Method for preparing aviation kerosene from distiller's grains

Abstract

This invention discloses a method for preparing aviation kerosene from distillers' grains, comprising: enzymatically hydrolyzing the raw material containing distillers' grains to obtain enzymatic hydrolysis products; sequentially drying and crushing the enzymatic hydrolysis products to obtain crushed material; gasifying the crushed material to obtain crude syngas; subjecting the crude syngas to decoking, desulfurization, and denitrification to obtain syngas; subjecting the syngas to Fischer-Tropsch synthesis under the action of a Fischer-Tropsch catalyst, and fractionating the products of the Fischer-Tropsch synthesis reaction to obtain high-carbon hydrocarbons and low-carbon hydrocarbons; hydrogenating the high-carbon hydrocarbons, followed by distillation and blending of the hydrogenation reaction products to obtain aviation kerosene. This application uses distillers' grains as raw material, and through enzymatic hydrolysis, gasification, purification, Fischer-Tropsch synthesis, and step-by-step refining, produces a complete component aviation kerosene in a single process, improving yield and added value, and realizing high-value utilization of solid waste.

Description

Technical Field

[0001] This invention relates to the field of aviation kerosene preparation technology, and more specifically, to a method for preparing aviation kerosene using distillers' grains as raw material. Background Technology

[0002] Syngas, a basic chemical raw material and energy carrier with CO and H2 as its core components and small amounts of CO2 and CH4, has a history of development that can be traced back to coal gasification technology in the late 19th century. Early on, it was mainly used to produce "water gas" through coal gasification, which was then used for urban lighting and heating. With the rise of petrochemicals in the mid-20th century, the development of syngas slowed down. Currently, driven by fossil fuel shortages, increasing environmental pressures, and the upgrading of the chemical industry, the value of syngas has once again become apparent. Today, syngas has become a key link between basic raw materials and high-value products, indispensable in industries such as fertilizers, methanol, olefins, and hydrogen energy. Especially under the global "dual-carbon" trend, the low-carbon production of syngas has become a core direction for industrial upgrading. The "Guiding Opinions on Accelerating the Green Development of Manufacturing" also proposes the large-scale application of short-process technologies such as one-step syngas-to-olefins production, further highlighting its strategic position.

[0003] The development of biomass gasification processes for syngas production is driven by multiple factors, including the profound transformation of the global energy structure and the demand for high-value utilization of syngas. It is a key path to breaking the dependence on fossil fuels, achieving carbon-neutral energy substitution, and innovating chemical raw materials. Biomass energy, as the only carbon-neutral renewable energy source that can be directly converted into high-value syngas, has abundant sources, including agricultural and forestry waste (straw, sawdust, nutshells), industrial organic waste (furfural residue, pharmaceutical residue), urban organic solid waste (kitchen waste, garden waste), and livestock manure. my country has huge annual biomass reserves. However, traditional treatment methods (landfill, incineration, composting) have problems such as large land occupation, secondary pollution (toxic gases, leachate), and low resource utilization. Syngas (mainly composed of CO and H2, supplemented with small amounts of CO2 and CH4), as a core intermediate product connecting biomass and downstream high-value products, can be further synthesized into liquid energy such as methanol, ethanol, and aviation fuel, or directly used for power generation and heating. It can also be used as a chemical raw material to prepare products such as olefins and ethylene glycol. It can not only replace fossil energy such as coal and natural gas, but also make up for the low efficiency of direct utilization of biomass energy (such as combustion). It can achieve zero carbon emissions in the fields of transportation, industry, and people's livelihood. Its technological breakthrough is of strategic significance for optimizing the energy structure and promoting the green transformation of the chemical industry.

[0004] However, existing biomass gasification technologies and supporting syngas treatment processes all have insurmountable shortcomings: from the perspective of the gasification stage, in fixed-bed gasification, the syngas produced by updraft furnaces has a high tar content (8-20 g / Nm³). 3A high moisture content (8%-15%) not only reduces the calorific value of syngas (typically below 12 MJ / Nm³), but also... 3 Furthermore, it is prone to clogging pipes and causing downstream catalyst poisoning. While downdraft gasifiers produce less tar, their thermal efficiency is poor. Both types of furnaces suffer from uneven air distribution leading to uneven combustion, resulting in low carbon conversion (ash slag carbon content 8%-15%). The effective gas (CO+H2) content in the syngas is less than 50%, making it difficult to meet the needs of chemical synthesis. Fluidized bed gasification is mostly atmospheric pressure air gasification, with N2 accounting for over 40% in the syngas, further diluting the effective gas content. It is only suitable for cogeneration, and the gasification temperature (700-950℃) cannot completely crack the tar, resulting in low methane conversion. Low efficiency (usually below 80%) requires complex tar purification (such as water washing and catalytic reforming) and methane reforming units, increasing investment and energy consumption. Although fluidized bed gasification has high temperature (1200-1400℃) and excellent syngas quality (effective gas ratio of over 70%), it requires raw material particle size to reach the micron level, high biomass fiber content and strong toughness, extremely high energy consumption for pulverization (30%-50% higher than coal pulverization), and easy blockage during the transportation process, making it difficult to supply materials stably. At the same time, the high silica-alumina ratio of ash slag easily corrodes the furnace body, and high pressure modification costs are expensive, resulting in poor economic efficiency for small and medium-sized projects.

[0005] From the perspective of syngas post-treatment, traditional processes still face multiple pain points: First, impurity removal is difficult. Alkali metals (K, Na) and chloride ions in syngas easily condense and scale on the surface of heat exchange equipment. Fine ash (particle size <10μm) treatment costs are high, and the black water produced by wet ash removal has a dust content far exceeding that of coal gasification processes. Subsequent treatment is complex and prone to secondary pollution. Second, effective gas quality and ratio control is difficult. Syngas has a high proportion of inert components such as CO2 and H2O. The H2 / CO ratio usually fluctuates between 0.5 and 1.5, which cannot be directly adapted to downstream processes such as methanol synthesis and Fischer-Tropsch synthesis. Additional adjustments are required through conversion reactions or hydrogen supplementation, increasing energy consumption and process complexity. Third, energy recovery is insufficient. The sensible heat of high-temperature syngas (1000-1400℃) is not effectively utilized. Most systems only cool down the gas, resulting in an energy loss of more than 30%, and failing to achieve the cascade utilization of steam by-products or preheating gasification agents. In addition, problems such as narrow compatibility of raw materials (high-silicon biomass such as rice husks have high ash melting points, and high-moisture biomass such as kitchen waste have low gasification efficiency) and short equipment operation cycles (high-temperature corrosion leads to less than 30 days of continuous operation) further restrict the industrialization process.

[0006] Against this backdrop, the research and development of biomass gasification to syngas production process routes focuses on four major goals: "quality improvement, cost reduction, efficiency enhancement, and expanded adaptability." It urgently requires breakthroughs in bottlenecks through full-chain technological innovation. On the one hand, in the gasification stage, technologies such as high-temperature pyrolysis (900-1300℃), microwave pyrolysis, and non-catalytic POX conversion are being developed to achieve complete tar removal (target <5g / Nm³). 3The project innovates staged gasification and pressurized oxygen-enriched gasification processes to improve carbon conversion efficiency (target >98%), and optimizes the H2 / CO ratio by adjusting the proportion of gasifying agents (O2 / steam / CO2). On the other hand, it develops purification technologies such as low-temperature methanol washing and high-efficiency cyclone separation in the syngas treatment stage to deeply remove impurities such as sulfur, nitrogen, and ash, while integrating radiant waste heat boilers and quench systems to achieve energy recovery. In addition, it develops pretreatment (sodium alkoxide modification, granulation) and co-gasification technologies for high-silicon and high-moisture biomass, and develops integrated equipment such as fluidized bed-flow bed coupled furnaces and three-stage pressurized gasification furnaces, coupling solar thermal storage and green electricity electrolysis to achieve energy complementarity. Through technologies such as CO2 recovery and ash residue preparation of hydrated calcium silicate solids, it achieves full utilization of resources, ultimately promoting the transformation of biomass gasification syngas production from decentralized and inefficient utilization to large-scale, high-value, and zero-carbon industrial applications, and contributing to the global energy transition.

