Device and method for preparing aviation kerosene from crude aromatic hydrocarbon

Abstract

The invention relates to a device and a method for preparing aviation kerosene from crude aromatic hydrocarbon. The device comprises a hydrogen supply unit, a hydrodeoxygenation unit, a first separation unit, a hydrogenation saturation unit, a hydrogenation ring opening unit, a second separation unit and a product recovery unit which are connected in sequence, the method is carried out by adopting the device for preparing the aviation kerosene from the crude aromatic hydrocarbon, so that the crude aromatic hydrocarbon is sequentially subjected to a hydrodeoxygenation reaction, a hydrogenation saturation reaction and a hydrogenation ring-opening reaction and is efficiently converted into the aviation kerosene through a synergistic effect; the high-added-value green aviation kerosene product has the advantages that the yield is preferably as high as 85% or above, the oxygen content is preferably as low as 25 mu g / g or below, the freezing point is preferably as low as-48 DEG C or below, and the energy density is preferably as high as 42.8 MJ / kg or above, and has excellent low-temperature fluidity and combustion performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of aviation kerosene preparation devices and methods, and particularly relates to a device and method for preparing aviation kerosene from crude aromatic hydrocarbons. BACKGROUND

[0002] With the rapid development of the global aviation industry, the demand for aviation kerosene continues to grow. Traditional aviation kerosene mainly relies on petroleum refining, but there are problems such as large resource consumption, high carbon emissions, and serious environmental pollution in the production process. In addition, the limited nature and non-renewable nature of petroleum resources also restrict the sustainable development of traditional aviation kerosene. Therefore, it is urgent to develop a green and renewable aviation kerosene substitute.

[0003] In recent years, the technical route of using renewable resources to prepare green aviation kerosene has attracted much attention. Among them, the technology of preparing crude aromatic hydrocarbons from carbon dioxide and hydrogen has great development potential due to its wide raw material sources and environmental friendliness. Crude aromatic hydrocarbons, as the product of carbon dioxide hydrogenation, have high carbon content and energy density, and are potential raw materials for preparing aviation kerosene. However, crude aromatic hydrocarbons prepared by carbon dioxide hydrogenation contain a large amount of oxygen-containing compounds such as alcohols, aldehydes or ketones, which result in poor stability and combustion performance, and are difficult to be directly used as aviation kerosene. Therefore, how to efficiently convert crude aromatic hydrocarbons into high-value-added and high-performance green aviation kerosene has become the focus of current technical research.

[0004] Currently, there have been some related researches and technical explorations on the conversion and utilization of crude aromatic hydrocarbons. For example, the hydrogenation treatment technology is used to refine crude aromatic hydrocarbons to remove oxygen-containing compounds and improve their stability and combustion performance; the hydrogenation saturation reaction is used to improve their low-temperature fluidity and calorific value; the catalytic cracking or reforming technology is used to adjust their carbon number distribution to meet the distillation range requirements of aviation kerosene.

[0005] For example, CN113372952A discloses a method for producing aviation kerosene from coal tar rich in cyclic hydrocarbons, which adopts a "low molecular weight alkane extraction-arene extraction-hydrogenation modification" three-stage coupling process to treat the coal tar rich in cyclic hydrocarbons. However, this method has the problems of excessive dependence on raw materials, strict distillation cutting, and the presence of phenols, pyridines, metals (Fe or Ca) and other substances in coal tar, which cannot be completely removed in the extraction and extraction steps, and the subsequent hydrogenation catalyst is easy to be poisoned and deactivated. In addition, there is still a large space for improvement in the performance indicators of the obtained aviation kerosene product.

[0006] However, there are few reports on the preparation of aviation kerosene from crude aromatic hydrocarbons by hydrogenation. How to provide a device and method for preparing aviation kerosene from crude aromatic hydrocarbons by hydrogenation, realize efficient and controllable hydrogenation reaction of crude aromatic hydrocarbons, and optimize the product distribution, is a technical difficulty to be solved in the field of preparing high-energy-density aviation fuel. SUMMARY

[0007] To solve the above technical problems, the present application provides a device and method for preparing aviation kerosene from crude aromatic hydrocarbons, which realizes efficient conversion of crude aromatic hydrocarbons, especially those produced by carbon dioxide hydrogenation, into high-value green aviation kerosene, and reduces dependence on fossil resources.

[0008] To achieve this purpose, the present application adopts the following technical solutions:

[0009] In a first aspect, the present application provides a device for preparing aviation kerosene from crude aromatic hydrocarbons, which comprises a hydrogen supply unit, a hydrodeoxygenation unit, a first separation unit, a hydrogenation saturation unit, a hydrogenation ring-opening unit, a second separation unit, and a product recovery unit connected in sequence.

