CN103773442B - Method for production of high-viscosity-index lubricant base oil by hydrogenation - Google Patents
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Abstract
The invention relates to a method for production of high-viscosity-index lubricant base oil by hydro-upgrading using APII base oil as a raw material. The method is as follows: the APII base oil is mixed with hydrogen, then enters into a hydro-upgrading reaction zone to contact with an amorphous silica alumina-containing hydro-upgrading catalyst for reaction, the polycyclic napthene ring-opening reaction is performed, and after fractional distillation of a reaction effluent, a lubricant base oil product with the viscosity index meeting APIIII base oil requirements is obtained. According to the method, the ring-opening reaction of polycyclic napthenes with more than two rings and polycyclic aromatic hydrocarbons in the APII base oil raw material is performed, the content of low viscosity index component polycyclic napthenes and the polycyclic aromatic hydrocarbons is reduced, the viscosity indexes of products are substantially increased, and APIIII base oil products with the viscosity indexes being greater than 120 are obtained.
Description
Technical field
The present invention relates to a kind of production method of base oil of high viscosity index lubricant, particularly adopt hydro-upgrading to produce the method for thick oil base oil.
Background technology
Lubricant base is divided into I class, II class, III class, IV class and V class by U.S. API.Wherein, I class oil uses as plain oil, and its viscosity index, sulphur content, saturated hydrocarbon content require all not high, mainly use solvent treatment, solvent dewaxing and clay-treated produced in conventional processes.II class and III class base oil have that saturated hydrocarbon content is high, sulphur content is very low, and saturated hydrocarbon content is greater than 90%, and viscosity index requires to be greater than 90 or be greater than 120, are used for allotment top-grade lubricating oil product.This II class and III class base oil, traditional solvent method is difficult to produce, and particularly process the refinery of sulfur-bearing intermediate base crude oil, traditional solvent method more cannot produce high-grade base oil.Along with hydrogenation method produces developing rapidly of Lubricating Oil Technique, intermediate base crude oil can only adopt hydro-upgrading or hydrotreatment-isomerization dewaxing-hydrofining to produce II class and III class base oil.
CN200910236126.8 describes the low intermediate base raw material of a kind of wax content, adopts solvent dewaxing-hydrofining-isomerization dewaxing production viscosity index to be greater than the method for 120 lubricant bases.
CN200380101085.2 describes a kind of with the raw material of wax content at least 50%, adopts hydrotreatment-catalytic dewaxing-hydrofining production viscosity index to be greater than the method for the lubricant base of 125.
CN97196410.6 describes the method that lubricant base is produced in a kind of hydrotreatment-isomerization dewaxing-hydrofining, and the method requires that the viscosity index of raw material is greater than 75, II class and III class base oil that production viscosity index is greater than 110.
The production method of above-mentioned existing base oil of high viscosity index lubricant is all with petroleum fractions, mainly vacuum distillate is raw material, adopt hydrotreatment-isomery (catalysis) dewaxing-hydrorefined technological process, the lubricant base that production viscosity index is greater than 120.The API III class lubricating oil base oil that prior art cannot be greater than 120 with the API I class base oil of conventional solvent explained hereafter for raw material production viscosity index.
The API III class lubricating oil base oil that prior art cannot be greater than 120 with the API I class base oil of conventional solvent explained hereafter for raw material production viscosity index.The inventive method with API I class base oil for raw material, dicyclo in raw material and the low-viscosity index component such as naphthenic hydrocarbon more than dicyclo and aromatic hydrocarbons are changed into the single-ring naphthene of high viscosity index (HVI) component by the catalyst for hydro-upgrading containing amorphous aluminum silicide adopting open-loop performance stronger by hydrogenation and ring-opening reaction, increase substantially the viscosity index of raw material, can the production viscosity index API III class lubricating oil base oil that is greater than 120, technological process is simple, opens the new way of producing API III class lubricating oil base oil.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of with the method for API I class base oil for raw material production high viscosity index (HVI) API III class lubricating oil base oil.
