阅读说明：本技术 一种废润滑油全加氢再生工艺及加氢催化剂的制备方法 (Full-hydrogenation regeneration process for waste lubricating oil and preparation method of hydrogenation catalyst ) 是由 李自夏 张贤明 冉印 于 2019-09-26 设计创作，主要内容包括：本发明提供一种废润滑油全加氢再生工艺：其步骤包括废润滑油预处理、加氢脱金属、加氢除杂原子和加氢改质,并且提供用于上述再生工艺的配套加氢催化剂。首先对废润滑油原料中的水分、机械杂质、胶质、沥青质和重金属杂质进行预处理,然后对残余的重金属杂质进一步加氢脱除,接着在加氢除杂原子催化剂的作用下,实现废润滑油中硫、氮、氧杂原子等非理想组分的脱除；最后在加氢改质催化剂的作用下,将正构烷烃转化成单支链或双支链异构烷烃,显著提高再生油的质量。该再生工艺产品收率高,再生后的润滑油产品质量能够达到润滑油基础油的标准要求。(The invention provides a full hydrogenation regeneration process of waste lubricating oil, which comprises the following steps: the steps of the method comprise the steps of waste lubricating oil pretreatment, hydrogenation demetalization, hydrogenation impurity removal atom and hydrogenation modification, and a matched hydrogenation catalyst for the regeneration process is provided. Firstly, preprocessing water, mechanical impurities, colloid, asphaltene and heavy metal impurities in the raw material of the waste lubricating oil, then further hydrogenating and removing the residual heavy metal impurities, and then removing non-ideal components such as sulfur, nitrogen, oxygen heteroatom and the like in the waste lubricating oil under the action of a hydrogenation impurity-removing atom catalyst; finally, under the action of the hydro-upgrading catalyst, the normal paraffin is converted into single-branched chain or double-branched chain isoparaffin, and the quality of the regenerated oil is obviously improved. The regeneration process has high product yield, and the quality of the regenerated lubricating oil product can meet the standard requirements of the lubricating oil base oil.)

1. A full hydrogenation regeneration process of waste lubricating oil is characterized in that: the method comprises the steps of waste lubricating oil pretreatment, hydrodemetallization, hydrogenation impurity removal atom and hydrogenation modification, and specifically comprises the following steps:

(1) The pretreatment comprises the steps of dehydrating and adsorbing the raw material waste lubricating oil for impurity removal, wherein the raw material waste lubricating oil firstly enters a dehydrating tank and is heated to 50 ~ 100 DEG^oC, dehydrating, and then entering a pretreatment reactor for adsorption and impurity removal under the operating conditions that the reaction temperature is 250 ~ 350^oC, volume space velocity of 0.2 ~ 1.6.6 h^-1Pressure 0.5 ~ 1.6.6 MPa, hydrogen-oil volume ratio 300 ~ 500 (v/v);

(2) Hydrodemetallization, namely, the pretreated waste lubricating oil enters a hydrodemetallization reactor to further remove residual metal impurities, wherein the operation condition is that the temperature is 260 ~ 360 DEG^oC, volume space velocity of 0.5 ~ 2.0.0 h^-1The pressure is 3.0 ~ 6.0.0 MPa, the volume ratio of hydrogen to oil is 300 ~ 500 (v/v), the hydrodemetallization catalyst takes macroporous alumina as a carrier, one or two metals of Mo and Ni are loaded as active components, and the loading amount of one active component is 5 ~ 10wt% in terms of oxide;

(3) Hydrogenation impurity removal atom, namely, feeding a hydrodemetallization product into a hydrogenation impurity removal atom reactor, carrying out hydrodeoxygenation, desulfurization, denitrification and dechlorination under the action of a catalyst, and removing unsaturated hydrocarbon components in the hydrodemetallization atom product through hydrogenation saturation under the operating condition that the temperature is 280 ~ 360 DEG^oC, volume space velocity of 0.5 ~ 2.0.0 h^-1The pressure is 3.0 ~ 8.0.0 MPa, the hydrogen-oil volume ratio is 300 ~ 800 (v/v), the hydrogenation heteroatom removal catalyst takes auxiliary agent modified macroporous alumina as a carrier, one or more than two metals in active components Co, Mo, Ni and W are loaded, the auxiliary agent is one or more than two metals in Li, K, Mg, B and P, based on the total weight of the catalyst, the content of the active components in the catalyst is respectively CoO 2 ~ 8wt%, MoO 2 is calculated by oxide, and the volume ratio of MoO is 300/v₃ 8~20 wt%，NiO 2~8 wt%，WO₃ 20 ~ 40 wt%, and the content of the auxiliary agent in the catalyst is Li calculated by oxide respectively₂O 0.5~5 wt%，K₂O 0.5~5 wt%，MgO 0.5~5 wt%，B₂O₃ 0.5~5 wt%，P₂O₅ 0.5 ~ 5wt% and the specific surface area of the macroporous alumina is more than or equal to 200 m²the pore volume is more than or equal to 0.4 ml/g;

