Method and device for determining hydrodesulfurization rate of sulfur-containing asphaltene in slurry bed heavy oil micro-interface enhanced reactor and electronic equipment

Abstract

The invention provides a method and a device for determining the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry bed heavy oil micro-interface enhanced reactor and electronic equipment. According to the scheme, a physical model of a micro-interface unit of a slurry bed heavy oil hydrogenation micro-interface reactor is creatively established, and a mathematical model of the energy dissipation rate is deduced based on the physical model; and further calculating the bubble size, the micro-bubble average rising speed of the micro-interface system, the gas content, the gas-liquid phase interface area, the gas-side mass transfer coefficient and the liquid-side mass transfer coefficient based on the mathematical model of the energy dissipation rate, and further calculating the desulfurization rate. Based on the calculation models, the influence of related factors on parameters of the sulfur-containing asphaltene hydrodesulfurization reaction process and the influence on the calculation result of the sulfur-containing asphaltene hydrodesulfurization rate can be analyzed more effectively by adjusting the operation pressure, the liquid hourly space velocity or the hydrogen-oil ratio in the sulfur-containing asphaltene hydrodesulfurization reaction process of the micro-interface enhanced reactor; therefore, the micro-interface reinforced hydrogenation reaction of the heavy oil in the slurry reactor is optimized.

Description

Technical Field

[0001] This application relates to the field of heavy oil hydrogenation technology, and in particular to a method, apparatus and electronic equipment for determining the hydrogenation desulfurization rate of sulfur-containing asphaltenes in a slurry bed heavy oil micro-interface enhanced reactor. Background Technology

[0002] The slurry bed hydrotreating reactor is a high-temperature, high-pressure reaction of heavy oil in the presence of hydrogen and a solid catalyst. The light fraction (product) is the result of the heavy oil undergoing both thermal cracking and hydrotreating. Slurry bed hydrotreating technology has attracted widespread attention from research institutions due to its strong adaptability to feedstocks and high conversion rate.

[0003] In existing technologies, the focus of research on slurry bed hydrogenation technology for heavy oil is mainly on novel and efficient heavy oil hydrogenation catalysts and the chemical mechanisms of the conversion process. However, the impact of hydrogen molecule mass transfer rate on the conversion rate of heavy oil, especially the conversion of sulfur-containing asphaltenes in heavy oil, catalyst deactivation, and coking, has not received sufficient attention. Summary of the Invention

[0004] This specification provides a method, apparatus, and electronic equipment for determining the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry bed heavy oil micro-interface enhanced reactor. The micro-interface enhancement technology is used to enhance the mass transfer of hydrogen molecules in the slurry bed multiphase reaction system to solve the above-mentioned problems.

[0005] To address the aforementioned technical problems, this specification provides a method for determining the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry-bed heavy oil micro-interface enhanced reactor. The method includes: obtaining reactor structural parameters, system property parameters, and operating parameters for the slurry-bed heavy oil micro-interface enhanced reaction; calculating the energy dissipation rate based on the reactor structural parameters, system property parameters, and operating parameters; calculating the bubble size based on the energy dissipation rate; calculating the rising velocity of a single bubble in an infinitely large static liquid phase based on the bubble size; calculating the average rising velocity of microbubbles in the micro-interface system based on the rising velocity of a single bubble in the infinitely large static liquid phase; calculating the gas holdup in the micro-interface enhanced reactor based on the average rising velocity of microbubbles in the micro-interface system; calculating the gas-liquid interface area, gas-side mass transfer coefficient, and liquid-side mass transfer coefficient based on the bubble size; calculating the macroscopic reaction rate of the sulfur-containing asphaltene hydrodesulfurization reaction in the micro-interface system based on the gas-side mass transfer coefficient and the liquid-side mass transfer coefficient; and calculating the desulfurization rate based on the macroscopic reaction rate.

[0006] In some embodiments, the energy dissipation rate is calculated based on the reactor structural parameters, system physical property parameters, and operating parameters, including calculating the energy dissipation rate according to the following formula:

[0007]

[0008] Where ε represents the energy dissipation rate within the micro-interface generator, W / kg; λ represents the gas-liquid ratio within the micro-interface generator; ρ L This represents the liquid phase density of a slurry-bed heavy oil hydrogenation system, in kg / m³. 3 V0 represents the volume of the micro-interface generator, in meters. 3 g represents the acceleration due to gravity, 9.81 m / s². 2 H0 represents the internal height of the slurry-bed heavy oil hydrotreating reactor, in meters (m); S0 represents the cross-sectional area of ​​the slurry-bed heavy oil hydrotreating reactor, in square meters (m²). 2 S1 represents the cross-sectional area of ​​the micro-interface generator outlet, in m³. 2 ;P m Q represents the operating pressure, Pa; ΔP represents the pressure difference between the inside and outside of the micro-interface generator, Pa; L0 The volumetric flow rate of fresh heavy oil in a slurry bed heavy oil hydrotreating reactor is expressed in m³. 3 / s.

[0009] In some embodiments, the energy dissipation rate calculation formula is determined based on the following conditions: the MIR is in a continuous steady-state operating state; the gas-liquid mixing process in the MIG is adiabatic and isothermal; the gas depressurization process is completed instantaneously, and the pressure in the MIG is the operating pressure; the changes in gas kinetic energy and gravitational potential energy of the gas-liquid two phases are ignored; and the gas is a single-component ideal gas.

[0010] In some embodiments, the macroscopic reaction rate of the hydrodesulfurization reaction of sulfur-containing asphaltene in the micro-interface system is calculated based on the gas-side mass transfer coefficient and the liquid-side mass transfer coefficient, including calculating the macroscopic reaction rate according to the following formula:

[0011]

[0012] Where, r s P represents the macroscopic reaction rate. m Indicates operating pressure, Pa; H A The Henry's law representing the concentration of hydrogen in heavy oil, expressed in Pa·m. 3 / mol;k G The gas-side mass transfer coefficient is expressed in m / s; k L The value represents the liquid-side mass transfer coefficient, in m / s; a represents the gas-liquid interface area, in m². 2 ;k HDS The intrinsic reaction rate constant (m) represents the hydrodesulfurization reaction of sulfur-containing asphaltenes in heavy oil. 3 / mol) 0.5 / m 3 cat.s); C s0 This indicates the sulfur content in the sulfur-containing asphaltenes of heavy oil feedstock, in mol / m³. 3 V C This indicates the catalyst volume in a slurry-bed heavy oil hydrotreating reactor, in m.3 Q L0 The volumetric flow rate of heavy oil at the inlet of the slurry bed heavy oil hydrotreating reactor, in m³. 3 / s.

[0013] In some embodiments, before calculating the macroscopic reaction rate of the hydrodesulfurization reaction of sulfur-containing asphaltene in the micro-interface system based on the gas-side mass transfer coefficient and the liquid-side mass transfer coefficient, the method further includes: calculating the intrinsic reaction rate constant of the hydrodesulfurization reaction of sulfur-containing asphaltene according to the following formula:

[0014]

[0015] Where, ρ c This indicates the density of the catalyst, in kg / m³. 3 ;w c This indicates the catalyst density and actual amount of catalyst used, w / w; ρ L This represents the liquid phase density of a slurry-bed heavy oil hydrogenation system, in kg / m³. 3 T represents the reaction temperature or operating temperature.

[0016] In some embodiments, the liquid-side mass transfer coefficient is calculated according to the following formula:

[0017] k L =D L / δ L

[0018] δ L ≈0.15d 32 / π

[0019] Where, k L D represents the liquid-side mass transfer coefficient, in m / s; L The liquid-phase diffusion coefficient of hydrogen in heavy oil is represented by m. 2 / s;δ L The thickness of the bubble-liquid film is expressed in meters (m) and d. 32 The value in meters represents the bubble diameter in a slurry bed heavy oil micro-interface hydrogenation enhanced reactor.

[0020] In some embodiments, calculating the rising velocity of a single bubble in an infinitely large static liquid phase based on the bubble size includes calculating the rising velocity of a single bubble in an infinitely large static liquid phase according to the following formula:

[0021]

[0022] Mo = gμ L 4 / ρ L σ L 3

[0023] d e '=d32 (ρ L g / σ L ) 1 / 2

[0024] Where v0 represents the rising velocity of a single bubble in an infinitely large, static liquid phase, in m / s; and g represents the acceleration due to gravity, 9.81 m / s². 2 μ L The ρ represents the liquid phase dynamic viscosity of the slurry bed heavy oil hydrotreating system, in Pa·s. L This represents the liquid phase density of a slurry-bed heavy oil hydrogenation system, in kg / m³. 3 ;σ L The d represents the interfacial tension between gas and liquid in a slurry bed heavy oil hydrogenation system, in N / m. 32 The K value represents the bubble diameter in a slurry bed heavy oil micro-interface hydroenhanced reactor, in meters (m). b c and n represent empirical constants.

[0025] In some embodiments, the method further includes: adjusting the following parameters during the hydrodesulfurization reaction of sulfur-containing asphaltene in a slurry-bed heavy oil micro-interface enhanced reactor: operating pressure, liquid hourly space velocity (LISH), and hydrogen-to-oil ratio; calculating the process parameters and hydrodesulfurization rate of sulfur-containing asphaltene in the slurry-bed heavy oil micro-interface system based on the adjusted parameters; determining the influence of operating pressure, LISH, and hydrogen-to-oil ratio on the process parameters and hydrodesulfurization rate of sulfur-containing asphaltene in the slurry-bed heavy oil micro-interface system based on the calculation results; and determining the target design parameters of the slurry-bed heavy oil hydrodesulfurization micro-interface reactor based on the influence characteristics.

[0026] The second aspect of this specification provides an apparatus for determining the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry-bed heavy oil micro-interface enhanced reactor, comprising: an acquisition unit for acquiring reactor structural parameters, system physical property parameters, and operating parameters of the slurry-bed heavy oil micro-interface enhanced reaction; a first calculation unit for calculating the energy dissipation rate based on the reactor structural parameters, system physical property parameters, and operating parameters; a second calculation unit for calculating the bubble size based on the energy dissipation rate; a third calculation unit for calculating the rising velocity of a single bubble in an infinitely large static liquid phase based on the bubble size; a fourth calculation unit for calculating the average rising velocity of microbubbles in the micro-interface system based on the rising velocity of a single bubble in the infinitely large static liquid phase; a fifth calculation unit for calculating the gas holdup in the micro-interface enhanced reactor based on the average rising velocity of microbubbles in the micro-interface system; a sixth calculation unit for calculating the gas-liquid interfacial area, gas-side mass transfer coefficient, and liquid-side mass transfer coefficient based on the bubble size; a seventh calculation unit for calculating the macroscopic reaction rate of the sulfur-containing asphaltene hydrodesulfurization reaction in the micro-interface system based on the gas-side mass transfer coefficient and the liquid-side mass transfer coefficient; and an eighth calculation unit for calculating the desulfurization rate based on the macroscopic reaction rate.

[0027] In some embodiments, the energy dissipation rate is calculated based on the reactor structural parameters, system physical property parameters, and operating parameters, including calculating the energy dissipation rate according to the following formula:

[0028]

[0029] Where ε represents the energy dissipation rate within the micro-interface generator, W / kg; λ represents the gas-liquid ratio within the micro-interface generator; ρ L This represents the liquid phase density of a slurry-bed heavy oil hydrogenation system, in kg / m³. 3 V0 represents the volume of the micro-interface generator, in meters. 3 g represents the acceleration due to gravity, 9.81 m / s². 2 H0 represents the internal height of the slurry-bed heavy oil hydrotreating reactor, in meters (m); S0 represents the cross-sectional area of ​​the slurry-bed heavy oil hydrotreating reactor, in square meters (m²). 2 S1 represents the cross-sectional area of ​​the micro-interface generator outlet, in m³. 2 ;P m Q represents the operating pressure, Pa; ΔP represents the pressure difference between the inside and outside of the micro-interface generator, Pa; L0 The volumetric flow rate of fresh heavy oil in a slurry bed heavy oil hydrotreating reactor is expressed in m³. 3 / s.

