CN101942321B - Method for producing base oil of lubricating oil by isomerization dewaxing - Google Patents
Method for producing base oil of lubricating oil by isomerization dewaxing Download PDFInfo
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Abstract
The invention discloses a method for producing the base oil of lubricating oil by isomerization dewaxing. Under hydroisomerization condition, crude oil and hydrogen pass through a hydroisomerization catalyst bed; a hydroisomerization catalyst comprises a TON type molecular sieve and 0.05 to 0.5 weight percent of active ingredients of platinum group metals; the hydroisomerization bed at least comprises two hydroisomerization catalysts; and along the flow direction of the crude oil and the hydrogen, the molecular sieve content of the hydroisomerization catalysts is sequentially increased. The method of the invention has the advantages of adjusting the components of the catalyst, improving the comprehensive reaction performance, maximally reducing the molecular sieve content and reducing the production cost at the same time of ensuring the activity of a reaction system.
Description
Technical field
The invention discloses a kind of production method of lubricant base, particularly hydroisomerizing produces the method for lubricant base.
Background technology
The higher macromole straight chain of a large amount of fusing points or few branched paraffin (referred to herein as wax) is contained, so its pour point is high, viscosity index is low and poor performance at low temperatures in lubricating oil distillate.Thus, will high melting-point wax removing wherein.Process for dewaxing conventional at present mainly contains solvent dewaxing, catalytic dewaxing and isomerization dewaxing.
Solvent dewaxing is exactly utilize wax solubility property in a solvent to remove, the shortcoming of this method be solvent select difficulty, waste a large amount of organic solvents, harmful and contaminate environment, facility investment and process cost are high.Catalytic dewaxing makes wax generation catalytic cracking in lubricating oil distillate exactly, generate more micromolecular hydro carbons, thus make base oil depression of pour point, P.4247388, US Patent No. is exactly the method using catalytic dewaxing with USP.4659311, the shortcoming of this method is due to a large amount of macromolecular cpds is converted into small-molecule substance, make base oil yield low, viscosity index loss is large, by product is worth low, compared with first two process for dewaxing, isomerization dewaxing makes macromole wax generation isomerization reaction generate isoparaffin, and the isoparaffin pour point lower than having with the wax phase of same molecular amount and high viscosity index, and be still retained in lubricating oil distillate, thus base oil yield is greatly enhanced, be subject to paying close attention to and having many documents and patent report greatly.
A lot of about the report of isomerization dewaxing catalyst at present, such as, US Patent No. P5990371,5833837,5817907,5149421,5135638,5110445,4919788,4419420,4601993,5699162,4518485 etc. reports and relates to Isodewaxing Technology and produce lubricant base, the acidic components wherein used mainly contain MOR, SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23, SSZ-32, Nu-10, KZ-2 and ISI-1 etc., and these materials can both make paraffinic hydrocarbon generation isomerization reaction to a certain extent.
Chinese patent CN1609175A discloses a kind of hydrotreating catalyst and preparation method thereof, and its acidic components adopt TON structure molecular screen, and hydrogenation metal component is one or more in Pt, Pd, Ru, Rh, nickel, cobalt, molybdenum and tungsten.Under certain appreciation condition, its base oil yield is 82.3%, viscosity index 105, condensation point-21 DEG C.
Chinese patent CN1952073A discloses a kind of lubricating oil and faces hydrogen dewaxing catalyst and preparation method thereof, its acidic components have TON and MFI structure characteristic simultaneously, hydrogenation precious metal is Pd, its content is 0.1wt% ~ 2.0wt%, under certain appreciation condition, its base oil yield is 80%, viscosity index 106, condensation point-22 DEG C.
Chinese patent CN1762594A discloses a kind of catalyst for hydroisomerizing paraffin and preparation method thereof, and its acidic components are ZSM-22/SAPO-11 composite molecular screen, ZSM-23/SAPO-11 composite molecular screen, EU-1/SAPO-11 composite molecular screen and NU-87/SAPO-11 composite molecular screen.Take n-dodecane as raw material, transformation efficiency is ~ 85%, isomerisation selectivity ~ 75%.
Isomerization dewaxing adopts the dual-function catalyst with special pore structure to make the high-melting-point long-chain n-praaffin in wax component and polycyclic naphthene hydrocarbon be converted into the isoparaffin of the lower one-sided chain of fusing point and the single-ring naphthene of belt length side chain.But the alkane fusing point that isomerisation degree is high is higher on the contrary, so just must control the isomerisation degree of wax molecule.
