CN112717946A - Spent lubricating oil hydrogenation regeneration catalyst and preparation method thereof - Google Patents
Spent lubricating oil hydrogenation regeneration catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 74
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 56
- 230000008929 regeneration Effects 0.000 title claims abstract description 55
- 238000011069 regeneration method Methods 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011218 binary composite Substances 0.000 claims abstract description 45
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 36
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 claims abstract description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 24
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 24
- 238000005470 impregnation Methods 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 22
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003980 solgel method Methods 0.000 claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 75
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000002699 waste material Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- CDXSJGDDABYYJV-UHFFFAOYSA-N acetic acid;ethanol Chemical compound CCO.CC(O)=O CDXSJGDDABYYJV-UHFFFAOYSA-N 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 11
- 229940010552 ammonium molybdate Drugs 0.000 claims description 11
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 11
- 239000011609 ammonium molybdate Substances 0.000 claims description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 5
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 238000011946 reduction process Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000010453 quartz Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 239000012494 Quartz wool Substances 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004951 benzene Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/0083—Lubricating greases
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a spent lubricating oil hydrogenation regeneration catalyst, which consists of a carrier and an active component, wherein the carrier is a binary composite carrier TiO synthesized by a sol-gel method2‑Al2O3The active components are CoO and MoO3And the mass content of CoO in the catalyst is 6-9%, MoO3The mass content of (A) is 15-30%; the invention also discloses a preparation method of the spent lubricating oil hydrogenation regeneration catalyst, which is characterized in that the metal salt impregnation liquid of the active component is added into the binary composite carrier TiO2‑Al2O3Obtaining a catalyst precursor, and then reducing. The invention introduces TiO with electron promotion effect into the carrier2The reduction capability of the catalyst is improved, and the pressure of the catalytic reaction condition of the catalyst is reduced; hair brushObviously adopts sol-gel method to prepare carrier, and improves nano TiO2The dispersing ability of the particles improves the overall reducing ability of the catalyst.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a spent lubricating oil hydrogenation regeneration catalyst and a preparation method thereof.
Background
In recent years, with the rapid development of the automobile industry and the machine industry, the demand for high-quality lubricating oil has been promoted. The capability of hydrogenation production of II and III base oil in China is far from meeting the demand. While the price of crude oil is continuously rising and the petroleum resources are gradually decreasing, the regeneration of waste oil is increasingly attracting attention of people, particularly the recycling of waste lubricating oil is expected to reach the quality level of new lubricating oil base oil.
The lubricating oil is mixed with water, dust and friction metal powder in the using process and is subjected to high temperature, high pressure and oxidation to cause the lubricating oil to deteriorate. The waste lubricating oil contains various toxic and harmful substances such as heavy metal, benzene series, polycyclic aromatic hydrocarbon and the like, and the environment pollution can be caused by improper treatment. But the deteriorated part of the waste lubricating oil only accounts for 10 to 25 percent, and the waste lubricating oil can be converted into products such as base oil, fuel oil and the like by a regeneration technology and reused. The method has important significance for relieving the shortage of petroleum resources in China and protecting the environment.
The regeneration process of the waste lubricating oil at home and abroad develops towards a hydrogenation process with less pollution and no pollution. The core of the hydrogenation regeneration of the lubricating oil is the development of a hydrogenation catalyst. CN101797509 proposes a catalyst for hydrogenation regeneration of waste lubricating oil, which is formed by loading active components W, Ni and Si on an alumina carrier, and the catalyst is used for hydrogenation regeneration of the whole fraction of the waste lubricating oil to remove S, N, O and heavy metal impurities in the waste lubricating oil, but the catalyst is applicable under a high pressure (15 MPa).
Disclosure of Invention
The technical problem to be solved by the invention is to provide a catalyst for hydrogenation regeneration of waste lubricating oil, aiming at the defects of the prior art. The catalyst adopts binary composite carrier TiO2-Al2O3As a carrier of the catalyst, by introducing TiO with electron promoting effect2So that the electron donating capability of the active metal in the active component is enhanced, thereby improving the reducing capability of the catalyst and reducing the catalysis of the catalystThe reaction conditions, especially the pressure of the catalyst for catalyzing the hydrogenation regeneration of the waste lubricating oil is reduced.
