A method for comprehensively utilizing high-chlorine and high-metal waste mineral oil and tire pyrolysis oil to obtain a regenerated oil product

Abstract

The application discloses a method for comprehensively utilizing high-chlorine and high-metal waste mineral oil and tire pyrolysis oil to obtain regenerated oil products, and belongs to the technical field of post-treatment of waste mineral oil and tire pyrolysis oil. The method comprises the following steps: (1) mixing the high-chlorine and high-metal waste mineral oil with circulating oil and feeding the mixture into a reactor A; (2) mixing effluent of the reactor A with tire pyrolysis oil and feeding the mixture into a reactor B; (3) separating effluent of the reactor B to obtain naphtha, oil component A and a residue; (4) feeding the oil component A into a reactor C to perform hydro-upgrading; and (5) separating effluent of the reactor C to obtain a second oil phase, feeding the second oil phase into a stripping stabilizer column and an atmospheric distillation column, and obtaining naphtha, light fuel oil, middle fuel oil and heavy fuel oil. The method can solve the problem that chlorine and metal elements are difficult to be simultaneously and efficiently removed in the regeneration and utilization of the high-chlorine and high-metal waste mineral oil and the tire pyrolysis oil, and improves the quality and yield of the regenerated oil products.

Description

Technical Field

[0001] This application relates to a method for obtaining recycled oil products by comprehensively utilizing high-chlorine and high-metal waste mineral oil and tire pyrolysis oil, belonging to the field of waste mineral oil and tire pyrolysis oil post-processing technology. Background Technology

[0002] Waste mineral oil mainly comes from sludge and oil residue generated during petroleum extraction and refining, sediments produced during mineral oil storage, and various waste lubricating oils. Hydrogenation upgrading of waste mineral oil is an excellent method. Waste tires are a common type of solid waste in daily life. Therefore, exploring a method for the high-value utilization of waste tires is of great significance. Pyrolysis of waste tires to obtain tire pyrolysis oil, followed by hydrogenation upgrading of the tire pyrolysis oil to obtain fuel oil, is a very effective means of resource utilization of waste tires.

[0003] In summary, both waste mineral oil and tire pyrolysis oil can be utilized through hydrotreating. Therefore, simultaneously hydrotreating both raw materials can reduce equipment investment and operating costs, improving overall economic efficiency. However, several technical challenges exist. First, both waste mineral oil and tire pyrolysis oil contain very high levels of chlorine and other metallic impurities. During hydrotreating, the high chlorine content reacts with hydrogen to produce large amounts of HCl gas. In the presence of water, HCl forms hydrochloric acid, causing corrosion of mechanical equipment and pipelines. This not only shortens equipment lifespan but also reduces pressure resistance, potentially leading to explosions. Furthermore, the high levels of metallic impurities can poison the hydrotreating catalyst and cause coking of the oil, clogging the reaction unit and threatening its safe operation. Second, the physical properties of waste mineral oil and tire pyrolysis oil differ, making simultaneous hydrotreating of both raw materials quite difficult.

[0004] Chinese patent application number 202311180648.7 discloses a pretreatment method for removing metals from waste mineral oil. The method involves extracting the waste mineral oil by preparing a salt solution of ammonium sulfate, ammonium bicarbonate, ammonium carbamate, ammonium carbonate, or ammonium phosphate, thereby achieving the precipitation of metals and removing them from the waste mineral oil. Although this treatment process can reduce the metal content in waste mineral oil, this method can only remove metal elements from waste mineral oil and has no effect on removing toxic impurities such as chlorine and sulfur. Furthermore, the operation process is relatively complex.

[0005] International patent application No. WOCN22130151 discloses a method and system for the continuous production of base oil from chlorosilicone-containing waste mineral oil. The waste mineral oil is fed into a thermal settling device for thermal settling. The settled waste mineral oil then enters a flash evaporation device, where the resulting light and heavy component oils undergo dechlorination reactions. After dechlorination, the heavy component oil is demetallized and distilled under reduced pressure before entering an adsorption desiliconization tank for adsorption desiliconization. The desiliconized oil is then hydrogenated and distilled to obtain solvent oil, high-quality base oil, and industrial white oil. This method can effectively solve problems such as coking, corrosion, blockage, and hydrogenation catalyst poisoning in the regeneration process of chlorosilicone-containing waste mineral oil. However, this method can only process a single type of waste mineral oil, and the dechlorination and demetallization steps are performed separately, making the operation relatively complex.

[0006] Chinese patent application number 202180088607.8 discloses a method for producing aviation fuel using waste polymer materials. The method involves blending waste tire pyrolysis oil middle fraction with kerosene / gas oil fraction obtained from crude oil refining, hydrogenating the feed mixture under hydrodesulfurization conditions, recovering liquid products through gas-liquid separation, and distilling the total liquid products into aviation fuel fractions and heavy fractions. This method utilizes waste polymer materials, maintains the quality of the produced oil, and has a low waste yield. However, this method requires the addition of crude oil refined from crude oil, and the proportion of tire pyrolysis oil added is too low (below 10 wt%).

[0007] Chinese patent application number 202011010111.2 reports a method for catalytic conversion of oil and gas from waste tire pyrolysis. The method involves directly feeding the oil and gas obtained from waste tire pyrolysis into a fixed-bed reactor filled with NaY-type molecular sieves modified with rare earth elements La and Ce, catalytically converting it into light oil and gas. After further condensation and cooling, the gas is separated into gasoline, diesel, and a small amount of tar. This method effectively improves the efficiency of the catalytic pyrolysis reaction, reduces carbon buildup, and simplifies the catalyst preparation process. However, impurities in the pyrolysis oil and gas can easily poison the catalyst.

[0008] Chinese patent application number 202210144341.0 discloses a method and system for producing jet fuel, white oil, and lubricating oil base oil by hydrogenation of waste oil. This method can effectively and economically produce high-quality, high-flash-point, high-density, low-energy-consumption jet fuel without using harmful impurities and water, and effectively removes solid impurities, chlorine, and other harmful impurities and water from waste oil. However, the various oils processed by this method need to be pre-mixed, increasing the number of steps. Furthermore, the concentrations of chlorine and metallic impurities in the raw oil are relatively low.

