Storage medium, method, device and equipment for predicting sulfur content in hydrogenation reaction components

Abstract

The invention discloses a storage medium, and a method, a device and equipment for predicting the content of sulfur in hydrogenation reaction components. The method comprises the following steps: respectively obtaining composition data of the hydrocarbon content and the sulfur content of raw materials and products, and carrying out lumped division; kinetic parameters of a hydrocarbon conversion reaction are calculated through the hydrocarbon conversion mechanism model; according to the function expression, constructing a sulfur transfer kinetic equation used for carrying out kinetic description on sulfur-containing resultant transfer; constructing a sulfur removal kinetic equation, and coupling the sulfur removal kinetic equation and the sulfur transfer kinetic equation into a desulfurization kinetic equation; and generating a hydrodesulfurization kinetic model according to the desulfurization kinetic equation: substituting the composition data and the kinetic parameters into the desulfurization kinetic equation to calculate hydrodesulfurization kinetic parameters. The method is more accurate in prediction of the sulfur content in the hydrogenation reaction components, so that the guiding significance of the prediction result on optimization of the hydrogenation process and improvement of the desulfurization efficiency is effectively improved.

Description

Technical Field

[0001] The present invention relates to the field of hydrogenation reactions, and particularly to a storage medium, a method, a device, and equipment for predicting the sulfur content in hydrogenation reaction components. Background Art

[0002] Sulfides can react with hydrogen to form hydrogen sulfide under high temperature and high pressure conditions, which can effectively reduce the sulfide content in residue oil. Based on this principle, the hydrodesulfurization (HDS) process, as an efficient desulfurization method, can not only improve the quality of petroleum products but also reduce environmental pollution.

[0003] In order to further promote the development of hydrodesulfurization technology to optimize the hydrogenation process and improve the desulfurization efficiency, in the prior art, the lumping method is generally adopted. According to the relative difficulty of the reaction, the residue oil is divided into lumps according to the sulfur content or "active sulfur" components and "inactive sulfur" components, etc.; then, based on the kinetic equation of residue oil hydrodesulfurization, a sulfur removal reaction model for sulfur-containing compounds is constructed to realize the prediction of the change in sulfur content during the residue oil hydrogenation process.

[0004] The inventors have found through research that the existing methods for predicting the change in sulfur content during the residue oil hydrogenation process have at least the following defects:

[0005] It can only characterize the desulfurization rate and desulfurization amount, lacking the characterization of sulfur transfer in sulfur-containing compounds, and cannot accurately predict the sulfur content in hydrogenation reaction components, thus reducing the guiding significance of the prediction results for optimizing the hydrogenation process and improving the desulfurization efficiency.

[0006] The information disclosed in this background art section is only intended to enhance the overall understanding of the present invention and should not be regarded as an admission or any form of implication that this information constitutes prior art already known to those of ordinary skill in the art. Summary of the Invention

[0007] The purpose of the present invention is to accurately predict the sulfur content in hydrogenation reaction components.

[0008] The present invention provides a method for predicting the sulfur content in hydrogenation reaction components, including the steps of:

[0009] S11. Respectively obtain the composition data of the hydrocarbon content and sulfur content of the raw material and the product, and perform lumping division according to the kinetic characteristics of the hydrogenation conversion reaction system;

[0010] S12. Calculate the kinetic parameters of the hydrocarbon conversion reaction by substituting the composition data into the mechanism model of hydrocarbon conversion; the kinetic parameters include the pre-exponential factor, activation energy, reaction kinetic order, hydrogen partial pressure index, hydrogen-oil ratio index, and relevant parameters of the activity influence factor between the lumps;

[0011] S13. Construct a sulfur transfer kinetic equation for kinetic description of sulfur-containing compound transfer according to a preset function expression; the function expression is used to characterize the corresponding relationship between hydrocarbon conversion and sulfur-containing compound conversion;

[0012] S14. Construct a sulfur removal kinetic equation, and couple the sulfur removal kinetic equation and the sulfur transfer kinetic equation into a desulfurization kinetic equation;

[0013] S15. Generate a hydrodesulfurization kinetic model according to the desulfurization kinetic equation, including: substituting the composition data and the kinetic parameters into the desulfurization kinetic equation to calculate the kinetic parameters of hydrodesulfurization.

[0014] On another aspect of the present invention, there is also provided a device for predicting the sulfur content in a hydroprocessing reaction component, including:

[0015] A composition data acquisition unit for respectively acquiring the composition data of the hydrocarbon content and sulfur content of the feedstock and the product, and performing lumping division according to the kinetic characteristics of the hydroconversion reaction system;

[0016] A kinetic parameter calculation unit for calculating the kinetic parameters of the hydrocarbon conversion reaction by substituting the composition data into the mechanism model of hydrocarbon conversion; the kinetic parameters include the relevant parameters of the pre-exponential factor, activation energy, reaction kinetic order, hydrogen partial pressure index, hydrogen-oil ratio index, and activity influence factor between the lumps;

[0017] A sulfur transfer kinetic description unit for constructing a sulfur transfer kinetic equation for kinetic description of sulfur-containing compound transfer according to a preset function expression; the function expression is used to characterize the corresponding relationship between hydrocarbon conversion and sulfur-containing compound conversion;

[0018] A sulfur removal kinetic description unit for constructing a sulfur removal kinetic equation, and coupling the sulfur removal kinetic equation and the sulfur transfer kinetic equation into a desulfurization kinetic equation;

[0019] A hydrodesulfurization kinetic model generation unit for generating a hydrodesulfurization kinetic model according to the desulfurization kinetic equation, including: substituting the composition data and the kinetic parameters into the desulfurization kinetic equation to calculate the kinetic parameters of hydrodesulfurization.

