A device and system for the resource utilization of residual oil

Abstract

This invention provides a device and system method for the resource utilization of residual oil, belonging to the field of residual oil resource utilization. The device replaces the traditional high-energy-consumption, low-separation-efficiency porous media adsorption method with a precision filtration device, achieving efficient separation of residues and oil products in the residual oil. This avoids the use of consumables while improving separation accuracy and efficiency. Using a dry residue extraction device, further separation of dry residue and residual oil can be achieved with a small amount of extractant. The separated dry residue is roasted in a precision incineration unit to obtain metallic ash, which is then further recovered as nickel, molybdenum, and vanadium through hydrometallurgy. The separated residual oil and extractant are processed in a delayed coking unit to obtain petroleum coke and distillate oil, thus achieving full recovery and utilization of slurry-bed residual oil. The process is highly efficient, low-cost, and suitable for large-scale industrial applications.

Description

Technical Field

[0001] This invention belongs to the field of residual oil resource utilization, and particularly relates to a device and system method for residual oil resource utilization. Background Technology

[0002] Slurry-bed hydrocracking is currently the preferred technology for converting heavy distillate oils, especially residue oils, into light distillate oils and petrochemical products. This technology boasts advantages such as strong feedstock adaptability, the ability to process feedstocks with high heavy metal and residual carbon content, high conversion rates, and long operating cycles. The removal rate of residual carbon and metals can reach 80-90%, making it an effective processing method for heavy oils and tail oils, including asphalt produced from heavy oil deasphalting, slurry oil from catalytic cracking units, and residual oil.

[0003] However, slurry-bed hydrocracking, while producing light distillate oils such as naphtha, kerosene, and diesel, also generates approximately 6% to 10% residue oil. This residue oil is not only dense and heavy in composition, but also contains a large amount of coke, catalysts (such as Mo), and heavy metals (such as Ni and V) generated during the reaction. Due to its poor properties, high metal content, and difficulty in secondary processing and utilization, properly handling this residue oil is a bottleneck problem that urgently needs to be solved in the development of slurry-bed residue hydrocracking processes.

[0004] CN113736509A proposes a method for treating residual oil from slurry-bed hydrotreating of residual oil. This method involves mixing the residual oil from slurry-bed hydrotreating of residual oil with solvent oil and porous material to obtain a mixture; separating the mixture to obtain saturated adsorbed porous material and mixed oil; and separating the mixed oil to obtain recovered solvent oil and treated residual oil. While this method is simple and easy to implement, it also has significant drawbacks: 1) It requires a large amount of solvent oil, 2 to 10 times the amount of residual oil, resulting in high energy consumption for subsequent distillation and separation; 2) The porous material accounts for 2% to 10% of the residual oil, leading to high consumption and excessive adsorption of residual oil, reducing the yield of purified residual oil, and requiring large subsequent processing volumes; 3) The treatment process is incomplete, involving only simple mixing and adsorption, producing only a mixture of solvent and residual oil and saturated adsorbed porous material.

[0005] CN119410908A proposes a method for extracting heavy metals from slurry-bed hydrotreated residue. Using residue as raw material and biomass-derived Camellia oleifera fruit shells as filter media, a vacuum-assisted thermal filtration method is employed to remove heavy metals from the slurry-bed residue. The filter residue is then subjected to air roasting and alkaline leaching to separate and recover vanadium, molybdenum, and nickel from the residual oil. The precipitation rates are 93.12% for molybdenum, 81.25% for vanadium, and 85.56% for nickel. However, the method has drawbacks: it requires the addition of a large amount of diluent, 2-6 times the volume of the residual oil, resulting in low metal recovery rates. Furthermore, it does not address the separation of the residual oil and solvent, making the process imperfect. Summary of the Invention

[0006] In view of the problems existing in the prior art, the present invention provides a device and system method for the resource utilization of residual oil. The device and system method realize the full-component recovery and utilization of residual oil, with high metal recovery rate and low petroleum coke ash content. While solving the bottleneck of slurry bed residual oil hydrogenation device, it also improves the added value of slurry bed residual oil.

[0007] To achieve the above-mentioned technical effects, the present invention adopts the following technical solution: One objective of this invention is to provide a device for the resource utilization of residual oil, which includes: Precision desolidification unit, delayed coking unit, precision incineration unit, and hydrometallurgical unit; The precision desolidification unit includes a precision filtration device and a dry residue extraction device. The residue outlet of the precision filtration device is connected to the raw material inlet of the dry residue extraction device via a homogenizer. The purified liquid outlet of the precision filtration device is connected to the raw material inlet of the delayed coking unit. The deoiled dry residue outlet of the dry residue extraction device is connected to the solid inlet of the precision incineration unit. The recovered liquid outlet of the dry residue extraction device is connected to the raw material inlet of the delayed coking unit. The metal ash outlet of the precision incineration unit is connected to the raw material inlet of the hydrometallurgical unit.

[0008] As a preferred technical solution of the present invention, an extractant inlet is provided on the pipeline connecting the residue outlet of the precision filtration device and the inlet of the dry residue extraction device.

[0009] As a preferred embodiment of the present invention, the delayed coking unit includes a coking furnace and a coking tower connected in series, and the raw material inlet of the delayed coking unit is located in the convection section of the coking furnace.

[0010] Preferably, an activated carbon inlet is provided on the pipeline connecting the purified liquid outlet of the precision filtration device and the raw material inlet of the delayed coking unit.

[0011] As a preferred technical solution of the present invention, the precision incineration unit includes a multi-chamber incineration device, wherein the multi-chamber incineration device is arranged sequentially along the direction of gravity as a drying and preheating zone, an organic matter roasting zone, a metal oxidation zone, and a cooling and burnout zone.

[0012] Preferably, the number of furnace layers in the multi-chamber incineration device is 8 to 11.

[0013] Preferably, layers 1-2 of the multi-chamber combustion device are drying and preheating zones, layers 3-(8-9) are organic matter roasting and metal oxidation zones, and layers (8-9)-(10-11) are cooling and burnout zones.

[0014] Preferably, the gas outlet of the delayed coking unit is connected to the 2nd to 5th layer air inlets of the multi-chamber combustion device.

[0015] As a preferred technical solution of the present invention, the hydrometallurgical unit includes an alkaline leaching process, a vanadium precipitation process, a molybdenum precipitation process, an acid leaching process, a nickel precipitation process, and a resin adsorption process.