[0009] Based on the above analysis, the reuse of high-chlorine, high-metal waste mineral oil and tire pyrolysis oil as fuel through regeneration can reduce the demand for traditional energy sources and achieve resource conservation and sustainable utilization. Simultaneously, regeneration technology can efficiently remove and collect chlorine and toxic heavy metals from the raw materials, preventing environmental damage, which is of great significance. Currently, the technology for processing high-chlorine, high-metal waste mineral oil and tire pyrolysis oil into recycled oil products is not yet perfect, the processing steps are complex, and the processing cost is high. Especially when these two types of waste oil are processed together, the differences in the physical properties of the raw materials and the mutual interference of various impurity elements make comprehensive processing even more difficult. Therefore, there is an urgent need for a method for the efficient treatment and reuse of these two types of waste oil. Summary of the Invention

[0010] To address the aforementioned issues, a method for comprehensively utilizing high-chloride, high-metal waste mineral oil and tire pyrolysis oil to obtain recycled oil products is provided. This method addresses the differences in the physicochemical properties of these two types of oils by first performing a graded pretreatment, followed by hydrogenation upgrading and hydrocracking to produce recycled oil products. This technology is simple to operate, efficiently removes chlorine and metallic impurities from the raw materials, and produces high-quality recycled oil products, offering significant environmental and economic benefits.

[0011] According to one aspect of this application, a method for obtaining recycled oil products by comprehensively utilizing high-chlorine and high-metal waste mineral oil and tire pyrolysis oil is provided, comprising the following steps:

[0012] (1) Mix high-chlorine and high-metal waste mineral oil with circulating oil, heat it to 380-420℃ in a heating furnace, mix in 200-2000ppm liquid catalyst, and then enter a suspended bed reactor A without solid catalyst packing for reaction.

[0013] (2) The effluent from the suspended bed reactor A is mixed with tire pyrolysis oil and then introduced into the suspended bed reactor B without solid catalyst at a temperature of 320-360℃ for reaction.

[0014] (3) The liquid effluent from the suspended bed reactor B is divided into two parts. One part is used as circulating oil, and the other part is depressurized and separated to obtain gas A and liquid A. The gas effluent from reactor B is injected with water to form a first mixture. The first mixture is separated to obtain gas B and liquid B. The liquid B is depressurized and separated to obtain dissolved gas, a first oil phase and a first water phase. The liquid A and the first oil phase are mixed and passed through a vacuum distillation column to obtain naphtha, oil fraction A and residue.

[0015] (4) The oil fraction A is sent to reactor C containing a solid catalyst for hydrogenation and upgrading;

[0016] (5) Water is injected into the effluent of reactor C to obtain a second mixture. The second mixture is separated to obtain a second oil phase, gas C and a second water phase. The second oil phase enters the stripping stabilizer and the atmospheric distillation column.

[0017] (6) Naphtha, light fuel oil and medium fuel oil are obtained from the atmospheric distillation column. The bottom oil of the atmospheric distillation column is used as heavy fuel oil or added to the hydrocracking reactor D packed with solid catalyst to carry out hydrocracking reaction to obtain hydrocracking material.

[0018] (7) The hydrocracking material is recycled to be mixed with oil A, and then enters reactor C for hydrotreating and upgrading.

[0019] This application adopts a three-stage hydrogenation process. In the first two steps (2) and (3), a low-temperature and low-pressure homogeneous hydrogenation method is used, which combines liquid catalyst with suspended bed reactor A and suspended bed reactor B, to perform low-cost hydrogenation and upgrading pretreatment on high-chlorine and high-metal waste mineral oil. The middle stage is a deep fixed-bed hydrorefining process. In order to improve the yield of light oil products, a fixed-bed hydrocracking reactor is added in the later stage to crack the heavy components.

[0020] Since high-chlorine, high-metal waste mineral oil contains more chlorine and metals than tire pyrolysis oil, in step (1), the high-chlorine, high-metal waste mineral oil reacts first, followed by a second reaction with the tire pyrolysis oil. This setup improves the processing efficiency of both raw materials and enhances the system's adaptability to the raw materials. The recycled oil obtained in step (3) is returned to the feed end and mixed with the high-chlorine, high-metal waste mineral oil, which heats the oil, increasing the temperature of the cold feed and shortening the subsequent heating time. This mitigates the problem of coking caused by prolonged residence time in the heater. Furthermore, it dilutes easily coking substances in the raw material, reducing their heat sensitivity and improving the heatability of the feed.

[0021] The above method uses a liquid catalyst for catalytic hydrogenation pretreatment of the raw materials. The liquid catalyst can be uniformly dispersed in the raw oil to efficiently remove chlorine and other metal elements from waste mineral oil and tire pyrolysis oil.

[0022] Optionally, the liquid catalyst comprises a catalyst substrate and an auxiliary agent, wherein the catalyst substrate is prepared by:

[0023] S1: A sulfur-containing molybdenum source ammonia solution is obtained by mixing a molybdenum source ammonia solution with potassium sulfide and reacting at 30-150℃ for 0.5-3h. The molar ratio of sulfur content of potassium sulfide to molybdenum is (2-6):1. Then, the sulfur-containing molybdenum source solution and nickel source ammonia solution are mixed and reacted at 30-150℃ for 0.5-3h. After filtration, washing with water and drying, a sulfur-containing nickel-molybdenum bimetallic salt complex is obtained. The volume ratio of nickel source ammonia solution to molybdenum source ammonia solution is 1:(1-2). The molar ratio of ammonia to nickel source in the nickel source ammonia solution is (1-10):1. The volume weight ratio of ammonia to molybdenum source in the molybdenum source ammonia solution is (1-2):1. The unit is ml / g.

