A method for ex situ sulfurization of hydrogenation catalyst

Abstract

The present invention is specifically an off-site sulfurization method for a hydrogenation catalyst, including the following parts: sulfurization preparation: a comprehensive inspection of the sulfurization equipment; judgment analysis: analyzing the various parameter information in the sulfurization process to obtain an evaluation index; optimal purge time: extracting the largest evaluation index, and recording the duration between the parameter monitoring time point corresponding to the maximum evaluation index and the start time of the inert gas purge as the optimal purge duration; sulfurization reaction. In the present invention, the analysis of the various parameters of the sulfurization equipment can accurately determine the optimal purge time, so that when the sulfurization reaction is subsequently carried out, the optimal purge time can be determined as the inert gas purge time of the sulfurization reaction, which can not only better exert the purge effect, but also reduce the consumption of the inert purge gas.

Description

Technical Field

[0001] The invention relates to the technical field of sulfurization, and in particular to an ex-situ sulfurization method of a hydrogenation catalyst. Background Art

[0002] The ex situ sulfidation of hydrogenation catalysts is divided into dry sulfidation and wet sulfidation.

[0003] During the dry vulcanization process, it is usually necessary to use inert gas to purge the internal space of the reactor to remove the air and impurity gases therein and create suitable conditions for the subsequent injection of the vulcanizing agent. The traditional practice is to determine whether the inert gas purge meets the requirements by monitoring the oxygen content at the outlet.

[0004] However, in actual operation, it is found that even if the oxygen content at the outlet has reached the standard value, it is still difficult to ensure that the internal space of the reactor is in the optimal environment for the injection of the sulfiding agent. If the inert gas is continuously purged to further improve the environment, although it can optimize the environment to a certain extent, it will significantly increase the consumption of inert gas, which undoubtedly increases the production cost and causes waste of resources.

[0005] Therefore, an ex situ sulfurization method for hydrogenation catalysts is needed to accurately determine the optimal time for purging inert gas during the dry sulfurization process. Summary of the invention

[0006] The purpose of the present invention is to solve the above-mentioned problems and to propose an ex situ sulfurization method for a hydrogenation catalyst.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] Includes the following parts:

[0009] Vulcanization preparation: Conduct a comprehensive inspection of the vulcanization equipment. After the inspection is completed, fill the vulcanization equipment with a set amount of catalyst. After the catalyst is filled, shut down the vulcanization equipment;

[0010] Judgment analysis: preset the allowable fluctuation range of the estimated time, take the minimum value within the allowable fluctuation range of the estimated time as the minimum estimated time, take the time when the minimum estimated time is reached as the starting time, obtain various parameter information in the vulcanization process at set time intervals from the starting time, analyze the various parameter information in the vulcanization process to obtain the evaluation index, and record the time when the various parameter information in the vulcanization process after the starting time is obtained as the parameter monitoring time point; the various parameter information includes the oxygen concentration and carbon dioxide concentration at the outlet of the vulcanization equipment, and the purge flow rate of the inert gas nitrogen;

[0011] Optimal purge time: Arrange the obtained evaluation indexes in descending order from left to right, extract the largest evaluation index, and record the duration between the parameter monitoring time point corresponding to the largest evaluation index and the start time of the inert gas purge as the optimal purge time;

[0012] Sulfurization reaction: After the inert gas purging of the vulcanization equipment is completed at the optimal purging time, the vulcanization reaction operation is carried out.

[0013] Preferably, the method further comprises:

[0014] Estimated time: Determine the flow rate of the inert purge gas nitrogen according to the size of the vulcanization equipment and the catalyst loading amount, multiply the flow rate of the nitrogen by the cross-sectional area of ​​the pipeline through which the nitrogen flows, and thus obtain the estimated flow rate of the inert purge gas nitrogen; divide the total volume of the vulcanization equipment reactor by the flow rate of the inert purge gas nitrogen to obtain the time required for the oxygen concentration at the outlet of the vulcanization equipment pipeline to reach the preset standard concentration, and record this time as the estimated time; purge the vulcanization equipment reactor with nitrogen of the preset concentration at a preset flow rate for the estimated time, and record the time when the inert gas purge starts as the start time, monitor the oxygen concentration at the outlet of the vulcanization equipment at set time intervals, and record the time when the oxygen concentration at the outlet of the vulcanization equipment is monitored as the oxygen monitoring time point, wherein the pressure and temperature information of the vulcanization equipment are also obtained at the oxygen monitoring time point.