At present these Production Technology of Lubricating Base Oils adopt the catalyzer of same activity to carry out isomerization reaction mostly, do not take into full account the impact of differential responses region material properties change on whole reaction system combined reaction performance under response behaviour.
Summary of the invention
For the deficiencies in the prior art, the present invention proposes a kind of production method of lubricant base, and while guarantee reaction system activity, adjustment catalyzer composition, improves combined reaction performance, reduce molecular sieve content to greatest extent, reduce production cost.
The method of producing base oil of lubricating oil by isomerization dewaxing of the present invention comprises following content: under hydroisomerizing condition, stock oil and hydrogen are by hydroisomerization catalyst bed, hydroisomerization catalyst comprises TON type molecular sieve and platinum metals active ingredient, in hydroisomerization catalyst, the weight content of platinum metals active ingredient is 0.05wt% ~ 0.5wt%, be preferably 0.1wt% ~ 0.4wt%, described hydroisomerization catalyst bed at least comprises two kinds of hydroisomerization catalysts, increase successively by the molecular sieve content of stock oil and hydrogen flow direction hydroisomerization catalyst catalyzer.In the hydroisomerization catalyst that molecular sieve content increases successively, the weight content difference 5wt% ~ 25wt% of adjacent hydroisomerization catalyst molecular sieve.
In Lubricating oil base oil producing method of the present invention, stock oil can be the various suitable stock oil in this area, owing to using platinum metals to be active metal, generally the impurity such as sulphur, nitrogen need be removed, as the vacuum distillate of hydrocracking tail oil, hydrotreatment, the diasphaltene wet goods of hydrotreatment in stock oil.
In Lubricating oil base oil producing method of the present invention, hydroisomerizing operational condition is processing condition known by the technical staff, and as reaction pressure is generally 1 ~ 15MPa, temperature of reaction is generally 280 ~ 400 DEG C, and during liquid, volume space velocity is generally 0.2 ~ 4h
-1, hydrogen to oil volume ratio is generally 100 ~ 1500.Concrete operations condition can require specifically to determine according to feedstock property and quality product.
In Lubricating oil base oil producing method of the present invention, the hydroisomerization catalyst that 2 ~ 5 kinds of molecular sieve content are different can be used, along reaction mass flowing direction, the molecular sieve content of hydroisomerization catalyst raises successively, often kind of hydroisomerization catalyst accounts for 10% ~ 90% of total hydroisomerization catalyst volume, is preferably 20% ~ 80%.Active metallic content in hydroisomerization catalyst also can be different, and the hydroisomerization catalyst active metallic content that preferred molecular sieve content is high is higher, to mate the different hydroisomerization catalyst of molecular sieve content.
In Lubricating oil base oil producing method of the present invention, hydroisomerization catalyst can select commercial catalyst, also can prepare according to prior art.TON type molecular sieve in hydroisomerization catalyst can be one or more in ZSM-22, SSZ-32, Nu-10, KZ-2 and ISI-1 etc., preferably containing ZSM-22 molecular sieve.The weight content of hydroisomerization catalyst Middle molecule sieve is the 10wt% ~ 90wt% of total catalyst weight, preferred 30wt% ~ 80wt%, more preferably 40wt% ~ 70wt%, the molecular sieve content of the various hydroisomerization catalysts that molecular sieve content is different is all in above-mentioned scope.Inorganic refractory oxide can also be contained in hydroisomerization catalyst, as one or more in aluminum oxide, titanium oxide, silicon oxide, boron oxide, magnesium oxide, zirconium white and clay, inorganic refractory oxide with final catalyst gauge content for 5wt% ~ 80wt%, be preferably 10wt% ~ 60wt%, be more preferably 15wt% ~ 40wt%.Platinum family active metal can be one or more in platinum, palladium, iridium, rhodium, osmium etc., preferably containing platinum.Hydroisomerization catalyst can be seated in a reactor, also can load in a plurality of reactors.