(4) Hydro-upgrading: the hydrogenation heteroatom removal product enters a hydrogenation modification reactionUnder the action of hydroupgrading catalyst, the normal paraffin with high condensation point is converted into isoparaffin with low condensation point to raise the quality of regenerated oil product, and its operation condition is that its temperature is 280 ~ 400^oC, volume space velocity of 0.5 ~ 2.0.0 h^-1the pressure is 3.0 ~ MPa, the hydrogen-oil volume ratio is 300 ~ (v/v), the hydrogenation modification catalyst takes a compound of one or more mesoporous molecular sieves of alumina and SAPO-11 molecular sieve, ultrastable USY molecular sieve, beta molecular sieve, MCM-11 molecular sieve or ZSM-5 molecular sieve as a carrier, and one or more than two metals of active components Co, Mo, Ni and W are loaded, the content of the active components in the catalyst is respectively CoO 2 ~ wt% and MoO 2 in oxide₃ 8~15 wt%，NiO 2~8 wt%，WO₃ 8 ~ 15 wt% and the specific surface area of alumina is more than or equal to 200 m²The volume of pores is more than or equal to 0.4 ml/g, and the weight ratio of the alumina to the mesoporous molecular sieve is 100 (10 ~ 50).

2. The process of fully hydrogenating regeneration of spent lubricating oil according to claim 1, wherein: the adsorbent in the pretreatment unit is activated alumina, and the specific surface area is more than or equal to 200 m²The pore volume is more than or equal to 0.4 ml/g.

3. The process of fully hydrogenating regeneration of spent lubricating oil according to claim 1, wherein: the hydrodemetallization catalyst takes macroporous alumina as a carrier and loads one or two of active components Mo and Ni, and the specific surface area of the macroporous alumina is more than or equal to 200 m²The pore volume is more than or equal to 0.4 ml/g, and the loading capacity of the active component is MoO calculated by oxide₃ 5~10 wt%，NiO 5~10 wt%。

4. The process for the total hydrogenation regeneration of spent lubricating oil according to claim 1, wherein: the hydrogenation impurity atom removal catalyst is prepared by the following steps:

a. The preparation of the catalyst carrier comprises the steps of fully and uniformly mixing alumina, sesbania powder and 65% concentrated nitric acid according to the mass ratio of 100 (1 ~ 3): (2 ~ 8) and a proper amount of distilled water, kneading, extruding into strips, drying at room temperature, and then drying at 100 ~ 130 ^oC drying for 3 ~ 8h, then400~600^oRoasting for 4 ~ 8h under C to obtain an alumina carrier;

b. Modifying the carrier of catalyst by modifying the carrier with assistant, which is one or more of Li, K, Mg, B and P, preparing co-immersion liquid with one or more of Li, K, Mg, B and P compounds, immersing the carrier in the co-immersion liquid, ageing the immersed carrier at room temperature for 3 ~ 8 hr, and ageing at 100 ~ 130 hr ^oC drying for 3 ~ 8h, then 400 ~ 1000 ^oRoasting for 4 ~ 8h under C to obtain modified carrier, wherein the content of the auxiliary agent in the catalyst is respectively Li in terms of oxide₂O 0.5~5 wt%，K₂O 0.5~5 wt%，MgO 0.5~5 wt%，B₂O₃ 0.5~5 wt%，P₂O₅ 0.5 ~ 5wt%, and during soaking, Li is used as precursor₂CO₃The precursor of K is K₂CO₃or KNO₃The precursor of Mg is Mg (NO)₃)₂Or MgCO₃The precursor of B is boric acid, and the precursor of P is phosphoric acid, potassium dihydrogen phosphate or ammonium dihydrogen phosphate;

