A processing method for high-silicon naphtha

Abstract

The present invention discloses a method for processing high-silicon naphtha, comprising the following steps: high-silicon naphtha, mixed gasoline and diesel raw materials, and hydrogen enter a light component reaction zone, undergo olefin saturation, desiliconization, and desulfurization reactions under certain temperature and pressure conditions, the effluent from the light component reaction zone enters a heavy component reaction zone after heat exchange for deep desulfurization and dearomatization reactions, and the effluent from the heavy component reaction zone is stripped and fractionated to obtain a diesel product and a naphtha product; wherein organic matter containing hydroxyl and / or carboxyl groups is added to the high-silicon naphtha and / or the mixed gasoline and diesel raw materials; a silicon trapping agent and a light distillate oil hydrogenation catalyst are graded in a hydrogenation reactor in the light component reaction zone, and a diesel hydrogenation catalyst is loaded in a hydrogenation reactor in the heavy component reaction zone. The present invention mixes high-silicon naphtha with coking gasoline and diesel, and through the zoned reactions of the light component and heavy component, fully utilizes the reaction heat, can achieve efficient removal of Si, and extend the operating cycle of the coking oil processing device.

Description

Technical Field

[0001] The invention belongs to the field of clean oil refining, and in particular relates to a processing method of high-silicon naphtha. Background Art

[0002] With overcapacity in my country's fuel oil market, refineries are shifting towards the chemical industry, particularly towards producing ethylene and aromatics as basic chemical feedstocks. Hydrogenation technology is being used to convert naphtha into ethylene cracking feedstock and reforming feed, creating greater value. Because reforming catalysts are precious metal catalysts, reforming feed quality requirements are stringent, typically requiring low sulfur (<0.5 ppm), low nitrogen (<0.5 ppm), and low impurity content (<0.5 ppm). For ethylene cracking feedstock, silicon content is required to be <0.1 ppm. Ethylene and reforming feedstocks primarily come from straight-run naphtha and coker naphtha, requiring hydrogenation to remove impurities. Existing technologies reveal that the silicon content in raw oil products is primarily cyclosiloxanes, which are relatively easy to remove under current hydrogenation process conditions, thereby minimizing toxicity to downstream catalysts. However, with the advancement of oil product development technology, other types of silicon compounds may be introduced into oil products. Existing reaction processes are unable to effectively reduce silicon content to standard requirements, necessitating the search for new solutions.

[0003] On the other hand, conventional coker naphtha hydrogenation processes also suffer from short operating cycles. This is partly due to the fact that, while silicon in the feedstock can be removed under certain conditions, it easily deposits and poisons the catalyst. Furthermore, the high olefin content in coker naphtha leads to intense heat release during the reaction, causing coking and carbon deposition on the catalyst surface and resulting in a pressure drop in the bed. Further process optimization and improved processing methods are needed to address the processing challenges of coker oil products.

[0004] CN200810113398.4 discloses a method for hydrorefining low-quality gasoline. The method involves reacting gasoline feedstock with a hydrogenation protective agent at low temperatures. The reaction effluent is then mixed with circulating oil and subsequently reacted with a hydrodesiliconizing agent and a hydrorefining catalyst at high temperatures. This method can process coker gasoline with high sulfur, high nitrogen, and high olefin content, and the refined gasoline fraction can meet the feed requirements of both reforming pre-hydrogenation units and steam cracking ethylene production plants. However, this method is not suitable for processing naphtha feedstocks with high silicon content, and it also fails to address the problem of catalyst bed coking caused by the high heat release during the coker gasoline hydrogenation process.

[0005] CN200910188090.0 discloses a coking naphtha silicon scavenger and its application. The coking naphtha silicon scavenger uses alumina as a carrier, silicon dioxide as an auxiliary agent, and W, Mo, and Ni as hydrogenation components. The pore volume of the coking naphtha silicon scavenger is 0.5-0.70 ml / g, and the specific surface area is 250-500 m 2 / g, the hydrogenation component content is 1%-20% in terms of oxide, and the acid content is 0.3-0.5mmol / g. The coking naphtha silicon scavenger of the present invention can effectively remove the impurity silicon contained in the coking naphtha, protecting the coking naphtha hydrorefining catalyst from permanent deactivation caused by silicon poisoning. Summary of the Invention

[0006] To address the above problems of high Si content in naphtha and difficulty in removing it, as well as difficulty in processing coker naphtha and short equipment operation cycle, the present invention proposes a processing method for high-silicon naphtha. High-silicon naphtha is mixed with coking gasoline and diesel for processing, and the light components and heavy components are reacted separately to fully utilize the reaction heat, which can achieve efficient Si removal and extend the operation cycle of the coker oil processing device.

