Regeneration method and application of waste lubricating oil

Abstract

The invention provides a regeneration method of waste lubricating oil. The regeneration method comprises the following steps: (1) pretreatment: carrying out physical adsorption pretreatment on the waste lubricating oil through an adsorbent; the pretreated waste lubricating oil is subjected to hydrofining in the presence of a catalyst, in the catalyst, the content of NiO or Co2O3 ranges from 5 wt% to 10 wt%, the content of MoO3 or WO3 ranges from 20 wt% to 28 wt%, the content of P2O5 ranges from 5 wt% to 8 wt%, the content of Al2O3 ranges from 54 wt% to 70 wt%, the pore diameter of the catalyst ranges from 12 nm to 18 nm, the pore volume ranges from 0.5 cm < 3 > / g to 0.8 cm < 3 > / g, and the specific surface area ranges from 100 m < 2 > / g to 203 m < 2 > / g; (3) dehydration and light hydrocarbon removal: carrying out dehydration and light hydrocarbon removal treatment on the hydrofined waste lubricating oil; and (4) fine filtration: performing fine filtration on the dehydrated and light hydrocarbon-removed waste lubricating oil. According to the regeneration method of the waste lubricating oil, a chemical hydrofining method instead of a physical method is adopted, and residual additives and solubilizers which cannot be removed by a traditional adsorption method are completely removed, so that waste oil regeneration can be realized by supplementing the additives and the solubilizers.

Description

Technical Field

[0001] The invention relates to the field of chemical waste lubricating oil regeneration, and in particular to a waste lubricating oil regeneration method and application. Background Art

[0002] As one of the main forms of renewable energy power generation, wind power generation has continued to increase its installed capacity in recent years. As of June 30, 2022, the total installed capacity of wind power connected to the grid in China exceeded 342 million kilowatts. As the core equipment of wind power generation, wind turbines are composed of rotor blades, shafts, gearboxes and generators. Wind power lubricants, especially main gear oils, as the "blood" of wind turbines, play a vital role in reducing the friction of rotating parts and ensuring the normal operation of the units. It is estimated that the current global consumption of wind turbine gear oil is between 20,000 and 40,000 tons, half of which comes from China. Considering the development trend of my country's energy transformation, the demand for domestic wind turbine lubricants will continue to grow rapidly in the future. Therefore, a large amount of waste wind turbine gear oil is generated in China every year. If it can be recycled, it will greatly reduce the emission of hazardous waste from wind power companies and save a large amount of operation and maintenance investment. Compared with waste automotive oil, although waste fan oil has a lower degree of deterioration, it has a large viscosity, a heavy distillation range, and there are differences in deteriorated components and additives. Therefore, the regeneration process applicable to automotive waste oil is not applicable to waste fan oil.

[0003] Document 1 (CN201910610947.7) discloses a wind turbine gear lubricant on-site regeneration system and method, which includes vacuum dehydration, regeneration, filtration, heating, automatic additive replenishment, oil quality online monitoring, cleaning and filling, magnetic filtration, circulating oil pump and oil suction valve. An on-site wind power gear oil quality online monitoring system is set up, and during the regeneration process, the oil quality index of the regenerated gear oil can be monitored online in real time to ensure that the oil quality after regeneration meets the requirements. Document 2 (CN201410040915.5) discloses a process for regenerating base oil from waste lubricating oil, which mainly involves filtering the hot waste oil after sedimentation, centrifugation-evaporation treatment through a three-stage ceramic membrane with membrane pores of 1-3 microns, 0.1-1 microns and less than 0.1 microns in turn, and then performing thin film evaporation at not less than 200°C, and performing three-stage molecular distillation on the evaporated residue to collect base oils of different viscosities. Document 3 (CN202111170469.6), the No. 320 wind power waste lubricating oil regeneration treatment process, realizes the recovery and regeneration of waste oil and treatment materials by adopting strong magnetic precipitation, comprehensive filtration, silica sand decolorization, silica sand recovery and other processes. The treatment process takes into account the environment while also reducing the overall treatment cost.

[0004] The existing regeneration scheme for fan oil is mainly based on physical methods, especially physical adsorption, filtration or a combination of the two. The problem is that the treatment effect is limited and the solubilizer and residual additive components in the waste oil cannot be completely removed. On the one hand, these substances make the subsequent quantitative addition of new additives and solubilizers difficult and uncontrollable. In addition, these residual components will conflict with the newly added additives and solubilizers, affecting the use of the regenerated oil. Therefore, the quality of the regenerated oil is not high and the life is not long. Therefore, there is an urgent need for a method for producing fan gear lubricating oil that can produce products with indicators and performance close to new oil. Summary of the invention

[0005] In view of the deficiencies in the prior art, the present invention provides a method for regenerating waste lubricating oil. The method adopts chemical hydrogenation refining rather than physical method, and can completely remove residual additives and solubilizers that cannot be removed by traditional adsorption methods, so that waste oil regeneration can be achieved by supplementing additives and solubilizers.

[0006] To achieve the above purpose, the present invention adopts the following technical solutions:

[0007] A first aspect of the present invention provides a method for regenerating waste lubricating oil, comprising the following steps:

[0008] (1) Pretreatment: The waste lubricating oil is pretreated by physical adsorption through an adsorbent;

[0009] (2) Hydrofining: The pretreated waste lubricating oil is subjected to hydrofining in the presence of a catalyst, wherein the content of NiO or Co2O3 is 5-10wt%, the content of MoO3 or WO3 is 20-28wt%, the content of P2O5 is 5-8wt%, the content of Al2O3 is 54-70wt%, and the pore diameter of the catalyst is 12-18nm and the pore volume is 0.5-0.8cm 3 / g, specific surface area is 100-203m 2 / g;

[0010] (3) Dehydration and removal of light hydrocarbons: Dehydration and removal of light hydrocarbons from the waste lubricating oil after hydrofining;

[0011] (4) Fine filtration: The waste lubricating oil that has been dehydrated and de-lightened is finely filtered.

[0012] The regeneration method provided by the present invention mainly adopts chemical hydrogenation refining rather than physical method, which can achieve complete decontamination and decolorization of waste fan oil to obtain nearly pure polyalphaolefin base oil. It can also completely remove residual additives and solubilizers that cannot be removed by traditional adsorption methods, so that waste oil regeneration can be achieved by supplementing additives and solubilizers.

