A process for processing high sulfur residuum

Abstract

The present application relates to the field of processing high sulfur residue oil, and discloses a method for processing high sulfur residue oil, which comprises the following steps: (1) carrying out a hydrodesulfurization reaction on a mixed raw material containing high sulfur residue oil and catalytic cracking heavy oil I, to obtain a hydrodesulfurization reaction stream; (2) separating the hydrodesulfurization reaction stream to obtain hydro-wax oil and hydro-reduced residue I; (3) carrying out a mild catalytic cracking reaction on the hydro-wax oil and a part of the hydro-reduced residue I, to obtain a mild catalytic cracking reaction stream; (4) separating the mild catalytic cracking reaction stream to obtain catalytic cracking heavy oil I; and (5) blending a part of the catalytic cracking heavy oil I with a part of the hydro-reduced residue I to obtain low-sulfur marine fuel. The method for processing high sulfur residue oil can produce light oil and low-sulfur marine fuel simultaneously and in large quantities, thereby reducing the production cost of the light oil and low-sulfur marine fuel.

Description

Technical Field

[0001] This invention relates to the field of processing high-sulfur residue oil, and more specifically, to a method for processing high-sulfur residue oil. Background Technology

[0002] Increasingly stringent environmental regulations worldwide have led to the widespread use of clean fuels. Following the clean production of bulk oils such as gasoline and diesel, low-sulfur clean marine fuel oil (referred to as marine fuel) has become one of the key oil products that the refining industry will focus on in the coming years.

[0003] The combustion of high-sulfur fuel oil produces pollutants such as sulfur oxides, nitrogen oxides, and particulate matter. To control pollution, countries around the world have begun to implement new sulfur emission limit regulations.

[0004] Currently, the market is mainly dominated by high-sulfur heavy marine fuel and light diesel marine fuel, with high-sulfur heavy marine fuel accounting for about 85% and light diesel marine fuel accounting for about 15%.

[0005] However, it is difficult to directly produce low-sulfur marine fuel with a sulfur content of no more than 0.5% by weight using the current blending components.

[0006] Because the residue hydrotreating unit is a high-pressure hydrotreating unit, the investment is large and the operating cost is high; at the same time, the cost of using the hydrotreating residue directly as a low-sulfur marine fuel or a low-sulfur marine fuel blending component is high, which will also cause the catalytic cracking unit that has been built and is matched with the residue hydrotreating unit to be idle.

[0007] If the hydrotreated atmospheric residue is subjected to vacuum distillation, the hydrotreated slag portion can be used as a marine fuel blending component, and the hydrotreated wax oil can be used as a feedstock for hydrocracking or catalytic cracking. This will increase the yield of high-value products, greatly reduce marine fuel costs, and improve the economic benefits of enterprises.

[0008] However, hydrotreated slag has a high sulfur content and high viscosity, so it is necessary to add low-viscosity, low-sulfur components to blend it in order to produce low-sulfur marine fuel.

[0009] After hydrotreating, high-sulfur residual oil can be used to produce low-sulfur marine fuel or blending components for low-sulfur marine fuel. For example, CN112300833A discloses a method for producing low-sulfur residual marine fuel. This method involves sequentially loading a hydrotreating protective catalyst, a hydrodemetallization catalyst, and a hydrodemetallization and desulfurization catalyst along the stream flow direction in a residual oil hydrotreating unit. This method exhibits good hydrotreating activity and better reaction stability, enabling long-term production of high-quality low-sulfur marine fuel.

[0010] Catalytic slurry oil is rich in polycyclic aromatic hydrocarbons, with high carbon content and low hydrogen content. After desolidification and desulfurization pretreatment, it can be used as a blending component for low-sulfur marine fuel. For example, CN111088068A discloses a method for producing low-sulfur marine fuel oil. This method involves mixing catalytic slurry oil with a first additive, followed by sedimentation separation to obtain a first material and residue. The first material undergoes a hydrogenation reaction under the action of a hydrogenation catalyst and hydrogen. The resulting liquid effluent enters a clarification unit, and the clarified oil obtained after separation is further subjected to solid-liquid separation to obtain purified slurry oil. The purified slurry oil is then mixed with hydrogenated tail oil from a high-sulfur feedstock to obtain low-sulfur marine fuel oil.