[0007] Existing technologies share a common problem of irrational energy structure: traditional processes generally rely on fossil fuels for supplementary energy; some green electricity application technologies have not solved the problem of energy fluctuations, requiring complex energy storage equipment and increasing costs. Existing pretreatment technologies generally suffer from the problem of "multiple devices and high operational complexity": most adopt a combination of multi-stage crushing and hot flue gas drying, resulting in a large number of devices and requiring professional personnel for operation; some use supercritical and other pretreatment technologies, which require high-pressure equipment, leading to high costs and complex operation. In the gasification stage, traditional processes either use fluidized bed solutions with multiple devices or rely on high-pressure gasification modes, resulting in not only equipment redundancy but also high safety risks.

[0008] In view of this, the present invention is proposed. Summary of the Invention

[0009] The purpose of this invention is to provide a method for preparing aviation kerosene from distillers' grains, thereby realizing the high added value utilization of distillers' grains.

[0010] This invention is implemented as follows: In a first aspect, the present invention provides a method for preparing aviation kerosene using distiller's grains as raw material, comprising: Raw materials containing distiller's grains are subjected to enzymatic hydrolysis to obtain enzymatic hydrolysis products; The enzymatic hydrolysis products are sequentially dried and crushed to obtain crushed material; The crushed material is gasified to obtain crude syngas; The crude syngas is subjected to decoking, desulfurization and denitrification to obtain syngas; The synthesis gas undergoes a Fischer-Tropsch synthesis reaction under the action of a Fischer-Tropsch catalyst, and the products of the Fischer-Tropsch synthesis reaction are fractionated to obtain high-carbon hydrocarbons and low-carbon hydrocarbons. The high-carbon hydrocarbon compound is subjected to a hydrogenation reaction, and then the hydrogenation product is distilled and blended to obtain aviation kerosene.

[0011] In an optional embodiment, the enzymatic hydrolysis reaction is carried out at a pH of 3-7 and a temperature of 40-80°C. And / or, the enzyme used is cellulase, the amount of cellulase added is 0.4-1.2% of the mass of the distiller's grains, and the enzymatic hydrolysis reaction time is 3-16 h; And / or, the moisture content of the crushed material is 20-40%; And / or, the drying temperature is 90-150℃, and the drying time is 10-30 min; And / or, the average particle size of the crushed material is 5-20 mm, and the bulk density is 0.5-0.9 t / m³. 3 ; And / or, the uniformity error of the gasification feed in the gasification step is ≤7%; And / or, the filling amount is 5-20% of the effective volume of the gasification chamber; And / or, the gasification is carried out in the presence of an iron-based catalyst.

[0012] In an optional embodiment, the drying temperature is 110-130℃ and the drying time is 15-20 min; And / or, the average particle size of the crushed material is 7-10 mm, and the bulk density is 0.6-0.8 t / m³. 3 ; And / or, the absolute value of the gasification feed uniformity error in the gasification step is ≤7%; And / or, the vaporization temperature is 700-800℃ and the vaporization time is 30-40min; And / or, the iron-based catalyst is a cerium, lanthanum, or zirconium-modified iron-based catalyst; And / or, the iron-based catalyst is an Fe-CaO catalyst, wherein the mass ratio of Fe to CaO in the Fe-CaO catalyst is 1:1-1:4, and the amount of Fe-CaO catalyst added is 3-10% of the dry weight of the distiller's grains.

[0013] In an optional embodiment, the low-carbon hydrocarbon compound is returned to participate in the Fischer-Tropsch synthesis reaction.

[0014] In an optional embodiment, the decoking process includes passing the crude syngas through an activated carbon tower to obtain decoked syngas. And / or, the desulfurization and denitrification include passing the decoked syngas sequentially through a zinc oxide desulfurization tower, an activated carbon fine desulfurization tower, and a pressure swing adsorption unit to obtain the syngas.

[0015] In an optional embodiment, the gas space velocity in the zinc oxide desulfurization tower and the activated carbon desulfurization tower is 0.3-1 m / s; And / or, the operating pressure of the pressure swing adsorption device is 0.3-0.7 MPa, the adsorption time is 10-60 min, the desorption time is 5-30 min, and the temperature is 20-30℃; And / or, the adsorbent in the pressure swing adsorption device is a composite adsorbent of molecular sieve and activated carbon, with a mass ratio of molecular sieve to activated carbon of 3:1-2:1.

[0016] In an optional embodiment, the Fischer-Tropsch synthesis reaction is carried out at a temperature of 200-350°C, a pressure of 2.0-6.0 MPa, and a synthesis gas hourly space velocity of 10,000-50,000 h⁻¹. -1 ; And / or, the hydrogenation reaction is carried out in the presence of an alumina-supported catalyst, wherein the alumina-supported catalyst is supported with at least one of Ni, Mo, W, Co, and Pt elements; And / or, the hydrogenation reaction is carried out at a temperature of 150-300℃, a pressure of 1.0-5 MPa, a hydrogen-to-oil ratio of 200-2500:1, and a mass hourly space velocity of 0.1-10 h⁻¹. -1 .

[0017] In an optional embodiment, the Fischer-Tropsch synthesis reaction is carried out at a temperature of 240-320°C, a pressure of 3-5.5 MPa, and a synthesis gas hourly space velocity of 15,000-30,000 h⁻¹. -1 ; And / or, the alumina-supported catalyst is supported on at least one of Ni, Mo, Co, and Fe elements, with a loading amount of 40-50 wt%; And / or, the hydrogenation reaction is carried out at a temperature of 180-260℃, a pressure of 2.0-3.5MPa, a hydrogen-to-oil ratio of 400-1800:1, and a mass hourly space velocity of 1-8h. -1 .

[0018] In an optional embodiment, the products of the Fischer-Tropsch synthesis reaction include a mixture of hydrocarbons, which includes alkanes, alkenes and aromatics, wherein the mass fraction of alkenes is greater than 50%, the mass fraction of hydrocarbons with more than 6 Cs is greater than 92%, and the mass fraction of hydrocarbons with more than 8 Cs is greater than 90%.

[0019] In an alternative implementation, all required energy is derived from hydropower, wind power, or solar power.

[0020] The present invention has the following beneficial effects: This application describes the preparation of aviation kerosene from distillers' grains. The process involves enzymatic hydrolysis, drying, crushing, gasification, purification, Fischer-Tropsch synthesis, hydrogenation saturation refining, and distillation to obtain a fully-component aviation kerosene. The advantages of this method include: converting low-value-added distillers' grains waste into high-energy-density, highly compliant aviation kerosene, thus upgrading biomass solid waste to high-end liquid fuel; employing a single closed-loop process to avoid multi-path switching and intermediate product discharge, reducing equipment redundancy and process losses; pre-deconstructing the cellulose / hemicellulose network in the distillers' grains during the enzymatic hydrolysis step, lowering the energy barrier for subsequent gasification reactions; synergistic control of moisture content and particle size distribution through drying and crushing, enhancing feed stability and gasification uniformity; coupled design of the gasification and purification stages, allowing the syngas to achieve an H2 / CO ratio and impurity levels suitable for Fischer-Tropsch synthesis without external hydrogen supplementation or water-vapor shift reaction; and enriching the key distillation range (C8–C9) of aviation kerosene through a step-by-step refining structure of fractionation-hydrogenation-distillation blending. 16 The components are processed and unsaturated bonds and oxygen-containing impurities are removed in a targeted manner to ensure that the final product meets the stringent performance requirements of aviation fuel. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention 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.

