A shale oil hydrotreating method and treatment system

Abstract

The present application relates to a kind of shale oil hydroprocessing method and processing system.The method comprises the following steps: S1, shale oil and hydrogen enter first reactor and contact with hydrogen protective agent and first hydrofining agent, carry out hydrofining reaction, obtain first reaction product;S2, the first reaction product is heated after passing through external heating device and enters second reactor, sequentially contact with second hydrofining agent, hydrocracking agent and hydrofining deep agent and carry out reaction, obtain second reaction product;S3, the second reaction product enters gas-liquid separator and carries out gas-liquid separation, obtain low-nitrogen hydrogenation shale oil.Can effectively avoid olefin, diolefin condensation coking problem, simultaneously can realize shale oil deep denitrification desulfurization at high temperature.

Description

Technical Field

[0001] This invention relates to the field of shale oil hydrotreating, and more specifically, to a shale oil hydrotreating method and system. Background Technology

[0002] Shale oil is a liquid product obtained from the dry distillation and pyrolysis of oil shale seed oil, and its composition differs from that of crude oil. Shale oil contains a high amount of nitrogen compounds and a large amount of unsaturated hydrocarbons, such as olefins and dienes. Unsaturated hydrocarbons and non-hydrocarbon compounds are the main reasons for the increased gum content, decreased stability, and darker color of shale oil. Currently, shale oil can be blended for use as marine fuel oil, or it can be processed through hydrotreating and other processes to obtain light oil products such as gasoline and diesel.

[0003] Hydrotreating is a process of upgrading petroleum products by reacting them with hydrogen under the catalytic action of a catalyst. It mainly includes hydrogenation reactions such as desulfurization, denitrification, deoxygenation, olefin saturation, aromatic saturation, and demetallization and removal of asphalt impurities. Current hydrotreating technologies typically involve heating the feedstock and hydrogen together in a furnace to the reaction temperature, usually around 280–430°C, before introducing them into the hydrotreating reactor where the hydrogenation reaction takes place within the catalyst bed. Conventional hydrotreating processes are suitable for natural petroleum and feedstocks with low olefin content.

[0004] Because shale oil contains a significant amount of unsaturated hydrocarbons, when conventional hydrotreating processes are used to process shale oil fractions, especially when the temperature inside the heater or heat exchanger lines reaches 200–300°C or higher, dienes rapidly undergo condensation reactions, easily leading to coking in the heater or heat exchanger lines. As the unit operates, the pressure differential in the heater or heat exchanger lines gradually increases until it blocks them. Simultaneously, the catalyst bed in the reactor also experiences a gradual increase in pressure differential due to the accumulation of coke particles, thus affecting the long-term stable operation of the unit.

[0005] Furthermore, the reaction chemistry of shale oil hydrotreating processes is quite complex. On the one hand, the hydrogenation reactions of olefins and dienes occur relatively easily compared to hydrodesulfurization and hydronitrogenation. Therefore, olefins and dienes with high content in shale oil can be removed at relatively low reaction temperatures. On the other hand, shale oil has high sulfur and nitrogen content, especially nitrogen content, which is much higher than that of conventional petroleum fractions, requiring higher reaction temperatures for effective denitrification and desulfurization. However, at higher reaction temperatures, the aromatic ring structures of nitrogen- and sulfur-containing compounds are limited by thermodynamic equilibrium during hydrogenation saturation, thus significantly restricting denitrification and desulfurization of shale oil. Therefore, it is necessary to rationally optimize the reaction chemistry process in shale oil hydrotreating.

[0006] US4022682 discloses a method for two-stage continuous catalytic hydroresorption of shale oil, after which the hydrotreated shale oil can be used as feedstock for riser catalytic cracking. The method is recommended under optimized process conditions (reaction temperature 371–427 °C, hydrogen partial pressure 8.3–12.4 MPa, volume hourly space velocity 0.5–2.0 h⁻¹). -1 In this method, with a hydrogen-to-oil volume ratio of 450–1260, shale oil and hydrogen first enter the first reactor to hydrogenate and saturate olefins and remove some sulfur and nitrogen. The effluent undergoes gas-liquid separation to eliminate some of the ammonia's influence on subsequent denitrification reactions. The liquid then enters the second reactor for further denitrification, reducing the nitrogen content of the liquid product to less than 2000–3000 ppm to meet the feed requirements for catalytic cracking. However, this method involves a relatively high reaction temperature above 315°C. At this temperature, the high olefin and diene content in the shale oil is prone to condensation, leading to problems such as coking in the furnace tubes, which is detrimental to the stable operation of the unit.

[0007] CN103773460A discloses a one-stage series hydrorefining method for shale oil diesel fractions. This method proposes that the high-temperature hydrotreated oil can be partially recycled and directly mixed and heated with the shale oil feed and hydrogen. After heating to 150–250°C, it enters the first reactor, where it mainly undergoes reactions involving saturated olefins and dienes. The effluent enters the second reactor, where desulfurization and denitrification hydrorefining reactions occur at 350–390°C. This method avoids the problem of diene condensation and coking during shale oil heating or heat exchange. However, because the temperature of the effluent from the first reactor is affected by both the feed contact heat exchange effect and the degree of reaction in the first reactor, the reaction temperature in the second reactor is difficult to adjust, significantly impacting the overall denitrification effect.

[0008] Based on the above analysis, US4022682 and CN103773460A patents proposed methods for hydrotreating shale oil from the perspectives of high-temperature denitrification and olefin saturation, respectively. However, the reaction chemistry processes in the hydrotreating of shale oil still need further optimization. Summary of the Invention

[0009] This invention provides a shale oil hydrotreating method and system that can effectively avoid the problem of olefin and diene condensation and coking, and can achieve deep denitrification of shale oil at high temperature, thereby providing feedstock for catalytic cracking or catalytic pyrolysis.

[0010] To achieve the above objectives, a first aspect of the present invention provides a method for hydrotreating shale oil, comprising the following steps:

[0011] S1. Shale oil and hydrogen are introduced into the first reactor and brought into contact with the hydrogenation protective agent and the first hydrogenation refining agent to carry out the hydrogenation refining reaction and obtain the first reaction product.

[0012] S2. The first reaction product is heated by an external heating device and then enters the second reactor, where it is sequentially reacted with the second hydrogenated refining agent, the hydrogenated cracking agent, and the hydrogenated deep refining agent to obtain the second reaction product.

[0013] S3. The second reaction product is fed into a gas-liquid separator for gas-liquid separation to obtain low-nitrogen hydrogenated shale oil.

