CN103773468B - A kind of method of producing base oil of lubricating oil by isomerization dewaxing - Google Patents
A kind of method of producing base oil of lubricating oil by isomerization dewaxing Download PDFInfo
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Abstract
The present invention relates to a kind of method of producing base oil of lubricating oil by isomerization dewaxing.First enter hydrocracking reaction district after the inventive method Raw oil mixes with hydrogen, with the Nobel metal hydrogen cracking catalyst contact reacts containing amorphous aluminum silicide, polycyclic naphthene hydrocarbon ring-opening reaction occurs; Reaction effluent directly enters hydroisomerization dewax reaction zone without separation, with hydroisomerization dewax catalyst exposure, carries out normal alkane isomerization reaction, obtains the base oil of high viscosity index lubricant that pour point meets the demands.The inventive method makes the above polycyclic naphthene hydrocarbon of dicyclo in raw material generation ring-opening reaction, reduce the content of low-viscosity index component polycyclic naphthene hydrocarbon in product, reduce the loss of isomerization dewaxing process viscosity index, obtain the base oil of high viscosity index lubricant that pour point meets the demands.
Description
Technical field
The present invention relates to a kind of production method of lubricant base, particularly adopt hydroisomerization dewax to produce the method for lubricant base.
Background technology
The object of hydroisomerization dewax makes normal alkane isomerization generate isoparaffin by hydroisomerization dewax catalyzer realize reducing raw material pour point and keep higher viscosity index.Hydroisomerization dewax catalyzer needs acidity and hydrogenation/dehydrogenation performance to match, and its acidity is generally provided by carrier, and hydrogenation/dehydrogenation activity is provided by metal component.
A lot of about the report of isomerization dewaxing catalyst at present, such as, US Patent No. 5990371US5833837, US5817907, US5149421, US5135638, US5110445, US4919788, US4419420, US4601993, US4599162, US4518485 etc. relate to Isodewaxing Technology, the acidic components that wherein isomerization dewaxing catalyst uses mainly contain mordenite, SAPO-11, SAPO-31, SAPO-41, ZSM-23, SSZ-32, TON type molecular sieve etc., and wherein TON type molecular sieve mainly contains ZSM-22, Nu-10, KZ-2 and ISI-1 etc.These mesoporous molecular sieves, all to make normal paraffin generation isomerization reaction, reduce for the purpose of pour point.
US5149421 and US4599162 all proposes Pt/ZSM-5 and Pt/SAPO-11 to be used jointly the method for carrying out isomerization dewaxing, owing to adopting ZSM-5 molecular sieve, causes base oil yield to reduce and viscosity index loss increase.
US5110445 proposes to adopt the catalyzer containing b molecular sieve to carry out the method for producing base oil of lubricating oil by isomerization dewaxing.
CN99113304.8 proposes a kind of method of isomerization dewaxing of connecting, and first paragraph adopts containing the b molecular sieve of the low acidity of high silicon and the catalyzer of at least one VIII noble metal component, and second segment adopts the catalyzer containing mesopore SAPO-11 molecular sieve.Be there is by one section of employing the macropore b molecular sieve catalyst of low acidity, it is made to carry out the isomerization reaction of wax molecule at relatively high temperatures, and keep lower lytic activity, reduce the load of two sections of SAPO-11 catalyzer, thus reach reduction base oil pour point, and keep the object of higher lubricant base yield.
The composite molecular screen AEL-MCM that CN200910242068.X describes the micro porous molecular sieve and mesoporous MCM-41 molecular sieve that a kind of employing has AEL topological framework produces the method for low cloud-point lube base oil as isomerization dewaxing catalyst.
Above-mentioned existing Isodewaxing Technology, all to adopt molecular sieve to make normal paraffin generation isomerization reaction in raw material, reduces for the purpose of base oil pour point.Because normal alkane isomerization reaction mechanism determines the process that existing isomerization dewaxing process is viscosity index reduction, therefore when production viscosity index is greater than the APIIII class base oil product of 120, require very high, generally between 135-145 to the viscosity index of isomerization dewaxing raw material.No matter adopt hydrocracking or hydrotreatment to produce isomerization dewaxing raw material, the viscosity index requirement all needing very high transformation efficiency just can reach so high, causes the significantly reduction of isomerization dewaxing raw material yield.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of producing base oil of lubricating oil by isomerization dewaxing.
