Slurry bed oil residue utilization system

Abstract

The utility model provides a slurry bed oil residue utilization system, including settlement unit (1), mixing unit (2), separation unit (3), ashing unit (4), solvent recovery unit (5), UV - ozone collaborative oxidation unit (7) and solvent oil storage tank (8). The utility model discloses through solvent recovery unit, UV - ozone collaborative oxidation unit and solvent oil storage tank form solvent circulation loop, significantly improve the utilization rate of solvent, reduce energy consumption, and through ashing unit combines metal recovery system, realize precious metal resource utilization.

Description

Technical Field

[0001] This utility model relates to the field of slurry bed oil residue utilization technology, and specifically to a slurry bed oil residue utilization system. Background Technology

[0002] Oil residue is a major byproduct of slurry bed residue hydrotreating units in petroleum refining, accounting for approximately 10%-12% of crude oil processing. Oil residue has a complex composition, mainly consisting of unconverted heavy hydrocarbons (such as asphaltenes and gums), polycyclic aromatic hydrocarbons (PAHs), sulfides, nitrides, and heavy metals (such as molybdenum, nickel, and vanadium, with contents reaching 2000-5000 ppm), along with impurities of degraded catalyst particles (1-50 μm in diameter).

[0003] Due to the high viscosity (>1000 mPa·s at room temperature), high ash content (5%-20%), and thermal instability of oil residue, its direct utilization faces multiple challenges: (1) Environmental pollution problems: Heavy metals (such as vanadium compounds) and polycyclic aromatic hydrocarbons in oil residue are highly toxic and carcinogenic. Traditional landfill or open-air dumping can easily pollute groundwater through rainwater leaching; when directly burning for power generation, heavy metals (such as nickel and molybdenum) will be emitted in the form of fly ash, causing atmospheric particulate matter pollution, and the combustion efficiency is low (calorific value is only 20-25 MJ / kg), which does not comply with environmental protection regulations; during the asphalt blending process (1) Sulfur and nitrogen impurities in oil residue will reduce the durability of asphalt and exacerbate the risk of chemical corrosion after road paving; (2) Waste of resources and low added value utilization: Light oil components (about 15%-30%) in oil residue are not effectively recovered and are directly discarded, resulting in energy loss; The content of precious metals (such as molybdenum and nickel) in the failed catalyst is as high as 1%-5%, and the existing process has not achieved efficient extraction; When oil residue is used as coking raw material, the coke yield is low (<30%) and the coke quality is poor (high sulfur and high ash content), and it can only be used for low-end metallurgical fuel.

[0004] Domestic and international research shows that the high-value utilization of oil residue needs to meet three core requirements: (1) graded and classified: to achieve efficient separation and directional conversion of light oil, precious metals and asphalt; (2) solvent utilization: to reduce solvent loss and energy consumption; (3) industrial feasibility: the process equipment needs to adapt to the continuous production requirements of refineries and avoid complex pretreatment (such as ultrafine grinding).

[0005] However, existing technologies have not simultaneously solved the aforementioned problems. For example, while traditional solvent extraction processes can partially purify asphaltenes, the recovery rate of precious metals is insufficient, and the solvent recycling rate is low; while pyrolysis technology can produce hydrogen, it cannot simultaneously achieve light oil refining and metal recovery. Therefore, developing a process system that integrates efficient separation, metal recovery, and high-value utilization of components has become a key requirement for the refining industry to achieve green transformation and resource efficiency improvement. Utility Model Content

[0006] The purpose of this invention is to solve the problems of low separation efficiency, difficulty in precious metal recovery, large solvent loss and serious pollution in existing oil residue utilization systems. It provides a slurry bed oil residue utilization system. The slurry bed oil residue utilization system of this invention achieves efficient separation of light oil, efficient recovery of precious metals and high recycling of solvents, while reducing energy consumption, improving the industrial adaptability and environmental protection of the system, and meeting the demand for high-value utilization of all components of oil residue.

