Method and system for processing aromatic-rich distillate

Abstract

The present invention relates to a method and system for processing hydrocarbon oils, particularly aromatic-rich fractionated oils, comprising: (1) introducing the aromatic-rich fractionated oil into a fifth reaction unit for hydrogenation saturation and then fractionating it to provide a first light component and a first heavy component; (2) introducing an aromatic-containing stream containing de-oiled asphalt and the first heavy component into a hydrogen dissolution unit to mix with hydrogen, and introducing the mixture into a first reaction unit for a hydrogenation reaction, wherein the first reaction unit is a liquid-phase hydrogenation reaction unit; (3) fractionating the liquid-phase product from the first reaction unit to provide a second light component and a second heavy component; (41) introducing the second light component into a second reaction unit for reaction; and (42) introducing the second heavy component into a delayed coking unit for reaction; or using the second heavy component as a component of low-sulfur marine fuel oil. The processing method provided by the present invention can realize high-value utilization of DOA.

Description

Technology Field

[0001] The present invention relates to the field of hydrocarbon oil processing, in particular to a method and system for processing aromatic-rich fractional oils. Background Technology

[0002] The high-efficiency conversion of residual oil is a core function for oil refining companies. Fixed-bed residual oil hydrogenation is a key technology for high-efficiency conversion and is characterized by superior product quality and mature methods.

[0003] However, the high content of asphaltenes and metals in the residual oil becomes a limiting factor in the operating time of the fixed-bed residual oil hydrogenation.

[0004] To address this problem, the Solvent Deasphalting (Demetallization) and Hydro-Catalytic Cracking (SHF) technology for residual oil, developed by the SINOPEC Petroleum Processing Research Institute (RIPP), is an innovative technology that maximizes the production of clean automotive fuel from low-value vacuum residual oil and extends operating time. However, due to the high softening point of De-asphaltene (DOA), transportation and utilization are difficult, limiting the popularization of SHF technology.

[0005] A novel combination method for producing propylene-rich products by hydrogenation-deep catalytic cracking (DCC) of residual oil is limited by the influence of asphaltenes and metals in the residual oil. The hydrogen content of the hydrogenated residual oil is low, the hydrogenation operation time of the residual oil is short, the propylene yield from DCC is low, and the economic benefits of the combination technology are limited.

[0006] In addition, in 2020, the sulfur fraction New low-sulfur marine fuel standard of 0.5 wt% and sulfur fraction A low-sulfur petroleum coke standard of 3.0 wt% is scheduled to be implemented. The technology to produce low-sulfur marine fuel (low-sulfur petroleum coke) at a low cost is also a task that needs to be urgently addressed at this time. The problem to be solved

[0007] Therefore, converting DOA into a material for the production of low-sulfur marine fuel or low-sulfur petroleum coke is a technical challenge that needs to be solved. means of solving the problem

[0008] The object of the present invention is to provide a novel method for processing aromatic-rich fraction oils that enables excellent hydrogenation results and long-term stable operation of the apparatus even at lower hydrogen partial pressures, lower hydrogen-to-oil ratios, and higher space velocities. Effects of the invention

[0009] To achieve the above objective, a first aspect of the present invention provides a method for processing an aromatic-rich fraction oil, comprising the following:

[0010] (1) A step of introducing an aromatic-rich fraction into a fifth reaction unit for hydrosaturation and then fractionating to provide a first light component and a first heavy component, wherein the first light component and the first heavy component have a cutting point of 100-250°C and the aromatic content in the first heavy component is 20% by weight or more;

[0011] (2) A step of introducing an aromatic-containing stream containing deoiled asphalt and a first heavy component into a hydrogen dissolving unit to mix with hydrogen, and introducing the mixed material into a first reaction unit for a hydrogenation reaction, wherein the first reaction unit comprises a mineral-rich precursor material and / or a hydrogenation catalyst, and the first reaction unit is a liquid-phase hydrogenation reaction unit, and the mineral-rich precursor material is a material capable of adsorbing at least one metal selected from V, Ni, Fe, Ca and Mg, and the deoiled asphalt and aromatic-containing stream are used in a ratio such that the mixed feedstock formed by the deoiled asphalt and aromatic-containing stream becomes a liquid state at a temperature of 400°C or lower;

[0012] (3) A step of fractionating the liquid product from the first reaction unit to provide a second light component and a second heavy component, wherein the cutting point of the second light component and the second heavy component is 240-450℃;

[0013] (41) A step of introducing a second light component into a second reaction unit for reaction to provide at least one product selected from a gasoline component, a diesel component and a BTX feedstock component, wherein the second reaction unit is at least one selected from the group consisting of a hydrocracking unit, a catalytic cracking unit and a diesel hydrogenation upgrade unit; and

[0014] (42) introducing the second heavy component into a delayed coking unit for reaction to provide at least one product selected from the group consisting of coker gasoline, coker diesel, coker wax oil and low sulfur petroleum coke; or using the second heavy component as a component of low sulfur marine fuel oil.

[0015] A second aspect of the present invention provides a system for processing an aromatic-rich fraction oil, comprising the following:

[0016] A third reaction unit providing a first light component and a first heavy component for hydrogenation saturation and fractionation of an aromatic-rich fraction oil;

[0017] A hydrogen dissolution unit in fluid communication with a third reaction unit for mixing hydrogen with an aromatic-containing stream containing a first heavy component from deoiled asphalt and a third reaction unit;

[0018] A first reaction unit that is in fluid communication with a hydrogen dissolution unit, which is a liquid phase hydrogenation reaction unit and is used to perform a hydrogenation reaction of a mixed material from a hydrogen dissolution unit;

[0019] A separation unit fluidly communicating with a first reaction unit for separating a liquid product from a first reaction unit;

[0020] At least one selected from the group consisting of a hydrocracking unit, a catalytic cracking unit, and a diesel hydrogenation upgrade unit, and a second reaction unit fluidly communicating with the separation unit for the reaction of a second light component obtained from the separation unit;

[0021] A delay coking unit fluidly communicating with a separation unit for the reaction of a second heavy component obtained in a separation unit, for providing at least one product selected from the group consisting of coker gasoline, coker diesel, coker wax oil, and low-sulfur petroleum coke;

[0022] An outlet fluidly communicating with a separation unit for discharging a second heavy component obtained from a separation unit from a system into a low-sulfur marine fuel oil fraction.

[0023] When the aromatic-rich fractional oil processing method according to the present invention is applied to residual oil treatment, a relatively excellent hydrogenation treatment effect and long-term stable operation of the device can be obtained even if the method is performed at a lower hydrogen partial pressure, a lower hydrogen-oil ratio, and a higher space velocity.

[0024] The present invention is suitable for the hydrogenation of atmospheric residue and vacuum residue, in particular for the hydrogenation of poor residue oil having a high metal content, a high carbon residue content, a high fused ring material content, and a high nitrogen content.

[0025] The present invention provides a de-oiled asphalt (DOA) hydrogenation treatment method capable of efficiently converting heavy oil and producing gasoline and BTX raw materials, and a system and method for flexibly producing low-sulfur marine fuel and low-sulfur petroleum coke. Brief explanation of the drawing

[0026] FIG. 1 is a flowchart for processing an aromatic-rich fraction oil according to a preferred embodiment of the present invention. FIG. 2 is a flowchart for processing an aromatic-rich fraction oil according to a first embodiment of the present invention. Specific details for implementing the invention

[0027] The endpoints and any values ​​of the ranges disclosed herein are not limited to exact ranges or values, and should be understood to include values ​​approximate to such ranges or values. In the case of numerical ranges, each range and each individual point value between the endpoint and the individual point value may be combined with one or more new numerical ranges, and such new numerical ranges should be interpreted as specifically disclosed herein.

[0028] As mentioned above, a first aspect of the present invention provides a method for processing an aromatic-rich fraction oil, comprising the following:

[0029] (1) A step of introducing an aromatic-rich fraction into a fifth reaction unit for hydrogenation saturation and then fractionating to provide a first light component and a first heavy component, wherein the first light component and the first heavy component have a cutting point of 100-250°C and the aromatic content in the first heavy component is 20% by weight or more;

[0030] (2) A step of introducing an aromatic-containing stream containing deoiled asphalt and a first heavy component into a hydrogen dissolving unit to mix with hydrogen, and introducing the mixed material into a first reaction unit for a hydrogenation reaction, wherein the first reaction unit comprises a mineral-rich precursor material and / or a hydrogenation catalyst, and the first reaction unit is a liquid-phase hydrogenation reaction unit, and the mineral-rich precursor material is a material capable of adsorbing at least one metal selected from V, Ni, Fe, Ca and Mg, and the deoiled asphalt and aromatic-containing stream are used in a ratio such that the mixed feedstock formed by the deoiled asphalt and aromatic-containing stream becomes a liquid state at a temperature of 400°C or lower;

[0031] (3) A step of fractionating the liquid product from the first reaction unit to provide a second light component and a second heavy component, wherein the cutting point of the second light component and the second heavy component is 240-450℃;

[0032] (41) A step of introducing a second light component into a second reaction unit for reaction to provide at least one product selected from a gasoline component, a diesel component and a BTX feedstock component, wherein the second reaction unit is at least one selected from the group consisting of a hydrocracking unit, a catalytic cracking unit and a diesel hydrogenation upgrade unit; and

[0033] (42) introducing the second heavy component into a delayed coking unit for reaction to provide at least one product selected from the group consisting of coker gasoline, coker diesel, coker wax oil and low sulfur petroleum coke; or using the second heavy component as a component of low sulfur marine fuel oil.

[0034] Preferably, the deoiled asphalt and aromatic-containing stream is used in a ratio such that the mixed feedstock formed from the deoiled asphalt and aromatic-containing stream becomes liquid at a temperature of 280°C or lower. More preferably, the deoiled asphalt and aromatic-containing stream is used in a ratio such that the mixed feedstock formed from the deoiled asphalt and aromatic-containing stream becomes liquid at a temperature of 100°C or lower.

[0035] Preferably, the hydrogenation saturation reaction performed in the third reaction unit is partially hydrogenated, and particularly preferably, the first light component and the first heavy component have a cutting point of 180°C.

[0036] Preferably, the hydrogen dissolution unit of the present invention is operated under conditions of a volume ratio of hydrogen supply to a mixed feedstock formed by deoiled asphalt and an aromatic-containing stream (i.e., volume ratio of hydrogen to oil) of 30-200, more preferably 50-150, an operating temperature of 300-450°C, and a pressure of 2-20 MPa.

[0037] According to the method of the present invention, the mixed material obtained after mixing with hydrogen in the hydrogen dissolution unit can be supplied to the first reaction unit in an upward flow mode or a downward flow mode. Preferably, the mixed material obtained after mixing with hydrogen in the hydrogen dissolution unit is supplied to the first reaction unit in an upward flow mode, thereby substantially preventing the hydrogen dissolved and dispersed in the oil from escaping by forming large bubbles during the reaction. By doing so, the hydrogenation reaction is provided with a sufficient hydrogen supply, thereby improving the hydrogenation treatment effect, further reducing the tendency of the catalyst to coke, allowing the catalyst to maintain higher catalytic activity, further extending the service life of the catalyst, and extending the stable operating period of the device.