[0020] On another aspect of the embodiments of the present invention, there is also provided a device for predicting the sulfur content in a hydroprocessing reaction component. The device for predicting the sulfur content in a hydroprocessing reaction component includes a computer program stored on a medium. The computer program includes program instructions. When the program instructions are executed by a computer, the computer executes the methods described in the above aspects and achieves the same technical effects.

[0021] On another aspect of the embodiments of the present invention, a storage medium is further provided, on which a computer program is stored. When the computer program is executed by a processor, each step of the sulfur content prediction method for the hydrogenation reaction components as described in any one of the above is implemented.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] During the high-temperature hydrogenation process of residue oil, it mainly involves thermal cracking and hydrocracking; during the reaction process, macromolecules are decomposed into small molecules by the breaking of relatively unstable chemical bonds. The inventor has found through research that residue oil macromolecules can be understood as a complex macromolecular structure composed of many small molecular fragments, and these small molecular fragments are connected to each other by relatively unstable chemical bonds; these unstable chemical bonds are cracked at high temperatures to form various small molecular fragments with different boiling points, thereby producing different product components. Among many small molecular fragments, some small molecular fragments contain sulfur. Therefore, during the cracking process of molecular fragments, sulfur will be transformed along with the cracking of molecular fragments. Thus, it can be deduced that there is a clear correlation between sulfur transfer and hydrocarbon conversion.

[0024] Based on the above understanding, in the present invention, according to the correlation between hydrocarbon conversion and sulfur transfer in the hydrogenation reaction, a function expression for characterizing the corresponding relationship between hydrocarbon conversion and sulfur compound conversion is constructed. In this way, through this function expression, a sulfur transfer kinetic equation capable of kinetic description of sulfur compound transfer can be generated according to the mechanism model of hydrocarbon conversion; then, by coupling the sulfur removal kinetic equation and the sulfur transfer kinetic equation, a hydrodesulfurization kinetic model capable of completely characterizing sulfur removal and sulfur transfer in the components during the hydrodesulfurization process is constructed.

[0025] Since the hydrodesulfurization kinetic model in the present invention can not only characterize the desulfurization rate and desulfurization amount, but also characterize the sulfur transfer in sulfur compounds, this makes the prediction of the sulfur content in the hydrogenation reaction components more accurate, and thus effectively improves the guiding significance of the prediction results for optimizing the hydrogenation process and improving the desulfurization efficiency.

[0026] The above description is only an overview of the technical solution of the present invention. In order to be able to more clearly understand the technical means of the present invention and implement it according to the content of the specification, and at the same time to make the above and other purposes, technical features and advantages of the present invention more understandable, one or more preferred embodiments are listed below and described in detail with reference to the accompanying drawings as follows. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is a step diagram of the sulfur content prediction method for the hydrogenation reaction components in the present invention;

[0028] Figure 2 It is a schematic structural diagram of a device for predicting the sulfur content in the hydrogenation reaction components described in the present invention;

[0029] Figure 3 It is a schematic structural diagram of a device for predicting the sulfur content in the hydrogenation reaction components described in the present invention. Specific embodiments

[0030] The following will describe in detail the specific embodiments of the present invention in conjunction with the accompanying drawings. However, it should be understood that the protection scope of the present invention is not limited by the specific embodiments.

[0031] Unless otherwise clearly stated, throughout the specification and claims, the term "comprising" or its variations such as "comprises" or "including" etc. will be understood to include the stated elements or components, without excluding other elements or other components.

[0032] In this article, for the convenience of description, spatial relative terms such as "below", "beneath", "under", "above", "over", "on" etc. can be used to describe the relationship between one element or feature and another element or feature in the drawings. It should be understood that the spatial relative terms are intended to encompass different directions of the object in use or operation in addition to the directions depicted in the figures. For example, if the object in the figure is flipped, the element described as "below" or "under" another element or feature will be oriented "above" the element or feature. Therefore, the exemplary term "below" can encompass both the below and above directions. The object can also have other orientations (rotated 90 degrees or other orientations) and the spatial relative terms used herein should be interpreted accordingly.

[0033] In this article, the terms "first", "second", etc. are used to distinguish two different elements or parts, and are not used to limit a specific position or relative relationship. In other words, in some embodiments, the terms "first", "second", etc. can also be interchanged with each other.

[0034] Embodiment 1

[0035] In order to accurately predict the sulfur content in the hydrogenation reaction components, as Figure 1 shown, in an embodiment of the present invention, a method for predicting the sulfur content in the hydrogenation reaction components is provided, including the steps:

[0036] S11. Respectively obtain the composition data of the hydrocarbon content and sulfur content of the raw material and the product, and perform lumping division according to the kinetic characteristics of the hydrogenation conversion reaction system;

[0037] In the embodiments of the present invention, the feedstock for residue hydroprocessing may include one or a mixture of several of gas oil, atmospheric residue, vacuum residue, and slurry oil; the products may include one or more of dry gas, liquefied petroleum gas, gasoline, diesel, gas oil, and residue.

[0038] The compositional data of the hydrocarbon content and sulfur content of the feedstock and products can be obtained through analysis; in addition, in the embodiments of the present invention, operating condition data such as reaction temperature time, reaction pressure, and space velocity also need to be obtained through various monitoring methods.

[0039] In the embodiments of the present invention, it is also necessary to perform lumping according to the kinetic characteristics of the hydroconversion reaction system; in this way, each lumping is regarded as a class of substances with the same reactivity, and the kinetic models established for each lumping can approximately describe the reaction performance of the original system, and then the kinetic model of the lumped components is established; generally, the number of lumpings is not less than 2.