The method that hydroisomerization dewax of the present invention produces lubricant base comprises following content: first enter hydrocracking reaction district after stock oil mixes with hydrogen, with the Nobel metal hydrogen cracking catalyst contact reacts containing amorphous aluminum silicide, there is polycyclic naphthene hydrocarbon ring-opening reaction; Reaction effluent directly enters hydroisomerization dewax reaction zone without separation, with hydroisomerization dewax catalyst exposure, carries out normal alkane isomerization reaction, obtains the base oil of high viscosity index lubricant that pour point meets the demands.
In the inventive method, stock oil is first by hydrocracking reaction district, with amorphous aluminum silicide Nobel metal hydrogen cracking catalyst contact reacts wherein, hydrocracking catalyst can make the above polycyclic naphthene hydrocarbon of the dicyclo in raw material generation ring-opening reaction, reduce the content of low-viscosity index component polycyclic naphthene hydrocarbon in product, improve the content of paraffinic hydrocarbons and the contour viscosity index constituents of single-ring naphthene, reduce the loss of viscosity index, then reaction effluent is by hydroisomerization dewax reaction zone and hydroisomerization dewax catalyst exposure, carry out normal alkane isomerization reaction and reduce product pour point, and then obtain the base oil of high viscosity index lubricant that pour point meets the demands.
In the inventive method, Lube basic oil material feedstocks can be one or more in hydrotreatment distillate, the frivolous oil of hydrotreatment, hydrotreatment sweat oil, hydrocracking tail oil.Described stock oil initial boiling point is generally 280 DEG C ~ 440 DEG C, and final boiling point is generally 450 DEG C ~ 700 DEG C.The sulphur content of raw material requires lower than 30mg/g, preferably lower than 15mg/g; Requirement of nitrogen lower than 5mg/g, preferably lower than 2mg/g, with meet hydroisomerization dewax reaction in use noble metal catalyst to the requirement of raw material impurity content.The hydrotreatment of distillate and frivolous oil or hydrocracking are this area ordinary method, generally use non-precious metal catalyst, and main purpose is the impurity such as deep removal sulphur, nitrogen.
Hydrocracking catalyst this area can being selected conventional containing the Nobel metal hydrogen cracking catalyst of amorphous aluminum silicide that the inventive method uses, as can commodity in use hydrocracking catalyst, also can prepare by this area general knowledge.Containing amorphous aluminum silicide 20wt% ~ 80wt%(wt% weight percent in the carrier of hydrocracking catalyst of the present invention), 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.Hydrocracking catalyst of the present invention is at least containing a kind of noble metal hydrogenating component, preferably platinum and palladium, and the mol ratio of platinum and palladium is 3:1 ~ 1:3, is preferably 2:1 ~ 1:2.Described noble metal hydrogenating component total content is 0.10wt% ~ 1.0wt%, is preferably 0.20wt% ~ 0.80wt%.
The reaction conditions in described hydrocracking reaction district is: temperature is 300 ~ 380 DEG C, preferably 320 ~ 350 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 0.6 ~ 1.8h
-1, hydrogen to oil volume ratio 400:1 ~ 1500:1, preferred 600:1 ~ 1000:1.
Described hydrocracking reaction district and hydroisomerization dewax reaction zone can be positioned at a reactor, form different beds; Or two or more reactors can be positioned at.
Preferred embodiments of the present invention fill in same reactor by the Nobel metal hydrogen cracking catalyst containing amorphous aluminum silicide and the layering of hydroisomerization dewax catalyzer, the volume ratio of hydrocracking catalyst and hydroisomerization dewax catalyzer is 0.2:1 ~ 2:1, is preferably 0.4:1 ~ 1:1.
