Method and device for determining contents of different sulfides in refined wax oil

Abstract

The invention provides a method and device for determining the content of different sulfides in refined wax oil. The method comprises the following steps: obtaining the content of each sulfide in a wax oil raw material; determining operation parameters adopted when the wax oil raw material is used for preparing the refined wax oil; according to the reaction characteristics of each sulfide, calculating the removal amount of each sulfide based on the operation parameters by adopting a corresponding desulfurization function relation; and subtracting the removal amount of each sulfide from the content of each sulfide in the wax oil raw material to obtain the content of each sulfide in the refined wax oil. According to the method, the defect that an existing lumped kinetics model cannot be established due to the lack of corresponding sulfur form analysis data is overcome.

Description

Technical Field

[0001] The present application relates to the chemical industry field, and specifically relates to a method and device for determining the content of different sulfides in refined wax oil, and a machine-readable storage medium. Background Art

[0002] The wax oil hydrogenation process mainly removes impurities such as sulfur, nitrogen, oxygen, and metals in the wax oil raw material. Among these impurities, process R & D personnel are most concerned about the removal effect of the sulfur content in the raw material, mainly because the amount of sulfur in the refined wax oil has a greater impact on the production of downstream devices. Therefore, developing a prediction model for the sulfur content for wax oil hydrogenation catalysts has become an urgent need for process R & D personnel.

[0003] The sulfur forms in the wax oil raw material are mainly divided into mercaptans, sulfides, disulfides, and thiophene group sulfides. The removal difficulties of these sulfides are different, resulting in different laws for their removal reactions. Limited by the current analysis level, whether it is the raw material or the product after hydrofining, the analysis data of the sulfur forms are severely lacking, so that the sulfur content in the wax oil is expressed as total sulfur, which makes it extremely difficult to establish a mechanism model for different sulfur forms in wax oil hydrogenation. Summary of the Invention

[0004] The purpose of the present invention is to provide a method for determining the content of different sulfides in refined wax oil. First step, determine the content of each sulfide in the raw material according to the proportion of different sulfides in the wax oil raw material. Second step, design a desulfurization function relation according to the characteristics of the hydrogenation reaction of different sulfides. Third step, according to the reaction characteristics of each sulfide, use the corresponding desulfurization function relation to calculate the removal amount of each sulfide based on the operating parameters. Fourth step, subtract the obtained removal amount of the corresponding sulfide from the content of each sulfide to obtain the content of different sulfides in the refined wax oil.

[0005] To achieve the above purpose, the first aspect of the present application provides a method for determining the content of different sulfides in refined wax oil, including: obtaining the content of each sulfide in the wax oil raw material; determining the operating parameters used when preparing the refined wax oil from the wax oil raw material; according to the reaction characteristics of each sulfide, using the corresponding desulfurization function relation to calculate the removal amount of each sulfide based on the operating parameters; and subtracting the removal amount of each sulfide from the content of each sulfide in the wax oil raw material to obtain the content of each sulfide in the refined wax oil.

[0006] In an embodiment of the present invention, each sulfide includes one or more of the following: mercaptan, disulfide, thiophene, benzothiophene group sulfide, and dibenzothiophene group sulfide.

[0007] In an embodiment of the present invention, different sulfides in each sulfide correspond to different desulfurization function relations.

[0008] In an embodiment of the present invention, the content of each sulfide in the wax oil raw material is determined by assuming that the proportion of each sulfide in a variety of wax oil raw materials is the same.

[0009] In an embodiment of the present invention, the desulfurization function relational expression is as follows:

[0010]

[0011] Wherein, △S i represents the desulfurization amount of the corresponding sulfide, k i represents the reaction rate constant of the corresponding sulfide, E i represents the activation energy of the corresponding sulfide, ai represents the pressure coefficient of the corresponding sulfide, bi represents the hydrogen-oil ratio coefficient of the corresponding sulfide, P represents the reaction pressure, H / O represents the hydrogen-oil ratio, R represents the gas constant, the value of which is 8.314, T represents the reaction temperature, and Vt represents the reaction space velocity.

