A residue hydrotreating method for improving desulfurization selectivity

Abstract

The present invention relates to a residue hydrotreating method for improving desulfurization selectivity. After the residue enters the first reaction zone of the fixed-bed residue hydrotreating and reacts, the reaction effluent is uniformly mixed with water containing an emulsifier and then enters the second reaction zone of the fixed-bed residue hydrotreating, where it contacts a residue hydrotreating catalyst and reacts. After separation in the second reaction zone of the fixed-bed residue hydrotreating, gas, hydrotreated naphtha, hydrotreated diesel, and hydrotreated tail oil are obtained. The obtained hydrotreated tail oil is a blending component for marine fuel or a feedstock for delayed coking. The present invention can reduce the sulfur content of the hydrotreated residue while keeping the carbon residue value unchanged, and can effectively reduce hydrogen consumption.

Description

Technical Field

[0001] The present invention relates to the technical field of residue hydrotreating, and particularly to a residue hydrotreating method for improving desulfurization selectivity. Background Art

[0002] At present, the heavy and inferior quality of crude oil around the world is becoming increasingly serious, while the demand for high-quality light oil products is constantly increasing. Therefore, the processing and full utilization of heavy oil have become the main topics of concern in the refining industry. Residue is the heaviest component in crude oil, with a large average relative molecular mass, high boiling point, high viscosity and polarity. It concentrates most of the sulfur-containing, nitrogen-containing, oxygen-containing compounds and resins in crude oil, as well as all the asphaltenes and heavy metals, which is the key point and difficulty in oil product processing.

[0003] The quality of petroleum coke products obtained by delayed coking is greatly affected by the variety of crude oil processed by refineries. Approximately 70% of the world's petroleum coke is high-sulfur, fuel-grade petroleum coke. In recent years, the state has successively introduced new environmental protection regulations, which has increased the environmental protection pressure unprecedentedly. The use of high-sulfur petroleum coke as a highly polluting product is significantly restricted, and the rigid demand in the fuel industry will shift to high-quality petroleum coke or alternative fuels. The demand for low-sulfur petroleum coke in downstream industries will increase significantly, while the demand for high-sulfur petroleum coke will shrink. It is expected that a situation of tight resources of low-sulfur petroleum coke and overcapacity of high-sulfur petroleum coke will be formed.

[0004] To solve the problem of high-sulfur coke, a process route of fixed-bed residue hydrotreating + delayed coking can be adopted. The sulfur content of the delayed coking feedstock can be reduced through fixed-bed residue hydrotreating, so that low-sulfur coke can be produced by delayed coking. Different from the ideal carbon residue value of catalytic cracking feedstock being relatively low, the ideal carbon residue value of the delayed coking feedstock is not less than 15%. This requires selective desulfurization to be achieved during the production of the delayed coking feedstock by the fixed-bed residue hydrotreating process, that is, while the desulfurization rate meets the requirements, the hydrogenation conversion rate of the carbon residue is minimized as much as possible.

[0005] In addition, with the continuous aggravation of global environmental problems, environmental protection regulations have been successively introduced at home and abroad to limit the sulfur mass fraction of marine fuel oil (hereinafter referred to as marine fuel). Facing the strictness of environmental protection regulations, it is generally believed that using low-sulfur heavy marine fuel (referring to residual marine fuel with a sulfur mass fraction not exceeding 0.5% or not exceeding 0.1%) will be the main solution for shipowners, and the cost of marine fuel seriously affects the choice of refueling locations by shipowners. The main blending component of low-sulfur heavy marine fuel is low-sulfur hydrotreated residue. Therefore, how to reduce the cost of hydrotreated residue has become a new challenge for the fixed-bed residue hydrotreating process. The requirements for the carbon residue value of low-sulfur heavy marine fuel are very loose. Therefore, if selective desulfurization can be achieved, the hydrogen consumption in the process can be reduced, thereby effectively reducing the cost of hydrotreated residue.

[0006] CN105505449A relates to a hydrogen - donating coking method. In this method, a hydrogen - donating agent is added to coking raw material residue oil at a ratio of 0.1 - 30 wt% as a mixed feedstock for coking reaction; the reaction temperature is 450 - 550 °C, the reaction pressure is 0.1 - 0.8 MPa, and the reaction residence time is 0.1 - 240 min; the hydrogen - donating agent is selected from hydro - treated catalytic cracking diesel or a narrow fraction of hydro - treated catalytic cracking diesel; the distillation range is between 200 - 350 °C. This method can increase the yield of coking liquid products and reduce the coke yield.