[0011] For example, CN101531923A discloses a method for combining catalytic cracking and hydrotreating of low-quality feedstock oil. The low-quality feedstock oil is hydrotreated, and the resulting hydrotreated residue is then subjected to catalytic cracking to obtain propylene, gasoline, catalytic cracked heavy oil, and other products. The catalytic cracked heavy oil enters the hydrotreating unit, and the hydrotreated catalytic cracked heavy oil is recycled to the catalytic cracking unit for further reaction to obtain propylene and gasoline. This method employs moderate catalytic cracking technology, which can reduce the yield of coke and dry gas during catalytic cracking, but it will generate some unconverted catalytic cracked heavy oil. Catalytic cracked heavy oil is also rich in polycyclic aromatic hydrocarbons, but compared to catalytic slurry oil, it has lower viscosity and lower sulfur content, making it easier to remove solids and allowing it to be used as a blending component for low-sulfur marine fuel without desulfurization.

[0012] It is known that most existing technologies achieve desulfurization of residual oil through residual oil hydrotreating units in order to obtain the main blending components of low-sulfur heavy marine fuel.

[0013] However, the high pressure, large investment, and high operating costs of residue hydrotreating units will increase the production cost of low-sulfur heavy marine fuel. Moreover, most residue hydrotreating units are currently matched with downstream catalytic cracking units, which will result in a waste of the processing capacity of the catalytic cracking unit after the production of low-sulfur marine fuel. Summary of the Invention

[0014] The purpose of this invention is to overcome the shortcomings of existing technologies that cannot utilize high-sulfur residue oil to simultaneously and in large quantities produce light oil products and low-sulfur marine fuel oil, while saving costs.

[0015] To achieve the above objectives, the present invention provides a method for processing high-sulfur residue oil, the method comprising:

[0016] (1) In the presence of a selective hydrodesulfurization catalyst, a mixed feedstock containing high-sulfur residue oil and recycled catalytic cracking heavy oil I is subjected to a hydrodesulfurization reaction to obtain a hydrodesulfurization reaction stream.

[0017] (2) The hydrodesulfurization reaction stream is separated to obtain hydrotreated gasoline, hydrotreated diesel, hydrotreated wax oil and hydrotreated slag I;

[0018] (3) In the presence of a catalytic cracking catalyst, the hydrotreated wax oil and a portion of the hydrotreated slag I are subjected to a moderate catalytic cracking reaction to obtain a moderate catalytic cracking reaction stream;

[0019] (4) The mild catalytic cracking reaction stream is separated to obtain catalytic cracking gasoline, catalytic cracking diesel and catalytic cracking heavy oil I; a portion of the catalytic cracking heavy oil I is recycled back to step (1) to form the mixed feedstock;

[0020] (5) The remaining portion of the catalytic cracking heavy oil I and the remaining portion of the hydrotreated slag I are blended to obtain low-sulfur marine fuel; in the low-sulfur marine fuel, the weight ratio of the catalytic cracking heavy oil I to the hydrotreated slag I is 0.1-2:1.

[0021] In the high-sulfur residue oil, the sulfur content by mass is greater than 3.0%, and the density of the high-sulfur residue oil at 20°C is greater than 0.97 g / cm³. 3 The kinematic viscosity at 100℃ is 500 mmHg. 2 / s-3200mm 2 / s.

[0022] The method for processing high-sulfur residue oil provided by this invention combines hydrodesulfurization treatment of catalytic cracking heavy oil with catalytic cracking, which can simultaneously and in large quantities produce light oil products and low-sulfur marine fuel oil from high-sulfur residue oil. This reduces the production cost of the light oil products and low-sulfur marine fuel oil obtained thereby, and makes effective use of petroleum resources.

[0023] In addition, the method for processing high-sulfur residue oil provided by the present invention has the following specific advantages:

[0024] (1) The method provided by the present invention can give full play to the hydrodesulfurization function of the residue hydrotreating unit and the conversion function of the catalytic cracking unit. The process is simple and reasonable and can improve the utilization efficiency of petroleum resources.

