Method and device for preparing biological aviation oil component through stepped denitrification and deoxidation of distillers' grains

Abstract

The invention discloses a method and a device for preparing a biological aviation oil component through stepped denitrification and deoxidation of distillers' grains, and relates to the field of resource carbon neutralization technology and sustainable aviation fuel. According to the method disclosed by the invention, the vinasse is matched with a certain proportion of plastic and then is quickly pyrolyzed to obtain low-nitrogen and low-oxygen bio-oil, the low-nitrogen and low-oxygen bio-oil is converted into high-value fuel oil rich in the aviation oil component through catalytic hydrogenation, and then the high-value fuel oil is subjected to rectification separation to prepare the biological aviation oil component. A specific amount of plastic is introduced in the vinasse pyrolysis process for co-pyrolysis, so that the conversion efficiency of preparing the low-nitrogen and low-oxygen bio-oil through vinasse pyrolysis is improved, and the process difficulty and cost of preparing the bio-aviation oil are greatly reduced. The device is used for realizing the method and mainly comprises a drying and crushing unit, a pyrolysis unit, a hydrogenation catalytic conversion and separation unit, a catalyst manufacturing unit and a tail gas treatment unit, and through series-parallel connection integration, the resource utilization rate of nitrogen elements in the vinasse is higher than 91%, and the yield of the biological aviation oil is as high as 26.8 wt%.

Description

Technical Field

[0001] The present invention belongs to the field of resource carbon neutrality technology and sustainable aviation fuel, and specifically relates to a method and device for preparing bio-aviation fuel components through cascaded denitrification and deoxygenation of distiller's grains. Background Art

[0002] Biojet fuel refers to an alternative aviation fuel that meets aviation standards and is produced from waste animal and vegetable oils, organic waste, and biomass. It is a key measure for the aviation industry to significantly reduce CO2 emissions and address carbon peak and carbon neutrality goals. Currently, many countries and regions have proposed biojet fuel plans. For example, the European Union mandates that the aviation industry use at least 70% biojet fuel by 2050; the United States has proposed a 30% biomass energy mix for transportation fuel by 2030; Boeing has pledged to use 100% sustainable biojet fuel on commercial aircraft by 2030; and my country has also proposed a plan to vigorously promote advanced biojet fuel, aiming to use 50,000 tons of biojet fuel by 2025 and to increase bioenergy's share of primary energy supply to 18% by 2050. This demonstrates that biojet fuel will play a crucial role and generate significant demand in the future global energy mix.

[0003] At present, the existing bio-jet fuel production technology relies on high-grade biomass resources (high-quality oils such as ground coke, palm oil, etc.), resulting in excessively high production costs and limited output. Biomass is the only renewable carbon source with zero-carbon properties throughout its life cycle. Therefore, the use of biomass alternative raw materials such as straw with low cost and high output to produce bio-jet fuel has begun to attract attention. Patent CN105331387A discloses a process for the thermal catalytic conversion and refining of biomass such as straw to prepare aviation fuel. By coupling the thermal catalytic conversion of biomass at high temperature with alkylation and hydrodeoxygenation, a bio-jet fuel yield of nearly 20% can be achieved. However, there is a bottleneck in the catalytic pyrolysis process where the catalyst is easily coked and deactivated, which affects the long-term stable operation of the device. In addition, biomass such as straw is widely produced and highly dispersed, and the collection, storage and transportation costs are high, which further increases the cost of preparing bio-jet fuel and restricts industrial development.

[0004] On the other hand, liquor is a traditional pillar industry in my country, generating over 50 million tons of distiller's grains annually. Distiller's grains have a complex composition, high moisture content, high acidity, and rich organic matter. If improperly stored or handled, they are prone to mold and spoilage, causing serious damage to the soil, water systems, and air. Currently, distiller's grains are primarily processed for animal husbandry or returned to farmland, which presents challenges such as poor economic returns, low nutritional value, and the potential for secondary pollution. Therefore, their high-value resource utilization is an urgent need for many domestic liquor companies. Distiller's grains are rich in organic matter such as cellulose and lignin, and can be rapidly pyrolyzed and converted into bio-oil. Further upgrading can then produce biogasoline, diesel, and aviation fuel.

[0005] my country's large-scale wine companies are relatively concentrated, which greatly reduces the collection and transportation costs of distiller's grains. Therefore, the preparation of bio-aviation fuel from distiller's grains has good application scenario needs and obvious advantages in large-scale application and promotion. However, distiller's grains contain a higher nitrogen content than other biomass, and a large amount of nitrogen-containing by-products can easily lead to equipment corrosion and blockage during the pyrolysis of distiller's grains to produce aviation fuel. In addition, because distiller's grains, like other biomass, have a high oxygen content, the pyrolysis oil has a low calorific value and poor stability, as well as problems such as coking and deactivation of the catalyst and high hydrogen consumption in the subsequent hydrogenation stage. The above reasons limit the conversion efficiency of distiller's grains pyrolysis to produce low-nitrogen and low-oxygen bio-oil, and also significantly increase the difficulty and cost of further processing and upgrading distiller's grains bio-oil into high-value-added bio-aviation fuel, thereby limiting the large-scale industrial development of distiller's grains pyrolysis to produce aviation fuel. At present, there are still no relevant patents that propose technical solutions for distiller's grains to produce aviation fuel and the above-mentioned related problems. Summary of the Invention

[0006] The present invention provides a method and apparatus for preparing bio-aviation fuel components by cascaded denitrification and deoxygenation of distiller's grains, aiming to improve the conversion efficiency of distiller's grains pyrolysis to produce low-nitrogen and low-oxygen bio-oil, and reduce the difficulty and cost of further preparing bio-aviation fuel from bio-oil.

[0007] The technical solution adopted by the present invention to solve the technical problem is: a method for preparing bio-aviation fuel components by cascade denitrification and deoxygenation of vinasse, comprising the following steps:

[0008] S1. Drying and dehydrating distiller's grains, mixing the dehydrated distiller's grains with plastic in a mass ratio of 1:X to obtain a raw material, and rapidly pyrolyzing the raw material in a pyrolysis device at a temperature of 500-800° C. to obtain primary denitrified and deoxygenated pyrolysis oil and gas and nitrogen-doped pyrolysis carbon; wherein X≤1;

[0009] S2, condensing the pyrolysis oil and gas obtained in step S1 to obtain low-nitrogen and low-oxygen bio-oil and non-condensable gas;

[0010] S3, hydro-upgrading the low-nitrogen and low-oxygen bio-oil obtained in step S2 using a hydro-upgrading treatment device equipped with an activated carbon-based catalyst to complete secondary deep denitrification and deoxygenation to obtain high-value fuel oil rich in aviation fuel components and ammonia-containing gas;

[0011] S4, subjecting the high-value fuel obtained in step S3 to a catalytic hydrogenation isomerization reaction, followed by fractionation and separation to obtain a bio-aviation fuel component;

[0012] S5. Wash the non-condensable gas 1 obtained in step S2 and the ammonia-containing gas obtained in step S3 with water to remove ammonia and carbon dioxide therefrom to obtain an ammonium carbonate solution and non-condensable gas 2; crystallize the ammonium carbonate solution to obtain ammonium carbonate solid; and transport the non-condensable gas 2 to the pyrolysis equipment in step S1 for combustion and heat supply;

[0013] S6. Activating the nitrogen-doped pyrolytic carbon obtained in step S1 by water vapor to form pores, thereby obtaining nitrogen-doped activated carbon and activated gas; the water vapor comprises water vapor generated by drying and dehydrating the vinasse; and loading the nitrogen-doped activated carbon with an active metal to obtain a catalyst, which can be used as the activated carbon-based catalyst used in step S3.

[0014] S7, transporting the activated gas obtained in step S6 to the hydrogenation and upgrading treatment equipment in step S3 for supplying hydrogen;

[0015] The low-nitrogen and low-oxygen bio-oil is a stable pyrolysis oil, the nitrogen content of which is less than 1 wt%, and the oxygen content of which is less than 20 wt%.

[0016] Furthermore, the plastic includes at least one of polyethylene, polypropylene, polystyrene, polyethylene terephthalate and polycarbonate.

[0017] Furthermore, in step S1, the plastic is removed from impurities and crushed before being used for compounding.

[0018] Furthermore, in step S1, the time of rapid pyrolysis is controlled within 2 to 60 seconds.

[0019] Furthermore, the pyrolysis equipment used in step S1 is a fluidized bed.