[0007] Existing naphtha desiliconization technology generally targets oil products with silicon contents below 100 ppm in the form of epoxysilanes. These Si species are relatively easy to remove under appropriate temperature and pressure conditions. However, in recent years, the silicon content in naphtha feedstock has gradually reached 300-1000 ppm. Research by the inventors has revealed that not only has the Si content in naphtha increased significantly, but the type of silicon compounds has also shifted, with an increasing concentration of alkylsilanes, silanols, or silyl ethers. These Si species are concentrated in the light fraction of naphtha. Using existing desiliconization methods and processes, it is difficult to achieve acceptable silicon content in raw oil products.

[0008] The high-silicon naphtha processing method of the present invention comprises the following steps: high-silicon naphtha, mixed gasoline and diesel raw materials and hydrogen enter a light component reaction zone, and carry out olefin saturation, desiliconization and desulfurization reactions under certain temperature and pressure conditions; the effluent of the light component reaction zone enters a heavy component reaction zone after heat exchange for deep desulfurization and dearomatization reactions; the effluent of the heavy component reaction zone is stripped and fractionated to obtain a diesel product and a naphtha product; wherein organic matter containing hydroxyl groups and / or carboxyl groups is added to the high-silicon naphtha and / or the mixed gasoline and diesel raw materials; a silicon scavenger and a light distillate oil hydrogenation catalyst are loaded in a graded manner in a hydrogenation reactor in the light component reaction zone, and a diesel hydrogenation catalyst is loaded in a hydrogenation reactor in the heavy component reaction zone.

[0009] In the method of the present invention, the high-silicon naphtha is at least one of straight-run naphtha, coker naphtha, and hydrogenated reformed naphtha; the sulfur content of the high-silicon naphtha is ≯1000 μg / g, the nitrogen content is ≯200 μg / g, and the silicon content is 1-3000 μg / g; the high-silicon naphtha contains at least one silicon-containing compound other than cyclic siloxane compounds and silane compounds; wherein the cyclic siloxane compound is a compound with a cyclic silicon-oxygen bond (-Si-O-) n , n≥3 main chain organosilicon compounds, such as those with the general formula (H2SiO) n , n≥3 compounds, or compounds in which H in the general formula is replaced by alkyl, halogen, etc.; the silane compound is a compound having Si n H 2n+2 , an organosilicon compound of the general formula n≥1.

[0010] In the method of the present invention, the proportion of coking gasoline and diesel in the mixed gasoline and diesel feedstock is ≮70wt%, the proportion of coking gasoline in the coking gasoline and diesel is ≯60wt%, the sulfur content of the mixed gasoline and diesel is ≯15000μg / g, the nitrogen content is ≯400μg / g, and the polycyclic aromatic hydrocarbon content is ≯50wt%. The mixed gasoline and diesel feedstock may also contain one or more of straight-run oil, catalytic cracking oil, ebullated-bed residue oil hydrogenation oil, and the like.

[0011] In the method of the present invention, olefin saturation and Si removal reactions and removal of small molecular sulfur in the diesel fraction mainly occur in the light component reaction zone; the process conditions of the light component reaction zone are: reaction pressure 0.5-5.0 MPa, preferably 1.0-4.0; hydrogen-to-oil volume ratio 100:1-500:1, preferably 150:1-350:1; volume space velocity 1-10.0 h -1 , preferably 2-6.0h -1 The reactor inlet temperature is 150-300°C, preferably 180-240°C. The loading ratio of the silicon scavenger and the light distillate oil hydrogenation catalyst is 1:5-3:1 from top to bottom. The active metal of the silicon scavenger is a metal oxide of Group VIB and / or a metal oxide of Group VIII. The carrier is alumina or alumina modified with an auxiliary agent. Based on the weight of the silicon scavenging catalyst, the content of the metal oxide of Group VIB is 5%-20%, preferably 5%-15%. The content of the metal oxide of Group VIII is 1%-8%, preferably 2%-5%. The specific surface area is 100-500m 2 / g, preferably 300~500m 2 / , pore volume of 0.3-1.2 mL / g, preferably 0.4-0.8 mL / g; light distillate oil hydrogenation catalyst is well known to those skilled in the art, the active metal is a Group VIB metal oxide and / or a Group VIII metal oxide, the carrier is alumina or alumina modified with an additive, based on the weight of the catalyst, the Group VIB metal oxide content is 5%-30%, preferably 5%-15%, and the Group VIII metal oxide content is 1%-15%, preferably 2%-6%; the specific surface area is 100-300 m 2 / g, preferably 120-260m 2 / g, and the pore volume is 0.3-1.2 mL / g, preferably 0.4-0.8 mL / g.