The inventive method comprises following content: enter hydro-upgrading reaction zone after API I class lubricating oil base oil mixes with hydrogen, with the catalyst for hydro-upgrading contact reacts containing amorphous aluminum silicide, polycyclic naphthene hydrocarbon and polycyclic aromatic hydrocarbons ring-opening reaction occurs; Reaction effluent obtains the base oil of high viscosity index lubricant that viscosity index is greater than 120 after being separated.
In the inventive method, API I class lubricating oil base oil enters hydro-upgrading reaction zone, with containing amorphous aluminum silicide catalyst for hydro-upgrading contact reacts, catalyst for hydro-upgrading can make the above polycyclic naphthene hydrocarbon of the dicyclo in raw material and polycyclic aromatic hydrocarbons generation ring-opening reaction, reduce the content of low-viscosity index component polycyclic naphthene hydrocarbon and polycyclic aromatic hydrocarbons in product, improve the content of paraffinic hydrocarbons and the contour viscosity index constituents of single-ring naphthene, increase substantially the viscosity index of raw material, obtain the API III class lubricating oil base oil that viscosity index is greater than 120.
In the inventive method, the viscosity index of API I class lubricating oil base oil is generally 60 ~ 90, and 100 DEG C of viscosity are generally 2.0mm
2/ s ~ 40.0mm
2/ s, is preferably 2.0mm
2/ s ~ 15.0mm
2/ s, pour point is generally lower than-12 DEG C.
What the inventive method used contains amorphous aluminum silicide containing in the catalyst for hydro-upgrading carrier of amorphous aluminum silicide.The amorphous aluminum silicide that described amorphous aluminum silicide can be commonly used for hydro-upgrading field.Containing amorphous aluminum silicide 20wt% ~ 80wt%(wt% weight percent in the carrier of catalyst for hydro-upgrading of the present invention), described carrier specific surface area is 200 ~ 500m
2/ g, pore volume is 0.15 ~ 0.90mL/g, and infrared acidity is generally 0.30 ~ 0.50mmol/g; Preferably containing amorphous aluminum silicide 40wt% ~ 70wt%, specific surface area is 300 ~ 400m
2/ g, pore volume is 0.40 ~ 0.70mL/g.Support of the catalyst pore distribution feature is that the pore volume of bore dia 4 ~ 16nm accounts for total pore volume 50% ~ 90%, and the pore volume being greater than 20nm accounts for total pore volume and is no more than 10%.The physico-chemical property that the present invention relates to amorphous aluminum silicide is: silica content is generally 5wt% ~ 70wt%, is preferably 15wt% ~ 45wt%; Pore volume is generally 0.6 ~ 1.6mL/g, is preferably 1.0 ~ 1.4mL/g; Specific surface is generally 400 ~ 550m
2/ g, is preferably 450 ~ 500m
2/ g; Infrared acidity is generally 0.25 ~ 0.55mmol/g, is preferably 0.35 ~ 0.45mmol/g.Catalyst for hydro-upgrading of the present invention contains the group VIB metal (with oxide basis) of 10wt% ~ 30wt% and the group VIII metal (with oxide basis) of 4wt% ~ 10wt%.The specific surface area of catalyst for hydro-upgrading is 220 ~ 300m
2/ g, pore volume is 0.3 ~ 0.6mL/g, and the pore volume of bore dia 3 ~ 10nm accounts for 75% ~ 95% of total pore volume, is preferably 85% ~ 95%.
The reaction conditions of described catalyst for hydro-upgrading reaction zone is: temperature is 300 ~ 420 DEG C, preferably 360 ~ 405 DEG C, and hydrogen dividing potential drop is 2.0 ~ 18.0MPa, preferably 10.0 ~ 15.0MPa, and volume space velocity is 0.4 ~ 6.0h
-1, preferably 0.4 ~ 1.8h
-1, hydrogen to oil volume ratio 400:1 ~ 1500:1, preferred 600:1 ~ 1000:1.
