Production method of high-smoke-point aviation kerosene product

Abstract

The invention relates to the field of chemical engineering, and discloses a production method of a high-smoke-point aviation kerosene product. The method comprises the following steps: (1) in the presence of hydrogen, carrying out gas-phase desulfurization reaction on an aviation kerosene raw material in a hydrodesulfurization reactor to obtain a gas-phase desulfurization reaction product; (2) the gas-phase desulfurization reaction product is subjected to gas-liquid separation, a gas-phase component and a liquid-phase component are obtained, and based on the total amount of the gas-phase desulfurization reaction product, the mass percentage of the liquid-phase component is 15-50%; (3) pressurizing the liquid-phase component, and then carrying out liquid-phase dearomatization reaction in a hydrodearomatization reactor to obtain a liquid-phase dearomatization reaction product; wherein the smoke point of the aviation kerosene raw material is 16-22 mm. According to the method, the aviation kerosene is used as a raw material to produce a high-smoke-point aviation kerosene product under a relatively mild process condition, meanwhile, the chemical reaction efficiency is also improved, and the energy consumption and the hydrogen consumption are reduced.

Description

Technical Field

[0001] The invention relates to the field of chemical industry, and in particular to a production method of a high smoke point aviation fuel product. Background Art

[0002] In recent years, China's civil aviation industry has continued to develop, and the demand for aviation fuel has continued to grow. On the other hand, with the adjustment of China's energy structure, the demand for diesel has slowed down year by year, and reducing the diesel-gasoline ratio has become the overall development trend of the adjustment of the refining structure. Cutting the jet fuel fraction to a heavier weight, that is, increasing the terminal distillation point of jet fuel, and cutting more diesel components into the jet fuel can increase the jet fuel yield and reduce diesel production, which is a good solution to the current problem of a sharp increase in jet fuel demand and a decrease in diesel demand. However, as the jet fuel fraction becomes heavier, some aromatics in diesel return to the jet fuel component, and the increase in the aromatic content in the jet fuel will cause the smoke point index of the jet fuel product to be unqualified. The pressure design level of the existing jet fuel device is relatively low, generally 3-4MPa, and the hydrogenation of aromatics in a fixed bed reaction environment requires a higher reaction pressure to achieve. It is difficult for the existing device to remove aromatics by means of pressurization, and the smoke point index cannot be significantly improved. Therefore, in order to achieve the production of high smoke point jet fuel products by cutting heavy jet fuel, it is necessary to increase the pressure of the device, resulting in energy waste.

[0003] However, from the perspective of the desulfurization and dearomatization reaction mechanisms in aviation fuel fractions, the requirements for the reaction environment are quite different. For the desulfurization reaction, the removal of small molecular mercaptans and sulfides mainly follows the direct desulfurization route, that is, hydrogenolysis. It does not require a high reaction pressure; and aromatics are mainly enriched in the heavy components of the cut weight, so it is sufficient to pressurize and dearomatize this part of the heavy components. If a high hydrogenation activity catalyst is used under high pressure reaction conditions, and desulfurization and dearomatization reactions occur at the same time, the desulfurization depth will be increased, resulting in poor lubricity of refined aviation fuel. At the same time, a part of thiophene sulfides will be removed through the hydrogenation path under high pressure, increasing chemical hydrogen consumption; on the other hand, the hydrogen sulfide produced in the desulfurization process will affect the hydrogenation dearomatization, and the generated hydrogen sulfide will reduce the hydrogen partial pressure, and the concentration of aromatics in the mixed components is low, which is not conducive to the efficient dearomatization reaction.

[0004] Patent application CN107233927A discloses a medium oil type hydrocracking catalyst and its preparation method. The modified β molecular sieve obtained by the method has a relatively balanced cracking performance, and the produced middle distillate oil has the characteristics of high smoke point of aviation kerosene. However, the catalyst is used to produce aviation kerosene using conventional fixed bed hydrogenation process technology, which has the disadvantages of high hydrogen consumption and low aviation kerosene yield.