The lube oil hydrogenation isomerization dewaxing catalyst that hydroisomerization dewax catalyzer can select this area conventional, as can commodity in use hydroisomerization dewax catalyzer, also can prepare by this area general knowledge.The carrier of hydroisomerization catalyst is generally mesoporous molecular sieve, generally includes mordenite, SSZ-32, SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23 molecular screen etc.Molecular sieve content is in the catalyst 30wt% ~ 80wt%, is preferably 40wt% ~ 70wt%, also can adds partial oxidation silicon in carrier; Active metal component be in Pt, Pd, Ru and Rh one or more, content is 0.1wt% ~ 5.0wt% in the catalyst.Adjuvant component can be one or more in boron, fluorine, chlorine and phosphorus, and content is in the catalyst 0.1wt% ~ 5.0wt%; The specific surface of hydroisomerization dewax catalyzer is 150 ~ 500m
2/ g, pore volume is 0.15 ~ 0.60mL/g.Need before using to carry out reduction treatment to catalyzer, make hydrogenation active metals be in reduction-state in reaction process.
The reaction conditions of described hydroisomerization dewax reaction zone is: temperature is 280 ~ 350 DEG C, preferably 310 ~ 340 DEG C, and hydrogen dividing potential drop is 2.0 ~ 18.0MPa, preferably 10.0 ~ 15.0MPa, and during raw material fluid, volume space velocity is 0.4 ~ 6.0h
-1, preferably 0.6 ~ 1.8h
-1, hydrogen to oil volume ratio 400:1 ~ 1500:1, preferred 600:1 ~ 1000:1.
The inventive method can also increase hydrofinishing reaction zone behind hydroisomerization dewax reaction zone, to improve color and the stability of base oil product.The hydrofinishing catalyzer used in described post-refining reaction zone is the reduced form Hydrobon catalyst of routine, and its active metal is one or both in Pt, Pd, or active metal can be reduced state nickel.In noble metal catalyst, active metal is generally 0.05% ~ 1% at the weight content of catalyzer, and in reduced state nickel catalyzer, active metal counts 30% ~ 80% with oxide weight.Support of the catalyst is generally Al
2o
3or Al
2o
3-SiO
2, or can simultaneously containing auxiliary agents such as P, Ti, B, Zr.Need before using to carry out conventional reduction to catalyzer, ensure that hydrogenation active metals is in reduction-state in reaction process.This field general goods catalyzer can be selected, or by the preparation of this area usual way.
Described hydrofinishing reaction conditions is: temperature is 200 ~ 300 DEG C, preferably 210 ~ 280 DEG C, and hydrogen dividing potential drop is 6.0 ~ 18.0MPa, preferably 10.0 ~ 15.0MPa, and volume space velocity is 0.3 ~ 3.0h
-1, be preferably 0.6 ~ 1.2h
-1, hydrogen to oil volume ratio 400:1 ~ 1500:1, preferred 600:1 ~ 800:1.
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.Because aromaticity content general in the isomerization dewaxing chargings such as hydrotreatment distillate, the frivolous oil of hydrotreatment or hydrocracking tail oil is very low, paraffinic hydrocarbons and single-ring naphthene sum are 60% ~ 80%, generally still have the above naphthenic hydrocarbon of the dicyclo of 20% ~ 40%.The inventive method by open-loop performance stronger containing amorphous aluminum silicide hydrocracking catalyst effect under, dicyclo and this part low-viscosity index component of the above naphthenic hydrocarbon of dicyclo are generated the single-ring naphthene of high viscosity index (HVI) component by ring-opening reaction, improve the viscosity index of raw material, significantly reduce because normal alkane isomerization in isomerization dewaxing process is isoparaffin, the viscosity index loss produced, match with the isomerization dewaxing catalyst with pour point depression function, achieve the object of producing low pour point, base oil of high viscosity index lubricant.
Compared with prior art, when producing APIIII class lubricating oil base oil, the viscosity index of the inventive method to isomerization dewaxing raw material is less demanding, general between 105 ~ 125, namely can the production viscosity index APIIII class lubricating oil base oil that is greater than 120, greatly reduce the operating severity of hydrotreatment or the hydrocracking process producing isomerization dewaxing raw material, hydrogen consumption and energy consumption, and significantly improve the yield of isomerization dewaxing raw material.