[0013] In some preferred embodiments, the adsorbent is selected from activated clay, silica gel or activated carbon, the adsorption temperature is 80-180°C, the time is 0.5-10 hours, and the mass ratio of the waste lubricating oil to the adsorbent is 5-50:1, preferably 25-50:1. Pretreatment is performed before the hydrofining process, and pretreatment is performed by physical adsorption, which can preliminarily remove mechanical impurities and some degraded components and non-ideal components such as residual additives, thereby reducing the processing pressure of the subsequent refining stage.

[0014] In some preferred embodiments, the hydrofining is carried out using a fixed bed hydrogenation device, and the fixed bed hydrogenation device at least includes a protective agent bed filled with a protective agent and a catalyst bed filled with the catalyst; preferably, the hydrofining temperature is 280-380°C, the pressure is 8-20MPa, and the mass space velocity is 0.1-3.0h -1 , hydrogen-oil volume ratio (i.e., hydrogen to waste lubricating oil volume ratio) 500:1-1000:1. Chemical hydrogenation refining can achieve complete decontamination and decolorization of waste fan oil to obtain purer polyalphaolefin base oil. And completely remove residual additives and solubilizers, so that waste oil regeneration can be achieved by supplementing additives and solubilizers, preventing residual additives and solubilizers from interfering with the subsequent regeneration process, thereby further affecting the properties of the regenerated oil.

[0015] In some preferred embodiments, the protective agent is selected from a demetallized / degelatinized asphaltene protective agent, and the mass ratio of the protective agent to the hydrotreating catalyst is 0.1:1-10:1, preferably 0.2:1-1:1, and more preferably 0.2:1-0.5:1.

[0016] In some preferred embodiments, the preparation process of the catalyst comprises the following steps:

[0017] (1) mixing macroporous pseudo-boehmite, a nickel or cobalt oxide precursor, a molybdenum or tungsten oxide precursor, and a phosphorus oxide precursor to obtain a primary mixture;

[0018] (2) adding the alcohol solution of the pore-enlarging agent to the primary mixture and continuing to mix to obtain a mixture;

[0019] (3) adding an alkaline peptizing agent and water to the mixed material, maintaining the pH value at 9-12, to obtain a mixed material;

[0020] (4) kneading the mixed material into a plastic body, extruding strips, and obtaining a molding material;

[0021] (5) drying and calcining the molding material to obtain the catalyst;

[0022] The pore size of the macroporous pseudo-boehmite is ≥10nm; the pore volume is ≥1.0cm3 / g.

[0023] The present invention adopts macroporous pseudo-boehmite, a pore-enlarging agent and an alkaline peptizing agent, maintains the pH value at 9-12, and obtains a mixed material; the mixed material is subjected to processes such as kneading, extrusion, drying, and roasting to prepare a hydrorefining catalyst with a large pore size and a large pore volume. This is beneficial to improving the mass transfer efficiency of the lubricating oil hydrorefining regeneration process, increasing the reaction space velocity, and reducing the operating cost.

[0024] In some preferred embodiments, the pore-enlarging agent is polyethylene glycol 3000, polyethylene glycol 4000, polyethylene glycol 6000 or polyethylene glycol 8000; the amount of the pore-enlarging agent added is 8-20wt% of the macroporous pseudo-boehmite; and / or

[0025] Preferably, the alcohol solution of the pore expanding agent is a C1-C4 saturated monohydric fatty alcohol solution of the pore expanding agent, more preferably an ethanol solution of the pore expanding agent; and / or

[0026] Preferably, the alkaline peptizing agent is ammonia water, triethylamine or ethylenediamine; more preferably, the amount of the alkaline peptizing agent added is 2-20wt% of the mixed material; more preferably, the peptization reaction time of the mixed material is 0.5-1.0h; and / or

[0027] Preferably, the macroporous pseudo-boehmite has a pore size of 10-12 nm and a pore volume of 1.0-1.2 cm 3 / g, specific surface area is 350-400m 2 / g; and / or

[0028] Preferably, the oxide precursor of nickel is basic nickel carbonate or nickel hydroxide; the oxide precursor of cobalt is basic cobalt carbonate or cobalt hydroxide; the oxide precursor of molybdenum is ammonium heptamolybdate or ammonium tetramolybdate; the oxide precursor of tungsten is ammonium tungstate or ammonium metatungstate; and the oxide precursor of phosphorus is diammonium phosphate.

[0029] The present application adds macroporous pseudo-boehmite, a pore-enlarging agent and an alkaline peptizing agent, maintains the pH at 9-12, makes the peptization reaction mild and easy to control, and can effectively maintain the large pore size of the macroporous pseudo-boehmite, thereby obtaining a hydrorefining catalyst with a large pore size and a large pore volume. Compared with other hydrorefining catalysts used in the petrochemical field, the hydrogenation catalyst prepared by using macroporous pseudo-boehmite, a metal oxide precursor, a polyethylene glycol pore-enlarging agent and an alkaline peptizing agent has a larger pore size, which is beneficial to reduce the mass transfer resistance of macromolecular wind turbine gear lubricating oil in the catalyst, improve production efficiency, and reduce the cost of lubricating oil regeneration.

[0030] The regeneration method provided by the present invention performs a dehydration and light hydrocarbon removal treatment after the hydrofining step, which can remove the water and light hydrocarbons generated in the hydrofining process, so that the regenerated lubricating oil meets the use requirements. This is particularly suitable for lubricating oils containing a large amount of solubilizing agents (the main component is oxygen-containing polyesters or ethers), such as lubricating oils used in the wind power field. The solubilizing agent will generate a large amount of water and light hydrocarbons during the hydrofining process. If there is no dehydration and light hydrocarbon removal step or the dehydration and light hydrocarbon removal step is before the hydrofining process, the large amount of water and light hydrocarbons generated cannot be removed, which can easily cause the water content and viscosity of the regenerated lubricating oil to be unqualified.

[0031] In some preferred embodiments, the dehydration and removal of light hydrocarbons are carried out by thin film evaporation, atmospheric distillation or reduced pressure distillation; preferably, the dehydration and removal of light hydrocarbons are carried out by reduced pressure distillation; the temperature of the dehydration and removal of light hydrocarbons is 100-300°C, the vacuum degree is 0.1-800Torr, and the time is 0.5-12h; preferably, the temperature of the dehydration and removal of light hydrocarbons is 150-250°C, the vacuum degree is 1-100Torr, and the time is 1-6h.