[0005] Patent application CN111088072A discloses a hydrocracking method for reducing the bromine index of heavy naphtha and increasing the smoke point of jet fuel. The method is to recycle the light jet fuel components rich in aromatics obtained by fractionation of the oil products after hydrofining and hydrocracking back to the hydrocracking unit, and the components rich in paraffin obtained by fractionation are used as the jet fuel product. However, the jet fuel yield produced by this method is low, the energy consumption of the device is large during the production process, and the product has a high content of paraffins, which easily causes the product to be unqualified. Summary of the invention

[0006] The purpose of the present invention is to overcome the technical problem in the prior art that the removal of sulfides and aromatics in aviation fuel fractions is placed in the same reaction system, resulting in excessive hydrogenation, and to provide a method for producing high smoke point aviation fuel products. The method uses aviation fuel as a raw material under milder process conditions to produce high smoke point aviation fuel products, while also improving the chemical reaction efficiency and reducing energy consumption and hydrogen consumption.

[0007] In order to achieve the above object, the present invention provides a method for producing a high smoke point aviation fuel product, wherein the method comprises the following steps: (1) In the presence of hydrogen, the jet fuel raw material is subjected to a gas phase desulfurization reaction in a hydrodesulfurization reactor to obtain a gas phase desulfurization reaction product; (2) separating the gas-phase desulfurization reaction product into gas and liquid to obtain a gas phase component and a liquid phase component, wherein the mass percentage of the liquid phase component is 15-50% based on the total amount of the gas-phase desulfurization reaction product; (3) pressurizing the liquid phase component, and then performing a liquid phase dearomatization reaction in a hydrodearomatization reactor to obtain a liquid phase dearomatization reaction product; Wherein, the smoke point of the aviation fuel raw material is 16-22mm.

[0008] Compared with the prior art, the method of the present invention has the following advantages: The method provided by the present invention realizes desulfurization and dearomatization with heavy cut jet fuel as raw material to produce high smoke point jet fuel products under milder operating conditions and a more simplified process flow. It is convenient for oil refining enterprises to increase the final distillation point of jet fuel fractions, increase the output of jet fuel products, and meet the needs of improving quality and efficiency. In the hydrodesulfurization reactor, only low hydrogen consumption desulfurization reaction occurs under low pressure conditions, reducing the hydrogen consumption of the reaction. The liquid phase components separated by gas and liquid undergo aromatic hydrogenation saturation reaction after pressurization. The entire reaction system does not require a hydrogen compressor in a fixed bed reaction system and a circulating oil pump in a liquid phase hydrogenation reaction system, which reduces investment costs, simplifies the process flow, improves reaction efficiency, and reduces the severity of the reaction.

[0009] The hydrogen of the present invention does not need to be recycled, thus eliminating the need for a circulating hydrogen compressor and significantly reducing the investment in device construction. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 It is a schematic diagram of the process flow of an embodiment of the present invention.

[0011] Reference numerals DETAILED DESCRIPTION The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0012] The description of the exemplary embodiments is intended to be read in conjunction with the accompanying drawings, which are considered a part of the entire written description. In the specification, relative terms such as "lower", "upper", "horizontal", "vertical", "above", "below", "upward", "downward", "top" and "bottom" and their derivatives (for example, "horizontally", "downwardly", "upwardly", etc.) should be interpreted as the directions shown in the drawings being described at the time. These relative terms are for convenience of description and do not require that the device be constructed or operated in a particular orientation. Unless otherwise specified, "connected" as used herein refers to a relationship whereby structures are directly or indirectly fixed or connected to each other through intermediate structures.

[0013] In the present invention, the symbol “≯” indicates not greater than, and the symbol “≮” indicates not less than.

[0014] The present invention provides a method for producing a high smoke point aviation fuel product, wherein the method comprises the following steps: (1) In the presence of hydrogen, the jet fuel raw material is subjected to a gas phase desulfurization reaction in a hydrodesulfurization reactor to obtain a gas phase desulfurization reaction product; (2) separating the gas-phase desulfurization reaction product into gas and liquid to obtain a gas phase component and a liquid phase component, wherein the mass percentage of the liquid phase component is 15-50% based on the total amount of the gas-phase desulfurization reaction product; (3) pressurizing the liquid phase component, and then performing a liquid phase dearomatization reaction in a hydrodearomatization reactor to obtain a liquid phase dearomatization reaction product; Wherein, the smoke point of the aviation fuel raw material is 16-22mm.

