Establishment method of hydrogen donor characteristic presumption system of direct coal liquefaction circulating solvent, presumption method and presumption system

Abstract

The invention discloses an establishment method of a direct coal liquefaction circulating solvent hydrogen supply characteristic presumption system, and an equivalent hydrogen supply component presumption method and device. The method comprises the following steps: acquiring actually measured data of hydrogen supply characteristics of each hydrogen supply solvent model; performing nonlinear fitting on hydrogen supply measured data of each hydrogen supply solvent model according to hydrogen supply reaction kinetics to obtain a hydrogen supply curve of the hydrogen supply amount of the hydrogen supply solvent model along with temperature or time change, and synthesizing the hydrogen supply curves of all the selected hydrogen supply solvent models to form a direct coal liquefaction circulating solvent hydrogen supply characteristic model. By establishing the direct coal liquefaction circulating solvent hydrogen supply system, the equivalent hydrogen supply component and the hydrogen supply amount of the circulating solvent to be detected can be presumed, so that the liquefaction reaction parameters and the hydrogen supply component proportion of the circulating solvent in the direct coal liquefaction process are adjusted, and the purposes of improving the coal conversion rate and the oil yield in the direct liquefaction process are achieved; and a researcher can conveniently simulate a hydrogen supply process of a circulating solvent with complex components.

Description

Technical Field

[0001] The present invention relates to the technical field of direct coal liquefaction, and in particular to a method for establishing a system for estimating hydrogen supply characteristics of a circulating solvent in direct coal liquefaction, and a method and system for estimating hydrogen supply components. Background Art

[0002] The hydrogen supply capacity of the circulating solvent is crucial to the direct coal liquefaction process.

[0003] In the direct coal liquefaction process, a preheated coal-oil slurry containing a catalyst and pulverized coal enters the liquefaction reactor, where it mixes with the recycled solvent from the separation tower. Under liquefaction conditions, bonds in the coal break, and the resulting free radical fragments are hydrogenated by the recycled solvent or hydrogen. During this process, the hydrogen supply capacity of the recycled solvent is a crucial indicator for ensuring the smooth and continuous progress of the liquefaction reaction. Comprehensive and comprehensive evaluation of the circulating solvent's hydrogen supply capacity is essential for improving its hydrogen supply performance and optimizing the direct coal liquefaction process.

[0004] At present, the methods for evaluating the hydrogen supply capacity of the solvent in the direct coal liquefaction cycle are mainly divided into two categories. One is based on the physical properties or structural characteristics of the solvent, and the characteristic factors or structural parameters are used to evaluate the hydrogen supply capacity of the solvent. This type of evaluation method includes the characteristic factor method, infrared absorption spectroscopy and 1 H nuclear magnetic resonance method (PDQI factor method), etc. Another type is to evaluate the hydrogen supply capacity of the circulating solvent based on the conversion rate or product yield of the model substance when the circulating solvent is liquefied with the coal model substance.

[0005] However, the above two methods have the following disadvantages:

[0006] (1) In the characteristic factor method, the characteristic factor K is obtained based on the physical properties of the solvent, and theoretically it is impossible to accurately evaluate the hydrogen donation characteristics of the solvent.

[0007] (2) Infrared absorption spectroscopy fails to effectively distinguish between carbon-hydrogen bonds in aliphatic hydrocarbons and aliphatic carbon-hydrogen bonds in hydrogenated aromatic rings, and the results obtained have large errors.

[0008] (3) The PDQI index ignores the hydrogen that can be donated at the α-position, γ-position, and other positions on the aliphatic ring. For example, under this definition, the PDQI value of dihydroanthracene (DHA) and dihydrophenanthrene (DHP), which are recognized as excellent hydrogen-donating solvent components, is 0, meaning that these two substances have no hydrogen-donating ability, which is obviously inconsistent with the facts. The composition and structure of real circulating solvents are usually more complex. If the PDQI index is used to reflect their hydrogen-donating ability, the hydrogen-donating ability of some hydrogen-donating components such as DHA or DHP may be ignored, resulting in inaccurate evaluation results.

[0009] (4) The hydrogen supply capacity of the circulating solvent obtained based on the conversion rate or product yield of the coal model is affected by the choice of the coal model and is limited by the difficulty of breaking the covalent bonds of the coal model. There may be a large error in judging the starting hydrogen supply temperature of the circulating solvent, and the evaluation results are limited.

[0010] Therefore, a method is urgently needed to infer the hydrogen supply composition and hydrogen supply characteristics of the circulating solvent. Summary of the Invention

[0011] (1) Purpose of the invention

[0012] The present invention aims to provide a method for establishing a system for estimating the hydrogen supply characteristics of a circulating solvent for direct coal liquefaction, as well as a method and system for estimating the hydrogen supply composition. The hydrogen supply performance of the circulating solvent is determined by fitting a hydrogen supply curve using measured data such as the circulating solvent's hydrogen supply amount, hydrogen supply temperature, and time under different conditions. This curve can be used to accurately estimate the hydrogen supply performance of the circulating solvent under test, facilitating analysis of the hydrogen supply process of the circulating solvent under test in the direct coal liquefaction reaction.

[0013] (2) Technical solution

[0014] To solve the above problems, the first aspect of the present invention provides a method for evaluating the hydrogen supply performance of a coal direct liquefaction circulating solvent, the method is used to infer the hydrogen supply composition and hydrogen supply amount of the coal direct liquefaction circulating solvent to be tested, the method requires to be established based on the hydrogen supply curves of at least three different hydrogen supply solvent model substances, the method comprising: obtaining a measured data set of the hydrogen supply amount of each hydrogen supply solvent model substance, the measured data set is a plurality of data obtained by measuring the direct coal liquefaction reaction of each hydrogen supply solvent model substance at different temperatures and times in the presence of a catalyst, each data is the hydrogen supply amount of the hydrogen supply solvent model substance at a specific temperature and time, and the plurality of data constitute the hydrogen supply amount data set of the hydrogen supply solvent model substance; performing nonlinear fitting on the hydrogen supply amount data set of each hydrogen supply solvent model substance according to kinetics to obtain a hydrogen supply curve of the hydrogen supply amount of the hydrogen supply solvent model substance varying with temperature or time, the hydrogen supply curves of all the selected hydrogen supply solvent model substances are mathematically added to constitute the hydrogen supply fitting curve, and the optimal solution of the mathematical addition is the degree of fit between the obtained hydrogen supply fitting curve and the hydrogen supply curve of the real coal liquefaction circulating solvent (i.e., the coefficient of determination R 2 ) is not lower than the preset value.

[0015] According to a second aspect of the present invention, a method for equivalently estimating the hydrogen supply component of a circulating solvent for direct coal liquefaction is provided, comprising: obtaining a hydrogen supply curve of the circulating solvent to be tested; performing an equivalent hydrogen supply fitting on the hydrogen supply curve of the circulating solvent for direct coal liquefaction to be tested based on the hydrogen supply curve of the hydrogen supply solvent model to obtain a fitting curve; and estimating the equivalent hydrogen supply component and proportion of the circulating solvent for direct coal liquefaction to be tested based on the hydrogen supply fitting curve and the type of circulating hydrogen supply solvent in the hydrogen supply solvent model.

[0016] According to the third aspect of the present invention, a method for preparing a circulating solvent for direct coal liquefaction is provided, comprising: estimating the equivalent hydrogen supply components and proportions of the circulating solvent for direct coal liquefaction to be prepared according to the method described in the second aspect; and adding at least one additional equivalent hydrogen supply component based on parameters such as the maximum hydrogen supply amount, initial hydrogen supply temperature, maximum hydrogen supply temperature, and effective hydrogen supply time of the circulating solvent for direct coal liquefaction, as well as the estimated equivalent hydrogen supply component, to adjust the hydrogen supply effect of the circulating solvent for direct coal liquefaction.

[0017] According to the fourth aspect of the present invention, a method for regulating hydrogen supply for a direct coal liquefaction reaction is provided, comprising: obtaining a circulating solvent in the direct coal liquefaction reaction; inferring the equivalent hydrogen supply components and proportions of the circulating solvent according to the method provided in the second aspect; and predicting and regulating the optimal process parameters of the direct coal liquefaction reaction based on parameters such as the proportion of the equivalent hydrogen supply components, the maximum hydrogen supply amount, the initial hydrogen supply temperature, the maximum hydrogen supply temperature, and the effective hydrogen supply time inferred from the circulating solvent.

