Polycyclic aromatic hydrocarbon extraction method and device, storage medium and electronic equipment

Abstract

The invention relates to a polycyclic aromatic hydrocarbon extraction method and device, a storage medium and electronic equipment. The method comprises the following steps: determining a first molecular structure model of each false component molecule in raw oil, and determining a second molecular structure model of an extraction agent molecule; determining a first sigma spectrogram of the raw oil according to the first molecular structure model, determining a second sigma spectrogram of the extraction agent according to the second molecular structure model, and determining corresponding third sigma spectrograms of the extraction agent under different water content conditions; according to the first sigma spectrogram, the second sigma spectrogram and the third sigma spectrogram, the corresponding equilibrium distribution properties of the false component molecules under different water content conditions of the extraction agent are determined, the equilibrium distribution properties comprise corresponding equilibrium distribution coefficients of the false component molecules under different water content conditions of the extraction agent, and / or the equilibrium distribution coefficients of the false component molecules under different water content conditions of the extraction agent are determined. The polycyclic aromatic hydrocarbon extraction rate of the raw oil under different water content conditions of the extraction agent; and carrying out polycyclic aromatic hydrocarbon extraction based on the equilibrium distribution property.

Description

Technical Field

[0001] The present disclosure relates to the field of petroleum processing, and in particular, to a method, device, storage medium and electronic equipment for extracting condensed aromatic hydrocarbons. Background Art

[0002] TDAE (Treated Distrillate Aromatic Extract, abbreviated as treated aromatic oil) uses high aromatic oil as raw material for secondary extraction agent refining to remove carcinogenic and teratogenic polycyclic aromatic hydrocarbons. The disadvantage of TDAE is that while meeting environmental protection standards, the yield of environmentally friendly rubber oil is low, that is, the extractant has low selectivity for carcinogenic polycyclic aromatic hydrocarbon components. Adding a certain amount of water to the extractant can improve the selectivity of the extractant for polycyclic aromatic hydrocarbon extraction, but due to the differences in raw oil products and extractants, the optimization of the water content of the extractant currently often requires a lot of operating experience and experimental data. This method takes a long time, the process is cumbersome and has great uncertainty, which is very inconvenient in actual application. Summary of the invention

[0003] The purpose of the present disclosure is to provide a method, device, storage medium and electronic device for extracting condensed ring aromatic hydrocarbons to solve the technical problems in the prior art.

[0004] According to a first aspect of the present disclosure, there is provided a method for extracting condensed aromatic hydrocarbons, comprising:

[0005] Determining a first molecular structure model of each pseudo-component molecule in the feedstock oil, and determining a second molecular structure model of the extractant molecule;

[0006] Determine a first sigma spectrum of the feedstock oil according to the first molecular structure model, determine a second sigma spectrum of the extractant according to the second molecular structure model, and determine a third sigma spectrum corresponding to the extractant under different water content conditions;

[0007] Determine the equilibrium distribution properties of the pseudo component molecules under different water contents of the extractant according to the first sigma spectrum, the second sigma spectrum and the third sigma spectrum, wherein the equilibrium distribution properties include the equilibrium distribution coefficients of the pseudo component molecules under different water contents of the extractant and / or the polycyclic aromatic hydrocarbon extraction rate of the feedstock oil under different water contents of the extractant;

[0008] The extraction of condensed ring aromatic hydrocarbons is carried out based on the equilibrium distribution property.

[0009] Optionally, determining the equilibrium distribution properties of the pseudo-component molecules under different water contents of the extractant according to the first sigma spectrum, the second sigma spectrum and the third sigma spectrum includes:

[0010] Determine, based on historical extraction experimental data of the extractant, a first equilibrium distribution coefficient corresponding to each pseudo-component molecule of the feedstock oil under the condition of zero water content of the extractant;

[0011] Determining the first type infinite dilution activity coefficient of each pseudo-component molecule of the feedstock oil under different water contents of the extractant according to the first sigma spectrum, the second sigma spectrum, and the third sigma spectrum;

[0012] Determining a second type of infinite dilution activity coefficient between pseudo-component molecules of the feedstock oil according to the first equilibrium partition coefficient and the first type of infinite dilution activity coefficient;

[0013] According to the first type infinite dilution activity coefficient and the second type infinite dilution activity coefficient, the equilibrium distribution properties corresponding to each pseudo-component molecule of the raw oil under different water content conditions of the extractant are determined.

[0014] Optionally, determining the third sigma spectrum corresponding to the extractant under different water content conditions according to the second molecular structure model includes:

[0015] Determine the fourth sigma spectrum of water molecules;

[0016] For any of the water content conditions, the third sigma spectrum corresponding to the extractant under the water content condition is obtained based on the second sigma spectrum corresponding to the extractant and the fourth sigma spectrum of the water molecules, as well as the molar fraction of the extractant under the water content condition.

[0017] Optionally, determining the first molecular structure model of each pseudo-component molecule in the feedstock oil comprises:

[0018] Determining the distribution data of hydrocarbons in the feed oil and the ratio data of different hydrogen atoms in the feed oil;

[0019] Calculating the average molecular configuration of each pseudo-component of the feedstock oil based on the distribution data and the ratio data;

[0020] According to the average molecular configuration of each pseudo-component, the first molecular structure model of each pseudo-component molecule is established.

[0021] Optionally, establishing the first molecular structure model of each pseudo-component molecule according to the average molecular configuration of each pseudo-component comprises:

[0022] According to the average molecular configuration of each pseudo-component, a first initial molecular structure model of each pseudo-component molecule is established;

[0023] The energy minimization method is used to perform geometric optimization on the first initial molecular structure model of each pseudo-component molecule to obtain the first molecular structure model of each pseudo-component molecule.

[0024] Optionally, the feedstock oil includes one or more of second-tier distillate oil, third-tier distillate oil, fourth-tier distillate oil, furfural extracted oil, catalytic slurry oil and catalytic diesel.

[0025] Optionally, the pseudo-component molecules include one or more of chain alkanes, cycloalkanes, monocyclic aromatic hydrocarbons, bicyclic aromatic hydrocarbons, tricyclic aromatic hydrocarbons, tetracyclic aromatic hydrocarbons, pentacyclic aromatic hydrocarbons and sulfur-containing condensed aromatic hydrocarbons.