[0025] (2) The method provided by the present invention transforms the existing catalytic cracking unit into a mild catalytic cracking unit, which will not cause the catalytic cracking unit that has been built and is matched with the residue hydrotreating unit to be idle.

[0026] (3) In the method provided by the present invention, the hydrodesulfurization reaction is preferably carried out in a residual oil hydrotreating unit, and the selective hydrodesulfurization process can reduce hydrogen consumption.

[0027] (4) The method provided by the present invention can flexibly adjust the ratio of light oil and low sulfur marine fuel in the product according to different market demands. Attached Figure Description

[0028] Figure 1This is a schematic diagram of the process flow of a preferred embodiment of the method for processing high-sulfur residue oil according to the present invention.

[0029] Explanation of reference numerals in the attached figures

[0030] 1. High-sulfur residue oil; 2. Fixed-bed residue oil hydrotreating unit

[0031] 3. Hydrodesulfurization reaction stream; 4. First separation system

[0032] 5. Gases 6. Hydrogenated gasoline

[0033] 7. Hydrogenated diesel oil 8. Hydrogenated wax oil

[0034] 9. Partial hydrotreating and slag reduction unit 10. Moderate catalytic cracking unit

[0035] 11. Gases 12. Catalytic cracking gasoline

[0036] 13. Catalytic cracked diesel oil 14. Catalytic cracked heavy oil I

[0037] 15. Filtration device 16. Another part of hydrotreating and slag reduction I

[0038] 17. A portion of the filtered catalytic cracking heavy oil. 18. Another portion of the filtered catalytic cracking heavy oil. Detailed Implementation

[0039] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0040] As mentioned above, the present invention provides a method for processing high-sulfur residue oil, the method comprising:

[0041] (1) In the presence of a selective hydrodesulfurization catalyst, a mixed feedstock containing high-sulfur residue oil and recycled catalytic cracking heavy oil I is subjected to a hydrodesulfurization reaction to obtain a hydrodesulfurization reaction stream.

[0042] (2) The hydrodesulfurization reaction stream is separated to obtain hydrotreated gasoline, hydrotreated diesel, hydrotreated wax oil and hydrotreated slag I;

[0043] (3) In the presence of a catalytic cracking catalyst, the hydrotreated wax oil and a portion of the hydrotreated slag I are subjected to a moderate catalytic cracking reaction to obtain a moderate catalytic cracking reaction stream;

[0044] (4) The mild catalytic cracking reaction stream is separated to obtain catalytic cracking gasoline, catalytic cracking diesel and catalytic cracking heavy oil I; a portion of the catalytic cracking heavy oil I is recycled back to step (1) to form the mixed feedstock;

[0045] (5) The remaining portion of the catalytic cracking heavy oil I and the remaining portion of the hydrotreated slag I are blended to obtain low-sulfur marine fuel; in the low-sulfur marine fuel, the weight ratio of the catalytic cracking heavy oil I to the hydrotreated slag I is 0.1-2:1.

[0046] In the high-sulfur residue oil, the sulfur content by mass is greater than 3.0%, and the density of the high-sulfur residue oil at 20°C is greater than 0.97 g / cm³. 3 The kinematic viscosity at 100℃ is 500 mmHg. 2 / s-3200mm 2 / s.

[0047] In a preferred embodiment, the high-sulfur residue oil has a carbon content of 10-30%, a nitrogen content of 0.1-1.0%, an asphaltene content of 3-30%, a nickel content of 10-200 ppm, and a vanadium content of 10-200 ppm.

[0048] More preferably, in the low-sulfur marine fuel, the weight ratio of the catalytic cracking heavy oil I to the hydrotreated slag I is 0.9-1.4:1.

[0049] Preferably, in step (1), the hydrodesulfurization reaction is carried out in a residue hydrotreating unit, which is a fixed-bed residue hydrotreating unit containing one or two to six reactors connected in series.

[0050] According to a particularly preferred embodiment, step (1) of the present invention includes: introducing a mixed feedstock containing high-sulfur residue oil and recycled catalytic cracking heavy oil I into a fixed-bed residue oil hydrotreating unit in the presence of a selective hydrodesulfurization catalyst to carry out a hydrodesulfurization reaction, thereby obtaining a hydrodesulfurization reaction stream.

