Method for preparing sustainable aviation fuel feedstock from organic mixed liquid hazardous waste resources

Abstract

The present application belongs to the technical field of waste resource utilization and synthetic fuel, and particularly relates to a method for preparing sustainable aviation fuel raw materials from organic mixed liquid hazardous waste. In the present application, the organic mixed liquid hazardous waste containing heterocyclic aromatic hydrocarbons or halogenated aromatic hydrocarbons is pretreated and then distilled to obtain a mixture mainly containing heterocyclic aromatic hydrocarbons or halogenated aromatic hydrocarbons and short-chain alkanes with a carbon number less than 8. The heterocyclic aromatic hydrocarbons or halogenated aromatic hydrocarbons are completely decomposed by high-temperature cracking, thereby eliminating the hazardous characteristics of the hazardous waste and producing CO and H2 as subsequent product raw materials. The short-chain alkanes in the liquid hazardous waste are separated and used as a polymerization substrate. The substrate is subjected to polymerization reaction, isomerization reaction and fractionation together with raw material gas and green hydrogen to obtain mixed hydrocarbons with a carbon number of 8 to 16 as sustainable aviation fuel raw materials. The present application realizes harmless treatment and resource utilization of the liquid hazardous waste containing heterocyclic aromatic hydrocarbons or halogenated aromatic hydrocarbons, has high process integration degree, and has remarkable economic and environmental benefits.

Description

Technical Field

[0001] This invention belongs to the field of waste resource utilization and synthetic fuel technology, specifically relating to a method for preparing sustainable aviation fuel feedstock from organic mixed liquid hazardous waste. Background Technology

[0002] With increasing pressure on carbon emissions in the global aviation industry, the development of sustainable aviation fuel (SAF) has become an industry consensus. SAF requires similar physicochemical properties to traditional aviation kerosene, while significantly reducing carbon emissions throughout its entire life cycle. Currently, the main raw materials for SAF production include biomass resources such as vegetable oils, waste oils, and agricultural and forestry waste, as well as synthetic fuels produced through the electro-liquid (PtL) route.

[0003] Chemical plants generate large quantities of hazardous liquid waste containing heterocyclic aromatic hydrocarbons (such as pyridine and quinoline) or halogenated aromatic hydrocarbons (such as chlorobenzene and bromobenzene) during production. These hazardous wastes are highly toxic, difficult to degrade, and prone to environmental pollution, and have been included in the "National Hazardous Waste List." Traditional disposal methods mainly involve incineration and secure landfill. Incineration not only wastes carbon and hydrogen resources but also generates secondary pollution (such as dioxins, HCl, and HBr); secure landfill occupies significant land resources and carries the risk of leakage. On the other hand, these hazardous liquid wastes typically contain a certain proportion of short-chain alkanes (C2-C8), which have potential resource utilization value.

[0004] In existing technologies, there are reports of converting hazardous waste containing halogenated aromatics or heterocyclic aromatics into syngas through high-temperature gasification. However, this usually involves gasifying all the waste liquid in a unified manner, without fully utilizing the short-chain alkane components. Meanwhile, the technology for preparing liquid fuels using syngas via Fischer-Tropsch synthesis is relatively mature, but an integrated process for preparing SAF by copolymerizing hazardous waste with short-chain alkanes has not yet been publicly reported. Summary of the Invention

[0005] In view of this, the purpose of this invention is to provide a method for the resource utilization of organic mixed liquid hazardous waste to prepare sustainable aviation fuel feedstock. The method provided by this invention can achieve the harmless treatment and high-value utilization of hazardous waste, and produce SAF products that meet the requirements of aviation fuel while eliminating the hazardous characteristics of hazardous waste.

[0006] To achieve the above objectives, the present invention provides the following technical solution: This invention provides a method for the resource recovery of organic mixed liquid hazardous waste to prepare sustainable aviation fuel feedstock, comprising the following steps: After pretreatment, the organic mixed liquid hazardous waste is separated by distillation to obtain short-chain alkanes with fewer than C8 atoms and a mixture mainly composed of heterocyclic aromatics or halogenated aromatics; the organic mixed liquid hazardous waste contains heterocyclic aromatics or halogenated aromatics. The mixture, which is mainly composed of heterocyclic aromatics or halogenated aromatics, is subjected to high-temperature cracking. The resulting cracked gas is purified to obtain a clean mixed gas. The clean mixed gas includes CO and H2. The clean mixed gas, green hydrogen, and the short-chain alkane with less than C8 are subjected to a polymerization reaction to obtain hydrocarbon products; The hydrocarbon products are subjected to an isomerization reaction, and the resulting isomers are fractionated to obtain a C8-C16 mixed hydrocarbon as a sustainable aviation fuel feedstock.

[0007] Preferably, the pretreatment includes one or more of filtration, centrifugation, and adsorption.

[0008] Preferably, the distillation separation process involves adding an extractant to a distillation column. The extractant alters the gas-liquid balance of the components, causing short-chain alkanes smaller than C8 to distill off from the top of the column, while heterocyclic aromatics or halogenated aromatics are discharged from the bottom of the column along with the extractant. The extractant is then separated in a recovery column and recycled.

[0009] Preferably, the extractant is phenol.

[0010] Preferably, the cutting temperature for the distillation separation is 50~150℃.

[0011] Preferably, the high-temperature pyrolysis temperature is 800~1400℃ and the pressure is 0.1~3.0MPa.