[0015] Preferably, after the inert gas purging of the vulcanization equipment is completed at the optimal purging time, the vulcanization reaction operation is performed, which specifically includes:

[0016] The temperature of the vulcanizing equipment is raised to the temperature range of the initial decomposition stage of the sulfiding agent at a set heating rate, and the sulfiding agent is waited to be decomposed into hydrogen sulfide and other small molecular substances; after the sulfiding is completed, the injection of the sulfiding agent is stopped; hydrogen is introduced to purge the sulfiding equipment until the purge is completed; nitrogen is introduced to cool the catalyst to the set temperature, and the catalyst is transferred to the hydrogenation reactor.

[0017] Preferably, the analysis of various parameter information in the vulcanization process to obtain the evaluation index includes the following steps:

[0018] A set number of identical vulcanization equipment are used to form a test group, and after analyzing and processing the vulcanization equipment in the test group, the vulcanization equipment that does not meet the test requirements is eliminated, and the vulcanization equipment that meets the test requirements is re-formed into a reference group;

[0019] Obtain the oxygen concentration at the outlet of each vulcanization equipment in the reference group at each parameter monitoring time point, and calculate the difference between the oxygen concentration at the outlet of each vulcanization equipment at each parameter monitoring time point and the preset standard concentration in turn, take the absolute value of the difference to obtain the standard deviation of the oxygen concentration at the outlet of each vulcanization equipment at each parameter monitoring time point, and record it as ,in is the vulcanizing equipment number within the reference group, , is the number of each parameter monitoring time point, ;

[0020] According to the above process of obtaining the standard deviation of oxygen concentration, the standard deviation of carbon dioxide concentration at the outlet of each vulcanization equipment in the reference group at each parameter monitoring time point is obtained and recorded as ;

[0021] Obtain the inert gas purge flow recorded by the flow meter on the gas pipeline at each parameter monitoring time point for each vulcanization equipment in the reference group and record it as ;

[0022] The standard deviation of oxygen concentration , standard deviation of carbon dioxide concentration , Inert gas purge flow Substituting into the formula: , and obtain the comprehensive index of each vulcanization equipment in the reference group at each parameter monitoring time point ,in , , They are the maximum allowable oxygen concentration, the maximum allowable carbon dioxide concentration, and the estimated flow rate of the inert purge gas nitrogen. , , are the weight factors corresponding to the standard deviation of oxygen concentration, standard deviation of carbon dioxide concentration, and inert gas purge flow rate, respectively. is the preset control coefficient;

[0023] The comprehensive indexes of all the vulcanization equipment in the reference group corresponding to each parameter monitoring time point are summed up in turn, and the summed value is divided by the total number of vulcanization equipment in the reference group to obtain the average comprehensive index of all the vulcanization equipment in the reference group at each parameter monitoring time point, and the average comprehensive index of all the vulcanization equipment in the reference group corresponding to each parameter monitoring time point is recorded as the evaluation index .

[0024] Preferably, the vulcanization equipment in the test group is analyzed and processed to remove the vulcanization equipment that does not meet the test requirements, and the vulcanization equipment that meets the test requirements is reconstructed into a reference group, which specifically includes:

[0025] Obtain the oxygen concentration corresponding to the oxygen monitoring time point corresponding to the minimum estimated time after each vulcanization equipment in the test group is simultaneously purged with inert gas, and calculate the difference between the oxygen concentration at the outlet of each vulcanization equipment and the preset standard concentration, take the absolute value of the calculated difference value to obtain the concentration standard difference value, and divide the concentration standard difference value of each vulcanization equipment by the preset standard concentration in turn to obtain the deviation coefficient of each vulcanization equipment;

[0026] At the start-up time of each vulcanization equipment, the pressure and temperature of each vulcanization equipment are monitored for a set time until the minimum estimated time is reached, and the monitoring time is recorded as the test time point;

[0027] Obtain the temperature of each vulcanization equipment at each test time point, extract the highest temperature and the lowest temperature of each vulcanization equipment at each test time point, calculate the difference between the highest temperature and the lowest temperature, so as to obtain the temperature difference extreme value of each vulcanization equipment at each test time point; respectively, accumulate the duration of the temperature difference extreme value of each vulcanization equipment within the minimum estimated time to obtain the extreme duration, and then divide the extreme duration of each vulcanization equipment by the minimum estimated duration to obtain the extreme temperature difference deviation coefficient of each vulcanization equipment;

[0028] According to the above process of obtaining the extreme deviation coefficient of each vulcanization equipment, the pressure of each vulcanization equipment is analyzed to obtain the extreme pressure difference deviation coefficient of each vulcanization equipment;

[0029] Preset the weight factors of the deviation coefficient, the extreme temperature difference deviation coefficient, and the extreme pressure difference deviation coefficient, and multiply the deviation coefficient, the extreme temperature difference deviation coefficient, and the extreme pressure difference deviation coefficient with their corresponding weight factors and then sum them to obtain the test index;

[0030] A test index threshold is preset, and the test index corresponding to each vulcanization equipment is matched with the preset test index threshold in turn, and the vulcanization equipment corresponding to the test index greater than the preset test index threshold is removed from the test group, and the remaining vulcanization equipment is reconstructed into a reference group.