[0040] In practical applications, the feedstock and products can be divided into several lumpings according to boiling point or carbon number, and the data includes the hydrocarbon content and sulfur content in the lumpings of the feedstock and products. The compositional data of the hydrocarbon content and sulfur content in the feedstock and products can be obtained by first separating according to the lumping division and then measuring the hydrocarbon content and sulfur content of each lumping. It can also be based on the distribution of hydrocarbon content and sulfur content with the component boiling point or carbon number, and perform mass spectrometry analysis on the feedstock and products to obtain the distribution data of hydrocarbon content and sulfur content with carbon number, or use high-temperature simulated distillation combined with hydrocarbon content and sulfur content determination analysis to obtain the distribution data of hydrocarbon content and sulfur content with the component boiling point.

[0041] S12. Calculate the kinetic parameters of the hydrocarbon conversion reaction by substituting the compositional data into the mechanism model of hydrocarbon conversion; the kinetic parameters include the pre-exponential factor, activation energy, reaction kinetic order, hydrogen partial pressure index, hydrogen-oil ratio index, and relevant parameters of the activity influence factor between the lumpings;

[0042] Among them, the relevant parameters of the activity influence factor may specifically include the activity influence parameter of nitrogen adsorption, the activity influence parameter of coke, the activity influence parameter of metal, and the activity influence parameter of hydrocarbon adsorption.

[0043] In the process of hydrodesulfurization, there are mainly two types of transformations of sulfur-containing compounds. One is the process of converting sulfur into hydrogen sulfide and removing it through hydrogenation, in which hydrogen interacts with the sulfur atoms in the compound. Therefore, this process can be directly described by the kinetic equation of sulfur content to determine the change of sulfur and its removal degree. The other is the sulfur conversion caused by converting large sulfur-containing macromolecular compounds into small sulfur-containing compounds through hydrocracking reaction. This chemical reaction process usually does not directly act on the sulfur atoms in the compound and cannot be simply described by the sulfur content in terms of kinetics.

[0044] During the high-temperature hydrocracking process of residuum, thermal cracking and hydrocracking are mainly involved. During the reaction process, macromolecules are decomposed into small molecules by breaking relatively unstable chemical bonds. Through research, the inventors found that residuum macromolecules can be understood as a complex macromolecular structure composed of many small molecular fragments, and these small molecular fragments are connected to each other by relatively unstable chemical bonds. These unstable chemical bonds are cracked at high temperatures to form various small molecular fragments with different boiling points, thereby producing different product components. Among numerous small molecular fragments, some contain sulfur. Therefore, during the cracking process of molecular fragments, sulfur will be transformed along with the cracking of molecular fragments.

[0045] Based on the above understanding, the inventors deduced that there is a clear correlation between sulfur transfer and hydrocarbon conversion in the hydrocracking reaction, that is, the transfer of sulfur-containing compounds can be kinetically described through hydrocarbon conversion.

[0046] In order to deduce the mechanism of sulfur transfer from the mechanism of hydrocarbon conversion, in the embodiments of the present invention, the kinetic parameters of hydrocarbon conversion reactions need to be calculated by substituting the compositional data into the mechanism model of hydrocarbon conversion.

[0047] The specific process of this step can be as follows:

[0048] Assume that hydrocarbons and sulfur-containing compounds are uniformly distributed in a unit volume, and the converted sulfur-containing compounds are uniformly distributed in the converted hydrocarbons, and only the heavy components can be converted into light components. At this time, the transfer of sulfur-containing compounds can be kinetically described by constructing the conversion relationship between hydrocarbons and sulfur-containing compounds.

[0049] The rate equation of hydrocarbon conversion during the hydrocracking reaction can include:

[0050]

[0051] Among them, F 影响因子 is the influence factor of catalyst activity, adsorption diffusion, etc. on hydrocarbon conversion. When a certain item is not considered in F 影响因子 , the value of this item is 1, including: when the influence of N on hydrocarbon conversion activity is not considered, f(N)=1; when the influence of adsorption on hydrocarbon conversion activity is not considered, f(adsorption)=1; when the influence of coke on hydrocarbon conversion activity is not considered, f(C)=1; when the influence of metal on hydrocarbon conversion activity is not considered, f(M)=1.

[0052] In addition, both i and j represent lumping serial numbers, and the larger the serial number, the heavier the components of the lumping; is the hydrocarbon content in lumping i; C ij is the hydrocarbon content converted from lumping i to lumping j; k ij$k_{ij}$ is the rate constant for the reaction of hydrocarbons in lumped component $i$ to form hydrocarbons in lumped component $j$; $n$ is the reaction kinetic order; $\beta$ is the hydrogen partial pressure exponent; $P$ H2 is the hydrogen partial pressure, MPa; $\gamma$ is the hydrogen-oil ratio exponent; $H$ 2 / oil is the hydrogen-oil ratio, which is an important operating parameter in the hydrogenation process and refers to the ratio of the hydrogen feed rate to the oil feed rate.

[0053] The relationship between the reaction rate constant $k$ and temperature conforms to the Arrhenius equation:

[0054]

[0055] where $k$ ij，0 is the pre-exponential factor for the reaction of hydrocarbons in lumped component $i$ to form hydrocarbons in lumped component $j$; $E$ a,ij is the activation energy value of the corresponding reaction, KJ / mol; $R$ is the molar gas constant, with a value of 8.3114 J / (mol·K); $T$ is the reaction temperature, K.

[0056] In the rate equation for hydrocarbon conversion in the embodiments of the present invention, the calculation formula of $F$ 影响因子 specifically may include:

[0057]

[0058] where $N$ is the basic nitrogen content, $k$ N is the nitrogen adsorption activity influence parameter;

[0059] where $t$ is the running time, $\alpha$ c , $\beta$ c , $\gamma$ c are the coke activity influence parameters;

[0060] $f(M)=1 - \theta \cdot W$; where $W$ is the ratio of the metal deposition amount to the total amount of the catalyst, and $\theta$ is the metal activity influence parameter;

[0061] $f(adsorption)=1 + d\omega$ A $+ e\omega$ 胶质沥青质 ; where $\omega$ A , $\omega$ 胶质沥青质 are the aromatic hydrocarbon and asphaltene contents, and $d$, $e$ are the hydrocarbon adsorption activity influence parameters.