[0014] Optionally, in step S1, the first hydrogenated refining agent includes a first carrier and a first active component loaded on the first carrier;

[0015] Optionally, the first carrier is selected from one or more of alumina and amorphous silica-alumina; preferably alumina; the first active component includes a first metal element combination, which is selected from one or more of Ni, Co, Mo and W; preferably, the content of the first active component in the form of metal oxide is 15-55% by weight, preferably 20-40% by weight, based on the total weight of the first hydrogenated refining agent.

[0016] Preferably, the volume ratio of the hydrogenation protective agent to the first hydrogenation refining agent is (0.01-0.5):1, more preferably (0.05-0.3):1.

[0017] Optionally, in step S1, the reaction conditions in the first reactor include: an inlet hydrogen pressure of 3.0–15.0 MPa, preferably 6.0–12.0 MPa; an inlet hydrogen-to-oil volume ratio of 150–1500, preferably 800–1200; a reaction temperature of 140–310°C, preferably 150–240°C; and a reaction rate of 0.5–5 h⁻¹. -1 The volume hourly space velocity (VHSV) passing through the first reactor is preferably 1–3 h⁻¹. -1 Volumetric hourly space velocity passes through the first reactor.

[0018] Optionally, in step S2, the second reactor is provided with a connected aromatic saturation zone, a cracking and upgrading zone and a deep refining zone in sequence along the material flow direction; the first reaction product is introduced into the aromatic saturation zone;

[0019] The aromatic saturation zone includes the second hydrogenation refining agent; the cracking and upgrading zone includes the hydrocracking agent; the deep refining zone includes the hydrogenation deep refining agent;

[0020] Preferably, the volume ratio of catalysts in the aromatic saturation zone, cracking and upgrading zone and deep refining zone of the second reactor is 1:(0.1-2.5):(0.01-0.5); more preferably 1:(0.2-1.5):(0.05-0.2).

[0021] Optionally, in step S2, the second hydrogenated refining agent includes a second carrier and a second active component loaded on the second carrier;

[0022] The second carrier is selected from one or more of alumina and amorphous silica-alumina; preferably alumina; the second active component includes a second metal element combination, which is selected from one or more of Ni, Co, Mo and W; preferably, the content of the second active component in the form of metal oxide is 15-55% by weight based on the total weight of the second hydrogenated refining agent, preferably 20-40% by weight.

[0023] Optionally, the hydrocracking agent includes a third support and an acidic component; the third support is selected from one or more of alumina, amorphous silica-alumina, and silica-containing alumina; the acidic component is selected from one or more of Y-type molecular sieve and β-type molecular sieve; optionally, based on the total weight of the hydrocracking agent, the content of the acidic component is 5-60% by weight, preferably 10-35% by weight;

[0024] Optionally, the hydrogenated deep refining agent includes a fourth carrier and a third active component loaded on the fourth carrier;

[0025] The fourth carrier is selected from one or more of alumina and amorphous silica-alumina; preferably alumina; the third active component includes a third metal element, which is selected from one or more of Ni, Co, Mo and W; preferably, the content of the third active component in the form of metal oxide is 15-55% by weight, preferably 20-40% by weight, based on the total weight of the hydrogenated deep refining agent.

[0026] Optionally, in step S2, the reaction conditions in the second reactor include:

[0027] The reaction temperature in the aromatic saturated region is 280–380°C, preferably 300–360°C; the reaction hydrogen pressure is 3.0–15.0 MPa, preferably 6.0–12.0 MPa; and the hydrogen-to-oil volume ratio is 150–1500, preferably 800–1200.

[0028] The reaction temperature in the cracking and upgrading zone is 310–390°C, preferably 320–360°C;

[0029] The reaction temperature in the deep refining zone is 320–420°C, preferably 350–400°C;

[0030] Optionally, the reactants are reacted at a concentration of 0.3–2 h. -1 The volumetric hourly space velocity (VHSV) passing through the second reactor is preferably 0.5–1.5 h⁻¹. -1 Volumetric space velocity passes through the second reactor;

[0031] Optionally, the average temperature in the second reactor is 330–420°C, preferably 350–400°C;

[0032] Preferably, the external heating device is a heating furnace.

[0033] Optionally, the method includes:

[0034] The second reaction product is fed into a gas-liquid separator for gas-liquid separation to obtain gaseous and liquid phase materials.

[0035] After removing light hydrocarbons from the liquid phase material, low-nitrogen hydrogenated shale oil is obtained;

[0036] The gaseous material is processed sequentially by a circulating hydrogen purification and gas separation system to obtain purified circulating hydrogen.

[0037] The purified recycled hydrogen and fresh hydrogen are mixed as raw material hydrogen, and at least a portion of the raw material hydrogen is introduced into the first reactor along with the shale oil.

[0038] Optionally, the method further includes returning a portion of the purified recycled hydrogen as cold hydrogen to the bed space of the first reactor to control the temperature of the first reactor; and

[0039] A portion of the purified recycled hydrogen is returned as cold hydrogen to the bed space of the second reactor to control the temperature of the second reactor.

[0040] Preferably, a cold hydrogen tank is provided between the beds of the first reactor and between the beds of the second reactor, so that the cold hydrogen is returned to the cold hydrogen tank in the first reactor and / or the second reactor.

[0041] Optionally, the method further includes:

[0042] The raw material hydrogen gas used to be introduced into the first reactor first enters the first heat exchanger and undergoes the first heat exchange treatment with the first heat exchange medium.

[0043] The raw material hydrogen from the first heat exchanger is mixed with shale oil and then enters the second heat exchanger to undergo a second heat exchange treatment with the second heat exchange medium.

[0044] The mixture of raw material hydrogen and shale oil that has undergone the second heat exchange treatment is introduced into the first reactor; preferably, the temperature of the raw material hydrogen and shale oil mixture after the second heat exchange treatment is 130-260°C, more preferably 150-210°C.

[0045] The second heat exchange medium of the second heat exchanger includes a second reaction product from the second reactor; the first heat exchange medium of the first heat exchanger includes a second reaction product from the first heat exchanger that has undergone a first heat exchange treatment.

[0046] The second reaction product, which has undergone the first heat exchange treatment in the first heat exchanger, is introduced into the gas-liquid separator.

[0047] Optionally, the initial boiling point of the shale oil is any value between 80℃ and 240℃, and the final boiling point is any value between 300℃ and 450℃.

[0048] Optionally, the shale oil contains 10-40% by weight of unsaturated hydrocarbons, 5-25% by weight of aromatics, 0.2-1.5% by weight of nitrogen, and 0.05-1.0% by weight of sulfur.

[0049] The low-nitrogen hydrogenated shale oil has a nitrogen content of 0.0005–0.0200% by weight and a sulfur content of 0.0005–0.0100% by weight.

