0056] S100, determining the residual activity weight m of the active component in the adsorbent to be removed corresponding to the current time t res ;

[0057] S200, mixing the adsorbent to be removed with a reducing gas for reduction treatment to obtain a reduced adsorbent, and determining the reduced sulfur content S of the reduced adsorbent at the current time t Red (t);

[0058] S300, the adsorbent to be removed is mixed with the regeneration gas 17 for regeneration treatment to obtain a regenerated adsorbent, and the weight M of the regenerated adsorbent generated at the current time t is determined. rePro (t);

[0059] S400, subjecting the reducing adsorbent and the sulfide-containing gasoline raw material to hydrodesulfurization adsorption treatment, and determining the weight M of the desulfurized liquid phase product generated at the current time t Pro (t) and the actual sulfur content S in the gasoline feedstock Pro (t);

[0060] S500, according to the residual active weight m res and the reduced sulfur content S Red(t), calculate the remaining sulfur content S of the reducing adsorbent corresponding to the next moment (t+1) after step S400 Ads (t+1), the calculation formula is: ; Wherein, N(S) is the relative atomic mass of sulfur, N(Act) is the relative molecular mass of the active component in the adsorbent to be removed, and n is the atomic ratio of non-sulfur elements to sulfur elements in the active component;

[0061] S600, according to the weight M of the desulfurized liquid phase product corresponding to the current time t Pro (t) and the regenerated adsorbent weight M rePro (t), combined with the actual sulfur content S Pro (t) and the residual sulfur content S Ads (t+1), a regeneration activity determination model is established within a certain catalytic reaction time period, and the adsorption desulfurization activity index δ corresponding to the adsorbent to be removed at the next time (t+1) is calculated. Act (t+1).

[0062] Catalytic gasoline adsorption desulfurization technology is based on the principle of adsorption conversion. It has essential differences in the removal of different sulfur compounds and the hydrogenation process. The removed sulfur can be directly fixed on the adsorbent, so that the sulfur in gasoline is effectively removed. The adsorbent desulfurization mechanism is completely different from the effect of the hydrogenation catalyst, which can overcome the technical difficulty of hydrogenation adsorption desulfurization technology in removing sulfur-containing compounds during the hydrogenation process. In addition, the olefin saturation in the adsorbent desulfurization process is less, and there is no H in the reaction product. 2 S formation, mild hydrogenation conditions and non-hydrogenation adsorbents avoid H 2 S reacts with olefins to form mercaptans, the octane number loss of desulfurized gasoline is small, and it is easier to obtain low-sulfur gasoline products.

[0063] The researchers of this application are specialized in the optimization technology research of removing trace sulfur by adsorption from catalytic cracking gasoline. In the previous research, they have carried out research on adsorbent preparation process, adsorbent tonnage scale-up preparation, catalytic gasoline fixed bed adsorption desulfurization process research, adsorbent long-cycle life investigation, and adsorbent in-device regeneration research, and obtained corresponding laboratory research results. Through the preparation and modification research of adsorbent, adsorption desulfurization reaction process and adsorbent regeneration process research, it is found that the adsorbent has good desulfurization performance and excellent regeneration performance. The adsorbent combined with fixed bed process can effectively remove sulfides in FCC gasoline 1 to achieve the purpose of deep desulfurization, and the octane number loss of gasoline after desulfurization is small, which meets the National V clean gasoline quality standard. However, the research difficulties based on adsorption desulfurization technology are mainly to develop new adsorbents with larger adsorption capacity, higher desulfurization activity, better adsorption selectivity, longer service life, and easier regeneration, as well as to develop optimized adsorption desulfurization process or combined process.

[0064] Therefore, this application improves and optimizes the original gasoline fixed-bed adsorption desulfurization process for producing National V gasoline quality standards, and proposes a combined process of distillation and heavy gasoline adsorption desulfurization to develop a complete set of application technologies that meet the National VI gasoline quality standards, providing technical reserves and application value for the low-cost production of National VI gasoline from petroleum.

[0065] In some embodiments, the present application proposes an activity measurement system for a catalytic cracking gasoline desulfurization adsorbent, comprising at least the following devices:

[0066] The distillation device is used for the distillation test of FCC gasoline 1. The FCC gasoline 1 with sulfur content meeting the National IV standard is used as raw material. The test determines the optimal fractionation temperature for the sulfur content of light gasoline 3 less than 10μg / g and the optimal operating conditions for gasoline fractionation and continuous distillation;

[0067] The fixed bed pilot reactor is used to test the optimal process conditions for fixed bed adsorption desulfurization.

[0068] In some embodiments, a stability test of single-cycle desulfurization of the adsorbent is completed on a fixed-bed pilot plant, and the regeneration process conditions of the reaction adsorbent are determined based on the activity determination method of the catalytic cracking gasoline desulfurization adsorbent. The test results are further verified, and the results of the desulfurization effect of repeated regeneration and recycling of the adsorbent and the service life of the adsorbent are analyzed.

