Condensed-ring aromatic hydrocarbon extraction method, device, storage medium and electronic equipment

Abstract

The present disclosure relates to a method and device for extracting condensed ring aromatic hydrocarbons, a storage medium and an electronic device, the method comprising: determining a first molecular structure model of each pseudo-component molecule in a raw oil, and determining a second molecular structure model of an extractant molecule; determining a first sigma spectrum of the raw oil according to the first molecular structure model, and determining a second sigma spectrum of the extractant according to the second molecular structure model, and determining a third sigma spectrum of the extractant under different water content conditions; determining the equilibrium distribution property 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, the equilibrium distribution property including the equilibrium distribution coefficient of each pseudo-component molecule under different water content conditions of the extractant, and / or the extraction rate of the condensed ring aromatic hydrocarbons of the raw oil under different water content conditions of the extractant; and performing the extraction of the condensed ring aromatic hydrocarbons based on the equilibrium distribution property.

Description

TECHNICAL FIELD

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

[0002] TDAE (Treated Distrillate Aromatic Extract, referred to as treated aromatic oil) is a secondary extractant refined from high aromatic oil to remove carcinogenic and teratogenic condensed ring aromatic hydrocarbons. The disadvantage of TDAE is that the yield of environmentally friendly rubber oil is low while meeting environmental protection standards, that is, the selectivity of the extractant to the carcinogenic condensed ring aromatic hydrocarbon component is low. Adding a certain amount of water to the extractant can improve the selectivity of the extractant to the condensed ring aromatic hydrocarbons, but due to the difference between the raw oil and the extractant, the optimization of the water content in the extractant often needs to rely on a large amount of operating experience and experimental data. This method is time-consuming, cumbersome and has great uncertainty, which is very inconvenient in practical application. SUMMARY

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

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

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

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

[0007] determining 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, the equilibrium distribution properties including the equilibrium distribution coefficients of each pseudo-component molecule under different water content conditions of the extractant, and / or the extraction rate of condensed ring aromatic hydrocarbons of the raw oil under different water content conditions of the extractant;

[0008] performing condensed ring aromatic hydrocarbon extraction based on the equilibrium distribution properties.

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

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

[0012] determining a second type of infinite dilution activity coefficient between pseudo-component molecules of the feedstock oil based on 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 includes:

[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 paraffins, 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 condensed-ring 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 raw oil, and to determine a second molecular structure model of the extractant molecule;

[0028] a second determining module, configured 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;

[0029] a third determination module, configured to determine, based on 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, the equilibrium distribution properties including the equilibrium distribution coefficients corresponding to the pseudo-component molecules under different water contents of the extractant, and / or the polycyclic aromatic hydrocarbon extraction rates of the feedstock under different water contents 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, a non-transitory computer-readable storage medium is provided, on which a computer program is stored, and when the program is executed by a processor, the steps of any one of the methods described in the first aspect are implemented.

[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 solution, based on the first molecular structure model of each pseudo-component molecule in the feedstock oil, the second molecular structure model of the extractant molecule, the first sigma spectrum of the feedstock oil, the second sigma spectrum of the extractant, and the third sigma spectrum corresponding to the extractant under different water contents, and then the sigma spectrum of each molecule, the equilibrium distribution properties corresponding to each pseudo-component molecule in the feedstock oil under different water contents 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 feedstock oil under different extractant water contents in a mixed system of oil, extractant and water can be predicted, and the production process can be adjusted according to the predicted optimal extractant water content, thereby achieving stable production operation of the extractant refining device and optimizing 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 detailed description, 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 showing a method for extracting condensed ring aromatic hydrocarbons according to an exemplary embodiment.

[0039] Figure 2 FIG. 1 is a sigma spectrum of feedstock oil according to an exemplary embodiment.

[0040] Figure 3 Sigma spectra of an extractant under different water contents 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 1 shows the extraction rates of eight pseudo-component molecules under different water contents of the extractant according to an exemplary embodiment.

[0043] Figure 6is a comparison chart of simulation values and experimental values of a furfural extract oil in a furfural solvent containing 1% and 5% water according to an example embodiment.

[0044] Figure 7 is a comparison chart of simulation values and experimental values of a reduced four-line furfural raw material oil in an NMP solvent containing 2% and 4% water according to an example embodiment.