[0015] In the present invention, the hydrogen in step (1) can be any hydrogen-containing gas that can provide hydrogen, which can be fresh hydrogen, recycled hydrogen, or hydrogen-rich gas. Those skilled in the art can clearly understand the hydrogen-containing gas described in the present invention after understanding the technical solution of the present invention.

[0016] In the present invention, there is no particular limitation on the type of aviation kerosene raw material, and preferably, it is a cut-weight aviation kerosene raw material. In the present invention, there is no particular limitation on the properties of aviation kerosene. Preferably, in step (1), the initial distillation point of the aviation kerosene raw material is 80-200°C, the final distillation point is 220-320°C, the S content is ≯5000μg / g, preferably ≯3000μg / g, the N content is ≯10μg / g, the smoke point is 20-22mm, and the aromatics content is 15-30v%.

[0017] In the present invention, there is no particular limitation on the type of hydrodesulfurization catalyst, and any hydrodesulfurization catalyst that can achieve the hydrodesulfurization reaction is applicable to the present invention. Preferably, in step (1), the gas phase desulfurization reaction is carried out under the conditions of a hydrodesulfurization catalyst, and the hydrodesulfurization catalyst includes a first carrier and a hydrogenation active metal.

[0018] In the present invention, there is no particular limitation on the type of the first carrier, and any carrier conventionally defined in the art is applicable to the present invention. Preferably, the first carrier is an inorganic refractory oxide, and more preferably at least one selected from alumina, amorphous silica-alumina, silicon dioxide and titanium oxide.

[0019] In the present invention, there is no particular limitation on the type of hydrogenation active metal, and active metals conventionally defined in the art are applicable to the present invention. Preferably, the hydrogenation active metal is selected from at least one of the metal components of Group VIB and / or at least one of the metal components of Group VIII; further preferably, the metal component of Group VIB is tungsten and / or molybdenum, and the metal component of Group VIII is nickel and / or cobalt.

[0020] In the present invention, preferably, based on the mass of the hydrodesulfurization catalyst, the content of the VIB metal component calculated as oxide is 10-20 wt %, and the content of the VIII metal component calculated as oxide is 1-9 wt %.

[0021] In the present invention, there is no particular limitation on the source of the hydrodesulfurization catalyst, which can be prepared by a conventional preparation method in the art or commercially available. For example, a commercial hydrodesulfurization catalyst can be used, such as the FH-40 series catalysts developed by Fushun Research Institute of Petrochemicals (FRIPP) of Sinopec, for example, FH-40A and FH-40B catalysts.

[0022] In the present invention, by matching the use of a high desulfurization activity catalyst in a hydrodesulfurization reactor, the desulfurization reaction is controlled to follow a reaction path with low hydrogen consumption, thereby reducing the chemical hydrogen consumption of the desulfurization reaction. At the same time, the hydrogen-to-oil volume ratio of the hydrodesulfurization reactor can also be reduced, thereby reducing the severity of the reaction.

[0023] In the present invention, preferably, in step (1), the conditions of the gas phase desulfurization reaction include: temperature of 220-400°C, hydrogen-to-oil volume ratio of 5-400, pressure of 0.1-2MPa, volume space velocity of 4-20h -1 ; Further preferably, in step (1), the conditions of the gas phase desulfurization reaction include: a temperature of 230-360°C, for example, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 330°C, 340°C, 350°C, 360°C and values ​​between any two groups; a hydrogen-to-oil volume ratio of 20-300, for example, 20, 50, 100, 150, 200, 250, 300 and values ​​between any two groups; a pressure of 0.5-1.5 MPa, for example, 0.5 MPa, 1 MPa, 1.5 MPa and values ​​between any two groups; and a volume space velocity of 4-8 h -1 , for example, it can be 4h -1 , 5h -1 , 6h -1 , 7h -1 , 8h -1 and the values ​​between any two groups. By controlling the conditions of the gas phase desulfurization reaction, only the hydrogenation removal reaction of sulfides occurs in the gas phase desulfurization reactor, thereby separating the desulfurization and dearomatization reactions, optimizing the reaction conditions respectively, and improving the efficiency of each reaction. It should be noted that during the gas phase hydrogenation reaction of step (1), not only the sulfur in the jet fuel raw material will be removed, but also some small molecular nitrogen compounds (such as fatty amines) therein will be removed.