[0022] This invention provides a method for preparing aviation kerosene using distiller's grains as raw material, comprising: Raw materials containing distiller's grains are subjected to enzymatic hydrolysis to obtain enzymatic hydrolysis products; The enzymatic hydrolysis products are sequentially dried and crushed to obtain crushed material; The crushed material is gasified to obtain crude syngas; The crude syngas is subjected to decoking, desulfurization and denitrification to obtain syngas; The synthesis gas undergoes a Fischer-Tropsch synthesis reaction under the action of a Fischer-Tropsch catalyst, and the products of the Fischer-Tropsch synthesis reaction are fractionated to obtain high-carbon hydrocarbons and low-carbon hydrocarbons. The high-carbon hydrocarbon compound is subjected to a hydrogenation reaction, and then the hydrogenation product is distilled and blended to obtain aviation kerosene.

[0023] This application presents a method for preparing aviation kerosene using distillers' grains as raw material. The method involves enzymatically hydrolyzing the distillers' grains, drying and pulverizing the enzymatic hydrolysis products, and then gasifying the enzymatic hydrolysis products to obtain crude syngas. The crude syngas is purified to remove sulfur and nitrogen compounds. The syngas is then passed through a Fischer-Tropsch reactor to obtain hydrocarbon compounds. Subsequently, the hydrocarbon compounds undergo hydrogenation saturation purification, and distillation yields a complete aviation kerosene product. This method reduces the amount of reaction equipment required while increasing the yield of aviation kerosene. The method described in this application has the following advantages: it transforms the originally low-value-added and difficult-to-treat distillery waste into high-energy-density and highly compliant aviation kerosene, achieving a targeted upgrade from biomass solid waste to high-end liquid fuel; through a single closed-loop process of "enzymatic hydrolysis—drying—crushing—gasification—purification—Fischer-Tropsch synthesis—fractionation—hydrogenation—distillation blending," it avoids multiple path switching and the discharge of intermediate products, reducing equipment redundancy and process losses; the enzymatic hydrolysis step pre-deconstructs the cellulose / hemicellulose network in the distillery waste, lowering the energy barrier for subsequent gasification reactions; drying and crushing synergistically control moisture content and particle size distribution, significantly enhancing feed stability and gasification reaction uniformity; the coupled design of the gasification and purification stages allows the syngas to directly obtain an H2 / CO ratio and impurity level suitable for Fischer-Tropsch synthesis without the need for external hydrogen supplementation or water-vapor conversion; relying on the tiered refining structure of fractionation—hydrogenation—distillation blending, it achieves the key distillation range of aviation kerosene (C8–C9). 16 Component enrichment and targeted removal of unsaturated bonds / oxygen-containing impurities ensure that the final product meets the stringent chemical and physical performance requirements of aviation fuel.

[0024] In an optional embodiment, the enzymatic hydrolysis reaction is carried out at a pH of 3-7 and a temperature of 40-80°C.

[0025] In an optional embodiment, the enzyme used is cellulase, and the amount of cellulase added is 0.4-1.2% of the mass of the distiller's grains, and the enzymatic hydrolysis reaction time is 3-16 hours.

[0026] In an optional embodiment, the moisture content of the crushed material is 20-40%.

[0027] In an optional embodiment, the drying temperature is 90-150℃ and the drying time is 10-30 min; preferably, the drying temperature is 110-130℃ and the drying time is 15-20 min.

[0028] In an optional embodiment, the average particle size of the crushed material is 5-20 mm, and the bulk density is 0.5-0.9 t / m³. 3 Preferably, the average particle size of the crushed material is 7-10 mm, and the bulk density is 0.6-0.8 t / m³. 3 .

[0029] In an optional implementation, the absolute value of the uniformity error of the gasification feed in the gasification step is ≤7%, preferably ≤5%.

[0030] In an optional embodiment, the vaporization temperature is 600-900℃ and the vaporization time is 20-50 min; preferably, the vaporization temperature is 700-800℃ and the vaporization time is 30-40 min.

[0031] In an optional implementation, the filling amount is 5-20% of the effective volume of the gasification chamber.

[0032] In an optional embodiment, the gasification is carried out in the presence of an iron-based catalyst, which is a cerium, lanthanum, or zirconium-modified iron-based catalyst or an Fe-CaO catalyst. The Fe-CaO catalyst has a Fe to CaO mass ratio of 1:1 to 1:4, and the Fe-CaO catalyst is added at 3-10% of the dry weight of the distiller's grains. Through the iron-based catalyst, the enzymatic hydrolysis products are directly converted into syngas suitable for Fischer-Tropsch synthesis without additional preparation.

[0033] In an optional embodiment, the decoking process includes passing the crude syngas through an activated carbon tower to obtain decoked syngas. In an optional embodiment, the desulfurization and denitrification include passing the decoked syngas sequentially through a zinc oxide desulfurization tower, an activated carbon fine desulfurization tower, and a pressure swing adsorption device to obtain the syngas.

[0034] In an optional embodiment, the gas space velocity in the zinc oxide desulfurization tower and the activated carbon desulfurization tower is 0.3-1 m / s.

[0035] In an optional embodiment, the operating pressure of the pressure swing adsorption device is 0.3-0.7 MPa, the adsorption time is 10-60 min, the desorption time is 5-30 min, and the temperature is 20-30℃.

[0036] In an optional embodiment, the adsorbent in the pressure swing adsorption device is a composite adsorbent of molecular sieve and activated carbon, with a mass ratio of molecular sieve to activated carbon of 3:1-2:1.

[0037] In an optional embodiment, the Fischer-Tropsch synthesis reaction is carried out at a temperature of 200-350°C, a pressure of 2.0-6.0 MPa, and a synthesis gas hourly space velocity of 10,000-50,000 h⁻¹. -1 Preferably, the Fischer-Tropsch synthesis reaction is carried out at a temperature of 240-320°C, a pressure of 3-5.5 MPa, and a syngas space velocity of 15000-30000 h⁻¹. -1 .

[0038] In an optional embodiment, the low-carbon hydrocarbon compound is returned to participate in the Fischer-Tropsch synthesis reaction.

[0039] In an optional embodiment, the hydrogenation reaction is carried out in the presence of an alumina-supported catalyst, wherein the alumina-supported catalyst is supported with at least one of Ni, Mo, W, Co, and Pt elements; preferably, the alumina-supported catalyst is supported with at least one of Ni, Mo, Co, and Fe elements, and the loading amount is 40-50 wt%.

[0040] In an optional embodiment, the hydrogenation reaction is carried out at a temperature of 150-300°C, a pressure of 1.0-5 MPa, a hydrogen-to-oil ratio of 200-2500:1, and a mass hourly space velocity of 0.1-10 h⁻¹. -1 Preferably, the hydrogenation reaction is carried out at a temperature of 180-260℃, a pressure of 2.0-3.5 MPa, a hydrogen-to-oil ratio of 400-1800:1, and a mass hourly space velocity of 1-8 h⁻¹. -1 .

[0041] In an optional embodiment, the products of the Fischer-Tropsch synthesis reaction include a mixture of hydrocarbons, which includes alkanes, alkenes and aromatics, wherein the mass fraction of alkenes is greater than 50%, the mass fraction of hydrocarbons with more than 6 Cs is greater than 92%, and the mass fraction of hydrocarbons with more than 8 Cs is greater than 90%.