In order to solve the technical problems, the invention adopts the technical scheme that: the catalyst for hydrogenation regeneration of the waste lubricating oil is characterized by comprising a carrier and an active component, wherein the carrier is a binary composite carrier TiO synthesized by a sol-gel method2-Al2O3The active components are CoO and MoO3And the mass content of CoO in the catalyst is 6-9%, MoO3The mass content of (A) is 15-30%; the specific surface area of the catalyst is 220m2/g～231m2The pore volume is 0.65 mL/g-0.70 mL/g, and the average pore diameter is 11 nm-12 nm.
The invention adopts a binary composite carrier TiO synthesized by a sol-gel method2-Al2O3As a carrier of the catalyst, the carrier contains Al2O3The method has the advantages of large specific surface area, proper pore structure, good mechanical strength and thermal stability, and simultaneously introduces TiO with electron promotion effect2The electron-donating capability of the active metal in the active component is enhanced, so that the reducing capability of the catalyst is improved, the catalytic reaction condition of the catalyst is reduced, and particularly the pressure of the catalyst for catalyzing the hydrogenation regeneration of the waste lubricating oil is reduced.
In addition, the invention also provides a method for preparing the spent lubricating oil hydrogenation regeneration catalyst, which is characterized by comprising the following steps:
step one, preparing binary composite carrier TiO2-Al2O3: deionized water, ethanol and acetic acid were mixed according to a 1: 2.5-3: mixing the titanium oxide and the titanium oxide in a volume ratio of 0.2-0.5, adjusting the pH value to 3-4 by using acetic acid to obtain an ethanol-acetic acid solution, slowly adding butyl titanate into the ethanol-acetic acid solution which is rapidly stirred to prepare titanium sol, and adding gamma-Al into the titanium sol2O3Continuously stirring until white sol is generated, centrifugally filtering, sequentially cleaning with absolute ethyl alcohol and deionized water, drying and roasting to obtain binary composite carrier TiO2-Al2O3(ii) a The gamma-Al2O3The added mass of the titanium dioxide is 70-90% of the mass of the butyl titanate;
step two, preparing a catalyst precursor: mixing cobalt salt, ammonium molybdate and deionized water according to the proportion of 1: 2-4: 8-10, regulating the pH value to 3-4 by adopting an acetic acid solution to obtain a transparent impregnation liquid, and adding the impregnation liquid into the binary composite carrier TiO prepared in the step one2-Al2O3Stirring, dipping, drying and roasting to obtain a catalyst precursor; the binary composite carrier TiO2-Al2O3The mass of the impregnation liquid is 35 to 60 percent of the mass of the impregnation liquid;
step three, catalyst preparation: and D, reducing the catalyst precursor obtained in the step two to obtain the spent lubricating oil hydrogenation regeneration catalyst.
The invention adopts a sol-gel method, uses ethanol as a phase separation medium and acetic acid as a catalyst, so that the ethyl titanate generates decomposition reaction after meeting water to obtain the nano TiO with good dispersibility2Particles of and TiO2Al is uniformly coated with nano-sized particles2O3To obtain binary composite carrier TiO2-Al2O3(ii) a Then, the dipping liquid containing metal salt is fully dipped by adopting a stirring dipping method and enters the binary composite carrier TiO2-Al2O3The active components are effectively loaded on the surface and in the pore channels, and after drying and roasting, a catalyst precursor is obtained and then reduced to obtain the spent lubricating oil hydrogenation regeneration catalyst.
The method is characterized in that the drying temperature in the first step and the drying temperature in the second step are both 110-130 ℃, and the drying time is both 10-12 hours; the roasting temperature is 400-600 ℃, and the roasting time is 4-6 h.
The method is characterized in that the cobalt salt in the second step is cobalt nitrate, cobalt acetate or cobalt carbonate.
The method is characterized in that the rotating speed of stirring and dipping in the step two is 150 r/min-350 r/min, and the time is 30 min-60 min.
The method is characterized in that the reduction in the third step adopts a temperature programming reduction process, and the specific process is as follows: purging the catalyst precursor for 30-60 min at 180-300 ℃ by adopting nitrogen at the flow rate of 100-200 mL/min, then switching to introduce hydrogen at the flow rate of 50-150 mL/min, heating to 500-700 ℃ at the rate of 3-5 ℃/min, preserving the heat for 4-7 h, cooling to room temperature in a hydrogen atmosphere, and finally passivating for 3h in the nitrogen atmosphere introduced at the flow rate of 50 mL/min. The optimized reduction process effectively removes oxygen in the reduction device and the catalyst precursor pore channel, and adopts hydrogen to carry out temperature programmed reduction reaction, so that metal salt roasting products on the surface of the catalyst precursor and in the pore channel are fully reduced, and the activity of the spent lubricating oil hydrogenation regeneration catalyst is ensured.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts binary composite carrier TiO2-Al2O3As a carrier of the catalyst, by introducing TiO with electron promoting effect2The electron-donating capability of the active metal in the active component is enhanced, so that the reducing capability of the catalyst is improved, the catalytic reaction condition of the catalyst is reduced, and particularly the pressure of the catalyst for catalyzing the hydrogenation regeneration of the waste lubricating oil is reduced.
