A method and system for producing a green aviation kerosene component

Abstract

This application relates to a method and system for preparing green aviation kerosene components, belonging to the field of aviation kerosene preparation technology. The method includes: conducting a double reforming reaction with a feed gas comprising CH4, CO2, and H2O under the action of a Ni-La / MgO catalyst to obtain syngas, wherein the molar ratio of H2 to CO in the syngas is (1.8~2.2):1; and conducting a Fischer-Tropsch synthesis reaction with the syngas under the action of a Fe-Mn-K catalyst. By using a Ni-La / MgO catalyst for the double reforming reaction, sintering and coking can be effectively suppressed, ensuring long-term stable operation of the reaction. Furthermore, the H2 / CO molar ratio in the syngas can be directly used for the Fischer-Tropsch synthesis reaction, effectively improving carbon utilization and reducing system energy consumption. After the Fischer-Tropsch synthesis reaction under the action of the Fe-Mn-K catalyst, the C8-C content in the product is significantly reduced. 16 The content of aviation kerosene fraction is ≥65wt%.

Description

Technical Field

[0001] This application relates to the field of liquid fuel technology, and in particular to a method and system for preparing green aviation kerosene components. Background Technology

[0002] Aviation kerosene, as a core fuel in the air transport sector, directly determines the safety and economy of air travel. C8-C... 16 Isoalkanes are ideal components of aviation kerosene, consisting of C8-C64... 16 Alkanes, produced through hydroisomerization, account for 70%–90% of aviation kerosene fractions and significantly influence key indicators such as calorific value, flash point, and freezing point, forming the basis for meeting the stringent requirements of aviation fuel. In recent years, with the advancement of global "dual carbon" goals and the continuous development of the aviation industry, the industrialization of sustainable aviation fuel (SAF) has become a crucial path to addressing carbon emissions in the aviation sector and reducing dependence on crude oil resources. C8-C... 16 As alkanes are the building blocks of SAFs (Salicylic Acid Fuels), breakthroughs and upgrades in their preparation technology have become a key research focus in the aviation fuel field. Simultaneously, for energy security strategic considerations, developing non-petroleum-based methods for preparing C8-C hydrocarbons is also crucial. 16 Alkanes, in order to diversify raw materials, have become an important development direction in the energy sector of various countries.

[0003] Some natural gas resources in the South my country Sea have high CO2 content, with some blocks exceeding 80%. Significant CO2 emissions occur during extraction and processing, resulting in low carbon resource utilization. With the development of green fuels and CCUS technology, utilizing carbon dioxide-rich natural gas through reforming to produce syngas, and then further synthesizing it into liquid fuels via Fischer-Tropsch synthesis, can be efficiently used to obtain C8-C for aviation kerosene. 16 Alkanes. However, the currently disclosed two-step "reforming → syngas → Fischer-Tropsch" technical route still has many technical bottlenecks, including insufficient catalyst stability, difficulty in matching gas composition to the requirements of the Fischer-Tropsch reaction, and low selectivity of aviation kerosene components (C8-C). 16 Problems such as the fraction content usually being less than 60%. Summary of the Invention

[0004] To address the aforementioned technical problems, this application provides a method and system for preparing green aviation kerosene components, effectively improving the issues of insufficient catalyst stability, difficulty in matching the composition of the product gas from the dual reforming reaction to the requirements of Fischer-Tropsch synthesis, and low selectivity of aviation kerosene components in existing preparation processes.

[0005] In a first aspect, embodiments of this application provide a method for preparing green aviation kerosene components, comprising the following steps: The feed gas, including CH4, CO2 and H2O, undergoes a double reforming reaction under the action of Ni-La / MgO catalyst to obtain syngas, in which the molar ratio of H2 to CO is (1.8~2.2):1. Syngas was subjected to Fischer-Tropsch synthesis reaction in the presence of a Fe-Mn-K catalyst.

[0006] In the above technical solution, this application employs a feed gas including CH4, CO2, and H2O to conduct a dual reforming reaction under the action of a Ni-La / MgO catalyst. The Ni-La / MgO catalyst exhibits strong metal-support interaction and high thermal stability, effectively suppressing sintering and coking, enabling the dual reforming reaction to operate stably over a long period. Furthermore, the molar ratio of H2 to CO in the obtained syngas is (1.8~2.2):1, requiring no additional hydrogen supplementation to meet the Fischer-Tropsch synthesis reaction conditions, thereby effectively improving carbon utilization and reducing system energy consumption. The syngas is then subjected to a Fischer-Tropsch synthesis reaction under the action of a Fe-Mn-K catalyst. By controlling chain growth, the C8-C content in the liquid fuel products is increased. 16 The mass percentage of alkane fractions is ≥65%.

[0007] This method is simple to operate, uses low-cost and highly stable catalysts, and can significantly improve the efficiency of aviation kerosene fractions (C8-C4). 16 The selectivity of carbon utilization can improve overall carbon utilization efficiency and achieve stable, continuous, and industrially scalable operation.

[0008] In some embodiments, the Ni-La / MgO catalyst comprises an MgO support and Ni and La supported on the MgO support; wherein the loading of Ni is 5wt% to 15wt% and the loading of La is 0.5wt% to 2wt%.

[0009] In the above technical solution, the loading of the active component Ni and the active promoter La in the Ni-La / MgO catalyst is controlled within an appropriate range. The basic sites of MgO facilitate CO2 adsorption and activation and inhibit coking, while the active component Ni provides sufficient active sites to ensure high catalytic activity in the dual-phase reaction. The active promoter La effectively disperses the active component Ni, enhances the basicity and oxygen migration ability of the MgO support, effectively inhibits catalyst coking and high-temperature sintering, and improves operational stability. The synergistic effect of the two components with the MgO support gives the catalyst high activity, high resistance to coking, and high stability, enabling long-term stable operation. Furthermore, the H2 / CO molar ratio of the synthesized gas precisely matches the requirements of subsequent Fischer-Tropsch synthesis, improving the overall carbon utilization rate and efficiency of the process.

[0010] Optionally, the MgO support includes at least one of nano-magnesium oxide, light magnesium oxide, or mesoporous magnesium oxide; more preferably, the MgO support is mesoporous magnesium oxide.

[0011] In some embodiments, the MgO support is mesoporous magnesium oxide, and the preparation method of mesoporous magnesium oxide includes the following steps: The magnesium source, organic ligand, and gas-releasing pore-forming agent were dissolved and mixed in water to obtain a precursor solution; The precursor solution is frozen or gelled and then dried to obtain a solid precursor. The solid precursor is pretreated at temperature T1 to allow the gas-releasing pore-forming agent to thermally decompose and generate gas. The temperature is then raised to T2 for calcination to obtain mesoporous magnesium oxide.