[0031] Preferably, the process of obtaining the comparison coefficient specifically includes the following parts:

[0032] Obtain the oxygen concentration of several set monitoring depths of the catalyst bed of each sulfiding equipment in the reference group at the parameter monitoring time point, calculate the oxygen concentration of adjacent monitoring depths in order from high to low depths to obtain the concentration difference of adjacent depths, and divide each adjacent depth concentration difference by the interval depth corresponding to the corresponding adjacent depth concentration difference and take the absolute value to obtain the concentration gradient corresponding to each adjacent depth concentration difference, which is recorded as ,in is the vulcanizing equipment number within the reference group, is the number of the concentration gradient, ;

[0033] Obtain the temperature and pressure of the vulcanizing equipment corresponding to each parameter monitoring time point of each vulcanizing equipment in the reference group, and record them as and The subsequent entry formula is: , and obtain the diffusion index corresponding to each vulcanization equipment in the reference group at each parameter monitoring time point ,in , are the molar masses of oxygen and nitrogen, respectively. , are the molecular diffusion volumes of oxygen and nitrogen respectively;

[0034] Substitute the obtained diffusion index into the formula: , and obtain the penetration time of each depth interval of the catalyst bed corresponding to the diffusion index of each sulfurization equipment in the reference group at each parameter monitoring time point ;in is the total thickness of the catalyst bed;

[0035] After summing up the penetration time of each depth interval of the catalyst bed corresponding to each sulfidation equipment in the reference group at each parameter monitoring time point, the summed value is divided by the number of catalyst bed depth intervals corresponding to each sulfidation equipment to obtain the average penetration time of each sulfidation equipment at each parameter monitoring time point, and then the average penetration time of each sulfidation equipment at each parameter monitoring time point is divided by the time between each parameter monitoring time point and the starting time to obtain the control coefficient. .

[0036] Preferably, the vulcanization equipment is comprehensively inspected during the vulcanization preparation, including appearance inspection, internal component inspection and electrical circuit inspection.

[0037] Preferably, the step of analyzing and processing the vulcanization equipment in the test group, removing the vulcanization equipment that does not meet the test requirements, and re-forming the vulcanization equipment that meets the test requirements into a reference group further includes:

[0038] The oxygen concentration monitored at each oxygen monitoring time point and the equipment number and location information of the eliminated vulcanization equipment that does not meet the test requirements are recorded as abnormal information, and the abnormal information is sent to the maintenance personnel's smart terminal. After receiving the oxygen concentration monitored at each oxygen monitoring time point and the equipment number and location information, the maintenance personnel will perform maintenance inspections on it.

[0039] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0040] 1. The present invention can accurately determine the optimal purge time by analyzing various parameters of the vulcanization equipment, so that when the vulcanization reaction is subsequently carried out, the optimal purge time can be set as the inert gas purge time of the vulcanization reaction, which can not only better exert the purge effect, but also reduce the consumption of the inert purge gas.

[0041] 2. The present invention analyzes and processes the vulcanization equipment in the test group, eliminates the vulcanization equipment that does not meet the test requirements, reconstructs the reference group, and calculates the deviation coefficient, extreme temperature difference deviation coefficient, and extreme pressure difference deviation coefficient of the vulcanization equipment to obtain the test index, thereby screening out the vulcanization equipment that meets the requirements and ensuring the quality and performance of the vulcanization equipment. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Further details, features and advantages of the present application are disclosed in the following description of exemplary embodiments in conjunction with the accompanying drawings, in which:

[0043] Figure 1 is a flow chart of the present invention; DETAILED DESCRIPTION

[0044] Several embodiments of the present application will be described in more detail below with reference to the accompanying drawings so that those skilled in the art can implement the present application. The present application can be embodied in many different forms and purposes and should not be limited to the embodiments described herein. These embodiments are provided to make the present application comprehensive and complete, and to fully convey the scope of the present application to those skilled in the art. The embodiments do not limit the present application.