[0020] Furthermore, in step S3, the hydrogen-to-oil ratio is controlled at 300-1000:1, the temperature of the hydrogenation upgrading treatment is controlled at 200-400°C, and the pressure of the hydrogenation upgrading treatment is controlled at 0.5-10 MPa.

[0021] Furthermore, in step S6, the mass ratio of activation water vapor to pyrolytic carbon is 0.5 to 2:1, the activation temperature is controlled at 700 to 1000° C., and the activation time is controlled at 0.5 to 5 h;

[0022] The active metal includes at least one of Ni, Co, Mo, Fe, Ce and Cu.

[0023] The present invention also provides a device for preparing bio-aviation fuel components by cascade denitrification and deoxygenation of distiller's grains, which is used to implement the above-mentioned method for preparing bio-aviation fuel components by cascade denitrification and deoxygenation of distiller's grains; the device comprises:

[0024] The drying and crushing unit is used to dry and dehydrate the wine lees and crush them into powder for mixing with plastic to obtain raw materials and water vapor;

[0025] The rapid pyrolysis unit is used to rapidly pyrolyze the raw materials and perform gas-solid separation to obtain pyrolysis oil and gas and nitrogen-doped pyrolysis carbon, and is used to condense the pyrolysis oil and gas to obtain low-nitrogen and low-oxygen bio-oil;

[0026] The hydrocatalytic conversion and separation unit is used for the hydrocatalytic conversion of low-nitrogen and low-oxygen bio-oil, and the distillation separation to obtain bio-aviation fuel components and bio-gasoline and diesel components;

[0027] A catalyst manufacturing unit, used to activate nitrogen-doped pyrolytic carbon through steam to create pores and load active metals;

[0028] The tail gas treatment unit is used to absorb ammonia and carbon dioxide in the non-condensable gas produced by the fast pyrolysis unit and / or the non-condensable gas produced by the catalyst manufacturing unit, and the unabsorbed non-condensable gas is used as fuel for the fast pyrolysis unit.

[0029] Furthermore, the drying and crushing unit includes a drying device and a crushing and matching device, and the discharge port of the drying device is connected to the feed port of the crushing and matching device;

[0030] The rapid pyrolysis unit includes a fluidized bed rapid pyrolyzer, an air flow separation bed, and a quenching tower. The feed inlet of the fluidized bed rapid pyrolyzer is connected to the discharge port of the crushing and mixing device. The feed inlet of the air flow separation bed is connected to the discharge port of the fluidized bed rapid pyrolyzer. The oil and gas inlet of the quenching tower is connected to the oil and gas outlet of the air flow separation bed.

[0031] The hydrocatalytic conversion and separation unit includes an oil storage tank, a fixed-bed hydrogenation reactor and a distillation tower, wherein the oil inlet of the oil storage tank is connected to the oil outlet of the quenching tower, the oil outlet of the oil storage tank is connected to the oil inlet of the fixed-bed hydrogenation reactor, and the oil outlet of the fixed-bed hydrogenation reactor is connected to the oil inlet of the distillation tower;

[0032] The catalyst manufacturing unit includes an activation reaction tower and a catalyst synthesis device, wherein the water vapor inlet of the activation reaction tower is connected to the water vapor outlet of the drying device, the pyrolytic carbon inlet of the activation reaction tower is connected to the pyrolytic carbon outlet of the air flow separation bed, the gas outlet of the activation reaction tower is connected to the gas inlet of the fixed bed hydrogenation reactor, and the feed inlet of the catalyst synthesis device is connected to the activated carbon outlet of the activation reaction tower;

[0033] The tail gas treatment unit includes a water scrubber and a crystallizer. The air inlet of the water scrubber is respectively connected to the tail gas outlet of the quenching tower and the tail gas outlet of the fixed bed hydrogenation reactor. The tail gas outlet of the water scrubber is connected to the gas inlet of the fluidized bed fast pyrolyzer. The liquid inlet of the crystallizer is connected to the liquid outlet of the water scrubber.

[0034] The beneficial effects of the present invention are:

[0035] (1) This method improves the conversion efficiency of lees pyrolysis to produce low-nitrogen and low-oxygen bio-oil, which greatly reduces the process difficulty and cost of preparing bio-aviation fuel. The lees are mixed with a certain proportion of plastics, and then rapidly pyrolyzed and initially denitrified and deoxygenated to convert them into stable low-nitrogen and low-oxygen bio-oil. The low-nitrogen and low-oxygen bio-oil is subjected to catalytic hydrogenation and quality-improvement treatment to complete secondary deep denitrification and deoxygenation, and isomerized into bio-oil rich in aviation fuel components, which is then separated by distillation to achieve the preparation of bio-aviation fuel. By introducing a specific amount of plastic into the lees pyrolysis process to produce oil, the composition quality of the lees pyrolysis oil can be improved while synergizing the lees deoxygenation and denitrification, thereby significantly reducing the nitrogen and oxygen content in the pyrolysis oil. This significantly reduces the hydrogen consumption in the subsequent hydrogenation and quality-improvement process, significantly extends the catalyst life, increases the carbon atom utilization rate, and significantly improves the quality of the bio-oil. This not only improves the conversion efficiency of lees pyrolysis to produce low-nitrogen and low-oxygen bio-oil, but also significantly reduces the process difficulty and cost of preparing bio-aviation fuel, and significantly improves the economic benefits.

[0036] (2) This method utilizes the plastic melting and carbonization process to not only fix nitrogen and solve the secondary pollution problem, but also realizes the high-value resource utilization of nitrogen in the lees. The plastic melting and carbonization process is used to greatly reduce the migration of nitrogen in the lees to the pyrolysis oil, and the nitrogen is converted into ammonium carbonate to the greatest extent and retained in the biochar, thus solving the problem of nitrogen in the form of NO x The problem of harmful gas release is solved. The obtained ammonium carbonate can be used as fertilizer, and the obtained nitrogen-doped biochar can be used as a catalyst carrier in the subsequent hydrogenation and upgrading stage; the nitrogen-doped biochar loaded with active metals is used as a catalyst, which is beneficial to improve the dispersion of active metals and promote the deoxygenation and isomerization effects of the hydrogenation process; it can be seen that this method also realizes the high-value resource utilization of nitrogen in the lees.

[0037] (3) This method and device not only efficiently and synergistically prepare high-value bio-jet fuel components based on distiller's grains and plastics, but also fully utilize the dehydration, hydrogen, and pyrolytic carbon produced in the process to achieve high-value resource utilization of all components. The water vapor from the drying and dehydration of the distiller's grains is used in the pyrolytic carbon water vapor activation stage. The hydrogen-rich by-product of the pyrolytic carbon activation process is used to provide hydrogen for bio-oil quality improvement. The activated pyrolytic carbon is used as a catalyst for bio-oil hydrogenation and quality improvement. By fully utilizing the gas, solid, and liquid three-phase products of the co-pyrolysis of plastics and distiller's grains, the material flow and energy flow in the entire process are closed-loop and complementary, which can efficiently achieve high-value resource utilization of all components of bulk organic solid waste distiller's grains and plastics.

[0038] The technical effects brought about or directly produced by other technical features of the present invention will be described in detail in the subsequent specific implementation methods. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a schematic diagram of the structure of an apparatus for preparing bio-aviation fuel components by cascaded denitrification and deoxygenation of vinasse provided by the present invention;

[0040] Marked in the figure: 1-drying and crushing unit, 11-drying device, 12-crushing and mixing device, 2-rapid pyrolysis unit, 21-fluidized bed rapid pyrolyzer, 22-air flow separation bed, 23-quenching tower, 3-hydrogenation catalytic conversion and separation unit, 31-oil storage tank, 32-fixed bed hydrogenation reactor, 33-distillation tower, 4-catalyst manufacturing unit, 41-activation reaction tower, 42-catalyst synthesis unit, 5-tail gas treatment unit, 51-water washing tower, 52-crystallizer. DETAILED DESCRIPTION

[0041] The present invention will be further described below in conjunction with the accompanying drawings and embodiments. Although various aspects of the embodiments are shown in the accompanying drawings, the drawings are not necessarily drawn to scale unless otherwise specified.

