A catalyst for hydrodenitrification of light distillate oil, and a preparation method and application thereof

Abstract

The present disclosure relates to a catalyst for hydrodenitrogenation of light distillate oil, a preparation method and application thereof, the catalyst comprising a carrier and a carbide of a first metal, a second metal active component and a third metal active component supported on the carrier; the first metal comprises W and / or Mo; the second metal active component comprises one or more of Fe component, Co component and Ni component; the third metal active component comprises Sb component and / or Bi component, the catalyst is used for hydrodenitrogenation reaction of light distillate oil, and better hydrogenation and denitrogenation effect can be obtained.

Description

Technical Field

[0001] This disclosure relates to the field of hydrodenitrification, and more specifically, to a catalyst for hydrodenitrification of light distillate oils, its preparation method, and its application. Background Technology

[0002] Heterocyclic compounds, aromatics, sulfur-containing compounds, and nitrogen-containing compounds in petroleum fuels not only reduce the cetane number of diesel fuel, but also affect fuel stability, shorten catalyst life, and increase the emission of harmful gases and particulate matter (PM) in the atmosphere.

[0003] Patent CN1015638B describes a method for preparing γ-Al₂O₃ support using a carbonization process. Experiments on diesel hydrodenitrification show that this method can improve desulfurization efficiency by an order of magnitude, reduce basic nitrogen by an order of magnitude, and reduce total nitrogen to ppm without changing process parameters. However, experiments on hydrorefining of towed oil to produce pentane oil, kerosene hydrorefining, and wax oil hydrorefining show slightly poor applicability and a relatively limited application range. Furthermore, the catalyst prepared by this simplified process exhibits relatively lower wear and pollution characteristics. Patent CN109718751A describes a method for preparing a hydrodenitrification catalyst support by physically expanding and adsorbing a solution containing an auxiliary agent, then mixing and molding it with a physical pore-expanding agent, followed by drying and calcination. The intermediate is then subjected to a series of sealed heat treatments and drying calcination. The active phase components are Group VIB and Group VIII metals. The prepared hydrodenitrogenation support and catalyst possess large pore size and volume characteristics. Testing with the residue oil hydrodenitrogenation process shows a high denitrification rate, along with high demetallization and desulfurization rates. However, the entire catalyst preparation process is complex and time-consuming. Patent CN104646006A involves mixing aluminum source, silicon source, pore-forming agent, and a small amount of solvent, then directly adding a compound or solution containing active components, followed by drying and calcination to prepare a hydrodenitrogenation catalyst. The catalyst achieves a denitrification rate of up to 73%, higher than the reference catalyst used in industrial applications. Compared to catalysts prepared by traditional impregnation methods, the dispersion of active metals is significantly higher, and the introduction of silicon can simultaneously modulate the acidity strength. However, all experimental tests were conducted using model compounds on a microreactor, and the scale-up process effect still needs further verification. Patent CN108993521A describes the preparation of a support and active component for a diesel hydrodenitrification catalyst. The support is a porous composite support prepared using polyamide-amine dendritic polymer as a pore-forming agent, and the active component is prepared by one or more impregnation loadings onto the support. Comparative hydrodenitrification microreactor experiments using coking diesel as feedstock show that it exhibits high hydrodenitrification activity.

[0004] In summary, existing catalysts cannot simultaneously achieve both hydrogenation and denitrification properties, and no single catalyst can achieve deep refining of distillate oils. Overall, there is still considerable room for improvement in the efficiency of existing hydrodenitrification, thus requiring the development of more efficient hydrodenitrification catalysts. Summary of the Invention

[0005] The purpose of this disclosure is to provide a catalyst for hydrodenitrogenation of light distillate oil, its preparation method, and its application. This catalyst, when used in the hydrodenitrogenation reaction of light distillate oil, can achieve a better hydrodenitrogenation effect.

[0006] To achieve the above objectives, the first aspect of this disclosure provides a catalyst for hydrodenitrogenation of light distillate oil, the catalyst comprising a support and a carbide of a first metal, a second metal active component, and a third metal active component supported on the support;

[0007] The first metal includes W and / or Mo;

[0008] The second metal active component includes one or more of Fe, Co, and Ni components;

[0009] The third metal active component includes Sb and / or Bi components.

[0010] Optionally, the support includes one or more of alumina, silica, zirconium oxide, Y-type molecular sieve and Beta molecular sieve; preferably alumina and / or silica.

[0011] Optionally, the content of the support is 50-90% by weight relative to the total weight of the catalyst;

[0012] Based on the metal element, the content of the first metal carbide is 8-40% by weight, the content of the second metal active component is 1-15% by weight, and the content of the third metal active component is 0.1-5% by weight.

[0013] Optionally, the catalyst further comprises a carbonate, which includes alkali metal carbonates and / or alkaline earth metal carbonates, preferably one or more of potassium carbonate, magnesium carbonate and calcium carbonate.

[0014] Optionally, the content of the carbonate, based on the metal element, is 0.1-10% by weight relative to the total weight of the catalyst, preferably 0.3-2% by weight.

[0015] Optionally, in the catalyst, the second active metal component and the third active metal component exist in a metallic state.

[0016] Optionally, the light distillate oil is a distillate oil with a final boiling point below 360°C, preferably one or more of naphtha, catalytic gasoline, diesel oil and jet fuel;

[0017] Optionally, the organic nitrogen content of the light distillate oil is 20-500 ppmw.

[0018] A second aspect of this disclosure provides a method for preparing a catalyst for hydrodenitrogenation of light distillate oils, the method comprising the following steps:

[0019] S1. The carrier is first impregnated by contacting an impregnation solution containing a first metal source, and then subjected to a first heat treatment to obtain a first product;

[0020] S2. Carbonize the first product in a carbon-containing reducing atmosphere to obtain the second product;

[0021] S3. Impregnate the second product with the second metal active component and the third metal active component;

[0022] The first metal element in the first metal source includes W and / or Mo;

[0023] The second metal active component includes one or more of Fe, Co, and Ni components;

[0024] The third metal active component includes Sb and / or Bi components.

[0025] Optionally, step S3 includes:

[0026] A. The second product is contacted with an impregnation solution containing a second metal source and a third metal source for a second impregnation, and then subjected to a second heat treatment under an inert atmosphere;

[0027] or,

[0028] Step S3 includes the following steps:

[0029] (1) The second product is contacted with an impregnation solution containing a second metal source for a third impregnation, and then subjected to a third heat treatment under an inert atmosphere to obtain a third product;

[0030] (2) The third product is contacted with an impregnation solution containing a third metal source for a fourth impregnation, and then subjected to a fourth heat treatment under an inert atmosphere;

[0031] or,

[0032] Step S3 includes the following steps:

[0033] a. The second product is contacted with an impregnation solution containing a third metal source for a fifth impregnation, and then subjected to a fifth heat treatment under an inert atmosphere to obtain a fourth product;

[0034] b. The fourth product is contacted with an impregnation solution containing a second metal source for a sixth impregnation, and then subjected to a sixth heat treatment under an inert atmosphere.

[0035] The second metal element in the second metal source includes one or more of Fe, Co and Ni;

[0036] The third metal element in the third metal source includes Sb and / or Bi.