[0010] The present application integrates the hydrodeoxygenation unit, the hydrogenation saturation unit, and the hydrogenation ring-opening unit, so that when aviation kerosene is subsequently prepared using them, the crude aromatic hydrocarbons undergo hydrodeoxygenation reaction, hydrogenation saturation reaction, and hydrogenation ring-opening reaction in sequence. The combination of these reactions produces high-value green aviation kerosene products with excellent performance indicators. Moreover, the device has a simple structure and high operational stability.

[0011] Preferably, the device further comprises a product stabilization treatment unit.

[0012] Preferably, the product stabilization treatment unit is arranged between the second separation unit and the product recovery unit.

[0013] Preferably, the product stabilization treatment unit is arranged between the hydrogenation saturation unit and the hydrogenation ring-opening unit, and between the second separation unit and the product recovery unit.

[0014] Preferably, the hydrogenation saturation unit and the product stabilization treatment unit are connected in a circulation manner.

[0015] Preferably, the product stabilization treatment unit comprises an analysis subunit and an adjustment subunit.

[0016] The analysis subunit is used to analyze the hydrocarbon composition in the product, and the adjustment subunit is used to intelligently adjust the system and optimize the distillation cut point.

[0017] Preferably, the device further comprises a hydrogen purification unit connected thereto.

[0018] Preferably, the hydrogen purification unit is connected to the first separation unit.

[0019] Preferably, the hydrogen purification unit is connected to the hydrogen supply unit.

[0020] Preferably, the hydrogen purification unit is connected with the second separation unit.

[0021] Preferably, the device further comprises a pretreatment unit and a treatment unit.

[0022] Preferably, the pretreatment unit is connected with the hydrodeoxygenation unit.

[0023] Preferably, the treatment unit comprises a first treatment unit, a second treatment unit and a third treatment unit.

[0024] Preferably, the first treatment unit is connected with the pretreatment unit.

[0025] Preferably, the second treatment unit is connected with the first separation unit.

[0026] Preferably, the third treatment unit is connected with the hydrogen purification unit.

[0027] Preferably, the first separation unit is connected with the first treatment unit.

[0028] In a second aspect, the present application provides a method for preparing aviation kerosene from crude aromatic hydrocarbons, which is performed by using the device for preparing aviation kerosene from crude aromatic hydrocarbons according to the first aspect.

[0029] The method according to the present application is performed by using the device for preparing aviation kerosene from crude aromatic hydrocarbons according to the first aspect, which realizes efficient conversion of crude aromatic hydrocarbons into high-value green aviation kerosene, and solves the problems of low removal efficiency of oxygen-containing compounds, uncontrollable product distribution and complex process in the prior art.

[0030] Preferably, the method comprises the following steps: introducing crude aromatic hydrocarbons and hydrogen and performing a hydrodeoxygenation reaction to obtain a deoxygenated product, performing a first separation on the deoxygenated product to obtain an aromatic hydrocarbon component, performing a hydrogenation saturation reaction on the aromatic hydrocarbon component to obtain a saturated product, performing a hydrogenation ring-opening reaction on the saturated product to obtain a ring-opening product, and performing a second separation on the ring-opening product to obtain a liquid-phase separation product, i.e. an aviation kerosene product.

[0031] Preferably, the crude aromatic hydrocarbons comprise heavy aromatic hydrocarbons, light aromatic hydrocarbons and oxygen-containing compounds.

[0032] Preferably, the crude aromatic hydrocarbons comprise, in terms of mass percentage, 60-85wt% of heavy aromatic hydrocarbons, 12-39.5wt% of light aromatic hydrocarbons and 0.5-3wt% of oxygen-containing compounds.

[0033] The heavy aromatic hydrocarbon is 60-85wt%, for example, 60wt%, 70wt%, 75wt%, 80wt% or 85wt%, etc.; the light aromatic hydrocarbon is 12-39.5wt%, for example, 12wt%, 20wt%, 25wt%, 30wt% or 39.5wt%, etc.; the oxygen-containing compound is 0.5-3wt%, for example, 0.5wt%, 1.5wt%, 2wt%, 2.5wt% or 3wt%, etc.

[0034] It is worth mentioning that the heavy aromatic hydrocarbon in the present application refers to C9 and above aromatic hydrocarbon, and the light aromatic hydrocarbon refers to C8 and below aromatic hydrocarbon.

[0035] Preferably, the reaction temperature of the hydrodeoxygenation reaction is 240-400℃, for example, 240℃, 260℃, 280℃, 300℃, 320℃, 340℃, 360℃, 380℃ or 400℃, etc.

