Process and system for hydroprocessing of spent lubricating oil

Abstract

The present disclosure relates to a method and system for waste lubricating oil hydrogenation regeneration, the method comprising: S1, contacting waste lubricating oil, carbon carrier catalyst and promoter in a slurry bed for hydrogenation pretreatment to obtain a hydrogenation mixture; S2, fractionating the hydrogenation mixture to obtain gas, distillate oil and residue; S3, performing solid-liquid separation on the residue to obtain waste agent and heavy lubricating oil; S4, contacting the distillate oil and the heavy lubricating oil with hydrogenation catalysts respectively in a high-pressure fixed-bed hydrogenation device for high-pressure hydrogenation reaction. The method of the present disclosure can effectively remove metal and non-metallic heteroatoms in waste oil, prolong the operation cycle of the device, and improve the color number and stability of the regenerated lubricating oil product.

Description

Technical Field

[0001] This disclosure relates to a method and system for the hydrogenation regeneration of waste lubricating oil. Background Technology

[0002] Waste lubricating oil refers to the oil that is removed from various machines and equipment during use due to oxidation, thermal decomposition, and contamination by impurities, resulting in its physicochemical properties reaching the required replacement levels. Waste lubricating oil contains carcinogens such as polycyclic aromatic hydrocarbons and heavy metals, classifying it as "special hazardous waste." Untreated discharge of such oil can cause serious pollution. However, since the total impurities are less than 10%, the remainder can be recycled. The price difference between the purchased waste lubricating oil and the recycled oil is several times, representing a significant profit margin and a promising market prospect, attracting widespread attention.

[0003] Existing waste lubricating oil regeneration technologies suffer from problems such as short equipment operating cycles, low product yield, poor base oil color, difficulty in recovering bright oil components, insufficient product flexibility, and low catalyst utilization. Summary of the Invention

[0004] The purpose of this disclosure is to provide a method and system for the hydrogenation regeneration of waste lubricating oil. This method can effectively remove metal and non-metal heteroatoms from waste oil and extend the operating cycle of the device, improve the color and stability of the regenerated lubricating oil products, and regenerate a variety of high-quality lubricating oil base oils and bright oil products.

[0005] To achieve the above objectives, the first aspect of this disclosure provides a method for hydrogenating and regenerating waste lubricating oil, the method comprising:

[0006] S1. Waste lubricating oil, carbon-supported catalyst and accelerator are contacted in a slurry bed for hydrogenation pretreatment to obtain a hydrogenated mixture;

[0007] S2. Fractionate the hydrogenated mixture to obtain gas, distillate oil and residue;

[0008] S3. The residue is subjected to solid-liquid separation to obtain waste agent and heavy lubricating oil.

[0009] S4. In the high-pressure fixed-bed hydrogenation unit, the distillate oil and the heavy lubricating oil are respectively brought into contact with the hydrogenation catalyst to carry out high-pressure hydrogenation reaction.

[0010] Optionally, in step S1, the conditions for the hydrogen pretreatment include: a reaction temperature of 300-480℃; a reaction pressure of 2-25 MPa; and a liquid hourly space velocity of 0.2-4 h⁻¹. -1 The volume ratio of hydrogen to the waste lubricating oil is 100-3000 Nm³. 3 / m.

[0011] Optionally, in step S1, the carbon-supported catalyst comprises a carbon-based support and an active metal component; based on the total weight of the carbon-supported catalyst and calculated by metal element, the content of the active metal component is 1-50% by weight.

[0012] The carbon-based carrier comprises carbon-containing materials with a carbon content greater than 80% by weight; the metal elements in the active metal component include one or more of Fe, Co, Mo, W and Ni.

[0013] Optionally, in step S1, the amount of the carbon-supported catalyst, calculated as metal element, relative to 1g of the waste lubricating oil is 20-10000μg, preferably 50-5000μg, and more preferably 100-3000μg.

[0014] Optionally, in step S1, the accelerator contains a sulfur-containing substance; preferably, the sulfur-containing substance is selected from one or more of carbon disulfide, sulfur, dimethyl disulfide and di-tert-butyl polysulfide.

[0015] The amount of the accelerator is 10-20000 μg relative to 1g of the waste lubricating oil, preferably 50-6000 μg.

[0016] Optionally, in step S2, the fractionation conditions include: a pressure of -90 kPa to -99 kPa, a bottom temperature of 320-370°C, and a cutting point between the distillate oil and the residue of 520-540°C.

[0017] Optionally, in step S4, along the flow direction of the distillate oil or the heavy lubricating oil, the hydrogenation catalyst includes a hydrogenation protection catalyst and a hydrogenation treatment catalyst;

[0018] Based on the total volume of the hydrogenation catalyst and by volume, the amount of the hydrogenation protection catalyst is 10-50%, and the amount of the hydrogenation treatment catalyst is 50-90%.

[0019] Optionally, in step S3, along the flow direction of the distillate oil and the heavy lubricating oil, the hydrotreating agent includes catalyst A, catalyst B and catalyst C arranged sequentially; by volume and based on the total volume of the hydrotreating agent, the content of catalyst A is 5-20%, the content of catalyst B is 10-50%, and the content of catalyst C is 30-85%.

[0020] The catalyst A contains a first hydrogenation active metal and a first support; the first hydrogenation active metal includes a Group VIB metal and optionally a Group VIII metal, the first support is selected from alumina and / or silica, the first support contains phosphorus, and the phosphorus content, based on the total weight of the first support and calculated as P2O5, is 0.1-8.0% by weight; based on the total weight of the catalyst A and calculated as oxides, the content of the Group VIB metal is greater than 0 and less than 10% by weight, and the content of the Group VIII metal is 0.2-5% by weight.

[0021] The catalyst B contains a second hydrogenation active metal and a second support; the second hydrogenation active metal includes a Group VIB metal and optionally a Group VB metal, the second support is selected from alumina and / or silicon oxide, the second support contains phosphorus and halogens, and based on the total weight of the second support, the phosphorus content is 0.1-8.0% by weight (P2O5) and the halogen content is 0.1-6% by weight (elemental); based on the total weight of the catalyst B and calculated as oxides, the content of the Group VIB metal is greater than 0.2% and less than 12% by weight, and the content of the Group VB metal is 0-12% by weight.

[0022] The catalyst C contains a third hydrogenation active metal and a third support; the third hydrogenation active metal includes Group VIB metals and optionally Group VIII metals; the third support is selected from alumina and / or silicon oxide; the third support contains phosphorus and halogens; based on the total weight of the third support, the phosphorus content (calculated as P2O5) is 0.1-8.0% by weight, and the halogen content (calculated as an element) is 0.1-6% by weight; based on the total weight of the catalyst C and calculated as oxides, the content of the Group VIB metal is 0.2-10% by weight, and the content of the Group VIII metal is less than 5% by weight.