[0007] CN102585897A relates to a hydro - upgrading method for heavy oil with low hydrogen content using hydrogen - donating hydrocarbons. A hydrogen - donating hydrocarbon stream rich in hydrogen - donating hydrocarbons is used in the hydro - upgrading process of heavy oil such as coal tar pitch, which has the effects of inhibiting the condensation and coking rate, increasing the yield of liquid products in the hydro - conversion process of coal tar heavy oil, improving product quality, reducing the reaction temperature rise, and enhancing the operation stability and safety of the unit. Summary of the Invention

[0008] The present invention aims to solve the problem of too low desulfurization selectivity when residue oil raw materials are used in hydrogenation to produce coking raw materials and heavy fuel oil for ships.

[0009] The residue oil hydro - treatment method for improving desulfurization selectivity provided by the present invention includes:

[0010] (l) The residue oil enters the first reaction zone of fixed - bed residue oil hydrogenation and undergoes a hydrogenation reaction under the action of hydrogen and a residue oil hydrogenation catalyst. The reaction effluent of the first reaction zone of fixed - bed residue oil hydrogenation is uniformly mixed with water containing an emulsifier, and the resulting mixture enters the second reaction zone of fixed - bed residue oil hydrogenation and reacts in contact with the residue oil hydrogenation catalyst. Among them, the weight ratio of residue oil to water is 100:1 - 20, and the weight ratio of emulsifier to water is 0.5 - 10:100;

[0011] (2) The reaction effluent of the second reaction zone of fixed - bed residue oil hydrogenation obtained in step (1) enters a hot high - pressure separator and is separated into a first gas - phase stream and a first liquid - phase stream; the obtained first gas - phase stream enters a cold high - pressure separator and is separated into a second gas - phase stream, a second liquid - phase stream, and acidic water;

[0012] (3) The first liquid - phase stream and the second liquid - phase stream enter a fractionating tower together for fractionation to obtain gas, hydro - treated naphtha, hydro - treated diesel, and hydro - treated tail oil. The obtained hydro - treated tail oil is a blending component for ship fuel or a raw material for delayed coking.

[0013] The present invention has no restrictions on residue oil raw materials, and both atmospheric residue oil and / or vacuum residue oil can be processed.

[0014] The present invention has no limitation on the mixing mode of water containing an emulsifier and the reaction effluent of the first reaction zone of fixed-bed residue hydrotreating. Any mixing mode that can achieve uniform mixing is applicable to the present invention.

[0015] In another embodiment of the present invention, after the water containing an emulsifier is mixed with cold hydrogen, they enter together between the catalyst beds of the second reaction zone of fixed-bed residue hydrotreating.

[0016] In one embodiment of the present invention, the weight ratio of residue oil to water is 100:3 - 12, and the weight ratio of emulsifier to water is 1.5 - 5:100.

[0017] The inventors of the present invention have found through research that the additional water added in the second reaction zone of fixed-bed residue hydrotreating can improve the selectivity of residue hydrodesulfurization. That is, under suitable reaction conditions, the sulfur content can be reduced while keeping the coke value of the product unchanged. Since the added water vaporizes and reduces the hydrogen partial pressure in the second reaction zone of fixed-bed residue hydrotreating, the inhibitory effect on the hydroconversion of coke is relatively obvious, thus improving the selectivity of hydrodesulfurization. In addition, the present invention optimizes the amount of water added. On the one hand, if the amount of water is too small, the effect of improving the selectivity of hydrodesulfurization is not obvious. On the other hand, adding too much water will have an adverse effect on the strength of the fixed-bed residue hydrotreating catalyst.

[0018] In one embodiment of the present invention, the function of the emulsifier in step (1) is to make the residue oil and water mix evenly; the emulsifier is a single surfactant or a mixture composed of a surfactant and other additives. The elements constituting the emulsifier are C, H, and at least one of S, N, and O. Based on the mass of the emulsifier, the sum of the mass fractions of S element and N element is 0 - 10%, preferably 0 - 5%.

[0019] In the present invention, the emulsifier can be commercially available commercial grades, and can be used alone or in combination of several emulsifiers, but the elements contained therein are limited to C, H, S, N, and O to ensure that no new elements are introduced into the system.