[0045] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by those of ordinary skill in the art to which this application belongs. It will be further understood that terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the relevant art and / or the context of this specification, and will not be interpreted in an idealized or overly formal sense unless explicitly defined as such herein.

[0046] See also Figure 1 As shown, the present invention provides a technical solution:

[0047] An ex situ sulfurization method for a hydrogenation catalyst comprises the following parts:

[0048] Vulcanization preparation: Conduct a comprehensive inspection of the vulcanization equipment. After the inspection is completed, fill the vulcanization equipment with a set amount of catalyst. After the catalyst is filled, shut down the vulcanization equipment;

[0049] Conduct a comprehensive inspection of the vulcanizing equipment, including:

[0050] Appearance inspection: Check whether the appearance of the reactor, pipeline, flange and other parts of the vulcanization equipment is deformed, cracked or damaged; whether the various connection parts of the vulcanization equipment, such as the interface of the pipeline, the connection between the valve and the pipeline, are well sealed; whether the anti-corrosion and wear-resistant coatings inside the vulcanization equipment are intact, and whether there is peeling, blistering and other phenomena;

[0051] Internal component inspection: Check the filling condition of the catalyst bed, including whether the catalyst is evenly distributed and whether there is any local accumulation or vacancy; check the gas delivery pipeline inside the equipment to ensure that there is no blockage inside the pipeline, such as impurities, debris, etc.; check whether the temperature sensor, pressure sensor, oxygen concentration sensor, and carbon dioxide concentration sensor in the equipment are installed correctly and whether the probe is clean to ensure that it can accurately measure temperature and pressure;

[0052] Electrical circuit inspection: Check whether the electrical circuit of the equipment is intact, whether the insulation is good, and whether there is a risk of short circuit or open circuit;

[0053] Estimated time: Determine the flow rate of the inert purge gas nitrogen according to the size of the vulcanization equipment and the catalyst loading amount, multiply the flow rate of the nitrogen by the cross-sectional area of ​​the pipeline through which the nitrogen flows, and thus obtain the estimated flow rate of the inert purge gas nitrogen; divide the total volume of the vulcanization equipment reactor by the flow rate of the inert purge gas nitrogen to obtain the time required for the oxygen concentration at the outlet of the vulcanization equipment pipeline to reach the preset standard concentration, and record this time as the estimated time; purge the vulcanization equipment reactor with nitrogen of the preset concentration at the preset flow rate for the estimated time, and record the time when the inert gas purge starts as the start time, monitor the oxygen concentration at the outlet of the vulcanization equipment at the set time interval, and record the time when the oxygen concentration at the outlet of the vulcanization equipment is monitored as the oxygen monitoring time point, wherein the pressure and temperature information of the vulcanization equipment are also obtained at the oxygen monitoring time point;

[0054] Judgment analysis: preset the allowable fluctuation range of the estimated time, take the minimum value within the allowable fluctuation range of the estimated time as the minimum estimated time, take the time when the minimum estimated time is reached as the starting time, obtain various parameter information in the vulcanization process at set time intervals from the starting time, analyze the various parameter information in the vulcanization process to obtain the evaluation index, and record the time when the various parameter information in the vulcanization process after the starting time is obtained as the parameter monitoring time point; the various parameter information includes the oxygen concentration and carbon dioxide concentration at the outlet of the vulcanization equipment, and the purge flow rate of the inert gas nitrogen;

[0055] The evaluation index is obtained by analyzing the various parameter information in the vulcanization process. The specific process includes the following parts:

[0056] A set number of identical vulcanization equipment is used to form a test group. After analyzing and processing the vulcanization equipment in the test group, the vulcanization equipment that does not meet the test requirements is eliminated, and the vulcanization equipment that meets the test requirements is reconstituted into a reference group, specifically including:

[0057] Obtain the oxygen concentration corresponding to the oxygen monitoring time point corresponding to the minimum estimated time after each vulcanization equipment in the test group is simultaneously purged with inert gas, and calculate the difference between the oxygen concentration at the outlet of each vulcanization equipment and the preset standard concentration, take the absolute value of the calculated difference value to obtain the concentration standard difference value, and divide the concentration standard difference value of each vulcanization equipment by the preset standard concentration in turn to obtain the deviation coefficient of each vulcanization equipment;

[0058] At the start-up time of each vulcanization equipment, the pressure and temperature of each vulcanization equipment are monitored for a set time until the minimum estimated time is reached, and the monitoring time is recorded as the test time point;