[0023] Preferably, the volume ratio of catalyst A, catalyst B and catalyst C is 1:(1-10):(1.5-17), more preferably 1:(2-5):(3-15);

[0024] Along the flow direction of the distillate oil or the heavy lubricating oil, the hydrotreating catalyst sequentially includes catalyst I and catalyst II;

[0025] The catalyst I comprises a hydrogenation catalyst Ia, which contains a first promoter, a fourth hydrogenation active metal component, and a fourth support; the first promoter comprises one or more of fluorine, boron, and phosphorus; the metal element in the fourth hydrogenation active metal component comprises one or more of Co, Mo, Ni, and W; the fourth support is selected from alumina and / or silicon oxide; based on the dry weight of the hydrogenation catalyst Ia, the content of the fourth hydrogenation active metal component, calculated as metal oxide, is 22-32% by weight, and the content of the first promoter is 3-10% by weight;

[0026] Preferably, the catalyst I further includes a hydrogenation catalyst Ib disposed upstream of the hydrogenation catalyst Ia; the hydrogenation catalyst Ib contains a fifth hydrogenation active metal component and a fifth support, and the content of the fifth hydrogenation active metal component, calculated as metal oxide, is 3-8% by weight based on the dry weight of the hydrogenation catalyst Ib; the fifth hydrogenation active metal component is selected from one or more of Co, Mo, Ni and W; the fifth support is selected from alumina and / or silicon oxide;

[0027] More preferably, the weight content of the fifth hydrogenation active metal component of the hydrogenation catalyst Ib is 10-30% of the weight content of the fourth hydrogenation active metal component of the hydrogenation catalyst Ia, preferably 12-25%; preferably, the volume ratio of the hydrogenation catalyst Ia to the hydrogenation catalyst Ib is (10-50):10.

[0028] The catalyst II contains a second promoter, a sixth hydrogenation active metal component, and a sixth support. The second promoter includes boron and / or phosphorus. The content of the sixth hydrogenation active metal component, based on the dry weight of the catalyst II and calculated as metal oxide, is 22-36% by weight. The sixth hydrogenation active metal component is selected from one or more of Co, Mo, Ni, and W. The sixth support is selected from alumina. The catalyst II is a fluorine-free hydrogenation catalyst, and the content of the second promoter is 2-8% by weight.

[0029] The content of the sixth hydrogenation active metal component of catalyst II is greater than or equal to the total content of the fourth and fifth hydrogenation active metal components of catalyst I.

[0030] Preferably, the volume ratio of catalyst I to catalyst II is (30:70)-(60:40).

[0031] Optionally, in step S4, the conditions for the high-pressure hydrogenation reaction of the distillate oil in contact with the hydroprotective catalyst and the conditions for the high-pressure hydrogenation reaction of the heavy lubricating oil in contact with the hydroprotective catalyst each independently include: a hydrogen partial pressure of 3-20 MPa and a hydrogen-to-oil volume ratio of 200-3000 Nm³. 3 / m 3 The reaction temperature is 260-380℃, and the volume hourly space velocity is 0.2-5h. -1 ;

[0032] Preferably, the hydrogen partial pressure is 5-12 MPa, and the hydrogen-to-oil volume ratio is 300-1800 Nm. 3 / m 3 The reaction temperature is 280-360℃, and the volume hourly space velocity is 0.3-3h. -1 .

[0033] Optionally, in step S3, the conditions for the high-pressure hydrogenation reaction of the distillate oil in contact with the hydrotreating catalyst and the conditions for the high-pressure hydrogenation reaction of the heavy lubricating oil in contact with the hydrotreating catalyst each independently include: a hydrogen partial pressure of 3-25 MPa and a hydrogen-to-oil volume ratio of 200-3000 Nm³. 3 / m 3 The reaction temperature of catalyst I is 260-420℃, and the volume hourly space velocity is 0.2-3h. -1 The reaction temperature of catalyst II is 240-380℃, and the volume hourly space velocity is 0.2-3h. -1 ;

[0034] Preferably, the hydrogen partial pressure is 5-20 MPa, and the hydrogen-to-oil volume ratio is 300-1800 Nm. 3 / m 3 The reaction temperature of catalyst I is 280-360℃, and the volume hourly space velocity is 0.3-2h. -1 The reaction temperature of catalyst II is 260-340℃, and the volume hourly space velocity is 0.3-2h. -1 .

[0035] Optionally, step S1 includes: introducing preheated waste lubricating oil, carbon-supported catalyst and preheated accelerator into the slurry bed respectively, and performing the hydrogen pretreatment in contact with each other in the slurry bed;

[0036] Preferably, the waste lubricating oil is subjected to a first heat exchange with the hydrogenated mixture, and then subjected to a second heat exchange with superheated hydrogen to obtain the preheated waste lubricating oil.

[0037] Preferably, the temperature of the preheated waste lubricating oil is 200-400℃, and the temperature of the preheated accelerator is 20-80℃.

[0038] Optionally, step S1 includes: contacting the waste lubricating oil, the carbon-supported catalyst, the promoter, and optionally the adsorbent in a slurry bed for hydrogenation pretreatment to obtain a hydrogenated mixture;

[0039] Preferably, the adsorbent is selected from one or more of calcium carbonate, calcium oxide, calcium hydroxide, activated carbon, and kaolin.

[0040] Optionally, step S1 includes: subjecting the waste lubricating oil, the carbon-supported catalyst, and the accelerator to hydrogen pretreatment by contacting them in a slurry bed in the presence of superheated steam and / or water.

[0041] The second aspect of this disclosure provides a system for the hydrogenation regeneration of waste lubricating oil using the method provided in the first aspect of this disclosure. The system includes: a slurry bed, a fractionation tower, a solid-liquid separation device, and a high-pressure fixed-bed hydrogenation device; the product outlet of the slurry bed is fluidly connected to the inlet of the fractionation tower, the residue outlet of the fractionation tower is fluidly connected to the inlet of the solid-liquid separation device, the liquid phase product outlet of the solid-liquid separation device is fluidly connected to the inlet of the high-pressure fixed-bed hydrogenation device, and the distillate oil outlet of the fractionation tower is fluidly connected to the inlet of the high-pressure fixed-bed hydrogenation device.

[0042] Optionally, along the flow direction of the material to be processed, the high-pressure fixed-bed hydrogenation device includes a hydrogenation protection reaction zone and a hydrogenation treatment reaction zone.

[0043] The advantages of this disclosure through the above technical solution are as follows:

[0044] (1) This disclosure uses slurry bed hydrotreating to pretreat the entire fraction of waste lubricating oil, which can effectively remove metal and non-metal heteroatoms from the waste oil and saturate some polycyclic aromatic hydrocarbons, reducing the severity of subsequent processing and extending the operating cycle of the subsequent fixed bed unit. At the same time, the use of carbon-supported catalyst can effectively reduce catalyst costs while ensuring the recovery and impurity removal requirements of the pretreatment liquid.

[0045] (2) The present invention separates the distillate oil and heavy lubricating oil from the hydrogenation mixture and sends them to the downstream high-pressure fixed bed hydrogenation unit for high-pressure hydrogenation treatment. This can reduce the bottom temperature of the subsequent product fractionation tower, prevent the generation of unstable substances at high temperature, improve the color and stability of the product, and regenerate a variety of high-quality lubricating base oils and bright oil products.

[0046] Other features and advantages of this disclosure will be described in detail in the following detailed description section. Attached Figure Description

[0047] The accompanying drawings are provided to further illustrate the present disclosure and form part of the specification. They are used together with the following detailed description to explain the present disclosure, but do not constitute a limitation thereof. In the drawings:

[0048] Figure 1 This is a flowchart illustrating a specific embodiment of the waste lubricating oil hydrogenation regeneration method disclosed herein. Detailed Implementation

[0049] The following provides a detailed description of specific embodiments of this disclosure. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit this disclosure.

