CN104611023B - Method for producing special lubricating oil base oil - Google Patents
Method for producing special lubricating oil base oil Download PDFInfo
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- CN104611023B CN104611023B CN201310540470.2A CN201310540470A CN104611023B CN 104611023 B CN104611023 B CN 104611023B CN 201310540470 A CN201310540470 A CN 201310540470A CN 104611023 B CN104611023 B CN 104611023B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/14—White oil, eating oil
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- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention discloses a method for producing special lubricating oil base oil. According to the method of the present invention, a wax oil raw material and hydrogen gas are mixed and then sequentially pass through at least two hydrogenation reaction zones connected in series, wherein each hydrogenation reaction zone sequentially comprises a refining dewaxing catalyst composite bed layer filled with a hydrodewaxing catalyst and a hydrorefining catalyst in a mixed manner and a hydrodewaxing catalyst bed layer according to the material flowing direction, and the reaction effluent obtained from the last hydrogenation reaction zone is subjected to separation and fractionation to obtain the lubricating oil base oil, the white oil and other products. With the method of the present invention, the temperature decrease during the hydrodewaxing process and the temperature increase during the hydrogenation process are subjected to reasonable combination utilization, such that the low freezing point lubricating oil base oil is produced while the hot spot temperature of the device is reduced and the operation period is prolonged; and the cold hydrogen consumption or the heating furnace fuel gas loss is reduced, and the operating cost is saved.
Description
Technical field
The present invention relates to a kind of production method of special lubricating oil base oil, especially a kind of being combined by catalyst are loaded
And level joins technology, for producing the method for hydrotreating of special lubricating oil base oil.
Background technology
Lubricant is the critically important oil product of a class, is the key factor driving moving component although its product only accounts for
The 2% about of crude runs, but varying because of its use condition, kind is up to hundreds of, and tight to prescription
Lattice, lubricating oil just belongs to one kind of lubricant.For miscellaneous lubricating oil it is impossible to every kind of all go to individually produce, for this reason,
In order to simplify its production, each state all using first making the lube base oil meeting certain standard, the then needs according to market
It is in harmonious proportion and is added additive, so that various products are obtained.
As can be seen here, although the kind of lubricating oil is a lot, it is all that system becomes based on base oil, and for from crude oil
The lube base oil produced, can be divided into paraffin base oil oil series, intermediate base base oil series and cycloalkanes according to standard
Base base oil series.In addition, the property of base oil belongs to relevant except the base with crude oil, largely additionally depend on used adding
Work method, for example widely used hydrogen addition technology can make the quality of lube base oil have greatly improved, including viscosity, viscosity
Some main character such as index, condensation point and colourity.
So, for the crude oil selected, the fundamental property of above-mentioned cited lubricating oil, it is suitable to select
Method of hydrotreating is adjusted to it, for example, select the Hydrofining Technology of routine can improve colourity of product etc.；It is hydrocracked
Technology can improve the viscosity of product, viscosity index (VI) etc.；Shape slective cracking and selective isomerization can improve condensation point of product etc., because
This, if it is desired to produce the lube base oil blend component of high quality and favourable price, in place of selecting the key which kind of hydrogen addition technology is success or failure.
And industrial at present widely used selective isomerization technique, from noble metal as catalyst active component, cost is relatively
Higher, and the adaptability of raw material is relatively poor, and shape slective cracking technology can make up that these are not enough, shape slective cracking technology also known as
Hydro dewaxing, refers in the presence of hydrogen, and the raw material of the content of wax is by urging containing active metal and the difunctional of molecular sieve
Agent surface, thus reduce wax molecule content therein.Its dewaxing principle is under certain operating conditions, makes raw material and hydrogen
Mixing is contacted with Hydrodewaxing catalyst, alkane in raw material, with short side alkane, the cycloalkane of belt length side chain and belt length side
It is cracked into small molecule the high condensation point compositional selecting such as aromatic hydrocarbons of chain, and other component does not change substantially, is finally reached fall
The purpose of the condensation point of low oil product, in its technique exclusive feature be course of reaction be the endothermic reaction, according to the difference of pour point depression depth,
Show different degrees of temperature drop, course of reaction hydrogen consumption is relatively low, adaptability to raw material is strong, energy consumption is relatively low, technique stream because it has
Journey is simple, can form many advantages, such as process integration or independent use with other hydrogenation processes, widely should therefore obtain
With.