[0051] Preferably, in step (1), the conditions of the hydrodesulfurization reaction are such that the kinematic viscosity of the resulting hydrodesulfurization reaction stream at 50°C is 100-4500 mm⁻¹. 2 / s.

[0052] Preferably, in step (1), the conditions for the hydrodesulfurization reaction are at least: a reaction temperature of 380℃-430℃, a reaction pressure of 8.0MPa-19.0MPa, and a volume hourly space velocity of 0.1-1.0h. -1 The hydrogen-to-oil volume ratio is 300-1500:1.

[0053] Preferably, in step (1), the selective hydrodesulfurization catalyst contains a support and an active metal component supported on the support, wherein the active metal element in the active metal component is a combination of at least one group VIB metal element and at least one group VIII metal element; the support is selected from at least one of alumina, silica and amorphous silica-alumina.

[0054] In a preferred embodiment, the content of the active metal component, calculated as oxide, in the selective hydrodesulfurization catalyst is 3-30% by weight, and the content of the support is 70-97% by weight, based on the total weight of the selective hydrodesulfurization catalyst.

[0055] More preferably, in the selective hydrodesulfurization catalyst, the active metal elements are molybdenum and cobalt, and the support is alumina.

[0056] According to a particularly preferred embodiment, in the selective hydrodesulfurization catalyst, the active metal elements are molybdenum and cobalt, the support is alumina, and based on the total weight of the selective hydrodesulfurization catalyst, the content of molybdenum, calculated as oxide, is 1-15% by weight, the content of cobalt, calculated as oxide, is 2-15% by weight, and the content of alumina as support is 70-97% by weight.

[0057] Preferably, in the hydrodesulfurization reaction, a hydrogenation protection catalyst and a hydrogenation demetallization catalyst are sequentially loaded upstream of the selective hydrodesulfurization catalyst. That is, preferably, in the hydrodesulfurization reaction, the mixed feedstock is sequentially contacted with the hydrogenation protection catalyst, the hydrogenation demetallization catalyst, and the selective hydrodesulfurization catalyst.

[0058] Preferably, in step (1), the hydrogenation protection catalyst, the hydrogenation demetallization catalyst, and the selective hydrogenation desulfurization catalyst are each independently a Raschig ring or a butterfly extrusion.

[0059] More preferably, in the hydrodesulfurization reaction, the average particle size of the hydroprotective catalyst is 3-5 mm, the average particle size of the hydrodemetallization catalyst is 1.1-1.8 mm, and the average particle size of the selective hydrodesulfurization catalyst is 1.1-1.5 mm.

[0060] According to a preferred embodiment, in the hydrodesulfurization reaction, the loading volume ratio of the hydroprotective catalyst, the hydrodemetallization catalyst, and the selective hydrodesulfurization catalyst is 0.04-0.1:0.5-1:1.

[0061] Preferably, the catalyst bed porosity of the hydrogenation protection catalyst is 0.6-0.85.

[0062] Preferably, the catalyst bed porosity of the hydrogenation demetallization catalyst is 0.35-0.55.

[0063] This invention does not impose any particular requirements on the specific types of the hydrogenation protection catalyst and the hydrogenation demetallization catalyst. Those skilled in the art can use various hydrogenation protection catalysts and hydrogenation demetallization catalysts known in the art in this invention. The examples provided in this invention illustrate specific types of hydrogenation protection catalysts and hydrogenation demetallization catalysts, which should not be construed as limiting the invention.

[0064] Preferably, in step (1), the desulfurization selectivity of the selective hydrodesulfurization catalyst is higher than 90%.

[0065] The desulfurization selectivity described in this invention is calculated as follows: (sulfur content in high-sulfur residue oil - sulfur content in hydrodesulfurization reaction stream) * (hydrogen content in hydrodesulfurization reaction stream - hydrogen content in high-sulfur residue oil) / sulfur content in high-sulfur residue oil * 100%.

[0066] More preferably, the selective hydrodesulfurization catalyst has a desulfurization selectivity of over 92%.

[0067] Preferably, the catalyst bed porosity of the selective hydrodesulfurization catalyst is 0.35-0.55.

