Method for obtaining regenerated oil product by comprehensively utilizing high-chlorine high-metal waste mineral oil and tire pyrolytic oil

Abstract

The invention discloses a method for obtaining a regenerated oil product by comprehensively utilizing high-chlorine high-metal waste mineral oil and tire pyrolytic oil, and belongs to the technical field of post-treatment of waste mineral oil and tire pyrolytic oil. The method comprises the following steps: (1) mixing high-chlorine high-metal waste mineral oil with circulating oil, and feeding the mixture into a reactor A; (2) mixing the effluent of the reactor A with tire pyrolytic oil, and feeding the mixture into a reactor B; (3) separating effluent of the reactor B to obtain naphtha, an oil component A and residues; (4) the oil component A enters a reactor C for hydrogenation upgrading; and (5) separating the effluent of the reactor C to obtain a second oil phase, and enabling the second oil phase to enter a steam stripping stabilizing tower and a normal-pressure rectifying tower to obtain naphtha, light fuel oil, medium fuel oil and heavy fuel oil. The method can solve the problem that chlorine and metal elements are difficult to efficiently remove at the same time in the recycling of high-chlorine high-metal waste mineral oil and tire pyrolytic oil at present, and improves the quality and yield of regenerated oil products.

Description

Technical Field

[0001] The present 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, and belongs to the technical field of post-processing of waste mineral oil and tire pyrolysis oil. Background Art

[0002] Waste mineral oil mainly comes from sludge and oil foot produced in the process of oil extraction and refining, sediment produced in the storage process of mineral oil, and various waste lubricants. Hydrogenation and upgrading of waste mineral oil is a good method. Waste tires are a common solid waste in life. Therefore, it is of great significance to explore a method for high-value utilization of waste tires. Pyrolysis of waste tires to obtain tire pyrolysis oil, and then hydrogenation and upgrading of 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 by hydrogenation. Therefore, if the two raw materials are hydrogenated at the same time, the investment and operation costs of the equipment can be reduced and the overall economic benefits can be improved, but there are also some technical problems. First, the content of chlorine and other metal impurity elements in waste mineral oil and tire pyrolysis oil is very high. During the hydrogenation process, the high content of chlorine will react with hydrogen to produce a large amount of HCl gas. HCl will form hydrochloric acid in the presence of water, causing corrosion of mechanical equipment or transportation pipelines, which will not only shorten the service life of the equipment, but also reduce the pressure resistance of the equipment, leading to the possibility of explosion accidents. A large amount of impurity metal elements can cause poisoning of the hydrogenation catalyst, and can also cause oil coking, block the reaction device, and threaten the safe operation of the device. Secondly, there are also differences in the various physical properties of waste mineral oil and tire pyrolysis oil, and the operation difficulty of hydrogenating the two raw materials at the same time is also relatively large.

[0004] A Chinese patent application with application number 202311180648.7 reports a waste mineral oil demetallization pretreatment method, which extracts the waste mineral oil by preparing a brine solution of ammonium sulfate, ammonium bicarbonate, ammonium carbamate, ammonium carbonate or ammonium phosphate to achieve metal precipitation, thereby removing the metal from the waste mineral oil. Although the treatment process can reduce the metal content in the waste mineral oil, the method can only remove metal elements in the waste mineral oil, and has no removal effect on toxic impurity elements such as chlorine and sulfur, and the operation process is relatively complicated.

[0005] The international patent application number WOCN22130151 reports a method and system for continuously producing base oil from waste mineral oil containing chlorine and silicon. The waste mineral oil is placed in a heat settling device for heat settling. After heat settling, the waste mineral oil is placed in a flash evaporation device, and the obtained light component oil and heavy component oil are subjected to dechlorination reaction respectively; after the dechlorination reaction, the heavy component oil is demetallized and vacuum distilled, and then placed in an adsorption desiliconization tank for adsorption desiliconization. After the desiliconization, the oil product is subjected to hydrogenation reaction and distillation to obtain solvent oil, high-quality base oil and industrial white oil. This method can effectively solve the problems of coking, corrosion, blockage and hydrogenation catalyst poisoning in the regeneration process of waste mineral oil containing chlorine and silicon. However, this method can only process a single waste mineral oil, and the dechlorination and demetallization steps are carried out separately, and the operation steps are relatively complicated.

[0006] A Chinese patent with application number 202180088607.8 reports a method for producing aviation fuel using waste polymer materials, wherein the intermediate fraction of waste tire pyrolysis oil is blended with the kerosene / gas oil fraction obtained from crude oil refining, the feed mixture is hydrogenated under hydrodesulfurization conditions, the liquid product is recovered by gas-liquid separation, and the total liquid product is distilled into an aviation fuel fraction and a heavy fraction. This method realizes the utilization of waste polymer materials, the quality of the produced oil products has not deteriorated, and the output of waste is low. However, this method requires the addition of oil products obtained from crude oil refining, and the proportion of tire pyrolysis oil added is too low (less than 10wt%).

