CN1351128A - Process for hydrorefining basic oil lubricating oil - Google Patents
Process for hydrorefining basic oil lubricating oil Download PDFInfo
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- CN1351128A CN1351128A CN 00123161 CN00123161A CN1351128A CN 1351128 A CN1351128 A CN 1351128A CN 00123161 CN00123161 CN 00123161 CN 00123161 A CN00123161 A CN 00123161A CN 1351128 A CN1351128 A CN 1351128A
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Abstract
A hydrorefining process for the basic oil of lubricating oil features use of two catalysts: the noble metal catalyst containing macroreticular aluminosilicon carrier and the noble metal catalyst containing Y molecular sieve. Said catalysts are filled at different layers in a reactor or in two different reactor which are serially connected. Said catalyst system features higher power resisting S poisoning, and hydroactivity. The processed basic oil features high optical stability and anti-oxidizing stability, and high viscosity index.
Description
The present invention relates to the hydrofining production method of the lubricant base and the food-level white oil of a kind of process for hydrorefining basic oil lubricating oil, particularly high viscosity index (HVI).
The process sequence of producing lubricant base depends on the specific needs of whole process.From oil, remove desulfuration, nitrogen and condensed-nuclei aromatics compound, increase and be positioned at before the dewaxing step as the upgrading step 1 of viscosity index, after the dewaxing is the hydrofinishing step, remove unsettled molecule, these unsettled molecules are included in the procedure of processing in front unconverted and generate in these procedure of processings.
Use hydrogenation method to produce lubricant base by the hydrocarbon oil crude material of all multi-sources.Traditional hydrogenation method is produced lubricant base technology and is generally: hydrocracking---catalytic dewaxing---hydrofining, perhaps solvent treatment---hydrotreatment---catalytic dewaxing---hydrofining.Hydrocracking is a kind of method for modifying that increases viscosity index by the molecule of removing low-viscosity index; Lube stock after the solvent treatment can remove desulfuration, nitrogen compound through hydrotreatment, and reactions such as open loop cracking saturated by aromatic hydrocarbons to a certain degree, naphthenic ring improve viscosity index.The purpose of catalytic dewaxing is to remove the dewax component, improves the low-temperature fluidity of lubricant base.Effective means is the pour point that reduces base oil by the hydroisomerization of wax component, and isomerization dewaxing not only can obtain high viscosity index but also can obtain high base oil yield.To be that the hydrogenation by alkene, diolefine and aromatic hydroxy compound is saturated remove these colour solids and to UV-light and the unsettled material of oxidizing medium to hydrorefined purpose.Hydrobon catalyst is a hydrogenation component with platinum metals or nickel usually, and the most frequently used is platinum, palladium or the combination of the two.
The continuous development of lubricating oil working method has proposed new requirement to Hydrobon catalyst, for example, sulphur content in the hydrofining section feeding may be very high, to such an extent as to conventional require very harsh platinum/aluminium oxide catalyst or high-nickel catalyst no longer to be suitable for this method to feed sulphur content.In recent years, the anti-sulphur mechanism research of relevant noble metal catalyst has obtained breakthrough progress, the anti-sulfur poisoning character free from worldly cares that platinum-the palladium noble metal component is shown that is supported on the acid carrier has not only obtained theoretically explaining more and more fully, and has obtained widespread use in the actual industrial reaction.
US5,993,644, US5,855,767, US5,879,539, US5,976, patent such as 354 and US6,030,921 has all been mentioned and has been adopted the lubricant base of noble metal catalyst after to isomerization dewaxing that contains acid carrier to carry out hydrorefined method, these catalyzer contain platinum and/or palladium and acid carrier, and its acid carrier comprises amorphous silicon aluminium and/or Y zeolite.These noble metal catalysts that contain acid carrier have stronger anti-sulfur poisoning ability and higher arene saturating activity.