[0042] In optional embodiments, all required energy is derived from hydropower, wind power, or solar power. Combining green electricity and waste heat recovery reduces energy consumption. Specifically, in some optional embodiments, the present invention adopts the following technical route: Under acidic conditions, in a green-electrically driven reactor, cellulase decomposes the distiller's grains into sugars, amino acids, and some small-molecule hydrocarbons. Subsequently, a green-electrically driven paddle dryer, using waste heat from the jet fuel and syngas unit as an auxiliary heat source, reduces the moisture content of the mixture to 20-40%. The recovered steam is sent to a steam pipeline to provide a heat source for the enzymatic hydrolysis reaction. A single-stage crusher, driven by green electricity, crushes the dried mixture. The pretreated mixture is sent to a single-stage cylindrical gasification chamber, where green electricity maintains the temperature. Under the action of a catalyst, crude syngas is generated. The crude syngas passes through an ambient temperature activated carbon tower, a two-stage series ambient temperature desulfurization tower, and a pressure swing adsorption denitrification device. The purified syngas enters a buffer tank, where the H2 / CO ratio is stabilized at 2.0 ± 0.2. Syngas enters a green electrically heated tubular reactor, where hydrocarbon compounds are obtained under the action of a Fischer-Tropsch catalyst. After passing through a fractionation column, high-carbon hydrocarbon compounds and low-carbon hydrocarbon compounds are obtained. The high-carbon hydrocarbons are then sent to the next reaction unit, while the low-carbon hydrocarbons are returned to the previous reactor to continue the reaction. In a green electrically heated fixed-bed hydrogenation reactor, under the action of a Ni-Mo catalyst, some of the unsaturated hydrocarbons in the high-carbon compounds undergo a reduction reaction to obtain saturated hydrocarbons. The crude product is then passed through a distillation column to obtain multi-component hydrocarbon compounds, which are then blended to obtain aviation kerosene that meets the standards.

[0043] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0044] Example 1 This embodiment provides a method for preparing aviation kerosene using distiller's grains as raw material, specifically including the following steps: Enzymatic pretreatment: The purified sorghum lees were fed into the enzymatic hydrolysis reactor at a solid-liquid ratio of 1:5. Deionized water was added at the same ratio, and stirring was started. The pH of the reaction system was adjusted to 5 using industrial-grade citric acid. Cellulase was then added at a rate of 0.8% of the dry weight of the lees. The reaction was maintained at 50°C using a green electric heater, and the mixture was stirred for 8 hours. After the reaction was completed, the pretreated lees were obtained.

[0045] Green Electricity Drying: The enzymatically hydrolyzed distiller's grains are fed into a green electricity-driven paddle dryer via a screw conveyor. Waste heat from the jet fuel synthesis unit serves as an auxiliary heat source. The green electric heating system controls the drying temperature at 110℃, with a material residence time of 15 minutes. The moisture content of the discharged material is monitored in real time during the drying process, ultimately reducing the moisture content of the distiller's grains to 33%. The steam generated during drying is condensed in a condenser and then fed into the steam network as a heat source for insulating the enzymatic hydrolysis reactor.

[0046] Single-stage crushing: The dried distiller's grains are fed into a jaw crusher. The equipment parameters are adjusted to control the average particle size of the crushed material to 7mm. After screening, the bulk density of the material is 0.7 t / m³. 3 The feed uniformity error is 3.2%, meeting the requirements for continuous and stable feeding in the gasification chamber. The crushed material is fed into the gasification feed hopper via a closed belt conveyor.

[0047] Primary catalytic gasification: Crushed distiller's grains are fed into the atmospheric pressure gasification chamber at a uniform rate of 0.05 t / h via a variable frequency screw feeder. Green electric heating maintains the gasification temperature at 760℃. The gasification chamber is filled with Fe-CeO catalyst (mass ratio Fe:CeO2=1 / 3), filling 17% of the effective volume of the chamber. The residence time of the material in the gasification chamber is 37 min. Under the action of the catalyst, the distiller's grains undergo pyrolysis, gasification, and tar cracking reactions, generating crude syngas mainly composed of H2 and CO. The tar cracking rate was measured to reach 96%.

[0048] Preliminary tar removal: After being cooled to room temperature, the crude syngas passes through an activated carbon tower at a space velocity of 0.6 m / s, where the activated carbon physically adsorbs the remaining tar. Samples were taken after treatment, and the tar content in the syngas was found to be 0.9 mg / m³, meeting the requirements of subsequent refining processes.

[0049] Ambient temperature desulfurization and denitrification: The syngas after coking first enters the primary zinc oxide desulfurization tower, where H2S reacts chemically with zinc oxide to form zinc sulfide, removing more than 90% of the sulfur components. It then enters the secondary activated carbon fine desulfurization tower, where the remaining sulfur components are deeply adsorbed, resulting in a syngas sulfur content of 0.04 ppm. The desulfurized syngas is then fed into a green electric pressure swing adsorption unit (PEA) at 0.4 MPa pressure, where molecular sieves selectively adsorb nitrogen components. The desorbed nitrogen is directly discharged into the air, resulting in a syngas nitrogen content of 0.3 ppm.

[0050] Qualified gas buffer: Purified syngas enters 15m 3 An atmospheric pressure buffer tank is equipped with an infrared component detector that monitors the H2 and CO content in real time. When the H2 / CO ratio deviates from 2.0±0.1, the PLC controller automatically adjusts the opening of the reflux valve, returning a portion of the syngas to the vaporization chamber to adjust the reaction conditions, ultimately stabilizing the H2 / CO ratio in the buffer tank at 2.0. When the H2 / CO molar ratio is greater than 2.1, the PLC controller automatically opens the reflux valve wider, increasing the flow rate of syngas returning to the vaporization chamber, reducing the H2 content and increasing the relative proportion of CO, causing the ratio to fall back to 2.0±0.1. When the H2 / CO molar ratio is less than 1.9, the PLC controller automatically closes the reflux valve, reducing the syngas return flow rate, increasing the H2 content and decreasing the relative proportion of CO, causing the ratio to rise back to the target range, ultimately stabilizing the H2 / CO ratio in the buffer tank at 2.0.

[0051] Aviation kerosene synthesis unit: Qualified synthesis gas is pressurized to 7 MPa and then fed into a green electric heating tubular Fischer-Tropsch reactor, with the reaction temperature controlled at 250℃ and the space velocity at 16000 h⁻¹. -1 The pressure was 3.3 MPa. Under the action of SFT-418 catalyst, H2 in the syngas underwent a Fischer-Tropsch synthesis reaction with CO, directionally generating C8-C16 hydrocarbon products, with the C8-C16 fraction accounting for 63% of the products. The Fischer-Tropsch products were then fed into a hydrogenation reactor, where green electric heating maintained the reaction temperature at 270°C and the mass hourly space velocity at 2.6 h⁻¹. -1 The pressure was 3.2 MPa, the hydrogen-to-oil ratio was 500:1, and the mass hourly space velocity was 1 h⁻¹. Hydrogenation refining was carried out under the action of an alumina-supported Ni-Mo catalyst (Ni loading 20 wt%, Mo loading 22 wt%) to remove unsaturated bonds and oxygen-containing compounds. The refined product was sent to an atmospheric distillation column, where it was distilled and blended to obtain aviation kerosene that met the standards.

[0052] Syngas composition: H2 content 66 wt%, CO content 33 wt%, active gas (H2+CO) 99 wt%, sulfur content 0.04 ppm, tar content 0.9 mg / m³ 3 .

[0053] Aviation kerosene product distribution: Its main components are alkanes, alkenes and aromatics, of which the mass fraction of alkenes is 2%, the mass fraction of hydrocarbons with C6 or more is 94%, and the mass fraction of hydrocarbons with C8 or more is 92%.

[0054] Example 2 This embodiment provides a method for preparing aviation kerosene using distiller's grains as raw material, specifically including the following steps: Enzymatic pretreatment: The purified corn distillers' grains were fed into the enzymatic hydrolysis reactor. Deionized water was added at a solid-liquid ratio of 1:5, and stirring was started. The pH of the reaction system was adjusted to 5 using industrial-grade citric acid. Cellulase was then added at a rate of 1% of the dry weight of the distillers' grains. The reaction was maintained at 50°C by electric heating and stirred for 5 hours.