[0026] According to a second aspect of the present disclosure, there is provided a polycyclic aromatic hydrocarbon extraction device, comprising:

[0027] A first determination module is used to determine a first molecular structure model of each pseudo-component molecule in the crude oil, and to determine a second molecular structure model of the extractant molecule;

[0028] a second determination module, for determining a first sigma spectrum of the feedstock oil according to the first molecular structure model, determining a second sigma spectrum of the extractant according to the second molecular structure model, and determining a third sigma spectrum corresponding to the extractant under different water content conditions;

[0029] A third determination module is used to determine the equilibrium distribution properties of the pseudo component molecules under different water content conditions of the extractant according to the first sigma spectrum, the second sigma spectrum and the third sigma spectrum, wherein the equilibrium distribution properties include the equilibrium distribution coefficients corresponding to the pseudo component molecules under different water content conditions of the extractant, and / or the polycyclic aromatic hydrocarbon extraction rate of the feedstock oil under different water content conditions of the extractant;

[0030] An extraction module is used for extracting condensed ring aromatic hydrocarbons based on the equilibrium distribution property.

[0031] According to a third aspect of the present disclosure, there is provided a non-temporary computer-readable storage medium having a computer program stored thereon, which implements the steps of any one of the methods described in the first aspect when executed by a processor.

[0032] According to a third aspect of the present disclosure, an electronic device includes:

[0033] a memory having a computer program stored thereon;

[0034] A processor is used to execute the computer program in the memory to implement the steps of any one of the methods in the first aspect.

[0035] Through the above technical scheme, according to the first molecular structure model of each pseudo-component molecule in the raw oil, and the second molecular structure model of the extractant molecule, the first sigma spectrum of the raw oil, the second sigma spectrum of the extractant, and the third sigma spectrum corresponding to the extractant under different water content conditions, and then the sigma spectrum of each molecule, the equilibrium distribution properties corresponding to each pseudo-component molecule in the raw oil under different water content conditions of the extractant are determined, so as to extract polycyclic aromatic hydrocarbons based on the equilibrium distribution properties. In this way, the equilibrium distribution properties corresponding to the pseudo-component molecules of the raw oil under different water contents of the extractant in the mixed system of oil, extractant and water can be predicted, so as to adjust the production process according to the predicted optimal water content of the extractant, thereby realizing the stable production operation of the extractant refining device and the optimization of the polycyclic aromatic hydrocarbon extraction process.

[0036] Other features and advantages of the present disclosure will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] The accompanying drawings are used to provide a further understanding of the present disclosure and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present disclosure but do not constitute a limitation of the present disclosure. In the accompanying drawings:

[0038] Figure 1 The present invention is a flow chart of a method for extracting condensed aromatic hydrocarbons according to an exemplary embodiment.

[0039] Figure 2 is a sigma spectrum of crude oil according to an exemplary embodiment.

[0040] Figure 3 Sigma spectra of an extractant under different water content conditions and sigma spectra of water molecules are shown according to an exemplary embodiment.

[0041] Figure 4 is a schematic diagram of a first molecular structure model according to an exemplary embodiment.

[0042] Figure 5 Graph showing the extraction rates of eight pseudo-component molecules under different water contents of the extractant according to an exemplary embodiment.

[0043] Figure 6It is a comparison chart of simulated calculated values ​​and experimental values ​​of furfural extracted oil in furfural solvents containing 1% and 5% water according to an exemplary embodiment.

[0044] Figure 7 It is a comparison chart of simulated calculated values ​​and experimental values ​​of furfural feedstock oil reduced by four lines in NMP solvent containing 2% and 4% water according to an exemplary embodiment.

[0045] Figure 8 It is a block diagram of a polycyclic aromatic hydrocarbon extraction device according to an exemplary embodiment.

[0046] Fig. 9 It is a block diagram of an electronic device according to an exemplary embodiment. DETAILED DESCRIPTION

[0047] The specific implementation of the present disclosure is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described herein is only used to illustrate and explain the present disclosure, and is not used to limit the present disclosure.

[0048] In the related art, in the process of polycyclic aromatic hydrocarbon extraction, the water content of the extractant directly affects the selectivity of the extractant for polycyclic aromatic hydrocarbons, and currently there is a lack of simulation and calculation methods for such systems. In addition, in existing process simulation technologies, a variety of semi-empirical models have been widely used to describe liquid-liquid phase equilibrium, but since a large amount of experimental work is required for regression of new parameters, their application in complex systems such as petroleum fractions is subject to certain limitations, and their accuracy cannot be guaranteed. Compared with traditional models, the COSMO model (COnduct-like Screening Model) is a thermodynamic model based on pure prediction of molecular structure quantum calculation. Its advantage is that it does not require any empirical parameters at all. The COSMO model can calculate the sigma spectrum of the molecule and the activity coefficient of the component at any temperature based only on the molecular structure of the pure component in the mixture.

[0049] In view of this, the present disclosure provides a method, device, storage medium and electronic device for extracting condensed aromatic hydrocarbons to solve the above technical problems.

[0050] Figure 1 FIG. 1 is a flow chart of a method for extracting condensed aromatic hydrocarbons according to an exemplary embodiment. Figure 1 As shown, the condensed aromatic hydrocarbon extraction method may include the following steps:

[0051] Step S11, determining the first molecular structure model of each pseudo-component molecule in the crude oil, and determining the second molecular structure model of the extractant molecule.

[0052] Step S12, determining a first sigma spectrum of the crude oil according to the first molecular structure model, determining a second sigma spectrum of the extractant according to the second molecular structure model, and determining a third sigma spectrum corresponding to the extractant under different water content conditions.

[0053] Step S13, determining the equilibrium distribution properties of the pseudo-component molecules under different water contents of the extractant according to the first sigma spectrum, the second sigma spectrum and the third sigma spectrum, wherein the equilibrium distribution properties include the equilibrium distribution coefficients of the pseudo-component molecules under different water contents of the extractant and / or the polycyclic aromatic hydrocarbon extraction rate of the crude oil under different water contents of the extractant.

[0054] Step S14, extracting condensed ring aromatic hydrocarbons based on equilibrium distribution properties.