[0012] Preferably, the catalyst used in the polymerization reaction is a Co / Al2O3 catalyst; the cobalt loading in the Co / Al2O3 catalyst is 10~20wt%.

[0013] Preferably, the polymerization reaction is carried out at a temperature of 180-240°C, a pressure of 1.5-3.0 MPa, and a space velocity of 800-1200 h⁻¹. -1 .

[0014] Preferably, the catalyst used in the isomerization reaction is a bifunctional molecular sieve; the bifunctional molecular sieve is a Pt / molecular sieve; and the platinum loading in the Pt / molecular sieve is 0.5~1.5 wt%.

[0015] Preferably, the isomerization reaction is carried out at a temperature of 280~380℃, a reaction pressure of 3.0~8.0MPa, and a hydrogen-to-oil volume ratio of 300~800.

[0016] This invention provides a method for the resource recovery of organic mixed liquid hazardous waste to prepare sustainable aviation fuel feedstock, comprising the following steps: After pretreatment, the organic mixed liquid hazardous waste is separated by distillation to obtain short-chain alkanes with fewer than C8 atoms and a mixture mainly composed of heterocyclic aromatics or halogenated aromatics; the organic mixed liquid hazardous waste contains heterocyclic aromatics or halogenated aromatics. The mixture, which is mainly composed of heterocyclic aromatics or halogenated aromatics, is subjected to high-temperature cracking. The resulting cracked gas is purified to obtain a clean mixed gas. The clean mixed gas includes CO and H2. The clean mixed gas, green hydrogen, and the short-chain alkane with less than C8 are subjected to a polymerization reaction to obtain hydrocarbon products; The hydrocarbon products are subjected to an isomerization reaction, and the resulting isomers are fractionated to obtain a C8-C16 mixed hydrocarbon as a sustainable aviation fuel feedstock.

[0017] Beneficial effects: 1. Harmlessness and resource utilization are unified: Heterocyclic aromatic hydrocarbons or halogenated aromatic hydrocarbons are completely decomposed through high-temperature pyrolysis, which completely eliminates the toxicity, corrosiveness and other harmful characteristics of hazardous waste. At the same time, the CO and H2 generated by pyrolysis are used as raw materials for polymerization reaction, realizing the organic unity of harmless treatment and resource utilization of hazardous waste.

[0018] 2. Significantly improved energy efficiency: By adopting a distillation and splitting strategy, short-chain alkanes are used directly as the polymerization substrate, and only heterocyclic aromatics or halogenated aromatics are cracked at high temperature. This avoids the energy waste of gasifying and rebuilding all components in one go, resulting in a significant improvement in process energy efficiency.

[0019] 3. Low carbon emissions: Introducing green hydrogen as a supplementary hydrogen source significantly reduces the carbon emissions throughout the product's life cycle, giving SAF greater sustainability.

[0020] 4. Excellent product quality: The final C8~C16 fraction has a high content of isoalkanes, excellent low-temperature fluidity, and extremely low aromatic content, fully complying with ASTM D7566 standards.

[0021] 5. Significant economic and environmental benefits: Transforming high-cost hazardous waste into high-value-added SAF products not only reduces hazardous waste disposal costs but also generates revenue from new energy products, while reducing environmental pollution, which aligns with the concept of a circular economy.

[0022] 6. Broad application prospects: This invention can be used for waste treatment and SAF production in enterprises that generate liquid hazardous waste containing heterocyclic aromatics or halogenated aromatics, such as chemical plants, pesticide plants, and pharmaceutical plants, and has broad prospects for industrial application. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the process for preparing sustainable aviation fuel feedstock from organic mixed liquid hazardous waste in an embodiment of the present invention. Detailed Implementation

[0024] This invention provides a method for the resource recovery of organic mixed liquid hazardous waste to prepare sustainable aviation fuel feedstock, comprising the following steps: After pretreatment, the organic mixed liquid hazardous waste is separated by distillation to obtain short-chain alkanes with fewer than C8 atoms and a mixture mainly composed of heterocyclic aromatics or halogenated aromatics; the organic mixed liquid hazardous waste contains heterocyclic aromatics or halogenated aromatics. The mixture, which is mainly composed of heterocyclic aromatics or halogenated aromatics, is subjected to high-temperature cracking. The resulting cracked gas is purified to obtain a clean mixed gas. The clean mixed gas includes CO and H2. The clean mixed gas, green hydrogen, and the short-chain alkane with less than C8 are subjected to a polymerization reaction to obtain hydrocarbon products; The hydrocarbon products are subjected to an isomerization reaction, and the resulting isomers are fractionated to obtain a C8-C16 mixed hydrocarbon as a sustainable aviation fuel feedstock.

[0025] Unless otherwise specified, the present invention does not have special requirements regarding the source of raw materials used, and commercially available products well known to those skilled in the art can be used. Unless otherwise specified, all percentage contents (wt%) mentioned in the present invention refer to mass fractions.

[0026] This invention involves pretreating organic mixed liquid hazardous waste and then performing distillation to separate it into short-chain alkanes with fewer than C8 atoms and a mixture mainly composed of heterocyclic aromatics or halogenated aromatics.

[0027] As one implementation method, the organic mixed liquid hazardous waste contains heterocyclic aromatic hydrocarbons or halogenated aromatic hydrocarbons, and is a waste liquid containing one or more of chlorobenzene, bromobenzene, pyridine and their homologues generated during the production process of a chemical plant. In specific embodiments, it is a chlorobenzene waste liquid, a bromobenzene waste liquid or a pyridine waste liquid.