[0018] According to a fifth aspect of the present invention, a system for estimating hydrogen supply characteristics of a circulating solvent for direct coal liquefaction is provided, wherein the circulating solvent hydrogen supply system is used to estimate the hydrogen supply composition and hydrogen supply amount of a circulating solvent for direct coal liquefaction to be tested, and the system is established based on the hydrogen supply curves of at least three different hydrogen supply solvent model substances, and the system comprises: an acquisition unit for acquiring measured data of each hydrogen supply solvent model substance, wherein the measured data comprises parameters such as the chemical structure, hydrogen supply curve, maximum hydrogen supply amount, initial hydrogen supply temperature, maximum hydrogen supply temperature, and effective hydrogen supply time of the hydrogen supply solvent model substance, and wherein these parameters of all hydrogen supply solvent model substances are collected to form a measured data set, wherein the measured data set is obtained by measuring under the condition of the presence of a catalyst, wherein each set of data is displayed as a data point in a two-dimensional coordinate, and the two-dimensional coordinate is The horizontal axis can be temperature or time, and the vertical axis is the hydrogen supply; the fitting unit uses kinetics to perform nonlinear fitting on the measured data of each hydrogen supply solvent model in the database to obtain a hydrogen supply curve of the hydrogen supply solvent model that changes with temperature or time. These hydrogen supply curves are used for the equivalent fitting of the hydrogen supply curve of the coal direct liquefaction circulating solvent by the following inference unit, thereby inferring the equivalent hydrogen supply component and composition ratio of the coal direct liquefaction circulating solvent; the inference unit selects at least three hydrogen supply solvent model objects in the database according to the composition characteristics of the coal direct liquefaction circulating solvent to be tested, and fits the coal direct liquefaction circulating oil hydrogen supply curve based on the hydrogen supply curve of the hydrogen supply solvent model object to infer the equivalent hydrogen supply component and ratio of the coal direct liquefaction circulating solvent to be tested (also called circulating solvent oil).

[0019] According to a sixth aspect of the present invention, a storage medium is provided, which stores a computer program, and when the computer program is executed by a processor, it implements the method described in the first aspect, or when the computer program is executed by the processor, it implements the method for equivalent estimation of hydrogen supply components of coal direct liquefaction circulating solvent according to the second aspect.

[0020] According to the seventh aspect of the present invention, an electronic device comprises a memory, a processor and a computer program stored in the memory and executable on the processor, wherein the processor implements the method for establishing the method for evaluating the hydrogen supply capacity of a coal direct liquefaction circulating solvent according to the first aspect when the program is executed, or the computer program implements the method for estimating the equivalent hydrogen supply component of a coal direct liquefaction circulating solvent according to the second aspect when the program is executed by the processor.

[0021] (3) Beneficial effects

[0022] The above technical solution of the present invention has the following beneficial technical effects:

[0023] (1) The system for estimating the hydrogen supply characteristics of the coal direct liquefaction circulating solvent established in the present invention is to fit the measured data of the coal direct liquefaction circulating solvent to be tested and a plurality of different hydrogen supply solvent model objects to obtain the respective hydrogen supply curves, and mathematically add the hydrogen supply curves of the hydrogen supply solvent model objects to obtain the fitting curve of the coal direct liquefaction circulating solvent hydrogen supply curve. By analyzing the fitting curve, the hydrogen supply amount of the coal direct liquefaction circulating solvent to be tested can be better estimated, which is convenient for analyzing the process of relay hydrogen supply of different hydrogen supply components of the circulating solvent in the coal direct liquefaction reaction.

[0024] (2) The present invention establishes an equivalent fitting model for the hydrogen supply characteristics of the coal direct liquefaction circulating solvent, which can infer parameters such as the hydrogen supply composition, hydrogen supply amount and hydrogen supply temperature of the coal direct liquefaction circulating solvent to be tested, and then can adjust the hydrogen supply component ratio of the circulating solvent during the coal direct liquefaction process, adjust the liquefaction reaction temperature, and thus improve the efficiency of the coal direct liquefaction reaction. It also makes it easier for researchers to simulate the hydrogen supply reaction process of the coal direct liquefaction circulating solvent with complex components. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a flow chart of a method for establishing a system for estimating hydrogen supply characteristics of a circulating solvent for direct coal liquefaction according to a first embodiment of the present invention;

[0026] FIG2( a ) is a schematic flow diagram of a method for estimating the hydrogen supply component of a circulating solvent for direct coal liquefaction according to a second embodiment of the present invention;

[0027] FIG2( b ) is a schematic diagram of estimating the hydrogen supply component of the circulating solvent for direct coal liquefaction according to the second embodiment of the present invention;

[0028] Figure 3 This is a schematic flow chart of a method for preparing circulating solvents for direct coal liquefaction according to a third embodiment of the present invention;

[0029] Figure 4 1 is a schematic flow chart of a method for controlling the reaction conditions of direct coal liquefaction provided by a fourth embodiment of the present invention;

[0030] Figure 5 Schematic diagram of a device for establishing a system for estimating hydrogen-donating characteristics of a hydrogen-donating solvent model provided in a fifth embodiment of the present invention;

[0031] Figure 6 Schematic diagram of an equivalent estimation device for hydrogen supply components of a circulating solvent for direct coal liquefaction according to a sixth embodiment of the present invention;

[0032] Figure 7 Schematic diagram of the hydrogen donation curve of the hydrogen donation solvent model provided in Example 1 of the present invention;

[0033] Figure 8Schematic diagram of the hydrogen supply curve of the coal direct liquefaction circulating solvent oil 1 provided in Example 2 of the present invention;

[0034] Figure 9 This is a schematic diagram of equivalent hydrogen supply fitting of the hydrogen supply curve of coal direct liquefaction circulating solvent oil 1 based on the hydrogen supply solvent model provided in Example 2 of the present invention;

[0035] Figure 10 Schematic diagram showing the degree of fit between the hydrogen supply curve of the coal direct liquefaction circulating solvent oil 1 and the equivalent hydrogen supply curve provided in Example 2 of the present invention;

[0036] Figure 11 Schematic diagram of the hydrogen supply curve of the coal direct liquefaction circulating solvent oil 2 provided in Example 3 of the present invention;

[0037] Figure 12 This is a schematic diagram of equivalent hydrogen supply fitting of the hydrogen supply curve of coal direct liquefaction circulating solvent oil 2 based on the hydrogen supply solvent model provided in Example 3 of the present invention;

[0038] Figure 13 It is a schematic diagram of the fitting degree between the hydrogen supply curve of the coal direct liquefaction circulating solvent oil 2 provided in Example 3 of the present invention and the equivalent hydrogen supply curve. DETAILED DESCRIPTION

[0039] To make the objectives, technical solutions, and advantages of the present invention more clearly understood, the present invention will be further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings. It should be understood that these descriptions are merely exemplary and are not intended to limit the scope of the present invention. In addition, in the following description, descriptions of well-known structures and technologies are omitted to avoid unnecessary confusion of the concepts of the present invention.

[0040] Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0041] In the description of the present invention, it should be noted that the terms "first", "second" and "third" are only used for descriptive purposes and should not be understood as indicating or implying relative importance.

[0042] In addition, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0043] The present invention will be described in more detail below with reference to the accompanying drawings. Numerous specific details of the present invention, such as processing techniques and technologies, are described below to facilitate a clearer understanding of the present invention. However, as will be appreciated by those skilled in the art, the present invention may be practiced without these specific details. Unless otherwise noted below, the various components below may be constructed using techniques known to those skilled in the art.

[0044] Figure 1 It is a flow chart of a method for establishing a system for estimating hydrogen supply characteristics of a circulating solvent in direct coal liquefaction according to a first embodiment of the present invention.

[0045] The system is used to estimate the hydrogen supply of the direct coal liquefaction circulating solvent to be tested, and the hydrogen supply solvent model provided in the embodiment includes hydrogen supply curves of at least three different hydrogen supply solvent model substances.