[0069] Specifically, in a specific embodiment of the present application, on a fixed bed device with a scale of 200mL / h, the process conditions for the adsorption desulfurization of heavy gasoline are determined by a fixed bed adsorption desulfurization experiment, so that its sulfur content is reduced to below 10μg / g, deep desulfurization is achieved, and the octane number loss of gasoline after desulfurization is minimized; on a fixed bed device with a scale of 1L / h, a pilot study on the combined process of gasoline distillation and fixed bed adsorption desulfurization is carried out to test the influence of reaction conditions on the desulfurization efficiency of the adsorbent, including the influence of process conditions such as adsorption temperature, adsorption pressure, liquid air velocity on the sulfur content, octane number, etc. of gasoline, and based on the activity determination method of the catalytic cracking gasoline desulfurization adsorbent, the regeneration conditions of the desulfurization adsorbent are determined according to the real-time collection of the weight and sulfur content of the regeneration-reduction reaction product, including the regeneration temperature, regeneration oxygen concentration, regeneration air velocity and regeneration pressure, etc., to determine the optimal adsorption desulfurization process conditions, so as to achieve a significant reduction in gasoline sulfur content and octane number loss, and improve the desulfurization stability, desulfurization effect, single-pass operation life of the adsorbent and the reuse effect of the regenerated adsorbent.

[0070] Specifically, the schematic diagram of the combined process of gasoline distillation and fixed bed adsorption desulfurization is as follows: Figure 3As shown. Among them, using FCC gasoline 1 whose sulfur content meets the National V standard as raw material, the FCC gasoline 1 is first cut and fractionated by distillation to separate out light gasoline 3 with a sulfur content of less than 10μg / g, and then the fixed bed adsorption desulfurization technology is used to perform fixed bed adsorption desulfurization on the separated heavy gasoline to reduce its sulfur content to less than 10μg / g, and finally the light gasoline 3 and the heavy gasoline 4 after adsorption desulfurization are blended according to the original fractionation ratio to obtain blended gasoline that meets the National VI gasoline quality standard.

[0071] Among them, the activity determination method of the catalytic cracking gasoline desulfurization adsorbent uses a combined process of gasoline distillation and fixed bed adsorption desulfurization as the technical basis of the desulfurization test, which is used to remove trace sulfur in FCC gasoline 1. The sulfur content and active weight change in gasoline are used as reference indicators, and the adsorption desulfurization activity index of the desulfurization adsorbent is calculated to characterize the reaction performance of adsorption desulfurization.

[0072] Further, in step S100, the method described in the present application uses one of X-ray diffraction, X-ray fluorescence spectroscopy or inductively coupled plasma spectroscopy to determine the residual active weight m of the active component in the adsorbent to be removed at the current time t res .

[0073] Furthermore, the method described in the present application adopts one of the oxygen bomb method, the coulometric method, the microcoulometry method, the ultraviolet fluorescence method, the electrical detection method or the infrared absorption method to measure the sulfur content. In step S200, the reduced sulfur content S in the reduced adsorbent at the current time t is calculated based on the weight of the reduced adsorbent and the sulfur element. Red (t); or, in step S400, the actual sulfur content S in the gasoline raw material at the current time t is calculated based on the weight of the sulfide-containing gasoline raw material and the sulfur element. Pro (t).

[0074] Furthermore, in step S400, the reducing adsorbent and the sulfide-containing gasoline feedstock are subjected to hydrodesulfurization adsorption treatment, and the hydrodesulfurization adsorption treatment includes: under the hydrogen state, the active components in the reducing adsorbent convert the sulfide in the gasoline feedstock into sulfur-containing intermediates, and the sulfide-containing gasoline feedstock is desulfurized and converted into a desulfurized liquid product.

[0075] Specifically, in this specific embodiment, before step S100 of the method, a pretreatment step of physical adsorption desulfurization is also included: using FCC gasoline 1 after hydrodesulfurization as raw material, the FCC gasoline 1 is pumped to the distillation fractionation tower 2 in the distillation fractionation module by using the feed module for cutting and fractionation, and light gasoline 3 and heavy gasoline 4 are obtained by separation; further, the light gasoline 3 obtained by separation by the distillation fractionation module passes through the preheater 5 and enters the first fixed bed reactor 6 (physical adsorption desulfurization fixed bed reactor) for physical adsorption desulfurization in a non-hydrogen state; in step S400, the heavy gasoline 4 obtained by fractionation of the distillation fractionation module is mixed with hydrogen 16 by using the heavy gasoline adsorption desulfurization module, and then enters the second fixed bed reactor 12 (hydrogen adsorption desulfurization fixed bed reactor) for hydro adsorption desulfurization to obtain reaction products, including tail gas 14 and desulfurized liquid products.

[0076] Further, in step S500, according to the remaining active weight m res and the reduced sulfur content S Red (t), calculate the remaining sulfur content S of the reducing adsorbent corresponding to the next moment (t+1) after step S400 Ads (t+1), its dimensionless calculation formula is: ;

[0077] Wherein, N(S) is the relative atomic mass of sulfur, N(Act) is the relative molecular mass of the active component in the adsorbent to be removed, and n is the atomic ratio of non-sulfur elements to sulfur elements in the active component.

