CN113004969A - Hydrogenation method for regeneration of waste lubricating oil - Google Patents
Hydrogenation method for regeneration of waste lubricating oil Download PDFInfo
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- CN113004969A CN113004969A CN202110221820.3A CN202110221820A CN113004969A CN 113004969 A CN113004969 A CN 113004969A CN 202110221820 A CN202110221820 A CN 202110221820A CN 113004969 A CN113004969 A CN 113004969A
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- lubricating oil
- hydrogenation
- regeneration
- alumina
- waste
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 53
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 52
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000008929 regeneration Effects 0.000 title claims abstract description 16
- 238000011069 regeneration method Methods 0.000 title claims abstract description 16
- 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 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003921 oil Substances 0.000 claims abstract description 12
- 239000002199 base oil Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000003223 protective agent Substances 0.000 claims abstract description 8
- 150000002739 metals Chemical class 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 230000001172 regenerating effect Effects 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 4
- 239000003463 adsorbent Substances 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 4
- 238000002386 leaching Methods 0.000 claims abstract description 4
- 239000004571 lime Substances 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 238000007670 refining Methods 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 24
- 239000011574 phosphorus Substances 0.000 claims description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 239000001226 triphosphate Substances 0.000 claims description 3
- 235000011178 triphosphate Nutrition 0.000 claims description 3
- 125000002264 triphosphate group Chemical class [H]OP(=O)(O[H])OP(=O)(O[H])OP(=O)(O[H])O* 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 239000010705 motor oil Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 14
- 238000006477 desulfuration reaction Methods 0.000 abstract description 7
- 230000023556 desulfurization Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 description 10
- 239000012535 impurity Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910003294 NiMo Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- KWUUWVQMAVOYKS-UHFFFAOYSA-N iron molybdenum Chemical group [Fe].[Fe][Mo][Mo] KWUUWVQMAVOYKS-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- -1 phosphorus compound Chemical class 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000000526 short-path distillation Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- C10M175/0008—Working-up used lubricants to recover useful products ; Cleaning with the use of adsorbentia
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1808—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with zinc, cadmium or mercury
-
- B01J35/393—
-
- 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
- C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
- C10M175/0041—Working-up used lubricants to recover useful products ; Cleaning by thermal processes by hydrogenation processes
-
- 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
Abstract
The invention discloses a hydrogenation method for regeneration of waste lubricating oil, which comprises the following steps that the waste lubricating oil is separated by a high-speed centrifuge and distilled under normal and reduced pressure, and then the waste lubricating oil is adsorbed, wherein alumina and graphene oxide are used as adsorbents to treat the waste lubricating oil; step two, pre-hydrogenation: the base oil fraction obtained by adsorption enters a pre-hydrogenation refining unit filled with a protective agent, and the operation conditions are as follows: the temperature is 250-320 ℃, the hydrogen partial pressure is 2.5-5.0 Mpa, the hydrogen-oil volume ratio is 300-400V/V, and the airspeed is 1.0-2.0 h < -1 >; the protective agent is prepared by carrying out acid leaching treatment on diatomite by using diluted sulfuric acid to separate to obtain aluminum in the diatomite and carrying one or two metals of cobalt and nickel after calcium sulfate obtained by using lime to neutralize is dried and ground. The hydrogenation method for regenerating the spent lubricating oil can improve the storage stability of the hydrogenated lubricating oil without reducing the desulfurization activity or the demetallization activity.
Description
The technical field is as follows:
the invention relates to the technical field of waste lubricating oil regeneration, in particular to a hydrogenation method for waste lubricating oil regeneration.