CN201010222066.7 discloses a kind of method that cycloalkyl distillate hydrogenation produces lube base oil.With ring
Alkyl distillate is raw material, and the one-stage serial hydrogenation technique using hydrotreating-hydrodewaxing-hydrofining produces lubrication
Oil base oil.The method successfully make use of the characteristic of different catalysts, has produced low pour point, the lubrication oil base of good security
Plinth oil.But because all kinds of catalyst independently load, the balance of the yield to lube cut and depression effeCt raising creates
Certain contradiction, reduces the life-span of Hydrodewaxing catalyst.
CN200410050735.1 disclose one kind be directly produced by paraffinic base crude oil distillate or lube base oil white
The production method of oil.Using one-stage serial technique, joined by different catalyst grades, different catalysts combination loading, collection hydrogenation
Prerefining, hydro dewaxing, hydrofining are in the technical process of one.The process is simple of the present invention, easy to operate, condition is delayed
With catalyst has very strong sulfur resistive, nitrogen ability, does not have strict restriction to the sulfur of raw oil, nitrogen content.But it is also sufficiently sharp
With the temperature drop of hydro dewaxing process and the temperature rise of hydrogenation process, plant energy consumption is larger, and hot(test)-spot temperature is higher, limited by service cycle.
CN98121075.9 discloses a kind of method producing high-grade low-freezing diesel oil by distillate.The method is using hydrogenation essence
System and hydro dewaxing one-stage serial flow process, including Hydrobon catalyst and two catalyst beds of Hydrodewaxing catalyst
Layer, hydro dewaxing adopts Ni/ZSM-5 catalyst.The method is larger in the temperature drop of Hydrodewaxing catalyst bed, diesel oil distillate
The raising of yield and depression effeCt is subject to a definite limitation, reduces the service life of Hydrodewaxing catalyst.
CN200910188163.6 discloses a kind of method of diesel oil hydrogenation pour point depression.The method is by adjusting catalyst
Property thus having that diesel oil depression effeCt is good, the feature of diesel oil distillate high income, but due to still using hydrofinishing with face hydrogen fall
The group technology of solidifying series connection, the contradiction between depression effeCt and diesel oil distillate yield remains unchanged and exists.
CN201010514141.7 discloses a kind of method of diesel hydro-pour-reducing.Although the method improves hydro dewaxing
The average reaction temperature of catalyst, using the temperature rise of refining agent, increases the utilization rate of pour point depression catalyst, but the outlet of each bed
Reaction temperature still of a relatively high, receive certain restriction service cycle.
Content of the invention
The problem existing for prior art, the present invention provides a kind of production method of special lubricating oil base oil.This
Hydro dewaxing and hydrofinishing are combined by bright method（Mixing）The mixed catalyst of filling carries out level with Hydrodewaxing catalyst and joins,
The temperature drop of hydro dewaxing process is reasonably combined utilization with the temperature rise in hydrogenation process, is lubricated oil base producing low condensation point
While plinth oil, reduce the hot(test)-spot temperature of device, extend service cycle；In addition can also be made up often using the art of this patent
Restore to norm to attach together and fill out process problem encountered, optimize the effect of mixed packing, fully different types of catalyst is carried out
Coupling；In addition reduce the consumption of cold hydrogen or the combustion gas loss of heating furnace, save operating cost, the spy producing in addition
Plant lube base oil arene content relatively low, severity of the techniques such as follow-up solvent refining etc. can be reduced and even save some phases
Close technique.