[0050] A second aspect of the present invention provides a shale oil hydrotreating system, the system comprising a first reactor, a second reactor, and a gas-liquid separator;

[0051] The first reactor includes a shale oil inlet, a hydrogen inlet, a first reaction product outlet, and a first catalyst layer; the first catalyst layer includes a hydrogenation protectant and a first hydrogenation refining agent; the first catalyst layer is configured as a single bed or multiple beds, and a cold hydrogen tank is provided between the beds of the first reactor;

[0052] The second reactor includes a second feedstock inlet, a second product outlet, and a second catalyst layer. The second catalyst layer, along the material flow direction, sequentially includes an aromatics saturation zone, a cracking and reforming zone, and a deep refining zone. The aromatics saturation zone is filled with a second hydrorefining agent, the cracking and reforming zone is filled with a hydrocracking agent, and the deep refining zone is filled with a deep hydrorefining agent. The second catalyst layer can be configured as a single-bed or multi-bed system, and a cold hydrogen tank is provided between the beds of the second reactor. The first feedstock inlet is located above the aromatics saturation zone, and the second product outlet is located at the bottom of the deep refining zone.

[0053] The second reactant inlet of the second reactor is connected to the first reactant outlet of the first reactor;

[0054] The gas-liquid separator includes a separation inlet, a gas phase outlet, and a liquid phase outlet; the separation inlet is connected to the second reaction product outlet of the second reactor.

[0055] Through the above technical solution, the present invention provides a shale oil hydrotreating method and system, which can perform low-temperature olefin and diene hydrosaturation treatment in a first reactor to increase the saturated hydrocarbon content in shale oil materials. The first reaction product is then further heated by an external heating device, which can flexibly adjust the inlet temperature of a second reactor. The first reaction product, having reached the reaction temperature of the second reactor, is then introduced into the second reactor, where it sequentially contacts a second hydrorefining agent, a hydrocracking agent, and a deep hydrorefining agent. This improves the treatment effect and allows for a better match between the reaction conditions and the reactions occurring when the reactants contact different treatment agents. This optimizes the shale oil hydrotreating method, effectively treating shale oil with high unsaturated hydrocarbon content, effectively avoiding olefin and diene condensation and coking problems, and improving the deep denitrification and desulfurization reaction effect while ensuring stable operation, thus also contributing to a longer operating cycle.

[0056] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0057] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the following detailed description to explain the invention, but do not constitute a limitation thereof. In the drawings:

[0058] Figure 1 This is an exemplary process flow diagram of the shale oil hydrotreating method and treatment system provided by the present invention.

[0059] Explanation of reference numerals in the attached figures

[0060] 01-Pipeline 02-Pipeline 03-Pipeline 04-Pipeline

[0061] 05-Pipeline 06-Pipeline 06-Pipeline 07-Pipeline

[0062] 08-Pipeline 09-Pipeline 010-Pipeline 011-Pipeline

[0063] 012-Pipeline 1-Second Heat Exchanger 2-First Reactor 3-Heating Furnace

[0064] 4-I-Aromatics Saturation Zone; 4-II-Cracking and Reforming Zone; 4-III-Deep Refining Zone; 5-First Heat Exchanger

[0065] 6-Gas-Liquid Separator Detailed Implementation

[0066] The following provides a detailed description of specific embodiments of the present invention. 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 the invention.

[0067] The first aspect of this invention provides a method for hydrotreating shale oil, comprising the following steps:

[0068] S1. Shale oil and hydrogen are introduced into the first reactor and brought into contact with the hydrogenation protective agent and the first hydrogenation refining agent to carry out the hydrogenation refining reaction and obtain the first reaction product.

[0069] S2. The first reaction product is heated by an external heating device and then enters the second reactor, where it is sequentially reacted with the second hydrogenated refining agent, the hydrogenated cracking agent, and the hydrogenated deep refining agent to obtain the second reaction product.

[0070] S3. The second reaction product is fed into a gas-liquid separator for gas-liquid separation to obtain low-nitrogen hydrogenated shale oil.

[0071] This invention provides a shale oil hydrotreating method that enables low-temperature hydrogenation saturation treatment of olefins and dienes in a first reactor to increase the saturated hydrocarbon content in the shale oil feedstock. The first reaction product is then further heated via an external heating device, which can flexibly adjust the inlet temperature of a second reactor. The first reaction product, having reached the reaction temperature of the second reactor, is then introduced into the second reactor, where it sequentially contacts a second hydrorefining agent, a hydrocracking agent, and a deep hydrorefining agent. This improves the treatment effect and allows for a better match between the reaction conditions and the reactions occurring when the reactants come into contact with different treatment agents. This optimizes the shale oil hydrotreating method, effectively treating shale oil with high unsaturated hydrocarbon content, effectively avoiding olefin and diene condensation and coking problems, and improving the deep denitrification and desulfurization reaction effect while ensuring stable operation.

[0072] The specific process principle of the shale oil hydrotreating method and system provided by this invention includes:

[0073] The first reactor is filled with a hydrotreating protectant and a first hydrorefining agent. In the first reactor, olefins and dienes contained in the shale oil readily undergo hydrotreating saturation reactions. Olefin saturation reactions preferentially occur in the upper and middle parts of the first reactor, while the lower and middle parts mainly experience minor desulfurization, denitrification, and aromatics saturation reactions. The second reactor consists of, from top to bottom, an aromatics saturation zone, a cracking and reforming zone, and a deep refining zone. The aromatics saturation zone is filled with the second hydrorefining agent, the cracking and reforming zone is filled with a hydrocracking agent, and the deep refining zone is filled with a hydrotreating agent. Deep refining zone; compared to the cracking reforming zone and the deep refining zone, the aromatic saturation zone is under low-temperature reaction conditions. Aromatic hydrocarbons and the aromatic ring structures of nitrogen- and sulfur-containing compounds undergo a high degree of hydrogenation saturation during hydrogenation, and denitrification and desulfurization reactions also occur. In the cracking reforming zone, the saturated ring structures of nitrogen- and sulfur-containing compounds mainly undergo ring-opening reactions, which can effectively reduce the dehydrogenation reaction of cycloalkane rings under high-temperature conditions and is conducive to deep denitrification. In the deep refining zone, materials from the cracking reforming zone can undergo further denitrification and desulfurization reactions to improve the treatment effect.

[0074] In one specific embodiment, the initial boiling point of the shale oil is any value between 80°C and 240°C, and the final boiling point is any value between 300°C and 450°C.

[0075] Optionally, the shale oil contains 10-40% by weight of unsaturated hydrocarbons, 5-25% by weight of aromatics, 0.2-1.5% by weight of nitrogen, and 0.05-1.0% by weight of sulfur.