[0046] like Figure 1 As shown, the method includes steps S101-S102:

[0047] Step S101: obtaining a measured data set of each hydrogen-donating solvent model.

[0048] The measured data are multiple data points obtained by performing direct liquefaction hydrogenation reactions on each hydrogen-donating solvent model in the presence of a catalyst at different temperatures or times. Each data point includes the reaction temperature or time, as well as the hydrogen supply of the corresponding hydrogen-donating solvent model.

[0049] Furthermore, the measured data is obtained by measuring the conversion rate of each hydrogen-donating solvent model substance at different temperatures or different times in the presence of a catalyst, and calculating its hydrogen supply amount based on the conversion rate of the hydrogen-donating solvent model substance, thereby obtaining multiple sets of measured data.

[0050] In one embodiment, the measured data include the starting hydrogen supply temperature Ti of the hydrogen supply solvent model, the maximum hydrogen supply amount Q HDS-H，max , the hydrogen supply amount of the hydrogen-donating solvent model substance at each temperature and each reaction time; wherein the sampling frequency of the measured data of the hydrogen-donating solvent model substance is the same, and in some embodiments, the sampling frequency may also be different.

[0051] It is understood that multiple direct coal liquefaction reactions can be conducted in advance to obtain more data, thereby establishing a hydrogen supply curve database for hydrogen-donating solvent model compounds. For example, direct coal liquefaction reactions can be conducted on each hydrogen-donating solvent model compound in the presence of a catalyst at different temperatures, and actual measurements can be performed using an instrument to obtain actual measured data. The actual measured data can be the hydrogen supply amount of the hydrogen-donating solvent model compound at each temperature.

[0052] It should be noted that, in order to facilitate the construction of the database, the various temperature values ​​selected for each hydrogen-donating solvent model are the same. For example, in the presence of a catalyst, each hydrogen-donating solvent model undergoes direct coal liquefaction reaction at temperatures of 200, 220, 240, 250, 280, 300, 320, 330, 340, 380, 420, and 460°C, respectively, and the selected reaction times are 1, 2, 3, 5, 30, 60, 120, and 150 min, respectively.

[0053] In this way, the hydrogen supply amount of each hydrogen-donating solvent model substance under the same reaction temperature and the same reaction time can be obtained.

[0054] The catalyst may include a metal active component-supported catalyst, comprising a support and an active component attached to the support. The support may include, but is not limited to, a carbon-based inert support such as coal char, biocoke, petroleum coke, activated carbon, or an inorganic support such as a molecular sieve or alumina. The active substance may be a metal sulfide or metal oxide having hydrogenation catalytic properties, including one or more of ferrous sulfide, molybdenum sulfide, ferrous trisulfide, and a multi-metal composite active component.

[0055] Optionally, the catalyst may be a ferrous sulfide catalyst supported by coal coke.

[0056] Optionally, the mass ratio of the catalyst to the hydrogen-donating solvent model is 1:10.

[0057] In one embodiment, the metal active component supported catalyst can be prepared by one of an impregnation method, a precipitation method, a thermal decomposition method, and an ion exchange method.

[0058] In one embodiment, when the ferrous sulfide catalyst supported on coal char is prepared by an impregnation method, the iron loading is 1% of the mass of the coal char according to a common ratio in the direct coal liquefaction process.

[0059] In one embodiment, each measured data may be obtained by measuring using one of gas chromatography, liquid chromatography, mass spectrometry, and chemical reaction methods.

[0060] Step S102, according to the kinetics, the measured data of each hydrogen supply solvent model are subjected to nonlinear fitting to obtain the hydrogen supply curve of the hydrogen supply amount of the hydrogen supply solvent model as a function of temperature or time. The hydrogen supply curves of all selected hydrogen supply solvent model objects are mathematically added to form the hydrogen supply fitting curve. The optimal solution of the mathematical addition is the solution when the obtained hydrogen supply fitting curve and the hydrogen supply curve of the actual circulating solvent of coal liquefaction have a fitting degree not less than (greater than or equal to) a preset value. Wherein the fitting degree is R 2, which can also be called correlation or determination coefficient, can be preset to 0.95. The hydrogen donation curves of all selected hydrogen donation solvent model substances constitute the hydrogen donation curve database of the hydrogen donation solvent model substance.

[0061] In one embodiment, the measured data of each hydrogen-donating solvent model are subjected to nonlinear fitting according to the kinetics to obtain the hydrogen-donating curve of the hydrogen-donating solvent model, including: performing nonlinear fitting according to the following formula

[0062] ln(1-Q HDS-H / Q HDS-H，max )=-kt

[0063] lnk=lnA-Ea / RT

[0064] A.e -Ea / RTi =0.001

[0065] Among them, Q HDS-H is the hydrogen supply amount of the hydrogen-donating solvent model, Q HDS-H，max is the maximum hydrogen supply capacity of the hydrogen-donating solvent model.

[0066] In an optional embodiment, the hydrogen-donating solvent model substance includes one or more of tetrahydronaphthalene, dihydroanthracene, dihydrophenanthrene, tetrahydroquinoline, tetrahydronaphthol, indane, tetrahydroanthracene, tetrahydrophenanthrene, octahydroanthracene, and octahydrophenanthrene.

[0067] In an optional embodiment, the hydrogen donation curve of the hydrogen-donating solvent model substance includes tetralin, and the hydrogen donation curve of tetralin is: Q H =-52.79+0.48*T-1.44×10 -3 *T 2 +1.46×10 -6 *T 3 .

[0068] In an optional embodiment, the hydrogen donation curve of the hydrogen-donating solvent model substance includes tetrahydroquinoline, and the hydrogen donation curve of tetrahydroquinoline is: Q H =47.56-0.25*T+8.25×10 -5 *T 2 -7.32×10 -7 *T 3 .

[0069] In an optional embodiment, the hydrogen donation curve of the hydrogen-donating solvent model substance includes tetrahydronaphthol, and the hydrogen donation curve of tetrahydronaphthol is: Q H =-183.76+1.66*T+5.09×10 -3 *T 2 -5.26×10 -6 *T 3 .

[0070] In an optional embodiment, the hydrogen donation curve of the hydrogen-donating solvent model substance includes dihydroanthracene, and the hydrogen donation curve of dihydroanthracene is: Q a =483.2-4.15*T+1.16×10 -2 *T 2 -1.06×10 -5 *T 3 ;

[0071] Among them, Q H represents the hydrogen supply amount of the hydrogen-donating solvent model substance, and T represents the reaction time.

[0072] 2 is a schematic flow diagram of a method for estimating the hydrogen supply component of a circulating solvent for direct coal liquefaction according to a second embodiment of the present invention;

[0073] As shown in FIG2 , the method includes steps S201 to S203:

[0074] In step S201, the dehydrogenation rate of the direct coal liquefaction circulating solvent to be tested at different temperatures or different times is obtained, and the hydrogen supply amount thereof is calculated based on the dehydrogenation rate.

[0075] Step S202: obtaining a hydrogen supply curve of the direct coal liquefaction circulating solvent to be tested.

[0076] In one embodiment, the process of constructing the hydrogen supply curve of the direct coal liquefaction circulating solvent to be tested may be the same as the process of establishing the hydrogen supply curve of the hydrogen supply curve of the hydrogen supply solvent model in the hydrogen supply curve database of the hydrogen supply solvent model in the first embodiment.

[0077] Specifically, the steps for constructing the hydrogen supply curve of the direct coal liquefaction circulating solvent to be tested include:

[0078] Obtain measured data for the direct coal liquefaction circulating solvent to be tested. The measured data are multiple data points obtained by performing direct coal liquefaction reactions on the direct coal liquefaction circulating solvent to be tested in the presence of a catalyst at different temperatures or for different times. Each data point includes the reaction temperature or time, as well as the corresponding hydrogen supply.

[0079] In one embodiment, the direct liquefaction reaction of the direct coal liquefaction circulating solvent to be tested can be measured by an instrument to obtain measured data. The measured data can be the hydrogen supply of the direct coal liquefaction circulating solvent at each temperature or time.

