Method for catalytic upgrading of oil products with participation of methane and application thereof

Abstract

This application discloses a method and application for catalytic upgrading of oil products involving methane. The method includes the following steps: reacting a stream containing activated methane and feedstock oil under the action of a first catalyst to achieve a heavy hydrocarbon cracking A stream; subjecting the A stream to a hydroisomerization reaction under the action of a second catalyst to obtain a B stream containing fuel oil that meets aviation fuel requirements; performing gas-liquid separation on the B stream, and deacidifying and desulfurizing the gaseous stream to obtain a methane-recovered gaseous stream; recycling at least a portion of the methane-recovered gaseous stream back into the stream containing activated methane to participate in the reaction; and separating the liquid stream containing upgraded hydrocarbons to obtain the upgraded oil product. This application provides a catalytic upgrading platform with low hydrogen dependence, high feedstock tolerance, low coking, and high yield of high-quality aviation kerosene and clean fuels through the synergistic effect of upstream methane activation, tail gas recirculation (removal of acidic gases), and dual-bed functional separation.

Description

Technical Field

[0001] This application relates to a method and application of methane-involved catalytic upgrading of oil products, belonging to the field of oil product upgrading technology. Background Technology

[0002] The global aviation industry's efforts to decarbonize have driven the rapid development of sustainable aviation fuel (SAF) production pathways. Major commercial SAF routes include hydrotreated esters and fatty acids (HEFA) and Fischer-Tropsch synthesis (FT), both of which rely on large-scale hydrogen or syngas production. In traditional HEFA processes, renewable triglyceride feedstocks undergo deep hydrodeoxygenation and hydroisomerization using externally supplied hydrogen, typically consuming over 50-70 kg of hydrogen per ton of feedstock. The FT route similarly requires reforming and water-gas shift steps to generate syngas before fuel synthesis and upgrading. Therefore, current SAF technologies are constrained by hydrogen availability, infrastructure complexity, and sensitivity to natural gas prices and electricity costs.

[0003] Meanwhile, commonly used raw materials for producing SAF include waste cooking oil, triglyceride-based raw materials, heavy crude oil, vacuum residue, etc.; each raw material has its limitations in the application process.

[0004] I. Limitations of Renewable Oil Applications Waste cooking oils and other lipid-based renewable feedstocks contain high levels of oxygen, typically in the form of triglycerides and free fatty acids. When processed in conventional hydrotreating or hydrocracking units, these feedstocks exhibit: 1) rapid catalyst deactivation due to water formation and localized hot spots; 2) high hydrogen consumption during hydrodeoxygenation; 3) limited control over carbon chain length distribution (without vigorous cracking); and 4) difficulty in achieving sufficiently low freezing points without a radical hydroisomerization step. Studies attempting to replace hydrogen with alternative reducing agents or processes operating under inert atmospheres have resulted in incomplete deoxygenation, excessive coke formation, or poor liquid product quality. Therefore, the upgrading of renewable oils remains closely coupled with hydrogen-intensive refining infrastructure.

[0005] II. Challenges in the Application of Heavy Crude Oil and Residue Oil Heavy crude oil, vacuum residue, and bitumen derivatives contain high concentrations of heteroatoms (sulfur and nitrogen), metals (such as nickel and vanadium), polycyclic aromatic hydrocarbons, and asphaltenes and gums. These components poison hydrotreating catalysts, accelerate coke formation, and cause a rapid increase in pressure drop in fixed-bed reactors. Traditional residue upgrading technologies, such as delayed coking, viscous cracking, and slurry-phase hydrocracking, suffer from the following drawbacks: high coke yield, significant liquid product loss; poor selectivity for middle fractions; complex solids handling; high hydrogen consumption; and limited tolerance to feedstock fluctuations. Furthermore, fixed-bed hydrotreating units are generally unsuitable for directly processing such feedstocks (unless extensive pretreatment or a protective bed is installed, even then, their operational life is limited).

[0006] III. Methane-assisted or non-hydrogenation-free processes Methane has long been considered a potential high-temperature hydrogen carrier and radical stabilizer. However, previous attempts to utilize methane in liquid-phase hydrocarbon upgrading processes have primarily been limited to: thermal cracking environments; aromatization or light olefin production; or hydrogen generation based on indirect reforming. These methods have failed to demonstrate the following capabilities: selectively upgrading oxidized renewable oils to a range of hydrocarbons suitable for jet fuels; achieving deep demetallization and asphaltenes conversion of heavy crude oils; controlling coke formation under fixed-bed conditions; or meeting the cryogenic flowability and volatility specifications of aviation fuels. Furthermore, previous systems lacked integrated recycling strategies capable of maintaining a methane-containing reactive atmosphere within the upgrading reactor while stabilizing cracking intermediates.

[0007] Given the aforementioned limitations, there has long been a need for alternative SAF production processes that could reduce or eliminate dependence on external hydrogen while still meeting the stringent volatility, freezing point, and stability requirements of aviation turbine fuels.

[0008] The present invention aims to address these unmet needs by providing a methane-assisted, cycle-enhanced dual-bed catalytic upgrade system capable of producing sustainable aviation fuels and clean transportation fuels from low-value feedstocks. Summary of the Invention

[0009] According to one aspect of this application, a methane-involved catalytic reforming method for oil products is provided. This method, with the participation of activated methane, converts renewable oil, petrochemical crude oil, etc., into jet-range hydrocarbons and clean transportation fuels, while reducing dependence on external hydrogen supply.

[0010] The methane-based catalytic upgrading method for oil products is characterized by comprising the following steps: The A stream containing activated methane and feedstock oil are reformed and reacted under the action of a first catalyst to achieve heavy hydrocarbon cracking. The A stream is subjected to a hydroisomerization reaction under the action of a second catalyst to obtain a B stream containing fuel that meets aviation fuel requirements. The B stream is subjected to gas-liquid separation to obtain a gaseous stream and a liquid stream containing modified hydrocarbons; the gaseous stream is subjected to deacidification and desulfurization treatment to obtain a methane recovery gaseous stream; at least a portion of the methane recovery gaseous stream is recycled into a stream containing activated methane to participate in the reaction; The liquid stream containing modified hydrocarbons is separated to obtain modified oil products.

[0011] This application utilizes a recirculating enhanced reactive gas management system—continuously circulating methane-containing tail gas—to establish and maintain a hydrogen-transfer-rich reactive atmosphere throughout the oil refining process. This is achieved by intentionally catalytically activating methane before it contacts the liquid feedstock, generating active free radicals and hydrogen donors. Through a dual-catalyst stepwise reaction, the overall reaction is spatially separated and can be independently optimized. The synergistic effect of these three components—not merely the sum of their individual effects—combines to achieve deep deoxidation, demetallization, controlled cracking, hydroisomerization, and coke suppression. In traditional refining processes, these processes require large external hydrogen supplies or result in rapid catalyst deactivation.

[0012] Optionally, the concentration of methane in the stream containing activated methane is at least 40 vol.

[0013] Optionally, the gas-liquid ratio of the stream containing activated methane to the feedstock oil is 100-5000 SCF / bbl.