[0038] The first light component is preferably supplied to a catalytic cracking unit to produce lower olefins. Specific operating conditions for the first light component supplied to the catalytic cracking unit to produce low-carbon olefins are not specifically limited by the present invention.

[0039] Particularly preferably, the second light component and the second heavy component have a cutting point of 350°C.

[0040] Preferably, in step (2), the deoiled asphalt and aromatic-containing stream is a mixed feedstock formed from the deoiled asphalt and aromatic-containing stream, with a viscosity of 400 mm at 100°C. 2 / s or less, more preferably 200 mm 2 / s or less, more preferably 100 mm 2 It is used as a ratio that makes it less than / s.

[0041] In step (2), the aromatic-containing stream further comprises aromatic hydrocarbons and / or aromatic oils, said aromatic oils being at least one selected from the group consisting of LCO, HCO, FGO (catalytic heavy component oil), ethylene tar, coal tar, coker diesel and coker wax oil.

[0042] Preferably, the aromatic hydrocarbon is one or more selected from benzene, toluene, xylene, naphthalene, methylnaphthalene, branched naphthalene, and aromatic hydrocarbons having two or more rings, and preferably is a polycyclic aromatic hydrocarbon having three or fewer rings or a mixture thereof. Particularly preferably, the aromatic hydrocarbon is benzene, toluene, xylene, naphthalene, at least one C 1-6 It is at least one selected from the group consisting of naphthalene substituted with an alkyl group and three or more aromatic hydrocarbons.

[0043] More preferably, the aromatic hydrocarbon content in the aromatic-rich fraction oil is 20 weight% or more, preferably 25 weight% or more, preferably 40 weight% or more, and more preferably 60 weight% or more.

[0044] Preferably, in step (2), de-oiled asphalt is obtained by applying a heavy oil feedstock to a solvent deasphalting method in a solvent deasphalting unit.

[0045] Preferably, the yield of de-oiled asphalt in the solvent deasphalting unit is 50 weight% or less, more preferably 40 weight% or less, and even more preferably 30 weight% or less.

[0046] According to a preferred embodiment, in step (2), the aromatic-containing stream is an aromatic-rich fractional oil, and the weight ratio of the de-oiled asphalt content to the aromatic-containing stream content is 1:10 to 50:10, more preferably 2:10 to 30:10; more preferably 3:10 to 15:10.

[0047] Preferably, the method of the present invention further comprises the step of recirculating the coker diesel and / or coker gas oil obtained in step (42) to the first reaction unit of step (1) for hydrogenation saturation.

[0048] Preferably, in step (1), the third reaction unit is at least one of a fixed-bed reactor, a moving-bed reactor, and a boiling-bed reactor.

[0049] Preferably, the third reaction unit has: a reaction temperature of 200-420°C, a reaction pressure of 2-18 MPa, and a liquid space velocity of 0.3-10 h per hour. -1 and is operated under conditions of a volume ratio of hydrogen to oil of 50-5000. More preferably, the third reaction unit is: reaction temperature 220-400°C, reaction pressure 2-15 MPa, liquid space velocity 0.3-5 h per hour. -1 and is operated under conditions of a volume ratio of hydrogen to oil of 50-4000.

[0050] A preferred embodiment of the third reaction unit of this fifth variant is provided below.

[0051] Partial hydrogenation saturation of aromatic-rich fractions in the presence of hydrogen is generally carried out under conditions where the partial hydrogenation saturation technology of aromatic-rich fractions is a fixed-bed / boiling-bed / moving-bed hydrogenation technology. Taking currently industrialized fixed-bed diesel or wax oil hydrogenation technology as an example, the reactor or reaction bed contains at least one hydrofining catalyst. The hydrofining catalyst used for partial hydrogenation saturation of aromatic-rich fractions is desirable to have good and moderate hydrogenation saturation activity and additionally prevents the tetralin-like structure from being saturated with a decahydronaphthalene or cycloalkane structure having a lower hydrogen donating capacity. In the case of such catalysts, porous refractory inorganic oxides such as alumina or molecular sieves are generally used as supports, oxides or sulfides of Group VIB and / or Group VIII metals such as W, Mo, Co, Ni, etc. are used as active ingredients, and various other auxiliary agents such as elements P, Si, F, B, etc., such as the RS series pretreatment catalyst developed by RIPP, are optionally added. The RS series catalyst is a NiMo catalyst.

[0052] The first reaction unit is particularly preferably a residual oil liquid phase hydrogenation reactor.

[0053] Preferably, in step (2), the first reaction unit has: a reaction temperature of 260-500°C, a reaction pressure of 2.0-20.0 MPa, a volume ratio of recirculated oil to crude oil at the inlet of the first reaction unit of 0.1:1-15:1, and a liquid space velocity of 0.1-1.5 h per hour. -1It is operated under the conditions of. The liquid volume space velocity and reaction pressure per hour are selected according to the properties of the material to be processed and the desired conversion rate and purification depth. The mixed feedstock formed by the deoiled asphalt and aromatic-containing stream is mixed with hydrogen and then supplied from the top of the reactor of the first reaction unit and passes through the catalyst bed layer from top to bottom; or the catalyst may be supplied from the bottom of the reactor of the first reaction unit and pass through the catalyst bed layer from bottom to top.

[0054] Preferably, in step (2), the mineral-rich precursor material comprises a support and an active component element loaded on the support, wherein the support is at least one selected from the group consisting of aluminum hydroxide, alumina, and silica, and the active component element is at least one metal element selected from the group consisting of Group VIB and Group VIII. More preferably, the active component of the mineral-rich precursor material is an oxide and / or sulfide of a metal element selected from Group VIB and Group VIII.

[0055] Preferably, in step (2), the mineral-rich precursor material has a loss on ignition of 3 weight% or more and a specific surface area of ​​80 m² 2 It has a weight of 0.9 g / g or more and a water absorption rate of 0.9 g / g or more. Loss on ignition refers to the percentage of reduced weight of the mineral-rich precursor material after roasting treatment at 600°C / 2h compared to the weight before roasting, and water absorption rate refers to the percentage of increased weight of the mineral-rich precursor material after immersion in water at room temperature (e.g., 25°C) for 30 minutes compared to the weight before immersion.

[0056] According to a preferred embodiment, in step (2), the first reaction unit is sequentially filled with a mineral-rich first precursor material and a mineral-rich second precursor material along the flow direction of the reactants, wherein the mineral-rich second precursor material has an ignition loss equal to or greater than that of the mineral-rich first precursor material.

[0057] According to a preferred embodiment, the mineral-rich first precursor material has a loss on ignition of 3 to 15 weight%, and the mineral-rich second precursor material has a loss on ignition of 15 weight% or more, which is more preferable.

[0058] According to a preferred embodiment, it is more preferable that the mineral-rich first precursor material and the mineral-rich second precursor material are loaded in a volume ratio of 5:95 to 95:5.

[0059] The hydrogenation catalyst of the present invention may be a graded combination of different catalysts, and preferably, the hydrogenation catalyst may catalyze at least hydrodemetallization and hydrodesulfurization reactions.

[0060] According to the present invention, the specific type of catalyst capable of catalyzing the hydrogenation demetalization reaction, the hydrogenation desulfurization reaction, the hydrogenation deasphalting reaction, and the hydrogenation decarbonization reaction is not particularly limited, and any catalyst capable of catalyzing said reactions commonly used in the art may be used.

[0061] The hydrogenation catalyst of the present invention may be used, for example, with a porous refractory inorganic oxide as a support, an oxide or sulfide of a Group VIB and / or Group VIII metal as an active component, and optionally with an auxiliary agent added.

[0062] Preferably, after the first reaction unit of the present invention has been operated for a long period, a mineral-rich precursor material is converted into a vanadium-rich material, and the vanadium content of the vanadium-rich material is 10 weight% or more; particularly preferably, an ore-rich precursor material is converted into a vanadium-rich material having a V content of 20 weight% or more, and high-value V2O5 can be directly purified therefrom.

[0063] A preferred embodiment of the first reaction unit of the present invention is provided below.

[0064] The hydrogenation treatment technology of the feedstock associated with the first reaction unit of the present invention is a liquid-phase hydrogenation treatment technology, and the reactor or reaction bed layer comprises at least a mineral-rich precursor material and / or a hydrogenation catalyst, wherein the mineral-rich precursor material is composed of two parts: a support having a strong ability to adsorb vanadium-containing organic compounds in oil and an active component having a hydrogenation activity function. The support is obtained mainly by extruding, molding, and drying silica, aluminum hydroxide, or a mixture of aluminum hydroxide and alumina. The surface of the support is rich in -OH groups. The support has a strong adsorption ability for vanadium-containing organic compounds in oil. The support has a loss on ignition of 5 wt% or more after roasting at 600°C for 2 hours. The active component mainly comprises oxides or sulfides of Group VIB and / or Group VIII metals such as W, Mo, Co, Ni, etc.

[0065] The hydrogenation catalyst associated with the aforementioned preferred embodiment is generally a heavy residue hydrogenation catalyst, and a heavy residue hydrogenation catalyst refers to a composite catalyst having functions such as heavy residue hydrogenation demetallation, hydrogenation desulfurization, and hydrogenation decarbonization. In the case of these catalysts, a porous refractory inorganic oxide such as alumina is generally used as a support, and oxides or sulfides of Group VIB and / or Group VIII metals such as W, Mo, Co, and Ni are used as active components, and various other auxiliary agents such as elements P, Si, F, and B, such as the RDM and RCS series heavy metals developed by RIPP, residue oil hydrogenation demetallation catalysts, and desulfurization catalysts are optionally added. Currently, multiple catalysts are often used together in liquid residue oil hydrogenation technology. In the present invention, it is preferable to use a mineral-rich precursor material, a hydrogenation demetallation desulfurization catalyst, and a hydrogenation desulfurization catalyst, and these are generally loaded in a sequence such that the feedstock comes into sequential contact with the mineral-rich precursor material, the hydrogenation demetallation desulfurization catalyst, and the hydrogenation desulfurization catalyst. Of course, there is a technique for loading a mixture of these catalysts.

[0066] According to a preferred embodiment, in step (41), the second reaction unit has: a reaction temperature of 360-420°C, a reaction pressure of 10.0-18.0 MPa, a volume ratio of hydrogen to oil of 600-2000, and a liquid volume space velocity of 1.0-3.0 h -1 It is a hydrocracking unit that operates under the conditions of

[0067] Preferably, at least one hydrogenation catalyst and at least one hydrocracking catalyst are loaded into the hydrocracking unit.

[0068] Preferably, the hydrocracking unit is a fixed-bed hydrocracking unit.

[0069] Where the second reaction unit is a hydrocracking unit, a preferred embodiment of the second reaction unit of the present invention is provided below.