[0080] Optionally, the selected multiple reaction temperatures and multiple reaction times are the same as the temperature and reaction time of the coal direct liquefaction reaction of the hydrogen supply solvent model when constructing the database, which can facilitate the subsequent estimation and calculation of the hydrogen supply component.

[0081] For example, the coal direct liquefaction circulating solvent to be tested is selected to undergo coal direct liquefaction reaction in the presence of a catalyst at temperatures of 200, 220, 240, 250, 280, 300, 320, 330, 340, 380, 420, and 460°C, respectively, and the selected reaction times are 1, 2, 3, 5, 30, 60, 120, and 150 minutes, respectively.

[0082] Step S203 , performing equivalent hydrogen supply fitting on the hydrogen supply curve of the direct coal liquefaction circulating solvent to be tested according to the hydrogen supply curve of the hydrogen supply solvent model object, to obtain a fitting curve.

[0083] Optionally, in this step, a polynomial fitting or exponential function fitting method may be used to obtain a hydrogen supply fitting curve of the direct coal liquefaction circulating solvent.

[0084] It can be understood that the purpose of fitting the hydrogen supply curves of the coal direct liquefaction circulating solvent to be tested with multiple hydrogen supply solvent model objects is to obtain the mass percentage of each hydrogen supply solvent model object equivalent to the coal direct liquefaction circulating solvent to be tested, that is, to infer the effective hydrogen supply components of the coal direct liquefaction circulating solvent, so as to further analyze the relay hydrogen supply process of each hydrogen supply component in the coal direct liquefaction circulating solvent to be tested through the hydrogen supply solvent model object.

[0085] In one embodiment, an equivalent hydrogen supply fitting is performed on the hydrogen supply curve of the coal direct liquefaction circulating solvent to be tested based on the hydrogen supply curve of the hydrogen supply solvent model to obtain a fitting curve, including:

[0086] The hydrogen supply Q of the circulating solvent for direct coal liquefaction OIL-H The hydrogen supply of the hydrogen-donating solvent model is Q HDS-H The proportions of several hydrogen-donating solvent models in the fitting curve are represented by a1, a2, a3, ...a n Numbered sequentially, where the non-hydrogen donating solvent is a n+1 , the solution target is ∑(Q SUM-H -Q OIL-H ) 2 Minimum, a1, a2, a3, ...a are calculated by the following constraints n , a n+1 The value of:

[0087] Q SUM-H =a1×Q HDS-1 +a2×Q HDS-2 +a3×Q HDS-3 ...+a n ×Q HDS-n

[0088] a n+1 =1-a1-a2-a3...-an

[0089] 0≤a1(a2 / a3 / ...a n / a n+1 )≤1.

[0090] The coefficient of determination R 2 When the preset value is exceeded, a fitting curve of hydrogen supply of the direct coal liquefaction circulating solvent to be tested is obtained.

[0091] It is understandable that the coefficient of determination R 2 It shows the effect of hydrogen supply curve fitting. When R 2 The closer the value is to 1, the better the equivalence between the hydrogen supply curve of the direct coal liquefaction circulating solvent to be tested and the equivalent hydrogen supply curve obtained by superimposing the hydrogen supply curves of multiple hydrogen supply solvent model substances at the solution ratio, that is, the more reliable the ratio of the hydrogen supply solvent model substances obtained by solution is.

[0092] In a preferred embodiment, the preset value is 0.95. In other words, when the coefficient of determination R 2 When it exceeds 0.95, it can be considered that the curve fit is good, and thus a fitting curve is obtained.

[0093] Step S204 , estimating the equivalent hydrogen supply components and proportions of the direct coal liquefaction circulating solvent to be tested based on the fitting curve and the types of hydrogen supply solvent models involved in the fitting curve.

[0094] In one embodiment, based on the fitting curve and the type of the hydrogen-donating solvent model involved, the equivalent hydrogen-donating components and ratios of the direct coal liquefaction circulating solvent to be tested are estimated, including:

[0095] According to the types of hydrogen-donating solvent model substances involved in the fitting curve, the proportion of hydrogen-donating solvent model substances and the proportion of non-hydrogen-donating solvents equivalent to the direct coal liquefaction circulating solvent to be tested are estimated.

[0096] It is understandable that the composition of a coal direct liquefaction circulating solvent is generally relatively complex, and may contain more than a dozen or even hundreds of solvent substances. Some solvents have the ability to supply hydrogen and are used as hydrogen-supplying solvents, while some do not have the ability to supply hydrogen and are used only as solvents.

[0097] Precisely because the composition of the circulating solvent for direct coal liquefaction is very complex, it is difficult to actually determine the specific components present in the circulating solvent for direct coal liquefaction and the proportion of components with hydrogen supply function using existing technical means. Based on this, during the direct coal liquefaction reaction, it is extremely difficult to accurately understand when the hydrogen supply components in the circulating solvent for direct coal liquefaction start to supply hydrogen, when they end to supply hydrogen, and the impact of the interaction between these hydrogen supply components on hydrogen supply. Even if we can determine that the hydrogen supply of these hydrogen supply components may be a relay process as the temperature and time change,

[0098] In order to better understand the method provided by the second embodiment of the present invention, please refer to Figure 2 (b). This method first calculates the hydrogen supply amount of the hydrogen supply solvent model based on its conversion rate to obtain the measured data points in the figure, and then performs kinetic fitting on all the measured data points in the figure, with a fitting degree of not less than 0.95, so as to obtain a hydrogen supply curve in which the hydrogen supply amount changes with liquefaction temperature or time. Then, the hydrogen supply curves of multiple hydrogen supply solvent model objects are mathematically added to obtain a hydrogen supply fitting curve, and the coefficients of the mathematical addition satisfy: a1+a2+a3...+a n ≤1. The fitting goal of the final fitting curve is to make the hydrogen supply fitting curve and the hydrogen supply curve of the circulating solvent oil as similar as possible, and the similarity between the two should not be less than 0.95. When the similarity is ≥0.95, the fitting curve is calculated based on a1 to a n The composition and proportion of the circulating solvent oil to be tested (the circulating hydrogen supply solvent to be tested) can be inferred from the numerical value.

[0099] The present embodiment can construct a database of hydrogen supply curves of hydrogen supply solvent model objects, and perform equivalent hydrogen supply fitting on the hydrogen supply curve of the direct coal liquefaction circulating solvent to be tested based on the database, and can infer which hydrogen supply solvent model objects the direct coal liquefaction circulating solvent to be tested can be equivalent to and their proportions. Since the hydrogen supply curve database of hydrogen supply solvent model objects contains information such as the starting hydrogen supply temperature and maximum hydrogen supply amount of each hydrogen supply solvent model object, the hydrogen supply composition and proportion of the direct coal liquefaction circulating solvent to be tested can be effectively inferred through this inference method. The mastery of this information will obviously help to deeply understand the hydrogenation path in the direct coal liquefaction reaction process, and then the temperature and time of the liquefaction reaction can be controlled, the hydrogen supply efficiency of the direct coal liquefaction circulating solvent can be improved, and the liquefaction conversion rate of coal can be improved.

[0100] Figure 3 It is a schematic flow chart of a method for preparing circulating solvent for direct coal liquefaction provided in a third embodiment of the present invention.

[0101] like Figure 3 As shown, the method includes:

[0102] Step S301: According to the method provided in the second aspect, the equivalent hydrogen supply component and ratio of the direct coal liquefaction circulating solvent to be prepared are estimated.

[0103] Step S302 , adding at least one equivalent non-hydrogen supply component according to the maximum hydrogen supply amount of each hydrogen supply solvent model and the estimated equivalent hydrogen supply component of the target coal direct liquefaction circulating solvent to adjust the proportion of the equivalent hydrogen supply component.

[0104] In this embodiment, the equivalent hydrogen-donating components and ratios of the direct coal liquefaction circulating solvent to be prepared can be estimated using the method provided in the second embodiment above. For example, the equivalent hydrogen-donating components of the direct coal liquefaction circulating solvent to be prepared are estimated to be the model hydrogen-donating solvents tetralin, dihydroanthracene, and tetrahydroquinoline, with their ratios being 10%, 20%, and 15%, respectively, with the remainder being non-hydrogen-donating solvents.

