CN101331214A

CN101331214A - Lubricant composition with improved solvency

Info

Publication number: CN101331214A
Application number: CNA2006800473899A
Authority: CN
Inventors: D·J·巴亚尔荣
Original assignee: ExxonMobil Research and Engineering Co
Current assignee: ExxonMobil Technology and Engineering Co
Priority date: 2005-12-15
Filing date: 2006-12-15
Publication date: 2008-12-24
Also published as: ZA200805203B

Abstract

Lubricating base oils/base stocks comprising one or more hydrodewaxate and/or hydroisomerate base stock(s) and/or base oil(s), GTL base stock(s) and/or base oil(s) or mixture thereof, preferably GTL base stock(s) and/or base oil(s) of improved solvency comprise said base stock combined with a Group I base stock/base oil selected from the group consisting of high viscosity Group I mineral oil, preferably Bright Stock. The solvency and the capability to solubilize performance additives of base oils comprising one or more hydrodewaxate and/or hydroisomerate base stock(s) and/or base oil(s), GTL base stock(s) and/or base oil(s) or mixture thereof, preferably GTL base stock(s) and/or base oil(s) is improved by the addition to said base oils of a Group I base oil/base stock selected from the group consisting of high viscosity Group I mineral oil, preferably Bright Stock.

Description

Possesses the lubricating oil composition that improves dissolving power

Background of invention

Technical field

The present invention relates to a kind of lubricant base/basestocks that is used to prepare the formulated oil that contains performance additive.

Background technology

Hydrocarbon base oil has the dissolution characteristics of the different abilities that influences its solubility property additive.The paraffin base oil of known altitude (promptly having low-level aromaticity) has the additive dissolution characteristics that is low to moderate poor level.For example, the hydrocarbon base oil of this type of low dissolving power comprises that it is 100% isoparaffin and to have be the poly-alpha olefins (PAO) of 0% aromatic content substantially.Similarly, wax isomery base oil/basestocks, particularly hydroisomerization fischer-tropsch (F-T) lubricating fluid (being commonly called gas to liquid (GTL) lubricant base/basestocks) are the paraffinic hydrocarbons types of very height and to have be 0% aromatic content substantially.Therefore, this type of wax isomery base oil is considered to possess low dissolving power and difference additive solubility property, and practical situation also are like this.

In order to address this problem, people expect only adding in the base oil/basestocks of the low dissolving power of this class and contain the dissolving power defective that the aromatic substances materials flow will as one man overcome this class base oil, and the improvement of dissolving power is preferably also only linear with every kind of composition inherent dissolving power (representing with aniline point).

Usually utilize amine benzene point to measure the dissolving power of lubricant base/basestocks, the difference of amine benzene point shown lubricant base/basestocks dissolving power difference and therefore be reflected on the ability of their solubility property additives.Reduction solubility property raising along with amine benzene point.

At present, Gao Du the paraffin base oil (as PAO) together the base oil alkyl oil that contains amido, ester, carboxyl, carbonyl, ether, fragrant or other chemical functionalities of dissolution aids (as: can) use together to offer the enough additive solvabilities of finished lube or functional liquid.

Similar with PAO, the paraffin GTL type wax of height derive base oil probably with alkyl altogether base oil be used in combination, for example contain the common base oil of aromatic substances, it can contain mineral oil (I class).Especially, the base oil/I class mineral oil combination of deriving of GTL type wax possesses the economic advantages of essence, and has the potential advantages with regard to the lower cost base oil mixture, and this lower cost base oil mixture can be used for formulated oil composition or functional liquid.

Use mineral oil to be easy to be embodied in aspects such as availability, cost, quality control, quantity as the advantage that is total to base oil.

US 2004/0094453 discloses a kind of method for preparing the lube base oil mixt, and it comprises that (a) reclaims with 100 ℃ of about 2mm of following kinematic viscosity ²/ s or above but be lower than 3mm ²/ s be the F-T of feature derive cut and (b) aforesaid F-T is derived cut mix with the petroleum derivation base oil of the mixture that is selected from I class base oil, II class base oil, III class base oil or two or three any above-mentioned conventional base oil, be about 3mm to prepare viscosity ²/ s or above blend lubricant base.Introduced in the literary composition and contained the derive formulated oil of base oil with 600 neutral heavy neutral oil blended F-T.100 ℃ of about 2.5mm of following KV ²The F-T of/s derive base oil also can with bright stock combination base oil with the preparation blend, but this blend can not be added to produce formulated oil.Viscosity, VI, pour point, CCS@-25 ℃, the TGA Noack volatility of this class blend have only been reported.

WO 2004/053030 relates to a kind of high viscosity that adopts and refers to-the low brookfield viscosity functional liquid of oil/basestocks.The invention oil B that a kind of described high viscosity index (HVI) base oil/basestocks is considered to be made by the F-T wax stock.This F-T wax base oil and comparison basis material make up and are added with 50/50 ratio.Can be clear that from the table 4 of WO2004/053030 described comparison basis material does not belong to bright stock, only be 7.614mm because the formulated oil that the additive by adding 11.379 volume % is only made in the described comparison basis material has produced a kind of viscosity ²If/s@100 ℃ blend is this viscosity of being estimated when being bright stock far below described comparison basis material.

United States Patent (USP) 6,627,779 have related to the blend lubricant base that contains the about 50wt% of the 99wt%-that has an appointment paraffin lube basestocks highly and the about 50wt% alkylaromatic of about 1wt%-, alkyl naphthene or its mixture.The paraffin basestocks of height (as the F-T lube basestocks of deriving) has poor additive solvability usually.In order to overcome this defective, this type of basestocks mixes as synthetic ester with various solubility promoters usually.But synthetic ester number lattice costliness, therefore prepared blend also is expensive.In order to address this problem, United States Patent (USP) 6,627,779 have instructed and have added the about 50wt% alkylaromatic of about 1wt%-, alkyl naphthene or its mixture especially to improve the dissolving power of described base oil in the paraffin F-T lubricant base of height.

Description of drawings

Fig. 1 is the synoptic diagram of the amine benzene point of the mixture of PAO/ bright stock under different bright stock concentration and wax isomer/bright stock mixture.

Summary of the invention

The dissolving power that has had been found that the base oil that contains one or more Hydrodewaxing bodies and/or hydroisomerizing body basestocks and/or base oil, GTL/ basestocks and/or base oil, its mixture, preferred GTL basestocks and/or base oil is non-linearly improved when described oil plant makes up with the I class basestocks that is selected from high viscosity mineral oil material, preferred light gloss varnish.

The improvement that the described base oil that contains one or more Hydrodewaxing bodies and/or hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil and its mixture, preferred GTL basestocks and/or base oil adds high viscosity mineral oil material, its dissolving power of preferred light gloss varnish combination back is shown after with the combination of like combinations ratio greater than PAO base oil/basestocks and identical full-bodied mineral oil, preferred light gloss varnish.

In first embodiment, the present invention relates to and be selected from the lubricant base that contains one or more Hydrodewaxing bodies and/or hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil and its mixture, preferred GTL basestocks and/or base oil of the I class base oil/basestocks combination of high viscosity mineral oil base oil/basestocks, preferred light gloss varnish.

In another embodiment, the present invention relates to the method for dissolving power that a kind of improvement contains the base oil of one or more Hydrodewaxing bodies and/or hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil and its mixture, preferred GTL basestocks and/or base oil, this method is by to wherein adding the I class base oil/basestocks that is selected from high viscosity mineral oil material, preferred light gloss varnish.

In another embodiment, the present invention relates to a kind of lubricating oil formulation, it comprises the base oil that contains one or more Hydrodewaxing bodies and/or hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil and its mixture, preferred GTL basestocks and/or base oil with the I class base oil that is selected from high viscosity mineral oil material, preferred light gloss varnish/basestocks combination, and contains at least a performance improvement additives of minor amount.

In another embodiment, the present invention relates to a kind of method for preparing the lubricating oil formulation, this method by to be selected from the high viscosity mineral oil material, add at least a performance improvement additives in the lubricant base that contains one or more Hydrodewaxing bodies and/or hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil and its mixture, preferred GTL basestocks and/or base oil of the I class base oil of preferred light gloss varnish/basestocks combination.

In another embodiment, the present invention relates to a kind of multifunctional additive for lubricating oils that contains at least a performance improvement additives, it is in the lubricant base that contains one or more Hydrodewaxing bodies and/or hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil and its mixture, preferred GTL basestocks and/or base oil that makes up with the I class base oil that is selected from high viscosity mineral oil material, preferred light gloss varnish/basestocks with meltage.

In another embodiment, need the present invention relates to the lubricated of lubricated machine, equipment etc., the lubricating oil that contains one or more Hydrodewaxing bodies and/or hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil and its mixture, preferred GTL basestocks and/or base oil that it makes up by the I class base oil/basestocks that adopts and be selected from high viscosity mineral oil material, preferred light gloss varnish, and/or by adopting the described lubricating oil that further contains at least a performance additive.

Surprisingly, when the amine benzene point of bright stock itself is considered to aniline point far above the following base oil that adds it, by to wherein adding I class high viscosity mineral oil material, preferred light gloss varnish, can improve Hydrodewaxing body and/or hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil and its mixture, preferred GTL basestocks and/or dissolving power, particularly the GTL wax Hydrodewaxing body of base oil and/or the dissolving power of hydroisomerizing body basestocks and/or base oil, as shown by the improvement (that is: reducing) of amine benzene point.Beat allly be, for example name a person for a particular job the I class high viscosity mineral oil material that is lower than the amine benzene point of the oil ingredient that constitutes described mixture or can be used to reduce amine benzene point/its solubility property of improvement of aforementioned base oil/basestocks, the amine benzene point of preferred light gloss varnish of the amine benzene of described oil mixt.

Amine benzene point (according to ASTM D611) is the very sensitive index of the dissolving power of lubricating oil fluid.Amine benzene point is represented with measurement to 0.1 ℃ temperature.The amine benzene point difference that is low to moderate 0.4～0.5 ℃ is considered to significantly, and can have practical influence to the compatibility (for example maximum additive concentration) of lubricating oil additive and the transparency that contains the lubricating oil composition of one or more additives.

Hydrodewaxing body among the present invention and/or hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil and its mixture, preferred GTL basestocks and/or base oil are the fluids with lubricant viscosity that is derivatized to through conversion by high pour point alkyl raw material (containing zero to the sulphur that can measure quantity, nitrogen and/or oxygen as this stock oil material).Described high pour point alkyl raw material is to transform (through one or more procedure of processings) one-tenth basestocks used herein and the suitable raw material of base oil, this material mainly is a hydrocarbonaceous material, form by linear hydrocarbon molecule fragment mainly, suitable raw material have be higher than about 30 ℃, preferably be higher than about 50 ℃, more preferably be higher than about 60 ℃, also more preferably be higher than about 70 ℃, (under specific circumstances) even more preferably be higher than about 80 ℃ pour point, pour point records by ASTM method D97.

An embodiment relates to wax Hydrodewaxing body and/or hydroisomerizing body base oil/basestocks, and it comes from mainly is the paraffinic hydrocarbons high pour point raw material of (comprising N-alkanes, isomeric alkane, cycloalkanes or its mixture).

A preferred implementation relates to the GTL base oil/basestocks that comes from the high pour point material that mainly is synthetic paraffinic hydrocarbons, and described synthetic paraffinic hydrocarbons is derived from fischer-tropsch hydrocarbon synthesis type technology.

One more preferably embodiment relate to GTL wax Hydrodewaxing body and/or the hydroisomerizing body base oil/basestocks that comes from the high pour point raw material that mainly is synthetic paraffinic hydrocarbons, described synthetic paraffinic hydrocarbons derived from based on molecule in conjunction with and/or reset the synthesis technique of chemistry.

A preferred embodiment relates to the GTL basestocks/base oil that comes from the high pour point material that mainly is synthetic paraffinic hydrocarbons, and described synthetic paraffinic hydrocarbons is derived from further being included in the F-T hydrocarbon synthesis type technology of using cobalt in the synthetic catalyst.