[0050] A first aspect of this disclosure provides a method for the hydroregeneration of waste lubricating oil, the method comprising:

[0051] S1. Waste lubricating oil, carbon-supported catalyst and accelerator are contacted in a slurry bed for hydrogenation pretreatment to obtain a hydrogenated mixture;

[0052] S2. Fractionate the hydrogenated mixture to obtain gas, distillate oil and residue;

[0053] S3. The residue is subjected to solid-liquid separation to obtain waste agent and heavy lubricating oil;

[0054] S4. In the high-pressure fixed-bed hydrogenation unit, the distillate oil and the heavy lubricating oil are respectively brought into contact with the hydrogenation catalyst to carry out a high-pressure hydrogenation reaction.

[0055] The method disclosed herein employs slurry-bed hydrotreating to pretreat the entire fraction of waste lubricating oil, effectively removing metal and non-metal heteroatoms from the waste oil and saturating some polycyclic aromatic hydrocarbons, thus reducing the severity of subsequent processing and extending the operating cycle of the subsequent fixed-bed unit. Simultaneously, the use of a carbon-supported catalyst effectively reduces catalyst costs while ensuring the recovery and impurity removal requirements of the pretreatment liquid. The hydrotreating mixture is separated into distillate oil and heavy lubricating oil, which are then fed into a downstream high-pressure fixed-bed hydrotreating unit for high-pressure hydrotreating. This reduces the bottom temperature of the product distillation column, prevents the formation of unstable substances at high temperatures, improves the product color and stability, and, after regeneration, yields various grades of high-quality lubricating oil base oils and bright oils.

[0056] In one specific embodiment of this disclosure, the conditions for the hydrogen pretreatment in step S1 include: a reaction temperature of 300-480℃; a reaction pressure of 2-25 MPa; and a liquid hourly space velocity of 0.2-4 h⁻¹. -1 The volume ratio of hydrogen to the waste lubricating oil (i.e., the hydrogen-to-oil volume ratio) is 100-3000 Nm³. 3 / m 3 Preferably, the reaction temperature is 350-450℃, the reaction pressure is 3-20MPa, and the liquid hourly space velocity is 0.25-3h. -1 The volume ratio of hydrogen to the waste lubricating oil is 200-3000 Nm³.3 / m 3 In this disclosure, by controlling the reaction conditions of hydrogen pretreatment and using a carbon-supported catalyst, the conversion rate of the lubricating oil base oil fraction (280-520℃) in waste lubricating oil can be kept below 15%, and the yield of the lubricating oil base oil fraction obtained from the regeneration process is high.

[0057] In one specific embodiment of this disclosure, in step S1, the carbon-supported catalyst comprises a carbon-based support and an active metal component; based on the total weight of the carbon-supported catalyst and calculated by metal element, the content of the active metal component is 1-50% by weight, preferably 5-40% by weight, more preferably 20-40% by weight; the carbon-based support comprises carbon-containing materials with a carbon content greater than 80% by weight, and the carbon-based support may include, but is not limited to, carbon black, activated carbon, coal powder, deoiled asphalt, etc.; the metal element in the active metal component includes one or more of Fe, Co, Mo, W and Ni, and preferably, the active metal component includes metal oxides.

[0058] According to this disclosure, the accelerator contains sulfur-containing substances well known to those skilled in the art, such as carbon disulfide, sulfur, dimethyl disulfide (DMDS), di-tert-butyl polysulfide, etc. In one specific embodiment, the amount of the accelerator relative to 1g of the waste lubricating oil is 10-20000μg, preferably 50-6000μg.

[0059] In one specific embodiment of this disclosure, in step S1, the amount of the carbon-supported catalyst, calculated as metal element, is 20-10000 μg, preferably 50-5000 μg, and more preferably 100-3000 μg, relative to 1g of the waste lubricating oil.

[0060] In one specific embodiment of this disclosure, the fractionation conditions in step S2 include: a pressure of -90 kPa to -99 kPa, a bottom temperature of 320-370°C, and a cutoff point between the distillate oil and the residue of 520-540°C. In one embodiment, the distillation range of the distillate oil is 300-540°C, preferably 320-520°C. In this embodiment, the total metal content of the distillate oil obtained by fractionation is not greater than 20 μg / g, and the content of n-heptane insolubles is not greater than 150 μg / g.

[0061] According to this disclosure, in step S3, the solid-liquid separation can be performed using methods well known to those skilled in the art, such as one or more combinations of filtration separation, centrifugal separation, membrane separation, and solvent extraction separation. In one specific embodiment of this disclosure, the solid-liquid separation is performed using solvent extraction separation, where the residue is contacted with an extractant for solvent extraction separation; the conditions for solvent extraction separation include: a temperature of 40-300°C; a pressure of 0.1-14 MPa; and the amount of extractant used relative to 1 part by weight of residue is 1-10 parts by weight, preferably 1-5 parts by weight. The extractant can be anything well known to those skilled in the art, such as at least one of C3-C8 alkanes, C3-C8 olefins, toluene, and light naphtha, preferably selected from C3-C5 alkanes and / or toluene.

[0062] In one specific embodiment of this disclosure, in step S4, along the flow direction of the distillate oil or the heavy lubricating oil, the hydrogenation catalyst includes a hydrogenation protection catalyst and a hydrogenation treatment catalyst; based on the total volume of the hydrogenation catalyst and by volume, the amount of the hydrogenation protection catalyst is 10-50%, and the amount of the hydrogenation treatment catalyst is 50-90%.

[0063] According to this disclosure, a variety of catalyst gradations are used in the high-pressure fixed-bed hydrogenation unit. In one specific embodiment of this disclosure, in step S4, along the flow direction of the distillate oil or the heavy lubricating oil, the hydrogenation protection catalyst sequentially includes catalyst A, catalyst B, and catalyst C; by volume and based on the total volume of the hydrogenation protection catalyst, the content of catalyst A is 5-20%, the content of catalyst B is 10-50%, and the content of catalyst C is 30-85%.

[0064] The catalyst A contains a first hydrogenation active metal and a first support; the first hydrogenation active metal includes a Group VIB metal and optionally a Group VIII metal, the first support is selected from alumina and / or silicon oxide, the first support contains phosphorus, and the phosphorus content, calculated as P2O5, is 0.1-8.0% by weight based on the total weight of the first support; based on the total weight of the catalyst A and calculated as oxides, the content of the Group VIB metal is greater than 0 and less than 10% by weight, preferably 0.5-8% by weight, and the content of the Group VII metal is 0.2-5% by weight, preferably 0.3-4% by weight;

[0065] The catalyst B contains a second hydrogenation active metal and a second support; the second hydrogenation active metal includes a Group VIB metal and optionally a Group VB metal, the second support is selected from alumina and / or silicon oxide, the second support contains phosphorus and halogens, and based on the total weight of the second support, the phosphorus content, calculated as P2O5, is 0.1-8.0% by weight, preferably 0.2-5% by weight, and the halogen content, calculated as an element, is 0.1-6% by weight, preferably 0.2-5% by weight; based on the total weight of the catalyst B and calculated as oxides, the content of the Group VIB metal is greater than 0.2% and less than 12% by weight, and the content of the Group VB metal is 0-12% by weight;

[0066] The catalyst C contains a third hydrogenation active metal and a third support; the third hydrogenation active metal includes Group VIB metals and optionally Group VIII metals; the third support is selected from alumina and / or silicon oxide; the third support contains phosphorus and halogen elements; based on the total weight of the third support, the phosphorus content, calculated as P2O5, is 0.1-8.0% by weight, preferably 0.2-5% by weight; the halogen content, calculated as an element, is 0.1-6% by weight, preferably 0.2-5% by weight; based on the total weight of the catalyst C and calculated as oxides, the content of the Group VIB metal is 0.2-10% by weight, and the content of the Group VIII metal is less than 5% by weight.