[0012] In an embodiment of the present invention, the method further includes: determining the total sulfur content in the refined wax oil according to the content of each sulfide in the refined wax oil; and comparing the total sulfur content in the refined wax oil with a preset value. When the total sulfur content in the refined wax oil is less than the preset value, introducing a sulfide with a more difficult removal difficulty than the respective sulfides into the respective sulfides, re-determining the removal amount of each sulfide based on the reaction characteristics of each sulfide by using the corresponding desulfurization function relational expression according to the operating parameters, and subtracting the removal amount of each sulfide from the content of each sulfide in the wax oil raw material to obtain the content of each sulfide in the refined wax oil.

[0013] In an embodiment of the present invention, the desulfurization function relational expressions corresponding to different intervals are as follows:

[0014]

[0015] Among them, the total desulfurization amount ΔSi is the total sulfur content S(original) of the wax oil raw material minus the total sulfur content S(product) of the refined wax oil. k1, k2, k3, k4, and k5 respectively represent the reaction rate constants of mercaptan, disulfide, thiophene, thiophene-based sulfide, and dibenzothiophene-based sulfide. E1, E2, E3, E4, and E5 respectively represent the activation energies of mercaptan, disulfide, thiophene, thiophene-based sulfide, and dibenzothiophene-based sulfide. P represents the reaction pressure, H / O represents the hydrogen-oil ratio, R represents the gas constant, the value of which is 8.314, T represents the reaction temperature, Vt represents the reaction space velocity, a1, a2, a3, a4, and a5 respectively represent the pressure coefficients of mercaptan, disulfide, thiophene, thiophene-based sulfide, and dibenzothiophene-based sulfide, and b1, b2, b3, b4, and b5 respectively represent the hydrogen-oil ratio coefficients of mercaptan, disulfide, thiophene, thiophene-based sulfide, and dibenzothiophene-based sulfide.

[0016] In an embodiment of the present invention, the operating parameters include one or more of the following: reaction pressure, reaction temperature, space velocity, and hydrogen-oil ratio.

[0017] The second aspect of the present application provides a device for determining the content of different sulfides in refined wax oil. The device includes: a memory; and a processor configured to use the above method to determine the content of different sulfides in refined wax oil.

[0018] The third aspect of the present application provides a machine-readable storage medium on which instructions are stored. When the instructions are executed by a processor, the processor is configured to execute the above method for determining the content of different sulfides in refined wax oil.

[0019] The fourth aspect of the present application provides a computer program product including a computer program. When the computer program is executed by a processor, the processor is configured to execute the above method for determining the content of different sulfides in refined wax oil.

[0020] Through the above technical solutions, by investigating different raw materials and different operating conditions (temperature, pressure, space velocity, hydrogen-oil ratio) of the wax oil hydrogenation catalyst, the removal situation of sulfides in the wax oil raw material after reaction can be obtained. According to the law that the proportions of different sulfur form compounds in similar wax oil raw materials are basically the same, the contents of different sulfides in the wax oil raw material can be calculated. By the characteristics of the hydrogenation reactions of different sulfides, different desulfurization expressions are designed; then, according to the ease of removal of different sulfides in the wax oil raw material, the sulfur content of the refined wax oil is divided into intervals, and corresponding desulfurization equations are designed, so as to establish a lumped kinetic model for the conversion of different forms of sulfides in wax oil hydrogenation. The above solutions make up for the defect that the existing lumped kinetic model cannot be established due to the lack of corresponding sulfur form analysis data.

[0021] By selecting the test set data, comparing the total sulfur content of the refined wax oil calculated in the embodiments of this case (i.e., the sum of the contents of different sulfides in the refined wax oil) with the sulfur content of the refined wax oil calculated by the model in the comparative example, it is found that the deviation between the total sulfur content of the refined wax oil calculated by the method of the embodiment and the actual value is very close to the deviation between the sulfur content of the refined wax oil calculated by the comparative example model and the actual value, which illustrates the effectiveness of the new method.

[0022] Other features and advantages of the embodiments of the present application will be described in detail in the subsequent specific implementation section. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The drawings are used to provide a further understanding of the embodiments of the present application, and constitute a part of the specification. Together with the following specific implementation, they are used to explain the embodiments of the present application, but do not constitute a limitation to the embodiments of the present application. In the drawings:

[0024] Figure 1 Schematically shows a flowchart of a method for determining the content of different sulfides in refined wax oil according to an embodiment of the present application.

[0025] Figure 2 Schematically shows a flowchart of a method for determining the content of different sulfides in refined wax oil according to another embodiment of the present application.