The invention provides a kind of production method of special lubricating oil base oil, including herein below：
After wax oil raw material is mixed, pass sequentially through the hydroconversion reaction zone of at least two series connection with hydrogen, by Flow of Goods and Materials direction
Each hydroconversion reaction zone includes the refined pour point depression catalysis by Hydrodewaxing catalyst and Hydrobon catalyst mixed packing successively
Agent composite bed and Hydrodewaxing catalyst bed；The reaction effluent that last hydroconversion reaction zone obtains is through separating and dividing
After evaporating, obtain the products such as lube base oil, white oil.
According to method of the present invention, wherein in each described hydroconversion reaction zone, wax oil raw material is with hydrogen first
By the refined pour point depression catalyst composite bed by Hydrodewaxing catalyst and Hydrobon catalyst mixed packing, it is hydrogenated with
Desulfurization, hydrodenitrogeneration, aromatic hydrocarbons saturation and pour point depression reaction；Reaction effluent passes through Hydrodewaxing catalyst bed again, carries out depth
Pour point depression reacts.
According to the method for hydrotreating of the present invention, described wax oil raw material is conventional crude lube stock, boiling range generally 250～
550 DEG C, typically all more than -10 DEG C, preferably condensation point is more than -5 DEG C for condensation point.The nitrogen content of described crude lube stock is in 1000 μ
Below g/g, generally 50～800 μ g/g, most preferably 100～500 μ g/g.If the organic nitrogen content mistake in wax oil raw material
Height, such as nitrogen content, can be multiple by the refined pour point depression catalyst of the first hydroconversion reaction zone in wax oil raw material in more than 1000 μ g/g
Before closing bed, beforehand through a hydrofinishing or hydrodenitrogenation catalyst bed, carry out part denitrogenation.Described lubricating oil
Raw material can be the wax of processing naphthene base crude, various straight run that intermediate base crude or paraffinic base crude oil obtain or secondary operations
The straight-run gas oil component of the naphthene base crude of oil etc., preferably time processing, can be former selected from processing LIAOHE CRUDE or Kelamayi
The various vacuum gas oil (VGO)s that oil obtains（VGO）, such as one of Liaohe River VGO, Kelamayi VGO or several.When production purpose
Not it is also possible to be selected from the various vacuum gas oil (VGO)s that processing paraffinic base crude oil obtains（VGO）, in such as grand celebration VGO, long celebrating VGO
One or more.Wax oil raw material do generally 500～550 DEG C, preferably 510～540 DEG C.
Described Hydrodewaxing catalyst adopts the catalyst containing shape slective cracking molecular sieve, including carrier and the gold being loaded
Belong to component.Described catalyst is typically with shape slective cracking molecular sieve and binding agent as carrier, golden with group VIB and/or the VIIIth race
Belong to for hydrogenation active metals component.Described shape slective cracking molecular sieve is hydrogen type molecular sieve, and described molecular sieve can be selected from Hydrogen
One or more of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 molecular sieve, preferably ZSM-
5 molecular sieves；The silica alumina ratio of described shape slective cracking molecular sieve generally 10～150, preferably 20～120.
Described group VIB metal is Mo and/or W, and described group VIII metal is Co and/or Ni.Weight with catalyst
On the basis of amount, for 1%～16%, the content of shape slective cracking molecular sieve is 50% to the content that hydrogenation active metals component is counted with oxide
～85%, the content of binding agent is 10%～40%.The heap density of Hydrodewaxing catalyst is typically in 0.65～0.75g cm-3, its
Normally use generally 380 DEG C～410 DEG C of temperature range.Described Hydrodewaxing catalyst can select existing various business
Industry catalyst, such as Fushun Petrochemical Research Institute（FRIPP）The Hydrodewaxing catalysts such as FDW-1, the FDW-3 developing；
Can also be prepared by the general knowledge of this area as needed, be for example referred to CN1952074A, CN1352231A,
Content disclosed in CN101143333A, CN102451748A prepares satisfactory Hydrodewaxing catalyst.
