Method, device and application of producing aviation kerosene from methanol

Abstract

The present invention discloses a method, device and application for producing aviation kerosene from methanol, and belongs to the field of petrochemical product processing technology. The method comprises: generating a methanol dehydration reaction product from a methanol raw material under the catalytic action of a first molecular sieve catalyst, separating and treating the methanol dehydration reaction product, and then mixing it with one or more of recycled fuel gas, recycled liquefied gas or recycled gasoline under the catalytic action of a second molecular sieve catalyst to generate a reaction oil gas, the reaction oil gas is fractionated to obtain a kerosene fraction, and the kerosene fraction is subjected to a hydrogenation and refining treatment to obtain aviation kerosene. The method for producing aviation kerosene using methanol as a raw material provided by the present invention has opened up a new way to produce aviation kerosene; the process flow is short and compact, and can effectively achieve energy conservation and emission reduction.

Description

Technical Field

[0001] The present invention belongs to the technical field of petrochemical product processing, and in particular relates to a method, device and application of producing aviation kerosene from methanol. Background Art

[0002] Currently, aviation kerosene is primarily composed of hydrocarbon compounds such as paraffins, cycloalkanes, and aromatics from different fractions of oil refineries, including straight-run and hydrocracked fractions. The carbon number distribution ranges from C9 to C16. Due to the unique operating environment of aviation kerosene, its performance requirements are very stringent, requiring it to have good low-temperature fluidity, a high net calorific value and density, a fast and complete combustion rate, and good stability.

[0003] Currently, jet fuel is primarily derived from petroleum products. First, it is produced by refining the kerosene fraction from crude oil distillation, and second, by hydrocracking heavy distillates. Additionally, a small amount of kerosene fractions are produced through Fischer-Tropsch synthesis. However, these fractions cannot be used as jet fuel alone and must be blended with petroleum-based jet fuel, with the blending ratio capped at 50%. In recent years, the production of jet fuel from waste cooking oil, composed of animal and vegetable oils, through hydroprocessing has also been applied, but production volumes are smaller.

[0004] However, methanol-to-olefins (MTO), methanol-to-propylene (MTP), methanol-to-aromatics (MTA), and methanol-to-gasoline (MTG) processes for producing hydrocarbon compounds from methanol are unable to produce hydrocarbon compounds that meet the requirements of kerosene fractions. Using methanol, a bulk commodity, to produce aviation kerosene is of great significance both in alleviating national oil security and expanding aviation kerosene production channels. However, no effective reports on technologies for producing aviation kerosene from methanol have been found in the prior art. Summary of the Invention

[0005] In view of the shortcomings of the prior art, one of the purposes of the present invention is to provide a method for producing aviation kerosene from methanol, thereby opening up a new approach to the kerosene production process.

[0006] A second object of the present invention is to provide a device for producing aviation kerosene from methanol, which has a simple process and strong feasibility.

[0007] The third object of the present invention is to provide a specific application of the above-mentioned device in the production of aviation kerosene from methanol.

[0008] In order to achieve the above object, the present invention adopts the following technical solutions:

[0009] A method for producing aviation kerosene from methanol comprises: using a methanol raw material to generate a methanol dehydration reaction product under the catalytic action of a first molecular sieve catalyst; separating and treating the methanol dehydration reaction product; subsequently mixing the product with one or more of recycled fuel gas, recycled liquefied petroleum gas, or recycled gasoline; and generating reaction oil gas under the catalytic action of a second molecular sieve catalyst; fractionating the reaction oil gas to obtain a kerosene fraction; and hydrorefining the kerosene fraction to obtain aviation kerosene.

[0010] As a further preferred embodiment of the technical solution of the present invention, the following steps are specifically included:

[0011] The methanol raw material is fed into a methanol dehydration reactor to generate a methanol dehydration reaction product under the catalytic action of a first molecular sieve catalyst. The methanol dehydration reaction product is condensed and cooled and then separated to obtain olefin-rich gas, olefin-rich oil product and water;

[0012] The olefin-rich gas is compressed and mixed with the olefin-rich oil product, and then mixed with one or more of recycled fuel gas, recycled liquefied gas or recycled gasoline, and then fed into a kerosene fraction reactor to obtain reaction oil and gas under the catalytic action of a second molecular sieve catalyst, and the obtained reaction oil and gas is fed into a gas-liquid separator to obtain liquid oil product, fuel gas, and liquefied gas;

[0013] The liquid oil product is sent to a fractionating tower to obtain a gasoline fraction, a kerosene fraction, and a diesel fraction;

[0014] The kerosene fraction is sent to a hydrotreating unit for treatment to obtain aviation kerosene.

[0015] As a further preferred embodiment of the technical solution of the present invention, the first molecular sieve catalyst is selected from one or more of ZSM-5 molecular sieve, Y-type molecular sieve, and SAPO-34 molecular sieve.