[0026] Figure 3 Is a prediction effect diagram of the sulfur content of the refined wax oil of the test data in the comparative example.

[0027] Figure 4 Is a prediction effect diagram of the sulfur content of the refined wax oil of the test data in the embodiment of the present application. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0028] To make the objectives, technical solutions, and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. It should be understood that the specific implementation described herein is only used to illustrate and explain the embodiments of the present application, and is not used to limit the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present application.

[0029] It should be noted that if there are directional indications (such as up, down, left, right, front, back...) involved in the embodiments of the present application, the directional indications are only used to explain the relative positional relationship and movement conditions between components in a specific posture (as shown in the drawings). If the specific posture changes, the directional indications will also change accordingly.

[0030] In addition, if there are descriptions such as "first" and "second" in the embodiments of this application, the descriptions of "first", "second", etc. are for descriptive purposes only, and should not be construed as indicating or implying their relative importance or implicitly indicating the quantity of the indicated technical features. Thus, features defined with "first" and "second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions between various embodiments may be combined with each other, but it must be based on what can be achieved by those of ordinary skill in the art. When the combination of technical solutions is contradictory or cannot be achieved, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection required by this application.

[0031] It should be noted that terms such as "feature", "feature variable", and "input parameter" have appeared many times in this case. These contents can represent the features of a "data prediction model" used to predict an "output parameter" based on an "input parameter" and can be used interchangeably. In addition, terms such as "model", "data prediction model", and "data-driven model" have appeared many times in this case, and these models can be used interchangeably.

[0032] Figure 1 A flowchart showing a method for determining the content of different sulfides in refined wax oil according to an embodiment of the present application is schematically shown. As Figure 1 shown, in an embodiment of the present application, a method for determining the content of different sulfides in refined wax oil is provided. The method includes the following steps:

[0033] Step S110, obtaining the content of each sulfide in the wax oil raw material.

[0034] The sulfur content in the wax oil raw material is mainly divided into mercaptan, disulfide, thiophene, benzothiophene sulfides, dibenzothiophene sulfides, etc. The proportion of different sulfides in the wax oil raw material can be determined, that is, mercaptan: disulfide: thiophene: benzothiophene sulfides: dibenzothiophene sulfides ≈ 1:2:1:12:4. If the difference between different wax oil raw materials is not obvious, the proportion of each sulfide in the raw material is basically the same. At this time, mercaptan: disulfide: thiophene: benzothiophene sulfides: dibenzothiophene sulfides ≈ 1:2:1:12:4. Multiplying the total sulfur of the wax oil raw material by the corresponding proportion can obtain the content of each sulfide. Of course, the present invention is not limited to this and may include other sulfides other than those listed here.

[0035] Step S120, determining the operating parameters adopted when preparing the refined wax oil using the wax oil raw material.

[0036] The operating parameters may include one or more of the following: reaction pressure, reaction temperature, space velocity, and hydrogen-oil ratio. Of course, the present invention is not limited to this and may include other operating parameters other than those listed here.

[0037] Step S130: According to the reaction characteristics of each sulfide, use the corresponding desulfurization function relation to calculate the removal amount of each sulfide based on the operating parameters.

[0038] The removal of sulfides is closely related to the operating conditions. Mercaptans and disulfides are significantly affected by the hydrogen-oil ratio; thiophenes, benzothiophene sulfides, and dibenzothiophene sulfides are significantly affected by the space velocity. Therefore, according to the characteristics presented by different sulfides under the operating conditions, the present invention designs corresponding function expressions. Mercaptans and disulfides are significantly affected by the hydrogen-oil ratio, so the hydrogen-oil ratio is placed in the denominator; while thiophenes, benzothiophene sulfides, and dibenzothiophene sulfides are significantly affected by the space velocity, so the space velocity is placed in the denominator. The detailed mathematical expression is shown as follows:

[0039]

[0040] Where, △S i represents the desulfurization amount of the corresponding sulfide, k i represents the reaction rate constant of the corresponding sulfide, E i represents the activation energy of the corresponding sulfide, ai represents the pressure coefficient of the corresponding sulfide, bi represents the hydrogen-oil ratio coefficient of the corresponding sulfide, P represents the reaction pressure, H / O represents the hydrogen-oil ratio, R represents the gas constant, whose value is 8.314, T represents the reaction temperature, and Vt represents the reaction space velocity.