[0068] Preferably, in step (2), the separation conditions are controlled such that the cutting point between the hydrogenated wax oil and the hydrogenated slag I is 500-580°C.

[0069] According to a particularly preferred embodiment, in step (2), the hydrodesulfurization reaction stream is separated into a gaseous stream and a liquid stream by a hot high-pressure separator; the gaseous stream is purified and pressurized before being recycled, and the liquid stream can be further converted into gas by controlling the separation conditions.

[0070] Preferably, in step (2), the separation conditions are controlled such that the viscosity of the hydrotreated slag I at 50°C is 1000 mm. 2 / s-4200mm 2 / s.

[0071] Preferably, in step (3), the conditions for the moderate catalytic cracking reaction are at least: a reaction temperature of 450-600°C and a volume hourly space velocity of 25-100 h⁻¹. -1 .

[0072] Preferably, in step (3), the catalytic cracking catalyst is selected from at least one of zeolite, inorganic oxide, and clay.

[0073] Preferably, in step (3), the catalytic cracking catalyst is a waste equilibrium catalyst with a cracking activity of not less than 45.

[0074] According to a preferred embodiment, the catalytic cracking catalyst is a catalytic cracking catalyst of grade MLC-500 produced by Sinopec Catalyst Changling Branch.

[0075] In this invention, the cracking activity is measured by the method specified in NB / SH / T 0952-2017.

[0076] Preferably, the mild catalytic cracking reaction is carried out in a mild catalytic cracking unit.

[0077] According to a particularly preferred embodiment, step (3) of the present invention includes: introducing the hydrotreated wax oil and a portion of the hydrotreated slag I into a moderate catalytic cracking unit in the presence of a catalytic cracking catalyst to carry out a moderate catalytic cracking reaction, thereby obtaining a moderate catalytic cracking reaction stream.

[0078] Preferably, the method of the present invention further includes: in step (3), before introducing the hydrotreated wax oil and a portion of the hydrotreated sludge I into the mild catalytic cracking unit, the hydrotreated wax oil to be introduced into the unit and the hydrotreated sludge I to be introduced into the unit are preheated to obtain preheated hydrotreated wax oil and preheated hydrotreated sludge I; then the preheated hydrotreated wax oil and the preheated hydrotreated sludge I are introduced into the mild catalytic cracking unit to carry out the mild catalytic cracking reaction.

[0079] This invention does not have any special requirements for the specific conditions of preheating treatment or the temperature of the preheated material. Those skilled in the art can determine these requirements by combining the knowledge known in the art. This invention will not elaborate further here, and those skilled in the art should not understand this as a limitation of the invention.

[0080] In a preferred embodiment, the moderate catalytic cracking device of the present invention includes a first reaction zone and a second reaction zone arranged sequentially along the liquid phase stream flow direction. It should be noted that the moderate catalytic cracking device does not specifically refer to having two reaction zones; rather, it refers to the fact that in the moderate catalytic cracking device, as the moderate catalytic cracking reaction proceeds, the catalytic cracking activity of the catalytic cracking catalyst continuously decreases; due to the continuous decrease in the catalytic cracking activity of the catalytic cracking catalyst, the mass content of the catalytic cracked heavy oil I continuously increases, thereby achieving the effect of moderate catalytic cracking.

[0081] According to a particularly preferred embodiment, the preheated hydrotreated wax oil and the preheated hydrotreated slag I are introduced into the mild catalytic cracking unit under the lifting action of steam to contact the catalytic cracking catalyst contained therein for macromolecular cracking reaction, thereby removing at least one impurity of metal, sulfur, and nitrogen from the hydrotreated wax oil and the hydrotreated slag I.

[0082] Preferably, after the preheated hydrotreated wax oil and the preheated hydrotreated slag I undergo the macromolecular cracking reaction, the resulting reaction stream is further subjected to cracking reaction, hydrogen transfer reaction and isomerization reaction.

[0083] Preferably, in step (4), the separation conditions are controlled such that the cutting point between the catalytic cracked diesel and the catalytic cracked heavy oil I is 280-380°C.

[0084] Preferably, in step (4), controlling the separation conditions can also yield dry gas, propylene, propane, and C4 hydrocarbons.