[0078] In some embodiments, in step S500, after the reducing adsorbent is subjected to hydrodesulfurization adsorption treatment at the current time t, a sulfurized adsorbent is obtained at the next time (t+1), and the active component of the reducing adsorbent corresponding to the current time t is converted into a sulfur-containing intermediate, such as Ni adsorbed and sulfurized to NiS or Ni 3 S 2 , ZnO is adsorbed and sulfurized to ZnS; wherein the sulfur content of the sulfur-containing intermediate in the sulfurized adsorbent is determined by calculating the sulfur element, which is the residual sulfur content S corresponding to the next moment (t+1) of the reduced adsorbent after step S400 Ads (t+1).

[0079] Further, in step S600, according to the weight M of the desulfurized liquid product corresponding to the current time t Pro (t) and the regenerated adsorbent weight M rePro (t), combined with the actual sulfur content S Pro (t) and the residual sulfur content S Ads(t+1), a regeneration activity determination model is established within a certain catalytic reaction time period, and the adsorption desulfurization activity index δ corresponding to the adsorbent to be removed at the next time (t+1) is calculated. Act The specific method of (t+1) is:

[0080] S601, inputting the weight M of the desulfurized liquid phase product corresponding to the current time t within a certain catalytic reaction time period Pro (t) and the regenerated adsorbent weight M rePro (t), establish a regeneration activity determination model, and output the unit regeneration activity capacity Cap corresponding to the adsorbent to be removed at the next time (t+1) unit (t+1), its dimensionless calculation formula is:

[0081]

[0082]

[0083]

[0084] Wherein, assuming that the catalytic reaction cycle of the adsorbent to be removed is T, the certain catalytic reaction time period starts from the previous catalytic reaction cycle (t-T+1) at the next moment (t+1) and calculates the unit regeneration activity capacity Cap corresponding to the next moment (t+1) unit (t+1), meanD(t) is the average capacity of regeneration activity corresponding to the current time t calculated from the previous catalytic reaction cycle (tT) at the current time t, meanD(i) is the average capacity of regeneration activity corresponding to time i; Desulf(t+1) is the real-time capacity of regeneration activity corresponding to the adsorbent to be removed at the next time (t+1), Desulf(i) is the real-time capacity of regeneration activity corresponding to time i, and i is a variable;

[0085] S602, according to the unit regeneration activity capacity Cap corresponding to the adsorbent to be removed at the next time (t+1), unit (t+1), calculate the adsorption desulfurization activity index δ corresponding to the adsorbent to be removed at the next time (t+1) Act (t+1), its dimensionless calculation formula is:

[0086]

[0087] Among them, the adsorption desulfurization activity index δ Act(t+1) is used to characterize the regeneration rate of the adsorbent to be removed at the next moment (t+1). Specifically, in order to optimize the process of deep desulfurization, the method establishes a regeneration activity measurement model through step S600, which is to measure the reaction activity of the desulfurization adsorbent in real time, calculate the unit regeneration activity capacity at the next moment according to the sulfidation parameters of the regeneration-reduction reaction at the current moment, and further calculate the adsorption desulfurization activity index at the next moment. Compared with the existing adsorbent activity measurement method, it greatly shortens the detection difficulty and activity measurement cycle, and does not need to repeatedly measure the relative activity of fresh adsorbents in the same catalytic reaction. The measurement and analysis process is simplified and systematized, which helps to realize real-time measurement and online regulation of the regeneration conditions of the desulfurization adsorbent on the complete production line, so as to achieve a dynamic balance between the optimal adsorption desulfurization process conditions and the adsorbent regeneration cycle performance.

[0088] Furthermore, after step S600, the method further comprises: according to the adsorption desulfurization activity index δ corresponding to the next moment (t+1), Act (t+1) Determine whether it is lower than the desulfurization threshold. If so, control step S200 to input reducing gas for reduction treatment, and control step S300 to stop inputting regeneration gas 17.

[0089] Furthermore, the reducing gas includes hydrogen 16, and the regenerating gas 17 includes nitrogen and oxygen.

[0090] Specifically, in this specific embodiment, the desulfurization threshold is a preset threshold. When the sulfur content of the reaction products generated in the catalytic reaction module and the heavy gasoline adsorption desulfurization module is lower than 10 μg / g, the corresponding measured adsorption desulfurization activity index average is calculated as the desulfurization threshold.

[0091] Furthermore, the structural block diagram of the activity measurement system of the catalytic cracking gasoline desulfurization adsorbent disclosed in the present invention is as follows: Figure 2 As shown, it at least includes: a processor, a memory, a data acquisition module and a control module;

[0092] The data acquisition module includes a detection sensor, a chemical measuring instrument and a wireless transmission unit, which are used for data sampling to obtain the residual activity weight, desulfurization liquid product weight, reduced sulfur content and actual sulfur content corresponding to the system at the current moment, and store them in the memory;

[0093] The wireless transmission unit is used for wireless communication connection, and transmits the data of the memory to the processor in real time for modeling operation, obtains the regeneration activity measurement model and calculates and outputs the adsorption desulfurization activity index corresponding to the next moment, and transmits it to the control module of the system synchronously;

[0094] The processor executes the computer program running in the following units of the system:

[0095] The active component weight collection unit is used to collect in real time the residual active weight of the active component in the adsorbent to be removed corresponding to the current time t, as well as the weight of the regenerated adsorbent generated after the regeneration treatment and the weight of the desulfurized liquid product generated after the hydrodesulfurization adsorption treatment;

[0096] Sulfur content determination unit, used to collect the reduced sulfur content of the reduced adsorbent and the actual sulfur content in the gasoline raw material in real time;

[0097] A residual sulfur content calculation unit, used to calculate the residual sulfur content of the reduced adsorbent at the next moment according to the residual active weight and the reduced sulfur content corresponding to the current moment;

[0098] The regeneration activity determination model establishment unit is used to establish a regeneration activity determination model within a certain catalytic reaction time period according to the weight of the desulfurization liquid phase product and the weight of the regenerated adsorbent corresponding to the current moment, combined with the actual sulfur content and the residual sulfur content, and calculate the adsorption desulfurization activity index corresponding to the adsorbent to be removed at the next moment;

[0099] The regeneration reduction reaction control unit is used to determine whether the adsorption desulfurization activity index corresponding to the next moment is lower than the desulfurization threshold. If so, the control module responds, the control system inputs reducing gas for reduction treatment, and the control system stops inputting regeneration gas 17.

[0100] In some embodiments, the activity determination system of the catalytic cracking gasoline desulfurization adsorbent includes a catalytic cracking gasoline distillation and fixed bed adsorption desulfurization combined system, and its process flow is as follows: Figure 5 As shown, using FCC gasoline 1 with sulfur content meeting the National IV standard (sulfur content not more than 50μg / g, olefin volume content not more than 28%) as raw material, a deep adsorption desulfurization experiment of FCC gasoline 1 was carried out in the distillation and heavy gasoline adsorption desulfurization combined system filled with desulfurization adsorbent. The combined system is mainly composed of a feed module, a distillation fractionation module, a feed preheating module, a catalytic reaction module, a regeneration-reduction module, a regeneration activity measurement module and a control module. The combined system module structure is shown in the figure below. Figure 6 As shown, the process of each module includes:

[0101] Feed module: FCC gasoline 1 is pumped from the feed tank to the distillation fractionation module using a feed pump;

[0102] Distillation fractionation module: FCC gasoline 1 is cut and fractionated through a rectification fractionation tower 2 to obtain light gasoline 3 and heavy gasoline 4 with a sulfur content of less than 10 μg / g;

[0103] Raw material preheating module: the light gasoline 3 obtained by the distillation fractionation module is transported to the first fixed bed reactor 6 for physical adsorption desulfurization in a non-hydrogen state after passing through the preheater 5 to obtain a physical adsorption desulfurization product 7. When the desulfurization rate of the light gasoline 3 reaches a critical value, the valve body is closed to stop transporting the light gasoline 3;

[0104] Catalytic reaction module: Open the pneumatic valve to input hydrogen 16 into the first fixed bed reactor 6, remove the sulfur element of the sulfide on the surface of the desulfurization adsorbent under the action of non-hydrogen adsorption, and the product output from the first fixed bed reactor 6 is separated by the first high-pressure separator 8 to output tail gas 9 and the first separated liquid product 10, wherein the tail gas 9 mainly contains H 2 ;

[0105] Regeneration-reduction module: close the valve body to stop delivering light gasoline 3, open the valve body to start delivering regeneration gas 17 into the first fixed bed reactor 6, when the adsorption desulfurization activity index fed back in real time by the regeneration activity measurement module is lower than the desulfurization threshold, close the valve body to stop delivering regeneration gas 17, open the pneumatic valve to input hydrogen 16 into the first fixed bed reactor 6, the desulfurization adsorbent undergoes a reduction reaction, and the active components of the desulfurization adsorbent are regenerated; wherein the regeneration gas 17 is mainly nitrogen and oxygen;

[0106] Heavy gasoline adsorption desulfurization module: The heavy gasoline 4 obtained by distillation and fractionation module is mixed with hydrogen 16 and transported to the heating furnace 11 for high-temperature reaction, and then enters the second fixed bed reactor 12 to obtain the reaction product, which is then transported to the second high-pressure separator 13 for separation to obtain tail gas 14 and the second separated liquid product 15, wherein the tail gas 14 mainly contains H 2 It can be recycled, and the liquid phase product 15 after the second separation is catalytic gasoline with a sulfur content reduced to below 10 μg / g;

[0107] Regeneration activity measurement module: real-time collection of the weight and sulfur content of the reaction products in the catalytic reaction module and the heavy gasoline adsorption desulfurization module, using the activity measurement method of the catalytic cracking gasoline desulfurization adsorbent, real-time measurement and feedback to obtain the adsorption desulfurization activity index, which is used to characterize the real-time regeneration activity of the desulfurization adsorbent; when the regeneration reduction threshold is lower than the desulfurization threshold, the pneumatic valve is opened to input hydrogen 16 and transport it to the first fixed bed reactor 6 and the second fixed bed reactor 12 respectively to complete the catalytic reduction reaction;

[0108] Control module: used to control the opening and closing of the feed pump, pneumatic valve or valve body in each module, as well as the real-time collection and measurement feedback of the regeneration activity measurement module.