[0041] Step S140: Subtract the removal amount of each sulfide from the content of each sulfide in the waxy oil raw material to obtain the content of each sulfide in the refined waxy oil.

[0042] The sulfur content in the waxy oil raw material is mainly divided into mercaptans, disulfides, thiophenes, benzothiophene sulfides, dibenzothiophene sulfides, etc. Mercaptans and disulfides are relatively easy to remove; thiophenes and benzothiophene sulfides are relatively difficult to remove; dibenzothiophene sulfides, especially 4,6-substituted dibenzothiophene sulfides, are the most difficult to remove. These reaction rules result in a certain sequence for the removal of different sulfides in the waxy oil raw material. Therefore, the present invention proposes a method for establishing a corresponding sulfide removal equation for different intervals of the remaining sulfur content in the refined waxy oil according to the removal difficulty and reaction rules of sulfides. Figure 2 Schematically shows a flowchart of a method for determining the content of different sulfides in refined waxy oil according to another embodiment of the present application. As Figure 2 shown, it further includes the following steps:

[0043] Step S210: Determine the total sulfur content in the refined waxy oil according to the content of each sulfide in the refined waxy oil.

[0044] Step S220: Compare the total sulfur content in the refined wax oil with a preset value (for example, 3000 ppm. Of course, the present invention is not limited thereto, and other values can also be adopted according to actual situations). When the total sulfur content in the refined wax oil is less than the preset value, introduce sulfides with a more difficult removal difficulty than the respective sulfides into the respective sulfides. Then, according to the reaction characteristics of the respective sulfides again, adopt the corresponding desulfurization function relation formula to calculate the removal amount of each sulfide based on the operating parameters, and subtract the removal amount of each sulfide from the content of each sulfide in the wax oil raw material to obtain the content of each sulfide in the refined wax oil.

[0045] In an embodiment of the present invention, the desulfurization function relation formulas corresponding to different intervals (for example, the interval where S(production) is greater than 3000 ppm and the interval where S(production) is less than 3000 ppm) are as follows:

[0046]

[0047] Wherein, the total desulfurization amount △Si is the total sulfur content S(raw) of the wax oil raw material minus the total sulfur content S(production) of the refined wax oil. k1, k2, k3, k4, and k5 respectively represent the reaction rate constants of mercaptans, disulfides, thiophenes, thiophene-based sulfides, and dibenzothiophene-based sulfides. E1, E2, E3, E4, and E5 respectively represent the activation energies of mercaptans, disulfides, thiophenes, thiophene-based sulfides, and dibenzothiophene-based sulfides. P represents the reaction pressure, H / O represents the hydrogen-oil ratio, R represents the gas constant, the value of which is 8.314, T represents the reaction temperature, Vt represents the reaction space velocity, a1, a2, a3, a4, and a5 respectively represent the pressure coefficients of mercaptans, disulfides, thiophenes, thiophene-based sulfides, and dibenzothiophene-based sulfides, and b1, b2, b3, b4, and b5 respectively represent the hydrogen-oil ratio coefficients of mercaptans, disulfides, thiophenes, thiophene-based sulfides, and dibenzothiophene-based sulfides.

[0048] Specifically, first calculate △Si using formula (2), substitute this value into formula (1) to obtain S(production), and compare this S(production) with 3000 ppm. When S(production) is less than 3000 ppm, use formula (3) to recalculate the content of each sulfide in the refined wax oil. Here, new sulfides, that is, dibenzothiophene-based sulfides, are introduced into the respective sulfides because if S(production) is less than 3000 ppm, it indicates that dibenzothiophene-based sulfides are likely to be removed as well.

[0049] Generally speaking, in view of the defect that the existing lumped kinetic model cannot establish a mechanism model for different sulfur forms, according to the reaction rules of different sulfides in the wax oil feedstock, different desulfurization equations are designed; then, according to the removal difficulty of different sulfides in the wax oil feedstock, the corresponding intervals of the sulfur content in the refined wax oil are divided, and a piecewise function for sulfide removal is designed; finally, by subtracting the amount of each sulfide removed from the amount of each sulfide in the wax oil feedstock, the remaining amount of each sulfide in the refined wax oil can be obtained.