[0012] In the above technical solution, the addition of an organic ligand can form a coordination dispersion system with the magnesium source, improving the uniformity of the precursor construction; the addition of a gas-releasing pore-forming agent decomposes and releases gas during the first calcination, forming an initial pore structure inside the precursor and reducing dependence on conventional complex external templates; freezing or gelling followed by drying can weaken the capillary shrinkage during conventional drying processes, reducing pore shrinkage and collapse caused by liquid surface tension during drying. This preparation method balances template simplification, pore structure control, and scalability, making it suitable for preparing mesoporous magnesium oxide materials with good pore connectivity and dispersibility. Optionally, the magnesium source includes at least one of magnesium nitrate, magnesium acetate, magnesium chloride, magnesium sulfate, or magnesium bicarbonate.

[0013] Optionally, the organic ligand is an ammonium salt of an organic acid, including at least one of citric acid, tartaric acid, malic acid, maleic acid, or ethylenediaminetetraacetic acid.

[0014] Optionally, the gas-releasing pore-forming agent includes at least one of ammonium bicarbonate or ammonium carbonate.

[0015] Optionally, the pretreatment temperature is 150℃≤T1<350℃, and the time is 0.5h~3h; the calcination temperature is 350℃≤T2<650℃, and the time is 0.5h~4h.

[0016] In some embodiments, the method for obtaining a Ni-La / MgO catalyst includes the following steps: dissolving a nickel salt and a lanthanum salt in water to obtain an impregnation solution; impregnating a MgO support with the impregnation solution, followed by drying and calcination to obtain the Ni-La / MgO catalyst.

[0017] In the above technical solution, Ni-La / MgO catalyst is prepared by impregnation with MgO support. The preparation process is simple and the conditions are mild. At the same time, it can make Ni and La components highly uniformly dispersed on MgO support, forming a stable metal-support interaction, which effectively improves catalyst activity, anti-sintering performance and operational stability, and is more suitable for long-cycle dual-cycle reaction requirements.

[0018] In some embodiments, the nickel salt is nickel nitrate and the lanthanum salt is lanthanum nitrate.

[0019] In the above technical solutions, both nickel nitrate and lanthanum nitrate have excellent water solubility, which is conducive to uniform dispersion during impregnation. They also react mildly with the MgO support without significant exothermic phenomena, which is beneficial to the formation of a highly active and stable Ni-La / MgO catalyst.

[0020] In some implementations, the impregnation step employs equal-volume impregnation.

[0021] In the above technical solution, the use of equal volume impregnation is beneficial for precise control of Ni and La metal loading, so that the active components are highly uniformly dispersed on the surface and in the pores of the MgO support, effectively reducing metal agglomeration and improving catalytic activity and stability; at the same time, the process is simple, has no waste liquid discharge, and has good reproducibility, making it suitable for industrial scale-up production.

[0022] In some embodiments, the calcination temperature is 400℃~600℃ and the time is 1h~10h.

[0023] In the above technical solution, under the above calcination conditions, it is beneficial for nickel salt and lanthanum salt to fully decompose into highly dispersed active metal oxides, thereby reducing agglomeration and sintering.

[0024] In some embodiments, after the impregnation step, the process further includes: static aging treatment at 20°C to 30°C for 12 to 18 hours.

[0025] In the above technical solution, static aging allows Ni and La metal ions to fully diffuse and uniformly adsorb onto the pores and surface of the MgO support, thereby improving the dispersion of the active components.

[0026] In some embodiments, the drying step is performed at a temperature of 100°C to 180°C for a duration of 18 hours to 24 hours.

[0027] In the above technical solution, drying conditions within a suitable range are conducive to the smooth removal of physically adsorbed water from the sample, reducing the migration and segregation of metal ions, and maintaining the uniform distribution of active components on the support; at the same time, it has little impact on the pore structure of the support, which is conducive to the formation of a highly dispersed and highly stable active phase by subsequent calcination, thereby improving the overall performance of the catalyst.

[0028] In some embodiments, the double-integration reaction is carried out at a temperature of 600°C to 750°C, a pressure of 0.2 MPa to 0.5 MPa, and a reaction space velocity of 1000 h⁻¹. -1 ~3000h -1 .

[0029] In the above technical solution, by controlling the dual reaction conditions and using a Ni-La / MgO catalyst, efficient and stable conversion of CH4 and CO2 can be achieved. This facilitates precise control of the molar ratio of H2 and CO in the syngas, further improving carbon utilization and reducing system energy consumption. Furthermore, the reaction conditions are mild and controllable, and the catalyst is less prone to coking and sintering, which is more conducive to long-term stable operation.

[0030] In some embodiments, the volume ratio of CH4, CO2 and H2O in the feed gas is 100:(27~43):(57~77). In the above technical solution, by adjusting the ratio of CH4, CO2 and H2O in the feed gas and matching it with the dual-reaction conditions, syngas with an H2 / CO molar ratio of (1.8~2.2):1 can be efficiently converted and produced in situ without additional adjustment of the hydrogen-carbon ratio. This is beneficial for improving carbon utilization, reducing system energy consumption, and synergistically enhancing the catalyst's anti-coking performance and extending operational stability.

[0031] In some embodiments, the molar ratio of Mn to Fe in the Fe-Mn-K catalyst is (5~15):100, and the molar ratio of K to Fe is (1~10):100.

[0032] In the above technical solution, in the Fe-Mn-K catalyst, Fe serves as the active center, Mn is used to adjust the iron phase structure, and K is used to adjust the surface alkalinity. By controlling the molar ratio of the three components within a suitable range, Mn can effectively optimize the active phase structure and improve dispersion and stability; K can effectively control the Fischer-Tropsch synthesis chain growth behavior and inhibit CH4 formation, thereby further improving C8... C 16 Selectivity of alkane fractions.

[0033] In some embodiments, the Fischer-Tropsch synthesis reaction is carried out at a temperature of 300°C to 330°C, a pressure of 2.0 MPa to 3.5 MPa, and a molar ratio of H2 to CO of (1.9 to 2.1):1.

[0034] In the above technical solution, by controlling the reaction conditions and raw material ratio, it is beneficial to achieve efficient conversion of syngas, promote chain growth reaction, and inhibit methane formation; at the same time, it is highly matched with the upstream dual-process pressure and hydrogen-to-carbon ratio, eliminating the need for additional hydrogen adjustment, resulting in high carbon utilization, low energy consumption, and good process stability.

[0035] Secondly, embodiments of this application provide a system for the method of the first aspect, comprising a feeding unit, a dual-reaction unit, a separation and pressurization unit, and a Fischer-Tropsch reaction unit connected in sequence; The feed gas enters the dual reforming unit via the feed unit for dual reforming, and the resulting synthesis gas enters the Fischer-Tropsch reaction unit via the separation and pressurization unit for Fischer-Tropsch synthesis; the Fischer-Tropsch reaction unit includes a Fischer-Tropsch fluidized bed reactor.