[0036] Preferably, the reaction pressure of the hydrodeoxygenation reaction is 2.0-5.0MPa, for example, 2.0MPa, 2.5MPa, 3.0MPa, 3.5MPa, 4.0MPa, 4.5MPa or 5.0MPa, etc.

[0037] Preferably, the volume ratio of hydrogen to oxygen-containing compound in the crude aromatic hydrocarbon in the hydrodeoxygenation reaction is (20-60):1, for example, 20:1, 30:1, 40:1, 50:1 or 60:1, etc.

[0038] Preferably, the liquid hourly space velocity on the catalyst in the hydrodeoxygenation reaction is 0.4-1.6h -1 , for example, 0.4 h -1 , 0.5 h -1 , 0.8 h -1 , 1.0 h -1 , 1.2 h -1 , 1.4 h -1 or 1.6 h -1 , etc.

[0039] Preferably, the oxygen content in the deoxygenated product after the hydrodeoxygenation reaction is ≤50μg / g, for example, 50μg / g, 45μg / g, 40μg / g, 35μg / g, 30μg / g, 20μg / g or 10μg / g, etc.

[0040] Preferably, the temperature of the first separation is 80-300℃, for example, 80℃, 100℃, 120℃, 150℃, 180℃, 200℃, 220℃, 250℃, 280℃ or 300℃, etc.

[0041] Preferably, the first separated pressure is 0.1-1 MPa, for example, it can be 0.1 MPa, 0.3 MPa, 0.5 MPa, 0.7 MPa or 1 MPa, etc.

[0042] Preferably, the reaction temperature of the hydrogenation saturation reaction is 160-360°C, for example, it can be 160°C, 200°C, 250°C, 300°C, 330°C or 360°C, etc.

[0043] Preferably, the reaction pressure of the hydrogenation saturation reaction is 2.0-7.0 MPa, for example, it can be 2.0 MPa, 3.0 MPa, 4.0 MPa, 5.0 MPa, 6.0 MPa or 7.0 MPa, etc.

[0044] Preferably, the hydrogen oil volume ratio in the hydrogenation saturation reaction is (600-1200):1, for example, it can be 600:1, 700:1, 800:1, 900:1, 1000:1, 1100:1 or 1200:1, etc.

[0045] Preferably, the liquid hourly space velocity of the catalyst in the hydrogenation saturation reaction is 1.0-4.5 h -1 , for example, it can be 1.0 h -1 , 1.5 h -1 , 2.0 h -1 , 2.5 h -1 , 3.0 h -1 , 3.5 h -1 , 4.0 h -1 or 4.5 h -1 , etc.

[0046] Preferably, the first mixed component includes saturated products and aromatic hydrocarbons.

[0047] Preferably, the reaction temperature of the hydrogenation ring-opening reaction is 300-400°C, for example, it can be 300°C, 320°C, 340°C, 360°C, 380°C or 400°C, etc.

[0048] Preferably, the reaction pressure of the hydrogenation ring-opening reaction is 2-7 MPa, for example, it can be 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa or 7 MPa, etc.

[0049] Preferably, the hydrogen oil volume ratio of the hydrogenation ring-opening reaction is (100-700):1, for example, it can be 100:1, 200:1, 300:1, 400:1, 500:1, 600:1 or 700:1, etc.

[0050] Preferably, the liquid hourly space velocity of the catalyst in the hydrogenation ring-opening reaction is 1.5-4.5 h-1 For example, it could be 1.5 hours. -1 2.0 h -1 2.5 h -1 3.0 h -1 3.5 h -1 4.0 h -1 Or 4.5 h -1 wait.

[0051] Preferably, the temperature of the second separation is 50~200℃, for example, it can be 50℃, 70℃, 100℃, 120℃, 150℃, 180℃ or 200℃, etc.

[0052] Preferably, the pressure of the second separation is 0.1~1 MPa, for example, it can be 0.1 MPa, 0.3 MPa, 0.5 MPa, 0.8 MPa or 1 MPa, etc.

[0053] Preferably, the method further includes pretreatment of the crude aromatic hydrocarbon prior to the hydrodeoxygenation reaction.

[0054] Preferably, the pretreatment includes any one or a combination of at least two of filtration, adsorption, or distillation, wherein typical but non-limiting combinations include a combination of filtration and adsorption, a combination of filtration and distillation, or a combination of adsorption and distillation, etc.

[0055] Preferably, the method further includes stabilizing the liquid phase separation product after the second separation.

[0056] Preferably, the first separation also yields gaseous components and oxygen-containing byproducts.

[0057] Preferably, the method further includes purifying the first separated gas components with hydrogen to obtain hydrogen and light hydrocarbons, wherein the hydrogen is recycled to the hydrodeoxygenation reaction, and the light hydrocarbons are recovered after a third treatment.

[0058] Preferably, the method further includes a second treatment of the oxygen-containing byproducts after the first separation for recovery.