[0037] Optionally, the impregnation solution containing the second metal source and the third metal source is an oil-soluble impregnation solution, and the solvent in the impregnation solution containing the second metal source and the third metal source includes one or more of methanol, ethanol, cyclohexane and toluene.

[0038] The impregnation solution containing the second metal source is an oil-soluble impregnation solution, and the solvent in the impregnation solution containing the second metal source includes one or more of methanol, ethanol, cyclohexane and toluene.

[0039] The impregnation solution containing the third metal source is an oil-soluble impregnation solution, and the solvent in the impregnation solution containing the second metal source includes one or more of methanol, ethanol, cyclohexane and toluene.

[0040] The second metal source includes one or more of the following: organometallic compounds of the second metal element, organic acid salts of the second metal element, and carbonyl compounds of the second metal element; preferably, it includes one or more of the following: cobalt naphthenate, iron acetate, nickel naphthenate, cobalt carbonyl, iron carbonyl, and nickel carbonyl.

[0041] The third metal source includes an organic acid salt of a third metal element and / or an organometallic compound of a third metal element, preferably one or more of bismuth acetate, bismuth citrate, antimony acetate, antimony isopropoxy, and antimony glycolate.

[0042] Optionally, the first impregnation, the second impregnation, the third impregnation, the fourth impregnation, the fifth impregnation, and the sixth impregnation are performed using an equal-volume impregnation method, wherein the conditions for the equal-volume impregnation method include: a time of 1-10 hours and a temperature of 60-140°C.

[0043] Optionally, the conditions for the first heat treatment include: a time of 1-10 hours and a temperature of 400-700°C;

[0044] The conditions for the second heat treatment include: a time of 1-10 hours and a temperature of 400-700℃;

[0045] The conditions for the third heat treatment include: a time of 1-10 hours and a temperature of 400-700℃;

[0046] The conditions for the fourth heat treatment include: a time of 1-10 hours and a temperature of 400-700℃.

[0047] The conditions for the fifth heat treatment include: a time of 1-10 hours and a temperature of 400-700℃;

[0048] The conditions for the sixth heat treatment include: a time of 1-10 hours and a temperature of 400-700℃.

[0049] Optionally, the weight ratio of the carrier, the first metal source (based on metal elements), the second metal source (based on metal elements), and the third metal source (based on metal elements) is (50-90):(8-40):(1-15):(0.1-5).

[0050] Optionally, step S1 further includes: drying the first impregnated solid at 60-140°C for 1-24 hours, and then performing the first heat treatment;

[0051] Step A further includes: drying the second impregnated solid at 60-140°C for 1-24 hours under an inert atmosphere, and then performing the second heat treatment;

[0052] Step (1) further includes: drying the solid after the third impregnation at 60-140°C for 1-24 hours under an inert atmosphere, and then performing the third heat treatment;

[0053] Step (2) further includes: drying the solid after the fourth impregnation at 60-140°C for 1-24 hours under an inert atmosphere, and then performing the fourth heat treatment;

[0054] Step a further includes: drying the solid after the fifth impregnation at 60-140°C for 1-24 hours under an inert atmosphere, and then performing the fifth heat treatment;

[0055] Step b further includes: drying the solid after the sixth impregnation at 60-140°C for 1-24 hours under an inert atmosphere, and then performing the sixth heat treatment.

[0056] Optionally, the support includes one or more of alumina, silica, zirconium oxide, Y-type molecular sieve and Beta molecular sieve, preferably alumina and / or silica;

[0057] The first metal source comprises a soluble salt of a first metal element, preferably one or more of ammonium molybdate, ammonium metatungstate, and ammonium paratungstate.

[0058] Optionally, in step S2, the carbon-containing reducing atmosphere contains a carbon-containing compound;

[0059] The carbon-containing compound includes one or more of alkanes having 2-5 carbon atoms and alkenes having 2-5 carbon atoms, preferably one or more of ethane, ethylene, n-propane, propylene, n-butane, 1-butene, and 2-butene.

[0060] In the carbon-containing reducing atmosphere, the content of the carbon-containing compound is 1-30% by volume;

[0061] Optionally, the carbon-containing reducing atmosphere contains hydrogen.

[0062] Optionally, the carbonization conditions include: heating to 100-500℃ at a heating rate of 1-20℃ / min, then heating to 600-800℃ at a heating rate of 0.1-1℃ / min, and maintaining the temperature for carbonization for 1-10 hours.

[0063] Optionally, the method further includes: passivating the second product obtained in step S2 under an inert atmosphere for 1-10 hours before proceeding to step S3;

[0064] In the inert atmosphere, the oxygen content is 0-5% by volume.

[0065] Optionally, the method further includes: mixing the first solid product obtained in step S3 with carbonate by ball milling for 20-40 hours;

[0066] Optionally, the carbonate includes alkali metal carbonates and / or alkaline earth metal carbonates, preferably one or more of potassium carbonate, magnesium carbonate and calcium carbonate;

[0067] Optionally, the weight ratio of the carbonate to the carrier, calculated as metal element, is (0.1-10):(50-90).

[0068] Optionally, the method further includes: reducing the second solid product obtained by ball milling;

[0069] The reduction process includes contacting the second solid product with hydrogen gas.

[0070] The third aspect of this disclosure provides a catalyst prepared using the method described in the second aspect of this disclosure.

[0071] The fourth aspect of this disclosure provides a method for hydrodenitrification of light distillate oil, the method comprising contacting the light distillate oil with a catalyst to carry out a hydrodenitrification reaction, the catalyst comprising the catalyst described in the first or third aspect of this disclosure.

[0072] Optionally, the light distillate oil is a distillate oil with a final boiling point below 360°C, preferably one or more of naphtha, catalytic gasoline, diesel oil and jet fuel;

[0073] Optionally, the organic nitrogen content of the light distillate oil is 20-500 ppmw.

[0074] Optionally, the conditions for the hydrodenitrification reaction include: a temperature of 100-400℃, a pressure of 0.2-20 MPa, and a mass hourly space velocity of 0.1-10 h⁻¹. -1 The hydrogen-to-oil volume ratio is 100-1000;

[0075] Preferably, the temperature is 150-350℃, the pressure is 0.5-15MPa, and the mass hourly space velocity is 0.2-3h. -1 The hydrogen-to-oil ratio is 200-600.

[0076] Through the above technical solution, the catalyst disclosed herein supports specific metal active components and is used in the hydrodenitrification reaction of light distillate oil to achieve good hydrodenitrification effect. Moreover, the preparation process is simple, the cost is low, and it is conducive to industrial promotion.

[0077] Other features and advantages of this disclosure will be described in detail in the following detailed description section. Detailed Implementation

[0078] The following provides a detailed description of specific embodiments of this disclosure. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of this disclosure.

[0079] The first aspect of this disclosure provides a catalyst for hydrodenitrogenation of light distillate oil, the catalyst comprising a support and a carbide of a first metal, a second metal active component, and a third metal active component supported on the support;

[0080] The first metal includes W and / or Mo;

[0081] The second metal active component includes one or more of Fe, Co, and Ni components;

[0082] The third metal active component includes Sb and / or Bi components.