[0032] The waste lubricating oil that has been dehydrated and light hydrocarbons removed is finely filtered, and the fine filtration adopts a membrane filtration method, preferably a hydrophobic membrane filtration, to further remove water and mechanical impurities and other substances in the waste lubricating oil. The method is simple to operate and easy to implement.

[0033] In some preferred embodiments, the fine filtration is performed by membrane filtration, preferably hydrophobic membrane filtration, with a membrane pore size of 100-3000 nm.

[0034] The waste lubricating oil that has been finely filtered needs to undergo a replenishing process, which is to add additives and solubilizers to the fan lubricating oil. The additives can be a single agent or a compound agent.

[0035] In some preferred embodiments, the regeneration method further comprises supplementing additives and solubilizers to the finely filtered waste lubricating oil; wherein the additives are selected from one or more of extreme pressure agents, friction modifiers, antioxidants, antifoaming agents, antiemulsifiers, rust inhibitors, dispersants, and metal deactivators; the solubilizer is selected from polyester or polyether solubilizers; the additive is added in an amount of 1-3% of the total mass of the finely filtered waste lubricating oil; the solubilizer is added in an amount of 2-15% of the total mass of the finely filtered waste lubricating oil.

[0036] In some preferred embodiments, in order to produce products with various indicators and performance closer to new oil, preferably, the additives include, by weight, 2-20 parts of extreme pressure agent, 1-10 parts of friction modifier, 0.1-5 parts of rust inhibitor, 0.1-5 parts of antioxidant, 0.01-5 parts of antifoaming agent, 0.05-5 parts of demulsifier, 1-5 parts of metal deactivator and 1-5 parts of dispersant.

[0037] More preferably, the extreme pressure agent is selected from a combination of one or more of triphenyl thiophosphate, tricresol phosphate, isobutylene sulfide, and thiophosphate complex ester amine; the friction modifier is selected from a combination of one or more of dialkyl disulfide amino formic acid molybdenum, benzotriazole fatty acid ammonium, triethyl phosphate, benzotriazole fatty amine, and alkyl thiophosphate molybdenum; the rust inhibitor is selected from a combination of one or more of petroleum sulfonate barium, dinonylnaphthalenesulfonic acid, dodecenylsuccinic acid, and benzotriazole; the antioxidant is selected from 2,6-di-tert-butyl-p-cresol, N-phenyl-α-naphthylamine, dialkyl The invention relates to a combination of one or more zinc dithiophosphates; the antifoaming agent is selected from one or a combination of two of dimethyl silicone oil and polyacrylate; the anti-emulsifier is selected from one or a combination of amine-type epoxide polymers, ethylene oxide, propane block polyether, polyethylene oxide-propylene oxide ether; the metal deactivator is selected from one or a combination of benzotriazole and thiadiazole; the dispersant is selected from one or a combination of polyisobutylene succinimide, polyisobutylene succinate, benzylamine, and sulfur-phosphorized polyisobutylene polyoxyethylene ester; the solubilizer is a polyol ester.

[0038] A second aspect of the present invention provides application of the above waste lubricating oil regeneration method to the regeneration of wind turbine gear lubricating oil.

[0039] The technical solution provided by the present invention has the following beneficial effects:

[0040] The present invention provides a method for regenerating waste lubricating oil, which adopts chemical method for hydrogenation refining instead of physical method, can achieve complete decontamination and decolorization of waste wind turbine oil, obtain nearly pure polyalphaolefin base oil, and can completely remove residual additives and solubilizers that cannot be removed by traditional adsorption methods, so that waste oil regeneration can be achieved by supplementing additives and solubilizers, and the interference of residual additives and solubilizers on the properties of regenerated oil can be prevented. The hydrogenation refining catalyst is prepared from macroporous pseudo-boehmite, metal oxide precursor, pore expander and alkaline peptizing agent, so that the peptization reaction is mild and easy to control, and the large pore size of macroporous pseudo-boehmite can be effectively maintained, which is conducive to improving the mass transfer efficiency of the hydrogenation refining regeneration process of waste wind turbine gear lubricating oil, increasing the reaction space velocity, and reducing the operating cost.

[0041] The present invention provides a method for regenerating waste lubricating oil, which adopts pretreatment technology to preliminarily remove mechanical impurities and non-ideal components, thereby reducing the processing pressure of the subsequent refining stage. After the hydrofining step, dehydration and light hydrocarbon removal are carried out to remove a large amount of water and light hydrocarbons generated after the hydrofining step, and a product with indicators and performance close to new oil can be produced. DETAILED DESCRIPTION

[0042] The present invention is further described below by means of specific embodiments. The embodiments of the present invention are only used as illustrations of the present invention and do not mean that the scope of the present invention is limited thereto.

[0043] In the following embodiments, the method for regenerating waste lubricating oil specifically comprises the following steps:

[0044] (1) Pretreatment: The waste lubricating oil is subjected to physical adsorption pretreatment by an adsorbent; the adsorbent is selected from activated clay, silica gel or activated carbon, the adsorption temperature is 80-180°C, the time is 0.5-10 hours, and the mass ratio of the waste lubricating oil to the adsorbent is 5-50:1, preferably 25-50:1.

[0045] (2) Hydrofining: The pretreated waste lubricating oil is subjected to hydrofining in the presence of a catalyst; the hydrofining is carried out using a fixed bed hydrogenation device, the fixed bed hydrogenation device at least comprising a protective agent bed filled with a protective agent and a catalyst bed filled with the catalyst; preferably, the hydrofining temperature is 280-380°C, the pressure is 8-20MPa, and the mass space velocity is 0.1-3.0h -1 , hydrogen-oil volume ratio 500:1-1000:1.

[0046] The catalyst contains 5-10 wt% NiO or Co2O3, 20-28 wt% MoO3 or WO3, 5-8 wt% P2O5, and 54-70 wt% Al2O3. The catalyst has a pore size of 12-18 nm and a pore volume of 0.5-0.8 cm 3 / g, specific surface area is 100-203m 2 / g.

[0047] The protective agent is selected from a demetallized / degelatinized asphaltene protective agent, and the mass ratio of the protective agent to the hydrotreating catalyst is 0.1:1-10:1, preferably 0.2:1-1:1, and more preferably 0.2:1-0.5:1.