c. The preparation method of the catalyst comprises loading metal active component by isovolumetric impregnation method, and comprises preparing Co-immersion liquid from one or more soluble salts of Co, Mo, Ni, and W and organic acid, impregnating modified carrier with the Co-immersion liquid, aging at room temperature for 3 ~ 8 hr, and aging at 100 ~ 130 hr ^oC drying for 3 ~ 8h, then 400 ~ 600 ^oRoasting for 4 ~ 8h under the condition of C to obtain the oxidation state catalyst, wherein the content of the active components in the catalyst is respectively CoO 2 ~ 8wt% and MoO calculated by oxide₃ 8~15 wt%，NiO 2~8 wt%，WO₃ 8 ~ 15 wt%, wherein the precursor of Co can be selected from cobalt nitrate or cobalt carbonate, the precursor of Mo can be selected from ammonium molybdate, the precursor of Ni can be selected from nickel nitrate, the precursor of W can be selected from ammonium metatungstate, the organic acid in the Co-immersion liquid is selected from one or a mixture of citric acid, glacial acetic acid, malonic acid, succinic acid, tartaric acid and malic acid, and the molar ratio of the organic acid to the active metal in the components is 0.5 ~ 3: 1.

5. The process for the total hydrogenation regeneration of spent lubricating oil according to claim 1, wherein: the hydro-upgrading catalyst is prepared by the following steps:

a. the preparation of the catalyst carrier comprises the following steps of preparing a carrier by fully and uniformly mixing the main components of macroporous alumina and one or more molecular sieves of SAPO-11 molecular sieve, ultrastable USY molecular sieve, beta molecular sieve, MCM-11 molecular sieve or ZSM-5 molecular sieve, and the mass ratio of the alumina, the molecular sieve, sesbania powder and 65% concentrated nitric acid of 100 (10 ~ 50) to (1 ~ 3) to (2 ~ 8) to a proper amount of distilled water, kneading, extruding into strips, drying at room temperature, and then drying in the air, wherein the dried catalyst carrier is prepared by 100 ~ 130 ^oC drying for 3 ~ 8h, then 400 ~ 600 ^oRoasting for 4 ~ 8h under C to obtain a hydrogenation modified catalyst carrier;

b. The preparation method of the catalyst comprises loading metal active component by isovolumetric impregnation method, and comprises preparing Co-immersion liquid from one or more soluble salts of Co, Mo, Ni, and W and organic acid, impregnating modified carrier with the Co-immersion liquid, aging at room temperature for 3 ~ 8 hr, and aging at 100 ~ 130 hr ^oC drying for 3 ~ 8h, then 400 ~ 600 ^oRoasting for 4 ~ 8h under the condition of C to obtain the oxidation state catalyst, wherein the content of the active components in the catalyst is respectively CoO 2 ~ 8wt% and MoO calculated by oxide₃ 8~15 wt%，NiO 2~8 wt%，WO₃ 8 ~ 15 wt%, wherein the precursor of Co can be selected from cobalt nitrate or cobalt carbonate, the precursor of Mo can be selected from ammonium molybdate, the precursor of Ni can be selected from nickel nitrate, the precursor of W can be selected from ammonium metatungstate, the organic acid in the Co-immersion liquid is selected from one or a mixture of citric acid, glacial acetic acid, malonic acid, succinic acid, tartaric acid and malic acid, and the molar ratio of the organic acid to the active metal in the components is 0.5 ~ 3: 1.

6. The method for preparing the hydrogenation heteroatom removal catalyst as claimed in claim 4, wherein the clover alumina carrier with the radial size of 1.1 ~ 2.0.0 mm and the length of 3 ~ 10mm is obtained by molding a kneader, a twin-screw extruder and a clover orifice plate in the step a, and the roasting operation is carried out in a muffle furnace at the roasting temperature of 520 DEG C^oC, roasting for 4 hours.

7. Root of herbaceous plantThe method for preparing the hydrogenation heteroatom removal catalyst as claimed in claim 4, wherein the method comprises the following steps: the content of the auxiliary agent used in the step b in the catalyst is respectively Li calculated as oxide₂O 3.0~5.0 wt%，K₂O 3.0~5.0 wt%，MgO 3.0~5.0 wt%，B₂O₃ 3.0~5.0 wt%，P₂O₅ 3 ~ 5wt%, wherein the precursor used for phosphorus is potassium dihydrogen phosphate.