The inventive method is by known to the analysis of the viscosity index of different sorts hydrocarbon in lubricating oil distillate, and the viscosity index of n-hexacosane is 177, and the viscosity index of normal-butyl docosane is 124, single-ring naphthene C
24h
28the viscosity index of (side chain carbon number is 18) is 160, tricyclic naphthenes hydrocarbon C
28h
52the viscosity index of (side chain carbon number is 14) is 40, thrcylic aromatic hydrocarbon C
32h
46(side chain carbon number is 18) viscosity index is 93.Because the pour point of normal paraffin is very high, the component of therefore desirable base oil of high viscosity index lubricant is isoparaffin and single-ring naphthene.API I class lubricating oil feed of base oil generally adopts solvent treatment, solvent dewaxing and clay-filtered " old three covers " technique to obtain, general still containing the above aromatic hydrocarbons of dicyclo of 5% ~ 15% and the above naphthenic hydrocarbon of dicyclo of 20% ~ 40%, viscosity index is not high, generally 60 ~ 90.The inventive method by open-loop performance stronger containing amorphous aluminum silicide catalyst for hydro-upgrading effect under, naphthenic hydrocarbon more than dicyclo and dicyclo and this part low-viscosity index component of polycyclic aromatic hydrocarbons are generated the single-ring naphthene of high viscosity index (HVI) component by hydrogenation and ring-opening reaction, significantly improve the viscosity index of raw material, achieve with the object of the API I class lubricating oil base oil API III class lubricating oil base oil that is raw material production viscosity index >120.
Embodiment
The raw material of the inventive method is viscosity index 60-90,100 DEG C of viscosity 2.0mm
2/ s ~ 40.0mm
2/ s, is preferably 2.0mm
2/ s ~ 15.0mm
2/ s, pour point is lower than the API I class lubricating oil base oil of-12 DEG C.
API I class lubricating oil feed of base oil, enter the hydrogenation ring-opening reaction that the above naphthenic hydrocarbon of dicyclo and polycyclic aromatic hydrocarbons are carried out in the hydro-upgrading reaction zone be filled with containing amorphous aluminum silicide catalyst for hydro-upgrading, polycyclic naphthene hydrocarbon and polycyclic aromatic hydrocarbons are converted into single-ring naphthene and paraffinic hydrocarbons, and reaction product obtains the API III class lubricating oil base oil that viscosity index is greater than 120 after fractionation.
The catalyst for hydro-upgrading that the present invention relates to can select commercial catalyst by character, also can prepare by this area knowledge.
Hydrocracking catalyst containing amorphous aluminum silicide can by existing patented technology preparations such as CN97122134.0, as as described in CN97122134.0, support of the catalyst contains amorphous aluminum silicide and aperture alumina binder, amorphous aluminum silicide content is 40wt% ~ 80wt%, amorphous aluminum silicide silicon oxide-containing 15%wt ~ 50wt%, the surface-area of carrier is 300 ~ 450m
2/ g, pore volume 0.45 ~ 0.80mL/g, infrared acidity is 0.30 ~ 0.50mmol/g.Group VIB metal (with oxide basis) containing 10wt% ~ 30wt% and the group VIII metal (with oxide basis) of 4wt% ~ 10wt%.
Further illustrate concrete scheme of the present invention below by embodiment, but be not limited to following embodiment.The present invention's API I class lubricating oil feed of base oil character used is in table 1, and the physico-chemical property of used catalyst is in table 2.
Embodiment 1 ~ 4
Embodiment 1 ~ 4 raw material is respectively 4 kinds of Lube basic oil material feedstocks listed in table 1, and catalyzer uses listed catalyzer in table 2 respectively, and catalyzer is implemented after carrying out sulfuration according to a conventional method.Raw material enters the hydro-upgrading reaction zone be filled with containing amorphous silicon Al catalysts, carries out the hydrogenation ring-opening reaction of the above naphthenic hydrocarbon of dicyclo and aromatic hydrocarbons, and reaction product obtains the API III class lubricating oil base oil that viscosity index is greater than 120 after fractionation.The reaction process condition of hydro-upgrading and gained base oil product character are specifically in table 3.