[0070] In step (41), a second light component is introduced into a second reaction unit for reaction using a fixed-bed hydrocracking technique. Taking as an example a conventional technique in the industry for hydrocracking wax oil by a fixed bed, the reactor or reaction bed comprises at least two hydrocracking catalysts, namely a pretreatment catalyst and a hydrocracking catalyst. Since the material obtained by fractionation after liquid-phase hydrotreatment has high metal, sulfur, and nitrogen content and a high carbon residue, it is desirable for the pretreatment catalyst to have strong demetallation activity and excellent desulfurization and denitrification activity to ensure subsequent hydrocracking catalyst activity. The hydrocracking catalyst preferably has excellent hydrocracking activity and high VGO conversion rate and HDS activity. In the case of such catalysts, porous refractory inorganic oxides such as alumina or molecular sieves are generally used as supports, oxides or sulfides of Group VIB and / or Group VIII metals such as W, Mo, Co, Ni, etc. are used as active components, and various other auxiliary agents such as elements P, Si, F, B, etc., such as the RS series pretreatment catalyst and RHC series hydrocracking catalyst developed by RIPP, are optionally added. The RS series catalyst is a NiW catalyst, and the RHC series catalyst is a NiMo molecular sieve catalyst.

[0071] According to another preferred embodiment, in step (41), the second reaction unit is a catalytic decomposition unit, and the catalytic decomposition unit is a fluid catalytic decomposition (FCC) unit.

[0072] According to another preferred embodiment, the technology used for the catalytic cracking of the second light component is Fluid Catalytic Cracking (FCC) technology, preferably LTAG technology developed by RIPP, which mainly produces gasoline fractions and liquefied gas.

[0073] Preferably, the fluid catalytic cracking unit is operated under conditions of: a reaction temperature of 500-600°C, a catalyst-to-oil ratio of 3-12, and a residence time of 0.6-6 seconds.

[0074] The catalyst-to-oil ratio of the present invention refers to the weight ratio of catalyst to oil unless otherwise specified.

[0075] According to another preferred embodiment, in step (41), the second reaction unit is a diesel hydrogenation upgrade unit, with a reaction temperature of 330-420°C, a reaction pressure of 5.0-18.0 MPa, a volume ratio of hydrogen to oil of 500-2000, and a liquid volume space velocity of 0.3-3.0 h per hour. -1 It operates under the conditions of.

[0076] Preferably, at least one diesel hydrogenation upgrade catalyst is loaded into the diesel hydrogenation upgrade unit.

[0077] The diesel hydrogenation upgrade catalyst may be the RS series pretreatment catalyst and the RHC-100 series diesel hydrocracking catalyst developed by RIPP.

[0078] According to a preferred embodiment, in step (42), a second heavy component is introduced into a delayed coking unit for reaction to provide at least one product selected from coker gasoline, coker diesel, coker wax oil and low-sulfur petroleum coke, wherein the delayed coking unit is operated under conditions of: a reaction temperature of 440-520°C and a residence time of 0.1-4 hours.

[0079] According to another preferred embodiment, in step (42), the sulfur content of the second heavy component is 1.8 weight% or less, and the second heavy component is introduced into a delayed coking unit for reaction to provide low-sulfur petroleum coke. More preferably, the sulfur content of the low-sulfur petroleum coke is 3 weight% or less.

[0080] Preferably, in step (42), the second heavy component is used as a low-sulfur marine fuel oil component, and the conditions are adjusted so that the sulfur content of the low-sulfur marine fuel oil component is 0.5 weight% or less.

[0081] According to the present invention, the specific operation for the solvent deasphalting treatment is not particularly limited, and conventional solvent deasphalting methods may be used. The operating parameters of the solvent deasphalting method are exemplified in the embodiments of the present invention and should not be understood by those skilled in the art as limiting the present invention.

[0082] The method of the present invention is suitable for the hydrogenation conversion of atmospheric pressure residue and vacuum residue, particularly for the hydrogenation conversion of poor residue oil that has a high metal content (Ni + V > 150 μg / g, especially Ni + V > 200 μg / g), a high carbon residue content (weight fraction of carbon residue > 17%, especially weight fraction of carbon residue > 20%), and a high content of fused cyclic materials.

[0083] As described above, a second aspect of the present invention provides a system for processing an aromatic-rich fraction oil comprising the following:

[0084] A third reaction unit providing a first light component and a first heavy component for hydrogenation saturation and fractionation of an aromatic-rich fraction oil;

[0085] A hydrogen dissolution unit in fluid communication with a third reaction unit for mixing hydrogen with an aromatic-containing stream containing a first heavy component from deoiled asphalt and a third reaction unit;

[0086] A first reaction unit that is in fluid communication with a hydrogen dissolution unit, which is a liquid phase hydrogenation reaction unit and is used to perform a hydrogenation reaction of a mixed material from a hydrogen dissolution unit;

[0087] A separation unit fluidly communicating with a first reaction unit for separating a liquid product from a first reaction unit;

[0088] At least one selected from the group consisting of a hydrocracking unit, a catalytic cracking unit, and a diesel hydrogenation upgrade unit, and a second reaction unit fluidly communicating with the separation unit for the reaction of a second light component obtained from the separation unit;

[0089] A delay coking unit fluidly communicating with a separation unit for the reaction of a second heavy component obtained in a separation unit, for providing at least one product selected from the group consisting of coker gasoline, coker diesel, coker wax oil, and low-sulfur petroleum coke;

[0090] An outlet fluidly communicating with a separation unit for discharging a second heavy component obtained from a separation unit from a system into a low-sulfur marine fuel oil fraction.

[0091] Preferably, the delayed coking unit fluidly communicates with the hydrogen dissolution unit to recirculate the coker gas oil and / or coker gas oil obtained from the delayed coking unit to the first reaction unit.

[0092] Preferably, the system further comprises a solvent deasphalting unit in fluid communication with a hydrogen dissolution unit, which is used to solvent deasphalt a heavy oil feedstock and to introduce the deasphalted asphalt obtained after solvent deasphalting into a hydrogen dissolution unit.

[0093] According to a preferred embodiment, in the system of the present invention, the second reaction unit is a hydrocracking unit.

[0094] According to another preferred embodiment, in the system of the present invention, the second reaction unit is a catalytic decomposition unit, and the catalytic decomposition unit is a fluidization catalytic decomposition unit.

[0095] According to another preferred embodiment, the second reaction unit in the system of the present invention is a diesel hydrogenation upgrade unit.

[0096] The present invention also provides a first variation of the method further comprising:

[0097] (11) A step of introducing heavy raw oil into a solvent deasphalting unit for solvent deasphalting treatment to provide deasphalted asphalt and deasphalted oil;

[0098] (12) A step of introducing deasphalted oil into a fourth hydrogenation unit for a hydrogenation reaction, and introducing the liquid effluent obtained from the fourth hydrogenation unit into a DCC unit for a reaction to provide propylene, LCO, HCO and slurry oil, wherein the fourth hydrogenation unit is a fixed-bed hydrogenation unit;

[0099] (1) Step (1) using an aromatic-rich fraction oil containing LCO and / or HCO from a DCC unit as the aromatic-rich fraction oil.

[0100] In this first variation, preferably, the method of the present invention further comprises the step of recirculating the coker diesel and / or coker gas oil obtained in step (42) to a third reaction unit for hydrogenation saturation.

[0101] Preferably, in step (12), the fourth reaction unit has: a reaction temperature of 280-400°C, a reaction pressure of 6.0-14.0 MPa, a volume ratio of hydrogen to oil of 600-1200, and a liquid space velocity of 0.3-2.0 h per hour. -1 It operates under the conditions of.

[0102] Preferably, in step (12), at least two hydrogenation catalysts are loaded into the fourth reaction unit. More preferably, in step (12), the hydrogenation catalyst is a catalyst capable of catalyzing at least one reaction selected from the group consisting of a hydrogenation demetallation reaction, a hydrogenation desulfurization reaction, and a hydrogenation decarbonization reaction. The hydrogenation catalyst is generally supported on a porous refractory inorganic oxide such as alumina. Particularly preferably, in step (12), the hydrogenation catalyst comprises alumina as a support and a metal element of Group VIB and / or Group VIII as an active component element, and optionally also comprises at least one auxiliary element selected from P, Si, F, and B. In the hydrogenation catalyst, the metal element of Group VIB and Group VIII may be, for example, W, Mo, Co, Ni, etc. In the hydrogenation catalyst, the active component may be an oxide and / or sulfide of the aforementioned active component element.

[0103] A preferred embodiment of the fourth reaction unit of the present invention is provided below:

[0104] The conditions for the third hydrogenation unit of deasphalted oil (DAO) in the presence of hydrogen are generally as follows: The hydrogenation technology of DAO is a fixed-bed hydrogenation technology. Taking currently industrialized fixed-bed heavy oil and residue oil hydrogenation technology as an example, the reactor or reaction bed contains at least two hydrogenation catalysts, and the heavy oil and residue oil hydrogenation catalysts refer to composite catalysts having functions such as hydrodemetallation, hydrodesulfurization, hydrodenitrification, and hydrodecarbonization for both heavy oil and residue oil. For these catalysts, a porous refractory inorganic oxide such as alumina is generally used as a support, and oxides or sulfides of Group VIB and / or Group VIII metals such as W, Mo, Co, Ni, etc. are used as active components, and various other auxiliary agents such as elements P, Si, F, B, etc., such as the RDM, RCS series heavy metals developed by RIPP, residue oil hydrodemetallation catalysts, and desulfurization catalysts are optionally added. Currently, multiple catalysts are often used together in fixed-bed residue hydroprocessing technology. Hydrodemetallization catalysts, hydrodesulfurization catalysts, and hydrodenitrification catalysts are used in a general loading sequence in which crude oil comes into sequential contact with the hydrodemetallization catalyst, hydrodesulfurization catalyst, and hydrodenitrification catalyst, although sometimes one or two catalysts are absent depending on the situation. For example, only the hydrodemetallization catalyst and the hydrodesulfurization catalyst are loaded, and the hydrodenitrification catalyst is not loaded. Of course, there is a technology for loading a mixture of these catalysts.

[0105] A method for processing an aromatic-rich fraction oil according to the present invention is described in more detail below with reference to FIGS. 1 and FIGS. 2.