The present invention, according to the feature of Lube basic oil material feedstocks hydroisomerizing technique, adopts the grating of suitable kind catalyzer, improves W-response performance.When reaction mass and catalyst exposure, the easy reactive component in raw material is more, if catalyst activity is higher, excessive isomerization reaction and coking reaction easily occurs, unfavorable to product property, and has certain influence to the steady running of catalyzer.Adopt the timing of different properties catalyst grade, the catalyzer that first raw material contacts has suitable character, and excessive isomerization reaction does not occur easy reactive component, is also conducive to controlling the side reactions such as coking; Along with the flowing of material, through the active high hydroisomerization catalyst of lower floor, easy reactive material is owing to there occurs appropriate isomerization reaction, reactive behavior is lower than other not easily iso-component in raw material, therefore the isomerization reaction of not easily iso-component in the mainly raw material occurred in high-activity hydrogenation heterogeneous catalyst bed, finally show as W-response performance to improve, and Beneficial Effect is produced to steady running.In addition, the inventive method is because use the catalyzer that moieties sieve content is lower, and molecular sieve price is higher, and therefore the inventive method can suitably reduce catalyzer cost.
Embodiment
The present invention considers that the alkane isomerization complexity of different chain length is different, and the sequencing of their generation isomerization reactions is different, by catalyzer grading loadings different for activity, gives full play to respective activity.
Below for the hydroisomerization catalyst containing ZSM-22 molecular sieve and active metal Pt, illustrate the inventive method and effect.
Containing refractory oxide aluminum oxide in hydroisomerization catalyst, ZSM-22 molecular sieve, hydrogenation metal component Pt.Wherein the content of ZSM-22 molecular sieve is the 10wt% ~ 90wt% of total catalyst weight, preferred 30wt% ~ 80wt%, more preferably 40wt% ~ 70wt%.Inorganic refractory oxide for 5wt% ~ 80wt% with final catalyst gauge content, is preferably 10wt% ~ 6wt%, is more preferably 15wt% ~ 40wt%.Active metal component is Pt, with final catalyst gauge content for 0.05wt% ~ 0.5wt%, is preferably 0.1wt% ~ 0.4wt%.
Catalyzer of the present invention conveniently Nobel-metal catalyst preparation method preparation.
(1) NaZSM-22 is exchanged into HZSM-22, through modifications such as dealumination complement silicons, the SiO of ZSM-22 molecular sieve
2/ Al
2o
3mol ratio is 80 ~ 120, specific surface area 200m
2/ g ~ 300m
2/ g, pore volume 0.20cm
3/ g ~ 0.40cm
3/ g, B acid amount is measured as 0.1mmol/g ~ 0.2mmol/g for 0.1mmol/g ~ 0.3mmol/g, L are sour.
(2) ZSM-22 molecular sieve, other inorganic refractory oxide, extrusion aid, peptizing agent and water together abundant kneading are become plastic paste, extruded moulding, obtain carrier through the last handling process such as super-dry, roasting.
(3) toward supported on carriers active metal component, by last handling processes such as drying, roastings, catalyzer of the present invention is obtained.
NaZSM-22 described in step (1) first adopts ion exchange method to be exchanged into HZSM-22, and solution used is for containing NH
4 +ion, NH
4 +volumetric molar concentration is 0.05mol/L ~ 10mol/L, and temperature is normal temperature ~ 200 DEG C, and pressure is keep solution to be the pressure of liquid phase, and the time is 1h ~ 24h, Gu the liquid/mass ratio of solution and molecular sieve is 5 ~ 20.Dealumination process, solution used is acidic solution, and be wherein selected from mineral acid and at least one in nitric acid, hydrochloric acid and sulfuric acid etc. containing at least one and be selected from organic acid in oxalic acid, acetic acid, citric acid etc., mineral acid and organic acid mol ratio are 10: 1 ~ 1: 1, H in solution
+volumetric molar concentration is 0.05mol/L ~ 10mol/L, and temperature is normal temperature ~ 300 DEG C, and pressure is normal pressure ~ 5MPa, and the time is 0.5h ~ 8h, and the mass ratio of solution and molecular sieve is 5 ~ 10.Mend silicon process, solution used, for containing Soluble silicon compounds solution, is preferably ammonium fluosilicate solution.Strength of solution is 1wt% ~ 10wt%, and temperature is normal temperature ~ 200 DEG C, and pressure is normal pressure ~ 5MPa, and the time is 0.5h ~ 12h, and the mass ratio of solution and molecular sieve is 5 ~ 10.