[0055] For example, according to the first sigma spectrum, the second sigma spectrum, and the third sigma spectrum, one or more of the composition of pseudo-component molecules in the extracted oil at different water contents, the composition of pseudo-component molecules in the raffinate oil, the mass yield of the extracted oil, and the mass yield of the raffinate oil can also be calculated and determined. The calculation method is not specifically limited in the embodiments of the present disclosure.

[0056] Through the above technical scheme, according to the first molecular structure model of each pseudo-component molecule in the raw oil, and the second molecular structure model of the extractant molecule, the first sigma spectrum of the raw oil, the second sigma spectrum of the extractant, and the third sigma spectrum corresponding to the extractant under different water content conditions, and then the sigma spectrum of each molecule, the equilibrium distribution properties corresponding to each pseudo-component molecule in the raw oil under different water content conditions of the extractant are determined, so as to extract polycyclic aromatic hydrocarbons based on the equilibrium distribution properties. In this way, the equilibrium distribution properties corresponding to the pseudo-component molecules of the raw oil under different water contents of the extractant in the mixed system of oil, extractant and water can be predicted, so as to adjust the production process according to the predicted optimal water content of the extractant, thereby realizing the stable production operation of the extractant refining device and the optimization of the polycyclic aromatic hydrocarbon extraction process.

[0057] In a possible manner, the feedstock oil includes one or more of the following: second-line distillate oil, third-line distillate oil, fourth-line distillate oil, furfural extracted oil, catalytic slurry oil, and catalytic diesel oil. The embodiments of the present disclosure are not limited to this.

[0058] For example, the extractant molecules may include one or more of furfural, N-methylpyrrolidone (NMP), dimethyl sulfoxide, sulfolane, and water, which are not limited in the present disclosure.

[0059] In a possible manner, the pseudo-component molecules include one or more of chain alkanes, cycloalkanes, monocyclic aromatic hydrocarbons, bicyclic aromatic hydrocarbons, tricyclic aromatic hydrocarbons, tetracyclic aromatic hydrocarbons, pentacyclic aromatic hydrocarbons, and sulfur-containing condensed aromatic hydrocarbons. The embodiments of the present disclosure are not limited to this.

[0060] It should be understood that the stock oil in the present disclosure embodiment of the present stock oil can be high aromatic oil, or it can be other stock oils containing condensed ring aromatics, and the present disclosure embodiment does not limit this. The pseudo component molecules of the stock oil can be divided into 8 kinds according to the different hydrocarbon composition and structure of the oil product, namely paraffin (P), cycloalkane (N), monocyclic aromatic hydrocarbons (MA), dicyclic aromatic hydrocarbons (DA), tricyclic aromatic hydrocarbons (3RA), tetracyclic aromatic hydrocarbons (4RA), pentacyclic aromatic hydrocarbons (5RA), sulfur-containing condensed ring aromatic hydrocarbons (SPA). Therefore, the sigma spectrogram of each pseudo component molecule in the stock oil can be established according to the molecular structure model corresponding to each molecule of the 8 pseudo components of the stock oil.

[0061] For example, the first sigma spectrum, the second sigma spectrum, and the third sigma spectrum can be determined by performing COSMO calculations on the molecules in the first molecular structure model and the second molecular structure model. av The ensemble average step over the area of ​​​​the molecule gives the surface screening charge density σ m , and its calculation formula (1) is:

[0062]

[0063] in, is the surface screen charge density of fragment n, r av is the finite radius of the standard segment, r n is the average radius of segment n calculated based on the segment surface area, d mn is the shortest distance between fragment m and fragment n.

[0064] Then, the sigma spectrum of the molecule is calculated based on the average charge value of the molecule. The calculation formula (2) for the average charge value is as follows:

[0065]

[0066] Among them, A i (σ) is the surface area of ​​all segments with surface shielding charge density σ, A i is the total surface area of ​​all segments, n i (σ) is the number of segments with surface screening charge density σ, n i is the total number of fragments.

[0067] For example, determining the second molecular structure model of the extractant molecule can be by obtaining the molecular data of the extractant from a preset parameter manual, and then using MS software to construct the second molecular structure model of the extractant molecule based on the acquired molecular data. The embodiment of the present disclosure does not specifically limit the method for constructing the second molecular structure model.

[0068] In a possible manner, the first molecular structure model for determining each pseudo-component molecule in the feedstock oil may be:

[0069] Determine the distribution data of hydrocarbons in the crude oil and the ratio data of different hydrogen atoms in the crude oil;

[0070] Based on the distribution data and the proportion data, the average molecular configuration of each pseudo-component of the feedstock oil is calculated;

[0071] According to the average molecular configuration of each pseudo-component, a first molecular structure model of each pseudo-component molecule is established.

[0072] It is worth noting that the high aromatic oil pseudo-component molecules are divided into 8 pseudo-components according to the different hydrocarbon compositions and structures of the oil products, and the average molecular configuration of the pseudo-components is described by the core, side chain and substituent. 1 The HNMR data determined the first molecular structure model of each pseudocomponent molecule in the crude oil.

[0073] In some embodiments, GC-FI TOF / MS data of the feedstock oil may be obtained first. 1 HNMR data, and then the distribution data of hydrocarbons in the crude oil was obtained by analyzing the GC-FI TOF / MS data, and the distribution data of hydrocarbons in the crude oil was obtained by analyzing the 1 The HNMR data is used to obtain the ratio data of different hydrogen atoms in the oil. Based on the distribution data of hydrocarbons and the ratio data of different hydrogen atoms, the number of aromatic rings, side chain length and number of substituents of each pseudo-component in the crude oil are calculated, thereby determining the average molecular configuration of each pseudo-component in the crude oil. Finally, the first molecular structure model of each pseudo-component molecule is established based on the average molecular configuration of each pseudo-component.

[0074] Figure 2 : is a sigma spectrum of a feedstock oil according to an exemplary embodiment. The horizontal axis represents the surface shielding charge density, and the vertical axis represents A i (σ)=P i (σ)A i , represents the probability of fragment distribution with a certain screening charge density. Figure 2As shown in the figure, the peaks of the sigma spectra of low polar molecules such as P and N are high and narrow, indicating that the distribution of their surface shielding charges is relatively concentrated and the charge density is low; in comparison, the peaks of the sigma spectra of relatively strong polar molecules such as 3RA, 4RA and 5RA are short and wide, indicating that the distribution of their surface shielding charges is relatively dispersed and the charge density is high. This difference in charge distribution causes the difference in the dielectric constant and polarity of the molecules.