[0055] Green Electricity Drying: The enzymatically hydrolyzed distiller's grains are fed into a green electricity-driven paddle dryer via a screw conveyor. Waste heat from the jet fuel synthesis unit serves as an auxiliary heat source. The green electricity heating controls the drying temperature at 110℃, with a material residence time of 18 minutes. The moisture content of the discharged material is monitored in real time during the drying process, ultimately reducing the moisture content of the distiller's grains to 32%. The steam generated during drying is condensed in a condenser and then fed into the steam network as a heat source for insulating the enzymatic hydrolysis reactor.

[0056] Single-stage crushing: The dried distiller's grains are fed into a jaw crusher. The equipment parameters are adjusted to control the average particle size of the crushed material to 8mm. After screening, the bulk density of the material is 0.6 t / m³. 3 The feed uniformity error is 4%, meeting the requirements for continuous and stable feeding into the gasification chamber. The crushed material is fed into the gasification feed hopper via a closed belt conveyor.

[0057] Primary catalytic gasification: Crushed distiller's grains are fed into the atmospheric pressure gasification chamber at a uniform rate of 0.05 t / h via a variable frequency screw feeder, and the gasification temperature is maintained at 750℃ by green electric heating. The gasification chamber is filled with Fe-CeO (mass ratio Fe:Ce=5 / 3) catalyst, with a filling amount of 10% of the effective volume of the gasification chamber, and the material residence time in the gasification chamber is 35 min. Under the action of the catalyst, the distiller's grains undergo pyrolysis, gasification, and tar cracking reactions to generate crude syngas mainly composed of H2 and CO. The tar cracking rate was measured to be 96.8%.

[0058] Preliminary tar removal: After being cooled to room temperature, the crude syngas passes through an activated carbon tower at a space velocity of 0.6 m / s, where the activated carbon physically adsorbs the remaining tar. Samples were taken after treatment, and the tar content in the syngas was found to be 0.6 mg / m³. 3 This meets the requirements of subsequent refining processes.

[0059] Ambient temperature desulfurization and denitrification: The syngas after coking first enters the primary zinc oxide desulfurization tower, where H2S reacts chemically with zinc oxide to form zinc sulfide, removing more than 90% of the sulfur components. It then enters the secondary activated carbon fine desulfurization tower, where the remaining sulfur components are deeply adsorbed, resulting in a syngas sulfur content of 0.06 ppm. The desulfurized syngas is then fed into a green electric pressure swing adsorption unit (PEA) at 0.4 MPa pressure, where molecular sieves selectively adsorb nitrogen components. The desorbed nitrogen is directly discharged into the air, resulting in a syngas nitrogen content of 0.5 ppm.

[0060] Qualified gas buffer: Purified syngas enters 15m 3 An atmospheric pressure buffer tank is equipped with an infrared component detector that monitors the H2 and CO content in real time. When the H2 / CO ratio deviates from 2.0±0.1, the PLC controller automatically adjusts the opening of the reflux valve, returning some of the syngas to the vaporization chamber to adjust the reaction conditions, ultimately stabilizing the H2 / CO ratio in the buffer tank at 2.05. When the H2 / CO molar ratio is greater than 2.1, the PLC controller automatically opens the reflux valve wider, increasing the flow rate of syngas returning to the vaporization chamber, reducing the H2 content and increasing the relative proportion of CO, causing the ratio to fall back to 2.0±0.1. When the H2 / CO molar ratio is less than 1.9, the PLC controller automatically closes the reflux valve, reducing the syngas return flow rate, increasing the H2 content and decreasing the relative proportion of CO, causing the ratio to rise back to the target range, ultimately stabilizing the H2 / CO ratio in the buffer tank at 2.0.

[0061] Aviation kerosene synthesis unit: Qualified synthesis gas is pressurized to 7 MPa and then fed into a green electric heating tubular Fischer-Tropsch reactor, with the reaction temperature controlled at 260℃ and the space velocity at 20,000 h⁻¹. -1 The pressure was 4.5 MPa. Under the action of the SFT-418 catalyst, H2 in the syngas underwent a Fischer-Tropsch synthesis reaction with CO, directionally generating C8-C16 hydrocarbon products, with the C8-C16 fraction accounting for 63% of the products. The Fischer-Tropsch products were then fed into a hydrogenation reactor, where green electric heating maintained the reaction temperature at 290 °C and the mass hourly space velocity at 1.2 h⁻¹. -1 Pressure 3.2 MPa, hydrogen-to-oil ratio 500:1, mass hourly space velocity 1.3 h⁻¹ -1 Hydrogenation refining was carried out using a Ni-Mo supported alumina catalyst (Ni loading 24 wt%, Mo loading 22 wt%). The refined product was fed into an atmospheric distillation column, where it was distilled and blended to obtain aviation kerosene that met the standards.

[0062] Syngas composition: H2 content 66wt%, CO content 33wt%, active gas (H2+CO) 99wt%, sulfur content 0.06ppm, tar content 0.6mg / m³ 3 .

[0063] Aviation kerosene product distribution: Its main components are alkanes, alkenes and aromatics, of which the mass fraction of alkenes is 4%, the mass fraction of hydrocarbons with C6 or more is 95%, and the mass fraction of hydrocarbons with C8 or more is 92%.

[0064] Example 3 This embodiment provides a method for preparing aviation kerosene using distiller's grains as raw material, specifically including the following steps: Enzymatic pretreatment: The purified beer lees were fed into the enzymatic hydrolysis reactor, and deionized water was added at a solid-liquid ratio of 1:4. Stirring was started, and the pH of the reaction system was adjusted to 4.8 with industrial-grade citric acid. Cellulase was then added at a rate of 1.2% of the dry weight of the lees. The reaction temperature was maintained at 55°C by electric heating, and the reaction was stirred for 5 hours.

[0065] Green Electricity Drying: The enzymatically hydrolyzed distiller's grains are fed into a green electricity-driven paddle dryer via a screw conveyor. Waste heat from the jet fuel synthesis unit serves as an auxiliary heat source. The green electric heating system controls the drying temperature at 105℃, with a material residence time of 16 minutes. The moisture content of the discharged material is monitored in real time during the drying process, ultimately reducing the moisture content of the distiller's grains to 34%. The steam generated during drying is condensed in a condenser and then fed into the steam network as a heat source for insulating the enzymatic hydrolysis reactor.

[0066] Single-stage crushing: The dried distiller's grains are fed into a jaw crusher. The equipment parameters are adjusted to control the average particle size of the crushed material to 6mm. After screening, the bulk density of the material is 0.65 t / m³. 3 The feed uniformity error is 4.1%, meeting the requirements for continuous and stable feeding in the gasification chamber. The crushed material is fed into the gasification feed hopper via a closed belt conveyor.

[0067] Primary catalytic gasification: Crushed distiller's grains are fed into the atmospheric pressure gasification chamber at a uniform rate of 0.06 t / h via a variable frequency screw feeder. Green electric heating maintains the gasification temperature at 720℃. The gasification chamber is filled with Fe-CeO (mass ratio Fe:Ce=3 / 1) catalyst, with a filling amount of 5.5% of the effective volume of the gasification chamber. The residence time of the material in the gasification chamber is 32 min. Under the action of the catalyst, the distiller's grains undergo pyrolysis, gasification, and tar cracking reactions, generating crude syngas mainly composed of H2 and CO. The tar cracking rate was measured to reach 95.3%.

[0068] Preliminary tar removal: After being cooled to room temperature, the crude syngas passes through an activated carbon tower at a space velocity of 0.6 m / s, where the activated carbon physically adsorbs the remaining tar. Samples were taken after treatment, and the tar content in the syngas was found to be 0.7 mg / m³. 3 .