Embodiment
The inventive method with one or more waxy oil in hydrotreatment distillate, the frivolous oil of hydrotreatment, hydrotreatment sweat oil or hydrocracking tail oil for raw material, first hydrocracking reaction district is entered after stock oil mixes with hydrogen, with the Nobel metal hydrogen cracking catalyst contact reacts containing amorphous aluminum silicide, there is polycyclic naphthene hydrocarbon ring-opening reaction; Reaction effluent directly enters hydroisomerization dewax reaction zone without separation, with hydroisomerization dewax catalyst exposure, carries out normal alkane isomerization reaction, obtains the base oil of high viscosity index lubricant that pour point meets the demands.
The various catalyzer 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, and amorphous aluminum silicide content is 40wt% ~ 80wt%, and 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.Amorphous aluminum silicide silicon oxide-containing 15%wt ~ 50wt%, active metal component is noble metal platinum and palladium, and content is in the catalyst 0.25wt% ~ 0.50wt%.
Hydroisomerization dewax catalyzer, also can by the existing patented technology preparation such as CN03133557.8, CN02133128.6 as the FIW-1 catalyzer of Fushun Petrochemical Research Institute's development and production.
As pressed as described in CN02133128.6, hydroisomerization dewax support of the catalyst is NU-10 molecular sieve or the ZSM-22 molecular sieve of aluminum oxide and TON structure; Molecular sieve content is in the catalyst 30wt% ~ 80wt%; Active metal component be in Pt, Pd, Ru, Rh and Ni one or more, content is in the catalyst 0.1wt% ~ 30.0wt%; Its specific surface is 150 ~ 500m
2/ g, pore volume is 0.15 ~ 0.60mL/g.
Further illustrate particular case of the present invention below by specific embodiment, but be not limited to following embodiment.The present invention's Lube basic oil material feedstocks 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 each catalyzer in table 2 respectively, implements after catalyzer reduces according to a conventional method.Raw material is introduced into the hydrocracking reaction district be filled with containing amorphous silicon Al catalysts, carry out the hydrogenation ring-opening reaction of the above naphthenic hydrocarbon of dicyclo, reaction effluent directly enters hydroisomerization dewax reaction zone without separation, with hydroisomerization dewax catalyst exposure, carry out normal alkane isomerization reaction, obtain the base oil of high viscosity index lubricant that pour point meets the demands.Reaction process condition and gained base oil product character are specifically in table 3.
Table 1 stock oil character
| Stock oil | Hydrocracking tail oil | Hydrotreatment VGO | Hydrotreatment DAO | Hydrotreatment sweat oil |
| Density, kg/m 3 | 846 | 862 | 878 | 839 |
| Boiling range scope, DEG C | 322～510 | 345～535 | 430～560 | 390～542 |
| Viscosity index | 124 | 108 | 111 | 138 |
| Pour point, DEG C | 32 | 34 | 38 | 32 |
| Sulphur, μ g/g | 5.0 | 14.0 | 12.5 | 8.0 |
| Nitrogen, μ g/g | 1.0 | 1.5 | 2.0 | 1.0 |
| Wax content, wt% | 29.8 | 18.7 | 26.8 | 39.2 |
| Mass spectrum forms, wt% | ||||
| Paraffinic hydrocarbons | 46.45 | 22.0 | 30.3 | 43.60 |
| Naphthenic hydrocarbon | 50.38 | 68.1 | 52.4 | 53.90 |
| One ring/bis-ring/tri-ring | 17.2/15.4/9.9 | 20.9/22.4/13.6 | 17.3/18.5/10.8 | 24.3/15.3/7.4 |