[0106] As illustrated in FIG. 1, an aromatic-rich fractionated oil (20) is supplied to a third reaction unit (21) for hydrogenation saturation and fractionated to provide a first light component and a first heavy component (22); the heavy oil feedstock (1) is supplied to a solvent deasphalting unit (2) for solvent deasphalting treatment to provide deasphalted asphalt (4) and deasphalted oil (3); An aromatic-containing stream comprising de-oiled asphalt (4) and a first heavy component (22) is mixed to form a mixed feedstock (6), which is mixed with hydrogen in a hydrogen dissolution unit (23), and the obtained mixed material is supplied to a first reaction unit (7) for a hydrogenation reaction, wherein the aromatic-containing stream preferably also includes an aromatic hydrocarbon (5) from the outside, wherein the first reaction unit comprises a hydrogenation catalyst and a mineral-rich precursor material capable of catalyzing at least one reaction selected from a hydrogenation demetalization reaction, a hydrogenation desulfurization reaction, a hydrogenation deasphalting reaction, and a hydrogenation decarbonization reaction, and the first reaction unit is a liquid-phase hydrogenation reaction unit; the liquid-phase product from the first reaction unit (7) is supplied to a separation unit (19) for fractionation to provide a second light component (8) and a second heavy component (9), wherein the second light component and the second heavy component have a cutoff point of 240-450°C; The second light component (8) is supplied to the second reaction unit (10) for reaction to provide at least one product selected from the gasoline component (13), the BTX feedstock component (12), and the diesel component (14), wherein the second reaction unit is at least one selected from the hydrocracking unit, the catalytic cracking unit, and the diesel hydrogenation upgrade unit; the second heavy component (9) is supplied to the delayed coking unit (11) for reaction to provide at least one product selected from the group consisting of coker gasoline (15), coker diesel (16), coker wax oil (17), and low-sulfur petroleum coke (18); or the second heavy component (9) is used as a low-sulfur marine fuel oil component.

[0107] As illustrated in FIG. 2, a heavy oil feedstock (1) is supplied to a solvent deasphalting unit (2) for solvent deasphalting treatment to provide deasphalted asphalt (4) and deasphalted oil (3); the deasphalted oil (3) is supplied to a fourth reaction unit (24) for a hydrogenation reaction, and the liquid effluent obtained from the fourth reaction unit (24) is supplied to a DCC unit (25) for reaction to provide propylene (26), LCO (27), HCO (28) and slurry oil (29); an aromatic-rich fraction oil (20) containing LCO (27) and / or HCO (28) from the DCC unit is supplied to a third reaction unit (21) for hydrogenation saturation and then fractionated to provide a first heavy component (22) and a first light component; A mixed feedstock (6) formed from an aromatic-containing stream comprising de-oiled asphalt (4) and a first heavy component (22) is supplied to a first reaction unit (7) for a hydrogenation reaction, wherein the aromatic-containing stream preferably also comprises an aromatic hydrocarbon (5) from the outside, and wherein the first reaction unit (7) comprises a hydrogenation catalyst and a mineral-rich precursor material capable of catalyzing at least one reaction selected from a hydrogenation demetalization reaction, a hydrogenation desulfurization reaction, a hydrogenation deasphalting reaction and a hydrogenation decarbonization reaction; and the liquid product from the first reaction unit (7) is supplied to a separation unit (19) for fractionation to provide a second light component (8) and a second heavy component (9); The second light component (8) is supplied to the second reaction unit (10) for reaction to provide at least one product selected from the group consisting of gasoline component (13), BTX feedstock component (12) and diesel component (14), or the second light component (8) is recycled to the DCC unit (25); the second heavy component (9) is supplied to the delayed coking unit (11) for reaction to provide at least one product selected from the group consisting of coker gasoline (15), coker diesel (16), coker wax oil (17) and low-sulfur petroleum coke (18);Or the second heavy component (9) is used as a low-sulfur marine fuel oil component.;

[0108] The technology of the present invention can efficiently convert heavy oil to produce gasoline and BTX raw materials, and provides a system and method for flexibly producing low-sulfur marine fuel and low-sulfur petroleum coke.

[0109] Compared to prior art, the present invention preferably adopts an effective combination of methods such as residual oil hydrogenation, hydrocracking, or catalytic cracking to convert low-value DOA into low-sulfur marine fuel components and low-sulfur petroleum coke that meet environmental protection requirements, thereby realizing high efficiency, environmental protection, and comprehensive utilization of heavy petroleum resources.

[0110] In addition, the technology provided by the present invention can efficiently convert DOA in a residue liquid-phase hydrogenation reactor, produce gasoline fractions and BTX raw materials, and provide raw materials for producing low-sulfur marine fuel and low-sulfur coke products.

[0111] The present invention is described in detail by the following examples. Unless otherwise specified, the following examples were carried out using the method flowchart illustrated in FIG. 1. Unless specifically mentioned, the following examples have the following common features:

[0112] Unless specifically stated otherwise, the results of Tables I-3 and II-4 of the following examples are the average of the results obtained from sampling tests every 25 hours by operating the device continuously for 100 hours.

[0113] Saturation experiments of partial hydrogenation reactions rich in aromatic fractions were performed in a medium-scaled fixed-bed diesel hydrogenation unit, and the total volume of the reactor was 200 mL. The hydrogenation catalyst and material used for partial hydrogenation saturation of aromatic-rich fraction oil in the following examples is the RS-2100 series hydrogenation catalyst developed by RIPP.

[0114] The liquid stream obtained by partial hydrogenation saturation was fractionated to provide a first light component and a first heavy component with a cutoff point of 180°C, wherein the first heavy component and DOA formed a mixed feedstock. A hydrogenation reaction test was performed on the mixed feedstock in a medium-scaled heavy oil liquid-phase hydrogenation treatment unit, and the total volume of the reactor was 200 mL. In the following examples, the materials used in the hydrogenation catalyst and the first reaction unit were the RG-30B protection catalyst developed by RIPP, mineral-rich precursor material 1, mineral-rich precursor material 2, the RDM-33B residue oil demetallation desulfurization transition catalyst and the RCS-31 desulfurization catalyst researched and developed by the Petrochemical Engineering Research Institute. Depending on the flow direction of the reactants, the hydrogenation protection catalyst, mineral-rich precursor material 1, mineral-rich precursor material 2, the hydrogenation demetallation and desulfurization catalyst, and the hydrogenation desulfurization catalyst were loaded sequentially. The loading ratio between catalysts in the first reaction unit is as follows: RG-30B: mineral-rich precursor material 1: mineral-rich precursor material 2: RDM-33B: RCS-31 = 6: 30: 30: 14: 20(V / V).

[0115] The second reaction unit was a fixed-bed hydrocracking unit, and the catalysts used were the RS-2100 purification catalyst and the RHC-131 hydrocracking catalyst developed by RIPP. The fixed-bed hydrocracking unit was operated under the following conditions: a reaction temperature of 370°C in the purification section, a reaction temperature of 385°C in the cracking section, a reaction pressure of 10 MPa, and a liquid volume space velocity of 2.0 h⁻¹.-1 and hydrogen / oil volume ratio = 1200:1.

[0116] Example A

[0117] Preparation of Mineral-Rich Precursor Material 1: 2000g of RPB110 pseudoboehmite produced by SINOPEC CATALYST CO.LTD CHANGLING DIVISION was used. 1000g was treated at 550°C for 2 hours to yield approximately 700g of alumina. The approximately 700g of alumina and the remaining 1000g of pseudoboehmite were thoroughly mixed. To this mixture, 40g of sesbania powder and 20g of citric acid were added, followed by 2200g of deionized water. The mixture was then kneaded, extruded into a strip, and dried at 300°C for 3 hours to produce a support of approximately 1730g. For saturation impregnation, 2100mL of a solution containing Mo and Ni was added, wherein the Mo content in the solution was calculated as MoO3 and was 5.5 A mineral-rich precursor material 1 was obtained by impregnating the material for 30 minutes and treating it at 180°C for 4 hours, with the Ni content calculated as 1.5 wt% and Ni content calculated as NiO, and its characteristics are presented in Table I-6.

[0118] Preparation of mineral-rich precursor material 2: 2000g of RPB220 pseudobohemite produced by SINOPEC CATALYST CO.LTD CHANGLING DIVISION was used, 30g of sesbania powder and 30g of citric acid were added to it, and 2400g of deionized water was added. The mixture was kneaded, extruded into a strip, and dried at 120°C for 5 hours to produce a support of approximately 2040g. For saturation impregnation, 2200mL of a solution containing Mo and Ni was added to it, wherein the Mo content in the solution was calculated as 7.5 wt% as MoO3 and the Ni content was calculated as 1.7 wt% as NiO. After impregnation for 30 minutes, the material was treated at 200°C for 3 hours to obtain mineral-rich precursor material 2, the characteristics of which are presented in Table I-6.

[0119] Preparation of mineral-rich precursor material 3: 2000g of commercially available silica was used, 30g of sesbania powder and 30g of sodium hydroxide were added to it, and 2400g of deionized water was added. The mixture was kneaded, extruded into a strip, and dried at 120°C for 5 hours to prepare a support. For saturation impregnation, 2200mL of a solution containing Mo and Ni was added to it, wherein the Mo content in the solution was 4.5 wt% calculated as MoO3 and the Ni content was 1.0 wt% calculated as NiO. After impregnation for 30 minutes, the material was treated at 200°C for 3 hours to obtain mineral-rich precursor material 3, the characteristics of which are presented in Table I-6.

[0120] Example I-1

[0121] In this embodiment, LCO produced at the Shanghai Petrochemical RLG plant was used as an aromatic-rich fraction, and the LCO hydrogenation reaction was performed at: a reaction temperature of 290°C, a reaction pressure of 4 MPa, and a liquid volume space velocity of 1 h per hour. -1 and operated under conditions of a hydrogen to oil volume ratio of 800:1.

[0122] The characteristics of LCO and the first heavy component 1 are presented in Table I-1.

[0123] DOA from vacuum residue was mixed with the first heavy component 1 in a weight ratio of 1:10, and the characteristics of the mixed feedstock are presented in Table I-2.

[0124] The mixed feedstock of DOA and the first heavy component 1 was first mixed with hydrogen in a hydrogen dissolution unit (volume ratio of hydrogen supply to the mixed feedstock formed by deoiled asphalt and heavy component 1: 100, operating temperature of the hydrogen dissolution unit: 320°C, pressure: 10 MPa), and the obtained mixture was supplied to the first reaction unit. The first reaction unit: reaction temperature: 360°C, reaction pressure: 10 MPa, liquid volume space velocity per hour: 0.6 h -1 and was operated at a volume ratio of 0.5:1 of recirculated oil to raw oil at the inlet of the first reaction unit. After hydrogenation, the characteristics of the mixed feedstock are presented in Table I-3.

[0125] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table I-4.

[0126] The second light component at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table I-5.

[0127] Example I-2

[0128] In this embodiment, HCO from the catalytic cracking unit of Shanghai Petrochemical was used as an aromatic-rich fraction oil, and the HCO hydrogenation reaction was performed at: a reaction temperature of 330°C, a reaction pressure of 6 MPa, and a liquid volume space velocity of 1 h -1 and operated under conditions of a hydrogen to oil volume ratio of 800:1.

[0129] The characteristics of HCO and the first heavy component 2 are presented in Table I-1.

[0130] DOA from vacuum residue was mixed with the first heavy component 2 in a weight ratio of 5:10, and the characteristics of the mixed feedstock are presented in Table I-2.