[0042] In the present invention, when the term "many" indicates quantity, it generally refers to a quantity of three or more, for example: "multiple" generally refers to three or more. The term "and / or" is merely a description of an association relationship of associated objects, indicating that three relationships may exist, for example: A and / or B, which can represent: A exists alone, A and B exist at the same time, and B exists alone. The term "including but not limited to" means that in addition to the listed example substances, other substances with similar properties can also be substituted. The term "aviation fuel" is the abbreviation of aviation kerosene, also known as "jet kerosene", which is composed of hydrocarbons of different fractions of alkanes, aromatics and olefins. The term "low-nitrogen and low-oxygen bio-oil" means that the bio-oil has a lower nitrogen content and oxygen content than the traditional biomass pyrolysis oil (N content > 2wt%) obtained by pyrolysis of wine lees by existing methods, and its nitrogen content is <1wt% and its oxygen content is <20wt%. The term "hydrogen-to-oil ratio" refers to the mass ratio of hydrogen and bio-oil in the hydrogenation process. The term "high-value fuel oil" refers to pyrolysis oil with significantly lower nitrogen and oxygen content, improved quality, and significantly increased value for direct use or trade compared to traditional biomass pyrolysis oil. The term "nitrogen-doped pyrolysis char" refers to the enrichment of nitrogen from distiller's grains in pyrolysis char formed by the pyrolysis of distiller's grains, forming pyrolysis char rich in nitrogen species. The term "nitrogen-doped activated carbon" refers to activated nitrogen-doped pyrolysis char with significantly improved pore structure and surface chemical properties. The term "stable pyrolysis oil" refers to pyrolysis oil that, due to its reduced nitrogen and oxygen content, is less susceptible to oxidation and deterioration during storage, affecting further processing, compared to traditional biomass pyrolysis oil. The shelf life of traditional biomass pyrolysis oil averages 2 to 6 months, while the shelf life of stable pyrolysis oil is over one year.

[0043] The present invention provides a method for preparing bio-aviation fuel components by cascaded denitrification and deoxygenation of distiller's grains, comprising the following steps S1-S7;

[0044] S1. Dry and dehydrate the vinasse, then combine the dehydrated vinasse with plastic in a mass ratio of 1:X to obtain a raw material. The raw material is rapidly pyrolyzed using a pyrolysis device at a temperature of 500-800°C to produce primary denitrified and deoxygenated pyrolysis oil and gas, and nitrogen-doped pyrolytic carbon; where X ≤ 1. In this step, the vinasse can also be dried and crushed before combining with the raw material. The plastic is generally removed from the raw material and crushed before combining with the raw material. During the rapid pyrolysis process, the plastic provides hydrogen to facilitate the rapid fluidized pyrolysis of the vinasse into pyrolysis oil and gas with lower nitrogen and oxygen contents, as well as nitrogen-enriched pyrolytic carbon, i.e., nitrogen-doped pyrolytic carbon. Plastics can be of many types, and generally, waste plastics with a wide range of sources and low prices are selected; preferably, the plastics include at least one of polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET) and polycarbonate (PC); wherein PE, PP and PS plastics are hydrogen-rich, oxygen-free high molecular polymer plastics, which can be completely decomposed during the pyrolysis process, and while increasing the content of alkanes, alkenes and aromatics in the pyrolysis oil, the molten state during pyrolysis inhibits the release of nitrogen-containing gases and hydrogen transfer, thereby promoting the enrichment of lees nitrogen in the pyrolysis charcoal or its conversion into NH3; PET and PC plastics are oxygen-containing high molecular polymer plastics, which can form plastic charcoal during the pyrolysis process, which can efficiently anchor lees nitrogen, retain more nitrogen in the pyrolysis charcoal, and thus reduce the migration of nitrogen into the pyrolysis oil and gas. The use of the above plastics alone or in graded form can effectively regulate the nitrogen in the lees, so that it is retained in the pyrolysis carbon or converted into NH3, thereby greatly reducing the nitrogen entering the pyrolysis oil and gas, and significantly improving the quality of the pyrolysis oil; lees include but are not limited to liquor lees, beer lees, and rice wine lees; before rapid pyrolysis, the lees can be subjected to elemental analysis to clarify the content of each element, especially the nitrogen content, so as to facilitate the determination of the type and proportion of compatible plastics, so as to further improve the quality of low-nitrogen and low-oxygen bio-oil; the lees and plastics can be loaded in a variety of ways, preferably blending or filling up and down; in order to take into account the pyrolysis effect and cost, the plastic to lees ratio is usually limited to no more than 1:1; the time for rapid pyrolysis is generally controlled at 2 to 60 seconds; the generated high-temperature pyrolysis oil and gas products and solid-phase pyrolysis carbon products can generally be separated by utilizing the density difference between the solid phase and the gas phase.

[0045] S2. Condensing the pyrolysis oil and gas obtained in step S1 to obtain low-nitrogen and low-oxygen bio-oil and non-condensable gas. In this step, the pyrolysis oil and gas are generally condensed by passing heat exchange with a cooling medium through a heat exchanger. By utilizing the different boiling points of the product molecules in the pyrolysis oil and gas, the large molecular organic matter therein is condensed to obtain low-nitrogen and low-oxygen bio-oil. The low-nitrogen and low-oxygen bio-oil is a stable pyrolysis oil with a nitrogen content of less than 1wt% and an oxygen content of less than 20wt%. However, small molecular gases such as H2, CH4, CO, CO2, NH3, and C2-C4 olefins therein are difficult to condense and will be separated from the pyrolysis oil. Non-condensable gas rich in ammonia can be obtained by collecting them. The temperature of the heat exchanger is generally set to -20 to 0°C. The heat exchanger can be of various types, such as a plate heat exchanger, a volumetric heat exchanger, a shell-and-tube heat exchanger, or one or more heat exchange equipment commonly used in the art.

[0046] S3, the low-nitrogen and low-oxygen bio-oil obtained in step S2 is subjected to a hydro-upgrading treatment process equipped with an activated carbon-based catalyst to perform a secondary deep denitrification and deoxygenation process to obtain high-value fuel oil and ammonia-containing gas rich in aviation fuel components. The main components of the ammonia-containing gas are small molecules such as CO, CH4, H2, CO2, NH3, and C2-C4 olefins. In this step, one of the main purposes of the hydro-upgrading process is deoxygenation and denitrification, that is, removing oxygen and nitrogen from oxygen-containing and nitrogen-containing compounds, specifically to reduce the oxygen and nitrogen content in the pyrolysis oil so that its elemental composition is closer to that of aviation fuel. Another main purpose is to saturate unsaturated bond compounds such as olefins in the pyrolysis oil.

[0047] Preferably, in step S3, the hydrogen-to-oil ratio is controlled at 300 to 1000:1, the temperature of the hydro-upgrading treatment is controlled at 200 to 400°C, and the pressure of the hydro-upgrading treatment is controlled at 0.5 to 10 MPa. By controlling the hydrogen-to-oil ratio at 300 to 1000:1, not only is an adequate supply of hydrogen ensured, but an appropriately high hydrogen-to-oil ratio helps to remove the heat generated during the reaction, inhibits the coking and carbon deposition of low-nitrogen and low-oxygen bio-oil on the catalyst surface, and helps to improve the stability and quality of the product; by controlling the temperature of the hydro-upgrading treatment at 200 to 400°C, the reaction can be carried out at an appropriate rate, ensuring production efficiency; by controlling the pressure of the hydro-upgrading treatment at 0.5 to 10 MPa, the balance of the reaction can be ensured, and the product quality and yield can be improved. The pressure of the hydro-upgrading treatment is further preferably 0.5 to 8 MPa.

[0048] S4. The high-value fuel obtained in step S3 is subjected to a catalytic hydroisomerization reaction, followed by distillation separation to obtain a bio-aviation fuel component. The purpose of this isomerization step is to increase the aromatic content in the bio-oil, making its composition and physicochemical properties more similar to those of aviation fuel. The bio-oil can typically be distilled and separated using conventional distillation equipment in the art to obtain aviation fuel and oxygenated components based on their boiling points. The oxygenated component has an oxygen content of less than 1 wt% and can be used as bio-gasoline or diesel.

[0049] S5. The non-condensable gas 1 obtained in step S2 and the ammonia-containing gas obtained in step S3 are washed with water to remove ammonia and carbon dioxide, thereby obtaining an ammonium carbonate solution and non-condensable gas 2. The ammonium carbonate solution is crystallized to obtain solid ammonium carbonate. The non-condensable gas 2 is transported to the pyrolysis equipment in step S1 for combustion and heat supply. In this step, the non-condensable gas 1 and the ammonia-containing gas are generally passed through a water scrubber 51 for washing. CO2 and NH3, being acidic and alkaline gases, respectively, promote mutual absorption to form an ammonium carbonate solution. The non-condensable gas 2 is the remaining non-condensable gas after washing the non-condensable gas 1 and the ammonia-containing gas. Its main components are CO, H2, CH4, and C2-C4 olefins. The pyrolysis equipment is preferably a fluidized bed.