Background art:
china is the third major lubricating oil consuming country in the world second only to America and Russia, and consumes more than 600 and 800 million tons of lubricating oil every year. With the increase of the number of motor vehicles and the increase of the consumption of lubricating oil, the amount of waste oil replaced by vehicles, equipment and the like per year is increased dramatically. If the waste lubricating oil is discarded, the waste lubricating oil brings great harm to the ecological environment and causes great waste of energy. Along with the gradual reduction of petroleum resources and the continuous rise of crude oil price, the contradiction between energy supply and demand is prominent, so the recycling of waste lubricating oil is a practical problem facing to environmental protection and energy conservation in China, and the attention of people is also gradually paid. At present, the domestic lubricating oil regeneration process is mainly a sulfuric acid-argil process, the regeneration rate of waste oil is low, about 60 percent, and a large amount of waste acid residues, waste alkali residues and sewage are generated in the process, so that serious secondary pollution is caused. The regeneration rate of the waste lubricating oil of the solvent extraction process developed successively is about 70 percent, and if high-content nitrogen and phosphorus organic wastewater is discharged into water in the process, water eutrophication can be caused, and water pollution can be caused. Therefore, the development and research of a new environment-friendly and economical waste lubricating oil regeneration process become urgent. At present, the distillation-hydrogenation process is researched and developed as the most environment-friendly, most operational and large-scale process in waste oil regeneration in western developed countries, but the storage stability of the regenerated lubricating oil is poor due to the defects of relatively complex process, relatively harsh operating conditions and the like of the hydrogenation regeneration process.
For example, chinese patent publication No. CN 102786985 provides a resource utilization method for waste lubricating oil, which distills waste lubricating oil to obtain fractions at a temperature of less than 500 ℃ and fractions at a temperature of more than 500 ℃, and the fractions at a temperature of less than 500 ℃ undergo a hydrofining reaction on a sulfide catalyst, and then the distillate is distilled to obtain gasoline, diesel oil and base oil distillate. And the fraction above 500 deg.C is subjected to reactive distillation and then hydrofining. The hydrogenation catalyst is a supported NiMo, NiW, CoMo and other sulfide catalyst.
Chinese patent, publication No. CN 102504933, provides a method for regenerating used lubricating oil, which comprises several steps of pretreatment, short-path distillation and hydrorefining of used lubricating oil, wherein the hydrogenation catalyst is iron-molybdenum or cobalt-molybdenum catalyst. The above problems are present.
The invention content is as follows:
the technical problem to be solved by the invention is to provide a hydrogenation method for regenerating used lubricating oil, which can improve the storage stability of hydrogenated lubricating oil under the condition of not reducing desulfurization activity or demetallization activity.
The technical scheme of the invention is to provide a hydrogenation method for regenerating waste lubricating oil, which comprises the following steps of separating the waste lubricating oil by a high-speed centrifuge, distilling under normal pressure and reduced pressure, then carrying out the following operations,
step one, adsorption, namely treating waste lubricating oil by using aluminum oxide and graphene oxide as adsorbents;
step two, pre-hydrogenation: the base oil fraction obtained by adsorption enters a pre-hydrogenation refining unit filled with a protective agent, and the operation conditions are as follows: the temperature is 250-320 ℃, the hydrogen partial pressure is 2.5-5.0 Mpa, the hydrogen-oil volume ratio is 300-400V/V, and the airspeed is 1.0-2.0 h < -1 >; the protective agent is prepared by carrying out acid leaching treatment on diatomite by using diluted sulfuric acid to separate to obtain aluminum in the diatomite and carrying one or two metals of cobalt and nickel after drying and grinding calcium sulfate obtained by using lime for neutralization, wherein the loading amount of active metals is 2-4% (wt) calculated by oxides;
step three, hydrofining: the oil material prepared by pre-hydrogenation enters a hydrogenation main reactor, and is subjected to a catalytic reaction under the action of a hydrogenation catalyst under the conditions that the hydrogen partial pressure is 7-9 Mpa and the temperature is 300-320 ℃, the liquid airspeed is 1h < -1 > to 3h < -1 >, and the lubricating oil base oil is prepared after the reaction; the hydrogenation catalyst takes alumina containing phosphorus and zinc as a carrier, and the alumina containing phosphorus comprises 0.1-3% of phosphorus-containing compound and 1-10% of zinc oxide particles with the average particle size of 2-12 mu m on the carrier according to the mass percentage.
Preferably, the alumina used as the carrier contains ferric oxide and sodium oxide with the mass percent not higher than 0.1%.
Preferably, the alumina may form a complex with one or more components selected from the group consisting of zeolite, boric acid, silica and zirconia and serve as a complex alumina support.
Preferably, the aluminum oxide carrier containing phosphorus and zinc is obtained by incorporating zinc and phosphorus into the aluminum oxide carrier and the aluminum oxide carrier.