[0050] The sulfur content in the wax oil feedstock is mainly divided into mercaptans, disulfides, thiophenes, benzothiophene sulfides, dibenzothiophene sulfides, etc. Mercaptans and disulfides are relatively easy to remove; thiophenes and benzothiophene sulfides are relatively difficult to remove; dibenzothiophene sulfides, especially those with 4,6-substituted dibenzothiophene sulfides, are the most difficult to remove. These reaction rules result in a certain sequence of removal of different sulfides in the wax oil feedstock. Therefore, the present invention proposes a method for establishing corresponding sulfide removal equations for different intervals of the remaining sulfur content in the refined wax oil according to the removal difficulty and reaction rules of sulfides. On the other hand, the removal of sulfides is closely related to the operating conditions. Mercaptans and disulfides are significantly affected by the hydrogen-oil ratio; thiophenes, benzothiophene sulfides, and dibenzothiophene sulfides are significantly affected by the space velocity. Therefore, the present invention designs corresponding function expressions according to the characteristics presented by different sulfides under operating conditions.

[0051] For the solution of the unknown parameters of the equations involved in the present invention, Python is used for coding, and the equation-solving library Sympy is called to solve the power equations. Sympy is a Python library for symbolic computing. It is completely written in Python and does not depend on external libraries. SymPy supports functions in aspects such as symbolic computing, high-precision computing, pattern matching, plotting, solving equations, calculus, combinatorics, discrete mathematics, geometry, probability and statistics, and physics. For the mathematical operations involved in the present invention, it can quickly and accurately obtain the operation results.

[0052] Collect several groups of pilot test evaluation data of wax oil hydrotreating catalysts. Divide all the data into three parts: the total sulfur content of the feedstock, the operating conditions, and the sulfur content of the refined wax oil, and organize them in an Excel table respectively for easy reading by the algorithm program. Divide all the data into two parts. One part is used to solve the equations, and the other part is used to test the effect of the established equations. The evaluation indexes are the mean absolute error (MAE), the mean relative error (MRE), and the determination coefficient R 2 . The relevant statistical parameters required are as follows, where

[0053]

[0054]

[0055]

[0056] In the above formula, n is the number of samples in the test set, and y i,actual represents the measured value of the sample, and y i,predicted represents the predicted value of the sample. MAE reflects the degree of deviation of all sample predicted values from the true value, MRE reflects the credibility of all sample prediction results, and R 2 reflects the fitting degree of the predicted value of the desulfurization relational expression to the true value.

[0057] In order to quantify the prediction effect of the new design method on new data, the present invention calculates the sulfur content of the refined wax oil of the test data in two ways: examples and comparative examples. Among them, the comparative example adopts the data-driven model method to predict the total sulfur content of the refined wax oil; the example adopts the form of solving the desulfurization equation, and the sum of the calculated contents of each sulfide is the total sulfur content of the refined wax oil. The present invention calculates the deviation of the predicted value of the sulfur content of the refined wax oil of the test data in the comparative example and the deviation of the calculated value of the sulfur content of the refined wax oil of the test data in the example respectively. By comparing the results of the two, the effectiveness of the inventive method is illustrated.

[0058] The method of the comparative example will now be described in detail as follows:

[0059] (1) Collect 119 sets of pilot evaluation data of a wax oil hydrotreating catalyst. These data include raw material sulfur content, operating conditions (temperature, pressure, space velocity, hydrogen-oil ratio), and total sulfur content of the refined wax oil. These data are respectively sorted into excel. All data are divided into a training set and a test set, with 99 sets of training set data and 20 sets of test set data.

[0060] (2) Use python to write code to establish a neural network model. Among them, the model inputs are raw material sulfur content and operating conditions (temperature, pressure, space velocity, hydrogen-oil ratio), and the model output is the total sulfur content of the refined wax oil. The training set data is used for model training, and the test set data is used to detect the prediction effect of the model.

[0061] (3) Taking the minimum average absolute error of the training set and the maximum determination coefficient R 2 of the model as the standard for the model to be trained well, use the model to predict the test set data.

[0062] The purpose of establishing the comparative example is to compare with the example to illustrate the effectiveness of the example.

[0063] The present invention will be further described in detail below through examples from the process of establishing the function expression and the process of using the function expression to determine the content of each sulfide in the refined wax oil, but the present invention is not limited thereto.