US5393408 mentions the precious metal/amorphous silicon aluminium catalyzer of a kind of macropore of employing and a kind of precious metal/amorphous silicon aluminium catalyzer of mesopore carries out hydrorefined process to the lubricant base after dewaxing.Macroporous catalyst can remove the above condensed-nuclei aromatics of three rings, and medium-pore catalyst has higher activity to one to the thrcylic aromatic hydrocarbon hydrogenation is saturated.When using separately, the activity of medium-pore catalyst is higher than macroporous catalyst, but inactivation is very fast.Two kinds of superimposed uses of catalyzer have activity and the better stability same with medium-pore catalyst.
Being carrier in the noble metal hydrogenation catalyst for refining of the anti-sulphur that previous patent is mentioned or with the Y zeolite, perhaps is carrier with the amorphous silicon aluminium, or the mixture of the two.Do not mention and to contain the two kinds of catalyzer series connection or the superimposed use of amorphous silicon aluminium and Y zeolite respectively.Though contain the noble metal catalyst of amorphous silicon aluminium and the noble metal catalyst that contains Y zeolite and the mixture of the two all because of the acidity of its carrier has certain anti-sulfur poisoning ability, in the process that removes sulphur, nitrogen and aromatic hydroxy compound, have different effects because of the difference of pore volume by the catalyzer of different preparing carriers.The macroporous catalyst that contains amorphous silicon aluminium can remove the above polycyclic aromatic hydrocarbons of three rings and macromolecular organosulfur, nitrogen compound effectively, and the bigger polar compound of these volumes causes the obstruction or the carbon deposit in aperture because of the duct that can't enter Y zeolite, and then cause catalyst deactivation, need harsh reaction conditions in order to keep activity of such catalysts, the result causes the over-drastic cracking and shortens the life cycle of catalyzer.Even being carried out mechanically mixing, amorphous silicon aluminium and Y zeolite also can't protect the Y zeolite duct not stopped up effectively by the bigger polar compound of these volumes.
The object of the present invention is to provide a kind of raising catalyst tolerates sulphur, nitrogen poisoning capability, delay catalyst deactivation, improve the process for hydrorefining basic oil lubricating oil of aromatic hydrocarbons saturation ratio, another object of the present invention is to provide a kind of production method of food-level white oil.
The inventive method is the macroporous catalyst that will the contain amorphous silicon aluminium use of connecting with the catalyzer that contains Y zeolite.Lubricant base carries out hydrofining by two kinds of catalyzer with different pore volumes, these two kinds of catalyzer can be in same reactor the layering filling, can connect does not have in two different reactors of gas separation unit in the middle of filling in yet.First bed or first reactor comprise a kind of noble metal catalyst that contains macropore sial carrier; Second bed or second reactor comprise a kind of noble metal catalyst that contains Y zeolite.
Two kinds of catalyzer layerings of the present invention fill in the same reactor, can reduce plant investment and process cost, and it is 1 that top contains the volume ratio that amorphous silicon aluminium catalyzer and bottom contain the catalyzer of Y zeolite: 0-0: 1, be preferably 3: 1-1: 1.
Two kinds of catalyzer of the present invention do not have in two reactors of gas separation unit in the middle of can connecting yet and filling in, and improve the handiness of operation.First reactor charge contains the amorphous silicon aluminium catalyzer, and second reactor charge contains the catalyzer of Y zeolite.The operational condition of two reactors is except that temperature, and other is all identical.Because to contain the Y zeolite catalyst activity higher, therefore the temperature of second reactor will be lower than first reactor, and this temperature head still depends on feed properties and to the specification of quality of product.In general, the temperature head of two reactors is in 10-80 ℃ of scope.
The related lubricant base of hydrorefining basic oil lubricating oil of the present invention is the lubricant base through catalytic dewaxing, solvent dewaxing, is preferably the lube base of isomerization dewaxing.