[0014] Optionally, the pressure during the modification reaction and the hydroisomerization reaction is controlled at 2-10 MPa and the temperature is controlled at 350-450℃.

[0015] Optionally, the liquid hourly space velocity (LHSV) is controlled to be 0.2-2.0 h⁻¹ during the modification reaction and the hydroisomerization reaction. -1 .

[0016] Optionally, the catalyst bed volume ratio of the reforming reaction and the hydroisomerization reaction is from 50:50 to 85:15. Preferably, the catalyst bed volume ratio of the reforming reaction and the hydroisomerization reaction is from 60:40 to 80:20.

[0017] Optionally, the first catalyst comprises a metal-modified acidic molecular sieve catalyst; The modified metal element is selected from at least one of transition metals, main group metals, and lanthanides; Preferably, the transition metal is selected from at least one of Group IB, Group VIB, and Group VIIIB metals, and the main group metal is a Group IIIA metal.

[0018] Optionally, the first catalyst is a metal-modified HZSM-5 and / or a Beta zeolite catalyst; The modified metallic element includes at least one of cerium, molybdenum, cobalt, silver, gallium, nickel, and tungsten; Preferably, the modified metal element content in the first catalyst is: cerium 1-10 wt%, molybdenum 1-10 wt%, cobalt 1-10 wt%, silver 0.1-3 wt%, gallium 0-2 wt%.

[0019] More preferably, the modified metal element content in the catalyst is: 5 wt% cerium, 5 wt% molybdenum, 5 wt% cobalt, 1 wt% silver, and 0-1 wt% gallium.

[0020] Optionally, the second catalyst comprises a zeolite catalyst supported on transition metals and main group metals, and / or a platinum-containing isomerization catalyst. Preferably, the transition metal is a Group IIB metal and the main group metal is a Group IIIA metal.

[0021] Optionally, the second catalyst is a Beta zeolite catalyst supported on gallium and zinc, wherein the gallium loading is 0.1-2 wt% and the zinc loading is 1-10 wt%. In the platinum-containing isomerization catalyst, the platinum loading is 0.1-1.0 wt%.

[0022] Preferably, in the Beta zeolite catalyst supported on gallium and zinc, the gallium loading is 1 wt% and the zinc loading is 5 wt%.

[0023] Optionally, the hydrogen sulfide concentration in the methane recovery gaseous stream is less than 100 ppmv; Optionally, the recycle ratio of the methane recovery gaseous stream is 0.5 to 10. Preferably, the recycle ratio of the methane recovery gaseous stream is 1 to 5.

[0024] Optionally, the feedstock oil is derived from at least one of renewable oil, recycled renewable oil, and fossil oil.

[0025] Optionally, the stream containing activated methane is obtained by activating the methane-containing stream before the modification reaction; Alternatively, the stream containing activated methane is obtained by activating the methane-containing stream during the reforming reaction.

[0026] Optionally, the activation method is heating and / or catalytic activation using an activation catalyst; When the stream containing activated methane is obtained by activating the stream containing methane during the reforming reaction, and catalytic activation is performed using an activating catalyst, the catalytic activator is packed upstream of the first catalyst, or the catalytic activator is mixed with the first catalyst and packed in a single pack.

[0027] Optionally, the activation temperature is 350-550°C.

[0028] Another aspect of this application provides a methane-involved oil catalytic reforming system, characterized in that it comprises: A crude oil storage unit is used to store crude oil. The methane activation unit is used to activate a methane-containing stream to obtain a stream containing activated methane. The reforming reaction unit includes at least two catalytic beds arranged in series: The first catalytic bed is filled with a first catalyst, which is used to upgrade the feedstock oil in the presence of a stream containing activated methane to obtain the A stream of heavy hydrocarbon cracking. The second catalyst bed is filled with a second catalyst for hydroisomerizing the A stream to obtain a B stream that meets the requirements of aviation fuel. The separation unit is used to perform gas-liquid separation on the B stream to obtain a gaseous stream and a liquid stream containing modified hydrocarbons, and to separate the liquid stream containing modified hydrocarbons again to obtain the modified oil product.

[0029] Optionally, the methane activation unit independently activates the methane-containing stream; Alternatively, the methane activation unit may be integrated within the reforming reaction unit.

[0030] Optionally, the methane activation unit includes an activation catalyst packed upstream of or inside the first catalyst bed.

[0031] Optionally, the activated catalyst and the first catalyst are arranged in a layered configuration, with the activated catalyst located upstream of the first catalyst bed.

[0032] Optionally, the activated catalyst and the first catalyst are mixed and packed together to form the first catalyst bed.

[0033] Optionally, the separation unit includes a gas-liquid separation unit and a fractionation unit; The gas-liquid separation unit is used to separate the B stream into a gaseous stream and a liquid stream containing modified hydrocarbons. The inlet of the gas-liquid separation unit is connected to the outlet of the second catalytic bed via a pipeline; The gas outlet of the gas-liquid separation unit is connected to the feed inlet of the methane activation unit through a pipeline to form a methane recycling loop. The outlet of the gas-liquid separation unit is connected to the inlet of the fractionation unit via a pipeline. The fractionation unit is used to separate the product from the liquid stream containing modified hydrocarbons.

[0034] Optionally, the separation unit further includes a gas phase purification unit; The gas phase purification unit is located between the gas-liquid separation unit and the methane activation unit, and is used to remove acidic and corrosive gaseous substances from the gaseous stream.

[0035] A third aspect of this application provides an oil refining catalytic bed, characterized in that it comprises, in sequence: The first catalytic bed is filled with a first catalyst, which is used to upgrade the feedstock oil in the presence of a stream containing activated methane to obtain the A stream of heavy hydrocarbon cracking. The second catalyst bed is filled with a second catalyst for hydroisomerizing the A stream to obtain a B stream that meets the requirements of aviation fuel. A methane-activated catalyst bed is disposed upstream of the first catalyst bed; Alternatively, the first catalyst bed is mixed and packed with a first catalyst and a methane-activated catalyst; Alternatively, the first catalyst bed is sequentially layered with a methane-activated catalyst and a first catalyst.

[0036] Optionally, the volume ratio of the first catalyst bed to the second catalyst bed is 60:40 to 80:20.

[0037] Optionally, the first catalyst comprises a metal-modified acidic molecular sieve catalyst; The modified metal element is selected from at least one of transition metals, main group metals, and lanthanides; Preferably, the transition metal is selected from at least one of Group IB, Group VIB, and Group VIIIB metals, and the main group metal is a Group IIIA metal.

[0038] Optionally, the first catalyst is a metal-modified HZSM-5 and / or a Beta zeolite catalyst; The modified metallic element includes at least one of cerium, molybdenum, cobalt, silver, gallium, nickel, and tungsten; Preferably, the modified metal element content in the catalyst is: cerium 1-10 wt%, molybdenum 1-10 wt%, cobalt 1-10 wt%, silver 0.1-3 wt%, gallium 0-2 wt%.

[0039] Optionally, the second catalyst comprises a zeolite catalyst supported on transition metals and main group metals, and / or a platinum-containing isomerization catalyst. Preferably, the transition metal is a Group IIB metal and the main group metal is a Group IIIA metal.