[0062] Input the analysis data obtained from the composition data and the operating condition data including reaction temperature, time, reaction pressure, and space velocity into the mechanism model of hydrocarbon conversion. Through the optimization method, by minimizing the sum of variances between the analyzed hydrocarbon content and the predicted hydrocarbon content, determine the kinetic parameters of the hydrocarbon conversion reaction;

[0063] In the embodiments of the present invention, the kinetic parameters of the hydrocarbon conversion reaction may specifically include:

[0064] The pre-exponential factor k between lumps ij，0 , activation energy E a,ij , reaction kinetic order n, hydrogen partial pressure index β, hydrogen-oil ratio index γ, and the influence factor F of catalyst activity, adsorption diffusion, etc. on hydrocarbon conversion 影响因子 Related parameters; the formula of the above optimization method includes:

[0065]

[0066] Among them, SSE is the sum of variances; is the hydrocarbon content analysis value; is the hydrocarbon content predicted value; m is the number of lumps.

[0067] S13. According to the preset function expression, construct a sulfur transfer kinetic equation for kinetic description of sulfur compound transfer; the function expression is used to characterize the corresponding relationship between hydrocarbon conversion and sulfur compound conversion;

[0068] It is assumed that hydrocarbons and sulfur compounds are uniformly distributed in a unit volume, and the converted sulfur compounds are uniformly distributed in the converted hydrocarbons, and only the heavy components can be converted into light components; at this time, the kinetic description of sulfur compound transfer can be carried out through the constructed conversion relationship between hydrocarbons and sulfur compounds.

[0069] Based on the above, in the embodiments of the present invention, the specific derivation process of the function expression used to characterize the clear correlation between sulfur transfer and hydrocarbon conversion in the hydrogenation reaction is as follows:

[0070] According to the following formula:

[0071]

[0072] It can be deduced that:

[0073]

[0074] Among them, S ij , C ij are the sulfur content and hydrocarbon content transferred from lumps i to lumps j respectively; is the sulfur compound transfer parameter transferred from lumps i to lumps j.

[0075] According to the mechanism model of hydrocarbon conversion and the function expression, the sulfur transfer kinetic equation can be obtained, specifically including:

[0076]

[0077] Among them, The sulfur compound transfer parameter for the transfer of lumped i to lumped j, whose initial value is only related to the feedstock composition; the sulfur compound transfer parameter changes according to the equation:

[0078]

[0079] where is the sulfur content in lumped i; is the hydrocarbon content in lumped i.

[0080] S14. Construct a sulfur removal kinetic equation, and couple the sulfur removal kinetic equation and the sulfur transfer kinetic equation into a desulfurization kinetic equation;

[0081] In the embodiments of the present invention, the sulfur removal kinetic equation can be constructed in a conventional manner, specifically:

[0082]

[0083]

[0084] where N is the basic nitrogen content, is the parameter for the influence of nitrogen adsorption on desulfurization activity;

[0085] where t is the running time, α cS , β cS , γ cS are the parameters for the influence of the desulfurization activity of coke;

[0086] f(M S ) = 1 - θ S ·W; where w is the ratio of the metal deposition amount to the total amount of the catalyst, and θ S is the parameter for the influence of the desulfurization activity of the metal;

[0087] f(adsorption S ) = 1 + d S ω A + e S ω 胶质沥青质 ; where ω A , ω 胶质沥青质 are the contents of aromatic hydrocarbons and asphaltenes, and d and e are the parameters for the influence of hydrocarbon adsorption on desulfurization activity;

[0088] In the sulfur removal kinetic equation, F 硫因子 is the influence factor of catalyst activity, adsorption diffusion, etc. on desulfurization activity. In F 硫因子If the influence of a certain item is not considered, the value of this item is 1. For example, when the influence of N on the desulfurization activity is not considered, f(NS) = 1; when the influence of adsorption on the desulfurization activity is not considered, f(adsorbed S) = 1; when the influence of coke on the desulfurization activity is not considered, f(CS) = 1; when the influence of metal on the desulfurization activity is not considered, f(MS) = 1; is the sulfur content in lumping i; k Si is the rate constant of the sulfur removal reaction in lumping i; n s is the kinetic order of the desulfurization reaction; β S is the hydrogen partial pressure index of the sulfur removal reaction; is the hydrogen partial pressure, MPa; γ S is the hydrogen-oil ratio index of sulfur removal; H 2 / oil is the hydrogen-oil ratio, which is an important operating parameter in the hydrogenation process and refers to the ratio of the hydrogen feed rate to the oil feed rate;

[0089] Among them, the relationship between the reaction rate constant k and the temperature conforms to the Arrhenius equation:

[0090]

[0091] Among them, k Si，0 is the pre-exponential factor of the sulfur removal reaction in lumping i; E a,Si is the activation energy of the desulfurization reaction, KJ / mol; R is the molar gas constant, with a value of 8.3114 J / (mol·K); T is the reaction temperature, K.

[0092] In addition, the sulfur transfer kinetic equation in the hydrogenation reaction process in the embodiments of the present invention may specifically include:

[0093]

[0094] In this way, considering both the removal and transfer of sulfur in the hydrogenation reaction, a desulfurization kinetic equation is coupled and formed, including:

[0095] The total sulfur conversion rate equation of lumping j:

[0096] Among them, i, j, and k represent the lumping serial numbers. The larger the serial number, the heavier the components of the lumping. i > j > k; m is the number of lumpings.