[0030] In some embodiments, the energy dissipation rate calculation formula is determined based on the following conditions: the MIR is in a continuous steady-state operating state; the gas-liquid mixing process in the MIG is adiabatic and isothermal; the gas depressurization process is completed instantaneously, and the pressure in the MIG is the operating pressure; the changes in gas kinetic energy and gravitational potential energy of the gas-liquid two phases are ignored; and the gas is a single-component ideal gas.

[0031] In some embodiments, the macroscopic reaction rate of the hydrodesulfurization reaction of sulfur-containing asphaltene in the micro-interface system is calculated based on the gas-side mass transfer coefficient and the liquid-side mass transfer coefficient, including calculating the macroscopic reaction rate according to the following formula:

[0032]

[0033] Where, r s P represents the macroscopic reaction rate. m Indicates operating pressure, Pa; H A The Henry's law representing the concentration of hydrogen in heavy oil, expressed in Pa·m. 3 / mol;k G The gas-side mass transfer coefficient is expressed in m / s; k L The value represents the liquid-side mass transfer coefficient, in m / s; a represents the gas-liquid interface area, in m². 2 ;k HDS The intrinsic reaction rate constant (m) represents the hydrodesulfurization reaction of sulfur-containing asphaltenes in heavy oil. 3 / mol) 0.5 / m 3 cat.s); C s0 This indicates the sulfur content in the sulfur-containing asphaltenes of heavy oil feedstock, in mol / m³. 3 V C This indicates the catalyst volume in a slurry-bed heavy oil hydrotreating reactor, in m. 3 Q L0 The volumetric flow rate of heavy oil at the inlet of the slurry bed heavy oil hydrotreating reactor, in m³. 3 / s.

[0034] In some embodiments, before calculating the macroscopic reaction rate of the hydrodesulfurization reaction of sulfur-containing asphaltene in the micro-interface system based on the gas-side mass transfer coefficient and the liquid-side mass transfer coefficient, the method further includes: calculating the intrinsic reaction rate constant of the hydrodesulfurization reaction of sulfur-containing asphaltene according to the following formula:

[0035]

[0036] Where, ρ c This indicates the density of the catalyst, in kg / m³. 3 ;w c This indicates the catalyst density and actual amount of catalyst used, w / w; ρ L This represents the liquid phase density of a slurry-bed heavy oil hydrogenation system, in kg / m³. 3 T represents the reaction temperature or operating temperature.

[0037] In some embodiments, the liquid-side mass transfer coefficient is calculated according to the following formula:

[0038] k L =D L / δ L

[0039] δ L ≈0.15d 32 / π

[0040] Where, k L D represents the liquid-side mass transfer coefficient, in m / s; L The liquid-phase diffusion coefficient of hydrogen in heavy oil is represented by m. 2 / s;δ L The thickness of the bubble-liquid film is expressed in meters (m) and d. 32 The value in meters represents the bubble diameter in a slurry bed heavy oil micro-interface hydrogenation enhanced reactor.

[0041] In some embodiments, calculating the rising velocity of a single bubble in an infinitely large static liquid phase based on the bubble size includes calculating the rising velocity of a single bubble in an infinitely large static liquid phase according to the following formula:

[0042]

[0043] Mo = gμ L 4 / ρ L σ L 3

[0044] d e '=d 32 (ρ L g / σ L ) 1 / 2

[0045] Where v0 represents the rising velocity of a single bubble in an infinitely large, static liquid phase, in m / s; and g represents the acceleration due to gravity, 9.81 m / s². 2 μ L The ρ represents the liquid phase dynamic viscosity of the slurry bed heavy oil hydrotreating system, in Pa·s. L This represents the liquid phase density of a slurry-bed heavy oil hydrogenation system, in kg / m³. 3 ;σ L The d represents the interfacial tension between gas and liquid in a slurry bed heavy oil hydrogenation system, in N / m. 32 The K value represents the bubble diameter in a slurry bed heavy oil micro-interface hydroenhanced reactor, in meters (m). b c and n represent empirical constants.

[0046] In some embodiments, the apparatus further includes: a first determining unit, configured to adjust the following parameters respectively during the hydrodesulfurization reaction of sulfur-containing asphaltene in a slurry-bed heavy oil micro-interface enhanced reactor: operating pressure, liquid hourly space velocity, and hydrogen-to-oil ratio, and calculate the process parameters and hydrodesulfurization rate of sulfur-containing asphaltene in the slurry-bed heavy oil micro-interface system based on the adjusted parameters, and determine the influence of operating pressure, liquid hourly space velocity, and hydrogen-to-oil ratio on the process parameters and hydrodesulfurization rate of sulfur-containing asphaltene in the slurry-bed heavy oil micro-interface system based on the calculation results; and a second determining unit, configured to determine the values ​​of the target design parameters of the slurry-bed heavy oil hydrodesulfurization micro-interface reactor based on the influence law.

[0047] A third aspect of this specification provides an electronic device, comprising: a memory and a processor, wherein the processor and the memory are communicatively connected to each other, the memory stores computer instructions, and the processor executes the computer instructions to implement the method for determining the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry bed heavy oil micro-interface enhanced reactor as described in any of the first aspects.

[0048] This manual provides a method, apparatus, and electronic equipment for determining the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry-bed heavy oil micro-interface enhanced reactor. It innovatively establishes a physical model for the micro-interface unit of the slurry-bed heavy oil hydrotreating micro-interface reactor, applicable to both purely pneumatic and purely hydraulic or gas-liquid combined operation conditions. Based on this physical model, a mathematical model for the energy dissipation rate is derived, which can then be used to further calculate the bubble size d. 32 The average rising velocity v of microbubbles in the micro-interface system 32 The desulfurization rate can be calculated by considering factors such as gas holdup, gas-liquid interphase area, gas-side mass transfer coefficient, and liquid-side mass transfer coefficient. Based on these calculation models, the effects of relevant factors on the hydrodesulfurization process parameters of sulfur-containing asphaltene in the slurry-bed heavy oil micro-interface enhanced reactor, as well as their impact on the calculated hydrodesulfurization rate, can be more effectively analyzed by adjusting operating pressure, liquid hourly space velocity, or hydrogen-to-oil ratio. This allows for the optimization of the slurry-bed heavy oil micro-interface enhanced hydrogenation reaction. Attached Figure Description

[0049] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0050] Figure 1 A simplified physical model diagram of the micro-interface formation process within the MIG;

[0051] Figure 2 This is a graph showing the relationship between the actual ventilation rate and the actual gas-liquid ratio within the MIG.

[0052] Figure 3 This is a schematic diagram of the method for determining the hydrogen transport capacity of the micro-interface enhancement reaction of slurry bed heavy oil provided in this specification.

[0053] Figure 4 A schematic diagram illustrating the effect of the average number of carbon atoms in the liquid phase on the dynamic viscosity of the liquid phase, provided in an embodiment of the present invention;

[0054] Figure 5 A schematic diagram illustrating the effect of the average number of carbon atoms in the liquid phase on the surface tension of the liquid phase, provided in an embodiment of the present invention;

[0055] Figure 6 The operating pressure P provided in the embodiments of the present invention m The average Sauter diameter d of bubbles in a slurry bed heavy oil hydrogenation system 32 Schematic diagram of the impact;

[0056] Figure 7 The operating pressure P provided in the embodiments of the present invention m The average bubble rise velocity v in the slurry bed heavy oil hydrogenation system 32 Schematic diagram of the impact;

[0057] Figure 8 The operating pressure P provided in the embodiments of the present invention m The gas holdup φ of the slurry bed heavy oil hydrogenation system G Schematic diagram of the impact;

[0058] Figure 9 The operating pressure P provided in the embodiments of the present invention m Schematic diagram showing the effect of the gas-liquid phase interface area 'a' on the slurry bed heavy oil hydrogenation system;

[0059] Figure 10 The operating pressure P provided in the embodiments of the present invention m The gas-side mass transfer coefficient k of the slurry bed heavy oil hydrogenation system G Schematic diagram of the impact;

[0060] Figure 11 The operating pressure P provided in the embodiments of the present invention m The liquid-side mass transfer coefficient k of the slurry bed heavy oil hydrogenation system L Schematic diagram of the impact;

[0061] Figure 12 The operating pressure P provided in the embodiments of the present invention m The liquid-side volumetric mass transfer coefficient k of the slurry bed heavy oil hydrogenation system L A schematic diagram illustrating the impact of a;

[0062] Figure 13 The operating pressure P provided in the embodiments of the present invention m Schematic diagram of the effect of sulfur-containing asphaltene on the desulfurization rate of the slurry bed heavy oil hydrotreating system;

[0063] Figure 14 The Liquid Time Space Velocity (LHSV) provided in this embodiment of the invention affects the average bubble rise velocity v in a slurry bed heavy oil hydrogenation system. 32 Schematic diagram of the impact;

[0064] Figure 15 The liquid time space velocity (LHSV) provided in this embodiment of the invention affects the gas holdup φ of the slurry bed heavy oil hydrogenation system. G Schematic diagram of the impact;

[0065] Figure 16 This is a schematic diagram illustrating the effect of liquid time space velocity (LHSV) on the gas-liquid interface area 'a' in a slurry bed heavy oil hydrogenation system, provided in an embodiment of the present invention.

[0066] Figure 17 The liquid time space velocity (LHSV) provided in this embodiment of the invention affects the liquid-side volumetric mass transfer coefficient k of the slurry bed heavy oil hydrogenation system. L A schematic diagram illustrating the impact of a;

[0067] Figure 18 This is a schematic diagram illustrating the effect of liquid time space velocity (LHSV) on the desulfurization rate of sulfur-containing asphaltene in a slurry bed heavy oil hydrotreating system, provided in an embodiment of the present invention.

[0068] Figure 19 The hydrogen-to-oil ratio comparison of the average bubble rise velocity v in the slurry bed heavy oil hydrogenation system provided in this embodiment of the invention 32 Schematic diagram of the impact;

[0069] Figure 20 The hydrogen-to-oil ratio of the slurry bed heavy oil hydrogenation system provided in this embodiment of the invention is used to compare the gas holdup φ. G Schematic diagram of the impact;

[0070] Figure 21 This is a schematic diagram illustrating the effect of the hydrogen-to-oil ratio on the gas-liquid interphase area 'a' in a slurry bed heavy oil hydrogenation system, provided in an embodiment of the present invention.

[0071] Figure 22 The hydrogen-to-oil ratio of the hydrogen-to-oil ratio in the slurry bed heavy oil hydrogenation system provided in this embodiment of the invention provides the liquid-side mass transfer coefficient k. L Schematic diagram of the impact;

[0072] Figure 23 The hydrogen-to-oil ratio comparison of the liquid-side volumetric mass transfer coefficient k in the slurry bed heavy oil hydrogenation system provided in this embodiment of the invention L A schematic diagram illustrating the impact of a;

[0073] Figure 24 This is a schematic diagram illustrating the effect of the hydrogen-to-oil ratio on the desulfurization rate of sulfur-containing asphaltene in a slurry bed heavy oil hydrotreating system, provided in an embodiment of the present invention.

[0074] Figure 25 This is a schematic diagram of the apparatus for determining the hydrodesulfurization rate of sulfur-containing asphaltenes in a slurry bed heavy oil micro-interface enhanced reactor provided in this manual;

[0075] Figure 26 A schematic diagram of the electronic device provided in this specification is shown. Detailed Implementation

[0076] To enable those skilled in the art to better understand the technical solutions in this application, the technical solutions in the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this application.