[0024] In the present invention, preferably, in step (1), the sulfur content in the gas phase desulfurization reaction product is 0.5-60wt% of the sulfur content of the aviation kerosene raw material, more preferably 10-50wt%, and even more preferably 15-25wt%. By controlling the gas phase desulfurization reaction so that the sulfur content in the gas phase desulfurization reaction product is within the above range, the depth of the desulfurization reaction can be effectively controlled to avoid deep desulfurization affecting the lubricity of the refined aviation kerosene product.

[0025] The present invention uses a small amount of heat exchange under high temperature conditions for the gas phase desulfurization reaction product, retains a large amount of reaction heat under the condition of ensuring the liquefaction of macromolecules, and meets the feeding conditions of the hydrodearomatization reactor, saving energy consumption. Preferably, the method also includes heat exchange and cooling the gas phase desulfurization reaction product before performing the gas-liquid separation. In the present invention, there is no special limitation on the heat exchange conditions, as long as the liquefaction of macromolecular heavy substances in the gas phase reaction product can be ensured.

[0026] In the present invention, the heat exchange can be performed in a heat exchange unit (preferably a heat exchanger). The present invention has no particular limitation on the specific type of the heat exchanger, for example, it can be a conventional commercial heat exchanger, such as a tubular heat exchanger.

[0027] In the present invention, there is no particular limitation on gas-liquid separation, which can be carried out in a gas-liquid separator. The gas-liquid separation is used to establish a gas-liquid balance of the effluent after heat exchange, so that the gas phase component flows out upward and the liquid phase component flows out downward. The present invention has a wide range of conditions for selecting the gas-liquid separation. Preferably, based on the total amount of the gas-phase desulfurization reaction product, the mass percentage of the liquid phase component is 25-35%. The use of this preferred embodiment is more conducive to accurately controlling the liquefaction ratio, so that the macromolecular substances that need further reaction enter the liquid phase component.

[0028] In the present invention, there is no particular limitation on the specific operating conditions and methods of the pressurization in step (3). Preferably, a booster pump is used as a booster unit to pressurize the liquid phase component so that the liquid phase component satisfies the conditions for the liquid phase dearomatization reaction. The present invention does not particularly limit the range of the pressurization.

[0029] In the present invention, there is no particular limitation on the type of hydrodearomatization catalyst used in the liquid phase dearomatization reaction. Preferably, in step (3), the liquid phase dearomatization reaction is carried out in the presence of a hydrodearomatization catalyst, and the hydrodearomatization catalyst is a precious metal catalyst and / or a non-precious metal catalyst.

[0030] In the present invention, there is no particular limitation on the type of the noble metal catalyst. Preferably, the noble metal catalyst comprises a second carrier and a noble metal element, and the noble metal element is Pd and / or Pt.

[0031] In the present invention, there is no particular limitation on the content of each component in the noble metal catalyst, with the purpose of achieving the hydrodearomatization reaction. Preferably, based on the noble metal catalyst, the content of Pd calculated as an element is 0.1-0.2wt%, and the content of Pt calculated as an element is 0.01-0.1wt%.

[0032] In the present invention, there is no particular limitation on the type of precious metal catalyst. Preferably, the non-metallic catalyst comprises a third carrier and a non-precious metal element, wherein the non-precious metal element is selected from at least one of the metal components of Group VIB and / or at least one of the metal components of Group VIII; further preferably, the metal component of Group VIB is tungsten and / or molybdenum, and the metal component of Group VIII is nickel and / or cobalt.

[0033] In the present invention, there is no particular limitation on the content of each component in the non-precious metal catalyst. Preferably, based on the mass of the non-precious metal catalyst, the content of the VIB metal component in terms of oxide is 10-20wt%, and the content of the VIII metal component in terms of oxide is 1-9wt%.