[0105] According to the hydrogen supply curve database of the constructed hydrogen supply solvent model, tetrahydroquinoline has the highest maximum hydrogen supply capacity and its hydrogen supply effect is best at 400-440℃. In order to improve the hydrogen supply capacity of the coal direct liquefaction circulating solvent to be prepared, the amount of tetrahydroquinoline can be increased by changing the liquefaction process or by external addition, thereby obtaining a new coal direct liquefaction circulating solvent with strong hydrogen supply capacity.

[0106] Figure 4 1 is a flow chart of a method for controlling the reaction conditions of direct coal liquefaction provided by a fourth embodiment of the present invention, the method comprising:

[0107] Step S401: obtaining a hydrogen supply curve of a circulating solvent in a direct coal liquefaction reaction.

[0108] Step S402: According to the method provided in the second embodiment, the equivalent hydrogen supply components and proportions of the direct coal liquefaction circulating solvent to be prepared are estimated.

[0109] Step S403, according to the maximum hydrogen supply amount, starting hydrogen supply temperature, hydrogen supply temperature and hydrogen supply time interval of each hydrogen supply solvent model substance in the hydrogen supply curve database of the hydrogen supply solvent model substance, and the estimated ratio of the equivalent hydrogen supply components of the target coal direct liquefaction circulating solvent, the coal direct liquefaction reaction conditions, including reaction temperature, time, pressure, coal feed amount, coal direct liquefaction initial oil fraction segment cutting ratio, and circulating solvent circulation amount.

[0110] In this embodiment, the equivalent hydrogen-donating components and ratios of the direct coal liquefaction circulating solvent to be prepared can be estimated using the method provided in the second embodiment above. For example, the equivalent hydrogen-donating components of the direct coal liquefaction circulating solvent to be prepared are estimated to be tetralin, dihydroanthracene, and tetrahydroquinoline, respectively, in the hydrogen-donating solvent model, with their ratios being 10%, 20%, and 15%, respectively, with the remainder being non-hydrogen-donating solvents.

[0111] According to the hydrogen supply curve database of the constructed hydrogen supply solvent model, the starting temperature of tetrahydroquinoline to donate hydrogen is 321°C, the starting temperature of tetralin is 330°C, and the starting temperature of dihydroanthracene is 293°C. The temperature at which coal free radicals are produced in large quantities is generally believed to be above 300°C, and the amount of free radicals produced below 300°C is relatively small. In order to match the hydrogen supply temperature of the coal direct liquefaction circulating solvent with the temperature at which coal bonds break and free radicals are produced, we can consider increasing the ratio of tetrahydroquinoline and tetralin and reducing the ratio of dihydroanthracene. In this way, various effective hydrogen supply components can supply hydrogen at the appropriate temperature, thereby increasing the effective hydrogen supply of the hydrogen supply solvent.

[0112] Figure 5 Schematic diagram of the device for establishing the estimation system provided by the fifth embodiment of the present invention. The system is used to estimate the hydrogen supply component and hydrogen supply amount of the direct coal liquefaction circulating solvent to be tested. The system is established based on the hydrogen supply curves of at least three different hydrogen supply solvent models. Figure 5 As shown, the device includes: a first acquiring unit and a first fitting unit.

[0113] Wherein, the first acquisition unit is used to obtain the measured data of each hydrogen supply solvent model, and the measured data is the hydrogen supply amount obtained by carrying out the direct coal liquefaction reaction of each hydrogen supply solvent model in the presence of a catalyst at different temperatures or times. The measured data include parameters such as the chemical structure, hydrogen supply curve, maximum hydrogen supply amount, initial hydrogen supply temperature, maximum hydrogen supply temperature, and effective hydrogen supply time of the hydrogen supply solvent model. Wherein, the measured data is a plurality of hydrogen supply amount data obtained by measuring the direct coal liquefaction reaction of each hydrogen supply solvent model in the presence of a catalyst at different temperatures. Each data includes the hydrogen supply amount of the hydrogen supply solvent model under different reaction temperatures or times.

[0114] It should be noted that the measurement and calculation methods of the measured data are the same as those provided in the first embodiment above, and will not be described in detail in this embodiment.

[0115] The first fitting unit is used to perform nonlinear fitting on the measured hydrogen supply data of each hydrogen supply solvent model substance according to kinetics to obtain a hydrogen supply curve of the hydrogen supply amount of the hydrogen supply solvent model substance varying with temperature or time. The hydrogen supply curves of all hydrogen supply solvent model substances constitute the hydrogen supply curve data set of the hydrogen supply solvent model substance.

[0116] In one embodiment, the first fitting unit performs nonlinear fitting on the measured hydrogen supply data of each hydrogen supply solvent model substance according to kinetics to obtain the hydrogen supply curve of the hydrogen supply solvent model substance, including: the first fitting unit performs nonlinear fitting by the following formula

[0117] ln(1-Q HDS-H / Q HDS-H，max )=-kt

[0118] lnk=lnA-Ea / RT

[0119] Ae -Ea / RTi =0.001

[0120] Among them, Q HDS-H is the hydrogen supply amount of the hydrogen-donating solvent model, Q HDS-H，max is the maximum hydrogen supply capacity of the hydrogen-donating solvent model.

[0121] In an optional embodiment, the hydrogen-donating solvent model substance includes one or more of tetrahydronaphthalene, dihydroanthracene, dihydrophenanthrene, tetrahydroquinoline, tetrahydronaphthol, indane, tetrahydroanthracene, tetrahydrophenanthrene, octahydroanthracene, and octahydrophenanthrene.

[0122] In an optional embodiment, the hydrogen donation curve of the hydrogen-donating solvent model substance includes tetralin, and the hydrogen donation curve of tetralin is: Q H =-52.79+0.48*T-1.44×10 -3 *T 2 +1.46×10 -6 *T 3 .

[0123] In an optional embodiment, the hydrogen donation curve of the hydrogen-donating solvent model substance includes tetrahydroquinoline, and the hydrogen donation curve of tetrahydroquinoline is: Q H =47.56-0.25*T+8.25×10 -5 *T 2 -7.32×10 -7 *T 3 .

[0124] In an optional embodiment, the hydrogen donation curve of the hydrogen-donating solvent model substance includes tetrahydronaphthol, and the hydrogen donation curve of tetrahydronaphthol is: Q H =-183.76+1.66*T+5.09×10 -3 *T 2 -5.26×10 -6 *T 3 .

[0125] In an optional embodiment, the hydrogen donation curve of the hydrogen-donating solvent model substance includes dihydroanthracene, and the hydrogen donation curve of dihydroanthracene is: QH =483.2-4.15*T+1.16×10 -2 *T 2 -1.06×10 -5 *T 3 ;

[0126] Among them, Q H represents the hydrogen supply amount of the hydrogen-donating solvent model substance, and T represents the reaction time.

[0127] Figure 6 This is a schematic diagram of a system for estimating hydrogen supply characteristics of a circulating solvent for direct coal liquefaction according to the sixth embodiment of the present invention. Figure 6 As shown, the device includes: a second acquisition unit, a selection and control unit, a second fitting unit and an inference unit.

[0128] The second acquisition unit is used to acquire the hydrogen supply curve of the direct coal liquefaction circulating solvent to be tested.

[0129] The selection and control unit is used to select a suitable hydrogen supply solvent model from the hydrogen supply curve database of the hydrogen supply solvent model, and the selection is based on the composition characteristics of the coal direct liquefaction circulating solvent to be tested, and the composition characteristics are based on typical hydrogen supply components in the coal direct liquefaction circulating solvent obtained by instrumental analysis.

[0130] A second fitting unit is configured to perform equivalent hydrogen supply fitting on the hydrogen supply curve of the direct coal liquefaction circulating solvent to be tested based on the hydrogen supply curve database of the hydrogen supply solvent model to obtain a fitting curve;

[0131] The estimating unit is used to estimate the equivalent hydrogen supply components and proportions of the direct coal liquefaction circulating solvent to be tested according to the types of hydrogen supply solvent models involved in the equivalent fitting curve.