Table 1 stock oil character
| Raw material | MVI 100 | MVI 400 | HVI 250 | HVI 120BS |
| Density, kg/m 3 | 868 | 863 | 878 | 883 |
| Boiling range scope, DEG C | 382～475 | 350～505 | 395～480 | 490-565 |
| Viscosity (100 DEG C), mm 2/s 1 | 4.125 | 8.550 | 6.481 | 22.68 |
| Viscosity index | 63 | 75 | 80 | 88 |
| Pour point, DEG C | -21 | -18 | -15 | -12 |
| Sulphur, μ g/g | 1230 | 1892 | 644 | 856 |
| Mass spectrum forms, wt% | ||||
| Paraffinic hydrocarbons | 19.57 | 17.32 | 31.89 | 35.13 |
| Naphthenic hydrocarbon | 53.98 | 53.57 | 48.60 | 44.27 |
| One ring/bis-ring/tri-ring | 13.1/14.4/15.9 | 11.64/12.1/16.2 | 11.1/15.5/16.4 | 7.24/6.5/9.8 |
| Fourth Ring/five rings/six ring | 9.28/1.3/0 | 10.03/3.2/0.4 | 4.1/1.5/0 | 12.2/6.5/2.03 |
| Aromatic hydrocarbons | 26.45 | 29.11 | 19.51 | 20.60 |
| One ring/bis-ring/tri-ring | 11.4/8.4/6.65 | 12.7/9.0/5.91 | 8.5/6.6/4.01 | 6.2/6.6/3.7 |
| Fourth Ring/five rings/six ring | 0.8/0/0 | 1.0/0.4/0.1 | 0.3/0.1/0 | 2.2/1.5/0.4 |
Table 2 catalyst property
| Catalyzer | Hydro-upgrading |
| Chemical constitution, wt% | |
| MoO 3 | 22.0 |
| NiO | 7.0 |
| Carrier forms, wt% | |
| SiO 2 | 36.0 |
| Al 2O 3 | 44.0 |
| Physical properties | |
| Physical dimension (φ × L), mm | (1.5-1.7)×(3～8) |
| Pore volume, mL/g | ≥0.30 |
| Specific surface area, m 2/g | ≥240 |
| 4-16nm pore volume, % | 77.0 |
| > 20nm pore volume, % | 6.0 |
The processing condition of table 3 embodiment and product property
| Test number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | MVI 100 | MVI 400 | HVI 250 | HVI 120BS |
| Processing condition | ||||
| Temperature of reaction, DEG C | 403 | 383 | 393 | 389 |
| Reaction pressure, MPa | 15.0 | 10.0 | 14.0 | 12.0 |
| Hydrogen to oil volume ratio | 850 | 1200 | 1000 | 1500 |
| Volume space velocity, h -1 | 0.75 | 0.8 | 1.25 | 0.9 |
| Base oil character | 385℃ +Cut | 350℃ +Cut | 400℃ +Cut | 500℃ +Cut |
| Yield, wt% | 64.05 | 66.12 | 73.22 | 76.02 |
| Pour point, DEG C | -12 | -18 | -15 | -9 |
| Viscosity (100 DEG C), mm/s 2 | 3.512 | 6.501 | 5.505 | 16.66 |
| Viscosity index (VI) | 121 | 120 | 124 | 125 |
| Mass spectrum forms, wt% | ||||
| Paraffinic hydrocarbons | 51.21 | 51.67 | 56.13 | 58.43 |
| Naphthenic hydrocarbon | 44.80 | 43.09 | 41.03 | 38.18 |
| One ring/bis-ring/tri-ring | 24.8/11.2/7.9 | 25.0/9.4/9.29 | 24.8/10.83/5.30 | 20.1/9.3/8.08 |
| Fourth Ring/five rings/six ring | 0.8/0.1/0 | 1.2/0.2/0 | 0.1/0/0 | 0.3/0.3/0.1 |
| Aromatic hydrocarbons | 3.99 | 5.24 | 2.84 | 3.39 |
In the present invention, 385 DEG C
+base oil refers to that initial boiling point temperature is more than or equal to the base oil product of 385 DEG C, lower same.
From table 3 embodiment 1 ~ 4, each data are known, the API I class lubricating oil feed of base oil of viscosity index 60 ~ 90, under the effect containing amorphous aluminum silicide catalyst for hydro-upgrading, there occurs the hydrogenation ring-opening reaction of the above naphthenic hydrocarbon of dicyclo and aromatic hydrocarbons, polycyclic naphthene hydrocarbon and polycyclic aromatic hydrocarbons are converted into single-ring naphthene and paraffinic hydrocarbons, significantly improve the viscosity index of raw material, the API III class lubricating oil base oil that viscosity index is greater than 120 can be obtained.