[0064] (1)Collect 119 sets of pilot evaluation data of a certain wax oil hydrotreating catalyst. These data include the sulfur content of the wax oil raw material, operating conditions (temperature, pressure, space velocity, hydrogen-oil ratio), and the sulfur content of the refined wax oil. Organize these data into Excel respectively. 99 sets of training data are used to solve the unknown coefficients of the equations, and 20 sets of data are used to test the prediction effect of the model / equation. The data sets used in the examples are the same as those in the comparative examples.

[0065] (2)Determine the contents of different sulfides in the wax oil raw material. According to the analysis data of various sulfides in the wax oil, if the differences between different wax oil raw materials are not obvious, the proportions of the main sulfides in the wax oil are basically the same. At this time, mercaptan: disulfide: thiophene: benzothiophene sulfides: dibenzothiophene sulfides in the wax oil raw material ≈ 1:2:1:12:4. Multiply the total sulfur content of the wax oil raw material by the proportion of each sulfide to obtain the content of each sulfide.

[0066] (3)Based on the reaction characteristics of various sulfides in the wax oil raw material under different operating conditions, use Python to write code and set the corresponding mathematical expressions. The removal of mercaptan and disulfide is relatively easy and is significantly affected by the hydrogen-oil ratio. Place the hydrogen-oil ratio in the denominator to expand its influence on the desulfurization reaction; while thiophene, benzothiophene sulfides, and dibenzothiophene sulfides are greatly affected by benzene ring adsorption and steric hindrance. Therefore, a certain contact time is required. Place the space velocity in the denominator to expand its influence on the desulfurization reaction. The detailed mathematical expressions are as follows:

[0067]

[0068] Among them, △S i represents the desulfurization amount of the corresponding sulfide, k i represents the reaction rate constant of the corresponding sulfide, E i represents the activation energy of the corresponding sulfide, ai represents the pressure coefficient of the corresponding sulfide, bi represents the hydrogen-oil ratio coefficient of the corresponding sulfide, P represents the reaction pressure, H / O represents the hydrogen-oil ratio, R represents the gas constant, whose value is 8.314, T represents the reaction temperature, and Vt represents the reaction space velocity.

[0069] (4)Fully consider the difficulty of removing different sulfides, and reverse-deduce the types of sulfides removed from the remaining sulfur content in the refined wax oil. If the sulfur content of the refined wax oil > 3000 ppm, then except for dibenzothiophene sulfides, other sulfides all participate in the reaction; if the sulfur content of the refined wax oil < 3000 ppm, then all sulfides participate in the reaction.

[0070] (5) Combine the methods in steps (3) and (4) to obtain the following desulfurization equations and conditional relationships. Among them, the total desulfurization amount △Si is the total sulfur content S(raw material) of the waxy oil raw material minus the total sulfur content S(product) of the refined waxy oil. k1, k2, k3, k4, and k5 respectively represent the reaction rate constants of mercaptan, disulfide, thiophene, thiophene sulfide, and dibenzothiophene sulfide. E1, E2, E3, E4, and E5 respectively represent the activation energies of mercaptan, disulfide, thiophene, thiophene sulfide, and dibenzothiophene sulfide. P represents the reaction pressure, H / O represents the hydrogen-oil ratio, R represents the gas constant, whose value is 8.314, T represents the reaction temperature, Vt represents the reaction space velocity, a1, a2, a3, a4, and a5 respectively represent the pressure coefficients of mercaptan, disulfide, thiophene, thiophene sulfide, and dibenzothiophene sulfide, and b1, b2, b3, b4, and b5 respectively represent the hydrogen-oil ratio coefficients of mercaptan, disulfide, thiophene, thiophene sulfide, and dibenzothiophene sulfide.

[0071]

[0072] (6) Substitute the prepared data into the above equations and use the special library sympy in python to solve the equations to find the unknown coefficients of the equations, namely, a1, a2, a3, a4, a5 and b1, b2, b3, b4, b5, to obtain the complete expression of waxy oil hydrodesulfurization.

[0073] (7) Substitute the operating conditions in the test data into the equations to obtain the removal amounts of various sulfides. Use the proportions of various sulfides in the waxy oil raw material to find the amounts of various sulfides in the waxy oil raw material, subtract the removal amounts of the corresponding sulfides, and the amounts of various sulfides in the refined waxy oil can be obtained. Add these amounts to calculate the total sulfur content of the refined waxy oil.