Described Hydrobon catalyst includes carrier and the hydrogenation metal being loaded.On the basis of the weight of catalyst,
Generally include metal component of group VIB in the periodic table of elements, such as tungsten and/or molybdenum are calculated as 10% ~ 35% with oxide, preferably 15% ~
30%；Group VIII metal such as nickel and/or cobalt are calculated as 1% ~ 7%, preferably 1.5% ~ 6% with oxide.Carrier aoxidizes for inorganic refractory
Thing, is selected generally from aluminium oxide, amorphous silicon aluminium, silicon dioxide, titanium oxide etc..Hydrobon catalyst can select existing each
Plant and be hydrocracked the modified acquisition of pretreatment commercial catalysts, such as Fushun Petrochemical Research Institute（FRIPP）Develop
3936th, 3996, the modified preparation of the hydrogenation catalyst such as FF-26, FF-36, FF-46；The general knowledge of this area can also be pressed as needed
It is prepared.
Described Hydrobon catalyst salic be the aluminium oxide that a kind of crystalline phase is boehmite, content is
40w%～80w%.According to the alumina support of this technology special preparation, contain macroporous aluminium oxide in Hydrobon catalyst and bond
Agent, on the basis of catalyst weight, macroporous aluminium oxide content is generally 60w%～85w%, preferably 65w%～80w%；Described macropore
The pore volume of aluminium oxide is 1.0～1.7mL/g, preferably>1.2～1.7mL/g（More than 1.2 to 1.7 mL/g）；Specific surface area is
200～550m2/ g, preferably 300～500m2/g.
In the method for the present invention, selected Hydrobon catalyst is in catalyst/support molding, preferably especially suitable
The sour peptizing techniques of this technique, the mixed acid of mineral acid and organic acid is added in forming process, enhances the ratio of catalyst
The properties such as surface area, intensity, also simplify the production procedure of catalyst in addition, reduce production cost, simultaneously it is also ensured that
The stability of macroporous aluminium oxide, makes prepared catalyst/support keep higher pore volume.This technology can be in industry at present
Gained is prepared in the modification in molding of wide variety of catalyst.Using the catalyst of this technology preparation, simultaneously in catalyst outward appearance
It has been also carried out optimization processing in shape, has preferably been prepared into tooth ball shape catalyst, be readily transported, load and mix.
Hydrobon catalyst after modified recited above, due to the change of carrying alumina volume property, is reaching phase
During with reaction depth, its activity will be weaker than about 10 DEG C of the Hydrobon catalyst of routine, is normally raised using temperature range
To 380 DEG C～400 DEG C.This kind of modified catalyst compared with Hydrodewaxing catalyst, heap density requirements difference in mixed process
Less than 0.05g cm-3.
The operating condition of refined pour point depression catalyst composite bed of described hydro dewaxing and Hydrobon catalyst composition is：
Reaction pressure 8.0～20.0 MPa, hydrogen to oil volume ratio 700：1～1600：1, volume space velocity is 0.1～10.0 h-1, reaction temperature
270 DEG C～460 DEG C；Preferred operations condition is reaction pressure 10.0～15.0 MPa, hydrogen to oil volume ratio 800：1～1200：1, body
Long-pending air speed 0.3～8.0 h-1, 315 DEG C～425 DEG C of reaction temperature.
The operating condition of described Hydrodewaxing catalyst bed is：Reaction pressure 8.0～20.0 MPa, hydrogen to oil volume ratio
600：1～1500：1, volume space velocity is 0.1～10.0 h-1, 260 DEG C～455 DEG C of reaction temperature；Preferred operations condition is reaction
Pressure 10.0～15.0 MPa, hydrogen to oil volume ratio 700：1～1100：1, volume space velocity 0.3～8.0 h-1, 310 DEG C of reaction temperature
～420 DEG C.
The method according to the invention, wherein in each hydroconversion reaction zone, described Hydrodewaxing catalyst bed and by
The admission space of the refined pour point depression beds of Hydrodewaxing catalyst and Hydrobon catalyst mixed packing is than for 1:10
～10:1, preferably 1:5～5:1.
In described refined pour point depression catalyst composite bed, Hydrodewaxing catalyst is combined dress with Hydrobon catalyst
Fill out, admission space is than for 1:10～10:1, preferably 1:5～5:1.