[0016] As a further preferred embodiment of the technical solution of the present invention, when the first molecular sieve catalyst is ZSM-5 molecular sieve, the silicon-aluminum ratio is greater than 150.

[0017] As a further preferred embodiment of the technical solution of the present invention, when the first molecular sieve catalyst is ZSM-5 molecular sieve, the silicon-aluminum ratio is greater than 250.

[0018] As a further preferred embodiment of the technical solution of the present invention, the methanol dehydration reactor is one of a fixed bed reactor, a moving bed reactor and a fluidized bed reactor.

[0019] As a further preferred embodiment of the technical solution of the present invention, the catalytic conditions of the first molecular sieve catalyst are: reaction temperature 450-550°C, reaction pressure 0.05-0.5 MPa, methanol feed space velocity 0.5-10 h -1 .

[0020] As a further preferred embodiment of the technical solution of the present invention, the catalytic conditions of the first molecular sieve catalyst are: reaction temperature 470-520°C, reaction pressure 0.1-0.3 MPa, methanol feed space velocity 1-3 h -1 .

[0021] As a further preferred embodiment of the technical solution of the present invention, the second molecular sieve catalyst is a ZSM-5 molecular sieve catalyst with a silicon-aluminum ratio of 25-120.

[0022] As a further preferred embodiment of the technical solution of the present invention, the silicon-aluminum ratio of the second molecular sieve catalyst is 38-90.

[0023] As a further preferred embodiment of the technical solution of the present invention, the catalytic conditions of the second molecular sieve catalyst are: reaction temperature 150-350°C, reaction pressure 3-10 MPa, feed space velocity 0.5-3 h -1 .

[0024] As a further preferred embodiment of the technical solution of the present invention, the catalytic conditions of the second molecular sieve catalyst are: reaction temperature 200-300°C, reaction pressure 3.5-5.5 MPa, feed space velocity 1-2 h -1 .

[0025] As a further preferred embodiment of the technical solution of the present invention, the conditions for hydrofining are: reaction temperature 250-400°C, reaction pressure 3-8 MPa, feed space velocity 0.5-3 h -1 , the hydrogen-to-oil volume ratio is 400-1000.

[0026] As a further preferred embodiment of the technical solution of the present invention, the conditions for hydrofining are: reaction temperature 300-350°C, reaction pressure 3.5-5.5 MPa, feed space velocity 1-2 h -1 , the hydrogen-to-oil volume ratio is 600-800.

[0027] As a further preferred embodiment of the technical solution of the present invention, the recycled fuel gas comes from the fuel gas, the recycled liquefied gas comes from the liquefied gas, and the recycled gasoline comes from the gasoline fraction.

[0028] As a further preferred embodiment of the technical solution of the present invention, the total recycling ratio of the recycled fuel gas, the recycled liquefied gas and the recycled gasoline is 0.3 to 1.5.

[0029] In a second aspect, the present invention also provides an apparatus for implementing the above method, comprising a methanol dehydration reactor, a three-phase separator, a kerosene fraction reactor, a gas-liquid separator, a fractionation tower, and a hydrotreating reactor; the methanol dehydration reactor is connected to the three-phase separator via a pipeline, the top and middle of the three-phase separator are both connected to the top of the kerosene fraction reactor via pipelines, the bottom of the kerosene fraction reactor is connected to the gas-liquid separator via a pipeline, the bottom of the gas-liquid separator is connected to the fractionation tower via a pipeline, and the fractionation tower is connected to the hydrotreating reactor via a pipeline.

[0030] As a further preferred embodiment of the technical solution of the present invention, the top and side walls of the gas-liquid separator are also connected to the top of the kerosene fraction reactor through a pipeline.

[0031] As a further preferred embodiment of the technical solution of the present invention, the top of the distillation tower is also connected to the top of the kerosene fraction reactor through a pipeline.

[0032] At the same time, the present invention also claims to protect the application of the above device in producing aviation kerosene from methanol.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] (1) The method for producing aviation kerosene from methanol provided by the present invention can achieve the purpose of producing aviation kerosene from methanol and open up a new way for the kerosene production process.

[0035] (2) The method for producing aviation kerosene from methanol provided by the present invention maximizes the dehydration of methanol to produce olefins in a short process flow. After simple separation in a three-phase separator, the olefins can be used as raw materials for polymerization, alkylation, etc.

[0036] (3) The method for producing aviation kerosene from methanol provided by the present invention can maximize the production of kerosene fractions through the recycling of gas and gasoline, and the kerosene fractions can be used to obtain aviation kerosene through hydrogenation and refining.

[0037] (4) The process of the present invention is compact and can effectively achieve energy conservation and emission reduction.

[0038] In summary, the process for producing aviation kerosene using methanol as raw material provided by the present invention is simple, has a high yield of the obtained aviation kerosene, and has good oil quality, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a schematic diagram of the process flow for producing aviation kerosene from methanol according to the present invention.