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

[0046] Figure 9 is a block diagram of an electronic device according to an example embodiment. DETAILED DESCRIPTION

[0047] The specific embodiments of the present disclosure will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely intended to illustrate and explain the present disclosure, and are not intended to limit the present disclosure.

[0048] In the related art, in the polycyclic aromatic hydrocarbon extraction process, the water content of the extractant directly affects the selectivity of the extractant to the polycyclic aromatic hydrocarbon, and the simulation calculation means for such a system is extremely scarce at present. In addition, in the existing process simulation technology, a variety of semi-empirical models have been widely used to describe liquid-liquid phase equilibrium, but due to the need for a large amount of experimental work to regress new parameters, the application in such a complex system as petroleum distillate will be limited to a certain extent, and its accuracy cannot be guaranteed. Compared with the traditional model, the COSMO model (COnduct-like Screening Model) is a pure prediction thermodynamic model based on molecular structure quantum calculation, and its advantage is that it does not need any empirical parameter at all. The COSMO model can calculate the sigma spectrum of the molecule only by the molecular structure of the pure component in the mixture, and can calculate the activity coefficient of the component at any temperature.

[0049] Therefore, the present disclosure provides a polycyclic aromatic hydrocarbon extraction method, device, storage medium and electronic device to solve the above technical problems.

[0050] Figure 1 is a flowchart of a polycyclic aromatic hydrocarbon extraction method according to an example embodiment. As shown in Figure 1 the polycyclic aromatic hydrocarbon extraction method can include the following steps:

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

[0052] Step S12, determining a first sigma spectrum of the raw 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 of the extractant under different water content conditions.

[0053] Step S13, determining 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, the equilibrium distribution properties including the equilibrium distribution coefficients of the pseudo-component molecules under different water content conditions of the extractant, and / or the extraction rate of the condensed polycyclic aromatic hydrocarbons of the raw oil under different water content conditions of the extractant.

[0054] Step S14, performing the extraction of the condensed polycyclic aromatic hydrocarbons based on the equilibrium distribution properties.

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

[0056] According to the above technical solution, the first sigma spectrum of the raw oil, the second sigma spectrum of the extractant, and the third sigma spectrum of the extractant under different water content conditions are determined 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, and then the sigma spectrum of each molecule is determined. The equilibrium distribution properties of each pseudo-component molecule in the raw oil under different water content conditions of the extractant are determined, and the extraction of the condensed polycyclic aromatic hydrocarbons is performed based on the equilibrium distribution properties. In this way, the equilibrium distribution properties of the pseudo-component molecules in the raw oil under different water content conditions of the extractant can be predicted in the mixed system of the oil, the extractant and the water, so that the production process is adjusted according to the optimal water content of the extractant, and the stable production operation of the extractant refining device and the optimization of the condensed polycyclic aromatic hydrocarbon extraction process are realized.

[0057] In a possible manner, the raw oil includes one or more of vacuum gas oil, vacuum gas oil, vacuum gas oil, furfural extract oil, catalytic oil slurry and catalytic diesel. The embodiments of the present disclosure are not limited in this regard.

[0058] For example, the extractant molecule can include one or more of furfural, N-methyl pyrrolidone (NMP), dimethyl sulfoxide, sulfolane, and water. The embodiments of the present disclosure are not limited in this regard.

[0059] In a possible manner, the pseudo-component molecules include one or more of paraffins, naphthenes, monocyclic aromatics, bicyclic aromatics, tricyclic aromatics, tetracyclic aromatics, pentacyclic aromatics, and sulfur-containing condensed ring aromatics. The embodiments of the present disclosure are not limited in this regard.

[0060] It should be understood that the raw oil in the embodiments of the present disclosure can be a high-aromatic oil, or other raw oil containing condensed ring aromatics, and the embodiments of the present disclosure are not limited in this regard. The pseudo-component molecules of the raw oil can be divided into eight types according to the different hydrocarbon compositions and structures of the oil, which are paraffins (P), naphthenes (N), monocyclic aromatics (MA), bicyclic aromatics (DA), tricyclic aromatics (3RA), tetracyclic aromatics (4RA), pentacyclic aromatics (5RA), and sulfur-containing condensed ring aromatics (SPA). Therefore, the sigma spectrum of each pseudo-component molecule in the raw oil can be established according to the molecular structure model corresponding to each molecule of the eight pseudo-components of the raw oil.