[0097] S15. Generate a hydrodesulfurization kinetic model according to the desulfurization kinetic equation, including: substituting the composition data and the kinetic parameters into the desulfurization kinetic equation to calculate the kinetic parameters of hydrodesulfurization.

[0098] After constructing the desulfurization kinetic equation, the kinetic parameters of the hydrodesulfurization kinetic model can be calculated by inputting the component data, the kinetic parameters of the hydrocarbon conversion reaction obtained in step S12, and the operating conditions data including reaction temperature time, reaction pressure, and space velocity;

[0099] The kinetic parameters of the hydrodesulfurization kinetic model in the embodiments of the present invention may specifically include the pre-exponential factor k of the sulfur removal reaction between lumps Si，0 , the activation energy E of sulfur removal a,Si , the reaction kinetic order n of sulfur removal s , the hydrogen partial pressure index β of sulfur removal S , the hydrogen-oil ratio index γ of sulfur removal S , the sulfur-containing compound transfer parameter η between lumps Sij , the influence factors F of catalyst activity, adsorption diffusion, etc. on sulfur removal 硫因子 related parameters; the formula of the above optimization method includes:

[0100]

[0101] Among them, SSE is the sum of variances; is the sulfur content analysis value; is the sulfur content predicted value; m is the number of lumps.

[0102] Further, in the embodiments of the present invention, the number of lumps can also be set to be relatively large (for example, more than 10). In this way, after obtaining the prediction results of the sulfur content of each lumped component respectively, according to the corresponding relationship between each product and the lumps, the sulfur content of each product can also be obtained. For example, the sulfur content of product gasoline can be obtained by adding up the prediction results of the lumps corresponding to product gasoline; similarly, the sulfur content of other products such as diesel can also be obtained.

[0103] In the prior art, for the lumping in the hydrodesulfurization model, if lumping is carried out according to boiling point or carbon number, generally only one lump is divided. This is because when lumping according to boiling point or carbon number, the sulfur-containing hydrocarbons in the high-boiling lump will transfer to the low-boiling lump. If sulfur transfer cannot be effectively calculated, the accuracy of the model is poor. If lumping is carried out according to sulfur type (such as lumping according to the difficulty of removal reaction; lumping according to sulfides, thiophenes, benzothiophenes), multiple lumps can be divided. This is because the conversion between various types of sulfur-containing compounds is extremely small or even non-existent. Therefore, accurate prediction can be achieved without considering sulfur transfer. However, lumping according to sulfur type will greatly increase the analysis difficulty, and it is even impossible to analyze the sulfur content of specific types for heavy oil.

[0104] In summary, according to the correlation between hydrocarbon conversion and sulfur transfer in the hydrogenation reaction in the embodiments of the present invention, a function expression for characterizing the corresponding relationship between hydrocarbon conversion and sulfur compound conversion is constructed. In this way, through this function expression, a sulfur transfer kinetic equation capable of kinetic description of sulfur compound transfer can be generated according to the mechanism model of hydrocarbon conversion; then, by coupling the sulfur removal kinetic equation and the sulfur transfer kinetic equation, a hydrodesulfurization kinetic model capable of completely characterizing sulfur removal and sulfur transfer in components during the hydrodesulfurization process is constructed.

[0105] Since the hydrodesulfurization kinetic model in the embodiments of the present invention can not only characterize the desulfurization rate and desulfurization amount, but also characterize the sulfur transfer in sulfur compounds, it makes the prediction of sulfur content in hydrogenation reaction components more accurate, and thus effectively improves the guiding significance of the prediction results for optimizing the hydrogenation process and improving the desulfurization efficiency.

[0106] Embodiment 2

[0107] On the other hand, in the embodiments of the present invention, a device for predicting sulfur content in hydrogenation reaction components is also provided. Figure 2 The structure diagram of the device for predicting sulfur content in hydrogenation reaction components provided by the embodiments of the present invention is shown. The device for predicting sulfur content in hydrogenation reaction components is Figure 1 The device corresponding to the method for predicting sulfur content in hydrogenation reaction components in the corresponding embodiment, that is, the method for predicting sulfur content in hydrogenation reaction components in the corresponding embodiment is implemented in the form of a virtual device. Figure 1 Each virtual module constituting the device for predicting sulfur content in hydrogenation reaction components can be executed by an electronic device, such as a network device, a terminal device, or a server. Specifically, the device for predicting sulfur content in hydrogenation reaction components in the embodiments of the present invention includes:

[0108] A composition data acquisition unit 01 is configured to respectively acquire the composition data of hydrocarbon content and sulfur content of the raw material and the product, and perform lumping division according to the kinetic characteristics of the hydrogenation conversion reaction system;

[0109] A kinetic parameter calculation unit 02 is configured to calculate the kinetic parameters of the hydrocarbon conversion reaction by substituting the composition data into the mechanism model of hydrocarbon conversion; the kinetic parameters include the pre-exponential factor, activation energy, reaction kinetic order, hydrogen partial pressure index, hydrogen-oil ratio index, and relevant parameters of the activity influence factor between the lumps;

[0110] A sulfur transfer kinetic description unit 03 is configured to construct a sulfur transfer kinetic equation for kinetic description of sulfur compound transfer according to a preset function expression; the function expression is used to characterize the corresponding relationship between hydrocarbon conversion and sulfur compound conversion;

[0111] A sulfur removal kinetics description unit 04 is used to construct a sulfur removal kinetics equation and couple the sulfur removal kinetics equation and the sulfur transfer kinetics equation into a desulfurization kinetics equation;

[0112] A hydrodesulfurization kinetics model generation unit 05 is used to generate a hydrodesulfurization kinetics model according to the desulfurization kinetics equation, including: substituting the composition data and the kinetic parameters into the desulfurization kinetics equation to calculate the kinetic parameters of hydrodesulfurization.