[0028] In one implementation, the pretreatment includes one or more of filtration, centrifugation, and adsorption, specifically filtration, centrifugation, and adsorption sequentially. The filtration is a plate and frame filter press or microfiltration. The pressure range of the plate and frame filter press is 0~0.6 MPa, specifically 0.2 MPa or 0.4 MPa. This invention does not limit the moisture content of the filter media after filtration. The microporous membrane used for microfiltration is made of polytetrafluoroethylene with a pore size of 0.45 μm. The adsorption material used for adsorption is activated carbon. The activated carbon is biomass granular activated carbon, specifically coconut shell activated carbon. This invention removes solid particulate matter and heavy metal ions from liquid hazardous waste through pretreatment.

[0029] In one embodiment, the equipment used for the distillation separation is a distillation column; the distillation separation process involves adding an extractant to the distillation column, which alters the gas-liquid balance of the components, causing short-chain alkanes smaller than C8 to distill off from the top of the column, while heterocyclic aromatics or halogenated aromatics are discharged from the bottom of the column along with the extractant. The extractant is then separated in a recovery column and recycled; the extractant is phenol; the extractant has a high boiling point.

[0030] As one implementation method, the cutting temperature of the distillation separation is 50~150℃, and in specific embodiments it is 65~125℃, 60~120℃ or 50~115℃, to obtain short-chain alkane fractions with boiling points lower than C8 alkanes and organic mixtures with boiling points higher than C8 alkanes, mainly heterocyclic aromatics or halogenated aromatics.

[0031] After obtaining a mixture mainly composed of heterocyclic aromatic hydrocarbons or halogenated aromatic hydrocarbons, the present invention performs high-temperature cracking on the mixture mainly composed of heterocyclic aromatic hydrocarbons or halogenated aromatic hydrocarbons, and the resulting cracked gas is purified to obtain a clean mixed gas; the clean mixed gas includes CO and H2.

[0032] In one implementation method, the equipment used for high-temperature pyrolysis is a fluidized bed pyrolysis furnace; the pyrolysis medium is oxygen-enriched air; the oxygen volume fraction in the oxygen-enriched air is ≥99%, specifically ≥99% or ≥99.5% in this embodiment; the temperature of the high-temperature pyrolysis is 800~1400℃, specifically 1100℃, 1200℃ or 1300℃ in this embodiment, and the pressure is 0.1~3.0MPa, specifically 1.2MPa, 1.5MPa or 2.0MPa in this embodiment. High-temperature pyrolysis completely decomposes the aromatic ring structure of heterocyclic aromatic hydrocarbons or halogenated aromatic hydrocarbons, eliminating their harmful properties, and simultaneously generating syngas mainly composed of CO and H2.

[0033] In one implementation method, the purification includes: the pyrolysis gas is first washed with an alkaline solution to remove acidic impurities, and then CO2 is removed by pressure swing adsorption to form a clean mixed gas mainly composed of CO and H2; the alkaline solution is a NaOH solution or a KOH solution; the concentration of the NaOH solution is 5~25wt%, specifically 10wt% or 15wt% in this embodiment; the concentration of the KOH solution is 10~30wt%, specifically 20wt% in this embodiment; the washing temperature is 40~90℃, specifically 60℃ or 70℃ in this embodiment, and the pressure is 0.5~2.0MPa, specifically 1.0MPa, 1.2MPa or 1.4MPa in this embodiment. The pressure is MPa, the gas-liquid volume ratio is 100~300:1, specifically 180:1 or 200:1 in the embodiments; the acidic impurities include hydrogen halides or nitrogen-containing compounds, specifically HCl or HBr in the embodiments; when the pyrolysis gas contains nitrogen-containing compounds, the pyrolysis gas is first acid-washed to remove the nitrogen-containing compounds, and then washed with alkaline solution; the nitrogen-containing compound is NH3; the reagent used for acid washing is H2SO4 solution; the concentration is 3~10wt%, specifically 5wt% in the embodiments; the acid washing temperature is 30~80℃, specifically 50℃ in the embodiments, and the pressure is 0.5~2.0MPa, specifically 1.5MPa in the embodiments.

[0034] During the purification process, the gas generated by high-temperature pyrolysis is first washed with alkaline solution to remove acidic impurities such as hydrogen halides (such as HCl, HBr) or nitrogen compounds (such as NH3), and then CO2 is removed by pressure swing adsorption (PSA) to form a clean mixed gas mainly composed of CO and H2.

[0035] After obtaining the clean mixed gas and the short-chain alkane with less than C8, the present invention performs a polymerization reaction on the clean mixed gas, green hydrogen and the short-chain alkane with less than C8 to obtain hydrocarbon products.

[0036] In one embodiment, the short-chain alkanes smaller than C8 are C2-C8 short-chain alkanes; the green hydrogen is generated by water electrolysis; the molar ratio of the short-chain alkanes smaller than C8 (calculated as C6), the clean mixed gas, and the green hydrogen is 1:15-18:38-40, specifically 1:15:38, 1:16:39, or 1:17:40 in specific embodiments, wherein, short-chain alkanes calculated as C6 refer to the molar mass of short-chain alkanes converted to the equivalent amount of hexane; the clean mixed gas is calculated as the total amount of CO and H2; the green hydrogen is calculated as the amount of H2; the catalyst used in the polymerization reaction is a Co / Al2O3 catalyst. The catalyst is a cobalt-containing agent; the cobalt loading in the Co / Al2O3 catalyst is 10-20 wt%, specifically 10 wt%, 15 wt%, or 20 wt% in the embodiments; the mass of the catalyst used in the polymerization reaction is 5-20% of the mass of the short-chain alkanes smaller than C8, specifically 10%, 12%, or 15% in the embodiments; the reaction temperature of the polymerization reaction is 180-240℃, specifically 200℃, 220℃, or 240℃ in the embodiments, the reaction pressure is 1.5-3.0 MPa, specifically 1.8 MPa, 2.0 MPa, or 2.5 MPa in the embodiments, and the space velocity is 800-1200 h⁻¹. -1 In a specific embodiment, it is 800h -1 1000h -1 or 1200h -1 .