[0132] In one embodiment, the second fitting unit performs equivalent hydrogen supply fitting on the hydrogen supply curve of the coal direct liquefaction circulating solvent to be tested to obtain a fitting curve, including: setting the hydrogen supply amount Q of the coal direct liquefaction circulating solvent to OIL-H The hydrogen supply of the hydrogen-donating solvent model is Q HDS-H The proportions of several hydrogen-donating solvent models in the fitting curve are represented by a1, a2, a3, ...a n Numbered sequentially, where the non-hydrogen donating solvent is a n+1 , the solution target is ∑(Q SUM-H -O IL-H ) 2 Minimum, a1, a2, a3, ...a are calculated by the following constraints n , a n+1 The value of:

[0133] Q SUM-H=a1×Q HDS-1 +a2×Q HDS-2 +a3×Q HDS-3 ...+a n ×Q HDs-n

[0134] a n+1 =1-a1-a2-a3...-a n

[0135] 0≤a1(a2 / a3 / ...a n / a5)≤1

[0136] The coefficient of determination R 2 When the preset value is exceeded, the fitting curve is obtained.

[0137] The methods provided by the present invention are described in detail below with reference to specific examples. Where specific experimental procedures or conditions are not specified in the following examples, the procedures or conditions may be performed according to conventional experimental procedures or conditions in the art. Reagents or instruments used, for which the manufacturer is not specified, are commercially available conventional products.

[0138] Example 1

[0139] This example uses four hydrogen-donating solvent model substances as examples to illustrate the construction process of the hydrogen-donating solvent model substance hydrogen-donating curve database. These four hydrogen-donating solvent model substances are 1,2,3,4-tetrahydronaphthalene (THN), 9,10-dihydroanthracene (DHA), 1,2,3,4-tetrahydroquinoline (THQ) and 1,2,3,4-tetrahydronaphthol (THNL).

[0140] Before constructing the database, direct coal liquefaction reactions were conducted at various temperatures and reaction times for each hydrogen-donating solvent model in the presence of a catalyst. The catalyst used was a ferrous sulfide catalyst supported on coal char prepared by the impregnation method, with the iron loading reaching 1% of the coal char mass. The mass ratio of catalyst to hydrogen-donating solvent model was 1:10.

[0141] The temperatures are 340, 380, 420, and 460°C, and the reaction time is 1, 2, 3, 5, 30, 60, and 120 minutes at each temperature.

[0142] In other words, 1,2,3,4-tetralin (THN) and the catalyst need to be mixed in a mass ratio of 10:1 and then reacted at temperatures of 340, 380, 420, and 460°C for 1, 2, 3, 5, 30, 60, and 120 minutes, respectively. Each time, the THN conversion amount is tested by gas chromatography and its hydrogen supply amount is calculated.

[0143] 9,10-Dihydroanthracene (DHA) and a catalyst were reacted in a mass ratio of 10:1 at temperatures of 340, 380, 420, and 460° C. for 1, 2, 3, 5, 30, 60, and 120 minutes, respectively. The conversion amount of DHA was measured by gas chromatography each time, and its hydrogen supply amount was calculated.

[0144] 1,2,3,4-Tetrahydroquinoline (THQ) and a catalyst were reacted in a mass ratio of 10:1 at temperatures of 340, 380, 420, and 460° C. for 1, 2, 3, 5, 30, 60, and 120 minutes, respectively. The conversion of THQ was measured by gas chromatography each time, and the hydrogen supply was calculated.

[0145] 1,2,3,4-Tetrahydronaphthol (THNL) and catalyst were reacted at a mass ratio of 10:1 at temperatures of 340, 380, 420, and 460° C. for 1, 2, 3, 5, 30, 60, and 120 minutes, respectively. The conversion of THNL was measured by gas chromatography each time, and the hydrogen supply was calculated.

[0146] In this way, the measured hydrogen supply data at multiple different temperatures or different times are obtained for each hydrogen supply solvent model.

[0147] Then, the measured data of 30 minutes of reaction at various temperatures were selected, and then the kinetic calculation was used to fit the selected measured data with a cubic spline function. The determination coefficients R of the hydrogen donation curves of the four hydrogen donation solvent models were 2 ≥0.97, which meets the fitting requirements, thus obtaining the hydrogen donation curves of the four hydrogen donation solvent model substances. The hydrogen donation curve equations of each hydrogen donation solvent model substance are detailed in Table 1 below. The hydrogen donation curve database of the hydrogen donation solvent model substance includes the hydrogen donation curves of these four hydrogen donation solvent model substances. For specific reference Figure 7 shown.

[0148] Table 1 Initial hydrogen supply temperature and maximum hydrogen supply amount of four hydrogen supply solvent models

[0149]

[0150] It should be noted that the starting hydrogen supply temperatures in Table 1 above were kinetically calculated based on the hydrogen supply curves of each hydrogen supply solvent model, and the maximum hydrogen supply capacity was also kinetically calculated based on the hydrogen supply curves. The hydrogen supply curve for tetralin indicates that tetralin begins to supply hydrogen to the direct coal liquefaction reaction at 330°C, and this component can provide a maximum hydrogen supply of 6.7 mmol / g. Tetrahydroquinoline begins to supply hydrogen to the direct coal liquefaction reaction at 321°C, and this component can provide a maximum hydrogen supply of 17.1 mmol / g. Tetralinol begins to supply hydrogen to the direct coal liquefaction reaction at 316°C, and this component can provide a maximum hydrogen supply of 11.6 mmol / g. Dihydroanthracene begins to supply hydrogen to the direct coal liquefaction reaction at 293°C, and this component can provide a maximum hydrogen supply of 9.4 mmol / g.

[0151] Example 2

[0152] A certain circulating solvent oil 1 obtained by a direct coal liquefaction process is mixed with a coal coke-supported ferrous sulfide catalyst in a mass ratio of 10:1. The catalyst is also a coal coke-supported ferrous sulfide catalyst prepared by an impregnation method, and the iron loading is 1% of the coal coke mass.

[0153] Then, the circulating solvent oil 1 was reacted in the presence of a catalyst at temperatures of 340, 380, 420, and 460° C. for 1, 2, 3, 5, 30, 60, and 120 minutes, respectively. The amount of hydrogen generated was tested by gas chromatography each time, and the hydrogen supply of the circulating solvent oil 1 at different reaction temperatures or times was calculated.

[0154] Then, similarly, the measured data of circulating solvent oil 1 and the reaction at various temperatures for 30 minutes were selected, and then the measured data of the selected circulating solvent oil 1 were fitted with a cubic spline function using kinetic calculations. The coefficient of determination R of circulating solvent oil 1 was 2 =0.97, which meets the fitting conditions, and the hydrogen supply curve of circulating solvent oil 1 is obtained. The fitting equation of the hydrogen supply curve is Q H =-265.01+2.09*T+5.51×10 -3 *T 2 -4.87×10 -6 *T 3 The curve diagram is as shown in the attached Figure 8 shown.

[0155] It can be seen from the hydrogen supply curve of the circulating solvent oil 1 that its initial hydrogen supply temperature is 347° C. and the maximum hydrogen supply amount is 3.8 mmol / g.

[0156] Then, the hydrogen supply curve of the circulating solvent oil 1 is equivalently fitted with the hydrogen supply curve of the hydrogen supply solvent model in the hydrogen supply curve database to obtain the coefficient R 2 =0.999 (see Figure 10 ), thus the ratio of the hydrogen-donating solvent model substances tetralin, tetrahydroquinoline, tetralinol, dihydroanthracene, and non-hydrogen-donating solvent contained in the circulating solvent oil 1 can be inferred, see Table 2 and Figure 9 .

[0157] Table 2 Hydrogen supply characteristics of circulating solvent oil 1 equivalent hydrogen supply solvent oil

[0158]

[0159]

[0160] According to the equivalent fitting calculation, it can be concluded that the presumed circulating solvent oil 1 contains 47.8% of tetralin, 0.5% of tetrahydroquinoline, and 10.1% of tetralinol, and the rest is non-circulating hydrogen-donating solvent, containing 41.6%.