[0016] The second objective of this invention is to provide a system method for the resource utilization of residual oil. This system method uses the apparatus provided in the first objective, and the system method includes the following steps: The residual oil enters the precision filtration device for precision filtration to obtain filter residue and desolidified purified oil. The filter residue and extractant are fed into a dry residue extraction device for deoiling treatment to obtain extract and deoiled dry residue. The deoiled dry residue is fed into a precision incineration unit for roasting to obtain metallic ash. The metallic ash is then fed into a hydrometallurgical unit for separation to obtain the target products: nickel metal compounds, vanadium metal compounds, and molybdenum metal compounds. The desolidified purified oil and extract enter the delayed coking unit for cracking and condensation to obtain petroleum coke, distillate oil and dry gas.

[0017] As a preferred technical solution of the present invention, the temperature of the precision filtration is 280~310℃.

[0018] Preferably, the pressure difference of the precision filter is 0.15~1.0 MPa.

[0019] Preferably, the flux of the precision filter is 0.1~0.6 m. 3 / m 2 ·h.

[0020] Preferably, the volume ratio of the extractant to the filter residue is 0.6 to 1.3:1.

[0021] Preferably, the temperature of the deoiling treatment is 150~200℃.

[0022] Preferably, the filter residue pressure drop after the deoiling treatment is 0.15~1.0 MPa.

[0023] As a preferred technical solution of the present invention, the temperature of the drying and preheating zone of the precision incineration unit is 430~480℃.

[0024] Preferably, the temperature of the organic matter roasting and metal oxidation zone of the precision incineration unit is 480~610℃.

[0025] Preferably, the temperature of the organic matter roasting and metal oxidation zones of the precision incineration unit is controlled according to a specific temperature distribution curve, with a temperature range between 480 and 610°C, and the outlet temperature of the organic matter roasting and metal oxidation zones is controlled below 550°C.

[0026] Preferably, the outlet temperature of the cooling burnout zone of the precision incineration unit is not higher than 300°C.

[0027] Preferably, the temperature difference between each layer in the precision incineration unit is no higher than 30°C.

[0028] As a preferred technical solution of the present invention, the separation process includes the following steps: The metal ash and alkaline solution are subjected to alkaline leaching process to obtain alkaline leaching residue and alkaline leaching solution. The alkaline leaching residue and acid solution are then subjected to acid leaching in the acid leaching process to obtain acid leaching residue and acid leaching solution. The acid leaching solution enters the resin adsorption process to remove molybdenum and vanadium, resulting in a nickel-containing adsorption residue. The nickel-containing adsorption residue is then subjected to a nickel precipitation process to obtain the target product: metallic nickel compound. The alkaline leaching solution and ammonium salt are introduced into the vanadium precipitation process for vanadium precipitation treatment to obtain metallic vanadium compounds and precipitate tail liquid. The precipitate tail liquid is mixed with acid and then fed into a molybdenum precipitation process to obtain a metallic molybdenum compound.

[0029] As a preferred technical solution of the present invention, the desolidified purified oil and extract are mixed with trace amounts of activated carbon and enter the convection section of the coking furnace in the coking unit. After being preheated in the convection section, the mixture enters the radiant section of the coking furnace for cracking treatment. The outlet temperature of the radiant section of the coking furnace is 495~505℃, the pressure is 0.30~0.40MPa, and the residence time is 25s~45s.

[0030] Preferably, the desolidified and purified oil enters the coking tower for coking reaction after passing through the radiant section of the coking furnace, with a temperature of 490~500℃, a pressure of 0.17~0.19MPa, and a residence time of 2~3h.

[0031] Preferably, the activated carbon is added at a ratio of 300 to 400 ppm.

[0032] Preferably, the activated carbon has a bulk particle size of 5-10 μm, and the proportion of particles with a particle size of less than 20 μm is greater than 95 wt%.

[0033] Preferably, the activated carbon is hollow activated carbon.

[0034] Preferably, the dry gas generated by the delayed coking unit enters the precision combustion unit to provide roasting heat energy.

[0035] Compared with the prior art, the present invention has at least the following beneficial effects: (1) The present invention provides a device and system method for the resource utilization of residual oil. The device and system method can realize the full-component recovery and utilization of slurry bed residual oil, solve the bottleneck of slurry bed residual oil hydrogenation device, and improve the added value of slurry bed residual oil.

[0036] (2) The present invention provides a device and system method for the resource utilization of residual oil. The device and system method consume no solvent (or diluent) and porous materials; the extractant is an oil slurry and the amount used is very small, only 0.1 to 0.2 times that of the residual oil. It can be entered into delayed coking together with the deconsolidated residual oil without separation.

[0037] (3) The present invention provides a device and system method for the resource utilization of residual oil. The device and system method have high metal recovery rates, including vanadium recovery rate greater than 95%, molybdenum recovery rate greater than 95%, and nickel recovery rate greater than 92%.

[0038] (4) The present invention provides a device and system method for the resource utilization of residual oil. The petroleum coke produced by the device and system method has low ash content, with ash content <0.2% by mass, sulfur content <1.2%, and volatile content 5-7%. Attached Figure Description

[0039] Figure 1 A schematic diagram of the process for the residual oil resource utilization device provided in a specific embodiment of the present invention.

[0040] In the figure: 1. Precision filtration device, 1.1 Precision filtration component, 2. Dry residue extraction device, 3. Precision incineration device, 3.1 Central shaft, 3.2 Rake arm, 3.3 Chamber partition plate, 4. Delayed coking unit, 5. Hydrometallurgical unit, 6. Homogenizer.

[0041] Figure 2 A schematic diagram of the multi-hearth incinerator in the residual oil resource utilization device provided for a specific embodiment of the present invention.

[0042] Figure 3 Temperature control curves for organic matter roasting and metal oxidation zones in the residual oil resource utilization system method provided in a specific embodiment of the present invention.

[0043] Figure 4 This is a schematic diagram of the hydrometallurgical unit in the residual oil resource utilization system method provided in a specific embodiment of the present invention. Detailed Implementation

[0044] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0045] This invention provides a device for the resource utilization of residual oil, which includes: Precision desolidification unit, delayed coking unit, precision incineration unit, and hydrometallurgical unit; The precision desolidification unit includes a precision filtration device and a dry residue extraction device. The residue outlet of the precision filtration device is connected to the raw material inlet of the dry residue extraction device via a homogenizer. The purified liquid outlet of the precision filtration device is connected to the raw material inlet of the delayed coking unit. The deoiled dry residue outlet of the dry residue extraction device is connected to the solid inlet of the precision incineration unit. The recovered liquid outlet of the dry residue extraction device is connected to the raw material inlet of the delayed coking unit. The metal ash outlet of the precision incineration unit is connected to the raw material inlet of the hydrometallurgical unit.