[0037] The polymerization reaction aims to extend the carbon chain. Using a Co / Al₂O₃ catalyst for this purpose demonstrates high selectivity for straight-chain and long-chain alkanes. The Co / Al₂O₃ catalyst was purchased from Shandong Jiahong Chemical Co., Ltd.

[0038] During the polymerization reaction, short-chain alkanes, serving as the substrate, undergo chain propagation reactions with CO and H2 under the catalysis of Co / Al2O3 to generate long-chain hydrocarbon products. The green hydrogen produced by water electrolysis provides an additional H2 source, ensuring a sufficient hydrogen-to-carbon ratio in the reaction system while reducing the carbon footprint of the products.

[0039] In this invention, "green hydrogen" refers to hydrogen produced by generating electricity from renewable energy sources (wind, solar, hydro, etc.) and then electrolyzing water. Its carbon emissions throughout its entire lifecycle are zero or extremely low, distinguishing it from gray hydrogen produced from fossil fuels or blue hydrogen produced from fossil fuels with carbon capture. Introducing green hydrogen not only optimizes the hydrogen-to-carbon ratio of the reaction system but also endows the final SAF product with significant low-carbon properties, meeting the requirements of the International Sustainable Development and Carbon Certification (ISCC) for SAF raw materials.

[0040] After obtaining the hydrocarbon products, the present invention performs an isomerization reaction on the hydrocarbon products, and fractionates the resulting isomerized products to obtain a C8-C16 mixed hydrocarbon as a sustainable aviation fuel feedstock.

[0041] In one embodiment, the catalyst used in the isomerization reaction is a bifunctional molecular sieve; the bifunctional molecular sieve is a Pt / molecular sieve, specifically a Pt / SAPO-11 catalyst in this embodiment; the platinum loading in the Pt / molecular sieve catalyst is 0.5~1.5wt%, specifically 0.5~1.0wt% in this embodiment; the mass of the catalyst used in the isomerization reaction is 1~5% of the mass of the hydrocarbon product, specifically 2%, 3% or 4% in this embodiment; the temperature of the isomerization reaction is 280~380℃, specifically 320℃, 340℃ or 360℃ in this embodiment; the reaction pressure is 3.0~8.0MPa, specifically 4.5MPa, 5.0MPa or 6.0MPa in this embodiment; and the hydrogen-to-oil volume ratio is 300~800, specifically 400, 500 or 600 in this embodiment. The hydrogen-to-oil volume ratio = hydrogen volume flow rate entering the reactor per unit time ÷ feedstock oil volume flow rate. In this invention, "oil" refers to the liquid-phase feed of the isomerization reactor, i.e., the hydrocarbon products obtained from upstream polymerization, and "hydrogen" refers to hydrogen gas. As one embodiment, the Pt / SAPO-11 catalyst is prepared as follows: Metal Pt is loaded onto a SAPO-11 molecular sieve support using an equal-volume impregnation method, followed by drying and calcination to obtain the Pt / SAPO-11 catalyst. The drying temperature is 100~140℃, specifically 120℃ in this embodiment, and the drying time is 8~16h, specifically 12h in this embodiment. The calcination temperature is 450~550℃, specifically 500℃ in this embodiment, and the holding time is 3~6h, specifically 4h in this embodiment. The SAPO-11 molecular sieve was purchased from Tianjin Nanhua Catalyst Co., Ltd. The isomerization reaction uses the Pt / SAPO-11 catalyst to increase the isoalkane content of the product and improve low-temperature fluidity.

[0042] In one embodiment, the equipment used for fractionation is a fractionation tower; the C8~C16 fraction obtained by fractionation meets the boiling range requirements of aviation kerosene, and its isoalkane content is not less than 60wt%, specifically 65wt%, 68wt%, or 72wt% in the embodiments; the top temperature of the fractionation tower is 150~250℃, the bottom temperature is 250~300℃, the operating pressure is atmospheric pressure to 0.5MPa, and the reflux ratio is 2:1~5:1, specifically atmospheric pressure operation, top temperature 180℃, bottom temperature 300℃, and reflux ratio 3:1 in the embodiments.

[0043] During fractionation, the side stream (middle section) fraction is C8~C16.

[0044] The C8-C16 fractions obtained by this invention meet the requirements for synthetic hydrocarbons (SPK) in the standard "GSO ASTM D7566:2024 Specification for Hydrocarbon-Containing Fuels for Aero-engines". The key indicators are as follows: density (15℃) 730~772 kg / m³ 3 Freezing point ≤ -40℃ (Jet A) or ≤ -47℃; flash point ≥ 38℃; aromatic content ≤ 0.5% (mass fraction); sulfur content ≤ 15 mg / kg; 10% distillation range, distillation temperature ≤ 205℃, final boiling point ≤ 300℃; net calorific value ≥ 42.8 MJ / kg; cycloalkanes content ≤ 15%; thermal stability (JFTOT) ≥ 325℃.