[0050] S6. The nitrogen-doped pyrolytic carbon obtained in step S1 is activated and pore-formed by water vapor to obtain nitrogen-doped activated carbon and activated gas; the water vapor includes water vapor generated by drying and dehydrating the lees; the nitrogen-doped activated carbon is loaded with active metal to obtain a catalyst, which can be used as the activated carbon-based catalyst used in step S3. In this step, the liquid water generated by cooling the activated water vapor can be used to wash the nitrogen-doped activated carbon, and the nitrogen-doped activated carbon can be loaded with active metal by forced impregnation, and the finished catalyst is obtained after calcination; the active metal includes but is not limited to at least one of Ni, Co, Mo, Fe, Ce and Cu; since a large amount of nitrogen is retained in the nitrogen-doped pyrolytic carbon, nitrogen helps to anchor and disperse the active metal during the preparation of the catalyst, so that the catalyst exhibits better catalytic activity; the obtained catalyst is applied to step S3, and in the hydrogenation catalytic process, it can not only tune the acidity strength of the catalyst surface, but also help to regulate the catalytic activity and product selectivity.

[0051] Preferably, in step S6, the mass ratio of activation water vapor to nitrogen-doped pyrolytic carbon is 0.5 to 2:1, the activation temperature is controlled at 700 to 1000°C, and the activation time is controlled at 0.5 to 5 hours. By controlling the mass ratio of activation water vapor to nitrogen-doped pyrolytic carbon to 0.5 to 2:1, the effectiveness of water vapor pore formation can be improved and an appropriate pore structure can be ensured; controlling the activation temperature at 700 to 1000°C can effectively improve the quality and performance of the nitrogen-doped pyrolytic carbon; and controlling the activation time at 0.5 to 5 hours can achieve sufficient pore formation and prevent the destruction of the pore structure caused by excessive activation, which would result in a decrease in mechanical properties such as strength of the nitrogen-doped activated carbon.

[0052] S7. The activated gas obtained in step S6 is transported to the hydrogenation and upgrading treatment equipment in step S3 for supplying hydrogen.

[0053] This method introduces a specific amount of plastic into the lees pyrolysis oil production process to co-pyrolyze, which can improve the composition of the lees pyrolysis oil while coordinating the deoxygenation and denitrification of the lees, thereby significantly reducing the nitrogen and oxygen content in the pyrolysis oil. This significantly reduces the hydrogen consumption in the subsequent hydrogenation and quality improvement process, significantly extends the life of the catalyst, and significantly improves the quality of the bio-oil. It not only improves the conversion efficiency of lees pyrolysis to low-nitrogen and low-oxygen bio-oil, but also greatly reduces the process difficulty and cost of preparing bio-aviation fuel, and significantly improves the economic benefits. At the same time, this method uses the plastic melting and carbonization process to significantly reduce the migration of nitrogen elements in lees into the pyrolysis oil, converting nitrogen to ammonium carbonate to the greatest extent and retaining it in the biochar, solving the problem of nitrogen in the form of NO x The problem of releasing harmful gases in the form of pollutants is solved. The obtained ammonium carbonate can be used as a fertilizer, and the obtained nitrogen-doped biochar can be used as a catalyst carrier in the subsequent hydrogenation and upgrading treatment stage; the nitrogen-doped biochar is loaded with active metals and then used as a catalyst, which is beneficial to improving the dispersibility of the active metals and promoting the deoxygenation and isomerization effects in the hydrogenation process, thereby realizing the high-value resource utilization of nitrogen in the lees. In addition, the present invention provides a method for preparing bio-aviation fuel components by cascaded denitrification and deoxygenation of lees, which utilizes lees and plastics to efficiently and synergistically prepare high-value bio-aviation fuel components, solving the problem of secondary pollution in the thermochemical conversion and utilization process caused by the high nitrogen content of lees. By making full use of the gas-solid-liquid three-phase product of the co-pyrolysis of plastics and lees, the entire process flow is closed-loop and complementary, which can efficiently realize the high-value resource utilization of all components of bulk organic solid waste lees and plastics.

[0054] like Figure 1 As shown, the present invention also provides a device for preparing bio-aviation fuel components by cascade denitrification and deoxygenation of distiller's grains, which is used to implement the above-mentioned method for preparing bio-aviation fuel components by cascade denitrification and deoxygenation of distiller's grains; the device comprises:

[0055] The drying and crushing unit 1 is used to dry and dehydrate the wine lees and crush them into powder for mixing with plastic to obtain raw materials and water vapor. The raw materials include wine lees powder and plastic powder, which are mixed or filled in a top-to-bottom manner. The obtained water vapor can be used in the subsequent activation process. The drying and crushing unit 1 generally includes a drying device 11 and a crushing and mixing device 12. The discharge port of the drying device 11 is connected to the feed port of the crushing and mixing device 12. The drying device 11 can dry the wine lees, and the crushing and mixing device 12 can crush the wine lees and plastic and mix them together.

[0056] The rapid pyrolysis unit 2 is used to rapidly pyrolyze the raw material and perform gas-solid separation to obtain pyrolysis oil gas and nitrogen-doped pyrolysis carbon, and to condense the pyrolysis oil gas to obtain low-nitrogen and low-oxygen bio-oil; the rapid pyrolysis unit 2 generally includes a fluidized bed rapid pyrolyzer 21, an air flow separation bed 22 and a quenching tower 23, the feed port of the fluidized bed rapid pyrolyzer 21 is connected to the discharge port of the crushing and mixing device 12, the feed port of the air flow separation bed 22 is connected to the discharge port of the fluidized bed rapid pyrolyzer 21, and the feed port of the air flow separation bed 22 is connected to the discharge port of the fluidized bed rapid pyrolyzer 21. The feed inlet is connected, and the oil and gas inlet of the quenching tower 23 is connected to the oil and gas outlet of the air flow separation bed 22; the fluidized bed fast pyrolyzer 21 can quickly pyrolyze the raw material into pyrolysis oil and gas and nitrogen-doped pyrolysis carbon, the air flow separation bed 22 can separate the pyrolysis oil and gas from the nitrogen-doped pyrolysis carbon, and the quenching tower 23 can condense the pyrolysis oil and gas into low-nitrogen and low-oxygen bio-oil and non-condensable gas, which includes small molecular gases such as CO, CO2, H2, CH4, C2-C4 olefins and NH3;

[0057] The hydrocatalytic conversion and separation unit 3 is used for the hydrocatalytic conversion of low-nitrogen and low-oxygen bio-oil, and distillation separation to obtain bio-aviation fuel components and bio-gasoline and diesel components; the hydrocatalytic conversion and separation unit 3 generally includes an oil storage tank 31, a fixed-bed hydrogenation reactor 32 and a distillation tower 33, the oil inlet of the oil storage tank 31 is connected to the oil outlet of the quenching tower 23, the oil outlet of the oil storage tank 31 is connected to the oil inlet of the fixed-bed hydrogenation reactor 32, and the oil outlet of the fixed-bed hydrogenation reactor 32 is connected to the oil inlet of the distillation tower 33; the oil storage tank 31 is used to store low-nitrogen and low-oxygen bio-oil, the fixed-bed hydrogenation reactor 32 is used to carry out secondary deep denitrification and deoxygenation of the low-nitrogen and low-oxygen bio-oil through catalytic hydrogenation and upgrading treatment, and isomerize it into bio-oil rich in aviation fuel components; the distillation tower 33 is mainly used to distill and separate the bio-oil to obtain bio-aviation fuel components.

[0058] Specifically, the rapid pyrolysis unit 2 rapidly pyrolyzes the raw material to obtain pyrolysis oil and gas and nitrogen-doped pyrolysis carbon after primary denitrification and deoxygenation. The main reactions that occur are as follows:

[0059] H+RO→R+H2O;

[0060] H+RN→R+NH3;

[0061] Char-C+RN→Char-C-N+R;

[0062] Char-C-O+NH3→Char-C-N+H2O.