[0034] In the present invention, there is no particular limitation on the types of the second carrier and the third carrier. Preferably, the second carrier and the third carrier are each independently an organic refractory oxide, and more preferably at least one selected from alumina, amorphous silica-alumina, silicon dioxide and titanium oxide.

[0035] In the present invention, there is no particular limitation on the sources of the precious metal catalyst and the non-precious metal catalyst. Those skilled in the art can prepare them by themselves through the preparation methods conventionally defined in the art, or can obtain them commercially. For example, the precious metal catalyst can be the FHDA-10 catalyst developed by Sinopec Fushun Research Institute of Petrochemical Industry (FRIPP); the non-precious metal catalyst can be the FH-40 series catalyst developed by Sinopec Fushun Research Institute of Petrochemical Industry (FRIPP), such as FH-40A and FH-40B catalysts.

[0036] In the present invention, the liquid phase dearomatization reaction conditions can be selected in a wide range. In step (3), the liquid phase dearomatization reaction conditions include: a pressure of 2-10 MPa, a temperature of 150-330°C, and a volume space velocity of 0.3-3 h -1 ; Further preferably, in step (3), the conditions of the liquid phase dearomatization reaction include: a pressure of 3-6 MPa, a temperature of 225-330°C, for example, 225°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C and values ​​between any two groups, and a volume space velocity of 0.5-1.5h -1 , for example, it 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 and values ​​between any two groups.

[0037] In the present invention, preferably, the pressure of the liquid phase dearomatization reaction is at least 1 MPa higher than the pressure of the gas phase desulfurization reaction, preferably 2-5 MPa higher. In this preferred embodiment, the reaction is carried out at low pressure, which greatly reduces the severity of the reaction and saves energy consumption.

[0038] In the present invention, preferably, the temperature of the liquid phase dearomatization reaction is at least 5° C. lower than the temperature of the gas phase desulfurization reaction, preferably 10-30° C. lower. In this preferred embodiment, macromolecules that need further reaction can be liquefied while retaining the reaction heat.

[0039] In the present invention, there is no particular limitation on the specific types of the hydrodesulfurization reactor and the hydrodearomatization reactor. Preferably, the hydrodesulfurization reactor and the hydrodearomatization reactor are each independently a fixed bed reactor.

[0040] In the present invention, there is no particular limitation on the application of the gas phase component and the liquid phase dearomatization reaction product obtained by gas-liquid separation, and they can be adaptively treated according to the specific needs of the product. For example, the gas phase component and the liquid phase dearomatization reaction product can be treated separately or together, preferably together. Preferably, the method further comprises subjecting the gas phase component of step (2) to an optional decontamination treatment to obtain a hydrogenated light component, which is then mixed with the liquid phase dearomatization reaction product of step (3) and subjected to a dehydrogenation treatment to obtain a high smoke point jet fuel product. The present invention does not particularly limit the specific operation and conditions of the dehydrogenation treatment, and it can be carried out according to conventional technical means in the art, preferably by stripping. In the present invention, the stripping can be carried out in a stripping unit such as a stripping tower.

[0041] In the present invention, a high smoke point aviation kerosene product is prepared by the above method. Preferably, the high smoke point aviation kerosene product has a smoke point greater than 23 mm, preferably greater than 25 mm, an S content less than 2000 μg / g, preferably less than 1000 μg / g, and an aromatics content less than 23 v%, preferably less than 20 v%.

[0042] According to a specific embodiment of the present invention, the aforementioned method of the present invention is as follows Figure 1In the system shown, the aviation fuel raw material and hydrogen 1 enter the hydrodesulfurization reactor 2 for gas phase desulfurization reaction to obtain a gas phase desulfurization reaction product 3. The gas phase desulfurization reaction product 3 enters the heat exchange unit 4 for heat exchange and cooling, and then enters the gas-liquid separation unit 5 for gas-liquid separation to obtain a gas phase component 7 and a liquid phase component 6. The liquid phase component 6 is pressurized by the booster unit 8 and enters the hydrodearomatization reactor 9 for liquid phase dearomatization reaction to obtain a liquid phase dearomatization reaction product 10. The gas phase component 7 and the liquid phase dearomatization reaction product 10 are mixed and then enter the stripping unit 11 for stripping to obtain a high smoke point aviation fuel product 12.