[0024] S2: The sulfur-containing nickel-molybdenum bimetallic salt complex is added to oleic acid and reacted at 50-200℃ for 0.5-5h to obtain intermediate product A. The molar ratio of oleic acid to molybdenum is (2-6):1. Then, intermediate product A is dissolved in aniline and straight-run gasoline in sequence and stirred evenly to obtain the catalyst body.

[0025] The weight of the auxiliary agent is 80-200% of the weight of the catalyst body, and the auxiliary agent is selected from chelating agents, organic acids, carboxylates, and 1,2,4-triazole in a weight ratio of 1:(0.1-0.2):(0.1-0.2):(0.1-0.2).

[0026] The volume-to-weight ratio of ammonia to molybdenum source in the above-mentioned ammonia-source aqueous solution refers to the ratio of the volume of ammonia to the weight of molybdenum source.

[0027] Optionally, the molybdenum source is selected from at least one of molybdenum trioxide and ammonium metamolybdate, and the nickel source is selected from at least one of nickel nitrate, nickel acetate, and nickel formate.

[0028] Optionally, in step S2, intermediate product A is dissolved in aniline to obtain a precursor solution, and the precursor solution is dissolved in straight-run gasoline and stirred evenly to obtain the catalyst body. The molar ratio of aniline to molybdenum is 0.5:1, and the weight ratio of straight-run gasoline to precursor solution is 5:1.

[0029] The liquid catalyst of this application consists of a catalyst substrate and an additive. The catalyst substrate is a single catalyst composed of bimetallic components. Firstly, it synergistically catalyzes the feedstock, improving its catalytic hydrogenation activity and inhibiting coking. Secondly, it can rapidly disperse in the feedstock oil and decompose into nano-nickel sulfide-modified active molybdenum sulfide without the need for potassium sulfide, thus improving the processing efficiency of the feedstock oil. However, due to the high metal content in the high-chlorine, high-metal waste mineral oil and tire pyrolysis oil of this application, the sulfur element in the liquid catalyst easily combines with metal elements to form metal sulfur precipitates, resulting in the loss of active sites in the liquid catalyst and reducing catalytic activity. Therefore, this application uses an additive containing a chelating agent, which can chelate with the metal in the feedstock, achieving the removal of metal elements and ensuring the normal operation of the liquid catalyst.

[0030] The additives use organic acids, carboxylates, 1,2,4-triazole and chelating agents in combination, which can improve the chelating effect of the chelating agent on metals, and further improve the removal efficiency and final removal amount of metals by the chelating agent.

[0031] Optionally, the organic acid is at least one of salicylic acid and glycolic acid;

[0032] The carboxylate is at least one of zinc acetate, sodium tartrate, and sodium alginate.

[0033] Researchers have developed many demetallizing chelating agents that can remove metals from crude oil, vegetable oil, or recycled oil. For example, patent CN112322340A describes a demetallizing agent that is a compound of organic acid, carboxylate, Schiff base, and chelating agent, which can remove iron from crude oil. However, when used in this application, it was found that the chelating agent in this demetallizing agent is not effective at high temperature and high salt conditions. Therefore, it can only be used in crude oil. The removal rate of iron metal in the catalytic hydrogenation of steps (1) and (2) of this application is very low, and the removal rate of other metals is even lower. Therefore, this application has prepared a new type of chelating agent, which, when combined with 1,2,4-triazole, can specifically remove iron, chromium, copper, lead, and vanadium metals from the two raw materials of this application, thereby ensuring the effective catalysis of the liquid catalyst.

[0034] Optionally, the chelating agent is prepared by:

[0035] S10: Dissolve 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane and methyl allyl alcohol polyoxyethylene ether in a solvent, add an initiator and react at 70-80℃ for 4-6 h to obtain a solution containing intermediate A;

[0036] S20: Add aminosulfonic acid and Lewis acid to the solution containing intermediate A, react at 120-125℃ for 4-5 hours, then cool to 100℃, add ethanolamine to neutralize and obtain a solution containing intermediate B.

[0037] S30: Add polystyrene solution and Lewis acid to the solution containing intermediate B, and react at 80-100°C to obtain crude product;

[0038] S40: The crude product is washed, purified, and dried to obtain the chelating agent.

[0039] In step S10 of the preparation of this chelating agent, 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane and methyl allyl alcohol polyoxyethylene ether are polymerized to form the first main body of the chelating agent. In step S20, aminosulfonic acid is used to sulfonate the hydroxyl groups of methyl allyl alcohol polyoxyethylene ether to introduce sulfonic acid and amino groups. These groups, in combination with 1,2,4-triazole, can improve the complexation effect on metals. In step S30, polystyrene is used as the second main body of the chelating agent. Its benzene ring can undergo Friedel-Crafts alkylation reaction with the vinyl group in the first main body to obtain the chelating agent. The introduction of polystyrene can improve the temperature and salt resistance of the chelating agent, thereby enabling the removal of metals under high temperature and high salt conditions. Meanwhile, the cyclotrisiloxane structure contained in the chelating agent can improve the dispersibility of the chelating agent in the raw materials. The structure of the first and second main bodies can make the chelating agent contain micropores, which are used to store the metals adsorbed by the chelating agent itself, as well as the metals adsorbed by carboxylates and 1,2,4-triazole coordination, to prevent the metals from escaping back into the system at high temperatures. The structure of the above-mentioned chelating agent can also specifically remove metals such as iron, chromium, copper, lead and vanadium in the raw materials, without removing nickel and molybdenum in the liquid catalyst, thus ensuring continuous catalytic hydrogenation of the raw materials.

[0040] Optionally, the solvent in step S10 is at least one of tetrahydrofuran, xylene, or dichloromethane.

[0041] Optionally, in step S10, the molar ratio of 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane to methyl allyl alcohol polyoxyethylene ether is (1-2):1;

[0042] In step S20, the molar ratio of methyl allyl alcohol polyoxyethylene ether to aminosulfonic acid is 1:(0.8-1.2).