Basestocks/base oil of the present invention comprises and is derived from one or more gases to the basestocks of liquid (GTL) material and/or one or more mixtures of base oil, and Hydrodewaxing, or hydroisomerizing/basestocks and/or the base oil of conventional catalytic (or solvent) dewaxing, it comes from natural wax or waxy feeds, mineral and/or non-mineral oil waxy feeds such as slack wax, natural wax, content of wax oil plant such as diesel oil, waxy fuel hydrocracking bottom product, content of wax raffinate, the hydrocracking thing, the thermally splitting product, or other mineral, mineral oil, or non-petroleum derivation waxy feeds for example is derived from the waxy feeds in gelatin liquefaction or the shale oil, mixture with these basestocks.

Following term of the present invention is explained as follows:

A) hydrocarbon materials of " wax "-Gao pour point at room temperature is 15 ℃-25 ℃ and generally exists with solid form, mainly is made up of the paraffin material;

B) " paraffin " material: any stable hydrocarbon, as alkane.The paraffin material can comprise straight-chain paraffin, branched paraffin (isoparaffin), naphthenic hydrocarbon (naphthenic hydrocarbon; Monocycle and/or many rings) and side chain naphthenic hydrocarbon;

C) " hydrogenation technique ": a kind of refinery practice, wherein heating raw and hydrogen under high temperature and pressure in the presence of catalyzer, are removed and/or are transformed comparatively undesirable composition and generate improved product usually;

D) " hydrotreatment ": a kind of catalytic hydrogenation process, wherein the hydrocarbon with sulfur-bearing and/or nitrogen changes into sulphur and/or nitrogen content hydrocarbon product still less, and has produced by product hydrogen sulfide and/or ammonia respectively; Similar, oxygen containing hydrocarbon also can be reduced into hydrocarbon and water;

E) " catalytic dewaxing ": a kind of Catalytic processes of routine wherein changes into the lower molecular weight class by cracking/cracked with normal paraffin (wax) and/or waxy hydrocarbon (as slight branching isoparaffin) and possesses required product pour point to guarantee final oil production (basestocks or base oil);

F) " hydroisomerization " (or isomerization): a kind of Catalytic processes wherein changes into branching or the isoparaffin of branching (isomer in this technology may need additional subsequently wax to remove step possess required product pour point to guarantee final oil production (basestocks or base oil)) more by rearrangement/isomerization with normal paraffin (wax) and/or slight branching isoparaffin;

G) " hydrocracking ": a kind of Catalytic processes, wherein hydrogenation is accompanied by the cracking of hydrocarbon/cracked, for example: change into than lighter hydrocarbons than heavy hydrocarbon, or aromatic hydrocarbons and/or naphthenic hydrocarbon (cycloalkanes) change into the acyclic branched alkane.

H) " Hydrodewaxing ": (ISODEWAXING of Chevron for example

Or the MSD W of Exxon Mobil Corporation ^TM) a kind of highly selective Catalytic processes, wherein change into more highly branched isoparaffin with single step or by use single catalyst or catalyst mixture by normal paraffin and the slightly isomerization of branched alkane/rearrangement realization wax, the product of gained does not need to separate conventional catalyst or the solvent dewaxing step obtains required product pour point;

I) term " hydroisomerizing body ", " isomer ", " catalytic dewaxing body " and " Hydrodewaxing body " is meant the product that makes by corresponding technology, except as otherwise noted.

Thereby term " hydroisomerization/catalytic dewaxing " is used to refer to the Catalytic processes that possesses following combined effect: by rearrangement/isomerization normal paraffin and/or waxy hydrocarbon are changed into the isoparaffin of branching more, (1) catalytic dewaxing subsequently be present in by cracking/cracked with minimizing and isomer in any residual normal paraffin or the amount of the isoparaffin of slight branching or (2) Hydrodewaxing to realize the further isomerization and the highly selective catalytic dewaxing of isomer, to reduce the product pour point.When this paper related to this term (or solvent), then described technology comprised solvent dewaxing after the hydroisomerization, its be used for realizing wax from the physical sepn of hydroisomerizing body to reduce the product pour point.

The GTL material is by gaseous carbon, hydrogen-containing compound and/or material composition for example hydrogen, carbonic acid gas, carbon monoxide, water, methane, ethane, ethene, acetylene, propane, propylene, propine, butane, butylene and butine is synthetic through one or many, combination, transform, reset and/or degraded/destructing technology is derived and the material that gets.GTL basestocks and/or base oil are the GTL materials with lubricant viscosity, and it derives from hydrocarbon usually, and for example the synthetic hydrocarbon of the content of wax itself derives from simpler gaseous carbon, hydrogen-containing compound and/or material composition as raw material.GTL basestocks and/or base oil comprise the oil of boiling point within the lubricating oil boiling range, its separated/classification from synthetic GTL material, for example also carry out final wax procedure of processing subsequently by distillation, this step is known WITH CATALYTIC DEWAXING TECHNIQUE or solvent dewaxing process, with preparation have reduction/lubricating oil of low pour point; The synthetic wax isomer, it contains for example Hydrodewaxing or the synthetic hydrocarbon of hydroisomerization/catalysis (or solvent) dewaxing; Hydrodewaxing or hydroisomerization/catalysis (or solvent) dewaxing fischer-tropsch (F-T) material (that is: hydrocarbon, waxy hydrocarbon, wax and similar oxygenatedchemicals); Preferred Hydrodewaxing or hydroisomerization/catalysis (or solvent) dewaxing F-T hydrocarbon, perhaps fischer-tropsch (F-T) wax of Hydrodewaxing or hydroisomerization/catalysis (or solvent) dewaxing, Hydrodewaxing or hydroisomerization/catalysis (or solvent) dewaxing synthetic wax or its mixture.

Be derived from the GTL basestocks and/or the base oil, particularly Hydrodewaxing of GTL material or hydroisomerization/catalysis (or solvent) dewaxing F-T material the derive feature of basestocks and/or base oil of the wax of basestocks and/or base oil and other Hydrodewaxings or hydroisomerization/catalysis (or solvent) dewaxing of deriving and be that usually 100 ℃ kinematic viscosity is about 2mm ²The about 50mm of/s- ²/ s, preferably about 3mm ²The about 50mm of/s- ²/ s, more preferably from about 3.5mm ²The about 30mm of/s- ²/ s is an example with the isomerization dewaxing deutero-GTL basestocks by F-T wax, and its kinematic viscosity of 100 ℃ is about 4mm ²/ s and viscosity index about 130.Preferred wax treatment process is the Hydrodewaxing technology that adopts single catalyst for hydrogenation de-waxing.Kinematic viscosity herein relates to the measurement with reference to ASTM method D445.

Be derived from the GTL basestocks and/or the base oil of GTL material, Hydrodewaxing particularly, or hydroisomerization/catalysis (or solvent) dewaxing F-T material derive basestocks and/or base oil, with other Hydrodewaxings, or the wax of hydroisomerization/catalysis (or solvent) dewaxing derive basestocks and/or base oil, it can be used as basestocks of the present invention and/or base oil composition, and feature is that usually pour point is-5 ℃ or lower approximately in addition, preferred-10 ℃ or lower approximately, more preferably from about-15 ℃ or lower, also more preferably from about-20 ℃ or lower, and may possess-25 ℃ or lower favourable pour point approximately in some cases, and useful pour point is-30 ℃ to-40 ℃ or lower approximately.If necessary, can be the dewaxing step that obtains required pour point and implement to separate.In the present invention, derive basestocks and/or base oil of used GTL or other Hydrodewaxing or hydroisomerization/catalysis (or solvent) dewaxing wax is that its pour point is about-30 ℃ or higher, preferred pact-25 ℃ or higher, more preferably-20 ℃ or higher those.Pour point relates to the measurement with reference to ASTM D97 and similar automatization version herein.

Be derived from the GTL basestocks of GTL material and/or base oil, particularly Hydrodewaxing or hydroisomerization/catalysis (or solvent) dewaxing F-T material derive basestocks and/or base oil and be usually that as the derive feature of basestocks and/or base oil of other these class waxes that can be used for the basestocks composition among the present invention viscosity index is 80 or higher, preferred 100 or higher, more preferably 120 or higher.In addition, at some in particular cases, the viscosity index of this type of basestocks and/or base oil can be preferred 130 or higher, and more preferably 135 or higher, even more preferably 140 or higher.The GTL basestocks that for example comes from GTL material, preferred F-T material, particularly F-T wax has 130 or higher viscosity index usually.Viscosity index herein relates to the measurement with reference to ASTM method D2270.

In addition, GTL basestocks and/or base oil generally are height alkanes (saturation ratio＞90%), and can contain and the monocycle alkane of acyclic isoparaffin combination and the mixture of polycyoalkane.The ratio of cycloalkanes in this combination (being naphthenic hydrocarbon) content changes with catalyzer that is adopted and temperature.And the sulphur and the nitrogen content of general GTL basestocks and/or base oil are very low, and the content of these elements is separately less than about 10ppm, more typically less than about 5ppm usually.The GTL basestocks that is obtained by the hydroisomerization of F-T material, particularly F-T wax/isomerization dewaxing and/or the sulphur and the nitrogen content of base oil are zero substantially.

In a preferred embodiment, GTL basestocks and/or base oil contain the paraffin material of mainly being made up of acyclic isoparaffin and only a spot of naphthenic hydrocarbon.These GTL basestocks and/or base oil generally contain by greater than 60wt% acyclic isoparaffin, be preferably greater than 80wt% acyclic isoparaffin, more preferably greater than 85wt% acyclic isoparaffin, the paraffin material most preferably formed greater than 90wt% acyclic isoparaffin.

The derive useful composition of basestocks and/or base oil and wax deutero-Hydrodewaxing, hydroisomerization/catalysis (or solvent) dewaxing basestocks of GTL basestocks and/or base oil, Hydrodewaxing or hydroisomerization/catalysis (or solvent) dewaxing F-T material, as wax isomer or Hydrodewaxing body, as United States Patent (USP) 6,080,301; Have open in 6,090,989 and 6,165,949.

Also being suitable for described basestocks and/or the base oil that comes from waxy feeds of the present invention is to come from Hydrodewaxing, or the mineral oil of hydroisomerization/catalysis (or solvent) dewaxing, non-mineral oil, non-oil, or the paraffin fluid with lubricant viscosity of the waxy feeds of natural origin, for example described raw material is to be selected from following one or more: diesel oil, slack wax, waxy fuel, liquid at the bottom of the hydrocracking tower, the hydrocarbon debris, natural wax, the hydrocracking thing, the pyrolytic cracking thing, foots oil, the wax that comes from gelatin liquefaction or shale oil, or other mineral oil that are fit to, non-mineral oil, non-oil, or natural origin deutero-wax stock, carbonatoms about 20 or higher, preferred about 30 or higher line style or branched hydrocarbyl radical compound, mixture with described isomer/isomerization dewaxing body basestocks and/or base oil.

Slack wax is meant the wax that reclaims from any content of wax hydrocarbon ils, comprise that synthetic oil is as F-T waxy oil or oil by solvent or automatic freezing dewaxing.Chilled solvent such as methyl ethyl ketone (MEK) are adopted in solvent dewaxing, methyl iso-butyl ketone (MIBK) (MIBK), and the MEK/MIBK mixture, MEK and toluene mixture, and automatic freezing dewaxing is low boiling hydrocarbon such as propane or the butane that adopts the liquefaction of pressurization.

It is zero that the slack wax that obtains from synthetic waxy oil such as F-T waxy oil does not have sulfur-bearing and/or nitrogen compound or content usually.The slack wax that obtains from oil may contain sulfur-bearing and nitrogen compound.This type of heteroatomic compound must be removed by hydrotreatment (and non-hydrocracking), for example by hydrogenating desulfurization (HDS) and hydrodenitrification (HDN) to avoid the follow-up poisoning/passivation of described hydroisomerization catalyst.