[0067] In a preferred embodiment of this disclosure, the volume ratio of catalyst A, catalyst B and catalyst C is 1:(1-10):(1.5-17), preferably 1:(2-5):(3-15).

[0068] In one specific embodiment of this disclosure, along the flow direction of the distillate oil or the heavy lubricating oil, the hydrotreating catalyst sequentially comprises catalyst I and catalyst II; catalyst I comprises hydrotreating catalyst Ia, which contains a first promoter, a fourth hydrotreating active metal component, and a fourth support; the first promoter comprises one or more of fluorine, boron, and phosphorus; the metal element in the fourth hydrotreating active metal component comprises one or more of Co, Mo, Ni, and W; the fourth support is selected from alumina and / or silicon oxide; based on the dry weight of the hydrotreating catalyst Ia, the content of the fourth hydrotreating active metal component, calculated as metal oxide, is 22-32% by weight, and the content of the first promoter is 3-10% by weight;

[0069] Preferably, the catalyst I further includes a hydrogenation catalyst Ib disposed upstream of the hydrogenation catalyst Ia; the hydrogenation catalyst Ib contains a fifth hydrogenation active metal component and a fifth support, and the content of the fifth hydrogenation active metal component, calculated as metal oxide, is 3-8% by weight based on the dry weight of the hydrogenation catalyst Ib; the fifth hydrogenation active metal component is selected from one or more of Co, Mo, Ni and W; the fifth support is selected from alumina and / or silicon oxide;

[0070] More preferably, the weight content of the fifth hydrogenation active metal component of the hydrogenation catalyst Ib is 10-30% of the weight content of the fourth hydrogenation active metal component of the hydrogenation catalyst Ia, preferably 12-25%; preferably, the volume ratio of the hydrogenation catalyst Ia to the hydrogenation catalyst Ib is (10-50):10.

[0071] Catalyst II contains a second promoter, a sixth hydrogenation active metal component, and a sixth support. The second promoter includes boron and / or phosphorus. Based on the dry weight of catalyst II, the content of the sixth hydrogenation active metal component, calculated as metal oxide, is 22-36% by weight. The sixth hydrogenation active metal component is selected from one or more of Co, Mo, Ni, and W. The sixth support is selected from alumina. Catalyst II is a fluorine-free hydrogenation catalyst, and the content of the second promoter is 2-8% by weight. The content of the sixth hydrogenation active metal component of catalyst II is greater than or equal to the total content of the fourth and fifth hydrogenation active metal components of hydrogenation catalyst I.

[0072] Preferably, the volume ratio of the hydrogenation catalyst I to the hydrogenation catalyst II is (30:70)-(60:40).

[0073] In one specific embodiment of this disclosure, in step S4, the conditions for the high-pressure hydrogenation reaction of the distillate oil in contact with the hydroprotective catalyst and the conditions for the high-pressure hydrogenation reaction of the heavy lubricating oil in contact with the hydroprotective catalyst each independently include: a hydrogen partial pressure of 3-20 MPa and a hydrogen-to-oil volume ratio of 200-3000 Nm. 3 / m 3 The reaction temperature is 260-380℃, and the volume hourly space velocity is 0.2-5h. -1 Preferably, the hydrogen partial pressure is 5-12 MPa, and the hydrogen-to-oil volume ratio is 300-1800 Nm. 3 / m 3 The reaction temperature is 280-360℃, and the volume hourly space velocity is 0.3-3h. -1 .

[0074] In one specific embodiment of this disclosure, in step S3, the conditions for the high-pressure hydrogenation reaction of the distillate oil in contact with the hydrotreating catalyst and the conditions for the high-pressure hydrogenation reaction of the heavy lubricating oil in contact with the hydrotreating catalyst each independently include: a hydrogen partial pressure of 3-25 MPa and a hydrogen-to-oil volume ratio of 200-3000 Nm³. 3 / m 3 The reaction temperature of catalyst I is 260-420℃, and the volume hourly space velocity is 0.2-3h. -1 The reaction temperature of catalyst II is 240-380℃, and the volume hourly space velocity is 0.2-3h. -1 Preferably, the hydrogen partial pressure is 5-20 MPa, and the hydrogen-to-oil volume ratio is 300-1800 Nm. 3 / m 3 The reaction temperature of catalyst I is 280-360℃, and the volume hourly space velocity is 0.3-2h. -1 The reaction temperature of catalyst II is 260-340℃, and the volume hourly space velocity is 0.3-2h. -1 .

[0075] In one specific embodiment of this disclosure, the method further includes step S5: introducing the reaction product obtained from the high-pressure hydrogenation reaction into a product fractionation tower for fractionation. Preferably, the distillate oil obtained in step S2 is stored in a storage tank, and / or the heavy lubricating oil obtained in step S3 is stored in a storage tank, so that the distillate oil and heavy lubricating oil are respectively fed into a high-pressure fixed-bed hydrogenation unit to contact the hydrogenation catalyst for high-pressure hydrogenation reaction. This can reduce the bottom temperature of the product fractionation tower, prevent the formation of unstable substances at high temperatures, and improve the color and stability of the product.

[0076] In one specific embodiment of this disclosure, step S1 includes: introducing preheated waste lubricating oil, carbon-supported catalyst, and preheated accelerator into the slurry bed, and performing the hydrogen pretreatment in contact within the slurry bed; preferably, after a first heat exchange with the hydrogenated mixture, the waste lubricating oil undergoes a second heat exchange with superheated hydrogen to obtain the preheated waste lubricating oil; preferably, the temperature of the preheated waste lubricating oil is 200-400℃, and the temperature of the preheated accelerator is 20-80℃. In this embodiment, energy recovery efficiency can be improved and coking problems in the heating furnace can be mitigated, which is beneficial for the continuous operation of the waste lubricating oil regeneration system.

[0077] In one specific embodiment of this disclosure, step S1 includes: contacting the waste lubricating oil, the carbon-supported catalyst, the promoter, and optionally the adsorbent in a slurry bed for hydrogenation pretreatment to obtain a hydrogenated mixture. In this embodiment, introducing the adsorbent into the slurry bed facilitates further removal of chlorine and metal atoms from the waste lubricating oil.

[0078] In this disclosure, the adsorbent may be one or more of those well known in the art, such as calcium carbonate, calcium oxide, calcium hydroxide, activated carbon, and kaolin.

[0079] In one specific embodiment of this disclosure, step S1 includes: contacting the waste lubricating oil, the carbon-supported catalyst, and the accelerator in a slurry bed for hydrogen pretreatment in the presence of superheated steam and / or water. In this embodiment, the presence of superheated steam and / or water in the slurry bed helps to slow down coking in the furnace and further remove heteroatom chlorine from the waste lubricating oil.