[0020] In the preferred case, the emulsifier includes one or more of sorbitan monooleate, sorbitan monostearate, polyoxyethylene sorbitan fatty acid ester, and alkylphenol polyoxyethylene ether.

[0021] In one embodiment of the present invention, the process conditions of the first reaction zone of fixed-bed residue hydrotreating are: hydrogen partial pressure 5.0 MPa - 22.0 MPa, reaction temperature 330 °C - 450 °C, liquid hourly space velocity 0.5 h -1～ 2.5 h -1 、hydrogen-oil ratio 350 - 1500;

[0022] The process conditions for the second reaction zone of fixed-bed residue hydrotreating are as follows: hydrogen partial pressure is 5.0 MPa to 22.0 MPa, reaction temperature is 330 °C to 450 °C, volumetric space velocity is 0.5 h -1 to 2.5 h -1 and hydrogen-oil ratio is 350 to 1500.

[0023] In one embodiment of the present invention, a hydrogenation protective agent and a hydrogenation demetallization agent are sequentially loaded in the first reaction zone of fixed-bed residue hydrotreating, and a hydrogenation desulfurization and decarbonization agent is loaded in the second reaction zone of fixed-bed residue hydrotreating. Based on the total volume of the residue hydrotreating catalyst, the loading amount of the hydrogenation protective agent is 1% to 20%, the loading amount of the hydrogenation demetallization agent is 20% to 60%, and the loading amount of the hydrogenation desulfurization and decarbonization agent is 30% to 70%.

[0024] In one embodiment of the present invention, each of the hydrogenation protective agent, the hydrogenation demetallization agent, and the hydrogenation desulfurization and decarbonization agent independently contains a carrier and an active metal component supported on the carrier. The active metal component is selected from at least one of Group VIB and / or Group VIII metal elements, and the carrier is selected from one or more of alumina, silica, and amorphous silica-alumina;

[0025] In the hydrogenation protective agent, based on the total amount of the hydrogenation protective agent, the content of the active metal component in terms of oxide is 1% to 12% by weight;

[0026] In the hydrogenation demetallization agent, based on the total amount of the hydrogenation demetallization agent, the content of the active metal component in terms of oxide is 6% to 15% by weight;

[0027] In the hydrogenation desulfurization and decarbonization agent, based on the total amount of the hydrogenation desulfurization and decarbonization agent, the content of the active metal component in terms of oxide is 8% to 25% by weight.

[0028] In the present invention, the hydrogenation desulfurization and decarbonization agent refers to a fixed-bed residue hydrotreating catalyst having both desulfurization and decarbonization functions, but the proportion of each function is not limited. The hydrogenation desulfurization agent, the hydrogenation decarbonization agent, or a combination of the two commonly used in fixed-bed residue hydrotreating technology can be regarded as the hydrogenation desulfurization and decarbonization agent of the present invention.

[0029] In the present invention, after the reaction effluent obtained from the second reaction zone of fixed-bed residue hydrotreating is subjected to gas-liquid separation, the resulting liquid-phase stream enters a fractionating tower for fractionation. In one embodiment of the present invention, before the first liquid-phase stream and the second liquid-phase stream enter the fractionating tower, gas-liquid separation is performed in a low-pressure separator, and the liquid-phase stream separated into low-pressure gas and acidic water enters the fractionating tower. The low-pressure separator is one or more.

[0030] In one embodiment of the present invention, the acidic water separated by the cold high-pressure separator in step (2) and the acidic water separated by the low-pressure separator enter the water treatment unit for sewage treatment. In one embodiment of the present invention, the treated water obtained can be recycled to step (1).

[0031] In the present invention, the fractionation tower separates gases, hydrotreated naphtha, hydrotreated diesel, and hydrotreated tail oil. The obtained hydrotreated naphtha can be used as a raw material for a reforming unit or an ethylene unit. The obtained hydrotreated diesel is a blending component for diesel products. The boiling range of the obtained hydrotreated tail oil is > 350 °C, and the obtained hydrotreated tail oil is a blending component for marine fuel or a raw material for delayed coking.