[0076] In one specific embodiment, the low-nitrogen hydrotreated shale oil obtained by the method of the present invention has a nitrogen content of 0.0005–0.0200 wt% (5–200 μg / g) and a sulfur content of 0.0005–0.0100 wt% (5–100 μg / g). The method provided by the present invention significantly reduces the nitrogen and sulfur content in the low-nitrogen hydrotreated shale oil, meeting the feed requirements for subsequent shale oil processing.

[0077] In one embodiment, in step S1, the reaction conditions in the first reactor include: an inlet hydrogen pressure of 3.0–15.0 MPa; an inlet hydrogen-to-oil volume ratio of 150–1500; a reaction temperature of 140–310 °C; and a reaction rate of 0.5–5 h⁻¹ for the reactants. -1 Volumetric hourly space velocity (VHSV) passes through the first reactor. In this invention, the reaction temperature in the first reactor is the average reaction temperature within the reactor.

[0078] In a preferred embodiment, the reaction conditions in the first reactor include: an inlet hydrogen pressure of 6.0–12.0 MPa, more preferably 10.0–12.0 MPa; an inlet hydrogen-to-oil volume ratio of 800–1200; a reaction temperature of 150–240°C; and a reaction rate of reactants of 1–3 h.-1 The volumetric hourly space velocity (VHSV) passes through the first reactor. According to this embodiment, conducting the hydrogenation reaction in the first reactor is beneficial for improving the saturation treatment efficiency of olefins and dienes in the first reactor.

[0079] In one embodiment, in step S1, the hydrogenation protectant is a conventionally used hydrogenation protectant with functions such as desilication and demetallization. It can be purchased through conventional channels or prepared using known methods. For example, hydrogenation protectants developed by Sinopec Research Institute of Petroleum Processing Co., Ltd., with grades such as RG-200, RG-1, RG-30A, RG-30B, and RSi-1, are examples.

[0080] In one specific embodiment, the hydrogenation protective agent and the first hydrogenation refining agent in the first reactor can also be arranged in separate zones from top to bottom according to the same type of agent.

[0081] In a preferred embodiment, the volume ratio of the hydrogenation protective agent to the first hydrogenation refining agent is (0.01-0.5):1.

[0082] In a preferred embodiment, the volume ratio of the hydrogenation protectant to the first hydrogenation refining agent is (0.05-0.3):1.

[0083] In a preferred embodiment, the first hydrogenated refining agent includes a first carrier and a first active component loaded on the first carrier;

[0084] Optionally, the first carrier is preferably one or more of alumina and amorphous silica-alumina;

[0085] The first active component includes a first metal element combination, which is selected from one or more of Ni, Co, Mo and W.

[0086] In a preferred embodiment, the content of the first active component in the form of a metal oxide is 15-55% by weight, preferably 20-40% by weight, based on the total weight of the first hydrogenated refining agent.

[0087] In this invention, the first hydrogenated refining agent can be a commercially available product or prepared by a known preparation method.

[0088] In one specific embodiment, in step S2, the second hydrogenated preparation includes a second carrier and a second active component loaded on the second carrier;

[0089] The second carrier is selected from one or more of alumina and amorphous silica-alumina; preferably alumina; the second active component includes a second metal element combination, which is selected from one or more of Ni, Co, Mo and W; preferably, the content of the second active component in the form of metal oxide is 15-55% by weight, more preferably 20-40% by weight, based on the total weight of the second hydrogenated refining agent.

[0090] In this invention, the second hydrogenated refining agent can be a commercially available product or prepared using known methods. Specifically, the first and second hydrogenated refining agents can be the same or different.

[0091] In one specific embodiment, in step S2, the hydrocracking agent includes a third carrier and an acidic component; the third carrier is selected from one or more of alumina, amorphous silica-alumina, and silica-containing alumina; the acidic component is selected from one or more of Y and β molecular sieves.

[0092] In a preferred embodiment, the content of the acidic component is 5-60% by weight, preferably 10-35% by weight, based on the total weight of the hydrocracking agent.

[0093] In this invention, the hydrocracking agent can be a commercially available product or prepared by a known method.

[0094] In one specific embodiment, in step S2, the deep refining agent includes a fourth carrier and a third active component loaded on the fourth carrier;

[0095] The fourth carrier is selected from one or more of alumina and amorphous silicon aluminum; preferably alumina; the third active component includes a third metal element combination, which is selected from one or more of Ni, Co, Mo and W.

[0096] In a preferred embodiment, the content of the third active component, in the form of a metal oxide, is 15-55% by weight, preferably 20-40% by weight, based on the total weight of the hydrogenated deep refining agent.

[0097] In this invention, the deep-purified preparation can be a commercially available product or prepared by a known preparation method.

[0098] In one embodiment, in step S2, the second reactor is provided with an aromatic saturation zone, a cracking and upgrading zone, and a deep refining zone connected sequentially along the material flow direction; preferably, the first reaction product is introduced into the aromatic saturation zone.

[0099] The aromatic saturation zone includes the second hydrogenation refining agent; the cracking modification zone includes the hydrogenation cracking agent; and the deep refining zone includes the hydrogenation deep refining agent.

[0100] In a preferred embodiment, the catalyst loading volume ratio in the aromatic saturation zone, cracking reforming zone, and deep refining zone of the second reactor is 1:(0.1-2.5):(0.01-0.5); preferably 1:(0.2-1.5):(0.05-0.2). By setting up an aromatic saturation zone, cracking reforming zone, and deep refining zone in the second reactor according to this embodiment, the hydrogenation treatment effect of the second reactor can be further improved.

[0101] In one embodiment, in step S2, the reaction conditions in the second reactor include: a reaction temperature of 280–380°C in the aromatic saturation zone, a reaction hydrogen pressure of 3.0–15.0 MPa, and a hydrogen-to-oil volume ratio of 150–1500; a reaction temperature of 310–390°C in the cracking and upgrading zone; a reaction temperature of 320–420°C in the deep refining zone; an average temperature of 330–420°C in the second reactor; and a reaction rate of 0.3–2 h. -1 Volumetric hourly space velocity passes through the second reactor.

[0102] In a preferred embodiment, in step S2, the reaction conditions in the second reactor include:

[0103] The reaction temperature in the aromatic saturation zone is 300–360°C, more preferably 350–360°C; the hydrogen pressure is 6.0–12.0 MPa, more preferably 10.0–12.0 MPa; the hydrogen-to-oil volume ratio is 800–1200; the reaction temperature in the cracking and upgrading zone is 320–360°C; the reaction temperature in the deep refining zone is 350–400°C; the average temperature in the second reactor is 350–400°C; and the reactants are reacted at a rate of 0.5–1.5 h / min. -1 The volume hourly space velocity (VHSV) passes through the second reactor. The reaction conditions in this embodiment are more favorable for the hydrogenation reaction in the second reactor.

[0104] In one specific embodiment, the method includes:

[0105] The second reaction product is fed into a gas-liquid separator for gas-liquid separation to obtain gaseous and liquid phase materials.