[0048] The preparation process of the catalyst comprises the following steps:

[0049] (1) mixing macroporous pseudo-boehmite, a nickel or cobalt oxide precursor, a molybdenum or tungsten oxide precursor, and a phosphorus oxide precursor to obtain a primary mixture;

[0050] (2) adding the alcohol solution of the pore-enlarging agent to the primary mixture and continuing to mix to obtain a mixture;

[0051] (3) adding an alkaline peptizing agent and water to the mixed material, maintaining the pH value at 9-12, to obtain a mixed material;

[0052] (4) kneading the mixed material into a plastic body, extruding strips, and obtaining a molding material;

[0053] (5) drying and calcining the molding material to obtain the catalyst;

[0054] The pore size of the macroporous pseudo-boehmite is ≥10nm; the pore volume is ≥1.0cm 3 / g.

[0055] The pore-enlarging agent is polyethylene glycol 3000, polyethylene glycol 4000, polyethylene glycol 6000 or polyethylene glycol 8000; the amount of the pore-enlarging agent added is 8-20wt% of the macroporous pseudo-boehmite; and / or

[0056] The alcohol solution of the pore-enlarging agent is a C1-C4 saturated monohydric fatty alcohol solution of the pore-enlarging agent, more preferably an ethanol solution of the pore-enlarging agent; and / or

[0057] The alkaline peptizing agent is ammonia water, triethylamine or ethylenediamine; more preferably, the amount of the alkaline peptizing agent added is 2-20wt% of the mixed material; more preferably, the peptization reaction time of the mixed material is 0.5-1.0h; and / or

[0058] The pore size of the macroporous pseudo-boehmite is 10-12 nm, and the pore volume is 1.0-1.2 cm 3 / g, specific surface area is 350-400m 2 / g; and / or

[0059] The oxide precursor of nickel is basic nickel carbonate or nickel hydroxide; the oxide precursor of cobalt is basic cobalt carbonate or cobalt hydroxide; the oxide precursor of molybdenum is ammonium heptamolybdate or ammonium tetramolybdate; the oxide precursor of tungsten is ammonium tungstate or ammonium metatungstate; and the oxide precursor of phosphorus is diammonium phosphate.

[0060] (3) Dehydration and removal of light hydrocarbons: Dehydration and removal of light hydrocarbons from the hydrorefined waste lubricating oil; thin film evaporation, atmospheric distillation or vacuum distillation are used for the dehydration and removal of light hydrocarbons; preferably, vacuum distillation is used for the dehydration and removal of light hydrocarbons; the temperature for the dehydration and removal of light hydrocarbons is 100-300°C, the vacuum degree is 0.1-800Torr, and the time is 0.5-12h; preferably, the temperature for the dehydration and removal of light hydrocarbons is 150-250°C, the vacuum degree is 1-100Torr, and the time is 1-6h.

[0061] (4) Fine filtration: The waste lubricating oil that has been dehydrated and de-lightened is finely filtered; the fine filtration is performed by membrane filtration, preferably hydrophobic membrane filtration, with a membrane pore size of 100-3000 nm.

[0062] (5) Additives and solubilizers: Add additives and solubilizers to the waste lubricating oil after fine filtration; the additives are selected from one or more of extreme pressure agents, friction modifiers, antioxidants, antifoaming agents, antiemulsifiers, rust inhibitors, dispersants, and metal deactivators; the solubilizer is selected from polyester or polyether solubilizers; the additive amount is 1-3% of the total mass of the waste lubricating oil after fine filtration; the solubilizer is 2-15% of the total mass of the waste lubricating oil after fine filtration.

[0063] Further, the additives include 2-20 parts of extreme pressure agent, 1-10 parts of friction modifier, 0.1-5 parts of rust inhibitor, 0.1-5 parts of antioxidant, 0.01-5 parts of antifoaming agent, 0.05-5 parts of demulsifier, 1-5 parts of metal deactivator and 1-5 parts of dispersant. Further, the extreme pressure agent is selected from a combination of one or more of triphenyl thiophosphate, tricresol phosphate, isobutylene sulfide, and thiophosphate complex ester amine; the friction modifier is selected from a combination of one or more of dithiodialkylamino molybdenum formate, benzotriazole fatty acid ammonium, triethyl phosphate, benzotriazole fatty amine, alkylthiophosphate molybdenum; the rust inhibitor is selected from a combination of one or more of petroleum sulfonate barium, dinonylnaphthalenesulfonic acid, dodecenylsuccinic acid, and benzotriazole; the antioxidant is selected from a combination of 2,6-di-tert-butyl-p-cresol, N-phenyl-α-naphthylamine, dioxane The antifoaming agent is selected from one or a combination of dimethyl silicone oil and polyacrylate; the anti-emulsifier is selected from one or a combination of amine-type epoxide polymers, ethylene oxide, propane block polyether, polyethylene oxide-propylene oxide ether; the metal deactivator is selected from one or a combination of benzotriazole and thiadiazole; the dispersant is selected from one or a combination of polyisobutylene succinimide, polyisobutylene succinate, benzylamine, sulfur-phosphorized polyisobutylene polyoxyethylene ester; the solubilizer is a polyol ester.

[0064] instrument:

[0065] Fixed bed hydrogenation reactor, pressure resistance 25Mpa, design operating temperature ≯600℃, stainless steel reactor, Beijing Sixintong Technology Co., Ltd.;

[0066] Real boiling point distiller, theoretical limit vacuum 0.1 Torr, heating temperature ≯500℃, i-Fischer, Germany;

[0067] YG-T2 extruder, Guangzhou Huagong Optoelectronics Technology Co., Ltd.

[0068] Example 1

[0069] Weigh 500g of waste lubricating oil and mix it with 20g of activated clay. The mass ratio of waste lubricating oil to adsorbent is 25:1. Stir and adsorb in a stirred tank at 160°C for 4h, unload and filter while hot to obtain pretreated oil.

[0070] The pretreated waste lubricating oil is refined by a fixed bed reactor including a protective agent bed filled with a protective agent and a catalyst bed filled with the catalyst, wherein the protective agent bed and the refining agent bed are respectively filled with 3g of protective agent and 7g of catalyst, the reaction temperature is 321°C, and the mass space velocity is 0.5h -1 , hydrogen-oil ratio 600:1, pressure 15Mpa.