[0109] Specifically, in a specific embodiment of the present application, the system uses FCC gasoline 1 whose sulfur content meets the National IV standard (total sulfur content is 298.6 μg / g, olefin content is 31.34 ω%) as raw material (Ningxia Petrochemical, catalytic cracking full-fraction gasoline), and according to the process flow of the catalytic cracking gasoline distillation and fixed-bed adsorption desulfurization combined system, a 200 ml fixed bed experimental device is selected, and the adsorbent filling amount for a single test is 50 ml. The method is used to measure the activity of the desulfurization adsorbent, and the adsorption desulfurization performance test is carried out under certain process conditions such as the gasoline feed volume space velocity, adsorption pressure, and hydrogen-to-oil volume ratio. The adsorption regeneration conditions of the system are further adjusted according to the adsorption desulfurization activity index to obtain experimental comparison results of the desulfurization rate and the adsorption desulfurization activity index to study the influence of the activity determination method on improving the desulfurization performance of the reaction adsorbent, and to investigate the desulfurization effect of repeated regeneration of the reaction adsorbent.

[0110] Specifically, in the activity determination system of the catalytic cracking gasoline desulfurization adsorbent, the experimental reference indicators of the distillation process of FCC gasoline 1 are: (1) distillation operating conditions of FCC gasoline 1: the bottom temperature of the distillation fractionation tower 2 is 190-200°C, and the distillation operation reflux ratio is 0.5-0.75; (2) after the distillation of FCC gasoline 1, the sulfur content of light gasoline 3 is less than 10 μg / g; (3) the loss rate of FCC gasoline 1 is less than 0.2%.

[0111] Specifically, in the activity determination system of the catalytic cracking gasoline desulfurization adsorbent, the experimental reference indicators of the fixed bed adsorption desulfurization process are: (1) fixed bed adsorption desulfurization process conditions: reaction temperature 330-370°C, pressure 1.5-2.5 MPa, liquid space velocity 3-7 h -1 , hydrogen-to-oil volume ratio of 50:1 to 100:1; (2) the heavy gasoline after distillation of FCC gasoline 1 is subjected to fixed-bed adsorption desulfurization to reduce the sulfur content to below 10 μg / g, and the loss of gasoline research octane number is less than 0.5 units; (3) the loss rate of FCC gasoline 1 is less than 0.2%.

[0112] Specifically, in the specific embodiments of the present application, the product quality index of the desulfurization adsorbent is selected as follows: Figure 4 As shown, the selected desulfurization adsorbent must meet the following requirements at the same time: (1) the stable sulfur capacity of both the fresh adsorbent and the regenerated adsorbent is greater than 15%; (2) under the stable sulfur capacity, the single-pass operation cycle of the adsorbent is 60 days, and the service life of the adsorbent reaches 2 to 3 years.

[0113] In some embodiments, the desulfurization adsorbent selected includes active components, such as Ni and ZnO, and the carrier is an aluminum source and a silicon source, such as Al 2 O 3 and SiO 2In the process of adsorption desulfurization, the selected desulfurization adsorbent mainly plays the role of desulfurization and sulfur storage. The active components in the adsorbent react with the aluminum source and the silicon source to generate inactive zinc aluminum spinel and willemite. For example, the Ni active center can convert the sulfide in the sulfur-containing hydrocarbon oil into Ni-S intermediates, and react sulfur with ZnO to generate ZnS under the reaction conditions of hydrogenation, capture the sulfur in the sulfur hydrocarbon oil and store it in the desulfurization adsorbent, and then remove the sulfur stored on the adsorbent through the regeneration system to restore the activity and achieve the regeneration of the desulfurization adsorbent.

[0114] Specifically, in this specific embodiment, the control variable method is used for comparative experiments, the activity measurement system of the catalytic cracking gasoline desulfurization adsorbent is set to be consistent within the above reference index range, and the adsorption desulfurization performance test is carried out under the condition of controlling the liquid space velocity, reduction temperature, hydrogen-to-oil volume ratio and other process conditions of FCC gasoline 1 (the initial process conditions are set as: reduction temperature of 310°C, reduction pressure of 2.0 MPa, liquid space velocity of 7 h -1 , the hydrogen-to-oil volume ratio is 60), and the adsorption regeneration conditions of the system are further adjusted according to the adsorption desulfurization activity index (the initial regeneration conditions are set as: regeneration temperature of 350°C, regeneration pressure of 0.1 MPa, regeneration H 2 Airspeed is 1000h -1 , Regeneration O 2 The desulfurization rate corresponding to FCC gasoline 1 calculated by the standard determination method is used as a standard control to characterize the overall catalytic adsorption desulfurization performance. The calculation formula is: X=(C 0 -C 1 ) / C 0 ×100%, X—desulfurization rate (%); C 0 —Sulfur content of gasoline raw materials (μg / g); C 1 -Sulfur content of the desulfurization product output by the system (μg / g).

