High-performance composite modified calcined petroleum coke and preparation method thereof

Abstract

The invention relates to the field of petroleum coke preparation, in particular to high-performance composite modified calcined petroleum coke and a preparation method thereof.The method comprises the steps that calcined petroleum coke, crystalline flake graphite powder, water-soluble cellulose ether, calcium oxide, copper chloride and sodium silicate are stirred, and in the intercalation reaction process, a temperature difference sample at each collection moment is obtained; obtaining a segmented sample in combination with anomaly detection; dividing the temperature control process of the sintering furnace based on the segmentation sample, confirming a temperature difference matrix of each interval, and obtaining a response difference value of each batch; adjusting temperature control parameters of the sintering furnace of the current batch to obtain a graphite intercalation compound; after the graphite intercalation compound is subjected to ball-milling crushing, the base material, water-soluble cellulose ether, sodium silicate and calcium oxide are added, stirring and mixing are continued, and the high-performance composite modified petroleum coke is obtained. The method aims at avoiding the situation that the product intercalation degree is not uniform due to the fact that the sintering reaction temperature is not uniform.

Description

Technical Field

[0001] This application relates to the field of petroleum coke preparation, and particularly to a high-performance composite modified calcined petroleum coke and its preparation method. Background Art

[0002] With the rapid development of modern industry, the demand for high-performance carbonaceous materials in many industries has been continuously increasing. In the aluminum smelting industry, high-quality carbonaceous anode materials play a crucial role in reducing energy consumption, improving the purity of aluminum, and enhancing production efficiency; in the field of battery manufacturing, high-performance carbon negative electrode materials can significantly enhance the charge and discharge performance of batteries and extend their service life. Calcined petroleum coke, as an important carbonaceous raw material, is widely used in the above industries due to its outstanding advantages such as good electrical conductivity and high carbon content. However, traditional calcined petroleum coke has certain shortcomings in performance. For example, when its sulfur content is relatively high, polluting gases will be released during use, which will not only have a negative impact on product quality but also cause adverse effects on the environment; at the same time, its pore structure and microscopic morphology are difficult to fully meet the stringent requirements of specific application scenarios.

[0003] To effectively solve these problems, the production technology of composite modified calcined petroleum coke has emerged. By implementing composite modification on calcined petroleum coke, its physical and chemical properties can be effectively optimized, and its application value in various industries can be improved, thus meeting the ever-upgrading industrial production requirements. At present, the production and preparation process of calcined petroleum coke has achieved automated operation. However, during the production process of different batches of materials, due to significant differences in the equipment parameter responses of different batches at each stage of production and preparation, the sintering reaction temperature is uneven, resulting in uneven intercalation degrees of the products, and further affecting the uniformity of product quality and performance. Summary of the Invention

[0004] In view of the above, it is necessary to provide a high-performance composite modified calcined petroleum coke and its preparation method to solve the above problems.

[0005] The first aspect of this application provides a method for preparing a high-performance composite modified calcined petroleum coke, and the method includes: Mix and stir calcined petroleum coke, flake graphite powder, water-soluble cellulose ether, calcium oxide, copper chloride, and sodium silicate. During the process of putting the stirred mixture into a sintering furnace in batches for intercalation reaction, obtain the temperature difference between the temperature data at each acquisition moment and the preset temperature data. Form a temperature difference sample by all the temperature differences in the same order of all batches, map all the temperature difference samples, and combine anomaly detection to obtain a segmented sample; Divide the sintering furnace temperature control process based on the segmented samples, combine the temperature difference samples corresponding to the divided intervals, confirm the temperature difference matrix for each divided interval, compare the responses of different batches to temperature control in the temperature difference matrix, and combine the data change trend of the temperature difference matrix to obtain the response difference value for each batch; adjust the parameters of the sintering furnace temperature control for the current batch according to the response difference value of the previous batch of the current batch to obtain graphite intercalation compounds. After ball milling and crushing the graphite intercalation compounds, add base materials, water-soluble cellulose ether, sodium silicate, and calcium oxide and continue to stir and mix. Granulate the mixed materials mechanically and obtain high-performance composite modified petroleum coke after encapsulation.