[0007] This utility model provides a slurry bed oil residue utilization system, including: A settling unit is used to receive slurry bed oil residue and settling the slurry bed oil residue into light oil and heavy oil; A mixing unit, connected to the settling unit, is used to receive the heavy oil and mix it with solvent oil to form a mixed oil. A separation unit, connected to the mixing unit, is used to receive the mixed oil and separate it into insoluble matter and filtered oil; An ashing unit, connected to the separation unit, is used to receive the insoluble matter and ashing it to generate ash residue; A solvent recovery unit, connected to the separation unit, is used to receive the filtered oil and separate it into solvent oil and asphaltenes; The UV-ozone synergistic oxidation unit is connected to the solvent recovery unit and is used to receive the solvent oil and oxidize and regenerate it to obtain regenerated solvent oil. A solvent oil storage tank is connected to both the mixing unit and the UV-ozone synergistic oxidation unit, and is used to receive the regenerated solvent oil and transport the stored solvent oil to the mixing unit.

[0008] To address the problems of low solvent recovery efficiency, difficulty in precious metal extraction, and inability to achieve closed-loop solvent recycling in existing oil sludge treatment systems, this invention proposes a slurry-bed oil sludge utilization system. In this system, a settling unit separates the slurry-bed oil sludge into light and heavy oils; a mixing unit mixes the solvent oil and heavy oils; a separation unit extracts insoluble matter and filtered oil; an ashing unit decomposes the insoluble matter to recover precious metals; simultaneously, a solvent recovery unit separates the filtered oil into solvent oil and asphaltenes; a UV-ozone synergistic oxidation unit oxidizes and regenerates the solvent oil to obtain regenerated solvent oil; a solvent oil storage tank receives the regenerated solvent oil and mixes it with the original solvent oil in the storage tank to obtain stored solvent oil; and then the stored solvent oil is transported to the mixing unit. This system achieves efficient separation of light oil, efficient recovery of precious metals, and efficient utilization of solvents.

[0009] Optionally, the UV-ozone synergistic oxidation unit includes: The UV-ozone reactor has its inlet connected to the solvent oil outlet of the solvent recovery unit, and its outlet connected to the solvent oil storage tank via a regenerated solvent oil pipeline. A viscosity sensor and a color sensor are installed on the regenerated solvent oil pipeline to detect the viscosity and color parameters of the regenerated solvent oil; An ozone concentration probe is installed inside the UV-ozone reactor to monitor the ozone concentration inside the reactor.

[0010] To address the problem of unstable solvent regeneration quality caused by the inability to monitor the reaction state in traditional oxidation units, this invention monitors the physical properties of the regenerated solvent oil using viscosity and color sensors. Combined with feedback from the ozone concentration probe inside the reactor, it controls the ozone injection amount and UV light intensity to ensure that the regenerated solvent oil meets the performance standards and improves the stability and controllability of the oxidation regeneration process.

[0011] Optionally, the settling unit is selected from one of a natural gravity settling device, a stirred settling device, or a centrifugal settling device.

[0012] The settling unit adopts a replaceable design, which can select natural gravity settling (low viscosity oil sludge), stirred settling (medium and high viscosity oil sludge), or centrifugal settling (high solid content oil sludge) modes according to the viscosity and solid content of the oil sludge, adapting to the oil sludge separation needs of different working conditions, and significantly improving the stratification efficiency of light oil and heavy oil.

[0013] Optionally, the settling unit is provided with a cooling device for controlling the temperature within the settling unit and a flow regulating valve for controlling the outflow of heavy oil.

[0014] To address the issues of oil evaporation and flow rate loss caused by high temperatures, the settling unit incorporates a cooling device (temperature control 100-300℃, preferably 100-200℃) and a flow regulating valve to reduce light oil evaporation losses while ensuring the stability of feed to the downstream mixing unit.

[0015] Optionally, the mixing unit is a pressure reactor equipped with a stirring device.

[0016] To reduce the local concentration difference between solvent oil and heavy oil, the mixing unit uses a pressure reactor (0.5-1.5MPa) with a stirring device to enhance the homogenization of the mixed oil and improve the separation efficiency of the subsequent separation unit for insoluble matter.