[0046] The residue oil produced by the slurry-bed residue oil hydrotreating unit has a solids content of 7-12 wt%, of which 90% is semi-coke and about 10% is metal sulfides or elemental metals. The residue oil is fluid above 200°C, exhibits a gradually increasing tendency to coke above 300°C, and is solid below 150°C. The total metal content in the residue oil is 8000-10000 ppm. Mo mainly originates from deactivated catalyst particles (MOS2), while Ni and V originate from the hydrocracking of heterocyclic compounds in the hydrotreating feedstock residue oil. Ni and V are mainly found in heterocyclic compounds (porphyrins). During the hydrocracking reaction, porphyrin compounds decompose, and Ni and V precipitate and settle on the catalyst particles, covering the active sites and leading to catalyst deactivation.

[0047] Slurry bed residual oil, due to its high metal and solid content, cannot be directly used in coking or other downstream units. High metal content easily causes pipeline wear, and high asphaltene content easily leads to coking and blockage, preventing long-term continuous operation. Furthermore, petroleum coke is of poor quality and has excessive metal content. Residual oil cannot be used as a coking blending feedstock; it can only be blended in small proportions as a gasification feedstock, and even then, it presents problems such as nozzle erosion and operational difficulties.

[0048] In this invention, the residual oil resource utilization device uses a precision filtration device instead of the traditional porous media method to separate the residue and oil in the residual oil, avoiding the use of consumables while improving separation accuracy and efficiency. Using a dry residue extraction device, further separation of dry residue and residual oil can be achieved with a small amount of extractant. The separated dry residue is roasted in a precision incineration unit to obtain metallic ash, which is then further separated and recovered by hydrometallurgy. The purified residual oil and extractant obtained after separation are processed in a delayed coking unit to obtain petroleum coke, distillate oil, and dry gas, thus realizing the full-component recovery and utilization of slurry-bed residual oil. The process is highly efficient, low-cost, and suitable for large-scale industrial applications.

[0049] In one specific embodiment of the present invention, an extractant inlet is provided on the homogenizer of the pipeline connecting the residue outlet of the precision filtration device and the inlet of the dry residue extraction device.

[0050] In one specific embodiment of the present invention, a precision filtration device is provided with a precision filtration component, the precision of which is 0.2~0.5μm and the surface roughness is less than 0.2μm.

[0051] In one specific embodiment of the present invention, the delayed coking unit includes a coking furnace and a coking tower connected in series, and the raw material inlet of the delayed coking unit is located in the convection section of the coking furnace.

[0052] In one specific embodiment of the present invention, an activated carbon inlet is provided on the pipeline connecting the purified liquid outlet of the precision filtration device and the raw material inlet of the delayed coking unit.

[0053] In one specific embodiment of the present invention, the precision incineration unit includes a multi-chamber incineration device, which is arranged sequentially along the direction of gravity as a drying and preheating zone, an organic matter roasting zone, a metal oxidation zone, and a cooling and burnout zone.

[0054] In one specific embodiment of the present invention, the number of furnace layers in the multi-chamber incineration device is 8 to 11.

[0055] In one specific embodiment of the present invention, layers 1 to 2 of the multi-chamber combustion device are drying and preheating zones, layers 3 to (8-9) are organic matter roasting and metal oxidation zones, and layers (8-9) to (10-11) are cooling and burnout zones.

[0056] In one specific embodiment of the present invention, the gas outlet of the delayed coking unit is connected to the 2nd to 5th layer air inlets of the multi-chamber combustion device.

[0057] In one specific embodiment of the present invention, a solid powder inlet is provided at the top of the multi-chamber incinerator, through which dry slag enters. Each furnace sidewall of the multi-chamber incinerator is provided with an air inlet. After the air enters the multi-chamber incinerator, it mixes with the dry slag in a counter-current and cross-current manner, resulting in an oxidation reaction.

[0058] In one specific embodiment of the present invention, the hydrometallurgical unit includes an alkaline leaching process, a vanadium precipitation process, a molybdenum precipitation process, an acid leaching process, a nickel precipitation process, and a resin adsorption process.

[0059] In one specific embodiment of the present invention, the alkaline leaching reactor in the alkaline leaching process is provided with a metal ash inlet, a first alkaline solution inlet, an alkaline leaching residue outlet, and an alkaline leaching liquid outlet; the acid leaching reactor in the acid leaching process is provided with a first acid solution inlet, a solid inlet, an acid leaching residue outlet, and an acid leaching liquid outlet; the alkaline leaching residue outlet in the alkaline leaching process is connected to the slurry inlet in the acid leaching process; the acid leaching liquid outlet in the acid leaching process is connected to the liquid inlet in the resin adsorption process; the nickel-containing adsorption residue outlet in the resin adsorption process is connected to the liquid inlet in the nickel precipitation process; the nickel precipitation reactor in the nickel precipitation process is provided with a second alkaline solution inlet and a nickel compound outlet; the alkaline leaching liquid outlet in the alkaline leaching process is connected to the liquid inlet in the vanadium precipitation process; the vanadium precipitation reactor in the vanadium precipitation process is provided with an ammonium salt inlet and a vanadium compound outlet; the precipitate tail liquid outlet in the vanadium precipitation process is connected to the liquid inlet in the molybdenum precipitation process; and the molybdenum precipitation reactor in the molybdenum precipitation process is provided with a second acid solution inlet and a molybdenum compound outlet.

[0060] In one specific embodiment of the present invention, the nickel plating process and the molybdenum plating process are each provided with a wastewater outlet, the wastewater outlet is connected to the liquid inlet of the second resin adsorption process, and the adsorption residue outlet of the second resin adsorption process is connected to the liquid inlet of the wastewater purification zone.

[0061] In one specific embodiment of the present invention, the eluent outlet of the resin adsorption process and the second resin adsorption process are connected to the liquid inlet of the vanadium precipitation process.