[0071] The protective agent is a demetallized / degelatinized asphaltene protective agent (FZC series hydrogenation protective agent of Fushun Petrochemical Research Institute), and the mass ratio of the protective agent to the hydrotreating catalyst is 3:7.

[0072] The catalyst preparation process includes the following steps:

[0073] Weigh 300g of macroporous pseudo-boehmite (YH-05), 28g of basic nickel carbonate, 103g of ammonium heptamolybdate, and 27g of ammonium dihydrogen phosphate and mix for 60min to obtain a primary mixture. Weigh 300040g of polyethylene glycol and dissolve it in 50g of ethanol, add the ethanol solution of polyethylene glycol to the primary mixture and continue mixing to obtain a mixture; the amount of polyethylene glycol added is 13wt% of the macroporous pseudo-boehmite. Add 100g of ammonia water (ammonia content 25%) and 10g of deionized water, keep the pH at 10, and stir, and the mixture is peptized for 1.0h to obtain a mixture; the amount of alkaline peptizing agent added is 15wt% of the mixture. Knead the mixture into a plastic body, the kneading time is 1h, and a preform with elasticity is formed. The preform is extruded to obtain a molded material; in the extrusion process, the mold is a clover-shaped with an opening diameter of 1.5mm. The catalyst was dried in an oven at 120°C for 2 h and calcined at 500°C for 3 h to obtain an oxide sample of the catalyst.

[0074] Based on the total weight of the catalyst, each component is expressed in the form of oxides. The catalyst composition includes: Al2O3 65.0wt%, MoO3 25.0wt%, NiO 5.0wt% and P2O55.0wt%. The pore size of the catalyst is 12nm and the pore volume is 0.5cm 3 / g, BET specific surface area is 203m 2 / g.

[0075] 1.0 g of catalyst was weighed and loaded into a stainless steel reactor. Before use, the catalyst was in-situ sulfurized by introducing sulfurized oil with a CS2 mass fraction of 5% and H2 to sulfurize nickel, cobalt, molybdenum, and tungsten metal oxides into sulfides. The sulfurization conditions were: temperature 300 ° C, mass space velocity 1.5 h -1 , pressure is 6.0MPa, hydrogen-oil ratio is 600:1, and time is 5h.

[0076] The waste lubricating oil after hydrofining is subjected to vacuum distillation at 250°C and 1 Torr for 4 hours to remove water and light hydrocarbons. The waste lubricating oil after dehydration and light hydrocarbons is filtered through a ceramic membrane with a pore size of 500nm.

[0077] The waste lubricating oil that has been finely filtered is supplemented with additives and solubilizers; 12.5 g of additives and 50 g of solubilizer are added to obtain regenerated fan gear lubricating oil A1.

[0078] The additives include 7.5g of triphenyl thiophosphate, 2g of ammonium benzotriazole fatty acid, 0.4g of benzotriazole, 0.5g of 2,6-di-tert-butyl-p-cresol, 0.025g of polyacrylate, 0.075g of ethylene oxide, 1g of benzotriazole, and 1g of polyisobutylene succinimide. The solubilizer is PRIOLUBE 3970 of Heda Polyol Ester.

[0079] Example 2

[0080] Weigh 500g of waste lubricating oil and mix it with 20g of activated clay. The mass ratio of waste lubricating oil to adsorbent is 25:1. Stir and adsorb in a stirred tank at 160°C for 4h, unload and filter while hot to obtain pretreated oil.

[0081] The pretreated waste lubricating oil is refined by a fixed bed reactor including a protective agent bed filled with a protective agent and a catalyst bed filled with the catalyst, wherein the protective agent bed and the refining agent bed are respectively filled with 3g of protective agent and 7g of catalyst, the reaction temperature is 321°C, and the mass space velocity is 0.5h -1 , hydrogen-oil ratio 600:1, pressure 15Mpa.

[0082] The protective agent is a demetallized / degelatinized asphaltene protective agent (HTP series hydrogenation protective agent of Liaoning Haitai Technology Development Co., Ltd.), and the mass ratio of the protective agent to the hydrotreating catalyst is 3:7.

[0083] The catalyst preparation process includes the following steps:

[0084] Weigh 300g of macroporous pseudo-boehmite (YH-05), 42g of basic nickel carbonate, 83g of ammonium heptamolybdate, and 44g of ammonium dihydrogen phosphate and mix for 60min to obtain a primary mixture. Weigh 30g of polyethylene glycol 4000 and dissolve it in 40g of ethanol, add the ethanol solution of polyethylene glycol to the primary mixture and continue mixing to obtain a mixture; the amount of polyethylene glycol added is 10wt% of the macroporous pseudo-boehmite. Add 100g of ammonia water (ammonia content 25%) and 20g of deionized water, keep the pH at 10, and stir, and the mixture is peptized for 0.5h to obtain a mixture; the amount of alkaline peptizing agent added is 15wt% of the mixture. Knead the mixture into a plastic body, and the kneading time is 1h to form a preform with elasticity. The preform is extruded to obtain a molding material; in the extrusion process, the mold is a clover-shaped with an opening diameter of 2.0mm. The catalyst was dried in an oven at 100°C for 5 h and calcined at 400°C for 5 h to obtain an oxide sample of the catalyst.

[0085] Based on the total weight of the catalyst, each component is expressed in the form of oxides. The catalyst composition includes: Al2O3 64.5wt%, MoO3 20.0wt%, NiO 7.5wt% and P2O 58.0wt%. The pore size of the catalyst is 15nm and the pore volume is 0.7cm 3 / g, BET specific surface area is 157m 2 / g.

[0086] 1.0 g of catalyst was weighed and loaded into a stainless steel reactor. Before use, the catalyst was in-situ sulfurized by introducing sulfurized oil with a CS2 mass fraction of 5% and H2 to sulfurize nickel, cobalt, molybdenum, and tungsten metal oxides into sulfides. The sulfurization conditions were: temperature 300 ° C, mass space velocity 1.5 h -1 , pressure is 6.0MPa, hydrogen-oil ratio is 600:1, and time is 5h.

[0087] The waste lubricating oil after hydrofining is subjected to vacuum distillation at 250°C and 1 Torr for 1 hour to remove water and light hydrocarbons. The waste lubricating oil after dehydration and light hydrocarbons is filtered through a ceramic membrane with a pore size of 500nm.