[0083] According to one embodiment of the present disclosure, in the catalyst, the second metal active component and the third metal active component exist in a metallic state.

[0084] To further achieve better hydrodenitrification, according to one embodiment of this disclosure, the first metal includes W and Mo.

[0085] In this disclosure, the support can be a conventional porous support in the art, such as one or more of alumina, silica, zirconium oxide, Y-type molecular sieve and Beta molecular sieve; preferably alumina and / or silica, and this disclosure does not specifically limit the type of alumina.

[0086] According to one embodiment of this disclosure, the support content is 50-90% by weight relative to the total weight of the catalyst; the content of the first metal carbide is 8-40% by weight, the content of the second metal active component is 1-15% by weight, and the content of the third metal active component is 0.1-5% by weight, based on metal elements; preferably, the support content is 55-83% by weight relative to the total weight of the catalyst; the content of the first metal carbide is 15-35% by weight, the content of the second metal active component is 1-10% by weight, and the content of the third metal active component is 0.3-4.5% by weight, based on metal elements. The catalyst having the above composition can achieve excellent hydrodenitrogenation performance in the hydrodenitrogenation reaction of light distillate oils. Wherein, when the first metal carbide includes both WC and MoC, the ratio of the two is not required, that is, any ratio of the two carbides can achieve the technical solution of this disclosure; when the second metal active component includes two or three of Fe, Co and Ni components, the ratio is not required, that is, any ratio of the active components can achieve the technical solution of this disclosure; when the third metal active component includes both Sb and Bi components, the ratio is not required, that is, any ratio of the active components can achieve the technical solution of this disclosure.

[0087] According to one embodiment of this disclosure, the catalyst further comprises a carbonate, including alkali metal carbonates and / or alkaline earth metal carbonates, preferably one or more of potassium carbonate, magnesium carbonate, and calcium carbonate; optionally, the carbonate content, based on the metal element, is 0.1-10% by weight relative to the total weight of the catalyst, preferably 0.3-2% by weight. The catalyst containing carbonates can further improve the hydrodenitrogenation effect.

[0088] According to one embodiment of this disclosure, the catalyst has an average particle size of 0.5-5 mm and a specific surface area of ​​50-300 m². 2 / g, total pore volume is 0.2-2cm³ 3 / g.

[0089] In this disclosure, the light distillate oil is a distillate oil with a final boiling point below 360°C, preferably one or more of naphtha, catalytic gasoline, diesel, and jet fuel; the organic nitrogen content of the light distillate oil is 20-500 ppmw; wherein, the types of nitrogen-containing organic compounds in the light distillate oil are conventional in the art, such as one or more of alkylamines, pyrrole and their alkyl-substituted derivatives, pyridine and their alkyl-substituted derivatives, carbazole and their alkyl-substituted derivatives, indole and their alkyl-substituted derivatives, and quinoline and their alkyl-substituted derivatives; the alkyl group has 1-5 carbon atoms, for example, it can be methyl, ethyl, n-propyl, isopropyl, etc.

[0090] In this disclosure, "alkyl-substituted derivative" means a derivative with an alkyl substituent, for example, "pyrrole and its alkyl-substituted derivatives" means pyrrole and pyrrole derivatives with alkyl substituents.

[0091] A second aspect of this disclosure provides a method for preparing a catalyst for hydrodenitrogenation of light distillate oils, the method comprising the following steps:

[0092] S1. The carrier is first impregnated by contacting an impregnation solution containing a first metal source, and then subjected to a first heat treatment to obtain a first product;

[0093] S2. Carbonize the first product in a carbon-containing reducing atmosphere to obtain the second product;

[0094] S3. Impregnate the second product with the second metal active component and the third metal active component;

[0095] The first metal element in the first metal source includes W and / or Mo;

[0096] The second metal active component includes one or more of Fe, Co, and Ni components;

[0097] The third metal active component includes Sb and / or Bi components.

[0098] According to one embodiment of this disclosure, the loading of the second metal active component and the third metal active component can be performed simultaneously or in stages. When the loading is performed in stages, the loading order is not required. Specifically, step S3 includes:

[0099] A. The second product is contacted with an impregnation solution containing a second metal source and a third metal source for a second impregnation, and then subjected to a second heat treatment under an inert atmosphere;

[0100] or,

[0101] Step S3 includes the following steps:

[0102] (1) The second product is contacted with an impregnation solution containing a second metal source for a third impregnation, and then subjected to a third heat treatment under an inert atmosphere to obtain a third product;

[0103] (2) The third product is contacted with an impregnation solution containing a third metal source for a fourth impregnation, and then subjected to a fourth heat treatment under an inert atmosphere;

[0104] or,

[0105] Step S3 includes the following steps:

[0106] a. The second product is contacted with an impregnation solution containing a third metal source for a fifth impregnation, and then subjected to a fifth heat treatment under an inert atmosphere to obtain a fourth product;

[0107] b. The fourth product is contacted with an impregnation solution containing a second metal source for a sixth impregnation, and then subjected to a sixth heat treatment under an inert atmosphere.

[0108] The second metal element in the second metal source includes one or more of Fe, Co and Ni;

[0109] The third metal element in the third metal source includes Sb and / or Bi.

[0110] According to one embodiment of this disclosure, in order to improve the dispersion of the metal source and further enhance the hydrodenitrification capability of the catalyst, the impregnation solution containing the second metal source and the third metal source is an oil-soluble impregnation solution, and the solvent in the impregnation solution containing the second metal source and the third metal source includes one or more of methanol, ethanol, cyclohexane, and toluene; the impregnation solution containing the second metal source is an oil-soluble impregnation solution, and the solvent in the impregnation solution containing the second metal source includes one or more of methanol, ethanol, cyclohexane, and toluene; the impregnation solution containing the third metal source is an oil-soluble impregnation solution, and the solvent in the impregnation solution containing the second metal source includes one or more of methanol, ethanol, cyclohexane, and toluene. This disclosure does not specify the concentration of the above impregnation solution.

[0111] According to one embodiment of this disclosure, the impregnation solution containing a first metal source can be an aqueous solution. The first metal source includes a soluble salt of a first metal element, preferably one or more of ammonium molybdate, ammonium metatungstate, and ammonium paratungstate.

[0112] According to one embodiment of this disclosure, the second metal source includes one or more of the following: organometallic compounds of the second metal element, organic acid salts of the second metal element, and carbonyl compounds of the second metal element. Preferably, it includes one or more of the following: cobalt naphthenate (CAS No.: 61789-51-3), ferric acetate (CAS No.: 10450-55-2), nickel naphthenate (CAS No.: 61788-71-4), cobalt carbonyl (CAS No.: 10210-68-1), ferric carbonyl (CAS No.: 13463-40-6), and nickel carbonyl (CAS No.: 13463-39-3).

[0113] According to one embodiment of this disclosure, the third metal source includes an organic salt of a third metal element and / or an organometallic compound of a third metal element, preferably one or more of bismuth acetate (CAS No.: 22306-37-2), bismuth citrate (CAS No.: 813-93-4), antimony acetate (CAS No.: 3643-76-3), antimony isopropoxy (CAS No.: 18770-47-3), and antimony glycol (CAS No.: 29736-75-2).