[0085] Preferably, in step (5), the method further includes: filtering the catalytic cracking heavy oil I before blending it with the hydroreducing slag I to obtain pretreated catalytic cracking heavy oil with a solid content of less than 100 ppm, and then blending the pretreated catalytic cracking heavy oil with a portion of the hydroreducing slag I.

[0086] This invention does not impose special requirements on the equipment and processes used for the filtration process; any commercially available filtration technology can be employed. However, preferably, to achieve better filtration results, the filtration process utilizes a flexible desolvation technique.

[0087] The following combination Figure 1 Preferred embodiments of the present invention will be described in detail, but are not intended to limit the invention. The method of the present invention includes:

[0088] S1: In the presence of a selective hydrodesulfurization catalyst, a mixed feedstock containing high-sulfur residue oil 1 and a portion of filtered catalytic cracking heavy oil 17 is introduced into a fixed-bed residue hydrotreating unit 2 to carry out a hydrodesulfurization reaction and obtain hydrodesulfurization reaction stream 3.

[0089] S2: The hydrodesulfurization reaction stream 3 is introduced into the first separation system 4 for separation to obtain gas 5, hydrotreated gasoline 6, hydrotreated diesel 7, hydrotreated wax oil 8 and hydrotreated slag I, respectively.

[0090] S3: In the presence of a catalytic cracking catalyst, the hydrotreated wax oil 8 and a portion of the hydrotreated sludge I9 are preheated to obtain preheated hydrotreated wax oil and preheated partial hydrotreated sludge I. The preheated hydrotreated wax oil and the preheated partial hydrotreated sludge I are introduced into the mild catalytic cracking unit 10 and the second separation system for catalytic cracking reaction and separation, respectively and sequentially. Specifically, the preheated hydrotreated wax oil and the preheated partial hydrotreated sludge I undergo the mild catalytic cracking reaction in the mild catalytic cracking unit to obtain a mild catalytic cracking reaction stream.

[0091] S4: The mild catalytic cracking reaction stream is introduced into the second separation system for separation to obtain gas 11, catalytic cracked gasoline 12, catalytic cracked diesel 13, and catalytic cracked heavy oil 114, respectively.

[0092] S5: The catalytic cracking heavy oil I14 is introduced into the filtration device 15 for filtration treatment. After filtering out solid particles, the filtered catalytic cracking heavy oil is obtained. A portion of the filtered catalytic cracking heavy oil 17 is circulated back to the fixed bed residue hydrotreating unit 2 via pipeline. Another portion of the filtered catalytic cracking heavy oil 18 is blended with another portion of hydrotreating residue reduction I16 to serve as a low-sulfur ship fuel burner.

[0093] The present invention will be described in detail below through examples, but this does not limit the invention. In the following examples, unless otherwise specified, the raw materials used are all commercially available products.

[0094] Unless otherwise specified, the following examples all use Figure 1 The process flow shown is as described below, and the process flow in each example will not be described in detail in the following embodiments.

[0095] The high-sulfur residue oil feedstocks used in the example are residue oil A and residue oil B, whose main properties are shown in Table 1.

[0096] The commercial brands of the catalysts used in the fixed-bed residue hydrotreating unit are RG-30B, RDM-202 and RFS-100, all of which are produced by Changling Catalyst Plant of Sinopec Catalyst Branch. Their main properties are shown in Table 2.

[0097] The catalytic cracking catalyst used in the example is MLC-500, produced by Sinopec Catalyst Changling Branch.

[0098] Table 1

[0099] High sulfur residuum number Resid A Resid B Density (20°C), g / cm 3 ]] 1.014 1.033 Kinematic viscosity (100°C), mm2 / s 2 / second 1204 3000 Carbon residue, wt% 17.4 22.7 Nitrogen, wt% 0.58 0.36 Sulfur, wt% 3.1 4.2 Asphaltene (C7 insolubles), wt% 10.4 12.4 Metal (Ni + V) content, ppm 202 187

[0100] Table 2

[0101]

[0102] Example 1

[0103] S1: In the presence of a hydroprotection catalyst, a hydrodemetallization catalyst, and a selective hydrodesulfurization catalyst, a mixture of residue oil A containing high-sulfur residue oil and partially filtered catalytic cracking heavy oil is introduced into a fixed-bed residue oil hydrotreating unit containing a fixed-bed reactor to carry out a hydrodesulfurization reaction and obtain a hydrodesulfurization reaction stream.