[0075] For example, the first molecular structure model of each pseudo-component molecule of the crude oil may be constructed using MS (Material Studio) software, which is not limited in the embodiments of the present disclosure.

[0076] In a possible manner, the third sigma spectrum corresponding to the extractant under different water content conditions determined according to the second molecular structure model may be:

[0077] Determine the fourth sigma spectrum of water molecules;

[0078] For any water content condition, the third sigma spectrum corresponding to the extractant under the water content condition is obtained according to the second sigma spectrum corresponding to the extractant and the fourth sigma spectrum of water molecules, as well as the molar fraction of the extractant under the water content condition.

[0079] For example, the fourth sigma spectrum of water molecules can also be calculated by COSMO thermodynamic simulation, which is not specifically limited in the embodiments of the present disclosure.

[0080] After determining the fourth sigma spectrum of water molecules, the sigma spectrum of the extractant under different water content conditions is calculated by the mixing rule. Specifically, for the mixture of extractant and water, its third sigma spectrum can be obtained by the average charge value of the molecules of the pseudo-components in the system, according to their molar fraction x i The weighted average is used to determine the calculation formula (3):

[0081]

[0082] Figure 3 sigma spectra of extractants under different water content conditions and sigma spectra of water molecules according to an exemplary embodiment. a is the sigma spectrum of pure extractants with 0 water content, b is the fourth sigma spectrum of water molecules, c, d and e are the third sigma spectrum of pure extractants with 1% water content, the third sigma spectrum of extractants with 3% water content, and the third sigma spectrum of extractants with 5% water content, respectively. Figure 3As shown in the figure, with the increase of water content in the extractant, the peak of the sigma spectrum of the mixed solvent gradually becomes narrower and wider, indicating that the addition of water can make the charge distribution more dispersed and increase the charge density, thereby improving the dielectric constant and polarity of the extractant, that is, improving the extraction selectivity of the extractant for polycyclic aromatic hydrocarbons.

[0083] In a possible manner, according to the average molecular configuration of each pseudo-component, the first molecular structure model of each pseudo-component molecule can be established as follows:

[0084] According to the average molecular configuration of each pseudo-component, a first initial molecular structure model of each pseudo-component molecule is established;

[0085] The energy minimization method is used to perform geometric optimization on the first initial molecular structure model of each pseudo-component molecule to obtain the first molecular structure model of each pseudo-component molecule.

[0086] It should be understood that, since the pseudo components of different crude oils are different, the molecular structure model can be geometrically optimized by the energy minimization method to obtain a representative and stable average molecular structure model. Specifically, first, the first initial molecular structure model of each pseudo component molecule can be established according to the average molecular configuration of each pseudo component, and then the initial molecular structure model constructed by the MS software can be geometrically optimized by the energy minimization method to obtain the molecular average structure model corresponding to each pseudo component in the crude oil, that is, Figure 4 In some embodiments, the Dmol3 module in the MS software can be used for the optimization function, GGA and VWN-BP are used, Quality is selected as Fine, and the convergence threshold is 10 -6 Of course, other methods may also be used to implement the present invention, which is not limited in the present disclosure.

[0087] In a possible manner, according to the first sigma spectrum, the second sigma spectrum and the third sigma spectrum, the equilibrium distribution properties corresponding to the pseudo-component molecules under different water contents of the extractant can be determined as follows:

[0088] According to historical extraction experimental data of the extractant, the first equilibrium distribution coefficient corresponding to each pseudo-component molecule of the raw oil under the condition of zero water content of the extractant is determined;

[0089] Determine the first infinite dilution activity coefficient of each pseudo-component molecule of the crude oil under different water content conditions of the extractant according to the first sigma spectrum, the second sigma spectrum and the third sigma spectrum;

[0090] Determining the second type infinite dilution activity coefficient between pseudo-component molecules of the feedstock oil according to the first equilibrium distribution coefficient and the first type infinite dilution activity coefficient;

[0091] Based on the first and second infinite dilution activity coefficients, the equilibrium distribution properties of each pseudo-component molecule of the crude oil under different water contents of the extractant are determined.

[0092] For example, the historical extraction experimental data may include the equilibrium distribution coefficient of a single pseudo-component molecule extractant under the condition of zero water content. However, since the crude oil includes multiple pseudo-component molecules, and the pseudo-component molecules affect each other, thereby affecting the extraction of the crude oil, the first equilibrium distribution coefficient corresponding to each pseudo-component molecule of the crude oil under the condition of zero water content of the extractant may be determined based on the known historical extraction experimental data. Specifically, it may be calculated according to the following calculation formula (4):

[0093]

[0094] Wherein, subscript i represents the pseudocomponent i of the oil product, subscripts E and R represent the extract oil and raffinate oil, respectively, and m i is the first equilibrium distribution coefficient of pseudo component i, x i,E is the mass fraction of pseudo component i in the extracted oil E, x i,R is the mass fraction of pseudo component i in the raffinate R, Yield E Yield is the mass yield of the extracted oil E to the raw oil. R is the mass yield of raffinate oil R to feedstock oil. Since the extraction rate of pseudo component i is the mass of pseudo component i in the extracted oil / the mass of pseudo component i in the feedstock oil, the extraction rate of pseudo component i is E i for:

[0095]

[0096] And, according to the calculation formula The first equilibrium distribution coefficient m of pseudo component i can also be derived i for:

[0097] For example, the calculation formula (6) for determining the first type infinite dilution activity coefficient of each pseudo-component molecule of the crude oil under different water content conditions of the extractant is:

[0098]

[0099] Where i is the solute, S is the solvent, and γ i,S is the first-type infinite dilution activity coefficient of solute i in solvent S, P i (σ m ) is the unit charge density σ m The distribution probability of the fragment, Γ i (σ m) is the charge density of solute i, σ m The fragment activity coefficient distribution, Γ S (σ m ) is the charge density of the solvent S, σ m The fragment activity coefficient distribution of is the remaining term for calculating the activity factor.