GTL///GTL/// ( ) /、GTL/// ( ) /、GTL/// ( ) /GTL/// ( ) / ( dumbbell blend ) 。

In a preferred implementation, GTL basestocks and/or base oil are F-T material (that is: hydrocarbon, waxy hydrocarbon, wax) by its deutero-GTL material.Slurry attitude F-T synthesis technique can be advantageously used in CO and hydrogen and especially one to adopt the F-T catalyzer that contains the catalytic cobalt composition be that raw material synthesizes the Schultz-Flory dynamic assignment factor alpha (Schultz-Flory kinetic alpha) to be provided for preparing required higher molecular weight paraffin.This technology is conventionally known to one of skill in the art.

In the F-T synthesis technique, contain H ₂Be catalytically converted into hydrocarbon and preferred liquid hydrocarbon with the synthetic gas of CO mixture.The molar ratio of hydrogen and carbon monoxide approximately can be widely changes to 4 from 0.5, but usually more in the scope of 0.7-2.75, more preferably the scope of 0.7-2.5.As everyone knows, the F-T synthesis technique comprises that catalyzer wherein is with the form of fixed bed, fluidized-bed or with the technology of the slurry form of granules of catalyst in the hydrocarbon slurry.The stoichiometry mol ratio is 2.0 in the F-T building-up reactions, but has the reason of the stoichiometric ratio known to a lot of non-those skilled in the art of use.In cobalt slurry hydrocarbon synthesis technique, H ₂Be generally about 2.1/1 with the material molar ratio of CO.With the described H that contains ₂Gone into the bottom of described slurry with the synthetic gas of CO mixture by bubbling, and the particle F-T synthetic catalyst in described slurries in the presence of under the condition of effective formation hydrocarbon, react, the part of described hydrocarbon under reaction conditions for liquid and contain described hydrocarbon slurries.Described synthetic hydrocarbon liquid is separated as filtrate by modes such as filtrations from described catalysed particulate, but also can adopt other separate modes such as centrifugal.Some of described synthetic hydrocarbon are come out from the hydrocarbon synthesis reactor top with unreacted synthetic gas and other gaseous reaction products with the form of steam.Usually some top hydrocarbon vapours are condensed into liquid state and merge with described hydrocarbon liquid filtrate.Thereby whether the initial boiling point of described filtrate can be according to having some hydrocarbon vapours that are condensed and its merging to change.According to described catalyzer and required product, the slurry hydrocarbon synthetic technological condition is different.Contain in the slurry hydrocarbon synthesis technique of catalyzer of supported cobalt composition in employing, effectively formation mainly contains C ₅₊Paraffin (C for example ₅₊-C ₂₀₀), preferred C ₁₀₊The representative condition of the hydrocarbon of paraffin comprises, temperature for example, and pressure and gas hourly space velocity rate, it is respectively at 320-850 °F, 80-600psi and 100-40,000V/hr/V is (with per hour the gaseous state CO and the H of every catalyst volume ₂The standard volume of mixture (0 ℃, 1 normal atmosphere) is represented) scope in.Term " C used herein ₅₊" be meant carbonatoms greater than 4 hydrocarbon, be 5 material and do not represent to exist carbonatoms.The carbon number of other scopes of being mentioned does not represent to exist the hydrocarbon of the ultimate value with described carbon number range similarly, perhaps has each interior carbon number of institute's scope of mentioning.Preferably, hydrocarbon synthesis reaction is that limited water gas shift reaction or the reaction of anhydrous gas reforming took place between synthesis phase hydrocarbon therein, more preferably anhydrous gas reforming reacts under the condition that takes place and carries out.Also preferred, described be reflected to realize being at least under 0.85, preferred at least 0.9 condition that more preferably at least 0.92 α distributes carry out, thereby synthetic more hydrocarbon with higher molecular weight of more wishing.This realizes in employing contains the slurry technology of catalyzer of catalytic cobalt composition.α as well known to those skilled in the art is meant Schultz-Flory dynamic assignment factor alpha.Although suitable F-T response type catalyzer comprises, for example one or more VIII class catalytic metals such as Fe, Ni, Co, Ru and Re, preferred described catalyzer comprises the cobalt catalyst component.In one embodiment catalyzer contain the cobalt of the catalytically effective amount on suitable inorganic carrier material and Re, Ru, Fe, Ni, Th, Zr, Hf, U, Mg and La one or more, preferably contain the catalyzer of one or more refractory metal oxides.The carrier that preferably is used for cobalt-containing catalyst contains titanium dioxide especially.The available Catalysts and its preparation method is known and through explanation, but non-limiting enforcement can be at for example United States Patent (USP) 4,568,663; 4,663,305; 4,542,122; Find in 4,621,072 and 5,545,674.

As mentioned above, described basestocks and/or base oil by its deutero-waxy feeds be meant come from mineral oil, non-mineral oil, non-oil or other natural origins, the particularly wax or the waxy feeds of slack wax or GTL material, preferred F-T material (being called as F-T wax).Described F-T wax preferably has 650-750 initial boiling point and preferably seethes with excitement constantly up at least 1050 terminal point.In hydroisomerization, also can adopt than the narrow fraction waxy feeds.The described normal paraffin waxy feeds of a part is converted to more lower boiling isoparaffin material.Therefore, must there be enough heavy normal paraffin materials to contain the isoparaffin of the isomer of boiling point in described lube range with generation.If also carry out catalytic dewaxing behind isomerization/isomerization dewaxing, some of described isomerization body/isomerization dewaxing body also will be hydrocracking into more lower boiling material in described conventional catalytic dewaxing.Therefore, the full boiling point of preferred described waxy feeds is more than 1050 °F (1050 °F+).

Mentioned herein to boiling range be defined as and be used to separate the following of described fraction and/or go up distillation temperature.(for example, described fraction constantly boiling is described or constitutes whole boiling range) that the implication of boiling range does not require that any material at the prescribed limit place must exist unless stated otherwise, it gets rid of boiling point at this extraneous material on the contrary.

Described waxy feeds preferably includes the whole 650-750+fraction that is formed by described hydrocarbon synthesis process, have initial boiling point between 650-750 and the preferred full boiling point more than 1050 determined by the operator, it was used for described synthetic catalyzer by the operator adopts and process variable is determined.Described fraction is called as " 650-750 °F+fraction " here.By contrast, " 650-750 ° " fraction " is meant to have unspecified initial boiling point and the fraction of the full boiling point in somewhere between 650-750.Waxy feeds can be processed as described whole fraction or as the subclass of the described whole fraction that makes by distillation or other isolation technique.Described waxy feeds generally contains greater than 90%, usually greater than 95%, be preferably greater than the paraffinic hydrocarbons of 98wt%, wherein major part is a normal paraffin.It has the sulphur and the nitrogen compound (for example, every kind less than 1wppm) of negligible quantity, and less than 2,000wppm, and preferably less than 1,000wppm is more preferably less than the oxygen of 500wppm, exists with the form of oxygenatedchemicals.The waxy feeds that can be used in the technology of the present invention that possesses above-mentioned characteristic adopts slurry F-T prepared to get by aforesaid by the catalyzer with catalytic cobalt composition.

From content of wax base-material (as, slack wax or F-T wax) preparation described lube basestocks technology can be feature with Hydrodewaxing or isomerization process.If with slack wax as raw material, then may implement pre-hydrotreating step to it well known to a person skilled in the art under the condition, with reduction (to the level that can effectively avoid poisoning of catalyst or passivation) or removal sulfur-bearing and nitrogenous compound, otherwise they will make hydroisomerization used in the later step or catalyst for hydrogenation de-waxing inactivation.If adopt F-T wax, then do not need above-mentioned pre-treatment because as mentioned above, only contain in this wax trace (less than about 10ppm, or more generally less than 5ppm to zero) sulphur or nitrogen compound.But, some catalyst for hydrogenation de-waxing that is used for F-T wax may benefit from the pre-hydroprocessing technique of removing oxygenatedchemicals and other may benefit from oxygenate treated technology.Can under the combination of catalyzer or single catalyst, carry out described hydroisomerization or Hydrodewaxing technology.Invert point is at about 500-20, under the pressure of 000kPa about 150 ℃-Yue 500 ℃.Can move in the presence of hydrogen in this technology, hydrogen partial pressure is the about 6000kPa of about 600-.Hydrogen is generally about 10-3500n.1.1. than ratio (hydrogen circulation rate) scope of described hydrocarbon feed ^-1(56-19,660SCF/bbl), the air speed of described raw material is generally about 0.1-20LHSV, preferred 0.1-10LHSV.

After any required hydrodenitrification or hydrogenating desulfurization, the hydrogenation technique that is used for being prepared by above-mentioned waxy feeds basestocks can adopt unbodied hydrocracking/hydroisomerisation catalysts, as lube oil hydrogenation cracking (LHDC) catalyzer, for example contain Co, Mo, Ni, W, the catalyzer of Mo etc. is on oxide carrier such as aluminum oxide, silicon-dioxide, silica/alumina, or crystalline hydrocracking/hydroisomerisation catalysts, the preferred zeolite catalyzer.

Other isomerization catalysts and the process quilt that hydrocracking, Hydrodewaxing or the hydroisomerizing of GTL material and/or content of wax material changes into basestocks and/or base oil is described in for example United States Patent (USP) 2,817,693; 4,900,407; 4,937,399; 4,975,177; 4,921,594; 5,200,382; 5,516,740; 5,182,248; 5,290,426; 5,580,442; 5,976,351; 5,935,417; 5,885,438; 5,965,475; 6,190,532; 6,375,830; 6,332,974; 6,103,099; 6,025,305; 6,080,301; 6,096,940; 6,620,312; 6,676,827; 6,383,366; 6,475,960; 5,059,299; 5,977,425; 5,935,416; 4,923,588; 5,158,671; With 4,897,178; EP 0324528 (B1), EP 0532116 (B1), EP 0532118 (B1), EP0537815 (B1), EP 0583836 (B2), EP 0666894 (B2), EP 0668342 (B1), EP 0776959 (A3), WO 97/031693 (A1), WO 02/064710 (A2), WO02/064711 (A1), WO 02/070627 (A2), WO 02/070629 (A1), WO03/033320 (A1), and English Patent 1,429,494; 1,350,257; 1,440,230; 1,390,359; WO 99/45085 and WO 99/20720.Particularly advantageous technology has been described in the european patent application 464546 and 464547.In United States Patent (USP) 4,594,172; 4,943,672; 6,046,940; 6,475,960; 6,103,099; 6,332,974; With 6,375, the technology that adopts the F-T wax stock has been described in 830.

Available hydrocarbon conversion catalyst in normal paraffin waxy feeds conversion formation isoparaffin base oil disclosed herein is a zeolite catalyst, as ZSM-5, and ZSM-11, ZSM-23, ZSM-35, ZSM-12, ZSM-38, ZSM-48, offretite, ferrierite, zeolite beta, zeolite θ, with zeolite α, as United States Patent (USP) 4,906,350 is disclosed.This class catalyzer and the metallic combination of VIII family are used, particularly palladium or platinum.As described in VIII family metal can be introduced into as ion-exchange by routine techniques in the zeolite catalyst.

In one embodiment, the conversion of waxy feeds can carried out under the combination of Pt/ zeolite beta and Pt/ZSM-23 catalyzer with in the presence of the hydrogen.In another embodiment, the technology of preparation lube basestocks is included in hydroisomerization and the dewaxing under the single catalyst, described catalyzer such as Pt/ZSM-35.In another embodiment, waxy feeds can be fed at the ZSM-48 of the metallic Z SM-48 that contains supported V III family, preferred load VIII class precious metal, more preferably in the catalyst for hydrogenation de-waxing catalysis of Pt/ZSM-48 with a step or two steps.In any case, all can obtain the available hydrocarbon base oil products.United States Patent (USP) 5,075 has been described catalyzer ZSM-48 in 269.Preferably, in the hydroisomerization of waxy feeds the ZSM-48 catalyzer of working load VIII family metal, preferably the platinum on ZSM-48 has been eliminated the demand to any follow-up independent dewaxing step.