[0007] Chinese patent application number 202011010111.2 reports a method for catalytic conversion of waste tire pyrolysis oil and gas. The oil and gas obtained by pyrolysis of waste tires are directly introduced into a fixed bed reactor filled with NaY molecular sieves modified with two rare earth elements La and Ce, and catalytically converted into light oil and gas. After further condensation and cooling, they are separated into gas, gasoline, diesel and a small amount of tar. This method effectively improves the efficiency of catalytic pyrolysis reaction, reduces the occurrence of carbon deposition, and simplifies the process of catalyst preparation. However, impurity elements in pyrolysis oil and gas can easily cause catalyst poisoning.

[0008] Chinese patent application number 202210144341.0 reports a method and system for producing jet fuel, white oil and lubricating oil base oil by hydrogenating waste oil. This method can effectively and economically prepare high-quality, high-flash point, high-density, low-energy-consumption aviation fuel without harmful impurities and water, and effectively remove solid impurities, chlorine, and other harmful impurities and water from waste oil. However, the various oil products treated by this method need to be mixed in advance, which increases the operation steps. In addition, the concentration of chlorine and metal impurities in the raw oil products is relatively low.

[0009] Based on the above analysis, waste mineral oil with high chlorine and high metal content and tire pyrolysis oil can be recycled and used as fuel to reduce the demand for traditional energy and achieve resource conservation and sustainable utilization. At the same time, with the help of regeneration technology, the chlorine element and toxic heavy metal elements in the raw materials can be efficiently removed and collected, avoiding their damage to the environment, which is of great significance. At present, the technology for treating waste mineral oil with high chlorine and high metal content and tire pyrolysis oil to obtain recycled oil products is still imperfect, the processing steps are complicated, and the processing cost is high. Especially when the above two waste oils are processed together, due to the differences in the physical properties of the raw materials and the mutual interference of various impurity elements, the comprehensive processing is more difficult. Therefore, there is an urgent need for a method for efficiently treating and recycling the above two waste oils. Summary of the invention

[0010] In order to solve the above problems, a method for obtaining recycled oil products by comprehensively utilizing high-chlorine and high-metal waste mineral oil and tire pyrolysis oil is provided. In view of the difference in the physical and chemical properties of high-chlorine and high-metal waste mineral oil and tire pyrolysis oil, the method first performs graded pretreatment on high-chlorine and high-metal waste mineral oil and tire pyrolysis oil, and then performs hydrogenation and hydrocracking to produce recycled oil products. The technology is simple to operate, can efficiently remove chlorine and metal impurity elements in the raw materials, and then produce high-quality recycled oil products, which has good environmental significance and economic benefits.

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

[0012] (1) High-chlorine and high-metal waste mineral oil is mixed with circulating oil, sent to a heating furnace to be heated to 380-420° C., mixed with 200-2000 ppm of liquid catalyst, and then fed into a suspended bed reactor A without solid catalyst loading for reaction;

[0013] (2) mixing the effluent of the suspended bed reactor A with tire pyrolysis oil and reacting the mixture in a suspended bed reactor B without solid catalyst at a temperature of 320-360° C.;

[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 decompressed and separated to obtain gas A and liquid A; the gas effluent from the 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 decompressed 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 tower to obtain naphtha, oil A and residue;

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

[0016] (5) injecting water into the effluent of reactor C to obtain a second mixture, separating the second mixture to obtain a second oil phase, gas C and a second water phase, and the second oil phase enters a stripping stabilization tower and an atmospheric distillation tower;

[0017] (6) naphtha, light fuel oil and medium fuel oil are obtained from the atmospheric distillation tower, and the bottom oil of the atmospheric distillation tower is used as heavy fuel oil or added to a hydrocracking reactor D filled with a solid catalyst for hydrocracking reaction to obtain a hydrocracking material;

[0018] (7) The hydrocracked material is circulated to be mixed with the oil fraction A and then enters the reactor C for hydrogenation and upgrading.

[0019] The present application adopts a three-stage hydrogenation process. In the front step (2) and step (3), a low-temperature and low-pressure homogeneous hydrogenation method using a liquid catalyst in combination with a suspended bed reactor A and a suspended bed reactor B is used to perform low-cost hydrogenation and quality improvement pretreatment on high-chlorine and high-metal waste mineral oil. The middle stage is a deep fixed bed hydrogenation refining. In order to increase the yield of light oil products, a fixed bed hydrocracking reactor is added in the rear stage to perform cracking processing on heavy components.