[0062] This invention provides a system method for the resource utilization of residual oil, which uses any of the residual oil resource utilization devices provided in the specific embodiments section. The system method includes the following steps: The residual oil enters the precision filtration device for precision filtration to obtain filter residue and desolidified purified oil. The filter residue and extractant are fed into a dry residue extraction device for deoiling treatment to obtain extract and deoiled dry residue. The deoiled dry residue is fed into a precision incineration unit for roasting to obtain metallic ash, and the metallic ash is fed into a hydrometallurgical unit for separation to obtain metallic nickel compounds, metallic vanadium compounds and metallic molybdenum compounds. The desolidified purified oil and extract enter the delayed coking unit for cracking and condensation to obtain petroleum coke, distillate oil and dry gas.

[0063] In one specific embodiment of the present invention, the temperature of the precision filtration is 280~310℃, such as 280℃, 285℃, 290℃, 295℃, 300℃, or 310℃, but is not limited to the listed values; other unlisted values ​​within this range also apply. If the temperature is too low, the viscosity of the residual oil is high, resulting in a large filtration resistance, which not only reduces the filtration flux but also causes clogging of the filter media pores, shortening the equipment's operating cycle; if the temperature is too high, it will exacerbate coking of the residual oil.

[0064] In one specific embodiment of the present invention, the differential pressure of the precision filter is 0.15~1.0 MPa, such as 0.15 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, or 1.0 MPa, but is not limited to the listed values; other unlisted values ​​within this range are also applicable. Setting the differential pressure too high will result in a thick filter cake, leading to poor backwashing performance; setting the differential pressure too low will shorten the filtration cycle, resulting in a reduced filtration yield.

[0065] In one specific embodiment of the present invention, the flux of the precision filter is 0.1~0.6 m. 3 / m 2 ·h, such as 0.1m 3 / m 2 h, 0.2 m 3 / m 2 ·h、0.3 m 3 / m 2 h, 0.4 m 3 / m 2 ·h、0.5 m 3 / m 2 ·h or 0.6 m 3 / m 2 The values ​​listed include, but are not limited to, the values ​​not listed within this range; other unlisted values ​​within this range also apply. Too high a filtration flux not only results in high filtration resistance but also easily leads to filter media clogging; too low a filtration flux results in high costs and low economic efficiency.

[0066] In one specific embodiment of the present invention, the volume ratio of the extractant to the filter residue is 0.6 to 1.3:1, such as 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1 or 1.3:1, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0067] In one specific embodiment of the present invention, the oil removal temperature is 150~200℃, such as 150℃, 160℃, 170℃, 180℃, 190℃, or 200℃, but is not limited to the listed values; other unlisted values ​​within this range also apply. Below 150℃, the system's fluidity is low, making normal extraction impossible; above 200℃, it will cause difficulties in handling the dried residue.

[0068] In one specific embodiment of the present invention, the filter residue pressure drop of the deoiling treatment is 0.15~1.0 MPa, such as 0.15 MPa, 0.2 MPa, 0.25 MPa, 0.3 MPa, 0.35 MPa, 0.4 MPa, 0.45 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa or 1.0 MPa, etc., but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0069] In one specific embodiment of the present invention, the extractant is a distillate rich in polyaromatics, preferably an oil slurry that can be used as a feedstock for delayed coking, thus avoiding extractant recovery and reducing operating costs. For example, the extractant can be oil slurry, recycled oil, or reformed C9. + wait.

[0070] In one specific embodiment of the present invention, the solid content of the dry slag obtained by the precision desolidification unit is 70-80 wt%. Among them, the content of metals such as molybdenum, vanadium, and nickel is 5-8 wt%, and the remaining solids are organic carbon; the metals in the dry slag exist in the form of sulfides and elements, wherein Mo metal exists in the form of MoS2, and V and Ni exist in the form of elemental metals and sulfides.

[0071] In one specific embodiment of the present invention, the metal content in the obtained desolidification and purification residue oil is less than 150 ppm, mainly existing in the form of organometallic compounds of vanadium and nickel. Tetrahydrofuran insolubles are less than 6 wt%, and C5 asphaltene is 38-40 wt%.

[0072] In one specific embodiment of the present invention, the oil yield of the precision deconsolidation unit is greater than 99%. The amount of extractant added is 5-10 wt% of the residual oil feedstock.

[0073] In one specific embodiment of the present invention, the precision incineration device can completely remove carbon and organic matter from the dry slag, while simultaneously converting metal sulfide or elemental metals and alloys into metal oxides.

[0074] In one specific embodiment of the present invention, the temperature of the drying and preheating zone of the precision incineration unit is 430~480℃, such as 430℃, 440℃, 450℃, 460℃, 470℃, or 480℃, but is not limited to the listed values; other unlisted values ​​within this range are also applicable. The drying and preheating zone preheats the dry residue and ensures that low-boiling-point substances in the material evaporate completely.

[0075] In one specific embodiment of the present invention, the temperature of the organic matter roasting and metal oxidation zone of the precision incineration unit is 480~610℃, such as 480℃, 490℃, 500℃, 510℃, 520℃, 530℃, 540℃, 550℃, 560℃, 570℃, 580℃, 590℃, 600℃, or 610℃, etc., but is not limited to the listed values; other unlisted values ​​within this range are also applicable. Preferably, the temperature distribution of the organic matter roasting and metal oxidation zone is as follows: Figure 3 As shown.

[0076] In one specific embodiment of the present invention, the outlet temperature of the organic matter roasting and metal oxidation zone of the precision incineration unit is less than 550°C, such as 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, or 540°C, but is not limited to the listed values; other unlisted values ​​within this range are also applicable. An outlet temperature of less than 550°C for the organic matter roasting and metal oxidation zone can prevent the sublimation of molybdenum.

[0077] In one specific embodiment of the present invention, the outlet temperature of the cooling burnout zone of the precision combustion unit is not higher than 300°C, such as 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, or 290°C, but is not limited to the listed values; other unlisted values ​​within this range also apply. The cooling burnout zone allows for further combustion of the remaining trace organic matter in the material, while low-valence metals are further oxidized to high-valence metal oxides. The high-temperature material is preheated by cold air, thereby achieving the purpose of cooling the material. Limiting the temperature of the cooling burnout zone to no higher than 300°C can further prevent the sublimation of molybdenum.

[0078] In one specific embodiment of the present invention, the temperature difference between each layer in the precision incineration unit is not higher than 30°C, such as 10°C, 12°C, 15°C, 18°C, 20°C, 22°C, 25°C, 28°C or 30°C, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0079] In one specific embodiment of the present invention, the metal ash obtained by the precision incineration unit has a carbon content of less than 0.5%, a metal oxide content of more than 97%, and an alloy content of less than 3%.