[0069] Ambient temperature desulfurization and denitrification: The syngas after coking first enters the primary zinc oxide desulfurization tower, where H2S reacts chemically with zinc oxide to form zinc sulfide, removing more than 90% of the sulfur components. It then enters the secondary activated carbon fine desulfurization tower, where the remaining sulfur components are deeply adsorbed, resulting in a syngas sulfur content of 0.5 ppm. The desulfurized syngas is then fed into a green electric pressure swing adsorption unit (PEA) at 0.4 MPa pressure, where molecular sieves selectively adsorb nitrogen components. The desorbed nitrogen is directly discharged into the air, resulting in a syngas nitrogen content of 0.3 ppm.

[0070] Qualified gas buffer: Purified syngas enters 15m 3 An atmospheric pressure buffer tank is equipped with an infrared component detector that monitors the H2 and CO content in real time. When the H2 / CO ratio deviates from 2.0±0.1, the PLC controller automatically adjusts the opening of the reflux valve, returning some of the syngas to the vaporization chamber to adjust the reaction conditions, ultimately stabilizing the H2 / CO ratio in the buffer tank at 2.05. When the H2 / CO molar ratio is greater than 2.1, the PLC controller automatically opens the reflux valve wider, increasing the flow rate of syngas returning to the vaporization chamber, reducing the H2 content and increasing the relative proportion of CO, causing the ratio to fall back to 2.0±0.1. When the H2 / CO molar ratio is less than 1.9, the PLC controller automatically closes the reflux valve, reducing the syngas return flow rate, increasing the H2 content and decreasing the relative proportion of CO, causing the ratio to rise back to the target range, ultimately stabilizing the H2 / CO ratio in the buffer tank at 2.0.

[0071] Aviation kerosene synthesis unit: Qualified synthesis gas is pressurized to 7 MPa and then fed into a green electric heating tubular Fischer-Tropsch reactor, with the reaction temperature controlled at 270℃ and the space velocity at 28,000 h⁻¹. -1 The pressure was 5.0 MPa. Under the action of SFT-418 catalyst, H2 in the syngas underwent a Fischer-Tropsch synthesis reaction with CO, directionally generating C8-C16 hydrocarbon products, with the C8-C16 fraction accounting for 70% of the products. The Fischer-Tropsch products were then fed into a hydrogenation reactor, where green electric heating maintained the reaction temperature at 255 °C and the mass hourly space velocity at 0.8 h⁻¹. -1 At a pressure of 3.0 MPa and a hydrogen-to-oil ratio of 500:1, hydrorefining was carried out under the action of a Ni-Mo supported alumina catalyst (Ni loading of 24 wt% and Mo loading of 22 wt%) to remove unsaturated bonds and oxygen-containing compounds. The refined product was sent to an atmospheric distillation column, where it was distilled and blended to obtain jet fuel.

[0072] Implementation effect Syngas composition: H2 content 66%, CO content 33%, active gas 99%, sulfur content 0.09ppm, tar content 0.7mg / m³ 3 .

[0073] Aviation kerosene product distribution: Its main components are alkanes, alkenes and aromatics, of which the mass fraction of alkenes is 26%, the mass fraction of hydrocarbons with C6 or more is 88%, and the mass fraction of hydrocarbons with C8 or more is 76%.

[0074] Example 4 This embodiment provides a method for preparing aviation kerosene using distiller's grains as raw material, specifically including the following steps: Enzymatic pretreatment: The purified mixed distillers' grains (corn distillers' grains + beer distillers' grains = 1:1) were fed into the enzymatic hydrolysis reactor. Deionized water was added at a solid-liquid ratio of 1:4.6, and stirring was started. The pH of the reaction system was adjusted to 5.5 with industrial-grade citric acid. Cellulase was then added at a rate of 1.1% of the dry weight of the distillers' grains. The reaction was maintained at 50°C by electric heating and stirred for 5.5 hours.

[0075] Green Electricity Drying: The enzymatically hydrolyzed distiller's grains are fed into a green electricity-driven paddle dryer via a screw conveyor. Waste heat from the jet fuel synthesis unit serves as an auxiliary heat source. The green electricity heating controls the drying temperature at 115℃, with a material residence time of 19 minutes. The moisture content of the discharged material is monitored in real time during the drying process, ultimately reducing the moisture content of the distiller's grains to 31%. The steam generated during drying is condensed in a condenser and then fed into the steam network as a heat source for insulating the enzymatic hydrolysis reactor.

[0076] Single-stage crushing: The dried distiller's grains are fed into a jaw crusher. The equipment parameters are adjusted to control the average particle size of the crushed material to 8mm. After screening, the bulk density of the material is 0.75 t / m³. 3 The feed uniformity error is 2.8%, meeting the requirements for continuous and stable feeding in the gasification chamber. The crushed material is fed into the gasification feed hopper via a closed belt conveyor.

[0077] Primary catalytic gasification: Crushed distiller's grains are fed into the atmospheric pressure gasification chamber at a uniform rate of 0.06 t / h via a variable frequency screw feeder. Green electric heating maintains the gasification temperature at 780℃. The gasification chamber is filled with Fe-ZrO (mass ratio Fe:Zr=5 / 1) catalyst, filling 7% of the effective volume of the chamber. The residence time of the material in the gasification chamber is 38 min. Under the action of the catalyst, the distiller's grains undergo pyrolysis, gasification, and tar cracking reactions, generating crude syngas mainly composed of H2 and CO. The tar cracking rate was measured to reach 97.5%.

[0078] Preliminary tar removal: After being cooled to room temperature, the crude syngas passes through an activated carbon tower at a space velocity of 0.6 m / s. The activated carbon physically adsorbs the remaining tar. Samples were taken after treatment, and the tar content in the syngas was found to be 0.9 mg / m³. 3 This meets the requirements of subsequent refining processes.

[0079] Ambient temperature desulfurization and denitrification: The syngas after coking first enters the primary zinc oxide desulfurization tower, where H2S reacts with zinc oxide to form zinc sulfide, removing more than 90% of the sulfur components. It then enters the secondary activated carbon fine desulfurization tower, where the remaining sulfur components are deeply adsorbed, resulting in a syngas sulfur content of 0.07 ppm. The desulfurized syngas is then fed into a green electric pressure swing adsorption unit (PEA) at 0.45 MPa, where molecular sieves selectively adsorb nitrogen components. The desorbed nitrogen is directly discharged into the air, resulting in a syngas nitrogen content of 0.5 ppm.

[0080] Qualified gas buffer: Purified syngas enters 15m 3 An atmospheric pressure buffer tank is equipped with an infrared component detector that monitors the H2 and CO content in real time. When the H2 / CO ratio deviates from 2.0±0.1, the PLC controller automatically adjusts the opening of the reflux valve, returning some of the syngas to the vaporization chamber to adjust the reaction conditions, ultimately stabilizing the H2 / CO ratio in the buffer tank at 2.05. When the H2 / CO molar ratio is greater than 2.1, the PLC controller automatically opens the reflux valve wider, increasing the flow rate of syngas returning to the vaporization chamber, reducing the H2 content and increasing the relative proportion of CO, causing the ratio to fall back to 2.0±0.1. When the H2 / CO molar ratio is less than 1.9, the PLC controller automatically closes the reflux valve, reducing the syngas return flow rate, increasing the H2 content and decreasing the relative proportion of CO, causing the ratio to rise back to the target range, ultimately stabilizing the H2 / CO ratio in the buffer tank at 2.0.