[0104] In the hydrodesulfurization reaction, the loading volume ratio of the hydroprotective catalyst, the hydrodemetallization catalyst, and the selective hydrodesulfurization catalyst is 0.05:1:1.

[0105] The operating conditions of the fixed-bed residue hydrotreating unit are shown in Table 3.

[0106] S2: The hydrodesulfurization reaction stream is introduced into a hot high-pressure separator for separation to obtain gas, hydrotreated gasoline, hydrotreated diesel, hydrotreated wax oil and hydrotreated slag I, respectively;

[0107] The hydrogenated gasoline has a distillation range of 45-180℃;

[0108] The property parameters of the hydrotreating slag reduction I are shown in Table 3;

[0109] S3: In the presence of a catalytic cracking catalyst, hydrotreated wax oil and a portion of hydrotreated residue I are preheated to obtain preheated hydrotreated wax oil and preheated partial hydrotreated residue I. The preheated hydrotreated wax oil and the preheated partial hydrotreated residue I are introduced into a mild catalytic cracking unit containing a mild catalytic cracking unit and a second separation system, where catalytic cracking reaction and separation are carried out sequentially. Specifically, the preheated hydrotreated wax oil and the preheated partial hydrotreated residue I undergo the mild catalytic cracking reaction in the mild catalytic cracking unit to obtain a mild catalytic cracking reaction stream.

[0110] The operating conditions of the mild catalytic cracking unit are: reaction temperature 500℃, volume hourly space velocity 50 h⁻¹. -1 ;

[0111] S4: The mild catalytic cracking reaction stream is introduced into the second separation system for separation to obtain gas, catalytic cracked gasoline, catalytic cracked diesel, and catalytic cracked heavy oil I, respectively;

[0112] The initial boiling point of the catalytic cracked diesel is 180°C, and the final boiling point is 350°C; the final boiling point of the catalytic cracked heavy oil I is 510°C.

[0113] The property parameters of the catalytic cracking heavy oil I are shown in Table 3;

[0114] S5: The catalytic cracking heavy oil I is introduced into a filtration device for filtration treatment. After filtering out solid particles, the filtered catalytic cracking heavy oil with properties as shown in Table 3 is obtained. Part of the filtered catalytic cracking heavy oil is circulated back to the fixed bed residue hydrotreating unit via pipeline. Part of the filtered catalytic cracking heavy oil is blended with part of the hydrotreating residue reduction unit I to be used as a low-sulfur ship fuel burner.

[0115] The properties of the low-sulfur marine fuel are shown in Table 3.

[0116] Example 2

[0117] This embodiment uses the same process as Embodiment 1, except that the high-sulfur residue oil used in this embodiment is residue oil B, and the process parameters are different.

[0118] The remaining parameters, conditions, and results of this embodiment are shown in Table 3.

[0119] Example 3

[0120] This embodiment uses the same process as Embodiment 1, except that the high-sulfur residue oil used in this embodiment is residue oil B, and the process parameters are different.

[0121] The remaining parameters, conditions, and results of this embodiment are shown in Table 3.

[0122] Example 4

[0123] This embodiment uses the same process as Embodiment 1, except that the high-sulfur residue oil used in this embodiment is residue oil B, and the process parameters are different.

[0124] The remaining parameters, conditions, and results of this embodiment are shown in Table 3.

[0125] Table 3

[0126]

[0127]

[0128] Table 4

[0129] Marine fuel index RMG180 RMG380 Si + Al, ppm ≯60 ≯60 Sulfur content, wt% ≯0.50 ≯0.50 50 °C viscosity, mm 2 / s]] ≯180 ≯380 Density (15°C), kg / m3 3 ]] ≯991 ≯991 Density (20°C), kg / m3 3 ]] ≯987.6 ≯987.6 CCAI ≯870 ≯870

[0130] As can be seen from the above results, the method of the present invention can produce low-sulfur marine fuel, and the various properties of the blended low-sulfur marine fuel can meet the requirements of RMG180 or RMG380 listed in Table 4.