[0080] The second aspect of this disclosure provides a system for the hydrogenation regeneration of waste lubricating oil using the method provided in the first aspect of this disclosure. The system includes: a slurry bed, a fractionation tower, a solid-liquid separation device, and a high-pressure fixed-bed hydrogenation device; the product outlet of the slurry bed is fluidly connected to the inlet of the fractionation tower, the residue outlet of the fractionation tower is fluidly connected to the inlet of the solid-liquid separation device, the liquid phase product outlet of the solid-liquid separation device is fluidly connected to the inlet of the high-pressure fixed-bed hydrogenation device, and the distillate oil outlet of the fractionation tower is fluidly connected to the inlet of the high-pressure fixed-bed hydrogenation device.

[0081] In one specific embodiment of this disclosure, the high-pressure fixed-bed hydrogenation device includes a hydrogenation protection reaction zone and a hydrogenation treatment reaction zone along the flow direction of the material to be treated.

[0082] The present disclosure is further described in detail below through examples.

[0083] The properties of the waste lubricating oil regenerated in the following examples and comparative examples are shown in Table 1. Unless otherwise specified, all reagents used were commercially available.

[0084] Table 1 Properties of waste lubricating oil

[0085]

[0086]

[0087] The carbon-supported catalyst C1 in the slurry bed was prepared by the following method:

[0088] (1) Preparation of carrier: Activated carbon (carbon content of more than 95% by weight) is dried and dehydrated at 120℃ and then pulverized into powder with a particle size of 20-60μm;

[0089] (2) Using Fe2(SO4)3 to prepare an aqueous solution of ferric sulfate as the metal source solution, the Fe content in the aqueous solution of ferric sulfate is 2.4g relative to 100mL of active metal source solution; after mixing 125mL of aqueous solution of ferric sulfate with 5g of carrier evenly, 20.16g of 28wt% ammonia solution is added while stirring to carry out precipitation reaction; the precipitation reaction conditions are: reaction temperature of 60℃ and reaction time of 60min; after washing the precipitate, the precipitate reaction product is subjected to solid-liquid separation to obtain solid material;

[0090] (3) After drying the solid material at 110℃ for 300 min, it was placed in a tube furnace and calcined at 490℃ for 300 min under N2 gas protection to obtain carbon-supported catalyst C1, the properties of which are shown in Table 2.

[0091] The preparation method of carbon-supported catalyst C2 is similar to that of carbon-supported catalyst C1. The difference is that in step (3), carbon-supported catalyst C2 is obtained after drying at 110℃ for 300 min and is no longer placed in a tube furnace for calcination. Its properties are shown in Table 2.

[0092] Table 2 Properties of carbon-supported catalysts C1 and C2

[0093] Fe, weight % <![CDATA[Specific surface area, m 2 / g]]> Particle size, μm metallic phase Metal particle size, nm C1 35.40 50.3 24.5 <![CDATA[Fe3O4]]> 22.37 C2 27.75 51.7 29.3 <![CDATA[Fe(OH)3]]> 31.59

[0094] Example 1

[0095] S1. Waste lubricating oil, carbon-supported catalyst and accelerator are contacted in a slurry bed for hydrogenation pretreatment to obtain a hydrogenated mixture;

[0096] S2. Fractionate the hydrogenated mixture to obtain gas, distillate oil and residue;

[0097] S3. Separate the residue into solid and liquid components to obtain tailings and heavy lubricating oil.

[0098] S4. In the high-pressure fixed-bed hydrogenation unit, distillate oil and heavy lubricating oil are respectively contacted with the hydrogenation catalyst to carry out high-pressure hydrogenation reaction. The high-pressure hydrogenation reaction product of distillate oil is introduced into the product fractionation tower for separation to obtain 150N lubricating oil base oil; the high-pressure hydrogenation reaction product of heavy lubricating oil is introduced into the product fractionation tower for separation to obtain 120BS bright oil.

[0099] The reaction conditions, product results, and product property analysis results for the above steps are shown in Table 5.

[0100] Along the flow direction of the distillate oil, the hydroprotection catalyst includes catalyst A, catalyst B and catalyst C arranged in sequence, and the composition of the catalyst is shown in Table 3.

[0101] Catalyst A contains 3.0 wt% MoO3, 0.5 wt% NiO and the balance support, wherein the content of P2O5 in the support accounts for 3.5 wt% of the support.

[0102] The alumina was prepared as follows: 2 L of aluminum sulfate solution with an Al2O3 concentration of 90 g / L was prepared, and 6 mL of concentrated phosphoric acid was added to obtain a phosphorus-containing aluminum sulfate solution. The phosphorus-containing aluminum sulfate solution and an 8% ammonia solution were added concurrently to a 5 L reaction vessel to allow precipitation. The precipitate was then filtered (XRD characterization showed the hydrated alumina precipitate to be amorphous). The reaction temperature was 45 °C, and the flow rate of the ammonia solution was controlled to maintain the pH of the reaction system at 6.0. In a 5-liter reaction vessel, filter cake, deionized water, and ammonium bicarbonate were mixed and slurried. The amount of ammonia added was adjusted to a pH of 9.2. The slurry was aged at 40°C for 240 minutes and then filtered. The filter cake was washed twice with deionized water and dried at 120°C for 14 hours to obtain hydrated alumina P1. XRD characterization showed that P2 had a boehmite-like structure. P1 was calcined at 600°C for 4 hours to obtain alumina A1. XRD characterization showed that A1 had a γ-alumina structure. 1000 grams of the prepared hydrated alumina P1 was weighed and added to 1440 ml of an aqueous solution containing 10 ml of nitric acid (a product of Tianjin Chemical Reagent Factory No. 3). The mixture was extruded on a twin-screw extruder to form a product with an outer diameter of... The butterfly-shaped strips were dried at 120°C for 4 hours to obtain a molded product. The molded product was then calcined at 600°C for 3 hours to obtain support Z1. 200 g of support Z1 was impregnated with 220 mL of a mixed solution of ammonium heptamolybdate and nickel nitrate with a MoO3 content of 28.8 g / L and a NiO5 content of g / L for 1 hour, dried at 120°C for 4 hours, and calcined at 400°C for 3 hours to obtain hydrogenation protection catalyst A.

[0103] Catalyst B contains 8.0 wt% MoO3, 1.6 wt% V2O5, and the balance support. Based on the dry weight of the support, the phosphorus content (P2O5) is 4.9 wt%, and the F content (fluorine) is 1.0 wt%.

[0104] The preparation method is as follows: 2 L of aluminum sulfate solution with an Al2O3 concentration of 50 g / L was prepared, and 5 mL of concentrated phosphoric acid (85% by weight, the same below) was added to obtain a phosphorus-containing aluminum sulfate solution. The above aluminum sulfate solution and an 8% ammonia solution were added concurrently to a 5 L reaction vessel for precipitation. The mixture was then filtered (XRD characterization showed the hydrated alumina precipitate to be amorphous). The reaction temperature was 40 °C, and the flow rate of the ammonia solution was controlled to maintain the pH of the reaction system at 5.5. In another 5 L reaction vessel, filter cake, deionized water, and ammonia were mixed and slurried. The amount of ammonia used was adjusted to maintain the pH of the slurry at 8.0. The slurry was aged at 65 °C for 60 minutes and then filtered. The filter cake was then treated with deionized water... The alumina was slurryed and washed twice with water, and the filter cake was dried at 120℃ for 24 hours to obtain hydrated alumina P2. P2 was calcined at 600℃ for 4 hours to obtain alumina A2. XRD characterization showed that P2 had a pseudoboehmite structure, and A2 had a γ-alumina structure. 1000g of the prepared hydrated alumina P2 was weighed and added to 1440ml of an aqueous solution containing 10ml of nitric acid (from Tianjin Chemical Reagent Factory No. 3) and 9.8g of ammonium fluoride. The solution was extruded into a butterfly-shaped strip with an outer diameter of φ1.4mm on a twin-screw extruder. The wet strip was dried at 120℃ for 4 hours to obtain a molded product. This molded product was calcined at 600℃ for 3 hours to obtain support Z2. 200g of support Z2 was impregnated in 220ml of a mixed solution of ammonium heptamolybdate and ammonium vanadate containing 80g / L MoO3 and 16g / L V2O5 for 1 hour, dried at 120℃ for 4 hours, and calcined at 400℃ for 3 hours to obtain catalyst B.