[0080] In one specific embodiment of the present invention, the composition ratio of the final metal ash obtained by the precision incineration unit will vary depending on the fluctuation of raw materials and the type of catalyst in different devices. As a representative example, the metal composition of the metal ash is: MoO3: 30~35 wt%, V2O5: 40~45 wt%, NiO: 9~12 wt%, with the balance being iron oxide, aluminum oxide, etc.

[0081] In one specific embodiment of the present invention, the separation process in hydrometallurgy includes the following steps: The metal ash and alkaline solution are subjected to alkaline leaching process to obtain alkaline leaching residue and alkaline leaching solution. The alkaline leaching residue and acid solution are then subjected to acid leaching in the acid leaching process to obtain acid leaching residue and acid leaching solution. The acid leaching solution is then subjected to a resin adsorption process for impurity removal to obtain a nickel-containing adsorption residue. The nickel-containing adsorption residue is then subjected to a nickel precipitation process to obtain a nickel metal compound. The alkaline leaching solution and ammonium salt are introduced into the vanadium precipitation process for vanadium precipitation treatment to obtain vanadium metal compounds and precipitate tail liquid. The precipitate tail liquid is mixed with acid and then fed into a molybdenum precipitation process to obtain a molybdenum metal compound.

[0082] In this invention, the purpose of hydrometallurgy is to perform wet separation of the metal ash produced by the precision incineration unit to obtain metal salts that can be directly used as catalyst raw materials. Because the metal ash contains high levels of molybdenum and vanadium, and molybdenum, nickel, and vanadium exist in oxide form, the acidic oxide properties of Mo and V are utilized to react with alkali to generate soluble sodium salts that enter the leaching solution; Ni remains in the leaching residue in oxide / hydroxide form. Then, the Ni in the alkali leaching residue is separated by acid leaching. Resin adsorption is employed to improve the purity and yield of the separated metals.

[0083] In one specific embodiment of the present invention, the acid leaching residue can be reused as a cement raw material.

[0084] In one specific embodiment of the present invention, the conditions for alkaline leaching treatment include: an alkali concentration of 1~3 mol / L, a liquid-to-solid ratio of 6~10:1 (L / g), a temperature of 90-120℃, a pressure of 0~0.3MPa (g), a reaction time of 1.2~2h, and an alkaline leaching endpoint pH controlled at 12~13.

[0085] In one specific embodiment of the present invention, the solute in the alkaline solution includes sodium hydroxide and / or sodium carbonate, preferably sodium carbonate.

[0086] In one specific embodiment of the present invention, the acid leaching conditions include: acid concentration of 1~2 mol / L, liquid-to-solid ratio of 6~8:1 (L / g), temperature of 60-80℃, reaction time of 2~4h, pH of the acid leaching endpoint controlled within the range of 3~4, and nickel leaching rate greater than 95%.

[0087] In one specific embodiment of the present invention, the acid solution includes sulfuric acid and / or hydrochloric acid, preferably sulfuric acid.

[0088] In one specific embodiment of the present invention, the conditions for impurity removal in the resin adsorption process are a pH of 7.5-9.5 and a space velocity of 5-10 h⁻¹. -1 .

[0089] In one specific embodiment of the present invention, the adsorption and desorption principle of the resin adsorption process is as follows: a weak base anion exchange resin is used.

[0090] Molybdenum adsorption: Positively charged resin adsorbs negatively charged molybdate ions. R-NH(CH3)2 + +HMoO4 - →R-NH(CH3)2 + ·HMoO4 - Molybdenum desorption: Molybdate ions detach from the resin and enter the solution to form ammonium molybdate / sodium molybdate. R-NH(CH3)2 + ·MoO4 2- +NH3·H2O→RN(CH3)2+(NH4)2MoO4 Vanadium adsorption: Positively charged resin adsorbs negatively charged polyvanadate ions. R-NH(CH3)2 + +H2V 10 O 28 4- →[R-NH(CH3)2 + ]4·H2V 10 O 28 4- Vanadium desorption: The resin is deprotonated and its positive charge disappears, and vanadium is converted into sodium orthovanadate. [R-NH(CH3)2 + ]4·H2V 10 O 28 4- +12 NaOH → RN(CH3)2+10Na3VO4+8H2O The mass concentration of ammonia in the molybdenum desorption solution can be 5-10%, and the mass concentration of sodium chloride can be 5-10%. The mass concentration of sodium hydroxide in the vanadium desorption solution can be 10-15%.

[0091] In one specific embodiment of the present invention, the resin regeneration principle of the resin adsorption process is hydrochloric acid rinsing, and the mass concentration of hydrochloric acid can be 5~10%.

[0092] In one specific embodiment of the present invention, the resin adsorption process can concentrate a 50 ppm dilute solution to 20,000 ppm (concentration factor > 400 times), with a vanadium recovery rate ≥ 97% and a molybdenum recovery rate ≥ 95%.

[0093] In one specific embodiment of the present invention, the adsorption resin used in the resin adsorption process can be a weak base anion exchange resin of different grades, such as D301, D314, RCX-5143, etc.

[0094] In one specific embodiment of the present invention, the conditions for nickel plating treatment include: using ammonia as the neutralizing alkali, with an NH3 volume fraction of 5-10%, a temperature of 50-60°C, a reaction time of 1-2 hours, and an endpoint pH controlled at 7-8. The purity of the product Ni(OH)2 is greater than 98%.

[0095] In one specific embodiment of the present invention, the conditions for the vanadium precipitation process include: ammonium salt concentration of 10-15% (mass concentration), ammonium-vanadium molar ratio of NH4:V = (1.2-1.5):1, endpoint pH controlled at 1.8-2.5, temperature of 40-50℃, and reaction time of 2-4 hours. The preferred ammonium salt is NH4Cl. The vanadium precipitation rate is greater than 98%, and the purity of the obtained ammonium metavanadate product is greater than 99%.

[0096] In one specific embodiment of the present invention, the conditions for the molybdenum precipitation process include: acid concentration of 1-2 mol / L, final pH value controlled at 2-3, temperature of 40-60℃, and reaction time of 2-4 h.

[0097] In one specific embodiment of the present invention, the acid solution used for molybdenum precipitation can be sulfuric acid.

[0098] In one specific embodiment of the present invention, the molybdenum precipitation rate of the neutralization and precipitation unit is greater than 98%, and the purity of the obtained molybdic acid product is greater than 98.5%.