| Fourth Ring/five rings/six ring | 5.68/2.2/0 | 7.8/3.4/0 | 5.8/0/0 | 4.4/2.0/0.5 |
| Aromatic hydrocarbons | 3.17 | 12.75 | 17.3 | 2.50 |
Table 2 catalyst property
| Catalyzer | Hydrocracking catalyst | Isomerization dewaxing catalyst | Post-refining catalyzer |
| Chemical constitution, wt% | |||
| Platinum | 0.25 | 0.35 | 0.3 |
| Palladium | 0.10 | — | 0.2 |
| Carrier forms, wt% | |||
| SiO 2 | 35.0 | — | 15.0 |
| Al 2O 3 | 42.0 | Surplus | Surplus |
| Molecular sieve | — | 65.0（ZSM-23） | — |
| Physical properties | |||
| Physical dimension (φ × L), mm | (1.5-1.7)×(3～8) | (1.4-1.6)×(3～8) | (1.4-1.6)×(3～8) |
| Pore volume, mL/g | ≥0.28 | ≥0.30 | ≮0.40 |
| Specific surface area, m 2/g | ≥200 | ≥180 | ≮180 |
| 4-16nm pore volume, % | 75.0 | — | — |
| > 20nm pore volume, % | 7.0 | — | — |
The processing condition of table 3 embodiment and product property
| Test number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | Hydrocracking tail oil | Hydrotreatment VGO | Hydrotreatment DAO | Hydrotreatment sweat oil |
| Hydrocracking process condition | ||||
| Temperature of reaction, DEG C | 365 | 370 | 375 | 330 |
| Reaction pressure, MPa | 10.0 | 12.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 800 | 1000 | 1000 | 1500 |
| Volume space velocity, h -1 | 0.8 | 1.0 | 1.2 | 1.5 |
| Isomerization dewaxing processing condition | ||||
| Temperature of reaction, DEG C | 315 | 320 | 330 | 345 |
| Reaction pressure, MPa | 10.0 | 12.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 800 | 1000 | 1000 | 1500 |
| Volume space velocity, h -1 | 1.0 | 1.2 | 1.2 | 1.5 |
| 350℃ +Base oil character | ||||
| Yield, wt% | 73.2 | 70.5 | 63.5 | 60.6 |
| Pour point, DEG C | -24 | -21 | -18 | -15 |
| Viscosity (100 DEG C), mm/s 2 | 4.334 | 5.755 | 6.498 | 3.951 |
| Viscosity index (VI) | 122 | 114 | 116 | 133 |
| DVI | -2 | +6 | +5 | -5 |
| Mass spectrum forms, wt% | ||||
| Paraffinic hydrocarbons | 56.99 | 35.46 | 41.87 | 55.22 |
| Naphthenic hydrocarbon | 39.94 | 52.04 | 41.15 | 42.38 |
| One ring/bis-ring/tri-ring | 20.76/13.4/3.9 | 29.44/15.4/5.6 | 21.14/16.4/2.66 | 28.66/10.3/2.31 |
| Fourth Ring/five rings/six ring | 1.68/0.2/0 | 1.2/0.4/0 | 0.95/0/0 | 1.01/0/0.1 |
| Aromatic hydrocarbons | 3.07 | 12.50 | 16.98 | 2.40 |
In the present invention, 350 DEG C
+refer to that initial boiling point temperature is more than or equal to 350 DEG C.
Comparative example 1 ~ 4
Identical with the Lube basic oil material feedstocks of embodiment 1 ~ 4, difference is the technological process adopting traditional single hydroisomerization dewax production basis oil, and hydroisomerization dewax catalyzer is identical with embodiment 1 ~ 4 with processing condition, and gained base oil product character is in table 4.
From table 3 embodiment and table 4 comparative example, each data are more known, and adopt traditional single hydroisomerization dewax to produce lubricant base, the base oil product viscosity index obtained loss is comparatively large, generally at 10 ~ 20 units; Adopt the technological process of the hydroisomerization dewax production basis oil described in the inventive method, the paraffinic hydrocarbons of the base oil product obtained and the obvious increase compared with raw material of single-ring naphthene content sum, viscosity index loss significantly reduces, and is generally less than 5 units.