[0017] Optionally, the separation unit is selected from one or a combination of belt vacuum filter, disc vacuum filter, plate and frame filter press or centrifuge.

[0018] The separation unit can be configured with combined filtration equipment, such as first removing large insoluble particles using a plate and frame filter press, and then separating micron-sized solid residues using a centrifuge. This process achieves more complete solid-liquid separation, significantly increases the amount of insoluble matter in the filtered oil, and reduces the load on the subsequent solvent recovery unit.

[0019] Optionally, the ashing unit is equipped with a microwave generator and a heating device.

[0020] To address the issues of high energy consumption and low metal recovery rate in traditional ashing processes, the ashing unit employs a microwave generator (2.45 GHz) in conjunction with other heating devices to control the temperature (200-700℃), accelerating the pyrolysis ashing process of insoluble substances, shortening the processing time, and significantly improving the recovery rate of precious metals.

[0021] Optionally, the solvent recovery unit includes: a membrane separation module for separating the filtered oil into a first part of solvent oil and asphaltene mixture, and a distillation column for distilling the asphaltene mixture into a second part of solvent oil and asphaltene components.

[0022] To address the issue of incomplete separation between solvent oil and asphaltenes, the solvent recovery unit utilizes a combination of a membrane separation module (0.1μm pore size) and a distillation column (120-180℃) to achieve efficient two-stage recovery of solvent oil, yielding a first portion of solvent oil and a second portion of solvent oil. Simultaneously, the high-purity asphaltenes obtained can be directly utilized as a resource.

[0023] Optionally, the settling unit is provided with a light oil outlet for conveying the light oil to the slurry bed hydrotreating unit.

[0024] The separated light oil is directed to the slurry bed hydrogenation unit via the light oil outlet, realizing the high-value utilization of light oil and reducing raw material costs.

[0025] Optionally, the system further includes a buffer unit for storing slurry bed oil residue, the buffer unit being connected to the settling unit to transport the slurry bed oil residue to the settling unit.

[0026] To address the clogging issue caused by fluctuations in the feed of slurry bed oil residue, a buffer unit was added to achieve temporary storage and stable supply of oil residue, ensuring continuous system operation and avoiding process interruptions caused by feed fluctuations.

[0027] Compared with the prior art, the present invention has the following beneficial effects: In the slurry bed oil residue utilization system of this invention, the sedimentation unit separates the slurry bed oil residue into light oil and heavy oil, and the mixing unit, separation unit and ashing unit are combined to achieve efficient extraction of precious metal ash residue; at the same time, the mixing unit, separation unit, solvent recovery unit, UV-ozone synergistic oxidation unit and solvent oil storage tank form a solvent circulation, which significantly improves the solvent oil recovery rate. Attached Figure Description

[0028] Figure 1 This is a schematic diagram of the slurry bed oil residue utilization system of this utility model.

[0029] Among them, 1-sedimentation unit; 2-mixing unit; 3-separation unit; 4-ashing unit; 5-solvent recovery unit; 6-buffer unit; 7-UV-ozone synergistic oxidation unit; 8-solvent oil storage tank. Detailed Implementation

[0030] The present invention will be further described below with reference to specific embodiments, but this does not constitute any limitation on the present invention.