[0077] This invention aims to improve the hydrogenation rate of a slurry bed heavy oil hydrogenation system. Due to the complex composition of heavy oil feedstock, this paper only uses the hydrodesulfurization reaction of sulfur-containing asphaltenes as a model reaction in the slurry bed heavy oil hydrogenation process, and focuses on investigating the effects of operating pressure, liquid hourly space velocity, and hydrogen-to-oil ratio on the desulfurization rate of the sulfur-containing asphaltenes in the slurry bed heavy oil hydrogenation system.

[0078] Sulfur-containing asphaltenes in heavy oil are difficult to convert during hydrocracking. Their core is a highly condensed fused aromatic ring system surrounded by alkyl and cycloalkyl structures of varying numbers and sizes. They represent the component with the highest degree of condensation in heavy oil and also contain heteroatoms such as S, N, O, and metals, resulting in a complex morphology and molecular structure. During the hydrocracking process of heavy oil, sulfur-containing asphaltenes mainly undergo two opposite reactions: hydrodesulfurization and cleavage (breaking down large molecules into smaller ones) and condensation (dehydrogenation and polymerization of small molecules into larger ones).

[0079] Due to the complex composition of heavy oil, this invention uses only the hydrodesulfurization reaction of sulfur-containing asphaltene as a model reaction for the slurry bed heavy oil hydrotreating process.

[0080] The following section details the derivation of a mathematical model for hydrogen transport in a slurry-bed heavy oil hydrotreating micro-interface reactor, applicable to both purely pneumatic and purely hydraulic or gas-liquid combined operation conditions.

[0081] 1. Analyze the parameters affecting hydrogen transport in the slurry bed heavy oil micro-interface hydrogenation reaction system.

[0082] The macroscopic reaction rate and feed conversion rate of the heavy oil hydrotreating system are determined by the total hydrogen molecule transport N in the liquid phase of the system. T The decision was made based on two mechanisms: pressure transport and interfacial transport, to determine the mass transfer of hydrogen within the reactor.

[0083] N T =N a +N p (1)

[0084] Where N a The hydrogen transport rate based on the interface hydrogen transport mechanism is expressed in mol; N. p The hydrogen transport rate is expressed in mol based on the pressure-based hydrogen transport mechanism.

[0085] 2. Obtain the hydrogen transport capacity N based on the interface hydrogen transport mechanism. a

[0086] Assuming the hydrogen bubbles in the system are of uniform size and the hydrogen transport rate across the gas-liquid interface is... Similarly, the hydrogen transport capacity N based on the interface hydrogen transport mechanism... a The total number of stable bubbles in the system, n0 (number of bubbles), and the average residence time t of heavy oil in the reactor e (s) are jointly determined, as shown in equation (2):

[0087]

[0088] Analysis of the movement process of heavy oil in the reactor, the average residence time t of heavy oil in the reactor. e It can be represented as:

[0089]

[0090] Among them, V L Let m be the volume of heavy oil in the reactor. 3 Q L The volumetric flow rate of fresh heavy oil entering the reactor is m 3 / s.

[0091] V L Determined by the relative motion between the hydrogen and heavy oil phases, analysis of the gas-liquid two-phase motion yields the following:

[0092]

[0093] Where H0 is the height of the reactor cavity, in meters (m); and S0 is the cross-sectional area of ​​the reactor, in meters (m²). 2 ;v 32 denoted as the average rising velocity of bubbles within the reactor, in m / s.

[0094] Substituting equation (4) into equation (3), we get:

[0095]

[0096] The total number of stable bubbles in the system, n0, is obtained from the conservation of gas volume and analysis of bubble motion, i.e.:

[0097]

[0098] Q G The volumetric flow rate of hydrogen is m. 3 / s;d 32 Let be the average diameter of the Sauter bubbles in the reactor, in meters (m).

[0099] Hydrogen transport rate at the gas-liquid interface Based on Fick's Law, that is:

[0100]

[0101] J z＝0 The mass flux of hydrogen at the gas-liquid interface of the gas bubble is expressed in mol / m³. 2 ;D L Let m be the liquid-phase diffusion coefficient of hydrogen in heavy oil. 2 / s; t is any time (s) during which the heavy oil resides in the reactor; C H * (mol / m 3 ) represents the saturated hydrogen concentration at the gas-liquid interface, calculated using Henry's Law as shown in equation (8):

[0102]

[0103] Where P m Operating pressure, Pa; H A Here is the Henry coefficient, Pa·m 3 / mol.

[0104] Substituting equations (5) to (8) into equation (2), we get:

[0105]

[0106] 3. Obtain the hydrogen transport volume N based on the pressure hydrogen transport mechanism. P

[0107] Hydrogen transport capacity N based on pressure transport mechanism P Both its limiting value and its limit value are determined by Henry's law, and are also subject to the bulk volume V of the heavy oil liquid phase. L Operating pressure P m and the average residence time t of heavy oil e Impact. Assume N P The limit of hydrogen solubility in the system is:

[0108] N p =V L ×C H * (10)

[0109] When the molar mass of heavy oil is M1 (kg / mol), C H * The following relationship exists between the mole fraction x of hydrogen in heavy oil:

[0110]

[0111] Where, ρ L The density of heavy oil is kg / m³ 3 .

[0112] From equations (4), (9), and (11), we get:

[0113]

[0114] 4. Obtain the total amount of hydrogen molecules transported.

[0115] From equations (1)(9)(12), we get:

[0116]

[0117] In equation (13), the average rising velocity v of the microbubbles in the micro-interface system is... 32 The structure-activity regulation mathematical model has been introduced in the prior art, and its expression is equation (14):

[0118]

[0119] In equation (14), v G (m / s) and v L (m / s) represent the apparent gas velocity and apparent liquid velocity, respectively, and are calculated according to the following equations (15) and (16):

[0120]

[0121]

[0122] In equation (14), v0 (m / s) is the rising velocity of a single bubble in an infinitely large static liquid phase, which can be calculated according to the following empirical equation (17):

[0123]

[0124] In equation (17):

[0125] Mo = gμ L 4 / ρ L σ L 3 (18)

[0126] d e '=d 32 (ρ L g / σ L ) 1 / 2 (19)

[0127] Among them, K b =K b0 Mo -0.038 Kb and K b0 It can be an empirical constant.

[0128] 5. Establishing a slurry-bed heavy oil micro-interface hydrogenation enhanced reactor with bubble size d 32 General Mathematical Model

[0129] Slurry bed heavy oil micro-interface hydroenhanced reactor bubble size d 32 The general mathematical model has been introduced in the prior art, and its expression is shown in equation (20):

[0130]

[0131] In equation (20):

[0132] d max =0.75(σ L / ρ L ) 0.6 ε -0.4 (twenty one)

[0133] d min =11.4(μ) L / ρ L ) 0.75 ε -0.25 (twenty two)

[0134] In equations (21) and (22), ε (W / kg) is the energy dissipation rate of the micro-interface unit.

[0135] 6. Establish a mathematical model for the energy dissipation rate of the micro-interface unit (MIG) in a slurry bed heavy oil micro-interface hydroenhanced reactor.

[0136] Figure 1 This is a simplified physical model diagram of the micro-interface formation process within the MIG. The rectangular region represents the interior of the cavity of the micro-interface generator (MIG), and Q... L0 This indicates the flow rate of the liquid entering the MIG chamber; the flow rate of the liquid entering the MIG chamber is the same as the flow rate of the liquid exiting the MIG chamber; Q G Q represents the flow rate of gas entering the MIG chamber; L1 This indicates the flow rate of the circulating fluid re-entering the MIG chamber from the outlet; D1 represents the diameter of the cylindrical MIG chamber; P m This indicates the operating pressure of the micro-interface enhanced reactor (MIR). 0-0 indicates the MIG inlet position, and 1-1 indicates the MIG outlet position.

[0137] based on Figure 1 The physical model shown illustrates the following physical processes occurring within the MIG:

[0138] Before the gas was introduced, the MIG was filled with a static reaction liquid. When the gas was introduced, due to the initial gas pressure P... G0 (Pa) and system operating pressure P m There is a pressure difference ΔP(Pa) between the gas and liquid phases. The gas transfers some of its static pressure energy to the liquid, causing turbulence and breaking the continuous gas phase into a dispersed bubble phase. The gas pressure itself rapidly decreases to the operating pressure within the micro-interface enhanced reactor (MIR). The resulting homogeneous gas-liquid mixture flows out of the MIG, with some liquid entering the MIG via internal circulation along with fresh liquid, serving as a medium for releasing the gas's static pressure energy. The energy required for the entire system to operate is almost entirely provided by gas pressure energy.

[0139] The above process can be analyzed from an energy perspective. During the process of a high-pressure gas entering the MIG and releasing its pressure energy, the system's energy is transferred and converted through gas-liquid interactions. The pressure energy released by the gas is converted into the kinetic energy of the liquid, the gas-liquid interface energy, and the internal energy dissipated due to friction.

[0140] To establish a mathematical model for the liquid energy dissipation rate ε within the MIG, this specification takes the gas-liquid two-phase system entering and exiting the MIG as the research object and makes the following assumptions:

[0141] ① The MIR operates in a continuous steady-state state;

[0142] ②The gas-liquid mixing process inside the MIG is adiabatic and isothermal;

[0143] ③ The gas decompression process is completed in a very short time, and the pressure inside the MIG is the operating pressure;

[0144] ④ Neglect the changes in gas kinetic energy and gravitational potential energy between the gas and liquid phases;

[0145] ⑤ The gas is a single-component ideal gas.

[0146] When the MIR is operating in steady state, for the gas and liquid phases entering and exiting the MIG as a whole, since no external force does work and the process is adiabatic and isothermal, the following energy conservation relationship holds:

[0147] 0 = ΔE L +ΔE G +ρ L V L ε (23)

[0148] In equation (23), ΔE L and ΔE G The mechanical energy changes, W and V, represent the changes in mechanical energy during the entry and exit of liquid and gas into and from the MIG, respectively. L Let m be the volume of the liquid inside the MIG. 3 ;ρ L V Lε represents the energy dissipated by the liquid within the MIG, including internal energy and bubble surface energy. From equation (23), we can obtain:

[0149]

[0150] To derive the mathematical expression for ε, it is necessary to modify ΔE in equation (24). L ΔE G and V L The calculation expressions for the three key parameters are established respectively.

[0151] I. Change in fluid mechanical energy ΔE when entering and exiting the MIG L

[0152] When the MIR is operating in steady state, two fluids enter the MIG: fresh fluid (flow rate Q). L0 m 3 / s) and circulating liquid (flow rate Q) L1 m 3 / s). For circulating fluids, since they have already acquired a certain amount of energy within the MIG, their energy density can be considered constant before and after entering and exiting the MIG. Therefore, when the changes in hydrostatic energy and gravitational potential energy are negligible, the change in the mechanical energy of the fluid entering and exiting the MIG only considers the change in the kinetic energy of the fresh fluid. In the above... Figure 1 Under the conditions, Q L0 Since its initial kinetic energy is relatively small, it can be ignored. Therefore, the change in mechanical energy during the process of fresh liquid entering and exiting the MIG can be expressed as:

[0153]

[0154] The term in parentheses on the right side of equation (25) represents the average outflow velocity of the gas-liquid mixture at the MIG outlet. Where S1 is the cross-sectional area of ​​the MIG outlet, in meters... 2 Q G The actual flow rate of the gas inside the MIG, m 3 / s. Let the actual gas-liquid ratio inside the MIG be λ, that is:

[0155]

[0156] Therefore, equation (25) can be simplified to equation (27):

[0157]

[0158] When the reactor is operating in steady state, the liquid in its main component is forced to flow out of the reactor due to the introduction of gas. Therefore, the flow rate of the liquid flowing out of the reactor can be approximated as equal to the actual gas flow rate. Based on the law of conservation of energy, the circulating liquid flow rate Q... L1 It can be derived mathematically as follows:

[0159]

[0160] In Equation (28), S0(m 2 ) and H0(m) are the cross-sectional area and the inner cavity height of the reactor respectively. By联立方程(26)和(28),MIG内实际气液比λ可按方程(29)计算

[0161]

[0162] When λ is constant, from Equation (29), we can get:

[0163]

[0164] Since the value inside the square root must be no less than 0, Equation (30) should satisfy the condition:

[0165] λ < S0 / S1 or S1 < S0 / λ (31)

[0166] Inequality (31) indicates that when the cross-sectional area of the reactor is constant, to maintain a large gas-liquid ratio in the MIG, there is an upper limit value for the cross-sectional area of the MIG; when the reactor structure is constant, if the required gas-liquid ratio in the MIG is larger, the actual gas flow rate in the MIG should also be larger, and vice versa. Figure 2 It is the relationship diagram of the actual gas flow rate and the actual gas-liquid ratio in the MIG.