[0115] Embodiment 1:

[0116] Under the same process conditions and adsorption regeneration conditions, the adsorption desulfurization activity index that changes with the adsorption reaction time is calculated according to the activity determination method. The average value of the adsorption desulfurization activity index at the corresponding operating time during the reaction time is multiplied by the conversion coefficient to obtain the desulfurization activity index (unit, %) corresponding to the reaction adsorbent during the system operation time. The system terminal synchronously records the product sulfur content (unit, μg / g) and the corresponding desulfurization rate (unit, %) of the liquid phase product 15 after the second separation. The comparison of the test results is shown in the figure below: Figure 7 As shown. Figure 7It can be seen that within the range of adsorption temperature, the desulfurization rate of FCC gasoline 1 gradually decreases with the continuous increase of operating time, while the change trend of the desulfurization activity index of the reaction adsorbent is relatively consistent with the trend of the desulfurization rate measured by the standard. Since the adsorption desulfurization reaction is irreversible, as the regeneration-reduction reaction continues, the conversion efficiency of sulfur-containing compounds in FCC gasoline 1 decreases, and the regeneration activity of the reaction adsorbent gradually decreases, which is the same as the change trend of the adsorption desulfurization activity index calculated by the activity measurement method. Correspondingly, the desulfurization activity of the reaction adsorbent decreases, resulting in a gradual increase in the sulfur content of the corresponding measured product of the liquid phase product 15 after the second separation. The test results show that the adsorption desulfurization activity index obtained by the method can be used to characterize the regeneration activity of the reaction adsorbent in the operating system in real time, as one of the qualitative standards for rapid and simple activity measurement.

[0117] Furthermore, the adsorption regeneration conditions of the system can be regulated according to the adsorption desulfurization activity index fed back in real time by the operating system, the influence of the activity determination method on improving the desulfurization performance of the reaction adsorbent can be studied, and the desulfurization effect of the repeated regeneration of the reaction adsorbent can be examined.

[0118] Embodiment 2:

[0119] Under the same process conditions and regeneration conditions, multiple regeneration-reduction tests were conducted, and the same reaction adsorbent and the combined process were selected to conduct adsorption desulfurization reactions, and the effect of the method on the adsorption desulfurization performance of repeated regeneration was compared. Among them, a fresh adsorbent was used as a standard group for a control test, and four regeneration-reduction tests were conducted and the results of the adsorption desulfurization activity index obtained by the activity determination method were compared as shown in the figure below: Figure 8 Accordingly, the sulfur content of the tail gas 9 and the tail gas 14 produced by the system is detected in real time using an ultraviolet fluorescence sulfur analyzer as a standard control group to obtain the corresponding product sulfur content comparison results. Fig. 9 As shown. It can be seen that as the regeneration-reduction reaction occurs, the system uses the activity measurement method to quickly measure the regeneration activity of the adsorbent, and adjusts the system in real time to optimize the regeneration conditions of the desulfurization adsorbent. In the early stage of the regeneration-reduction reaction, under the condition of ensuring an 80% desulfurization rate, it runs for a total of 70 hours, and the breakthrough sulfur capacity is 10.9%. Figure 8 and Fig. 9 Comparing the four regeneration-reduction tests of the reaction adsorbent, it can be seen that although the desulfurization effect of the regenerated adsorbent decreases slightly with the increase in the number of regenerations, the regeneration performance of the adsorbent remains at a good level, and its adsorption desulfurization activity index is close to the desulfurization effect of the fresh adsorbent, and the average absolute deviation between the two is 0.027. Similarly, comparing the change curve of the product sulfur content measured by the standard under the same reaction, the desulfurization effect of a single regeneration is closest to the measurement result of the fresh adsorbent, which is in line with the activity law of repeated regeneration, and multiple regenerations have no significant effect on the desulfurization effect.

[0120] Embodiment 3:

[0121] On the basis of Examples 1 and 2, a blank determination comparison experiment was conducted, and the test results of direct determination of an adsorption desulfurization reaction using the same reaction adsorbent and the combined process were used as a blank control group. The results of the fourth regeneration-reduction test in which the regeneration conditions of the system were regulated by the activity determination method were compared with those of the blank control group. The desulfurization rate corresponding to FCC gasoline 1 was calculated by the standard determination method as a comparison of the experimental results. Fig.10 As shown. It can be seen that when the same desulfurization adsorbent undergoes a regeneration-reduction reaction, the adsorption desulfurization reaction using the activity determination method can obtain better regeneration activity, and its standard determined desulfurization rate is closer to the desulfurization effect of the fresh adsorbent. It is precisely because the method of the present invention can be used to regulate and optimize the regeneration conditions of the operating system in real time, further accelerate its reaction rate with the active components in the adsorbent, reduce the competitive adsorption of sulfur atoms by other hydrocarbon groups, promote the complete adsorption desulfurization reaction between sulfur-containing compounds and the reaction adsorbent, and continuously optimize the adsorbent regeneration-reduction reaction rate, so that the adsorption desulfurization activity index is consistent with the change trend of the desulfurization rate, and can achieve the best dynamic balance between the adsorption desulfurization reaction and the adsorbent regeneration cycle performance.