[0006] Among them, the mass ratio of calcined petroleum coke, flake graphite powder, water-soluble cellulose ether, calcium oxide, copper chloride, and sodium silicate for stirring is: 80~83:7~10:3.5~4:3~4.5:3~3.5:1~2; use a paddle-type stirring paddle, the stirring speed is 100~200 revolutions per minute, the power is set to 5~15 kw, and the duration is 20 minutes.

[0007] Among them, the time for the intercalation reaction is 2~4 hours, and the reaction temperature is 500~600 °C.

[0008] Among them, the process of mapping all the temperature difference samples and obtaining the segmented samples in combination with anomaly detection includes: Calculate the mean and variance of all the data in each temperature difference sample, and use them as the horizontal and vertical coordinates in the two-dimensional coordinate system respectively; Use anomaly detection to obtain the anomaly points for all the data points in the coordinate system, and use the temperature difference samples corresponding to the anomaly points as the segmented samples.

[0009] Among them, the process of dividing the sintering furnace temperature control process based on the segmented samples, combining the temperature difference samples corresponding to the divided intervals, and confirming the temperature difference matrix for each divided interval is specifically: Use the acquisition moment corresponding to the segmented samples as the segmentation moment, divide the time intervals corresponding to all the temperature difference samples, and obtain several divided intervals; Use the matrix composed of the temperature difference samples within the same divided interval as the temperature difference matrix corresponding to each divided interval.

[0010] Among them, the process of comparing the responses of different batches to temperature control in the temperature difference matrix and obtaining the response difference value for each batch in combination with the data change trend of the temperature difference matrix includes: Use the temperature difference matrix of each divided interval as the input, and use the objective weighting method to obtain the weights corresponding to each row of data in the temperature difference matrix; Calculate the absolute value of the difference between the weight values corresponding to the temperature difference data of each batch in the temperature difference matrix and the weight values corresponding to the temperature difference data of other batches, and take the average value of all the absolute values as the consistency difference of each batch; Analyze the trend statistic of each batch in each temperature difference matrix, obtain the average level of the positive fusion of the trend statistic of each batch in all temperature difference matrices and the consistency difference, and obtain the response difference value of each batch.

[0011] Among them, adjusting the parameters of the sintering furnace temperature control according to the response difference value of the previous batch of the current batch specifically includes: Obtain the normalization result of all response difference values of the previous batch of the current batch. If the normalization result is greater than the preset judgment threshold, adjust the control parameters of the sintering furnace of the current batch. The adjustment formula is: ; where 、 respectively represent the sintering furnace control parameters of the th and the th batches; represents the normalization result of the response difference value of the th batch; Otherwise, take the sintering furnace control parameters of the previous batch as the sintering furnace control parameters of the current batch.

[0012] Among them, the rotation speed for ball milling and crushing is 150 - 250 revolutions per minute.

[0013] Among them, the mass ratio of adding the base material, water-soluble cellulose ether, sodium silicate and calcium oxide and continuing to stir and mix is 100:3.5 - 4:1 - 2:3 - 4.5; the stirring rotation speed is 100 - 200 revolutions per minute, and stir for 15 - 20 minutes.

[0014] In a second aspect, the embodiments of the present application further provide a high-performance composite modified calcined petroleum coke, which is obtained through the method for preparing a high-performance composite modified calcined petroleum coke.

[0015] In the above solution, in view of the fact that the temperature control accuracy has a significant impact on maintaining activity and diffusion ability, once the sintering reaction temperature is uneven, the reaction rates in different regions will be different, which will in turn cause the intercalation degree of the products to be uneven, seriously affecting the uniformity of the product quality and performance. To address this problem, the present application proposes a high-performance composite modified calcined petroleum coke and its preparation method, which specifically includes steps such as raw material preparation and detection, particle size screening, uniform stirring by a first dry powder mixer, base material preparation, base material crushing, base material particle size screening, second dry powder mixer mixing and stirring, mechanical granulation, and quantitative packaging. An industrial control system is introduced to precisely control the preparation and production process of each stage.