2. The pressure of the catalyst for hydrogenation regeneration of the waste lubricating oil is reduced to 7MPa, and the application range of the catalyst is expanded.
3. The invention adopts a sol-gel method to ensure that the nano TiO is2Particles are coated on Al2O3To obtain binary composite carrier TiO2-Al2O3In the presence of Al2O3On the premise of specific surface area, the nano TiO is improved2The dispersing ability of the particles is beneficial to improving the integral reducing ability of the catalyst.
4. According to the invention, the stirring impregnation method is adopted to load the metal salt of the active component, and the waste lubricating oil hydrogenation regeneration catalyst is obtained after reduction, so that the loading capacity of the active component is effectively ensured, and the catalyst has higher reinforced catalytic activity and selectivity.
The technical solution of the present invention is further described in detail by examples below.
Detailed Description
Example 1
The catalyst for hydrogenation regeneration of the waste lubricating oil comprises a carrier and an active component, wherein the carrier is a binary composite carrier TiO synthesized by a sol-gel method2-Al2O3The active components are CoO and MoO3And the mass content of CoO in the catalyst is 8.4 percent, and MoO3The mass content of (b) was 17.9%.
The preparation method of the spent lubricating oil hydrogenation regeneration catalyst of the embodiment comprises the following steps:
step one, preparing binary composite carrier TiO2-Al2O3: mixing 10mL of deionized water, 25mL of ethanol and 2mL of acetic acid, adjusting the pH value to 3 by using the acetic acid to obtain an ethanol-acetic acid solution, slowly adding 2.00g of butyl titanate into the ethanol-acetic acid solution which is quickly stirred to prepare titanium sol, and adding 1.80g of gamma-Al into the titanium sol2O3Continuously stirring until white sol is generated, centrifugally filtering, sequentially cleaning with absolute ethyl alcohol and deionized water, drying at 110 ℃ for 12h and roasting at 400 ℃ for 6h to obtain binary composite carrier TiO2-Al2O3；
Step two, preparing a catalyst precursor: 2.4028g of cobalt nitrate, 4.8056g of ammonium molybdate and 19.2231g of deionized water are mixed until the cobalt nitrate, the ammonium molybdate and the deionized water are completely dissolved, acetic acid solution is adopted to adjust the pH value to 3, transparent impregnation liquid is obtained, and then 13.2158g of binary composite carrier TiO prepared in the step one is added into the impregnation liquid2-Al2O3Stirring and dipping at 150r/min for 60min, drying at 110 ℃ for 12h and roasting at 400 ℃ for 6h to obtain a catalyst precursor;
step three, catalyst preparation: and D, adding the catalyst precursor obtained in the step two into a temperature control area of a quartz tube, supporting two ends of the quartz tube by quartz cotton, purging the catalyst precursor for 60min at 180 ℃ by adopting nitrogen at a flow rate of 100mL/min, switching to introduce hydrogen at a flow rate of 50mL/min, heating to 500 ℃ at a rate of 3 ℃/min, preserving the heat for 7h, cooling to room temperature in a hydrogen atmosphere, and finally passivating for 3h in a nitrogen atmosphere introduced at a flow rate of 50mL/min to obtain the spent lubricating oil hydrogenation regeneration catalyst, which is marked as catalyst A.
Comparative example 1
The waste lubricating oil hydrogenation regeneration catalyst of the comparative example consists of a carrier and an active component, wherein the carrier is a binary composite carrier TiO synthesized by a sol-gel method2-Al2O3The active components are CoO and MoO3And the mass content of CoO in the catalyst is 8.4 percent, and MoO3The mass content of (b) was 17.9%.