[0040] Optionally, the second catalyst is a Beta zeolite catalyst supported on gallium and zinc, wherein the gallium loading is 0.1-2 wt% and the zinc loading is 1-10 wt%. In the platinum-containing isomerization catalyst, the platinum loading is 0.1-1.0 wt%.

[0041] Optionally, the first catalyst bed is also used to achieve deoxygenation and / or demetallization of the feedstock oil.

[0042] In a fourth aspect, this application provides a sustainable aviation fuel blending component, characterized in that it is obtained using the aforementioned methane-based oil catalytic reforming method, and the sustainable aviation fuel blending component has the following characteristics: a) Freezing point of -40°C or lower b) Oxygen content below 0.1 wt%, and c) Final boiling point not exceeding 300℃.

[0043] The beneficial effects that this application can produce include: 1. By using the method of this application for oil upgrading, the demand for external hydrogen supply for deoxygenation, saturation and stabilization reactions is significantly reduced or eliminated, and the capital expenditure related to hydrogen production, compression, storage and safety systems is reduced, enabling deployment and application in areas lacking large-scale hydrogen energy infrastructure. Compared with the hydrogen-intensive SAF pathway, it reduces life cycle greenhouse gas emissions.

[0044] 2. The method described in this application achieves deep demetallization and asphaltenes conversion under fixed-bed conditions. Compared with single-bed or single-pass reactor configurations, it significantly suppresses coke formation and converts most of the residue oil into naphtha and middle-range products. It also improves API density and viscosity to levels suitable for pipeline transportation and conventional refinery processing. In other words, the method described in this application can be directly used to obtain SAF blending components.

[0045] 3. The method of this application stabilizes the free radical intermediate through methane activation and recycling, and inhibits the condensation reaction that leads to coke formation. The protective bed function of the first catalyst layer traps metals and heavy aromatics before contact with the refined catalyst; the removal of acidic gases in the circulation loop prevents sulfur accumulation, protects the catalyst and compression equipment, and achieves longer online operating time and lower catalyst replacement frequency.

[0046] 4. The method of this application can be applied to a variety of raw materials, including renewable oils, acidified oils, animal fats, heavy crude oil, vacuum residue and mixed feedstocks; it can tolerate high levels of oxygen, metals, sulfur, nitrogen and asphaltenes, without the need for extensive pretreatment; by adjusting the operating conditions and fractionation cut-off points, it can switch between SAF production mode and heavy crude oil upgrading mode.

[0047] 5. The system of this application integrates the functions of modification, stabilization and isomerization in a single reactor vessel through spatially separated catalyst beds. In SAF applications, it eliminates the need for separate hydrogenation treatment and hydrogenation isomerization reactors. At the same time, it uses recycled process gas as the main reaction medium, which reduces the supply requirement of fresh gas and simplifies the process steps and equipment.

[0048] 6. In feedstock upgrading, the method and system of this application reduce hydrogen consumption, improve methane utilization efficiency, and lower operating costs; furthermore, the higher liquid fuel yield and lower coke yield also improve the overall process profitability. In addition, it can monetize low-value or problematic feedstocks (including waste oil and extra-heavy crude oil), supporting modular and distributed deployment at pilot, demonstration, and commercial scales, thus offering significant economic advantages.

[0049] 7. The method described in this application for the disposal of renewable oils and other materials realizes the value of waste cooking oil and refinery residues, reducing disposal needs; it reduces greenhouse gas emissions related to hydrogen production and coke formation; it reduces the sulfur and metal content in the final product, reduces downstream emissions and catalyst poisoning, and has good environmental benefits. Attached Figure Description

[0050] Figure 1 This is a schematic diagram of a methane-assisted feedstock oil reforming process according to this application; Figure 2 This is a schematic diagram of the structure of the reforming reaction unit in this application; Figure 3 This is a simulated distillation curve of the feedstock oil and the product oil after different process modifications in Example 3 of this application.

[0051] List of components and reference numerals: V-1, Feedstock Storage Unit; P-101, Feed Pump; P-102, Transfer Pump; C-101, Methane Compression Unit; C-102, Circulating Gas Compression Unit; H-101, Feed Heating Unit; R-101, Methane Activation Unit; R-102, Reforming Reaction Unit; S-101, Gas Phase Purification Unit; T-101, Fractionation Unit; V-101, Hot High-Pressure Separation Unit; V-103, Low-Pressure Separation Unit; D-1, First Catalyst Bed; D-2, Second Catalyst Bed. Detailed Implementation

[0052] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0053] Unless otherwise specified, the raw materials and catalysts used in the embodiments of this application were all purchased commercially.

[0054] According to one embodiment of this application, a methane-involved oil catalytic reforming system, such as... Figure 1 As shown, it includes: Crude oil storage unit V-1 is used to store crude oil; The methane activation unit R-101 is used to activate a methane-containing stream to obtain a stream containing activated methane. The reforming reaction unit R-102 includes at least two catalytic beds arranged in series. The first catalytic bed D-1 is filled with the first catalyst, which is used to upgrade the feedstock oil in the presence of a stream containing activated methane to obtain the A stream of heavy hydrocarbon cracking. The second catalytic bed D-2 is filled with a second catalyst for hydroisomerizing the A stream to obtain a B stream that meets the requirements of aviation fuel. The separation unit includes a gas-liquid separation unit and a fractionation unit; The gas-liquid separation unit is used to separate the B stream into a gaseous stream and a liquid stream containing modified hydrocarbons. The inlet of the gas-liquid separation unit is connected to the outlet of the second catalytic bed via a pipeline; The gas outlet of the gas-liquid separation unit is connected to the feed inlet of the methane activation unit R-101 through a pipeline to form a methane recycling loop; a gas phase purification unit is also provided between the gas-liquid separation unit and the methane activation unit R-101 to remove acidic and corrosive gaseous substances from the gaseous stream. The outlet of the gas-liquid separation unit is connected to the inlet of the fractionation unit T-101 via a pipeline. The fractionation unit T-101 is used to separate the product from the liquid stream containing modified hydrocarbons.

[0055] In some embodiments, the raw oil in the raw oil storage unit V-1 needs to be heated before it is pumped into the reforming reaction unit R-102 by the raw oil pump P-101. Therefore, a feed heating furnace H-101 is provided between the raw oil storage unit V-1 and the reforming reaction unit R-102 to heat the raw oil.

[0056] In some embodiments, the methane-containing stream is compressed by the methane compression unit C-101 and then fed into the methane activation unit R-101.

[0057] The process described in this application is applicable to a variety of hydrocarbon- and oxygen-containing feedstocks, including renewable sources, fossil sources, and mixed streams. Specific feedstocks include, but are not limited to: waste cooking oil (WCO); used frying oil and restaurant grease; animal fats and tallow; triglyceride-based vegetable oils (soybean oil, rapeseed oil, palm oil, linseed oil, jatropha oil); acidified oils and distillation residues from biodiesel production; heavy crude oil with an API gravity of 20 or less; extra-heavy crude oil and bitumen-derived oils; vacuum residue, atmospheric residue, and deasphalted oils; and mixtures of any of the above feedstocks.