[0012] In the method of the present invention, the hydrogenation reactor in the light component reaction zone is fed with a medium temperature (130-180)°C heating furnace when it is started up. After the bed shows a significant temperature rise (above 40°C), the heating furnace is stopped and the feed temperature requirement can be met by heat exchange between the feed at room temperature (20-40°C) and the reactor outlet logistics.

[0013] In the method of the present invention, the organic compound containing hydroxyl and / or carboxyl groups is an alcohol or an organic acid, more preferably a C1-C10 alcohol and / or acid, more preferably a C2-C8 alcohol and / or acid; and most preferably a C2-C6 alcohol and / or acid. The alcohol and / or acid includes monohydric alcohols, dihydric alcohols, trihydric alcohols, monobasic acids, dibasic acids, and tribasic acids. As a more specific embodiment, the organic compound containing hydroxyl and / or carboxyl groups is selected from at least one of ethanol, ethylene glycol, propanol, propylene glycol, glycerol, butanol, butanediol, butanetriol, pentanol, acetic acid, oxalic acid, tartaric acid, succinic acid, glycolic acid, and citric acid. The organic compound containing hydroxyl and / or carboxyl groups facilitates the removal of the above-mentioned stable silicon compound. The specific principle may be that the hydroxyl and carboxyl groups in the organic matter help to break the Si-O or Si-C bonds, exposing Si atoms, and then removing the silicon-trapped agent; the mass content of the organic matter containing hydroxyl and / or carboxyl groups in the high-silicon naphtha is 0.01wt%-5wt%, preferably 0.5wt%-3.5wt%, and more preferably 1wt%-3.0wt%.

[0014] In the method of the present invention, the sulfur content of the effluent from the light component reaction zone is ≯500 μg / g, and the Si content is ≯1 μg / g.

[0015] In the method of the present invention, deep desulfurization and dearomatization of the diesel component mainly occurs in the heavy component reaction zone; the process conditions of the heavy component reaction zone are: reaction pressure 2.0-8.0 MPa, preferably 3.5-6.5 MPa; hydrogen-to-oil volume ratio 100:1-600:1, preferably 200:1-500:1; volume space velocity 0.1-5.0 h-1 , preferably 0.5-3.0h -1 The reactor inlet temperature is 250-400°C, preferably 260-330°C. The diesel hydrogenation catalyst is well known to those skilled in the art. The active metal is a Group VIB metal oxide and / or a Group VIII metal oxide. Based on the weight of the hydrogenation catalyst, the Group VIB metal oxide content is 5%-30%, preferably 15%-25%, and the Group VIII metal oxide content is 1%-15%, preferably 3%-8%. The carrier is alumina or additive-modified alumina. The additive is one or more of B, P, Mg, Zr or Si. Based on the weight of the carrier, the additive, calculated as oxide, accounts for 3%-15%, preferably 3%-10%.

[0016] The method of the present invention addresses the difficulties in removing Si from high-silicon naphtha and the long-term operation limitations of coking units. A low-energy, low-cost process route is designed to process inferior oil products and provide qualified naphtha as a chemical raw material and automotive diesel product. The specific advantages are as follows:

[0017] (1) Due to the high olefin content in coking gasoline, a large amount of heat is released during the reaction, which is more suitable for the effective removal of high-silicon species. In addition, the conventional coking gasoline hydrogenation process is a gas phase reaction. If the olefin content is too high, the reaction heat cannot be effectively controlled, the bed temperature rises too quickly, and the olefin condensation causes a bed pressure drop. The inventors found that the silicides in high-silicon naphtha and the olefins in coking oil overlap in the distillation range. When high-silicon naphtha is mixed with coking gasoline and diesel feedstock, under the corresponding reaction conditions, a certain proportion of liquid components exists in the feedstock, which can effectively absorb the latent heat of vaporization. In addition, the olefin content in coking diesel is relatively low, which can dilute the olefin content of the feedstock, further controlling the reaction temperature and extending the operation cycle of the device.