[0043] In step S30, the molar ratio of polystyrene to 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane in the polystyrene solution is 1:(1500-1800).

[0044] Optionally, the polystyrene has a molecular weight of 150,000 to 200,000.

[0045] Optionally, the pH after neutralization of ethanolamine is 6-8.

[0046] Optionally, the amount of the initiator is 0.5-2 wt% of the amount of methyl allyl alcohol polyoxyethylene ether;

[0047] In step S20, the amount of Lewis acid used is 1-2 wt% of the amount of aminosulfonic acid used;

[0048] The amount of Lewis acid used in step S30 is 2-5 wt% of the polystyrene.

[0049] Optionally, the initiator is selected from azobisisobutyronitrile (AIBN).

[0050] Optionally, the Lewis acid is any one or more selected from AlCl3, BF3, SbCl5, FeBr3, FeCl3, SnCl4, TiCl4, and ZnCl2.

[0051] Optionally, the chlorine content in the tire pyrolysis oil is 20-300 ppm, and the metal content in the tire pyrolysis oil is 50-500 ppm.

[0052] Preferably, the chlorine content in the tire pyrolysis oil is 200-300 ppm, and the metal content in the tire pyrolysis oil is 400-500 ppm.

[0053] Optionally, the chlorine content in the high-chlorine, high-metal waste mineral oil is 500-2000 ppm, and the metal content in the high-chlorine, high-metal waste mineral oil is 1000-10000 ppm.

[0054] Preferably, the chlorine content in the high-chlorine, high-metal waste mineral oil is 1500-2000 ppm, and the metal content in the high-chlorine, high-metal waste mineral oil is 8000-10000 ppm.

[0055] Optionally, the pressure in reactors A, B, C and D is 1-6 MPa, preferably 2-5 MPa.

[0056] All of the above reactors are low-pressure reactors. The low-pressure reaction conditions are relatively mild, which helps to extend the service life of hydrotreating and liquid catalysts. The low-pressure operating conditions also help to concentrate the products more on naphtha, light fuel oil and medium fuel oil components. At the same time, the low-pressure conditions do not impose harsh requirements on the reaction equipment, which can reduce equipment investment costs and operating costs and improve economic efficiency.

[0057] Optionally, the reaction temperature of reactor C is 320-380℃, and the reaction temperature of reactor D is 400-450℃.

[0058] Optionally, the weight ratio of the high-chlorine, high-metal waste mineral oil to the circulating oil in step (1) is (5-20):1;

[0059] In step (2), the weight ratio of the tire pyrolysis oil to the high-chlorine, high-metal waste mineral oil is 1:(1-10).

[0060] Optionally, the hydrogen-to-oil ratio in the suspended bed reactor A is 400-1000, and the volumetric hourly space velocity is 0.1-2.0 h⁻¹. -1 The hydrogen-to-oil ratio in suspended bed reactor B is 200-500, and the volumetric hourly space velocity is 0.1-2.0 h⁻¹. -1 The hydrogen-to-oil ratio in the suspended bed reactor C is 400-600, and the volumetric space velocity is 0.1-1.8 h⁻¹. -1 The hydrogen-to-oil ratio in the suspended bed reactor D is 400-800, and the volumetric space velocity is 0.1-1.5 h⁻¹. -1 .

[0061] Optionally, the solid catalyst used in reactor C is a catalyst in which molybdenum, nickel and / or cobalt are supported on alumina, and the catalyst needs to be pre-sulfurized before use; the solid catalyst used in reactor D is a tungsten-nickel catalyst containing molecular sieves, and the catalyst needs to be pre-sulfurized before use.

[0062] The beneficial effects of this application include, but are not limited to:

[0063] 1. The method of this application can simultaneously process tire pyrolysis oil and high-chlorine, high-metal waste mineral oil, and convert chlorine in the raw materials into hydrogen chloride, while removing metal elements by complexation, thereby reducing their impact on subsequent reactions and improving the quality of the final product.

[0064] 2. The method of this application can treat tire pyrolysis oil and high-chlorine, high-metal waste mineral oil and hydrogenate the oil under low-pressure conditions, which can significantly reduce the investment cost of the equipment and improve the safety of the process operation. Attached Figure Description

[0065] The accompanying drawings, which are included to provide a further understanding of this application and form part of this application, illustrate exemplary embodiments and are used to explain this application, but do not constitute an undue limitation of this application. In the drawings:

[0066] Figure 1 This is a schematic diagram of the system for obtaining recycled oil products by comprehensively utilizing high-chlorine and high-metal waste mineral oil and tire pyrolysis oil, as described in Embodiment 1 of this application.

[0067] List of components and reference numerals:

[0068] 1. High-chloride, high-metal waste mineral oil buffer tank; 2. High-chloride, high-metal waste mineral oil pressurizing pump; 3. Heating furnace; 4. Liquid catalyst storage tank; 5. Liquid catalyst injection pump; 6. Reactor A; 7. Tire pyrolysis oil buffer tank; 8. Tire pyrolysis oil pressurizing pump; 9. Reactor B; 10. First hydrogenation gas phase cooler; 11. First hydrogenation cold high-pressure separator; 12. First hydrogenation cold low-pressure separator; 13. First hydrogenation circulation pump; 14. First hydrogenation hot low-pressure separator; 15. Circulating hydrogen compressor; 16. Fresh hydrogen compressor; 17. Wash water storage tank; 18. Wash water injection pump; 19. Vacuum distillation column; 20. Oil residue separator; 21. Reactor C; 22. Second hydrogenation cooler; 23. Second hydrogenation cold high-pressure separator; 24. Second hydrogenation cold low-pressure separator; 25. Stripping stabilizer; 26. Atmospheric distillation column; 27. Reactor D. Detailed Implementation

[0069] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0070] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0071] Unless otherwise specified, the methods used in the embodiments of this application are conventional methods in the prior art.