[0106] After removing light hydrocarbons from the liquid phase material, the low-nitrogen hydrogenated shale oil is obtained;

[0107] The gaseous material is processed sequentially by a circulating hydrogen purification and gas separation system to obtain purified circulating hydrogen.

[0108] The purified recycled hydrogen and fresh hydrogen are mixed as raw material hydrogen and fed into the first reactor along with shale oil.

[0109] In this invention, for the process of removing light hydrocarbons from liquid phase materials, commonly used processing devices can be added according to actual conditions to further improve the oil quality of low-nitrogen hydrogenated shale oil; in this invention, gas phase materials are purified and then recycled.

[0110] In a preferred embodiment, such as Figure 1 As shown, the method further includes returning a portion of the purified recycled hydrogen as cold hydrogen to the bed space of the first reactor to control the temperature of the first reactor; and returning a portion of the purified recycled hydrogen as cold hydrogen to the bed space of the second reactor to control the temperature of the second reactor.

[0111] Preferably, a cold hydrogen tank is provided between the beds of the first reactor and a cold hydrogen tank is provided between the beds of the second reactor, so that the cold hydrogen is returned to the cold hydrogen tank in the first reactor and / or the second reactor. The location and number of cold hydrogen tanks in the first and second reactors can be set according to actual needs. The amount of cold hydrogen introduced is adjusted according to the target temperature inside the reactor.

[0112] This invention helps control the temperature in both reactors and prevents the temperature inside the reactors from becoming too high by returning the lower-temperature circulating hydrogen to the cold hydrogen tank between the beds of the first and second reactors.

[0113] In a preferred embodiment, such as Figure 1 As shown, the raw material hydrogen gas used to introduce into the first reactor first enters the first heat exchanger and undergoes a first heat exchange treatment with the first heat exchange medium.

[0114] The raw material hydrogen from the first heat exchanger is mixed with shale oil and then enters the second heat exchanger to undergo a second heat exchange treatment with the second heat exchange medium.

[0115] The mixture of raw material hydrogen and shale oil that has undergone the second heat exchange treatment is introduced into the first reactor; preferably, the temperature of the raw material hydrogen and shale oil mixture after the second heat exchange treatment is 130-260°C, more preferably 150-210°C.

[0116] The second heat exchange medium of the second heat exchanger includes a second reaction product from the second reactor; the first heat exchange medium of the first heat exchanger includes a second reaction product from the first heat exchanger that has undergone a first heat exchange treatment.

[0117] The second reaction product, which has undergone the first heat exchange treatment in the first heat exchanger, is introduced into the gas-liquid separator.

[0118] This invention utilizes the waste heat from the second product generated in the reactor to preheat mixed hydrogen, shale oil, etc., which require preheating. This not only makes full use of the waste heat of the materials but also increases the temperature of the materials entering the reactor, thereby improving the efficiency of the hydrogenation reaction in the reactor.

[0119] A second aspect of the present invention provides a shale oil hydrotreating system, the system comprising a first reactor 2, a second reactor, and a gas-liquid separator 6;

[0120] The first reactor 2 includes a shale oil inlet, a hydrogen inlet, a first reaction product outlet, and a first catalyst layer; the first catalyst layer includes a hydrogenation protective agent and a first hydrogenation refining agent; the first catalyst layer can be configured as a single bed or multiple beds, and a cold hydrogen tank is provided between the beds of the first reactor;

[0121] The second reactor includes a second feedstock inlet, a second product outlet, and a second catalyst layer. The second catalyst layer, along the material flow direction, sequentially includes an aromatics saturation zone 4-I, a cracking and reforming zone 4-II, and a deep refining zone 4-III. The aromatics saturation zone 4-I is filled with a second hydrorefining agent, the cracking and reforming zone 4-II is filled with a hydrocracking agent, and the deep refining zone 4-III is filled with a deep hydrorefining agent. The second catalyst layer can be configured as a single-bed or multi-bed reactor, with a cold hydrogen tank between the beds. The first feedstock inlet is located at the top of the aromatics saturation zone 4-I, and the second product outlet is located at the bottom of the deep refining zone 4-III.

[0122] The second reactant inlet of the second reactor is connected to the first reactant outlet of the first reactor 2;

[0123] The gas-liquid separator 6 includes a separation inlet, a gas phase outlet, and a liquid phase outlet; the separation inlet is connected to the second reaction product outlet of the second reactor.

[0124] In one specific embodiment, the gas phase outlet of the gas-liquid separator is connected to both the circulating hydrogen purification system and the gas separation system to simplify the process. Figure 1 Not shown in the diagram. Furthermore, the outlet of the circulating hydrogen purification system and the gas separation system is circulating hydrogen; among them, the liquid phase outlet of the gas-liquid separator can be connected to the subsequent processing device, such as a light hydrocarbon removal device.

[0125] In one embodiment, the system further includes a first heat exchanger 5, a second heat exchanger 1, and a heating furnace 3;

[0126] The first heat exchanger 5 is provided with a first heating inlet, a first heating outlet, a first cooling inlet, and a first cooling outlet; the second heat exchanger 1 is provided with a second heating inlet, a second heating outlet, a second cooling inlet, and a second cooling outlet.

[0127] The first heating inlet of the first heat exchanger 5 is connected to the gas phase outlet of the hydrogen and gas-liquid separator 6, and the first heating outlet is connected to the second heating inlet of the second heat exchanger 1; the first cooling inlet is connected to the second cooling outlet of the second heat exchanger 1, and the second cooling outlet is connected to the separation inlet of the gas-liquid separator 6; the first heating inlet of the second heat exchanger 1 and the first heating outlet of the first heat exchanger 5 are respectively connected to the shale oil source; the first heating outlet is connected to the shale oil inlet of the first reactor 2; and the first cooling inlet is connected to the second reaction product outlet of the second reactor.

[0128] The first heat exchanger 5 and the second heat exchanger 1 are both heat exchangers or combinations of heat exchangers that are the main components of this invention, and do not limit this invention. Other heat exchangers may be provided as needed.

[0129] All the devices used in this invention are conventional structures in the art.