8. The method for preparing the hydrogenation heteroatom removal catalyst according to claim 4, wherein the content of the active component in the catalyst in the step c is respectively CoO 5 ~ 8wt% and MoO calculated by oxide₃ 10~15 wt%，NiO 5~8 wt%，WO₃ 10 ~ 15 wt%, the organic acid in the co-immersion liquid is selected from citric acid, and the molar ratio of the organic acid to the active metal is 2: 1.

9. The method for producing a hydro-upgrading catalyst according to claim 5, characterized in that: and b, fully and uniformly mixing the alumina, the molecular sieve, the sesbania powder and 65% concentrated nitric acid in the step a according to the mass ratio of 100:30:3:5 and a proper amount of distilled water, wherein the molecular sieve is preferably one or two of SAPO-11 molecular sieves or ZSM-5 molecular sieves.

10. The process for preparing a hydrogenation upgrading catalyst according to claim 5, characterized in that the step a uses a kneader, a twin-screw extruder and a clover orifice plate to form and obtain the clover-shaped alumina-molecular sieve composite carrier, the radial size of the carrier is 1.1 ~ 2.1.1 mm, the length is 3 ~ 10mm, the roasting temperature is 520 mm^oC, roasting for 4 hours, wherein the content of the active component in the catalyst in the step b is respectively CoO 5 ~ 8wt% and MoO calculated by oxide₃ 10~15 wt%，NiO 5~8 wt%，WO₃ 10 ~ 15 wt%, the organic acid in the co-immersion liquid is selected from citric acid, and the molar ratio of the organic acid to the active metal is 2: 1.

Technical Field

The invention belongs to the technical fields of oil refining chemical industry, environmental protection and energy, and relates to a full hydrogenation regeneration method of waste lubricating oil.

Background

With the increasing awareness of environmental protection and the increasing strictness of environmental laws, the treatment and recycling of used lubricating oils are becoming more and more important. The waste lubricating oil is discarded or burnt, which not only causes resource waste, but also causes serious pollution to the environment. The lubricating oil consists of base oil and additives, and although the properties of the lubricating oil change after a period of use and the lubricating oil needs to be replaced, the waste lubricating oil still contains the base oil and the additives mainly and has the content of more than 90 percent. The waste lubricating oil can be regenerated and utilized, even into high-quality lubricating base oil, by the process of removing impurities in the waste lubricating oil and regenerating deteriorated components. Compared with the method for producing base oil by adopting crude oil, the method for regenerating the waste lubricating oil has the advantages of high yield and low cost, and the waste lubricating oil is regenerated, so that the consumption of the crude oil in the lubricating oil production in China is reduced, and the method helps to alleviate the energy crisis to a certain extent, so that the waste oil regeneration has important environmental and economic benefits.

The regeneration treatment technology of the waste lubricating oil mainly goes through 3 processes of acid-soil method, acid-free method, hydrogenation method and the like, the process adopted by the base oil of the waste lubricating oil regenerated by the waste lubricating oil in China is a distillation light component removal-acid cleaning-clay refining process, and a large amount of acid waste residue, alkali waste residue and sewage are generated in the sulfuric acid-clay process, so that not only is serious secondary pollution caused, but also the regeneration rate of the waste oil is low. The solvent extraction process does not use an acid solution, but the process has the disadvantage of producing large amounts of waste chemicals and waste water. The current more advanced process is a distillation-hydrogenation process, and the process is also the most environment-friendly, economic and operable waste oil regeneration process at present, and good economic benefit is obtained in actual production. The hydrogenation economy is superior to the old process due to high yield, low consumption and continuous production. Compared with solvent refined oil, the hydrogenated oil has improved color, oxidation stability and emulsifiability resistance, obviously reduced sulfur content, slightly reduced viscosity and carbon residue, and unchanged viscosity index and flash point.

The regeneration method of the waste oil reported in the patents USP3919076, USP4073719 and USP4073720 comprises: dehydration, fuel oil removal, solvent extraction, distillation, clay treatment and hydrogenation. In this process, it is necessary to use different kinds of solvents, such as propane or mixed solutions of ethanol and acetone, and before vacuum distillation, solvent extraction is used to reduce the generation of coke and fouling precursors in the spent oil that has been dehydrated and de-fueled oil. The distillation product is further upgraded by clay and hydrogenation treatment. The main disadvantages of this process are the complexity of the solvent recovery system, the high energy consumption and the generation of waste chemicals during the water/solvent separation process.