[0040] In the figure, 1. methanol feed; 2. methanol dehydration reactor; 3. methanol dehydration reaction product; 4. three-phase separator; 5. olefin-rich gas; 6. olefin-rich oil product; 7. olefin-rich oil and gas; 8. process water; 9. kerosene fraction reaction feed; 10. kerosene fraction reactor; 11. reaction oil and gas; 12. gas-liquid separator; 13. fuel gas; 14. liquefied gas; 15. liquid oil product; 16. recycled fuel gas; 17. fuel gas out of the unit; 18. recycled liquefied gas; 19. liquefied gas out of the unit; 20. distillation tower; 21. gasoline fraction; 22. recycled gasoline; 23. gasoline out of the unit; 24. kerosene fraction; 25. diesel fraction; 26. hydrogen; 27. hydrotreating unit feed; 28. hydrotreating reactor; 29. aviation kerosene. DETAILED DESCRIPTION

[0041] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0042] It should be emphasized that, if specific conditions are not specified in the examples, conventional conditions or conditions recommended by the manufacturer were followed. Reagents or instruments used without manufacturer specified are all commercially available conventional products.

[0043] See also Figure 1 The present invention provides a method for producing aviation kerosene from methanol, comprising: generating a methanol dehydration reaction product 3 from a methanol raw material (methanol feed 1) under the catalytic action of a first molecular sieve catalyst; separating and treating the methanol dehydration reaction product 3; and subsequently mixing the methanol dehydration reaction product 3 with one or more of recycled fuel gas 16, recycled liquefied gas 18, or recycled gasoline 22 (to obtain a kerosene fraction reaction feed 9) under the catalytic action of a second molecular sieve catalyst to generate a reaction oil gas 11; fractionating the reaction oil gas 11 to obtain a kerosene fraction; and hydrorefining the kerosene fraction to obtain aviation kerosene 29.

[0044] Specifically, the method for producing aviation kerosene from methanol provided by the present invention comprises the following steps:

[0045] A methanol raw material (methanol feed 1) is fed into a methanol dehydration reactor 2, where a methanol dehydration reaction product 3 is generated under the catalytic action of a first molecular sieve catalyst. The methanol dehydration reaction product 3 is condensed and cooled, and then separated to obtain an olefin-rich gas 5, an olefin-rich oil product 6, and water (process water 8);

[0046] The olefin-rich gas 5 is compressed and mixed with the olefin-rich oil product 6, and then mixed with one or more of recycled fuel gas 16, recycled liquefied gas 18, or recycled gasoline 22 (to obtain kerosene fraction reaction feed 9), which is then fed into a kerosene fraction reactor 10. Under the catalytic action of a second molecular sieve catalyst, a reaction oil and gas 11 is obtained. The obtained reaction oil and gas 11 is fed into a gas-liquid separator 12 to obtain a liquid oil product 15, fuel gas 13, and liquefied gas 14.

[0047] The liquid oil product 15 is fed into a fractionating tower 20 to obtain a gasoline fraction 21, a kerosene fraction 24, and a diesel fraction 25;

[0048] The kerosene fraction 24 is sent to a hydrotreating device (hydrotreating reactor 28 ) for treatment to obtain aviation kerosene 29 .

[0049] In the above technical solution, a first molecular sieve catalyst is used to generate olefin-rich hydrocarbon compounds through methanol dehydration reaction; the olefin-rich hydrocarbon compounds undergo polymerization (superposition) reaction, aromatization reaction, and alkylation reaction under the action of a second molecular sieve catalyst to generate hydrocarbon compounds mainly composed of kerosene fractions; the separated kerosene fractions are subjected to hydrogenation and refining to remove olefins to obtain aviation kerosene. The process of producing aviation kerosene from methanol of the present invention has opened up a new way to produce aviation kerosene. Methanol can maximize the production of olefins and some aromatics under the action of the first molecular sieve catalyst, thereby improving high-quality raw materials for the production of kerosene fractions by olefin polymerization and aromatic alkylation; under the action of the second molecular sieve catalyst, olefin polymerization reaction and aromatic alkylation are effectively controlled to maximize the production of hydrocarbon compounds in the kerosene fraction; the kerosene fraction is hydrogenated and converted into alkanes by hydrogenation through hydrogenation to produce qualified aviation kerosene. The entire process has strong consistency, and the maximum production of aviation kerosene from methanol can be achieved through organic combination. The basic principles involved in the above-mentioned process are as follows:

[0050] (1) Methanol dehydration reaction

[0051] Under the action of ZSM-5 molecular sieve catalyst, methanol is dehydrated to produce light olefins with very high selectivity. About 85% of the carbon is converted into C2~C8 olefins, of which propylene is the largest. In addition, alkanes and aromatics are also produced, as shown in the following reaction formula.