[0059] Preferably, the first separation also yields wastewater, which is then treated to meet discharge standards.

[0060] Preferably, a gaseous component is also obtained after the second separation.

[0061] Preferably, the method further includes purifying the second separated gaseous components with hydrogen to obtain hydrogen and light hydrocarbons, wherein the hydrogen is recycled to the hydrodeoxygenation reaction, and the light hydrocarbons are recovered after a third treatment.

[0062] Preferably, the first separation and the second separation each independently include any one or a combination of at least two of distillation, extraction, or adsorption separation, wherein typical but non-limiting combinations include combinations of distillation and extraction, combinations of extraction and adsorption separation, or combinations of distillation and adsorption separation, etc.

[0063] Preferably, the hydrogen purification process includes pressure swing adsorption and / or membrane separation.

[0064] Preferably, the second treatment includes catalytic oxidation and / or biodegradation.

[0065] Preferably, the first treatment includes any one or a combination of at least two of physical treatment, chemical treatment, or biological treatment, wherein typical but non-limiting combinations include combinations of physical and chemical treatment, combinations of physical and biological treatment, or combinations of chemical and biological treatment, etc.

[0066] Preferably, the density of the aviation kerosene is 0.75~0.85 g / cm³. 3 For example, it could be 0.75 g / cm³. 3 0.78 g / cm 3 0.80 g / cm 3 0.82 g / cm 3 Or 0.85 g / cm 3 wait.

[0067] Preferably, the freezing point of the aviation kerosene is ≤-47℃, for example, it can be -47℃, -48℃, -49℃, -50℃, -51℃ or -52℃, etc.

[0068] Preferably, the flash point of the aviation kerosene is ≥38℃, for example, it can be 38℃, 40℃, 42℃, 45℃, 48℃ or 50℃, etc.

[0069] Preferably, the oxygen content of the aviation kerosene is ≤25μg / g, for example, it can be 25μg / g, 23μg / g, 20μg / g, 15μg / g or 10μg / g, etc.

[0070] Preferably, the energy density of the aviation kerosene is ≥42.8 MJ / kg, for example, it can be 42.8 MJ / kg, 43.0 MJ / kg, 43.5 MJ / kg, 44.0 MJ / kg, 44.5 MJ / kg or 45.0 MJ / kg, etc.

[0071] Compared with the prior art, the present invention has at least the following beneficial effects:

[0072] (1) The apparatus for preparing aviation kerosene from crude aromatics provided by the present invention integrates a hydrodeoxygenation unit, a hydrosaturation unit and a hydroring-opening unit, so that the subsequent aviation kerosene prepared by it has a high product yield, and the obtained aviation kerosene product has excellent low-temperature fluidity and combustion performance. The apparatus has a simple structure and high operational stability.

[0073] (2) The method for preparing aviation kerosene from crude aromatics provided by the present invention uses crude aromatics, especially crude aromatics produced by carbon dioxide hydrogenation, as raw materials. It adopts a process combining hydrogenation deoxygenation reaction, hydrogenation saturation reaction and hydrogenation ring-opening reaction to prepare high-value-added green aviation kerosene. The yield is preferably as high as 85% or more, the oxygen content is preferably as low as 25 μg / g or less, the freezing point is preferably as low as -48℃ or less, and the energy density is preferably as high as 42.8 MJ / kg or more. This reduces the dependence on fossil resources and realizes the recycling of CO2 resources. Attached Figure Description

[0074] Figure 1 This is a schematic diagram of the connection relationship of the apparatus for preparing aviation kerosene from crude aromatics provided in Embodiment 1 of the present invention.

[0075] In the diagram: 1. Hydrogen supply unit; 2. Hydrogenation and deoxygenation unit; 3. First separation unit; 4. Hydrogenation saturation unit; 5. Hydrogenation ring-opening unit; 6. Second separation unit; 7. Product recovery unit; 8. Product stabilization treatment unit; 9. Hydrogen purification unit; 10. Pretreatment unit; 11. First treatment unit; 12. Second treatment unit; 13. Third treatment unit. Detailed Implementation

[0076] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments. However, the following examples are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention is determined by the claims.

[0077] The process parameters for each step in the methods for preparing aviation kerosene from crude aromatics provided in Examples 1 to 4 are shown in Table 1.

[0078] Table 1

[0079]

[0080] I. Implementation Examples

[0081] Example 1

[0082] This embodiment provides an apparatus for preparing aviation kerosene from crude aromatics, such as... Figure 1As shown, the device includes a hydrogen supply unit 1, a hydrogen deoxygenation unit 2, a first separation unit 3, a hydrogen saturation unit 4, a hydrogen ring-opening unit 5, a second separation unit 6, and a product recovery unit 7 connected in sequence.