[0063] The hydrocatalytic conversion and separation unit 3 processes the low-nitrogen and low-oxygen bio-oil through catalytic hydrogenation to complete secondary deep denitrification and deoxygenation, and isomerizes it into bio-oil rich in aviation fuel components. The main reactions that occur are as follows:

[0064]

[0065] For example Figure 1 As shown, in some embodiments, the device further includes:

[0066] The catalyst manufacturing unit 4 is used to activate nitrogen-doped pyrolytic carbon by water vapor to form pores and load active metals; the catalyst manufacturing unit 4 generally includes an activation reaction tower 41 and a catalyst synthesis device 42, the water vapor inlet of the activation reaction tower 41 is connected to the water vapor outlet of the drying device 11, the pyrolytic carbon inlet of the activation reaction tower 41 is connected to the pyrolytic carbon outlet of the air flow separation bed 22, the gas outlet of the activation reaction tower 41 is connected to the gas inlet of the fixed bed hydrogenation reactor 32, and the feed port of the catalyst synthesis device 42 is connected to the activated carbon outlet of the activation reaction tower 41; the activation reaction tower 41 can use water vapor as an activator to activate the pyrolytic carbon to form pores into activated carbon and activated gas, the activated gas includes small molecular gases such as CO, CO2, H2, NH3, etc., and the activated gas can be used to supply hydrogen to the fixed bed hydrogenation reactor 32; the catalyst synthesis device 42 can load active metals such as Ni, Co, Fe, Ce and Cu on the activated carbon;

[0067] The tail gas treatment unit 5 is used to absorb the ammonia and carbon dioxide in the non-condensable gas produced by the fast pyrolysis unit 2 and / or the non-condensable gas produced by the catalyst manufacturing unit 4, and the non-condensable gas not absorbed is used as the fuel of the fast pyrolysis unit 2; the tail gas treatment unit 5 generally includes a water scrubber 51 and a crystallizer 52, the air inlet of the water scrubber 51 is connected to the tail gas outlet of the quenching tower 23 and the tail gas outlet of the fixed bed hydrogenation reactor 32 respectively, and the tail gas outlet of the water scrubber 51 is connected to the fuel outlet of the fluidized bed fast pyrolysis reactor 21. The gas inlet is connected to the crystallizer 52, and the liquid inlet is connected to the liquid outlet of the water washing tower 51; the water washing tower 51 is used to wash the non-condensable gas (non-condensable gas 1) generated by the rapid pyrolysis unit 2 and / or the non-condensable gas (ammonia-containing gas) generated by the catalyst manufacturing unit 4, so that the acidic gas CO2 and the alkaline gas NH3 promote each other's absorption to form an ammonium carbonate solution; the gas not absorbed after washing is non-condensable gas 2, which includes small molecular gases such as CO, H2, CH4, C2-C4 olefins, etc.

[0068] The catalyst manufacturing unit 4 activates the pyrolytic carbon to create pores, and the main reactions that occur are as follows:

[0069] C+H2O→H2+CO;

[0070] CO+H2O→H2+CO2;

[0071] R-N+H2→R+NH3.

[0072] Comparative Example 1

[0073] Production of bio-aviation fuel components from vinasse pyrolysis-hydrogenation upgrading

[0074] Using separate vinasse as raw material, pyrolysis-hydrogenation upgrading treatment is carried out to produce bio-aviation fuel components. The specific process is as follows:

[0075] S1. The lees were dried at 105°C and rapidly pyrolyzed in a fluidized bed at 600°C to produce pyrolysis oil and pyrolysis char. The pyrolysis char yield was 33.9 wt %, and the nitrogen content in the pyrolysis char was 2.6 wt %. "wt %" refers to the mass ratio relative to the raw material and is expressed in the same manner in the following steps.

[0076] S2. The pyrolysis oil and gas obtained in step S1 are condensed through a heat exchanger to collect pyrolysis oil and non-condensable gas. The yield of pyrolysis oil is 42.11 wt %, the nitrogen content in the pyrolysis oil is 4.7 wt %, and the yield of non-condensable gas is 23.99 wt %. The non-condensable gas mainly includes CO, CO2, CH4, and NH3.

[0077] S3. The pyrolysis oil in step S2 is added to the fixed bed hydrogenation reactor 32 for hydrodeoxygenation, denitrogenation and isomerization reaction. The temperature of the hydro-upgrading treatment is 350° C., the pressure of the hydro-upgrading treatment is 6 MPa, and the hydrogen-to-oil ratio is 800:1.

[0078] S4. The fuel obtained in step S3 is subjected to a catalytic hydrogenation isomerization reaction, and the obtained bio-oil is separated by distillation to obtain a bio-aviation fuel component and a bio-gasoline and diesel component. The yield of the bio-aviation fuel component is 6.7wt% and the nitrogen content is 1.1wt%; the yield of the bio-gasoline and diesel component is 15.5% and the nitrogen content is 0.9wt%.

[0079] S5. The non-condensable gas produced in steps S2 and S3 is fully washed with water to obtain an ammonium carbonate solution, and the remaining non-condensable gas is refluxed to the fluidized bed for direct combustion to provide heat.

[0080] S6. The pyrolytic carbon separated in step S1 is activated by water vapor to form pores at an activation temperature of 700°C and an activation time of 1 hour. The mass ratio of activation water to pyrolytic carbon is 1:1. Subsequently, 5 wt% Ni and 5 wt% Co metal are loaded by forced impregnation to prepare an activated carbon catalyst (NiCo-AC). The activated carbon catalyst (NiCo-AC) can be used for the catalytic reaction in step S3.

[0081] S7. The activated gas obtained in step S6 is transported to the fixed bed hydrogenation reactor 32 in step S3 for supplying hydrogen.

[0082] The yields and physicochemical properties of the relevant products and materials of this comparative example are shown in Table 1.

[0083] Example 1

[0084] Hydrogen-rich PE waste plastics synergistically treated with lees pyrolysis-hydrogenation to produce bio-aviation fuel components

[0085] In this embodiment, hydrogen-rich non-carbon-forming plastic PE and distiller's grains are used as raw materials. The raw materials are subjected to pyrolysis-hydrogenation upgrading treatment to produce a bio-aviation fuel group using the method of the present invention. The specific process is as follows:

[0086] S1, PE waste plastic, and distiller's grains were dried and crushed at 105°C, then passed through a 50-mesh mesh. They were then mixed in a 2:5 mass ratio to produce a mixed material. The mixed material was then rapidly pyrolyzed in a fluidized bed at 600°C to produce pyrolysis oil and nitrogen-doped pyrolytic carbon. The yield of the nitrogen-doped pyrolytic carbon was 20.8 wt%, and the nitrogen content in the nitrogen-doped pyrolytic carbon was 3.0 wt%. "wt%" refers to the mass ratio relative to the mixed material and is expressed similarly in the following steps.

[0087] S2. The pyrolysis oil and gas obtained in step S1 are condensed through a heat exchanger to collect low-nitrogen and low-oxygen bio-oil and non-condensable gas. The yield of the low-nitrogen and low-oxygen bio-oil is 50.0 wt %, the nitrogen content in the low-nitrogen and low-oxygen bio-oil is 2.1 wt %, and the yield of the non-condensable gas is 29.2%. The non-condensable gas mainly includes CO, H2, CH4, NH3, and C2-C4 olefins.

[0088] S3. The low-nitrogen and low-oxygen bio-oil in step S2 is added to the fixed-bed hydrogenation reactor 32 for hydrodeoxygenation, denitrification and isomerization reactions. The temperature of the hydro-upgrading treatment is 300° C., the pressure of the hydro-upgrading treatment is 4 MPa, and the hydrogen-to-oil ratio is 500:1.

[0089] S4. The high-value fuel obtained in step S3 is subjected to a catalytic hydrogenation isomerization reaction, and the obtained bio-oil is separated by distillation to obtain a bio-aviation fuel component and a bio-gasoline and diesel component. The yield of the bio-aviation fuel component is 24.6wt% and the nitrogen content is 0.05wt%; the yield of the bio-gasoline and diesel component is 9.9wt% and the nitrogen content is 0.08wt%.

[0090] S5. The non-condensable gas produced in steps S2 and S3 is fully washed with water to obtain an ammonium carbonate solution, and the remaining non-condensable gas is refluxed to the fluidized bed for direct combustion to provide heat.

[0091] S6. The nitrogen-doped pyrolytic carbon separated in step S1 is activated by water vapor to form pores at an activation temperature of 700°C and an activation time of 1 hour. The mass ratio of activation water to nitrogen-doped pyrolytic carbon is 1:1. Subsequently, 5 wt% Ni and 5 wt% Co metal are loaded by forced impregnation to prepare a nitrogen-doped activated carbon catalyst (NiCo-AC). This activated carbon catalyst (NiCo-AC) can be used for the catalytic reaction in step S3.

[0092] S7. The activated gas obtained in step S5 is transported to the fixed bed hydrogenation reactor 32 in step S3 for supplying hydrogen.

[0093] It can be seen that the method of the present invention successfully realizes the production of bio-aviation fuel components from low-value bulk solid waste distiller's grains. The yields and physicochemical properties of the relevant products and materials of this embodiment are shown in Table 1.