[0114] According to one embodiment of this disclosure, the first impregnation, second impregnation, third impregnation, fourth impregnation, fifth impregnation, and sixth impregnation are performed using an equal-volume impregnation method. The conditions for the equal-volume impregnation method include: a time of 1-10 hours and a temperature of 60-140°C. The conditions for the first impregnation, second impregnation, third impregnation, fourth impregnation, fifth impregnation, and sixth impregnation can be the same or different. The operation steps of the equal-volume impregnation method are conventional in the art and will not be described in detail here.

[0115] According to one embodiment of this disclosure, the weight ratio of the carrier, the first metal source (based on metal elements), the second metal source (based on metal elements), and the third metal source (based on metal elements) is (50-90):(8-40):(1-15):(0.1-5), preferably (55-83):(15-35):(1-10):(0.3-4.5).

[0116] According to one embodiment of this disclosure, step S1 further includes: drying the first impregnated solid at 60-140°C for 1-24 hours, and then performing the first heat treatment.

[0117] According to one embodiment of this disclosure, step A further includes: drying the second impregnated solid at 60-140°C for 1-24 hours under an inert atmosphere, and then performing the second heat treatment.

[0118] According to one embodiment of this disclosure, step (1) further includes: drying the solid after the third impregnation at 60-140°C for 1-24 hours under an inert atmosphere, and then performing the third heat treatment.

[0119] According to one embodiment of this disclosure, step (2) further includes: drying the fourth impregnated solid at 60-140°C for 1-24 hours under an inert atmosphere, and then performing the fourth heat treatment.

[0120] According to one embodiment of this disclosure, step a further includes: drying the solid after the fifth impregnation at 60-140°C for 1-24 hours under an inert atmosphere, and then performing the fifth heat treatment.

[0121] According to one embodiment of this disclosure, step b further includes: drying the sixth impregnated solid at 60-140°C for 1-24 hours under an inert atmosphere, and then performing the sixth heat treatment.

[0122] In this disclosure, the drying method is conventional in the art, such as drying in a drying oven.

[0123] In this disclosure, the heat treatment method is conventional in the art, such as calcination.

[0124] In this disclosure, the inert atmosphere may include, for example, nitrogen and / or helium, and the oxygen content in the inert atmosphere is 0-5% by volume.

[0125] According to one embodiment of this disclosure, the conditions for the first heat treatment include: a time of 1-10 hours, preferably 1-7 hours; and a temperature of 400-700°C, preferably 350-650°C.

[0126] According to one embodiment of this disclosure, the conditions for the second heat treatment include: a time of 1-10 hours, preferably 1-7 hours; and a temperature of 400-700°C, preferably 350-650°C.

[0127] According to one embodiment of this disclosure, the conditions for the third heat treatment include: a time of 1-10 hours, preferably 1-7 hours; and a temperature of 400-700°C, preferably 350-650°C.

[0128] According to one embodiment of this disclosure, the conditions for the fourth heat treatment include: a time of 1-10 hours, preferably 1-7 hours; and a temperature of 400-700°C, preferably 350-650°C.

[0129] According to one embodiment of this disclosure, the conditions for the fifth heat treatment include: a time of 1-10 hours, preferably 1-7 hours; and a temperature of 400-700°C, preferably 350-650°C.

[0130] According to one embodiment of this disclosure, the conditions for the sixth heat treatment include: a time of 1-10 hours, preferably 1-7 hours; and a temperature of 400-700°C, preferably 350-650°C.

[0131] According to one embodiment of this disclosure, the carbon-containing reducing atmosphere contains a carbon-containing compound; the carbon-containing compound includes one or more of alkanes having 2-5 carbon atoms and alkenes having 2-5 carbon atoms, preferably including one or more of ethane, ethylene, n-propane, propylene, n-butane, 1-butene, and 2-butene; in the carbon-containing reducing atmosphere, the content of the carbon-containing compound is 1-30% by volume; the carbon-containing reducing atmosphere contains hydrogen, and the content of hydrogen is not specifically required. Preferably, the carbon-containing reducing atmosphere is composed of a carbon-containing compound and hydrogen.

[0132] According to one embodiment of this disclosure, the carbonization conditions include: heating to 100-500°C at a heating rate of 1-20°C / min, then heating to 600-800°C at a heating rate of 0.1-1°C / min, and maintaining the temperature for carbonization for 1-10 hours.

[0133] According to one embodiment of this disclosure, to prevent the carbides from spontaneously combusting in air, the method further includes: passivating the second product obtained in step S2 under an inert atmosphere for 1-10 hours before proceeding to step S3; wherein the inert atmosphere includes nitrogen and / or helium; and the oxygen content in the inert atmosphere is 0-5% by volume.

[0134] According to one embodiment of this disclosure, the method further includes: mixing the first solid product obtained in step S3 with carbonate by ball milling for 20-40 hours; specifically, the carbonate includes alkali metal carbonate and / or alkaline earth metal carbonate, preferably including one or more of potassium carbonate, magnesium carbonate and calcium carbonate; the weight ratio of the carbonate to the carrier, calculated by metal element, is (0.1-10):(50-90), preferably (0.3-2):(55-83).

[0135] According to one embodiment of this disclosure, the method further includes: reducing the second solid product obtained by ball milling; the reduction treatment includes: contacting the second solid product with hydrogen gas at a temperature of 300-600°C, a hydrogen gas pressure of 0.5-5 MPa, and a time of 3-6 hours.

[0136] This third aspect of the disclosure provides a catalyst prepared using the method described in the second aspect of the disclosure. This catalyst has the same characteristics as the catalyst for hydrodenitrogenation of light distillate oils described in the first aspect of the disclosure, and will not be repeated here.

[0137] The fourth aspect of this disclosure provides a method for hydrodenitrification of light distillate oil, the method comprising contacting the light distillate oil with a catalyst to carry out a hydrodenitrification reaction, the catalyst comprising the catalyst described in the first or third aspect of this disclosure.

[0138] In this disclosure, the hydrodenitrification reaction can be carried out in a fixed-bed reactor.

[0139] According to one embodiment of this disclosure, the conditions for the hydrodenitrification reaction include: a temperature of 100-400°C, a pressure of 0.2-20 MPa, and a mass hourly space velocity of 0.1-10 h⁻¹. -1 The hydrogen-to-oil ratio is 200-600; preferably, the temperature is 150-350℃, the pressure is 0.5-15MPa, and the mass hourly space velocity is 0.2-3h. -1 The hydrogen-to-oil ratio is 150-550.

[0140] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way.

[0141] All raw materials used in the examples were obtained through commercial purchases and, unless otherwise specified, were of analytical grade.

[0142] The instrument used for XRD testing was the RIGAKU TTR-3.

[0143] Example 1

[0144] Catalyst A was prepared using the following steps:

[0145] (1) Silicon oxide was contacted with an aqueous solution of ammonium molybdate for a first impregnation. The first impregnation method was an equal volume impregnation method, the time was 1 h, and the temperature was 70 °C. The impregnated solid was dried at 120 °C for 12 h, and then calcined at 550 °C for 4 h to obtain the first product.