[0105] Catalyst C contains 8.0 wt% WO3, 1.6 wt% NiO, and the balance support. Based on the total weight of the support, the phosphorus content (P2O5) is 1.5 wt%, and the F content (fluorine) is 1.0 wt%.

[0106] The alumina was prepared as follows: 2 L of aluminum sulfate solution with an Al2O3 concentration of 50 g / L was prepared, and 5 mL of concentrated phosphoric acid (85% by weight) was added to obtain a phosphorus-containing aluminum sulfate solution. The aluminum sulfate solution and an 8% ammonia solution were added concurrently to a 5 L reaction vessel to allow precipitation. The precipitate was then filtered (XRD characterization showed the hydrated alumina precipitate to be amorphous). The reaction temperature was 40 °C, and the flow rate of the ammonia solution was controlled to maintain the pH of the reaction system at 5.5. In a 5-liter reaction vessel, filter cake, deionized water, and ammonia were mixed and slurried. The amount of ammonia was adjusted to a pH of 8.0. The slurry was aged at 65°C for 60 minutes and then filtered. The filter cake was washed twice with deionized water and dried at 120°C for 24 hours to obtain hydrated alumina P3. P3 was calcined at 600°C for 4 hours to obtain alumina A3. XRD characterization showed that P3 had a boehmite-like structure and A3 had a γ-alumina structure. 1000g of the prepared hydrated alumina P3 was weighed and added to 1440ml of an aqueous solution containing 10ml of nitric acid (from Tianjin Chemical Reagent Factory No. 3) and 9.8g of ammonium fluoride. The solution was extruded into a butterfly-shaped strip with an outer diameter of φ1.4mm on a twin-screw extruder. The wet strip was dried at 120°C for 4 hours to obtain a molded product. This molded product was calcined at 600°C for 3 hours to obtain carrier Z3.

[0107] Take 200 g of support Z3, impregnate it for 1 hour with 220 mL of a mixed solution of ammonium heptamolybdate and nickel nitrate containing 80 g / L MoO3 and 16 g / L NiO, dry it at 120 °C for 4 hours, and calcine it at 400 °C for 3 hours to obtain heavy oil hydrogenation catalyst C.

[0108] Table 3 Composition of catalysts A, B, and C

[0109]

[0110] Along the flow direction of distillate oil or heavy lubricating oil base oil, the hydrotreating catalysts sequentially include hydrotreating catalyst Ib, hydrotreating catalyst Ia, and catalyst II. The composition of the catalysts is shown in Table 4.

[0111] The hydrogenation catalyst Ia contains 2.4 wt% NiO, 2.1 wt% MoO3, 21 wt% WO3, 0.8 wt% P2O5 and 73.7 wt% silica-alumina support.

[0112] The solution was prepared by dissolving 3127g of Al2(SO4)3·18H2O (analytical grade, [Al2(SO4)3·18H2O] content ≥99 wt%, water-insoluble matter ≤0.02 wt%, chloride (Cl) ≤0.002 wt%, iron (Fe) ≤0.003 wt%, the same below) and 845g of 98% sulfuric acid (concentration 98 wt%, analytical grade, the same below) in 4968g of deionized water to prepare solution I (pH value 0.34, Al2O3 content 85 g / L). 2070g of sodium silicate solution (analytical grade, molecular formula: Na2SiO3·9H2O, content (as Na2O): 19.3-22.8 wt%, iron ≤0.02 wt%, heavy metals (as Pb) ≤0.001 wt%, the same below) was diluted with water to prepare solution II (containing 40 g / L SiO2, pH value 13.58). Under vigorous stirring, solution II and 1.75g ​​of ferrous sulfate (analytical grade, Beijing Yili Fine Chemicals Co., Ltd., the same below) were added to solution I to prepare a transparent silicon-aluminum mixed solution III. The pH of silicon-aluminum mixed solution III was 3.1, and the SiO2 / Al2O3 mass ratio was 3.0. Dilute ammonia water (containing 5 wt% NH3) was mixed with the above silicon-aluminum solution III at a stirring speed of 3000 RPM, wherein the ammonia water was added at a rate that adjusted the pH of the mixture to within the range of 8.0 ± 0.3.

[0113] After the ammonia water was added, the resulting product was stirred at 55-60℃ for 5 hours, filtered, and the resulting filter cake was mixed with hot deionized water, slurried, and filtered. This step was repeated 4 times. The filter cake was dried at 120℃ overnight to obtain the precursor SAS-1 of the silicon-aluminum composite material carrier. Based on the weight of the added ferrous sulfate and the obtained precursor SAS-1 of the silicon-aluminum composite material carrier, the iron content in the precursor of the silicon-aluminum composite material carrier, calculated as Fe2O3, was 0.09% by weight.

[0114] 1000 grams of the precursor of the above-mentioned silicon-aluminum composite material carrier SAS-1 was extruded into strips to obtain clover-shaped strips with a diameter of 1.3 mm. The wet clover-shaped strips were then dried at 120°C for 4 hours and then calcined in a tube furnace at 600°C for 4 hours with air to obtain catalyst carrier strips.

[0115] 3.12 g of concentrated phosphoric acid (85% by weight, analytical grade, Beijing Chemical Plant, hereinafter the same) and 40 mL of deionized water were heated to 75 °C, then mixed with 2.76 g of basic nickel carbonate (industrial grade, from Changling Catalyst Plant, hereinafter the same) and 5.73 g of molybdenum trioxide (industrial grade, from Changling Catalyst Plant, hereinafter the same), and the mixture was heated and stirred until dissolved. The solution was clear and transparent, and cooled to room temperature to obtain solution I. 62.96 g of ammonium metatungstate (industrial grade, Sichuan Zigong Hard Alloy Plant, hereinafter the same) and 20.68 g of nickel nitrate (analytical grade, Beijing Shuanghuan Chemical Reagent Plant, hereinafter the same) were added to 80 mL of deionized water and stirred until dissolved to obtain solution II. Solutions I and II were mixed at room temperature and adjusted to 160 mL with deionized water to obtain solution III. 200 g of the above support strip was impregnated with solution III for 1 hour, then removed and dried at 120 °C for 4 hours, and then calcined in air at 450 °C for 4 hours to obtain hydrogenation catalyst I.

[0116] The hydrogenation catalyst Ib uses commercially available RG-1 catalyst, produced by Changling Catalyst Factory, containing 1.0 wt% NiO, 5.5 wt% MoO3, and the remainder alumina support.

[0117] Catalyst II contains 3.2 wt% NiO, 1.1 wt% CoO, 15.1 wt% WO3, 13.6 wt% MoO3 and 5.0 wt% P2O5 and the balance alumina support.