[0052] nCH3OH→C2H4+C3H6+C4H8+C5H 10 +C6H 12 +……+nH2O

[0053] nCH3OH→C6H6+C7H8+C8H 10 +……+nH2O

[0054] nCH3OH→C2H6+C3H8+C4H10 +C5H 12 +C6H 14 +……+nH2O

[0055] (2) Kerosene fraction production - olefin polymerization reaction

[0056] Using a ZSM-5 molecular sieve acidic catalyst, under appropriate process conditions, olefin polymerization is controlled to produce a distillate oil mainly composed of kerosene fractions, as shown in the following reaction formula.

[0057] 4C3H6→C 12 H 24

[0058] (3) Kerosene fraction production - aromatization reaction

[0059] Under the action of ZSM-5 molecular sieve acidic catalyst, light olefins can also generate aromatics through aromatization reaction, as shown in the following reaction formula.

[0060] 2C3H6→C6H 10 +H2

[0061] (4) Kerosene fraction production - alkylation reaction

[0062] Under the action of ZSM-5 molecular sieve acidic catalyst, aromatic hydrocarbons and olefins undergo alkylation reaction to produce alkyl aromatic hydrocarbons, as shown in the following reaction formula.

[0063] C6H6+C4H8→C 10 H 14

[0064] (5) Aviation kerosene production - hydrogenation reaction

[0065] Due to the characteristics of aviation kerosene, its olefin content is required not to exceed 5%. Qualified aviation kerosene can be obtained by hydrogenating the kerosene fraction, as shown in the following reaction formula.

[0066] C 12 H 24 +H2→C 12 H 26

[0067] Specifically, in the methanol dehydration reaction process, industrial methanol feedstock enters the methanol dehydration reactor 2, where methanol dehydration is carried out under the action of a molecular sieve catalyst to maximize the production of olefins; the methanol dehydration reaction product is condensed and cooled and then enters a three-phase separator to obtain olefin-rich gas 5, olefin-rich oil product 6, and process water 8, respectively; in order to increase the production of olefins by methanol dehydration, methanol feed can be mixed with water vapor or process by-product dry gas or liquefied gas, etc. In some embodiments, the methanol dehydration olefin production catalyst is a molecular sieve catalyst, which includes ZSM-5 molecular sieve, Y-type molecular sieve, SAPO-34 molecular sieve, etc., which can be used as active components alone or as active components after mixing; that is, the first molecular sieve catalyst is selected from one or more of ZSM-5 molecular sieve, Y-type molecular sieve, and SAPO-34 molecular sieve. Preferably, the molecular sieve is a ZSM-5 molecular sieve with a silicon-to-aluminum ratio greater than 150; preferably, the silicon-to-aluminum ratio of the ZSM-5 molecular sieve is greater than 250.

[0068] In some embodiments, the methanol dehydration reactor can be a fixed bed reactor, a moving bed reactor, or a fluidized bed reactor, preferably a fluidized bed reactor. Fluidized bed reactors have the advantages of convenient catalyst reaction and regeneration operations, easy heat removal during the reaction process, and uniform and controllable temperature within the reactor.

[0069] In some embodiments, the process parameters in the methanol dehydration reactor, i.e., the catalytic conditions of the first molecular sieve catalyst, are: reaction temperature 450-550°C, reaction pressure 0.05-0.5 MPa, methanol feed space velocity 0.5-10 h -1 Preferably, the reaction temperature is 470-520°C, the reaction pressure is 0.1-0.3 MPa, and the methanol feed space velocity is 1-3 h -1 It is understood that, in some embodiments, the reaction temperature may be any specific value among 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, or any value within the range of 450-550°C; the reaction pressure may be any specific value among 0.05MPa, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, 0.5MPa, or any value within the range of 0.05-0.5MPa; the methanol feed space velocity may be 1h -1 , 1.1h -1 , 1.2h -1 , 1.3h -1 , 1.4h -1 , 1.5h -1 , 1.6h -1 , 1.7h -1 , 1.8h-1 , 1.9h -1 , 2h -1 , 2.1h -1 , 2.2h -1 , 2.3h -1 , 2.4h -1 , 2.5h -1 , 2.6h -1 , 2.7h -1 , 2.8h -1 , 2.9h -1 , 3h -1 Any specific value or 1 to 3 hours -1 Any value in the range.

[0070] Specifically, during the kerosene fraction production process, olefin-rich gas 5 from the three-phase separator 4 is compressed and mixed with an olefin-rich oil product 6. This is then mixed with a portion of the fuel gas, liquefied gas, and gasoline produced by the combined process and fed into the kerosene fraction reactor 10. The reaction products enter the gas-liquid separator 12, where they are separated into fuel gas, liquefied gas, and liquid oil products. A portion of the fuel gas is recycled and a portion is discharged from the reactor; a portion of the liquefied gas is recycled and a portion is discharged from the reactor; the liquid oil product is fed into a fractionating tower, where it is separated into gasoline, kerosene, and diesel fractions. A portion of the gasoline fraction is recycled and a portion is discharged from the reactor; the diesel fraction is discharged directly from the reactor; and the kerosene fraction undergoes hydrofining and de-olefination. In some embodiments, the second molecular sieve catalyst is a ZSM-5 molecular sieve catalyst having a silicon-to-aluminum ratio of 25 to 120; preferably, the silicon-to-aluminum ratio of the second molecular sieve catalyst is 38 to 90.