[0045] The innovative aspects of this invention are as follows: 1. Raw material innovation: Using mixed hydrocarbon hazardous waste containing heterocyclic aromatics or halogenated aromatics generated by chemical plants as raw materials, the hazardous waste that traditionally requires high-cost disposal is transformed into valuable carbon and hydrogen sources for SAF production, realizing "treating waste with waste and turning waste into treasure".

[0046] 2. Collaborative innovation of harmlessness and resource utilization: Heterocyclic aromatic hydrocarbons or halogenated aromatic hydrocarbons are completely decomposed through high-temperature pyrolysis, eliminating their toxicity, corrosiveness and other harmful properties. At the same time, CO and H2 are generated during the pyrolysis process as raw materials for subsequent polymerization reactions, thus achieving the organic unity of harmless treatment and resource utilization.

[0047] 3. Distillation and Cascade Utilization Innovation: Short-chain alkanes in liquid hazardous waste are separated by distillation and directly used as substrates for polymerization reactions, avoiding the energy waste of completely decomposing and rebuilding existing short-chain alkanes. Only heterocyclic aromatics or halogenated aromatics that are difficult to utilize directly are subjected to high-temperature cracking, significantly improving process energy efficiency and carbon utilization.

[0048] 4. Innovative Tri-Source Polymerization: Short-chain alkanes (base material), CO and H2 generated from high-temperature cracking (raw material gas), and green hydrogen generated from water electrolysis (supplementary hydrogen source) are copolymerized. The introduction of green hydrogen not only optimizes the hydrogen-carbon ratio of the reaction, but also significantly reduces the carbon emissions of the product throughout its entire life cycle, giving SAF greater sustainability.

[0049] 5. System integration innovation: The entire process forms a complete chain of "hazardous waste pretreatment - distillation and fractionation - high temperature cracking - purification - three-source polymerization - isomerization - fractionation". The materials and energy of each unit are closely coupled, realizing the full utilization of liquid hazardous waste containing heterocyclic aromatics or halogenated aromatics.

[0050] This invention completely decomposes heterocyclic aromatics or halogenated aromatics through high-temperature pyrolysis, eliminating their harmful properties while generating CO and H2 as raw materials for subsequent products. Short-chain alkanes in the liquid hazardous waste are separated and used as substrates for polymerization reactions, which are then polymerized with raw gas and green hydrogen. This achieves the harmless treatment and resource utilization of liquid hazardous waste containing heterocyclic aromatics or halogenated aromatics. The process has a high degree of integration and significant economic and environmental benefits.

[0051] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments thereof, but they should not be construed as limiting the scope of protection of the present invention.

[0052] Example 1 (using chlorobenzene-containing waste liquid as raw material) (1) Take 1000 kg of chlorobenzene-containing liquid hazardous waste generated by a chemical plant. The composition of the waste is as follows: chlorobenzene 35%, n-hexane 20%, n-heptane 10%, water 20%, solid impurities and others 15%. After removing solid impurities by plate and frame filtration (pressure 0.2 MPa) and centrifugation, heavy metal ions are removed by adsorption of coconut shell activated carbon to obtain 830 kg of pretreated liquid. (2) 830 kg of pretreated liquid was fed into a distillation column, and the temperature at the top of the column was controlled at 65~125℃. Phenol was added as an extractant to change the gas-liquid balance of the components, so that the alkanes were distilled off from the top of the column, and the chlorobenzene and extractant were discharged from the bottom of the column. The extractant was then separated and recycled in the recovery column, and 230 kg of C2~C7 short-chain alkane fraction (mainly n-hexane and n-heptane) and 290 kg of mixture mainly composed of chlorobenzene (chlorobenzene content of about 92wt%) were separated. The remainder was water and light components. (3) 290 kg of chlorobenzene mixture was fed into a fluidized bed pyrolysis furnace. Oxygen-enriched air (oxygen volume fraction ≥ 99.5%) was used as the pyrolysis medium. High-temperature pyrolysis was carried out at 1200℃ and 1.5 MPa. The crude syngas produced by pyrolysis was washed with an alkaline solution (15 wt% NaOH solution, washing temperature 60℃, pressure 1.2 MPa, gas-liquid volume ratio 200:1) to remove acidic gases such as HCl. Then, CO2 was removed by pressure swing adsorption (PSA) to obtain a clean mixed gas of approximately 310 Nm³. 3 (Volume composition: H2 48%, CO 42%, CO2 <1%, HCl <10ppm, the remainder being N2, CH4, etc.) (4) Take 230 kg of short-chain alkanes (approximately 2.7 kmol as C6) separated in step (2), and add them to the polymerization reactor along with the clean mixed gas (approximately 43.2 kmol as CO + H2) obtained in step (3) and the green hydrogen produced by water electrolysis in a molar ratio of 1:16:39. Add 23 kg of Co / Al2O3 catalyst (cobalt loading of 15 wt%, purchased from Shandong Jiahong Chemical Co., Ltd.), and set the reaction temperature to 220℃, pressure to 2.0 MPa, and space velocity to 1000 h⁻¹.-1 The reaction yielded approximately 380 kg of a mixture of long-chain hydrocarbons. (5) 380 kg of long-chain hydrocarbon mixture was subjected to isomerization reaction. The catalyst was Pt / SAPO-11 (the catalyst was prepared by loading metal Pt on SAPO-11 molecular sieve support by equal volume impregnation method, with a loading of 0.5 wt%, drying at 120℃ for 12 h, and calcining at 500℃ for 4 h. SAPO-11 molecular sieve was purchased from Tianjin Nanhua Catalyst Co., Ltd.). The catalyst mass was 7.6 kg. The reaction temperature was 340℃, the pressure was 5.0 MPa, the hydrogen-to-oil volume ratio was 500, and the reaction product entered the fractionation tower. The tower was operated at atmospheric pressure, with a top temperature of 180℃, a bottom temperature of 300℃, and a reflux ratio of 3:1. About 310 kg of C8~C16 fraction was cut off. (6) The C8~C16 fraction obtained was tested and found to have a density (15℃) of 0.752 g / cm³. 3 Freezing point -52℃, flash point 43℃, aromatic content <0.5%, isoalkanes content 68wt%, all indicators meet the requirements for synthetic hydrocarbons (SPK) in the standard "GSO ASTM D7566:2024 Specification for Hydrocarbon-Containing Fuels for Aero-engine Turbines". Key indicator values ​​are as follows: density (15℃) 730~772kg / m³ 3 Freezing point ≤ -40℃ (Jet A) or ≤ -47℃; flash point ≥ 38℃; aromatic content ≤ 0.5% (mass fraction); sulfur content ≤ 15 mg / kg; 10% distillation range, distillation temperature ≤ 205℃, final boiling point ≤ 300℃; net calorific value ≥ 42.8 MJ / kg; cycloalkanes content ≤ 15%; thermal stability (JFTOT) ≥ 325℃, can be directly used as a sustainable aviation fuel feedstock.