[0146] (2) The first product was heated to 300°C in a mixed atmosphere of methane and hydrogen at a heating rate of 10°C / min, and then heated to 800°C at a heating rate of 0.5°C / min. The mixture was carbonized at a constant temperature for 2 hours to obtain the second product. The content of ethane in the mixed atmosphere was 20% by volume.

[0147] (3) Passivate the second product in a mixed atmosphere of helium and oxygen for 2 hours, wherein the oxygen content in the mixed atmosphere is 1% by volume.

[0148] (4) The solid obtained in step (3) is contacted with an ethanol solution of cobalt naphthenate for a third impregnation. The third impregnation method is the equal volume impregnation method, the time is 1 h, and the temperature is 70 °C. The impregnated solid is dried at 120 °C for 12 h in an inert atmosphere (nitrogen atmosphere), and then calcined at 500 °C for 6 h to obtain the third product.

[0149] (5) The third product was contacted with an ethanol solution of bismuth acetate for a fourth impregnation. The fourth impregnation method was an equal volume impregnation method, the time was 1 h, and the temperature was 70 °C. The impregnated solid was dried at 120 °C for 12 h in an inert atmosphere (nitrogen atmosphere) and then calcined at 500 °C for 6 h to obtain catalyst A. The parameters of the catalyst are listed in Table 1. By XRD analysis, molybdenum was in the form of carbide.

[0150] The weight ratios of silicon oxide, the first metal source (based on metal elements), the second metal source (based on metal elements), and the third metal source (based on metal elements) are shown in Appendix 1.

[0151] Example 2

[0152] Catalyst B was prepared using the following steps:

[0153] (1) Silicon oxide was first impregnated by contacting an aqueous solution of ammonium molybdate and ammonium metatungstate. The first impregnation method was equal volume impregnation, the time was 1 h, and the temperature was 70 °C. The impregnated solid was dried at 120 °C for 12 h and then calcined at 550 °C for 4 h to obtain the first product.

[0154] (2) The first product was heated to 300°C in a mixed atmosphere of methane and hydrogen at a heating rate of 10°C / min, and then heated to 800°C at a heating rate of 0.5°C / min. The mixture was carbonized at a constant temperature for 2 hours to obtain the second product. The content of ethane in the mixed atmosphere was 20% by volume.

[0155] (3) Passivate the second product in a mixed atmosphere of helium and oxygen for 2 hours, wherein the oxygen content in the mixed atmosphere is 1% by volume.

[0156] (4) The solid obtained in step (3) is contacted with an ethanol solution of cobalt naphthenate for a third impregnation. The third impregnation method is the equal volume impregnation method, the time is 1 h, and the temperature is 70 °C. The impregnated solid is dried at 120 °C for 12 h in an inert atmosphere (nitrogen atmosphere), and then calcined at 500 °C for 6 h to obtain the third product.

[0157] (5) The third product was contacted with an ethanol solution of bismuth acetate for a fourth impregnation. The fourth impregnation method was an equal volume impregnation method, the time was 1 h, and the temperature was 70 °C. The impregnated solid was dried at 120 °C for 12 h in an inert atmosphere (nitrogen atmosphere) and then calcined at 500 °C for 6 h to obtain catalyst B. The parameters of the catalyst are listed in Table 1. XRD analysis showed that tungsten and molybdenum were both in the form of carbides.

[0158] The weight ratios of silicon oxide, the first metal source (based on metal elements), the second metal source (based on metal elements), and the third metal source (based on metal elements) are shown in Appendix 1.

[0159] Example 3

[0160] Catalyst C was prepared using the following steps:

[0161] (1) Silicon oxide was first impregnated by contacting an aqueous solution of ammonium molybdate and ammonium metatungstate. The first impregnation method was equal volume impregnation, the time was 1 h, and the temperature was 70 °C. The impregnated solid was dried at 120 °C for 12 h and then calcined at 550 °C for 4 h to obtain the first product.

[0162] (2) The first product was heated to 300°C in a mixed atmosphere of methane and hydrogen at a heating rate of 10°C / min, and then heated to 800°C at a heating rate of 0.5°C / min. The mixture was carbonized at a constant temperature for 2 hours to obtain the second product. The content of ethane in the mixed atmosphere was 20% by volume.

[0163] (3) Passivate the second product in a mixed atmosphere of helium and oxygen for 2 hours, wherein the oxygen content in the mixed atmosphere is 1% by volume.

[0164] (4) The solid obtained in step (3) is contacted with an ethanol solution of ferric acetate for a third impregnation. The third impregnation method is an equal volume impregnation method, the time is 1 h, and the temperature is 70 °C. The impregnated solid is dried at 120 °C for 12 h under an inert atmosphere (nitrogen atmosphere), and then calcined at 500 °C for 6 h to obtain the third product.

[0165] (5) The third product was contacted with an ethanol solution of antimony acetate for a fourth impregnation. The fourth impregnation method was an equal volume impregnation method, the time was 1 h, and the temperature was 70 °C. The impregnated solid was dried at 120 °C for 12 h in an inert atmosphere (nitrogen atmosphere) and then calcined at 500 °C for 6 h to obtain catalyst C. The parameters of the catalyst are listed in Table 1. XRD analysis showed that tungsten and molybdenum were both in the form of carbides.

[0166] The weight ratios of silicon oxide, the first metal source (based on metal elements), the second metal source (based on metal elements), and the third metal source (based on metal elements) are shown in Appendix 1.

[0167] Example 4

[0168] Catalyst D was prepared using the following steps:

[0169] (1) Silicon oxide was first impregnated by contacting an aqueous solution of ammonium molybdate and ammonium metatungstate. The first impregnation method was equal volume impregnation, the time was 1 h, and the temperature was 70 °C. The impregnated solid was dried at 120 °C for 12 h and then calcined at 550 °C for 4 h to obtain the first product.

[0170] (2) The first product was heated to 300°C in a mixed atmosphere of methane and hydrogen at a heating rate of 10°C / min, and then heated to 800°C at a heating rate of 0.5°C / min. The mixture was carbonized at a constant temperature for 2 hours to obtain the second product. The content of ethane in the mixed atmosphere was 20% by volume.

[0171] (3) Passivate the second product in a mixed atmosphere of helium and oxygen for 2 hours, wherein the oxygen content in the mixed atmosphere is 1% by volume.

[0172] (4) The solid obtained in step (3) is contacted with an ethanol solution of ferric acetate for a third impregnation. The third impregnation method is an equal volume impregnation method, the time is 1 h, and the temperature is 70 °C. The impregnated solid is dried at 120 °C for 12 h under an inert atmosphere (nitrogen atmosphere), and then calcined at 500 °C for 6 h to obtain the third product.

[0173] (5) The third product is contacted with an ethanol solution of antimony acetate for a fourth impregnation. The fourth impregnation method is the equal volume impregnation method, the time is 1 hour, and the temperature is 70°C. The impregnated solid is dried at 120°C for 12 hours under an inert atmosphere (nitrogen atmosphere), and then calcined at 500°C for 6 hours.