[0059] Obtain the temperature of each vulcanization equipment at each test time point, extract the highest temperature and the lowest temperature of each vulcanization equipment at each test time point, calculate the difference between the highest temperature and the lowest temperature, so as to obtain the temperature difference extreme value of each vulcanization equipment at each test time point; respectively, accumulate the duration of the temperature difference extreme value of each vulcanization equipment within the minimum estimated time to obtain the extreme duration, and then divide the extreme duration of each vulcanization equipment by the minimum estimated duration to obtain the extreme temperature difference deviation coefficient of each vulcanization equipment;

[0060] According to the above process of obtaining the extreme deviation coefficient of each vulcanization equipment, the pressure of each vulcanization equipment is analyzed to obtain the extreme pressure difference deviation coefficient of each vulcanization equipment;

[0061] Preset the weight factors of the deviation coefficient, the extreme temperature difference deviation coefficient, and the extreme pressure difference deviation coefficient, and multiply the deviation coefficient, the extreme temperature difference deviation coefficient, and the extreme pressure difference deviation coefficient with their corresponding weight factors and then sum them to obtain the test index;

[0062] Preset a test index threshold, match the test index corresponding to each vulcanization equipment with the preset test index threshold in turn, remove the vulcanization equipment corresponding to the test index greater than the preset test index threshold from the test group, and reconstitute the remaining vulcanization equipment into a reference group;

[0063] The oxygen concentration monitored at each oxygen monitoring time point and the equipment number and location information of the eliminated vulcanization equipment that does not meet the test requirements are recorded as abnormal information, and the abnormal information is sent to the intelligent terminal of the maintenance personnel. After receiving the oxygen concentration monitored at each oxygen monitoring time point and the equipment number and location information, the maintenance personnel will perform maintenance inspection and processing;

[0064] Obtain the oxygen concentration at the outlet of each vulcanization equipment in the reference group at each parameter monitoring time point, and calculate the difference between the oxygen concentration at the outlet of each vulcanization equipment at each parameter monitoring time point and the preset standard concentration in turn, take the absolute value of the difference to obtain the standard deviation of the oxygen concentration at the outlet of each vulcanization equipment at each parameter monitoring time point, and record it as ,in is the vulcanizing equipment number within the reference group, , is the number of each parameter monitoring time point, ;

[0065] According to the above process of obtaining the standard deviation of oxygen concentration, the standard deviation of carbon dioxide concentration at the outlet of each vulcanization equipment in the reference group at each parameter monitoring time point is obtained and recorded as ;

[0066] Obtain the inert gas purge flow recorded by the flow meter on the gas pipeline at each parameter monitoring time point for each vulcanization equipment in the reference group and record it as ;

[0067] The standard deviation of oxygen concentration , standard deviation of carbon dioxide concentration , Inert gas purge flow Substituting into the formula: , and obtain the comprehensive index of each vulcanization equipment in the reference group at each parameter monitoring time point ,in , , They are the maximum allowable oxygen concentration, the maximum allowable carbon dioxide concentration, and the estimated flow rate of the inert purge gas nitrogen. , , are the weight factors corresponding to the standard deviation of oxygen concentration, standard deviation of carbon dioxide concentration, and inert gas purge flow rate, respectively. is the preset control coefficient;

[0068] The comprehensive indexes of all the vulcanization equipment in the reference group corresponding to each parameter monitoring time point are summed up in turn, and the summed value is divided by the total number of vulcanization equipment in the reference group to obtain the average comprehensive index of all the vulcanization equipment in the reference group at each parameter monitoring time point, and the average comprehensive index of all the vulcanization equipment in the reference group corresponding to each parameter monitoring time point is recorded as the evaluation index ;

[0069] The process of obtaining the comparison coefficient specifically includes the following parts:

[0070] Obtain the oxygen concentration of several set monitoring depths of the catalyst bed of each sulfiding equipment in the reference group at the parameter monitoring time point, calculate the oxygen concentration of adjacent monitoring depths in order from high to low depths to obtain the concentration difference of adjacent depths, and divide each adjacent depth concentration difference by the interval depth corresponding to the corresponding adjacent depth concentration difference and take the absolute value to obtain the concentration gradient corresponding to each adjacent depth concentration difference, which is recorded as ,in is the vulcanizing equipment number within the reference group, is the number of the concentration gradient, ;

[0071] Obtain the temperature and pressure of the vulcanizing equipment corresponding to each parameter monitoring time point of each vulcanizing equipment in the reference group, and record them as and The subsequent entry formula is: , and obtain the diffusion index corresponding to each vulcanization equipment in the reference group at each parameter monitoring time point ,in , are the molar masses of oxygen and nitrogen, respectively. , are the molecular diffusion volumes of oxygen and nitrogen respectively;