[0161] Example 3

[0162] A heavy oil circulating solvent oil 2 obtained by a direct coal liquefaction process, whose distillate temperature is higher than that of circulating solvent oil 1, is mixed with a coal coke-supported ferrous sulfide catalyst in a mass ratio of 10:1. The catalyst is also a coal coke-supported ferrous sulfide catalyst prepared by an impregnation method, and the iron loading is 1% of the coal coke mass.

[0163] Then, the circulating solvent oil 2 was reacted in the presence of a catalyst at temperatures of 340, 380, 420, and 460° C. for 1, 2, 3, 5, 30, 60, and 120 minutes, respectively. The amount of hydrogen generated was tested by gas chromatography each time, and the hydrogen supply of the circulating solvent oil 2 at different temperatures or times was calculated.

[0164] Then, similarly, the measured data of circulating solvent oil 2 and the reaction at various temperatures for 30 minutes were selected, and then the measured data of the selected circulating solvent oil 2 were fitted with a cubic spline function using kinetic calculations. The coefficient of determination R of circulating solvent oil 2 was 2 =0.99, which meets the fitting conditions, and the hydrogen supply curve of circulating solvent oil 2 is obtained. The curve can be found in Figure 11 , the hydrogen supply curve fitting equation is: Q H =-740.47+5.86*T-1.55×10 -2 *T 2 +1.37×10 -5 *T 3 .

[0165] It can be seen from the hydrogen supply curve of the circulating solvent oil 2 that its initial hydrogen supply temperature is 360° C. and the maximum hydrogen supply amount is 7.6 mmol / g.

[0166] Then, the hydrogen supply curve of the circulating solvent oil 2 is fitted equivalently to obtain the coefficient of determination R 2 =0.994 (see Figure 13 ), thus the ratio of the hydrogen-donating solvent model substances tetralin, tetrahydroquinoline, tetralinol, dihydroanthracene, and non-hydrogen-donating solvent contained in the circulating solvent oil 2 can be inferred, see Table 3 and Figure 12 .

[0167] Table 3 Hydrogen supply characteristics of circulating solvent oil 2 equivalent hydrogen supply solvent oil

[0168]

[0169] According to the above equivalent fitting calculation, it can be concluded that the circulating solvent oil 2 contains 17.4% of tetralin and 44.8% of tetralinol, and the rest is non-circulating hydrogen-donating solvent, containing 37.8%.

[0170] It can be seen from Examples 2 and 3 that the estimation method of the present invention can equivalently estimate the hydrogen supply component in the direct coal liquefaction circulating solvent to be tested, and then adjust the hydrogen supply component ratio of the hydrogen supply solvent during the direct coal liquefaction process to achieve effective hydrogen supply to coal free radicals, thereby improving the efficiency of the direct coal liquefaction reaction, and also facilitating researchers to study and simulate the reaction process of a circulating hydrogen supply solvent with complex components.

[0171] It should be understood that the above-described specific embodiments of the present invention are merely illustrative or illustrative of the principles of the present invention and do not constitute limitations of the present invention. Therefore, any modifications, equivalent substitutions, improvements, etc. made without departing from the spirit and scope of the present invention should be included within the scope of protection of the present invention. In addition, the appended claims are intended to cover all variations and modifications that fall within the scope and metes and bounds of the appended claims, or equivalents thereof.

[0172] The present invention has been described above with reference to the embodiments thereof. However, these embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention. The scope of the present invention is defined by the appended claims and their equivalents. Those skilled in the art may make various substitutions and modifications without departing from the scope of the present invention, and such substitutions and modifications are intended to fall within the scope of the present invention.

[0173] Although the embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and modifications may be made to the embodiments of the present invention without departing from the spirit and scope of the present invention. Obviously, the above embodiments are merely examples for clarity of description and are not intended to limit the embodiments. Those skilled in the art will appreciate that other variations or modifications may be made based on the above description. It is not necessary and impossible to enumerate all embodiments here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

[0174] It will be understood by those skilled in the art that embodiments of the present invention may be provided as methods, systems, or computer program products. Thus, the present invention may take the form of an entirely hardware embodiment, an entirely software embodiment, or an embodiment combining software and hardware. Furthermore, the present invention may take the form of a computer program product implemented on one or more computer-usable storage media (including but not limited to magnetic disk storage, CD-ROM, optical storage, etc.) containing computer-usable program code.

[0175] The present invention is described with reference to methods, systems, and flowcharts and / or block diagrams according to embodiments of the present invention. It should be understood that each process and / or block in the flowcharts and / or block diagrams, as well as combinations of processes and / or blocks in the flowcharts and / or block diagrams, can be implemented by computer program instructions. These computer program instructions can be provided to a processor of a general-purpose computer, a special-purpose computer, an embedded processor, or other programmable data processing device to produce a machine, so that the instructions executed by the processor of the computer or other programmable data processing device generate instructions for implementing the processes in the flowcharts and / or block diagrams. Figure 1 a process or multiple processes and / or boxes Figure 1 A device that provides the functions specified in a block or multiple blocks.

Claims

1. A method for establishing a system for estimating hydrogen supply characteristics of circulating solvents in direct coal liquefaction, characterized in that: The system is used to estimate the hydrogen supply composition and hydrogen supply amount of a direct coal liquefaction circulating solvent to be tested. The system is established based on the hydrogen supply curves of at least three different hydrogen supply solvent models. The method includes: Obtaining a measured data set of hydrogen supply of each hydrogen-donating solvent model substance, wherein the measured data set is a plurality of data obtained by measuring a direct coal liquefaction reaction of each hydrogen-donating solvent model substance at different temperatures and times in the presence of a catalyst, wherein each data point is the hydrogen supply of the hydrogen-donating solvent model substance at a specific temperature and time, and the plurality of data points constitute the hydrogen supply data set of the hydrogen-donating solvent model substance; According to the dynamics, the hydrogen supply data set of each hydrogen supply solvent model is nonlinearly fitted to obtain the hydrogen supply curve of the hydrogen supply solvent model as a function of temperature or time. The hydrogen supply curves of all the selected hydrogen supply solvent model objects are mathematically added to form the hydrogen supply fitting curve. The optimal solution of the mathematical addition is the solution when the degree of fit between the obtained hydrogen supply fitting curve and the hydrogen supply curve of the actual circulating solvent of coal liquefaction is not lower than the preset value.

2. The method according to claim 1, characterized in that After the measured hydrogen supply data set is subjected to kinetic calculation, at least the hydrogen supply start temperature T of the hydrogen supply solvent model and the actual circulating solvent of direct coal liquefaction is obtained. i , Maximum hydrogen supply Q HDS-H，max , the amount of hydrogen supplied at different reaction times at each temperature; The sampling frequencies of the measured data of the hydrogen-donating solvent model and the actual circulating solvent of direct coal liquefaction are the same or different.

3. The method according to claim 1 or 2, characterized in that The method of performing nonlinear fitting on the measured hydrogen supply amount data set of each hydrogen supply solvent model substance according to the kinetics to obtain the hydrogen supply curve of the hydrogen supply solvent model substance comprises: performing nonlinear fitting by the following formula Q HDS-H =Q HDS-H，max (1-e -kt ) ln(1-Q HDS-H / Q HDS-H，max )=-kt lnk=lnA-Ea / RT A e -Ea / RTi =0.001 Wherein, QHDs-H is the hydrogen supply amount of the hydrogen-donating solvent model, QHD S-H，max is the maximum hydrogen supply of the hydrogen-donating solvent model, k is the rate constant (min -1 ), A is the pre-exponential factor (min -1 ), Ea is the apparent activation energy (J·mol -1 ), R is the molar gas constant (8.314 J·mol -1 ·K -1 ).

4. The method according to claim 1 or 2, characterized in that The hydrogen-donating solvent model substance includes but is not limited to one or more of 1,2,3,4-tetrahydronaphthalene (tetrahydronaphthalene), 9,10-dihydroanthracene (dihydroanthracene), 9,10-dihydrophenanthrene (dihydrophenanthrene), 1,2,3,4-tetrahydroquinoline, 5,6,7,8-tetrahydroquinoline (both are referred to as tetrahydroquinoline), 5,6,7,8-tetrahydronaphthol (tetrahydronaphthol), indane, 1,2,3,4-tetrahydroanthracene (tetrahydroanthracene), 1,2,3,4-tetrahydrophenanthrene (tetrahydrophenanthrene), 1,2,3,4,5,6,7,8-octahydroanthracene (octahydroanthracene), and 1,2,3,4,5,6,7,8-octahydrophenanthrene (octahydrophenanthrene).