[0094] Example 2

[0095] Production of bio-jet fuel components from charred PET waste plastics by synergistic pyrolysis and hydrogenation of distiller's grains

[0096] In this embodiment, hydrogen-rich carbon-forming plastic PET and distiller's grains are used as raw materials, and the raw materials are subjected to pyrolysis-hydrogenation upgrading treatment to produce bio-aviation fuel components by the method of the present invention. The specific process is as follows:

[0097] S1, PET waste plastic, and distiller's grains were dried and crushed at 105°C, then passed through a 100-mesh filter. They were then mixed in a 2:5 mass ratio to produce a mixed material. The mixed material was then rapidly pyrolyzed in a fluidized bed at 550°C to produce pyrolysis oil and nitrogen-doped pyrolytic char (PFC). The yield of the PFC was 23.1 wt%, and the nitrogen content in the PFC was 2.9 wt%. "wt%" refers to the mass ratio relative to the mixed material and is expressed similarly in the following steps.

[0098] S2. The pyrolysis oil and gas obtained in step S1 are condensed through a heat exchanger to collect low-nitrogen and low-oxygen bio-oil and non-condensable gas. The yield of the low-nitrogen and low-oxygen bio-oil is 53.6 wt %, the nitrogen content in the low-nitrogen and low-oxygen bio-oil is 1.3 wt %, and the yield of the non-condensable gas is 23.3 wt %. The non-condensable gas mainly includes CO, CO2, H2, CH4, and NH3.

[0099] S3. The low-nitrogen and low-oxygen bio-oil in step S2 is added to the fixed-bed hydrogenation reactor 32 for hydrodeoxygenation, denitrification and isomerization reactions. The temperature of the hydro-upgrading treatment is 300° C., the pressure of the hydro-upgrading treatment is 4 MPa, and the hydrogen-to-oil ratio is 500:1.

[0100] S4. The high-value fuel obtained in step S3 is subjected to a catalytic hydrogenation isomerization reaction, and the obtained bio-oil is separated by distillation to obtain a bio-aviation fuel component and a bio-gasoline and diesel component. The yield of the bio-aviation fuel component is 17.3wt% and the nitrogen content is 0.03wt%; the yield of the bio-gasoline and diesel component is 14.7wt% and the nitrogen content is 0.04wt%.

[0101] S5. The non-condensable gas produced in steps S2 and S3 is fully washed with water to obtain an ammonium carbonate solution, and the remaining non-condensable gas is refluxed to the fluidized bed for direct combustion to provide heat.

[0102] S6. The nitrogen-doped pyrolytic carbon separated in step S1 is activated by water vapor to form pores at an activation temperature of 700°C and an activation time of 1 hour. The mass ratio of activation water to nitrogen-doped pyrolytic carbon is 1:1. Subsequently, 5 wt% Ni and 5 wt% Co metal are loaded by forced impregnation to prepare a nitrogen-doped activated carbon catalyst (NiCo-AC). This activated carbon catalyst (NiCo-AC) can be used for the catalytic reaction in step S3.

[0103] S7. The activated gas obtained in step S6 is transported to the fixed bed hydrogenation reactor 32 in step S3 for supplying hydrogen.

[0104] It can be seen that the method of the present invention successfully realizes the production of bio-aviation fuel components from low-value bulk solid waste distiller's grains. The yields and physicochemical properties of the relevant products and materials of this embodiment are shown in Table 1.

[0105] Example 3

[0106] Preparation of bio-aviation fuel components from PE+PET mixed plastics by synergistic vinasse pyrolysis-hydrogenation upgrading

[0107] In this embodiment, PE+PET mixed plastic and distiller's grains are used as raw materials, and the raw materials are subjected to pyrolysis-hydrogenation upgrading treatment to produce bio-aviation fuel components by the method of the present invention. The specific process is as follows:

[0108] S1, PE+PET mixed plastic, and distiller's grains were dried and crushed at 105°C and passed through a 20-mesh filter. They were then mixed in a 1:1 mass ratio (PE:PET = 1:1) to obtain a mixed raw material. The mixed raw material was then rapidly pyrolyzed in a fluidized bed at 600°C to produce pyrolysis oil and nitrogen-doped pyrolytic carbon. The yield of the nitrogen-doped pyrolytic carbon was 21.1 wt%, and the nitrogen content in the nitrogen-doped pyrolytic carbon was 3.2 wt%. "wt%" refers to the mass ratio relative to the mixed raw material and is expressed in the same manner in the following steps.

[0109] S2. The pyrolysis oil and gas obtained in step S1 are condensed through a heat exchanger to collect low-nitrogen and low-oxygen bio-oil and non-condensable gas. The yield of the low-nitrogen and low-oxygen bio-oil is 52.1 wt %, the nitrogen content in the low-nitrogen and low-oxygen bio-oil is 0.8 wt %, and the yield of the non-condensable gas is 26.8 wt %. The non-condensable gas mainly includes CO, H2, CH4, NH3, and C2-C4 olefins.

[0110] S3. The low-nitrogen and low-oxygen bio-oil in step S2 is added to the fixed-bed hydrogenation reactor 32 for hydrodeoxygenation, denitrification and isomerization reactions. The temperature of the hydrogenation treatment is 300° C., the pressure is 4 MPa, and the hydrogen-to-oil ratio is 500:1.

[0111] S4. The high-value fuel obtained in step S3 is subjected to a catalytic hydrogenation isomerization reaction, and the obtained bio-oil is separated by distillation to obtain a bio-aviation fuel component and a bio-gasoline and diesel component. The yield of the bio-aviation fuel component is 26.8wt% and the nitrogen content is 0.01wt%; the yield of the bio-gasoline and diesel component is 11.9wt% and the nitrogen content is 0.02wt%.

[0112] S5. The non-condensable gas produced in steps S2 and S3 is fully washed with water to obtain an ammonium carbonate solution, and the remaining non-condensable gas is refluxed to the fluidized bed for direct combustion to provide heat.

[0113] S6. The nitrogen-doped pyrolytic carbon separated in step S1 is activated by water vapor to form pores at an activation temperature of 700°C and an activation time of 1 hour. The mass ratio of activation water to nitrogen-doped pyrolytic carbon is 1:1. Subsequently, 5 wt% Ni and 5 wt% Co metal are loaded by forced impregnation to prepare a nitrogen-doped activated carbon catalyst (NiCo-AC). This activated carbon catalyst (NiCo-AC) can be used for the catalytic reaction in step S3.

[0114] S7. The activated gas obtained in step S6 is transported to the fixed bed hydrogenation reactor 32 in step S3 for supplying hydrogen.

[0115] It can be seen that the method of the present invention successfully realizes the production of bio-aviation fuel components from low-value bulk solid waste distiller's grains. The yields and physicochemical properties of the relevant products and materials of this embodiment are shown in Table 1.

[0116] Example 4

[0117] PE plastics and vinasse pyrolysis-hydrogenation treatment to produce bio-aviation fuel components

[0118] In this embodiment, hydrogen-rich carbon-forming plastic PE and distiller's grains are used as raw materials, and the raw materials are subjected to pyrolysis-hydrogenation upgrading treatment to produce bio-aviation fuel components by the method of the present invention. The specific process is as follows:

[0119] S1, PE waste plastic, and distiller's grains were dried and crushed at 105°C, then passed through a 100-mesh filter and mixed in a 1:5 mass ratio to produce a mixed material. The mixed material was then rapidly pyrolyzed in a fluidized bed at 700°C to produce pyrolysis oil and nitrogen-doped pyrolytic carbon. The yield of the nitrogen-doped pyrolytic carbon was 21.3 wt%, and the nitrogen content in the nitrogen-doped pyrolytic carbon was 2.4 wt%. "wt%" refers to the mass ratio relative to the mixed material and is expressed similarly in the following steps.

[0120] S2. The pyrolysis oil and gas obtained in step S1 are condensed through a heat exchanger to collect low-nitrogen and low-oxygen bio-oil and non-condensable gas. The yield of the low-nitrogen and low-oxygen bio-oil is 46.2 wt %, the nitrogen content in the low-nitrogen and low-oxygen bio-oil is 2.5 wt %, and the yield of the non-condensable gas is 32.5 wt %. The non-condensable gas mainly includes CO, CO2, H2, CH4, and NH3.

[0121] S3. The low-nitrogen and low-oxygen bio-oil in step S2 is added to the fixed-bed hydrogenation reactor 32 for hydrodeoxygenation, denitrification and isomerization reactions. The temperature of the hydro-upgrading treatment is 350° C., the pressure of the hydro-upgrading treatment is 5 MPa, and the hydrogen-to-oil ratio is 700:1.