Preferably, the phosphorus-containing compound includes any one or a combination of orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphates and tetraphosphates.
Further, the used lubricating oil is used internal combustion engine oil or used industrial lubricating oil.
Compared with the prior art, the invention has the following advantages after adopting the scheme: the storage stability of hydrogenated lubricating oil can be improved under the condition of not reducing desulfurization activity or demetallization activity, the hydrogenation process is simplified, and a proper hydrogenation catalyst is selected, the hydrogenation active component of the hydrogenation catalyst is loaded on zinc oxide particles with specific sizes and a phosphorus-containing alumina carrier, and the desulfurization activity of heavy hydrocarbon oil in the lubricating oil is very remarkable; in addition, by performing hydrogenation using the hydrogenation catalyst, a lubricant base oil which is less likely to generate precipitates and has excellent storage stability can be obtained.
The specific implementation mode is as follows:
the invention is further illustrated with respect to specific embodiments below:
example one
A hydrogenation method for regenerating used lubricating oil includes such steps as high-speed centrifugal separation of used lubricating oil, ordinary-vacuum distillation,
step one, adsorption, namely treating waste lubricating oil by using aluminum oxide and graphene oxide as adsorbents;
step two, pre-hydrogenation: the base oil fraction obtained by adsorption enters a pre-hydrogenation refining unit filled with a protective agent, and the operation conditions are as follows: the temperature is 260 ℃, the hydrogen partial pressure is 3.5Mpa, the hydrogen-oil volume ratio is 350V/V, and the airspeed is 1.5h < -1 >; the protective agent is prepared by carrying out acid leaching treatment on diatomite by using diluted sulfuric acid to separate to obtain aluminum in the diatomite and carrying one or two metals of cobalt and nickel after drying and grinding calcium sulfate obtained by using lime for neutralization, wherein the loading amount of active metals is 3 percent (wt) calculated by oxides;
step three, hydrofining: the oil material prepared by pre-hydrogenation enters a hydrogenation main reactor, and is reacted under the action of a hydrogenation catalyst, the catalytic reaction is carried out under the conditions that the hydrogen partial pressure is 8Mpa and the temperature is 320 ℃, the liquid airspeed is 2h < -1 >, and the lubricating oil base oil is prepared after the reaction; the hydrogenation catalyst takes alumina containing phosphorus and zinc as a carrier, and the alumina containing phosphorus comprises 1 percent of phosphorus-containing compound and 4 percent of zinc oxide particles with the average particle size of 7 mu m on the carrier according to mass percentage.
The separation operation of the high-speed centrifuge is that lubricating oil enters the high-speed centrifuge to separate part of moisture, impurities and solid particles, and before separation, silicon dioxide can be added to adsorb the impurities and then the impurities are separated;
performing atmospheric and vacuum distillation on the waste lubricating oil separated by the high-speed centrifuge, wherein light gasoline and diesel oil fractions with the boiling points of 230 ℃ are distilled out through atmospheric distillation; distilling under reduced pressure to obtain base oil fraction with boiling point of 365 ℃;
the alumina used as the carrier contains ferric oxide and sodium oxide in a mass percent of not more than 0.1%, and of course, the lower the impurities contained in the alumina, the better the effect.
Preferably, the alumina can form a complex with one or more components selected from the group consisting of zeolite, boric acid, silica and zirconia and serve as a complex alumina support, and in addition, zinc and phosphorus can also be incorporated into the alumina support complex alumina support to obtain a phosphorus-containing zinc-containing alumina support. Zinc and phosphorus are added as components for improving the quality of the active center to improve the desulfurization activity and residual carbon removal activity of the active metal, and have a function of accurately forming an active metal sulfur phase having high activity.
In the hydrogenation catalyst according to the invention, zinc oxide particles having an average particle diameter of 2 μm to 12 μm, preferably 4 μm to 10 μm and more preferably 5 μm to 9 μm are used. When the average particle diameter of the zinc oxide particles contained in the carrier is 12 μm or less, sufficient interaction with alumina is obtained, so that hydrogenated heavy hydrocarbon oil having sufficient storage stability can be obtained. On the other hand, when the average particle diameter of zinc oxide particles contained in the carrier is 2 μm or more, zinc is easily mixed with alumina in producing the phosphorus-containing zinc-containing alumina carrier.