The preparation method of the spent lubricating oil hydrogenation regeneration catalyst of the comparative example comprises the following steps:
step one, preparing binary composite carrier TiO2-Al2O3: mixing 10mL of deionized water, 25mL of ethanol and 2mL of acetic acid, adjusting the pH value to 3 by using the acetic acid to obtain an ethanol-acetic acid solution, then adding 2.00g of butyl titanate into the ethanol-acetic acid solution, dispersing for 10min under ultrasonic waves, stirring and adding 1.80g of gamma-Al2O3Continuously stirring until white sol is generated, centrifugally filtering, sequentially cleaning with absolute ethyl alcohol and deionized water, drying at 110 ℃ for 12h and roasting at 400 ℃ for 6h to obtain binary composite carrier TiO2-Al2O3；
Step two, preparing a catalyst precursor: 2.4028g of cobalt nitrate, 4.8064g of ammonium molybdate and 19.2222g of deionized water are mixed until the cobalt nitrate, the ammonium molybdate and the deionized water are completely dissolved, acetic acid solution is adopted to adjust the pH value to 3, transparent impregnation liquid is obtained, and then 13.2158g of binary composite carrier TiO prepared in the step one is added into the impregnation liquid2-Al2O3Stirring and dipping at 150r/min for 60min, drying at 110 ℃ for 12h and roasting at 400 ℃ for 6h to obtain a catalyst precursor;
step three, catalyst preparation: adding the catalyst precursor obtained in the step two into a temperature control area of a quartz tube, supporting two ends of the quartz tube by quartz cotton, purging the catalyst precursor for 60min at 180 ℃ by adopting nitrogen at a flow rate of 100mL/min, then switching to introduce hydrogen at a flow rate of 50mL/min, heating to 500 ℃ at a rate of 3 ℃/min, preserving heat for 7h, cooling to room temperature in a hydrogen atmosphere, and finally, cooling to room temperature in the hydrogen atmospherePassivating for 3h in nitrogen atmosphere introduced at the flow rate of 50mL/min to obtain the spent lubricating oil hydrogenation regenerated catalyst, which is marked as catalyst A0。
Example 2
The catalyst for hydrogenation regeneration of the waste lubricating oil comprises a carrier and an active component, wherein the carrier is a binary composite carrier TiO synthesized by a sol-gel method2-Al2O3The active components are CoO and MoO3And the mass content of CoO in the catalyst is 7.3 percent, and MoO3The mass content of (A) is 15.6%.
The preparation method of the spent lubricating oil hydrogenation regeneration catalyst of the embodiment comprises the following steps:
step one, preparing binary composite carrier TiO2-Al2O3: mixing 10mL of deionized water, 30mL of ethanol and 5mL of acetic acid, adjusting the pH value to 4 by using the acetic acid to obtain an ethanol-acetic acid solution, slowly adding 2.50g of butyl titanate into the ethanol-acetic acid solution which is quickly stirred to prepare titanium sol, and adding 2.13g of gamma-Al into the titanium sol2O3Continuously stirring until white sol is generated, centrifugally filtering, sequentially cleaning with absolute ethyl alcohol and deionized water, drying at 130 ℃ for 10h and roasting at 600 ℃ for 4h to obtain binary composite carrier TiO2-Al2O3；
Step two, preparing a catalyst precursor: 2.4032g of cobalt carbonate, 4.8066g of ammonium molybdate and 19.2254g of deionized water are mixed to be completely dissolved, the pH value is adjusted to 3 by adopting an acetic acid solution to obtain a transparent impregnation liquid, and then 15.8611g of binary composite carrier TiO prepared in the step one is added into the impregnation liquid2-Al2O3Stirring and soaking at 350r/min for 30min, drying at 130 ℃ for 10h, and roasting at 600 ℃ for 4h to obtain a catalyst precursor;
step three, catalyst preparation: and D, adding the catalyst precursor obtained in the step two into a temperature control area of a quartz tube, supporting two ends of the quartz tube by quartz wool, purging the catalyst precursor for 30min at 300 ℃ by adopting nitrogen at a flow rate of 200mL/min, then switching to introduce hydrogen at a flow rate of 150mL/min, heating to 700 ℃ at a speed of 5 ℃/min, preserving heat for 4h, cooling to room temperature in a hydrogen atmosphere, and finally passivating for 3h in a nitrogen atmosphere introduced at a flow rate of 50mL/min to obtain the spent lubricating oil hydrogenation regeneration catalyst, which is marked as catalyst B.
Example 3
The catalyst for hydrogenation regeneration of the waste lubricating oil comprises a carrier and an active component, wherein the carrier is a binary composite carrier TiO synthesized by a sol-gel method2-Al2O3The active components are CoO and MoO3And the mass content of CoO in the catalyst is 7.0 percent, and MoO3The mass content of (A) is 20.0%.