[0122] S4. The high-value fuel obtained in step S3 is subjected to a catalytic hydrogenation isomerization reaction, and the obtained bio-oil is separated by distillation to obtain a bio-aviation fuel component and a bio-gasoline and diesel component. The yield of the bio-aviation fuel component is 21.1wt% and the nitrogen content is 0.04wt%; the yield of the bio-diesel component is 12.3wt% and the nitrogen content is 0.08wt%.

[0123] S5. The non-condensable gas produced in steps S2 and S3 is fully washed with water to obtain an ammonium carbonate solution, and the remaining non-condensable gas is refluxed to the fluidized bed for direct combustion to provide heat.

[0124] S6. The nitrogen-doped pyrolytic carbon separated in step S1 is activated by water vapor to form pores at an activation temperature of 800°C and an activation time of 2 hours. The mass ratio of activation water to nitrogen-doped pyrolytic carbon is 2:1. Subsequently, Ni and Co metals are loaded by forced impregnation to prepare a nitrogen-doped activated carbon catalyst (NiCo-AC), which can be used for the catalytic reaction in step S3.

[0125] S7. The activated gas obtained in step S6 is transported to the fixed bed hydrogenation reactor 32 in step S3 for supplying hydrogen.

[0126] It can be seen that the method of the present invention successfully realizes the production of bio-aviation fuel components from low-value bulk solid waste distiller's grains. The yields and physicochemical properties of the relevant products and materials of this embodiment are shown in Table 1.

[0127] Example 5

[0128] PE plastics and vinasse pyrolysis-hydrogenation treatment to produce bio-aviation fuel components

[0129] In this embodiment, PE plastic and distiller's grains are used as raw materials, and the raw materials are subjected to pyrolysis-hydrogenation upgrading treatment to produce bio-aviation fuel components by the method of the present invention. The specific process is as follows:

[0130] S1, PE plastic, and distiller's grains were dried and crushed at 105°C, then passed through an 80-mesh mesh and mixed in a 3:5 mass ratio to produce a mixed material. The mixed material was then rapidly pyrolyzed in a fluidized bed at 500°C to produce pyrolysis oil and nitrogen-doped pyrolytic carbon (PFC). The yield of the PFC was 14.9 wt%, and the nitrogen content in the PFC was 2.1 wt%. "wt%" refers to the mass ratio relative to the mixed material and is expressed similarly in the following steps.

[0131] S2. The pyrolysis oil and gas obtained in step S1 are condensed through a heat exchanger to collect low-nitrogen and low-oxygen bio-oil and non-condensable gas. The yield of the low-nitrogen and low-oxygen bio-oil is 42.1 wt %, the nitrogen content in the low-nitrogen and low-oxygen bio-oil is 2.3 wt %, and the yield of the non-condensable gas is 32 wt %. The non-condensable gas mainly includes CO, H2, CH4, NH3, and C2-C4 olefins.

[0132] S3. Add the low-nitrogen and low-oxygen bio-oil in step S2 into the fixed-bed hydrogenation reactor 32 for hydrodeoxygenation, denitrification and isomerization reactions. The temperature of the hydrogenation treatment is 250° C., the pressure is 3 MPa, and the hydrogen-to-oil ratio is 300:1.

[0133] S4. The high-value fuel obtained in step S3 is subjected to a catalytic hydrogenation isomerization reaction, and the obtained bio-oil is separated by distillation to obtain a bio-aviation fuel component and a bio-gasoline and diesel component. The yield of the bio-aviation fuel component is 18.3wt% and the nitrogen content is 0.07wt%; the yield of the bio-diesel component is 8.8wt% and the nitrogen content is 0.11wt%.

[0134] S5. The non-condensable gas produced in steps S2 and S3 is fully washed with water to obtain an ammonium carbonate solution, and the remaining non-condensable gas is refluxed to the fluidized bed for direct combustion to provide heat.

[0135] S6. The nitrogen-doped pyrolytic carbon separated in step S1 is activated by steam to form pores at an activation temperature of 800°C for 3 hours, and a mass ratio of activation water to nitrogen-doped pyrolytic carbon of 0.5:1. Subsequently, Ni and Co metals are loaded by forced impregnation to prepare a nitrogen-doped activated carbon catalyst (NiCo-AC), which can be used for the catalytic reaction in step S3.

[0136] S7. The activated gas obtained in step S5 is transported to the fixed bed hydrogenation reactor 32 in step S3 for supplying hydrogen.

[0137] It can be seen that the method of the present invention successfully realizes the production of bio-aviation fuel components from low-value bulk solid waste distiller's grains. The yields and physicochemical properties of the relevant products and materials of this embodiment are shown in Table 1.

[0138] Table 1: Yields and physicochemical properties of the products of Comparative Example 1 and Examples 1-5

[0139]

[0140]

[0141] As can be seen from Table 1, the method provided by the present invention for preparing bio-aviation fuel components through cascaded denitrification and deoxygenation of wine lees can significantly increase the bio-aviation fuel yield from 0.067 kg / kg·raw material of wine lees pyrolysis alone to a maximum of 0.268 kg / kg·raw material through the co-pyrolysis of plastic and wine lees, and can also produce bio-gasoline and diesel with a maximum of 0.147 kg / kg·raw material as a by-product. This is mainly because plastics can improve the composition and properties of wine lees pyrolysis oil while simultaneously promoting the deoxygenation and denitrification of wine lees pyrolysis oil, thereby reducing the difficulty of subsequent processes and improving product conversion efficiency. At the same time, the generated pyrolysis residue can be activated by steam and loaded with active metals to obtain an activated carbon catalyst with a maximum of 0.189 kg / kg·raw material, which has a good pore structure (specific surface area can reach up to 432.1 m 2 / g) and was successfully used as a high-efficiency hydrodeoxygenation-isomerization catalyst to promote the efficient and directional conversion of low-value pyrolysis oil into high-value bio-aviation fuel components; in addition, the plastic also promotes the release of gaseous nitrogen in the form of NH3, and by absorbing NH3 and CO2 in the exhaust gas, it can also produce ammonium carbonate fertilizer with a by-product content of up to 0.039kg / kg·raw material.

[0142] In addition, it can be found that different types of plastics have different effects on the nitrogen element in the pyrolysis process of wine lees, and the grading of different plastics can achieve directional transfer and efficient utilization of nitrogen. The pyrolysis process of completely decomposed hydrogen-rich plastics such as PE can inhibit the release of nitrogen-containing gases, thereby slightly increasing the nitrogen content in the pyrolysis char. At the same time, due to the hydrogen-rich characteristics, more nitrogen enters the gas phase in the form of NH3, which greatly reduces the nitrogen content in the pyrolysis oil. Oxygen-containing plastics such as PET do not completely decompose during the pyrolysis process, but form plastic pyrolysis char, which can anchor nitrogen-containing gases and promote nitrogen enrichment in the pyrolysis char, thereby significantly reducing the nitrogen content in the pyrolysis oil and increasing the NH3 content to a certain extent. In addition, the combination of different plastics can better regulate the migration and conversion of nitrogen, reduce the nitrogen content in the pyrolysis oil, improve the quality of the pyrolysis oil, regulate the distribution of the final product, and increase the yield of bio-aviation fuel.

[0143] In addition, the results of pyrolysis-hydrogenation treatment of different proportions of PE plastic and distiller's grains under different working conditions to produce bio-aviation fuel also show that the blending ratio, pyrolysis temperature, hydrotreatment conditions (temperature, pressure, hydrogen-to-oil ratio), catalyst preparation parameters, etc. will affect the yield and quality of the final product. For example, if the co-pyrolysis temperature of plastic distiller's grains is too low (such as 500°C), it may lead to incomplete pyrolysis of the plastic, producing wax (7%), resulting in a decrease in the yield of pyrolysis oil and gas. Although a high pyrolysis temperature (such as 700°C) will not produce significant wax, it will also lead to excessive decomposition of the pyrolysis oil, resulting in a decrease in the yield and an increase in the yield of pyrolysis gas. Therefore, it is advisable to control the pyrolysis temperature at around 600°C.

[0144] The description of various embodiments of the present invention is presented herein for illustrative purposes only and is not intended to be exhaustive or limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terms used herein are selected to best explain the principles of the embodiments, practical applications, or technological advancements, or to enable others skilled in the art to understand the embodiments disclosed herein, as compared to commercially available technology.