[0130] The following is about the adoption Figure 1 The specific process flow for shale oil hydrotreating in the shale oil hydrotreating system shown is illustrated by example:

[0131] Shale oil from pipeline 01 is mixed with mixed hydrogen from pipeline 02 (heated by the first heat exchanger 5), and then introduced into the second heat exchanger 1 to exchange heat with the second reaction product from pipeline 06. The heated mixture of shale oil and mixed hydrogen then enters the first reactor 2 via pipeline 03 to undergo olefin and diene saturation reactions, denitrification, desulfurization, and aromatic saturation reactions. The first reaction product enters the heater 3 via pipeline 04 for heating, and then enters the second reactor via pipeline 05. In the second reactor, the reactants first contact the second hydrorefining agent in the aromatic saturation zone 4-I, mainly undergoing hydrorefining reactions of aromatics and aromatic ring structures containing nitrogen and sulfur compounds, as well as denitrification and desulfurization reactions. Then, they contact the hydrocracking agent in the cracking reforming zone 4-II of the second reactor, mainly undergoing ring-opening reactions of cycloalkane rings, before entering the second reactor. In the deep refining zone 4-III of the reactor, deep denitrification and desulfurization reactions occur, ultimately yielding the second reaction product. The hot second reaction product is cooled down by heat exchange in the second heat exchanger 1 via pipeline 06, then enters the first heat exchanger 5 via pipeline 07 to exchange heat with mixed hydrogen and cool down again. After that, it enters the gas-liquid separator 6 via pipeline 08 for gas-liquid phase separation. The liquid phase product, after removing light hydrocarbons, flows out as low-nitrogen hydrotreated shale oil via pipeline 012. The gas phase product, after purification, enters the pipeline 09 as circulating hydrogen, where it mixes with fresh hydrogen from pipeline 010 to form mixed hydrogen. Part of the mixed hydrogen is used as cold hydrogen in each bed of the first and second reactors via pipeline 011 to control the temperature in the first and second reactors, while another part is circulated into the first heat exchanger 5 to further exchange heat with the cooled second reaction product from the second heat exchanger 1 to raise its temperature.

[0132] The present invention will be further described in detail below through examples.

[0133] All raw materials used in the examples can be obtained through commercial purchases. The catalysts used are catalysts developed by Sinopec Research Institute of Petroleum & Chemical Industry Co., Ltd., and are all produced by China Petroleum & Chemical Corporation Catalyst Co., Ltd. Changling Branch.

[0134] Example 1

[0135] use Figure 1 The process flow shown is used for shale oil hydrotreating (pilot test).

[0136] The shale oil Y used in this embodiment has a distillation range of 180–430°C; the shale oil Y contains 33% by weight of unsaturated hydrocarbons, 23% by weight of aromatics, 1.02% by weight of nitrogen, and 0.41% by weight of sulfur.

[0137] like Figure 1 The catalyst loading status shown is as follows:

[0138] The catalyst loading method in the first reactor includes, from top to bottom: RG-200, RG-30A, RG-30B, RG-1, RSi-1, and RN-32V; RG-200, RG-30A, RG-30B, RG-1, and RSi-1 are hydrogenation protective agents, and the loading volume ratio of RG-200, RG-30A, RG-30B, RG-1, and RSi-1 is 4:5:5:5:6; RN-32V is the first hydrogenation refining agent, and the loading volume ratio of all hydrogenation protective agents to the first hydrogenation refining agent is 0.2:1.

[0139] The catalyst loading method in the second reactor includes three types of catalysts from top to bottom: RN-32V, RHC-131, and RN-32V in the aromatic saturation zone, cracking and upgrading zone, and deep refining zone; the volume ratio of RN-32V, RHC-131, and RN-32V is 1:0.30:0.1.

[0140] The specific steps of this implementation include:

[0141] Shale oil from pipeline 01 is mixed with mixed hydrogen from pipeline 02 after being heated by the first heat exchanger 5 (where the volumetric flow rate of shale oil Y is 500 mL / h), and then introduced into the second heat exchanger 1 for heat exchange with the second reaction product from pipeline 06; after heat exchange and heating (to 150-210℃), the mixture containing shale oil and hydrogen enters the first reactor 2 via pipeline 03; the reaction conditions in the first reactor include: hydrogen partial pressure at the inlet of the first reactor is 8.0 MPa, the inlet hydrogen-to-oil volume ratio is 800, and the average reaction temperature of the first reactor is controlled within the range of 150-210℃; the reactants are reacted at a rate of 3.0 h.-1 Volumetric hourly space velocity passes through the first reactor; the first reaction product is obtained via the first reactor;

[0142] The first reaction product enters the external heating device (heater 3) via pipeline 04 for heating. After being heated, it enters the second reactor via pipeline 05. The reaction conditions in the second reactor include: an average reaction temperature of 340℃ in the aromatic saturation zone, a reaction pressure of 8MPa, and a hydrogen-to-oil volume ratio of 800; an average reaction temperature of 345℃ in the cracking and upgrading zone; and an average reaction temperature of 350℃ in the deep refining zone. The reactants are reacted at a rate of 1.0 h / min. -1 The volumetric space velocity passes through the second reactor; the second reaction product is obtained via the second reactor.

[0143] The hot second reaction product is cooled down (to 150-240°C) in the second heat exchanger 1 via pipeline 06, and then enters the first heat exchanger 5 via pipeline 07 to exchange heat with the mixed hydrogen and cool down again (the second reactant is cooled to 40-60°C, and the mixed hydrogen is heated to 50-100°C). It then enters the gas-liquid separator 6 via pipeline 08 for gas-liquid phase separation. The liquid phase product, low-nitrogen hydrotreated shale oil, flows out via pipeline 012 (the liquid phase product can also enter a light hydrocarbon removal unit for further separation). The gas phase product is processed sequentially by the circulating hydrogen purification and gas separation system, and then enters pipeline 09 as circulating hydrogen to mix with fresh hydrogen from pipeline 010 to form mixed hydrogen. Part of the mixed hydrogen is used as cold hydrogen for each bed in the first and second reactors via pipeline 011; the other part is recycled into the first heat exchanger 5 to further exchange heat with the cooled second reaction product from the second heat exchanger 1 to raise its temperature.

[0144] Low-NOx hydrogenated shale oil HY-1 was obtained from gas-liquid separator 6. The main components of the feedstock shale oil Y and the product low-NOx hydrogenated shale oil HY-1 are listed in Table 1.

[0145] Example 2

[0146] This embodiment describes shale oil hydrotreating using the method of Example 1, but differs from Example 1 in that the reaction conditions in the second reactor are changed, specifically including:

[0147] In the second reactor: the average reaction temperature in the aromatic saturated zone is 340℃, the reaction hydrogen pressure is 8.0MPa, and the hydrogen-to-oil volume ratio is 800.

[0148] The average reaction temperature in the cracking and upgrading zone is 355℃;

[0149] The average reaction temperature in the deep refining zone is 350°C;

[0150] The reactants were reacted at a rate of 1.0 h. -1 Volumetric hourly space velocity passes through the second reactor.

[0151] The low-NOx hydrotreated shale oil HY-2 obtained from gas-liquid separator 6. The main components of the low-NOx hydrotreated shale oil HY-2 are listed in Table 1.