[0174] (6) The solid product obtained by calcination in step (5) was mixed with potassium carbonate by ball milling for 25 h to obtain catalyst D. The parameters of the catalyst are listed in Table 1. XRD analysis showed that tungsten and molybdenum were both in carbide form.

[0175] The weight ratios of silicon dioxide, the first metal source (calculated as metal element), the second metal source (calculated as metal element), and the third metal source (calculated as metal element) are shown in Appendix 1; the weight ratios of potassium carbonate (calculated as metal element) and the solid product in step (6) are shown in Appendix 1.

[0176] Example 5

[0177] Catalyst E was prepared using the following steps.

[0178] (1) Silicon oxide is contacted with an aqueous solution of ammonium metatungstate for a first impregnation. The first impregnation method is the equal volume impregnation method, the time is 1 hour, and the temperature is 70°C. The impregnated solid is dried at 120°C for 12 hours and then calcined at 550°C for 4 hours to obtain the first product.

[0179] (2) The first product was heated to 300°C in a mixed atmosphere of methane and hydrogen at a heating rate of 10°C / min, and then heated to 800°C at a heating rate of 0.5°C / min. The mixture was carbonized at a constant temperature for 2 hours to obtain the second product. The content of ethane in the mixed atmosphere was 20% by volume.

[0180] (3) Passivate the second product in a mixed atmosphere of helium and oxygen for 2 hours, wherein the oxygen content in the mixed atmosphere is 1% by volume.

[0181] (4) The solid obtained in step (3) is contacted with a methanol solution of nickel naphthenate for a third impregnation. The third impregnation method is the equal volume impregnation method, the time is 1 h, and the temperature is 70 °C. The impregnated solid is dried at 120 °C for 12 h in an inert atmosphere (nitrogen atmosphere), and then calcined at 500 °C for 6 h to obtain the third product.

[0182] (5) The third product was contacted with an ethanol solution of bismuth acetate for a fourth impregnation. The fourth impregnation method was an equal volume impregnation method, the time was 1 h, and the temperature was 70 °C. The impregnated solid was dried at 120 °C for 12 h in an inert atmosphere (nitrogen atmosphere) and then calcined at 500 °C for 6 h to obtain catalyst E. The parameters of the catalyst are listed in Table 1. XRD analysis showed that tungsten was in the form of carbide.

[0183] The weight ratios of silicon oxide, the first metal source (based on metal elements), the second metal source (based on metal elements), and the third metal source (based on metal elements) are shown in Appendix 1.

[0184] Example 6

[0185] Catalyst F was prepared using the following steps:

[0186] (1) Alumina was contacted with an aqueous solution of ammonium paratungstate for the first impregnation. The first impregnation method was the equal volume impregnation method, the time was 1 h, and the temperature was 70 °C. The impregnated solid was dried at 110 °C for 24 h, and then calcined at 400 °C for 3 h to obtain the first product.

[0187] (2) The first product was heated to 500°C at a heating rate of 5°C / min in a mixed atmosphere of methane and hydrogen, and then heated to 750°C at a heating rate of 10°C / min. The product was carbonized at a constant temperature for 2 hours to obtain the second product. The content of ethane in the mixed atmosphere was 12% by volume.

[0188] (3) The second product was passivated for 5 hours in a mixed atmosphere of helium and oxygen, with the oxygen content in the mixed atmosphere being 0.5% by volume.

[0189] (4) The solid obtained in step (3) is contacted with a toluene solution of nickel naphthenate for a third impregnation. The third impregnation method is the equal volume impregnation method, the time is 1 h, and the temperature is 70 °C. The impregnated solid is dried at 110 °C for 24 h in an inert atmosphere (helium atmosphere), and then calcined at 450 °C for 10 h to obtain the third product.

[0190] (5) The third product was contacted with a cyclohexane solution of antimony acetate for a fourth impregnation. The fourth impregnation method was an equal volume impregnation method, the time was 1 h, and the temperature was 70 °C. The impregnated solid was dried at 110 °C for 14 h in an inert atmosphere (helium atmosphere) and then calcined at 450 °C for 10 h to obtain catalyst F. The parameters of the catalyst are listed in Table 1. XRD analysis showed that the tungsten was in the form of carbides.

[0191] The weight ratios of alumina, the first metal source (based on metal element), the second metal source (based on metal element), and the third metal source (based on metal element) are shown in Appendix Table 1.

[0192] Example 7

[0193] Catalyst G was prepared using the following steps:

[0194] (1) Silicon oxide was contacted with an aqueous solution of ammonium molybdate for a first impregnation. The first impregnation method was an equal volume impregnation method, the time was 1 h, and the temperature was 70 °C. The impregnated solid was dried at 120 °C for 12 h, and then calcined at 550 °C for 4 h to obtain the first product.

[0195] (2) The first product was heated to 300°C in a mixed atmosphere of methane and hydrogen at a heating rate of 10°C / min, and then heated to 800°C at a heating rate of 0.5°C / min. The mixture was carbonized at a constant temperature for 2 hours to obtain the second product. The content of ethane in the mixed atmosphere was 20% by volume.

[0196] (3) The second product was passivated in a mixed atmosphere of helium and oxygen for 2 hours, with the oxygen content in the mixed atmosphere being 1% by volume.

[0197] (4) The solid obtained in step (3) was contacted with an ethanol solution containing cobalt naphthenate and bismuth acetate for a second impregnation. The second impregnation method was an equal volume impregnation method, the time was 1 h, and the temperature was 70 °C. The impregnated solid was dried at 120 °C for 12 h under an inert atmosphere (nitrogen atmosphere) and then calcined at 500 °C for 6 h to obtain catalyst G. The parameters of the catalyst are listed in Table 1. By XRD analysis, molybdenum was in the form of carbide.

[0198] The weight ratios of silicon oxide, the first metal source (based on metal elements), the second metal source (based on metal elements), and the third metal source (based on metal elements) are shown in Appendix 1.

[0199] Example 8

[0200] Catalyst H was prepared using the following steps:

[0201] (1) Silicon oxide was contacted with an aqueous solution of ammonium molybdate for a first impregnation. The first impregnation method was an equal volume impregnation method, the time was 1 h, and the temperature was 70 °C. The impregnated solid was dried at 120 °C for 12 h, and then calcined at 550 °C for 4 h to obtain the first product.

[0202] (2) The first product was heated to 300°C in a mixed atmosphere of methane and hydrogen at a heating rate of 10°C / min, and then heated to 800°C at a heating rate of 0.5°C / min. The mixture was carbonized at a constant temperature for 2 hours to obtain the second product. The content of ethane in the mixed atmosphere was 20% by volume.

[0203] (3) The second product was passivated in a mixed atmosphere of helium and oxygen for 2 hours, with the oxygen content in the mixed atmosphere being 1% by volume.

[0204] (4) The solid obtained in step (3) is contacted with an ethanol solution of bismuth acetate for a fifth impregnation. The fifth impregnation method is the equal volume impregnation method, the time is 1 h, and the temperature is 70 °C. The impregnated solid is dried at 120 °C for 12 h under an inert atmosphere (nitrogen atmosphere), and then calcined at 500 °C for 6 h to obtain the fourth product.