[0113] Since the working principle and beneficial effects of the sulfur content prediction device in the hydrogenation reaction components in the embodiments of the present invention have been described and explained in Figure 1 the corresponding sulfur content prediction method for hydrogenation reaction components, they can be referred to each other and will not be elaborated here.

[0114] Embodiment III

[0115] Corresponding to the method embodiment, in the embodiments of the present invention, a sulfur content prediction device for hydrogenation reaction components is further provided, such as a terminal, a server, etc. Among them, the server can be an independent physical server, or a server cluster or distributed system composed of multiple physical servers, or a cloud server providing basic cloud computing services such as cloud services, cloud databases, cloud computing, cloud functions, cloud storage, network services, cloud communications, middleware services, domain name services, security services, CDN, and big data and artificial intelligence platforms. The terminal can be a smart phone, a tablet computer, a notebook computer, a desktop computer, etc., but is not limited thereto.

[0116] An example diagram of the hardware structure block diagram of the sulfur content prediction device for hydrogenation reaction components provided in the embodiments of the present invention, as Figure 3 shown, may include:

[0117] A processor 1, a communication interface 2, a memory 3, and a communication bus 4;

[0118] Among them, the processor 1, the communication interface 2, and the memory 3 complete mutual communication through the communication bus 4;

[0119] Optionally, the communication interface 2 can be an interface of a communication module, such as an interface of a GSM module;

[0120] The processor 1 may be a central processing unit CPU, or a specific integrated circuit ASIC (Application Specific Integrated Circuit), or one or more integrated circuits configured to implement the embodiments of the present application.

[0121] The memory 3 may include high-speed RAM memory and may also include non-volatile memory, such as at least one disk memory.

[0122] Among them, the processor 1 is specifically configured to execute the computer program stored in the memory 3 to perform the following steps:

[0123] S11. Respectively obtain the composition data of the hydrocarbon content and sulfur content of the raw material and the product, and perform lumping division according to the kinetic characteristics of the hydroconversion reaction system;

[0124] S12. Calculate the kinetic parameters of the hydrocarbon conversion reaction by substituting the composition data into the mechanism model of hydrocarbon conversion; the kinetic parameters include the pre-exponential factor, activation energy, reaction kinetic order, hydrogen partial pressure index, hydrogen-oil ratio index, and relevant parameters of the activity influence factor between the lumps;

[0125] S13. Construct a sulfur transfer kinetic equation for kinetic description of sulfur compound transfer according to a preset function expression; the function expression is used to characterize the corresponding relationship between hydrocarbon conversion and sulfur compound conversion;

[0126] S14. Construct a sulfur removal kinetic equation, and couple the sulfur removal kinetic equation and the sulfur transfer kinetic equation into a desulfurization kinetic equation;

[0127] S15. Generate a hydrodesulfurization kinetic model according to the desulfurization kinetic equation, including: substituting the composition data and the kinetic parameters into the desulfurization kinetic equation to calculate the kinetic parameters of hydrodesulfurization.

[0128] The above product can execute the method provided by the embodiment of the present invention, and has the corresponding function modules and beneficial effects of the execution method. For technical details not described in detail in this embodiment, reference can be made to the sulfur content prediction method for hydrogenation reaction components provided by the embodiment of the present invention.

[0129] Embodiment 4

[0130] In the embodiment of the present invention, a storage medium is further provided. The storage medium can store a program suitable for execution by a processor, and the program is used for:

[0131] S11. Respectively obtain the composition data of the hydrocarbon content and sulfur content of the raw material and the product, and perform lumping division according to the kinetic characteristics of the hydroconversion reaction system;

[0132] S12. By substituting the composition data into the mechanism model of hydrocarbon conversion, calculate the kinetic parameters of the hydrocarbon conversion reaction; the kinetic parameters include the pre-exponential factor, activation energy, reaction kinetic order, hydrogen partial pressure index, hydrogen-oil ratio index, and relevant parameters of the activity influence factor between the lumps;

[0133] S13. According to the preset function expression, construct a sulfur transfer kinetic equation for kinetic description of sulfur compound transfer; the function expression is used to characterize the corresponding relationship between hydrocarbon conversion and sulfur compound conversion;

[0134] S14. Construct a sulfur removal kinetic equation, and couple the sulfur removal kinetic equation and the sulfur transfer kinetic equation into a desulfurization kinetic equation;

[0135] S15. Generate a hydrodesulfurization kinetic model according to the desulfurization kinetic equation, including: substituting the composition data and the kinetic parameters into the desulfurization kinetic equation to calculate the kinetic parameters of hydrodesulfurization.

[0136] Optionally, the refinement function and expansion function of the program can refer to the above description.

[0137] The above products can execute the method provided by the embodiments of the present invention, and have corresponding functional modules and beneficial effects for executing the method. For technical details not described in detail in this embodiment, reference can be made to the methods provided in other embodiments of the present invention.

[0138] Those of ordinary skill in the art can realize that the units and algorithm steps of each example described in combination with the embodiments disclosed herein can be implemented by electronic hardware, or by a combination of computer software and electronic hardware. Whether these functions are executed in hardware or software depends on the specific application and design constraints of the technical solution. Professional technicians can use different methods to implement the described functions for each specific application, but such implementation should not be considered to exceed the scope of this application.

[0139] In several embodiments provided by the present application, it should be understood that the disclosed systems, devices, and methods can be implemented in other ways. Another point, the couplings or direct couplings or communication connections shown or discussed with each other can be through some interfaces, and the indirect couplings or communication connections of devices or units can be in electrical, mechanical, or other forms.