[0083] The apparatus further includes a stabilization unit; the product stabilization unit 8 is disposed between the hydrogenation saturation unit 4 and the hydrogenation ring-opening unit 5; and the product stabilization unit 8 is disposed between the second separation unit 6 and the product recovery unit 7; the hydrogenation saturation unit 4 and the product stabilization unit 8 are cyclically connected; the product stabilization unit 8 includes an analysis subunit and an adjustment subunit;

[0084] The device further includes a hydrogen purification unit 9 connected to the first separation unit 3; the hydrogen purification unit 9 is connected to the hydrogen supply unit 1; and the hydrogen purification unit 9 is connected to the second separation unit 6.

[0085] The device further includes a pretreatment unit 10 and a processing unit; the pretreatment unit 10 is connected to the hydrogen deoxygenation unit 2; the processing unit includes a first processing unit 11, a second processing unit 12 and a third processing unit 13; the first processing unit 11 is connected to the pretreatment unit 10; the second processing unit 12 is connected to the first separation unit 3; the third processing unit 13 is connected to the hydrogen purification unit 9; the first separation unit 3 is connected to the first processing unit 11.

[0086] This embodiment also provides a method for preparing aviation kerosene from crude aromatics. The method is carried out using the apparatus for preparing aviation kerosene from crude aromatics described in this embodiment, using crude aromatics produced by carbon dioxide hydrogenation as raw material, and using the process parameters shown in Example 1 in Table 1.

[0087] The method includes the following steps:

[0088] Crude aromatics and hydrogen are introduced and subjected to the hydrogenation deoxygenation reaction to obtain a deoxygenated product. The deoxygenated product is then separated into aromatic components through a first separation process. The aromatic components are then subjected to a hydrogenation saturation reaction to obtain a saturated product. The saturated product is then subjected to a hydrogenation ring-opening reaction to obtain a ring-opening product. The ring-opening product is then subjected to a second separation process to obtain a liquid-phase separation product, which is aviation kerosene.

[0089] The pretreatment includes first dehydrating the crude aromatic hydrocarbons in a dehydration tower, and then adsorbing them in an adsorption tower (filled with activated clay) to remove colloids and solid impurities.

[0090] The hydrodeoxygenation reaction is carried out in a fixed-bed reactor (loaded with Ni-Mo / Al2O3 catalyst) to obtain deoxygenated products;

[0091] The first separation includes gas-liquid separation of the deoxygenated product to obtain a gaseous component and a liquid product; the gaseous component is purified with hydrogen and reused in the hydrodeoxygenation reaction; the liquid product enters a distillation column to separate light hydrocarbons, oxygen-containing byproducts and wastewater, and to obtain an intermediate fraction, namely an aromatic component (deoxygenated aromatics).

[0092] The hydrogenation saturation reaction includes mixing the aromatic components with hydrogen and feeding them into a fixed-bed reactor (loaded with Pt / Al2O3 catalyst) to carry out the hydrogenation saturation reaction and obtain saturated products;

[0093] The hydrogenation ring-opening reaction includes mixing the saturated product with hydrogen and feeding it into a fixed-bed reactor (Ni-W / USY molecular sieve catalyst) to carry out the hydrogenation ring-opening reaction and obtain the ring-opening product;

[0094] The second separation includes the ring-opening product undergoing gas-liquid separation to obtain a gaseous component and a liquid product. The gaseous component is then purified with hydrogen, and the hydrogen is reused in the hydrodeoxygenation reaction. The light hydrocarbons are then recovered after a third treatment. The liquid product is then subjected to product stabilization treatment to obtain aviation kerosene.

[0095] The product stabilization process includes monitoring the hydrocarbon composition of the liquid product using an online near-infrared spectroscopy (NIR) analyzer, optimizing the fraction cut point using an intelligent blending system to control the final boiling point to approximately 300°C, and adding a trace amount of antioxidant (2,6-di-tert-butyl-p-cresol, with the amount of antioxidant added being 8 μg / g based on the liquid product).

[0096] Example 2

[0097] This embodiment provides an apparatus for preparing aviation kerosene from crude aromatics, wherein the apparatus is sequentially connected to a hydrogen supply unit, a hydrodeoxygenation unit, a first separation unit, a hydrosaturation unit, a hydroring-opening unit, a second separation unit, and a product recovery unit;

[0098] The apparatus further includes a product stabilization unit; the product stabilization unit is disposed between the second separation unit and the product recovery unit; the hydrogenation saturation unit is cyclically connected to the product stabilization unit; the product stabilization unit includes an analysis subunit and an adjustment subunit;

[0099] The device further includes a hydrogen purification unit connected to it; the hydrogen purification unit is connected to the first separation unit; the hydrogen purification unit is connected to the hydrogen supply unit; and the hydrogen purification unit is connected to the second separation unit.