[0020] Since the high-chlorine and high-metal waste mineral oil has more chlorine and metal content than tire pyrolysis oil, the high-chlorine and high-metal waste mineral oil in step (1) reacts first, and then reacts with the tire pyrolysis oil in a two-step manner. The above arrangement can improve the processing efficiency of the two raw material oils and improve the adaptability of the processing system to the raw materials. The circulating oil obtained in step (3) returns to the feed end and mixes with the high-chlorine and high-metal waste mineral oil, which can promote the circulating oil to heat the high-chlorine and high-metal waste mineral oil, increase the temperature of the cold feed, and shorten the subsequent heating time accordingly. The problem of aggravated coking of the material in the heater due to the long residence time is alleviated. It also dilutes the easily coked substances in the raw materials, reduces their thermal sensitivity, and improves the heatability of the feed.

[0021] In the above method, a liquid catalyst is used to perform catalytic hydrogenation pretreatment on the raw material. The liquid catalyst can be evenly dispersed in the raw oil to efficiently remove chlorine and other metal elements in waste mineral oil and tire pyrolysis oil.

[0022] Optionally, the liquid catalyst comprises a catalyst body and an auxiliary agent, and the preparation method of the catalyst body is:

[0023] S1: Mix a molybdenum source ammonia solution and potassium sulfide, react at 30-150°C for 0.5-3h to obtain a sulfur-containing molybdenum source solution, wherein the molar ratio of the sulfur content of the potassium sulfide to molybdenum is (2-6):1, then mix the sulfur-containing molybdenum source solution and a nickel source ammonia solution, react at 30-150°C for 0.5-3h, filter, wash with water, and dry to obtain a sulfur-containing nickel-molybdenum bimetallic salt complex, wherein the volume ratio of the nickel source ammonia solution to the molybdenum source ammonia solution is 1:(1-2), the molar ratio of ammonia water to the nickel source in the nickel source ammonia solution is (1-10):1, and the volume weight ratio of ammonia water to the molybdenum source in the molybdenum source ammonia solution is (1-2):1, in units of ml / g;

[0024] S2: adding the sulfur-containing nickel-molybdenum bimetallic salt complex to oleic acid, reacting at 50-200° C. for 0.5-5 h to obtain an intermediate product A, wherein the molar ratio of oleic acid to molybdenum is (2-6):1, and then dissolving the intermediate product A in aniline and straight-run gasoline in turn and stirring to obtain a 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 a chelating agent, an organic acid, a carboxylate, 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 water to molybdenum source in the above-mentioned molybdenum source ammonia water solution refers to the ratio of the volume of ammonia water to the weight of the 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, the 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 a catalyst body, the molar ratio of aniline to molybdenum is 0.5:1, and the weight ratio of straight-run gasoline to the precursor solution is 5:1.

[0029] The liquid catalyst of the present application is composed of a catalyst body and an auxiliary agent. The catalyst body is a single catalyst composed of bimetallic materials. First, it can synergistically catalyze the raw materials, improve the catalytic hydrogenation activity of the raw materials and inhibit coke formation. Second, it can also be quickly dispersed in the raw oil, and can be decomposed into active metal molybdenum sulfide modified with nano-nickel sulfide without adding potassium sulfide, thereby improving the processing efficiency of the raw oil. However, due to the high metal content in the high-chlorine and high-metal waste mineral oil and tire pyrolysis oil of the present application, the sulfur element in the liquid catalyst is easy to combine with the metal element to form a metal sulfur precipitate, thereby causing the loss of active sites of the liquid catalyst and reducing the catalytic activity. Therefore, the present application adopts an auxiliary agent containing a chelating agent, which can chelate with the metal in the raw material to achieve the removal of the metal element and ensure the normal operation of the liquid catalyst.

[0030] The auxiliary agent is formulated with organic acid, carboxylate, 1,2,4-triazole and chelating agent, which can improve the chelating effect of the chelating agent on the metal, and further improve the removal efficiency and final removal amount of the chelating agent on the metal.

[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] At present, researchers have also developed many demetallizing chelating agents that can remove crude oil, vegetable oil or recycled oil. For example, patent CN112322340A has developed a deironifying agent, which is compounded with organic acid, carboxylate, Schiff base and chelating agent, and can remove iron from crude oil. However, when it is used in the present application, it is found that the chelating agent in the deironifying agent is not effective under 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 the present application is very low, and the removal rate of other metals is even lower. Therefore, the present application prepares a new type of chelating agent, which can be combined with 1,2,4-triazole to specifically remove iron, chromium, copper, lead and vanadium metals from the two raw materials of the present application, thereby ensuring the effective catalysis of the liquid catalyst.