[0167] From Figure 2 it can be seen that the actual gas-liquid ratio in the MIG increases with the increase of the gas flow rate, but when the gas flow rate increases to a certain value, the influence of the gas flow rate on the gas-liquid ratio is small. Substituting Equation (30) into Equation (27), we can get:

[0168]

[0169] Equation (32) is the mathematical model of the change in the mechanical energy of the liquid flowing in and out of the MIG. Among them, the relationship between the actual gas-liquid ratio λ in the MIG and the gas-liquid ratio λ0 before entering the MIG should be clarified to facilitate the control of the actual operating conditions.

[0170] Since the gas is an ideal gas, therefore, the gas flow rate Q G0 (m 3 / s) before entering the MIG and the actual gas flow rate Q G in the MIG have the following relationship:[[ID= forty-five]]

[0171]

[0172] Substituting Equation (33) into Equation (30), we can get:

[0173]

[0174] Therefore, λ0 and λ have the following relationship:

[0175]

[0176] or,

[0177]

[0178] II. Changes in the mechanical energy of gases entering and exiting the MIG

[0179] Because of the low gas density, only the change in gas static pressure energy is considered during the process of gas entering the MIG and forming microbubbles. Let the initial gas flow rate and pressure entering the MIG be Q, respectively. G0 (m 3 / s) and P G0 (Pa), then the change in mechanical energy ΔE during the gas entering and exiting the MIG. G for

[0180] ΔE G =P G0 Q G0 ln(P m / P G0 (37)

[0181] because

[0182] P G0 =P m +ΔP (38)

[0183] therefore

[0184]

[0185] The following sections of this paper will explore the effect of operating pressure under a fixed gas-liquid ratio, but P m It affects the actual intake airflow within the MIG, namely:

[0186]

[0187] In equation (40), Q G * (m 3 / s) and P G * (1.01×10 5 Pa) represents the gas flow rate and supply pressure under standard conditions, respectively, and their values ​​are generally constant. To ensure that the actual gas-liquid ratio remains constant under changing operating pressure, let...

[0188]

[0189] Since the gas is an ideal gas, the actual gas flow rate Q in the reactor is... G for:

[0190]

[0191] From equations (41) and (42), we can obtain:

[0192]

[0193] From equations (34) and (43), we can obtain:

[0194]

[0195] Equation (44) shows that when the operating pressure P m When the required gas-liquid ratio λ is constant, k m It is certain. In other words, if P is changed... m When λ needs to be maintained at a constant value, the actual gas supply flow rate Q G0 Adjustments can be made according to equation (34). Combining equations (39), (41), and (44), we can obtain:

[0196]

[0197] Equation (45) is the expression for the change in mechanical energy of the gas inside the MIG. As can be seen from equation (45), the magnitude of the static pressure energy released by the gas is related to the initial gas pressure, operating pressure, actual gas-liquid ratio, and reactor structure.

[0198] III. Liquid volume inside the MIG

[0199] When the MIG volume V0(m 3 At a given time, V L and its liquid content φ L Relevant, namely:

[0200] V L =V0φ L (46)

[0201] φ L Determined by the gas-liquid ratio λ within the MIG, i.e.:

[0202]

[0203] From equations (46) and (47), we can obtain:

[0204]

[0205] Equation (48) is the formula for calculating the liquid volume inside the MIG. Among them, λ can be calculated by equation (36).

[0206] To maximize the release of the pressure energy released by the gas and break it into micron-sized bubbles, a certain amount of liquid is required as a medium. Equation (48) shows that the larger the gas-liquid ratio in the MIG, the smaller the actual amount of liquid in the MIG. Therefore, in order to ensure that there is an appropriate amount of liquid in the MIG for the maximum release of gas pressure energy, the actual gas-liquid ratio in the MIG should not be too large.

[0207] Substituting equations (32), (45), and (48) into equation (24), we get:

[0208]

[0209] The establishment of gas holdup φ for the slurry bed heavy oil micro-interface hydrogenation system G The mathematical modeling method is as follows:

[0210] φ G =v G / v 32 (50)

[0211] The method for establishing a mathematical model of the gas-liquid interface area 'a' for the slurry bed heavy oil micro-interface hydrogenation system is as follows:

[0212] a=6φ G / d 32 (51)

[0213] The gas-side mass transfer coefficient k was established for the slurry-bed heavy oil micro-interface hydrogenation system. G The mathematical modeling method is as follows:

[0214]

[0215] in:

[0216] D G The gas-phase diffusion coefficient is calculated according to the simplified Chapman-Enskog equation (53):

[0217]

[0218] In equation (53), M A υ is the molar mass of a hydrogen molecule, in g / mol. A Molar volume of a hydrogen molecule, cm 3 / mol.

[0219] t 32 (s) is the residence time of the bubble in the system, calculated according to equation (54):

[0220]

[0221] The liquid-side mass transfer coefficient k is established for the slurry-bed heavy oil micro-interface hydrogenation system. L The mathematical modeling method is as follows:

[0222] k L =D L / δ L (55)

[0223] in:

[0224] D L (m 2 / s) is the liquid phase diffusion coefficient of hydrogen in heavy oil, calculated according to the Wilke-Chang equation (56):

[0225]

[0226] In equation (56), χ is the association factor of heavy oil molecules, which can generally be taken as 1.

[0227] δ L (m) is the thickness of the bubble liquid film, calculated according to equation (57):

[0228] δ L ≈0.15d 32 / π (57)

[0229] The macroscopic reaction rate r for hydrodesulfurization of sulfur-containing asphaltenes in a slurry bed heavy oil micro-interface system. s The mathematical modeling method is as follows:

[0230]

[0231] In equation (58): H A (Pa·m 3 / mol) is the Henry's coefficient of hydrogen in heavy oil, which can be calculated according to equation (59):

[0232]

[0233] In equation (59), M1 is the molar mass of heavy oil, kg / mol.

[0234] In equation (58): k HDS Let m be the intrinsic reaction rate constant for the hydrodesulfurization reaction of sulfur-containing asphaltenes in heavy oil. 3 / mol) 0.5 / m 3 cat.s); C s0 The sulfur content in sulfur-containing asphaltenes in heavy oil feedstock, in mol / m 3 V c (m 3The volume of catalyst in the slurry-bed heavy oil hydrotreating reactor is calculated using equation (60):

[0235]

[0236] In equation (60), ρ c (kg / m 3 ) and w c (w / w) represents the catalyst density and the actual amount of catalyst used, respectively.

[0237] The desulfurization rate η of the hydrodesulfurization reaction of sulfur-containing asphaltene in the slurry bed heavy oil micro-interface system. s The method is as follows:

[0238]

[0239] The mathematical model parameters for the hydrodesulfurization rate of sulfur-containing asphaltenes in the above-mentioned slurry-bed heavy oil micro-interface enhanced reactor include the average diameter d of microbubbles in the slurry-bed heavy oil micro-interface hydrogenation system. 32 Microbubble rising velocity v 32 , gas content φ G Gas-liquid interphase area a, gas-side mass transfer coefficient k G and liquid-side mass transfer coefficient k L The macroscopic reaction rate r of hydrogenation desulfurization of sulfur-containing asphaltene s Desulfurization rate η of hydrodesulfurization reaction with sulfur-containing asphalt. s .

[0240] Furthermore, the mathematical model parameters for the hydrodesulfurization rate of sulfur-containing asphaltenes in the aforementioned slurry-bed heavy oil micro-interface enhanced reactor also include the energy dissipation rate of the micro-interface generator, the gas-phase diffusion coefficient, and the liquid-phase diffusion coefficient. The process parameters involved in the mathematical model for calculating the hydrodesulfurization rate of sulfur-containing asphaltenes are already described in existing technologies and will not be repeated here. This invention optimizes the calculation process to more reasonably calculate the desulfurization rate of sulfur-containing asphaltenes in the heavy oil hydrodesulfurization reaction in a slurry-bed micro-interface reactor.

[0241] Furthermore, the molar volume of hydrogen molecules is calculated according to equation (62):

[0242]

[0243] Among them, the critical parameter value of hydrogen (critical pressure P) c Critical temperature T c and critical molar volume V A,c As shown in Table 1:

[0244] Table 1 Critical parameters of hydrogen gas

[0245] substance <![CDATA[P c (Well)]]> <![CDATA[T c (K)]]> <![CDATA[V A,c (cm 3 / mol)]]> hydrogen <![CDATA[1.313×10 6 ]]> 33.19 64.147

[0246] Furthermore, the calculation of the physical properties of heavy oil feedstock, with the average molar mass as follows:

[0247] The carbon number and boiling point range of naphtha, diesel, and wax oil fractions are shown in Table 2.

[0248] Table 2. Carbon number and boiling point range of major fractions

[0249]

[0250] The third column in Table 2 shows the average boiling point T of the fractions estimated using the arithmetic mean method. b .

[0251] Once the boiling points T of each fraction are determined b Then, the molar mass of PNA can be calculated using the following three formulas:

[0252]

[0253]

[0254]

[0255] By combining the mass fraction of PNA in each fraction, the molar mass of each fraction can be calculated, and the average molar mass M of the system can be further obtained. B The average number of carbon atoms (NC) of the system can be determined based on the following relationship between the average molar mass and the number of carbon atoms.

[0256] M B =14NC-4 (66)

[0257] Other physical properties can be calculated using the following formula:

[0258]

[0259] Where θ is the physical property parameter to be calculated (such as specific gravity SG, critical pressure P). C Comparison temperature T r (etc.), the calculation methods for the other parameters are already recorded in the existing technology, and will not be described in detail here.

[0260] Furthermore, the calculation of the liquid phase dynamic viscosity of the heavy oil hydrotreating system is as follows:

[0261] For predicting the viscosity of petroleum fraction mixtures at any temperature, the API-TDB recommended equation (68).

[0262]

[0263] Among them, T F Temperature in Fahrenheit, TF =1.8T(K)-459.67, μ T (cP) and ρ T (g / cm 3 ( ) are respectively the temperature T R The dynamic viscosity and density of the petroleum fraction mixture, and the coefficients A and B, can be calculated using equations (69) and (70), respectively.

[0264] A = log 10 v0+0.8696 (69)

[0265] B = 0.28008 × log 10 v0+1.8616 (70)

[0266] Where v0(cST) is the kinematic viscosity of the petroleum fraction mixture at 100°F (310.93K). The specific gravity SG and average boiling point T of the mixture are... b When known, v0 can be calculated using equation (71).

[0267] v0 = v ref +v cor (71)

[0268] Furthermore, in equation (71) v ref and v cor They can be calculated according to the following equations (72) and (73) respectively.

[0269] logv ref = -1.35579 + 8.16059 × 10 -4 T bR +8.38505×10 -7 T bR 2 (72)

[0270] logv cor =A1+A2W (73)

[0271] In equation (72), T bR (Rankine scale) represents the average boiling point of a mixture, T. bR =1.8T(K). In equation (73), W is the Watson factor, which can be calculated according to equation (74).