[0088] The waste lubricating oil that has been finely filtered is supplemented with additives and solubilizers; 12.5 g of additives and 50 g of solubilizer are added to obtain regenerated fan gear lubricating oil A2.

[0089] The additives include 7.5g of triphenyl thiophosphate, 2g of ammonium benzotriazole fatty acid, 0.4g of benzotriazole, 0.5g of 2,6-di-tert-butyl-p-cresol, 0.025g of polyacrylate, 0.075g of ethylene oxide, 1g of benzotriazole, and 1g of polyisobutylene succinimide. The solubilizer is PRIOLUBE 3970 of Heda Polyol Ester.

[0090] Example 3

[0091] Weigh 500g of waste lubricating oil and mix it with 20g of activated clay. The mass ratio of waste lubricating oil to adsorbent is 25:1. Stir and adsorb in a stirred tank at 160°C for 4h, unload and filter while hot to obtain pretreated oil.

[0092] The pretreated waste lubricating oil is refined by a fixed bed reactor including a protective agent bed filled with a protective agent and a catalyst bed filled with the catalyst, wherein the protective agent bed and the refining agent bed are respectively filled with 3g of protective agent and 7g of catalyst, the reaction temperature is 321°C, and the mass space velocity is 0.5h -1 , hydrogen-oil ratio 600:1, pressure 15Mpa.

[0093] The protective agent is a demetallized / degelatinized asphaltene protective agent (DFB series hydrogenation protective agent of Fushun Xinrui Catalyst Co., Ltd.), and the mass ratio of the protective agent to the hydrotreating catalyst is 3:7.

[0094] The catalyst preparation process includes the following steps:

[0095] Weigh 300g of macroporous pseudo-boehmite (YH-05), 61g of basic nickel carbonate, 104g of ammonium heptamolybdate, and 38g of ammonium dihydrogen phosphate and mix for 60min to obtain a primary mixture. Weigh 600045g of polyethylene glycol and dissolve it in 50g of ethanol, add the ethanol solution of polyethylene glycol to the primary mixture and continue mixing to obtain a mixture; the amount of polyethylene glycol added is 15wt% of the macroporous pseudo-boehmite. Add 100g of ammonia water (ammonia content 25%) and 5g of deionized water, keep the pH at 9, and stir, and the mixture is peptized for 0.5h to obtain a mixture; the amount of alkaline peptizing agent added is 14wt% of the mixture. Knead the mixture into a plastic body, the kneading time is 1h, and a preform with elasticity is formed. The preform is extruded to obtain a molding material; in the extrusion process, the mold is a clover-shaped with an opening diameter of 3.0mm. The catalyst was dried in an oven at 110°C for 4 h and calcined at 600°C for 4 h to obtain an oxide sample of the catalyst.

[0096] Based on the total weight of the catalyst, each component is expressed in the form of oxides. The catalyst composition includes: Al2O3 60.0wt%, MoO3 23.5wt%, NiO 10.0wt% and P2O 56.5wt%. The pore size of the catalyst is 18nm and the pore volume is 0.8cm 3 / g, BET specific surface area is 102m 2 / g.

[0097] 1.0 g of catalyst was weighed and loaded into a stainless steel reactor. Before use, the catalyst was in-situ sulfurized by introducing sulfurized oil with a CS2 mass fraction of 5% and H2 to sulfurize nickel, cobalt, molybdenum, and tungsten metal oxides into sulfides. The sulfurization conditions were: temperature 300 ° C, mass space velocity 1.5 h -1 , pressure is 6.0MPa, hydrogen-oil ratio is 600:1, and time is 5h.

[0098] The waste lubricating oil after hydrofining is subjected to vacuum distillation at 250°C and 1 Torr for 2 hours to remove water and light hydrocarbons. The waste lubricating oil after dehydration and light hydrocarbons is filtered through a ceramic membrane with a pore size of 500nm.

[0099] The waste lubricating oil that has been finely filtered is supplemented with additives and solubilizers; 12.5 g of additives and 50 g of solubilizer are added to obtain regenerated fan gear lubricating oil A3.

[0100] The additives include 7.5g of triphenyl thiophosphate, 2g of ammonium benzotriazole fatty acid, 0.4g of benzotriazole, 0.5g of 2,6-di-tert-butyl-p-cresol, 0.025g of polyacrylate, 0.075g of ethylene oxide, 1g of benzotriazole, and 1g of polyisobutylene succinimide. The solubilizer is PRIOLUBE 3970 of Heda Polyol Ester.

[0101] Example 4

[0102] In Example 4, no additives and solubilizers were added, and other steps were the same as in Example 1 to obtain regenerated base oil A4.

[0103] Example 5

[0104] The hydrofining temperature of Example 5 is 319°C and the mass space velocity is 1.3h -1 The ratio of hydrogen to waste lubricating oil is 600:1, the pressure is 8 MPa, and the rest is the same as in Example 4 to obtain regenerated base oil A5.

[0105] Example 6

[0106] Weigh 500g of waste lubricating oil and mix it with 10g of activated clay, with the mass ratio of waste lubricating oil to adsorbent being 50:1. Pass nitrogen gas and stir and adsorb in a stirred tank at 90°C for 2h. Discharge and filter while hot to obtain pretreated oil.

[0107] The hydrofining step is the same as that of Example 4. The waste lubricating oil after hydrofining is subjected to vacuum distillation at 150°C and 10 Torr for 1 hour to remove water and light hydrocarbons. The waste lubricating oil after dehydration and light hydrocarbons is filtered through a ceramic membrane with a pore size of 1000 nm. The other steps are the same as those of Example 4 to obtain regenerated base oil A6.

[0108] Example 7

[0109] The steps of pretreatment, hydrotreating, dehydration and removal of light hydrocarbons, and fine filtration in Example 7 are the same as those in Example 1.

[0110] The waste lubricating oil that has been finely filtered is supplemented with additives and solubilizers; 10.5 g of additives and 40 g of solubilizer are added to obtain regenerated fan gear lubricating oil A7.

[0111] The additives include 2.5g of triphenyl thiophosphate, 5g of isobutylene sulfide, 1g of triethyl phosphate, 0.4g of dinonylnaphthalenesulfonic acid, 0.5g of N-phenyl-α-naphthylamine, 0.04g of dimethyl silicone oil, 0.5g of thiadiazole, and 0.5g of polyisobutylene succinate. The solubilizer is PRIOLUBE 3970 of Heda Polyol Ester.