[0071] In some embodiments, the kerosene fraction reactor 10 can be a fixed bed reactor, a moving bed reactor, or a fluidized bed reactor, preferably a moving bed reactor. The moving bed reactor has the characteristics of convenient catalyst reaction-regeneration operation and high reaction process efficiency. The process parameters in the kerosene fraction reactor, that is, the catalytic conditions of the second molecular sieve catalyst are: reaction temperature 150-350°C, reaction pressure 3-10 MPa, feed space velocity 0.5-3h -1 Preferably, the reaction temperature is 200-300°C, the reaction pressure is 3.5-5.5 MPa, and the feed space velocity is 1-2 h -1It can be understood that the reaction temperature can be any specific value among 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, or any value within the range of 150-350°C; the reaction pressure can be any specific value among 3MPa, 3.5MPa, 4MPa, 4.5MPa, 5MPa, 5.5MPa, 6MPa, 6.5MPa, 7MPa, 7.5MPa, 8MPa, 8.5MPa, 9MPa, 9.5MPa, 10MPa, or any value within the range of 3-10MPa; the feed space velocity can be 0.5h -1 , 0.6h -1 , 0.7h -1 , 0.8h -1 , 0.9h -1 , 1h -1 , 1.1h -1 , 1.2h -1 , 1.3h -1 , 1.4h -1 , 1.5h -1 , 1.6h -1 , 1.7h -1 , 1.8h -1 , 1.9h -1 , 2h -1 , 2.1h -1 , 2.2h -1 , 2.3h -1 , 2.4h -1 , 2.5h -1 , 2.6h -1 , 2.7h -1 , 2.8h -1 , 2.9h -1 , 3h -1 Any specific value or 0.5~3h -1 The recycled fuel gas is derived from the fuel gas, the recycled liquefied gas is derived from the liquefied gas, and the recycled gasoline is derived from the gasoline fraction. The total recycling ratio of the recycled fuel gas, recycled liquefied gas, and recycled gasoline is 0.3 to 1.5, preferably 0.5 to 0.8.

[0072] Specifically, in the process of producing aviation kerosene from kerosene fractions, the kerosene fraction 24 from the fractionating tower 20 is mixed with hydrogen and enters the hydrotreating reactor 28. The kerosene fraction is hydrotreated to remove olefins and produce aviation kerosene 29. The kerosene hydrotreating fixed-bed reactor can be filled with a conventional commercial distillate oil hydrotreating catalyst, such as RN-1. In some embodiments, the conditions for hydrotreating are: reaction temperature of 250-400°C, reaction pressure of 3-8 MPa, and feed space velocity of 0.5-3 h -1 , the hydrogen-oil volume ratio is 400-1000; preferably, the reaction temperature is 300-350°C, the reaction pressure is 3.5-5.5 MPa, and the feed space velocity is 1-2h -1 , the hydrogen-to-oil volume ratio is 600-800. It can be understood that the reaction temperature can be any specific value among 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, or any value within the range of 250-450°C; the reaction pressure can be any specific value among 3MPa, 3.5MPa, 4MPa, 4.5MPa, 5MPa, 5.5MPa, 6MPa, 6.5MPa, 7MPa, 7.5MPa, 8MPa, or any value within the range of 3-8MPa; the feed space velocity can be 0.5h -1 , 0.6h -1 , 0.7h -1 , 0.8h -1 , 0.9h -1 , 1h -1 , 1.1h -1 , 1.2h -1 , 1.3h -1 , 1.4h -1 , 1.5h -1 , 1.6h -1 , 1.7h -1 , 1.8h -1 , 1.9h -1 , 2h -1 , 2.1h -1 , 2.2h -1 , 2.3h -1 , 2.4h -1 , 2.5h -1 , 2.6h -1 , 2.7h -1 , 2.8h -1 , 2.9h -1 , 3h -1 Any specific value or 0.5~3h-1 the hydrogen-to-oil volume ratio can be any specific value among 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800 or any value within the range of 400 to 1000.

[0073] In some embodiments, a device for producing aviation kerosene from methanol is also provided, comprising a methanol dehydration reactor 2, a three-phase separator 4, a kerosene fraction reactor 10, a gas-liquid separator 12, a fractionation tower 20, and a hydrotreating reactor 28; the methanol dehydration reactor 2 is connected to the three-phase separator 4 via a pipeline, the top and middle of the three-phase separator 4 are connected to the top of the kerosene fraction reactor 10 via pipelines, the bottom of the kerosene fraction reactor 10 is connected to the gas-liquid separator 12 via a pipeline, the bottom of the gas-liquid separator 12 is connected to the fractionation tower 20 via a pipeline, and the fractionation tower 20 is connected to the hydrotreating reactor 28 via a pipeline.