[0031] Example like Figure 1 As shown, the slurry bed oil residue utilization system includes a settling unit 1, a mixing unit 2, a separation unit 3, an ashing unit 4, a solvent recovery unit 5, a buffer unit 6, a UV-ozone synergistic oxidation unit 7, and a solvent oil storage tank 8. The functions and connections of each device are as follows: Settling Unit 1: It adopts a centrifugal settling device with a built-in stainless steel centrifugal drum, and the speed is adjustable from 1000 to 3000 rpm; Cooling device: A circulating oil cooling jacket is installed on the outer wall of the settling unit. The flow rate of cooling oil is controlled by a temperature sensor (±1℃ accuracy) and PLC to maintain the settling temperature at 100-200℃. Flow control valve: An electric control valve is installed at the heavy oil outlet to automatically adjust the flow rate of heavy oil according to the liquid level signal inside the centrifuge; Light oil outlet: A light oil outlet pipe is installed at the top and connected to the feed inlet of the slurry bed hydrogenation unit via a gear pump; Mixing Unit 2: A vertical pressure reactor with a volume of 2 m³ 3 The material is 316L stainless steel; Stirring device: Built-in double-layer turbine impeller (speed 100-200 rpm), nitrogen gas is introduced into the bottom to pressurize to 1.2-1.8 MPa; Mixing process: Heavy oil and solvent oil are fed into the reactor and stirred for 30-60 minutes to form a homogeneous mixed oil; Separation Unit 3: Includes a belt vacuum filter and a horizontal screw centrifuge; The belt vacuum filter has a filtration area of ​​10 m². 2 The filter cloth has a pore size of 10 μm and is used to separate insoluble matter with a particle size >10 μm; the horizontal screw centrifuge has a separation factor of 3000g and is used to further separate fine insoluble matter with a particle size of 1-10 μm, with the final filtered oil containing <0.1 wt% impurities. Ashing unit 4: Equipped with a microwave generator and a heating device; Microwave generator: frequency 2450 MHz, power adjustable from 0-5 kW; Heating device: Built-in electric heating rod (temperature range 200-700℃), coaxially arranged with the microwave generator; Ashing process: Insoluble matter is ashed for 30 minutes under the combined action of microwave and thermal radiation; Solvent recovery unit 5 includes a ceramic nanofiltration membrane separation module and a packed distillation column; Ceramic nanofiltration membrane separation module: The ceramic nanofiltration membrane has a pore size of 0.1μm and an operating pressure of 2 MPa. It can recover 70-80% of the solvent oil (first part of the solvent oil) from the filtered oil. Packed distillation column: The remaining asphaltene mixture enters a packed distillation column (15 trays), where the second solvent oil is distilled off at 120-180℃ and a vacuum of -0.08 MPa; the total recovery rate of the first and second solvent oils is ≥95%. Buffer Unit 6: Vertical storage tank (3 m³ volume) 3 The unit is equipped with a level gauge; the buffer unit 6 receives and temporarily stores the slurry bed oil residue, which is then pumped by a screw pump (flow rate 1-3 m³ / h). 3 ( / h) continuously conveyed to settling unit 1; UV-ozone synergistic oxidation unit 7: includes a quartz glass reaction chamber (volume 500 L), a UV lamp assembly (wavelength 254nm, power 100 W × 10 lamps) and an ozone injection system; Ozone is dispersed into the solvent oil through a venturi tube at a concentration of 50-100 ppm; The UV-ozone synergistic oxidation unit 7 is also equipped with an online viscosity sensor (range 0-100 mPa·s), a color sensor (detection range 0-500 Hazen), and an ozone concentration probe. The sensors are installed on the regenerated solvent oil pipeline; the ozone concentration probe is fixed to the inner wall of the reactor. The sensor signal is transmitted to the PLC to dynamically adjust the ozone injection rate and the number of UV lamps turned on. Solvent oil storage tank 8: Volume 5 m³ 3The material is carbon steel lined with fluoropolymer. Solvent oil storage tank 8 contains solvent oil. The inlet of the storage tank is connected to UV-ozone co-oxidation unit 7, which is used to receive regenerated solvent oil and mix the regenerated solvent oil with the original solvent oil in solvent oil storage tank 8 to obtain stored solvent oil. The outlet of the storage tank is connected to the solvent oil inlet of mixing unit 2 through a metering pump (flow accuracy ±1%) to transport the stored solvent oil to mixing unit 2.

[0032] Working principle: (1) Pretreatment and preliminary separation of slurry bed oil residue: The slurry-bed oil residue (containing catalyst particles, asphaltene, unreacted heavy oil, etc.) first enters a stainless steel buffer tank. The level gauge, through a level sensor, regulates the flow rate of the slurry-bed oil residue into settling unit 1 to ensure continuous and stable system operation.