[0074] (8) Establish a comparative data-driven model to predict the sulfur content of the refined waxy oil in the test set data and obtain the corresponding predicted values.

[0075] (9) Calculate the errors between the sulfur content of the refined waxy oil calculated in step (7) of the example and the sulfur content of the refined waxy oil predicted by the comparative model in step (8) and the actual sulfur content of the refined waxy oil in the test set.

[0076] Statistically analyze the two groups of data in step (9), and the detailed statistical results are shown in Table (1). Comparing the test results of the sulfur content of the refined waxy oil in the example and the comparative example for the new data, it can be seen that the mean absolute error MAE, mean relative error MRE, and determination coefficient R 2 are all relatively close, indicating the effectiveness of this method.

[0077] Table 1 Comparison of the Prediction Effects of the Refined Wax Oil Sulfur Content in the Comparative Examples and Embodiments on Test Data

[0078]

[0079] Figure 3 This is the prediction effect diagram of the refined wax oil sulfur content in the comparative example for the test data. Figure 4 This is the prediction effect diagram of the refined wax oil sulfur content in the embodiment of the present application for the test data. It can be seen that the prediction effect of this case is relatively close to the actual value. By comparing Figure 3 and Figure 4 , it can also be found that the prediction effect of this case is relatively close to the prediction effect in the comparative example.

[0080] Those skilled in the art should understand that the embodiments of the present application can be provided as methods, systems, or computer program products. Therefore, the present application can take the form of a complete hardware embodiment, a complete software embodiment, or an embodiment combining software and hardware aspects. Moreover, the present application can take the form of a computer program product implemented on one or more computer-usable storage media (including but not limited to disk storage, CD-ROM, optical storage, etc.) containing computer-usable program code.

[0081] The present application is described with reference to the flowcharts and / or block diagrams of methods, devices (systems), and computer program products according to the embodiments of the present application. It should be understood that each process and / or block in the flowchart and / or block diagram can be implemented by computer program instructions, and the combination of the processes and / or blocks in the flowchart and / or block diagram can also be implemented. These computer program instructions can be provided to the processor of a general-purpose computer, a special-purpose computer, an embedded processor, or other programmable data processing devices to generate a machine, so that the instructions executed by the processor of the computer or other programmable data processing devices generate a device for implementing the functions specified in Figure 1 one process or multiple processes and / or blocks Figure 1 one block or multiple blocks.

[0082] These computer program instructions can also be stored in a computer-readable memory that can direct a computer or other programmable data processing device to work in a specific manner, so that the instructions stored in the computer-readable memory generate a manufactured product including an instruction device, and the instruction device implements the functions specified in Figure 1 one process or multiple processes and / or blocks Figure 1 one block or multiple blocks.

[0083] These computer program instructions can also be loaded onto a computer or other programmable data processing device, so that a series of operation steps are executed on the computer or other programmable device to generate a computer-implemented process, and thus the instructions executed on the computer or other programmable device provide for implementing the steps of the function specified in one process Figure 1 one process or multiple processes and / or blocks Figure 1 steps of the function specified in one block or multiple blocks.

[0084] In a typical configuration, a computing device includes one or more processors (CPUs), an input / output interface, a network interface, and memory.

[0085] The memory may include non-permanent memory in the form of computer-readable media, random access memory (RAM) and / or non-volatile memory such as read-only memory (ROM) or flash memory (flash RAM). The memory is an example of computer-readable media.

[0086] Computer-readable media includes permanent and non-permanent, removable and non-removable media, and information storage can be implemented by any method or technology. The information can be computer-readable instructions, data structures, program modules, or other data. Examples of computer storage media include, but are not limited to, phase change memory (PRAM), static random access memory (SRAM), dynamic random access memory (DRAM), other types of random access memory (RAM), read-only memory (ROM), electrically erasable programmable read-only memory (EEPROM), flash memory or other memory technologies, compact disc read-only memory (CD-ROM), digital versatile disc (DVD) or other optical storage, magnetic cassette tapes, magnetic disk storage or other magnetic storage devices, or any other non-transmission media that can be used to store information accessible by a computing device. As defined herein, computer-readable media does not include transitory media such as modulated data signals and carrier waves.