The catalyzer pore volume that first bed on hydrofining reactor top or first reactor are loaded is 0.5-1.0cm
3/ g.SiO in the macropore sial carrier that the first bed catalyzer is contained
2Content is 25-50wt%, and pore volume is 0.6-1.4cm
3/ g, specific surface area 300-500m
2/ g.Can prepare by the co-precipitation or the cogelled technology of routine.This catalyzer also contains a kind of adhesive oxides, is preferably aluminum oxide.The ratio of aluminum oxide and macropore sial carrier is 20: 80-40: 60.
The catalyzer that second bed or second reactor are loaded contains Y zeolite.The SiO of this Y zeolite
2/ Al
2O
3Mol ratio is 10-40; Unit cell parameters is 2.422-2.445nm; Sodium oxide content is less than 0.15wt%; Relative crystallinity is preferably 98%-100% greater than 95%.This catalyzer also contains a kind of adhesive oxides, is preferably aluminum oxide.The ratio of aluminum oxide and Y zeolite is 20: 80-40: 60.
Two kinds of catalyzer all contain at least a noble metal hydrogenation component, the preferably alloy of platinum and palladium.The amount that is supported on platinum on the carrier and palladium must be enough to guarantee the hydrogenation of lube oil base stocks, and the mol ratio of platinum and palladium is 2.5: 1-1: 2.5, be preferably 1: 1.5.The total amount of platinum and palladium is 0.2-1.2wt%.Two kinds of catalyzer all adopt certain density [Pt (NH
3)
4]
2+With [Pd (NH
3)
4]
2+The carrier of mixing solutions after to roasting pore volume impregnation or excess solution dipping such as carry out.The pH value of mixing solutions can obtain the preferred metal dispersity in the scope of 8-10 the time.
The preferred scheme of the present invention is that two kinds of catalyzer layerings are filled in the same reactor, can reduce plant investment and process cost like this, it is 1 that top contains the volume ratio that amorphous silicon aluminium catalyzer and bottom contain the catalyzer of Y zeolite: 0-0: 1, be preferably 3: 1-1: 1.
The charging of catalytic dewaxing section of the present invention is that boiling range is 250～620 ℃, is preferably 310～550 ℃ waxy hydrocarbon oil plant, and particularly suitable raw material has VGO hydrocracking tail oil, solvent-refined oil hydrotreatment tail oil.Also can use hydrotreatment tail oil and the slack wax and the soft wax etc. of propane deasphalting oil.
Isomerization dewaxing catalyst can contain mesoporous molecular sieve, comprises mesoporous molecular sieves such as SAPO-11, SAPO-31, SAPO-41, mordenite, ZSM-22, ZSM-23, SSZ-32, is preferably SAPO-11; The beta-molecular sieve that also can contain high silica alumina ratio, SiO
2/ Al
2O
3Greater than 100: 1, or greater than 200: 1, more preferably greater than 500: 1; The mixture that perhaps contains above-mentioned two molecular sieve analogs.The operational condition of isomerization dewaxing section is: reaction pressure 2.8-15.0Mpa, preferably 4.0-10.0Mpa.Temperature of reaction 280-420 ℃, be preferably 320-400 ℃, air speed (LHSV) is 0.2-2.0h
-1, be preferably 0.5-1.5h
-1
The effluent of isomerization dewaxing section directly enters the hydrofining section.The hydrofining section is equipped with dual catalyst of the present invention, and hydrofining section operational condition is: reaction pressure 2.8-15.0MPa, preferably 4.0-10.0MPa.Temperature of reaction is 170-320 ℃, is preferably 180-280 ℃, and air speed (LHSV) is 0.1-10.0h
-1, be preferably 0.2-4.0h
-1, be preferably 0.5-2.0h
-1, hydrogen to oil volume ratio 300-800.
But according to the inventive method production viscosity index greater than 100 or greater than 120 base oil of high viscosity index lubricant and viscosity index greater than 140 superhigh viscosity index base oil for lubricating oil and food-level white oil.