The preparation method of the spent lubricating oil hydrogenation regeneration catalyst of the embodiment comprises the following steps:
step one, preparing binary composite carrier TiO2-Al2O3: mixing 10mL of deionized water, 27mL of ethanol and 3mL of acetic acid, adjusting the pH value to 3.5 by using the acetic acid to obtain an ethanol-acetic acid solution, slowly adding 3.00g of butyl titanate into the ethanol-acetic acid solution which is quickly stirred to prepare titanium sol, and adding 2.40g of gamma-Al into the titanium sol2O3Continuously stirring until white sol is generated, centrifugally filtering, sequentially cleaning with absolute ethyl alcohol and deionized water, drying at 120 ℃ for 11h and roasting at 500 ℃ for 5h to obtain binary composite carrier TiO2-Al2O3；
Step two, preparing a catalyst precursor: 2.4028g of cobalt acetate, 7.2081g of ammonium molybdate and 21.6254g of deionized water are mixed until the cobalt acetate, the ammonium molybdate and the deionized water are completely dissolved, the pH value is adjusted to 3.5 by adopting an acetic acid solution to obtain a transparent impregnation liquid, and then 14.0563g of the binary composite carrier TiO prepared in the step one is added into the impregnation liquid2-Al2O3Stirring and soaking for 45min at the speed of 250r/min, drying for 11h at the temperature of 120 ℃, and roasting for 5h at the temperature of 500 ℃ to obtain a catalyst precursor;
step three, catalyst preparation: and D, adding the catalyst precursor obtained in the step two into a temperature control area of a quartz tube, supporting two ends of the quartz tube by quartz cotton, purging the catalyst precursor for 40min at 240 ℃ by adopting nitrogen at a flow rate of 150mL/min, switching to introduce hydrogen at a flow rate of 100mL/min, heating to 600 ℃ at a speed of 4 ℃/min, preserving the temperature for 5h, cooling to room temperature in a hydrogen atmosphere, and finally passivating for 3h in a nitrogen atmosphere introduced at a flow rate of 50mL/min to obtain the spent lubricating oil hydrogenation regeneration catalyst, which is marked as catalyst C.
Example 4
The catalyst for hydrogenation regeneration of the waste lubricating oil comprises a carrier and an active component, wherein the carrier is a binary composite carrier TiO synthesized by a sol-gel method2-Al2O3The active components are CoO and MoO3And the mass content of CoO in the catalyst is 7.2 percent, and MoO3The mass content of (A) is 30.8%.
The preparation method of the spent lubricating oil hydrogenation regeneration catalyst of the embodiment comprises the following steps:
step one, preparing binary composite carrier TiO2-Al2O3: mixing 10mL of deionized water, 30mL of ethanol and 5mL of acetic acid, adjusting the pH value to 4 by using the acetic acid to obtain an ethanol-acetic acid solution, slowly adding 3.50g of butyl titanate into the ethanol-acetic acid solution which is quickly stirred to prepare titanium sol, and adding 2.63g of gamma-Al into the titanium sol2O3Continuously stirring until white sol is generated, centrifugally filtering, sequentially cleaning with absolute ethyl alcohol and deionized water, drying at 130 ℃ for 10h and roasting at 600 ℃ for 4h to obtain binary composite carrier TiO2-Al2O3；
Step two, preparing a catalyst precursor: 2.4027g of cobalt carbonate, 9.6108g of ammonium molybdate and 24.0268g of deionized water are mixed to be completely dissolved, the pH value is adjusted to 3 by adopting an acetic acid solution to obtain a transparent impregnation liquid, and then 12.9745g of binary composite carrier TiO prepared in the step one is added into the impregnation liquid2-Al2O3Stirring and soaking at 350r/min for 30min, drying at 130 ℃ for 10h, and roasting at 600 ℃ for 4h to obtain a catalyst precursor;
step three, catalyst preparation: and D, adding the catalyst precursor obtained in the step two into a temperature control area of a quartz tube, supporting two ends of the quartz tube by quartz wool, purging the catalyst precursor for 30min at 300 ℃ by adopting nitrogen at a flow rate of 200mL/min, switching to introduce hydrogen at a flow rate of 150mL/min, heating to 700 ℃ at a speed of 5 ℃/min, preserving heat for 4h, cooling to room temperature in a hydrogen atmosphere, and finally passivating for 3h in a nitrogen atmosphere introduced at a flow rate of 50mL/min to obtain the spent lubricating oil hydrogenation regeneration catalyst, which is marked as catalyst D.