[0131] The mixed feedstock of DOA, hydrogenated HCO, and First Heavy Component 2 was first mixed with hydrogen in a hydrogen dissolution unit (volume ratio of hydrogen supply to the mixed feedstock formed by deoiled asphalt and First Heavy Component 2: 100, operating temperature of the hydrogen dissolution unit: 320°C, pressure: 10 MPa), and the obtained mixture was supplied to a First Reaction Unit. The First Reaction Unit: reaction temperature: 380°C, reaction pressure: 10 MPa, liquid volume space velocity per hour: 0.6 h -1 and was operated at a volume ratio of 0.5:1 of recirculated oil to raw oil at the inlet of the first reaction unit. After hydrogenation, the characteristics of the mixed feedstock are presented in Table I-3.

[0132] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table I-4.

[0133] The second light component at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table I-5.

[0134] Example I-3

[0135] In this example, the same LCO as in Example I-1 was used as an aromatic-rich fractional oil, and the LCO hydrogenation reaction was performed at: a reaction temperature of 320°C, a reaction pressure of 6 MPa, and a liquid volume space velocity of 1 h per hour. -1 and operated under conditions of a hydrogen to oil volume ratio of 800:1.

[0136] The characteristics of LCO and the first heavy component 3 are presented in Table I-1.

[0137] DOA from vacuum residue was mixed with the first heavy component 3 in a weight ratio of 10:10, and the characteristics of the mixed feedstock are presented in Table I-2.

[0138] The mixed feedstock of DOA and the first heavy component 3 was first mixed with hydrogen in a hydrogen dissolution unit (volume ratio of hydrogen supply to the mixed feedstock formed by deoiled asphalt and the first heavy component 3: 100, operating temperature of the hydrogen dissolution unit: 320°C, pressure: 8 MPa), and the obtained mixture was supplied to the first reaction unit. The first reaction unit: reaction temperature: 370°C, reaction pressure: 8 MPa, liquid volume space velocity per hour: 0.6 h -1 and was operated at a volume ratio of 0.5:1 of recirculated oil to raw oil at the inlet of the first reaction unit. After hydrogenation, the characteristics of the mixed feedstock are presented in Table I-3.

[0139] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table I-4.

[0140] The second heavy component was coked at a reaction temperature of 500°C for 0.5 hours to obtain petroleum coke with a sulfur content of 2.7 wt% (yield 32 wt%).

[0141] The second light component at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table I-5.

[0142] Example I-4

[0143] In Example I-4, coal tar from a coal tar unit in China was used as the aromatic-rich fraction. The hydrogenation reaction of the coal tar was performed at: a reaction temperature of 300°C, a reaction pressure of 10 MPa, and a liquid volume space velocity of 0.8 h⁻¹. -1 and operated under conditions of a hydrogen to oil volume ratio of 800:1.

[0144] The characteristics of coal tar and the first heavy component 4 are presented in Table I-1.

[0145] DOA from vacuum residue was mixed with the first heavy component 4 in a weight ratio of 15:10, and the characteristics of the mixed feedstock are presented in Table I-2.

[0146] The mixed feedstock of DOA and the first heavy component 4 was first mixed with hydrogen in a hydrogen dissolution unit (volume ratio of hydrogen supply to the mixed feedstock formed by deoiled asphalt and the first heavy component 4: 100, operating temperature of the hydrogen dissolution unit: 320°C, pressure: 12 MPa), and the obtained mixture was supplied to the first reaction unit. The first reaction unit: reaction temperature: 350°C, reaction pressure: 12 MPa, liquid volume space velocity per hour: 0.6 h -1 and was operated at a volume ratio of 2:1 of recirculated oil to raw oil at the inlet of the first reaction unit. After hydrogenation, the characteristics of the mixed feedstock are presented in Table I-3.

[0147] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table I-4.

[0148] The second light component at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table I-5.

[0149] Example I-5

[0150] Except for the following, a method similar to Example I-3 was used:

[0151] In this embodiment, the hydrogenation treatment of the first reaction unit was operated at a temperature of 395°C.

[0152] Other conditions were the same as in Example I-3.

[0153] The characteristics of the mixed feedstock after hydrogenation are presented in Table I-3.

[0154] The main physicochemical properties of the second heavy component obtained above at a temperature above 350℃ are presented in Table I-3.

[0155] Example I-6

[0156] In Example I-6, the feedstock, catalyst loading, and operating conditions of the heavy oil liquid-phase hydroprocessor were the same as in Example I-1, except as follows:

[0157] After hydrogenating the same mixed feedstock as in Example I-1 with liquid heavy oil, the reaction temperature was increased by 3°C every 30 days, and the operation was stopped after 360 days of operation of the hydrogenation test.

[0158] Mineral-rich precursor material 1 and mineral-rich precursor material 2, which were initially loaded into the reactor, became V-rich material 1 and V-rich material 2, with V content of 76 wt% and 71 wt%, respectively, by roasting analysis after reaction. Since these materials exhibit a V content more than 10 times higher than that of natural ore, they are high-quality materials capable of producing high-value V2O5.

[0159] Example I-7

[0160] A catalytic cracking test was performed on the second light component obtained in Example I-3 at a temperature of less than 350°C using a small-scale catalytic cracking fixed fluidized bed test apparatus, wherein the catalyst was catalytic cracking catalyst MLC-500 produced by SINOPEC CATALYST CO.LTD CHANGLING DIVISION; and the fluidized catalyst unit was operated under conditions of a reaction temperature of 540°C, a catalyst-to-oil ratio of 6, and a residence time of 2 seconds.

[0161] As a result, the product gasoline was obtained in a yield of 42 wt%, and the RON octane rating of the gasoline was 92.

[0162] Example I-8

[0163] Except for feeding the obtained second heavy component to a delayed coking unit for reaction to obtain coker gasoline, coker diesel, and coker wax oil, the procedure in this embodiment was similar to that of Example I-1.

[0164] The delayed coking unit was operated under conditions of a reaction temperature of 510℃ and a residence time of 0.6 hours.

[0165] The coker diesel had a sulfur content of 0.26 wt%, a condensation point of -11°C, and a cetane number of 48.

[0166] The coker wax oil had a sulfur content of 1.12 wt% and a condensation point of 32°C.

[0167] Coker gasoline was obtained with a yield of 14.7%, a sulfur content of 0.10 wt%, and a MON of 61.8.

[0168] Coker diesel and coker wax oil were recirculated to the third reaction unit and mixed with LCO1 for hydrogenation treatment, and the reaction conditions were the same as in Example I-1.

[0169] The characteristics of the mixture of coker diesel, coker wax oil and LCO and the characteristics of the first heavy component (8) are shown in Table I-1.

[0170] DOA from vacuum residue was mixed with the first heavy component (8) in a weight ratio of 1:10, and the characteristics of the mixed feedstock are shown in Table I-2.

[0171] The mixed feedstock of DOA and the first heavy component (8) was first mixed with hydrogen in a hydrogen dissolution unit (volume ratio of hydrogen supply to the mixed feedstock formed by deoiled asphalt and the first heavy component (8) is 100, operating temperature of the hydrogen dissolution unit is 320°C and pressure is 8 MPa), and the obtained mixed material was supplied to a first reaction unit. The first reaction unit is: reaction temperature 360°C, reaction pressure 8 MPa, liquid volume space velocity per hour 0.3 h -1 and was operated at a volume ratio of 0.5:1 of recirculated oil to raw oil at the inlet of the first reaction unit. After hydrogenation, the characteristics of the mixed feedstock are presented in Table I-3.

[0172] The liquid product obtained from the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table I-4.

[0173] The second light component at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table I-5.

[0174] Example I-9

[0175] Tests were conducted on the second light component obtained in Example I-1 at a temperature of less than 350°C using a diesel hydrocracking device, and a diesel component was obtained.

[0176] Operating conditions are: reaction temperature 360℃, reaction pressure 10 MPa, hydrogen-to-oil volume ratio 1000, and liquid volume space velocity 1.0 h -1 It was.

[0177] As a result, the diesel component had a sulfur content of 5 ppm, a condensation point of -32°C, and a cetane number of 53.

[0178] Example I-10

[0179] The procedure of this embodiment was similar to Example I-1, except that the catalyst loading in the first reaction unit was as follows:

[0180] According to the flow direction of the reactants, the hydrogenation protection catalyst, mineral-rich precursor material 1, hydrogenation demetallation and desulfurization catalyst, and hydrogenation desulfurization catalyst were loaded sequentially. The loading ratio between the catalysts in the first reaction unit is as follows: RG-30B: mineral-rich precursor material 1: RDM-33B: RCS-31 = 6: 60: 14: 20 (V / V).

[0181] The characteristics of the mixed feedstock after hydrogenation are presented in Table I-3.

[0182] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table I-4.

[0183] The second light component at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table I-5.

[0184] Example I-11

[0185] The procedure of this embodiment was similar to Example I-1, except that the catalyst loading in the first reaction unit was as follows:

[0186] According to the flow direction of the reactants, the hydrogenation protection catalyst, mineral-rich precursor material 2, mineral-rich precursor material 1, hydrogenation demetallation and desulfurization catalyst, and hydrogenation desulfurization catalyst were loaded sequentially. The loading ratio between the catalysts in the first reaction unit is as follows: RG-30B: mineral-rich precursor material 2: mineral-rich precursor material 1: RDM-33B: RCS-31 = 6: 30: 30: 14: 20 (V / V).

[0187] The characteristics of the mixed feedstock after hydrogenation are presented in Table I-3.

[0188] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table I-4.

[0189] The second light component at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table I-5.

[0190] Example I-12

[0191] The procedure of this embodiment was similar to Example I-1, except that the catalyst loading in the first reaction unit was as follows:

[0192] According to the flow direction of the reactants, the hydrogenation protection catalyst, the hydrogenation demetallation and desulfurization catalyst, and the hydrogenation desulfurization catalyst were loaded sequentially. The loading ratio between the catalysts in the first reaction unit is as follows: RG-30B: RDM-33B: RCS-31 = 15: 35: 50 (V / V).

[0193] The characteristics of the mixed feedstock after hydrogenation are presented in Table I-3.

[0194] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table I-4.

[0195] The second light component at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table I-5.

[0196] Example I-13

[0197] The procedure of this embodiment was similar to Example I-1, except that the catalyst loading in the first reaction unit was as follows:

[0198] According to the flow direction of the reactants, the hydrogenation protection catalyst, mineral-rich precursor material 3, hydrogenation demetallation and desulfurization catalyst, and hydrogenation desulfurization catalyst were loaded sequentially. The loading ratio between the catalysts in the first reaction unit is as follows: RG-30B: mineral-rich precursor material 3: RDM-33B: RCS-31 = 10: 40: 20: 30(V / V).

[0199] The characteristics of the mixed feedstock after hydrogenation are presented in Table I-3.

[0200] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table I-4.

[0201] The second light component at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table I-5.

[0202] Comparative Example I-1

[0203] The catalyst and apparatus were similar to those in Example I-1, except for the following:

[0204] In this comparative example, the aromatic-rich fraction oil QY (aromatic content 20 wt%) was mixed directly with DOA without passing through a partial hydrogenation saturation unit. DOA and QY were mixed in a weight ratio of 1:10, and the characteristics of the mixed feedstock are presented in Table I-2.