[0140] The units described as separate components may or may not be physically separated, and the components shown as units may or may not be physical units, that is, they may be located in one place, or they may be distributed to multiple network units. Some or all of the units can be selected according to actual needs to achieve the purpose of the solution of this embodiment.

[0141] In addition, in each embodiment of the present application, each functional unit can be integrated into one processing unit, can exist physically alone for each unit, or two or more units can be integrated into one unit.

[0142] It should be understood that in the embodiments of the present application, the dependent claims, each embodiment, and features can be combined with each other to achieve the solution of the foregoing technical problems.

[0143] If the said function is implemented in the form of a software functional unit and sold or used as an independent product, it can be stored in a computer-readable storage medium. Based on such an understanding, the technical solution of the present application, in essence, or the part that contributes to the prior art, or a part of this technical solution, can be embodied in the form of a software product. This computer software product is stored in a storage medium and includes several instructions to enable a computer device (which can be a personal computer, a server, or a network device, etc.) to execute all or part of the steps of the methods described in each embodiment of the present application. The foregoing storage medium includes: various media such as USB flash drives, mobile hard disks, read-only memories (ROM, Read-Only Memory), random access memories (RAM, Random Access Memory), magnetic disks, or optical discs that can store program codes.

[0144] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present application. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for predicting sulfur content in hydrogenation reaction components, characterized in that, it includes the steps: S11. Respectively obtain the composition data of hydrocarbon content and sulfur content of the raw material and the product, and perform lumping division according to the kinetic characteristics of the hydrogenation conversion reaction system; S12. Calculate the kinetic parameters of the hydrocarbon conversion reaction by substituting the composition data into the mechanism model of hydrocarbon conversion; the kinetic parameters include the pre-exponential factor, activation energy, reaction kinetic order, hydrogen partial pressure index, hydrogen-oil ratio index, and related parameters of the activity influence factor between the lumps; S13. According to the preset function expression, construct a sulfur transfer kinetic equation for kinetic description of sulfur compound transfer; the function expression is used to characterize the corresponding relationship between hydrocarbon conversion and sulfur compound conversion; S14. Construct a sulfur removal kinetic equation, and couple the sulfur removal kinetic equation and the sulfur transfer kinetic equation into a desulfurization kinetic equation; S15. Generate a hydrodesulfurization kinetic model according to the desulfurization kinetic equation, including: substituting the composition data and the kinetic parameters into the desulfurization kinetic equation to calculate the kinetic parameters of hydrodesulfurization.

2. The method for predicting sulfur content in hydrogenation reaction components according to claim 1, characterized in that, the raw material includes one or more of wax oil, atmospheric residue, vacuum residue, and slurry oil.

3. The method for predicting sulfur content in hydrogenation reaction components according to claim 1, characterized in that, the product includes one or more of dry gas, liquefied petroleum gas, gasoline, diesel, wax oil, and residue.

4. The method for predicting sulfur content in hydrogenation reaction components according to claim 1, characterized in that, it includes: dividing the raw material and the product into multiple lumps according to boiling point and / or carbon number; the number of lumps is greater than 10.

5. The method for predicting sulfur content in hydrogenation reaction components according to any one of claims 1 to 4, characterized in that, the calculation of the kinetic parameters of the hydrocarbon conversion reaction by substituting the composition data into the mechanism model of hydrocarbon conversion includes: the rate equation of hydrocarbon conversion in the hydrogenation reaction process includes: Among them, F 影响因子 is the influence factor of catalyst activity, adsorption diffusion, etc. on hydrocarbon conversion. When the influence of a certain item is not considered in F 影响因子 , the value of this item is 1, including: when the influence of N on hydrocarbon conversion activity is not considered, f(N)=1; when the influence of adsorption on hydrocarbon conversion activity is not considered, f(adsorption)=1; when the influence of coke on hydrocarbon conversion activity is not considered, f(C)=1; when the influence of metal on hydrocarbon conversion activity is not considered, f(M)=1; i and j represent lumping serial numbers, and the larger the serial number, the heavier the components of the lumping; C Hi is the hydrocarbon content in lumping i; C ij is the hydrocarbon content converted from lumping i to lumping j; k ij is the rate constant for the reaction of hydrocarbons in lumping i to form hydrocarbons in lumping j; n is the reaction kinetic order; β is the hydrogen partial pressure index; P H2 is the hydrogen partial pressure, MPa; γ is the hydrogen-oil ratio index; H 2 / oil is the hydrogen-oil ratio; the relationship between the reaction rate constant k and temperature conforms to the Arrhenius equation: Among them, k ij，0 is the pre-exponential factor for the hydrocarbon reaction in lumping i to produce the hydrocarbon in lumping j; E a,ij is the activation energy value of the corresponding reaction, KJ / mol; R is the molar gas constant, with a value of 8.3114 J / (mol·K); T is the reaction temperature, K.

6. The method for predicting sulfur content in hydrogenation reaction components according to claim 5, characterized in that, the calculation of the kinetic parameters of the hydrocarbon conversion reaction by substituting the composition data into the mechanism model of hydrocarbon conversion includes: The analysis data obtained from the composition data and the operating condition data including reaction temperature time, reaction pressure and space velocity are input into the mechanism model of hydrocarbon conversion. Through the optimization method, by minimizing the sum of variances between the analyzed hydrocarbon content and the predicted hydrocarbon content, the kinetic parameters of the hydrocarbon conversion reaction are determined; the kinetic parameters of the hydrocarbon conversion reaction include the pre-exponential factor k between lumps ij，0 , activation energy E a,ij , reaction kinetic order n, hydrogen partial pressure index β, hydrogen-oil ratio index γ, and influence factors F such as catalyst activity and adsorption diffusion on hydrocarbon conversion 影响因子 related parameters; the formula of the optimization method includes: where SSE is the sum of variances; is the hydrocarbon content analysis value; is the hydrocarbon content predicted value; m is the number of lumps.