Claims (10)
1. the method for a hydro-upgrading production base oil of high viscosity index lubricant, comprise the steps: that API I class lubricating oil base oil enters hydro-upgrading reaction zone after mixing with hydrogen, with the catalyst for hydro-upgrading contact reacts containing amorphous aluminum silicide, there is polycyclic naphthene hydrocarbon and polycyclic aromatic hydrocarbons ring-opening reaction; Reaction effluent obtains the base oil of high viscosity index lubricant that viscosity index is greater than 120 after being separated, and the carrier of described catalyst for hydro-upgrading is containing amorphous aluminum silicide 20wt% ~ 80wt%, and specific surface area is 200 ~ 500m
2/ g, pore volume is 0.15 ~ 0.90mL/g, and infrared acidity is 0.30 ~ 0.50mmol/g.
2. in accordance with the method for claim 1, it is characterized in that: the viscosity index of described API I class lubricating oil base oil is 60 ~ 90, and pour point is lower than-12 DEG C, and 100 DEG C of viscosity are 2.0mm
2/ s ~ 40.0mm
2/ s.
3. in accordance with the method for claim 2, it is characterized in that: described API I class lubricating oil base oil 100 DEG C of viscosity are 2.0mm
2/ s ~ 15.0mm
2/ s.
4. in accordance with the method for claim 1, it is characterized in that: in the carrier hole distribution of described catalyst for hydro-upgrading, bore dia is that the pore volume that the pore volume in the hole of 4-16nm accounts for the hole of 50 ~ 90%, >20nm of total pore volume is no more than 10% of total pore volume.
5. in accordance with the method for claim 4, it is characterized in that: the physico-chemical property of amorphous aluminum silicide is: silica content is 5wt% ~ 70wt%, pore volume is 0.6 ~ 1.6mL/g, and specific surface area is 400 ~ 550m
2/ g, infrared acidity is 0.25 ~ 0.55mmol/g.
6. in accordance with the method for claim 1, it is characterized in that: with catalyzer be benchmark with oxide basis, described catalyst for hydro-upgrading contains the metal component of group VIB of 10wt% ~ 30wt% and the metal component of group VIII of 4wt% ~ 10wt%.
7. in accordance with the method for claim 1, it is characterized in that: the specific surface area of described hydrogenation transformation of the way catalyzer is 220 ~ 300m
2/ g, pore volume is 0.3 ~ 0.6mL/g, and the pore volume of bore dia 3 ~ 10nm accounts for 75% ~ 95% of total pore volume, and infrared acidity is 0.30 ~ 0.5mmol/g.
8. in accordance with the method for claim 7, it is characterized in that: in described hydrogenation transformation of the way catalyzer, the pore volume of bore dia 3 ~ 10nm accounts for 85% ~ 95% of total pore volume.
9. in accordance with the method for claim 1, it is characterized in that: the reaction conditions of described hydro-upgrading reaction zone is: temperature of reaction is 300 ~ 420 DEG C, hydrogen dividing potential drop is 2.0 ~ 18.0MPa, and volume space velocity is 0.4 ~ 6.0h
-1, hydrogen to oil volume ratio 400:1 ~ 1500:1.
10. in accordance with the method for claim 1, it is characterized in that: the reaction conditions of described hydro-upgrading reaction zone is: temperature of reaction is 360 ~ 405 DEG C, hydrogen dividing potential drop is 10.0 ~ 15.0MPa, and volume space velocity is 0.4 ~ 1.8h
-1, hydrogen to oil volume ratio 600:1 ~ 1000:1.
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| CN111378499B (en) * | 2018-12-31 | 2021-10-08 | 中国石油化工股份有限公司 | Combined method for producing high-quality lubricating oil base oil and environment-friendly aromatic oil |
| CN111378500B (en) * | 2018-12-31 | 2021-12-07 | 中国石油化工股份有限公司 | Combination method for producing high-quality lubricating oil base oil and environment-friendly aromatic oil |
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