[0061] For example, the first sigma spectrum, the second sigma spectrum, and the third sigma spectrum can be determined by performing COSMO calculation on the molecules in the first molecular structure model and the second molecular structure model. Specifically, the surface shielding charge density σ av of the molecule can be obtained through an ensemble average step over an area with a radius r m , and the calculation formula (1) is as follows:

[0062]

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

[0064] Then, the sigma spectrum of the molecule is calculated according to the charge average value of the molecule, and the calculation formula (2) of the charge average value is as follows:

[0065]

[0066] wherein A i (σ) is the surface area of the segment with the surface shielding charge density σ, A i is the total surface area of all segments, n i (σ) is the number of segments with the surface shielding charge density σ, and n i is the total number of segments.

[0067] For example, the second molecular structure model of the extractant molecules can be obtained from a preset parameter manual, and then the MS software is used to construct the second molecular structure model of the extractant molecules according to the obtained molecular data. The construction method of the second molecular structure model is not limited in the embodiments of the present disclosure.

[0068] In a possible manner, the first molecular structure model of each pseudo-component molecule in the raw oil can be:

[0069] The distribution data of hydrocarbons in the raw oil and the proportion data of different hydrogen atoms in the raw oil are determined.

[0070] According to the distribution data and the proportion data, the molecular average configuration of each pseudo-component in the raw oil is calculated.

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

[0072] It is worth noting that the pseudo-component molecules of high aromatic oil are divided into 8 pseudo-components according to the different hydrocarbon compositions and structures of the oil, and the molecular average configuration of the pseudo-component is described by the core, the side chain and the substituent group. Therefore, the first molecular structure model of each pseudo-component molecule in the raw oil can be determined according to the GC-FI TOF / MS data and 1 HNMR data of the raw oil.

[0073] In some embodiments, the GC-FI TOF / MS data and 1 HNMR data of the raw oil can be obtained first, and then the distribution data of hydrocarbons in the raw oil is obtained by analyzing the GC-FI TOF / MS data, and the proportion data of different hydrogen atoms in the oil is obtained by analyzing the 1 HNMR data of the raw oil. Based on the distribution data of hydrocarbons and the proportion data of different hydrogen atoms, the number of aromatic rings, the length of side chain and the number of substituents of each pseudo-component in the raw oil are calculated, so as to determine the molecular average configuration of each pseudo-component in the raw oil. Finally, the first molecular structure model of each pseudo-component molecule is established according to the molecular average configuration of each pseudo-component.

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

[0075] For example, a first molecular structure model of each pseudo-component molecule of the raw oil can be constructed by 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 of the extractant under different water content conditions can be determined according to the second molecular structure model.

[0077] The fourth sigma spectrum of the water molecule is determined.

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

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

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

[0081]

[0082] Figure 3 The sigma spectrum of the extractant under different water content conditions and the sigma spectrum of the water molecule are shown according to an example embodiment. Wherein a is the sigma spectrum of the pure extractant with 0 water content, b is the fourth sigma spectrum of the water molecule, c, d and e are respectively the third sigma spectrum of the pure extractant with 1% water content, the third sigma spectrum of the extractant with 3% water content and the third sigma spectrum of the extractant with 5% water content. As shown in FIG. 2, the sigma spectrum of the extractant under different water content conditions is different from the sigma spectrum of the water molecule, which is not limited in the embodiments of the present disclosure. Figure 3As shown in the figure, with the increase of water content in the extractant, the peak type 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, establishing the first molecular structure model of each pseudo-component molecule may be:

[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 feedstock oils are different, the molecular structure model can be geometrically optimized by the energy minimization method to obtain a representative and stable molecular average structure model. Specifically, first, based on the molecular average configuration of each pseudo component, a first initial molecular structure model of each pseudo component molecule can be established, and then the initial molecular structure model constructed by the MS software can be geometrically optimized using the energy minimization method to obtain the molecular average structure model corresponding to each pseudo component in the feedstock oil, that is, Figure 4 In some embodiments, the Dmol3 module in the MS software can be used for implementation, and the optimization function uses GGA and VWN-BP, the Quality is selected as Fine, and the convergence threshold is 10 -6 Of course, other methods may also be used to implement this, and the embodiments of this disclosure do not limit this.