[0036] In the above technical solution, by successively passing the feed gas through a dual reforming unit and a Fischer-Tropsch reaction unit, the fraction of aviation kerosene (C8–C4) can be effectively improved. 16 This improves the selectivity of carbon utilization, enhances overall carbon utilization efficiency, and enables stable, continuous, and industrially scalable operation. Furthermore, by employing a fluidized bed reactor in the Fischer-Tropsch reaction unit, unlike a fixed-bed reactor, the fluidized bed reactor can form a uniform gas-liquid-solid interface, ensuring a small internal temperature gradient (temperature distribution within ±3℃) and maintaining the catalyst in a stable fluidized state, resulting in high heat transfer efficiency. This makes it suitable for the narrow chain growth window and high reaction temperature sensitivity requirements of aviation kerosene production.

[0037] In some embodiments, a gas distributor is provided at the inlet of the Fischer-Tropsch fluidized bed reactor, through which the synthesis gas enters the reaction chamber of the Fischer-Tropsch fluidized bed reactor.

[0038] In the above technical solution, by setting up a gas distributor, it is beneficial to achieve uniform gas distribution, improve the stability of the reaction system, and enhance the reaction efficiency.

[0039] In some embodiments, a preheating unit is also provided between the feeding unit and the dual-reaction unit. The preheating unit is thermally coupled to the Fischer-Tropsch reaction unit and is used to preheat the feed gas entering the preheating unit using the heat of reaction released by the Fischer-Tropsch synthesis reaction as a heat source.

[0040] In the above technical solution, since the Fischer-Tropsch synthesis reaction is an exothermic reaction, the process intensification design in this application can achieve energy coupling through system heat exchange, thereby effectively reducing energy consumption and reducing equipment investment and operating costs. Attached Figure Description

[0041] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0042] Figure 1 This is a process flow diagram of a method for preparing green aviation kerosene components provided in one embodiment of this application.

[0043] Figure 2This is a schematic diagram of a system for preparing green aviation kerosene components, provided as an embodiment of this application.

[0044] Explanation of reference numerals in the attached figures: 1-CO2 feed assembly; 2-CH4 feed assembly; 3-N2 feed assembly; 4-H2O feed assembly; 5-Heating furnace; 6-Mixer; 7-Preheating furnace; 8-Dual reforming reactor; 8-1-Heating jacket; 9-First condenser; 10-Cold high-efficiency separation tank; 11-Reformed water collection tank; 12-First buffer tank; 13-Compressor; 14-Second buffer tank; 15-Fischer-Tropsch fluidized bed reactor; 15-1-Insulation jacket; 15-2-Gas distributor; 16-Hot high-efficiency separation tank; 17-Second condenser; 18-Heavy oil product tank; 19-Three-phase separator; 20-Light oil product tank; 21-C1-C4 light hydrocarbon components; 22-Fischer-Tropsch water collection tank. Detailed Implementation

[0045] The following detailed description, with appropriate reference to the accompanying drawings, discloses embodiments of the method and system for preparing green aviation kerosene components according to this application. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided to enable those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.

[0046] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for a specific parameter, it is also expected that ranges of 60~110 and 80~120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this application, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0~5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0047] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0048] With the development of natural gas, green fuels, and CCUS technology, syngas can be produced by reforming carbon-rich natural gas (high methane content, with simultaneous enrichment of carbon dioxide), and then further synthesized into liquid fuels through Fischer-Tropsch synthesis. This process can be efficiently used to obtain aviation kerosene components (C8-C4). 16 Alkanes). However, the currently disclosed two-step "reforming → syngas → Fischer-Tropsch" technical route still has many technical bottlenecks, including insufficient catalyst stability, difficulty in matching gas composition to the requirements of the Fischer-Tropsch reaction, and low selectivity of aviation kerosene (C8-C). 16 Problems such as the fraction content typically being less than 60% are addressed. For example, patent CN119685047A proposes a two-step process combining Ni / MgO-Al2O3 reforming and Co-molecular sieve bifunctional catalysis, achieving Co-directional encapsulation through an acid-base pair strategy to improve the C8-C ratio of aviation kerosene. 16 Selectivity of alkane fractions. This technical solution presents challenges in catalyst preparation and requires precise control of active metal distribution; the overall process has high energy consumption, and catalyst lifespan and recycling issues remain unresolved; the product contains C8-C... 16 The mass percentage of alkane fractions can only reach a maximum of 70.5 wt%.

[0049] Based on this, this application utilizes a feed gas comprising CH4, CO2, and H2O to conduct a dual reforming reaction under the action of a Ni-La / MgO catalyst. The Ni-La / MgO catalyst exhibits strong metal-support interaction and high thermal stability, effectively suppressing sintering and coking, enabling the dual reforming reaction to operate stably over long periods. Furthermore, the resulting syngas has a molar ratio of H2 to CO of (1.8~2.2):1, requiring no additional hydrogen supplementation to meet the Fischer-Tropsch synthesis reaction conditions, thereby effectively improving carbon utilization and reducing system energy consumption. Conducting the Fischer-Tropsch synthesis reaction with the syngas under the action of a Fe-Mn-K catalyst allows for the regulation of the chain growth factor, resulting in a higher concentration of C8-C in the liquid fuel products. 16 The mass percentage of alkane fractions is ≥65%.

[0050] This method is simple to operate, uses low-cost and highly stable catalysts, and can significantly improve the efficiency of aviation kerosene fractions (C8-C4). 16 The selectivity of carbon utilization can improve overall carbon utilization efficiency and achieve stable, continuous, and industrially scalable operation.

[0051] It should be noted that in the Ni-La / MgO catalyst, MgO is used as the support, Ni is used as the active component, and La is used as the active promoter; the Fe-Mn-K catalyst is a composite metal oxide, including iron oxide, manganese oxide and potassium oxide, wherein Mn is used to regulate the structure and dispersion of the iron active phase, and K is used to regulate the basicity of the catalyst surface and the product selectivity.

[0052] Figure 1 For a process flow diagram of a method for preparing green aviation kerosene components provided in one embodiment of this application, please refer to [link / reference]. Figure 1 The method includes the following steps: S1: The feed gas containing CH4, CO2 and H2O undergoes a double reforming reaction under the action of Ni-La / MgO catalyst to obtain syngas, in which the molar ratio of H2 to CO is (1.8~2.2):1.

[0053] As an example, the molar ratio of H2 to CO in the synthesis gas can be any one of the following values, or a value between any two values: 1.8:1, 1.85:1, 1.9:1, 1.95:1, 2.0:1, 2.1:1, 2.2:1.

[0054] In some embodiments, the Ni-La / MgO catalyst comprises an MgO support and Ni and La supported on the MgO support; wherein the loading of Ni is 5wt% to 15wt% and the loading of La is 0.5wt% to 2wt%.

[0055] As an example, the Ni loading is any one of 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, or any value between any two of these values; the La loading is any one of 0.5wt%, 1wt%, 1.5wt%, 2wt%, or any value between any two of these values.

[0056] Optionally, the MgO support includes at least one of nano-magnesium oxide, light magnesium oxide, or mesoporous magnesium oxide; more preferably, the MgO support is mesoporous magnesium oxide.