If need, the dewaxing step can be followed one or more that make solvent dewaxing, catalytic dewaxing or Hydrodewaxing technology, can make the dewaxing of all hydroisomerization bodies or 650-750+fraction, this depends on the desired use of existing 650-750-material, if it was not separated from described higher material before described dewaxing.In solvent dewaxing, the hydroisomerization body can contact with chilled solvent, as acetone, methyl ethyl ketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK), the MEK/MIBK mixture, or the MEK/ toluene mixture or the like, and further freezing to be settled out described higher pour point material as content of wax solid, be to separate the raffinate it from described solvent-laden lubricating oil fraction then.Described raffinate further is chilled in the scraper plate cooler surface usually to remove more wax solid.Also can adopt the automatic freezing dewaxing of low molecular weight hydrocarbon such as propane, wherein said hydroisomerizing body with mix as liquid propane gas, its at least a portion is flashed with freezing described hydroisomerizing body to being settled out wax.By filtration, membrane sepn or centrifugal wax is separated from described raffinate.Gas proposes described solvent from described raffinate then, carries out classification afterwards with preparation available base of optimum selection material of the present invention.Also having well-known is catalytic dewaxing, and it makes described hydroisomerizing body and hydrogen reaction under suitable dewaxing catalyst under the condition of the pour point of the described hydroisomerizing body of effective reduction.Catalytic dewaxing also changes into the described hydroisomerizing body of a part than low-boiling point material, for example boiling range 650-750 °F-, its separated and described basestocks fraction from heavier 650-750+basestocks fraction is divided into two or more basestocks.Described separation than low-boiling point material can be before 650-750+material be classified into required basestocks or during carry out.

Can adopt any dewaxing catalyst of the pour point that can reduce the hydroisomerizing body, those of lube basestocks of high yield preferably can be provided by described hydroisomerizing body.Comprise shape-selective molecular sieve, when itself and at least a catalytic metal composition make up, can be used for making petroleum fractions to dewax, also comprise as ferrierite mordenite through demonstration, ZSM-5, ZSM-11, ZSM-23, it is SAPO ' s that ZSM-35, ZSM-22 are also referred to as zeolite θ or TON and aluminium silicophosphate molecular sieve.Find to possess unforeseeable especially effectively dewaxing catalyst and contained precious metal, preferred Pt, itself and H-mordenite are compound.Dewaxing can be finished by described catalyzer in fixed bed, fluidized-bed or slurry attitude bed.Typical dewaxing condition comprises the about 400-600 of temperature °F, pressure 500-900psig, H in the flow through reactors ₂Treatment rate 1500-3500SCF/B and LHSV are 0.1-10, preferred 0.2-2.0.Usually dewaxing with the initial boiling point that will be not more than 40wt%, preferably be not more than 30wt% is that 650-750 hydroisomerizing body changes into the material that boiling point is lower than its initial boiling point.

Derive basestocks and/or base oil of GTL basestocks and/or base oil, hydrodewaxed or hydroisomerization/catalysis (solvent) dewaxing wax possesses the II class that is better than conventional API and the useful kinematic viscosity of III class basestocks, therefore can be used for the present invention highly beneficially.This type of GTL basestocks and/or base oil possess obviously higher kinematic viscosity, in the time of 100 ℃ up to about 20-50mm ²/ s, and commercial in comparison II class base oil can have 100 ℃ the time up to about 15mm ²The kinematic viscosity of/s, commercial III class base oil are higher than about 10mm in the time of can having 100 ℃ ²The kinematic viscosity of/s.With respect to the more limited kinematic viscosity range of II class and III class basestocks and base oil, the higher motion range of viscosities of GTL basestocks and/or base oil is used for the present invention can provide additional favourable advantage in the formulated oil Composition Aspects.

Among the present invention, the Hydrodewaxing body, or the mixture of the mixture of mixture, GTL basestocks and/or the base oil of hydroisomerizing body/catalysis (solvent) dewaxing body basestocks and/or base oil or its mixture, preferred GTL basestocks and/or base oil, can constitute all or part of base oil.

Preferably coming from the basestocks of GTL material and/or waxy feeds and/or base oil is characterized by and mainly contain the paraffin composition and feature also is high saturates level, be low to moderate zero sulphur, be low to moderate zero nitrogen, be low to moderate zero aromatic substances, and its color be water white substantially.

Preferred GTL liquid hydrocarbon composition is a kind of composition that contains the paraffinic hydrocarbons composition, its degree of branching that records by the percentage of methyl hydrogen (BI) and the branching degree of approximation (CH that records by the percentage that repeats mesomethylene carbon (its four or more carbon) for removing from end group or side chain ₂〉=4) as follows: (a) BI-0.5 (CH ₂〉=4)＞15; (b) BI+0.85 (CH ₂〉=4) be that integral body records＜45, with described liquid hydrocarbon composition.

Preferred GTL basestocks and/or base oil further possess following feature, if necessary, and less than the aromatic substances of 0.1wt%, less than the nitrogenous compound of 20wppm, less than the sulfocompound of 20wppm, pour point is lower than-18 ℃, preferably be lower than-30 ℃, preferred BI 〉=25.4 and (CH ₂〉=4)≤22.5.Their nominal boiling point is 370 ℃ ⁺, average per 100 carbon atoms in respect of on average be less than 10 hexyls or more long-chain branch and average per 100 carbon atoms in respect of more than 16 methyl branches.They also possess being combined as of feature such as dynamic viscosity (recording by CCS under 40 ℃) and kinematic viscosity (100 ℃ of performance values that obtained by formula): DV (under 40 ℃)＜2900 (KV under 100 ℃)-7000.

Preferred GTL basestocks and/or base oil also possess the feature that contains the branched alkane mixture, it is characterized in that GTL lubrication base material and/or base oil contain the mixture of at least 90% branched alkane, and wherein said branched alkane is that carbon chain lengths is about C ₂₀-C ₄₀, molecular weight is that about 280-562, boiling range are about 650-1050 alkane, wherein said branched alkane contains at the most that the free carbon index of 4 alkyl branches and wherein said branched alkane is at least about 3.

Hereinbefore, the described degree of branching (BI), the branching degree of approximation (CH ₂〉=4) and the mensuration of free carbon index (FCI) as follows:

The degree of branching

Adopt Bruker 360MHz AMX spectrograph to use CDCl ₃In 10% solution obtain the NMR spectrum of 359.88MHz 1H solution.TMS is interior chemical shift benchmark.CDCl ₃Solvent peak value occurs 7.28.All spectrum are to adopt 90 degree pulses (10.9 μ s) under the quantitative conditions, and pulse delay time, 30s (was the longest proton spin-lattice relaxation time (T ₁) at least five times) and 120 scanning obtain to guarantee good signal-to-noise.

According to following zone definitions H atomic type:

9.2-6.2ppm fragrant ring hydrogen;

6.2-4.0ppm the olefinic carbon atom on hydrogen;

4.0-2.1ppm aromatic ring α position on benzylic hydrogen;

2.1-1.4ppm alkane CH methyne hydrogen;

1.4-1.05ppm alkane CH ₂Methylene radical hydrogen;

1.05-0.5ppm alkane CH ₃Methyl hydrogen.

The degree of branching (BI) is according to the percentage calculation of non-benzylic methyl hydrogen in the 0.5-1.05ppm scope and total non-benzylic aliphatic series hydrogen in the 0.5-2.1ppm scope.

The branching degree of approximation(CH ₂〉=4)

Adopt Bruker 360MHz AMX spectrograph to adopt at CDCl ₃In 10% solution obtain 90.5MHz ³CMR monopulse and 135 undistorted polarization transfers strengthen (DEPT) NMR spectrum.TMS is interior chemical shift benchmark. ¹³CDCl in the C spectrum ₃Solvent three peaks occur at 77.23ppm.All monopulses spectrum is to adopt 45 degree pulses (6.3 μ s), pulse delay time 60s (to be the longest carbon nuclear spin lattice relaxation time (T under the quantitative conditions ₁) at least five times) to guarantee the complete relaxation of sample, adopt 200 scanning guaranteeing good signal-to-noise, and adopt the WALTZ-16 proton-decoupled to obtain.

Pass through 135DEPT ¹³C atomic type CH is differentiated in C NMR test ₃, CH ₂, and CH.At all ¹³In the C NMR spectrum at the main CH in ≈ 29.8ppm place ₂Response is because of equal value from end group or side chain (CH ₂＞4) remove four or more multiple multiple mesomethylene carbon cause.Mainly based on the mesomethylene carbon of removing at the methyl carbon or the methyl from side chain of side chain end ¹³C chemical potential in-migration is determined the side chain type.

Free carbon index (FCI).FCI represents with carbosilane unit and is to be positioned in the isomeric alkane apart from least 5 carbon atoms of end carbon with apart from the standard of the carbon number of 4 carbon of side chain.Described terminal methyl group or branched carbon meter are done " one ", and the carbon among the FCI is apart from the straight chain terminal methyl group or apart from the 5th or bigger carbon of side chain methane carbon.This type of carbon appears between the 29.9ppm-29.6ppm in carbon-13 spectrum.Their measurement is as follows:

A) calculate the average carbon number of molecule in the described sample, its by with enough accuracy at the lubricating oil material by simply with described sample oil molecule amount divided by 14 (CH ₂Molecular weight) and realize;

B) with total carbon-13 integral area (chart division or area index) divided by step a calculate average carbon number to obtain the integral area of each carbon in the sample;

C) area between the 29.9ppm-29.6ppm in the measure sample; With

D) divided by step b calculate each carbon integral area and obtain FCI.

Can using arbitrarily, Fourier transform NMR spectrograph carries out the branching measurement.Preferably, adopt spectrograph to carry out described measurement with 7.0T or bigger magnet.In any case after mass spectrum, UV or NMR (not having aromatics carbon) measured, spectrum width was limited at the saturated carbon zone, about 0-80ppm vs.TMS (tetramethylsilane).With the 15-25wt% solution of 45 degree pulse excitation deuterochloroforms, then be 0.8 second collection time.For non-homogeneous intensity data is minimized, postponed to break and the described proton-decoupled instrument of connection during described collection at 10 seconds before the excitation pulse.Total testing time is 11-80 minute.Carry out DEPT and APT sequence according to the document description that the deviation of turning down is arranged on Varian or the Bruker operational manual.

DEPT is meant that undistorted polarization transfer strengthens method.DEPT does not show quaternary carbon.DEPT 45 parts provide the signal of the carbon of all bonding protons.90 of DEPT show CH carbon.DEPT 135 shows CH and CH ₃Make progress and CH ₂180 degree out-phase (downwards).APT is meant that proton connects experiment.It makes all carbon be observed, if but CH and CH ₃Make progress, then quaternary carbon and CH ₂Downwards.Described sequence is useful, because each branched chain methyl should have corresponding C H and described methyl clearly to discern mutually by chemical shift and thing.Can determine the branching characteristic of each sample and suppose that in calculating entire sample is an isomeric alkane by C-13NMR.N-alkanes or cycloalkanes for the variable quantity that may exist in the oil samples are not revised.Adopt field ionization mass spectrum (FIMS) to measure cycloalkanes content.

The synthetic hydrocarbon of GTL basestocks and/or base oil, Hydrodewaxing or hydroisomerization/catalysis (solvent) dewaxing basestocks and/or base oil, for example hydroisomerization or the Hydrodewaxing content of wax has low or is zero sulphur and phosphorus content as F-T waxy hydrocarbon basestocks and/or base oil.For meeting restricted increasing environmental planning, OEM and oil formula Designers are tending towards producing sulfate ash, p and s content formulated oil less and less.This oil is called as low SAPS oil, will depend on the original sulphur of inherent own and phosphorus content is low or be the use of zero base oil.The adjustable additive of this oil during as base oil.Compare with the lubricating oil that adopts the oil allotment of conventional mineral oil basis, even additive that comprises in the described prescription or additive kind contain sulphur and/or phosphorus, the formulated oil that makes also will be lower or low SAPS oil.