[0072] Substitute the obtained diffusion index into the formula: , and obtain the penetration time of each depth interval of the catalyst bed corresponding to the diffusion index of each sulfurization equipment in the reference group at each parameter monitoring time point ;in is the total thickness of the catalyst bed;

[0073] After summing up the penetration time of each depth interval of the catalyst bed corresponding to each sulfidation equipment in the reference group at each parameter monitoring time point, the summed value is divided by the number of catalyst bed depth intervals corresponding to each sulfidation equipment to obtain the average penetration time of each sulfidation equipment at each parameter monitoring time point, and then the average penetration time of each sulfidation equipment at each parameter monitoring time point is divided by the time between each parameter monitoring time point and the starting time to obtain the control coefficient. ;

[0074] Optimal purge time: Arrange the obtained evaluation indexes in descending order from left to right, extract the largest evaluation index, and record the duration between the parameter monitoring time point corresponding to the largest evaluation index and the start time of the inert gas purge as the optimal purge time;

[0075] Sulfurization reaction: After the inert gas purge of the vulcanization equipment is completed at the optimal purge time, the vulcanization reaction operation is carried out, which specifically includes:

[0076] The temperature of the vulcanizing equipment is raised to the temperature range of the initial decomposition stage of the vulcanizing agent at a set heating rate, and the vulcanizing agent is waited for to be decomposed into hydrogen sulfide and other small molecular substances; the temperature of the vulcanizing equipment is continuously raised until it reaches a predetermined temperature range, and the temperature of the vulcanizing equipment is maintained in the temperature range until the active metal oxide is vulcanized to form a sulfided metal; after the vulcanization is completed, the injection of the vulcanizing agent is stopped; hydrogen is introduced to purge the vulcanizing equipment until the purge is completed;

[0077] Nitrogen is introduced to replace hydrogen, and the catalyst at the catalyst bed in the sulfidation equipment is controlled to cool down at a set cooling rate until the catalyst is cooled to a set temperature, and the catalyst cooled to the set temperature is transferred to the hydrogenation reactor through a conveying device equipped with the sulfidation equipment;

[0078] The appearance, internal components and electrical circuits of the vulcanizing equipment are inspected, and the number and location information of the vulcanizing equipment that does not meet the vulcanization reaction requirements after the inspection is sent to the intelligent terminal of the maintenance personnel. After receiving the number and location information of the vulcanizing equipment that does not meet the vulcanization reaction requirements, the maintenance personnel will perform maintenance inspection on it.

[0079] The above formulas are obtained by collecting a large amount of data and performing software simulation, and a formula close to the actual value is selected. The influencing weight factor and specific coefficient value in the formula are set by technical personnel in this field according to actual conditions, and can be adjusted and modified later.

[0080] The above description of the embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for ex situ sulfurization of a hydrogenation catalyst, characterized in that: Includes the following parts: Vulcanization preparation: Conduct a comprehensive inspection of the vulcanization equipment. After the inspection is completed, fill the vulcanization equipment with a set amount of catalyst. After the catalyst is filled, shut down the vulcanization equipment; Judgment analysis: preset the allowable fluctuation range of the estimated time, take the minimum value within the allowable fluctuation range of the estimated time as the minimum estimated time, and take the time when the minimum estimated time is reached as the starting time. From the starting time, obtain the various parameter information in the vulcanization process at the set time intervals. Substitute the standard deviation of oxygen concentration, standard deviation of carbon dioxide concentration, inert gas purge flow rate and preset control coefficient into the formula to obtain the comprehensive index of each vulcanization equipment in the reference group at each parameter monitoring time point, and analyze the various parameter information in the vulcanization process to obtain the evaluation index: After summing up the penetration times of each depth interval of the catalyst bed corresponding to each sulfurization equipment in the reference group at each parameter monitoring time point, the summed value is divided by the number of catalyst bed depth intervals corresponding to each sulfurization equipment to obtain the average penetration time of each sulfurization equipment at each parameter monitoring time point, and then the average penetration time of each sulfurization equipment at each parameter monitoring time point is divided by the time between each parameter monitoring time point and the starting time to obtain the control coefficient; The acquisition time of each parameter information in the vulcanization process after the start time is recorded as the parameter monitoring time point; wherein each parameter information includes the oxygen concentration and carbon dioxide concentration at the outlet of the vulcanization equipment, and the purge flow rate of the inert gas nitrogen; Optimal purge time: Arrange the obtained evaluation indexes in descending order from left to right, extract the largest evaluation index, and record the duration between the parameter monitoring time point corresponding to the largest evaluation index and the start time of the inert gas purge as the optimal purge time; Sulfurization reaction: After the inert gas purging of the vulcanization equipment is completed at the optimal purging time, the vulcanization reaction operation is carried out.