[0032] The present invention improves the desulfurization selectivity of residue hydrotreating by adding water. Under suitable conditions, the sulfur content can be reduced while maintaining the carbon residue value of the hydrotreated residue unchanged. The present invention can effectively reduce hydrogen consumption and provide high-quality raw materials for delayed coking or low-sulfur high-quality blending components for heavy marine fuel oil. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 is a schematic diagram of one embodiment of the residue hydrotreating method for improving desulfurization selectivity provided by the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0034] The present invention will be further described below in conjunction with the drawings, but the present invention is not limited thereby.

[0035] Figure 1 is a schematic diagram of one embodiment of the residue hydrotreating method for improving desulfurization selectivity of the present invention. As Figure 1 shown, the residue from pipeline 1 is mixed with hydrogen from pipeline 4 and then enters the first fixed-bed residue hydrotreating reaction zone 2 together. A hydrotreating reaction is carried out under the action of hydrogen and a residue hydrotreating catalyst. The reaction effluent of the first fixed-bed residue hydrotreating reaction zone 2 is withdrawn through pipeline 3 and uniformly mixed with water containing an emulsifier from pipeline 5. The obtained mixture enters the second fixed-bed residue hydrotreating reaction zone 7 through pipeline 6 and reacts in contact with the residue hydrotreating catalyst. The reaction effluent of the second fixed-bed residue hydrotreating reaction zone 7 enters the hot high-pressure separator 9 through pipeline 8 for gas-liquid separation, separating to obtain a first gas-phase stream and a first liquid-phase stream. The first gas-phase stream enters the cold high-pressure separator 11 through pipeline 10 for further gas-liquid separation, separating to obtain a second gas-phase stream, a second liquid-phase stream, and acidic water. The obtained second gas-phase stream removes H 2After S, it enters the recycle hydrogen compressor 13 through pipeline 12. After being pressurized, it is mixed with fresh hydrogen from pipeline 14 and then mixed with residue oil through pipeline 4. The acidic water separated by the cold high-pressure separator 11 is discharged from the unit through pipeline 15. The first liquid-phase stream obtained from the hot high-pressure separator 9 is mixed with the second liquid-phase stream obtained from the cold high-pressure separator 11 through pipeline 16, and then enters the fractionating tower 18 through pipeline 17 to separate gas, hydrotreated naphtha, hydrotreated diesel, and hydrotreated tail oil. Among them, the gas, hydrotreated naphtha, and hydrotreated diesel are sent out of the unit through pipelines 19, 20, and 21 respectively, and the hydrotreated tail oil is drawn out through pipeline 22 and used as a blending component for marine fuel or a feedstock for delayed coking.

[0036] The present invention will be further described below in conjunction with embodiments, but the present invention is not limited thereby.

[0037] The residue oil hydrogenation tests of the examples and comparative examples were carried out in a fixed-bed double-tube reactor. A hydrogenation protective agent and a hydrogenation demetallization agent were loaded in the first reactor (referred to as the first reactor for short), and a hydrogenation desulfurization and decarbonization agent was loaded in the second reactor (referred to as the second reactor for short). The filling volume ratio of the three was 1:4:6. Among them, the commercial brand of the hydrogenation protective agent was RG-30B, the commercial brand of the hydrogenation demetallization agent was RDM-32, and the commercial brand of the hydrogenation desulfurization and decarbonization agent was RMS-30, all produced by Zibo Qimao Catalyst Co., Ltd.

[0038] Example 1

[0039] The properties of the residue oil are shown in Table 1. The residue oil and hydrogen enter the first reactor together and contact the hydrogenation protective agent and the hydrogenation demetallization agent in sequence for hydrogenation reaction. The reaction effluent of the first reactor is uniformly mixed with water containing an emulsifier, and the resulting mixture enters the second reactor and contacts the hydrogenation desulfurization and decarbonization agent for reaction. Its reaction effluent enters the hot high-pressure separator and is separated into a first gas-phase stream and a first liquid-phase stream; the first gas-phase stream enters the cold high-pressure separator and is separated into a second gas-phase stream, a second liquid-phase stream, and acidic water; the first liquid-phase stream and the second liquid-phase stream enter the fractionating tower together for fractionation to obtain gas, hydrotreated naphtha, hydrotreated diesel, and hydrotreated tail oil. Among them, the weight ratio of the residue oil to water is 100:3, and the weight ratio of the emulsifier to water is 1.5:100. The test conditions are as follows: hydrogen partial pressure 15.0 MPa, temperature of the first reactor 380 °C, temperature of the second reactor 390 °C, hydrogen-oil ratio 700 Nm 3 / m 3 , and the liquid hourly space velocity of the residue oil is 0.25 h -1 . The properties of the hydrotreated naphtha, hydrotreated diesel, and hydrotreated residue oil are shown in Table 2. The hydrogen consumption of this example is 1.33%.