[0057] In some embodiments, the MgO support is mesoporous magnesium oxide, and the preparation method of mesoporous magnesium oxide includes the following steps: (1) Dissolve and mix the magnesium source, organic ligand and gas-releasing pore-forming agent in water to obtain a precursor solution; (2) The precursor solution is frozen or gelled and then dried to obtain a solid precursor; (3) The solid precursor is pretreated at temperature T1 to allow the gas-releasing pore-forming agent to thermally decompose and generate gas. The temperature is then raised to T2 for calcination to obtain mesoporous magnesium oxide.

[0058] In some embodiments, in step (1), the magnesium source includes at least one of magnesium nitrate, magnesium acetate, magnesium chloride, magnesium sulfate, or magnesium bicarbonate. The organic ligand is an ammonium salt of an organic acid, including at least one of citric acid, tartaric acid, malic acid, maleic acid, or ethylenediaminetetraacetic acid. The degassing pore-forming agent includes at least one of ammonium bicarbonate or ammonium carbonate.

[0059] Optionally, step (1) includes: dissolving a magnesium source in water to obtain a magnesium source solution; adding an organic ligand to form a coordination dispersion system; and adding a gas-releasing pore-forming agent to obtain a precursor solution.

[0060] Understandably, when adding a gas-releasing pore-forming agent, the system temperature should be kept as low as possible, for example, 0℃~10℃.

[0061] Optionally, a structure modifier may be added to the precursor solution, including at least one of sorbitol, glycerol, erythritol, and glucose.

[0062] Optionally, a neutral elutable salt may be added to the precursor solution, and the product may be washed after step (3) to remove the neutral elutable salt; the neutral elutable salt may include at least one of sodium chloride, potassium chloride, or sodium sulfate. Through the confinement effect of the neutral elutable salt, the sintering of magnesium oxide particles and excessive grain growth can be inhibited during the calcination conversion process, and secondary pores can be further formed after subsequent desalting, thereby improving the stability and connectivity of the pore structure.

[0063] In some embodiments, in step (2), the freezing and shaping method can be one of drip freezing, spray freezing or mold pre-freezing; the drying method can be freeze drying or low-temperature vacuum drying.

[0064] Furthermore, the pretreatment temperature is 150℃≤T1<350℃, and the time is 0.5h~3h; the calcination temperature is 350℃≤T2<650℃, and the time is 0.5h~4h.

[0065] As an example, the pretreatment temperature T1 is 150℃, 180℃, 220℃, 320℃, etc., and the time is 0.5h, 1h, 2h, 3h, etc.; the calcination temperature T2 is 350℃, 380℃, 450℃, 480℃, 500℃, 550℃, 650℃, etc., and the time is 0.5h, 1h, 2h, 3h, 4h, etc.

[0066] Understandably, the pretreatment process may include segmented treatment at different temperatures, such as treatment at 180℃ for 1 hour and treatment at 320℃ for 1 hour; similarly, the calcination stage may also include step-by-step calcination at different temperatures, such as holding at 380℃ for 2 hours and holding at 550℃ for 1 hour.

[0067] In some embodiments, the method for producing Ni-La / MgO catalyst includes the following steps: dissolving nickel salt and lanthanum salt in water to obtain an impregnation solution; impregnating an MgO support with the impregnation solution, followed by drying and calcination to obtain the Ni-La / MgO catalyst.

[0068] Furthermore, nickel salts include nickel nitrate, and lanthanum salts include lanthanum nitrate. Even further, nickel salts are Ni(NO3)2·6H2O, and lanthanum salts are La(NO3)3·6H2O.

[0069] Furthermore, the impregnation step employs equal-volume impregnation. Equal-volume impregnation means that the volume of the impregnation solution is exactly equal to the saturated absorption capacity of the MgO support.

[0070] Furthermore, the roasting temperature is 400℃~600℃, and the time is 1h~10h. As an example, the roasting temperature is any one value or any two values ​​among 400℃, 450℃, 500℃, 550℃, and 600℃; the time is any one value or any two values ​​among 1h, 3h, 5h, 8h, and 10h.

[0071] Furthermore, after the impregnation step, the process includes: a static aging treatment at 20°C to 30°C for 12 to 18 hours. As an example, the static aging treatment is carried out at room temperature for any one of the following times: 12 hours, 14 hours, 15 hours, 16 hours, or 18 hours, or any value between any two times.

[0072] Furthermore, in the drying step, the temperature is 100℃~180℃, and the drying time is 18h~24h. As an example, the drying temperature is any one of 100℃, 130℃, 150℃, 160℃, and 180℃, or a value between any two of these values; the drying time is any one of 18h, 19h, 20h, and 24h, or a value between any two of these values.

[0073] As an example, the method for producing the Ni-La / MgO catalyst includes the following steps: dissolving Ni(NO3)2·6H2O and La(NO3)3·6H2O in water to obtain an impregnation solution; impregnating the MgO support in the impregnation solution in equal volumes; aging the MgO support at 20℃~30℃ for 12h~18h; drying the MgO support at 100℃~180℃ for 18h~24h; and then calcining the MgO support at 400℃~600℃ for 1h~10h to obtain the Ni-La / MgO catalyst.

[0074] In some embodiments, the double dual integration reaction is carried out at a temperature of 580°C to 670°C, a pressure of 0.2 MPa to 0.5 MPa, and a reaction space velocity of 1000 h⁻¹. -1 ~3000h -1 .

[0075] As an example, the temperature of the double-unit reaction is any value or any two values ​​between 580°C, 600°C, 630°C, 650°C, and 670°C; the pressure is any value or any two values ​​between 0.2 MPa, 0.3 MPa, 0.4 MPa, and 0.5 MPa; and the reaction space velocity is 1000 h⁻¹. -1 1500h -1 2000h -1 3000h -1 The value of any point in the array or the value between any two points.

[0076] In some embodiments, the volume ratio of CH4, CO2 and H2O in the feed gas is 100:(27~43):(57~77), for example, the volume ratio of CH4, CO2 and H2O can be 100:28:60, 100:35:65, 100:40:70, 100:42:76, etc.

[0077] S2: The syngas is subjected to Fischer-Tropsch synthesis reaction in the presence of a Fe-Mn-K catalyst.

[0078] In some embodiments, in the Fe-Mn-K catalyst, the molar ratio of Mn to Fe is (5~15):100, and the molar ratio of K to Fe is (1~10):100.

[0079] As an example, the molar ratio of Mn to Fe is any one of the following: 3:100, 6:100, 8:100, 10:100, 15:100, or any value between any two of these values; the molar ratio of K to Fe is any one of the following: 1:100, 2:100, 5:100, 8:100, 10:100, or any value between any two of these values.

[0080] In some embodiments, the Fischer-Tropsch synthesis reaction is carried out at a reaction temperature of 300°C to 330°C, a reaction pressure of 2.0 MPa to 3.5 MPa, and a molar ratio of H2 to CO of (1.9 to 2.1):1.

[0081] As an example, the reaction temperature is any value or a value between any two of 300°C, 310°C, 320°C, and 330°C; the reaction pressure is any value or a value between any two of 2.0 MPa, 2.5 MPa, 3.0 MPa, and 3.5 MPa; and the molar ratio of H2 to CO is any value or a value between any two of 1.9:1, 2.0:1, and 2.1:1.