[0043] The present invention will be further described below in conjunction with embodiments, but it should be understood that the protection scope of the present invention is not limited by the embodiments.

[0044] In the present invention, unless otherwise explicitly stated, percentages and contents are all based on mass.

[0045] Combine the following Figure 1 The process flow of the present invention is described in detail.

[0046] The jet fuel feedstock and hydrogen 1 enter the hydrodesulfurization reactor 2, where a gas phase desulfurization reaction occurs to obtain a gas phase desulfurization reaction product 3; the gas phase desulfurization reaction product 3 enters the heat exchange unit 4 (heat exchanger), and after being cooled by the heat exchanger, enters the gas-liquid separation unit 5 (gas-liquid separator) for gas-liquid separation to obtain a gas phase component 7 and a liquid phase component 6, the gas phase component 7 is discharged upward from the gas-liquid separator, and the liquid phase component 6 is discharged downward from the gas-liquid separator, and then enters the hydrodearomatization reactor 9 through the booster unit 8 (boosting pump) to obtain a liquid phase dearomatization reaction product 10, the gas phase component 7 is mixed with the liquid phase dearomatization reaction product 10 and enters the stripping unit 11 (stripping tower), and finally a high smoke point jet fuel product 12 is obtained.

[0047] In the following examples and comparative examples, chemical hydrogen consumption refers to the mass percentage of hydrogen consumed per unit mass of raw material.

[0048] The wear scar diameter of high smoke point jet fuel products is measured according to the petrochemical standard SH / T 0687-2017.

[0049] Examples 1-3 Use Figure 1Schematic diagram of the process. Two 100mL fixed-bed hydrogenation reactors are connected in series, namely the hydrodesulfurization reactor and the hydrodearomatization reactor. A heat exchanger, a gas-liquid separator and a booster pump are set between the reactors. The hydrodesulfurization reactor is filled with 30mL Mo-Co type hydrogenation catalyst A, and the hydrodearomatization reactor is filled with 70mL Mo-Ni type hydrogenation catalyst B. A gas phase outlet is set above the gas-liquid separator. After being connected to the outlet of the hydrodearomatization reactor, the gas phase components and the liquid phase dearomatization products enter the stripping tower together to obtain a high smoke point jet fuel product.

[0050] Heavy jet fuel was used as the raw material. The properties of the catalyst are shown in Table 1, the properties of the raw oil are shown in Table 2, and the reaction process conditions and results are shown in Table 3.

[0051] Example 4 The same process flow as in Example 1-3 was adopted, except that the hydrogen-to-oil volume ratio at the inlet of the hydrodesulfurization reactor was increased. The catalyst properties are shown in Table 1, the feed oil properties are shown in Table 2, and the reaction process conditions and results are shown in Table 3.

[0052] Example 5 The same process flow as in Example 1-3 was used, except that the separation conditions for gas-liquid separation were changed. The properties of the catalyst are shown in Table 1, the properties of the feedstock oil are shown in Table 2, and the reaction process conditions and results are shown in Table 3.

[0053] Example 6 The same process flow as in Example 1-3 was used, except that the hydrogen-to-oil volume ratio at the inlet of the hydrodesulfurization reactor was reduced, and the booster system (boost pump) of the hydrodearomatization reactor was changed to a booster and hydrogen mixing system. 3 The amount of hydrogen required for the liquid phase component is 20Nm 3 The hydrodesulfurization reactor 1 was loaded with 30 mL of Mo-Co type hydrogenation catalyst A, and the hydrodearomatization reactor 2 was loaded with 70 mL of Mo-Ni type hydrogenation catalyst B. The properties of the raw materials and catalysts were the same as those in Examples 1-3, and the reaction process conditions and results are shown in Table 3.