[0272]

[0273] SG is the specific gravity of the mixture at 15.56℃ (60°F), which can be approximated by the easily determined specific gravity at 20℃. The coefficients A1 and A2 in equation (73) can be calculated using equations (75) and (76), respectively:

[0274] A1 = c1 + c2T bR +c3T bR 2 +c4T bR 3 (75)

[0275] A2=d1+d2T bR +d3T bR 2 +d4T bR 3 (76)

[0276] The coefficients in equations (72) and (73) have been recorded in the prior art and will not be described in detail here.

[0277] Furthermore, the intrinsic reaction rate constant for the hydrodesulfurization reaction of sulfur-containing asphaltene in the heavy oil hydrotreating system is calculated as follows:

[0278] Since the stoichiometric ratio of hydrogen (let's call it A) and sulfur-containing asphaltene (let's call it B) can be approximated as 1:1, the intrinsic reaction rate constant k of the hydrodesulfurization reaction of sulfur-containing asphaltene is... HDS This can be equivalent to the intrinsic reaction rate constant k of sulfur-containing asphaltene. B 0 k B 0 It can be calculated using equation (77):

[0279]

[0280] To facilitate subsequent calculations, the intrinsic reaction rate constants k of A and B are converted to volume and simplified in terms of units. HDS and k B This can be represented by equation (78):

[0281]

[0282] Where T represents the reaction temperature or operating temperature (assuming that the heat of reaction in the reactor is completely removed and the system maintains a constant operating temperature), and K represents the temperature at which the reaction occurs.

[0283] Based on the above analysis, this specification provides a method for determining the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry-bed heavy oil micro-interface enhanced reactor, such as... Figure 3 As shown, the method includes the following steps:

[0284] S10: Obtain reactor structural parameters, system physical property parameters, and operating parameters for the slurry bed heavy oil micro-interface enhancement reaction.

[0285] The reactor structural parameters include at least one of the following: the volume V0 of the micro-interface generator, the height H0 of the inner cavity of the slurry bed heavy oil hydrogenation reactor, the cross-sectional area S0 of the slurry bed heavy oil hydrogenation reactor, and the cross-sectional area S1 of the outlet of the micro-interface generator.

[0286] The system physical properties include at least one of the following: liquid phase density of the slurry bed heavy oil hydrogenation system, gas-liquid interfacial tension of the slurry bed heavy oil hydrogenation system, and liquid phase dynamic viscosity of the slurry bed heavy oil hydrogenation system.

[0287] Operating parameters include at least one of the following: operating pressure P m The pressure difference ΔP between the inside and outside of the micro-interface generator, and the volumetric flow rate Q of fresh heavy oil in the slurry bed heavy oil hydrotreating reactor. L0 The gas-liquid ratio λ inside the micro-interface generator.

[0288] S20: Calculate the energy dissipation rate based on the reactor structural parameters, system physical property parameters, and operating parameters.

[0289] Specifically, the energy dissipation rate can be calculated according to the above formula (49).

[0290] In formula (49), ε represents the energy dissipation rate within the micro-interface generator, W / kg; λ represents the gas-liquid ratio within the micro-interface generator; ρ L This represents the liquid phase density of a slurry-bed heavy oil hydrogenation system, in kg / m³. 3 V0 represents the volume of the micro-interface generator, in meters. 3 g represents the acceleration due to gravity, 9.81 m / s². 2 H0 represents the internal height of the slurry-bed heavy oil hydrotreating reactor, in meters (m); S0 represents the cross-sectional area of ​​the slurry-bed heavy oil hydrotreating reactor, in square meters (m²). 2 S1 represents the cross-sectional area of ​​the micro-interface generator outlet, in m³. 2 ;P m Q represents the operating pressure, Pa; ΔP represents the pressure difference between the inside and outside of the micro-interface generator, Pa; L0 The volumetric flow rate of fresh heavy oil in a slurry bed heavy oil hydrotreating reactor is expressed in m³. 3 / s.

[0291] S30: Calculate the bubble size based on the energy dissipation rate.

[0292] Specifically, the bubble size can be calculated using the formulas (20), (21) and (22) above.

[0293] In formulas (20)-(22), d 32 The diameter of the bubbles in a slurry bed heavy oil micro-interface hydroenhanced reactor is expressed in meters (m). max d min σ represents the maximum and minimum bubble diameters within the micro-interface generator, in meters (m);L The interfacial tension of the gas-liquid interface in a slurry bed heavy oil hydrogenation system is expressed in N / m; ρ L This represents the liquid phase density of a slurry-bed heavy oil hydrogenation system, in kg / m³. 3 μ L ε represents the dynamic viscosity of the liquid phase in the slurry bed heavy oil hydrogenation system, Pa·s; ε represents the energy dissipation rate in the micro-interface generator, W / kg.

[0294] S40: Calculate the rising velocity of a single bubble in an infinitely large static liquid phase based on the bubble size.

[0295] Specifically, the rising velocity of a single bubble in an infinitely large static liquid phase can be calculated using the formulas (17)-(19) above.

[0296] In formulas (17)-(19), v0 represents the rising velocity of a single bubble in an infinitely large static liquid phase, m / s; g represents the acceleration due to gravity, 9.81 m / s². 2 μ L The ρ represents the liquid phase dynamic viscosity of the slurry bed heavy oil hydrotreating system, in Pa·s. L This represents the liquid phase density of a slurry-bed heavy oil hydrogenation system, in kg / m³. 3 ;σ L The d represents the interfacial tension between gas and liquid in a slurry bed heavy oil hydrogenation system, in N / m. 32 The K value represents the bubble diameter in a slurry bed heavy oil micro-interface hydroenhanced reactor, in meters (m). b c and n represent empirical constants. For heavy oil hydrogenation systems, c can take a value of 1.2 and n can take a value of 1.4.

[0297] S50: Calculate the average rising velocity of microbubbles in the micro-interface system based on the rising velocity of a single bubble in an infinitely large static liquid phase.

[0298] Specifically, the average rising velocity of microbubbles in the micro-interface system can be calculated according to the above formulas (14)-(16).

[0299] In formulas (14)-(16), v 32 v0 represents the average rising velocity of microbubbles in the micro-interface system, in m / s; v0 represents the rising velocity of a single bubble in an infinitely large, still liquid, in m / s; v0 G V represents apparent gas velocity, m / s; L Q represents the apparent liquid velocity, in m / s; G The volumetric flow rate of hydrogen at the inlet of a slurry-bed heavy oil hydrotreating reactor, expressed in m³. 3 / s;Q L The volumetric flow rate of heavy oil at the inlet of the slurry bed heavy oil hydrotreating reactor, in m³. 3 / s.

[0300] S60: Calculate the gas holdup in the micro-interface enhanced reactor based on the average rising velocity of microbubbles in the micro-interface system.

[0301] Specifically, the gas holdup in the micro-interface enhanced reactor can be calculated according to the above formula (50).

[0302] In formula (50), φ G The gas holdup in the micro-interface enhanced reactor is expressed as %; v G V represents apparent gas velocity, m / s; 32 This represents the average rising speed of microbubbles in the micro-interface system.

[0303] S70: Calculate the gas-liquid interface area, gas-side mass transfer coefficient, and liquid-side mass transfer coefficient based on the bubble size.

[0304] Specifically, the gas-liquid interfacial area can be calculated according to the above formula (51). In formula (51), a represents the gas-liquid interfacial area, m 2 ;φ G The gas holdup in the micro-interface enhanced reactor is expressed as %; d 32 The value in meters represents the bubble diameter in a slurry bed heavy oil micro-interface hydrogenation enhanced reactor.

[0305] The gas-side mass transfer coefficient can be calculated using the above formula (52). In formula (52), k G The gas-side mass transfer coefficient is expressed in m / s; d 32 The diameter of the bubbles in a slurry bed heavy oil micro-interface hydroenhanced reactor is expressed in meters (m). 32 D represents the residence time of bubbles in the micro-interface system, expressed in seconds. G The gas-phase diffusion coefficient, m 2 / s.

[0306] The liquid-side mass transfer coefficient can be calculated using the formulas (55) and (57) above. In formula (55), k L D represents the liquid-side mass transfer coefficient, in m / s; L The liquid-phase diffusion coefficient of hydrogen in heavy oil is represented by m. 2 / s;δ L Let d represent the thickness of the bubble liquid film, in meters (m). In formula (57), d... 32 The value in meters represents the bubble diameter in a slurry bed heavy oil micro-interface hydrogenation enhanced reactor.

[0307] S80: The macroscopic reaction rate of the hydrodesulfurization reaction of sulfur-containing asphaltene in the micro-interface system, calculated based on the gas-side mass transfer coefficient and the liquid-side mass transfer coefficient.

[0308] Specifically, the macroscopic reaction rate of the hydrodesulfurization reaction of sulfur-containing asphaltene in the micro-interface system can be calculated according to the above formula (58).

[0309] In formula (58), r s P represents the macroscopic reaction rate. m Indicates operating pressure, Pa; H A The Henry's law representing the concentration of hydrogen in heavy oil, expressed in Pa·m. 3 / mol;k G The gas-side mass transfer coefficient is expressed in m / s; k L The value represents the liquid-side mass transfer coefficient, in m / s; a represents the gas-liquid interface area, in m². 2 ;k HDS The intrinsic reaction rate constant (m) represents the hydrodesulfurization reaction of sulfur-containing asphaltenes in heavy oil. 3 / mol) 0.5 / m 3 cat.s); C s0 This indicates the sulfur content in the sulfur-containing asphaltenes of heavy oil feedstock, in mol / m³. 3 V C This indicates the catalyst volume in a slurry-bed heavy oil hydrotreating reactor, in m. 3 Q L0 The volumetric flow rate of heavy oil at the inlet of the slurry bed heavy oil hydrotreating reactor, in m³. 3 / s.

[0310] S90: Calculate the desulfurization rate based on the macroscopic reaction rate.

[0311] Specifically, the desulfurization rate can be calculated according to the above formula (61).

[0312] In formula (61), η s H0 represents the desulfurization rate; H0 represents the height of the slurry bed heavy oil hydrotreating reactor, in meters; S0 represents the cross-sectional area of ​​the slurry bed heavy oil hydrotreating reactor, in meters. 2 ;r s Indicates the macroscopic reaction rate; Q L0 The volumetric flow rate of heavy oil at the inlet of the slurry bed heavy oil hydrotreating reactor, in m³. 3 / s;C s0 This indicates the sulfur content in the sulfur-containing asphaltenes of heavy oil feedstock, in mol / m³. 3 .

[0313] This manual provides a method for determining the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry-bed heavy oil micro-interface enhanced reactor. It innovatively establishes a physical model for the micro-interface unit of the slurry-bed heavy oil hydrotreating micro-interface reactor, applicable to both purely pneumatic and purely hydraulic or gas-liquid combined operation conditions. Based on this physical model, a mathematical model for the energy dissipation rate is derived. This mathematical model can then be used to further calculate the bubble size d. 32 The average rising velocity v of microbubbles in the micro-interface system 32The desulfurization rate can be calculated by considering factors such as gas holdup, gas-liquid interphase area, gas-side mass transfer coefficient, and liquid-side mass transfer coefficient. Based on these calculation models, the effects of relevant factors on the hydrodesulfurization process parameters of sulfur-containing asphaltene in the slurry-bed heavy oil micro-interface enhanced reactor, as well as their impact on the calculated hydrodesulfurization rate, can be more effectively analyzed by adjusting operating pressure, liquid hourly space velocity, or hydrogen-to-oil ratio. This allows for the optimization of the slurry-bed heavy oil micro-interface enhanced hydrogenation reaction.

[0314] In some embodiments, the method for determining the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry bed heavy oil micro-interface enhanced reactor provided in this specification further includes the following steps S100 and S110.