[0033] Settling unit 1 is equipped with a cooling device that circulates cooling medium to control the temperature of the oil residue at 100-300℃ (the specific temperature is dynamically adjusted according to the viscosity of the oil residue) to avoid high-temperature coking and promote stratification.

[0034] Sedimentation unit 1 employs a centrifugal sedimentation device. Under centrifugal force (typically set at 1000-3000 r / min), light oils with significant density differences (density < 0.9 g / cm³) are settled. 3 ) and heavy oil (density > 1.1 g / cm³) 3 Rapid stratification. Light oil is pumped from the top outlet to the slurry bed hydrogenation unit via a gear pump for reuse as feedstock; heavy oil is discharged from the bottom outlet via an electric regulating valve and enters mixing unit 2.

[0035] (2) Solvent mixing and solid-liquid separation of heavy oil: Solvent oil, including regenerated solvent oil, stored in solvent oil storage tank 8, is mixed with heavy oil. In a pressure reactor, mixing is performed using a double-layered stirring paddle (100-200 r / min) while nitrogen is introduced to replace air. Stirring is carried out for 30 minutes at 150°C and 1.5 MPa to ensure the solvent oil fully dissolves the soluble components in the heavy oil, forming a mixed oil. The high temperature and pressure conditions reduce the viscosity of the oil residue, and the polar properties of the solvent oil selectively dissolve some of the heavy components, while undissolved solid catalyst particles and some stubborn asphaltene form suspended particles.

[0036] A two-stage separation process is adopted: First stage (belt vacuum filter): The mixed oil enters the belt vacuum filter, where insoluble particles larger than 10μm are trapped on the surface of the filter cloth (nylon material, 10μm pore size) to form a filter cake. The filter cake mainly consists of undissolved catalyst particles (such as catalysts containing vanadium and nickel) and coke; the filtrate (filtrate oil) contains solvent oil, dissolved asphaltenes, and a small amount of gum.

[0037] Second stage (horizontal screw centrifuge): The filtered oil is further separated into fine insoluble matter with a particle size of 1-10μm under centrifugal force (separation factor 3000g), and the final filtered oil has a impurity content of <0.1 wt%.

[0038] The filter cake enters the ashing unit 4; the filtered oil enters the solvent recovery unit 5.

[0039] (3) Solvent recovery and regeneration: The filtered oil first passes through a ceramic nanofiltration membrane (0.1 μm pore size) at an operating pressure of 2 MPa, utilizing the molecular sieve effect to retain large-molecule asphaltenes, yielding the first fraction of solvent oil. The retained asphaltenes mixture enters a packed distillation column and undergoes vacuum distillation at 180°C (vacuum degree -0.08 MPa) to separate the second fraction of solvent oil and solid asphaltenes. The asphaltenes are then transported via pipeline to the asphaltenes utilization unit. The first and second fractions of solvent oil are combined and then enter the UV-ozone synergistic oxidation unit 7.

[0040] Solvent oil flows into a UV-ozone reactor, where a UV lamp (254nm wavelength) excites ozone (50ppm O3 concentration) to generate highly reactive hydroxyl radicals (·OH), which degrade trace organic matter (such as colloids and polycyclic aromatic hydrocarbons) remaining in the solvent. The reaction takes 60 minutes, during which the color decreases from 300 PCU to 20 PCU, and the viscosity stabilizes at its initial value (e.g., below 5 cP). A viscosity sensor monitors solvent flowability, a color sensor detects the degree of oxidation, and an ozone concentration probe adjusts the ozone injection rate to ensure that the regenerated solvent oil performs comparably to the original solvent oil.

[0041] The regenerated solvent oil enters the solvent oil storage tank 8 and mixes with the original solvent oil in the solvent oil storage tank 8 to obtain the stored solvent oil, which is then supplied to the mixing unit 2 as needed by the metering pump to form a cycle.