[0118] The catalyst was prepared as follows: 200.0 g of industrial alumina support was weighed and impregnated with 168.0 mL of an aqueous solution containing 59.1 g of ammonium metatungstate, 51.9 g of ammonium paramolybdate, and 3.4 g of phosphoric acid for 1 hour. It was then dried at 120°C for 6 hours and calcined at 330°C for 6 hours to obtain catalyst intermediate Z1. Half the weight of intermediate Z1 was sulfided with H2 containing 10.0% H2S by volume at 380°C and atmospheric pressure for 5 hours to obtain catalyst intermediate Z2. Intermediate Z2 was further impregnated with 53.0 mL of an aqueous solution containing 10.8 g of basic nickel carbonate, 3.4 g of basic cobalt carbonate, and 10.1 g of phosphoric acid for 1 hour, and then dried at 100°C under nitrogen purging for 8 hours to obtain catalyst II.

[0119] Table 4 Composition of hydrogenation catalysts Ia, II, and Ib

[0120]

[0121] Examples 2-7

[0122] Waste lubricating oil was treated using the same method as in Example 1, except that the reaction conditions were different, as shown in Table 5.

[0123] Example 8

[0124] Waste lubricating oil was treated using the same method as in Example 1, except that step S1 included: after the waste lubricating oil and the hydrogenated mixture underwent a first heat exchange, it underwent a second heat exchange with superheated hydrogen to obtain preheated waste lubricating oil at a temperature of 370°C.

[0125] Preheated waste lubricating oil, carbon-supported catalyst, and accelerator at 40°C are introduced into a slurry bed and subjected to hydrogen pretreatment in the presence of superheated steam.

[0126] Comparative Example 1

[0127] Waste lubricating oil was processed using a conventional vacuum fractionation-hydrorefining process. The properties of the base oil intermediates obtained from vacuum fractionation are shown in Table 6. The yield of the base oil intermediates after vacuum fractionation was 82%. After hydrorefining, the yield of the base oil was approximately 96%. Specific process parameters are shown in Table 7.

[0128] Table 5

[0129]

[0130]

[0131]

[0132] In the table, catalyst dosage (μg / g) refers to the amount of carbon-supported catalyst, calculated as metal element, relative to 1g of the waste lubricating oil. Accelerator dosage (μg / g) refers to the amount of accelerator relative to 1g of the waste lubricating oil.

[0133] Catalyst I includes hydrogenation catalyst Ia and hydrogenation catalyst Ib. The reaction conditions for hydrogenation catalyst Ia and hydrogenation catalyst Ib are the same, as shown in the table for catalyst I.

[0134] Table 6

[0135] nature Chlorine content, mg / kg 70 Sulfur content, mg / kg 674 Total acid value, mgKOH / g 0.24 Fe, mg / kg <1 Ni, mg / kg <1 V, mg / kg <1 Na, mg / kg <1 Ca, mg / kg <1 Si, mg / kg 61 Nitrogen content, mg / kg 245 <![CDATA[Viscosity at 40℃, mm 2 / s]]> 31.71 <![CDATA[Viscosity at 100°C, mm 2 / s]]> 5.535 <![CDATA[Density at 20°C, kg / m 3 > 854.5 Refractive index at 20℃ 1.4718 Residual char, % (w) <0.05 Total aromatics, % (w) 7.7

[0136] Table 7

[0137]

[0138]

[0139] As can be seen from the above, the method disclosed herein can effectively remove metal and non-metal heteroatoms from waste oil and extend the operating cycle of the device, improve the color and stability of the regenerated lubricating oil products, and regenerate a variety of high-quality lubricating oil base oils and bright oil products.

[0140] The preferred embodiments of this disclosure have been described in detail above. However, this disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this disclosure, various simple modifications can be made to the technical solutions of this disclosure, and these simple modifications all fall within the protection scope of this disclosure.

[0141] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, this disclosure will not describe the various possible combinations separately.

[0142] Furthermore, various different embodiments of this disclosure can be combined in any way, as long as they do not violate the spirit of this disclosure, they should also be regarded as the content disclosed in this disclosure.

Claims

1. A method for hydroregeneration of waste lubricating oil, the method comprising: S1. Waste lubricating oil, carbon-supported catalyst and accelerator are contacted in a slurry bed for hydrogenation pretreatment to obtain a hydrogenated mixture; S2. Fractionate the hydrogenated mixture to obtain gas, distillate oil and residue; S3. The residue is subjected to solid-liquid separation to obtain waste agent and heavy lubricating oil. S4. In the high-pressure fixed-bed hydrogenation unit, the distillate oil and the heavy lubricating oil are respectively brought into contact with the hydrogenation catalyst to carry out high-pressure hydrogenation reaction.

2. The method according to claim 1, wherein, In step S1, the conditions for the hydrogen pretreatment include: a reaction temperature of 300-480℃; a reaction pressure of 2-25 MPa; and a liquid hourly space velocity of 0.2-4 h⁻¹. -1 The volume ratio of hydrogen to the waste lubricating oil is 100-3000 Nm³. 3 / m.

3. The method according to claim 1, wherein, In step S1, the carbon-supported catalyst comprises a carbon-based support and an active metal component; based on the total weight of the carbon-supported catalyst and calculated by metal element, the content of the active metal component is 1-50% by weight. The carbon-based carrier comprises carbon-containing materials with a carbon content greater than 80% by weight; the metal elements in the active metal component include one or more of Fe, Co, Mo, W and Ni.

4. The method according to claim 1, wherein, In step S1, the amount of the carbon-supported catalyst, calculated as metal element, is 20-10000 μg relative to 1g of the waste lubricating oil, preferably 50-5000 μg, and more preferably 100-3000 μg.

5. The method according to claim 1, wherein, In step S1, the accelerator contains a sulfur-containing substance; preferably, the sulfur-containing substance is selected from one or more of carbon disulfide, sulfur, dimethyl disulfide and di-tert-butyl polysulfide. The amount of the accelerator is 10-20000 μg relative to 1g of the waste lubricating oil, preferably 50-6000 μg.

6. The method according to claim 1, wherein, In step S2, the fractionation conditions include: a pressure of -90 kPa to -99 kPa, a bottom temperature of 320-370°C, and a cutting point between the distillate oil and the residue of 520-540°C.

7. The method according to claim 1, wherein, In step S4, along the flow direction of the distillate oil or the heavy lubricating oil, the hydrogenation catalyst includes a hydrogenation protection catalyst and a hydrogenation treatment catalyst; Based on the total volume of the hydrogenation catalyst and by volume, the amount of the hydrogenation protection catalyst is 10-50%, and the amount of the hydrogenation treatment catalyst is 50-90%.