[0034] Optionally, the preparation method of the chelating agent is:

[0035] S10: dissolving 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane and methyl allyl alcohol polyoxyethylene ether in a solvent, adding an initiator and reacting at 70-80° C. for 4-6 hours to obtain a solution containing intermediate A;

[0036] S20: adding sulfamic acid and Lewis acid to the solution containing intermediate A, reacting at 120-125° C. for 4-5 hours, then cooling to 100° C., adding ethanolamine for neutralization to obtain a solution containing intermediate B;

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

[0038] S40: washing, purifying and drying the crude product to obtain the chelating agent.

[0039] In the preparation step S10 of the chelating agent, 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane and methyl allyl alcohol polyoxyethylene ether are polymerized as the first main body of the chelating agent, and in the step S20, the aminosulfonic acid is used to sulfonate the hydroxyl group of the methyl allyl alcohol polyoxyethylene ether to introduce sulfonic acid and amino groups, which can improve the complexing effect on metals when combined with 1,2,4-triazole. In the step S30, polystyrene is used as the second main body of the chelating agent, and its benzene ring can undergo Friedel-Crafts alkylation reaction with the vinyl in the first main body to obtain a chelating agent. The introduction of the polystyrene can improve the temperature and salt resistance of the chelating agent, so that the metal can be removed under high temperature and high salt conditions. At the same time, the cyclotrisiloxane structure contained in the chelating agent structure can improve the dispersibility of the chelating agent in the raw material. The structure of the first body and the second body can make micropores exist in the chelating agent for storing the metal adsorbed by the chelating agent itself and the metal adsorbed by the carboxylate and 1,2,4-triazole coordination, so as to prevent the metal from escaping into the system again at high temperature. The structure of the above-mentioned chelating agent can also realize the removal of only the metals such as iron, chromium, copper, lead and vanadium in the raw material, without removing the nickel and molybdenum in the liquid catalyst, so as to ensure the continuous catalytic hydrogenation of the raw material.

[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 molecular weight of the polystyrene is 150,000-200,000.

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

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

[0047] The amount of Lewis acid used in step S20 accounts for 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.

[0050] Optionally, the Lewis acid is any one or more of 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 and high-metal waste mineral oil is 500-2000ppm, and the metal content in the high-chlorine and high-metal waste mineral oil is 1000-10000ppm.

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

[0055] Optionally, the pressures in the reactor A, the reactor B, the reactor C and the reactor D are all 1-6 MPa, preferably 2-5 MPa.

[0056] The above-mentioned reactors are all low-pressure, and the reaction conditions of this low pressure are relatively mild, which helps to extend the service life of hydrogenation and liquid catalysts; low-pressure operating conditions also help the products to be more concentrated in naphtha, light fuel oil and medium fuel oil components; at the same time, low-pressure conditions are not demanding on the reaction device, which can reduce equipment investment costs and operating costs and improve economic benefits.

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

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

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

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

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

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

[0063] 1. The method of the present application can realize the simultaneous treatment of tire pyrolysis oil and high-chlorine and high-metal waste mineral oil, and convert the chlorine element in the raw material into hydrogen chloride, and the metal element is removed by complexation, thereby reducing its impact on subsequent reactions and improving the quality of the final product.

[0064] 2. The method of the present application can achieve the treatment of tire pyrolysis oil and high-chlorine and high-metal waste mineral oil and the hydrogenation and quality improvement of oil products under low-pressure conditions, which can greatly reduce the investment cost of the device and improve the safety of process operation. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

[0066] Figure 1 This is a schematic diagram of the structure of the system involved in Example 1 of the present application that uses comprehensive utilization of high-chlorine and high-metal waste mineral oil and tire pyrolysis oil to obtain recycled oil products.

[0067] List of parts and reference numerals:

[0068] 1. Buffer tank for high-chlorine and high-metal waste mineral oil; 2. Pressure pump for high-chlorine and high-metal waste mineral oil; 3. Heating furnace; 4. Liquid catalyst storage tank; 5. Liquid catalyst filling pump; 6. Reactor A; 7. Tire pyrolysis oil buffer tank; 8. Tire pyrolysis oil pressure 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. Washing water storage tank; 18. Washing water filling pump; 19. Vacuum distillation tower; 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 stabilization tower; 26. Atmospheric distillation tower; 27. Reactor D. DETAILED DESCRIPTION