[0016] Meanwhile, aiming at the key issue of the influence of sintering parameter control on the properties of petroleum coke during the production process, this application focuses on analyzing the temperature deviation during the preparation of different batches of petroleum coke and the tendency characteristics of the temperature deviation during the control process. On this basis, the control parameters during the sintering process are optimized and adjusted, effectively avoiding the situation of uneven intercalation degree of products caused by uneven sintering reaction temperature, solving the problem that the product quality and performance uniformity are affected, and thus significantly improving the preparation quality of high-performance composite modified petroleum coke. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a flowchart of the steps of a method for preparing high-performance composite modified calcined petroleum coke provided by an embodiment of this application; Figure 2 It is a control flowchart of the temperature parameters during the intercalation reaction process provided by an embodiment of this application. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0018] In the description of the embodiments of this application, words such as "exemplary", "or", "for example" are used to represent examples, illustrations or explanations. Any embodiment or design solution described as "exemplary" or "for example" in the embodiments of this application should not be construed as being more preferred or having more advantages than other embodiments or design solutions. Exactly speaking, the use of words such as "exemplary", "or", "for example" is intended to present relevant concepts in a specific manner.

[0019] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which this application belongs. The terms used in the description of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0020] In addition, it should be noted that the terms "first", "second" in this application and the accompanying drawings are used to distinguish similar objects and are not used to describe a specific order or sequence. For the methods disclosed in the embodiments of this application or shown in the flowcharts, including one or more steps for implementing the method, without departing from the protection scope of this application, the execution order of multiple steps can be interchanged with each other, and some steps can also be deleted.

[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which this application belongs.

[0022] The following specifically describes the specific solutions of a high-performance composite modified calcined petroleum coke and its preparation method provided by this application with reference to the accompanying drawings.

[0023] Embodiment 1 Please refer to Figure 1 , which shows the step flow chart of a preparation method of a high-performance composite modified calcined petroleum coke provided in Embodiment 1 of the present application. The method includes the following steps: S1, Raw material preparation and detection Prepare calcined petroleum coke, flake graphite powder, water-soluble cellulose ether, calcium oxide, copper chloride and sodium silicate. Use chemical analysis instruments to detect the purity, impurity content, etc. of each raw material to ensure compliance with production requirements. In this application, a spectral analyzer is used to detect trace elements in the raw materials.

[0024] S2, Particle size screening Use a vibrating screen to screen the particle size of the calcined petroleum coke. Specifically, a sieve mesh of 100-200 meshes is selected to remove particles that do not meet the particle size requirements, facilitating subsequent uniform stirring and mixing.

[0025] S3, First dry powder mixer for uniform stirring According to the mass ratio of 80:7:3.5:3:3:1, add the calcined petroleum coke, flake graphite powder, water-soluble cellulose ether, calcium oxide, copper chloride and sodium silicate to the dry powder mixer. Start the mixer, set the stirring speed to 200 revolutions per minute, set the power to 5 kw, select a paddle-type stirring paddle, and stir for 20 minutes to make the raw materials fully mixed and ensure the stirring effect. During the uniform stirring process of the dry powder mixer, the stirring speed is collected in real time through a speed sensor; and the collected data is transmitted to the industrial control system in real time, and the stirring speed during the dry powder stirring and mixing process is controlled in real time through the industrial control system.

[0026] S4, Base material preparation Divide the mixture after the stirring and mixing is completed into equal parts and add them to the vacuum sintering furnace in batches. Set the temperature in the furnace at Perform Intercalation reaction for 4 hours to prepare - Graphite intercalation compound; During the above treatment process, the temperature data during the reaction process is collected in real time through the set temperature sensor, and the collected temperature data is transmitted to the industrial control system in real time. The control flow chart of the temperature parameters during the intercalation reaction through the industrial control system is as Figure 2 shown.

[0027] The vacuum environment created by the vacuum sintering furnace can effectively prevent the oxidation of graphite and copper chloride in the mixture at high temperatures, reduce the generation of impurities, ensure the purity of the graphite intercalation compound, and at the same time remove the volatile impurities in the raw materials, improving the purity and efficiency of the intercalation reaction. The reaction temperature is set at , at this time It has a certain activity, which can overcome the interlayer force of graphite to complete intercalation without damaging the graphite structure or causing decomposition due to too high temperature.

[0028] The temperature data is collected in real time through a temperature sensor and transmitted to the industrial control system for regulation to ensure that the reaction temperature is stable at ; among them, the controller for the temperature control of the sintering furnace in the industrial control system is a PID controller, and the initial values of the parameters of the PID controller are determined by the attenuation curve method.