8. The method according to claim 7, wherein, In step S3, along the flow direction of the distillate oil and the heavy lubricating oil, the hydrotreating agent includes catalyst A, catalyst B and catalyst C arranged sequentially; by volume and based on the total volume of the hydrotreating agent, the content of catalyst A is 5-20%, the content of catalyst B is 10-50%, and the content of catalyst C is 30-85%. The catalyst A contains a first hydrogenation active metal and a first support; the first hydrogenation active metal includes a Group VIB metal and optionally a Group VIII metal, the first support is selected from alumina and / or silica, the first support contains phosphorus, and the phosphorus content, based on the total weight of the first support and calculated as P2O5, is 0.1-8.0% by weight; based on the total weight of the catalyst A and calculated as oxides, the content of the Group VIB metal is greater than 0 and less than 10% by weight, and the content of the Group VIII metal is 0.2-5% by weight. The catalyst B contains a second hydrogenation active metal and a second support; the second hydrogenation active metal includes a Group VIB metal and optionally a Group VB metal, the second support is selected from alumina and / or silicon oxide, the second support contains phosphorus and halogens, and based on the total weight of the second support, the phosphorus content is 0.1-8.0% by weight (P2O5) and the halogen content is 0.1-6% by weight (elemental); based on the total weight of the catalyst B and calculated as oxides, the content of the Group VIB metal is greater than 0.2% and less than 12% by weight, and the content of the Group VB metal is 0-12% by weight. The catalyst C contains a third hydrogenation active metal and a third support; the third hydrogenation active metal includes Group VIB metals and optionally Group VIII metals; the third support is selected from alumina and / or silicon oxide; the third support contains phosphorus and halogens; based on the total weight of the third support, the phosphorus content (calculated as P2O5) is 0.1-8.0% by weight, and the halogen content (calculated as an element) is 0.1-6% by weight; based on the total weight of the catalyst C and calculated as oxides, the content of the Group VIB metal is 0.2-10% by weight, and the content of the Group VIII metal is less than 5% by weight. Preferably, the volume ratio of catalyst A, catalyst B and catalyst C is 1:(1-10):(1.5-17), more preferably 1:(2-5):(3-15); Along the flow direction of the distillate oil or the heavy lubricating oil, the hydrotreating catalyst sequentially includes catalyst I and catalyst II; The catalyst I comprises a hydrogenation catalyst Ia, which contains a first promoter, a fourth hydrogenation active metal component, and a fourth support; the first promoter comprises one or more of fluorine, boron, and phosphorus; the metal element in the fourth hydrogenation active metal component comprises one or more of Co, Mo, Ni, and W; the fourth support is selected from alumina and / or silicon oxide; based on the dry weight of the hydrogenation catalyst Ia, the content of the fourth hydrogenation active metal component, calculated as metal oxide, is 22-32% by weight, and the content of the first promoter is 3-10% by weight; Preferably, the catalyst I further includes a hydrogenation catalyst Ib disposed upstream of the hydrogenation catalyst Ia; the hydrogenation catalyst Ib contains a fifth hydrogenation active metal component and a fifth support, and the content of the fifth hydrogenation active metal component, calculated as metal oxide, is 3-8% by weight based on the dry basis weight of the hydrogenation catalyst Ib. The fifth hydrogenation active metal component is selected from one or more of Co, Mo, Ni and W; the fifth support is selected from alumina and / or silicon oxide; More preferably, the weight content of the fifth hydrogenation active metal component of the hydrogenation catalyst Ib is 10-30% of the weight content of the fourth hydrogenation active metal component of the hydrogenation catalyst Ia, preferably 12-25%; preferably, the volume ratio of the hydrogenation catalyst Ia to the hydrogenation catalyst Ib is (10-50):

10. The catalyst II contains a second promoter, a sixth hydrogenation active metal component, and a sixth support. The second promoter includes boron and / or phosphorus. The content of the sixth hydrogenation active metal component, based on the dry weight of the catalyst II and calculated as metal oxide, is 22-36% by weight. The sixth hydrogenation active metal component is selected from one or more of Co, Mo, Ni, and W. The sixth support is selected from alumina. The catalyst II is a fluorine-free hydrogenation catalyst, and the content of the second promoter is 2-8% by weight. The content of the sixth hydrogenation active metal component of catalyst II is greater than or equal to the total content of the fourth and fifth hydrogenation active metal components of catalyst I. Preferably, the volume ratio of catalyst I to catalyst II is (30:70)-(60:40).

9. The method according to claim 7, wherein, In step S4, the conditions for the high-pressure hydrogenation reaction of the distillate oil in contact with the hydroprotected catalyst and the conditions for the high-pressure hydrogenation reaction of the heavy lubricating oil in contact with the hydroprotected catalyst each independently include: a hydrogen partial pressure of 3-20 MPa and a hydrogen-to-oil volume ratio of 200-3000 Nm³. 3 / m 3 The reaction temperature is 260-380℃, and the volume hourly space velocity is 0.2-5h. -1 ; Preferably, the hydrogen partial pressure is 5-12 MPa, and the hydrogen-to-oil volume ratio is 300-1800 Nm. 3 / m 3 The reaction temperature is 280-360℃, and the volume hourly space velocity is 0.3-3h. -1 .

10. The method according to claim 8, wherein, In step S3, the conditions for the high-pressure hydrogenation reaction of the distillate oil and the hydrotreating catalyst, and the conditions for the high-pressure hydrogenation reaction of the heavy lubricating oil and the hydrotreating catalyst, each independently include: a hydrogen partial pressure of 3-25 MPa and a hydrogen-to-oil volume ratio of 200-3000 Nm³. 3 / m 3 The reaction temperature of catalyst I is 260-420℃, and the volume hourly space velocity is 0.2-3h. -1 The reaction temperature of catalyst II is 240-380℃, and the volume hourly space velocity is 0.2-3h. -1 ; Preferably, the hydrogen partial pressure is 5-20 MPa, and the hydrogen-to-oil volume ratio is 300-1800 Nm. 3 / m 3 The reaction temperature of catalyst I is 280-360℃, and the volume hourly space velocity is 0.3-2h. -1 The reaction temperature of catalyst II is 260-340℃, and the volume hourly space velocity is 0.3-2h. -1 .

11. The method according to claim 1, wherein, Step S1 includes: introducing preheated waste lubricating oil, carbon-supported catalyst and preheated accelerator into the slurry bed respectively, and performing the hydrogen pretreatment in contact with each other in the slurry bed; Preferably, the waste lubricating oil is subjected to a first heat exchange with the hydrogenated mixture, and then subjected to a second heat exchange with superheated hydrogen to obtain the preheated waste lubricating oil. Preferably, the temperature of the preheated waste lubricating oil is 200-400℃, and the temperature of the preheated accelerator is 20-80℃.

12. The method according to claim 1, wherein, Step S1 includes: contacting the waste lubricating oil, the carbon-supported catalyst, the promoter, and optionally the adsorbent in a slurry bed for hydrogenation pretreatment to obtain a hydrogenated mixture; Preferably, the adsorbent is selected from one or more of calcium carbonate, calcium oxide, calcium hydroxide, activated carbon, and kaolin.

13. The method according to claim 1, wherein, Step S1 includes: contacting the waste lubricating oil, the carbon-supported catalyst, and the accelerator in a slurry bed for hydrogen pretreatment in the presence of superheated steam and / or water.

14. A system for hydrogenating and regenerating waste lubricating oil using any one of claims 1-13, the system comprising: Slurry bed, fractionation tower, solid-liquid separation unit and high-pressure fixed bed hydrogenation unit; The product outlet of the slurry bed is fluidly connected to the inlet of the fractionation tower, the residue outlet of the fractionation tower is fluidly connected to the inlet of the solid-liquid separation device, the liquid phase product outlet of the solid-liquid separation device is fluidly connected to the inlet of the high-pressure fixed-bed hydrogenation device, and the distillate oil outlet of the fractionation tower is fluidly connected to the inlet of the high-pressure fixed-bed hydrogenation device.

15. The system according to claim 14, wherein, Along the flow direction of the material to be processed, the high-pressure fixed-bed hydrogenation device includes a hydrogenation protection reaction zone and a hydrogenation treatment reaction zone.

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