Compared with prior art, the present invention program has following advantage:
(1) quality product height.Compare with catalytic dewaxing process with traditional solvent dewaxing, the inventive method can be produced the food-level white oil that is rich in isoparaffin, improves the light stability and the anti-oxidative stability of lubricant base, produces high viscosity index (HVI) base oil and food-level white oil.The purpose of the hydrorefining basic oil lubricating oil after the dewaxing is to remove alkene, diolefine, aromatic hydrocarbons and sulphur, nitrogen compound etc. to UV-light and the unsettled material of oxidizing medium and with look with the material of flavor is arranged.There are some researches show that the above polycyclic aromatic hydrocarbons of three rings is to cause lubricating oil to the light and the oxidizing medium factors of instability, the macroporous catalyst that only contains amorphous silicon aluminium could remove the bigger polycyclic aromatic hydrocarbons of these volumes effectively; And one encircle to thrcylic aromatic hydrocarbon and containing easier removing on the catalyzer of Y zeolite.During hydrorefining basic oil lubricating oil after therefore the present invention is used to dewax, can can produce qualified food-level white oil, pharmaceutical grade white oil and cosmetics-stage white oil with alkene, diolefine, aromatic hydrocarbons and sulphur, nitrogen compound etc. to UV-light and the unsettled material of oxidizing medium and with look with there is the material of flavor to be removed to extremely low degree.
(2) processing condition relax, arene engaging scraping rate height, and catalyst life is long.The placed in-line catalyst system of the present invention has higher sulfur poisoning-resistant ability and higher hydrogenation activity, can carry out hydrofining to lubricant base under the demulcent condition, so running period is long.Adopt the present invention program, behind the bigger catalyst removal condensed-nuclei aromatics of the pore volume of first bed or first reactor, what volume was less one encircles to thrcylic aromatic hydrocarbon easier removing on the catalyzer that contains Y zeolite of second bed or second reactor.Like this, not only improve the arene engaging scraping rate, can prolong hydrofining section life of catalyst again.Have higher activity owing to contain the catalyzer of Y zeolite than the catalyzer that contains amorphous silicon aluminium, therefore series connection catalyst system of the present invention is than US5, and the amorphous catalyst system of two kinds of different pore volumes of 393,408 has higher arene saturating activity.
(3) technical process is simple, flexible operation.The present invention program can adopt the agent of a reactor charge two-stage catalytic, also can adopt two tandem reactors, does not need tripping device between the tandem reactor, can satisfy the requirement of the different conditions of production.
Embodiment
The operational condition of each conversion zone can require suitably to regulate according to a conventional method according to feedstock property, foreign matter content and quality product.The following examples only describe preferred version of the present invention with regard to a kind of raw material, do not constitute limiting the scope of the invention.
Embodiment 1
The catalyst A 1 that contains the macropore sial is equipped with on hydrofining reactor of the present invention top, and its preparation method is: with SiO
2/ Al
2O
3Weight ratio is 35/65, pore volume is that 1.204ml/g, specific surface area are 467m
2The macropore sial of/g mixes in 65/35 ratio (weight ratio) with gama-alumina, add the concentrated nitric acid of 5wt% (accounting for the carrier total amount) and an amount of water mix pinch, extruded moulding, after drying, the roasting with certain density [Pt (NH
3)
4] Cl
2[Pd (NH
3)
4] (NO
3)
2Mixing solutions flood, the pH value of steeping fluid is 9, the steeping fluid volume is two times of carrier bulk.2 hours after-filtration after 8 hours, carry out the segmentation roasting through 110 ℃ of dryings, 150 ℃ 2 hours, 280 ℃ 2 hours, 480 ℃ 4 hours.Make catalyst A 1, pore volume is 0.820cm
3/ g, specific surface area are 346m
2/ g, bulk density are 0.45g/ml.Platinum content is 0.28wt% in the catalyzer, and palladium content is 0.35wt%.