[0042] (4) Ashing of insoluble substances and metal recovery: The filter cake enters a microwave ashing furnace (frequency 2450 MHz, power 0-5 kW). Microwaves penetrate the material, selectively heating polar substances (such as metal oxides) to rapidly remove volatiles and break up particle agglomerations, a process that takes 30 minutes. The pretreated material is then transferred to an electric heating device (temperature control accuracy ±10℃) and calcined at 600℃ for 2 hours to completely remove residual organic matter, generating ash rich in precious metals such as vanadium and nickel. The ash is transported through a closed pipeline to a metal recovery system, where vanadium and nickel are extracted through processes such as acid leaching and extraction, achieving resource utilization.

[0043] As can be clearly seen from the above description of the embodiments, this utility model forms a solvent circulation loop through a solvent recovery unit, a UV-ozone synergistic oxidation unit, and a solvent oil storage tank, significantly improving solvent utilization and reducing energy consumption; the ashing unit, combined with a metal recovery system, enables the resource utilization of precious metals; and the fully automated control (such as level controllers and metering pumps) ensures stable system operation. This system combines high efficiency, environmental friendliness, and economy, and is suitable for the comprehensive treatment of slurry bed oil residue in the oil refining industry.

[0044] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A slurry-bed oil residue utilization system, characterized in that, include: Settling unit (1) is used to receive slurry bed oil residue and settle the slurry bed oil residue into light oil and heavy oil; A mixing unit (2) is connected to the settling unit (1) and is used to receive the heavy oil and mix it with solvent oil to form a mixed oil. A separation unit (3) is connected to the mixing unit (2) for receiving the mixed oil and separating it into insoluble matter and filtered oil; Ashing unit (4), which is connected to the separation unit (3), is used to receive the insoluble matter and ash it to generate ash residue; Solvent recovery unit (5), which is connected to the separation unit (3), is used to receive the filtered oil and separate it into solvent oil and asphaltenes; The UV-ozone synergistic oxidation unit (7) is connected to the solvent recovery unit (5) and is used to receive the solvent oil and oxidize and regenerate it to obtain regenerated solvent oil. Solvent oil storage tank (8), which is connected to the mixing unit (2) and the UV-ozone synergistic oxidation unit (7) respectively, is used to receive the regenerated solvent oil and transport the stored solvent oil to the mixing unit (2).

2. The system according to claim 1, characterized in that, The UV-ozone synergistic oxidation unit (7) includes: The UV-ozone reactor has its inlet connected to the solvent oil outlet of the solvent recovery unit (5), and its outlet connected to the solvent oil storage tank (8) via a regenerated solvent oil pipeline. A viscosity sensor and a color sensor are installed on the regenerated solvent oil pipeline to detect the viscosity and color parameters of the regenerated solvent oil. An ozone concentration probe is installed inside the UV-ozone reactor to monitor the ozone concentration inside the reactor.

3. The system according to claim 1, characterized in that, The settling unit (1) is selected from one of the following: natural gravity settling device, stirred settling device or centrifugal settling device.

4. The system according to claim 1, characterized in that, The settling unit (1) is equipped with a cooling device for controlling the temperature inside the settling unit (1) and a flow regulating valve for controlling the outflow of heavy oil.

5. The system according to any one of claims 1-4, characterized in that, The mixing unit (2) is a pressure reactor equipped with a stirring device.

6. The system according to any one of claims 1-4, characterized in that, The separation unit (3) is selected from one or a combination of belt vacuum filter, disc vacuum filter, plate and frame filter press or centrifuge.

7. The system according to any one of claims 1-4, characterized in that, The ashing unit (4) is equipped with a microwave generator and a heating device.

8. The system according to any one of claims 1-4, characterized in that, The solvent recovery unit (5) includes: a membrane separation module for dividing the filtered oil into a first part of solvent oil and asphalt mixture, and a distillation tower for distilling the asphalt mixture into a second part of solvent oil and asphalt components.

9. The system according to any one of claims 1-4, characterized in that, The settling unit (1) is provided with a light oil outlet for conveying the light oil to the slurry bed hydrogenation unit.

10. The system according to any one of claims 1-4, characterized in that, The system also includes a buffer unit (6) for storing slurry bed oil residue, the buffer unit (6) being connected to the settling unit (1) to transport the slurry bed oil residue to the settling unit (1).

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