Industrial, thermal impregnation is also a method of separating additive molecules and precipitated polymers (see U.S. Pat. No. 4,4033859). U.S. Pat. No. 4,4101414 discloses a method of distillation pretreatment of raw oil in thin film evaporators, 249 ~ 345,345^oand the NOx, light component distillate oil and residual moisture can be removed by heating for at least 4 hours between C.

Patent CA1209512 provides a waste oil regeneration method, and the waste oil regeneration process in the invention comprises: (1) heating and dipping the waste oil; (2) removing the conversion product with lower boiling point from the heated waste oil under normal pressure or reduced pressure; (3) distilling and removing the heated oil product; (4) feeding distilled waste oil into a protective agent bed layer containing an active material; (5) and carrying out hydrotreatment on the waste oil treated by the protective agent.

CN201610879648.X discloses a process for regenerating used lubricating oil by hydrogenation. The process comprises a pretreatment unit, a hydrogenation regeneration unit and a separation unit. Wherein the carrier used by the hydrogenation regeneration catalyst is a compound or a mixture of MSU-G, SBA-15 and HMS, and the active component is molybdenum nitride Mo₂N, tungsten nitride W₂N, molybdenum carbide Mo₂C and tungsten carbide WC, and Cr as assistant₂O₃、ZrO₂、CeO₂、V₂O₅And NbOPO₄A mixture of (a). The process can control the sulfur content in the regenerated lubricating oil to be lower than 5 ppm and the total nitrogen content to be within 10 ppm.

CN100445355C provides a spent lubricating oil hydrogenation regeneration method, which comprises the following steps: dehydration → filtration → adsorption → prehydrogenation and refining → hydrorefining. Wherein the adsorbent is oxidizedThe pre-hydrogenation refining protective agent is prepared by loading one or more active metals of molybdenum, nickel and tungsten on an alumina carrier, the loading amount of the active metals is 5 percent ~ 10 percent, CN100434170C provides a preparation method of a hydrofining catalyst, the hydrofining catalyst is formed by loading an active component W, Ni and an auxiliary agent P on the alumina carrier, and the contents of the active component and the auxiliary agent are WO based on the total mass of the catalyst₃25 ~ 35%, NiO2.0% ~ 7.0.0%, P2.0% ~ 5.5.5%, the invention can regenerate the used lubricating oil into the lubricating oil base oil or blending component, the recovery rate of the used lubricating oil can reach above 90%.

The patent CN201310393537.4 provides a regeneration process of waste lubricating oil and a preparation method of a hydrogenation catalyst aiming at the problems of high energy consumption, serious secondary pollution, low quality of obtained products, poor quality of raw materials of the waste lubricating oil, complex composition and the like of a waste lubricating oil regeneration technology, the regeneration process comprises visbreaking pretreatment, atmospheric and vacuum distillation, prehydrogenation and hydrorefining, wherein the visbreaking pretreatment is carried out on adsorbent porous porcelain balls, active alumina, porous silica or carclazyte, a protective agent is prepared by loading one or more metal components of molybdenum, tungsten, cobalt and nickel on an active macroporous alumina carrier, the metal loading amount is 1 ~ 5wt% calculated as an oxide, the main component of the hydrogenation catalyst carrier is aluminum hydroxide dry glue, and the auxiliary component is SiO selected as an auxiliary component₂Y molecular sieve or MCM-41 molecular sieve, and the final hydrofining catalyst is a vulcanized MoNiP catalyst. The invention can regenerate the waste lubricating oil into the lubricating oil base oil or the blending component, and the process has the characteristics of no pollution, convenient operation, wide application range of raw materials, higher product quality and the like.