[0074] In some embodiments, the top and sidewalls of the gas-liquid separator 12 are also connected to the top of the kerosene fraction reactor 10 through pipelines.

[0075] In some embodiments, the top of the fractionation tower 20 is also connected to the top of the kerosene fraction reactor 10 through a pipeline.

[0076] Further reading Figure 1 The process of the present invention is described in detail as follows:

[0077] Industrial methanol feedstock (methanol feed 1) enters methanol dehydration reactor 2, where it is dehydrated over molecular sieve catalyst I to maximize olefin production. The olefin-rich methanol dehydration reaction product 3 is condensed and cooled before entering a three-phase separator 4 to produce olefin-rich gas 5, olefin-rich oil product 6, and process water 8.

[0078] The olefin-rich gas 5 from the three-phase separator 4 is compressed and mixed with the olefin-rich oil product 6 to obtain the olefin-rich oil gas 7, which is then mixed with the recycled fuel gas 16, recycled liquefied gas 18 and recycled gasoline 22 produced by this process to obtain the kerosene fraction reaction feed 9, which is then sent to the kerosene fraction reactor 10. The obtained reaction oil gas 11 enters the gas-liquid separator 12; the gas-liquid separator 12 separates the fuel gas 13, liquefied gas 14 and liquid oil product 15; a part of the fuel gas (i.e., recycled fuel gas 16) is recycled, and a part of the recycled fuel gas 16 is recycled. The fuel gas is separated and discharged from the device (i.e., the fuel gas discharged from the device 17); a portion of the liquefied gas is recycled (i.e., the recycled liquefied gas 14), and a portion of the liquefied gas is discharged from the device (i.e., the liquefied gas discharged from the device 19); the liquid oil product 15 is sent to a fractionating tower 20, where it is fractionated into a gasoline fraction 21, a kerosene fraction 24, and a diesel fraction 25; a portion of the gasoline is recycled (i.e., the recycled gasoline 22), and a portion of the gasoline is discharged from the device (i.e., the gasoline discharged from the device 23); the diesel fraction 25 is directly discharged from the device; the kerosene fraction 24 is subjected to hydrotreating and olefin removal.

[0079] The kerosene fraction 24 from the fractionating tower is mixed with hydrogen 26 and enters a hydrotreating reactor 28; the kerosene fraction 24 is hydrotreated to remove olefins and produce aviation kerosene 29.

[0080] The method, device and application of producing aviation kerosene from methanol of the present invention are further described below with reference to specific embodiments.

[0081] Example 1

[0082] See also Figure 1 A device for producing aviation kerosene from methanol includes a methanol dehydration reactor 2, a three-phase separator 4, a kerosene fraction reactor 10, a gas-liquid separator 12, a fractionating tower 20, and a hydrotreating reactor 28; the methanol dehydration reactor 2 is connected to the three-phase separator 4 via a pipeline, the top and middle of the three-phase separator 4 are connected to the top of the kerosene fraction reactor 10 via pipelines, the bottom of the kerosene fraction reactor 10 is connected to the gas-liquid separator 12 via a pipeline, the bottom of the gas-liquid separator 12 is connected to the fractionating tower 20 via a pipeline, and the fractionating tower 20 is connected to the hydrotreating reactor 28 via a pipeline;

[0083] The top and side walls of the gas-liquid separator 12 are also connected to the top of the kerosene fraction reactor 10 through pipelines.

[0084] The top of the fractionation tower 20 is also connected to the top of the kerosene fraction reactor 10 through a pipeline.

[0085] Example 2

[0086] See also Figure 1 A method for producing aviation kerosene from methanol using the apparatus described in Example 1, wherein the typical process parameters are as follows:

[0087] Methanol dehydration to olefins process: Using ZSM-5 molecular sieve catalyst, where the ZSM-5 molecular sieve has a silicon-aluminum ratio of 350; methanol dehydration reaction to produce olefins in a fluidized bed reactor; process conditions are reactor reaction temperature 465°C, reaction pressure 0.1MPa (gauge pressure), feed space velocity 2.0h -1 , methanol / water is 1:1.

[0088] Olefin oligomerization process for producing kerosene fractions: Using ZSM-5 molecular sieve catalyst, where the ZSM-5 molecular sieve has a silicon-aluminum ratio of 55; olefin oligomerization is carried out in a moving bed reactor to produce kerosene fractions; the process conditions are reactor reaction temperature 250°C, reaction pressure 5.0 MPa (gauge pressure), feed space velocity 1.5 h -1 , gas and gasoline recycling ratio is 0.8.