[0072] Example 1

[0073] refer to Figure 1 This embodiment relates to a system for comprehensively utilizing high-chloride, high-metal waste mineral oil and tire pyrolysis oil to obtain recycled oil products, comprising: a high-chloride, high-metal waste mineral oil feeding group, including a high-chloride, high-metal waste mineral oil buffer tank 1, a high-chloride, high-metal waste mineral oil pressurization pump 2, and a heating furnace 3; a liquid catalyst feeding group, including a liquid catalyst storage tank 4 and a liquid catalyst injection pump 5; a suspended bed reactor A6; a tire pyrolysis oil feeding group, including a tire pyrolysis oil buffer tank 7 and a tire pyrolysis oil pressurization pump 8; a suspended bed reactor B9; and a first hydrogenation treatment group, including a first hydrogenation gas phase cooling group. Unit 10, First Hydrogenation Cold High-Pressure Separator 11, First Hydrogenation Cold Low-Pressure Separator 12, First Hydrogenation Circulation Pump 13, First Hydrogenation Hot Low-Pressure Separator 14, Circulating Hydrogen Compressor 15; Fresh Hydrogen Compressor 16; Water Injection Group, including Wash Water Storage Tank 17, Wash Water Injection Pump 18; Vacuum Distillation Tower 19, Oil Residue Separator 20, Reactor C21; Second Hydrogenation Processing Group, including Second Hydrogenation Cooler 22, Second Hydrogenation Cold High-Pressure Separator 23, Second Hydrogenation Cold Low-Pressure Separator 24; Stripping Stabilizer 25, Atmospheric Distillation Tower 26, Reactor D27.

[0074] The system operates as follows:

[0075] (1) High-chloride and high-metal waste mineral oil is injected from the high-chloride and high-metal waste mineral oil buffer tank 1 into the heating furnace 3 through the high-chloride and high-metal waste mineral oil injection pump 2 and mixed with the circulating oil. Then it enters the reactor A6. The liquid catalyst in the liquid catalyst storage tank 4 is injected into the reactor A6 through the liquid catalyst injection pump 5 and mixed with the high-chloride and high-metal waste mineral oil. Hydrogenation is achieved in the suspended bed reactor A6.

[0076] (2) The effluent from the suspended bed reactor A6 flows into the reactor B9. The tire pyrolysis oil from the tire pyrolysis oil buffer tank 7 is pumped into the suspended bed reactor B9 by the tire pyrolysis oil pressurizing pump 8 and mixed with the effluent from the suspended bed reactor A6 to achieve hydrogenation again.

[0077] (3) Part of the liquid effluent from the suspended bed reactor B9 is used as circulating oil and mixed with high-chlorine and high-metal waste mineral oil through the first hydrogenation circulating pump 13. The remaining part is first depressurized and then separated into gas A and liquid A through the first hot low-pressure separator 14. Gas A is discharged as waste gas. After that, water is injected into the gas effluent from reactor B9 through the washing water storage tank 17 and the washing water injection pump 18 to form a first mixture containing three phases of oil, water and gas. The first mixture is passed through the first hydrogenation gas phase cooler 10 and then enters the first hydrogenation cold high-pressure separator 11 to separate gas B and liquid B. Gas B is pressurized by the circulating hydrogen compressor 15 and then combined with the fresh hydrogen added by the fresh hydrogen compressor 16 and enters reactor A6. Liquid B is depressurized and separated by the first hydrocooled low-pressure separator 12 to obtain dissolved gas, a first oil phase and a first aqueous phase. The dissolved gas is discharged as waste gas and the first aqueous phase is discharged as wastewater. Liquid A and the first oil phase are mixed and passed through the vacuum distillation tower 19 to obtain naphtha, oil fraction A and residue. The residue is passed through the oil residue separator 20 to obtain residual oil and oil residue. The oil residue is discharged externally and the residual oil is returned to the high-chlorine and high-metal waste mineral buffer tank 1 to be mixed with high-chlorine and high-metal waste mineral oil or treated as residual oil.

[0078] (4) Oil fraction A is sent to reactor C21 containing a solid catalyst for hydrotreating and upgrading;

[0079] (5) Water is injected into the effluent of reactor C21 through washing water storage tank 17 and washing water injection pump 18 to obtain a second mixture. The second mixture is passed through the second hydrogenation cooler 22 and the second hydrogenation cold high-pressure separator 23 to obtain separated gas and separated liquid. The separated gas is then pressurized by the circulating hydrogen compressor 15 and combined with the fresh hydrogen added by the fresh hydrogen compressor 16 into reactor A6. The separated liquid is depressurized and separated by the second hydrogenation cold low-pressure separator 24 to obtain a second oil phase, gas C and a second water phase. Gas C is discharged as waste gas and the second water phase is discharged as waste water. The second oil phase enters the stripping stabilizer 25 and the atmospheric distillation column 26. The gas flowing out of the stripping stabilizer 25 is discharged as waste gas.

[0080] (6) Naphtha, light fuel oil and medium fuel oil are obtained from the outlet of atmospheric distillation column 26. The bottom oil of atmospheric distillation column 26 can be used as heavy fuel oil or added to hydrocracking reactor D27 filled with solid catalyst to carry out hydrocracking reaction to obtain hydrocracking material.

[0081] (7) The hydrocracking feedstock is mixed with oil A and then fed into reactor C21 for hydrotreating.

[0082] This system enables the one-step processing of high-chlorine, high-metal waste mineral oil and tire pyrolysis oil to produce high-quality recycled oil products such as naphtha, light fuel oil, medium fuel oil, and heavy fuel oil, which has significant environmental and economic benefits.

[0083] Example 2

[0084] This embodiment relates to a method for obtaining recycled oil products by comprehensively utilizing high-chlorine and high-metal waste mineral oil and tire pyrolysis oil. The method adopts the system and operating mode of Embodiment 1, and includes the following steps:

[0085] (1) Mix high-chlorine and high-metal waste mineral oil (chlorine content of 1500-2000ppm and metal content of 8000-10000ppm) with circulating oil, heat it to 380-420℃ in a heating furnace, mix in 200-2000ppm liquid catalyst and then enter a suspended bed reactor A without solid catalyst packing for reaction.