[0018] (2) Fully utilize the heat of the olefin saturation reaction in the coking oil for Si removal, and stop using the heating furnace, thus saving energy and reducing consumption. The present invention only requires the use of a heating furnace to preheat the raw materials in the initial stage of operation. Since the olefin content in the coking gasoline and diesel is high, the rapid reaction heat release can increase the reactor outlet logistics temperature. At this time, the heating furnace can be stopped, and the room temperature raw materials can be used to exchange heat with the light component reaction zone reactor outlet logistics to meet the feed temperature, thus fully utilizing the reaction heat to save energy and reduce consumption. In addition, since the Si species in high-silicon naphtha need to be removed at a higher temperature, this reaction condition can also be used to achieve efficient Si removal.

[0019] (3) Taking advantage of the fact that alcohol and / or acid are beneficial for hydrogenation desiliconization, a small amount of alcohol and / or acid is added to the light component reaction zone reactor to facilitate the removal of silicon-containing compounds. The silicon compounds in the above-mentioned oil products are more stable than epoxysilane compounds or silane compounds. It is difficult to remove them to a satisfactory level using the existing desiliconization conditions and silicon trapping agents. The present invention uses a method of adding organic matter containing hydroxyl and / or carboxyl groups to facilitate the removal of the above-mentioned stable silicon compounds. The specific principle may be that the hydroxyl and carboxyl groups in the organic matter facilitate the breaking of Si-O or Si-C bonds, exposing Si atoms, which are then removed by the silicon trapping agent. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 Schematic diagram of the naphtha hydrogenation process unit used in the examples. DETAILED DESCRIPTION

[0021] by Figure 1 The implementation process of the high-silicon naphtha processing method of the present invention is illustrated as an example: high-silicon naphtha, mixed gasoline and diesel raw materials 1 and hydrogen 2 pass through the heat exchanger 3 and enter the light component reaction zone hydrogenation reactor 4, where olefin saturation, desiliconization and desulfurization reactions are carried out under certain temperature and pressure conditions. The reaction effluent 5 passes through the heat exchanger 3 and enters the heavy component reaction zone hydrogenation reactor 6 for deep desulfurization and dearomatization reactions. The effluent 7 enters the stripping and fractionation system 8, and finally a diesel product and qualified naphtha 9 are obtained as chemical raw materials. The top gas 10 enters the hydrogen purification system for recycling.

[0022] Examples 1-2

[0023] exist Figure 1 In the process flow, a catalyst bed is installed in the light component reaction zone reactor. A total of 60 mL of graded silica trap A and light distillate hydrogenation catalyst B are loaded, with a volume ratio of 1:2. A catalyst bed is installed in the heavy component reaction zone reactor, with 60 mL of diesel hydrogenation catalyst C. The feedstock is a blend of high-silica naphtha, coker gasoline, and coker diesel, with a mass ratio of 20:50:30. See Table 1 for feedstock properties and Table 2 for catalyst properties.

[0024] 1.0 wt% succinic acid was added to high-silica naphtha supplied by a Sinopec refinery. The feedstock contained 437 μg / g of silicon. Nuclear magnetic resonance analysis revealed the silicon species to be tetramethylsilane, dimethoxydimethylsilane, tetraethylsilane, and tetramethylcyclosiloxane. The reaction conditions and results are shown in Table 3.

[0025] Examples 3-4

[0026] exist Figure 1In the process flow, a catalyst bed is installed in the light component reaction zone reactor. A total of 60 mL of graded silica trap A and light distillate hydrogenation catalyst B are loaded, with a volume ratio of 1:2. A catalyst bed is installed in the heavy component reaction zone reactor, with 60 mL of diesel hydrogenation catalyst C. The feedstock is a blend of high-silica naphtha, coker gasoline, and coker diesel, with a mass ratio of 20:50:30. See Table 1 for feedstock properties and Table 2 for catalyst properties.

[0027] 1.0 wt% ethanol was added to high-silicon naphtha supplied by a Sinopec refinery. The feedstock contained 437 μg / g of silicon. Nuclear magnetic resonance analysis revealed the silicon species to be tetramethylsilane, dimethoxydimethylsilane, tetraethylsilane, and tetramethylcyclosiloxane. The reaction conditions and results are shown in Table 3.