[0315] S100: In the hydrodesulfurization reaction of sulfur-containing asphaltene in a slurry bed heavy oil micro-interface enhanced reactor, the following parameters were adjusted: operating pressure, liquid hourly space velocity (LISH), and hydrogen-to-oil ratio. Based on the adjusted parameters, the process parameters and hydrodesulfurization rate of sulfur-containing asphaltene in the slurry bed heavy oil micro-interface system were calculated. Based on the calculation results, the influence of operating pressure, LISH, and hydrogen-to-oil ratio on the process parameters and hydrodesulfurization rate of sulfur-containing asphaltene in the slurry bed heavy oil micro-interface system were determined.

[0316] S110: Determine the target design parameters for the slurry bed heavy oil hydrogenation micro-interface reactor based on the aforementioned influence laws.

[0317] The target design parameters mentioned above may include at least one of the following: reactor height, reactor cross-sectional area, heavy oil density, heavy oil molar mass, operating pressure, operating temperature, liquid hourly space velocity, and hydrogen-to-oil ratio.

[0318] According to the two embodiments above Figures 4 to 24 Based on the observed patterns and actual needs, the target design parameters for the slurry bed heavy oil hydrogenation micro-interface reactor are determined.

[0319] This invention simulates the interrelationships of various operating parameters involved in the micro-interface enhanced hydrogenation reaction of heavy oil in a slurry bed. See details below. Figures 4 to 24 As shown.

[0320] Figure 4 This is a schematic diagram illustrating the effect of the average number of carbon atoms in the liquid phase on the dynamic viscosity of the liquid phase, provided as an embodiment of the present invention.

[0321] Figure 5 This is a schematic diagram illustrating the effect of the average number of carbon atoms in the liquid phase on the gas-liquid interfacial tension, provided as an embodiment of the present invention.

[0322] Figure 6The operating pressure P provided in the embodiments of the present invention m For the average diameter d of the bubble Sauter 32 A diagram illustrating the impact. (From...) Figure 6 It can be seen that, with the operating pressure P m The increase of d 32 There has been some reduction, but the magnitude is not large.

[0323] Figure 7 The operating pressure P provided in the embodiments of the present invention m The average rising velocity v of bubbles in a slurry bed heavy oil hydrotreating reactor 32 A diagram illustrating the impact.

[0324] Figure 8 The operating pressure P provided in the embodiments of the present invention m The gas holdup φ in a slurry bed heavy oil hydrogenation reactor G A diagram illustrating the impact. Figure 8 It can be seen that φ G With P m It decreases as it increases.

[0325] Figure 9 The operating pressure P provided in the embodiments of the present invention m A schematic diagram showing the effect of the gas-liquid interface area 'a'. Figure 9 It can be seen that a follows P m The value of P gradually decreases as the bubbles in the system increase. However, the smaller the bubbles in the system, the lower the value of P. m The smaller the influence on the gas-liquid interface area 'a', the better.

[0326] Figure 10 The operating pressure P provided in the embodiments of the present invention m For the gas-side mass transfer coefficient k of the bubble G A diagram illustrating the impact. (From...) Figure 10 It can be seen that k in a slurry bed heavy oil hydrogenation reactor G With bubble size d 32 The decrease in d increases, especially when d increases. 32 When it is at the micrometer level, k G With d 32 The decrease was accompanied by a significant increase; Figure 10 It also shows that for macrobubbles with diameters on the order of millimeters, P m For k G The impact is relatively small for small interfaces, but more significant for micro-interface systems.

[0327] Figure 11 The operating pressure P provided in the embodiments of the present invention m Mass transfer coefficient k on the bubble-liquid side L Schematic diagram illustrating the influence of k in a slurry-bed heavy oil hydrotreating reactor. L With bubble size d32 The decrease in d increases, especially when d increases. 32 When it is at the micrometer level, k L With d 32 The decrease was accompanied by a significant increase; Figure 11 It also shows that for macrobubbles with diameters on the order of millimeters, P m For k L The impact is relatively small for small interfaces, but more significant for micro-interface systems.

[0328] Figure 12 The operating pressure P provided in the embodiments of the present invention m Regarding the liquid-side volumetric mass transfer coefficient k L A diagram illustrating the influence of 'a'. Figure 12 It can be seen that for d 32 For millimeter-scale macrobubble systems, k L a with P m The increase is slightly reduced; for slurry-bed heavy oil micro-interface hydrogenation systems, P... m For k L The effect of a is almost negligible. This indicates that reducing P... m The hydrogen dissolution rate of the slurry bed heavy oil micro-interface system was not significantly affected.

[0329] Figure 13 The operating pressure P provided in the embodiments of the present invention m The effect on the desulfurization rate of sulfur-containing asphalt. Figure 13 It can be seen that the desulfurization of sulfur-containing asphaltene in the slurry bed heavy oil hydrotreating system varies with d 32 The decrease leads to an increase. Because some sulfur atoms in sulfur-containing asphaltene molecules are difficult to remove through hydrogenation, the desulfurization rate during the hydrogenation process is unlikely to reach 100%. Figure 13 It also shows that the desulfurization rate of sulfur-containing asphaltene increases with P. m The increase is due to the rise in temperature, but this variation pattern applies to the bubble d in the slurry bed heavy oil micro-interface system. 32 Larger (d) 32 Greater than 5.0 mm) and smaller (d) 32 Cases smaller than 0.5 mm are not applicable; for slurry-bed heavy oil micro-interface reactors, when d 32 When the thickness is less than 0.5 mm, the desulfurization rate of sulfur-containing asphaltene is affected by P. m The impact is relatively small, so the operating pressure can be appropriately reduced while maintaining a high desulfurization rate of sulfur-containing asphalt.

[0330] Figure 14 The Liquid Time Space Velocity (LHSV) provided in this embodiment of the invention affects the average bubble rise velocity v of the slurry bed heavy oil micro-interface system. 32 A diagram illustrating the impact. (From...) Figure 14 It can be seen that LHSV affects v 32The impact is almost negligible.

[0331] Figure 15 The liquid hourly space velocity (LHSV) provided in this embodiment of the invention affects the gas holdup φ of the slurry bed heavy oil micro-interface system. G A diagram illustrating the impact. (From...) Figure 15 It can be seen that: (1) For the macrobubble system (d 32 (greater than 1.0 mm), d 32 For φ G The impact is relatively small, but φ G (2) For slurry bed heavy oil micro-interface systems, φ increases with increasing LHSV; G With d 32 The decrease in LHSV significantly increases the value of φ. G It also has an impact, but when d 32 When the diameter is small (e.g., less than 0.2 mm), LHSV affects φ. G The impact is limited.

[0332] Figure 16 This is a schematic diagram illustrating the effect of liquid time space velocity (LHSV) on the gas-liquid interface area 'a' in a slurry bed heavy oil system, as provided in an embodiment of the present invention. Figure 16 It can be seen that: (1) the gas-liquid interphase area a of the slurry bed heavy oil system increases with d 32 The decrease is accompanied by an increase, especially when the bubble size of the slurry bed heavy oil system increases. 32 When the size is in the micrometer range (less than 1.0 mm), the gas-liquid interphase area *a* of the system increases with *d*. 32 The decrease of d shows a rapid increasing trend; (2) Increasing LHSV is beneficial to increasing the gas-liquid interface area a of the slurry bed heavy oil hydrogenation macrobubble system; however, for the slurry bed heavy oil hydrogenation micro-interface system, the gas-liquid interface area a also increases with the increase of LHSV, but when d 32 When the size is small (e.g., less than 0.2 mm), the above-mentioned effects of LHSV are relatively small.

[0333] Figure 17 The liquid hourly space velocity (LHSV) provided in this embodiment of the invention affects the liquid-side volumetric mass transfer coefficient k of the slurry bed heavy oil system. L A diagram illustrating the influence of 'a'. Figure 17 It can be seen that LHSV is related to k L The influence of a Figure 16 Similarly, this indicates that the liquid-side volumetric mass transfer coefficient k in a slurry-bed heavy oil system... L The change in 'a' is mainly dominated by the gas-liquid interface area 'a'.

[0334] Figure 18 This is a schematic diagram illustrating the effect of liquid time space velocity (LHSV) on the desulfurization rate of sulfur-containing asphaltene in a slurry bed heavy oil system, provided in an embodiment of the present invention. Figure 18It can be seen that: (1) For the slurry bed heavy oil hydrotreating macrobubble system, LHSV has little effect on the desulfurization rate of sulfur-containing asphaltene in the slurry bed heavy oil system; (2) For the slurry bed heavy oil hydrotreating micro-interface system, the desulfurization of sulfur-containing asphaltene in the slurry bed heavy oil hydrotreating system decreases with the increase of LHSV, and vice versa.

[0335] Figure 19 The hydrogen-to-oil ratio comparison of the average bubble rise velocity v in the slurry bed heavy oil hydrogenation system provided in this embodiment of the invention 32 A diagram illustrating the impact. Figure 19 It can be seen that, regardless of whether it is a macrobubble system or a micro-interface system, the average bubble rise velocity v of hydrogen-oil compared to that of the slurry-bed heavy oil hydrotreating system is... 32 The impact is almost negligible.

[0336] Figure 20 The hydrogen-to-oil ratio of the slurry bed heavy oil hydrogenation system provided in this embodiment of the invention is used to compare the gas holdup φ. G A diagram illustrating the impact. (From...) Figure 20 It can be seen that increasing the hydrogen-to-oil ratio is beneficial to increasing the gas content of the system, and vice versa.

[0337] See Figure 21 The diagram shown illustrates the effect of the hydrogen-to-oil ratio on the gas-liquid interface area 'a' in a slurry-bed heavy oil hydrogenation system according to an embodiment of the present invention. Figure 21 It can be seen that increasing the hydrogen-to-oil ratio is beneficial to increasing the gas-liquid interphase area of ​​the system, and vice versa.

[0338] See Figure 22 As shown, the liquid-side mass transfer coefficient k of the hydrogen-to-oil ratio slurry bed heavy oil hydrogenation system provided in this embodiment of the invention is... L Schematic diagram of the impact; by Figure 22 It can be seen that the liquid-side mass transfer coefficient k of the hydrogen-oil ratio system is... L The impact is relatively small.

[0339] See Figure 23 As shown, the liquid-side volumetric mass transfer coefficient k of the hydrogen-to-oil ratio slurry-bed heavy oil hydrogenation system provided in this embodiment of the invention is... L A schematic diagram illustrating the influence of a; by Figure 23 It can be seen that the liquid-side mass transfer coefficient k of the hydrogen-oil ratio system is... L The impact is relatively small.

[0340] See Figure 24 The diagram shown illustrates the effect of the hydrogen-to-oil ratio on the desulfurization rate of sulfur-containing asphaltene in a slurry-bed heavy oil hydrotreating system, as provided in this embodiment of the invention. Figure 24It can be seen that: (1) for the slurry bed heavy oil hydrotreating macrobubble system, the hydrogen-to-oil ratio has little effect on the desulfurization rate of sulfur-containing asphaltenes in the slurry bed heavy oil system; (2) for the slurry bed heavy oil hydrotreating micro-interface system, the desulfurization rate of sulfur-containing asphaltenes in the slurry bed heavy oil hydrotreating system also decreases with the increase of the hydrogen-to-oil ratio, but when d 32 When the size is small (e.g., less than 0.2 mm), the above-mentioned effect of the hydrogen-oil ratio is relatively small.