[0099] In one specific embodiment of the present invention, the final vanadium metal recovery rate of the hydrometallurgical unit is greater than 95%, the molybdenum recovery rate is greater than 95%, and the nickel recovery rate is greater than 92%.

[0100] In one specific embodiment of the present invention, the desolidified purified oil and extract are mixed with activated carbon and then fed into a coking furnace. After being heated in the convection section, the mixture enters the radiation section for pre-cracking reaction. The outlet temperature of the radiation section of the coking furnace is 495~505℃, the pressure is 0.30~0.40MPa, and the residence time is 25s~45s. The outlet temperature of the radiant section of the coking furnace can be 495℃, 496℃, 497℃, 498℃, 499℃, 500℃, 501℃, 502℃, 503℃, 504℃, or 505℃, etc.; the pressure can be 0.30MPa, 0.31 MPa, 0.32 MPa, 0.33 MPa, 0.34 MPa, 0.35 MPa, 0.36 MPa, 0.37 MPa, 0.38 MPa, 0.39 MPa, or 0.40 MPa, etc.; and the residence time can be 25 s, 30 s, 35 s, 40 s, or 45 s, etc., but is not limited to the listed values. Other unlisted values ​​within the above ranges also apply. A pre-cracking reaction temperature below 495℃ will reduce the cracking reaction rate and fail to achieve the purpose of pre-reaction; a temperature above 505℃ will cause the asphaltene to easily condense and coke, clogging the furnace tubes. Residence time shorter than 25 s results in low pre-conversion rate, while residence time longer than 45 s easily leads to coking and furnace tube blockage.

[0101] In one specific embodiment of the present invention, the material is pre-cracking in the radiant section of the coking furnace and then enters the coking tower for coking reaction. The temperature is 490~500℃, the pressure is 0.17~0.19MPa, and the residence time is 2~3h. The temperature can be 490℃, 491℃, 492℃, 493℃, 494℃, 495℃, 496℃, 497℃, 498℃, 499℃, or 500℃, the pressure can be 0.17 MPa, 0.175 MPa, 0.18 MPa, 0.185 MPa, or 0.19 MPa, and the residence time can be 2 h, 2.1 h, 2.2 h, 2.3 h, 2.4 h, 2.5 h, 2.6 h, 2.7 h, 2.8 h, 2.9 h, or 3 h, but is not limited to the listed values; other unlisted values ​​within the above ranges are also applicable. The coking temperature of petroleum coke residue oil is slightly lower than that of conventional coking feedstock. However, if the temperature is below 490℃, the cracking and coking reaction rate will be too low. If the temperature is above 500℃, the reaction rate will be too fast, and the removal of light hydrocarbons from the reaction system will be incomplete, which will reduce the quality of petroleum coke.

[0102] In this invention, a certain proportion of activated carbon is added before the deconsolidated purified oil and extract enter the delayed coking unit to adsorb macromolecular organometallic compounds in the purified residue oil, which can reduce the metal content in petroleum coke and improve the quality of petroleum coke.

[0103] In one specific embodiment of the present invention, the addition ratio of activated carbon is 300~400 ppm, such as 300 ppm, 310 ppm, 320 ppm, 330 ppm, 340 ppm, 350 ppm, 360 ppm, 370 ppm, 380 ppm, 390 ppm or 400 ppm, etc., but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0104] In one specific embodiment of the present invention, the activated carbon has a main particle size of 5-10 μm, and the proportion of particles with a particle size of less than 20 μm is greater than 95 wt%. If the activated carbon particle size is too large, it will not be conducive to the activated carbon being carried out of the system by the dry gas; if the activated carbon particle size is too small, it will increase the cost and have limited effect on improving the quality of petroleum coke.

[0105] In one specific embodiment of the present invention, the activated carbon is hollow activated carbon.

[0106] In one specific embodiment of the present invention, the dry gas generated by the delayed coking unit enters the precision combustion unit for roasting.

[0107] In this invention, the delayed coking unit employs low-temperature, low-pressure coking to extend the residence time. To improve the completion rate of the cracking and coking reaction of the purified residue oil, the reaction needs to be completed in series at low temperatures in both the coking furnace and the coking tower. Furthermore, the pre-reaction conversion rate in the radiant section of the coking furnace needs to be greater than 12%. The pre-reaction in the radiant section of the coking furnace is mainly cracking, while cracking and coking occur simultaneously in the coking tower.

[0108] In one specific embodiment of the present invention, the product distribution ratio (mass) of the delayed coking unit is as follows: petroleum coke, 30%~32%, distillate oil, 65%~68%, and dry gas, 3%~5%.

[0109] In one specific embodiment of the present invention, the petroleum coke has the following characteristics: ash content <0.2wt%, sulfur content <1.2wt%, and volatile matter content 5-7wt%.

[0110] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0111] It should be clarified that any use of the process provided in the embodiments of the present invention or any substitution or change of conventional data falls within the protection and disclosure scope of the present invention.