[0100] The device further includes a pretreatment unit and a processing unit; the pretreatment unit is connected to the hydrogen deoxygenation unit; the processing unit includes a first processing unit, a second processing unit, and a third processing unit; the first processing unit is connected to the pretreatment unit; the second processing unit is connected to the first separation unit; the third processing unit is connected to the hydrogen purification unit; and the first separation unit is connected to the first processing unit.

[0101] This embodiment also provides a method for preparing aviation kerosene from crude aromatics. Except for using the apparatus for preparing aviation kerosene from crude aromatics described in this embodiment and using the process parameters shown in Example 2 of Table 1, the method is the same as that in Example 1.

[0102] Example 3

[0103] This embodiment provides an apparatus for preparing aviation kerosene from crude aromatics. The apparatus includes a hydrogen supply unit, a hydrodeoxygenation unit, a first separation unit, a hydrosaturation unit, a hydroring-opening unit, a second separation unit, and a product recovery unit connected in sequence.

[0104] The apparatus further includes a product stabilization unit; the product stabilization unit is disposed between the hydrogenation saturation unit and the hydrogenation ring-opening unit, and is also disposed between the second separation unit and the product recovery unit; the product stabilization unit includes an analysis subunit and an adjustment subunit;

[0105] The device further includes a hydrogen purification unit connected to it; the hydrogen purification unit is connected to the first separation unit; the hydrogen purification unit is connected to the hydrogen supply unit; the hydrogen purification unit is connected to the hydrogen supply unit.

[0106] The device further includes a pretreatment unit and a processing unit; the pretreatment unit is connected to the hydrogen deoxygenation unit; the processing unit includes a first processing unit, a second processing unit, and a third processing unit; the first processing unit is connected to the pretreatment unit; the second processing unit is connected to the first separation unit; the third processing unit is connected to the hydrogen purification unit; and the first separation unit is connected to the first processing unit.

[0107] This embodiment also provides a method for preparing aviation kerosene from crude aromatics. Except for using the apparatus for preparing aviation kerosene from crude aromatics described in this embodiment and using the process parameters shown in Example 3 of Table 1, the method is the same as that in Example 1.

[0108] Example 4

[0109] This embodiment provides a method for preparing aviation kerosene from crude aromatics. Except for using the apparatus for preparing aviation kerosene from crude aromatics as described in Example 1 and using the process parameters described in Example 4 of Table 1, the method is the same as that in Example 1.

[0110] Example 5

[0111] This embodiment provides an apparatus for preparing aviation kerosene from crude aromatics. The apparatus is identical to that in Embodiment 1 except that it does not include a product stabilization treatment unit.

[0112] This embodiment also provides a method for preparing aviation kerosene from crude aromatics. Except for the use of the apparatus for preparing aviation kerosene from crude aromatics described in this embodiment, the method is the same as that in Embodiment 1.

[0113] Example 6

[0114] This embodiment provides an apparatus for preparing aviation kerosene from crude aromatics. The apparatus is the same as in Embodiment 1 except that the hydrogenation saturation unit and the product stabilization treatment unit are not cyclically connected, that is, there is only a one-way connection from the hydrogenation saturation unit to the product stabilization treatment unit and the product stabilization treatment unit is not reconnected to the hydrogenation saturation unit.

[0115] This embodiment also provides a method for preparing aviation kerosene from crude aromatics. Except for the use of the apparatus for preparing aviation kerosene from crude aromatics described in this embodiment, the method is the same as that in Embodiment 1.

[0116] Example 7

[0117] This embodiment provides an apparatus for preparing aviation kerosene from crude aromatics. The apparatus is the same as that in Embodiment 1 except that the pretreatment unit is not provided.

[0118] This embodiment also provides a method for preparing aviation kerosene from crude aromatics. Except for the use of the apparatus for preparing aviation kerosene from crude aromatics described in this embodiment, the method is the same as that in Embodiment 1.

[0119] Example 8

[0120] This embodiment provides a method for preparing aviation kerosene from crude aromatics. Except for the reaction temperature of the hydrogenation ring-opening reaction being 280°C, the method is the same as in Example 1.

[0121] Example 9

[0122] This embodiment provides a method for preparing aviation kerosene from crude aromatics. Except for the reaction temperature of the hydrogenation ring-opening reaction being 420°C, the method is the same as in Example 1.

[0123] II. Comparative Example

[0124] Comparative Example 1

[0125] This comparative example provides an apparatus for preparing aviation kerosene from crude aromatics. The apparatus is identical to that in Example 1 except that the hydrogenation ring-opening unit is not included.