[0205] In the same manner as in Example I-1, the mixed feedstock of the comparative example was first mixed with hydrogen in a hydrogen dissolution unit, and the resulting mixture was supplied to a first reaction unit for hydrogenation treatment. The characteristics of the product are presented in Table I-3.

[0206] The liquid product obtained by hydrogenation treatment in the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table I-4.

[0207] The second light component at a temperature of less than 350°C was tested in a fixed-bed hydrocracking unit to obtain hydrocracking products, and their characteristics are presented in Table I-5.

[0208] Comparative Example I-2

[0209] The catalyst and apparatus were similar to those in Example I-1, except for the following:

[0210] In this comparative example, the aromatic-rich fraction oil QY was mixed directly with DOA without passing through a partial hydrogenation saturation unit. DOA and QY were mixed in a weight ratio of 2:10, and the characteristics of the mixed feedstock are presented in Table I-2.

[0211] In the same manner as in Example I-1, the mixed feedstock of the comparative example was first mixed with hydrogen in a hydrogen dissolution unit, and the resulting mixture was supplied to a first reaction unit for hydrogenation treatment. The characteristics of the product are presented in Table I-3.

[0212] The liquid product obtained by hydrogenation treatment in the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table I-4.

[0213] The second light component at a temperature of less than 350°C was tested in a fixed-bed hydrocracking unit to obtain hydrocracking products, and their characteristics are presented in Table I-5.

[0214] Comparative Example I-3

[0215] The catalyst and apparatus were similar to those in Example I-1, except for the following:

[0216] In this comparative example, the aromatic-rich fraction oil QY was mixed directly with DOA without passing through a partial hydrogenation saturation unit. DOA and QY were mixed in a weight ratio of 3:10. The mixed feedstock contained a large amount of solids (at 100°C), so the subsequent experiment could not be performed.

[0217] Table I-1: Characteristics of aromatic-rich fractions before and after hydrogenation

[0218]

[0219] Table I-2: Characteristics of Mixed Feedstocks

[0220]

[0221] Table I-2 (continued): Characteristics of mixed feedstocks

[0222]

[0223] Table I-3: Characteristics of the product after liquid phase hydrogenation treatment

[0224]

[0225] Table I-4: Characteristics of the Second Heavy Component

[0226]

[0227] Table I-5: Characteristics of Hydrocracking Products

[0228]

[0229] Table I-6: Characteristics of Mineral-Rich Precursor Substances

[0230]

[0231] Example B

[0232] Solvent deasphalting was performed using vacuum residue as a feedstock, and the solvent was a hydrocarbon mixture containing butane (butane content 70 wt%), wherein solvent deasphalting was performed at 120°C with a solvent:vacuum residue = 3:1 (weight ratio), and a DAO yield of 70 wt% and a DOA yield of 30 wt% were obtained.

[0233] The characteristics of the obtained DAO and DOA are presented in Table II-1.

[0234] The characteristics of the obtained DAO and DOA are presented in Table II-1.

[0235] Example II-1

[0236] The DAO and DOA used in the examples were derived from Example II-B.

[0237] The characteristics of the liquid product obtained from the DAO subjected to the hydrogenation reaction in the fourth reaction unit are presented in Table II-1. The liquid product was fed to the DCC unit for reaction to provide LCO1 and HCO1.

[0238] LCO1 was hydrogenated and saturated in the third reaction unit and then fractionated to yield the first light component 1 and the first heavy component 1. The hydrogenation reaction in the third reaction unit was: reaction temperature 290°C, reaction pressure 4 MPa, liquid volume space velocity 1 h -1 and operated under conditions of a hydrogen to oil volume ratio of 800:1. The characteristics of LCO1 and the first heavy component 1 are presented in Table II-2.

[0239] DOA and the first heavy component 1 were mixed in a weight ratio of 1:10, and the characteristics of the mixed feedstock are presented in Table II-3.

[0240] DOA and the first heavy component 1 were mixed with hydrogen in a hydrogen dissolution unit to obtain a mixed material (see Table II-3 for the hydrogen content). For the mixed material, the first reaction unit was set to: reaction temperature 360°C, reaction pressure 10 MPa, and liquid volume space velocity 0.3 h⁻¹. -1 and was operated at a volume ratio of 0.5:1 of recirculated oil to raw oil at the inlet of the first reaction unit. After hydrogenation, the characteristics of the mixed feedstock are presented in Table II-4.

[0241] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table II-5.

[0242] The second light fraction at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table II-6.

[0243] Example II-2

[0244] The DAO and DOA used in the examples were derived from Example II-B.

[0245] The characteristics of the liquid product obtained from the DAO subjected to the hydrogenation reaction in the fourth reaction unit are presented in Table II-1. The liquid product was fed to the DCC unit for reaction to provide LCO2 and HCO2.

[0246] HCO2 was hydrogenated and saturated in the third reaction unit and then fractionated to yield the first light component 2 and the first heavy component 2. The hydrogenation reaction in the third reaction unit was: reaction temperature 330°C, reaction pressure 6 MPa, liquid volume space velocity 1 h -1 and operated under conditions of a hydrogen to oil volume ratio of 800:1. The characteristics of HCO2 and the first heavy component 2 are presented in Table II-2.

[0247] DOA and the first heavy component 2 were mixed in a weight ratio of 5:10, and the characteristics of the mixed feedstock are presented in Table II-3.

[0248] DOA and the first heavy component 2 were mixed with hydrogen in a hydrogen dissolution unit to obtain a mixed material (see Table II-3 for the hydrogen content). For the mixed material, the first reaction unit was set to: reaction temperature 380°C, reaction pressure 8 MPa, and liquid volume space velocity 0.3 h⁻¹. -1 and was operated at a volume ratio of 0.5:1 of recirculated oil to raw oil at the inlet of the first reaction unit. After hydrogenation, the characteristics of the mixed feedstock are presented in Table II-4.

[0249] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table II-5.

[0250] The second light fraction at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table II-6.

[0251] Example II-3

[0252] The DAO and DOA used in the examples were derived from Example II-B.

[0253] The characteristics of the liquid product obtained from the DAO that underwent the hydrogenation reaction in the fourth reaction unit are presented in Table II-1. The liquid product was fed to the DCC unit (under the same conditions as in Example II-1) for reaction to provide LCO1 and HCO1.

[0254] LCO1 was hydrogenated and saturated in the third reaction unit and then fractionated to yield the first light component 3 and the first heavy component 3. The hydrogenation reaction in the third reaction unit was: reaction temperature 320°C, reaction pressure 6 MPa, liquid volume space velocity 1 h -1 and operated under conditions of a hydrogen-to-oil volume ratio of 800:1. The characteristics of LCO1 and the first heavy component 3 are presented in Table II-2.

[0255] DOA and the first heavy component 3 were mixed in a weight ratio of 10:10, and the characteristics of the mixed feedstock are presented in Table II-3.

[0256] DOA and the first heavy component 3 were mixed with hydrogen in a hydrogen dissolution unit to obtain a mixed material (see Table II-3 for the hydrogen content). For the mixed material, the first reaction unit was set to: reaction temperature 370°C, reaction pressure 8 MPa, and liquid volume space velocity 0.3 h⁻¹. -1 and was operated at a volume ratio of 0.5:1 of recirculated oil to raw oil at the inlet of the first reaction unit. After hydrogenation, the characteristics of the mixed feedstock are presented in Table II-4.

[0257] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table II-5.

[0258] The second heavy component was coked at a reaction temperature of 500°C for 0.5 hours to obtain petroleum coke with a sulfur content of 2.7 wt% (yield 31 wt%).

[0259] The second light fraction at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table II-6.

[0260] Example II-4

[0261] The DAO and DOA used in the examples were derived from Example II-B.

[0262] The characteristics of the liquid product obtained from the DAO that underwent the hydrogenation reaction in the fourth reaction unit are presented in Table II-1. The liquid product was supplied to the DCC unit (operating under the same conditions as Example II-1) for reaction to provide LCO1 and HCO1.

[0263] The aromatic-rich fraction oil used in this example was coal tar from a coal tar unit in China (see Table II-1 for characteristics) and LCO1. LCO1 and coal tar were used in a weight ratio of 1:1. The aromatic-rich fraction oil was hydrogenated and saturated in the third reaction unit and then fractionated to yield the first light component 4 and the first heavy component 4. The hydrogenation reaction in the third reaction unit was performed at: a reaction temperature of 300°C, a reaction pressure of 10 MPa, and a liquid volume space velocity of 0.8 h⁻¹. -1 and operated under conditions of a hydrogen-to-oil volume ratio of 800:1. The characteristics of the aromatic-rich fraction oil and the first heavy component 4 are presented in Table II-2.

[0264] DOA and the first heavy component 4 were mixed in a weight ratio of 15:10, and the characteristics of the mixed feedstock are presented in Table II-3.

[0265] DOA and the first heavy component 4 were mixed with hydrogen in a hydrogen dissolution unit to obtain a mixed material (see Table II-3 for the hydrogen content). For the mixed material, the first reaction unit was set to: reaction temperature 350°C, reaction pressure 12 MPa, and liquid volume space velocity 0.3 h⁻¹. -1 and was operated at a volume ratio of 0.5:1 of recirculated oil to raw oil at the inlet of the first reaction unit. After hydrogenation, the characteristics of the mixed feedstock are presented in Table II-4.

[0266] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table II-5.

[0267] The second light fraction at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table II-6.

[0268] Example II-5

[0269] Except for the following, a method similar to Example II-3 was used:

[0270] In this embodiment, the hydrogenation treatment of the first reaction unit was operated at a temperature of 395°C.

[0271] Other conditions were the same as in Example II-3.

[0272] The characteristics of the mixed feedstock after hydrogenation are presented in Table II-4.

[0273] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table II-5.

[0274] Example II-6

[0275] The catalyst loading and hydrogenation treatment conditions were the same as in Example II-4.

[0276] After hydrogenating the same mixed feedstock as in Example II-4 in the primary reaction unit, the reaction temperature was increased by 3°C every 30 days, and the operation was stopped after 360 days of operation of the hydrogenation test.

[0277] Mineral-rich precursor material 1 and mineral-rich precursor material 2, initially loaded into the reactor, became V-rich material 1 and V-rich material 2, with V content of 69 wt% and 60 wt%, respectively, by roasting analysis after reaction, and are high-quality materials capable of producing high-value V2O5.

[0278] Example II-7

[0279] Catalytic cracking tests were conducted on the second light component at a temperature of less than 350°C derived from Example II-3 using a small-scale catalytic cracking fixed fluidized bed test apparatus, wherein the catalyst was catalytic cracking catalyst MLC-500 produced by SINOPEC CATALYST CO.LTD CHANGLING DIVISION; and the fluidization catalyst unit was operated under conditions of a reaction temperature of 540°C, a catalyst-to-oil ratio of 6, and a residence time of 3 seconds.

[0280] As a result, the product gasoline was obtained in a yield of 40 wt%, and the RON octane rating of the gasoline was 93.