2. The method for ex situ sulfurization of a hydrogenation catalyst according to claim 1, characterized in that: The method further comprises: Estimated time: Determine the flow rate of the inert purge gas nitrogen according to the size of the vulcanization equipment and the catalyst loading amount, multiply the flow rate of the nitrogen by the cross-sectional area of ​​the pipeline through which the nitrogen flows, and thus obtain the estimated flow rate of the inert purge gas nitrogen; divide the total volume of the vulcanization equipment reactor by the flow rate of the inert purge gas nitrogen to obtain the time required for the oxygen concentration at the outlet of the vulcanization equipment pipeline to reach the preset standard concentration, and record this time as the estimated time; purge the vulcanization equipment reactor with nitrogen of the preset concentration at a preset flow rate for the estimated time, and record the time when the inert gas purge starts as the start time, monitor the oxygen concentration at the outlet of the vulcanization equipment at set time intervals, and record the time when the oxygen concentration at the outlet of the vulcanization equipment is monitored as the oxygen monitoring time point, wherein the pressure and temperature information of the vulcanization equipment are also obtained at the oxygen monitoring time point.

3. The method for ex situ sulfurization of a hydrogenation catalyst according to claim 1, characterized in that: After the inert gas is purged on the vulcanization equipment at the optimal purging time, the vulcanization reaction operation is performed, which specifically includes: The temperature of the vulcanizing equipment is raised to the temperature range of the initial decomposition stage of the sulfiding agent at a set heating rate, and the sulfiding agent is waited to be decomposed into hydrogen sulfide and other small molecular substances; after the sulfiding is completed, the injection of the sulfiding agent is stopped; hydrogen is introduced to purge the sulfiding equipment until the purge is completed; nitrogen is introduced to cool the catalyst to the set temperature, and the catalyst is transferred to the hydrogenation reactor.

4. The method for ex situ sulfurization of a hydrogenation catalyst according to claim 1, characterized in that: The evaluation index is obtained by analyzing the various parameter information in the vulcanization process. The specific process includes the following parts: A set number of identical vulcanization equipment are used to form a test group, and after analyzing and processing the vulcanization equipment in the test group, the vulcanization equipment that does not meet the test requirements is eliminated, and the vulcanization equipment that meets the test requirements is re-formed into a reference group; Obtain the oxygen concentration at the outlet of each vulcanization equipment in the reference group at each parameter monitoring time point, and calculate the difference between the oxygen concentration at the outlet of each vulcanization equipment at each parameter monitoring time point and the preset standard concentration in turn, take the absolute value of the difference to obtain the standard deviation of the oxygen concentration at the outlet of each vulcanization equipment at each parameter monitoring time point, and record it as ,in is the vulcanizing equipment number within the reference group, , is the number of each parameter monitoring time point, ; According to the above process of obtaining the standard deviation of oxygen concentration, the standard deviation of carbon dioxide concentration at the outlet of each vulcanization equipment in the reference group at each parameter monitoring time point is obtained and recorded as ; Obtain the inert gas purge flow recorded by the flow meter on the gas pipeline at each parameter monitoring time point for each vulcanization equipment in the reference group and record it as ; The standard deviation of oxygen concentration , standard deviation of carbon dioxide concentration , Inert gas purge flow Substituting into the formula: , and obtain the comprehensive index of each vulcanization equipment in the reference group at each parameter monitoring time point ,in , , They are the maximum allowable oxygen concentration, the maximum allowable carbon dioxide concentration, and the estimated flow rate of the inert purge gas nitrogen. , , are the weight factors corresponding to the standard deviation of oxygen concentration, standard deviation of carbon dioxide concentration, and inert gas purge flow rate, respectively. is the preset control coefficient; The comprehensive indexes of all the vulcanization equipment in the reference group corresponding to each parameter monitoring time point are summed up in turn, and the summed value is divided by the total number of vulcanization equipment in the reference group to obtain the average comprehensive index of all the vulcanization equipment in the reference group at each parameter monitoring time point, and the average comprehensive index of all the vulcanization equipment in the reference group corresponding to each parameter monitoring time point is recorded as the evaluation index .