[0040] Example 2

[0041] The residue oil raw material, emulsifier, process flow, and test conditions used in Example 2 are the same as those in Example 1. The difference from Example 1 is that in Example 2, the weight ratio of residue oil A to water is 100:5, and the weight ratio of emulsifier to water is 2.5:100. After the device runs stably, a sample of hydrogenated residue oil is collected every 24 hours, and a total of 3 samples are collected. The properties of the hydrogenated residue oil are shown in Table 3.

[0042] Example 3

[0043] The process flow and test conditions used in Example 3 are the same as those in Example 1. The difference from Example 1 is that the weight ratio of residue oil to water is 100:10, and the weight ratio of emulsifier to water is 4:100. The properties of the generated hydrogenated residue oil are shown in Table 3.

[0044] Comparative Example 1

[0045] The residue oil raw material, emulsifier, process flow, and test conditions used in this comparative example are the same as those in Example 1. Compared with Example 1, in this comparative example, the water containing emulsifier is mixed with the residue oil and enters the first reactor. The test conditions are: hydrogen partial pressure 15.0 MPa, first reactor temperature 380 °C, second reactor temperature 390 °C, hydrogen-oil ratio 700 Nm 3 / m 3 , and the residue oil space velocity is 0.25 h -1 . The properties of the generated hydrogenated residue oil are shown in Table 3.

[0046] Comparative Example 2

[0047] The residue oil raw material, process flow, and test conditions used in this comparative example are the same as those in Example 1. Compared with Example 1, in this comparative example, the raw material oil is only residue oil. The test conditions are: hydrogen partial pressure 15.0 MPa, first reactor temperature 380 °C, second reactor temperature 390 °C, hydrogen-oil ratio 700 Nm 3 / m 3 , and the liquid hourly space velocity of the residue oil is 0.25 h -1 . The properties of the generated hydrogenated residue oil are shown in Table 3. The hydrogen consumption of this comparative example is 1.47%.

[0048] Comparative Example 3

[0049] The residue oil raw material, process flow, and test conditions used in this comparative example are the same as those in Example 2. Compared with Example 2, no emulsifier is added in this comparative example. The test conditions are: hydrogen partial pressure 15.0 MPa, first reactor temperature 380 °C, second reactor temperature 390 °C, hydrogen-oil ratio 700 Nm 3 / m 3 , and the liquid hourly space velocity of the residue oil is 0.25 h -1 . A sample of hydrogenated residue oil is collected every 24 hours, and a total of 3 samples are collected. The properties of the obtained hydrogenated residue oil are shown in Table 3.

[0050] Comparative Example 4

[0051] The residue raw material, emulsifier, process flow and test conditions used in this comparative example are the same as those in Example 2. Compared with Example 2, the only difference is that the weight ratio of residue to water in this comparative example is 100:0.5. The test conditions are as follows: hydrogen partial pressure 15.0 MPa, temperature of the first reactor 380 °C, temperature of the second reactor 390 °C, hydrogen-oil ratio 700 Nm 3 / m 3 , and the hourly space velocity of the residue liquid is 0.25 h -1 . The properties of the hydrotreated residue are shown in Table 3.

[0052] Comparative Example 5

[0053] The residue raw material, emulsifier, process flow and test conditions used in this comparative example are the same as those in Example 2. Compared with Example 2, the only difference is that the weight ratio of residue to water in this comparative example is 100:22. The test conditions are as follows: hydrogen partial pressure 15.0 MPa, temperature of the first reactor 380 °C, temperature of the second reactor 390 °C, hydrogen-oil ratio 700 Nm 3 / m 3 , and the hourly space velocity of the residue liquid is 0.25 h -1 . The properties of the hydrotreated residue are shown in Table 3.