The catalyst B 1 that contains Y zeolite is equipped with in hydrofining reactor of the present invention bottom, and its preparation method is: with SiO
2/ Al
2O
3Mol ratio is 12, unit cell parameters is 2.438nm, sodium oxide content is less than 0.15wt%, relative crystallinity is that 98% Y zeolite mixes in 65/35 ratio (weight ratio) with gama-alumina, add the concentrated nitric acid of 5wt% (accounting for the carrier total amount) and an amount of water mix pinch, extruded moulding, after drying, the roasting with certain density [Pt (NH
3)
4] Cl
2[Pd (NH
3)
4] (NO
3)
2Mixing solutions flood, the pH value of steeping fluid is 9, the steeping fluid volume is two times of carrier bulk.2 hours after-filtration after 8 hours, carry out the segmentation roasting through 110 ℃ of dryings, 150 ℃ 2 hours, 280 ℃ 2 hours, 480 ℃ 4 hours.Make catalyst B 1, pore volume is 0.478cm
3/ g, specific surface area are 532m
2/ g, bulk density are 0.72g/ml.Platinum content is 0.36wt% in the catalyzer, and palladium content is 0.35wt%.
Catalyzer below the same procedure preparation:
Table 1 contains the amorphous silicon aluminium catalyzer and forms and character
| Contain the amorphous silicon aluminium catalyzer | ?????A2 | ?????A3 | |
| Pore volume, cm 3/g | ????0.595 | ????0.942 | |
| Specific surface area, m 2/g | ????286 | ????425 | |
| Silicon-aluminium | ????SiO 2/Al 2O 3Weight ratio | ????45/55 | ????25/75 |
| Pore volume, cm 3/g | ????0.663 | ????1.32 | |
| Specific surface area, m 2/g | ????310 | ????463 | |
| Content, wt% | ????70 | ????80 | |
| Metal | Platinum/palladium mol ratio | ????1/1.5 | ????1.8/1 |
| Total content, wt% | ????0.6 | ????1.0 | |
Table 2 contains the Y zeolite catalyzer and forms and character
| Contain the Y zeolite catalyzer | ?????B2 | ?????B3 | |
| Pore volume, ml/g | ????0.421 | ????0.397 | |
| Specific surface area, m 2/g | ????482 | ????435 | |
| Molecular sieve | ????SiO 2/Al 2O 3Mol ratio | ????25 | ????35 |
| Lattice constant, nm | ????2.428 | ????2.423 | |
| Relative crystallinity, % | ????100 | ????98 | |
| Content, wt% | ????65 | ????75 | |
| Metal | The Pt/Pd mol ratio | ????1.5/1 | ????1/2.1 |
| Total content, wt% | ????0.6 | ????1.1 | |
Embodiment 2
With a kind of hydrocracking tail oil be raw material through isomerization dewaxing---unifining process is produced food-level white oil.Test is carried out on the 200ml small hydrogenation device.Isomerization dewaxing catalyst is a kind of Pd/SAPO-11 catalyzer, and wherein (Si/Si+Al+P) mol ratio of SAPO-11 is 0.21, and content is 65wt%, and Pd content is 0.5wt%, and all the other are the tackiness agent aluminum oxide.The isomerization dewaxing product all enters the hydrofinishing section, and the hydrofining section is equipped with the catalyst A 1 and catalyst B 1 described in the embodiment 1.Catalyst A 1 is 1: 1 with the volume ratio of catalyst B 1.The processing condition of isomerization dewaxing and hydrofining section and the character of charging see Table 3.The product liquid of this process cuts according to the desired range of viscosities of the food-level white oil of the different trades mark through true boiling point distillation, and the product property of various different boiling scopes all satisfies the index request (seeing Table 4) of petrochemical industry food-level white oil.Before catalyzer advances raw material, in the presence of hydrogen, reduced 4 hours at 260 ℃ of constant temperature.