[0028] Comparative Example 1

[0029] exist Figure 1 In the process flow, a catalyst bed is installed in the light component reaction zone reactor. A total of 60 mL of graded silica trap A and light distillate hydrogenation catalyst B are loaded, with a volume ratio of 1:2. A catalyst bed is installed in the heavy component reaction zone reactor, with 60 mL of diesel hydrogenation catalyst C. The feedstock is a blend of high-silica naphtha, coker gasoline, and coker diesel, with a mass ratio of 20:50:30. See Table 1 for feedstock properties and Table 2 for catalyst properties.

[0030] No organic acid or alcohol was added to the high-silica naphtha, which was supplied by a Sinopec refinery. The raw material contained 437 μg / g of silicon. Nuclear magnetic resonance analysis revealed the silicon species to be tetramethylsilane, dimethoxydimethylsilane, tetraethylsilane, and tetramethylcyclosiloxane. The reaction conditions and results are shown in Table 3.

[0031] Comparative Example 2

[0032] A conventional fixed-bed coking gasoline and diesel hydrogenation process was used to set up a reactor, in which 20 mL of silicon scavenger A and 100 mL of diesel hydrogenation catalyst C were loaded in a graded manner. The properties of the raw materials and the catalyst were the same as those in the example.

[0033] 1.0 wt% ethanol was added to high-silicon naphtha supplied by a Sinopec refinery. The feedstock contained 437 μg / g of silicon. Nuclear magnetic resonance analysis revealed the silicon species to be tetramethylsilane, dimethoxydimethylsilane, tetraethylsilane, and tetramethylcyclosiloxane. The reaction conditions and results are shown in Table 3.

[0034] Comparative Example 3

[0035] A conventional fixed-bed coking gasoline and diesel hydrogenation process was used to set up a reactor, in which 20 mL of silicon scavenger A and 100 mL of diesel hydrogenation catalyst C were loaded in a graded manner. The properties of the raw materials and the catalyst were the same as those in the example.

[0036] No organic acid or alcohol was added to the high-silica naphtha, which was supplied by a Sinopec refinery. The raw material contained 437 μg / g of silicon. Nuclear magnetic resonance analysis revealed the silicon species to be tetramethylsilane, dimethoxydimethylsilane, tetraethylsilane, and tetramethylcyclosiloxane. The reaction conditions and results are shown in Table 3.

[0037] Table 1 Properties of crude oil

[0038]

[0039] Table 2 Catalyst properties

[0040]

[0041] Table 3 Process conditions and results

[0042]

[0043] The evaluation results in Table 3 demonstrate that the naphtha processing method of the present invention, through the addition of alcohols and optimized process conditions, achieves efficient Si removal. Compared to conventional coking gasoline and diesel hydrogenation technology, the present device exhibits no significant Si deposition during the degassing process and exhibits no coking or carbon accumulation, demonstrating its long-term operational performance.

Claims

1. A method for processing high-silicon naphtha, characterized in that The method comprises the following steps: high-silicon naphtha, mixed gasoline and diesel feedstocks and hydrogen enter a light component reaction zone, and carry out olefin saturation, desiliconization and desulfurization reactions under certain temperature and pressure conditions; the effluent from the light component reaction zone enters a heavy component reaction zone after heat exchange for deep desulfurization and dearomatization reactions; the effluent from the heavy component reaction zone is stripped and fractionated to obtain diesel products and naphtha products; wherein organic matter containing hydroxyl groups and / or carboxyl groups is added to the high-silicon naphtha and / or mixed gasoline and diesel feedstocks; a silicon scavenger and a light distillate oil hydrogenation catalyst are loaded in a graded manner in a hydrogenation reactor in the light component reaction zone, and a diesel hydrogenation catalyst is loaded in a hydrogenation reactor in the heavy component reaction zone; The high-silicon naphtha has a sulfur content of ≯1000 μg / g, a nitrogen content of ≯200 μg / g, and a silicon content of 1-3000 μg / g; the high-silicon naphtha contains at least one silicon-containing compound other than cyclic siloxane compounds and silane compounds; The organic matter containing hydroxyl and / or carboxyl groups is selected from at least one of ethanol, ethylene glycol, propanol, propylene glycol, glycerol, butanol, butylene glycol, butanetriol, pentanol, acetic acid, oxalic acid, tartaric acid, succinic acid, glycolic acid and citric acid.

2. The method according to claim 1, wherein: The cyclic siloxane compound is a cyclic silicon-oxygen bond (-Si-O-) n , n≥3 is an organic silicon compound with a main chain, or a compound in which H is replaced by an alkyl or halogen; the silane compound is an organic silicon compound with Si n H 2n+2 , an organosilicon compound of the general formula n≥1.