[0054] Comparative Example 6

[0055] The residue raw material, emulsifier, process flow and test conditions used in this comparative example are the same as those in Example 2. Compared with Example 2, the only difference is that the weight ratio of emulsifier to water in this comparative example is 12:100. The test conditions are as follows: hydrogen partial pressure 15.0 MPa, temperature of the first reactor 380 °C, temperature of the second reactor 390 °C, hydrogen-oil ratio 700 Nm 3 / m 3 , and the hourly space velocity of the residue liquid is 0.25 h -1 . The properties of the hydrotreated residue are shown in Table 3.

[0056] Comparative Example 7

[0057] The residue raw material, emulsifier, process flow and test conditions used in this comparative example are the same as those in Example 2. Compared with Example 2, the only difference is that the weight ratio of emulsifier to water in this comparative example is 0.3:100. The test conditions are as follows: hydrogen partial pressure 15.0 MPa, temperature of the first reactor 380 °C, temperature of the second reactor 390 °C, hydrogen-oil ratio 700 Nm 3 / m 3 , and the hourly space velocity of the residue liquid is 0.25 h -1 . The properties of the hydrotreated residue are shown in Table 3.

[0058] As can be seen from Table 3, the sulfur contents of the hydrotreated resids in Examples 1 to 3 are 0.23%, 0.24% (average value of three samples), and 0.24% respectively, and the Conradson carbon values are 6.81%, 6.97% (average value of three samples), and 7.00% respectively. Compared with Comparative Example 1 and Comparative Example 2, the sulfur content of the hydrotreated resid remains unchanged, but the Conradson carbon value increases, indicating that the sulfur content can be reduced while maintaining the Conradson carbon value of the product unchanged by controlling the operating conditions. It can be seen from Comparative Example 1 and Comparative Example 2 that injecting water into the first reactor also has the effect of improving the hydrodesulfurization selectivity, but it is not as obvious as directly injecting water into the second reactor.

[0059] As can be seen from Table 3, the Conradson carbon values of the three samples in Example 2 are relatively stable, while the changes in the Conradson carbon values of the three hydrotreated resid samples without adding emulsifier in Comparative Example 3 are relatively large, indicating that whether water and resid can be mixed evenly will affect the stability of the product properties.

[0060] As can be seen from Example 2, Comparative Example 4 and Comparative Example 5, if the addition amount of water is not within the range, good technical effects cannot be achieved. If the addition amount is too small, the technical effects cannot be reflected, and if the addition amount is too large, the catalyst structure will be damaged, thus reducing the technical effects.

[0061] In the present invention, the desulfurization selectivity is defined as the ratio of the desulfurization rate to the Conradson carbon conversion rate. Through a large number of experimental studies, the inventors of the present invention have shown that for the same feedstock oil under the same reaction conditions, by some conventional technical means, the absolute value of the desulfurization selectivity can increase by at most 0.06. Further, it can be seen from Table 3 that by comparing the desulfurization selectivity data of Example 3 and Comparative Example 2, through the addition of water, the desulfurization selectivity increases from 2.07 to 2.24, the absolute value increases by 0.17, and the percentage increases by 8.2%. It can be seen that the desulfurization selectivity can be effectively improved by the addition of water.

[0062] Table 1 Properties of Resid Feedstock

[0063] <![CDATA[Density (20 °C), kg / m 3 > 956.6 <![CDATA[Viscosity (100 °C), mm 2 / s]]> 108.5 CCR, wt% 10.99 S, wt% 1.28 N, ppm 3300 Ni + V, ppm 90.6

[0064] Table 2 Properties and Yields of Hydrogenation Products in Example 1

[0065] Hydrotreated naphtha Hydrotreated diesel Hydrotreated residue CCR, wt% - - 6.86 S, wt% 50 ppm 200 ppm 0.23 N, ppm 80 ppm 300 ppm 2580 Ni + V, ppm - - 29.0 <![CDATA[Yield * , wt%]]> 1.95 8.08 89.32

[0066] *Based on the resid feed.