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

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

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

[0072] Example 1

[0073] refer to Figure 1 The present embodiment relates to a system for obtaining recycled oil products by comprehensively utilizing high-chlorine and high-metal waste mineral oil and tire pyrolysis oil, comprising: a high-chlorine and high-metal waste mineral oil feeding group, which includes a high-chlorine and high-metal waste mineral oil buffer tank 1, a high-chlorine and high-metal waste mineral oil pressure pump 2 and a heating furnace 3; a liquid catalyst feeding group, which includes a liquid catalyst storage tank 4 and a liquid catalyst filling pump 5; a suspended bed reactor A6; a tire pyrolysis oil feeding group, a tire pyrolysis oil buffer tank 7, a tire pyrolysis oil pressure pump 8; a suspended bed reactor B9; a first hydroprocessing group, which includes a first hydrogenation gas phase cooling The invention relates to a hydrogenation reactor 10, a first hydrogenation cold high-pressure separator 11, a first hydrogenation cold low-pressure separator 12, a first hydrogenation circulating pump 13, a first hydrogenation hot low-pressure separator 14, and a circulating hydrogen compressor 15; a fresh hydrogen compressor 16; a water injection group, which includes a washing water storage tank 17 and a washing water filling pump 18; a vacuum distillation tower 19, an oil residue separator 20, and a reactor C21; a second hydrotreatment group, which includes a second hydrogenation cooler 22, a second hydrogenation cold high-pressure separator 23, and a second hydrogenation cold low-pressure separator 24; a stripping stabilization tower 25, an atmospheric distillation tower 26, and a reactor D27.

[0074] The system operates in the following steps:

[0075] (1) The high-chlorine and high-metal waste mineral oil is injected from the high-chlorine and high-metal waste mineral oil buffer tank 1 into the heating furnace 3 through the high-chlorine and high-metal waste mineral oil filling pump 2 to mix with the circulating oil, and then enters the reactor A6. The liquid catalyst in the liquid catalyst storage tank 4 is injected into the reactor A6 through the liquid catalyst filling pump 5 to mix with the high-chlorine and high-metal waste mineral oil, and hydrogenation is performed in the suspended bed reactor A6;

[0076] (2) The effluent of the suspended bed reactor A6 flows into the reactor B9, and the tire pyrolysis oil in the tire pyrolysis oil buffer tank 7 is pumped into the suspended bed reactor B9 through the tire pyrolysis oil booster pump 8 to mix with the effluent of the suspended bed reactor A6 to achieve hydrogenation again;

[0077] (3) A portion of the liquid effluent from the suspended bed reactor B9 is used as circulating oil and is mixed with high-chlorine and high-metal waste mineral oil through the first hydrogenation circulating pump 13. The remaining portion is first decompressed and then separated into gas A and liquid A through the first hot low-pressure separator 14. Gas A is discharged as waste gas. Thereafter, water is injected into the gas effluent from the reactor B9 through the washing water storage tank 17 and the washing water filling pump 18 to form a first mixture containing oil, water and gas. The first mixture passes through the first hydrogenation gas phase cooler 10 and then enters the first hydrogenation cold high-pressure separator 11 for separation to obtain 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 to enter the reactor A6. Liquid B is decompressed and separated by the first hydrogenation cold low-pressure separator 12 to obtain dissolved gas, a first oil phase and a first water phase. The dissolved gas is discharged as waste gas, and the first water phase is discharged as waste water. Liquid A and the first oil phase are mixed and passed through a vacuum distillation tower 19 to obtain naphtha, oil fraction A and residue. The residue is passed through an oil-residue separator 20 to obtain residual oil and oil residue. The oil residue is discharged for treatment, and the residual oil is returned to the high-chlorine and high-metal waste mineral buffer tank 1 to be mixed with the high-chlorine and high-metal waste mineral oil or treated as residual oil.

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

[0079] (5) Water is injected into the outflow of the reactor C21 through the washing water storage tank 17 and the washing water filling pump 18 to obtain a second mixture, and the second mixture is sequentially 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 to enter the 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. The gas C is discharged as waste gas, and the second water phase is discharged as waste water. The second oil phase enters the stripping stabilization tower 25 and the atmospheric distillation tower 26, and the gas flowing out of the stripping stabilization tower 25 is discharged as waste gas;

[0080] (6) The outflow of the atmospheric distillation tower 26 obtains naphtha, light fuel oil and medium fuel oil. The bottom oil of the atmospheric distillation tower 26 can be used as heavy fuel oil, or added to a hydrocracking reactor D27 filled with a solid catalyst to perform a hydrocracking reaction to obtain a hydrocracking material;

[0081] (7) The hydrocracked material is mixed with the oil fraction A and then enters the reactor C21 for hydrogenation and upgrading.

[0082] This system can process high-chlorine and high-metal waste mineral oil and tire pyrolysis oil in one step to produce high-quality recycled oil products such as naphtha, light fuel oil, medium fuel oil and heavy fuel oil, which has good environmental significance and economic benefits.