For at least two described hydroconversion reaction zones, wherein said refined pour point depression catalyst composite bed drops with facing hydrogen
Solidifying beds, can be separately positioned in two or more beds of a reactor；Or can be respectively provided with
In the hydrogenation reactor that two or more are connected.
Compared with prior art, the inventive method has advantages below：
1st, in the inventive method, in each hydroconversion reaction zone, raw oil first passes through refined pour point depression beds, right
Wax oil raw material is processed, carry out hydrodesulfurization, hydrodenitrogeneration, aromatic hydrocarbons saturation and pour point depression reaction, this reaction show as heat absorption with
The synergistic effect of heat release.Raw oil after pour point depression process is processed passes through Hydrodewaxing catalyst bed again, carries out depth
Degree pour point depression reaction, this reaction shows as the endothermic reaction, and all in all, because hydrogenation reaction shows as exothermic reaction, this process is produced
Raw temperature rise；And hydro dewaxing reacts for selecting the reaction of type molecular sieve cracking, heat effect shows as the endothermic reaction, and process produces temperature drop；
This two kinds of catalyst are carried out level and joins compound filling, its respective heat release and endothermic effect can be made full use of, realize reacting
The comprehensive utilization of the heat of journey, will not produce excessive temperature rise and temperature drop effect, and affect depression effeCt, so that entirely urging
The hot(test)-spot temperature of agent bed reduces, and both can ensure that the yield of lube base oil, and had also achieved more preferable depression effeCt.And
Wax oil raw material is first contacted with refined pour point depression catalyst, and adaptability to raw material is stronger, carries out level using Hydrodewaxing catalyst in addition and joins,
Compared with industrial at present wide variety of selective isomerization, also there is catalyst low cost, and the lubrication produced
Oil base oil arene content is relatively low, and viscosity is high, can use as special lubricating oil base oil, additionally due to unifining process
Aromatic hydrocarbons saturation can also reduce severity of the techniques such as follow-up solvent refining etc..
2nd, in process aspect, in each hydroconversion reaction zone, all show essentially identical effect.Thus in series connection at least
In two hydroconversion reaction zones, described hydrogenation reaction shows as comprehensive cumulative effect of optimization.Compared with prior art, this
Bright on the basis of not changing device flow process, only by the compound filling of catalyst and grading composition, from local by the height of device
Warm spot is effectively rationally utilized with low temperature point, reduces the hot(test)-spot temperature of device, reasonably decreases the bulk temperature ladder of device
Degree, extends the service life of catalyst, decreases the yield of side-product, improve economic benefit.In addition this combination and routine
Hydro dewaxing group technology compare, because the heat of course of reaction has obtained more reasonably utilizing, can between two reaction zones
Beaten or not liquid hydrogen injection with few, the combustion gas of the consumption and heating furnace that therefore also reduce cold hydrogen is lost, and saves operating cost.
3rd, especially select suitable Hydrobon catalyst and technique to use cooperatively in the present invention, there is very big adaptability
And advantage.During by it with Hydrodewaxing catalyst mixed packing, can reach and more excellent load in mixture effect, it is to avoid because density
During the catalyst mixed packing that difference is excessive, in irregular shape and causes, the uneven problem of distribution of particles is simultaneously modified also suitable
The reactivity reducing Hydrobon catalyst, so can preferably be mated with Hydrodewaxing catalyst, be made two
Person's activity quite, to play its each maximum effect in same temperature ranges stated, while reducing product condensation point, also may be used
With improve product quality.If additionally, be provided with hydrodenitrogeneration reactor before mixing bed gone out it is also possible to reduce denitrification reactor
Mouth and the temperature difference mixing bed inlet, decrease the consumption of cold hydrogen, improve the safety coefficient of plant running, reached more
Excellent Temperature Matching effect.
Brief description
Fig. 1 is a kind of grading loading schematic diagram of embodiment of the inventive method；Had from single reactor layering filling
The mode of operation of two hydroconversion reaction zones.
Specific embodiment
Below in conjunction with the accompanying drawings a kind of production method of special lubricating oil base oil of the present invention is described in detail.