[0112] Comparative Example 1

[0113] In Comparative Example 1, the hydrofining step of Example 4 was omitted, and the other steps were the same as those of Example 4 to obtain the regenerated base oil R1.

[0114] Comparative Example 2

[0115] In Comparative Example 2, the dehydration and light hydrocarbon removal steps of Example 4 were omitted, and the other steps were the same as those of Example 4, to obtain the regenerated base oil R2.

[0116] Comparative Example 3

[0117] Comparative Example 3 The preparation method of the hydrorefining catalyst of the refining agent in the hydrorefining step specifically includes the following steps: Weigh 300g of macroporous pseudo-boehmite (YH-05), 64.5g of nickel nitrate hexahydrate, 103g of ammonium heptamolybdate, and 27g of ammonium dihydrogen phosphate, and mix them in a kneader for 60 minutes to obtain a primary mixture. Add 120g of deionized water and stir to obtain a mixed material. Knead the mixed material into a plastic body for 1 hour to form a preform with elasticity. The preform is formed by extrusion to obtain a molded material; in the extrusion process, the mold is a clover-shaped material with an opening diameter of 1.5mm. Dry in an oven at 120°C for 2 hours and roast at 500°C for 3 hours to obtain an oxide sample of the catalyst.

[0118] Based on the total weight of the catalyst, each component is expressed in the form of oxides. The catalyst composition includes: Al2O3 65.0wt%, MoO3 25.0wt%, NiO 5.0wt% and P2O55.0wt%. The pore size of the catalyst is 5nm and the pore volume is 0.27cm 3 / g, BET specific surface area is 187m 2 / g.

[0119] The other steps are the same as those in Example 4 to obtain regenerated base oil R3.

[0120] Comparative Example 4

[0121] In Comparative Example 4, the dehydration and light hydrocarbon removal step was moved before the hydrofining step, and the other steps were the same as those in Example 4 to obtain the regenerated base oil R4.

[0122] The performance indicators of lubricating oil regenerated by different methods are shown in Table 1.

[0123] Table 1

[0124]

[0125]

[0126] Examples 1-7 are the performance indicators of lubricating oils regenerated by different methods. Examples 1-3 and 7 are groups supplemented with additives and solubilizers, and Examples 4-6 are groups not supplemented with additives and solubilizers. Examples 4-6 did not supplement additives and solubilizers, and the kinematic viscosity was greater than 380 mm 2 / s, which are significantly higher than the kinematic viscosities of Comparative Examples 1, 2 and 4. The higher kinematic viscosity indicates better regeneration effect, especially better hydrofining effect. Examples 1-3 and 7 are further supplemented with additives and solubilizers on the basis of Example 4, and the kinematic viscosity is close to 320 mm of the new lubricating oil. 2 / s, indicating that the supplementation of additives and solubilizers has achieved better results. The acid values ​​of Examples 4-6 are all lower than 0.2 mgKOH / g, which are significantly lower than the acidity of Comparative Examples 1 and 3, which also indicates that the regeneration effect, especially the hydrofining effect, is better. Comparative Example 1 fails to completely remove residual additives and solubilizers due to the lack of a hydrofining step, so the acid value is too large. Comparative Example 3 does not use a hydrofining catalyst with a larger pore size and pore volume structure, and the hydrogenation effect is not ideal, so the residual additives and solubilizers cannot be completely removed, so the acid value is too large. Examples 1-3 and Example 7 further supplement additives and solubilizers on the basis of Example 4, and the acid values ​​are close to the acid value range of new lubricating oil 0.5-1.2 mgKOH / g, indicating that the supplementation of additives and solubilizers has achieved better results. The moisture content of Examples 1-7 is all lower than 80 ppm, while Comparative Example 2 omits the dehydration step, and Comparative Example 4 does not achieve the dehydration purpose of this application because the dehydration step is before the hydrofining step, so the moisture content of Comparative Examples 1 and Comparative Examples 4 is seriously exceeded. The Fe content of Examples 1-7 was not detected. The P content of Examples 4-6 was extremely low or undetectable, the S content was relatively low, and the O content was extremely low or undetectable, indicating that the regeneration method of the present application can effectively remove residual additives and solubilizers in waste lubricating oil. Examples 1-3 and Example 7 further supplemented additives and solubilizers on the basis of Example 4, and the P content was close to the P content range of new lubricating oil 100-300ppm, the S content was close to the S content range of new lubricating oil 2000-4000ppm, and the O content was close to the O content range of new lubricating oil 0.2-2.0%. Comparative Example 1 failed to completely remove residual additives and solubilizers due to the lack of a hydrofining step, so the P content, S content and O content were all too large. Comparative Example 3 failed to completely remove residual additives and solubilizers due to the lack of a hydrofining catalyst with a larger pore size and pore volume structure, so the P content and S content were both too large. Since the dehydration and light hydrocarbon removal step was omitted in Comparative Example 2, the dehydration and light hydrocarbon removal step in Comparative Example 4 before the hydrofining step did not achieve the purpose of the present application, but rather more light hydrocarbons remained, resulting in an excessively high O content in the regenerated oil.

[0127] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. A method for regenerating waste lubricating oil, characterized in that: The following steps are involved: (1) Pretreatment: The waste lubricating oil is pretreated by physical adsorption through an adsorbent; (2) Hydrofining: The pretreated waste lubricating oil is subjected to hydrofining in the presence of a catalyst, wherein the content of NiO or Co2O3 is 5-10wt%, the content of MoO3 or WO3 is 20-28wt%, the content of P2O5 is 5-8wt%, the content of Al2O3 is 54-70wt%, and the pore diameter of the catalyst is 12-18nm and the pore volume is 0.5-0.8cm 3 / g, specific surface area of ​​100-203m 2 / g; (3) Dehydration and removal of light hydrocarbons: Dehydration and removal of light hydrocarbons from the waste lubricating oil after hydrofining; (4) Fine filtration: The waste lubricating oil that has been dehydrated and de-lightened is finely filtered.

2. The method for regenerating waste lubricating oil according to claim 1, characterized in that: The adsorbent is selected from activated clay, silica gel or activated carbon, the adsorption temperature is 80-180° C., the adsorption time is 0.5-10 hours, and the mass ratio of the waste lubricating oil to the adsorbent is 5-50:

1.