Be used for the motor car engine low SAPS formulated oil of (comprising activation igniting and ignition), its sulphur content is 0.7wt% or still less, preferred 0.6wt% or still less, more preferably 0.5wt% or still less, 0.4wt% or still less most preferably, ash oontent is 1.2wt% or still less, preferred 0.8wt% or still less, more preferably 0.4wt% or still less, and phosphorus content is 0.18% or still less, preferred 0.1wt% or still less, more preferably 0.09wt% or still less, 0.08wt% or still less most preferably, in some cases, even preferred 0.05wt% or still less.

Hydrodewaxing body and/or hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil, or its mixture, preferred GTL basestocks and/or base oil can account for the 5-100 weight % of the total amount of described Hydrodewaxing body and/or hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil or its mixture, preferred GTL basestocks and/or base oil, preferred 40-100 weight %, more preferably 70-100 weight %, the amount that is adopted will be decided according to the requirement of final lubricating oil by the producer.

I class high viscosity mineral oil oil plant is made up of high viscosity alkyl lubricating oil, and refining and dewaxing also come from mineral sources through height for this lubricating oil, has＜90% saturates, and 100 ℃ kinematic viscosity (according to ASTM D445) generally is about 12mm ²/ s and Geng Gao, preferably about 18mm ²/ s and Geng Gao, more preferably from about 24mm ²/ s and Geng Gao, even preferably about 28mm ²/ s and Geng Gao.They generally have about 120mm ²/ s, preferred about 60mm ²/ s, 40mm more preferably from about ²/ s@100 ℃ high whole viscosity.The density that this class lubricating oil is 60 (according to ASTM D4052) generally is about 0.885-0.920g/cm ³, preferably about 0.890-0.915g/cm ³And 0.895-0.910g/cm more preferably from about ³The viscosity index of this/this class lubricating oil generally is about 90-100.The available pour point of this/this class lubricating oil (according to ASTM D97) is about 0 ℃ or lower, and preferred-3 ℃ or lower, more preferably-6 ℃ or lower.Preferred oil is bright stock.

Because its higher viscosity, this class high viscosity I class mineral oil, particularly bright stock, be particularly useful for than low viscosity basestocks/base oil combination, because described mixing oil can obtain higher useful viscosity.The viscosity of this mixed lubrication oil compositions will be useful especially for the mechanical system of lubricated high-temperature service.Therefore the invention provides in the unique advantage of improving aspect the higher available lubricating oil composition viscosity two of lubricating oil composition dissolving power and acquisition.

The combination of one or more Hydrodewaxing bodies and/or hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil or its mixture, preferred GTL basestocks and/or base oil and described high viscosity I class mineral oil can be produced the base oil that possesses following feature, and 100 ℃ kinematic viscosity is 6mm ²/ s or higher, preferred 7mm ²/ s or higher, more preferably 8mm ²/ s or higher, most preferably 9mm ²/ s or higher and good/improved dissolving power.

High viscosity I class mineral oil is added into described one or more Hydrodewaxing bodies and/or hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil or its mixture, in preferred GTL basestocks and/or the base oil, based on containing one or more Hydrodewaxing bodies and/or hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil or its mixture, there are about 1-55% in the basestocks of preferred GTL basestocks and/or base oil and the mixture total weight amount of described high viscosity I class mineral oil, the high viscosity I class mineral oil of preferred about 5-55%, the high viscosity I class mineral oil of 10-55% more preferably from about, even the high viscosity I class mineral oil of 20-55% more preferably from about.

More than Ding Yi basestocks and/or base oil mixture can mix with conventional basestocks, I class as American Petroleum Institute's definition, the II class, the III class, IV class and/or V class basestocks, this mixture constitutes the main body of any described combination, promptly account for any described base oil combination greater than 50wt%, be preferably greater than 60wt%, more preferably greater than 75wt%.In addition, the mixture of one or more Hydrodewaxing bodies and/or hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil or its mixture, preferred GTL basestocks and/or base oil and high viscosity I class base oil can mix with one or more suitable additives of significant quantity to form lubricating oil composition.

Typical example additives includes, but not limited to oxidation retarder, antioxidant, dispersion agent, purification agent, corrosion inhibitor, rust-preventive agent, metal passivator, anti-wear agent, extreme-pressure additive, anti-adhesive agent, pour point reducer, wax modifiers, viscosity index improver, viscosity modifier, viscosity index improver, fluid loss agent, seal compatibility additive, friction modifiers, lubricant, stainproofing agent, developer, defoamer, emulsion splitter, emulsifying agent, viscosifying agent, wetting agent, jelling agent, tackiness additive, tinting material and other.About the summary of many typical additives, can be with reference to Klamann in Lubricants and Related Products, VerlagChemie, Deerfield Beach, FL; ISBN 0-89573-177-0.Also can be with reference to by NoyesData Corporation of Parkridge, " the Lubricant Additives " of the M.W.Ranney book that NJ (1973) publishes.

Final lubricating oil contains described lube basestocks or base oil, adds at least a performance additive.

The kind and the consumption of the performance additive that is used in combination with lubricating oil composition of the present invention will not be subjected to the restriction of embodiment described herein.

Anti-wear agent and EP additive

Many lubricating oil need add anti-wear agent and/or extreme pressure (EP) additive so that enough wear-resistant protections to be provided.Increasing regulation about for example engine oil performance has shown the trend to the improvement antiwear characteristics of described oil.Anti-wear agent and extreme pressure (EP) additive plays a role by the friction and wear that reduces metal parts.

Although many dissimilar anti-wear agents are arranged, the main wear agent that is used for crank case of internal combustion engine oil recent decades is an alkylthio phosphate metal salt, dialkyl dithiophosphoric acid metal-salt particularly, wherein main metal ingredient is a zinc, or zinc dialkyl dithiophosphate (ZDDP).The general formula of ZDDP compound is generally Zn[SP (S) (OR ¹) (OR ²)] ₂, R wherein ¹And R ²Be C ₁-C ₁₈Alkyl, preferred C ₂-C ₁₂Alkyl.These alkyl can be straight chain or branching.The consumption of general ZDDP is about 0.4-1.4wt% of total lubricating oil composition, but also can advantageously use higher or lower amount usually.

But, it is found that the phosphorus in these additives has disadvantageous effect to oxygen sensor in the automobile and the catalyzer in the catalytic converter.Making this influence minimized a kind of mode is to use the not alternative part or all of ZDDP of phosphorated anti-wear agent.

Multiple non-phosphorus additive also can be used as anti-wear agent.Olefine sulfide just can be used as anti-wear agent and extreme-pressure additive.Sulfur-bearing alkene can comprise that the aliphatics, aromatic yl aliphat, the alicyclic olefin that contain 3-30 the carbon atom of having an appointment, preferred 3-20 carbon atom make by vulcanizing multiple organic materials.Olefin(e) compound contains the two keys of at least one non-aromatics.The general formula of this compound is

R ³R ⁴C＝CR ⁵R ⁶

R wherein ³-R ⁶In each be hydrogen or alkyl independently.Preferred alkyl is an alkyl or alkenyl.R ³-R ⁶In any two can be connected to form ring.Other information about olefine sulfide and preparation thereof can be quoted it herein in full with reference to United States Patent (USP) 4,941,984.

In United States Patent (USP) 2,443,264; 2,471,115; 2,526,497; With 2,591, disclose in 577 and adopted the polysulfide of thiophosphoric acid and thiophosphatephosphorothioate as lubricating oil additive.United States Patent (USP) 3,770,854 disclose interpolation phosphorothioate disulphide as anti-wear agent, antioxidant, and extreme-pressure additive.United States Patent (USP) 4; 501; 678 disclose in lubricating oil and to adopt alkylthio carbamino compound (for example, two (dibutyl) thiocarbamoyl) and molybdenum compound (for example: di-isopropyl-phosphorodithioic acid sulfuration oxygen molybdenum) and phosphorus ester (for example: phosphorous acid dibutyl ester) make up as anti-wear agent.United States Patent (USP) 4,758,362 disclose the employing carbamate additives so that improved resistance to abrasion or extreme pressure property to be provided.United States Patent (USP) 5,693,598 disclose the employing thiocarbamate as anti-wear agent.Thiocarbamate/molybdenum mixture such as molybdenum-sulfane base dithiocarbamate trimer compositions (R=C ₈-C ₁₈Alkyl) also is the available anti-wear agent.If wish the low SAP formulated oil of preparation, then adopt or add this type of material and should keep minimum.

The glycerols ester also can be used as anti-wear agent.For example also can adopt single-, two-and trioleate, monopalmitate and single myristate.

ZDDP and other provide the composition combination of antiwear characteristics.United States Patent (USP) 5,034,141 disclose sulfo-O,O-diethyl dithiobis compound (for example: the octylsulfo O,O-diethyl dithiobis) and the thiophosphoric acid metal-salt (for example: combination ZDDP) can improve antiwear characteristics.United States Patent (USP) 5,034,142 disclose employing alkoxyalkyl yellow acid metal-salt (for example: ethoxyethyl group yellow acid nickel) and O,O-diethyl dithiobis (for example: diethoxy ethyl O,O-diethyl dithiobis) make up and improve antiwear characteristics with ZDDP.

Preferred anti-wear agent comprises p and s compound such as zinc dithiophosphate and/or sulphur, nitrogen, boron, molybdenum dithiophosphate, molybdenum dithiocarbamate and multiple organo-metallic-molybdenum derivatives, it comprises heterogeneous ring compound, for example dimercaptothiodiazole, sulfydryl diazosulfide, triazine etc., also can adopt alicyclic, amine, alcohol, ester, dibasic alcohol, trivalent alcohol, fatty amide etc.The consumption of examples of such additives can be about 0.01-6wt%, preferably about 0.01-4wt%.The compound of similar ZDDP provides limited hydroperoxide decomposition ability, it is shown with disclosed compound significantly to be lower than this patent requirement, and can from prescription, remove, perhaps residual as if having, be maintained at Cmin to help to produce low SAP formulated oil.

Viscosity index improver

Viscosity index improver (being also referred to as the VI improving agent, viscosity modifier, and viscosity modifier) provides the lubricating oil with high temperature and cold operation.This class additive has been given shear stability under the temperature that raises and the acceptable viscosity under the low temperature.

Suitable viscosity index improver comprises high-molecular-weight hydrocarbons, polyester and serve as the viscosity index improver type dispersion agent of viscosity index improver and dispersion agent simultaneously.The typical molecular weight of these polymkeric substance is about 10,000-1,000,000, more be typically about 20,000-500,000, also more be typically about 50,000-200,000.

The example of suitable viscosity index improver is the polymkeric substance and the multipolymer of methacrylic ester, divinyl, alkene or alkylated styrenes.Polyisobutene is a kind of viscosity index improver commonly used.Another kind of suitable viscosity index improver is that (for example: the multipolymer of the alkylmethacrylate of multiple chain length), wherein some prescription also can be made pour point reducer to polymethacrylate.Other suitable viscosity index improvers comprise the multipolymer of ethene and propylene, the hydrogenation segmented copolymer of vinylbenzene and isoprene, and polyacrylic ester is (for example: the multipolymer of the acrylate of multiple chain length).Specific examples comprises that molecular weight is 50,000-200,000 styrene-isoprene or styrene butadiene based polyalcohol.

The consumption of viscosity index improver can be about 0.01-8wt%, is preferably about 0.01-4wt%.

Antioxidant

Antioxidant can stop base oil oxidative degradation in use.This degraded can cause settling on the metallic surface, greasy filth occurs or lubricating oil viscosity increases.Those skilled in the art know a variety of oxidation retarder that can be used for lubricating oil composition.Reference example such as Klamann inLubricants and Related Products, book of quoting previously and United States Patent (USP) 4,798,684 and 5,084,197, above document are incorporated this paper in full by reference into.