[0082] In addition, this application also provides a system used in the above method. Figure 2Please refer to the structural schematic diagram of a system for preparing green aviation kerosene components provided in one embodiment of this application. Figure 2 The system includes a feed unit, a dual reforming reaction unit, a separation and pressurization unit, and a Fischer-Tropsch reaction unit connected in sequence. The feed gas enters the dual reforming reaction unit through the feed unit to carry out the dual reforming reaction, and the resulting synthesis gas enters the Fischer-Tropsch reaction unit through the separation and pressurization unit to carry out the Fischer-Tropsch synthesis reaction.

[0083] In some embodiments, the feeding unit includes a CO2 feeding assembly 1, a CH4 feeding assembly 2, an H2O feeding assembly 4, a heating furnace 5, and a mixer 6. Liquid water enters the heating furnace 5 through the H2O feeding assembly 4 and is heated to form water vapor, which then enters the mixer 6 to mix with CO2 and CH4 to form raw material gas.

[0084] Furthermore, the feeding unit also includes an N2 feeding assembly 3, which is used to provide nitrogen for pressure testing, purging, replacement, or post-reaction cooling.

[0085] In some embodiments, a preheating unit is further provided between the feeding unit and the dual-reaction unit. The preheating unit and the Fischer-Tropsch reaction unit are thermally coupled to preheat the feed gas entering the preheating unit using the heat of reaction released by the Fischer-Tropsch synthesis reaction as a heat source.

[0086] Furthermore, the dual reforming reaction unit includes a dual reforming reactor 8, the Fischer-Tropsch reaction unit includes a Fischer-Tropsch fluidized bed reactor 15, and the preheating unit includes a preheating furnace 7. The preheating furnace 7 is located between the mixer 6 and the dual reforming reactor 8. The liquid hydrocarbon products obtained after the reaction in the Fischer-Tropsch fluidized bed reactor 15 enter the preheating furnace 7 to preheat the feed gas. The Ni-La / MgO catalyst is placed in the dual reforming reactor 8. The preheated feed gas enters the dual reforming reactor 8 to undergo a dual reforming reaction to obtain synthesis gas.

[0087] Furthermore, a heating jacket 8-1 is also provided outside the dual reactor 8 to heat the reaction system.

[0088] In some embodiments, the separation and pressurization unit includes a first condenser 9, a cold high-efficiency separation tank 10, a first buffer tank 12, a compressor 13, and a second buffer tank 14 connected in sequence. The inlet of the first condenser 9 is connected to the material outlet of the dual-stage reforming reactor 8, and the material outlet of the second buffer tank 14 is connected to the material inlet of the Fischer-Tropsch fluidized bed reactor 15. Further, the cold high-efficiency separation tank 10 is also connected to a reformed water collection tank 11.

[0089] The syngas product obtained in the dual-phase reactor 8 first enters the first condenser 9 for cooling, and then enters the cold high-pressure separator 10 for gas-liquid two-phase separation. The separated liquid enters the reformed water collection tank 11 from the bottom after the liquid level is controlled by the control loop. The top gas enters the first buffer tank 12 for settling, then enters the compressor 13 for pressurization, and finally enters the Fischer-Tropsch fluidized bed reactor 15 after being buffered, metered and flow controlled by the second buffer tank 14. The Fe-Mn-K catalyst is set in the Fischer-Tropsch fluidized bed reactor 15.

[0090] In some embodiments, a gas distributor 15-2 is provided at the inlet of the Fischer-Tropsch fluidized bed reactor 15, through which the synthesis gas enters the reaction chamber of the Fischer-Tropsch fluidized bed reactor 15.

[0091] This application does not specifically limit the structural composition of the gas distributor 15-2; any conventional microbubble generator can be used in this application. As an example, the gas distributor 15-2 can refer to the structural configuration of the multiphase mixer in patent CN116585987A.

[0092] Furthermore, the Fischer-Tropsch fluidized bed reactor 15 is a stirred tank with a volume of 1L. A filter is also installed at the top of the stirred tank to filter the produced reaction effluent and maintain a stable liquid level inside the tank.

[0093] Furthermore, the Fischer-Tropsch fluidized bed reactor 15 is also provided with an insulation jacket 15-1.

[0094] In some embodiments, the system further includes a product separation unit connected to the preheating unit for separating the heat-exchanged hydrocarbon products to obtain green aviation kerosene components.

[0095] Furthermore, the product separation unit includes a thermal high-efficiency separator 16, a second condenser 17, a heavy oil product tank 18, a three-phase separator 19, a light oil product tank 20, and a Fischer-Tropsch water collection tank 22. The material inlet of the thermal high-efficiency separator 16 is connected to the material outlet of the preheating furnace 7. The top material outlet of the thermal high-efficiency separator 16 is connected to the second condenser 17, and the bottom material outlet is connected to the heavy oil product tank 18. The second condenser 17 is connected to the three-phase separator 19, and the bottom of the three-phase separator 19 is connected to the light oil product tank 20 and the Fischer-Tropsch water collection tank 22, respectively. The C1-C4 light hydrocarbon components 21 are discharged and enter a gas chromatograph for composition determination.

[0096] The liquid fuel product after heat exchange enters the high-temperature separation tank 16 for gas-liquid two-phase separation. The heavy product separated at the bottom enters the heavy oil product tank 18 after the liquid level is controlled by the control loop. The gas separated at the top enters the three-phase separator 19 after being cooled by the second condenser 17. In the three-phase separator 19, C1-C4 light hydrocarbon components 21, light oil products and water are further separated.

[0097] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0098] The following examples and comparative examples all use... Figure 2 The system shown is used.

[0099] Example 1 This embodiment provides a method for preparing green aviation kerosene components, including the following steps: (1) First, weigh 12.64g Ni(NO3)2·6H2O (corresponding to a Ni loading of 10wt%) and 1.57g La(NO3)3·6H2O (corresponding to a La loading of 2wt%) and dissolve them in 19 mL of deionized water to prepare an impregnation solution; add 22g of mesoporous MgO support (produced by Hebei Meixi Biotechnology Co., Ltd., with a specific surface area of ​​124m²) 2 Ni and La were loaded into the impregnation solution by adding a sample (with an average pore size of 5.85 nm) and then loading them by an equal-volume impregnation method. The impregnated sample was aged at room temperature (approximately 25 °C) for 15 h, dried at 150 °C for 19 h, and then calcined at 520 °C for 4 h to obtain the Ni-La / MgO catalyst.

[0100] (2) Weigh 60.60g Fe(NO3)3·9H2O, 5.37g Mn(NO3)2 solution (concentration 50%), 1.52g KNO3 and 75.6g citric acid monohydrate into a crucible, and then weigh 71.55g deionized water into the mixture. Stir for 1h in an oil bath at 50℃, then heat to 120℃ and stir for 2h. Transfer the crucible to an oven and dry at 120℃ for 12h. Then transfer it to a muffle furnace and calcine at 350℃ for 4h to obtain the Fe-Mn-K catalyst. The molar ratio of Mn to Fe is 10:100 and the molar ratio of K to Fe is 10:100.