[0100] For example, Table 1 shows the first infinite dilution activity coefficients of 8 pseudo-component molecules of the crude oil under different water contents of the extractant. in, For γ i,S The extreme value is when the amount of solvent S tends to infinity. As shown in Table 1, as the first type infinite dilution activity coefficient of the pseudo-component molecule in furfural gradually decreases, its corresponding solubility gradually increases.

[0101] Table 1

[0102]

[0103] Then, the second infinite dilution activity coefficient between the pseudo-component molecules of the feedstock oil can be determined based on the first equilibrium distribution coefficient and the first infinite dilution activity coefficient:

[0104] It is worth noting that when the real system is a multi-component liquid-liquid equilibrium distribution system, in order to simplify the calculation, the multi-component system can be divided into 8 independent ternary systems ijS according to 8 pseudo components. For each ternary system, one of the 8 pseudo components is selected as solute i, the set of other components in the 8 pseudo components is set as solute j, and the extractant used is set as solvent S.

[0105] In the above-mentioned oil-extraction mixed system, the solute j contains multiple components, and it is difficult to calculate the second-type infinite dilution activity coefficient under different water contents of the solvent. To this end, it is assumed that in the same system, the second type infinite dilution activity coefficient is a constant that does not change with the water content in the solvent S. This means that the change in the first equilibrium distribution coefficient is only affected by the first type infinite dilution activity coefficient impact.

[0106] For example, for a ternary liquid-liquid equilibrium partition system of ijS, the two-phase partition of the liquid-liquid equilibrium can be expressed by the equilibrium partition coefficient m i To express it, the calculation formula (7) is as follows:

[0107]

[0108] in, represents the first-kind infinite dilution activity coefficient of solute i in solvent S, It represents the second-kind infinite dilution activity coefficient of solute i in solute j.

[0109] Table 2 shows the second type infinite dilution activity coefficients between the eight pseudocomponent molecules

[0110] Table 2

[0111]

[0112] Finally, regression prediction can be performed based on the first-type infinite dilution activity coefficient and the second-type infinite dilution activity coefficient to determine the equilibrium distribution properties corresponding to each pseudo-component molecule of the crude oil under different water content conditions of the extractant.

[0113] Taking furfural as the extractant as an example, Table 3 shows the equilibrium distribution coefficients m of 8 pseudo-component molecules in furfural with different water contents.

[0114] Table 3

[0115]

[0116] Figure 5 The figure shows the extraction rates of 8 pseudo-component molecules under different water contents of the extractant according to an exemplary embodiment. The horizontal axis is the water content in the extractant, and the vertical axis is the extraction rate. When the water content in the extractant is 5%, the extraction rates of pseudo-components P, N, MA, DA, 3RA, 4RA, and 5RA are shown from top to bottom. Figure 5 As shown in the figure, with the increase of water content in the extractant, the extraction rates of the eight pseudo components are all decreasing, resulting in an increase in the yield of the raffinate oil. However, when the extractant is less than 3%, the extraction rates of lighter components such as P, N, MA, and DA decrease significantly, while the extraction rate of polycyclic aromatic hydrocarbons does not change much, which will lead to an increase in the selectivity of the solvent system for polycyclic aromatic hydrocarbons. However, as the water content continues to increase, the effect of this effect will become significant, and the extraction rates of all pseudo components will decrease significantly, resulting in a decrease in the selectivity of the extractant for polycyclic aromatic hydrocarbons. Based on this, the appropriate water content of the extractant during the extraction process should be 1% to 3%.

[0117] Through the above scheme, the first equilibrium distribution coefficients m of the eight pseudo components in pure solvent can be determined according to the historical extraction experimental data, and the first equilibrium distribution coefficients m and the first infinite dilution activity coefficients Calculate the second infinite dilution activity coefficient Assuming the second infinite dilution activity coefficient After the water content is converted into a constant that does not change with the water content, the equilibrium distribution coefficient and extraction rate at different water contents of the extractant can be calculated, thereby determining the optimal water content of the extractant according to the separation requirements.

[0118] Table 4 shows the properties of furfural extracted oil and raffinate oil after anhydrous furfural extraction.

[0119] Table 4

[0120]

[0121] For example, according to the properties of the furfural extracted oil in Table 4, a characterization model can be performed to obtain 8 pseudo components of the furfural extracted oil and various molecular average configurations of furfural.

[0122] For example, the COSMO thermodynamic simulation can be performed on the eight pseudo-components and various molecular average configurations of furfural according to calculation formulas (1) and (2) to obtain the corresponding sigma spectra.

[0123] For example, the sigma spectrum of a mixed solvent of furfural and different water contents can be calculated according to calculation formula (3).

[0124] For example, the simulated extraction temperature is 60°C, and the volume ratio of the agent to oil used in the simulation is furfural: water: oil = 3:0.1 to 0.5:1. The first infinite dilution activity coefficients of the eight pseudo-component molecules in furfural with different water contents can be calculated according to formula (6).

[0125] For example, the equilibrium distribution coefficients and extraction rates of the eight pseudo-component molecules in the furfural solvent under the extraction conditions of anhydrous furfural can be calculated based on the data of the furfural extracted oil and the raffinate oil after furfural extraction obtained by extraction of pure furfural in Table 4 by calculation formula (4) and calculation formula (5); and m obtained by calculation formula (7) and calculation formula (4) or calculation formula (5) i , the activity coefficients between the eight pseudocomponent molecules under experimental conditions can be calculated That is the second type of infinite dilution activity coefficient, and it can predict the extraction rates of eight pseudo-component molecules in mixed solvents when the water content of furfural is 1-5%.

[0126] In some embodiments, it is possible to set The 8 pseudo-component molecules calculated above in different water content solvents are unchanged. The equilibrium distribution coefficients m of the eight pseudo-component molecules in solvents with different water contents were calculated by formula (7): i , then we can use formula (5) and m i The extraction rates of eight pseudo-component molecules in solvents with different water contents were determined by calculation.i , and then determine the extraction rates of eight pseudo-component molecules in mixed solvents when the water content of furfural is 1-5%.