Example 5
The catalyst for hydrogenation regeneration of the waste lubricating oil comprises a carrier and an active component, wherein the carrier is a binary composite carrier TiO synthesized by a sol-gel method2-Al2O3The active components are CoO and MoO3And the mass content of CoO in the catalyst is 6.7 percent, and MoO3The mass content of (b) is 28.0%.
The preparation method of the spent lubricating oil hydrogenation regeneration catalyst of the embodiment comprises the following steps:
step one, preparing binary composite carrier TiO2-Al2O3: mixing 10mL of deionized water, 30mL of ethanol and 5mL of acetic acid, adjusting the pH value to 4 by using the acetic acid to obtain an ethanol-acetic acid solution, slowly adding 4.00g of butyl titanate into the ethanol-acetic acid solution which is quickly stirred to prepare titanium sol, and adding 2.80g of gamma-Al into the titanium sol2O3Continuously stirring until white sol is generated, centrifugally filtering, sequentially cleaning with absolute ethyl alcohol and deionized water, drying at 130 ℃ for 10h and roasting at 600 ℃ for 4h to obtain binary composite carrier TiO2-Al2O3；
Step two, preparing a catalyst precursor: 2.4028g of cobalt carbonate, 9.6112g of ammonium molybdate and 24.0293g of deionized water are mixed to be completely dissolved, the pH value is adjusted to 3 by adopting an acetic acid solution to obtain a transparent impregnation liquid, and then 14.4174g of binary composite carrier TiO prepared in the step one is added into the impregnation liquid2-Al2O3Stirring and soaking at 350r/min for 30min, drying at 130 ℃ for 10h, and roasting at 600 ℃ for 4h to obtain a catalyst precursor;
step three, catalyst preparation: and D, adding the catalyst precursor obtained in the step two into a temperature control area of a quartz tube, supporting two ends of the quartz tube by quartz wool, purging the catalyst precursor for 30min at 300 ℃ by adopting nitrogen at a flow rate of 200mL/min, then switching to introduce hydrogen at a flow rate of 150mL/min, heating to 700 ℃ at a speed of 5 ℃/min, preserving heat for 4h, cooling to room temperature in a hydrogen atmosphere, and finally passivating for 3h in a nitrogen atmosphere introduced at a flow rate of 50mL/min to obtain the spent lubricating oil hydrogenation regeneration catalyst, which is marked as catalyst E.
The physical and chemical properties and the catalytic performance of the spent lubricating oil hydrogenation regenerated catalyst prepared in the examples 1 to 5 and the comparative example 1 of the invention are detected and evaluated.
(1) The main physical properties of the spent lubricating oil hydrogenation regeneration catalysts prepared in examples 1 to 5 of the present invention and comparative example 1 were measured, and the results are shown in table 1 below.
TABLE 1
As can be seen from Table 1, the specific surface area, pore volume and average pore diameter of the spent lubricating oil hydrogenation regeneration catalysts prepared in examples 1 to 5 of the present invention are all smaller than those of comparative example 1, wherein the specific surface area, pore volume and average pore diameter of the spent lubricating oil hydrogenation regeneration catalyst prepared in example 1 are much smaller than those of comparative example 1, which illustrates that TiO only prepared by ultrasonic dissolution is superior to that of comparative example 12Larger particles are coated on gamma-Al2O3Compared with the carrier on the surface, the invention adopts the binary composite carrier TiO synthesized by the sol-gel method2-Al2O3So that nano TiO is formed2Particles are coated on Al2O3To obtain binary composite carrier TiO2-Al2O3Clogging up gamma-Al2O3Partial pore channels on the surface of the carrier cause that the specific surface area, the pore volume and the average pore diameter of the composite carrier are reduced.
(2) The performance evaluation of the spent lubricating oil hydrogenation regeneration catalysts prepared in examples 1, 3, 5 and 1 of the present invention was performed by using the pretreated whole-cut spent lubricating oil as a raw material, which had a black appearance color and no obvious particles, and whose physicochemical properties and physicochemical properties of acceptable lubricating oils are shown in table 2 below(ii) a Catalyst A, catalyst C, catalyst E and catalyst A0Tabletting and crushing, and then respectively loading into a fixed bed high-pressure hydrogenation device qualified by nitrogen pressure test and leakage test for catalytic hydrogenation regeneration, wherein the process conditions are as follows: the temperature is 340 ℃, the pressure is 7.0MPa, the volume ratio of hydrogen to oil is 600:1, and the space velocity is 1.2h-1(ii) a The results of the physical and chemical properties of the full-range spent lubricating oil hydrogenation regeneration products obtained after catalytic hydrogenation regeneration of each catalyst are shown in the following table 3.