As shown in figure 1, the basic oil producing method flow process of the present invention is as follows：
Raw oil 1 enters reactor 3 with hydrogen 2 after reactor inlet mixes, and passes sequentially through from top to bottom and connects step by step
Hydro dewaxing and hydrorefined composite catalyst bed 4, Hydrodewaxing catalyst bed 5, hydro dewaxing and hydrofinishing
Composite bed 6 and Hydrodewaxing catalyst bed 7, obtain reaction effluent 8 from reactor bottom discharge laggard through water filling 9
Enter to high-pressure separator 10, top obtains gas 11 and passes through circulating hydrogen compressor 12, obtains recycle hydrogen 14 after mixing with new hydrogen 13
Use as supplementary hydrogen or cold hydrogen；Liquid phase that middle and lower part obtains enters low pressure separator 17, and top is discharged after low point of gas 18 goes
Continuous process, middle and lower part obtains liquid phase 20 and enters subsequent fractionation system；Acid water 15 and low pressure that high-pressure separator 10 bottom is discharged
Sour water processing meanss are gone to carry out following process after acid water 19 mixing that separator 17 bottom is discharged.
Followed by specific embodiment, the basic oil producing method of the present invention is further described.List in table 1
The property of used catalyst in embodiment.The property of raw materials used oil is listed in table 2.
The main physico-chemical property of table 1 catalyst and activity contrast.
| Catalyst | FF-46 | FF-46G | FDW-3 |
| Catalyst type | Hydrofinishing | Hydrofinishing | Hydro dewaxing |
| Wherein macroporous aluminium oxide, % | 5 | 29 | |
| Pore volume, cm3/g | 0.50 | 1.25 | — |
| Specific surface area, m2/g | 200 | 210 | — |
| Catalyst physical properties | |||
| Shape | Tooth ball | Tooth ball | Tooth ball |
| Diameter, mm | 2.5 | 2.5 | 2.5 |
| Mechanical strength, N/cm | ≮150 | ≮130 | ≮100 |
| Active component | Mo-Ni | Mo-Ni | Ni |
| Tenor, % | 29.0 | 22.2 | 2.0 |
| Natural loading density, t/m3 | 0.88～0.98 | 0.65～0.75 | 0.65～0.75 |
| Average pore size/nm | 4.44 | 7.75 | — |
| Reach temperature during same reaction depth/DEG C | 371 | 380 | — |
| Normally use temperature (just-latter stage)/DEG C | 370～390 | 380～400 | 380～400 |
Comparative example 1
Comparative example 1 is the device producing lube base oil using hydrofinishing, hydro dewaxing one-stage serial flow process.Including
Hydrobon catalyst bed and Hydrodewaxing catalyst bed.Comparative example 1 produces the lubrication oil base of the identical trade mark with embodiment 1
Plinth oil.The catalyst, raw oil and the lube product condensation point that use are all same as Example 1.Operation result is listed in table 3.
Comparative example 2
Comparative example 2 is the device producing lube base oil using hydrofinishing, hydro dewaxing one-stage serial flow process.With reality
Apply example 1 and control essentially identical base oil yield, the product condensation point produced is different.The catalyst of comparative example 2 use, raw material
Oil and base oil product yield are all same as Example 1, and Catalyst packing is with comparative example 1.Operation result is listed in table 3.
Embodiment 1
Using the technological process shown in Fig. 1, using loading in mixture and level is joined serial flow and produced lube base oil.Embodiment 1
Include the hydroconversion reaction zone of two series connection, in the refined pour point depression catalyst composite bed of each reaction zone, hydro dewaxing is catalyzed
The mixed volume of agent and Hydrobon catalyst is than for 1:2, the total consumption of catalyst and comparative example 1 and comparative example 2 all same.Implement
Used in example 1, Hydrobon catalyst is FF-46 catalyst, and Hydrodewaxing catalyst is FDW-3 catalyst, described catalyst
It is the commercial catalyst of Fushun Petrochemical Research Institute's development and production.
Operating condition and result of the test are listed in table 3.