[0112] Example 1 This embodiment provides a device for the resource utilization of residual oil, the structure of which is as follows: Figure 1 As shown, the device includes: Precision desolidification unit, delayed coking unit, precision incineration unit, and hydrometallurgical unit; The precision desolidification unit includes a precision filtration device 1 and a dry residue extraction device 2. The precision filtration device 1 is equipped with a precision filtration component 1.1. The residue outlet of the precision filtration device 1 is connected to the inlet of the dry residue extraction device 2 through a homogenizer 6. The homogenizer 6 is equipped with an extractant inlet. The purified liquid outlet of the precision filtration device 1 is connected to the raw material inlet of the delayed coking unit 4. The dry residue outlet of the dry residue extraction device 2 is connected to the solid powder inlet of the precision incineration device 3. The recovered liquid (extract liquid) outlet of the dry residue extraction device 2 is connected to the raw material inlet of the delayed coking unit 4. The metal ash outlet of the precision incineration device 3 is connected to the material inlet of the hydrometallurgical unit 5. The precision incineration device 3 includes a drying and preheating zone, an organic matter roasting and metal oxidation zone, and a cooling and burnout zone arranged sequentially along the direction of gravity; the precision incineration device 3 is a multi-hearth incinerator with multiple incineration chambers connected in series, and the multi-hearth incinerator has 10 chamber layers; the first and second chambers of the multi-hearth incinerator are drying and preheating zones, the third to eighth chambers are organic matter roasting and metal oxidation zones, and the eighth to tenth chambers are cooling and burnout zones; the gas outlet of the delayed coking unit 4 is connected to the air inlet of the second to fifth chambers of the multi-hearth incinerator; The delayed coking unit 4 includes a coking furnace and a coking tower connected in series. The raw material inlet of the delayed coking unit 4 is located in the convection section of the coking furnace. An activated carbon inlet is provided on the pipeline connecting the purified liquid outlet of the precision filter device 1 and the raw material inlet of the delayed coking unit 4. Hydrometallurgical unit 5 includes an alkaline leaching process, a vanadium precipitation process, a molybdenum precipitation process, an acid leaching process, a nickel precipitation process, and a resin adsorption process. The reactor for the alkaline leaching process is equipped with a metal ash inlet, a first alkaline solution inlet, an alkaline leaching residue outlet, and an alkaline leaching liquid outlet. The reactor for the acid leaching process is equipped with a first acid solution inlet, a solid inlet, an acid leaching residue outlet, and an acid leaching liquid outlet. The alkaline leaching residue outlet of the alkaline leaching process is connected to the liquid inlet of the acid leaching process. The acid leaching liquid outlet of the acid leaching process is connected to the liquid inlet of the resin adsorption process. The nickel-containing adsorption residue outlet of the resin adsorption process is connected to the liquid inlet of the nickel precipitation process. The reactor for the nickel precipitation process is equipped with a second alkaline solution inlet and a nickel-gold inlet. The alkali leaching process has an outlet for the compound; the alkali leaching process's alkali leaching solution outlet is connected to the liquid inlet of the vanadium precipitation process. The vanadium precipitation process's reactor is equipped with an ammonium salt inlet and a vanadium metal compound outlet. The vanadium precipitation process's precipitate tail liquid outlet is connected to the liquid inlet of the molybdenum precipitation process. The molybdenum precipitation process's reactor is equipped with a second acid inlet and a molybdenum-containing product outlet. The nickel precipitation process and the molybdenum precipitation process each have their own independent wastewater outlets. The wastewater outlets are connected to the liquid inlet of the second resin adsorption process. The adsorption residue outlet of the second resin adsorption process is connected to the liquid inlet of the wastewater purification zone. The eluent outlets of the resin adsorption process and the second resin adsorption process are connected to the liquid inlet of the vanadium precipitation process.

[0113] Application Example 1-10 Raw material: Residual oil from the bottom of the fractionation tower in a slurry-bed hydrotreating unit. The physical properties of the residual oil are: solid content 10%, metal weight 8670 ppm, C5 asphaltene 37%, initial boiling point 356℃. The process flow is as follows: The residual oil resource utilization device provided in Example 1 is used. The precision filter component 1.1 in the precision filter device 1 uses a 0.2~0.5μm precision filter medium and oil slurry as the extractant. The precision incineration device 3 uses a 10-layer multi-hearth incinerator. Dry gas carrying carbon particles is mixed with air from layers 2~5, and then fed into the multi-hearth incinerator as fuel. The roasting section uses... Figure 3 Curve temperature control, hydrometallurgical unit adopts Figure 4 process.

[0114] The implementation process parameters and product characteristics of Application Examples 1-10 are shown in Tables 1 and 2.

[0115] Table 1. Data from the precision filtration, delayed coking, and precision incineration units in Application Examples 1-10

[0116] Table 2. Hydrometallurgical unit data for Application Examples 1-10

[0117] Comparative Examples 1-3 The raw materials are the same as those used in Examples 1-10; Process steps (1) Mix the residual oil and diluent and heat to melt them to obtain mixed residual oil; (2) Mix the mixed residue oil and biomass filter media, and then perform vacuum-heat filtration while hot to obtain filter cake and first filtrate; (3) The filter cake is roasted to obtain the sintered product; (4) The sintered product is immersed in the first alkaline solution and then filtered to obtain alkaline leaching solution and filter residue; (5) Add the first acidic solution to the filter residue to dissolve it, then filter it to obtain the second filtrate. Add the second alkaline solution to the second filtrate to precipitate it, then filter it to obtain nickel hydroxide precipitate. After sintering the nickel hydroxide precipitate, nickel oxide product is obtained. (6) Add ammonium salt to the alkaline leaching solution to promote the formation of precipitate between ammonium ions and vanadium ions in the alkaline leaching solution. Then filter to obtain vanadium precipitate and third filtrate. After sintering the vanadium precipitate, V2O5 product is obtained. (7) Add a second acidic solution to the third filtrate to promote the reaction of MoO4. 2- With H + The reaction occurs, producing H2MoO4 precipitate, which is then filtered to obtain molybdenum precipitate. The molybdenum precipitate is then calcined to obtain MoO3 product.

[0118] The first and second alkaline solutions are both sodium hydroxide solutions with a concentration of 0.5~2 mol / L, the first acidic solution is hydrochloric acid with a concentration of 1~2 mol / L, and the second acidic solution is nitric acid with a concentration of 1~2 mol / L.

[0119] The process parameters and metal yields for Comparative Examples 1 to 3 are shown in Table 3.

[0120] Table 3. Process parameters and metal recovery rates for Comparative Examples 1-3

[0121] The metal recovery results of Comparative Examples 1-3 and Application Examples 1-10 show that Comparative Examples 1-3, which use the traditional method of diluting and filtering slurry bed residue oil, followed by simple roasting of the filter cake before metal extraction, have significantly lower vanadium / molybdenum / nickel recovery rates than Application Examples 1-10. Furthermore, the consumption of diluent and filter media is high, making it impossible to achieve full-component resource utilization of the residue oil. Application Examples 1-10, on the other hand, achieve full-component recovery and utilization of slurry bed residue oil, with no solvent (or diluent) or porous material consumption; the extractant is an oil slurry, and the amount used is extremely small, only 0.1 to 0.2 times that of the residue oil, allowing it to enter delayed coking together with the deconsolidated residue oil without separation; the vanadium recovery rate is greater than 95%, the molybdenum recovery rate is greater than 95%, and the nickel recovery rate is greater than 92%.

[0122] Comparative Example 4 In this comparative example, the precision incineration unit is a single-hearth furnace. After air is introduced into the single-hearth furnace, it is directly roasted with the deoiled dry residue at 610°C. All other conditions are the same as in Example 1.

[0123] The metal recovery rates of vanadium / molybdenum / nickel in the dry slag are 83.5% / 85% / 80.5%, respectively.