[0087] It should also be noted that the term "comprising", "including" or any other variation thereof is intended to cover non-exclusive inclusion, so that a process, method, commodity or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, commodity or device. Without further limitation, an element defined by the statement "including one..." does not exclude the existence of another identical element in the process, method, commodity or device including the element.

[0088] The above are only the embodiments of the present application and are not intended to limit the present application. For those skilled in the art, various changes and modifications can be made to the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included within the scope of the claims of the present application.

Claims

1. A method for determining the content of different sulfides in refined wax oil, comprising: Obtaining the content of each sulfide in the wax oil raw material; Determining the operating parameters adopted when preparing the refined wax oil using the wax oil raw material; According to the reaction characteristics of each sulfide, using the corresponding desulfurization function relationship to calculate the removal amount of each sulfide based on the operating parameters; and Subtracting the removal amount of each sulfide from the content of each sulfide in the wax oil raw material to obtain the content of each sulfide in the refined wax oil.

2. The method according to claim 1, wherein The sulfides include one or more of the following: mercaptan, disulfide, thiophene, benzothiophene sulfides, and dibenzothiophene sulfides.

3. The method according to claim 1, wherein, Different sulfides in the sulfides correspond to different desulfurization function relationships.

4. The method according to claim 1, wherein, The content of each sulfide in the wax oil raw material is determined by assuming that the proportion of each sulfide in multiple wax oil raw materials is the same.

5. The method according to claim 1, wherein, The desulfurization function relationship is as follows: Among them, △S i represents the desulfurization amount of the corresponding sulfide, k i represents the reaction rate constant of the corresponding sulfide, E i represents the activation energy of the corresponding sulfide, ai represents the pressure coefficient of the corresponding sulfide, bi represents the hydrogen-oil ratio coefficient of the corresponding sulfide, P represents the reaction pressure, H / O represents the hydrogen-oil ratio, R represents the gas constant, the value of which is 8.314, T represents the reaction temperature, and Vt represents the reaction space velocity.

6. The method according to claim 1, wherein The method further includes: Determining the total sulfur content in the refined wax oil according to the content of each sulfide in the refined wax oil; and Comparing the total sulfur content in the refined wax oil with a preset value. When the total sulfur content in the refined wax oil is less than the preset value, introducing sulfides with a more difficult removal difficulty than the sulfides into the sulfides, and again according to the reaction characteristics of each sulfide, using the corresponding desulfurization function relationship to calculate the removal amount of each sulfide based on the operating parameters, and subtracting the removal amount of each sulfide from the content of each sulfide in the wax oil raw material to obtain the content of each sulfide in the refined wax oil.

7. The method according to claim 6, wherein, The desulfurization function relationships corresponding to different intervals are as follows: Wherein, the total desulfurization amount △Si is the total sulfur content S(original) of the wax oil raw material minus the total sulfur content S(product) of the refined wax oil, k1, k2, k3, k4, k5 respectively represent the reaction rate constants of mercaptan, disulfide, thiophene, thiophene sulfides, and dibenzothiophene sulfides, E1, E2, E3, E4, E5 respectively represent the activation energies of mercaptan, disulfide, thiophene, thiophene sulfides, and dibenzothiophene sulfides, P represents the reaction pressure, H / O represents the hydrogen-oil ratio, R represents the gas constant, the value of which is 8.314, T represents the reaction temperature, Vt represents the reaction space velocity, a1, a2, a3, a4, a5 respectively represent the pressure coefficients of mercaptan, disulfide, thiophene, thiophene sulfides, and dibenzothiophene sulfides, and b1, b2, b3, b4, b5 respectively represent the hydrogen-oil ratio coefficients of mercaptan, disulfide, thiophene, thiophene sulfides, and dibenzothiophene sulfides.

8. The method according to any one of claims 1-7, wherein, The operating parameters include one or more of the following: reaction pressure, reaction temperature, space velocity, and hydrogen-oil ratio.

9. An apparatus for determining the content of different sulfides in refined wax oil, characterized in that, The device includes: A memory; and A processor configured to execute the method for determining the content of different sulfides in refined wax oil according to any one of claims 1-8.

10. A machine-readable storage medium having instructions stored thereon, characterized in that, When executed by the processor, the instruction causes the processor to be configured to execute the method for determining the content of different sulfides in refined wax oil according to any one of claims 1 to 8.

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