[0058] In schemes using renewable oils as feedstocks, the feedstock typically contains 5-15 wt% oxygen, primarily in the form of triglycerides, fatty acids, and glycerides. Water content can range from 0.1 to 5 wt%, and free fatty acid content can range from 1 to 30 wt%.

[0059] In the implementation plan for heavy crude oil, the feedstock may contain: 1-7 wt% sulfur; 0.1-1 wt% nitrogen; 50-500 ppm metals (Ni + V); 5-25 wt% saturated carbon; and 5-20 wt% asphaltenes.

[0060] Prior to the introduction of the upgraded reactor, the feedstock may optionally undergo one or more of the following pretreatment steps: Filtration or sedimentation to remove particulate matter; dehydration; desalination; mild heat conditioning; mixing with light hydrocarbons.

[0061] The above pretreatment is optional and not necessary for the operation of this application, because the dual-catalytic bed architecture can tolerate large fluctuations in feedstock.

[0062] I. Methane Activation Unit In this application, the gas stream incorporating the methane activation unit comprises methane, and may further include: Recycle tail gas from the separation section; light hydrocarbons (C2-C4); hydrogen (0-30 vol%); inert gases (such as nitrogen) or carbon dioxide.

[0063] In a specific implementation, the gas stream preferably contains at least 40 vol% methane, and more preferably at least 60 vol% methane.

[0064] The methane activation unit is used to heat the gaseous stream to a temperature sufficient to induce partial activation of methane molecules before they come into contact with the liquid feed in the reforming reaction unit.

[0065] The control conditions for the methane activation process include: Temperature: 350-550℃, preferably 420-480℃; Pressure: 0.5-10 MPa; Gas hourly space velocity: 500-20000 h⁻¹ -1 .

[0066] Heating methods can include electric heaters, induction heating, flame heaters, or a combination of the above.

[0067] In some embodiments, the methane activation unit further includes a catalytic activation zone filled with an activation catalyst. The catalyst is selected to promote the formation of hydrogen donors, methyl radicals, or other reactive intermediates, while minimizing complete reforming or combustion of methane. In specific implementations, transition metal oxides, alumina or silica catalysts supported on noble metals, metal-doped zeolite or mixed metal oxide catalysts, etc., can be used. These activation catalysts are all commonly used methane activation catalysts in existing industries.

[0068] This application incorporates a dedicated methane activation unit upstream of the reforming reaction unit. This allows recycle gas and / or fresh methane to be heated and contacted with an activation catalyst at a high temperature before entering the liquid-phase upgrading zone. The methane activation unit typically operates at 350-550°C to: 1) partially activate methane molecules; 2) generate hydrogen donor fragments and free radicals; 3) pretreat the gas stream for rapid interactions with oxygen-containing compounds and heavy hydrocarbon molecules; and 4) reduce the harshness required by the reforming reaction unit. By activating methane before contact with the liquid feed, this application fundamentally differs from conventional processes where methane is either inert, combusted, or reformed externally. The pre-activated methane stream directly participates in the upgrading chemical reactions within the reforming reaction unit, achieving effective deoxygenation and stabilization without relying on an external hydrogen production unit.

[0069] This application achieves the following by setting up a methane activation unit upstream of the reforming reaction: generating active methane derivatives that can participate in hydrogen transfer reactions; increasing the effective reduction capacity of the gas phase; mitigating the temperature gradient in the reforming reaction unit; enabling the reforming reaction unit to operate at lower harshness; and promoting coke suppression by stabilizing cracked hydrocarbon fragments.

[0070] The activated gas stream can be directly introduced into the inlet of the modification reaction unit and mixed with the liquid feed; or it can be introduced through a separate gas distributor.

[0071] By activating methane prior to feedstock reforming, this application establishes a reaction environment fundamentally different from conventional hydrotreating, inert gas cracking, or reforming-based systems.

[0072] II. Modification Reaction Unit The structure of the reforming reaction unit is as follows:Figure 2 As shown, a fixed-bed reactor is preferably used, made of alloy steel suitable for high-temperature and high-pressure hydrocarbon applications. The reactor can be arranged vertically or horizontally and may include internal distributors for the liquid and gas phases, thermocouple sheaths for axial temperature monitoring, and pressure relief devices.

[0073] The reforming reaction unit is provided with at least two catalyst beds arranged in series, including: a first catalyst bed and a second catalyst bed; The first catalytic bed is used to upgrade the feedstock and acts as a sacrificial protective bed to capture metal contaminants and coke precursors, thereby protecting the downstream isomerization catalyst from premature deactivation. Therefore, it must achieve at least one or more functions: hydrodeoxygenation and decarboxylation of oxygen-containing species; removal of metals from nickel, vanadium and iron compounds; conversion of asphaltenes and gums; controlled cracking of high-boiling hydrocarbons; initial molecular reconstruction and saturation of unstable intermediates.

[0074] To achieve the above-mentioned effects, the first catalyst packed in the first catalyst bed is a metal-modified acidic molecular sieve catalyst; The catalyst support is selected from HZSM-5, Beta zeolite or a combination thereof, with a silicon-to-aluminum ratio (Si / Al) between 50 and 300.

[0075] The modified metal is selected from one or more combinations of cerium, molybdenum, cobalt, silver, gallium, nickel, and tungsten.

[0076] The loading of modified metals (as a percentage of the total catalyst by weight) is: cerium 1-10 wt%, molybdenum 1-10 wt%, cobalt 1-10 wt%, silver 0.1-3 wt%, gallium 0-2 wt%.

[0077] In some embodiments, the first catalyst is an HZSM-5 catalyst supported on 5 wt% cerium, 5 wt% molybdenum, 5 wt% cobalt, 1 wt% silver and 0-1 wt% gallium.

[0078] The catalysts in this application are all prepared by impregnation and loading, that is, the support is impregnated in a solution containing mixed metal salts, dried, calcined and reduced to obtain catalyst powder. In use, the catalyst powder is usually pressed into tablets with an appropriate amount of binder, and then crushed and sieved to the required mesh size for later use.

[0079] Specifically, the preparation method of the first catalyst can be as follows: Calculate the required amount of metal salts based on the metal loading in the scheme (Ce 5 wt%, Mo 5 wt%, Co 5 wt%, Ag 1 wt%, Ga 0-1 wt%), wherein the Ce source is cerium nitrate Ce(NO3)3·6H2O, and the Mo source is ammonium molybdate (NH4)6Mo7O. 24The Co source is cobalt nitrate Co(NO3)3·6H2O, the Ag source is silver nitrate AgNO3, and the Ga source is gallium nitrate Ga(NO3)3·9H2O. The above metal salts are dissolved in deionized water in stoichiometric proportions to prepare a mixed impregnation solution. The solution volume needs to be determined in advance by measuring the saturated water absorption of the support using an equal-volume impregnation method. The processed and dried HZSM-5 support is added to the prepared mixed impregnation solution and impregnated at room temperature with stirring for 6-12 h. After impregnation, the mixture is slowly evaporated to near dryness in a water bath at 80-100℃, and then dried overnight (approximately 12 h) in an oven at 110-120℃ to obtain the catalyst precursor. The catalyst precursor is placed in a muffle furnace and heated to 500-550℃ at a heating rate of 2-5℃ / min, and calcined in air atmosphere for 4-6 h; then reduced at 400-500℃ in a H2 / N2 mixed gas flow (e.g., 10% H2 / 90% N2) for 2-4 h to obtain the first catalyst powder.