Table 3 isomerization dewaxing and hydrofining segment process condition and feed properties
| Operational condition | The isomerization dewaxing section | The hydrofining section |
| Pressure, Mpa | ????8.0 | ????8.0 |
| Temperature, ℃ | ????360 | ????220 |
| Liquid hourly space velocity, h -1 | ????0.6 | ????1.0 |
| Hydrogen-oil ratio (v/v) | ????800 | ????800 |
| Feed properties | ||
| Sulphur, μ g/g | ????12.8 | ????＜1 |
| Nitrogen, μ g/g | ????2.0 | ????＜1 |
| Aromatic hydrocarbons, wt% | ????3.7 | ????1.2 |
| Viscosity, 100 ℃, cst | ????4.782 | ????4.698 |
| Viscosity index (pressed oil) | ????121 | ????120 |
| Pour point, ℃ | ????38 | ????-18 |
| Boiling range, D1160, v% | ||
| ????10％ | ????340 | ????332 |
| ????50％ | ????462 | ????453 |
| ????90％ | ????512 | ????509 |
Table 4 white oil product property
| The white oil trade mark | ???10 # | ???15 # | ???26 # | ???36 # |
| Viscosity, 40 ℃, mm 2/s | ??8.787 | ??13.06 | ??28.72 | ??39.15 |
| Viscosity index | ??100 | ??105 | ??124 | ??126 |
| Pour point, ℃ | ??-36 | ??-27 | ??-18 | ??-12 |
| Flash-point (opening), ℃ | ??190 | ??182 | ??254 | ??200 |
| Colourity, number (Sai Shi) | ??＞+30 | ??＞+30 | ??＞+30 | ??＞+30 |
| Heavy metal, μ g/g | ??＜10 | ??＜10 | ??＜10 | ??＜10 |
| Arsenic, μ g/g | ??＜1 | ??＜1 | ??＜1 | ??＜1 |
| Lead, μ g/g | ??＜1 | ??＜1 | ??＜1 | ??＜1 |
| Solid paraffin | By | By | By | By |
| Readily carbonizable substance | By | By | By | By |
| Ultraviolet absorptivity/cm 260-420nm | ? ??＜0.1 | ? ??＜0.1 | ? ??＜0.1 | ? ??＜0.1 |
Embodiment 3
Production high-viscosity index lubricating oil basis.
Two kinds of method for preparing catalyst are with embodiment 1, and lube base raw material and isomerization dewaxing process thereof are with embodiment 2.The results are shown in Table 5.
Table 5 preparation base oil of high viscosity index lubricant experimental result
Annotate: scheme 3 is for using two tandem reactors.
| Reaction conditions and result | ?????1 | ?????2 | ?????3 |
| Temperature, ℃ | ????200 | ????220 | ????234/192 |
| Pressure, MPa | ????8.0 | ????8.0 | ????8.0 |
| Hydrogen-oil ratio | ????400 | ????600 | ????500 |
| Air speed, h -1 | ????1.5 | ????2.0 | ????3.0 |
| Catalyzer | ????A2/B3 | ????A2/B2 | ????A3/B3 |
| The catalyst volume ratio | ????2∶1 | ????1∶1 | ????1∶1 |
| ＞350 ℃ of base oils: viscosity index | ? ????123 | ? ????124 | ? ????120 |
| Rotary oxygen bomb, min | ????200 | ????220 | ????188 |
Embodiment 4
Scheme 1 and alternative catalyst life contrast experiment among the embodiment 3.Alternative contains the Y zeolite catalyzer for only using among the embodiment 1, processing condition are identical with scheme 1.Comparative result is listed in the table 6.
Table 6 stability experiment result
| Runtime, hour | ????200 | ????1000 | ????2000 | |
| Temperature of reaction, ℃ | Scheme 1 | ????200 | ????202 | ????205 |
| Relatively | ????200 | ????205 | ????210 | |
| The ultraviolet absorptivity of No. 36 white oils of Huo Deing therefrom, cm (260-420nm) | Scheme 1 | ????＜0.1 | ????＜0.1 | ????＜0.1 |
| Relatively | ????＜0.1 | ????0.115 | ????0.238 | |
Claims (21)
1, a kind of base oil of high viscosity index lubricant adds hydrogen production method, under the lube hydrotreating condition, lube base raw material and hydrogen are passed through Hydrobon catalyst, it is characterized in that described Hydrobon catalyst is two kinds of catalyzer that contain the macropore amorphous silicon aluminium and contain Y zeolite, lube base raw material and hydrogen are at first by containing the beds of macropore amorphous silicon aluminium, then by containing the beds of Y zeolite.