7. The method for predicting sulfur content in hydrogenation reaction components according to claim 6, characterized in that, the function expression includes: Among them, S ij and C ij are respectively the sulfur content and hydrocarbon content transferred from lumping i to lumping j; is the sulfur compound transfer parameter transferred from lumping i to lumping j; the sulfur transfer kinetic equation includes: Among them, is the sulfur compound transfer parameter for the transfer of lumped i to lumped j, and its initial value is only related to the raw material composition; the sulfur compound transfer parameter changes according to the equation: Among them, is the sulfur content in lumping i, is the hydrocarbon content in lumping i.

8. The method for predicting sulfur content in hydrogenation reaction components according to claim 7, characterized in that, coupling the sulfur removal kinetic equation and the sulfur transfer kinetic equation into a desulfurization kinetic equation includes: the sulfur removal kinetic equation in the hydrogenation reaction process includes: Among them, F 硫因子 is the influence factor of catalyst activity, adsorption diffusion, etc. on desulfurization activity. When the influence of a certain item is not considered in F 硫因子 , the value of this item is 1, including: when the influence of N on desulfurization activity is not considered, f(NS) = 1; when the influence of adsorption on desulfurization activity is not considered, f(adsorption S) = 1; when the influence of coke on desulfurization activity is not considered, f(CS) = 1; when the influence of metal on desulfurization activity is not considered, f(MS) = 1; is the sulfur content in lumping i; k Si is the rate constant of the sulfur removal reaction in lumping i; n s is the kinetic order of the desulfurization reaction; β S is the hydrogen partial pressure index of the sulfur removal reaction; is the hydrogen partial pressure, MPa; H 2 / oil is the hydrogen-oil ratio; γ S is the hydrogen-oil ratio index of sulfur removal; where the relationship between the reaction rate constant k and temperature conforms to the Arrhenius equation: Among them, k Si，0 is the pre-exponential factor of the sulfur removal reaction in lumped i; E a,Si is the activation energy of the desulfurization reaction, KJ / mol; R is the molar gas constant, with a value of 8.3114 J / (mol·K); T is the reaction temperature, K. the sulfur transfer kinetic equation in the hydrogenation reaction process includes: simultaneously considering the removal and transfer of sulfur in the hydrogenation reaction, and coupling to form the desulfurization kinetic equation, including: Lumped total sulfur conversion rate equation: Among them, i, j, and k represent lumping serial numbers. The larger the serial number, the heavier the components of the lumping. i > j > k; m is the number of lumpings.

9. The method for predicting sulfur content in hydrogenation reaction components according to claim 8, characterized in that generating a hydrodesulfurization kinetic model according to the desulfurization kinetic equation, including: Input the component data, the kinetic parameters of the hydrocarbon conversion reaction, and the operating condition data including reaction temperature, time, reaction pressure, and space velocity into the desulfurization kinetic equation. Through the optimization method, minimize the variance sum between the analyzed sulfur content and the predicted sulfur content to determine the kinetic parameters of the hydrodesulfurization kinetic model; the kinetic parameters of the hydrodesulfurization kinetic model include the pre-exponential factor k for sulfur removal reactions between lumps Si，0 , the activation energy E for sulfur removal a,Si , the reaction kinetic order n for sulfur removal s , the hydrogen partial pressure exponent β for sulfur removal S , the hydrogen-to-oil ratio exponent γ for sulfur removal S , the sulfur-containing compound transfer parameter between lumps , the influence factor F of catalyst activity, adsorption diffusion, etc. on sulfur removal 硫因子 related parameters; the formula of the optimization method includes: where SSE is the sum of variances; is the sulfur content analysis value; is the sulfur content predicted value; m is the number of lumps.

10. A device for predicting sulfur content in hydrogenation reaction components, characterized in that including: A composition data acquisition unit for respectively acquiring the composition data of the hydrocarbon content and sulfur content of the raw material and the product, and dividing the lumping according to the kinetic characteristics of the hydroconversion reaction system; the number of lumpings is not less than 2; A kinetic parameter calculation unit for calculating the kinetic parameters of the hydrocarbon conversion reaction by substituting the composition data into the mechanism model of hydrocarbon conversion; the kinetic parameters include the pre-exponential factor, activation energy, reaction kinetic order, hydrogen partial pressure index, hydrogen-oil ratio index, and relevant parameters of the activity influence factor between the lumpings; A sulfur transfer kinetics description unit for constructing a sulfur transfer kinetics equation for kinetic description of sulfur-containing compound transfer according to a preset function expression; The function expression is used to characterize the corresponding relationship between hydrocarbon conversion and sulfur-containing compound conversion; A sulfur removal kinetics description unit for constructing a sulfur removal kinetics equation and coupling the sulfur removal kinetics equation and the sulfur transfer kinetics equation into a desulfurization kinetics equation; A hydrodesulfurization kinetic model generation unit for generating a hydrodesulfurization kinetic model according to the desulfurization kinetic equation, including: substituting the composition data and the kinetic parameters into the desulfurization kinetic equation to calculate the kinetic parameters of hydrodesulfurization.

11. A device for predicting sulfur content in hydrogenation reaction components, characterized in that including: A memory for storing a computer program; A processor for calling and executing the computer program to implement the steps of the method for predicting sulfur content in hydrogenation reaction components according to any one of claims 1-9.

12. A storage medium, characterized in that including a software program, and the software program is suitable for being executed by a processor to implement the steps of the method for predicting sulfur content in hydrogenation reaction components according to any one of claims 1-9.

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