3. The method according to claim 1, wherein: The proportion of coking gasoline and diesel in the mixed gasoline and diesel feedstock is ≮70wt%, the proportion of coking gasoline in the coking gasoline and diesel is ≯60wt%, the sulfur content of the mixed gasoline and diesel is ≯15000μg / g, the nitrogen content is ≯400μg / g, the polycyclic aromatic hydrocarbon content is ≯50wt%, and the other components of the mixed gasoline and diesel feedstock are one or more of straight-run oil, catalytic cracking oil, and boiling bed residue oil hydrogenation oil.

4. The method according to claim 1, wherein: The raw materials for mixed gasoline and diesel are coking gasoline and diesel, the proportion of coking gasoline to coking gasoline and diesel is ≯60wt%, the sulfur content of the mixed gasoline and diesel is ≯15000μg / g, the nitrogen content is ≯400μg / g, and the polycyclic aromatic hydrocarbon content is ≯50wt%.

5. The method according to claim 1, wherein: Process conditions of the light component reaction zone: reaction pressure 0.5-5.0 MPa; hydrogen-oil volume ratio 100:1-500:1; volume space velocity 1-10.0 h -1 ; Reactor inlet temperature 150-300℃.

6. The method according to claim 1, wherein: Process conditions of the light component reaction zone: reaction pressure 1.0~4.0MPa; hydrogen-oil volume ratio 150:1~350:1; volume space velocity 2-6.0h -1 ; Reactor inlet temperature 180~240℃.

7. The method according to claim 1, wherein: The silicon scavenger and the light distillate oil hydrogenation catalyst are loaded in a volume ratio of 1:5 to 3:1, and are loaded from top to bottom. The active metal of the silicon scavenger is a Group VIB metal oxide and / or a Group VIII metal oxide, and the carrier is alumina or alumina modified with an additive. Based on the weight of the silicon scavenger catalyst, the Group VIB metal oxide content is 5%-20%, and the Group VIII metal oxide content is 1%-8%. The specific surface area is 100-500m 2 / g, pore volume of 0.3-1.2mL / g; the active metal of the light distillate oil hydrogenation catalyst is a Group VIB metal oxide and / or a Group VIII metal oxide, the carrier is alumina or alumina modified with an additive, and the Group VIB metal oxide content is 5%-30% and the Group VIII metal oxide content is 1%-15% based on the weight of the catalyst; the specific surface area is 100-300m 2 / g, and the pore volume is 0.3-0.8mL / g.

8. The method according to claim 1, wherein: When the hydrogenation reactor in the light component reaction zone is started up, the feed temperature is 130~180℃ in the heating furnace. After the bed temperature rises by more than 40℃, the heating furnace is stopped and the feed temperature requirement is met by heat exchange with the reactor outlet logistics at room temperature of 20~40℃.

9. The method according to claim 1, wherein: The mass content of the organic matter containing hydroxyl and / or carboxyl groups in the high-silica naphtha is 0.01wt%-5wt%.

10. The method according to claim 1, wherein: The sulfur content of the effluent from the light component reaction zone is ≯500 μg / g, and the Si content is ≯1 μg / g.

11. The method according to claim 1, wherein: Process conditions of the heavy component reaction zone: reaction pressure 2.0-8.0 MPa; hydrogen-to-oil volume ratio 100:1-600:1; volume space velocity 0.1-5.0 h -1 The reactor inlet temperature is 250-400°C. The active metal of the diesel hydrogenation catalyst is a Group VIB metal oxide and / or a Group VIII metal oxide, and the Group VIB metal oxide content is 5%-30%, and the Group VIII metal oxide content is 1%-15%, based on the weight of the hydrogenation catalyst. The carrier is alumina or additive-modified alumina, and the additive is one or more of B, P, Mg, Zr or Si. The additive, calculated as oxide, accounts for 3%-15% based on the weight of the carrier.

12. The method according to claim 11, wherein: Process conditions of the heavy component reaction zone: reaction pressure 3.5~6.5MPa; hydrogen-oil volume ratio 200:1-500:1; volume space velocity 0.5-3.0h -1 ; Reactor inlet temperature 260-330℃.

13. The method according to claim 11, wherein: In the diesel hydrogenation catalyst, based on the weight of the hydrogenation catalyst, the content of the Group VIB metal oxide is 15%-25%, and the content of the Group VIII metal oxide is 3%-8%.

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