The processing condition of table 4 comparative example and product property
| Test number | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Isomerization dewaxing processing condition | ||||
| Temperature of reaction, DEG C | 315 | 320 | 330 | 345 |
| Reaction pressure, MPa | 10.0 | 12.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 800 | 1000 | 1000 | 1500 |
| Volume space velocity, h -1 | 1.0 | 1.2 | 1.2 | 1.5 |
| 350℃ +Base oil character | ||||
| Yield, wt% | 75.2 | 72.5 | 63.9 | 63.9 |
| Pour point, DEG C | -21 | -24 | -15 | -18 |
| Viscosity (100 DEG C), mm/s 2 | 4.727 | 6.011 | 6.885 | 4.348 |
| Viscosity index (VI) | 112 | 95 | 100 | 118 |
| DV | -12 | -13 | -11 | -20 |
| Mass spectrum forms, wt% | ||||
| Paraffinic hydrocarbons | 46.35 | 33.86 | 30.18 | 44.50 |
| Naphthenic hydrocarbon | 50.50 | 53.43 | 52.64 | 53.02 |
| One ring/bis-ring/tri-ring | 17.32/15.1/10.1 | 20.2/18.9/10.3 | 16.9/18.6/11.3 | 23.67/14.6/7.1 |
| Fourth Ring/five rings/six ring | 5.82/2.16/0 | 2.72/1.31/0 | 5.84/0/0 | 4.51/2.74/0.4 |
| Aromatic hydrocarbons | 3.15 | 12.71 | 17.18 | 2.48 |
Embodiment 5 ~ 6
Identical with the Lube basic oil material feedstocks of embodiment 1 ~ 2, difference is to increase behind hydroisomerization dewax reaction zone to supplement hydrofining reaction district, and post-refining catalyst property is in table 2, and reaction process condition and gained base oil product character are specifically in table 5.
Comparative example 5 ~ 6
Identical with the Lube basic oil material feedstocks of comparative example 1 ~ 2, difference is to increase hydrofining reaction district behind hydroisomerization dewax reaction zone, and post-refining catalyst property is in table 2, and reaction process condition and gained base oil product character are specifically in table 5.
From table 5 embodiment and comparative example, each data are more known, and adopt traditional single hydroisomerization dewax to produce lubricant base, the base oil product viscosity index obtained loss is more general at 10-20 unit; Adopt the technological process of the hydroisomerization dewax production basis oil described in the inventive method, the paraffinic hydrocarbons of the base oil product obtained and the obvious increase compared with raw material of single-ring naphthene content sum, viscosity index loss significantly reduces, and is generally less than 5 units.
Comparative example 7
Comparative example 7 with hydrocracking tail oil listed in table 1 for raw material, catalyzer adopts grading loading mode disclosed in CN99113304.8, after reducing in conventional manner, implement according to the isomerization dewaxing identical with embodiment 5 and post-refining process condition, the reaction conditions of b molecular sieve catalyst is determined with reference to embodiment in CN99113304.8.Raw material is introduced into and is filled with silicon-aluminum containing than the b molecular sieve catalyst being 212 (molecular sieve content is 65wt%) bed, then reaction product enters hydroisomerization dewax beds listed in table 2, carry out hygrogenating isomerization reaction, finally carry out hydrofinishing and obtain lubricant base object product.Processing condition and gained base oil product character are in table 6.
From table 6, in embodiment 5 and comparative example 7, each data are more known, adopt the mode of b molecular sieve catalyst and isomerization dewaxing catalyst grating compared with the inventive method, although higher lubricant base yield can be kept, but because above for dicyclo in raw material cycloalkanes is that the ability of single-ring naphthene is poor by b molecular sieve catalyst, therefore base oil product viscosity index is still lost larger, be 10 units, be difficult to meet the needs that production viscosity index is greater than the APIIII class lubricating oil base oil of 120.