[0086] (2) The effluent from the suspended bed reactor A is mixed with tire pyrolysis oil (chlorine content of 200-300ppm and metal content of 400-500ppm) and then introduced into the suspended bed reactor B without solid catalyst at a temperature of 320-360℃ for reaction.

[0087] (3) The liquid effluent from the suspended bed reactor B is divided into two parts. One part is used as circulating oil, and the other part is depressurized and separated to obtain gas A and liquid A. The gas effluent from reactor B is injected with water to form a first mixture. The first mixture is separated to obtain gas B and liquid B. Liquid B is depressurized and separated to obtain dissolved gas, first oil phase and first water phase. Liquid A and first oil phase are mixed and passed through a vacuum distillation tower to obtain naphtha, oil A and residue.

[0088] (4) The oil fraction A is sent to reactor C containing a solid catalyst for hydrogenation and upgrading;

[0089] (5) Water is injected into the effluent of reactor C to obtain a second mixture. The second mixture is separated to obtain a second oil phase, gas C and a second water phase. The second oil phase enters the stripping stabilizer and the atmospheric distillation column.

[0090] (6) Naphtha, light fuel oil and medium fuel oil are obtained from the atmospheric distillation column. The bottom oil is added to the hydrocracking reactor D packed with solid catalyst to carry out hydrocracking reaction and obtain hydrocracking material.

[0091] (7) The hydrocracking material is recycled to be mixed with oil A, and then enters reactor C for hydrotreating and upgrading.

[0092] Following the steps described above, the same batch of high-chlorine, high-metal waste mineral oil and the same batch of tire pyrolysis oil were processed, with different parameter conditions set according to the numbers in Tables 1 and 2. In Tables 1 and 2, "-" indicates that the method is the same as in Method 3#.

[0093] In Table 1, the liquid catalyst used in step (1) of method 1# comprises a catalyst substrate and an auxiliary agent. The preparation method of the catalyst substrate is as follows:

[0094] S1: A sulfur-containing molybdenum source solution was obtained by mixing molybdenum trioxide ammonia solution with potassium sulfide and reacting at 150℃ for 0.5h. The molar ratio of sulfur content of potassium sulfide to molybdenum was 2:1. Then, the sulfur-containing molybdenum source solution was mixed with nickel nitrate ammonia solution and reacted at 150℃ for 0.5h. After filtration, washing with water and drying, a sulfur-containing nickel-molybdenum bimetallic salt complex was obtained. The volume ratio of nickel nitrate ammonia solution to molybdenum trioxide ammonia solution was 1:1. The molar ratio of ammonia to nickel nitrate in the nickel nitrate ammonia solution was 1:1. The volume-to-weight ratio of ammonia to molybdenum trioxide in the molybdenum trioxide ammonia solution was 2:1. The unit is ml / g.

[0095] S2: A bimetallic salt complex containing sulfur, nickel, and molybdenum was added to oleic acid and reacted at 200°C for 0.5 h to obtain intermediate product A. The molar ratio of oleic acid to molybdenum was 2:1. Then, intermediate product A was dissolved in aniline to obtain a precursor solution. The precursor solution was dissolved in straight-run gasoline and stirred evenly to obtain the catalyst body. The molar ratio of aniline to molybdenum was 0.5:1, and the weight ratio of straight-run gasoline to precursor solution was 5:1.

[0096] The additive accounts for 80% of the bulk catalyst weight and consists of a chelating agent, salicylic acid, zinc acetate, and 1,2,4-triazole in a weight ratio of 1:0.1:0.2:0.1.

[0097] The preparation method of the chelating agent is as follows:

[0098] S10: Dissolve 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane and methyl allyl alcohol polyoxyethylene ether in a molar ratio of 1:1 in a mixed solvent of tetrahydrofuran, water and ethanol (volume ratio of tetrahydrofuran, water and ethanol is 3:1:1), add azobisisobutyronitrile and react at 80°C for 4 h to obtain a solution containing intermediate A. The amount of azobisisobutyronitrile is 0.5 wt% of the amount of methyl allyl alcohol polyoxyethylene ether.

[0099] S20: Add aminosulfonic acid and BF3 to a solution containing intermediate A. The molar ratio of aminosulfonic acid to methyl allyl alcohol polyoxyethylene ether is 0.8:1. The amount of BF3 is 1 wt% of the amount of aminosulfonic acid. React at 125°C for 4 h. Then cool down to 100°C and add ethanolamine to neutralize to obtain a solution containing intermediate B. The pH after neutralization with ethanolamine is 6.

[0100] S30: Add a chloroform solution of polystyrene and BF3 to a solution containing intermediate B. The molar ratio of polystyrene to 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane in the chloroform solution of polystyrene is 1:1800. The molecular weight of polystyrene is 200,000. The amount of BF3 is 2 wt% of polystyrene. The reaction is carried out at 80°C to obtain the crude product.

[0101] S40: The crude product is washed with tetrahydrofuran, purified by soaking in chloroform, and dried to obtain the chelating agent.

[0102] The liquid catalyst used in step (1) of methods 2# and 3# comprises a catalyst substrate and an auxiliary agent. The preparation method of the catalyst substrate is as follows:

[0103] S1: An ammonium metamolybdate ammonia solution was mixed with potassium sulfide and reacted at 30°C for 3 hours to obtain a sulfur-containing molybdenum source solution. The molar ratio of sulfur content in potassium sulfide to molybdenum was 6:1. Then, the sulfur-containing molybdenum source solution was mixed with nickel acetate ammonia solution and reacted at 30°C for 3 hours. After filtration, washing with water, and drying, a sulfur-containing nickel-molybdenum bimetallic salt complex was obtained. The volume ratio of nickel acetate ammonia solution to ammonium metamolybdate ammonia solution was 1:2. The molar ratio of ammonia to nickel acetate in the nickel acetate ammonia solution was 10:1. The volume-to-weight ratio of ammonia to ammonium metamolybdate in the ammonium metamolybdate ammonia solution was 1:1. The unit is ml / g.