[0122] In summary, the experimental results of Examples 1 to 3 show that in order to optimize the process of deep desulfurization, the technical solution of the present application is to measure the reaction activity of the desulfurization adsorbent in real time and regulate the regeneration environment of the adsorbent, which can effectively achieve the dynamic balance between the optimal adsorption desulfurization process conditions and the adsorbent regeneration cycle performance. At the same time, it can greatly reduce the sulfur content and octane number loss of gasoline, improve the desulfurization stability, desulfurization effect, single-pass operation life of the adsorbent and the reuse effect of the regenerated adsorbent.

[0123] The activity determination method of a catalytic cracking gasoline desulfurization adsorbent described in the present application can be run in computing devices such as desktop computers, notebooks, PDAs, and cloud data centers. The activity determination method of a catalytic cracking gasoline desulfurization adsorbent includes, but is not limited to, a processor and a memory. Those skilled in the art can understand that the example is only an example of an activity determination method of a catalytic cracking gasoline desulfurization adsorbent, and does not constitute a limitation on the activity determination method of a catalytic cracking gasoline desulfurization adsorbent, and may include more or less components than the example, or a combination of certain components, or different components, for example, the activity determination method of a catalytic cracking gasoline desulfurization adsorbent may also include input and output devices, network access devices, buses, etc.

[0124] The processor may be a central processing unit (CPU), or other general-purpose processors, digital signal processors (DSP), application-specific integrated circuits (ASIC), field-programmable gate arrays (FPGA) or other programmable logic devices, discrete component gate circuits or transistor logic devices, discrete hardware components, etc. The general-purpose processor may be a microprocessor or any conventional processor, etc. The processor is the control center of the activity determination method of the catalytic cracking gasoline desulfurization adsorbent, and uses various interfaces and lines to connect the various sub-areas of the entire activity determination method of the catalytic cracking gasoline desulfurization adsorbent.

[0125] The memory can be used to store the computer program and / or module, and the processor realizes various functions of the activity determination method of a catalytic cracking gasoline desulfurization adsorbent by running or executing the computer program and / or module stored in the memory and calling the data stored in the memory. The memory can mainly include a program storage area and a data storage area, wherein the memory can include a high-speed random access memory and can also include a non-volatile memory, such as a hard disk, a memory, a plug-in hard disk, a smart memory card (Smart Media Card, SMC), a secure digital (SecureDigital, SD) card, a flash card (Flash Card), at least one disk storage device, a flash memory device, or other volatile solid-state storage devices.

[0126] Although the description of the present disclosure has been quite detailed and specifically describes several described embodiments, it is not intended to be limited to any of these details or embodiments or any particular embodiment, so as to effectively cover the intended scope of the present disclosure. In addition, the above description of the present disclosure is based on the embodiments foreseeable by the inventors, and its purpose is to provide a useful description, and those non-substantial changes to the present disclosure that have not yet been foreseen may still represent equivalent changes to the present disclosure.

Claims

1. A method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent, characterized in that: The method specifically comprises the following steps: S100, determining the residual activity weight m of the active component in the adsorbent to be removed corresponding to the current time t res ; S200, mixing the adsorbent to be removed with a reducing gas for reduction treatment to obtain a reduced adsorbent, and determining the reduced sulfur content S of the reduced adsorbent at the current time t Red (t); S300, mixing the adsorbent to be removed with the regeneration gas for regeneration treatment to obtain a regenerated adsorbent, and determining the weight M of the regenerated adsorbent generated at the current time t rePro (t); S400, subjecting the reducing adsorbent and the sulfide-containing gasoline raw material to hydrodesulfurization adsorption treatment, and determining the weight M of the desulfurized liquid phase product generated at the current time t Pro (t) and the actual sulfur content S in the gasoline feedstock Pro (t); S500, according to the residual active weight m res and the reduced sulfur content S Red (t), calculate the remaining sulfur content S of the reducing adsorbent corresponding to the next moment (t+1) after step S400 Ads (t+1), the calculation formula is: ; Wherein, N(S) is the relative atomic mass of sulfur, N(Act) is the relative molecular mass of the active component in the adsorbent to be removed, and n is the atomic ratio of non-sulfur elements to sulfur elements in the active component; S600, according to the weight M of the desulfurized liquid phase product corresponding to the current time t Pro (t) and the regenerated adsorbent weight M rePro (t), combined with the actual sulfur content S Pro (t) and the residual sulfur content S Ads (t+1), a regeneration activity determination model is established within a certain catalytic reaction time period, and the adsorption desulfurization activity index δ corresponding to the adsorbent to be removed at the next time (t+1) is calculated. Act (t+1); Among them, in step S600, according to the weight M of the desulfurized liquid phase product corresponding to the current time t Pro (t) and the regenerated adsorbent weight M rePro (t), combined with the actual sulfur content S Pro (t) and the residual sulfur content S Ads (t+1), a regeneration activity determination model is established within a certain catalytic reaction time period, and the adsorption desulfurization activity index δ corresponding to the adsorbent to be removed at the next time (t+1) is calculated. Act The specific method of (t+1) is: S601, inputting the weight M of the desulfurized liquid phase product corresponding to the current time t within a certain catalytic reaction time period Pro (t) and the regenerated adsorbent weight M rePro (t), establish a regeneration activity determination model, and output the unit regeneration activity capacity Cap corresponding to the adsorbent to be removed at the next time (t+1) unit (t+1), its dimensionless calculation formula is: ； ； ； Wherein, assuming that the catalytic reaction cycle of the adsorbent to be removed is T, the certain catalytic reaction time period starts from the previous catalytic reaction cycle (t-T+1) at the next moment (t+1) and calculates the unit regeneration activity capacity Cap corresponding to the next moment (t+1) unit (t+1), meanD(t) is the average capacity of regeneration activity corresponding to the current time t calculated from the previous catalytic reaction cycle (tT) at the current time t, meanD(i) is the average capacity of regeneration activity corresponding to time i; Desulf(t+1) is the real-time capacity of regeneration activity corresponding to the adsorbent to be removed at the next time (t+1), Desulf(i) is the real-time capacity of regeneration activity corresponding to time i, and i is a variable; S602, according to the unit regeneration activity capacity Cap corresponding to the adsorbent to be removed at the next time (t+1), unit (t+1), calculate the adsorption desulfurization activity index δ corresponding to the adsorbent to be removed at the next time (t+1) Act (t+1), its dimensionless calculation formula is: ； Among them, the adsorption desulfurization activity index δ Act (t+1) is used to characterize the regeneration rate of the adsorbent to be removed at the next moment (t+1).