[0080] The second catalytic bed is used for isomerization and purification. It is required to perform at least one or more functions: hydroisomerization of straight-chain alkanes; improvement of low-temperature flow properties, including freezing point; purification of residual oxygen-containing compounds; and stabilization of hydrocarbons in the jet stream.

[0081] To achieve the above-mentioned effects, the second catalyst packed in the second catalyst bed is a gallium-zinc modified Beta zeolite catalyst, wherein the gallium loading is 0.1-2 wt% and the zinc loading is 1-10 wt%. In a preferred embodiment, the gallium loading is 1 wt% and the zinc loading is 5 wt%.

[0082] In some alternative implementations, a noble metal isomerization catalyst is used, such as a platinum-supported SAPO-11 catalyst, a platinum-negative Beta zeolite catalyst, or a combination thereof; wherein the platinum loading is 0.1-1.0 wt%.

[0083] The preparation method of the second catalyst is basically the same as that of the first catalyst, except that when Beta zeolite is used as the support, the purchased support is pretreated to become an H-type support. The pretreatment method is a conventional method.

[0084] During implementation, these beds are physically separated, for example, by inert ceramic or alumina layers, to prevent mixing and allow for independent optimization of catalytic function. This spatial separation of modification and isomerization functions allows each bed in the modification reaction unit to independently control acidity and metal activity, reduces aromatization intensity in the isomerization zone, improves resistance to metal poisoning and scaling, enhances control over product boiling range and freezing point, and improves operational stability and catalyst lifetime.

[0085] By combining a dual-bed architecture with upstream methane activation and enhanced methane circulation gas management, the reforming reaction unit achieves oil reforming effects that cannot be achieved with a single-bed or pure hydrogen system.

[0086] The controlled conditions for the reforming reaction process include: temperature of 350-450℃ (which can be divided along the length of the reactor); pressure of 2-10 MPa; and liquid hourly space velocity (LHSV) of 0.2-2.0 h⁻¹. -1 The gas-liquid ratio is 100-5000 standard cubic feet per barrel (SCF / bbl) equivalent. Control conditions can be adjusted accordingly for different feedstock types or product quality targets.

[0087] In some embodiments, the control conditions of the modification reaction unit are as follows: Reactor inlet gas composition: methane 40-95 vol%; hydrogen 0-30 vol%; light hydrocarbons (C2-C4) 0-20 vol%; inert gases: 0-20 vol%.

[0088] Specifically, for a given raw material, the control conditions for the modification reaction process are as follows: ① Used for upgrading renewable oils to SAF: Temperature 380-430℃; Pressure 3-6 MPa; LHSV 0.5-1.2 h -1 The gas-liquid ratio of the feedstock containing activated methane is 1000-3000 SCF / bbl.

[0089] ② Used for upgrading heavy crude oil: Temperature: 400-450℃; Pressure: 4-8 MPa; LHSV: 0.2-0.8 h -1 The gas-liquid ratio of the feedstock containing activated methane is 1000-3000 SCF / bbl.

[0090] Furthermore, when used in SAF production, i.e., when product quality is the control objective, the reforming reaction is configured to produce jet-range hydrocarbon fractions with the following characteristics: Final boiling point ≤300℃; freezing point ≤ -40℃; oxygen content ≤0.1 wt%; sulfur content ≤10 ppm; calorific value ≥42MJ / kg.

[0091] III. Separation Unit The gas-liquid separation unit in the separation unit can be a high-pressure separation unit V-101, which separates the stream flowing out of the reforming reaction unit into a gas phase and a liquid phase. The liquid phase contains condensed liquid hydrocarbons and entrained water, while the gas phase contains methane, light hydrocarbons (C2-C4), in-situ generated hydrogen, carbon monoxide and carbon dioxide (in small amounts), and trace amounts of hydrogen sulfide or ammonia.

[0092] The liquid phase can be directly fed into the fractionation unit T-101 for oil separation based on boiling point differences, yielding different distillate products such as naphtha, diesel, and modified residue oil. In some embodiments, the liquid phase is further degassed in the low-pressure separation unit V-103 before being fed into the fractionation unit T-101.

[0093] The gas phase contains methane, which can be recovered and reintroduced into the system, forming a circulating loop for the recovered methane gaseous stream. This loop, combined with the upstream methane activation unit, maintains a methane-rich atmosphere in the reforming reaction unit. Since the gas phase contains acidic and corrosive substances including, but not limited to, carbon dioxide (CO2), hydrogen sulfide (H2S), carbonyl sulfide (COS), and trace amounts of thiols, these can be removed before circulation using the gas phase purification unit S-101. In practice, a wet gas scrubbing unit can be used, which may include: an amine absorption tower using aqueous solutions of alkanolamines (such as MEA, DEA, MDEA, or mixtures thereof); an alkaline aqueous solution scrubber using sodium hydroxide, potassium carbonate, or similar alkaline solutions; a physical solvent absorption system; and combinations of the above equipment. The purpose of gas phase purification is to reduce the concentration of acidic gases to a level compatible with downstream equipment and catalyst protection. Therefore, specific components should be controlled, for example: H2S concentration less than 10-100 ppmv; CO2 concentration reduced by 50-99% depending on the operating mode.

[0094] Purifying the gaseous methane recovery stream before it enters the circulation loop can reduce corrosion of the compression unit, pipelines, and heat exchangers, prevent the accumulation of acidic gases in the circulation loop, protect the downstream catalyst bed from sulfur poisoning, and improve the stability of methane activation performance.

[0095] The gas stream leaves the gas phase purification unit and is essentially free of condensable liquids and acidic contaminants before being sent to the compression stage.

[0096] In some embodiments, at least a portion of the purified methane recovery gaseous stream can be compressed by the circulating gas compression unit C-102 and then sent to the methane activation unit R-101 for circulation.

[0097] The gas phase obtained from degassing in the low-pressure separation unit V-103 can also be recycled and reintroduced into the system along the same path.

[0098] The circulation loop of the methane recovery gaseous stream can be equipped with flow control valves and pressure control valves to control the circulation ratio of the methane recovery gaseous stream. The circulation ratio can be from 0.5 to 10, preferably from 1 to 5. It should be noted that the circulation ratio of the methane recovery gaseous stream refers to the volumetric flow rate of the methane recovery gaseous stream divided by the volumetric flow rate of the fresh methane feed.

[0099] This application establishes a closed or semi-closed recirculation loop in which the gaseous effluent (containing methane and light hydrocarbons) from the reforming reaction unit is separated and returned to the process. The recirculated stream is compressed as needed and mixed with fresh methane to form a controlled reactive gas feed.

[0100] The above cyclic configuration: 1) increased the effective residence time of methane in the system; 2) stabilized the gas phase composition at the reactor inlet; 3) enhanced in-situ hydrogen transfer and free radical end-capping reaction; 4) inhibited olefin polymerization and coke formation; and 5) improved catalyst lifetime and liquid product yield.