[0104] S2: A bimetallic salt complex containing sulfur, nickel, and molybdenum was added to oleic acid and reacted at 50°C for 5 hours to obtain intermediate product A. The molar ratio of oleic acid to molybdenum was 6:1. Then, intermediate product A was dissolved in aniline to obtain a precursor solution. The precursor solution was dissolved in straight-run gasoline and stirred evenly to obtain the catalyst body. The molar ratio of aniline to molybdenum was 0.5:1, and the weight ratio of straight-run gasoline to precursor solution was 5:1.

[0105] The weight of the additive is 200% of the weight of the catalyst body. The additive consists of a chelating agent, glycolic acid, sodium tartrate and 1,2,4-triazole in a weight ratio of 1:0.2:0.1:0.2.

[0106] The preparation method of the chelating agent is as follows:

[0107] S10: Dissolve 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane and methyl allyl alcohol polyoxyethylene ether in a molar ratio of 2:1 in a mixed solvent of tetrahydrofuran, water and ethanol (volume ratio of tetrahydrofuran, water and ethanol is 3:1:1), add azobisisobutyronitrile and react at 70°C for 6 h to obtain a solution containing intermediate A. The amount of azobisisobutyronitrile is 2 wt% of the amount of methyl allyl alcohol polyoxyethylene ether.

[0108] S20: Add aminosulfonic acid and BF3 to a solution containing intermediate A. The molar ratio of aminosulfonic acid to methyl allyl alcohol polyoxyethylene ether is 1.2:1. The amount of BF3 is 2 wt% of the amount of aminosulfonic acid. React at 120°C for 5 h, then cool to 100°C and add ethanolamine to neutralize to obtain a solution containing intermediate B. The pH after neutralization with ethanolamine is 8.

[0109] S30: Add a chloroform solution of polystyrene and BF3 to a solution containing intermediate B. The molar ratio of polystyrene to 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane in the chloroform solution of polystyrene is 1:1500. The molecular weight of polystyrene is 150,000. The amount of BF3 is 5 wt% of polystyrene. The reaction is carried out at 100°C to obtain the crude product.

[0110] S40: The crude product is washed with tetrahydrofuran, purified by soaking in chloroform, and dried to obtain the chelating agent.

[0111] Table 1

[0112]

[0113]

[0114] Note: The "-" in the table indicates that it is the same as method 3#.

[0115] Table 2

[0116]

[0117] Note: The "-" in the table indicates that it is the same as method 3#.

[0118] Test Example 1

[0119] The acid values ​​of naphtha, light fuel oil, medium fuel oil, and heavy fuel oil prepared by the above method in Example 2 were determined according to GB / T 258-2016, and the content of sulfur, chlorine, and metal elements was tested by elemental analysis. The test results are shown in Tables 3 and 4 below.

[0120] Table 3

[0121]

[0122]

[0123] Table 4

[0124]

[0125] Example 3

[0126] This embodiment relates to a method for obtaining recycled oil products by comprehensively utilizing high-chlorine, high-metal waste mineral oil and tire pyrolysis oil. This method has the same steps as method 3# in embodiment 2, with the following specific differences:

[0127] Method 11#

[0128] The difference between this method and Method 3# is that p-aminodiphenylimine is used instead of 1,2,4-triazole in the catalyst promoter, while the rest is the same as Method 3#.

[0129] Method 12#

[0130] The difference between this method and Method 3# is that the catalyst promoter consists of a chelating agent, glycolic acid, sodium tartrate, and 1,2,4-triazole in a weight ratio of 0.5:0.2:0.1:0.2, while the rest is the same as in Method 3#.

[0131] Method 13#

[0132] The difference between this method and method 3# is that step S30 is omitted in the preparation of the chelating agent. Step S20 yields a solution containing intermediate B, which is then distilled, washed, purified, and dried to obtain the chelating agent. The rest is the same as method 3#.

[0133] Method 14#

[0134] The difference between this method and method 3# is that in step S10 of the preparation of the chelating agent, the molar ratio of 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane and methyl allyl alcohol polyoxyethylene ether is 3:1, while the rest is the same as method 3#.

[0135] Method 15#

[0136] The difference between this method and Method 3# is that in step S20 of the preparation of the chelating agent, the molar ratio of methyl allyl alcohol polyoxyethylene ether to aminosulfonic acid is 1:0.5, while the rest is the same as Method 3#.

[0137] Method 16#

[0138] The difference between this method and Method 3# is that in step S30 of the preparation of the chelating agent, the molar ratio of polystyrene to 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane is 1:1000, while the rest is the same as Method 3#.

[0139] Test Example 2

[0140] The acid values ​​of naphtha, light fuel oil, medium fuel oil, and heavy fuel oil prepared by the above method in Example 3 were determined according to GB / T 258-2016, and the contents of sulfur, chlorine, and metal elements were tested by elemental analysis. The test results are shown in Tables 5 and 6 below.

[0141] Table 5

[0142]

[0143]

[0144] Table 6

[0145]

[0146] As can be seen from Examples 2 and 3 above, the method of this application can process high-chlorine, high-metal waste mineral oil and tire pyrolysis oil to obtain recycled oil products. Since the raw materials processed in Examples 2 and 3 have high chlorine and metal content in the high-chlorine, high-metal waste mineral oil and tire pyrolysis oil, when the same method is used to process tire pyrolysis oil with chlorine content of 20-200ppm and metal content of 50-400ppm and waste mineral oil with chlorine content of 500-1500ppm and metal content of 1000-8000ppm, the yield of each product obtained is further higher than that of Method 3#, and the residual sulfur, chlorine, metal content and acid value of each oil product are further lower than those of Method 3#.