2. The method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent according to claim 1, characterized in that: In step S100, the residual active weight m of the active component in the adsorbent to be removed corresponding to the current time t is determined by using one of X-ray diffraction, X-ray fluorescence spectroscopy or inductively coupled plasma spectroscopy. res .

3. The method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent according to claim 1, characterized in that: The sulfur content is determined by using one of the oxygen bomb method, the coulometric method, the microcoulometry method, the ultraviolet fluorescence method, the electrical detection method or the infrared absorption method. In step S200, the reduced sulfur content S in the reduced adsorbent at the current time t is determined by calculating the sulfur element based on the weight of the reduced adsorbent. Red (t); or, in step S400, the actual sulfur content S in the gasoline raw material at the current time t is calculated based on the weight of the sulfide-containing gasoline raw material and the sulfur element. Pro (t).

4. The method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent according to claim 1, characterized in that: In step S400, the reducing adsorbent and the sulfide-containing gasoline feedstock are subjected to hydrodesulfurization adsorption treatment, and the hydrodesulfurization adsorption treatment method includes: in the presence of hydrogen, the active components in the reducing adsorbent convert the sulfides in the gasoline feedstock into sulfur-containing intermediates, and the sulfide-containing gasoline feedstock is desulfurized and converted into a desulfurized liquid product.

5. The method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent according to claim 1, characterized in that: After step S600, the method further comprises: according to the adsorption desulfurization activity index δ corresponding to the next moment (t+1), Act (t+1) Determine whether it is lower than the desulfurization threshold. If so, control step S200 to input reducing gas for reduction treatment, and control step S300 to stop inputting regeneration gas.

6. The method for determining the activity of a catalytic cracking gasoline desulfurization adsorbent according to claim 5, characterized in that: The reducing gas includes hydrogen, and the regenerating gas includes nitrogen and oxygen.

7. An activity measurement system for realizing the activity measurement method of a catalytic cracking gasoline desulfurization adsorbent according to any one of claims 1 to 6, characterized in that: At least: A processor, a memory, a data acquisition module and a control module, wherein the data acquisition module includes a detection sensor, a chemical measuring instrument and a wireless transmission unit, and is used for data sampling to obtain the residual activity weight, desulfurization liquid product weight, reduced sulfur content and actual sulfur content corresponding to the system at the current moment, and store them in the memory; the wireless transmission unit is used for wireless communication connection, and transmits the data in the memory to the processor in real time for modeling operation, obtains the regeneration activity measurement model and calculates and outputs the adsorption desulfurization activity index corresponding to the next moment, and transmits it to the control module of the system synchronously; The processor executes the computer program to run in the following units of the system: The active component weight collection unit is used to collect in real time the residual active weight of the active component in the adsorbent to be removed corresponding to the current time t, as well as the weight of the regenerated adsorbent generated after the regeneration treatment and the weight of the desulfurized liquid product generated after the hydrodesulfurization adsorption treatment; Sulfur content determination unit, used to collect the reduced sulfur content of the reduced adsorbent and the actual sulfur content in the gasoline raw material in real time; A residual sulfur content calculation unit, used to calculate the residual sulfur content of the reducing adsorbent corresponding to the next moment according to the residual active weight and the reduced sulfur content corresponding to the current moment; A regeneration activity determination model establishment unit is used to establish a regeneration activity determination model within a certain catalytic reaction time period according to the weight of the desulfurization liquid phase product and the weight of the regenerated adsorbent corresponding to the current moment, combined with the actual sulfur content and the residual sulfur content, to calculate the adsorption desulfurization activity index corresponding to the adsorbent to be removed at the next moment; The regeneration reduction reaction control unit is used to determine whether the adsorption desulfurization activity index corresponding to the next moment is lower than the desulfurization threshold. If so, the control module responds, the control system inputs reducing gas for reduction treatment, and the control system stops inputting regeneration gas.

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