As the compound of phosphorus contained in the hydrogenation catalyst support of the present invention, various compounds can be used. Examples of the phosphorus compound include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphates and tetraphosphates. In this example, orthophosphoric acid was used.
The hydrogenation method can improve the storage stability of the hydrogenated lubricating oil under the condition of not reducing the desulfurization activity or the demetallization activity, simplifies the hydrogenation process, particularly selects a proper hydrogenation catalyst, has hydrogenation active components loaded on zinc oxide particles with specific sizes and a phosphorus-containing alumina carrier, and has very remarkable desulfurization activity on heavy hydrocarbon oil in the lubricating oil; in addition, by performing hydrogenation using the hydrogenation catalyst, a lubricant base oil which is less likely to generate precipitates and has excellent storage stability can be obtained.
The foregoing is illustrative of the preferred embodiments of the present invention only and is not to be construed as limiting the claims. All the equivalent structures or equivalent process changes made by the description of the invention are included in the scope of the patent protection of the invention.
Claims (6)
1. A hydrogenation method for regenerating waste lubricating oil is characterized in that: comprises the following steps that the following operations are carried out after the waste lubricating oil is separated by a high-speed centrifuge and distilled under normal and reduced pressure,
step one, adsorption, namely treating waste lubricating oil by using aluminum oxide and graphene oxide as adsorbents;
step two, pre-hydrogenation: enabling the base oil fraction obtained through adsorption to enter a pre-hydrogenation refining unit filled with a protective agent, wherein the protective agent is obtained by performing acid leaching treatment and separation on diatomite through dilute sulfuric acid to obtain aluminum in the diatomite and loading one or two metals of cobalt and nickel after drying and grinding calcium sulfate obtained through lime neutralization, and the loading amount of active metals is 2-4% (wt) calculated by oxides;
step three, hydrofining: the oil material prepared by pre-hydrogenation enters a hydrogenation main reactor, and is subjected to a catalytic reaction under the action of a hydrogenation catalyst under the conditions that the hydrogen partial pressure is 7-9 Mpa and the temperature is 300-320 ℃, the liquid airspeed is 1h < -1 > to 3h < -1 >, and the lubricating oil base oil is prepared after the reaction; the hydrogenation catalyst takes alumina containing phosphorus and zinc as a carrier, and the alumina containing phosphorus comprises 0.1-3% of phosphorus-containing compound and 1-10% of zinc oxide particles with the average particle size of 2-12 mu m on the carrier according to the mass percentage.
2. The hydrogenation process for regeneration of spent lubricating oil according to claim 1, characterized in that: the alumina used as the carrier contains ferric oxide and sodium oxide with the mass percent not higher than 0.1%.
3. The hydrogenation process for regeneration of spent lubricating oil according to claim 1, characterized in that: the alumina may be formed into a composite with one or more components selected from the group consisting of zeolite, boric acid, silica and zirconia and used as a composite alumina support.
4. The hydrogenation process for spent lubricating oil regeneration according to claim 3, wherein: and (3) incorporating zinc and phosphorus into the alumina carrier and the aluminum oxide carrier to obtain the aluminum oxide carrier containing phosphorus and zinc.
5. The hydrogenation process for regeneration of spent lubricating oil according to claim 1, characterized in that: the phosphorus-containing compound comprises any one or combination of several of orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphates and tetraphosphates.
6. The hydrogenation process for regeneration of spent lubricating oil according to claim 5, characterized in that: the waste lubricating oil is waste internal combustion engine oil and waste industrial lubricating oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110221820.3A CN113004969A (en) | 2021-02-27 | 2021-02-27 | Hydrogenation method for regeneration of waste lubricating oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110221820.3A CN113004969A (en) | 2021-02-27 | 2021-02-27 | Hydrogenation method for regeneration of waste lubricating oil |
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|---|---|
| CN113004969A true CN113004969A (en) | 2021-06-22 |
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| CN202110221820.3A Pending CN113004969A (en) | 2021-02-27 | 2021-02-27 | Hydrogenation method for regeneration of waste lubricating oil |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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