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

[0088] Based on historical extraction experimental data of the extractant, determine 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;

[0089] Determine the first infinite dilution activity coefficient of each pseudo-component molecule of the crude oil under different water contents 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 based on the first equilibrium partition coefficient and the first type infinite dilution activity coefficient;

[0091] According to the first type of infinite dilution activity coefficient and the second type of infinite dilution activity coefficient, the corresponding equilibrium distribution properties of each pseudo-component molecule of the raw oil under different water content conditions of the extractant are determined.

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

[0093]

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

[0095]

[0096] and according to the calculation formula the first equilibrium distribution coefficient m i of the pseudo-component i can also be derived as:

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

[0098]

[0099] wherein i is a solute, S is a solvent, γ i,S is the first type of infinite dilution activity coefficient of the solute i in the solvent S, P i (σ m ) is the distribution probability of a segment with a unit charge density of σ m , 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, 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, 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 type infinite dilution activity coefficient between the pseudo-component molecules of the crude oil can be determined based on the first equilibrium distribution coefficient and the first type infinite dilution activity coefficient.

[0104] It is worth noting that when the real system is a multicomponent liquid-liquid equilibrium partition system, to simplify the calculation, the multicomponent system can be divided into eight independent ternary systems ijS according to the eight pseudo-components. For each ternary system, one of the eight pseudo-components is selected as the solute i, the set of the other eight pseudo-components is set as the solute j, and the extractant used is set as the 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 content conditions of the solvent. To this end, it is assumed that in the same system, the second type of infinite dilution activity coefficient is a constant that does not change with the water content in the solvent S. This means that the change of 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, is the first type of infinite dilution activity coefficient of solute i in solvent S, is the second type of infinite dilution activity coefficient of solute i in solute j.

[0109] Table 2 is the second type of infinite dilution activity coefficient between 8 kinds of pseudo-component molecules

[0110] Table 2

[0111]

[0112] Finally, according to the first type of infinite dilution activity coefficient and the second type of infinite dilution activity coefficient, regression prediction can be carried out to determine the corresponding equilibrium distribution property of each pseudo-component molecule of the raw oil under the condition of different water content of the extractant.

[0113] Taking the extractant as furfural, Table 3 is the equilibrium distribution coefficient m of 8 kinds of pseudo-component molecules in different water content of furfural.

[0114] Table 3

[0115]

[0116] Figure 5 is the extraction rate of 8 kinds of pseudo-component molecules in the extractant under the condition of different water content according to an exemplary embodiment. Among them, 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%, from top to bottom, the extraction rates of pseudo-components P, N, MA, DA, 3RA, 4RA and 5RA are in turn. As shown in Figure 5 with the increase of water content in the extractant, the extraction rates of the 8 kinds of pseudo-components are all decreasing, resulting in the increase of the yield of raffinate oil. However, when the water content in the extractant is less than 3%, the extraction rates of P, N, MA, DA and other light components decrease significantly, while the extraction rates of polycyclic aromatic hydrocarbons change little, which will lead to the increase of the selectivity of the solvent system to polycyclic aromatic hydrocarbons. However, with the continuous increase of water content, the effect of this influence will become significant, and the extraction rates of all pseudo-components will decrease significantly, resulting in the decrease of the selectivity of the extractant to polycyclic aromatic hydrocarbons. Based on this, the appropriate water content of the extractant in the extraction process should be 1% to 3%.

[0117] Through the above scheme, the first equilibrium distribution coefficient m of 8 kinds of pseudo-components under pure solvent can be determined according to the historical extraction experimental data, and the second type of infinite dilution activity coefficient is calculated by the first equilibrium distribution coefficient m and the first type of infinite dilution activity coefficient Under the assumption that the second type of infinite dilution activity coefficient The equilibrium distribution coefficient and extraction rate under different water content of the extractant can be calculated, and the optimal water content of the extractant can be determined according to the separation requirements.

[0118] Table 4 is the properties of the furfural extract oil and the raffinate oil after being extracted by anhydrous furfural.

[0119] Table 4

[0120]

[0121] Exemplarily, according to the properties of the furfural extract oil in Table 4, the furfural extract oil can be characterized and modeled to obtain eight pseudo-components and various molecular average configurations of furfural.