The processing condition of table 5 comparative example 5 ~ 6 and product property
| Test number | Embodiment 5 | Embodiment 6 | Comparative example 5 | Comparative example 6 |
| Stock oil | Hydrocracking tail oil | Hydrotreatment VGO | Hydrocracking tail oil | Hydrotreatment VGO |
| Hydrocracking process condition | ||||
| Temperature of reaction, DEG C | 365 | 370 | ||
| Reaction pressure, MPa | 10.0 | 12.0 | ||
| Hydrogen to oil volume ratio | 800 | 1000 | ||
| Volume space velocity, h -1 | 0.8 | 1.0 | ||
| Isomerization dewaxing processing condition | ||||
| Temperature of reaction, DEG C | 315 | 320 | 315 | 320 |
| Reaction pressure, MPa | 10.0 | 12.0 | 10.0 | 12.0 |
| Hydrogen to oil volume ratio | 800 | 1000 | 800 | 1000 |
| Volume space velocity, h -1 | 1.0 | 1.2 | 1.0 | 1.2 |
| Post-refining process condition | ||||
| Temperature of reaction, DEG C | 220 | 230 | 240 | 260 |
| Reaction pressure, MPa | 10.0 | 12.0 | 10.0 | 12.0 |
| Hydrogen to oil volume ratio | 800 | 1000 | 800 | 1000 |
| Volume space velocity, h -1 | 1.0 | 1.2 | 0.8 | 1.0 |
| 350℃ +Base oil character | ||||
| Yield, wt% | 73.1 | 70.5 | 75.2 | 72.4 |
| Pour point, DEG C | -21 | -18 | -21 | -21 |
| Viscosity (100 DEG C), mm/s 2 | 4.319 | 5.550 | 4.522 | 5.915 |
| Viscosity index (VI) | 123 | 115 | 113 | 98 |
| DVI | -1 | +7 | -11 | -10 |
| Mass spectrum forms, wt% | ||||
| Paraffinic hydrocarbons | 56.95 | 35.46 | 46.35 | 33.84 |
| Naphthenic hydrocarbon | 42.51 | 59.19 | 53.0 | 60.38 |
| One ring/bis-ring/tri-ring | 21.36/12.1/4.73 | 29.65/15.35/7.9 | 15.42/17.0/10.1 | 20.65/19.5/10.42 |
| Fourth Ring/five rings/six ring | 3.42/0.9/0 | 4.09/2.2/0 | 7.82/2.66/0 | 6.85/2.96/0 |
| Aromatic hydrocarbons | 0.54 | 5.35 | 0.65 | 5.78 |
The processing condition of table 6 comparative example 7 and product property
| Test number | Embodiment 5 | Comparative example 7 |
| Hydrocracking process condition | ||
| Catalyzer | Pt-Pd/ amorphous aluminum silicide | Pd/b |
| Temperature of reaction, DEG C | 365 | 360 |
| Reaction pressure, MPa | 10.0 | 10.0 |
| Hydrogen to oil volume ratio | 800 | 800 |
| Volume space velocity, h -1 | 0.8 | 0.9 |
| Isomerization dewaxing processing condition | ||
| Temperature of reaction, DEG C | 315 | 315 |
| Reaction pressure, MPa | 10.0 | 10.0 |
| Hydrogen to oil volume ratio | 800 | 800 |
| Volume space velocity, h -1 | 1.0 | 1.0 |
| Post-refining process condition | ||
| Temperature of reaction, DEG C | 240 | 240 |
| Reaction pressure, MPa | 10.0 | 10.0 |
| Hydrogen to oil volume ratio | 800 | 800 |
| Volume space velocity, h -1 | 0.8 | 0.8 |
| 350℃ +Base oil character | ||
| Yield, wt% | 73.1 | 72.7 |
| Pour point, DEG C | -21 | -21 |
| Viscosity index (VI) | 123 | 114 |
| DVI | -1 | -10 |
| Mass spectrum forms, wt% | ||
| Paraffinic hydrocarbons | 56.95 | 51.38 |
| Naphthenic hydrocarbon | 42.51 | 48.02 |
| One ring/bis-ring/tri-ring | 21.36/12.1/4.73 | 14.28/13.26/11.98 |
| Fourth Ring/five rings/six ring | 3.42/0.9/0 | 5.02/3.28/0.2 |
| Aromatic hydrocarbons | 0.54 | 0.60 |
Claims (9)
1. a method for producing base oil of lubricating oil by isomerization dewaxing, comprises the steps:
(1) first stock oil enter hydrocracking reaction district after mixing with hydrogen, with the Nobel metal hydrogen cracking catalyst contact reacts containing amorphous aluminum silicide, polycyclic naphthene hydrocarbon ring-opening reaction occurs;
(2) step (1) gained reaction effluent directly enters hydroisomerization dewax reaction zone without separation, with hydroisomerization dewax catalyst exposure, carries out normal alkane isomerization reaction, obtains lube base oil production;
Described stock oil is one or more in hydrotreatment distillate, the frivolous oil of hydrotreatment, hydrocracking tail oil, described hydrotreatment distillate, the frivolous oil of hydrotreatment or hydrocracking tail oil charging paraffin and single-ring naphthene sum are 60wt% ~ 80wt%, the above naphthenic hydrocarbon 20wt% ~ 40wt% of dicyclo, the carrier of described hydrocracking catalyst 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, and described hydrocracking catalyst contains at least one noble metal component, and bullion content is 0.1wt% ~ 1.0wt%.