[0083] Example 2

[0084] This embodiment relates to a method for obtaining a regenerated oil product by comprehensively utilizing high-chlorine and high-metal waste mineral oil and tire pyrolysis oil. The method is performed using the system and the operation mode of the system in Embodiment 1, and comprises the following steps:

[0085] (1) High-chlorine and high-metal waste mineral oil (chlorine content of 1500-2000 ppm, metal content of 8000-10000 ppm) is mixed with circulating oil, sent to a heating furnace to be heated to 380-420° C., mixed with 200-2000 ppm of liquid catalyst, and then enters a suspended bed reactor A without solid catalyst loading for reaction;

[0086] (2) mixing the effluent of the suspended bed reactor A with tire pyrolysis oil (chlorine content of 200-300 ppm, metal content of 400-500 ppm), and reacting the mixture in a suspended bed reactor B without solid catalyst loading at a temperature of 320-360° C.;

[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 decompressed and separated to obtain gas A and liquid A. The gas effluent from the reactor B is injected with water to form a first mixture, and the first mixture is separated to obtain gas B and liquid B. The liquid B is decompressed 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 tower to obtain naphtha, oil A and residue.

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

[0089] (5) injecting water into the effluent of reactor C to obtain a second mixture, separating the second mixture to obtain a second oil phase, gas C and a second water phase, and the second oil phase enters a stripping stabilization tower and an atmospheric distillation tower;

[0090] (6) Naphtha, light fuel oil and medium fuel oil are obtained from the atmospheric distillation tower, and the bottom oil is added to a hydrocracking reactor D filled with a solid catalyst for hydrocracking reaction to obtain a hydrocracking material;

[0091] (7) The hydrocracked material is circulated to be mixed with the oil fraction A and then enters the reactor C for hydrogenation and upgrading.

[0092] According to the above steps, the same batch of high-chlorine and high-metal waste mineral oil and the same batch of tire pyrolysis oil were treated, and different parameter conditions were set according to the numbers in Table 1 and Table 2, where "-" in Table 1 and Table 2 represents the same as method 3#:

[0093] The liquid catalyst used in step (1) of method 1# in Table 1 includes a catalyst body and an auxiliary agent, and the preparation method of the catalyst body is:

[0094] S1: Mixing an aqueous molybdenum trioxide solution with an ammonia solution of potassium sulfide and reacting them at 150°C for 0.5h to obtain a sulfur-containing molybdenum source solution, wherein the molar ratio of the sulfur content of potassium sulfide to molybdenum is 2:1. Then, mixing the sulfur-containing molybdenum source solution with an ammonia solution of nickel nitrate, reacting them at 150°C for 0.5h, filtering, washing, and drying to obtain a sulfur-containing nickel-molybdenum bimetallic salt complex, wherein the volume ratio of the ammonia solution of nickel nitrate to the ammonia solution of molybdenum trioxide is 1:1, the molar ratio of ammonia water to nickel nitrate in the ammonia solution of nickel nitrate is 1:1, and the volume weight ratio of ammonia water to molybdenum trioxide in the ammonia solution of molybdenum trioxide is 2:1, in units of ml / g;

[0095] S2: adding a sulfur-containing nickel-molybdenum bimetallic salt complex to oleic acid, reacting at 200°C for 0.5h to obtain an intermediate product A, wherein the molar ratio of oleic acid to molybdenum is 2:1, then dissolving the intermediate product A in aniline to obtain a precursor solution, dissolving the precursor solution in straight-run gasoline and stirring evenly to obtain a catalyst body, wherein the molar ratio of aniline to molybdenum is 0.5:1, and the weight ratio of straight-run gasoline to the precursor solution is 5:1;

[0096] The weight of the auxiliary agent is 80% of the weight of the catalyst main body, and the auxiliary agent 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:

[0098] S10: dissolving 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 (the volume ratio of tetrahydrofuran, water and ethanol is 3:1:1), adding azobisisobutyronitrile and reacting at 80° C. for 4 hours to obtain a solution containing intermediate A, wherein the amount of azobisisobutyronitrile accounts for 0.5wt% of the amount of methyl allyl alcohol polyoxyethylene ether;

[0099] S20: adding aminosulfonic acid and BF3 to the solution containing intermediate A, wherein the molar ratio of aminosulfonic acid to methyl allyl alcohol polyoxyethylene ether is 0.8:1, and the amount of BF3 accounts for 1wt% of the amount of aminosulfonic acid; reacting at 125°C for 4h, then cooling to 100°C, adding ethanolamine for neutralization to obtain a solution containing intermediate B, and the pH after neutralization with ethanolamine is 6;

[0100] S30: adding a chloroform solution of polystyrene and BF3 to a solution containing intermediate B, wherein 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, and the amount of BF3 is 2wt% of the polystyrene, and reacting at 80°C to obtain a crude product;

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

[0102] The liquid catalyst used in step (1) of method 2# and method 3# comprises a catalyst body and an auxiliary agent, and the preparation method of the catalyst body is:

[0103] S1: Mix an ammonium metamolybdate ammonia aqueous solution with potassium sulfide and react at 30°C for 3 hours to obtain a sulfur-containing molybdenum source solution, wherein the molar ratio of the sulfur content of potassium sulfide to molybdenum is 6:1. Then, mix the sulfur-containing molybdenum source solution with an nickel acetate ammonia aqueous solution, react at 30°C for 3 hours, filter, wash with water, and dry to obtain a sulfur-containing nickel-molybdenum bimetallic salt complex, wherein the volume ratio of the nickel acetate ammonia aqueous solution to the ammonium metamolybdate ammonia aqueous solution is 1:2, the molar ratio of ammonia water to nickel acetate in the nickel acetate ammonia aqueous solution is 10:1, and the volume weight ratio of ammonia water to ammonium metamolybdate in the ammonium metamolybdate ammonia aqueous solution is 1:1, in units of ml / g;

[0104] S2: adding a sulfur-containing nickel-molybdenum bimetallic salt complex to oleic acid, reacting at 50°C for 5 hours to obtain an intermediate product A, wherein the molar ratio of oleic acid to molybdenum is 6:1, then dissolving the intermediate product A in aniline to obtain a precursor solution, dissolving the precursor solution in straight-run gasoline and stirring evenly to obtain a catalyst body, wherein the molar ratio of aniline to molybdenum is 0.5:1, and the weight ratio of straight-run gasoline to the precursor solution is 5:1;

[0105] The weight of the auxiliary agent is 200% of the weight of the catalyst main body, and the auxiliary agent consists of a chelating agent, hydroxyacetic 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:

[0107] S10: dissolving 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 (the volume ratio of tetrahydrofuran, water and ethanol is 3:1:1), adding azobisisobutyronitrile and reacting at 70°C for 6h to obtain a solution containing intermediate A, wherein the amount of azobisisobutyronitrile accounts for 2wt% of the amount of methyl allyl alcohol polyoxyethylene ether;

[0108] S20: adding aminosulfonic acid and BF3 to the solution containing intermediate A, wherein the molar ratio of aminosulfonic acid to methyl allyl alcohol polyoxyethylene ether is 1.2:1, and the amount of BF3 accounts for 2wt% of the amount of aminosulfonic acid; reacting at 120°C for 5h, then cooling to 100°C, adding ethanolamine for neutralization to obtain a solution containing intermediate B, and the pH after neutralization with ethanolamine is 8;

[0109] S30: adding a chloroform solution of polystyrene and BF3 to a solution containing intermediate B, wherein 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, and the amount of BF3 is 5wt% of the polystyrene, and reacting at 100° C. to obtain a crude product;

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

[0111] Table 1

[0112]

[0113]

[0114] Note: The “-” in the table means the same as method 3#

[0115] Table 2

[0116]

[0117] Note: The “-” in the table means the same as method 3#

[0118] Test Example 1

[0119] The acid value of naphtha, light fuel oil, medium fuel oil and heavy fuel oil prepared by the above method of Example 2 was measured 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 a regenerated oil product by comprehensively utilizing high-chlorine and high-metal waste mineral oil and tire pyrolysis oil. The method has the same steps as the method 3# in Example 2, with the following specific differences:

[0127] Method 11#

[0128] The difference between this method and method 3# is that p-aminodiphenylimine is used in the catalyst auxiliary agent to replace 1,2,4-triazole, and the rest is the same as method 3#.

[0129] Method 12#

[0130] The difference between this method and method 3# is that the catalyst auxiliary agent 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, and the rest is the same as method 3#.

[0131] Method 13#

[0132] The difference between this method and method 3# is that step S30 is not performed in the preparation of the chelating agent, and step S20 obtains a solution containing intermediate B, which is 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 the preparation of the chelating agent, the molar ratio of 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane to methyl allyl alcohol polyoxyethylene ether in step S10 is 3:1, and the rest is the same as method 3#.

[0135] Method 15#

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

[0137] Method 16#

[0138] The difference between this method and method 3# is that in the preparation of the chelating agent, the molar ratio of polystyrene to 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane in step S30 is 1:1000, and 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 of Example 3 were measured 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] According to the above-mentioned Examples 2 and 3, it can be seen that the method of the present application can process high-chlorine and high-metal waste mineral oil and tire pyrolysis oil to obtain regenerated oil products. Since the high-chlorine and high-metal waste mineral oil and tire pyrolysis oil in the raw materials treated in Examples 2 and 3 have high chlorine and metal elements, when the same method is used to treat tire pyrolysis oil with a chlorine content of 20-200ppm and a metal content of 50-400ppm and waste mineral oil with a chlorine content of 500-1500ppm and a metal content of 1000-8000ppm, the yield of each product obtained is further higher than that of Method 3#, and the residual sulfur element, chlorine element, metal element content and acid value in each oil product are further lower than those of Method 3#.