[0145] In this article, various embodiments of the present invention may be presented in the form of ranges. It should be understood that the description in range form is merely for convenience and brevity and should not be construed as a hard limit to the scope of the invention. Therefore, the description of a range should be considered to specifically disclose all possible sub-ranges and individual values within the range. For example, a description of a range such as from 1 to 6 should be considered to specifically disclose sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual values within the range, such as 1, 2, 3, 4, 5, 6, which has nothing to do with the width of the range.

[0146] It should be understood that certain features of the invention described in the context of separate embodiments for the sake of clarity may also be provided in combination in a single embodiment. Conversely, various features of the invention described in the context of a single embodiment for the sake of brevity may also be provided individually or in any suitable subcombination, or in any other described embodiment of the invention, where appropriate. Certain features described in the context of various embodiments are not considered essential features of those embodiments unless the embodiment would not function without those features.

[0147] All publications, patents, and patent applications mentioned herein are incorporated herein by reference in their entirety, to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated as being incorporated herein by reference. In addition, the citation or identification of any reference herein should not be construed as an admission that such reference is available as prior art to the present invention. To the extent that section headings are used, such headings should not be construed as necessarily limiting.

Claims

1. A method for preparing bio-aviation fuel components by cascade denitrification and deoxygenation of vinasse, characterized in that: The following steps are involved: S1. Drying and dehydrating distiller's grains, mixing the dehydrated distiller's grains with plastic in a mass ratio of 1:X to obtain a raw material, and rapidly pyrolyzing the raw material in a pyrolysis device at a temperature of 500-800° C. to obtain primary denitrified and deoxygenated pyrolysis oil and gas and nitrogen-doped pyrolysis carbon; wherein X≤1; S2, condensing the pyrolysis oil and gas obtained in step S1 to obtain low-nitrogen and low-oxygen bio-oil and non-condensable gas 1; S3, hydrogenating and upgrading the low-nitrogen and low-oxygen bio-oil obtained in step S2 using a hydrotreating device equipped with an activated carbon-based catalyst to complete secondary deep denitrification and deoxygenation to obtain high-value fuel oil rich in aviation fuel components and ammonia-containing gas; S4, subjecting the high-value fuel obtained in step S3 to a catalytic hydrogenation isomerization reaction, followed by fractionation and separation to obtain a bio-aviation fuel component; S5. Wash the non-condensable gas 1 obtained in step S2 and the ammonia-containing gas obtained in step S3 with water to remove ammonia and carbon dioxide therefrom to obtain an ammonium carbonate solution and non-condensable gas 2; crystallize the ammonium carbonate solution to obtain ammonium carbonate solid; and transport the non-condensable gas 2 to the pyrolysis equipment in step S1 for combustion and heat supply; S6. Activating the nitrogen-doped pyrolytic carbon obtained in step S1 by water vapor to form pores, thereby obtaining nitrogen-doped activated carbon and activated gas; the water vapor comprises water vapor generated by drying and dehydrating the vinasse; and loading the nitrogen-doped activated carbon with an active metal to obtain a catalyst, which can be used as the activated carbon-based catalyst used in step S3. S7, transporting the activated gas obtained in step S6 to the hydroprocessing equipment in step S3 for supplying hydrogen; The low-nitrogen and low-oxygen bio-oil is a stable pyrolysis oil, the nitrogen content of which is less than 1 wt%, and the oxygen content of which is less than 20 wt%.

2. The method for preparing bio-aviation fuel components by cascade denitrification and deoxygenation of vinasse according to claim 1, characterized in that: The plastic includes at least one of polyethylene, polypropylene, polystyrene, polyethylene terephthalate and polycarbonate.

3. The method for preparing bio-aviation fuel components by cascade denitrification and deoxygenation of vinasse according to claim 2, characterized in that: In step S1, the plastic is cleaned of impurities and crushed before being used for compounding.

4. The method for preparing bio-aviation fuel components by cascaded denitrification and deoxygenation of vinasse according to claim 1, characterized in that: In step S1, the time of rapid pyrolysis is controlled to be 2 to 60 seconds.

5. The method for preparing bio-aviation fuel components by cascade denitrification and deoxygenation of vinasse according to claim 4, characterized in that: The pyrolysis equipment used in step S1 is a fluidized bed.

6. The method for preparing bio-aviation fuel components by cascaded denitrification and deoxygenation of vinasse according to any one of claims 1 to 5, characterized in that: In step S3, the hydrogen-to-oil ratio is controlled at 300-1000:1, the temperature of the hydrogenation upgrading treatment is controlled at 200-400°C, and the pressure of the hydrogenation upgrading treatment is controlled at 0.5-10 MPa.

7. The method for preparing bio-aviation fuel components by cascaded denitrification and deoxygenation of vinasse according to claim 6, characterized in that: In step S6, the mass ratio of activation water vapor to pyrolytic carbon is 0.5-2:1, the activation temperature is controlled at 700-1000°C, and the activation time is controlled at 0.5-5h; The active metal includes at least one of Ni, Co, Mo, Fe, Ce and Cu.

8. A device for preparing bio-aviation fuel components by cascade denitrification and deoxygenation of vinasse, characterized in that: A method for preparing bio-aviation fuel components by cascaded denitrification and deoxygenation of distiller's grains as claimed in any one of claims 1 to 7; the device comprises: The drying and crushing unit (1) is used to dry and dehydrate the wine lees and crush them into powder for mixing with plastic to obtain raw materials and water vapor; A rapid pyrolysis unit (2) is used for rapidly pyrolyzing the raw material and performing gas-solid separation to obtain pyrolysis oil gas and nitrogen-doped pyrolysis carbon, and for condensing the pyrolysis oil gas to obtain low-nitrogen and low-oxygen bio-oil; A hydrocatalytic conversion and separation unit (3) is used for the hydrocatalytic conversion of low-nitrogen and low-oxygen bio-oil, and distillation separation to obtain bio-aviation fuel components and bio-gasoline and diesel components; A catalyst manufacturing unit (4) is used to activate nitrogen-doped pyrolytic carbon through water vapor to create pores and load active metals; The tail gas treatment unit (5) is used to absorb ammonia and carbon dioxide in the non-condensable gas produced by the rapid pyrolysis unit (2) and / or the non-condensable gas produced by the catalyst manufacturing unit (4), and the unabsorbed non-condensable gas is used as fuel for the rapid pyrolysis unit (2).

9. The device for preparing bio-aviation fuel components by cascaded denitrification and deoxygenation of vinasse according to claim 8, characterized in that: The drying and crushing unit (1) comprises a drying device (11) and a crushing and matching device (12), wherein the discharge port of the drying device (11) is connected to the feed port of the crushing and matching device (12); The rapid pyrolysis unit (2) comprises a fluidized bed rapid pyrolyzer (21), an air flow separation bed (22) and a quenching tower (23), wherein the feed port of the fluidized bed rapid pyrolyzer (21) is connected to the discharge port of the crushing and mixing device (12), the feed port of the air flow separation bed (22) is connected to the discharge port of the fluidized bed rapid pyrolyzer (21), and the oil and gas inlet of the quenching tower (23) is connected to the oil and gas outlet of the air flow separation bed (22); The hydrocatalytic conversion and separation unit (3) comprises an oil storage tank (31), a fixed-bed hydrogenation reactor (32) and a distillation tower (33), wherein the oil inlet of the oil storage tank (31) is connected to the oil outlet of the quenching tower (23), the oil outlet of the oil storage tank (31) is connected to the oil inlet of the fixed-bed hydrogenation reactor (32), and the oil outlet of the fixed-bed hydrogenation reactor (32) is connected to the oil inlet of the distillation tower (33); The catalyst manufacturing unit (4) comprises an activation reaction tower (41) and a catalyst synthesis device (42), wherein the water vapor inlet of the activation reaction tower (41) is connected to the water vapor outlet of the drying device (11), the pyrolysis carbon inlet of the activation reaction tower (41) is connected to the pyrolysis carbon outlet of the air flow separation bed (22), the gas outlet of the activation reaction tower (41) is connected to the gas inlet of the fixed bed hydrogenation reactor (32), and the feed port of the catalyst synthesis device (42) is connected to the activated carbon outlet of the activation reaction tower (41); The tail gas treatment unit (5) comprises a water scrubber (51) and a crystallizer (52), wherein the air inlet of the water scrubber (51) is connected to the tail gas outlet of the quenching tower (23) and the tail gas outlet of the fixed bed hydrogenation reactor (32), respectively; the tail gas outlet of the water scrubber (51) is connected to the fuel gas inlet of the fluidized bed rapid pyrolyzer (21); and the liquid inlet of the crystallizer (52) is connected to the liquid outlet of the water scrubber (51).

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