[0205] (5) The fourth product was contacted with an ethanol solution of cobalt naphthenate for a third impregnation. The third impregnation method was an equal volume impregnation method, the time was 1 h, and the temperature was 70 °C. The impregnated solid was dried at 120 °C for 12 h under an inert atmosphere (nitrogen atmosphere) and then calcined at 500 °C for 6 h to obtain catalyst H. The parameters of the catalyst are listed in Table 1. By XRD analysis, molybdenum was in the form of carbide.

[0206] The weight ratios of silicon oxide, the first metal source (based on metal elements), the second metal source (based on metal elements), and the third metal source (based on metal elements) are shown in Appendix 1.

[0207] Comparative Example 1

[0208] Catalyst X-1 was prepared using the method described in Example 2, except that steps (4) and (5) were omitted. The parameters of the catalyst are listed in Table 1. XRD analysis showed that both tungsten and molybdenum were in carbide form.

[0209] Comparative Example 2

[0210] Catalyst X-2 was prepared using the method described in Example 2, except that step (4) was omitted. The parameters of the catalyst are listed in Table 1. XRD analysis showed that both tungsten and molybdenum were in carbide form.

[0211] Comparative Example 3

[0212] Catalyst X-3 was prepared using the method described in Example 2, except that step (5) was omitted. The parameters of the catalyst are listed in Table 1. XRD analysis showed that both tungsten and molybdenum were in carbide form.

[0213] Test case

[0214] A fixed-bed reactor was used to perform hydrodenitrification on straight-run diesel (Yanshan straight-run diesel, properties listed in Table 2). Specifically, 5g of catalyst was loaded into a reaction tube, with both ends filled with quartz sand. Initially, reduction was carried out under a 1MPa H2 atmosphere at 520℃ for 4 hours. After reduction, the temperature was lowered to a set point of 240℃, and the system pressure was adjusted to 8MPa, the hydrogen-to-oil ratio to 800, and the mass hourly space velocity (HHSV) to 1 h⁻¹. -1 After the reaction was completed, the products were collected and analyzed. The results are listed in Table 3.

[0215] Table 1

[0216]

[0217] In Table 1, W represents the tungsten carbide content as a metal element relative to the total weight of the catalyst;

[0218] Mo represents the content of molybdenum carbide as a metallic element relative to the total weight of the catalyst;

[0219] Fe represents the content of the Fe component as a metallic element relative to the total weight of the catalyst;

[0220] Co represents the content of the Co component as a metal element relative to the total weight of the catalyst;

[0221] Ni represents the content of the Ni component as a metallic element relative to the total weight of the catalyst;

[0222] Sb represents the content of the Sb component as a metal element relative to the total weight of the catalyst;

[0223] Bi represents the content of the Bi component as a metal element relative to the total weight of the catalyst;

[0224] Carbonate content refers to the amount of carbonate relative to the total weight of the catalyst, expressed as a metal element.

[0225] The term "support" refers to the amount of support relative to the total weight of the catalyst.

[0226] The contents of the above-mentioned metal components and carbonates were obtained by ICP analysis using a PerkinElmer 7300DV instrument.

[0227] The amount of each component in the catalyst is the amount of feed.

[0228] Table 2

[0229] project numerical values Organic nitrogen content / ppmw 320 Organic sulfur content / ppmw 50 Aromatic content / weight % 25 Density / g / mL 0.820 Final boiling point / °C 250

[0230] Table 3

[0231]

[0232]

[0233] Table 3 shows the test method for the organic nitrogen content in the product, which is based on the Chinese petrochemical industry standard SH / T0704 (referencing ASTM D5762). The sample is delivered to a high-temperature combustion tube containing oxygen via a boat-type sample introduction system. Nitrogen is oxidized to nitric oxide in an oxygen atmosphere. Nitric oxide reacts with ozone to form excited-state nitrogen dioxide, which emits light during decay. The emitted light signal is detected by a photomultiplier tube to calculate the nitrogen content. The instrument used is an ANTEK MultiTek nitrogen analyzer (USA).

[0234] Based on the above data, it can be seen that the catalyst disclosed herein can achieve a good hydrodenitrogenation effect when used in the hydrodenitrogenation reaction of light distillate oil.

[0235] The preferred embodiments of this disclosure have been described in detail above. However, this disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this disclosure, various simple modifications can be made to the technical solutions of this disclosure, and these simple modifications all fall within the protection scope of this disclosure.

[0236] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, this disclosure will not describe the various possible combinations separately.

[0237] Furthermore, various different embodiments of this disclosure can be combined in any way, as long as they do not violate the spirit of this disclosure, they should also be regarded as the content disclosed in this disclosure.

Claims

1. A method for hydrodenitrification of light distillate oil, the method comprising contacting the light distillate oil with a catalyst to carry out a hydrodenitrification reaction, the catalyst comprising a support and a carbide of a first metal, a second metal active component and a third metal active component supported on the support; The first metal includes W and / or Mo; The second metal active component includes one or more of Fe, Co, and Ni components; The third metal active component includes Sb component and / or Bi component; Relative to the total weight of the catalyst, the content of the first metal carbide is 8-40% by weight, the content of the second metal active component is 1-15% by weight, and the content of the third metal active component is 0.1-5% by weight.

2. The method according to claim 1, wherein, The carrier includes one or more of alumina, silica, zirconium oxide, Y-type molecular sieve and Beta molecular sieve.

3. The method according to claim 1, wherein, The carrier is alumina and / or silicon oxide.

4. The method according to claim 1, wherein, The content of the support is 50-90% by weight relative to the total weight of the catalyst.

5. The method according to claim 1, wherein, The catalyst also contains carbonates, including alkali metal carbonates and / or alkaline earth metal carbonates.

6. The method according to claim 5, wherein, The carbonates include one or more of potassium carbonate, magnesium carbonate, and calcium carbonate.

7. The method according to claim 5, wherein, The content of the carbonate, in terms of metal elements, is 0.1-10% relative to the total weight of the catalyst.

8. The method according to claim 5, wherein, The content of the carbonate, in terms of metal elements, is 0.3-2% by weight relative to the total weight of the catalyst.

9. The method according to claim 1, wherein, In the catalyst, the second and third metal active components exist in a metallic state.

10. The method according to claim 1, wherein, The light distillate oil is a distillate oil with a final boiling point below 360°C.

11. The method according to claim 1, wherein, The light distillate oil is one or more of naphtha, catalytic gasoline, diesel, and jet fuel.

12. The method according to claim 1, wherein, The organic nitrogen content of the light distillate oil is 20-500 ppmw.

13. The method according to claim 1, wherein, The method for preparing the catalyst includes the following steps: S1. The carrier is first impregnated by contacting an impregnation solution containing a first metal source, and then subjected to a first heat treatment to obtain a first product; S2. Carbonize the first product in a carbon-containing reducing atmosphere to obtain the second product; S3. Impregnate the second product with the second metal active component and the third metal active component; The first metal element in the first metal source includes W and / or Mo; The second metal active component includes one or more of Fe, Co, and Ni components; The third metal active component includes Sb and / or Bi components.