[0281] Example II-8

[0282] Except for feeding the obtained second heavy component to a delayed coking unit for reaction to obtain coker gasoline, coker diesel, and coker wax oil, the procedure in this example was similar to Example II-1.

[0283] The delayed coking unit was operated under conditions of a reaction temperature of 510℃ and a residence time of 0.6 hours.

[0284] The coker diesel had a sulfur content of 0.26 wt%, a condensation point of -11°C, and a cetane number of 48.

[0285] The coker wax oil had a sulfur content of 1.12 wt% and a condensation point of 32°C.

[0286] Coker gasoline was obtained with a yield of 14.7%, a sulfur content of 0.10 wt%, and a MON of 61.8.

[0287] Coker diesel and coker wax oil were recirculated to a third reaction unit and mixed with LCO1 for hydrogenation saturation, then fractionated to provide a first light component (8) and a first heavy component (8) having a cutting point of 180°C, and the reaction conditions were the same as in Example II-1. The characteristics of the mixed oil of coker diesel, coker wax oil and LCO1 and the characteristics of the first heavy component (8) are presented in Table II-2.

[0288] The DOA of Example II-B and the first heavy component (8) were mixed in a weight ratio of 1:10, and the characteristics of the mixed feedstock are shown in Table II-3.

[0289] DOA and the first heavy component (8) were mixed with hydrogen in a hydrogen dissolution unit to obtain a mixed material (see Table II-3 for the hydrogen content). The first reaction unit had: a reaction temperature of 360°C, a reaction pressure of 8 MPa, and a liquid volume space velocity of 0.3 h per hour. -1 and operated under conditions of a hydrogen to oil volume ratio of 800:1. After hydrogenation, the characteristics of the mixed feedstock are presented in Table II-4.

[0290] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table II-5.

[0291] The second light fraction at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table II-6.

[0292] Example II-9

[0293] A test was conducted on the second light component obtained in Example II-1 at a temperature of less than 350°C using a diesel hydrogenation upgrade device, and a diesel component was obtained.

[0294] The diesel hydrogenation upgrade unit has: a reaction temperature of 360℃, a reaction pressure of 12 MPa, a hydrogen-to-oil volume ratio of 1000, and a liquid volume-to-space velocity of 1.0 h -1 It was operated under the conditions of.

[0295] As a result, the diesel component had a sulfur content of 5 ppm, a condensation point of -33℃, and a cetane number of 53.

[0296] Example II-10

[0297] The procedure of this example was similar to Example II-1, except that the catalyst loading in the first reaction unit was as follows:

[0298] According to the flow direction of the reactants, the hydrogenation protection catalyst, mineral-rich precursor material 1, hydrogenation demetallation and desulfurization catalyst, and hydrogenation desulfurization catalyst were loaded sequentially. The loading ratio between the catalysts in the first reaction unit is as follows: RG-30B: mineral-rich precursor material 1: RDM-33B: RCS-31 = 6: 60: 14: 20 (V / V).

[0299] The characteristics of the mixed feedstock after hydrogenation are presented in Table II-4.

[0300] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table II-5.

[0301] The second light fraction at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table II-6.

[0302] Example II-11

[0303] The procedure of this example was similar to Example II-1, except that the catalyst loading in the first reaction unit was as follows:

[0304] According to the flow direction of the reactants, the hydrogenation protection catalyst, mineral-rich precursor material 2, mineral-rich precursor material 1, hydrogenation demetallation and desulfurization catalyst, and hydrogenation desulfurization catalyst were loaded sequentially. The loading ratio between the catalysts in the first reaction unit is as follows: RG-30B: mineral-rich precursor material 2: mineral-rich precursor material 1: RDM-33B: RCS-31 = 6: 30: 30: 14: 20 (V / V).

[0305] The characteristics of the mixed feedstock after hydrogenation are presented in Table II-4.

[0306] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table II-5.

[0307] The second light fraction at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table II-6.

[0308] Example II-12

[0309] The procedure of this example was similar to Example II-1, except that the catalyst loading in the first reaction unit was as follows:

[0310] According to the flow direction of the reactants, the hydrogenation protection catalyst, the hydrogenation demetallation and desulfurization catalyst, and the hydrogenation desulfurization catalyst were loaded sequentially. The loading ratio between the catalysts is as follows: RG-30B : RDM-33B : RCS-31 = 15 : 40 : 45 (V / V).

[0311] The characteristics of the mixed feedstock after hydrogenation are presented in Table II-4.

[0312] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table II-5.

[0313] The second light fraction at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table II-6.

[0314] Example II-13

[0315] The procedure of this example was similar to Example II-1, except that the catalyst loading in the first reaction unit was as follows:

[0316] According to the flow direction of the reactants, the hydrogenation protection catalyst, mineral-rich precursor material 3, hydrogenation demetallation and desulfurization catalyst, and hydrogenation desulfurization catalyst were loaded sequentially. The loading ratio between the catalysts is as follows: RG-30B : mineral-rich precursor material 3 : RDM-33B : RCS-31 = 10 : 40 : 25 : 35 (V / V).

[0317] The characteristics of the mixed feedstock after hydrogenation are presented in Table II-4.

[0318] The liquid product obtained by the treatment of the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table II-5.

[0319] The second light fraction at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table II-6.

[0320] Comparative Example II-1

[0321] The catalyst and apparatus were similar to those in Example II-1, except for the following:

[0322] In this comparative example, the aromatic-rich fraction oil QY (aromatic content 20 wt%) was mixed directly with DOA without passing through a partial hydrogenation saturation unit. DOA and QY were mixed in a weight ratio of 1:10, and the characteristics of the mixed feedstock are presented in Table II-3.

[0323] After mixing the mixed material with hydrogen in the hydrogen dissolution unit, the obtained mixed material (the hydrogen content thereof is referenced in Table II-3) was hydrogenated in the first reaction unit, and the characteristics of the product are presented in Table II-4.

[0324] The liquid product obtained by hydrogenation treatment in the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table II-5.

[0325] The second light fraction at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table II-6.

[0326] Comparative Example II-2

[0327] The catalyst and apparatus were similar to those in Example II-1, except for the following:

[0328] In this comparative example, the aromatic-rich fraction oil QY was mixed directly with DOA without passing through a partial hydrogenation saturation unit. DOA and QY were mixed in a weight ratio of 2:10, and the characteristics of the mixed feedstock are presented in Table II-3.

[0329] After mixing the mixed material with hydrogen in the hydrogen dissolution unit, the obtained mixed material (the hydrogen content thereof is referenced in Table II-3) was hydrogenated in the first reaction unit, and the characteristics of the product are presented in Table II-4.

[0330] The liquid product obtained by hydrogenation treatment in the first reaction unit was fractionated, and the characteristics of the second heavy component at a temperature of 350°C or higher are presented in Table II-5.

[0331] The second light fraction at a temperature of less than 350°C was tested in the second reaction unit to obtain a hydrocracking product, and its characteristics are presented in Table II-6.

[0332] Comparative Example II-3

[0333] The catalyst and apparatus were similar to those in Example II-1, except for the following:

[0334] In Comparative Example II-3, the aromatic-rich fraction oil QY was mixed directly with DOA without passing through a partial hydrogenation saturation unit. DOA and QY were mixed in a weight ratio of 3:10. The mixed feedstock contained a large amount of solids (at 100°C), so the subsequent experiment could not be performed.

[0335] Table II-1: Characteristics of liquid products after hydrogenation treatment by DOA, DAO, and the 4th reaction unit

[0336]

[0337] Table II-2: Characteristics of Aromatic-Rich Fractions Before and After Hydrogenation

[0338]

[0339] Table II-3: Characteristics of Mixed Feedstocks

[0340]

[0341] Table II-3 (continued): Characteristics of mixed feedstocks

[0342]

[0343] Table II-4: Characteristics of the product after hydrogenation treatment of the mixed material

[0344]

[0345] Table II-5: Characteristics of the Second Heavy Component

[0346]

[0347] Table II-6: Characteristics of Hydrocracking Products

[0348]

[0349] Table II-7: Characteristics of Mineral-Rich Precursor Substances

[0350]

[0351] From the above results, it can be seen that the technology of the present invention enables high-quality raw materials for producing low-sulfur ship fuel or low-sulfur coke products from DOA.

[0352] In addition, the technology of the present invention can provide high-quality gasoline products that meet the national V standards.

[0353] Although preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, many simple modifications may be made to the technical solution of the present invention, including combining various technical features in other appropriate ways, and such simple modifications and combinations should be considered as part of the disclosure of the present invention and are all within the scope of the present invention.

Claims

Claim 1 A method for processing an aromatic-rich fraction oil, characterized by comprising the following: (11) introducing a heavy oil feedstock into a solvent deasphalting unit for solvent deasphalting treatment to provide deoiled asphalt and deasphalted oil; (12) introducing the deasphalted oil into a fourth reaction unit for a hydrogenation reaction, and introducing the liquid effluent obtained from the fourth reaction unit into a DCC unit for reaction to provide propylene, LCO, HCO, and slurry oil; (1) introducing the aromatic-rich fraction oil containing LCO and / or HCO from the DCC unit into a third reaction unit for hydrosaturation and then fractionating to provide a first light component and a first heavy component, wherein the first light component and the first heavy component have a cutting point of 100-250°C, and the first heavy component A step in which the component has an aromatic content of 20 weight% or more; (2) a step of introducing an aromatic-containing stream comprising deoiled asphalt from step (11) and a first heavy component from step (1) into a hydrogen dissolution unit to mix with hydrogen to form a mixed material, and introducing the mixed material into a first reaction unit for a hydrogenation reaction, wherein the deoiled asphalt and the aromatic-containing stream are used in a ratio such that the mixed feedstock formed by the deoiled asphalt and the aromatic-containing stream becomes a liquid state at a temperature of 400°C or lower; (3) a step of fractionating the liquid product from the first reaction unit to provide a second light component and a second heavy component, wherein the cutoff point of the second light component and the second heavy component is 240-450°C;(41) a step of introducing a second light component into a second reaction unit for reaction to provide at least one product selected from a gasoline component, a diesel component and a BTX feedstock component, wherein the second reaction unit is at least one selected from the group consisting of a hydrocracking unit, a catalytic cracking unit and a diesel hydrogenation upgrade unit; and (42) a step of introducing a second heavy component into a delayed coking unit for reaction to provide at least one product selected from the group consisting of coker gasoline, coker diesel, coker wax oil and low-sulfur petroleum coke; or a step of using the second heavy component as a component of low-sulfur marine fuel oil.; Claim 2 A method according to claim 1, wherein in step (2), the first reaction unit comprises a mineral-rich precursor material and / or a hydrogenation catalyst, the first reaction unit is a liquid-phase hydrogenation reaction unit, and the mineral-rich precursor material is a material capable of adsorbing at least one metal selected from V, Ni, Fe, Ca and Mg. Claim 3 In claim 1, in step (2), the oil-free asphalt and aromatic-containing stream is a mixed feedstock formed from the oil-free asphalt and aromatic-containing stream, with a viscosity of 400 mm at 100°C. 2 A method used at a rate that makes it less than or equal to / s. Claim 4 In claim 1, at step (2), the aromatic-containing stream further comprises an aromatic hydrocarbon and / or an aromatic oil, wherein (i) the aromatic oil is at least one selected from the group consisting of LCO, HCO, FGO, ethylene tar, coal tar, coker diesel and coker wax oil; and (ii) the aromatic hydrocarbon is benzene, toluene, xylene, naphthalene, at least one C 1-6 At least one selected from the group consisting of naphthalene substituted with an alkyl group and tricyclic or higher aromatic hydrocarbons; or (iii) the aromatic oil is at least one selected from the group consisting of LCO, HCO, FGO, ethylene tar, coal tar, coker diesel, and coker wax oil, and the aromatic hydrocarbon is benzene, toluene, xylene, naphthalene, at least one C 1-6 A method comprising at least one selected from the group consisting of naphthalene substituted with an alkyl group and a tricyclic or longer aromatic hydrocarbon. Claim 5 A method according to claim 1, wherein the aromatic-rich fraction oil has an aromatic content of 20 weight% or more. Claim 6 A method according to claim 1, wherein the yield of de-oiled asphalt in the solvent deasphalting unit is 50 weight% or less. Claim 7 A method according to claim 1, wherein in step (2), the weight ratio of the deoiled asphalt content to the aromatic-containing stream content is 1:10 to 50:

10. Claim 8 A method according to claim 1, further comprising the step of recirculating the coker diesel and / or coker wax oil obtained in step (42) to the third reaction unit of step (1) for hydrogenation saturation. Claim 9 In claim 1, in step (1), (i) the third reaction unit is at least one of a fixed bed reactor, a moving bed reactor, and a boiling bed reactor; or (ii) the third reaction unit is: a reaction temperature of 200-420°C, a reaction pressure of 2-18 MPa, and a liquid space velocity of 0.3-10 h -1 and operated under conditions of a volume ratio of hydrogen to oil of 50-5000; or (iii) the third reaction unit is at least one of a fixed-bed reactor, a moving-bed reactor, and a boiling-bed reactor, with a reaction temperature of 200-420°C, a reaction pressure of 2-18 MPa, and a liquid space velocity of 0.3-10 h per hour. -1 and a method operated under conditions of a volume ratio of hydrogen to oil of 50-5000. Claim 10 In claim 8, in step (2), the first reaction unit is: reaction temperature 260-500°C, reaction pressure 2.0-20.0 MPa, volume ratio of recirculated oil to feedstock oil at the inlet of the first reaction unit 0.1:1-15:1 and liquid space velocity 0.1-1.5 h -1 A method that operates under the conditions of. Claim 11 In paragraph 2, at step (2), the mineral-rich precursor material has a loss on ignition of 3 weight% or more and a specific surface area of ​​80 m² 2 A method having a water absorption rate of 0.9 g / g or more and a water absorption rate of 0.9 g / g or more. Claim 12 In claim 11, in step (2), the mineral-rich precursor material comprises a support and an active component element loaded on the support, wherein the support is at least one selected from the group consisting of aluminum hydroxide, alumina and silica, and the active component element is at least one metal element selected from the group consisting of group VIB and group VIII. Claim 13 In claim 12, in step (2), a mineral-rich first precursor material and a mineral-rich second precursor material are sequentially loaded into a first reaction unit according to the flow direction of the reactants, and the mineral-rich second precursor material has a loss on ignition equal to or greater than that of the mineral-rich first precursor material. Claim 14 A method according to claim 13, wherein (i) the mineral-rich first precursor material has a loss on ignition of 3-15 weight% and the mineral-rich second precursor material has a loss on ignition of 15 weight% or more; (ii) the mineral-rich first precursor material and the mineral-rich second precursor material are loaded in a volume ratio of 5:95 to 95:5; or (iii) the mineral-rich first precursor material has a loss on ignition of 3-15 weight% and the mineral-rich second precursor material has a loss on ignition of 15 weight% or more, and the mineral-rich first precursor material and the mineral-rich second precursor material are loaded in a volume ratio of 5:95 to 95:

5. Claim 15 In claim 1, at step (41), (i) the second reaction unit is a hydrocracking unit, with a reaction temperature of 360-420°C, a reaction pressure of 10.0-18.0 MPa, a volume ratio of hydrogen to oil of 600-2000, and a liquid volume space velocity of 1.0-3.0 h -1 Operated under the conditions of; or (ii) the second reaction unit is a hydrocracking unit, with a reaction temperature of 360-420°C, a reaction pressure of 10.0-18.0 MPa, a volume ratio of hydrogen to oil of 600-2000, and a liquid volume space velocity of 1.0-3.0 h -1 A method operated under the conditions of, wherein at least one hydrogenation treatment catalyst and at least one hydrocracking catalyst are loaded into the hydrocracking unit. Claim 16 In claim 1, at step (41), the second reaction unit is a catalytic cracking unit, and the catalytic cracking unit is a fluid catalytic cracking unit; wherein the fluid catalytic cracking unit is operated under conditions of: a reaction temperature of 500-600°C, a catalyst-to-oil ratio of 3-12, and a residence time of 0.6-6 seconds. Claim 17 In claim 1, at step (41), (i) the second reaction unit is a diesel hydrogenation upgrading unit, with a reaction temperature of 330-420°C, a reaction pressure of 5.0-18.0 MPa, a volume ratio of hydrogen to oil of 500-2000, and a liquid volume space velocity of 0.3-3.0 h -1 (ii) operated under the conditions of; or (ii) the second reaction unit is a diesel hydrogenation upgrade unit, with a reaction temperature of 330-420°C, a reaction pressure of 5.0-18.0 MPa, a volume ratio of hydrogen to oil of 500-2000, and a liquid volume space velocity of 0.3-3.0 h -1 A method that operates under the conditions of, wherein at least one diesel hydrogenation upgrade catalyst is loaded into the diesel hydrogenation upgrade unit. Claim 18 In claim 1, (i) in step (42), the second heavy component is introduced into a delayed coking unit for reaction to provide at least one product selected from coker gasoline, coker diesel, coker wax oil, and low-sulfur petroleum coke, wherein the delayed coking unit is operated under conditions of: a reaction temperature of 440-520°C and a residence time of 0.1-4 hours; or (ii) in step (42), the sulfur content of the second heavy component is 1.8 weight% or less, and the second heavy component is introduced into a delayed coking unit for reaction to provide low-sulfur petroleum coke, the low-sulfur petroleum coke having a sulfur content of 3 weight% or less; or (iii) in step (42), the sulfur content of the second heavy component is 1.8 wt% or less, and the second heavy component is introduced into a delay coking unit for reaction to provide low-sulfur petroleum coke, the low-sulfur petroleum coke having a sulfur content of 3 wt% or less, wherein the delay coking unit is operated under conditions of: a reaction temperature of 440-520°C and a residence time of 0.1-4 hours, a method. Claim 19 A method according to claim 1, wherein in step (42), the second heavy component is used as a low-sulfur marine fuel oil component, and the conditions are adjusted so that the low-sulfur marine fuel oil component has a sulfur content of 0.5 weight% or less. Claim 20 In claim 1, (i) in step (12), the fourth reaction unit is: reaction temperature 280-400°C, reaction pressure 6.0-14.0 MPa, volume ratio of hydrogen to oil 600-1200 and liquid space velocity 0.3-2.0 h -1 (ii) operated under the conditions of; (ii) in step (12), at least two hydrogenation catalysts are loaded into the fourth reaction unit; at least one hydrogenation catalyst is a catalyst capable of catalyzing at least one reaction selected from the group consisting of hydrodemetallization, hydrodesulfurization, and hydrodecarbonization; and at least one hydrogenation catalyst comprises alumina as a support and a metal element of Group VIB and / or Group VIII as an active component element, and optionally at least one auxiliary element selected from P, Si, F, and B; or (iii) in step (12), the fourth reaction unit is: reaction temperature 280-400°C, reaction pressure 6.0-14.0 MPa, volume ratio of hydrogen to oil 600-1200, and liquid space velocity 0.3-2.0 h -1 A method operated under the conditions of, wherein at least two hydrogenation catalysts are loaded into a fourth reaction unit; at least one hydrogenation catalyst is a catalyst capable of catalyzing at least one reaction selected from the group consisting of a hydrogenation demetallation reaction, a hydrogenation desulfurization reaction, and a hydrogenation decarbonization reaction; and at least one hydrogenation catalyst comprises alumina as a support and a metal element of group VIB and / or VIII as an active component element, and optionally at least one auxiliary element selected from P, Si, F and B. Claim 21 A system for processing aromatic-rich fractional oil, comprising: a solvent deasphalting unit used to solvent deasphalt a heavy oil feedstock and to provide deasphalted asphalt and deasphalted oil; a fourth reaction unit fluidly communicating with the solvent deasphalting unit, as a fixed-bed reaction unit, for the hydrogenation reaction of deasphalted oil from the solvent deasphalting unit; a DCC unit fluidly communicating with the fourth reaction unit for the reaction of a liquid effluent obtained from the fourth reaction unit to provide propylene, LCO, HCO, and slurry oil; a third reaction unit providing a first light component and a first heavy component for hydrosaturation and fractionation of the aromatic-rich fractional oil; a hydrogen dissolution unit fluidly communicating with the third reaction unit for mixing an aromatic-containing stream comprising deasphalted asphalt and the first heavy component from the third reaction unit with hydrogen; and a liquid hydrogenation reaction unit and a hydrogen dissolution A first reaction unit fluidly communicating with a hydrogen dissolution unit, used to perform a hydrogenation reaction of a mixed material from a unit; a separation unit fluidly communicating with the first reaction unit, for fractionating a liquid product from the first reaction unit to provide a second light component and a second heavy component; a second reaction unit fluidly communicating with the separation unit, at least one selected from the group consisting of a hydrocracking unit, a catalytic cracking unit, and a diesel hydrogenation upgrade unit, for the reaction of the second light component obtained from the separation unit; and a delayed coking unit fluidly communicating with the separation unit, for the reaction of the second heavy component obtained from the separation unit, to provide at least one product selected from the group consisting of coker gasoline, coker diesel, coker wax oil, and low-sulfur petroleum coke.A system comprising a discharge port fluidly communicating with a separation unit for discharging a second heavy component obtained from a separation unit from the system as a low-sulfur marine fuel oil fraction, wherein the DCC unit fluidly communicates with a third reaction unit for transporting an aromatic-rich fraction oil containing LCO and / or HCO from the DCC unit to a third reaction unit for use as an aromatic-rich fraction oil. Claim 22 In paragraph 21, the delay coking unit is in fluid communication with a hydrogen dissolution unit to recirculate coker diesel and / or coker wax oil obtained from the delay coking unit to a first reaction unit. Claim 23 In paragraph 21, the solvent deasphalting unit is a system that fluidly communicates with the hydrogen dissolution unit, which is used to introduce the de-oiled asphalt obtained after solvent deasphalting into the hydrogen dissolution unit. Claim 24 delete Claim 25 delete Claim 26 delete

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