[0053] Example 2 (using bromobenzene-containing waste liquid as raw material) (1) Take 1200 kg of bromobenzene-containing liquid hazardous waste generated by a chemical plant. The composition of the liquid is: bromobenzene 30%, n-pentane 15%, n-hexane 12%, water 18%, solid impurities and others 25%. After plate and frame filter (pressure of 0.4 MPa), centrifugation and coconut shell activated carbon adsorption pretreatment, 960 kg of pretreated liquid is obtained. (2) 960 kg of pretreated liquid was fed into a distillation column, and the temperature at the top of the column was controlled at 60~120℃. Phenol was added as an extractant to change the gas-liquid balance of the components, so that the alkanes were distilled off from the top of the column, and the bromobenzene and extractant were discharged from the bottom of the column. The extractant was then separated and recycled in the recovery column, and 260 kg of C2~C7 short-chain alkane fraction (mainly n-pentane and n-hexane) and 310 kg of a mixture mainly composed of bromobenzene (bromobenzene content of about 90 wt%) were separated. The remainder was water and light components. (3) 310 kg of a bromobenzene-containing mixture was fed into a fluidized bed pyrolysis furnace. Oxygen-enriched air (oxygen volume fraction ≥ 99.5%) was used as the pyrolysis medium. High-temperature pyrolysis was performed at 1100 °C and 1.2 MPa. The crude syngas produced was washed with an alkaline solution (20 wt% KOH solution, washing temperature 70 °C, pressure 1.0 MPa, gas-liquid volume ratio 180:1) to remove acidic gases such as HBr. Then, CO2 was removed by pressure swing adsorption (PSA) to obtain a clean mixed gas of approximately 330 Nm³. 3 (Volume composition: H2 46%, CO 44%, CO2 <1%, HBr <10ppm, the remainder being N2, CH4, etc.) (4) Take 260 kg of short-chain alkanes (approximately 3.0 kmol as C6) separated in step (2), and add them to the polymerization reactor along with the clean mixed gas (approximately 51.0 kmol as CO + H2) obtained in step (3) and the green hydrogen generated by water electrolysis in a molar ratio of 1:17:40. Add 31.2 kg of Co / Al2O3 catalyst (cobalt loading of 10 wt%, purchased from Shandong Jiahong Chemical Co., Ltd.), and set the reaction temperature to 200℃, pressure to 1.8 MPa, and space velocity to 800 h⁻¹. -1 The reaction yielded approximately 420 kg of a mixture of long-chain hydrocarbons. (5) 420 kg of long-chain hydrocarbon mixture was subjected to isomerization reaction. The catalyst was Pt / SAPO-11 (the catalyst was prepared by loading metal Pt on SAPO-11 molecular sieve support by equal volume impregnation method, with a loading of 0.5 wt%, drying at 120℃ for 12 h, and calcining at 500℃ for 4 h. SAPO-11 molecular sieve was purchased from Tianjin Nanhua Catalyst Co., Ltd.). The catalyst mass was 12.6 kg. The reaction temperature was 320℃, the pressure was 4.5 MPa, the hydrogen-to-oil volume ratio was 400, and the reaction product entered the fractionation tower. The tower was operated at atmospheric pressure, with a top temperature of 180℃, a bottom temperature of 300℃, and a reflux ratio of 3:1. About 350 kg of C8~C16 fraction was cut off. (6) The density of the obtained C8~C16 fraction (15℃) was measured to be 0.748 g / cm³. 3 It has a freezing point of -55℃, a flash point of 41℃, an aromatic hydrocarbon content of <0.5%, and an isoalkanes content of 72wt%. All indicators meet the requirements for synthetic hydrocarbons (SPK) in the standard "GSO ASTM D7566:2024 Specification for Hydrocarbon Fuels for Aero Turbine Engines".