[0054] Comparative Example 1 A conventional fixed-bed hydrogenation process for aviation kerosene was adopted, and a hydrogenation reactor was set up. The reactor was loaded with 100 mL of Mo-Co type light distillate oil hydrogenation catalyst A. After the reactor, low fractionation, stripping and other processes were set up according to the conventional method to obtain aviation kerosene products. After hydrogen sulfide was removed, the hydrogen was pressurized and recycled by a circulating hydrogen compressor. The properties of the raw materials and catalysts were the same as those in Examples 1-3, and the reaction process conditions and results are shown in Table 3.

[0055] Table 1 Table 2 Table 3 As can be seen from Table 3, the hydrogen-to-oil volume ratio at the inlet of the hydrodesulfurization reactor in Example 4 is too large, which makes liquefaction difficult during the gas-liquid separation process, and a part of the aromatics enter the gas phase component without hydrogenation reaction, and the product smoke point is low. In Example 5, the heat exchange in the gas-liquid separation process is large, and the liquefaction ratio is high, but reheating is required during the liquid phase reaction to meet the reaction conditions, and the energy consumption is relatively high. In Example 6, since the hydrogen consumption of the hydrodesulfurization reactor is low, the hydrogen-to-oil volume ratio is reduced. However, due to the reduction in the hydrogen partial pressure, the difficulty of gasifying the raw materials becomes greater, and a higher reaction temperature is required, resulting in excessive removal of sulfides and increased energy consumption and hydrogen consumption. At the same time, in order to provide enough hydrogen source for the liquid phase hydrodearomatization reaction again, it is necessary to add a hydrogen mixer, resulting in increased investment costs.

[0056] Comparative Example 1 uses conventional fixed-bed hydrogenation technology and a traditional catalyst loading system. The reactor pressure is relatively high, resulting in simultaneous desulfurization and dearomatization, which affect each other. The reaction conditions cannot be optimized for a certain reaction. The depth of sulfide removal under high pressure affects the lubricity of the product and the hydrogen consumption is relatively high; the hydrogen is recycled, which consumes a lot of energy. However, under the premise that the pressure of the hydrodesulfurization reactor is significantly reduced, the reaction system of the present invention divides the desulfurization and dearomatization into two reaction systems, and the reaction conditions are optimized in a targeted manner, which can better retain the sulfides of aviation coal, improve lubricity, and obtain a better dearomatization effect; the sulfides are removed through the hydrogenolysis path, which reduces hydrogen consumption; the hydrogen does not need to be recycled, which reduces energy consumption.

[0057] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for producing a high smoke point aviation fuel product, characterized in that: The method comprises the following steps: (1) In the presence of hydrogen, the jet fuel raw material is subjected to a gas phase desulfurization reaction in a hydrodesulfurization reactor to obtain a gas phase desulfurization reaction product; (2) separating the gas-phase desulfurization reaction product into gas and liquid to obtain a gas phase component and a liquid phase component, wherein the mass percentage of the liquid phase component is 15-50% based on the total amount of the gas-phase desulfurization reaction product; (3) pressurizing the liquid phase component, and then performing a liquid phase dearomatization reaction in a hydrodearomatization reactor to obtain a liquid phase dearomatization reaction product; Wherein, the smoke point of the aviation fuel raw material is 16-22mm.

2. The method according to claim 1, wherein: In step (1), the initial distillation point of the jet fuel raw material is 80-200°C, the final distillation point is 220-320°C, the S content is ≯5000μg / g, preferably ≯3000μg / g, the N content is ≯10μg / g, the smoke point is 20-22mm, and the aromatics content is 15-30v%.

3. The method according to claim 1 or 2, wherein: In step (1), the gas phase desulfurization reaction is carried out under the condition of a hydrodesulfurization catalyst, and the hydrodesulfurization catalyst includes a first carrier and a hydrogenation active metal; Preferably, the first carrier is an inorganic refractory oxide, further preferably at least one selected from alumina, amorphous silica-alumina, silicon dioxide and titanium oxide; Preferably, the hydrogenation active metal is selected from at least one of the Group VIB metal components and / or at least one of the Group VIII metal components; Further preferably, the Group VIB metal component is tungsten and / or molybdenum, and the Group VIII metal component is nickel and / or cobalt; Preferably, based on the mass of the hydrodesulfurization catalyst, the content of the VIB metal component calculated as oxide is 10-20 wt %, and the content of the VIII metal component calculated as oxide is 1-9 wt %.