[0029] During the production and preparation of calcined petroleum coke, the temperature control process in the reaction furnace has differences in temperature uniformity during the reaction process due to the change in the stability of the heating element, resulting in differences in the intercalation reaction between different batches; therefore, when determining the temperature adjustment parameters for the current batch, the differences in the response speed of temperature control between different batches are fully considered, and then the temperature control response parameters in the current industrial system are adjusted. The specific adjustment process is as follows: (1) Compare the temperature control deviations in the reaction processes of different batches in the industrial control system to obtain segmented samples.

[0030] For each batch up to the current production of calcined petroleum coke, obtain the temperature data at each acquisition moment during the base material preparation reaction process of each batch. Take the difference between each temperature data and the set standard temperature as the temperature difference at the acquisition moment, and construct a temperature difference sample for the temperature differences at the same order acquisition moments during the base material preparation reaction processes of all batches , and denote the th temperature difference sample during the base material preparation reaction processes of all batches as , where , , are the temperature differences at the th acquisition moment during the base material preparation reaction processes of the 1st batch, the 2nd batch, and the th batch respectively; in this embodiment, the standard temperature value is ; the implementer can adjust it according to the actual situation.

[0031] Data mapping is performed on all temperature difference samples. The mapping method is as follows: the mean and variance of all data in each temperature difference sample are calculated, and they are used as the horizontal and vertical coordinates in the two-dimensional coordinate system, so that each temperature difference sample is mapped to a data point in the two-dimensional coordinate system. All data points are used as input, and the anomaly detection method is used to detect and obtain the anomaly points, and the temperature difference samples corresponding to the anomaly points are used as segmentation samples. Compared with directly performing anomaly detection on temperature difference samples, mapping the mean and variance and then performing anomaly detection can accurately compare the control response differences of different batches in the preparation process at different time periods. Among them, commonly used methods for anomaly detection include but are not limited to the local outlier factor algorithm and the DBSCAN algorithm.

[0032] (2) The sintering furnace temperature control process is divided according to the segmented samples, and a deviation comparison analysis is performed based on the division results.

[0033] For the temperature difference samples and segmented samples obtained in the above process, the acquisition time corresponding to the segmented samples is used as the segmentation time, and the time intervals corresponding to all temperature difference samples are divided; specifically, for example, the segmentation time corresponding to the segmented samples is , and , if the time interval is [ ],in , Respectively represent the 1st and mth acquisition moments; then the division intervals are [ 、[ 、[ and[ ]; the temperature difference samples in the same partition interval The matrix formed in the order of acquisition time is used as the temperature difference matrix corresponding to each divided interval; for example, the divided interval [ The temperature difference matrix composed of the temperature difference samples corresponding to ] is It should be understood that each row of the temperature difference matrix corresponds to the temperature difference value of the same batch within the corresponding divided interval.

[0034] In order to accurately reflect the differences in temperature control responses of different batches within the divided intervals corresponding to each temperature difference matrix, each temperature difference matrix is ​​taken as input, and the CRITIC method is used to obtain the weight corresponding to each row of data in the temperature difference matrix. The absolute value of the difference between the weight corresponding to each row of data in the temperature difference matrix and the weight corresponding to each other row of data is calculated, and the average of all the absolute values ​​is taken as the consistency difference of each row of data.

[0035] According to the consistency difference of each row of data in all divided temperature difference matrices for each batch and the trend characteristics of data changes in each temperature difference matrix, calculate the response difference value of the sintering furnace temperature control in the preparation production process of each batch. Specifically: analyze the trend statistic of each batch in each temperature difference matrix; obtain the average level of the positive fusion of the trend statistic and the consistency difference of each batch in all temperature difference matrices to get the response difference value of each batch.

[0036] In this embodiment, the trend statistic is calculated by using the trend verification method, which is a well-known prior art and will not be elaborated here; the positive fusion of multiple variables adopts the calculation method of multiplication; the average level is calculated by using the method of taking the mean.

[0037] It should be understood that the larger the calculation result of the response difference value, the greater the deviation of the industrial control system for temperature control in regulating the temperature at different times during the preparation process, and the greater the response difference of the industrial control system for temperature control.