[0341] Due to the extremely complex composition of heavy oil hydrotreating systems, this paper uses the hydrodesulfurization process of sulfur-containing asphaltenes as a model reaction. To theoretically investigate the impact of micro-interface enhancement technology on the hydrodesulfurization rate of sulfur-containing asphaltenes in this system, this invention first constructs a mathematical model for mass transfer and reaction structure-activity relationship regulation based on the heavy oil hydrotreating system in a slurry bed. Based on this, using the desulfurization reaction of the sulfur-containing asphaltenes component in the heavy oil as a model reaction, theoretical calculations are used to investigate the operating pressure P within the heavy oil hydrotreating slurry bed reactor. m The effects of liquid hourly space velocity (LHSV) and hydrogen-to-oil ratio on the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry bed heavy oil micro-interface enhancer are analyzed through examples, and the following conclusions are drawn:

[0342] 1. Under the investigated operating pressure P m Within the range (4-18 MPa), the hydrodesulfurization rate of sulfur-containing asphaltene increases with P. m The value increases with the increase of the gas bubble size; for slurry bed heavy oil hydrotreating micro-interface systems, when the gas bubble size is small, P increases. m The aforementioned effects are relatively small; therefore, reducing the bubble size in the above system can reduce P. m And maintain a high hydrodesulfurization rate of sulfur-containing asphalt.

[0343] 2. Within the investigated liquid hourly space velocity (LHSV) range (0.1-0.4 h⁻¹) -1 Within the slurry bed heavy oil hydrotreating micro-interface system, the hydrodesulfurization rate of sulfur-containing asphaltenes is much higher than that of the macrobubble system, increasing LHSV and decreasing the hydrodesulfurization rate of sulfur-containing asphaltenes in the slurry bed heavy oil hydrotreating micro-interface system.

[0344] 3. Within the investigated hydrogen-to-oil ratio range (400-1000), the hydrodesulfurization rate of sulfur-containing asphaltenes in the slurry bed heavy oil hydrotreating micro-interface system is much higher than that in the macrobubble system. When the bubble size of the system is small enough, the above-mentioned influence of the hydrogen-to-oil ratio is small or even negligible. Increasing the hydrogen-to-oil ratio increases the hydrodesulfurization rate of sulfur-containing asphaltenes in the slurry bed heavy oil hydrotreating micro-interface system.

[0345] This specification also provides a device for determining the hydrodesulfurization rate of sulfur-containing asphaltenes in a slurry-bed heavy oil micro-interface enhanced reactor, which can be used to achieve... Figure 3 The method for determining the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry-bed heavy oil micro-interface enhanced reactor is shown. (For example...) Figure 25As shown, the device includes an acquisition unit 10, a first calculation unit 20, a second calculation unit 30, a third calculation unit 40, a fourth calculation unit 50, a fifth calculation unit 60, a sixth calculation unit 70, a seventh calculation unit 80, and an eighth calculation unit 90.

[0346] The acquisition unit 10 is used to acquire the reactor structural parameters, system physical property parameters, and operating parameters of the slurry bed heavy oil micro-interface enhancement reaction.

[0347] The first calculation unit 20 is used to calculate the energy dissipation rate based on the reactor structural parameters, system physical property parameters, and operating parameters.

[0348] The second calculation unit 30 is used to calculate the bubble size based on the energy dissipation rate.

[0349] The third calculation unit 40 is used to calculate the rising velocity of a single bubble in an infinitely large static liquid phase based on the bubble size.

[0350] The fourth calculation unit 50 is used to calculate the average rising velocity of microbubbles in the micro-interface system based on the rising velocity of a single bubble in an infinitely large static liquid phase.

[0351] The fifth calculation unit 60 is used to calculate the gas holdup in the micro-interface enhanced reactor based on the average rising velocity of microbubbles in the micro-interface system.

[0352] The sixth calculation unit 70 is used to calculate the gas-liquid interface area, gas-side mass transfer coefficient, and liquid-side mass transfer coefficient based on the bubble size.

[0353] The seventh calculation unit 80 is used to calculate the macroscopic reaction rate of the hydrodesulfurization reaction of sulfur-containing asphaltene in the micro-interface system based on the gas-side mass transfer coefficient and the liquid-side mass transfer coefficient.

[0354] The eighth calculation unit 90 is used to calculate the desulfurization rate based on the macroscopic reaction rate.

[0355] In some embodiments, the energy dissipation rate is calculated based on the reactor structural parameters, system physical property parameters, and operating parameters, including calculating the energy dissipation rate according to the following formula:

[0356]

[0357] Where ε represents the energy dissipation rate within the micro-interface generator, W / kg; λ represents the gas-liquid ratio within the micro-interface generator; ρ L This represents the liquid phase density of a slurry-bed heavy oil hydrogenation system, in kg / m³. 3 V0 represents the volume of the micro-interface generator, in meters. 3 g represents the acceleration due to gravity, 9.81 m / s². 2H0 represents the internal height of the slurry-bed heavy oil hydrotreating reactor, in meters (m); S0 represents the cross-sectional area of ​​the slurry-bed heavy oil hydrotreating reactor, in square meters (m²). 2 S1 represents the cross-sectional area of ​​the micro-interface generator outlet, in m³. 2 ;P m Q represents the operating pressure, Pa; ΔP represents the pressure difference between the inside and outside of the micro-interface generator, Pa; L0 The volumetric flow rate of fresh heavy oil in a slurry bed heavy oil hydrotreating reactor is expressed in m³. 3 / s.

[0358] In some embodiments, the energy dissipation rate calculation formula is determined based on the following conditions: the MIR is in a continuous steady-state operating state; the gas-liquid mixing process in the MIG is adiabatic and isothermal; the gas depressurization process is completed instantaneously, and the pressure in the MIG is the operating pressure; the changes in gas kinetic energy and gravitational potential energy of the gas-liquid two phases are ignored; and the gas is a single-component ideal gas.

[0359] In some embodiments, the macroscopic reaction rate of the hydrodesulfurization reaction of sulfur-containing asphaltene in the micro-interface system is calculated based on the gas-side mass transfer coefficient and the liquid-side mass transfer coefficient, including calculating the macroscopic reaction rate according to the following formula:

[0360]

[0361] Where, r s P represents the macroscopic reaction rate. m Indicates operating pressure, Pa; H A The Henry's law representing the concentration of hydrogen in heavy oil, expressed in Pa·m. 3 / mol;k G The gas-side mass transfer coefficient is expressed in m / s; k L The value represents the liquid-side mass transfer coefficient, in m / s; a represents the gas-liquid interface area, in m². 2 ;k HDS The intrinsic reaction rate constant (m) represents the hydrodesulfurization reaction of sulfur-containing asphaltenes in heavy oil. 3 / mol) 0.5 / m 3 cat.s); C s0 This indicates the sulfur content in the sulfur-containing asphaltenes of heavy oil feedstock, in mol / m³. 3 V C This indicates the catalyst volume in a slurry-bed heavy oil hydrotreating reactor, in m. 3 Q L0 The volumetric flow rate of heavy oil at the inlet of the slurry bed heavy oil hydrotreating reactor, in m³. 3 / s.

[0362] In some embodiments, before calculating the macroscopic reaction rate of the hydrodesulfurization reaction of sulfur-containing asphaltene in the micro-interface system based on the gas-side mass transfer coefficient and the liquid-side mass transfer coefficient, the method further includes: calculating the intrinsic reaction rate constant of the hydrodesulfurization reaction of sulfur-containing asphaltene according to the following formula:

[0363]

[0364] Where, ρ c This indicates the density of the catalyst, in kg / m³. 3 ;w c This indicates the catalyst density and actual amount of catalyst used, w / w; ρ L This represents the liquid phase density of a slurry-bed heavy oil hydrogenation system, in kg / m³. 3 T represents the reaction temperature or operating temperature.

[0365] In some embodiments, the liquid-side mass transfer coefficient is calculated according to the following formula:

[0366] k L =D L / δ L

[0367] δ L ≈0.15d 32 / π

[0368] Where, k L D represents the liquid-side mass transfer coefficient, in m / s; L The liquid-phase diffusion coefficient of hydrogen in heavy oil is represented by m. 2 / s;δ L The thickness of the bubble-liquid film is expressed in meters (m) and d. 32 The value in meters represents the bubble diameter in a slurry bed heavy oil micro-interface hydrogenation enhanced reactor.

[0369] In some embodiments, calculating the rising velocity of a single bubble in an infinitely large static liquid phase based on the bubble size includes calculating the rising velocity of a single bubble in an infinitely large static liquid phase according to the following formula:

[0370]

[0371] Mo = gμ L 4 / ρ L σ L 3

[0372] d e '=d 32 (ρ L g / σ L ) 1 / 2

[0373] Where v0 represents the rising velocity of a single bubble in an infinitely large, static liquid phase, in m / s; and g represents the acceleration due to gravity, 9.81 m / s². 2 μ L The ρ represents the liquid phase dynamic viscosity of the slurry bed heavy oil hydrotreating system, in Pa·s. L This represents the liquid phase density of a slurry-bed heavy oil hydrogenation system, in kg / m³. 3 ;σ L The d represents the interfacial tension between gas and liquid in a slurry bed heavy oil hydrogenation system, in N / m. 32 The K value represents the bubble diameter in a slurry bed heavy oil micro-interface hydroenhanced reactor, in meters (m). b c and n represent empirical constants.

[0374] In some embodiments, the apparatus further includes a first determining unit and a second determining unit.

[0375] The first determining unit is used to adjust the following parameters during the hydrodesulfurization reaction of sulfur-containing asphaltene in a slurry-bed heavy oil micro-interface enhanced reactor: operating pressure, liquid hourly space velocity (LISH), and hydrogen-to-oil ratio. Based on the adjusted parameters, it calculates the process parameters and hydrodesulfurization rate of sulfur-containing asphaltene in the slurry-bed heavy oil micro-interface system. Based on the calculation results, it determines the influence of operating pressure, LISH, and hydrogen-to-oil ratio on the process parameters and hydrodesulfurization rate of sulfur-containing asphaltene in the slurry-bed heavy oil micro-interface system.

[0376] The second determining unit is used to determine the values ​​of the target design parameters for the slurry bed heavy oil hydrogenation micro-interface reactor based on the aforementioned influence laws.

[0377] The description and function of the above-mentioned device can be understood by referring to the section on the determination method of sulfur-containing asphaltene hydrodesulfurization rate in slurry bed heavy oil micro-interface enhanced reactor, and will not be repeated here.

[0378] This invention also provides an electronic device, such as... Figure 26 As shown, the electronic device may include a processor 2601 and a memory 2602, wherein the processor 2601 and the memory 2602 may be connected via a bus or other means. Figure 26 Taking the example of a connection between China and Israel via a bus.

[0379] Processor 2601 can be a central processing unit (CPU). Processor 2601 can also be other general-purpose processors, digital signal processors (DSPs), application-specific integrated circuits (ASICs), field-programmable gate arrays (FPGAs), or other programmable logic devices, discrete gate or transistor logic devices, discrete hardware components, or combinations of the above types of chips.

[0380] Memory 2602, as a non-transitory computer-readable storage medium, can be used to store non-transitory software programs, non-transitory computer-executable programs, and modules, such as the program instructions / modules corresponding to the method for determining the hydrodesulfurization rate of sulfur-containing asphaltene in the slurry bed heavy oil micro-interface enhanced reactor in this embodiment of the invention (e.g., Figure 25 The acquisition unit 10, first calculation unit 20, second calculation unit 30, third calculation unit 40, fourth calculation unit 50, fifth calculation unit 60, sixth calculation unit 70, seventh calculation unit 80, and eighth calculation unit 90 are shown. The processor 2601 executes various functional applications and data processing by running non-transitory software programs, instructions, and modules stored in the memory 2602, thereby realizing the method for determining the hydrodesulfurization rate of sulfur-containing asphaltene in the slurry bed heavy oil micro-interface enhanced reactor in the above method embodiment.

[0381] The memory 2602 may include a program storage area and a data storage area. The program storage area may store the operating system and applications required for at least one function; the data storage area may store data created by the processor 2601, etc. Furthermore, the memory 2602 may include high-speed random access memory and may also include non-transitory memory, such as at least one disk storage device, flash memory device, or other non-transitory solid-state storage device. In some embodiments, the memory 2602 may optionally include memory remotely located relative to the processor 2601, and these remote memories may be connected to the processor 2601 via a network. Examples of such networks include, but are not limited to, the Internet, corporate intranets, local area networks, mobile communication networks, and combinations thereof.