2, in accordance with the method for claim 1, it is characterized in that the described catalyzer that contains the macropore amorphous silicon aluminium and contain catalyzer layering filling in same reactor of Y zeolite, or series connection does not have in two reactors of gas separation unit in the middle of filling in.
3, in accordance with the method for claim 2, it is characterized in that the pore volume that contains macropore amorphous silicon aluminium catalyzer in described first bed or first reactor is 0.5-1.0cm
3/ g.
4, in accordance with the method for claim 2, it is characterized in that macropore that described first bed or first reactor catalyst are contained does not have the SiO of type sial
2Content is 25-50wt%, and pore volume is 0.6-1.4cm
3/ g, specific surface area 300-500m
2/ g.
5, in accordance with the method for claim 2, it is characterized in that described first bed or first reactor catalyst contain a kind of adhesive oxides, the part by weight of binding agent and macropore amorphous silicon aluminium is 20: 80-40: 60.
6, in accordance with the method for claim 2, the SiO that it is characterized in that the Y zeolite that described second bed or second reactor catalyst contain
2/ Al
2O
3Mol ratio is 10-40; Unit cell parameters is 2.422-2.445nm; Sodium oxide content is less than 0.15wt%; Relative crystallinity is greater than 95%.
7, in accordance with the method for claim 6, the relative crystallinity that it is characterized in that described Y zeolite is 98%-100%.
8, in accordance with the method for claim 6, it is characterized in that described catalyzer contains a kind of adhesive oxides, the weight ratio of binding agent and Y zeolite is 20: 80-40: 60.
9,, it is characterized in that described binding agent is an aluminum oxide according to claim 5 or 6 described methods.
10, in accordance with the method for claim 2, it is characterized in that two kinds of catalyzer all contain at least a noble metal hydrogenation component, metal content is 0.2-1.2wt%.。
11, in accordance with the method for claim 10, it is characterized in that described catalyzer contains platinum and palladium, the mol ratio of platinum and palladium is 2.5: 1-1: 2.5.
12, in accordance with the method for claim 2, it is characterized in that the described amorphous silicon aluminium that contains is 3 with the volume ratio that contains two kinds of catalyzer of Y zeolite: 1-1: 1.
13, in accordance with the method for claim 2, it is characterized in that the condition of hydrofining reaction is when two kinds of catalyzer layerings are seated in the same reactor: temperature of reaction is 170 ℃-320 ℃, and reaction pressure is 2.8MPa-15.0MPa, hydrogen to oil volume ratio is 300-800, and volume space velocity is 0.1h
-1-10h
-1
14, in accordance with the method for claim 2, it is characterized in that the condition of hydrofining reaction is when two kinds of catalyzer layerings are seated in the same reactor: temperature of reaction is 180 ℃-280 ℃, and reaction pressure is 4.0MPa-10.0MPa, and volume space velocity is 0.5h
-1-2h
-1
15, in accordance with the method for claim 2, it is characterized in that the temperature of reaction of second reactor is than low 10-80 ℃ of first reactor when two kinds of catalyzer do not have in the middle of filling in respectively with series system in two reactors of gas separation unit.
16, in accordance with the method for claim 1, it is characterized in that lubricant base raw material elder generation's process catalytic dewaxing or solvent dewaxing process before entering the hydrofining section.
17, in accordance with the method for claim 1, it is characterized in that lubricant base raw material elder generation's process isomerization dewaxing technology before entering the hydrofining section.
18, in accordance with the method for claim 17, the charging that it is characterized in that isomerization dewaxing technology is that boiling range is 250～620 ℃, is preferably 310～550 ℃ waxy hydrocarbon oil plant.