[0101] (3) Using carbon-rich natural gas with a volume ratio of CH4 to CO2 of 100:33 as raw material, steam is introduced, with a volume ratio of steam to CH4 of 61:100. The Ni-La / MgO catalyst prepared in step (1) is used. The preheated raw material gas is introduced into the double-stage reaction unit and subjected to a reaction at 700℃, 0.2MPa, and a space velocity of 1000h. -1 Under certain conditions, a double-integration reaction is carried out to produce syngas with an H2 / CO molar ratio of approximately 2.0.

[0102] (4) The synthesis gas enters the Fischer-Tropsch fluidized bed reactor and uses the Fe-Mn-K catalyst prepared in step (2) to carry out the Fischer-Tropsch synthesis reaction at 300℃ and 2MPa to obtain liquid fuel. The liquid fuel enters the preheating furnace to exchange heat with the raw gas, and then enters the product separation monomer for separation to obtain green aviation kerosene components.

[0103] Example 2 This embodiment provides a method for preparing green aviation kerosene components, including the following steps: (1) First, weigh 18.96g Ni(NO3)2·6H2O (corresponding to a Ni loading of 15wt%) and 0.79g La(NO3)3·6H2O (corresponding to a La loading of 1wt%) and dissolve them in 18mL of deionized water to prepare an impregnation solution; add 21g of mesoporous MgO support (produced by Hebei Meixi Biotechnology Co., Ltd., with a specific surface area of ​​124m²) 2 Ni and La were loaded into the impregnation solution by adding a sample (with an average pore size of 5.85 nm) and then loading the sample with La using an equal-volume impregnation method. The impregnated sample was aged at room temperature (approximately 25 °C) for 15 h, dried at 110 °C for 20 h, and then calcined at 500 °C for 4 h to obtain the Ni-La / MgO catalyst.

[0104] (2) Weigh 60.60g Fe(NO3)3·9H2O, 2.68g Mn(NO3)2 solution (concentration 50%), 0.76g KNO3 and 69.31g citric acid monohydrate into a crucible, then weigh 66.68g deionized water into the mixture. Stir for 1h in an oil bath at 50℃, then heat to 120℃ and stir for 2h. Transfer the crucible to an oven and dry at 120℃ for 12h. Then transfer it to a muffle furnace and calcine at 350℃ for 4h to obtain the Fe-Mn-K catalyst. The molar ratio of Mn to Fe is 5:100 and the molar ratio of K to Fe is 5:100.

[0105] (3) Using carbon-rich natural gas with a volume ratio of CH4 to CO2 of 100:41 as raw material, steam was introduced, with a volume ratio of steam to CH4 of 72:100. The Ni-La / MgO catalyst prepared in step (1) was used. The preheated raw material gas was introduced into the double reforming unit. The double reforming reaction was carried out at 650℃, 0.4MPa, and space velocity of 3000h. -1 Under certain conditions, a double-integration reaction is carried out to produce syngas with an H2 / CO molar ratio of approximately 2.1.

[0106] (4) The synthesis gas enters the Fischer-Tropsch fluidized bed reactor and uses the Fe-Mn-K catalyst prepared in step (2) to carry out the Fischer-Tropsch synthesis reaction at 320℃ and 3MPa to obtain liquid fuel. The liquid fuel enters the preheating furnace to exchange heat with the feed gas, and then enters the product separation monomer for separation to obtain green aviation kerosene components.

[0107] Example 3 This embodiment provides a method for preparing green aviation kerosene components, including the following steps: (1) First, weigh 8.85g Ni(NO3)2·6H2O (corresponding to a Ni loading of 7wt%) and 0.40g La(NO3)3·6H2O (corresponding to a La loading of 0.5wt%) and dissolve them in 20mL of deionized water to prepare an impregnation solution; add 23g of mesoporous MgO support (produced by Hebei Meixi Biotechnology Co., Ltd., with a specific surface area of ​​124m²) 2 Ni-La catalyst (with an average pore size of 5.85 nm) was added to the impregnation solution and Ni and La were loaded by equal-volume impregnation. The impregnated sample was aged at room temperature (about 25 °C) for 14 h, dried at 130 °C for 22 h, and then calcined at 500 °C for 5 h to obtain Ni-La / MgO catalyst.

[0108] (2) Weigh 60.60g Fe(NO3)3·9H2O, 5.37g Mn(NO3)2 solution (concentration 50%), 1.52g KNO3 and 75.6g citric acid monohydrate into a crucible, and then weigh 71.55g deionized water into the mixture. Stir for 1h in an oil bath at 50℃, then heat to 120℃ and stir for 2h. Transfer the crucible to an oven and dry at 120℃ for 12h. Then transfer it to a muffle furnace and calcine at 350℃ for 4h to obtain the Fe-Mn-K catalyst. The molar ratio of Mn to Fe is 10:100 and the molar ratio of K to Fe is 10:100.

[0109] (3) Using carbon-rich natural gas with a volume ratio of CH4 to CO2 of 100:35 as raw material, steam was introduced, with a volume ratio of steam to CH4 of 68:100. The Ni-La / MgO catalyst prepared in step (1) was used. The preheated raw material gas was introduced into the double-stage reaction unit and subjected to a reaction at 730°C, 0.5 MPa, and a space velocity of 2500 h⁻¹. -1 Under certain conditions, a double-integration reaction is carried out to produce syngas with an H2 / CO molar ratio of approximately 2.1.

[0110] (4) The synthesis gas enters the Fischer-Tropsch fluidized bed reactor and uses the Fe-Mn-K catalyst prepared in step (2) to carry out the Fischer-Tropsch synthesis reaction at 310℃ and 2.5MPa to obtain liquid fuel. The liquid fuel enters the preheating furnace to exchange heat with the feed gas, and then enters the product separation monomer for separation to obtain green aviation kerosene components.

[0111] Example 4 This embodiment provides a method for preparing green aviation kerosene components, including the following steps: (1) First, weigh 15.17g Ni(NO3)2·6H2O (corresponding to a Ni loading of 12wt%) and 1.18g La(NO3)3·6H2O (corresponding to a La loading of 1.5wt%) and dissolve them in 19mL of deionized water to prepare an impregnation solution; add 22g of mesoporous MgO support (produced by Hebei Meixi Biotechnology Co., Ltd., with a specific surface area of ​​124m²) 2 Ni and La were loaded into the impregnation solution by adding a sample (with an average pore size of 5.85 nm) and then loading them using an equal-volume impregnation method. The impregnated sample was aged at room temperature (approximately 25 °C) for 15 h, dried at 120 °C for 20 h, and then calcined at 500 °C for 4 h to obtain the Ni-La / MgO catalyst.