[0152] Example 3

[0153] This embodiment describes the hydrotreating of shale oil using the method described in Example 1. The difference from Example 1 is that the hydrogen pressure in both the first and second reactors is changed to 10.0 MPa.

[0154] The low-NOx hydrotreated shale oil HY-3 was obtained from gas-liquid separator 6. The main components of the low-NOx hydrotreated shale oil HY-3 are listed in Table 1.

[0155] Comparative Example 1

[0156] This comparative example describes shale oil hydrotreating as described in Example 1, but differs from Example 1 in that the catalyst loading in the second reactor and the second reaction conditions are changed, specifically including:

[0157] In the second reactor: the cracking and refining zone and the deep refining zone are no longer set up, and the hydrotreating agent and the deep refining agent are no longer loaded. Only the aromatic saturation zone is set up and the hydrorefining agent RN-32V is loaded.

[0158] In the second reactor: the average reaction temperature in the aromatic saturated zone is 340℃, the hydrogen pressure is 8.0 MPa, and the hydrogen-to-oil volume ratio is 800; the reactants are reacted at a rate of 1.0 h⁻¹. -1 Volumetric hourly space velocity passes through the second reactor.

[0159] The low-NOx hydrogenated shale oil D1-HY obtained from gas-liquid separator 6. The main components of the low-NOx hydrogenated shale oil D1-HY are listed in Table 1.

[0160] Comparative Example 2

[0161] This comparative example describes shale oil hydrotreating as described in Example 1, but differs from Example 1 in that the catalyst loading in the second reactor and the second reaction conditions are changed, specifically including:

[0162] In the second reactor: the cracking and refining zone and the deep refining zone are no longer set up, and the hydrotreating agent and the deep refining agent are no longer loaded. Only the aromatic saturation zone is set up and the hydrorefining agent RN-32V is loaded.

[0163] In the second reactor: the average reaction temperature in the aromatic saturated zone is 360℃, the hydrogen pressure is 8.0 MPa, and the hydrogen-to-oil volume ratio is 800; the reactants are reacted at a rate of 1.0 h⁻¹. -1 Volumetric hourly space velocity passes through the second reactor.

[0164] The low-NOx hydrogenated shale oil D2-HY obtained from gas-liquid separator 6. The main components of the low-NOx hydrogenated shale oil D2-HY are listed in Table 1.

[0165] Comparative Example 3

[0166] This comparative example describes shale oil hydrotreating as described in Example 1, but differs from Example 1 in that the catalyst loading in the second reactor and the second reaction conditions are changed, specifically including:

[0167] In the second reactor: the cracking and refining zone and the deep refining zone are no longer set up, and the hydrotreating agent and the deep refining agent are no longer loaded. Only the aromatic saturation zone is set up and the hydrorefining agent RN-32V is loaded.

[0168] In the second reactor: the average reaction temperature in the aromatic saturated zone is 380℃, the hydrogen pressure is 8.0 MPa, and the hydrogen-to-oil volume ratio is 800; the reactants are reacted at a rate of 1.0 h⁻¹. -1 Volumetric hourly space velocity passes through the second reactor.

[0169] The low-NOx hydrogenated shale oil D3-HY obtained from gas-liquid separator 6. The main components of the low-NOx hydrogenated shale oil D3-HY are listed in Table 1.

[0170] Table 1

[0171]

[0172]

[0173] From the data in Table 1 above, we can see that:

[0174] Compared with shale oil feedstock Y, the low-nitrogen hydrogenated shale oils HY-1 to HY-3 obtained by the shale oil hydrotreating method provided by this invention have extremely low nitrogen and sulfur contents, good desulfurization and denitrification effects, and can meet the feed requirements of catalytic cracking or catalytic pyrolysis.

[0175] Comparing Examples 1-3 with Comparative Examples 1-3, the second reactor in Comparative Examples 1-3 was not partitioned and was only filled with hydrorefining agent. The sulfur and nitrogen contents of the hydrotreated shale oil obtained in Comparative Examples 1-3 were significantly higher than those in Examples 1-3, failing to achieve the desired denitrification and desulfurization effects. This demonstrates that the method provided by this invention can achieve better denitrification and desulfurization effects.

[0176] Furthermore, comparing Example 1 with Example 2, Example 2 involves hydrogenation treatment at the reaction temperature in the second reactor according to the preferred embodiment of the present invention, which can improve the denitrification and desulfurization effect of hydrogenated shale oil.

[0177] Furthermore, comparing Example 1 with Example 3, Example 3 involves hydrogenation treatment according to the hydrogen pressure in the preferred embodiment of the present invention, which can improve the denitrification and desulfurization effect of hydrogenated shale oil.

[0178] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0179] 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, the present invention will not describe the various possible combinations separately.

[0180] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A method for hydrotreating shale oil, characterized in that, Includes the following steps: S1. Shale oil and hydrogen are introduced into the first reactor and brought into contact with the hydrogenation protective agent and the first hydrogenation refining agent to carry out the hydrogenation refining reaction and obtain the first reaction product. S2. The first reaction product is heated by an external heating device and then enters the second reactor, where it is sequentially reacted with the second hydrogenated refining agent, the hydrogenated cracking agent, and the hydrogenated deep refining agent to obtain the second reaction product. S3. The second reaction product is fed into a gas-liquid separator for gas-liquid separation to obtain low-nitrogen hydrogenated shale oil. In step S2, the second reactor is provided with a connected aromatic saturation zone, a cracking and reforming zone, and a deep refining zone sequentially along the material flow direction; the first reaction product is introduced into the aromatic saturation zone; the aromatic saturation zone includes the second hydrorefining agent; the cracking and reforming zone includes the hydrocracking agent; the deep refining zone includes the hydrorefining deep refining agent; the catalyst loading volume ratio in the aromatic saturation zone, cracking and reforming zone, and deep refining zone of the second reactor is 1:(0.1~2.5):(0.01~0.5); The reaction conditions in the second reactor include: The reaction temperature in the aromatic saturated region is 300~360℃, the reaction hydrogen pressure is 6.0~12.0MPa, and the hydrogen-to-oil volume ratio is 800~1200. The reaction temperature in the cracking and reforming zone is 320~360℃; The reaction temperature in the deep refining zone is 350~400℃; The reactants are reacted at a rate of 0.5~1.5h. -1 Volumetric hourly space velocity passes through the second reactor.

2. The method according to claim 1, characterized in that, In step S1, the first hydrogenated preparation includes a first carrier and a first active component loaded on the first carrier.

3. The method according to claim 2, characterized in that, The first carrier is selected from one or two of alumina and amorphous silica-alumina; the first active component includes a first metal element combination, which is selected from one or more of Ni, Co, Mo and W.