[0081] Aviation kerosene synthesis unit: Qualified syngas is pressurized to 6 MPa and then fed into a green electric heating tubular Fischer-Tropsch reactor, with the reaction temperature controlled at 180℃ and the space velocity at 60,000 h⁻¹. -1 The pressure was 4.2 MPa. Under the action of SFT-418 catalyst, H2 in the syngas underwent a Fischer-Tropsch synthesis reaction with CO, directionally generating C8-C16 hydrocarbon products, with the C8-C16 fraction accounting for 40% of the products. The Fischer-Tropsch products were then fed into a hydrogenation reactor, where green electric heating maintained the reaction temperature at 295°C and the mass hourly space velocity at 0.5 h⁻¹. -1 At a pressure of 3.4 MPa and a hydrogen-to-oil ratio of 500:1, hydrorefining was carried out under the action of a Ni-Mo supported alumina catalyst (Ni loading of 21 wt% and Mo loading of 20 wt%) to remove unsaturated bonds and oxygen-containing compounds. The refined product was sent to an atmospheric distillation column, where it was distilled and blended to obtain jet fuel.

[0082] Implementation effect Syngas composition: H2 content 66 wt%, CO content 33 wt%, active gas 99 wt%, sulfur content 0.07 ppm, tar content 0.9 mg / m³ 3 .

[0083] Aviation kerosene product distribution: Its main components are alkanes, alkenes and aromatics, of which the mass fraction of alkenes is 13%, the mass fraction of hydrocarbons with C6 or more is 67%, and the mass fraction of hydrocarbons with C8 or more is 60%.

[0084] Comparative Example 1 Green Electricity Drying: The purified sorghum lees are fed into a green electric-driven paddle dryer via a screw conveyor. Waste heat from the aviation kerosene synthesis unit serves as an auxiliary heat source. The green electric heating system controls the drying temperature at 110℃, with a material residence time of 15 minutes. The moisture content of the discharged material is monitored in real time during the drying process, ultimately reducing the moisture content of the lees to 33%. The steam generated during drying is condensed in a condenser and then fed into the steam network as a heat source for the enzymatic hydrolysis reactor.

[0085] Single-stage crushing: The dried distiller's grains are fed into a jaw crusher. The equipment parameters are adjusted to control the average particle size of the crushed material to 7mm. After screening, the bulk density of the material is 0.7 t / m³. 3 The feed uniformity error is 3.2%, meeting the requirements for continuous and stable feeding in the gasification chamber. The crushed material is fed into the gasification feed hopper via a closed belt conveyor.

[0086] Primary catalytic gasification: Crushed distiller's grains are fed into the atmospheric pressure gasification chamber at a uniform rate of 0.05 t / h via a variable frequency screw feeder, and the gasification temperature is maintained at 760℃ by green electric heating. The gasification chamber is filled with Fe-CeO catalyst (Fe:CeO=1 / 3), with a filling amount of 17% of the effective volume of the gasification chamber, and the material residence time in the gasification chamber is 37 min. Under the action of the catalyst, the distiller's grains undergo pyrolysis, gasification, and tar cracking reactions to generate crude syngas mainly composed of H2 and CO. The tar cracking rate was measured to be 96%.

[0087] Preliminary tar removal: After being cooled to room temperature, the crude syngas passes through an activated carbon tower at a space velocity of 0.6 m / s, where the activated carbon physically adsorbs the remaining tar. Samples were taken after treatment, and the tar content in the syngas was found to be 4.2 mg / m³.

[0088] Ambient temperature desulfurization and denitrification: The syngas after coking first enters the primary zinc oxide desulfurization tower, where H2S reacts chemically with zinc oxide to form zinc sulfide, removing more than 90% of the sulfur components. It then enters the secondary activated carbon fine desulfurization tower, where the remaining sulfur components are deeply adsorbed, resulting in a syngas sulfur content of 0.4 ppm. The desulfurized syngas is then fed into a green electric pressure swing adsorption unit (PEA) at 0.4 MPa pressure, where molecular sieves selectively adsorb nitrogen components. The desorbed nitrogen is directly discharged into the air, resulting in a syngas nitrogen content of 0.3 ppm.

[0089] Qualified gas buffer: Purified syngas enters a 15m³ atmospheric pressure buffer tank, where an infrared component detector monitors the H2 and CO content in real time. When the H2 / CO ratio deviates from 2.0±0.1, the PLC controller automatically adjusts the opening of the reflux valve, returning a portion of the syngas to the vaporization chamber to adjust reaction conditions, ultimately stabilizing the H2 / CO ratio in the buffer tank at 2.0. When the H2 / CO molar ratio is greater than 2.1, the PLC controller automatically opens the reflux valve wider, increasing the flow rate of syngas returning to the vaporization chamber, reducing the H2 content and increasing the relative proportion of CO, causing the ratio to fall back to 2.0±0.1. When the H2 / CO molar ratio is less than 1.9, the PLC controller automatically closes the reflux valve, reducing the syngas return flow rate, increasing the H2 content and decreasing the relative proportion of CO, causing the ratio to rise back to the target range, ultimately stabilizing the H2 / CO ratio in the buffer tank at 2.0.

[0090] Aviation kerosene synthesis unit: Qualified syngas, pressurized to 7 MPa, is fed into a green-electrically heated tubular Fischer-Tropsch reactor. The reaction temperature is controlled at 250°C, space velocity (HSV) at 16000 h⁻¹, and pressure at 3.3 MPa. Under the action of SFT-418 catalyst, H₂ and CO in the syngas undergo a Fischer-Tropsch synthesis reaction, directionally generating C8-C16 hydrocarbon products, with the C8-C16 fraction accounting for 63% of the products. The Fischer-Tropsch products are then fed into a hydrotreating reactor, where green-electric heating maintains the reaction temperature at 270°C, HSV at 2.6 h⁻¹, and pressure at 3.2 MPa, with a hydrogen-to-oil ratio of 500:1 and HSV at 1 h⁻¹. Hydrotreating is performed under the action of an alumina-supported Ni-Mo catalyst (Ni loading 20 wt%, Mo loading 22 wt%) to remove unsaturated bonds and oxygen-containing compounds. The refined product is fed into an atmospheric distillation column, where distillation and blending yield aviation kerosene that meets the standards.

[0091] The composition of the syngas is as follows: H2 content 66 wt%, CO content 33 wt%, active gas (H2+CO) 99 wt%, sulfur content 0.4 ppm, and tar content 4.2 mg / m3.

[0092] Aviation kerosene product distribution: Its main components are alkanes, alkenes and aromatics, of which the mass fraction of alkenes is 2%, the mass fraction of hydrocarbons with C6 or more is 94%, and the mass fraction of hydrocarbons with C8 or more is 92%.

[0093] The properties of the full-component aviation kerosene prepared in each embodiment are shown in Table 1, where the indicators are in accordance with the requirements of the GB6537-2018 standard for "No. 3 Jet Fuel".

[0094] Table 1

[0095] In existing technologies, distillers' grains are mostly disposed of as feed or in landfills, which are low-value-added methods. Furthermore, biomass gasification generally faces problems such as high moisture content and uneven particle size in the raw materials, leading to gasification instability. This application specifically designs a pretreatment process: the green electricity drying stage uses waste heat as an auxiliary heat source to precisely reduce the moisture content of the distillers' grains to 20-40%, reducing green electricity consumption and providing a heat source for enzymatic hydrolysis through steam recovery, thus achieving energy recycling. Single-stage crushing controls the particle size and bulk density of the material, and the feed uniformity error is within a controllable range, solving the industry pain point of uneven feed in biomass gasification from the source. Simultaneously, the enzymatic hydrolysis step converts the distillers' grains into sugars, amino acids, and small-molecule hydrocarbons, decomposing complex components in advance and laying the foundation for subsequent gasification reactions, significantly improving the quality of the finished oil compared to direct gasification.