[0101] Unlike single-pass inert or pure hydrogen gas operation, this loop establishes a continuous methane-assisted upgrade environment, substantially altering the reaction pathway within the catalyst bed.

[0102] Recycling the gaseous methane stream can stabilize the methane concentration at the reactor inlet, improve the effective utilization rate of methane, enhance the hydrogen transfer reaction, mitigate the temperature gradient within the catalyst bed, reduce the coke formation rate, and improve catalyst stability and operating life.

[0103] In summary, this application provides a catalytic upgrade platform for low hydrogen dependence, high feedstock tolerance, low coking, and high-yield high-quality jet fuel and clean fuel through the synergistic effect of upstream methane activation, tail gas recirculation (removal of acidic gases), and dual-bed functional separation. It is significantly superior to existing hydrotreating, cracking, and conventional methane-assisted processes in terms of technology, economy, and environment.

[0104] Converting waste cooking oil into a range of hydrocarbon compounds for sustainable aviation fuel. Raw waste cooking oil exhibits the following properties: Density (20℃): 923.2 kg / m³ 3 Viscosity (40℃) 63.5 mm 2 / s; Freezing point -16℃; Free fatty acid content 1.54 wt%; Total acid value 3.87 mg KOH / g; Oxygen content 12.63 wt%; Calorific value: 37.0 MJ / kg.

[0105] These values ​​are characteristic of highly oxygenated triglyceride-based feedstocks, which are unsuitable for direct use as transportation fuel.

[0106] Example 1 The process conditions configured in this embodiment are as follows: The reforming reaction unit is a fixed-bed reactor with a total catalyst volume of 600 mL. The first catalyst bed is 300 mL, and the catalyst is a metal-modified HZSM-5 catalyst (approximately 2 wt% Ce, 2 wt% Mo, 2 wt% Co, 0.5 wt% Ag, and 0.2 wt% Ga). The second catalyst bed is 300 mL, and the catalyst is a Ga-Zn modified Beta zeolite catalyst (approximately 0.5 wt% Ga and 2 wt% Zn).

[0107] An inert alumina layer was placed between the two beds.

[0108] Before entering the reactor, fresh methane and methane-rich gas recovered from the tail gas are heated to 400°C in a methane activation unit containing 250 mL of activating catalyst (Ni / Al2O3-based catalyst). The tail gas from the reforming reaction unit is separated, treated with CO2 and H2S removal in a wet scrubber, compressed, and then recycled to the inlet of the methane activation unit. The recycle ratio of the methane-rich gas recovered from the tail gas is maintained between 0.5 and 2 (relative to the volume of fresh methane), with a gas flow pressure of 0.5-3 MPa and a gas hourly space velocity of 500-1000 h⁻¹. -1 .

[0109] The reaction conditions of the reforming reaction unit are controlled as follows: reactor temperature 380-400℃; pressure approximately 3.5 MPa; LHSV 0.5-0.8 h⁻¹. -1 The reactor inlet methane concentration is >60 vol%; the gas-liquid ratio of the stream containing activated methane and the feedstock is 100-1000 SCF / bbl.

[0110] Example 2 The process conditions configured in this embodiment are as follows: The reforming reaction unit is a fixed-bed reactor with a total catalyst volume of 600 mL. The first catalyst bed is 500 mL, and the catalyst is a metal-modified Beta zeolite catalyst (10 wt% Ce, 10 wt% Mo, 10 wt% Co, 3 wt% Ag, 2 wt% Ga). The second catalyst bed is 100 mL, and the catalyst is a Ga-Zn modified Beta zeolite catalyst (2 wt% Ga and 10 wt% Zn).

[0111] An inert alumina layer was placed between the two beds.

[0112] Before entering the reactor, fresh methane and methane-rich gas recovered from the tail gas are heated to 480°C in a methane activation unit containing 250 mL of activating catalyst (Ni / Al2O3-based catalyst). The tail gas from the reforming reaction unit is separated, treated with CO2 and H2S removal in a wet scrubber, compressed, and then recycled to the inlet of the methane activation unit. The recycle ratio of the methane-rich gas recovered from the tail gas is maintained between 4 and 6 (relative to the volume of fresh methane), with a gas flow pressure of 7-10 MPa and a gas hourly space velocity of 1000-2000 h⁻¹. -1 .

[0113] The reaction conditions of the reforming reaction unit are controlled as follows: reactor temperature 420-430℃; pressure 6 MPa; LHSV 1.0-1.2 h⁻¹. -1 The reactor inlet methane concentration is >60 vol%; the gas-liquid ratio of the stream containing activated methane and the feedstock is 3500-5000 SCF / bbl.

[0114] Example 3 The reforming reaction unit is a fixed-bed reactor with a total catalyst volume of 600 mL. The first catalyst bed is 420 mL, and the catalyst is a metal-modified HZSM-5 catalyst (approximately 5 wt% Ce, 5 wt% Mo, 5 wt% Co, 1 wt% Ag, and 0-1 wt% Ga). The second catalyst bed is 180 mL, and the catalyst is a Ga-Zn modified Beta zeolite catalyst (approximately 1 wt% Ga and 5 wt% Zn).

[0115] An inert alumina layer was placed between the two beds.

[0116] Before entering the reactor, fresh methane and methane-rich gas recovered from the tail gas are heated to approximately 450°C in a methane activation unit containing 250 mL of activating catalyst (Ni / Al2O3-based catalyst). The tail gas from the reforming reaction unit is separated, treated with CO2 and H2S removal in a wet scrubber, compressed, and then recycled to the inlet of the methane activation unit. The recycle ratio of the methane-rich gas recovered from the tail gas is maintained between 1 and 3 (relative to the volume of fresh methane), with a gas flow pressure of 3-5 MPa and a gas hourly space velocity of 3000-5000 h⁻¹. -1 .

[0117] The reaction conditions of the reforming reaction unit are controlled as follows: reactor temperature 400-420℃; pressure approximately 5 MPa; LHSV 0.8-1.0 h⁻¹. -1 The reactor inlet methane concentration is >60 vol%; the gas-liquid ratio of the stream containing activated methane and the feedstock oil is 1000-3000 SCF / bbl.

[0118] Comparative Example 1 In this embodiment, the aforementioned waste edible oils are upgraded using a basic methane-assisted process. The process method used differs from that in this application in that: the methane in the tail gas is not recycled into the process; the methane is not activated before entering the upgrading reaction unit; and the upgrading reaction unit contains only one catalyst bed with identical catalyst composition, which can be understood as a mixture of catalysts.

[0119] In both processes, the reaction conditions and reactor volume remain the same.

[0120] Table 1 shows a comparison of the properties of untreated waste edible oil raw materials (WCO-raw materials) and the fuel products (WCO-products) produced under the processes of Example 3 and Comparative Example 1.