Embodiment 2
Using the technological process shown in Fig. 1, using loading in mixture and level is joined serial flow and produced lube base oil.Embodiment 1
Include the hydroconversion reaction zone of two series connection, in the refined pour point depression catalyst composite bed of each reaction zone, hydro dewaxing is catalyzed
The mixed volume of agent and Hydrobon catalyst is than for 1:2, the total consumption of catalyst and comparative example 1 and comparative example 2 all same.Implement
Used in example 2, Hydrobon catalyst is FF-46G catalyst, and Hydrodewaxing catalyst is FDW-3 catalyst, described catalysis
Agent is the commercial catalyst of Fushun Petrochemical Research Institute's development and production.
Operating condition and result of the test are listed in table 3.
Table 2 raw oil property list.
| Project | Raw oil |
| Source | Decompressed wax oil |
| Density (20 DEG C)/g cm-3 | 0.9410 |
| Boiling range scope/DEG C | 309～525 |
| Nitrogen/μ g g-1 | 1900 |
| Sulfur/μ g g-1 | 2800 |
| Condensation point/DEG C | 4 |
Table 3 process condition and result.
| Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | |
| Catalyst forms | FF-46/FDW-3 | FF-46/FDW-3 | (FF-46+FDW-3)/FDW-3 | (FF-46G+FDW-3)/FDW-3 |
| Reaction pressure/MPa | 15.0 | 15.0 | 15.0 | 15.0 |
| Average reaction temperature/DEG C | 385/380 | 385/375 | 386*/380/386*/380 | 390*/380/390*/380 |
| LHSV/h-1 | 2.0/2.0 | 2.0/2.0 | 4.0**/4.0/4.0**/4.0 | 4.0**/4.0/4.0**/4.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Base oil condensation point/DEG C | -13 | -6 | -14 | -15 |
| >350 DEG C of yields, wt% | 66.4 | 70.5 | 71.5 | 72.7 |
| Base oil viscosity index | 27 | 38 | 27 | 21 |
| Bed peak temperature/DEG C | 400 | 401 | 396 | 393 |
| Cold hydrogen consumption amount/benchmark | 0.97 | 1.81 | 1.0 | 0.96 |
* average reaction temperature is the weighted mean of refined pour point depression beds；
* volume space velocity is the volume space velocity of refined pour point depression beds.
Can be seen that the modified catalyst of embodiment 2 use from above embodiment, it is more excellent to have a mixed effect, focus
Temperature is lower, simultaneously the higher feature of base oil yield, additionally, the maximum feature of the inventive method is, for processing wax oil
For raw material, special lubricating oil base oil, such as transformer oil, refrigerator oil, rubber filling material etc. can be produced, have former
Material adaptability is stronger, the feature of catalyst low cost, and the lube base oil impurity content of production is few, is ensureing certain base oil
The condensation point of raw material can be reduced in the case of yield, can be also the industrial chemicals of high-quality simultaneously with white oil that by-product goes out and Petroleum
And the drawbacks of make up conventional mixed packing；In addition the inventive method also has that hot(test)-spot temperature is low, and service cycle is long, cold hydrogen consumption
Measure low feature；The lube base oil arene content produced is relatively low, can reduce the harshness of the techniques such as follow-up solvent refining
Degree even saves some related process；For enterprise, while completing quality product production task, in human and material resources
And very big advantage is had on energy consumption.
Claims (12)
1. a kind of production method of special lubricating oil base oil, including herein below：After wax oil raw material is mixed with hydrogen, lead to successively
Cross the hydroconversion reaction zone of at least two series connection, by Flow of Goods and Materials direction, each hydroconversion reaction zone includes being urged by hydro dewaxing successively
The refined pour point depression composite catalyst bed of agent and Hydrobon catalyst mixed packing and Hydrodewaxing catalyst bed；Finally
The reaction effluent that one hydroconversion reaction zone obtains through separation and fractional distillation after, obtain lube base oil, white oil product；
Wherein, in each described hydroconversion reaction zone, Hydrodewaxing catalyst bed and by Hydrodewaxing catalyst and hydrogenation essence
The admission space of the refined pour point depression composite catalyst bed of catalyst mixed packing processed is than for 1:10～10:1；Described compound urge
In agent bed, the admission space of Hydrodewaxing catalyst and Hydrobon catalyst is than for 1:10～10:1.