The above patent contents show that products meeting the standards of lubricant base oils can be obtained by using the hydrogenation regeneration method. From the environmental point of increasing deterioration, hydrofining eliminates the three-waste treatment of the traditional refining, is beneficial to the purification of ecological environment, and can remove the non-ideal components (oxygen-containing compounds, sulfur-containing compounds, nitrogen-containing compounds, polycyclic aromatic hydrocarbons, colloid and asphaltene) in the waste lubricating oil through hydrofining. In addition, because the types and the use amounts of the additives in the lubricating oil are increased, before the used lubricating oil is subjected to hydrofining, metal impurities in the used lubricating oil are removed by pre-hydrogenation, so that the hydrofining catalyst can be ensured to operate for a long time. However, the quality requirement for the lubricant products in the 21 st century is to produce high performance lubricants, and base oils with low kinematic viscosity, low volatility, and high viscosity index must be used. The standard of general lubricating oil base oil released in 2009 in China currently is seven varieties in three categories according to the content of saturated hydrocarbon and the viscosity index, wherein the category I is four varieties of base oil, namely Medium Viscosity Index (MVI), High Viscosity Index (HVI), high viscosity index deep refining (HVIS) and high viscosity index low freezing point (HVIW); II is divided into two varieties of base oil of High Viscosity Index Hydrogenation (HVIH) and high viscosity index high quality Hydrogenation (HVIP); group III is only provided with very high viscosity index hydrogenation (VHVI) base oil of one variety. The low freezing point base oil (HVIW) and the deep refined base oil (HVIS) have lower pour point and low volatility, the performance is superior to the base oil with the class I viscosity index and the high viscosity index, and the tendency of more environment protection, more energy conservation and higher quality is required for the vehicle lubricating oil in the future in China. Therefore, the quality of the hydrorefined lubricating oil needs to be further improved. The key technology for improving the quality of the lubricating oil is to isomerize the alkane in the lubricating oil and reduce the condensation point of the lubricating oil.

Disclosure of Invention

The invention aims to provide a more environment-friendly waste lubricating oil full hydrogenation regeneration process and a preparation method of a matched catalyst, aiming at increasing the regeneration difficulty of waste lubricating oil by increasing the types and the dosage of additives for improving the quality of lubricating oil products in China and increasing the demand of China on high-grade lubricating oil base oil with low condensation point and high viscosity index, and the waste lubricating oil is dehydrated and adsorbed in the early stage and then is subjected to pre-hydrogenation, hydrofining and later-stage hydrogenation modification to realize the dehydration, removal of mechanical impurities, colloid removal, asphaltene removal, demetallization, deoxidation, desulfurization, denitrification and dechlorination of the waste lubricating oil, and under the action of a hydrogenation modification catalyst, the alkane isomerization function is realized, the condensation point of the regenerated oil is reduced, and the regenerated oil reaches the standards of high-viscosity low-condensation point (HVIW) and high-viscosity deep-refining (HVIS) base oil. The method for regenerating the waste lubricating oil avoids secondary pollution generated in the process, and can obtain the regenerated oil with higher oil product quality. The technical scheme at least comprises pretreatment, hydrodemetallization, hydrogenation impurity removal atoms and hydrogenation modification, and the specific processes are as follows:

(1) The pretreatment comprises the steps of dehydrating and adsorbing the raw material waste lubricating oil for impurity removal, wherein the raw material waste lubricating oil firstly enters a dehydrating tank and is heated to 50 ~ 100 DEG^oC, dehydrating, and then entering a pretreatment reactor for adsorption and impurity removal under the operating conditions that the reaction temperature is 250 ~ 350^oC, volume space velocity of 0.2 ~ 1.6.6 h^-1The pressure is 0.5 ~ 1.6.6 MPa, the volume ratio of hydrogen to oil is 300 ~ 500 (v/v), the adsorption treatment is to treat the waste lubricating oil by using active alumina as an adsorbent, and through the process, the water, mechanical impurities, colloid, asphaltene and most heavy metal impurities in the waste lubricating oil are removed;

(2) Hydrodemetallization, namely, the pretreated waste lubricating oil enters a pre-hydrogenation unit to further remove residual metal impurities, wherein the operation condition is that the temperature is 260 ~ 360 DEG^oC, volume space velocity of 0.5 ~ 2.0.0 h^-1The pressure is 3.0 ~.0 MPa, the hydrogen-oil volume ratio is 300 ~ (v/v), the subsequent hydrofining catalyst can be protected from being blocked and poisoned by metal impurities through the process, and the service life of the hydrofining catalyst is prolonged, wherein the pre-hydrogenation catalyst takes macroporous alumina as a carrier, and one or two metals of Mo and Ni as active components, and the loading of the active components is 5 ~ wt% in terms of oxides;