[0089] Kerosene hydrorefining process for producing aviation kerosene: Using RN-1 catalyst, kerosene hydrorefining is carried out in a fixed bed reactor to produce aviation kerosene; the process conditions are reactor reaction temperature 330℃, reaction pressure 4.5MPa (gauge pressure), feed space velocity 1.0h -1 , hydrogen / oil (volume) 700.

[0090] The material balance of aviation kerosene produced from methanol is shown in Table 1.

[0091] Table 1 Material balance of producing aviation kerosene from methanol in Example 2

[0092]

[0093] The main properties of the produced aviation kerosene are shown in Table 2.

[0094] Table 2 Main properties of aviation kerosene in Example 1

[0095]

[0096]

[0097] As can be seen from Table 1, when using methanol to produce aviation kerosene, the aviation kerosene yield accounts for 24.89% of the methanol feed (accounting for 56.89% of the methanol carbon yield), so methanol production of aviation kerosene is a very good aviation kerosene production method.

[0098] It can be seen from Table 2 that the main properties of aviation kerosene produced using methanol meet the technical standards of aviation kerosene.

[0099] Example 3

[0100] See also Figure 1A method for producing aviation kerosene from methanol using the apparatus described in Example 1, wherein the typical process parameters are as follows:

[0101] Methanol dehydration to olefins process: Using SAPO-34 molecular sieve catalyst, methanol dehydration reaction is carried out in a fluidized bed reactor to produce olefins; the process conditions are reaction temperature 495℃, reaction pressure 0.1MPa (gauge pressure), feed space velocity 2.0h -1 , methanol / water is 1:1.

[0102] Olefin oligomerization process for producing kerosene fractions: Using ZSM-5 molecular sieve catalyst, where the ZSM-5 molecular sieve has a silicon-aluminum ratio of 55; olefin oligomerization is carried out in a moving bed reactor to produce kerosene fractions; the process conditions are reactor reaction temperature 250°C, reaction pressure 5.0 MPa (gauge pressure), feed space velocity 1.5 h -1 , gas and gasoline recycling ratio is 0.8.

[0103] Kerosene hydrorefining process for producing aviation kerosene: Using RN-1 catalyst, kerosene hydrorefining is carried out in a fixed bed reactor to produce aviation kerosene; the process conditions are reactor reaction temperature 330℃, reaction pressure 4.5MPa (gauge pressure), feed space velocity 1.0h -1 , hydrogen / oil (volume) 700.

[0104] The material balance of methanol-based aviation kerosene production is shown in Table 3.

[0105] Table 3 Material balance of aviation kerosene produced by methanol in Example 3

[0106]

[0107] The main properties of the produced aviation kerosene are shown in Table 4.

[0108] Table 4 Main properties of aviation kerosene in Example 3

[0109]

[0110] As can be seen from Table 3, when using methanol to produce aviation kerosene, the aviation kerosene yield accounts for 22.82% of the methanol feed (accounting for 49.88% of the methanol carbon yield), so methanol production of aviation kerosene is a very good aviation kerosene production method.

[0111] It can be seen from Table 4 that the main properties of aviation kerosene produced using methanol meet the technical standards of aviation kerosene.

[0112] It's worth noting that, as the olefins produced using SAPO-34 zeolite catalysts are primarily ethylene and propylene, the resulting kerosene fraction is less than that produced using ZSM-5 zeolite catalysts, where the olefins are primarily propylene and higher. Furthermore, when methanol is produced using ZSM-5 zeolite catalysts, aromatics are also generated alongside olefins, allowing for a higher yield of kerosene fractions through alkylation. Therefore, ZSM-5 zeolite is a preferred catalyst for methanol dehydration.

[0113] In summary, the process for producing aviation kerosene using methanol as raw material provided by the present invention is simple, has a high yield of the obtained aviation kerosene, and has good oil quality, and has broad application prospects.

[0114] While the present invention is illustrated by the aforementioned embodiments, the present invention is not limited to these embodiments, nor does it necessarily rely on these embodiments for implementation. Those skilled in the art will appreciate that any improvements to the present invention, equivalent replacements for individual raw materials in the present invention, additions of auxiliary ingredients, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A method for producing aviation kerosene from methanol, characterized in that: include: The methanol raw material is catalyzed by a first molecular sieve catalyst to generate a methanol dehydration reaction product, the methanol dehydration reaction product is separated and treated, and then mixed with one or more of recycled fuel gas, recycled liquefied petroleum gas, or recycled gasoline to generate reaction oil gas under the catalytic action of a second molecular sieve catalyst. The reaction oil gas is fractionated to obtain a kerosene fraction, and the kerosene fraction is hydrorefined to obtain aviation kerosene. Wherein, the second molecular sieve catalyst is a ZSM-5 molecular sieve catalyst; Wherein, the first molecular sieve catalyst is selected from one or more of ZSM-5 molecular sieve, Y-type molecular sieve, and SAPO-34 molecular sieve; Wherein, when the first molecular sieve catalyst is ZSM-5 molecular sieve, the silicon-aluminum ratio is greater than 150; The catalytic conditions of the first molecular sieve catalyst are as follows: reaction temperature 450-550°C, reaction pressure 0.05-0.5 MPa, methanol feed space velocity 0.5-10 h -1 ; Wherein, the silicon-aluminum ratio of the second molecular sieve catalyst is 25 to 120; The catalytic conditions of the second molecular sieve catalyst are as follows: reaction temperature 150-350°C, reaction pressure 3-10 MPa, feed space velocity 0.5-3h -1 ; The conditions for hydrofining are: reaction temperature 250-400℃, reaction pressure 3-8MPa, feed space velocity 0.5-3h -1 , the hydrogen-to-oil volume ratio is 400-1000.