2. in accordance with the method for claim 1, it is characterized in that: the sulphur content of described stock oil is less than 30mg/g, and nitrogen content is less than 5mg/g.
3. in accordance with the method for claim 1, it is characterized in that: in the carrier hole distribution of described hydrocracking catalyst, 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.
4. in accordance with the method for claim 1, it is characterized in that, the physico-chemical property of described amorphous aluminum silicide is: silica content is 5wt% ~ 70wt%, and 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.
5. in accordance with the method for claim 1, it is characterized in that: described hydrocracking catalyst precious metal is platinum and palladium, the mol ratio of platinum and palladium is 3:1-1:3.
6. in accordance with the method for claim 1, it is characterized in that: the reaction conditions in described hydrocracking reaction district is: temperature of reaction 300 ~ 380 DEG C, hydrogen dividing potential drop 2.0 ~ 18.0MPa, volume space velocity 0.4 ~ 6.0h
-1, hydrogen to oil volume ratio 400:1 ~ 1500:1.
7. in accordance with the method for claim 1, it is characterized in that: the carrier of described hydroisomerization dewax catalyzer is mesoporous molecular sieve, mesoporous molecular sieve comprises mordenite, SSZ-32, SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23 molecular screen, and molecular sieve content is in the catalyst 30wt% ~ 80wt%; Active metal component is one or more in Pt, Pd, Ru, Rh and Ni, and content is in the catalyst 0.1wt% ~ 5.0wt%.
8. in accordance with the method for claim 1, it is characterized in that: the reaction conditions of described hydroisomerization dewax reaction zone is: temperature of reaction 280 ~ 350 DEG C, hydrogen dividing potential drop 2.0 ~ 18.0MPa, volume space velocity 0.4 ~ 6.0h
-1, hydrogen to oil volume ratio 400:1 ~ 1500:1.
9. in accordance with the method for claim 1, it is characterized in that: behind hydroisomerization dewax reaction zone, increase hydrofinishing reaction zone, the processing condition of described hydrofinishing reaction zone are: temperature of reaction 200 ~ 300 DEG C, hydrogen dividing potential drop 6.0 ~ 18.0MPa, volume space velocity 0.3 ~ 3.0h
-1, hydrogen to oil volume ratio 400:1 ~ 1500:1.
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| CN113976171B (en) * | 2020-07-27 | 2024-01-30 | 国家能源投资集团有限责任公司 | Catalyst composition and method for producing low-freezing point diesel oil and high-viscosity index lubricating oil base oil |
| US20220213394A1 (en) * | 2021-01-07 | 2022-07-07 | Chevron U.S.A. Inc. | Processes for catalyzed ring-opening of cycloparaffins |
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| CN1218089A (en) * | 1997-11-24 | 1999-06-02 | 中国石油化工总公司 | Catalyst carrier containing difunctional amorphous aluminum silicide and preparation thereof |
| CN1836028A (en) * | 2003-06-19 | 2006-09-20 | 切夫里昂美国公司 | Fuels and lubricants using layered bed catalysts in hydrotreating waxy feeds, including fischer-tropsch wax |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218089A (en) * | 1997-11-24 | 1999-06-02 | 中国石油化工总公司 | Catalyst carrier containing difunctional amorphous aluminum silicide and preparation thereof |
| CN1836028A (en) * | 2003-06-19 | 2006-09-20 | 切夫里昂美国公司 | Fuels and lubricants using layered bed catalysts in hydrotreating waxy feeds, including fischer-tropsch wax |
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