[0121] Table 1

[0122] As shown in Table 1, waste cooking oil has high oxygen content, is viscous, acidic, and has poor low-temperature flow properties, making it unsuitable for aviation or diesel applications. The basic methane-assisted process achieves significant deoxygenation and viscosity reduction; however, the product's freezing point remains critical (-32°C), acidity is still detectable, and the product density is still higher than typical jet fuel. This product is more suitable for diesel blending than aviation fuel. Compared to the basic methane-assisted process, the process in this application, through the introduction of upstream methane activation, tail gas recirculation, and dual catalytic bed access, results in a significant change in fuel quality: a lower freezing point exceeding 17°C; a viscosity reduction of approximately 70%; oxygen content reduced to below 0.05 wt%, approaching a complete hydrocarbon composition; acid value reduced to below the detectable limit; density within the typical aviation kerosene range; and low-temperature flow properties meeting or exceeding aviation fuel requirements.

[0123] Using petrochemical industry standard oil analysis methods, chromatographic simulation of true boiling point distillation was performed, and the results are as follows: Figure 3 As shown, WCO feedstock is a typical heavy oil, with almost all components having boiling points above 340℃, making it unsuitable for direct use as a light fuel (such as gasoline or diesel). The oil product after upgrading using a basic methane-assisted process has already achieved significant lightening, with the final boiling point decreasing from 620℃ to 360℃ and the 50% distillation temperature decreasing from 450℃ to 290℃, indicating that the heavy macromolecules have been cracked into smaller molecules. However, after modification using the method described in this application, the oil product is further lightened, with the final boiling point decreasing to 280℃ and the 50% distillation temperature to only 200℃. The fractions are entirely concentrated in the boiling point range of gasoline / naphtha (initial boiling point -200℃), achieving a complete conversion of heavy WCO feedstock into light fuel. In terms of fraction proportion, the method described in this application achieves 100% conversion of heavy components into light components, and the proportion of light fractions is significantly increased.

[0124] The aforementioned performance improvements can be attributed to the following synergistic effects: continuous transfer of methane-derived hydrogen driven by exhaust gas recirculation; free radical chemistry enhancement effect induced by upstream methane activation; and functional separation of deep quality improvement and isomerization reactions by the dual-catalyst bed.

[0125] The above comparison results prove that the integrated system of this application can directly convert waste cooking oil into sustainable aviation fuel blending components without relying on external hydrogen supply, and has fuel properties that cannot be achieved by basic methane-assisted process configurations.

[0126] Upgrading of heavy crude oil Heavy crude oil exhibits the following properties: Viscosity (50℃): 17500 ± 200 mPa·s; API specific gravity: 11.8°API; Density (20℃): 0.984 g / cm³ 3 Sulfur content 4.25 wt%; Nitrogen content 0.45 wt%; Metal (Ni + V) content 238 ppm; Asphaltene content 14.5 wt%.

[0127] These values ​​are characteristic of heavy, highly polluted crude oil, which is difficult to process in traditional fixed-bed hydrotreating units.

[0128] Example 4 The system configuration and control process in the entire process scheme are basically the same as in Example 3, except that: The reaction conditions of the modification reaction unit are controlled as follows: The reactor temperature is 400-420℃; the pressure is approximately 4.5 MPa; and the liquid hourly space velocity is 0.2-0.4 h⁻¹. -1 The reactor inlet methane concentration is >60 vol%; the gas-liquid ratio of the stream containing activated methane and the feedstock oil is 500-1500 SCF / bbl.

[0129] Example 5 The system configuration and control process in the entire process scheme are basically the same as in Example 3, except that: The reaction conditions of the modification reaction unit are controlled as follows: The reactor temperature was 440-450℃; the pressure was 8 MPa; and the liquid hourly space velocity was 0.5-0.7 h⁻¹. -1 The reactor inlet methane concentration is >80 vol%; the gas-liquid ratio of the stream containing activated methane and the feedstock oil is 3500-4500 SCF / bbl.

[0130] Example 6 The system configuration and control process in the entire process scheme are basically the same as in Example 3, except that: The reaction conditions of the modification reaction unit are controlled as follows: The reactor temperature is 420-450℃; the pressure is approximately 6 MPa; and the liquid hourly space velocity is 0.3-0.6 h⁻¹. -1 The reactor inlet methane concentration is >60 vol%; the gas-liquid ratio of the stream containing activated methane and the feedstock oil is 2000-3000 SCF / bbl.

[0131] Comparative Example 2 In this embodiment, the above-mentioned heavy crude oil is upgraded using the same method as the basic methane-assisted process in Comparative Example 1.

[0132] Table 2 shows a comparison of the properties of heavy crude oil feedstock and the fuel products produced under the two processes of Example 6 and Comparative Example 2.

[0133] Table 2

[0134] As shown in Table 2, the viscosity and API density of heavy crude oil are significantly improved after upgrading using the basic methane-assisted process; however, the metal removal rate, asphaltene conversion rate, and coke inhibition rate are limited, and a considerable amount of residual oil remains. In contrast, the viscosity of the oil upgraded by the process described in this application is less than one-third of that upgraded by the basic methane-assisted process, while the API density is increased by approximately 4.7 units. It almost completely inhibits coke formation, achieves deep metal removal and asphaltene conversion, and converts most of the distillate into naphtha and middle-range products.

[0135] The above comparison results show that the system of this application can achieve stable and low coke upgrading of heavy crude oil, while the product has improvements in viscosity, API density, impurity removal and distillate yield, which cannot be achieved by using a single-bed, one-pass reactor configuration.

[0136] The methane-involved catalytic reforming method for oil products described in this application has significant technical, economic, and environmental advantages compared to traditional hydrotreating, hydrocracking, HEFA-based sustainable aviation fuel (SAF) production, and previously reported methane-assisted reforming methods. These advantages stem from (i) upstream methane activation, (ii) tail gas purification and recycling, and (iii) the integrated combination of functional separation using a dual-catalyst bed.

[0137] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for catalytic upgrading of oil products involving methane, characterized in that, Includes the following steps: The A stream containing activated methane and feedstock oil are reformed and reacted under the action of a first catalyst to achieve heavy hydrocarbon cracking. The A stream is subjected to a hydroisomerization reaction under the action of a second catalyst to obtain a B stream containing fuel that meets aviation fuel requirements. The B stream is subjected to gas-liquid separation to obtain a gaseous stream and a liquid stream containing modified hydrocarbons; The gaseous stream is subjected to deacidification and desulfurization treatment to obtain a methane recovery gaseous stream; at least a portion of the methane recovery gaseous stream is recycled into a stream containing activated methane to participate in the reaction; The liquid stream containing modified hydrocarbons is separated to obtain modified oil products.

2. The method according to claim 1, characterized in that, The concentration of methane in the stream containing activated methane is at least 40 vol.

3. The method according to claim 1, characterized in that, The gas-liquid ratio of the stream containing activated methane and the feedstock oil is 100-5000 SCF / bbl.

4. The method according to claim 1, characterized in that, The pressure is controlled at 2-10 MPa and the temperature is controlled at 350-450℃ during the reforming reaction and the hydroisomerization reaction.

5. The method according to claim 1, characterized in that, The liquid hourly space velocity (LHSV) is controlled to be 0.2-2.0 h⁻¹ during the modification reaction and the hydroisomerization reaction. -1 .

6. The method according to claim 1, characterized in that, The catalyst bed volume ratio of the reforming reaction and the hydroisomerization reaction is 50:50 to 85:

15.