2. in accordance with the method for claim 1 it is characterised in that described wax oil raw material condensation point is more than -10 DEG C, nitrogen content
In below 1000 μ g/g.
3. in accordance with the method for claim 1 it is characterised in that the nitrogen content of described wax oil raw material is in more than 1000 μ g/g,
Before wax oil raw material passes through the refined pour point depression catalyst composite bed of the first hydroconversion reaction zone, beforehand through a hydrofinishing
Beds, carry out part denitrogenation.
4. in accordance with the method for claim 1 it is characterised in that the doing as 500～550 DEG C of described wax oil raw material.
5. in accordance with the method for claim 1 it is characterised in that the operating condition of described Hydrodewaxing catalyst bed is：
Reaction pressure 8.0～20.0 MPa, hydrogen to oil volume ratio 600：1～1500：1, volume space velocity is 0.1～10.0 h-1, reaction temperature
260 DEG C～455 DEG C；The operating condition of described composite bed is：Reaction pressure 8.0～20.0 MPa, hydrogen to oil volume ratio 700：1
～1600：1, volume space velocity is 0.1～10.0 h-1, 270 DEG C～460 DEG C of reaction temperature.
6. in accordance with the method for claim 1 it is characterised in that described Hydrodewaxing catalyst is with shape slective cracking molecular sieve
It is carrier with binding agent, with group VIB and/or group VIII metal for hydrogenation active metals component, with the weight of catalyst as base
Standard, for 1% ~ 16%, the content of shape slective cracking molecular sieve is 50% ~ 85% to the content that hydrogenation active metals are counted with oxide, binding agent
Content be 10% ~ 40%.
7. according to the method described in claim 1 or 6 it is characterised in that the heap density of described Hydrodewaxing catalyst is
0.65～0.75g cm-3, the heap density of described Hydrobon catalyst is 0.65～0.75g cm-3, wherein hydrofinishing
Catalyst is less than or equal to 0.05 g cm with the difference of the heap density of Hydrodewaxing catalyst-3.
8. in accordance with the method for claim 1 it is characterised in that on the basis of the weight of catalyst, described hydrofinishing
Catalyst tungsten and/or molybdenum in terms of oxide 10% ~ 35%, nickel and/or cobalt in terms of oxide 1% ~ 7%, carrier aoxidizes for inorganic refractory
Thing, selected from one or more of aluminium oxide, amorphous silicon aluminium, silicon dioxide, titanium oxide.
9. aoxidize it is characterised in that containing macropore in described Hydrobon catalyst in accordance with the method for claim 8
Aluminum, on the basis of catalyst weight, macroporous aluminium oxide content is 60w%～85w%；The pore volume of described macroporous aluminium oxide be 1.0～
1.7mL/g, specific surface area is 200～550m2/g.
10. in accordance with the method for claim 2 it is characterised in that described wax oil raw material condensation point is more than -5 DEG C, nitrogen content
For 100～500 μ g/g.
11. in accordance with the method for claim 4 it is characterised in that the doing as 510～540 DEG C of described wax oil raw material.
12. in accordance with the method for claim 9 it is characterised in that the content of described macroporous aluminium oxide is 65w%～80w%,
The pore volume of macroporous aluminium oxide is more than 1.2 to 1.7 mL/g, and specific surface area is 300～500m2/g.
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| CN1508229A (en) * | 2002-12-19 | 2004-06-30 | 中国石油化工股份有限公司 | Method for producing low-freezing diesel oil from fractional oil |
| CN1676585A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | Method for preparing lubricating oil base oil |
| CN1769380A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | One-step hydrogenation method for producing super white oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508229A (en) * | 2002-12-19 | 2004-06-30 | 中国石油化工股份有限公司 | Method for producing low-freezing diesel oil from fractional oil |
| CN1676585A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | Method for preparing lubricating oil base oil |
| CN1769380A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | One-step hydrogenation method for producing super white oil |
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