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

[0123] Exemplarily, the sigma spectrum of the mixture solvent of furfural and water with different water content can be calculated according to the calculation formula (3).

[0124] Exemplarily, the first type of infinite dilution activity coefficient of the eight pseudo-component molecules in furfural with different water content can be calculated according to the calculation formula (6) under the simulation extraction temperature of 60°C and the agent-oil volume ratio of furfural: water: oil = 3: 0.1-0.5: 1.

[0125] Exemplarily, according to the data of the furfural extract oil and the raffinate oil after being extracted by furfural in Table 4, the equilibrium distribution coefficient and the extraction rate of the eight pseudo-component molecules in the furfural solvent under the extraction condition of anhydrous furfural can be calculated by the calculation formula (4) and the calculation formula (5); and the m i The activity coefficients between the eight pseudo-component molecules under the experimental conditions can be calculated i.e. the second type of infinite dilution activity coefficient, and the extraction rate of the eight pseudo-component molecules in the mixed solvent under the condition of 1-5% water content of furfural can be predicted by calculation.

[0126] In some embodiments, the water content of the furfural extractant can be set The activity coefficients of the eight pseudo-component molecules in the solvent with different water content calculated according to the above calculation The equilibrium distribution coefficient m i of the eight pseudo-component molecules in the solvent with different water content can be calculated by the calculation formula (7), and then the extraction rate E i of the eight pseudo-component molecules in the solvent with different water content can be calculated by the formula (5) and mi and then determine the extraction rates of the eight pseudo-components in the mixed solvent under the condition that the furfural water content is 1-5%.

[0127] Figure 6 is a comparison chart of the simulation values and experimental values of the furfural extract oil in furfural solvents with 1% and 5% water content according to an exemplary embodiment. As shown in Figure 6 the left side shows a comparison of the simulation values and experimental values of the extraction rate of the furfural extract oil in furfural solvents with 1% water content according to the embodiment of the present disclosure, and the right side shows a comparison of the simulation values and experimental values of the extraction rate of the furfural extract oil in furfural solvents with 5% water content according to the embodiment of the present disclosure. The shaded part in the chart is the experimental value, and the black part is the simulation value of the extraction rate according to the embodiment of the present disclosure. According to Figure 6 it can be seen that the simulation values and experimental values are in good agreement, and when the water content of furfural is 5%, the extraction rate of 3-5 ring aromatic hydrocarbons is significantly lower than that when the water content of furfural is 1%, which will result in more 3-ring or more condensed ring aromatic hydrocarbons remaining in the raffinate oil. Therefore, the water content of furfural is preferably 1%.

[0128] As a comparison, when the water content of furfural is 1%, the raffinate oil yield is 52.74%, and the PCA (condensed ring aromatic hydrocarbon compound) content is 2.98%, not only the raffinate oil yield is increased by 10 percentage points, but also the PCA content meets the requirement of <3%; when the water content of furfural 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 reduced four-line furfural raw oil and the raffinate oil after extraction by anhydrous NMP are shown.

[0130] Table 5

[0131]

[0132]

[0133] Exemplarily, according to the properties of the reduced four-line furfural raw oil in Table 5, the characteristic modeling can be performed. The average molecular configuration of the eight pseudo-components of the reduced four-line furfural raw oil and NMP is obtained.

[0134] Exemplarily, according to the calculation formulas (1) and (2), the COSMO thermodynamic simulation of the average molecular configuration of the eight pseudo-components and NMP is performed, and the corresponding sigma spectrum is obtained.

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

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

[0137] Exemplarily, according to the data obtained by the pure NMP extraction in Table 5, the equilibrium distribution coefficients and the extraction rates of the eight pseudo-component molecules in the NMP solvent under the condition can be calculated by the calculation formula (4) and the calculation formula (5); and the activity coefficients between the eight pseudo-component molecules under the experimental condition can be calculated according to the calculation formula (7). that is, the second infinite dilution activity coefficients, and the extraction rates of the eight pseudo-component molecules in the mixed solvent under the condition that the water content in the NMP is 1-5% can be calculated and predicted.