14. The method according to claim 13, wherein, Step S3 includes: A. The second product is contacted with an impregnation solution containing a second metal source and a third metal source for a second impregnation, and then subjected to a second heat treatment under an inert atmosphere; or, Step S3 includes the following steps: (1) The second product is contacted with an impregnation solution containing a second metal source for a third impregnation, and then subjected to a third heat treatment under an inert atmosphere to obtain a third product; (2) The third product is contacted with an impregnation solution containing a third metal source for a fourth impregnation, and then subjected to a fourth heat treatment under an inert atmosphere; or, Step S3 includes the following steps: a. The second product is contacted with an impregnation solution containing a third metal source for a fifth impregnation, and then subjected to a fifth heat treatment under an inert atmosphere to obtain a fourth product; b. The fourth product is contacted with an impregnation solution containing a second metal source for a sixth impregnation, and then subjected to a sixth heat treatment under an inert atmosphere. The second metal element in the second metal source includes one or more of Fe, Co and Ni; The third metal element in the third metal source includes Sb and / or Bi.

15. The method according to claim 14, wherein, The impregnation solution containing the second metal source and the third metal source is an oil-soluble impregnation solution, and the solvent in the impregnation solution containing the second metal source and the third metal source includes one or more of methanol, ethanol, cyclohexane and toluene. The impregnation solution containing the second metal source is an oil-soluble impregnation solution, and the solvent in the impregnation solution containing the second metal source includes one or more of methanol, ethanol, cyclohexane and toluene. The impregnation solution containing the third metal source is an oil-soluble impregnation solution, and the solvent in the impregnation solution containing the second metal source includes one or more of methanol, ethanol, cyclohexane and toluene. The second metal source includes one or more of the following: organometallic compounds of the second metal element, organoacid salts of the second metal element, and carbonyl compounds of the second metal element; The third metal source includes organic acid salts of a third metal element and / or organometallic compounds of a third metal element.

16. The method of claim 14, wherein, The second metal source includes one or more of cobalt naphthenate, iron acetate, nickel naphthenate, cobalt carbonyl, iron carbonyl, and nickel carbonyl.

17. The method of claim 14, wherein, The third metal source includes one or more of bismuth acetate, bismuth citrate, antimony acetate, antimony isopropoxy, and antimony glycolate.

18. The method according to claim 14, wherein, The first, second, third, fourth, fifth, and sixth impregnation methods are equal-volume impregnation methods, and the conditions for the equal-volume impregnation method include: a time of 1-10 hours and a temperature of 60-140°C.

19. The method of claim 14, wherein, The conditions for the first heat treatment include: a time of 1-10 hours and a temperature of 400-700℃; The conditions for the second heat treatment include: a time of 1-10 hours and a temperature of 400-700℃; The conditions for the third heat treatment include: a time of 1-10 h and a temperature of 400-700℃. The conditions for the fourth heat treatment include: a time of 1-10 h and a temperature of 400-700℃. The conditions for the fifth heat treatment include: a time of 1-10 h and a temperature of 400-700℃. The conditions for the sixth heat treatment include: a time of 1-10 h and a temperature of 400-700℃.

20. The method of claim 14, wherein, The weight ratio of the carrier, the first metal source (based on metal elements), the second metal source (based on metal elements), and the third metal source (based on metal elements) is (50-90):(8-40):(1-15):(0.1-5).

21. The method according to claim 14, wherein, Step S1 further includes: drying the first impregnated solid at 60-140°C for 1-24 hours, and then performing the first heat treatment; Step A further includes: drying the second impregnated solid at 60-140°C for 1-24 hours under an inert atmosphere, and then performing the second heat treatment; Step (1) further includes: drying the solid after the third impregnation at 60-140°C for 1-24 hours under an inert atmosphere, and then performing the third heat treatment; Step (2) further includes: drying the solid after the fourth impregnation at 60-140°C for 1-24 hours under an inert atmosphere, and then performing the fourth heat treatment; Step a further includes: drying the solid after the fifth impregnation at 60-140°C for 1-24 hours under an inert atmosphere, and then performing the fifth heat treatment; Step b further includes: drying the solid after the sixth impregnation at 60-140°C for 1-24 hours under an inert atmosphere, and then performing the sixth heat treatment.

22. The method according to claim 13, wherein, The carrier includes one or more of alumina, silica, zirconium oxide, Y-type molecular sieve and Beta molecular sieve; The first metal source includes a soluble salt of a first metal element.

23. The method according to claim 13, wherein, The first metal source includes one or more of ammonium molybdate, ammonium metatungstate, and ammonium paratungstate.

24. The method according to claim 13, wherein, The carrier is alumina and / or silicon oxide.

25. The method according to claim 13, wherein, In step S2, the carbon-containing reducing atmosphere contains carbon-containing compounds; The carbon-containing compounds include one or more of alkanes having 2-5 carbon atoms and alkenes having 2-5 carbon atoms; In the carbon-containing reducing atmosphere, the content of the carbon-containing compound is 1-30% by volume.

26. The method of claim 25, wherein, The carbon-containing compound includes one or more of ethane, ethylene, n-propane, propylene, n-butane, 1-butene, and 2-butene.

27. The method according to claim 13, wherein, The carbon-containing reducing atmosphere contains hydrogen.

28. The method according to claim 13, wherein, The carbonization conditions include: heating to 100-500℃ at a heating rate of 1-20℃ / min, then heating to 600-800℃ at a heating rate of 0.1-1℃ / min, and maintaining the temperature for carbonization for 1-10 hours.

29. The method according to claim 13, wherein, The method further includes: passivating the second product obtained in step S2 under an inert atmosphere for 1-10 hours before proceeding to step S3; In the inert atmosphere, the oxygen content is 0-5% by volume.

30. The method according to claim 13, wherein, The method further includes: mixing the first solid product obtained in step S3 with carbonate by ball milling for 20-40 hours.

31. The method according to claim 30, wherein, The carbonates include alkali metal carbonates and / or alkaline earth metal carbonates.

32. The method according to claim 30, wherein, The carbonates include one or more of potassium carbonate, magnesium carbonate, and calcium carbonate.

33. The method according to claim 30, wherein, The weight ratio of the carbonate to the carrier, calculated by metal element, is (0.1-10):(50-90).

34. The method according to claim 30, wherein, The method further includes: reducing the second solid product obtained by ball milling; The reduction process includes contacting the second solid product with hydrogen gas.

35. The method according to claim 1, wherein, The light distillate oil is a distillate oil with a final boiling point below 360°C.

36. The method according to claim 1, wherein, The light distillate oil is one or more of naphtha, catalytic gasoline, diesel, and jet fuel.

37. The method according to claim 1, wherein, The organic nitrogen content of the light distillate oil is 20-500 ppmw.

38. The method according to claim 1, wherein, The conditions for the hydrodenitrification reaction include: a temperature of 100-400℃, a pressure of 0.2-20 MPa, and a mass hourly space velocity of 0.1-10 h⁻¹. -1 The hydrogen-to-oil volume ratio is 100-1000.

39. The method according to claim 1, wherein, The conditions for the hydrogenation denitrification reaction include: a temperature of 150-350℃, a pressure of 0.5-15 MPa, and a mass hourly space velocity of 0.2-3 h⁻¹. -1 The hydrogen-to-oil ratio is 200-600.

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