[0096] Current biomass gasification processes largely rely on fossil fuels, often resulting in insufficient utilization of green electricity and waste of waste heat. This application constructs a dual-drive system of "green electricity + waste heat": core processes such as drying, crushing, gasification heating, and gas compression are all driven by green electricity, avoiding carbon emissions from fossil fuels; the drying process reuses waste heat from jet fuel and syngas units, and enzymatic hydrolysis and insulation reuse the water vapor generated during drying, forming a closed loop of energy cascade utilization, reducing energy consumption compared to traditional applications. Furthermore, the entire process involves no additional fossil fuel input, and combined with the carbon-neutral nature of biomass, the produced jet fuel achieves low carbon emissions throughout its entire life cycle, aligning with the requirements of zero-carbon industrial park construction policies and addressing the shortcomings of existing technologies in terms of green attributes.

[0097] The core challenge of biomass gasification is the high levels of tar, sulfur, and nitrogen impurities, and the difficulty in matching the H2 / CO ratio to the requirements of Fischer-Tropsch synthesis. This application achieves precise control through a three-stage purification system: the first-stage catalytic gasification uses an iron-based catalyst to increase the tar cracking rate to ≥95% at 600-900℃, reducing tar formation at the source; the ambient-temperature activated carbon tower further reduces the tar content to ≤10mg / m³. 3 To prevent equipment blockage, a two-stage series desulfurization tower (zinc oxide + activated carbon) efficiently removes sulfur and nitrogen impurities, protecting the activity of downstream catalysts. Simultaneously, the green-electrically driven pressure swing adsorption unit stabilizes the H2 / CO ratio at 2.0±0.2, eliminating the need for additional water-gas shift adjustment and directly meeting the feed requirements for Fischer-Tropsch synthesis. This solves the problems of large fluctuations in syngas composition and high purification costs associated with existing technologies.

[0098] Existing Fischer-Tropsch synthesis methods for producing jet fuel suffer from insufficient selectivity for long-chain hydrocarbons and require complex post-processing of the products. This application optimizes synthesis parameters to provide a suitable environment for the formation of C9-C16 jet fuel fractions; the hydrorefining process utilizes appropriate catalysts and reaction conditions to effectively remove unsaturated bonds and improve product stability. Compared to traditional catalysts, Ni-Mo catalysts exhibit higher hydrorefining activity. Combined with precisely controlled parameters, this significantly improves the selectivity of jet fuel fractions, allowing them to directly meet aviation kerosene standards after distillation and blending, reducing subsequent refining steps and lowering production costs.

[0099] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing aviation kerosene using distiller's grains as raw material, characterized in that, include: Raw materials containing distiller's grains are subjected to enzymatic hydrolysis to obtain enzymatic hydrolysis products; The enzymatic hydrolysis products are sequentially dried and crushed to obtain crushed material; The crushed material is gasified to obtain crude syngas; The crude syngas is subjected to decoking, desulfurization and denitrification to obtain syngas; The synthesis gas undergoes a Fischer-Tropsch synthesis reaction under the action of a Fischer-Tropsch catalyst, and the products of the Fischer-Tropsch synthesis reaction are fractionated to obtain high-carbon hydrocarbons and low-carbon hydrocarbons. The high-carbon hydrocarbon compound is subjected to a hydrogenation reaction, and then the hydrogenation product is distilled and blended to obtain aviation kerosene.

2. The method for preparing aviation kerosene from distiller's grains according to claim 1, characterized in that, The enzymatic hydrolysis reaction has a pH of 3-7 and a temperature of 40-80℃. And / or, the enzyme used is cellulase, the amount of cellulase added is 0.4-1.2% of the mass of the distiller's grains, and the enzymatic hydrolysis reaction time is 3-16 h; And / or, the moisture content of the crushed material is 20-40%; And / or, the drying temperature is 90-150℃, and the drying time is 10-30 min; And / or, the average particle size of the crushed material is 5-20mm, and the bulk density is 0.5-0.9t / m 3 ; And / or, the uniformity error of the gasification feed in the gasification step is ≤7%; And / or, the amount of crushed material filling is 5-20% of the effective volume of the gasification chamber; And / or, the gasification is carried out in the presence of an iron-based catalyst.

3. The method for preparing aviation kerosene from distiller's grains according to claim 2, characterized in that, The drying temperature is 110-130℃, and the drying time is 15-20 minutes; And / or, the average particle size of the crushed material is 7-10mm, the bulk density is 0.6-0.8t / m 3 ; And / or, the absolute value of the gasification feed uniformity error in the gasification step is ≤7%; And / or, the vaporization temperature is 700-800℃ and the vaporization time is 30-40min; And / or, the iron-based catalyst is a cerium, lanthanum, or zirconium-modified iron-based catalyst; And / or, the iron-based catalyst is an Fe-CaO catalyst, wherein the mass ratio of Fe to CaO in the Fe-CaO catalyst is 1:1-1:4, and the amount of Fe-CaO catalyst added is 3-10% of the dry weight of the distiller's grains.

4. The method for preparing aviation kerosene from distiller's grains according to claim 1, characterized in that, The low-carbon hydrocarbon compounds are returned to participate in the Fischer-Tropsch synthesis reaction.

5. The method for preparing aviation kerosene from distiller's grains according to claim 1, characterized in that, The decoking process involves passing the crude syngas through an activated carbon tower to obtain decoked syngas. And / or, the desulfurization and denitrification include passing the decoked syngas sequentially through a zinc oxide desulfurization tower, an activated carbon fine desulfurization tower, and a pressure swing adsorption device to obtain the syngas.

6. The method for preparing aviation kerosene from distiller's grains according to claim 5, characterized in that, The gas space velocity in the zinc oxide desulfurization tower and the activated carbon fine desulfurization tower is 0.3-1 m / s; And / or, the operating pressure of the pressure swing adsorption device is 0.3-0.7 MPa, the adsorption time is 10-60 min, the desorption time is 5-30 min, and the temperature is 20-30℃; And / or, the adsorbent in the pressure swing adsorption device is a composite adsorbent of molecular sieve and activated carbon, with a mass ratio of molecular sieve to activated carbon of 3:1-2:

1.

7. The method for preparing aviation kerosene from distiller's grains according to claim 1, characterized in that, The temperature of the Fischer-Tropsch synthesis reaction is 200-350°C, the pressure is 2.0-6.0 MPa, and the space velocity of the synthesis gas is 10,000-50,000 h -1 ; And / or, the hydrogenation reaction is carried out in the presence of an alumina-supported catalyst, wherein the alumina-supported catalyst is supported with at least one of Ni, Mo, W, Co, and Pt elements; and / or, the temperature of the hydrogenation reaction is 150-300°C, the pressure is 1.0-5 MPa, the hydrogen / oil ratio is 200-2500:1, and the mass space velocity is 0.1-10 h -1 .

8. The method for preparing aviation kerosene from distiller's grains according to claim 7, characterized in that, The Fischer-Tropsch synthesis reaction takes place at temperatures of 240-320℃, pressures of 3-5.5 MPa, and syngas hourly space velocities of 15,000-30,000 h⁻¹. -1 ; And / or, the alumina-supported catalyst is supported on at least one of Ni, Mo, Co, and Fe elements, with a loading amount of 40-50 wt%; And / or, the hydrogenation reaction is carried out at a temperature of 180-260℃, a pressure of 2.0-3.5MPa, a hydrogen-to-oil ratio of 400-1800:1, and a mass hourly space velocity of 1-8h. -1 .

9. The method for preparing aviation kerosene from distiller's grains according to claim 1, characterized in that, The products of the Fischer-Tropsch synthesis reaction include a mixture of hydrocarbons, which includes alkanes, alkenes and aromatics, wherein the mass fraction of alkenes is greater than 50%, the mass fraction of hydrocarbons with more than 6 Cs is greater than 92%, and the mass fraction of hydrocarbons with more than 8 Cs is greater than 90%.

10. The method for preparing aviation kerosene from distiller's grains according to claim 1, characterized in that, All the required energy comes from hydropower, wind power, or solar power.

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