(3) Hydrogenation impurity removal atom, namely, the waste lubricating oil after pre-hydrogenation enters a hydrogenation impurity removal atom unit under the operation condition that the temperature is 280 ~ 360^oC, volume space velocity of 0.5 ~ 2.0.0 h^-1The pressure is 3.0 ~ 8.0.0 MPa, the volume ratio of hydrogen to oil is 300 ~ 800 (v/v), the non-ideal components (oxygen-containing compound, sulfur-containing compound, nitrogen-containing compound, polycyclic aromatic hydrocarbon, colloid, asphaltene) in the waste lubricating oil are removed by the process, and the oxidation instability of the regenerated oil is improved by hydrogenating unsaturated hydrocarbon in the waste oilB. One or more than two of P, wherein the content of the active components in the catalyst is respectively CoO 2 ~ 8wt% and MoO calculated by oxide based on the total weight of the catalyst₃ 8~20 wt%，NiO 2~8 wt%，WO₃20 ~ 40 wt%, and the content of the auxiliary agent in the catalyst is Li calculated by oxide respectively₂O 0.5~5 wt%，K₂O 0.5~5 wt%，MgO 0.5~5 wt%，B₂O₃ 0.5~5 wt%，P₂O₅ 0.5 ~ 5wt% and the specific surface area of the macroporous alumina is more than or equal to 200 m²The pore volume is more than or equal to 0.4 ml/g;

The preparation method of the catalyst for preferentially hydrogenating and removing the heteroatom comprises the following specific steps of:

a. The preparation of the catalyst carrier comprises the steps of fully and uniformly mixing alumina, sesbania powder and concentrated nitric acid according to the mass ratio of 100 (1 ~ 3): (2 ~ 8) and a proper amount of distilled water, kneading, extruding into strips, drying at room temperature, and then drying at 100 ~ 130 ^oCDried for 3 ~ 8h, then at 400 ~ 600 ^oCRoasting for 4 ~ 8h to obtain an alumina carrier;

b. Modifying the carrier of catalyst by modifying the carrier with assistant, which is one or more of Li, K, Mg, B and P, preparing co-immersion liquid with one or more of Li, K, Mg, B and P compounds, immersing the carrier in the co-immersion liquid, ageing the immersed carrier at room temperature for 3 ~ 8 hr, and ageing at 100 ~ 130 hr ^oCDried for 3 ~ 8h, and then at 400 ~ 1000 ^oCRoasting for 4 ~ 8h to obtain a modified carrier, wherein the contents of the auxiliary agents in the catalyst are respectively Li in terms of oxides₂O 0.5~5 wt%，K₂O 0.5~5 wt%，MgO 0.5~5 wt%，B₂O₃ 0.5~5 wt%，P₂O₅ 0.5 ~ 5wt%, and during soaking, Li is used as precursor₂CO₃the precursor of K is K₂CO₃Or KNO₃The precursor of Mg is Mg (NO)₃)₂Or MgCO₃The precursor of B is boric acid, and the precursor of P is phosphoric acid or ammonium dihydrogen phosphate;

c. Preparation of the catalyst: the method adopts an equal-volume impregnation method to load metal active components, and comprises the following specific steps: by using one or more of Co, Mo, Ni, WPreparing co-soaking solution from various soluble salts and organic acid, soaking modified carrier with the co-soaking solution, aging at room temperature for 3 ~ 8h at 100 ~ 130% ^oCDried for 3 ~ 8h, then at 400 ~ 600 ^oCRoasting for 4 ~ 8h to obtain the oxidation state catalyst, wherein the content of the active components in the catalyst is respectively CoO 2 ~ 8wt% and MoO calculated by oxide₃ 8~15 wt%，NiO 2~8 wt%，WO₃ 8 ~ 15 wt%, wherein the precursor of Co can be selected from cobalt nitrate or cobalt carbonate, the precursor of Mo can be selected from ammonium molybdate, the precursor of Ni can be selected from nickel nitrate, the precursor of W can be selected from ammonium metatungstate, the organic acid in the Co-immersion liquid is selected from one or a mixture of citric acid, glacial acetic acid, malonic acid, succinic acid, tartaric acid and malic acid, and the molar ratio of the organic acid to the active metal in the components is 0.5 ~ 3: 1;