[0126] This comparative example also provides a method for preparing aviation kerosene from crude aromatics. Except for using the apparatus for preparing aviation kerosene from crude aromatics described in this comparative example, the method is the same as that in Example 1.

[0127] Comparative Example 2

[0128] This comparative example provides an apparatus for preparing aviation kerosene from crude aromatics. The apparatus is identical to that in Example 1 except that it does not include the hydrogenation saturation unit.

[0129] This comparative example also provides a method for preparing aviation kerosene from crude aromatics. Except for using the apparatus for preparing aviation kerosene from crude aromatics described in this comparative example, the method is the same as that in Example 1.

[0130] III. Tests and Results

[0131] The yield, oxygen content, density, freezing point, and energy density of aviation kerosene obtained by the methods for preparing aviation kerosene from crude aromatics provided in the above examples or comparative examples were tested respectively, and the results are shown in Table 2.

[0132] Table 2

[0133]

[0134] The data in Table 2 shows that:

[0135] (1) As can be seen from Examples 1 to 4, the apparatus and method for preparing aviation kerosene from crude aromatics provided by the present invention achieves efficient conversion of crude aromatics produced by carbon dioxide hydrogenation into aviation kerosene. Moreover, the aviation kerosene prepared has excellent performance indicators, with a yield of over 85%, an oxygen content as low as below 25 μg / g, and a density of 0.785~0.800 g / cm³. 3 Within this range, the freezing point is as low as -47℃, the flash point is in the range of 38~42℃, and the energy density is as high as 42.8MJ / kg or more.

[0136] (2) As can be seen from the combined embodiments 1 and 5 to 7, the present invention further optimizes the device by including a product stabilization treatment unit, and further optimizes the hydrogenation saturation unit and the product stabilization treatment unit to be cyclically connected; the device also includes a pretreatment unit; further improving the stable operation of the device, thereby further improving the performance of the obtained aviation kerosene.

[0137] (3) As can be seen from the combined examples 1, 8 and 9, the present invention further improves the efficient conversion of cycloalkanes to chain alkanes in the saturated products by further optimizing the reaction temperature of the hydrogenation ring-opening reaction to 300~400℃, and further improves the performance of the obtained aviation kerosene.

[0138] (4) As can be seen from the comprehensive comparison of Example 1 with Comparative Examples 1 and 2, since Comparative Example 1 did not have a hydrogenation ring-opening unit, it was impossible to effectively convert cycloalkanes into alkanes, resulting in a low yield of the final product, poor low-temperature fluidity, and an excessively high freezing point, which reduced the performance of the obtained aviation kerosene. Since Comparative Example 2 did not have a hydrogenation saturation unit, a deep condensation reaction occurred, generating polycyclic aromatic hydrocarbons and further forming coke, which led to rapid deactivation of the ring-opening catalyst and an increase in the pressure drop of the reactor bed, thus affecting the yield and performance of the aviation kerosene. This shows that the present invention, by combining the hydrogenation deoxygenation unit, the hydrogenation saturation unit, and the hydrogenation ring-opening unit, allows the crude aromatic hydrocarbons to undergo hydrogenation deoxygenation, hydrogenation saturation, and hydrogenation ring-opening reactions in sequence, which synergistically improves the quality and performance of the obtained aviation kerosene, giving it excellent low-temperature fluidity and combustion performance.

[0139] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. An apparatus for preparing aviation kerosene from crude aromatics, characterized in that, The device includes a hydrogen supply unit, a hydrogen deoxygenation unit, a first separation unit, a hydrogen saturation unit, a hydrogen open-loop unit, a second separation unit, and a product recovery unit connected in sequence.

2. The apparatus according to claim 1, characterized in that, The device also includes a product stabilization processing unit; Preferably, the product stabilization treatment unit is disposed between the second separation unit and the product recycling unit; Preferably, the product stabilization treatment unit is disposed between the hydrogenation saturation unit and the hydrogenation ring-opening unit, and the product stabilization treatment unit is disposed between the second separation unit and the product recovery unit; Preferably, the hydrogenation saturation unit is cyclically connected to the product stabilization treatment unit; Preferably, the product stabilization processing unit includes an analysis subunit and an adjustment subunit.

3. The apparatus according to claim 1 or 2, characterized in that, The device also includes a connected hydrogen purification unit; Preferably, the hydrogen purification unit is connected to the first separation unit; Preferably, the hydrogen purification unit is connected to the hydrogen supply unit; Preferably, the hydrogen purification unit is connected to the second separation unit.