[0127] Figure 6 1 is a comparison chart of simulated calculated values ​​and experimental values ​​of furfural extracted oil in furfural solvents containing 1% and 5% water according to an exemplary embodiment. Figure 6 As shown, the left side shows the comparison between the simulated calculated value and the experimental value of the extraction rate of furfural extracted oil in a furfural solvent with a water content of 1% according to the embodiment of the present disclosure, and the right side shows the comparison between the simulated calculated value and the experimental value of the extraction rate of furfural extracted oil in a furfural solvent with a water content of 5% according to the embodiment of the present disclosure. The shaded part in the figure is the experimental value, and the black part is the simulated calculated value of the extraction rate obtained according to the embodiment of the present disclosure. Figure 6 It can be seen that the simulation value is in good agreement with the experimental value. When the furfural water content is 5%, the extraction rate of 3-5 ring aromatic hydrocarbons is significantly lower than that when the furfural water content is 1%, which will result in more 3-ring or more polycyclic aromatic hydrocarbons being retained in the raffinate oil. Therefore, the preferred furfural water content is 1%.

[0128] In comparison, when the furfural water content is 1%, the raffinate oil yield is 52.74%, and the PCA (condensed ring aromatic hydrocarbon compound) content is 2.98%. Not only is the raffinate oil yield increased by 10 percentage points, but it also meets the requirement of PCA content <3%. When the furfural water content is 5%, the raffinate oil yield is 62.61%, and the PCA content is 5.98%.

[0129] Exemplarily, as shown in Table 5, the properties of the furfural-reduced feedstock oil and the raffinate oil after extraction with anhydrous NMP are shown.

[0130] Table 5

[0131]

[0132]

[0133] For example, according to the properties of the furfural feedstock oil of reduced four lines in Table 5, a characteristic model can be performed on it, and eight pseudo components of the furfural feedstock oil of reduced four lines and various molecular average configurations of NMP are obtained.

[0134] Exemplarily, the COSMO thermodynamic simulation is performed on the eight pseudo-components and various molecular average configurations of NMP according to calculation formulas (1) and (2) to obtain the corresponding sigma spectra.

[0135] For example, according to calculation formula (3), the sigma spectrum of a mixed solvent of NMP+different water contents can be calculated.

[0136] For example, the simulated extraction temperature is 60°C, and the volume ratio of the agent to oil used in the simulation is NMP: water: oil = 3:0.1 to 0.5:1. According to calculation formula (6), the first-type infinite dilution activity coefficients of the eight pseudo-component molecules in NMP with different water contents can be calculated.

[0137] For example, according to the data obtained by pure NMP extraction in Table 5, the equilibrium distribution coefficients and extraction rates of the eight pseudo-component molecules in NMP solvent under the conditions can be calculated by calculation formula (4) and calculation formula (5); the activity coefficients between the eight pseudo-component molecules under the experimental conditions can be calculated by calculation formula (7): That is, the second type of infinite dilution activity coefficient, and can calculate and predict the extraction rates of eight pseudo-component molecules in a mixed solvent when the water content of NMP is 1-5%.

[0138] like Figure 7 As shown, the simulated calculated values ​​and experimental values ​​of furfural feedstock oil with reduced water content of 2% and 4% in NMP solvent are compared. Among them, the circle and diamond respectively represent the experimental value of the water content of 2% and the simulated calculated value of the extraction rate obtained according to the embodiment of the present disclosure. When the water content is 2%, the experimental values ​​of the extraction rates of the 8 pseudo-component molecules are greater than the simulated calculated values. The triangle and square respectively represent the experimental value of the water content of 4% and the simulated calculated value of the extraction rate obtained according to the embodiment of the present disclosure. When the water content is 2%, the experimental values ​​of the extraction rates of the pseudo-component molecules MA and DA are less than the simulated calculated values, and the experimental values ​​of the extraction rates of the remaining pseudo-component molecules are greater than the simulated calculated values. Therefore, it can be seen that the simulation value is in good agreement with the experimental value. When the water content of NMP is 4%, the extraction rate of 3-5 ring aromatics is significantly lower than that of NMP with a water content of 4%, which will result in more 3-ring or more polycyclic aromatics being retained in the raffinate. Therefore, the preferred NMP water content is 2%.

[0139] In comparison, when the water content of NMP is 2%, the raffinate oil yield is 70.16% and the PCA content is 2.38%. Not only is the raffinate oil yield increased by 8 percentage points, but the requirement of PCA content <3% is also met; when the water content of NMP is 4%, the raffinate oil yield is 75.61% and the PCA content is 3.74%.

[0140] In the above embodiment, molecular modeling is first performed on the raw oil and the extractant, and then the sigma spectra of each of the 8 pseudo components of the raw oil and the sigma spectra of the extractants with different water contents are calculated through COSMO thermodynamic simulation. Finally, the first equilibrium distribution coefficient is calculated through the sigma spectra of various molecules and the experimental data of pure solvent extraction, and the equilibrium distribution coefficients and extraction rates of the 8 pseudo component molecules in the oil-extractant mixed system and the 8 pseudo component molecules at different extractant water contents are calculated. Therefore, this scheme can realize the rapid optimization of the extractant water content in the oil-extractant system, and improve the raffinate oil yield under the premise of meeting PCA <3%, which has practical guiding significance for the optimization of the polycyclic aromatic hydrocarbon extraction process.

[0141] Figure 8 FIG. 1 is a block diagram of a polycyclic aromatic hydrocarbon extraction device according to an exemplary embodiment. Figure 8 As shown, the polycyclic aromatic hydrocarbon extraction device 800 includes a first determination module 801 , a second determination module 802 , a third determination module 803 and an extraction module 804 .

[0142] The first determination module 801 is used to determine the first molecular structure model of each pseudo-component molecule in the raw oil and the second molecular structure model of each molecule in the extractant;

[0143] A second determination module 802 is used to determine a first sigma spectrum of the feedstock oil according to the first molecular structure model, determine a second sigma spectrum of the extractant according to the second molecular structure model, and determine a third sigma spectrum corresponding to the extractant under different water content conditions;

[0144] A third determination module 803 is used to determine the equilibrium distribution properties corresponding to the pseudo component molecules under different water content conditions of the extractant according to the first sigma spectrum, the second sigma spectrum and the third sigma spectrum, wherein the equilibrium distribution properties include the equilibrium distribution coefficients corresponding to the pseudo component molecules under different water content conditions of the extractant, and the polycyclic aromatic hydrocarbon extraction rate of the extractant for the feedstock oil under different water content conditions;

[0145] The extraction module 804 is used to extract condensed aromatic hydrocarbons based on the equilibrium distribution property.