(4) Hydro-upgrading, namely, the product after hydro-impurity removal enters a hydro-upgrading unit under the operation condition that the temperature is 280 ~ 400^oC, volume space velocity of 0.5 ~ 2.0.0 h^-1The hydro-upgrading catalyst takes a compound of one or more mesoporous molecular sieves of alumina, SAPO-11 molecular sieve, ultrastable USY molecular sieve, beta molecular sieve, MCM-11 molecular sieve or ZSM-5 molecular sieve as a carrier and one or more metals of active components Co, Mo, Ni and W, wherein the content of the active components in the catalyst is respectively CoO 2 ~ wt% and MoO 2 ~ wt%, calculated by oxide, and the content of the active components in the catalyst is 300 ~ (v/v)₃ 8~15 wt%，NiO 2~8 wt%，WO₃ 8 ~ 15 wt% and the specific surface area of alumina is more than or equal to 200 m²The volume of pores is more than or equal to 0.4 ml/g, and the weight ratio of the alumina to the mesoporous molecular sieve is 100 (10 ~ 50);

The preparation method of the preferable hydro-upgrading catalyst comprises the following specific steps:

a. preparation of a catalyst carrier: the main components of the carrier are macroporous alumina, SAPO-11 molecular sieve and ultrastable USY moleculeOne or more molecular sieve compounds selected from sieve, beta molecular sieve, MCM-11 molecular sieve or ZSM-5 molecular sieve, alumina, molecular sieve, sesbania powder and concentrated nitric acid according to the mass ratio of 100 (10 ~ 50) to (1 ~ 3) to (2 ~ 8) and a proper amount of distilled water are fully and uniformly mixed, kneaded, extruded and formed, dried at room temperature and then placed in 100 ~ 130 ^oCDried for 3 ~ 8h, then at 400 ~ 600 ^oCRoasting for 4 ~ 8h to obtain a hydrogenation modified catalyst carrier;

b. The preparation method of the catalyst comprises loading metal active component by isovolumetric impregnation method, and comprises preparing Co-immersion liquid from one or more soluble salts of Co, Mo, Ni, and W and organic acid, impregnating modified carrier with the Co-immersion liquid, aging at room temperature for 3 ~ 8 hr, and aging at 100 ~ 130 hr ^oCDried for 3 ~ 8h, then at 400 ~ 600 ^oCroasting for 4 ~ 8h to obtain the oxidation state catalyst, wherein the content of the active components in the catalyst is respectively CoO 2 ~ 8wt% and MoO calculated by oxide₃ 8~15 wt%，NiO 2~8 wt%，WO₃ 8 ~ 15 wt%, wherein the precursor of Co can be selected from cobalt nitrate or cobalt carbonate, the precursor of Mo can be selected from ammonium molybdate, the precursor of Ni can be selected from nickel nitrate, the precursor of W can be selected from ammonium metatungstate, the organic acid in the Co-immersion liquid is selected from one or a mixture of citric acid, glacial acetic acid, malonic acid, succinic acid, tartaric acid and malic acid, and the molar ratio of the organic acid to the active metal in the components is 0.5 ~ 3: 1;

In conclusion, the method for fully hydrogenating and regenerating the waste lubricating oil can remove various non-ideal components in the waste lubricating oil through the combination of pretreatment, hydrogenation demetalization, hydrogenation impurity removal atoms and hydrogenation modification, and the quality of the regenerated oil product can reach the standards of high-viscosity low-condensation (HVIW) and high-viscosity deep refined (HVIS) base oil. The method has simple process flow and strong operability, and does not produce secondary pollution such as waste acid residue, waste alkali residue, waste argil, sewage and the like in the process. The adsorbent, the pre-hydrogenation catalyst, the hydrofining catalyst and the hydro-upgrading catalyst used in the invention have the characteristics of large specific surface area, large pore volume, good stability, high activity, good selectivity and long service life, and are beneficial to the continuous operation of the regeneration process.

Drawings

The invention is further described below with reference to the figures and examples.

FIG. 1 is a schematic diagram of a process for regenerating a spent lubricating oil by total hydrogenation according to the present invention.

Detailed Description

The process for regenerating used lubricating oil and the method for preparing the catalyst according to the present invention will be described in further detail with reference to the following examples.