19, in accordance with the method for claim 18, the charging that it is characterized in that described isomerization dewaxing technology is hydrotreatment oil, slack wax or the soft wax of VGO hydrocracking tail oil, VGO propane deasphalting oil.
20, in accordance with the method for claim 1, the viscosity index that it is characterized in that the lubricant base after the described hydrofining is higher than 100.
21, a kind of production method of food-level white oil is a raw material with the lube base after the described hydrofining of claim 1, carries out the boiling range cutting, obtains the food-level white oil of various labels.
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| CN100400625C (en) * | 2005-10-19 | 2008-07-09 | 中国石油化工股份有限公司 | Hydrogenation process of producing food-level white oil |
| CN102041088A (en) * | 2009-10-13 | 2011-05-04 | 上海孚科狮化工科技有限公司 | Hydrogenation process of base oil for synthetic lubricating oil |
| CN102311785A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for hydrogenating naphthenic base distillate to produce lubricating oil basic oil |
| CN103627432A (en) * | 2012-08-23 | 2014-03-12 | 中国石油化工股份有限公司 | Hydrogenation method for producing diesel oil with low condensation point and lubricant basic oil |
| CN103627428A (en) * | 2012-08-23 | 2014-03-12 | 中国石油化工股份有限公司 | Hydrogenation method for producing lubricant basic oil with low condensation point |
| CN103627430A (en) * | 2012-08-23 | 2014-03-12 | 中国石油化工股份有限公司 | Hydrogenation method used for direct production of low-condensation point lubricant base oil |
| CN103773467A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for producing lubricant base oil by hydrogenation isomerization dewaxing |
| CN104888772A (en) * | 2014-03-03 | 2015-09-09 | 中国石油化工股份有限公司 | Oxidation catalyst, preparation method and application thereof |
| CN106590737A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Method for processing high aromatic hydrocarbon inferior raw oil |
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-
2000
- 2000-10-26 CN CNB001231618A patent/CN1195828C/en not_active Expired - Lifetime
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| CN100400625C (en) * | 2005-10-19 | 2008-07-09 | 中国石油化工股份有限公司 | Hydrogenation process of producing food-level white oil |
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| CN102311785B (en) * | 2010-07-07 | 2015-05-13 | 中国石油化工股份有限公司 | Method for hydrogenating naphthenic base distillate to produce lubricating oil basic oil |
| CN102311785A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for hydrogenating naphthenic base distillate to produce lubricating oil basic oil |
| CN103627430B (en) * | 2012-08-23 | 2015-08-26 | 中国石油化工股份有限公司 | The method of hydrotreating of the low Solidification Point Lube Base Oils of a kind of direct production |
| CN103627430A (en) * | 2012-08-23 | 2014-03-12 | 中国石油化工股份有限公司 | Hydrogenation method used for direct production of low-condensation point lubricant base oil |
| CN103627428A (en) * | 2012-08-23 | 2014-03-12 | 中国石油化工股份有限公司 | Hydrogenation method for producing lubricant basic oil with low condensation point |
| CN103627432B (en) * | 2012-08-23 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of method of hydrotreating producing low freezing point diesel fuel and lubricant base |
| CN103627432A (en) * | 2012-08-23 | 2014-03-12 | 中国石油化工股份有限公司 | Hydrogenation method for producing diesel oil with low condensation point and lubricant basic oil |
| CN103627428B (en) * | 2012-08-23 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of method of hydrotreating producing low Solidification Point Lube Base Oils |
| CN103773467A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for producing lubricant base oil by hydrogenation isomerization dewaxing |
| CN104888772A (en) * | 2014-03-03 | 2015-09-09 | 中国石油化工股份有限公司 | Oxidation catalyst, preparation method and application thereof |
| CN106590737A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Method for processing high aromatic hydrocarbon inferior raw oil |
| CN106590743A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Method for producing lubricant base oil |
| CN106590737B (en) * | 2015-10-20 | 2018-07-31 | 中国石油化工股份有限公司 | A method of the high aromatic hydrocarbons inferior feedstock oil of processing |
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