[0112] (2) Weigh 60.60g Fe(NO3)3·9H2O, 5.37g Mn(NO3)2 solution (concentration 50%), 1.52g KNO3 and 75.6g citric acid monohydrate into a crucible, then weigh 71.55g deionized water into the mixture. Stir for 1h in an oil bath at 50℃, then heat to 120℃ and stir for 2h. Transfer the crucible to an oven and dry at 120℃ for 12h. Then transfer it to a muffle furnace and calcine at 350℃ for 4h to obtain the Fe-Mn-K catalyst. The molar ratio of Mn to Fe is 10:100 and the molar ratio of K to Fe is 10:100.

[0113] (3) Using carbon-rich natural gas with a volume ratio of CH4 to CO2 of 100:33 as raw material, steam was introduced, with a volume ratio of steam to CH4 of 61:100. The Ni-La / MgO catalyst prepared in step (1) was used. The preheated raw material gas was introduced into the double-stage reaction unit and subjected to a reaction at 620°C, 0.3 MPa, and a space velocity of 2000 h⁻¹. -1 Under certain conditions, a double-integration reaction is carried out to produce syngas with an H2 / CO molar ratio of approximately 2.0.

[0114] (4) The synthesis gas enters the Fischer-Tropsch fluidized bed reactor and uses the Fe-Mn-K catalyst prepared in step (2) to carry out the Fischer-Tropsch synthesis reaction at 305℃ and 2.2MPa to obtain liquid fuel. The liquid fuel enters the preheating furnace to exchange heat with the feed gas, and then enters the product separation monomer for separation to obtain green aviation kerosene components.

[0115] Example 5 This embodiment provides a method for preparing green aviation kerosene components, including the following steps: (1) First, weigh 6.32g Ni(NO3)2·6H2O (corresponding to a Ni loading of 5wt%) and 1.57g La(NO3)3·6H2O (corresponding to a La loading of 2wt%) and dissolve them in 30mL of deionized water to prepare an impregnation solution; add 22g of mesoporous MgO support (produced by Hebei Meixi Biotechnology Co., Ltd., with a specific surface area of ​​124m²) 2 Ni and La were loaded into the impregnation solution by adding a sample (with an average pore size of 5.85 nm) and then loading them using an equal-volume impregnation method. The impregnated sample was aged at room temperature (approximately 25 °C) for 12 h, dried at 110 °C for 18 h, and then calcined at 500 °C for 4 h to obtain the Ni-La / MgO catalyst.

[0116] (2) Weigh 60.60g Fe(NO3)3·9H2O, 5.37g Mn(NO3)2 solution (concentration 50%), 1.52g KNO3 and 75.6g citric acid monohydrate into a crucible, then weigh 71.55g deionized water into the mixture. Stir for 1h in an oil bath at 50℃, then heat to 120℃ and stir for 2h. Transfer the crucible to an oven and dry at 120℃ for 12h. Then transfer it to a muffle furnace and calcine at 350℃ for 4h to obtain the Fe-Mn-K catalyst. The molar ratio of Mn to Fe is 10:100 and the molar ratio of K to Fe is 10:100.

[0117] (3) Using carbon-rich natural gas with a volume ratio of CH4 to CO2 of 100:33 as raw material, steam was introduced, with a volume ratio of steam to CH4 of 61:100. The Ni-La / MgO catalyst prepared in step (1) was used. The preheated raw material gas was introduced into the double-stage reaction unit and subjected to a reaction at 620°C, 0.3 MPa, and a space velocity of 2000 h⁻¹. -1 Under certain conditions, a double-integration reaction is carried out to produce syngas with an H2 / CO molar ratio of approximately 2.0.

[0118] (4) The synthesis gas enters the Fischer-Tropsch fluidized bed reactor and uses the Fe-Mn-K catalyst prepared in step (2) to carry out the Fischer-Tropsch synthesis reaction at 330℃ and 3.5MPa to obtain liquid fuel. The liquid fuel enters the preheating furnace to exchange heat with the feed gas, and then enters the product separation monomer for separation to obtain green aviation kerosene components.

[0119] Example 6 This embodiment provides a method for preparing green aviation kerosene components, which differs from Example 1 in that: In step (1), a nano-MgO carrier (produced by Hebei Magnesium Biotechnology Co., Ltd., with a specific surface area of ​​59 m²) is used. 2 / g, with an average pore size of 1.3nm) to replace mesoporous MgO support.

[0120] Example 7 This embodiment provides a method for preparing green aviation kerosene components, which differs from Example 1 in that: Step (1) The preparation method of the mesoporous MgO support includes: 25.6 g of Mg(NO3)2 was dissolved in 80 mL of deionized water to obtain a magnesium salt solution. 3.84 g of citric acid was dissolved in 20 mL of deionized water, and ammonia was added dropwise to adjust the pH to 6.8 to obtain an ammonium citrate solution. The ammonium citrate solution was added to the magnesium salt solution, and the mixture was stirred at room temperature for 20 min. Then, 3.0 g of sorbitol was added, and the mixture was stirred for another 15 min to obtain a mixed solution. Separately, 9.5 g of ammonium bicarbonate was dissolved in 50 mL of ice water and slowly added dropwise to the obtained mixed solution at approximately 3°C over a period of 30 min. After the addition was complete, the mixture was stirred for another 20 min to obtain the precursor slurry.

[0121] The precursor slurry was dropped into liquid nitrogen and rapidly frozen, and then freeze-dried at -50°C for 18 hours to obtain a solid precursor.

[0122] The solid precursor was placed in a furnace for calcination: first, it was heated to 180℃ for 1 hour, then heated to 320℃ for 2 hours, and finally heated to 500℃ for 2 hours. After natural cooling, mesoporous MgO support was obtained.

[0123] Example 8 This embodiment provides a method for preparing green aviation kerosene components, which differs from Example 1 in that: In step (4), no gas distributor is installed in the Fischer-Tropsch fluidized bed reactor.

[0124] Example 9 This embodiment provides a method for preparing green aviation kerosene components, which differs from Example 1 in that: In step (4), the liquid fuel is directly fed into the product separation unit for separation. Instead of using the liquid fuel product to preheat the raw gas, an electric heating jacket is used to preheat the raw gas.

[0125] Some of the preparation process parameters in the above embodiments and comparative examples are shown in Tables 1 and 2.

[0126] Table 1. Some preparation process parameters in the double-integration reaction

[0127] Table 2. Some preparation process parameters in the Fischer-Tropsch synthesis reaction.

[0128] Performance testing and results analysis The liquid fuels obtained in the above embodiments and comparative examples were subjected to performance tests. The test results are shown in Table 3. The specific test methods are as follows: (1) C5+ product selectivity The products were characterized using a combined gas-liquid analysis method. The reaction tail gas was analyzed by online gas chromatography, with TCD used to detect H2, CO, CO2, and inert internal standard gas, and FID used to detect CH4 and C2+ hydrocarbon products. The condensed oil phase and waxy products were weighed, quantified with internal standard, and their carbon number distribution was analyzed by GC-FID, followed by component qualitative analysis using GC-MS. For heavy wax components, high-temperature gas chromatography was used to supplement the determination of their high-boiling-point fraction distribution.