The available antioxidant comprises hindered phenol.This class phenolic antioxidant is the neutrality or the alkaline metal salt of ashless (no metal) phenolic compound or some phenolic compound.Typical phenolic antioxidant compound is the hindered phenol that contains three-dimensional blocked hydroxyl group, and these also comprise wherein said hydroxyl those derivatives of the dihydroxyl aryl compound of ortho position or contraposition each other mutually.Typical phenolic antioxidant comprises the hindered phenol of C6+ alkyl replacement and the alkylidene group coupled derivative of this type of hindered phenol.The example of this class phenol material is the 2-tertiary butyl-4-heptyl phenol; The 2-tertiary butyl-4-octyl phenol; The 2-tertiary butyl-4-4-dodecylphenol; 2,6-di-t-butyl-4-heptyl phenol; 2,6-di-t-butyl-4-4-dodecylphenol; 2-methyl-6-tert butyl-4-heptyl phenol; With 2-methyl-6-tert butyl-4-4-dodecylphenol.Other available hindered mono-phenolic antioxidants can comprise for example is obstructed 2,6-dialkyl group-phenol type propanoate ester derivatives.Bisphenol antioxidant can be advantageously used in the present invention and make up.The example of ortho position link coupled phenol comprises: 2,2 '-two (the 4-heptyl-6-tertiary butyl-phenol); 2,2 '-two (the 4-octyl groups-6-tertiary butyl-phenol); With 2.2 '-two (the 4-dodecyls-6-tertiary butyl-phenol).Contraposition link coupled diphenol for example comprises 4,4 '-two (2, the 6-di-tert-butylphenol) and 4,4 '-methylene radical-two (2, the 6-di-tert-butylphenol).

The non-phenols oxidation retarder of available comprises the aromatic amine antioxidant, but their former states are used or are used in combination with phenols.The representative instance of non-phenol antioxidant comprises: alkylation and non-alkylating aromatic amine for example general formula are R ⁸R ⁹R ¹⁰The aromatic monoamine of N, wherein R ⁸Be the aromatic group of aliphatics, aromatics or replacement, R ⁹Be the aromatic group of aromatics or replacement, R ¹⁰Be H, alkyl, aryl or R ¹¹S (O) _xR ¹², R wherein ¹¹Be alkylidene group, alkenylene or inferior aralkyl, R ¹²Be senior alkyl or thiazolinyl, aryl or alkaryl, x is 0,1 or 2.Aliphatic group R ⁸Can contain about 20 carbon atoms of 1-, preferably contain 6-12 the carbon atom of having an appointment.Described aliphatic group is saturated aliphatic group.Preferably, R ⁸And R ⁹All be the aromatic group of aromatics or replacement, described aromatic group can be condensed ring aromatic group such as naphthyl.Aromatic group R ⁸And R ⁹Can link together with other groups such as S.

The aromatic amine antioxidant generally has the alkyl substituent at least about 6 carbon atoms.The example of aliphatic group comprises hexyl, heptyl, octyl group, nonyl and decyl.Normally, aliphatic group does not contain and surpasses 14 carbon atom.The general type of available amine antioxidant comprises diphenylamine, phenyl napthyl amine, phenothiazines, imines dibenzyl base class (imidodibenzyl), biphenyl phenylenediamine in the present composition.Also can adopt the mixture of two or more aromatic amines.Also can adopt the polyamine antioxidant.The special case of available aromatic amine antioxidant comprises among the present invention: p, p '-dioctyl diphenylamine; Uncle-octyl phenyl-alpha-naphthylamine; Phenyl-a-naphthylamine; With right-octyl phenyl-alpha-naphthylamine.

Sulfenyl phenolate and basic metal or alkaline earth salt also are the available antioxidants.

The another kind of antioxidant that can be used for lubricating oil composition is an oil-soluble copper compounds.Any suitable oil-soluble copper compounds can be sneaked in the lubricating oil.Suitable copper antioxidant example comprises dialkyl sulfo-or phosphorodithioic acid copper and carboxylic acid mantoquita (natural existence or synthetic).Other suitable mantoquitas comprise copper dithiocarbamate(s), Sulfonates, phenates class and methyl ethyl diketone salt.Known alkalescence, neutrality or acid monovalence and/or the cupric salt that comes from alkenyl succinic acid or acid anhydrides is especially effective.

Preferred anti-oxidants comprises hindered phenol, arylamines.This class antioxidant can use separately or be used in combination mutually by class.The consumption of this additive can be about 0.01-5wt%, preferably about 0.01-1.5wt%, and more preferably 0-is less than 1.5wt%, and most preferably zero.

Purification agent

Purification agent is usually used in the lubricating composition.Typical purification agent is long-chain hydrophobic part and the less negatively charged ion of described molecule or the anionic material of oleophobic hydrophilic parts that contains described molecule.The anionicsite of purification agent comes from organic acid such as sulfur acid, carboxylic acid, phosphoric acid, phenol or its mixture usually.Counter ion are alkaline earth or basic metal normally.

The salt that contains the described metal of remarkable stoichiometry is described to neutral salt, and has the total basicnumber (TBN records by ASTM D2896) of 0-80.Many compositions are peralkaline, contain a large amount of metal base, and wherein said metal base is to be got with sour gas (as carbonic acid gas) reaction by excessive metallic compound (for example metal hydroxides or oxide compound).The available purification agent can be a neutral, gentle peralkaline or highly peralkaline.

At least a portion purification agent is peralkaline ideally.During overbased detergent helps and the acidic impurities that produces in the burning process and carried secretly by described oil.Usually, described super-alkaline substance has the ratio of counting metal ion and anionicsite in about 1.05: 1～50: 1 purification agent with equivalent.More preferably this ratio is about 4: 1～25: 1.The purification agent that makes is a kind of overbased detergent, and its TBN is generally about 150 or higher, common about 250 to 450 or higher.Preferably, described parlkaline positively charged ion is sodium, calcium or magnesium.The present invention can adopt the mixture of the purification agent with TBN.

Preferred purification agent comprises the basic metal or the alkaline earth salt of sulfonic acid class, phenols, carboxylic-acid, phosphoric acid class and salicylic acid.

The sulfonic acid that sulfonate can make by the sulfonation of the aromatic hydrocarbons that generally replaced by alkyl prepares.The example of hydrocarbon comprises the hydrocarbon that those are made by alkylation benzene,toluene,xylene, naphthalene, biphenyl and their halide derivative (for example: chlorobenzene, toluene(mono)chloride and chloronaphthalene).Alkylating reagent has about 3-70 carbon atom usually.Alkylaryl sulfonate contains usually has an appointment 9 to 80 or more carbon atom, more generally is about 16 to 60 carbon atoms.

Disclose many overbased metal salts of multiple sulfonic acid among the book Klamann in Lubricants and Related Products that quotes previously, it can be used as the purification agent and the dispersion agent of lubricating oil.By Cleveland, in the book of that the Lezius-Hiles Co. (1967) of Ohio publishes, that C.V.Smallheer and R.K.Smith showed " Lubricant Additives " by name many overbased sulfonates that can be used as purification agent/dispersion agent are disclosed similarly.

The alkaline-earth metal phenates is another kind of available purification agent.This class purification agent can be by the oxyhydroxide of alkaline-earth metal or oxide compound (for example: CaO, Ca (OH) ₂, BaO, Ba (OH) ₂, MgO, Mg (OH) ₂) make with alkylphenol or sulfenyl phenolate reaction.The available alkyl comprises straight chain or branching C ₁-C ₃₀Alkyl, preferred C ₄-C ₂₀The example of suitable phenols comprises isobutyl-phenol, 2-ethylhexyl phenol, nonylphenol, dodecyl phenol etc.It should be noted that initial alkylphenol can contain the alkyl substituent for straight chain or branching independently of one another more than 1.When adopting the unvulcanised alkylphenol, can prepare vulcanizate by method well known in the art.These class methods comprise the mixture of heating alkylphenol and vulcanizing agent (comprising element sulphur, sulfur halide such as sulfur dichloride etc.), then with described phenol red and alkaline-earth metal alkali reaction.

Carboxylic metallic salt also is the available purification agent.This class carboxylic acid purification agent can and be removed free water and makes by alkaline metal cpds and at least a carboxylic acid reaction from reaction product.This compounds can be crossed alkalization to obtain required TBN level.The purification agent that is made by Whitfield's ointment is the purification agent that a class preferably comes from carboxylic acid.The available salicylate comprises the chain alkyl salicylate.One class available composition has general formula

Wherein R is hydrogen atom or the alkyl with about 30 carbon atoms of 1-, and n is the integer of 1-4, and M is an alkaline-earth metal.Preferred R group is C at least ₁₁, preferred C ₁₃Or bigger alkyl chain.The substituting group that R can randomly not influenced the purification agent function replaces.The preferred calcium of M, magnesium or barium.More preferably M is a calcium.

The Whitfield's ointment that alkyl replaces can be made by the Kolbe reaction by phenols.About this compounds synthetic Additional Information, referring to United States Patent (USP) 3,595,791, it incorporates this paper in full by reference into.The salicylic metal-salt that alkyl replaces can by metal-salt in polar solvent such as water or ethanol metathesis and make.

The phosphoric acid alkaline earth salt also can be used as purification agent.

Purification agent can be simple purification agent or known mixing or compound purification agent.Back one class purification agent can provide the performance of two kinds of purification agents and need not the multiple material that blend separates.Referring to for example United States Patent (USP) 6,034,039.

Preferred purification agent comprises phenol calcium class, calcium sulphonate class, calcium salicylate class, phenol magnesium class, sulfonic acid magnesium class, the relevant composition with other of magnesium salicylate class (comprising the boronation purification agent).Usually, the purification agent total concn is about 0.01-6.0wt%, preferably about 0.1-0.4wt%.

Dispersion agent

In running of an engine, can produce non-oil soluble oxidized byproduct.Dispersion agent then can help to keep this class by product to be dissolved form, thereby reduces their depositions in the metallic surface.Dispersion agent can be ashless or become ash naturally.Preferably, dispersion agent is ashless.So-called ashless dispersant does not form the organic substance of ash content in fact when being meant burning.For example, containing metal or boronation do not have metal dispersion and are considered to ashless.On the contrary, containing metal dispersion agent discussed above then forms ash content when burning.

Suitable dispersion agent generally contains the polar group that is connected to relative high molecular hydrocarbon chain.Described polar group contains at least a element of nitrogen, oxygen or phosphorus usually.Typical hydrocarbon chain contains 50-400 carbon atom.

Chemically, many dispersion agents can with phenates, sulfonate, sulfuration phenates, salicylate, naphthenate, stearate, carbaminate, thiocarbamate, phosphorus derivant be feature.Especially a useful class dispersion agent is the alkenyl succinic acid derivative, and it is generally by long-chain substituted alkenyl succinic acid compound, normally the reaction of substituted succinyl oxide and poly-hydroxy or polyamines based compound makes.The long chain alkyl group that constitutes the oleophilic moiety be provided at the deliquescent described molecule in the oil is polyisobutenyl normally.Many examples of this class dispersion agent all are known in the commercial and document.The United States Patent (USP) of for example having described this class dispersion agent is 3,172,892; 3,2145,707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012; 3,630,904; 3,632,511; 3,787,374 and 4,234,435.The dispersion agent of other types is in United States Patent (USP) 3,036,003; 3,200,107; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574; 3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; State in 5,705,458.In the european patent application of application number 471071, can find more descriptions, therefore as a reference about dispersion agent.Above-mentioned full patent texts is incorporated this paper by reference into.

It is the polarity dispersion agent that alkyl replaces succinic acid compound.Especially, succinimide, succinate or the succinate amide compound that is made by the alkyl replacement succinic acid compound that preferably has at least 50 carbon atoms in described hydrocarbon substituent and at least one normal alkylene amines reaction is particularly advantageous.