2. The method for producing aviation kerosene from methanol according to claim 1, characterized in that: The specific steps include: The methanol raw material is fed into a methanol dehydration reactor to generate a methanol dehydration reaction product under the catalytic action of a first molecular sieve catalyst. The methanol dehydration reaction product is condensed and cooled and then separated to obtain olefin-rich gas, olefin-rich oil product and water; The olefin-rich gas is compressed and mixed with the olefin-rich oil product, and then mixed with one or more of recycled fuel gas, recycled liquefied gas or recycled gasoline, and then fed into a kerosene fraction reactor to obtain reaction oil and gas under the catalytic action of a second molecular sieve catalyst, and the obtained reaction oil and gas is fed into a gas-liquid separator to obtain liquid oil product, fuel gas, and liquefied gas; The liquid oil product is sent to a fractionating tower to obtain a gasoline fraction, a kerosene fraction, and a diesel fraction; The kerosene fraction is sent to a hydrotreating unit for treatment to obtain aviation kerosene.

3. The method for producing aviation kerosene from methanol according to claim 1, characterized in that: When the first molecular sieve catalyst is ZSM-5 molecular sieve, the silicon-aluminum ratio is greater than 250.

4. The method for producing aviation kerosene from methanol according to claim 2, characterized in that: The methanol dehydration reactor is one of a fixed bed reactor, a moving bed reactor and a fluidized bed reactor.

5. The method for producing aviation kerosene from methanol according to claim 4, characterized in that: The catalytic conditions of the first molecular sieve catalyst are: reaction temperature 470-520°C, reaction pressure 0.1-0.3 MPa, methanol feed space velocity 1-3 h -1 .

6. The method for producing aviation kerosene from methanol according to claim 1, characterized in that: The silicon-aluminum ratio of the second molecular sieve catalyst is 38-90.

7. The method for producing aviation kerosene from methanol according to claim 1, characterized in that: The catalytic conditions of the second molecular sieve catalyst are: reaction temperature 200-300 ° C, reaction pressure 3.5-5.5 MPa, feed space velocity 1-2 h -1 .

8. The method for producing aviation kerosene from methanol according to claim 1, characterized in that: The conditions for hydrofining are: reaction temperature 300-350℃, reaction pressure 3.5-5.5MPa, feed space velocity 1-2h -1 , the hydrogen-to-oil volume ratio is 600-800.

9. The method for producing aviation kerosene from methanol according to claim 1 or 2, characterized in that: The recycled fuel gas comes from the fuel gas, the recycled liquefied gas comes from the liquefied gas, and the recycled gasoline comes from the gasoline fraction.

10. The method for producing aviation kerosene from methanol according to claim 9, characterized in that: The total recycling ratio of recycled fuel gas, recycled liquefied gas and recycled gasoline is 0.3 to 1.

5.

11. A device for implementing the method according to any one of claims 1 to 10, characterized in that: The invention comprises a methanol dehydration reactor (2), a three-phase separator (4), a kerosene fraction reactor (10), a gas-liquid separator (12), a fractionation tower (20), and a hydrofining reactor (28); the methanol dehydration reactor (2) is connected to the three-phase separator (4) through a pipeline, the top and the middle of the three-phase separator (4) are connected to the top of the kerosene fraction reactor (10) through pipelines, the bottom of the kerosene fraction reactor (10) is connected to the gas-liquid separator (12) through a pipeline, the bottom of the gas-liquid separator (12) is connected to the fractionation tower (20) through a pipeline, and the fractionation tower (20) is connected to the hydrofining reactor (28) through a pipeline.

12. The device according to claim 11, characterized in that The top and side walls of the gas-liquid separator (12) are also connected to the top of the kerosene fraction reactor (10) through pipelines.

13. The device according to claim 11, characterized in that The top of the fractionation tower (20) is also connected to the top of the kerosene fraction reactor (10) through a pipeline.

14. Use of the device according to any one of claims 11 to 13 in producing aviation kerosene from methanol.

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