[0382] The one or more modules are stored in the memory 2602, and when executed by the processor 2601, they perform the following: Figure 1 The method for determining the hydrodesulfurization rate of sulfur-containing asphaltene in the slurry bed heavy oil micro-interface enhanced reactor shown in the embodiment.

[0383] The specific details of the above-mentioned electronic device can be understood by referring to the relevant descriptions and effects in the method embodiments, and will not be repeated here.

[0384] This specification also provides a computer storage medium storing computer program instructions, which, when executed, implement the steps of the method for determining the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry bed heavy oil micro-interface enhanced reactor described above.

[0385] This specification also provides a computer program product comprising a computer program that, when executed by a processor, implements the steps of the method for determining the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry bed heavy oil micro-interface enhanced reactor described above.

[0386] Those skilled in the art will understand that all or part of the processes in the methods of the above embodiments can be implemented by a computer program instructing related hardware. The program can be stored in a computer-readable storage medium, and when executed, it can include the processes of the embodiments of the above methods. The storage medium can be a magnetic disk, optical disk, read-only memory (ROM), random access memory (RAM), flash memory, hard disk drive (HDD), or solid-state drive (SSD), etc.; the storage medium can also include combinations of the above types of memory.

[0387] The various embodiments in this specification are described in a progressive manner. For the same or similar parts between the various embodiments, please refer to each other. The focus of each embodiment is to describe the differences from other embodiments.

[0388] The systems, devices, modules, or units described in the above embodiments can be implemented by computer chips or entities, or by products with certain functions.

[0389] For ease of description, the above devices are described separately by function as various units. Of course, in implementing this application, the functions of each unit can be implemented in one or more software and / or hardware.

[0390] As can be seen from the above description of the embodiments, those skilled in the art can clearly understand that this application can be implemented by means of software plus necessary general-purpose hardware platforms. Based on this understanding, the technical solution of this application, in essence, or the part that contributes to the prior art, can be embodied in the form of a software product. This computer software product can be stored in a storage medium, such as ROM / RAM, magnetic disk, optical disk, etc., and includes several instructions to cause a computer device (which may be a personal computer, server, or network device, etc.) to execute certain parts of the methods of various embodiments of this application.

[0391] This application can be used in a wide variety of general-purpose or special-purpose computer system environments or configurations. For example: personal computers, server computers, handheld or portable devices, tablet devices, multiprocessor systems, microprocessor-based systems, set-top boxes, programmable consumer electronics devices, network PCs, minicomputers, mainframe computers, distributed computing environments including any of the above systems or devices, etc.

[0392] This application can be described in the general context of computer-executable instructions, such as program modules, that are executed by a computer. Generally, program modules include routines, programs, objects, components, data structures, etc., that perform a specific task or implement a specific abstract data type. This application can also be practiced in distributed computing environments where tasks are performed by remote processing devices connected via a communication network. In distributed computing environments, program modules can reside in local and remote computer storage media, including storage devices.

[0393] Although this application has been described through embodiments, those skilled in the art will know that this application has many modifications and variations without departing from the spirit of this application, and it is intended that the appended claims cover such modifications and variations without departing from the spirit of this application.

Claims

1. A method for determining the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry-bed heavy oil micro-interface enhanced reactor, characterized in that, include: To obtain the reactor structural parameters, system physical property parameters, and operating parameters for the micro-interface enhancement reaction of slurry bed heavy oil; The energy dissipation rate is calculated based on the reactor structural parameters, system physical property parameters, and operating parameters. Calculate the bubble size based on the energy dissipation rate; Calculate the rising velocity of a single bubble in an infinitely large static liquid phase based on the bubble size; Calculate the average rising velocity of microbubbles in a micro-interface system based on the rising velocity of a single bubble in an infinitely large static liquid phase. The gas holdup in the micro-interface enhanced reactor is calculated based on the average rising velocity of microbubbles in the micro-interface system. Calculate the gas-liquid interphase area, gas-side mass transfer coefficient, and liquid-side mass transfer coefficient based on the bubble size; The macroscopic reaction rate of the hydrodesulfurization reaction of sulfur-containing asphaltene in the micro-interface system is calculated based on the gas-side mass transfer coefficient and the liquid-side mass transfer coefficient. The desulfurization rate is calculated based on the macroscopic reaction rate.

2. The method according to claim 1, characterized in that, The energy dissipation rate is calculated based on the reactor structural parameters, system physical property parameters, and operating parameters, including the calculation of the energy dissipation rate using the following formula: Where ε represents the energy dissipation rate within the micro-interface generator, W / kg; λ represents the gas-liquid ratio within the micro-interface generator; ρ L This represents the liquid phase density of a slurry-bed heavy oil hydrogenation system, in kg / m³. 3 V0 represents the volume of the micro-interface generator, in meters. 3 g represents the acceleration due to gravity, 9.81 m / s². 2 H0 represents the internal height of the slurry-bed heavy oil hydrotreating reactor, in meters (m); S0 represents the cross-sectional area of ​​the slurry-bed heavy oil hydrotreating reactor, in square meters (m²). 2 S1 represents the cross-sectional area of ​​the micro-interface generator outlet, in m³. 2 ;P m Q represents the operating pressure, Pa; ΔP represents the pressure difference between the inside and outside of the micro-interface generator, Pa; L0 The volumetric flow rate of fresh heavy oil in a slurry bed heavy oil hydrotreating reactor is expressed in m³. 3 / s.

3. The method according to claim 2, characterized in that, The energy dissipation rate calculation formula is determined based on the following conditions: The MIR operates in a continuous steady-state state. The gas-liquid mixing process inside the MIG is adiabatic and isothermal. The gas decompression process is completed instantaneously, and the pressure inside the MIG is the operating pressure; Neglecting the changes in gas kinetic energy and gravitational potential energy between the gas and liquid phases; The gas is a single-component ideal gas.

4. The method according to claim 1, characterized in that, The macroscopic reaction rate of the hydrodesulfurization reaction of sulfur-containing asphaltene in the micro-interface system is calculated based on the gas-side mass transfer coefficient and the liquid-side mass transfer coefficient, including the calculation of the macroscopic reaction rate according to the following formula: Where, r s P represents the macroscopic reaction rate. m Indicates operating pressure, Pa; H A The Henry's law representing the concentration of hydrogen in heavy oil, expressed in Pa·m. 3 / mol;k G The gas-side mass transfer coefficient is expressed in m / s; k L The value represents the liquid-side mass transfer coefficient, in m / s; a represents the gas-liquid interface area, in m². 2 ;k HDS The intrinsic reaction rate constant (m) represents the hydrodesulfurization reaction of sulfur-containing asphaltenes in heavy oil. 3 / mol) 0.5 / m 3 cat.s); C s0 This indicates the sulfur content in the sulfur-containing asphaltenes of heavy oil feedstock, in mol / m³. 3 V C This indicates the catalyst volume in a slurry-bed heavy oil hydrotreating reactor, in m. 3 Q L0 The volumetric flow rate of heavy oil at the inlet of the slurry bed heavy oil hydrotreating reactor, in m³. 3 / s.

5. The method according to claim 4, characterized in that, Before calculating the macroscopic reaction rate of the hydrodesulfurization reaction of sulfur-containing asphaltene in the micro-interface system based on the gas-side mass transfer coefficient and the liquid-side mass transfer coefficient, the following steps are also included: The intrinsic reaction rate constant for the hydrodesulfurization reaction of sulfur-containing asphaltenes can be calculated using the following formula: Where, ρ c This indicates the density of the catalyst, in kg / m³. 3 ;w c This indicates the catalyst density and actual amount of catalyst used, w / w; ρ L This represents the liquid phase density of a slurry-bed heavy oil hydrogenation system, in kg / m³. 3 T represents the reaction temperature or operating temperature.

6. The method according to claim 1, characterized in that, Calculate the liquid-side mass transfer coefficient using the following formula: k L =D L / d L d L ≈0.15d 32 / p Where, k L D represents the liquid-side mass transfer coefficient, in m / s; L The liquid-phase diffusion coefficient of hydrogen in heavy oil is represented by m. 2 / s;δ L The thickness of the bubble-liquid film is expressed in meters (m) and d. 32 The value in meters represents the bubble diameter in a slurry bed heavy oil micro-interface hydrogenation enhanced reactor.

7. The method according to claim 1, characterized in that, Calculating the rising velocity of a single bubble in an infinitely large static liquid phase based on bubble size includes calculating the rising velocity of a single bubble in an infinitely large static liquid phase using the following formula: Mo=gμ L 4 / r L s L 3 d e '=d 32 (r L g / s L ) 1 / 2 Where v0 represents the rising velocity of a single bubble in an infinitely large, static liquid phase, in m / s; and g represents the acceleration due to gravity, 9.81 m / s². 2 μ L The ρ represents the liquid phase dynamic viscosity of the slurry bed heavy oil hydrotreating system, in Pa·s. L This represents the liquid phase density of a slurry-bed heavy oil hydrogenation system, in kg / m³. 3 ;σ L The d represents the interfacial tension between gas and liquid in a slurry bed heavy oil hydrogenation system, in N / m. 32 The K value represents the bubble diameter in a slurry bed heavy oil micro-interface hydroenhanced reactor, in meters (m). b c and n represent empirical constants.

8. The method according to claim 1, characterized in that, The method further includes: In the hydrodesulfurization reaction of sulfur-containing asphaltene in a slurry bed heavy oil micro-interface enhanced reactor, the following parameters were adjusted: operating pressure, liquid hourly space velocity (LISH), and hydrogen-to-oil ratio. Based on the adjusted parameters, the process parameters and hydrodesulfurization rate of sulfur-containing asphaltene in the slurry bed heavy oil micro-interface system were calculated. The influence of operating pressure, LISH, and hydrogen-to-oil ratio on the process parameters and hydrodesulfurization rate of sulfur-containing asphaltene in the slurry bed heavy oil micro-interface system were determined based on the calculation results. Based on the aforementioned influence patterns, the target design parameters for the slurry-bed heavy oil hydrogenation micro-interface reactor were determined.

9. A device for determining the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry-bed heavy oil micro-interface enhanced reactor, characterized in that, include: The acquisition unit is used to acquire reactor structural parameters, system physical property parameters, and operating parameters for the micro-interface enhancement reaction of slurry bed heavy oil. The first calculation unit is used to calculate the energy dissipation rate based on the reactor structural parameters, system physical property parameters, and operating parameters. The second calculation unit is used to calculate the bubble size based on the energy dissipation rate; The third calculation unit is used to calculate the rising velocity of a single bubble in an infinitely large static liquid phase based on the bubble size. The fourth calculation unit is used to calculate the average rising velocity of microbubbles in the micro-interface system based on the rising velocity of a single bubble in an infinitely large static liquid phase. The fifth calculation unit is used to calculate the gas holdup in the micro-interface enhanced reactor based on the average rising velocity of microbubbles in the micro-interface system. The sixth calculation unit is used to calculate the gas-liquid interphase area, gas-side mass transfer coefficient, and liquid-side mass transfer coefficient based on the bubble size. The seventh calculation unit is used to calculate the macroscopic reaction rate of the hydrodesulfurization reaction of sulfur-containing asphaltene in the micro-interface system based on the gas-side mass transfer coefficient and the liquid-side mass transfer coefficient. The eighth calculation unit is used to calculate the desulfurization rate based on the macroscopic reaction rate.

10. An electronic device, characterized in that, include: The system includes a memory and a processor, which are interconnected. The memory stores computer instructions, and the processor executes these computer instructions to implement the method for determining the hydrodesulfurization rate of sulfur-containing asphaltene in a slurry bed heavy oil micro-interface enhanced reactor as described in any one of claims 1 to 8.

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