Succinimide is formed by the condensation reaction of alkenyl succinic anhydride and amine.Molar ratio can change according to described polyamine.For example, the mol ratio of alkenyl succinic anhydride and TEPA can be about 1: 1～about 5: 1.Representative example is in United States Patent (USP) 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; With 3,652,616; 3,948,800 and Canadian Patent 1,094,044 on have openly, above-mentioned full patent texts is incorporated this paper by reference into.

Succinate is formed by the condensation reaction of alkenyl succinic anhydride and alcohol or polyvalent alcohol.Molar ratio can change according to used alcohol or polyvalent alcohol.For example, the condensation product of alkenyl succinic anhydride and tetramethylolmethane is a kind of available dispersion agent.

The succinate acid amides is formed by the condensation reaction of alkenyl succinic anhydride and hydramine.For example, the hydramine of Shi Heing comprises that ethoxylation gathers alkyl polyamine, the poly-alkyl polyamine of propoxylation and polyalkenyl polyamine such as polyethylenepolyamine.An example is the propoxylation hexanediamine.Representative example is at United States Patent (USP) 4,426, discloses in 305, and it incorporates this paper by reference into.

The molecular weight of above used alkenyl succinic anhydride is generally between 800-2500.Above goods can carry out afterreaction with multiple reaction reagent such as sulphur, oxygen, formaldehyde, carboxylic acid such as oleic acid and boron compound such as boric acid ester or height boronation dispersion agent.Described dispersion agent can be by the boronation in every mole of dispersant reaction product about 0.1-5 mole boron.

The Mannich base dispersion agent is made by alkylphenol, formaldehyde and amine reaction.With reference to United States Patent (USP) 4,767,551, it incorporates this paper by reference into.Processing material and catalyzer, as oleic acid and sulfonic acid also as described in the part of reaction mixture.The molecular weight of alkylphenol is 800-2500.Typical example is in United States Patent (USP) 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; With 3,803, open in 039, incorporate this paper in full by reference at this.

The hydroxy aromatic compound that the Mannich condensation product of available typical polymer amount aliphatic acid modification can replace by high molecular weight alkyl among the present invention or contain HN (R) ₂The reactant of group makes.

The example of the hydroxy aromatic compound that high molecular weight alkyl replaces is poly-propyl phenoxy, poly-butylphenol and other poly-alkylphenols.This alkylphenol of birdsing of the same feather flock together can pass through at alkylation catalyst such as BF ₃Existence under with high molecular weight polypropylene, polybutene and other polyolefin compounds with the phenol alkylation to be 600-100 at molecular-weight average, provide alkyl substituent on the phenyl ring of 000 phenol and obtain.

Contain HN (R) ₂The example of the reactant of group is the alkene polyamine, mainly is polyethylenepolyamine.What other representational was suitable for the preparation of Mannich condensation product contains at least one HN (R) ₂The organic compound of group is known, and comprises single-and two-amido alkane and their replacement analogue, for example ethamine and diethanolamine; Aromatic diamine is phenylenediamine, diaminonaphthalene for example; Heterocyclic amine, for example morpholine, pyrroles, tetramethyleneimine, imidazoles, imidazolidine and piperidines; Trimeric cyanamide and their replacement analogue.

The example of alkene polyamine reactants comprises the mixture of quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren, penten, six ethylidene, seven amine, seven ethylidene, eight amine, eight ethylidene, nine amine, nine ethylidene, ten amine and ten ethylidene undecylamines and this class amine, have the mixture corresponding to the described amine of the nitrogen content of alkene polyamine, its formula is foregoing H ₂N-(Z-NH-) _nH, the Z in the preceding formula are that divalence ethylidene and n are 1-10.Corresponding propylene polyamine such as propylene diamine and two-, three-, four-, five propylidene three-, four-, five-and hexamine also be the reactant that suits.The alkene polyamine usually can be by ammonia and saturated dihalide, reaction obtains as dichloro-alkane.Therefore the alkene polyamine of reaction acquisition that has 2-6 carbon atom by 2-11 moles of ammonia and 1-10 mole and be positioned at the dichloro-alkane of the chlorine on the different carbon is the alkene polyamine reactants that suits.

The aldehyde reaction thing that is used to prepare available high molecular products of the present invention comprises fatty aldehyde such as formaldehyde (being also referred to as Paraformaldehyde 96 and formalin), acetaldehyde and alcohol aldehyde (acetaldol).The reactant of preferred formaldehyde or generation formaldehyde.

It is well known to a person skilled in the art that alkyl replaces amine ashless dispersant additive, referring to, for example United States Patent (USP) 3,275, and 554; 3,438,757; 3,565,804; 3,755,433; 3,822,209 and 5,084,197, above-mentioned document is incorporated this paper in full by reference at this.

Preferred dispersing agent comprises boronation and non-boronation succinimide, it comprises that wherein said hydrocarbyl succinic imide is derived from the polyisobutene of alkylene such as the about 500-5000 of Mn or the mixture of this type of alkylene from single succinimide, double amber imide and/or single-and those derivatives of the mixture of two-succinimide.Other preferred dispersing agent comprise succinate class and succinamides, alkylphenol polyamine coupling Mannich adducts, the relevant composition with other of their capped derivatives.The consumption of this class additive can be about 0.1-20wt%, preferred 0.1-8wt%.

Pour point reducer

Can in composition of the present invention, add conventional pour point reducer (being also referred to as the mobile improving agent of lubricating oil) if desired.This class pour point reducer can add in the lubricating oil composition of the present invention to reduce that fluid will flow or minimum temperature can be toppled over the time.Suitable pour point reducer example comprises the ter-polymers of condensation product, vinyl carboxylic acid polymkeric substance and dialkyl group fumarate, fatty acid vinyl ester and the allyl vinyl ether of polymethacrylate, polyacrylic ester, polyacrylamide, haloalkane chloroflo and aromatic substance.United States Patent (USP) 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655,479; 2,666,746; 2,721,877; 2.721,878; With 3,250, available pour point reducer and/or its preparation method have been described in 715, above-mentioned document is incorporated this paper in full by reference at this.The consumption of this additive is about 0.01-5wt%, preferred 0.01-1.5wt%.

Corrosion inhibitor

Corrosion inhibitor can be used to reduce the corrosion of the metal part that contacts with lubricating oil composition.Suitable corrosion inhibitor comprises thiadiazole.Referring to, for example United States Patent (USP) 2,719, and 125; 2,719,126; With 3,087,932, be incorporated herein by reference in full at this.The consumption of this additive can be about 0.01-5wt%, is preferably about 0.01-1.5wt%.

The seal compatibility additive

The seal compatibility additive can be helped the elastic sealing element that expands by causing fluidic chemical reaction and elastomeric physical change.Suitable lubricating oil comprises organophosphate (ester), aromatic ester, aromatic hydrocarbon, ester class (for example, butyl benzyl phthalic ester) and polybutene succinyl oxide with the seal compatibility additive.The consumption of this additive can be about 0.01-3wt%, is preferably about 0.01-2wt%.

Defoamer

Defoamer can advantageously be added in the lubricating oil composition.This class additive can prevent the formation of stable foam.Silicone resin and organic polymer all are typical defoamers.For example, polysiloxane such as silicone oil or polydimethylsiloxane can provide the froth breaking characteristic.Defoamer is that commerce can get, and can be conventional use with other additives such as emulsion splitter on a small quantity; The consumption of this class additive of combination is usually less than 1%, often less than 0.1%.

Inhibitor and rust-preventive agent

Rust-preventive agent (or corrosion inhibitor) is the additive that the chemical erosion of water or other pollutents is avoided in the lubricated metallic surface of protection.Many these class additives are that commerce can get; They have at Klamann in Lubricants and Related Products (book of quoting previously) and relate to.

One class rust-preventive agent is selective wetting metallic surface and the polar compound of protecting it with oil film.Another kind of rust-preventive agent absorbs moisture by being introduced into water-in-oil emulsion, has only the described metallic surface of described oil contact like this.Another kind of rust-preventive agent adheres on the metal to form non-reacted surface by chemical mode.The example of suitable additive comprises zinc dithiophosphate, metal phenates, basic metal sulfonate, lipid acid and amine.The consumption of this additive can be about 0.01-5wt%, is preferably about 0.01-1.5wt%.

Friction improver

Friction improver is any material that can change by the frictional coefficient on the surface of any lubricating oil that contains this material or hydrodynamic lubrication.Friction improver, be also referred to as the friction depressant, or lubricating quality agent or oiliness improver, with this additive of other performances that can change base oil, formulated oil composition or functional fluid with the frictional coefficient that improves lubricated surface, if desired, can be used in combination with base oil of the present invention and lubricating oil composition effectively.Can reduce friction improver particularly advantageous and the base oil of the present invention or the lubricating oil composition combination of frictional coefficient.Friction improver can comprise containing metal compound or material and ashless compound, or its mixture.Metallic friction improver can comprise metal-salt or metal ligand mixture, and wherein metal can comprise basic metal, alkaline earth or magnesium-yttrium-transition metal.This metallic friction improver also possesses low ash content characteristic.Transition metal can comprise Mo, Sb, Sn, Fe, Cu, Zn and other.Part comprises the polar molecule functional group of alkyl derivative and other O, N, S or P that contain significant quantity alone or in combination of polyalcohols, glycerols, partial ester glycerols, thio-alcohol, carboxylic acid esters, amino formate, thiocarbamates, dithiocarbamate, phosphoric acid ester, group thiophosphate, dithio acid esters, amides, acid imide, amine, thiazoles, thiadiazole, dithiazole class, diazoles, triazole species, alcohols.Especially it can be effective especially containing the Mo compound, as molybdenum dithiocarbamate, molybdenum (DTC), molybdenum dithiophosphate, molybdenum (DTP), molybdenum-amine, molybdenum (Am), molybdenum-alkoxide, molybdenum-alcohol-acid amides etc.Referring to United States Patent (USP) 5,824,627; United States Patent (USP) 6,232,276; United States Patent (USP) 6,153,564; United States Patent (USP) 6,143,701; United States Patent (USP) 6,110,878; United States Patent (USP) 5,837,657; United States Patent (USP) 6,010,987; United States Patent (USP) 5,906,968; United States Patent (USP) 6,734,150; United States Patent (USP) 6,730,638; United States Patent (USP) 6,689,725; United States Patent (USP) 6,569,820; WO 99/66013; WO 99/47629; WO98/26030.

Ashless friction improver also can comprise the lubricating substance that contains the significant quantity polar group, for example the alkyl base oil of hydroxyl, glyceryl ester, partial glyceride, glyceride derivative etc.Polar group in the friction improver comprises the alkyl of O, the N, S or the P that contain significant quantity alone or in combination.Other especially effectively friction improvers comprise the salt (containing ash content and ashless derivative) of the carboxylic acid esters of for example fatty acid, aliphatic alcohols, fatty acyl amide, fatty ester class, hydroxyl and comparable synthetic long chain hydrocarbon groups acids, alcohols, amides, ester class, hydroxycarboxylic acid esters class etc.Aliphatic organic acid, aliphatic amide and sulfide aliphatic acid also can be used as suitable friction improver in some cases.

The useful concentrations of friction improver can be about 0.01wt% to 10-15wt% or higher, and preferable range is about 0.1wt%-5wt% usually.The concentration of molybdenum-containing material matter is represented with molybdenum concentration usually.The favourable concentration range of molybdenum can be about 10ppm-3000ppm or higher, and preferable range is about 20-2000ppm usually, and preferred in some cases scope can be about 30-1000ppm.The friction improver of all kinds can use separately or mix use with material among the present invention.Usually the mixture of two or more friction improvers or friction improver and optional surfactant mixtures also are ideal.

Typical additive capacity

For the lubricating oil composition that contains one or more above-described additives, additive expects that to be enough to showing it amount of effect is mixed in the described composition.The typical amounts that can be used for the examples of such additives among the present invention is as shown in table 1 below.