4. The apparatus according to any one of claims 1 to 3, characterized in that, The device further includes a preprocessing unit and a processing unit; Preferably, the pretreatment unit is connected to the hydrodeoxygenation unit; Preferably, the processing unit includes a first processing unit, a second processing unit, and a third processing unit; Preferably, the first processing unit is connected to the preprocessing unit; Preferably, the second processing unit is connected to the first separation unit; Preferably, the third processing unit is connected to the hydrogen purification unit; Preferably, the first separation unit is connected to the first processing unit.

5. A method for preparing aviation kerosene from crude aromatics, characterized in that, The method is carried out using the apparatus for preparing aviation kerosene from crude aromatics as described in any one of claims 1 to 4.

6. The method according to claim 5, characterized in that, The method includes the following steps: introducing crude aromatics and hydrogen and performing the hydrogenation deoxygenation reaction to obtain a deoxygenated product; the deoxygenated product is subjected to a first separation to obtain an aromatic component; the aromatic component is then subjected to a hydrogenation saturation reaction to obtain a saturated product; the saturated product is then subjected to a hydrogenation ring-opening reaction to obtain a ring-opening product; and the ring-opening product is then subjected to a second separation to obtain a liquid-phase separation product, which is aviation kerosene. Preferably, the crude aromatic hydrocarbons include heavy aromatic hydrocarbons, light aromatic hydrocarbons, and oxygen-containing compounds; Preferably, the crude aromatics, by mass percentage, comprise: 60-85 wt% heavy aromatics, 12-39.5 wt% light aromatics, and 0.5-3 wt% oxygen-containing compounds.

7. The method according to claim 6, characterized in that, The reaction temperature for the hydrodeoxygenation reaction is 240~400℃; Preferably, the reaction pressure of the hydrodeoxygenation reaction is 2.0~5.0 MPa; Preferably, the volume ratio of hydrogen to oxygen-containing compounds in the crude aromatic hydrocarbon during the hydrodeoxygenation reaction is (20~60):1; Preferably, the liquid hourly space velocity (LHSV) on the catalyst during the hydrodeoxygenation reaction is 0.4–1.6 h⁻¹. -1 ; Preferably, the oxygen content in the deoxygenation product after the hydrodeoxygenation reaction is ≤50 μg / g; Preferably, the temperature of the first separation is 80~300℃; Preferably, the pressure of the first separation is 0.1~1 MPa; Preferably, the reaction temperature of the hydrogenation saturation reaction is 160~360℃; Preferably, the reaction pressure of the hydrogenation saturation reaction is 2.0~7.0 MPa; Preferably, the hydrogen-to-oil volume ratio in the hydrogenation saturation reaction is (600~1200):1; Preferably, the liquid hourly space velocity (LHSV) of the catalyst during the hydrogenation saturation reaction is 1.0 to 4.5 h⁻¹. -1 ; Preferably, the reaction temperature of the hydrogenation ring-opening reaction is 300~400℃; Preferably, the reaction pressure of the hydrogenation ring-opening reaction is 2~7 MPa; Preferably, the hydrogen-to-oil volume ratio in the hydrogenation ring-opening reaction is (100~700):1; Preferably, the liquid hourly space velocity (LHSV) of the catalyst during the hydrogenation ring-opening reaction is 1.5–4.5 h⁻¹. -1 , Preferably, the temperature of the second separation is 50~200℃; Preferably, the pressure of the second separation is 0.1~1MPa.

8. The method according to claim 6 or 7, characterized in that, The method further includes pretreatment of the crude aromatics prior to the hydrodeoxygenation reaction; Preferably, the pretreatment includes any one or a combination of at least two of filtration, adsorption, or distillation; Preferably, the method further includes stabilizing the liquid phase separation product after the second separation.

9. The method according to any one of claims 6 to 8, characterized in that, The first separation also yields gaseous components and oxygen-containing byproducts; Preferably, the method further includes purifying the first separated gas components with hydrogen to obtain hydrogen and light hydrocarbons, wherein the hydrogen is recycled to the hydrodeoxygenation reaction, and the light hydrocarbons are recovered after a third treatment; Preferably, the method further includes a second treatment of the oxygen-containing byproducts after the first separation for recovery; Preferably, a gaseous component is also obtained after the second separation. Preferably, the method further includes purifying the second separated gaseous components with hydrogen to obtain hydrogen and light hydrocarbons, wherein the hydrogen is recycled to the hydrodeoxygenation reaction, and the light hydrocarbons are recovered after a third treatment.

10. The method according to any one of claims 6 to 9, characterized in that, The density of the aviation kerosene is 0.75~0.85 g / cm³. 3 ; Preferably, the freezing point of the aviation kerosene is ≤-47℃; Preferably, the flash point of the aviation kerosene is ≥38°C; Preferably, the oxygen content of the aviation kerosene is ≤25μg / g; Preferably, the energy density of the aviation kerosene is ≥42.8 MJ / kg.

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