Inorganic refractory oxide described in step (2) can be selected from one or more in aluminum oxide, titanium oxide, silicon oxide, boron oxide, magnesium oxide, zirconium white and clay, is preferably aluminum oxide and/or silicon oxide, is more preferably aluminum oxide.Its precursor can be selected from boehmite, pseudo-boehmite, diaspore, gibbsite and visit in aluminium stone one or more, be preferably pseudo-boehmite; Peptizing agent refers to mineral acid and/or organic acid, is preferably one or more mixtures in nitric acid, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, citric acid; Extrusion aid refers to the material being conducive to extrusion molding, is preferably sesbania powder, starch, carboxymethyl cellulose, carbon black, stone mill powder, citric acid etc.
The condition that is dry and roasting of catalyzer described in step (3) is as follows: drying temperature is normal temperature ~ 300 DEG C, and be preferably 100 DEG C ~ 150 DEG C, time of drying is 1 ~ 48 hour; Maturing temperature can be 400 DEG C ~ 800 DEG C, and be preferably 500 DEG C ~ 700 DEG C, roasting time can be 0.5 ~ 24 hour, is preferably 2 ~ 8 hours.
The inventive method is applicable to long chain alkane isomerization and production of lube base oils.
The present invention is by using the catalyzer grading loading of differing molecular sieve content, catalyzer classifications different for activity is loaded, consider in raw material that first the alkane being easy to isomery utilize the activity of active low catalyzer, and the activity of the catalyzer that the alkane being difficult to isomery in raw material utilizes later active high, make all catalyzer in reactor can give full play to respective activity, while not reducing product property, reduce molecular sieve content to greatest extent, thus reduce production cost.
Be further described the present invention below by embodiment, it does not limit use range of the present invention, and the percentage composition related to is weight percentage.
The process of embodiment 1ZSM-22 molecular sieve
Get 100 grams, NaZSM-22 molecular sieve, be that the ammonium nitrate solution of 10% exchanges 4 hours at 80 DEG C by 500 grams of concentration, then repeat above-mentioned exchange once; Be the nitric acid of 0.5mol/L and volumetric molar concentration by 800 grams of volumetric molar concentrations be that the tartaric mixing solutions of 0.2mol/L was 90 DEG C of process 4 hours; Use 1000 grams of (NH again
4)
2siF
6concentration be the aqueous solution of 3% 85 DEG C of process 4 hours, through filtering, washing, 110 DEG C of dryings 8 hours and 550 DEG C of roastings obtain the HZSM-22 of final dealumination complement silicon for 4 hours.
The preparation of embodiment 2 carrier
65 grams, HZSM-22 molecular sieve prepared by Example 1, pseudo-boehmite (butt 72%) 28 grams, 21 grams, SB powder (butt 72%), 2 grams, sesbania powder, mix, then 30ml deionized water and 2.5ml concentrated nitric acid (66.5w%) abundant kneading on rolling machine is added, make it to become paste plastic, banded extruder is extruded the cylindrical bars of diameter 1.5mm, 110 DEG C of dryings 8 hours, then in air atmosphere, 550 DEG C of roastings obtain carrier D-1 (molecular sieve accounts for 65% of final support of the catalyst weight) for 4 hours
50 grams, HZSM-22 molecular sieve prepared by Example 1, pseudo-boehmite (butt 72%) 42 grams, 28 grams, SB powder (butt 72%), 2 grams, sesbania powder, mix, then 40ml deionized water and 2.5ml concentrated nitric acid (66.5w%) abundant kneading on rolling machine is added, make it to become paste plastic, banded extruder is extruded the cylindrical bars of diameter 1.5mm, 110 DEG C of dryings 8 hours, then in air atmosphere, 550 DEG C of roastings obtain carrier D-2 (molecular sieve accounts for 50% of final support of the catalyst weight) for 4 hours
40 grams, HZSM-22 molecular sieve prepared by Example 1, pseudo-boehmite (butt 72%) 48 grams, 35 grams, SB powder (butt 72%), 2 grams, sesbania powder, mix, then 50ml deionized water and 2.5ml concentrated nitric acid (66.5w%) abundant kneading on rolling machine is added, make it to become paste plastic, banded extruder is extruded the cylindrical bars of diameter 1.5mm, 110 DEG C of dryings 8 hours, then in air atmosphere, 550 DEG C of roastings obtain carrier D-3 (molecular sieve accounts for 40% of final support of the catalyst weight) for 4 hours
Embodiment 3 catalyst preparing
Carrier D-1, D-2 and D-3 prepared by Example 2, use Pt (NH respectively
4)
4cl
2solution carries out saturated dipping, and then 110 DEG C of dryings 6 hours, in air atmosphere, 500 DEG C of roastings 4 hours, obtain catalyzer C-1, catalyzer C-2, catalyzer C-3 respectively, by weight containing Pt 0.3% in catalyzer.