[0038] (3)Optimize and adjust the parameters of the sintering furnace control in the preparation process of the current batch according to the response difference value of the temperature control in the production process of the previous batch to obtain the graphite intercalation compound.

[0039] In the production process of high-performance composite modified calcined petroleum coke, if there is no significant difference in the temperature control response speed in the production process of the previous batch, the control parameters of the sintering furnace in the production process of the current batch will not be optimized and adjusted; otherwise, the control parameters of the sintering furnace in the production process of the current batch will be optimized and adjusted. For example, in the production process of the previous batch, if the industrial system is relatively stable in controlling the temperature within the set range and there is no significant change in the temperature control deviation at different times compared with other batches that have been produced, it indicates that the PID controller for sintering furnace temperature control in the industrial control system responds in a timely manner under the set proportional parameter; otherwise, it indicates that the PID controller in the industrial control system for temperature control in the production process of the previous batch does not respond in a timely manner under the set proportional parameter, resulting in a significant difference in the control response.

[0040] Therefore, in this application, the response difference values of the temperature control of all batches are used as inputs, and the normalization method is used to obtain the normalization results of all the response difference values of the temperature control. To avoid excessive optimization and adjustment during the production process, the judgment threshold for optimization and adjustment is set to 0.2 in this application. If the normalization result of the response difference value of the temperature control of the previous batch is calculated to be greater than the judgment threshold, the control parameters of the sintering furnace for the preparation production of the current batch will be adjusted. The specific adjustment relationship is: ; where 、 respectively represent the th and the th sintering furnace control parameters during the preparation and production processes of batches. The sintering furnace control parameters are the proportional parameters in the controller. The greater the adjustment range of the control parameters, the faster the response to the temperature fluctuations during the preparation and production process of the current batch, and thus the temperature can be kept stable. represents the normalized result of the response difference value during the preparation and production process of the th batch.

[0041] Based on the above process, for the production of the current batch, if there is no significant difference in the control response speed during the production process of the previous batch, it indicates that the temperature sensor can accurately collect temperature data in real time during the current production stage and transmit it to the controller in the industrial control system for controlling the temperature of the sintering furnace. At the same time, the normalized result of the response difference value of the temperature control of the previous batch calculated is less than the judgment threshold, and the control parameters of the controller for the temperature control of the industrial production system in the previous batch are retained, so that the controller can smoothly adjust the output power of the control signal during the production process of the current batch; otherwise, the control parameters of the controller are adjusted accordingly to avoid the oscillation of the sintering furnace temperature control caused by delay or overshoot, which affects the quality of the sintering preparation production.

[0042] Precise sintering temperature control during the production process of graphite intercalation compounds can better maintain activity and diffusion ability, ensure that the intercalation reaction proceeds at the expected rate and manner, and stabilize the structure and performance of the product; therefore, the sintering furnace control parameters during the preparation and production process of each batch are adjusted and determined, and based on the adjusted and determined results, the stability during the preparation and production process is maintained through the industrial control system, thereby reducing the difference in product quality consistency between different batches of production preparations to obtain graphite intercalation compounds.

[0043] S5, Base material crushing The graphite intercalation compound is crushed by a jaw crusher. After preliminary crushing, it is pulverized by a ball mill to make its particle size reach 200 mesh, and the rotational speed of the ball mill is set at 250 revolutions per minute. The rotational speed data of the ball mill is collected in real time through the set rotational speed sensor and transmitted to the industrial control system in real time, and the rotational speed during the base material crushing process is controlled in real time through the industrial control system.

[0044] S6, Base material particle size screening The crushed and ball-milled base material is screened for particle size through a vibrating screen to ensure that the particle size meets the requirement of 200 mesh, and too large or too small particles are removed. The sieve mesh is selected as 200 mesh.

[0045] S7, Second dry powder mixer mixing Raw material ratio addition: Add the base material, water-soluble cellulose ether, sodium silicate, and calcium oxide to a dry powder mixer according to a mass ratio of 100:3.5:1:3. Turn on the mixer, set the stirring speed at 100 revolutions per minute, and stir for 20 minutes to fully mix the materials evenly. Collect the real-time stirring speed data through the set rotational speed sensor and transmit the collected data to the industrial control system in real time, and control the stirring speed in real time through the industrial production control system.