[0124] Comparative Example 5 In this comparative example, except that no activated carbon was added during delayed coking, all other conditions were the same as in Example 1.

[0125] The petroleum coke has an ash content of 1.8 wt%, a sulfur content of 3.4 wt%, and a volatile matter content of 5.2 wt%.

[0126] The applicant declares that the present invention is illustrated through the above embodiments to describe the detailed products and methods of the present invention, but the present invention is not limited to the detailed products and methods described above, that is, it does not mean that the present invention must rely on the detailed products and methods described above to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions for the products of the present invention, additions of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A device for the resource utilization of residual oil, characterized in that, The residual oil resource utilization device includes: Precision desolidification unit, delayed coking unit, precision incineration unit, and hydrometallurgical unit; The precision desolidification unit includes a precision filtration device and a dry residue extraction device. The residue outlet of the precision filtration device is connected to the raw material inlet of the dry residue extraction device via a homogenizer. The purified liquid outlet of the precision filtration device is connected to the raw material inlet of the delayed coking unit. The dry residue outlet of the dry residue extraction device is connected to the solid inlet of the precision incineration unit. The recovered liquid outlet of the dry residue extraction device is connected to the raw material inlet of the delayed coking unit. The metal ash outlet of the precision incineration unit is connected to the raw material inlet of the hydrometallurgical unit.

2. The residual oil resource utilization device according to claim 1, characterized in that, An extractant inlet is provided on the pipeline connecting the residue outlet of the precision filtration device and the raw material inlet of the dry residue extraction device.

3. The residual oil resource utilization device according to claim 1, characterized in that, The delayed coking unit includes a coking furnace and a coking tower connected in series, and the raw material inlet of the delayed coking unit is located in the convection section of the coking furnace. An activated carbon inlet is provided on the pipeline connecting the purified liquid outlet of the precision filtration device and the raw material inlet of the delayed coking unit.

4. The residual oil resource utilization device according to claim 1, characterized in that, The precision incineration unit includes a multi-chamber incineration device, which includes a drying and preheating zone, an organic matter roasting zone, a metal oxidation zone, and a cooling and burnout zone arranged sequentially along the direction of gravity. The multi-chamber combustion device has 8 to 11 furnace layers; The first and second layers of the multi-chamber combustion device are drying and preheating zones, the third to (8-9) layers are organic matter roasting and metal oxidation zones, and the (8-9) to (10-11) layers are cooling and burnout zones. The gas outlet of the delayed coking unit is connected to the air inlets of the 2nd to 5th layers of the multi-chamber combustion device.

5. The residual oil resource utilization device according to claim 1, characterized in that, The hydrometallurgical unit includes an alkaline leaching process, a vanadium precipitation process, a molybdenum precipitation process, an acid leaching process, a nickel precipitation process, and a resin adsorption process.

6. A system and method for the resource utilization of residual oil, characterized in that, The system method uses the residual oil resource utilization device according to any one of claims 1-5, and the system method includes the following steps: The residual oil enters the precision filtration device for precision filtration to obtain filter residue and desolidified purified oil. The filter residue and extractant are fed into a dry residue extraction device for deoiling treatment to obtain extract and deoiled dry residue. The deoiled dry residue is fed into a precision incineration unit for roasting to obtain metallic ash. The metallic ash is then fed into a hydrometallurgical unit for separation to obtain the target products: nickel metal compounds, vanadium metal compounds, and molybdenum metal compounds. The desolidified purified oil and extract enter the delayed coking unit for cracking and condensation to obtain petroleum coke, distillate oil and dry gas.

7. The system method according to claim 6, characterized in that, The temperature of the precision filter is 280~310℃; The pressure difference of the precision filter is 0.15~1.0 MPa; The flux of the precision filter is 0.1~0.6 m. 3 / m 2 ·h; The volume ratio of the extractant to the filter residue is 0.6~1.3:1; The oil removal process is performed at a temperature of 150~200℃; The filter residue pressure drop after the deoiling treatment is 0.15~1.0 MPa.

8. The system method according to claim 6, characterized in that, The temperature of the drying and preheating zone of the precision incineration unit is 430~480℃; The temperature of the organic matter roasting and metal oxidation zone of the precision incineration unit is 480~610℃; The temperature of the organic matter roasting and metal oxidation zone of the precision incineration unit is controlled according to a specific temperature distribution curve, with a temperature range of 480~610℃, and the outlet temperature of the organic matter roasting and metal oxidation zone is controlled below 550℃. The outlet temperature of the cooling burnout zone of the precision incineration unit shall not exceed 300°C; The temperature difference between each layer in the precision incineration unit does not exceed 30°C.

9. The system method according to claim 6, characterized in that, The separation process includes the following steps: The metal ash and alkaline solution are subjected to alkaline leaching process to obtain alkaline leaching residue and alkaline leaching solution. The alkaline leaching residue and acid solution are then subjected to acid leaching in the acid leaching process to obtain acid leaching residue and acid leaching solution. The acid leaching solution enters the resin adsorption process to remove molybdenum and vanadium, resulting in a nickel-containing adsorption residue. The nickel-containing adsorption residue is then subjected to a nickel precipitation process to obtain the target product: metallic nickel compound. The alkaline leaching solution and ammonium salt are introduced into the vanadium precipitation process for vanadium precipitation treatment to obtain metallic vanadium compounds and precipitate tail liquid. The precipitate tail liquid is mixed with acid and then fed into a molybdenum precipitation process to obtain a metallic molybdenum compound.

10. The system method according to claim 6, characterized in that, The desolidified purified oil and extract are mixed with trace amounts of activated carbon and enter the convection section of the coking furnace in the coking unit. After being preheated in the convection section, they enter the radiation section for cracking treatment. The outlet temperature of the radiation section of the coking furnace is 495~505℃, the pressure is 0.30~0.40MPa, and the residence time is 25s~45s. The desolidified and purified oil enters the coking tower after passing through the radiant section of the coking furnace for coking reaction. The operating conditions of the coking tower are: temperature 490~500℃, pressure 0.17~0.19MPa, and residence time 2~3h. The activated carbon is added at a ratio of 300~400 ppm; The activated carbon has a bulk particle size of 5-10 μm, with particles smaller than 20 μm accounting for more than 95 wt%. The activated carbon is hollow activated carbon; The dry gas generated by the delayed coking unit enters the precision combustion unit to provide roasting heat energy.

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