[0147] The above description is merely an embodiment of this application, and the scope of protection of this application is not limited to these specific embodiments, but is determined by the claims of this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the technical concept and principles of this application should be included within the scope of protection of this application.

Claims

1. A method for obtaining recycled oil products by comprehensively utilizing high-chlorine, high-metal waste mineral oil and tire pyrolysis oil, characterized in that, Includes the following steps: (1) Mix high-chlorine and high-metal waste mineral oil with circulating oil, heat it to 380-420℃ in a heating furnace, mix in 200-2000ppm liquid catalyst, and then enter a suspended bed reactor A without solid catalyst packing for reaction; (2) The effluent from the suspended bed reactor A is mixed with tire pyrolysis oil and then introduced into the suspended bed reactor B without solid catalyst at a temperature of 320-360℃ for reaction; (3) The liquid effluent from the suspended bed reactor B is divided into two parts. One part is used as circulating oil, and the other part is depressurized and separated to obtain gas A and liquid A. The gas effluent from reactor B is injected with water to form a first mixture. The first mixture is separated to obtain gas B and liquid B. The liquid B is depressurized and separated to obtain dissolved gas, a first oil phase and a first water phase. The liquid A and the first oil phase are mixed and passed through a vacuum distillation column to obtain naphtha, oil fraction A and residue. (4) The oil fraction A is sent to reactor C containing a solid catalyst for hydrogenation and upgrading; (5) Water is injected into the effluent of reactor C to obtain a second mixture. The second mixture is separated to obtain a second oil phase, gas C and a second water phase. The second oil phase enters the stripping stabilizer and the atmospheric distillation column. (6) Naphtha, light fuel oil and medium fuel oil are obtained from the atmospheric distillation column. The bottom oil of the atmospheric distillation column is used as heavy fuel oil or added to the hydrocracking reactor D packed with solid catalyst for hydrocracking reaction to obtain hydrocracking material. (7) The hydrocracking feedstock is recycled to be mixed with oil A, and then enters reactor C for hydrotreating and upgrading; The liquid catalyst comprises a catalyst substrate and an additive, and the catalyst substrate is prepared by: S1: A sulfur-containing molybdenum source ammonia solution is obtained by mixing a molybdenum source ammonia solution with potassium sulfide and reacting at 30-150℃ for 0.5-3h. The molar ratio of sulfur content of potassium sulfide to molybdenum is (2-6):

1. Then, the sulfur-containing molybdenum source solution and nickel source ammonia solution are mixed and reacted at 30-150℃ for 0.5-3h. After filtration, washing with water and drying, a sulfur-containing nickel-molybdenum bimetallic salt complex is obtained. The volume ratio of nickel source ammonia solution to molybdenum source ammonia solution is 1:(1-2). The molar ratio of ammonia to nickel source in the nickel source ammonia solution is (1-10):

1. The volume weight ratio of ammonia to molybdenum source in the molybdenum source ammonia solution is (1-2):

1. The unit is ml / g. S2: The sulfur-containing nickel-molybdenum bimetallic salt complex is added to oleic acid and reacted at 50-200℃ for 0.5-5h to obtain intermediate product A. The molar ratio of oleic acid to molybdenum is (2-6):

1. Then, intermediate product A is dissolved in aniline and straight-run gasoline in sequence and stirred evenly to obtain the catalyst body. The weight of the auxiliary agent is 80-200% of the weight of the catalyst body, and the auxiliary agent is composed of a chelating agent, organic acid, carboxylate and 1,2,4-triazole in a weight ratio of 1:(0.1-0.2):(0.1-0.2):(0.1-0.2).

2. The method according to claim 1, characterized in that, The chelating agent is prepared by: S10: Dissolve 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane and methyl allyl alcohol polyoxyethylene ether in a solvent, add an initiator and react at 70-80℃ for 4-6 h to obtain a solution containing intermediate A; S20: Add aminosulfonic acid and Lewis acid to the solution containing intermediate A, react at 120-125℃ for 4-5 hours, then cool to 100℃, add ethanolamine to neutralize and obtain a solution containing intermediate B. S30: Add polystyrene solution and Lewis acid to the solution containing intermediate B, and react at 80-100°C to obtain crude product; S40: The crude product is washed, purified, and dried to obtain the chelating agent.

3. The method according to claim 2, characterized in that, In step S10, the molar ratio of 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane and methyl allyl alcohol polyoxyethylene ether is (1-2):1; In step S20, the molar ratio of methyl allyl alcohol polyoxyethylene ether to aminosulfonic acid is 1:(0.8-1.2). In step S30, the molar ratio of polystyrene to 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane in the polystyrene solution is 1:(1500-1800).

4. The method according to claim 2, characterized in that, The amount of the initiator is 0.5-2 wt% of the amount of methyl allyl alcohol polyoxyethylene ether. The amount of Lewis acid used in step S20 is 1-2 wt% of the amount of aminosulfonic acid used. The amount of Lewis acid used in step S30 is 2-5 wt% of the polystyrene.

5. The method according to claim 1, characterized in that, The chlorine content in the tire pyrolysis oil is 20-300 ppm, and the metal content in the tire pyrolysis oil is 50-500 ppm.

6. The method according to claim 1, characterized in that, The chlorine content in the high-chlorine, high-metal waste mineral oil is 500-2000 ppm, and the metal content in the high-chlorine, high-metal waste mineral oil is 1000-10000 ppm.

7. The method according to claim 1, characterized in that, The pressure in reactors A, B, C, and D is 1-6 MPa.

8. The method according to claim 7, characterized in that, The pressure in reactors A, B, C, and D is 2-5 MPa.

9. The method according to claim 1, characterized in that, The reaction temperature in reactor C is 320-380℃, and the reaction temperature in reactor D is 400-450℃.

10. The method according to claim 1, characterized in that, The weight ratio of the high-chlorine, high-metal waste mineral oil to the circulating oil in step (1) is (5-20):1; In step (2), the weight ratio of the tire pyrolysis oil to the high-chlorine, high-metal waste mineral oil is 1:(1-10).

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