[0129] C5+ selectivity is calculated based on carbon molarity, according to the proportion of carbon molarity in all C5 and above gaseous, liquid, and waxy hydrocarbon products to the total carbon molarity of CO conversion; a full carbon balance check is also performed.

[0130] (2) C8-C in C5+ products 16 content Compositional analysis of C5+ liquid products was performed using gas chromatography. After heating, melting, and mixing the samples, and adding internal standards, the carbon number distribution of hydrocarbon products was determined using GC-FID. A C5–C5 standard was established using a mixture of n-alkane standards. 30 Retention time scale; each component is divided into C5–C7 and C8–C8 based on retention time and GC-MS qualitative results. 16 and C 17 + Fraction. C8–C 16 The content is calculated as the ratio of the sum of the masses of each component within the carbon number range to the total mass of the C5+ liquid product.

[0131] (3) Power consumption The main design parameters of the system for preparing green aviation kerosene components are as follows: the rated power of the dual-reactor electric furnace is 2.5 kW, the rated power of the Fischer-Tropsch synthesis reactor heater is 3.6 kW, the rated power of the heating cable is 0.8 kW, and if an additional preheater is added, the preheater heater power is 1.8 kW. Assuming that all heating equipment operates continuously at full power, the power consumption of the system is the sum of the power consumption of each part.

[0132] Table 3. Liquid fuel performance test results

[0133] As can be seen from Tables 1 to 3, the preparation processes used in Examples 1 to 9 of this application have low energy consumption, high selectivity for C5+ liquid fuel products (hydrocarbons with ≥5 carbon atoms), and include aviation kerosene C8-C... 16 The target alkanes have a high content. Specifically, the selectivity of C5+ products is ≥70%, and the C8-C... 16 The content of the target alkane fraction is ≥65wt%, and can reach up to 80wt%.

[0134] A comparison of Examples 1 and 2-8 shows that the composition of the feed gas, the dual catalysts and reaction conditions, as well as the catalysts and reaction conditions for the Fischer-Tropsch synthesis reaction, can synergistically affect product selectivity and C8-C content. 16 Content of the target alkane fraction. A comparison of Examples 1 and 9 shows that preheating the feed gas with liquid fuel products can effectively reduce the overall reaction energy consumption.

[0135] The embodiments described above are some, but not all, of the embodiments of this application. The detailed description of the embodiments of this application is not intended to limit the scope of the claimed application, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this application without inventive effort are within the scope of protection of this application.

Claims

1. A method for preparing green aviation kerosene components, characterized in that, Includes the following steps: A feed gas comprising CH4, CO2, and H2O is subjected to a double reforming reaction in the presence of a Ni-La / MgO catalyst to obtain syngas, wherein the molar ratio of H2 to CO in the syngas is (1.8~2.2):

1. The syngas was subjected to a Fischer-Tropsch synthesis reaction in the presence of a Fe-Mn-K catalyst.

2. The method according to claim 1, characterized in that, The Ni-La / MgO catalyst comprises an MgO support and Ni and La supported on the MgO support; wherein the loading of Ni is 5wt%~15wt% and the loading of La is 0.5wt%~2wt%. Optionally, the MgO support includes at least one of nano-magnesium oxide, light magnesium oxide, or mesoporous magnesium oxide; Optionally, the MgO support is mesoporous magnesium oxide.

3. The method according to claim 2, characterized in that, The MgO support is mesoporous magnesium oxide, and the preparation method of the mesoporous magnesium oxide includes the following steps: The magnesium source, organic ligand, and gas-releasing pore-forming agent were dissolved and mixed in water to obtain a precursor solution; The precursor solution is frozen or gelled and then dried to obtain a solid precursor. The solid precursor is pretreated at temperature T1 to allow the gas-releasing pore-forming agent to thermally decompose and generate gas. The temperature is then raised to T2 for calcination to obtain mesoporous magnesium oxide. Optionally, the magnesium source includes at least one of magnesium nitrate, magnesium acetate, magnesium chloride, magnesium sulfate, or magnesium bicarbonate; Optionally, the organic ligand is an ammonium salt of an organic acid, wherein the organic acid includes at least one of citric acid, tartaric acid, malic acid, maleic acid, or ethylenediaminetetraacetic acid; Optionally, the gas-releasing pore-forming agent includes at least one of ammonium bicarbonate or ammonium carbonate; Optionally, the pretreatment temperature is 150℃≤T1<350℃ and the time is 0.5h~3h; the calcination temperature is 350℃≤T2<650℃ and the time is 0.5h~4h.

4. The method according to claim 1, characterized in that, The preparation method of the Ni-La / MgO catalyst includes the following steps: Nickel salt and lanthanum salt are dissolved in water to obtain an impregnation solution; The Ni-La / MgO catalyst is obtained by impregnating the MgO support with the impregnation solution, followed by drying and calcination. Optionally, the nickel salt is nickel nitrate, and the lanthanum salt is lanthanum nitrate; Optionally, the impregnation step employs equal-volume impregnation; Optionally, the calcination temperature is 400℃~600℃, and the time is 1h~10h; Optionally, after the impregnation step, the process further includes: static aging treatment at 20℃~30℃ for 12h~18h; Optionally, the drying step is performed at a temperature of 100°C to 180°C for 18 hours to 24 hours.

5. The method according to claim 1, characterized in that, The double-integration reaction was carried out at a temperature of 600℃~750℃, a pressure of 0.2MPa~0.5MPa, and a reaction space velocity of 1000h⁻¹. -1 ~3000h -1 ; Optionally, the volume ratio of CH4, CO2 and H2O in the feed gas is 100:(27~43):(57~77).

6. The method according to claim 1, characterized in that, In the Fe-Mn-K catalyst, the molar ratio of Mn to Fe is (5~15):100, and the molar ratio of K to Fe is (1~10):

100.

7. The method according to claim 1, characterized in that, In the Fischer-Tropsch synthesis reaction, the reaction temperature is 300℃~330℃, the reaction pressure is 2.0MPa~3.5MPa, and the molar ratio of H2 to CO is (1.9~2.1):

1.

8. A system for use in the method of any one of claims 1 to 7, characterized in that It includes a feed unit, a dual reaction unit, a separation and pressurization unit, and a Fischer-Tropsch reaction unit connected in sequence; The feed gas enters the dual reforming unit via the feed unit for dual reforming, and the resulting synthesis gas enters the Fischer-Tropsch reaction unit via the separation and pressurization unit for Fischer-Tropsch synthesis; the Fischer-Tropsch reaction unit includes a Fischer-Tropsch fluidized bed reactor.

9. The system of claim 8, wherein, A gas distributor is provided at the inlet of the Fischer-Tropsch fluidized bed reactor, through which the syngas enters the reaction chamber of the fluidized bed reactor.

10. The system of claim 8, wherein, A preheating unit is also provided between the feeding unit and the dual reaction unit. The preheating unit is thermally coupled to the Fischer-Tropsch reaction unit and is used to preheat the raw gas entering the preheating unit by using the heat of reaction released by the Fischer-Tropsch synthesis reaction as a heat source.

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