[0054] Example 3 (using pyridine-containing waste liquid as raw material) (1) Take 1000 kg of pyridine-containing hazardous liquid generated by a chemical plant. The composition of the liquid is as follows: pyridine 32%, n-butane 12%, n-hexane 14%, water 22%, solid impurities and others 20%. After microfiltration (the microporous membrane is made of polytetrafluoroethylene with a pore size of 0.45 μm), centrifugation and coconut shell activated carbon adsorption pretreatment, 820 kg of pretreated liquid is obtained. (2) 820 kg of pretreated liquid was fed into a distillation column, and the temperature at the top of the column was controlled at 50~115℃. Phenol was added as an extractant to change the gas-liquid balance of the components, so that the alkanes were distilled off from the top of the column, and the pyridine and extractant were discharged from the bottom of the column. The extractant was then separated and recycled in the recovery column, and 210 kg of C2~C7 short-chain alkane fraction (mainly n-butane and n-hexane) and 270 kg of a mixture mainly composed of pyridine (pyridine content of about 88wt%) were separated. The remainder was water and light components. (3) 270 kg of pyridine-containing mixture was fed into a fluidized bed pyrolysis furnace. Oxygen-enriched air (oxygen volume fraction ≥ 99%) was used as the pyrolysis medium. High-temperature pyrolysis was carried out at 1300℃ and 2.0 MPa. The crude syngas produced by pyrolysis was first acid-washed (5 wt% H2SO4 solution, washing temperature 50℃, pressure 1.5 MPa) to remove nitrogen-containing compounds such as NH3, then washed with alkaline solution (10 wt% NaOH solution to neutralize residual acid mist, washing temperature 60℃, pressure 1.4 MPa) to remove residual acidic gases. Finally, CO2 was removed by pressure swing adsorption (PSA) to obtain a clean mixed gas of approximately 290 Nm³. 3 (Volume composition: H2 50%, CO 40%, CO2 <1%, NH3 <5ppm, the remainder being N2, CH4, etc.) (4) Take 210 kg of short-chain alkanes (approximately 2.4 kmol as C6) separated in step (2), and add them to the polymerization reactor along with the clean mixed gas (approximately 36.0 kmol as CO + H2) obtained in step (3) and the green hydrogen produced by water electrolysis in a molar ratio of 1:15:38. Add 31.5 kg of Co / Al2O3 catalyst (cobalt loading of 20 wt%, purchased from Shandong Jiahong Chemical Co., Ltd.), and set the reaction temperature to 240℃, pressure to 2.5 MPa, and space velocity to 1200 h⁻¹. -1 The reaction yielded approximately 350 kg of a mixture of long-chain hydrocarbons. (5) 350 kg of long-chain hydrocarbon mixture was subjected to isomerization reaction. The catalyst was Pt / SAPO-11 (the catalyst was prepared by loading metal Pt on SAPO-11 molecular sieve support by equal volume impregnation method, with a loading amount of 0.5 wt%, drying at 120℃ for 12 h, and calcining at 500℃ for 4 h. SAPO-11 molecular sieve was purchased from Tianjin Nanhua Catalyst Co., Ltd.). The catalyst mass was 14.0 kg. The reaction temperature was 360℃, the pressure was 6.0 MPa, the hydrogen-to-oil volume ratio was 600, and the reaction product entered the fractionation tower. The tower was operated at atmospheric pressure, with a top temperature of 180℃, a bottom temperature of 300℃, and a reflux ratio of 3:1. About 290 kg of C8~C16 fraction was cut off. (6) The C8~C16 fraction obtained was tested and found to have a density (15℃) of 0.755 g / cm³. 3 It has a freezing point of -50℃, a flash point of 44℃, an aromatic hydrocarbon content of <0.5%, and an isoalkanes content of 65wt%. All indicators meet the requirements for synthetic hydrocarbons (SPK) in the standard "GSO ASTM D7566:2024 Specification for Hydrocarbon Fuels for Aero Turbine Engines".

[0055] Comparative Example 1 (Traditional Full Gasification Route) 1000 kg of chlorobenzene-containing waste liquid was directly fed into a fluidized bed gasifier without distillation. Using oxygen-enriched air (oxygen volume fraction ≥99%) as the gasification medium, high-temperature gasification was performed at 1300℃ and 2.0 MPa. The resulting crude synthesis gas was washed with an alkaline solution (15 wt% NaOH solution, washing temperature 60℃, pressure 1.2 MPa, gas-liquid volume ratio 200:1) to remove acidic gases such as HCl. Then, CO2 was removed by pressure swing adsorption (PSA) to obtain a clean mixed gas of approximately 480 Nm³. 3 (Volume composition: H2 45%, CO 40%, CO2 <1%, HCl <10ppm, the remainder being N2, CH4, etc.) This clean mixed gas (approximately 21.4 kmol as CO + H2) and electrolyzed water green hydrogen were added to the polymerization reactor at a molar ratio (based on total carbon atoms) of 1:42 (due to the lack of short-chain alkane substrate, more H2 was needed to adjust the hydrogen-carbon ratio). The catalyst was Co / Al2O3, the reaction temperature was 220℃, the pressure was 2.0 MPa, and the space velocity was 1000 h⁻¹. -1 The reaction yielded approximately 360 kg of a mixture of long-chain hydrocarbons. After isomerization (under the same conditions as in Example 1) and fractionation, approximately 210 kg of the C8-C16 fraction was obtained.