[0131] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for processing high-sulfur residual oil, characterized in that, The method includes: (1) In the presence of a selective hydrodesulfurization catalyst, a mixed feedstock containing high-sulfur residue oil and recycled catalytic cracking heavy oil I is subjected to hydrodesulfurization reaction to obtain a hydrodesulfurization reaction stream. (2) The hydrodesulfurization reaction stream is separated to obtain hydrotreated gasoline, hydrotreated diesel, hydrotreated wax oil and hydrotreated slag I; (3) In the presence of a catalytic cracking catalyst, the hydrotreated wax oil and a portion of the hydrotreated slag I are subjected to a moderate catalytic cracking reaction to obtain a moderate catalytic cracking reaction stream; (4) The mild catalytic cracking reaction stream is separated to obtain catalytic cracking gasoline, catalytic cracking diesel and catalytic cracking heavy oil I; a portion of the catalytic cracking heavy oil I is recycled back to step (1) to form the mixed feedstock; (5) The remaining portion of the catalytic cracking heavy oil I and the remaining portion of the hydrotreating and slag-reducing oil I are blended to obtain low-sulfur marine fuel; in the low-sulfur marine fuel, the weight ratio of the catalytic cracking heavy oil I to the hydrotreating and slag-reducing oil I is 0.1-2:

1. In the high-sulfur residue oil, the sulfur content by mass is greater than 3.0%, and the density of the high-sulfur residue oil at 20°C is greater than 1.014 g / cm³. 3 The kinematic viscosity at 100℃ is 500 mmHg. 2 / s-3200mm 2 / s, with a residual carbon content of 17.4-30%.

2. The method according to claim 1, wherein, In step (1), the nitrogen content of the high-sulfur residue oil is 0.1-1.0%, the asphaltene content is 3-30%, the nickel content is 10-200 ppm, and the vanadium content is 10-200 ppm.

3. The method according to claim 1 or 2, wherein, In step (1), the conditions of the hydrodesulfurization reaction are such that the kinematic viscosity of the resulting hydrodesulfurization reaction stream at 50°C is 100-4500 mm. 2 / s.

4. The method according to claim 1 or 2, wherein, In step (1), the conditions for the hydrodesulfurization reaction must at least meet the following requirements: reaction temperature of 380℃-430℃, reaction pressure of 8.0MPa-19.0MPa, and volume hourly space velocity of 0.1-1.0h. -1 The hydrogen-to-oil volume ratio is 300-1500:

1.

5. The method according to claim 1 or 2, wherein, In step (1), the selective hydrodesulfurization catalyst contains a support and an active metal component supported on the support. The active metal element in the active metal component is a combination of at least one group VIB metal element and at least one group VIII metal element. The support is selected from at least one of alumina, silica and amorphous silica-alumina.

6. The method according to claim 5, wherein, In the selective hydrodesulfurization catalyst, the active metal elements are molybdenum and cobalt, and the support is alumina.

7. The method according to claim 1 or 2, wherein, In step (1), the selective hydrodesulfurization catalyst has a desulfurization selectivity of over 90%.

8. The method according to claim 1 or 2, wherein, In step (2), the separation conditions are controlled such that the cutting point between the hydrogenated wax oil and the hydrogenated slag I is 500-580°C.

9. The method according to claim 1 or 2, wherein, In step (3), the conditions for the moderate catalytic cracking reaction must at least satisfy: a reaction temperature of 450-600℃ and a volume hourly space velocity of 25-100 h⁻¹. -1 .

10. The method according to claim 1 or 2, wherein, In the low-sulfur marine fuel, the weight ratio of the catalytic cracking heavy oil I to the hydrotreated slag I is 0.9-1.4:

1.

11. The method according to claim 1 or 2, wherein, In step (4), the separation conditions are controlled such that the cutting point between the catalytic cracked diesel and the catalytic cracked heavy oil I is 280-380°C.

12. The method according to claim 1 or 2, wherein, In step (5), the method further includes: before blending with the hydroreducing slag I, filtering the catalytic cracking heavy oil I to obtain pretreated catalytic cracking heavy oil with a solid content of less than 100 ppm, and then blending the pretreated catalytic cracking heavy oil with a portion of the hydroreducing slag I.

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