[0146] Optionally, the third determining module 803 is used to:

[0147] Determine, based on historical extraction experimental data of the extractant, a first equilibrium distribution coefficient corresponding to each pseudo-component molecule of the feedstock oil under the condition of zero water content of the extractant;

[0148] Determining the first type infinite dilution activity coefficient of each pseudo-component molecule of the feedstock oil under different water contents of the extractant according to the first sigma spectrum, the second sigma spectrum, and the third sigma spectrum;

[0149] Determining a second type of infinite dilution activity coefficient between pseudo-component molecules of the feedstock oil according to the first equilibrium partition coefficient and the first type of infinite dilution activity coefficient;

[0150] According to the first type infinite dilution activity coefficient and the second type infinite dilution activity coefficient, the equilibrium distribution properties corresponding to each pseudo-component molecule of the raw oil under different water content conditions of the extractant are determined.

[0151] Optionally, the second determining module 802 is used to:

[0152] Determine the fourth sigma spectrum of water molecules;

[0153] For any of the water content conditions, the third sigma spectrum corresponding to the extractant under the water content condition is obtained based on the second sigma spectrum corresponding to the extractant and the fourth sigma spectrum of the water molecules, as well as the molar fraction of the extractant under the water content condition.

[0154] Optionally, the first determining module 801 is used to:

[0155] Determining the distribution data of hydrocarbons in the feed oil and the ratio data of different hydrogen atoms in the feed oil;

[0156] Calculating the average molecular configuration of each pseudo-component of the feedstock oil based on the distribution data and the ratio data;

[0157] According to the average molecular configuration of each pseudo-component, the first molecular structure model of each pseudo-component molecule is established.

[0158] Optionally, the first determining module 801 is used to:

[0159] According to the average molecular configuration of each pseudo-component, a first initial molecular structure model of each pseudo-component molecule is established;

[0160] The energy minimization method is used to perform geometric optimization on the first initial molecular structure model of each pseudo-component molecule to obtain the first molecular structure model of each pseudo-component molecule.

[0161] Optionally, the feedstock oil includes one or more of second-tier distillate oil, third-tier distillate oil, fourth-tier distillate oil, furfural extracted oil, catalytic slurry oil and catalytic diesel.

[0162] Optionally, the pseudo-component molecules include one or more of chain alkanes, cycloalkanes, monocyclic aromatic hydrocarbons, bicyclic aromatic hydrocarbons, tricyclic aromatic hydrocarbons, tetracyclic aromatic hydrocarbons, pentacyclic aromatic hydrocarbons and sulfur-containing condensed aromatic hydrocarbons.

[0163] Regarding the device in the above embodiment, the specific manner in which each module performs operations has been described in detail in the embodiment of the method, and will not be elaborated here.

[0164] The present disclosure also provides a computer-readable storage medium having computer program instructions stored thereon, and the program instructions, when executed by a processor, implement the steps of the condensed-ring aromatic hydrocarbon extraction method provided by the present disclosure.

[0165] The present disclosure also provides an electronic device, comprising:

[0166] a memory having a computer program stored thereon;

[0167] The processor is used to execute the computer program in the memory to implement the steps of the polycyclic aromatic hydrocarbon extraction method provided by the present disclosure.

[0168] Fig. 9 FIG. 1 is a block diagram of an electronic device according to an exemplary embodiment. Fig. 9 As shown, the electronic device 700 may include: a processor 701 and a memory 702. The electronic device 700 may also include one or more of a multimedia component 703, an input / output (I / O) interface 704, and a communication component 705.

[0169] The processor 701 is used to control the overall operation of the electronic device 700 to complete all or part of the steps in the above-mentioned storage method. The memory 702 is used to store various types of data to support the operation of the electronic device 700. These data may include instructions for any application or method used to operate on the electronic device 700, as well as application-related data, such as contact data, messages sent and received, pictures, audio, video, etc. The memory 702 can be implemented by any type of volatile or non-volatile storage device or a combination thereof, such as static random access memory (Static Random Access Memory, referred to as SRAM), electrically erasable programmable read-only memory (Electrically Erasable Programmable Read-Only Memory, referred to as EEPROM), erasable programmable read-only memory (Erasable Programmable Read-Only Memory, referred to as EPROM), programmable read-only memory (Programmable Read-Only Memory, referred to as PROM), read-only memory (Read-Only Memory, referred to as ROM), magnetic memory, flash memory, magnetic disk or optical disk. The multimedia component 703 may include a screen and an audio component. The screen may be, for example, a touch screen, and the audio component is used to output and / or input audio signals. For example, the audio component may include a microphone for receiving external audio signals. The received audio signal may be further stored in the memory 702 or sent through the communication component 705. The audio component also includes at least one speaker for outputting audio signals. The I / O interface 704 provides an interface between the processor 701 and other interface modules, and the other interface modules may be keyboards, mice, buttons, etc. These buttons may be virtual buttons or physical buttons. The communication component 705 is used for wired or wireless communication between the electronic device 700 and other devices. Wireless communication, such as Wi-Fi, Bluetooth, Near Field Communication (NFC), 2G, 3G, 4G, NB-IOT, eMTC, or other 5G, etc., or a combination of one or more of them, is not limited here. Therefore, the corresponding communication component 705 may include: Wi-Fi module, Bluetooth module, NFC module, etc.

[0170] In an exemplary embodiment, the electronic device 700 can be implemented by one or more application specific integrated circuits (ASIC), digital signal processors (DSP), digital signal processing devices (DSPD), programmable logic devices (PLD), field programmable gate arrays (FPGA), controllers, microcontrollers, microprocessors or other electronic components to perform the above-mentioned polycyclic aromatic hydrocarbon extraction method.