[0046] S8, mechanical granulation Make the mixed materials into spherical particles with a diameter of 0.5 - 1.5 mm through a mechanical granulation device. The mechanical granulation device selects an extrusion granulator, and the screw speed of the extrusion granulator is set at 30 revolutions per minute. Collect the data of the screw speed of the extrusion granulator in real time through the set rotational speed sensor, and transmit the collected data to the industrial control system in real time, and control the screw speed of the extrusion granulator in real time through the industrial control system.

[0047] S9, quantitative packaging Quantitatively weigh the granulated product through an electronic weighing device, and package it through an automatic packaging machine according to the specified packaging specifications to obtain a high-performance composite modified calcined petroleum coke; the packaging speed is 10 - 30 packages per minute.

[0048] Example 2 Please refer to Figure 1 , which shows the step flow chart of a method for preparing a high-performance composite modified calcined petroleum coke provided in Embodiment 2 of the present application. The method is the same as the steps in Embodiment 1; among them, in S3, add calcined petroleum coke, flake graphite powder, water-soluble cellulose ether, calcium oxide, copper chloride, and sodium silicate to a dry powder mixer according to a mass ratio of 83:10:4:4.5:3.5:2, set the stirring speed at 200 revolutions per minute, and set the power at 15 kw; in S4, the reaction time in the furnace is 3 hours; in S5, the rotational speed of the ball mill is set at 250 revolutions per minute; in S7, add the base material, water-soluble cellulose ether, sodium silicate, and calcium oxide to a dry powder mixer according to a mass ratio of 100:4:2:4.5. Turn on the mixer, set the stirring speed at 200 revolutions per minute, and stir for 15 minutes; in S8, the screw speed of the extrusion granulator is set at 60 revolutions per minute.

[0049] Example 3 Please refer to Figure 1, which shows the process flow chart of a method for preparing a high-performance composite modified calcined petroleum coke provided in Embodiment 3 of the present application. The steps of this method are the same as those in Embodiment 1. Among them, in S3, according to the mass ratio of 80:10:3.5:4:3.5:1, calcined petroleum coke, flake graphite powder, water-soluble cellulose ether, calcium oxide, copper chloride, and sodium silicate are added to a dry powder mixer. The stirring speed is set at 200 revolutions per minute, and the power is set at 5 kw. In S4, the reaction time in the furnace is 2 hours. In S5, the rotation speed of the ball mill is set at 150 revolutions per minute. In S7, according to the mass ratio of 100:3.5:1:4, the base material, water-soluble cellulose ether, sodium silicate, and calcium oxide are added to the dry powder mixer. The mixer is started, and the stirring speed is set at 100 revolutions per minute and stirred for 20 minutes. In S8, the screw rotation speed of the extrusion granulator is set at 45 revolutions per minute.

[0050] Specifically, the comparison of the parameters of the calcined petroleum coke obtained in the present application and the petroleum coke produced by the traditional method in terms of bulk resistivity, impulse current tolerance, and power frequency current tolerance is shown in the following table. Among them, Embodiment 1 and Embodiment 2 adopt the preparation method in the present application, and Comparative Example 1 and Comparative Example 2 do not adopt the method of optimizing the production process control, but the specific implementation processes and parameters: Embodiment 1 and Comparative Example 1 are the same, and Embodiment 2 and Comparative Example 2 are the same.

[0051] Table 1: Comparison Table of Calcined Petroleum Coke Parameters Among them, the conventional impulse current test is 10 - 50 KA, and the conventional power frequency current test is 1 - 10 KA. represents the resistance difference before and after the impulse.

[0052] Through the analysis of the test data in the table, it can be seen that after the optimization and adjustment of the production process, the petroleum coke produced in Embodiment 1 and Embodiment 2 exhibits better performance. Compared with Comparative Example 1 and Comparative Example 2, the bulk resistivity of the petroleum coke produced in Embodiment 1 and Embodiment 2 is lower. At the same time, in the impulse current tolerance and power frequency current tolerance tests, the resistance change of the petroleum coke in Embodiment 1 and Embodiment 2 is significantly smaller. This means that the resistance change of the petroleum coke under impulse current or power frequency current is smaller, with better conductivity and stronger impulse resistance, and can effectively withstand the current fluctuation without significant resistance change. The differences in these performance parameters fully demonstrate that the preparation method of the present application can effectively improve the quality characteristics of petroleum coke reflected in terms of bulk resistivity, impulse current tolerance, and power frequency current tolerance, and significantly improve the product performance.