Embodiment 4
Catalyzer grading distribution scheme is: catalyzer C-3: catalyzer C-2: catalyzer C-1=3: 3: 4.
Embodiment 5
Catalyzer grading distribution scheme is: catalyzer C-3: catalyzer C-2: catalyzer C-1=3: 5: 2.
Embodiment 6
Catalyzer grading distribution scheme is: catalyzer C-3: catalyzer C-2: catalyzer C-1=2: 3: 5.
Embodiment 7
Catalyzer grading distribution scheme is: catalyzer C-3: catalyzer C-1=5: 5.
Embodiment 8
Catalyzer grading distribution scheme is: catalyzer C-3: catalyzer C-2=5: 5.
Embodiment 9
Catalyzer grading distribution scheme is: catalyzer C-2: catalyzer C-1=5: 5.
Comparative example 1
Catalyzer grading distribution scheme is: loading catalyst C-3 completely.
Comparative example 2
Catalyzer grading distribution scheme is: loading catalyst C-2 completely.
Comparative example 3
Catalyzer grading distribution scheme is: loading catalyst C-1 completely.
Catalyzer C-1, catalyzer C-2, catalyzer C-3 specifically load situation in table 1.Evaluate stock oil character in table 2, appreciation condition and the results are shown in Table 3.
Table 1 catalyst loading situation
| C-3 | C-2 | C-1 | |
| Embodiment 4 | 3 | 3 | 4 |
| Embodiment 5 | 3 | 5 | 2 |
| Embodiment 6 | 2 | 3 | 5 |
| Embodiment 7 | 5 | / | 5 |
| Embodiment 8 | 5 | 5 | / |
| Embodiment 9 | / | 5 | 5 |
| Comparative example 1 | All | / | / |
| Comparative example 2 | / | All | / |
| Comparative example 3 | / | / | All |
Table 2 stock oil character
| Project | Raw material |
| Density (20 DEG C), kg/m 3 | 861.1 |
| Sulphur, μ g/g | 4.0 |
| Nitrogen, μ g/g | 1.2 |
| Viscosity (40 DEG C), mm/s 2 | 29.69 |
| (100℃)，mm/s 2 | 5.47 |
| C/H | 85.82/14.08 |
| Pour point, DEG C | 21 |
| Flash-point (opening), DEG C | 198 |
| Wax content, % | 9.8 |
| Boiling range, DEG C (D1160) | |
| IBP/10％ | 227/399 |
| 30％/50％ | 428/441 |
| 70％/90％ | 455/469 |
| 95％/EBP | 477/500 |
Table 3 appreciation condition and result
| Catalyzer is numbered | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Processing condition | |||||||||
| Reaction pressure, MPa | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 |
| Volume space velocity, h -1 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Hydrogen to oil volume ratio | 800 | 800 | 800 | 800 | 800 | 800 | 800 | 800 | 800 |
| Temperature of reaction, DEG C | 320 | 320 | 320 | 320 | 320 | 320 | 320 | 320 | 320 |
| C 5 +Liquid is received, % | 95.2 | 94.2 | 94.7 | 94.6 | 95.2 | 94.5 | 95.5 | 95.0 | 94.5 |
| Product slates | |||||||||
| C 5～130℃ | 4.4 | 4.1 | 4.3 | 3.6 | 4.0 | 3.8 | 4.1 | 3.9 | 3.8 |
| 130℃～280℃ | 3.3 | 3.5 | 3.1 | 3.4 | 3.3 | 3.2 | 3.0 | 3.7 | 2.8 |
| 280℃～350℃ | 5.7 | 4.5 | 5.4 | 6.0 | 5.2 | 6.0 | 5.2 | 5.4 | 5.2 |
| 350℃ + | 81.8 | 82.1 | 81.9 | 81.6 | 82.6 | 81.5 | 83.2 | 82.0 | 82.6 |
| 350℃ +Neutral oil character | |||||||||
| Viscosity, 40 DEG C, mm 2/s | 37.88 | 38.53 | 38.01 | 37.67 | 38.13 | 37.64 | 37.96 | 38.27 | 38.12 |
| Viscosity index | 103 | 105 | 107 | 101 | 103 | 98 | 96 | 102 | 103 |
| Pour point, DEG C | -21 | -24 | -22 | -21 | -24 | -18 | -18 | -21 | -21 |
Claims (10)
1. the method for a producing base oil of lubricating oil by isomerization dewaxing, comprise following content: under hydroisomerizing condition, stock oil and hydrogen are by hydroisomerization catalyst bed, hydroisomerization catalyst comprises TON type molecular sieve and platinum metals active ingredient, in hydroisomerization catalyst, the weight content of platinum metals active ingredient is 0.05wt% ~ 0.5wt%, it is characterized in that: described hydroisomerization catalyst bed at least comprises two kinds of hydroisomerization catalysts, increase successively by the molecular sieve content of stock oil and hydrogen flow direction hydroisomerization catalyst.