5. The method according to claim 1 or 2, characterized in that The hydrogen donation curve of the hydrogen donation solvent model substance includes tetralin, and the hydrogen donation curve of tetralin is: Q H =-52.79+0.48*T-1.44×10 -3 *T 2 +1.46×10 -6 *T 3 and / or, The hydrogen donation curve of the hydrogen donation solvent model substance includes tetrahydroquinoline, and the hydrogen donation curve of tetrahydroquinoline is: Q H =47.56-0.25*T+8.25×10 -5 *T 2 -7.32×10 -7 *T 3 and / or, The hydrogen donation curve of the hydrogen-donating solvent model substance includes tetralin, and the hydrogen donation curve of tetralin is: Q H =-183.76+1.66*T+5.09×10 -3 *T 2 -5.26×10 -6 *T 3 and / or, The hydrogen donation curve of the hydrogen donation solvent model substance includes dihydroanthracene, and the hydrogen donation curve of dihydroanthracene is: Q H =483.2-4.15*T+1.16×10 -2 *T 2 -1.06×10< -5 *T 3 ; Among them, Q H represents the hydrogen supply amount of the hydrogen-donating solvent model substance, and T represents the reaction time.

6. A method for estimating the equivalent hydrogen supply component of a circulating solvent for direct coal liquefaction, characterized in that: include: Obtaining a hydrogen supply curve of the circulating solvent to be tested; According to the hydrogen supply curve of the hydrogen supply solvent model, an equivalent hydrogen supply fitting is performed on the hydrogen supply curve of the direct coal liquefaction circulating solvent to be tested to obtain a fitting curve; According to the hydrogen supply fitting curve and the types of circulating hydrogen supply solvents in the hydrogen supply solvent model, the equivalent hydrogen supply components and proportions of the direct coal liquefaction circulating solvent to be tested are estimated.

7. The method according to claim 6, characterized in that According to the hydrogen supply curve of the hydrogen supply solvent model, an equivalent hydrogen supply fitting is performed on the hydrogen supply curve of the direct coal liquefaction circulating solvent to be tested to obtain a fitting curve, including: Let the hydrogen supply of the circulating solvent for direct coal liquefaction be Q OIL-H， The hydrogen supply amount of the hydrogen-donating solvent model is Q HDS-n The proportions of several hydrogen-donating solvent models in the fitting curve are represented by a1, a2, a3...a n Numbered sequentially, the proportion of non-hydrogen donating solvent is a n+1 , the sum of the hydrogen supply of the hydrogen-donating solvent model Q is obtained using the following formula: sUM-H , Q SUM-H =a1×Q HDs-1 +a2×Q HDS-2 +a3×Q HDS-3 ……+a n ×Q HDS-n . The solution target is ∑(Q SUM-H -Q OIL-H ) 2 Minimum, a1, a2, a3, a4...a are calculated by the following constraints n , a n+1 The value of: <h2 style=";text-align:left;direction:ltr">a<h2 style=";text-align:left;direction:ltr"> n+1 <h2 style=";text-align:left;direction:ltr"> =1-a1-a2-a3-a4-......a<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr">0≤a1(a2 / a3 / ......a<h2 style=";text-align:left;direction:ltr"> n <h2 style=";text-align:left;direction:ltr"> / a<h2 style=";text-align:left;direction:ltr"> n+1 <h2 style=";text-align:left;direction:ltr"> )≤1 Q SUM-H With Q OIL-H The goodness of fit is called the coefficient of determination R 2 , when the coefficient of determination R 2 When the preset value is exceeded, the hydrogen supply fitting curve is obtained.

8. The method according to claim 6, characterized in that The preset value is 0.

95.

9. The method according to any one of claims 6 to 8, characterized in that: According to the equivalent hydrogen supply fitting curve and the type of hydrogen supply solvent model involved in the fitting curve, the equivalent hydrogen supply component and ratio of the direct coal liquefaction circulating solvent to be tested are inferred, including: According to the equivalent hydrogen supply fitting curve and the type of the hydrogen supply solvent model, the proportion of each hydrogen supply solvent model and the proportion of the non-hydrogen supply solvent contained in the equivalent hydrogen supply fitting curve of the coal direct liquefaction circulating solvent to be tested are estimated.

10. A method for preparing circulating solvent for direct coal liquefaction, characterized in that: include: According to the method according to any one of claims 6 to 9, the equivalent hydrogen supply component and ratio of the direct coal liquefaction circulating solvent to be prepared are estimated; According to the parameters such as the maximum hydrogen supply amount, the initial hydrogen supply temperature, the maximum hydrogen supply temperature, the effective hydrogen supply time, and the estimated equivalent hydrogen supply component of the coal direct liquefaction circulating solvent, at least one equivalent hydrogen supply component is additionally added to adjust the hydrogen supply effect of the coal direct liquefaction circulating solvent.

11. A method for regulating hydrogen supply in direct coal liquefaction reaction, characterized in that: Obtaining a circulating solvent in a direct coal liquefaction reaction, and estimating the equivalent hydrogen supply component and ratio of the circulating solvent according to the method according to any one of claims 6 to 9; Based on the parameters such as the ratio of each equivalent hydrogen supply component, maximum hydrogen supply amount, initial hydrogen supply temperature, maximum hydrogen supply temperature, effective hydrogen supply time, etc. obtained by the circulating solvent, the optimal process parameters of the direct coal liquefaction reaction are predicted and controlled.

12. A system for estimating hydrogen supply characteristics of circulating solvent in direct coal liquefaction, characterized in that: The circulating solvent hydrogen supply system is used to estimate the hydrogen supply composition and hydrogen supply amount of the circulating solvent to be tested for direct coal liquefaction. The system is established based on the hydrogen supply curves of at least three different hydrogen supply solvent models. The system includes: (1) an acquisition unit, configured to acquire measured data for each hydrogen-donating solvent model substance, wherein the measured data include parameters such as the chemical structure, hydrogen-donating curve, maximum hydrogen-donating amount, initial hydrogen-donating temperature, maximum hydrogen-donating temperature, and effective hydrogen-donating time of the hydrogen-donating solvent model substance, and wherein these parameters of all hydrogen-donating solvent model substances are collected to form a measured data set, wherein the measured data set is obtained by measuring in the presence of a catalyst; (2) A fitting unit, which performs nonlinear fitting on the hydrogen supply amount data set of each hydrogen supply solvent model substance according to kinetics to obtain a hydrogen supply curve of the hydrogen supply amount of the hydrogen supply solvent model substance that changes with temperature or time. The hydrogen supply curves of all or part of the selected hydrogen supply solvent model substances are mathematically added to form the hydrogen supply fitting curve. The optimal solution of the mathematical addition is the solution when the obtained hydrogen supply fitting curve is the same as the hydrogen supply curve of the real circulating solvent of coal liquefaction. (3) an estimating unit, which fits the hydrogen supply curve of the coal direct liquefaction circulating solvent to be estimated based on the hydrogen supply curve of the hydrogen supply solvent model, and estimates the equivalent hydrogen supply components and proportions of the coal direct liquefaction circulating solvent to be measured.

13. A storage medium, characterized in that: The storage medium stores a computer program, which, when executed by a processor, implements a method for establishing a method for evaluating the hydrogen supply capacity of a coal direct liquefaction circulating solvent as described in any one of claims 1 to 5, or, when executed by a processor, implements a method for estimating the equivalent hydrogen supply component of a coal direct liquefaction circulating solvent as described in any one of claims 6 to 9.

14. An electronic device comprising a memory, a processor, and a computer program stored in the memory and executable on the processor, wherein: When the processor executes the computer program, it implements the method for establishing the evaluation of the hydrogen supply capacity of the coal direct liquefaction circulating solvent as described in any one of claims 1 to 5, or, when the computer program is executed by the processor, it implements the method for estimating the equivalent hydrogen supply component of the coal direct liquefaction circulating solvent as described in any one of claims 6 to 9.

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