[0138] As shown in Table 5, the simulation calculation values and the experimental values of the reduced four-line furfural raw oil in the NMP solvent with a water content of 2% and 4% are shown. Figure 7 The round and diamond shapes respectively represent the experimental values and the simulation calculation values of the extraction rates of the eight pseudo-component molecules with a water content of 2% obtained according to the embodiments of the present disclosure, and the experimental values of the extraction rates of the eight pseudo-component molecules with a water content of 2% are all greater than the simulation calculation values. The triangular and square shapes respectively represent the experimental values and the simulation calculation values of the extraction rates of the eight pseudo-component molecules with a water content of 4% obtained according to the embodiments of the present disclosure, and the experimental values of the extraction rates of the pseudo-component molecules MA and DA with a water content of 2% are less than the simulation calculation values, and the experimental values of the extraction rates of the other pseudo-component molecules are all greater than the simulation calculation values. Therefore, it can be seen that the simulation values and the experimental values are in good agreement, and the extraction rates of the 3-5 ring aromatic hydrocarbons with a water content of 4% in the NMP are significantly reduced compared with the water content of 4% in the NMP, which will result in more 3-ring or more condensed ring aromatic hydrocarbons remaining in the raffinate oil. Therefore, the water content of the NMP is preferably 2%.

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

[0140] In the above embodiment, first, the raw oil and the extractant are subjected to molecular modeling, then the sigma spectrum of each pseudo-component of the eight pseudo-components of the raw oil and the sigma spectrum of the extractant with different water contents are calculated through COSMO thermodynamic simulation, and finally the first equilibrium distribution coefficient calculated from the sigma spectrum of each molecule and the experimental data of the pure solvent extraction is used to calculate the equilibrium distribution coefficient of the eight pseudo-component molecules in the oil-extractant mixed system and the extraction rate of the eight pseudo-component molecules under different water contents of the extractant. Therefore, the present scheme can quickly optimize the water content of the extractant in the oil-extractant system, improve the raffinate oil yield under the premise of meeting PCA < 3%, and has practical guiding significance for the optimization of the extraction process of polycyclic aromatic hydrocarbons.

[0141] Figure 8 is a block diagram of a polycyclic aromatic hydrocarbon extraction device according to an exemplary embodiment. As shown in Figure 8 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 configured to determine a first molecular structure model of each pseudo-component molecule in the raw oil and a second molecular structure model of each molecule in the extractant.

[0143] The second determination module 802 is configured to determine a first sigma spectrum of the raw oil according to the first molecular structure model, and determine a second sigma spectrum of the extractant according to the second molecular structure model, and determine a third sigma spectrum of the extractant under different water content conditions.

[0144] The third determination module 803 is configured to determine the corresponding equilibrium distribution properties of each pseudo-component molecule under different water content conditions of the extractant according to the first sigma spectrum, the second sigma spectrum, and the third sigma spectrum, the equilibrium distribution properties including the corresponding equilibrium distribution coefficients of each pseudo-component molecule under different water content conditions of the extractant, and the polycyclic aromatic hydrocarbon extraction rate of the extractant for the raw oil under different water content conditions.

[0145] The extraction module 804 is configured to perform polycyclic aromatic hydrocarbon extraction based on the equilibrium distribution properties.

[0146] Optionally, the third determination module 803 is configured to:

[0147] determine the first equilibrium distribution coefficient of each pseudo-component molecule of the raw oil under the zero water content condition of the extractant according to the historical extraction experimental data of the extractant.

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

[0149] determining a second type of infinite dilution activity coefficient between pseudo-component molecules of the feedstock oil based on 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 configured 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 configured 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 configured 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 paraffins, cycloparaffins, monocyclic aromatics, bicyclic aromatics, tricyclic aromatics, tetracyclic aromatics, pentacyclic aromatics, and sulfur-containing condensed ring aromatics.

[0163] With regard to the apparatus in the above-described embodiments, the specific manner in which each module performs operations has been described in detail in the embodiments related to the method, and will not be described in detail here.

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

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

[0166] a memory having stored thereon computer programs;

[0167] a processor configured to execute the computer programs in the memory to implement the steps of the condensed ring aromatic extraction method provided by the present disclosure.