Note that many additives come from the manufacturer shipping, and in prescription, used the base oil solvent of specified quantitative.Correspondingly, other mentioned dosage relate to the amount (for described composition do not contain the solvent part) of activeconstituents among the weight number in the following table and the present invention.Following wt% is based on the gross weight of described lubricating oil composition.

Table 1

The typical amounts of various lubricating oil families

Embodiment

With F-T wax isomer GTL class base oil, particularly 100 ℃ of kinematic viscosity is 4mm ²The GTL4 of/s with and PAO, particularly 100 ℃ of kinematic viscosity of above-mentioned mineral oil combination be 4mm ²The PAO4 of/s compares, with mineral derived base oil, particularly 100 ℃ of kinematic viscosity be 4-32mm ²The I class mineral oil combination of/s.Base oil characteristic such as table 2 are listed.

The combination (as shown in table 3) of wax isomer base oil, particularly GTL4 and mineral oil and the combination (as shown in table 4) of PAO, particularly PAO4 and mineral oil are compared.Picture GTL/SPN 100, GTL/SPN 600, and the binary combination of PAO/SPN 100 and PAO/SPN 600 is the same comes comparison GTL4/ bright stock (with 50: binary combination 50wt%) and PAO4/ bright stock are (with 50: binary combination 50wt%) by measuring separately aniline point.Other binary mixture SPN 100/SPN 600 and SPN 100/ bright stock are compared.Shown among table 3 and table 4 and Fig. 1 pure base oil with 50: the comparing result of 50wt% blended combination.(with 50: aniline point 50wt%) is than the GTL4/ bright stock mixture aniline point of expection lower (low 1.7 ℃ of aniline point) for the GTL4/ bright stock.More surprisingly, the aniline point of GTL4/ bright stock (with 50: 50 weight) is lower than the aniline point (low 0.5 ℃ of aniline point) that PAO4/ bright stock (with 50: 50 weight) records.This novelty and beat all result have proved that the GTL that makes up with bright stock is having significant improvement with respect to the PAO with the combination of same light gloss varnish aspect the dissolving power.

And, among the present invention the most beat all advantage as shown in Figure 1, the aniline point that wherein contains the wax isomer (GTL4) that reaches as high as about 55% bright stock concentration/bright stock combination is lower than the aniline point of independent wax isomer (GTL4) or is lower than independent bright stock aniline point.

Table 2

The base oil characteristic

Base oil	KV@100℃ (mm ²/s)	KV@40℃ (mm ²/s)	Aniline point (℃)	Viscosity index	Density (g/cm ³)	Pour point (℃)
Base oil	KV@100℃ (mm ²/s)	KV@40℃ (mm ²/s)	Aniline point (℃)	Viscosity index	Density (g/cm ³)	Pour point (℃)	GTL4 PAO4 SPN 100 (mineral oil) SPN 600 (mineral oil) bright stock	3.8 4.0 4.0 12.2 31.8	15.3 17.9 20.2 115.3 487.8	120.4 120.2 96.3 113.4 123.1	143 124 95 96 96	0.8133 0.8192 0.8649 0.8841 0.9017	≤-12 -54 -15 -12 ≤-6

Table 3

Wax isomer-mineral oil combination: aniline point performance

Table 4

PAO-mineral oil combination: aniline point performance

Claims

1. the method for the ability of the dissolving power of improving base oil and solubility property additive, this base oil contains one or more Hydrodewaxing bodies and/or hydroisomerizing body basestocks and base oil, hydroisomerizing body basestocks and base oil, GTL basestocks and base oil and its mixture, by add high viscosity I class mineral oil in described base oil, described base oil has 3mm ²/ s～about 50mm ²100 ℃ of kinematic viscosity of/s, described high viscosity I class mineral oil are characterised in that its 100 ℃ of kinematic viscosity are about 12mm ²/ s and Geng Gao, and the amount that is added into the high viscosity I class mineral oil in the described base oil is the about 1-55wt% high viscosity of the gross weight I class mineral oil based on the mixture of described one or more Hydrodewaxing body basestocks, hydroisomerizing body basestocks, GTL basestocks or its mixture and described high viscosity I class mineral oil.

2. the method for claim 1,100 ℃ of kinematic viscosity of wherein said high viscosity I class mineral oil are about 18mm ²/ s and Geng Gao.

3. the method for claim 1,100 ℃ of kinematic viscosity of wherein said high viscosity I class mineral oil are about 24mm ²/ s and Geng Gao.

4. the method for claim 1,100 ℃ of kinematic viscosity of wherein said high viscosity I class mineral oil are about 28mm ²/ s and Geng Gao.

5. as claim 1,2,3 or 4 described methods, 60 ℃ of density of wherein said high viscosity I class mineral oil are about 0.8885-0.920g/cm ³With VI be about 90-100.

6. as claim 1,2,3 or 4 described methods, wherein said high viscosity I class mineral oil is added in the described base oil that contains one or more Hydrodewaxing body basestocks and base oil, hydroisomerizing body basestocks and base oil, GTL basestocks and base oil or its mixture with the amount based on the high viscosity I class mineral oil of the about 5-55wt% of gross weight of described mixture.

7. as claim 1,2,3 or 4 described methods, wherein said high viscosity I class mineral oil is added in the described base oil that contains one or more Hydrodewaxing body basestocks and base oil, hydroisomerizing body basestocks and base oil, GTL basestocks and base oil or its mixture with the amount based on the high viscosity I class mineral oil of the about 10-55wt% of gross weight of described mixture.

8. method as claimed in claim 5, wherein said high viscosity I class mineral oil is added in the described base oil that contains one or more Hydrodewaxing body basestocks and base oil, hydroisomerizing body basestocks and base oil, GTL basestocks and base oil or its mixture with the amount based on the high viscosity I class mineral oil of the about 5-55wt% of gross weight of described mixture.

9. method as claimed in claim 5, wherein said high viscosity I class mineral oil is added in the described base oil that contains one or more Hydrodewaxing body basestocks and/or base oil, hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil or its mixture with the amount based on the high viscosity I class mineral oil of the about 10-55wt% of gross weight of described mixture.

10. as claim 1,2,3 or 4 described methods, 100 ℃ of kinematic viscosity of wherein said base oil are about 3.5mm ²/ s-30mm ²/ s.

11. method as claimed in claim 5,100 ℃ of kinematic viscosity of wherein said base oil are about 3.5mm ²/ s-30mm ²/ s.

12. method as claimed in claim 8,100 ℃ of kinematic viscosity of wherein said base oil are about 3.5mm ²/ s-30mm ²/ s.

13. as claim 1,2,3 or 4 described methods, wherein said base oil is GTL material Hydrodewaxing body or hydroisomerizing body.

14. as claim 1,2,3 or 4 described methods, wherein said base oil is fischer-tropsch material Hydrodewaxing body or hydroisomerizing body.

15. one kind has the lube stock that improves dissolving power, it comprises the base oil that contains one or more Hydrodewaxing body basestocks and/or base oil, hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil or its mixture and the high viscosity I class mineral oil of 1-55wt%, and described I class mineral oil is characterised in that its 100 ℃ of kinematic viscosity are about 12mm ²/ s and Geng Gao.

16. lube stock as claimed in claim 15,100 ℃ of kinematic viscosity of wherein said base oil are about 3.5mm ²/ s-30mm ²/ s.

17. the described lube stock of claim 15, wherein said base oil are GTL material Hydrodewaxing body or hydroisomerizing body.

18. the described lube stock of claim 15, wherein said base oil are fischer-tropsch material Hydrodewaxing body or hydroisomerizing body.

19. as claim 15,16,17 or 18 described lube stocks, 100 ℃ of kinematic viscosity of wherein said high viscosity I class mineral oil are about 18mm ²/ s and Geng Gao.

20. lube stock as claimed in claim 19,100 ℃ of kinematic viscosity of wherein said high viscosity I class mineral oil are about 24mm ²/ s and Geng Gao.

21. lube stock as claimed in claim 20,100 ℃ of kinematic viscosity of wherein said high viscosity I class mineral oil are about 28mm ²/ s and Geng Gao.

22. as claim 15,16,17 or 18 described lube stocks, 60 density of wherein said high viscosity I class mineral oil are about 0.885-0.920g/cm ³With VI be about 90-100.

23. a lubricating oil formulation, it comprises 100 ℃ of kinematic viscosity is 3mm ²/ s-50mm ²Base oil/the basestocks that contains one or more Hydrodewaxing body basestocks and/or base oil, hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil or its mixture of/s; 100 ℃ of kinematic viscosity are about 12mm ²The high viscosity I class mineral oil of/s and Geng Gao, the amount that described I class mineral oil exists are the 1-55wt% based on the gross weight of described one or more Hydrodewaxing body basestocks and/or base oil, hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil or its mixture and described high viscosity I class mineral oil; At least a performance additive with addition.

24. lubricating oil formulation as claimed in claim 23,100 ℃ of kinematic viscosity of wherein said base oil are about 3.5mm ²/ s-30mm ²/ s.

25. lubricating oil formulation as claimed in claim 23, wherein said base oil are GTL material Hydrodewaxing body or hydroisomerizing body.

26. lubricating oil formulation as claimed in claim 23, wherein said base oil are fischer-tropsch material Hydrodewaxing body or hydroisomerizing body.

27. as claim 2,24,25 or 26 described lubricating oil formulations, 100 ℃ of kinematic viscosity of wherein said high viscosity I class mineral oil are about 18mm ²/ s and Geng Gao.

28. lubricating oil formulation as claimed in claim 27,100 ℃ of kinematic viscosity of wherein said high viscosity I class mineral oil are about 24mm ²/ s and Geng Gao.

29. lubricating oil formulation as claimed in claim 28,100 ℃ of kinematic viscosity of wherein said high viscosity I class mineral oil are about 28mm ²/ s and Geng Gao.

30. as claim 23,24,25 or 26 described lubricating oil formulations, 60 density of wherein said high viscosity I class mineral oil are about 0.885-0.920g/cm ³With VI be about 90-100.

31. a lubricating oil additive concentrate, it contains the performance additive of at least a meltage with lube stock, and it is 3mm that this lube stock comprises 100 ℃ of kinematic viscosity ²/ s-50mm ²The base oil that contains one or more Hydrodewaxing body basestocks and/or base oil, hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil or its mixture of/s and 100 ℃ of kinematic viscosity are about 12mm ²The high viscosity I class mineral oil of/s and Geng Gao, the amount that described high viscosity I class mineral oil exists are the 1-55wt% based on the gross weight of described one or more Hydrodewaxing body basestocks and/or base oil, hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil or its mixture and described high viscosity I class mineral oil.

32. lubricating oil additive concentrate as claimed in claim 31, wherein said 100 ℃ of kinematic viscosity that contain the base oil of one or more Hydrodewaxing body basestocks and/or base oil, hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil or its mixture are about 3.5mm ²/ s-30mm ²/ s.

33. lubricating oil additive concentrate as claimed in claim 31, the wherein said base oil that contains one or more Hydrodewaxing body basestocks and/or base oil, hydroisomerizing body basestocks and/or base oil, GTL basestocks and/or base oil or its mixture is a GTL material isomer.

34. lubricating oil additive concentrate as claimed in claim 33, wherein said base oil are fischer-tropsch material Hydrodewaxing body or hydroisomerizing body.

35. as claim 31,32,33 or 34 described lubricating oil additive concentrates, 100 ℃ of kinematic viscosity of wherein said high viscosity I class mineral oil are about 18mm ²/ s and Geng Gao.

36. lubricating oil additive concentrate as claimed in claim 35,100 ℃ of kinematic viscosity of wherein said high viscosity I class mineral oil are about 24mm ²/ s and Geng Gao.

37. lubricating oil additive concentrate as claimed in claim 36,100 ℃ of kinematic viscosity of wherein said high viscosity I class mineral oil are about 28mm ²/ s and Geng Gao.

38. lubricating oil additive concentrate as claimed in claim 37,60 density of wherein said high viscosity I class mineral oil are about 0.885-0.920g/cm ³With VI be about 90-100.