[0067] Table 3 Properties of Resid Feedstock and Hydrotreated Resid

[0068]

[0069]

Claims

1. A residue hydrotreating method for improving desulfurization selectivity, comprising: (l) The residue oil enters the first reaction zone of the fixed-bed residue oil hydrotreating unit, where a hydrotreating reaction occurs under the action of hydrogen and the residue oil hydrotreating catalyst. The reaction effluent from the first reaction zone of the fixed-bed residue oil hydrotreating unit is uniformly mixed with water containing an emulsifier, and the resulting mixture enters the second reaction zone of the fixed-bed residue oil hydrotreating unit and reacts upon contact with the residue oil hydrotreating catalyst. Among them, the weight ratio of the residue oil to water is 100:1 to 20, and the weight ratio of the emulsifier to water is 0.5 to 10:

100. The process conditions for the first reaction zone of the fixed-bed residue oil hydrotreating unit are as follows: hydrogen partial pressure 5.0 MPa to 22.0 MPa, reaction temperature 330 °C to 450 °C, liquid hourly space velocity 0.5 h -1~ to 2.5 h -1 , hydrogen-oil ratio 350 to 1500; The process conditions for the second reaction zone of the fixed-bed residue oil hydrotreating unit are as follows: hydrogen partial pressure 5.0 MPa to 22.0 MPa, reaction temperature 330 °C to 450 °C, space velocity 0.5 h -1 to 2.5 h -1 , hydrogen-oil ratio 350 to 1500; A hydrogenation protecting agent and a hydrogenation demetallization agent are successively filled in the first reaction zone of the fixed-bed residue hydrotreating. A hydrogenation desulfurization and decarbonization agent is filled in the second reaction zone of the fixed-bed residue hydrotreating. Based on the total volume of the residue hydrotreating catalyst, the filling amount of the hydrogenation protecting agent is 1-20%, the filling amount of the hydrogenation demetallization agent is 20-60%, and the filling amount of the hydrogenation desulfurization and decarbonization agent is 30-70%; (2) The reaction effluent from the second reaction zone of the fixed-bed residue hydrotreating obtained in step (1) enters a hot high-pressure separator and is separated into a first gas-phase stream and a first liquid-phase stream; the obtained first gas-phase stream enters a cold high-pressure separator and is separated into a second gas-phase stream, a second liquid-phase stream and acidic water; (3) The first liquid-phase stream and the second liquid-phase stream enter a fractionating tower together for fractionation to obtain gas, hydrotreated naphtha, hydrotreated diesel and hydrotreated tail oil. The obtained hydrotreated tail oil is a blending component for marine fuel or a feedstock for delayed coking.

2. The method according to claim 1, characterized in that, the weight ratio of residue to water is 100:3-12, and the weight ratio of emulsifier to water is 1.5-5:

100.

3. The method according to claim 1, characterized in that, in step (1), the function of the emulsifier is to make the residue and water mix evenly; the emulsifier is a single surfactant or a mixture composed of a surfactant and other additives. The elements constituting the emulsifier are C, H and at least one of S, N, O. Based on the mass of the emulsifier, the sum of the mass fractions of S element and N element is 0-10%.

4. The method according to claim 3, characterized in that, based on the mass of the emulsifier, the sum of the mass fractions of S element and N element is 0-5%.

5. The method according to claim 3, characterized in that, the emulsifier includes one or more of sorbitan monooleate, sorbitan monostearate, polyoxyethylene sorbitan fatty acid ester, alkylphenol polyoxyethylene ether.

6. The method according to claim 1, characterized in that, each of the hydrogenation protecting agent, the hydrogenation demetallization agent and the hydrogenation desulfurization and decarbonization agent independently contains a carrier and an active metal component supported on the carrier. The active metal component is selected from at least one of Group VIB and / or Group VIII metal elements. The carrier is selected from one or more of alumina, silica and amorphous silica-alumina; in the hydrogenation protecting agent, based on the total amount of the hydrogenation protecting agent, calculated as the oxide, the content of the active metal component is 1-12% by weight; in the hydrogenation demetallization agent, based on the total amount of the hydrogenation demetallization agent, calculated as the oxide, the content of the active metal component is 6-15% by weight; in the hydrogenation desulfurization and decarbonization agent, based on the total amount of the hydrogenation desulfurization and decarbonization agent, calculated as the oxide, the content of the active metal component is 8-25% by weight.

7. The method according to claim 1, characterized in that, after the water containing the emulsifier is mixed with cold hydrogen, they enter together between the catalyst beds in the second reaction zone of the fixed-bed residue hydrotreating.

8. The method according to claim 1, characterized in that, Before the first liquid-phase logistics and the second liquid-phase logistics enter the fractionating column, gas-liquid separation is carried out in a low-pressure separator, and the liquid-phase logistics separated into low-pressure gas and acidic water enter the fractionating column.

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