[0168] Figure 9 is a block diagram of an electronic device according to an exemplary embodiment. As shown in Figure 9 the electronic device 700 can include a processor 701 and a memory 702. The electronic device 700 can 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. For example, this data may include instructions for any application or method operating on the electronic device 700, as well as application-related data, such as contact information, sent and received messages, 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 (SRAM), electrically erasable programmable read-only memory (EEPROM), erasable programmable read-only memory (EPROM), programmable read-only memory (PROM), read-only memory (ROM), magnetic storage, 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 above-mentioned other interface modules may be a keyboard, a mouse, 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: a Wi-Fi module, a Bluetooth module, an NFC module, etc.

[0170] In an exemplary embodiment, the electronic device 700 can be implemented by one or more Application Specific Integrated Circuit (ASIC), Digital Signal Processor (DSP), Digital Signal Processing Device (DSPD), Programmable Logic Device (PLD), Field Programmable Gate Array (FPGA), controller, microcontroller, microprocessor or other electronic elements for performing the above-mentioned method of extracting fused ring aromatic hydrocarbons.

[0171] In another exemplary embodiment, a computer readable storage medium including program instructions is also provided, which, when executed by a processor, implement the steps of the above-mentioned method of extracting fused ring aromatic hydrocarbons. For example, the computer readable storage medium can be the above-mentioned memory 702 including program instructions, which can be executed by the processor 701 of the electronic device 700 to complete the above-mentioned method of extracting fused ring aromatic hydrocarbons.

[0172] In another exemplary embodiment, a computer program product is also provided, which contains a computer program capable of being executed by a programmable device, and the computer program has code portions for executing the above-mentioned method of extracting fused ring aromatic hydrocarbons when executed by the programmable device.

[0173] The preferred embodiments of the present disclosure are described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the above-described embodiments. Within the technical concept of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

[0174] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction, and in order to avoid unnecessary repetition, the present disclosure will not further describe various possible combinations.

[0175] Furthermore, any combination of the various different embodiments of the present disclosure can also be made, as long as it does not deviate from the idea of the present disclosure, and it should also be considered as disclosed by the present disclosure.

Claims

1. A method for extracting condensed ring aromatic hydrocarbons, characterized in that: include: Determining a first molecular structure model of each pseudo-component molecule in the feed oil, and determining a second molecular structure model of the extractant molecule; 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 of the extractant under different water content conditions; determining, based on 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, the equilibrium distribution properties including the equilibrium distribution coefficients corresponding to the pseudo-component molecules under different water contents of the extractant, and / or the extraction rate of condensed-ring aromatic hydrocarbons of the feedstock under different water contents of the extractant; Extracting condensed ring aromatic hydrocarbons based on the equilibrium distribution property; Wherein, 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: Determining, based on historical extraction experimental data of the extractant, a first equilibrium partition coefficient corresponding to each pseudo-component molecule of the feedstock oil under a zero water content condition of the extractant; determining, based on the first sigma spectrum, the second sigma spectrum, and the third sigma spectrum, a first type infinite dilution activity coefficient of each pseudo-component molecule of the feedstock oil under different water contents of the extractant; determining a second type of infinite dilution activity coefficient between pseudo-component molecules of the feedstock oil based on 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.

2. The method according to claim 1, characterized in that 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.

3. 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.

4. The method according to claim 3, 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.

5. The method according to any one of claims 1 to 4, 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.

6. The method according to any one of claims 1 to 4, 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.

7. A condensed-ring 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 raw oil, and to determine a second molecular structure model of the extractant molecule; a second determining module, configured 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; a third determination module, configured to determine, based on 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, the equilibrium distribution properties including the equilibrium distribution coefficients corresponding to the pseudo-component molecules under different water contents of the extractant, and / or the polycyclic aromatic hydrocarbon extraction rates of the feedstock under different water contents of the extractant; An extraction module, configured to extract condensed-ring aromatic hydrocarbons based on the equilibrium distribution property; The third determining module is used for: Determining, based on historical extraction experimental data of the extractant, a first equilibrium partition coefficient corresponding to each pseudo-component molecule of the feedstock oil under a zero water content condition of the extractant; determining, based on the first sigma spectrum, the second sigma spectrum, and the third sigma spectrum, a first type infinite dilution activity coefficient of each pseudo-component molecule of the feedstock oil under different water contents of the extractant; determining a second type of infinite dilution activity coefficient between pseudo-component molecules of the feedstock oil based on 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.

8. 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 according to any one of claims 1 to 6 are implemented.

9. 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 6.

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