7. The method according to claim 1, characterized in that, The first catalyst comprises a metal-modified acidic molecular sieve catalyst; The modified metal element is selected from at least one of transition metals, main group metals, and lanthanides; Preferably, the transition metal is selected from at least one of Group IB, Group VIB, and Group VIIIB metals, and the main group metal is a Group IIIA metal.

8. The method according to claim 7, characterized in that, The first catalyst is a metal-modified HZSM-5 and / or a Beta zeolite catalyst; The modified metallic element includes at least one of cerium, molybdenum, cobalt, silver, gallium, nickel, and tungsten; Preferably, the modified metal element content in the first catalyst is: cerium 1-10 wt%, molybdenum 1-10 wt%, cobalt 1-10 wt%, silver 0.1-3 wt%, gallium 0-2 wt%.

9. The method according to claim 1, characterized in that, The second catalyst includes zeolite catalysts supported on transition metals and main group metals, and / or platinum-containing isomerization catalysts; Preferably, the transition metal is a Group IIB metal and the main group metal is a Group IIIA metal.

10. The method according to claim 9, characterized in that, The second catalyst is a Beta zeolite catalyst supported on gallium and zinc, wherein the gallium loading is 0.1-2 wt% and the zinc loading is 1-10 wt%. In the platinum-containing isomerization catalyst, the platinum loading is 0.1-1.0 wt%.

11. The method according to claim 1, characterized in that, The concentration of hydrogen sulfide in the methane recovery gaseous stream is less than 100 ppmv.

12. The method according to claim 1, characterized in that, The recycle ratio of the methane recovery gaseous stream is 0.5 to 10.

13. The method according to claim 1, characterized in that, The feedstock oil is derived from at least one of renewable oil, recycled renewable oil, and fossil oil.

14. The method according to claim 1, characterized in that, The stream containing activated methane is obtained by activating the methane-containing stream before the modification reaction. Alternatively, the stream containing activated methane is obtained by activating the methane-containing stream during the reforming reaction.

15. The method according to claim 14, characterized in that, The activation method is heating and / or catalytic activation using an activation catalyst; When the stream containing activated methane is obtained by activating the stream containing methane during the reforming reaction, and catalytic activation is performed using an activating catalyst, the catalytic activator is packed upstream of the first catalyst, or the catalytic activator is mixed with the first catalyst and packed in a single pack.

16. The method according to claim 14, characterized in that, The activation temperature is 350-550℃.

17. A methane-involved oil catalytic reforming system, characterized in that, include: A crude oil storage unit is used to store crude oil. The methane activation unit is used to activate a methane-containing stream to obtain a stream containing activated methane. The reforming reaction unit includes at least two catalytic beds arranged in series: The first catalytic bed is filled with a first catalyst, which is used to upgrade the feedstock oil in the presence of a stream containing activated methane to obtain the A stream of heavy hydrocarbon cracking. The second catalyst bed is filled with a second catalyst for hydroisomerizing the A stream to obtain a B stream that meets the requirements of aviation fuel. The separation unit includes a gas-liquid separation unit and a fractionation unit; The gas-liquid separation unit is used to separate the B stream into a gaseous stream and a liquid stream containing modified hydrocarbons. The inlet of the gas-liquid separation unit is connected to the outlet of the second catalytic bed via a pipeline; The gas outlet of the gas-liquid separation unit is connected to the feed inlet of the methane activation unit through a pipeline to form a methane recycling loop. The outlet of the gas-liquid separation unit is connected to the inlet of the fractionation unit via a pipeline. The fractionation unit is used to separate the liquid stream containing modified hydrocarbons to obtain modified oil products.

18. The system according to claim 17, characterized in that, The methane activation unit independently activates the methane-containing stream; Alternatively, the methane activation unit may be integrated within the reforming reaction unit.

19. The system according to claim 18, characterized in that, The methane activation unit includes an activation catalyst packed upstream of or inside the first catalyst bed.

20. The system according to claim 19, characterized in that, The activated catalyst and the first catalyst are arranged in a layered configuration, with the activated catalyst located upstream of the first catalyst bed.

21. The system according to claim 19, characterized in that, The activated catalyst and the first catalyst are mixed and packed together to form the first catalyst bed.

22. The system according to claim 17, characterized in that, The separation unit also includes a gas phase purification unit; The gas phase purification unit is located between the gas-liquid separation unit and the methane activation unit, and is used to remove acidic and corrosive gaseous substances from the gaseous stream.

23. An oil refining catalytic bed, characterized in that, Including the following settings in sequence: The first catalytic bed is filled with a first catalyst, which is used to upgrade the feedstock oil in the presence of a stream containing activated methane to obtain the A stream of heavy hydrocarbon cracking. The second catalyst bed is filled with a second catalyst for hydroisomerizing the A stream to obtain a B stream that meets the requirements of aviation fuel. A methane-activated catalyst bed is disposed upstream of the first catalyst bed; Alternatively, the first catalyst bed is mixed and packed with a first catalyst and a methane-activated catalyst; Alternatively, the first catalyst bed is sequentially layered with a methane-activated catalyst and a first catalyst.

24. The catalytic bed according to claim 23, characterized in that, The volume ratio of the first catalyst bed to the second catalyst bed is 60:40 to 80:

20.

25. The catalytic bed according to claim 23, characterized in that, The first catalyst comprises a metal-modified acidic molecular sieve catalyst; The modified metal element is selected from at least one of transition metals, main group metals, and lanthanides; Preferably, the transition metal is selected from at least one of Group IB, Group VIB, and Group VIIIB metals, and the main group metal is a Group IIIA metal.

26. The catalytic bed according to claim 25, characterized in that, The first catalyst is a metal-modified HZSM-5 and / or a Beta zeolite catalyst; The modified metallic element includes at least one of cerium, molybdenum, cobalt, silver, gallium, nickel, and tungsten; Preferably, the modified metal element content in the catalyst is: cerium 1-10 wt%, molybdenum 1-10 wt%, cobalt 1-10 wt%, silver 0.1-3 wt%, gallium 0-2 wt%.

27. The catalytic bed according to claim 23, characterized in that, The second catalyst includes zeolite catalysts supported on transition metals and main group metals, and / or platinum-containing isomerization catalysts; Preferably, the transition metal is a Group IIB metal and the main group metal is a Group IIIA metal.

28. The catalytic bed according to claim 27, characterized in that, The second catalyst is a Beta zeolite catalyst supported on gallium and zinc, wherein the gallium loading is 0.1-2 wt% and the zinc loading is 1-10 wt%. In the platinum-containing isomerization catalyst, the platinum loading is 0.1-1.0 wt%.

29. The catalytic bed according to claim 23, characterized in that, The first catalyst bed is also used to achieve deoxygenation and / or demetallization of the feedstock oil.

30. A sustainable aviation fuel blending component, characterized in that, The sustainable aviation fuel blending component, obtained by the methane-involved catalytic reforming method according to any one of claims 1-16, has the following characteristics: a) Freezing point of -40°C or lower b) Oxygen content below 0.1 wt%, and c) Final boiling point not exceeding 300℃.

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