3. The method for regenerating waste lubricating oil according to claim 1, characterized in that: The hydrofining is carried out using a fixed bed hydrogenation device, which at least includes a protective agent bed filled with a protective agent and a catalyst bed filled with the catalyst; preferably, the hydrofining temperature is 280-380°C, the pressure is 8-20MPa, and the mass space velocity is 0.1-3.0h -1 , hydrogen-oil volume ratio 500:1-1000:

1.

4. The method for regenerating waste lubricating oil according to claim 3, characterized in that: The protective agent is selected from a demetallized / degelatinized asphaltene protective agent, and the mass ratio of the protective agent to the catalyst is 0.1:1-10:1, preferably 0.2:1-1:1, and more preferably 0.2:1-0.5:

1.

5. The method for regenerating waste lubricating oil according to claim 3, characterized in that: The preparation process of the catalyst comprises the following steps: (1) mixing macroporous pseudo-boehmite, a nickel or cobalt oxide precursor, a molybdenum or tungsten oxide precursor, and a phosphorus oxide precursor to obtain a primary mixture; (2) adding the alcohol solution of the pore-enlarging agent to the primary mixture and continuing to mix to obtain a mixture; (3) adding an alkaline peptizing agent and water to the mixed material, maintaining the pH value at 9-12, to obtain a mixed material; (4) kneading the mixed material into a plastic body, extruding strips, and obtaining a molding material; (5) drying and calcining the molding material to obtain the catalyst; The pore size of the macroporous pseudo-boehmite is ≥10nm; the pore volume is ≥1.0cm 3 / g.

6. The method for regenerating waste lubricating oil according to claim 5, characterized in that: The pore-enlarging agent is polyethylene glycol 3000, polyethylene glycol 4000, polyethylene glycol 6000 or polyethylene glycol 8000; the amount of the pore-enlarging agent added is 8-20wt% of the macroporous pseudo-boehmite; and / or Preferably, the alcohol solution of the pore expanding agent is a C1-C4 saturated monohydric fatty alcohol solution of the pore expanding agent, more preferably an ethanol solution of the pore expanding agent; and / or Preferably, the alkaline peptizing agent is ammonia water, triethylamine or ethylenediamine; more preferably, the amount of the alkaline peptizing agent added is 2-20wt% of the mixed material; more preferably, the peptization reaction time of the mixed material is 0.5-1.0h; and / or Preferably, the macroporous pseudo-boehmite has a pore size of 10-12 nm and a pore volume of 1.0-1.2 cm 3 / g, specific surface area is 350-400m 2 / g; and / or Preferably, the oxide precursor of nickel is basic nickel carbonate or nickel hydroxide; the oxide precursor of cobalt is basic cobalt carbonate or cobalt hydroxide; the oxide precursor of molybdenum is ammonium heptamolybdate or ammonium tetramolybdate; the oxide precursor of tungsten is ammonium tungstate or ammonium metatungstate; and the oxide precursor of phosphorus is diammonium phosphate.

7. The method for regenerating waste lubricating oil according to any one of claims 1 to 6, characterized in that: The dehydration and removal of light hydrocarbons are carried out by thin film evaporation, atmospheric distillation or reduced pressure distillation; preferably, reduced pressure distillation is used for the dehydration and removal of light hydrocarbons; the temperature for the dehydration and removal of light hydrocarbons is 100-300°C, the vacuum degree is 0.1-800Torr, and the time is 0.5-12h; preferably, the temperature for the dehydration and removal of light hydrocarbons is 150-250°C, the vacuum degree is 1-100Torr, and the time is 1-6h.

8. The method for regenerating waste lubricating oil according to any one of claims 1 to 7, characterized in that: The fine filtration adopts membrane filtration, preferably hydrophobic membrane filtration, and the membrane pore size is 100-3000nm.

9. The method for regenerating waste lubricating oil according to any one of claims 1 to 8, characterized in that: The regeneration method further comprises supplementing additives and solubilizing agents to the finely filtered waste lubricating oil; Wherein, the additive is selected from one or more of extreme pressure agents, friction modifiers, antioxidants, antifoaming agents, antiemulsifiers, rust inhibitors, dispersants, and metal deactivators; the solubilizer is selected from polyester or polyether solubilizers; The additive is added in an amount of 1-3% of the total mass of the waste lubricating oil after fine filtration; the solubilizing agent is added in an amount of 2-15% of the total mass of the waste lubricating oil after fine filtration; Preferably, the additives include, by weight, 2-20 parts of extreme pressure agent, 1-10 parts of friction modifier, 0.1-5 parts of rust inhibitor, 0.1-5 parts of antioxidant, 0.01-5 parts of antifoaming agent, 0.05-5 parts of demulsifier, 1-5 parts of metal deactivator and 1-5 parts of dispersant; More preferably, the extreme pressure agent is selected from a combination of one or more of triphenyl thiophosphate, tricresol phosphate, isobutylene sulfide, and thiophosphate complex ester amine; the friction modifier is selected from a combination of one or more of dialkyl disulfide amino formic acid molybdenum, benzotriazole fatty acid ammonium, triethyl phosphate, benzotriazole fatty amine, and alkyl thiophosphate molybdenum; the rust inhibitor is selected from a combination of one or more of petroleum sulfonate barium, dinonylnaphthalenesulfonic acid, dodecenylsuccinic acid, and benzotriazole; the antioxidant is selected from 2,6-di-tert-butyl-p-cresol, N-phenyl-α-naphthylamine, dialkyl The invention relates to a combination of one or more zinc dithiophosphates; the antifoaming agent is selected from one or a combination of two of dimethyl silicone oil and polyacrylate; the anti-emulsifier is selected from one or a combination of amine-type epoxide polymers, ethylene oxide, propane block polyether, polyethylene oxide-propylene oxide ether; the metal deactivator is selected from one or a combination of benzotriazole and thiadiazole; the dispersant is selected from one or a combination of polyisobutylene succinimide, polyisobutylene succinate, benzylamine, and sulfur-phosphorized polyisobutylene polyoxyethylene ester; the solubilizer is a polyol ester.

10. Use of the waste lubricating oil regeneration method according to any one of claims 1 to 9 for regenerating lubricating oil for fan gears.

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