[0056] Comparative Example 2 (Direct Aggregation Without Splitting) 830 kg of the same pretreated liquid as in Example 1 (without distillation separation) was added to the polymerization reactor along with a clean mixed gas (generated from the cracking of an equal amount of chlorobenzene-containing mixture) and electrolyzed water and green hydrogen at a molar ratio (based on the total carbon atoms in the pretreated liquid) of 1:18:40. Because the pretreated liquid contained a large amount of heterocyclic / halogenated aromatic hydrocarbons such as chlorobenzene, their aromatic ring structures were difficult to effectively undergo ring-opening polymerization under Co / Al2O3 catalyst conditions, and chlorine easily caused permanent catalyst poisoning. The conversion rate after the reaction was 32%, yielding approximately 280 kg of a hydrocarbon mixture (of which approximately 90 kg was unreacted chlorobenzene). After gas stripping to separate the unreacted aromatic hydrocarbons, isomerization, and fractionation, approximately 180 kg of C8-C16 fraction was obtained, and the product chlorine content was >50 ppm, which did not meet the requirements for SAF feedstock in the "GSO ASTM D7566:2024 Specification for Hydrocarbon Fuels for Aero-engines".

[0057] Comparative Example 3 (without added green hydrogen) Using the same raw materials and process conditions as in Example 1, but without adding electrolyzed water hydrogen in the polymerization step, only the clean mixed gas generated from cracking (H2 / CO≈1.14) was used for the polymerization reaction. Due to the insufficient hydrogen-to-carbon ratio, the polymerization reaction was incomplete, with a CO conversion rate of only about 45%, yielding approximately 220 kg of a long-chain hydrocarbon mixture. After isomerization and fractionation, approximately 170 kg of the C8-C16 fraction was obtained, but the product had low saturation (iodine value >120 g I2 / 100 g), an isoalkane content of only 42 wt%, and a freezing point of only -38°C, which did not meet the low-temperature fluidity requirements for aviation fuel.

[0058] Performance testing The comparison results between Example 1 and Comparative Examples 1-3 are summarized in Table 1.

[0059] Table 1 Summary of comparison results between Example 1 and Comparative Examples 1-3

[0060] As shown in Table 1, calculations indicate that, compared to Comparative Example 1 (full gasification route), Example 1 of this invention achieves approximately 48% higher target product yield and approximately 20% lower energy consumption per unit product; compared to Comparative Example 2 (direct polymerization without splitting), product yield is increased by approximately 72%, and the risk of catalyst poisoning is avoided; compared to Comparative Example 3 (without adding green hydrogen), product yield is increased by approximately 82%, and the product's low-temperature fluidity is significantly improved. In summary, the distillation splitting strategy and green hydrogen replenishment strategy of this invention have significant technical advantages and economic value, reducing carbon emissions over the entire life cycle by more than 35% compared to Comparative Example 1.

[0061] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for the resource utilization of organic mixed liquid hazardous waste to prepare sustainable aviation fuel feedstock, characterized in that, Includes the following steps: After pretreatment, the organic mixed liquid hazardous waste is separated by distillation to obtain short-chain alkanes with fewer than C8 atoms and a mixture mainly composed of heterocyclic aromatics or halogenated aromatics; the organic mixed liquid hazardous waste contains heterocyclic aromatics or halogenated aromatics. The mixture, which is mainly composed of heterocyclic aromatics or halogenated aromatics, is subjected to high-temperature cracking. The resulting cracked gas is purified to obtain a clean mixed gas. The clean mixed gas includes CO and H2. The clean mixed gas, green hydrogen, and the short-chain alkane with less than C8 are subjected to a polymerization reaction to obtain hydrocarbon products; The hydrocarbon products are subjected to an isomerization reaction, and the resulting isomers are fractionated to obtain a C8-C16 mixed hydrocarbon as a sustainable aviation fuel feedstock.

2. The method according to claim 1, characterized in that, The pretreatment includes one or more of filtration, centrifugation, and adsorption.

3. The method according to claim 1, characterized in that, The distillation separation process involves adding an extractant to a distillation column. The extractant alters the gas-liquid balance of the components, causing short-chain alkanes smaller than C8 to distill off from the top of the column, while heterocyclic aromatics or halogenated aromatics are discharged from the bottom of the column along with the extractant. The extractant is then separated and recycled in a recovery column.

4. The method according to claim 3, characterized in that, The extractant is phenol.

5. The method according to claim 1, characterized in that, The cutting temperature for the distillation separation is 50~150℃.

6. The method according to claim 1, characterized in that, The high-temperature pyrolysis temperature is 800~1400℃, and the pressure is 0.1~3.0MPa.

7. The method according to claim 1, characterized in that, The catalyst used in the polymerization reaction is a Co / Al2O3 catalyst; the cobalt loading in the Co / Al2O3 catalyst is 10~20wt%.

8. The method according to claim 1 or 7, characterized in that, The polymerization reaction is carried out at a temperature of 180-240℃, a pressure of 1.5-3.0 MPa, and a space velocity of 800-1200 h⁻¹. -1 .

9. The method according to claim 1, characterized in that, The catalyst used in the isomerization reaction is a bifunctional molecular sieve; the bifunctional molecular sieve is a Pt / molecular sieve; and the platinum loading in the Pt / molecular sieve is 0.5~1.5 wt%.

10. The method according to claim 1 or 9, characterized in that, The isomerization reaction is carried out at a temperature of 280~380℃, a reaction pressure of 3.0~8.0MPa, and a hydrogen-to-oil volume ratio of 300~800.

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