[0147] The above is only the embodiment of the present application, and the protection scope of the present application is not limited by these specific embodiments, but is determined by the claims of the present application. For those skilled in the art, the present application can have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the technical ideas and principles of the present application should be included in the protection scope of the present application.

Claims

1. A method for obtaining recycled oil products by comprehensive utilization of high-chlorine and high-metal waste mineral oil and tire pyrolysis oil, characterized in that: The steps include: (1) High-chlorine and high-metal waste mineral oil is mixed with circulating oil, sent to a heating furnace to be heated to 380-420° C., mixed with 200-2000 ppm of liquid catalyst, and then fed into a suspended bed reactor A without solid catalyst loading for reaction; (2) The effluent from the suspended bed reactor A is mixed with tire pyrolysis oil and then introduced into a suspended bed reactor B without solid catalyst loading at a temperature of 320-360° C. 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 decompressed and separated to obtain gas A and liquid A; the gas effluent from the 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 decompressed 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 tower to obtain naphtha, oil A and residue; (4) sending the oil fraction A to a reactor C containing a solid catalyst for hydrogenation and upgrading; (5) injecting water into the effluent of reactor C to obtain a second mixture, separating the second mixture to obtain a second oil phase, gas C and a second water phase, and the second oil phase enters a stripping stabilization tower and an atmospheric distillation tower; (6) naphtha, light fuel oil and medium fuel oil are obtained from the atmospheric distillation tower, and the bottom oil of the atmospheric distillation tower is used as heavy fuel oil or added to a hydrocracking reactor D filled with a solid catalyst for hydrocracking reaction to obtain a hydrocracking material; (7) The hydrocracked material is circulated to be mixed with the oil fraction A and then enters the reactor C for hydrogenation and upgrading.

2. The method according to claim 1, characterized in that The liquid catalyst comprises a catalyst body and an auxiliary agent, and the preparation method of the catalyst body is: S1: Mix a molybdenum source ammonia solution and potassium sulfide, react at 30-150°C for 0.5-3h to obtain a sulfur-containing molybdenum source solution, wherein the molar ratio of the sulfur content of the potassium sulfide to molybdenum is (2-6):1, then mix the sulfur-containing molybdenum source solution and a nickel source ammonia solution, react at 30-150°C for 0.5-3h, filter, wash with water, and dry to obtain a sulfur-containing nickel-molybdenum bimetallic salt complex, wherein the volume ratio of the nickel source ammonia solution to the molybdenum source ammonia solution is 1:(1-2), the molar ratio of ammonia water to the nickel source in the nickel source ammonia solution is (1-10):1, and the volume weight ratio of ammonia water to the molybdenum source in the molybdenum source ammonia solution is (1-2):1, in units of ml / g; S2: adding the sulfur-containing nickel-molybdenum bimetallic salt complex to oleic acid, reacting at 50-200° C. for 0.5-5 h to obtain an intermediate product A, wherein the molar ratio of oleic acid to molybdenum is (2-6):1, and then dissolving the intermediate product A in aniline and straight-run gasoline in turn and stirring to obtain a catalyst body; The weight of the auxiliary agent is 80-200% of the weight of the catalyst body, and the auxiliary agent is selected from a chelating agent, an organic acid, a carboxylate, and 1,2,4-triazole in a weight ratio of 1:(0.1-0.2):(0.1-0.2):(0.1-0.2).

3. The method according to claim 2, characterized in that The preparation method of the chelating agent is: S10: dissolving 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane and methyl allyl alcohol polyoxyethylene ether in a solvent, adding an initiator and reacting at 70-80° C. for 4-6 hours to obtain a solution containing intermediate A; S20: adding sulfamic acid and Lewis acid to the solution containing intermediate A, reacting at 120-125° C. for 4-5 hours, then cooling to 100° C., adding ethanolamine for neutralization to obtain a solution containing intermediate B; S30: adding a polystyrene solution and a Lewis acid to the solution containing the intermediate B, and reacting at 80-100° C. to obtain a crude product; S40: washing, purifying and drying the crude product to obtain the chelating agent.

4. The method according to claim 3, characterized in that 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; 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).

5. The method according to claim 3, characterized in that: The amount of the initiator used accounts for 0.5-2wt% of the amount of methyl allyl alcohol polyoxyethylene ether used; The amount of Lewis acid used in step S20 accounts for 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.

6. 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.

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

8. The method according to claim 1, characterized in that The pressures in the reactor A, the reactor B, the reactor C and the reactor D are all 1-6 MPa, preferably 2-5 MPa.

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

10. The method according to claim 1, characterized in that The weight ratio of the high-chlorine and 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 and high-metal waste mineral oil is 1:(1-10).

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