4. The method according to claim 3, characterized in that, The first carrier is aluminum oxide.

5. The method according to claim 2, characterized in that, The content of the first active component in the form of metal oxide is 15 to 55% by weight based on the total weight of the first hydrogenated refining preparation.

6. The method according to claim 5, characterized in that, The content of the first active component in the form of metal oxide is 20-40% by weight based on the total weight of the first hydrogenated refining preparation.

7. The method according to claim 1, characterized in that, In step S1, the volume ratio of the hydrogenation protective agent to the first hydrogenation refining agent is (0.01~0.5):

1.

8. The method according to claim 7, characterized in that, In step S1, the volume ratio of the hydrogenation protective agent to the first hydrogenation refining agent is (0.05~0.3):

1.

9. The method according to claim 1, characterized in that, In step S1, the reaction conditions in the first reactor include: inlet hydrogen pressure of 3.0~15.0 MPa, inlet hydrogen-to-oil volume ratio of 150~1500, reaction temperature of 140~310℃, and reactant feed at a rate of 0.5~5 h⁻¹. -1 Volumetric hourly space velocity passes through the first reactor.

10. The method according to claim 9, characterized in that, In step S1, the reaction conditions in the first reactor include: inlet hydrogen pressure of 6.0~12.0 MPa; inlet hydrogen-to-oil volume ratio of 800~1200; reaction temperature of 150~240℃; and reactant concentration of 1~3 h. -1 Volumetric hourly space velocity passes through the first reactor.

11. The method according to claim 1, characterized in that, The volume ratio of catalysts in the aromatic saturation zone, cracking and upgrading zone, and deep refining zone of the second reactor is 1:(0.2~1.5):(0.05~0.2).

12. The method according to claim 1, characterized in that, In step S2, the second hydrogenated formulation includes a second carrier and a second active component loaded on the second carrier; The second carrier is selected from one or two of alumina and amorphous silica-alumina; the second active component includes a second metal element combination, which is selected from one or more of Ni, Co, Mo and W.

13. The method according to claim 12, characterized in that, The second carrier is aluminum oxide.

14. The method according to claim 12, characterized in that, The content of the second active component, in the form of metal oxide, is 15 to 55% by weight based on the total weight of the second hydrogenated refining agent.

15. The method according to claim 14, characterized in that, The content of the second active component, in the form of metal oxide, is 20-40% by weight based on the total weight of the second hydrogenated refining agent.

16. The method according to claim 1, characterized in that, In step S2, the hydrocracking agent includes a third support and an acidic component; the third support is selected from one or more of alumina, amorphous silica-alumina, and silica-containing alumina; the acidic component is selected from one or two of Y-type molecular sieves and β-type molecular sieves.

17. The method according to claim 16, characterized in that, The content of the acidic component is 5-60% by weight, based on the total weight of the hydrocracking agent.

18. The method according to claim 17, characterized in that, The content of the acidic component is 10-35% by weight, based on the total weight of the hydrocracking agent.

19. The method according to claim 1, characterized in that, In step S2, the hydrogenated deep refining agent includes a fourth carrier and a third active component loaded on the fourth carrier; The fourth carrier is selected from one or two of alumina and amorphous silica-alumina; the third active component includes a third metal element, which is selected from one or more of Ni, Co, Mo and W.

20. The method according to claim 19, characterized in that, The fourth carrier is aluminum oxide.

21. The method according to claim 19, characterized in that, The content of the third active component, in the form of metal oxide, is 15-55% by weight based on the total weight of the hydrogenated deep refining agent.

22. The method according to claim 21, characterized in that, The content of the third active component, in the form of metal oxide, is 20-40% by weight based on the total weight of the hydrogenated deep refining agent.

23. The method according to claim 1, characterized in that, In step S2, the average temperature in the second reactor is 330~420℃.

24. The method according to claim 23, characterized in that, In step S2, the average temperature in the second reactor is 350~400℃.

25. The method according to claim 1, characterized in that, In step S2, the external heating device is a heating furnace.

26. The method according to claim 1, characterized in that, The method includes: The second reaction product is fed into a gas-liquid separator for gas-liquid separation to obtain gaseous and liquid phase materials. After removing light hydrocarbons from the liquid phase material, low-nitrogen hydrogenated shale oil is obtained; The gaseous material is processed sequentially by a circulating hydrogen purification and gas separation system to obtain purified circulating hydrogen. The purified recycled hydrogen and fresh hydrogen are mixed as feedstock hydrogen, and at least a portion of the feedstock hydrogen is introduced into the first reactor along with the shale oil.

27. The method according to claim 26, characterized in that, The method further includes returning a portion of the purified recycled hydrogen as cold hydrogen to the bed space of the first reactor to control the temperature of the first reactor. as well as A portion of the purified recycled hydrogen is returned as cold hydrogen to the bed space of the second reactor to control the temperature of the second reactor.

28. The method according to claim 27, characterized in that, A cold hydrogen tank is provided between the beds of the first reactor and a cold hydrogen tank is provided between the beds of the second reactor, so that the cold hydrogen is returned to the cold hydrogen tank in the first reactor and / or the second reactor.

29. The method according to claim 26, characterized in that, The method also includes: The raw material hydrogen gas used to be introduced into the first reactor first enters the first heat exchanger and undergoes the first heat exchange treatment with the first heat exchange medium. The raw material hydrogen from the first heat exchanger is mixed with shale oil and then enters the second heat exchanger to undergo a second heat exchange treatment with the second heat exchange medium. The mixture of raw material hydrogen and shale oil, which has undergone the second heat exchange treatment, is then introduced into the first reactor; The second heat exchange medium of the second heat exchanger includes a second reaction product from the second reactor; the first heat exchange medium of the first heat exchanger includes a second reaction product from the first heat exchanger that has undergone a first heat exchange treatment. The second reaction product, which has undergone the first heat exchange treatment in the first heat exchanger, is introduced into the gas-liquid separator.

30. The method according to claim 29, characterized in that, The method includes: the temperature of the mixture of raw material hydrogen and shale oil after the second heat exchange treatment is 130~260℃.

31. The method according to claim 30, characterized in that, The method includes: the temperature of the mixture of raw material hydrogen and shale oil after the second heat exchange treatment is 150~210℃.

32. The method according to claim 1, characterized in that, The initial boiling point of the shale oil is any value between 80℃ and 240℃, and the final boiling point is any value between 300℃ and 450℃.

33. The method according to claim 32, characterized in that, The shale oil contains 10-40% by weight of unsaturated hydrocarbons, 5-25% by weight of aromatics, 0.2-1.5% by weight of nitrogen, and 0.05-1.0% by weight of sulfur. The low-nitrogen hydrogenated shale oil has a nitrogen content of 0.0005~0.0200% by weight and a sulfur content of 0.0005~0.0100% by weight.

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