TABLE 2
The "-" in Table 2 indicates the absence of this requirement.
As can be seen from Table 2, the physicochemical properties of the used oil raw material used for evaluating the performance of the spent lubricating oil hydrogenation regeneration catalyst of the invention are far from meeting the use requirements of qualified lubricating oil.
TABLE 3
| Item | Catalyst A | Catalyst C | Catalyst E | Catalyst A0 |
| Viscosity index | 126 | 125 | 120 | 114 |
| Kinematic viscosity (mm) at 40 ℃2·s-1) | 28.92 | 29.12 | 29.85 | 30.74 |
| Kinematic viscosity (mm) at 100 ℃2·s-1) | 5.46 | 5.47 | 5.48 | 5.48 |
| Freezing point (. degree. C.) | -23 | -22 | -19 | -17 |
| Open flash point (. degree.C.) | 200 | 200 | 202 | 204 |
| Color intensity | 0.3 | 0.4 | 0.5 | 1.0 |
| Total S content (ppm) | 12.3 | 14.1 | 16.3 | 22.4 |
| Total N content (ppm) | 6.1 | 8.0 | 10.0 | 13.2 |
| Total Cl content (ppm) | ＜0.1 | ＜0.1 | 0.3 | 0.4 |
| Yield (%) | 94.3 | 96.5 | 97.2 | 98.4 |
As can be seen from table 3, the physical and chemical properties of the whole fraction used lube oil regenerated products obtained by the catalysis of the used lube oil hydrogenation regenerated catalysts prepared in examples 1, 3, 5 and 1 of the present invention are all improved, wherein the performance of the catalyst product of catalyst C prepared in example 2 is the best, which shows that the hydrogenation regeneration catalytic performance of catalyst C is the best. The effect of the hydrogenation regeneration catalytic performance of the catalyst A prepared in the example 1 is better than that of the catalyst A prepared in the comparative example 1, and each physical and chemical performance index of the regenerated product of the full-fraction waste lubricating oil obtained by catalysis basically meets the standard of qualified lubricating oil, which shows that the binary composite carrier TiO prepared by the sol-gel method is adopted in the invention2-Al2O3As a carrier of the catalyst, the catalyst is improvedThe reduction capability of the full-cut spent lubricating oil under lower pressure (7MPa) is realized, but the reduction capability of the catalyst A is strong, so that long-chain alkane in the full-cut spent lubricating oil is cracked, and the yield of the regenerated product of the full-cut spent lubricating oil obtained by catalyzing the catalyst A is slightly lower than that of the catalyst A in the comparative example 10。
(3) The catalyst C prepared in example 3 with the best hydrogenation regeneration catalytic performance is selected, the hydrogenation regeneration catalytic performance of the catalyst C is evaluated under different pressures in the range of 6.0MPa to 9.0MPa, the corresponding evaluation process is shown in (2), the physicochemical properties of the regenerated product of the whole-fraction waste lubricating oil obtained after the catalyst is subjected to catalytic hydrogenation regeneration under different pressure conditions are detected, and the results are shown in table 4 below.
TABLE 4
| Item | 6.0MPa | 7.0MPa | 8.0MPa | 9.0MPa |
| Viscosity index | 114 | 125 | 131 | 136 |
| Kinematic viscosity (mm) at 40 ℃2·s-1) | 30.73 | 29.12 | 27.33 | 26.29 |
| Kinematic viscosity (mm) at 100 ℃2·s-1) | 5.48 | 5.47 | 5.32 | 5.28 |
| Freezing point (. degree. C.) | -17 | -22 | -25 | -29 |
| Open flash point (. degree.C.) | 204 | 200 | 198 | 195 |
| Color intensity | 1.1 | 0.4 | 0.3 | 0.3 |
| Total S content (ppm) | 19 | 14.1 | 8.6 | 5.1 |
| Total N content (ppm) | 11.4 | 8.0 | 4.4 | 2.7 |
| Total Cl content (ppm) | 1.1 | ＜0.1 | ＜0.1 | ＜0.1 |
| Yield (%) | 97.9 | 96.5 | 96.3 | 96.2 |
As can be seen from Table 4, as the reaction pressure increases, since the pressure of the hydrogen partial pressure also increases, the equilibrium of the catalytic reaction shifts toward the hydrogenation reaction, the improvement of the hydrogen partial pressure also inhibits the coking and carbon deposition on the surface of the catalyst, and the two jointly act to effectively improve the catalytic effect, so that various physical and chemical properties of the regenerated product of the full-fraction waste lubricating oil obtained by the catalysis of the catalyst C are improved, when the reaction pressure is 0.7MPa, the physicochemical properties of the regenerated product of the full-fraction waste lubricating oil obtained by catalyzing by the catalyst C already meet the preparation requirements of qualified lubricating oil, with the continuous increase of the reaction pressure, the viscosity index of the whole fraction waste lubricating oil regenerated product obtained by the catalysis of the catalyst C is gradually increased, and the viscosity is reduced, so that the reaction pressure is increased, and more aromatic hydrocarbons in the whole fraction waste lubricating oil regenerated product are hydrogenated and saturated to form naphthene; meanwhile, with the increase of the reaction pressure, the yield of the regenerated product of the full-fraction waste lubricating oil obtained by the catalysis of the catalyst C is basically stable, which shows that the reaction pressure is increased, the cracking reaction in the catalytic hydrogenation regeneration process is less, and the increase of the pressure can cause the increase of the equipment investment cost. In comprehensive consideration, the best applicable pressure condition of the catalyst is 7.0 MPa.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention still belong to the protection scope of the technical solution of the invention.