5. The method for ex situ sulfurization of a hydrogenation catalyst according to claim 4, characterized in that: The vulcanization equipment in the test group is analyzed and processed to remove the vulcanization equipment that does not meet the test requirements, and the vulcanization equipment that meets the test requirements is reconstructed into a reference group, specifically including: Obtain the oxygen concentration corresponding to the oxygen monitoring time point corresponding to the minimum estimated time when each vulcanization equipment in the test group is simultaneously purged with inert gas, and calculate the difference between the oxygen concentration at the outlet of each vulcanization equipment and the preset standard concentration, take the absolute value of the calculated difference value to obtain the concentration standard difference value, and divide the concentration standard difference value of each vulcanization equipment by the preset standard concentration in turn to obtain the deviation coefficient of each vulcanization equipment; At the start-up time of each vulcanization equipment, the pressure and temperature of each vulcanization equipment are monitored for a set time until the minimum estimated time is reached, and the monitoring time is recorded as the test time point; Obtain the temperature of each vulcanization equipment at each test time point, extract the highest temperature and the lowest temperature of each vulcanization equipment at each test time point, calculate the difference between the highest temperature and the lowest temperature, so as to obtain the temperature difference extreme value of each vulcanization equipment at each test time point; respectively, accumulate the duration of the temperature difference extreme value of each vulcanization equipment within the minimum estimated time to obtain the extreme duration, and then divide the extreme duration of each vulcanization equipment by the minimum estimated duration to obtain the extreme temperature difference deviation coefficient of each vulcanization equipment; According to the above process of obtaining the extreme deviation coefficient of each vulcanization equipment, the pressure of each vulcanization equipment is analyzed to obtain the extreme pressure difference deviation coefficient of each vulcanization equipment; Preset the weight factors of the deviation coefficient, the extreme temperature difference deviation coefficient, and the extreme pressure difference deviation coefficient, and multiply the deviation coefficient, the extreme temperature difference deviation coefficient, and the extreme pressure difference deviation coefficient with their corresponding weight factors and then sum them to obtain the test index; A test index threshold is preset, and the test index corresponding to each vulcanization equipment is matched with the preset test index threshold in turn, and the vulcanization equipment corresponding to the test index greater than the preset test index threshold is removed from the test group, and the remaining vulcanization equipment is reconstructed into a reference group.

6. The method for ex situ sulfurization of a hydrogenation catalyst according to claim 4, characterized in that: The process of obtaining the comparison coefficient specifically includes the following parts: Obtain the oxygen concentration of several set monitoring depths of the catalyst bed of each sulfiding equipment in the reference group at the parameter monitoring time point, calculate the oxygen concentration of adjacent monitoring depths in order from high to low depths to obtain the concentration difference of adjacent depths, and divide each adjacent depth concentration difference by the interval depth corresponding to the corresponding adjacent depth concentration difference and take the absolute value to obtain the concentration gradient corresponding to each adjacent depth concentration difference, which is recorded as ,in is the vulcanizing equipment number within the reference group, is the number of the concentration gradient, ; Obtain the temperature and pressure of the vulcanizing equipment corresponding to each parameter monitoring time point of each vulcanizing equipment in the reference group, and record them as and The subsequent entry formula is: , and obtain the diffusion index corresponding to each vulcanization equipment in the reference group at each parameter monitoring time point ,in , are the molar masses of oxygen and nitrogen, respectively. , are the molecular diffusion volumes of oxygen and nitrogen respectively; Substitute the obtained diffusion index into the formula: , and obtain the penetration time of each depth interval of the catalyst bed corresponding to the diffusion index of each sulfurization equipment in the reference group at each parameter monitoring time point ;in is the total thickness of the catalyst bed.

7. The method for ex situ sulfurization of a hydrogenation catalyst according to claim 1, characterized in that: During the vulcanization preparation, a comprehensive inspection of the vulcanization equipment is performed, specifically including an appearance inspection, an internal component inspection, and an electrical circuit inspection.

8. The method for ex situ sulfurization of a hydrogenation catalyst according to claim 5, characterized in that: The method of analyzing and processing the vulcanization equipment in the test group, removing the vulcanization equipment that does not meet the test requirements, and re-forming the vulcanization equipment that meets the test requirements into a reference group, also includes: The oxygen concentration monitored at each oxygen monitoring time point and the equipment number and location information of the eliminated vulcanization equipment that does not meet the test requirements are recorded as abnormal information, and the abnormal information is sent to the maintenance personnel's smart terminal. After receiving the oxygen concentration monitored at each oxygen monitoring time point and the equipment number and location information, the maintenance personnel will perform maintenance inspections on it.

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