4. The method according to any one of claims 1 to 3, wherein: In step (1), the conditions of the gas phase desulfurization reaction include: temperature of 220-400°C, hydrogen-to-oil volume ratio of 5-400, pressure of 0.1-2 MPa, volume space velocity of 4-20 h -1 ; Preferably, in step (1), the conditions for the gas phase desulfurization reaction include: temperature of 230-360°C, hydrogen-to-oil volume ratio of 20-300, pressure of 0.5-1.5 MPa, volume space velocity of 4-8 h -1 ; Preferably, in step (1), the sulfur content in the gas phase desulfurization reaction product is 0.5-60wt% of the sulfur content of the aviation kerosene feedstock, more preferably 10-50wt%, and even more preferably 15-25wt%.

5. The method according to any one of claims 1 to 4, wherein: The method further comprises, before performing the gas-liquid separation, subjecting the gas-phase desulfurization reaction product to heat exchange and cooling; Preferably, based on the total amount of the gas phase desulfurization reaction product, the mass percentage of the liquid phase component is 25-35%.

6. The method according to any one of claims 1 to 5, wherein: In step (3), the liquid phase dearomatization reaction is carried out in the presence of a hydrodearomatization catalyst, and the hydrodearomatization catalyst is a noble metal catalyst and / or a non-noble metal catalyst; Preferably, the noble metal catalyst comprises a second carrier and a noble metal element, and the noble metal element is Pd and / or Pt; Preferably, based on the noble metal catalyst, the content of Pd calculated as an element is 0.1-0.2wt%, and the content of Pt calculated as an element is 0.01-0.1wt%; Preferably, the non-metallic catalyst comprises a third carrier and a non-precious metal element, wherein the non-precious metal element is selected from at least one of the metal components of Group VIB and / or at least one of the metal components of Group VIII; further preferably, the metal component of Group VIB is tungsten and / or molybdenum, and the metal component of Group VIII is nickel and / or cobalt; Preferably, based on the mass of the non-precious metal catalyst, the content of the VIB metal component calculated as oxide is 10-20wt%, and the content of the VIII metal component calculated as oxide is 1-9wt%; Preferably, the second carrier and the third carrier are each independently an organic refractory oxide, and more preferably at least one selected from alumina, amorphous silica-alumina, silicon dioxide and titanium oxide.

7. The method according to any one of claims 1 to 6, wherein: In step (3), the conditions of the liquid phase dearomatization reaction include: pressure of 2-10 MPa, temperature of 150-330°C, volume space velocity of 0.3-3h -1 ; Preferably, in step (3), the conditions of the liquid phase dearomatization reaction include: pressure of 3-6 MPa, temperature of 225-330°C, volume space velocity of 0.5-1.5 h -1 .

8. The method according to any one of claims 1 to 7, wherein: The pressure of the liquid phase dearomatization reaction is at least 1 MPa higher than the pressure of the gas phase desulfurization reaction, preferably 2-5 MPa higher; Preferably, the temperature of the liquid phase dearomatization reaction is at least 5°C lower than the temperature of the gas phase desulfurization reaction, preferably 10-30°C lower.

9. The method according to any one of claims 1 to 8, wherein: The hydrodesulfurization reactor and the hydrodearomatization reactor are each independently a fixed bed reactor.

10. The method according to any one of claims 1 to 9, wherein: The method further comprises optionally subjecting the gas phase component of step (2) to impurity removal treatment to obtain a hydrogenated light component, which is then mixed with the liquid phase dearomatization reaction product of step (3) and subjected to a hydrogen sulfide removal treatment to obtain a high smoke point aviation fuel product; Preferably, the high smoke point aviation fuel product has a smoke point greater than 23 mm, preferably greater than 25 mm, an S content less than 2000 μg / g, preferably less than 1000 μg / g, and an aromatics content less than 23 v%, preferably less than 20 v%.

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