[0171] In another exemplary embodiment, a computer-readable storage medium including program instructions is also provided, and when the program instructions are executed by a processor, the steps of the above-mentioned polycyclic aromatic hydrocarbon extraction method are implemented. For example, the computer-readable storage medium can be the above-mentioned memory 702 including program instructions, and the above-mentioned program instructions can be executed by the processor 701 of the electronic device 700 to complete the above-mentioned polycyclic aromatic hydrocarbon extraction method.

[0172] In another exemplary embodiment, a computer program product is also provided. The computer program product includes a computer program executable by a programmable device, and the computer program has a code portion for executing the above-mentioned condensed-ring aromatic hydrocarbon extraction method when executed by the programmable device.

[0173] The preferred embodiments of the present disclosure are described in detail above in conjunction with the accompanying drawings; however, the present disclosure is not limited to the specific details in the above embodiments. Within the technical concept of the present disclosure, a variety of simple modifications can be made to the technical solution of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

[0174] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present disclosure will not further describe various possible combinations.

[0175] In addition, various embodiments of the present disclosure may be arbitrarily combined, and as long as they do not violate the concept of the present disclosure, they should also be regarded as the contents disclosed by the present disclosure.

Claims

1. A method for extracting condensed aromatic hydrocarbons, characterized in that: include: Determining a first molecular structure model of each pseudo-component molecule in the feedstock oil, and determining a second molecular structure model of the extractant molecule; Determine a first sigma spectrum of the feedstock oil according to the first molecular structure model, determine a second sigma spectrum of the extractant according to the second molecular structure model, and determine a third sigma spectrum corresponding to the extractant under different water content conditions; Determine the equilibrium distribution properties of the pseudo component molecules under different water contents of the extractant according to the first sigma spectrum, the second sigma spectrum and the third sigma spectrum, wherein the equilibrium distribution properties include the equilibrium distribution coefficients of the pseudo component molecules under different water contents of the extractant and / or the polycyclic aromatic hydrocarbon extraction rate of the feedstock oil under different water contents of the extractant; The extraction of condensed ring aromatic hydrocarbons is carried out based on the equilibrium distribution property.

2. The method according to claim 1, characterized in that The step of determining the equilibrium distribution properties of the pseudo-component molecules under different water contents of the extractant according to the first sigma spectrum, the second sigma spectrum, and the third sigma spectrum includes: Determine, based on historical extraction experimental data of the extractant, a first equilibrium distribution coefficient corresponding to each pseudo-component molecule of the feedstock oil under the condition of zero water content of the extractant; Determining the first type infinite dilution activity coefficient of each pseudo-component molecule of the feedstock oil under different water contents of the extractant according to the first sigma spectrum, the second sigma spectrum, and the third sigma spectrum; Determining a second type of infinite dilution activity coefficient between pseudo-component molecules of the feedstock oil according to the first equilibrium partition coefficient and the first type of infinite dilution activity coefficient; According to the first type infinite dilution activity coefficient and the second type infinite dilution activity coefficient, the equilibrium distribution properties corresponding to each pseudo-component molecule of the raw oil under different water content conditions of the extractant are determined.

3. The method according to claim 1, characterized in that: The step of determining the third sigma spectrum corresponding to the extractant under different water content conditions according to the second molecular structure model includes: Determine the fourth sigma spectrum of water molecules; For any of the water content conditions, the third sigma spectrum corresponding to the extractant under the water content condition is obtained based on the second sigma spectrum corresponding to the extractant and the fourth sigma spectrum of the water molecules, as well as the molar fraction of the extractant under the water content condition.

4. The method according to claim 1, characterized in that: The method of determining the first molecular structure model of each pseudo-component molecule in the feedstock oil comprises: Determining the distribution data of hydrocarbons in the feed oil and the ratio data of different hydrogen atoms in the feed oil; Calculating the average molecular configuration of each pseudo-component of the feedstock oil based on the distribution data and the ratio data; According to the average molecular configuration of each pseudo-component, the first molecular structure model of each pseudo-component molecule is established.

5. The method according to claim 4, characterized in that The step of establishing the first molecular structure model of each pseudo-component molecule according to the average molecular configuration of each pseudo-component comprises: According to the average molecular configuration of each pseudo-component, a first initial molecular structure model of each pseudo-component molecule is established; The energy minimization method is used to perform geometric optimization on the first initial molecular structure model of each pseudo-component molecule to obtain the first molecular structure model of each pseudo-component molecule.

6. The method according to any one of claims 1 to 5, characterized in that: The raw oil includes one or more of the following: second-tier distillate oil, third-tier distillate oil, fourth-tier distillate oil, furfural extracted oil, catalytic slurry oil and catalytic diesel oil.

7. The method according to any one of claims 1 to 5, characterized in that The pseudo-component molecules include one or more of chain alkanes, cycloalkanes, monocyclic aromatic hydrocarbons, bicyclic aromatic hydrocarbons, tricyclic aromatic hydrocarbons, tetracyclic aromatic hydrocarbons, pentacyclic aromatic hydrocarbons and sulfur-containing condensed aromatic hydrocarbons.

8. A polycyclic aromatic hydrocarbon extraction device, characterized in that: include: A first determination module is used to determine a first molecular structure model of each pseudo-component molecule in the crude oil, and to determine a second molecular structure model of the extractant molecule; a second determination module, for determining a first sigma spectrum of the feedstock oil according to the first molecular structure model, determining a second sigma spectrum of the extractant according to the second molecular structure model, and determining a third sigma spectrum corresponding to the extractant under different water content conditions; A third determination module is used to determine the equilibrium distribution properties of the pseudo component molecules under different water content conditions of the extractant according to the first sigma spectrum, the second sigma spectrum and the third sigma spectrum, wherein the equilibrium distribution properties include the equilibrium distribution coefficients corresponding to the pseudo component molecules under different water content conditions of the extractant, and / or the polycyclic aromatic hydrocarbon extraction rate of the feedstock oil under different water content conditions of the extractant; An extraction module is used for extracting condensed ring aromatic hydrocarbons based on the equilibrium distribution property.

9. A non-transitory computer-readable storage medium having a computer program stored thereon, characterized in that: When the program is executed by a processor, the steps of the method described in any one of claims 1 to 7 are implemented.

10. An electronic device, characterized in that: include: a memory having a computer program stored thereon; A processor, configured to execute the computer program in the memory to implement the steps of the method according to any one of claims 1 to 7.

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