[0053] Based on the same inventive concept as the above method, the embodiment of the present application also provides a high-performance composite modified calcined petroleum coke, which is obtained by the above method for preparing a high-performance composite modified calcined petroleum coke.

[0054] In summary, in view of the significant impact of temperature control accuracy on maintaining activity and diffusion ability, once the sintering reaction temperature is uneven, the reaction rates in different regions will vary, resulting in uneven intercalation degrees of the products, seriously affecting the quality and performance uniformity of the products. To address this issue, the present application proposes a high-performance composite modified calcined petroleum coke and its preparation method, which specifically includes steps such as raw material preparation and detection, particle size screening, uniform stirring in the first dry powder mixer, base material preparation, base material crushing, base material particle size screening, mixing and stirring in the second dry powder mixer, mechanical granulation, and quantitative packaging. An industrial control system is introduced to precisely control the preparation and production processes at each stage.

[0055] Meanwhile, regarding the key issue of the impact of sintering parameter control on the performance of petroleum coke during the production process, the present application focuses on analyzing the temperature deviation during the preparation of different batches of petroleum coke and the tendency characteristics of the temperature deviation during the control process. On this basis, the control parameters during the sintering process are optimized and adjusted, effectively avoiding the situation of uneven intercalation degrees of the products caused by uneven sintering reaction temperature, and solving the problem of the affected quality and performance uniformity of the products, thereby significantly improving the preparation and production quality of high-performance composite modified petroleum coke.

[0056] The flowcharts and block diagrams in the accompanying drawings illustrate the possible architectures, functions, and operations of systems, methods, and computer program products according to the embodiments of the present application. In this regard, each block in the flowchart or block diagram may represent a module, a program segment, or a part of code, and the module, program segment, or part of code contains one or more executable instructions for implementing the specified logical function. In some alternative implementations, the functions marked in the blocks may occur in a different order than marked in the accompanying drawings. For example, two consecutive blocks may actually be executed substantially in parallel, and they may sometimes be executed in the reverse order, depending on the functions involved. In the descriptions corresponding to the flowcharts and block diagrams in the accompanying drawings, the operations or steps corresponding to different blocks may also occur in a different order than disclosed in the descriptions, and sometimes there is no specific order between different operations or steps. For example, two consecutive operations or steps may actually be executed substantially in parallel, and they may sometimes be executed in the reverse order, depending on the functions involved. Each block in the block diagram and / or flowchart, and the combination of blocks in the block diagram and / or flowchart, can be implemented by a dedicated hardware-based system for performing the specified functions or actions, or can be implemented by a combination of dedicated hardware and computer instructions.

[0057] For those skilled in the art, it is obvious that the present application is not limited to the details of the above-described exemplary embodiments, and the present application can be implemented in other specific forms without departing from the basic characteristics of the present application. Therefore, from any point of view, the above-described embodiments of the present application should be regarded as exemplary and non-limiting; modifying the technical solutions recorded in the foregoing embodiments, or equivalently replacing some of the technical features therein, does not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application, and should all be included within the protection scope of the present application.

Claims

1. A method for preparing high-performance composite modified calcined petroleum coke, characterized in that: The method comprises the following steps: Calcined petroleum coke, flake graphite powder, water-soluble cellulose ether, calcium oxide, cupric chloride and sodium silicate are mixed and stirred, and the stirred mixture is put into a sintering furnace in batches for intercalation reaction, and the temperature difference between the temperature data at each acquisition moment and the preset temperature data is obtained, and all the temperature differences in the same order of all batches are combined into a temperature difference sample, and all the temperature difference samples are mapped, and combined with anomaly detection, a segmented sample is obtained; The temperature control process of the sintering furnace is divided based on the segmented samples, and the temperature difference matrix of each divided interval is confirmed in combination with the temperature difference samples corresponding to the divided intervals, and the responses of different batches to the temperature control in the temperature difference matrix are compared, and the response difference value of each batch is obtained in combination with the data change trend of the temperature difference matrix; according to the response difference value of the previous batch of the current batch, the parameters of the sintering furnace temperature control of the current batch are adjusted to obtain the graphite intercalation compound; After the graphite intercalation compound is crushed by ball milling, base material, water-soluble cellulose ether, sodium silicate and calcium oxide are added and stirred and mixed continuously. The mixed material is mechanically granulated and packaged to obtain high-performance composite modified petroleum coke.