2. according to method described in claim 1, it is characterized in that: the TON type molecular sieve that hydroisomerization catalyst comprises is one or more in ZSM-22, Nu-10, KZ-2 and ISI-1.
3. according to the method described in claim 1 or 2, it is characterized in that: in the hydroisomerization catalyst that molecular sieve content increases successively, the weight content difference 5wt% ~ 25wt% of molecular sieve in hydroisomerization catalyst.
4. in accordance with the method for claim 1, it is characterized in that: in hydroisomerization catalyst, the weight content of TON type molecular sieve is the 10wt% ~ 90wt% of total catalyst weight.
5. in accordance with the method for claim 1, it is characterized in that: in hydroisomerization catalyst, the weight content of TON type molecular sieve is the 30wt% ~ 80wt% of total catalyst weight.
6. in accordance with the method for claim 1, it is characterized in that: use the hydroisomerization catalyst that 2 ~ 5 kinds of molecular sieve content are different, along reaction mass flowing direction, the molecular sieve content of hydroisomerization catalyst raises successively, and often kind of hydroisomerization catalyst accounts for 10% ~ 90% of total hydroisomerization catalyst volume.
7. in accordance with the method for claim 6, it is characterized in that: often kind of hydroisomerization catalyst accounts for 20% ~ 80% of total hydroisomerization catalyst volume.
8. in accordance with the method for claim 1, it is characterized in that: hydroisomerizing operational condition is reaction pressure is 1 ~ 15MPa, and temperature of reaction is 280 ~ 400 DEG C, and during liquid, volume space velocity is 0.2 ~ 4h
-1, hydrogen to oil volume ratio is 100 ~ 1500.
9. in accordance with the method for claim 1, it is characterized in that: containing inorganic refractory oxide in hydroisomerization catalyst, inorganic refractory oxide with final hydroisomerization catalyst weighing scale content for 5wt% ~ 80wt%.
10. in accordance with the method for claim 1, it is characterized in that: stock oil is hydrocracking tail oil, the vacuum distillate of hydrotreatment or the deasphalted oil of hydrotreatment.
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| CN107286981B (en) * | 2016-04-05 | 2019-04-16 | 中国石油化工股份有限公司 | A kind of preparation method of lube base oil |
| CN107286979B (en) * | 2016-04-05 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of preparation method of lube base oil |
| CN107286978B (en) * | 2016-04-05 | 2019-07-23 | 中国石油化工股份有限公司 | A kind of preparation method of lube base oil |
| CN107286982B (en) * | 2016-04-05 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of preparation method of lube base oil |
| CN107286980B (en) * | 2016-04-05 | 2019-03-08 | 中国石油化工股份有限公司 | A kind of preparation method of lube base oil |
| CN108102698B (en) * | 2016-11-25 | 2020-07-03 | 中国石油化工股份有限公司 | Method for producing lubricating oil base oil |
| CN106964398B (en) * | 2017-03-09 | 2019-07-02 | 武汉凯迪工程技术研究总院有限公司 | Hydroisomerizing dewaxing catalyst and preparation method thereof |
| CN111073696B (en) * | 2018-10-18 | 2022-03-01 | 中国海洋石油集团有限公司 | Method for reducing cloud point of base oil of high-viscosity lubricating oil and base oil of lubricating oil |
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