Claims (6)
1. The catalyst for hydrogenation regeneration of the waste lubricating oil is characterized by comprising a carrier and an active component, wherein the carrier is a binary composite carrier TiO synthesized by a sol-gel method2-Al2O3The active components are CoO and MoO3And the mass content of CoO in the catalyst is 6-9%, MoO3The mass content of (A) is 15-30%; the specific surface area of the catalyst is 220m2/g～231m2The pore volume is 0.65 mL/g-0.70 mL/g, and the average pore diameter is 11 nm-12 nm.
2. A process for preparing the spent lubricating oil hydroregenerated catalyst of claim 1, comprising the steps of:
step one, preparing binary composite carrier TiO2-Al2O3: deionized water, ethanol and acetic acid were mixed according to a 1: 2.5-3: mixing the titanium oxide and the titanium oxide in a volume ratio of 0.2-0.5, adjusting the pH value to 3-4 by using acetic acid to obtain an ethanol-acetic acid solution, slowly adding butyl titanate into the ethanol-acetic acid solution which is rapidly stirred to prepare titanium sol, and adding gamma-Al into the titanium sol2O3Continuously stirring until white sol is generated, centrifugally filtering, sequentially cleaning with absolute ethyl alcohol and deionized water, drying and roasting to obtain binary composite carrier TiO2-Al2O3(ii) a The gamma-Al2O3The added mass of the titanium dioxide is 70-90% of the mass of the butyl titanate;
step two, preparing a catalyst precursor: mixing cobalt salt, ammonium molybdate and deionized water according to the proportion of 1: 2-4: 8-10, regulating the pH value to 3-4 by adopting an acetic acid solution to obtain a transparent impregnation liquid, and adding the impregnation liquid into the binary composite carrier TiO prepared in the step one2-Al2O3Soaking with stirring, oven drying, and mixingRoasting to obtain a catalyst precursor; the binary composite carrier TiO2-Al2O3The mass of the impregnation liquid is 35 to 60 percent of the mass of the impregnation liquid;
step three, catalyst preparation: and D, reducing the catalyst precursor obtained in the step two to obtain the spent lubricating oil hydrogenation regeneration catalyst.
3. The method according to claim 2, wherein the drying temperature in the first step and the drying temperature in the second step are both 110-130 ℃ and the drying time is both 10-12 h; the roasting temperature is 400-600 ℃, and the roasting time is 4-6 h.
4. The method of claim 2, wherein the cobalt salt in step two is cobalt nitrate, cobalt acetate or cobalt carbonate.
5. The method as claimed in claim 2, wherein the rotation speed of the stirring and dipping in the second step is 150r/min to 350r/min, and the time is 30min to 60 min.
6. The method according to claim 2, wherein the reduction in step three employs a temperature programmed reduction process, which comprises the following steps: purging the catalyst precursor for 30-60 min at 180-300 ℃ by adopting nitrogen at the flow rate of 100-200 mL/min, then switching to introduce hydrogen at the flow rate of 50-150 mL/min, heating to 500-700 ℃ at the rate of 3-5 ℃/min, preserving the heat for 4-7 h, cooling to room temperature in a hydrogen atmosphere, and finally passivating for 3h in the nitrogen atmosphere introduced at the flow rate of 50 mL/min.
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