2. The method for preparing high-performance composite modified calcined petroleum coke according to claim 1, characterized in that: The mass ratio of the calcined petroleum coke, flake graphite powder, water-soluble cellulose ether, calcium oxide, cupric chloride and sodium silicate for stirring is: 80~83:7~10:3.5~4:3~4.5:3~3.5:1~2; a paddle-type stirring paddle is used, the stirring speed is 100~200 rpm, the power is set to 5~15kw, and the stirring time is 20 minutes.

3. The method for preparing high-performance composite modified calcined petroleum coke according to claim 1, characterized in that: The intercalation reaction is carried out for 2 to 4 hours at a reaction temperature of 500 to 600°C.

4. The method for preparing high-performance composite modified calcined petroleum coke according to claim 1, characterized in that: The process of mapping all temperature difference samples and combining anomaly detection to obtain segmented samples includes: Calculate the mean and variance of all data in each temperature difference sample as the horizontal and vertical coordinates in the two-dimensional coordinate system; All data points in the coordinate system are detected using anomaly detection to obtain abnormal points, and the temperature difference samples corresponding to the abnormal points are used as segmentation samples.

5. The method for preparing high-performance composite modified calcined petroleum coke according to claim 1, characterized in that: The sintering furnace temperature control process is divided based on the segmented samples, and the temperature difference matrix of each divided interval is determined in combination with the temperature difference samples corresponding to the divided intervals, which is specifically: The collection time corresponding to the segmented sample is used as the segmentation time, and the time interval corresponding to all temperature difference samples is divided to obtain a number of divided intervals; The matrix composed of temperature difference samples in the same divided interval is used as the temperature difference matrix corresponding to each divided interval.

6. The method for preparing high-performance composite modified calcined petroleum coke according to claim 1, characterized in that: The comparison of the responses of different batches to temperature control in the temperature difference matrix, combined with the data change trend of the temperature difference matrix, obtains the response difference value of each batch, including: The temperature difference matrix of each divided interval is taken as input, and the objective weighting method is used to obtain the weight corresponding to each row of data in the temperature difference matrix; Calculate the absolute value of the difference between the corresponding weight of each batch of temperature difference data in the temperature difference matrix and the corresponding weight of other batches of temperature difference data, and take the average of all the absolute values ​​as the consistency difference of each batch; The trend statistics of each batch in each temperature difference matrix are analyzed, and the average level of the trend statistics of each batch in all temperature difference matrices is forward fused with the consistency difference to obtain the response difference value of each batch.

7. The method for preparing high-performance composite modified calcined petroleum coke according to claim 1, characterized in that: The parameters of the sintering furnace temperature control of the current batch are adjusted according to the response difference value of the previous batch of the current batch, specifically: The normalized result of all response difference values ​​of the previous batch of the current batch is obtained. If the normalized result is greater than the preset judgment threshold, the control parameters of the sintering furnace of the current batch are adjusted. The adjustment formula is: ;in, , Respectively represent , Sintering furnace control parameters for each batch; Indicates Normalized results of response difference values ​​of batches; Otherwise, the sintering furnace control parameters of the previous batch are used as the sintering furnace control parameters of the current batch.

8. The method for preparing high-performance composite modified calcined petroleum coke according to claim 1, characterized in that: The rotation speed of the ball milling is 150-250 rpm.

9. The method for preparing high-performance composite modified calcined petroleum coke according to claim 1, characterized in that: The base material, water-soluble cellulose ether, sodium silicate and calcium oxide are added and stirred and mixed in a mass ratio of 100:3.5-4:1-2:3-4.5; the stirring speed is 100-200 rpm, and the stirring is performed for 15-20 minutes.

10. A high-performance composite modified calcined petroleum coke, characterized in that: The method is obtained by a high-performance composite modified calcined petroleum coke preparation method as described in any one of claims 1 to 9.

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