CN101889070A - Base oil formulations - Google Patents

Abstract

Base oil formulation containing a mineral derived base oil and a Fischer-Tropsch derived light base oil. The Fischer-Tropsch oil may be used to upgrade an under- processed mineral oil. The Fischer-Tropsch oil causes less of an increase in volatility than predicted by theory. It may therefore be used to improve a property of a base oil formulation containing a mineral derived base oil, the property being selected from cold flow properties, viscosity profile and oxidative stability, whilst still achieving a target maximum volatility X for the formulation, by adding to the formulation a concentration c of a Fischer-Tropsch derived light base oil, wherein c is higher than the maximum concentration c' of the Fischer-Tropsch derived light base oil which theory would predict could be added without increasing the volatility of the formulation above the target maximum X.

Description

Base oil formulations

Technical field

The present invention relates to base oil formulations and preparation thereof and application, and relate to of the application of the oil of some type at the base oil formulations that is used for new purpose.

Background technology

Known heavy hydrocarbon oil is used for multiple application as base oil, for example as the base oil that is used for lubricant formulations, electric insulating oil and hydraulic fluid.This base oil is mineral oil typically, for example is petroleum derivation.

It is also known that and use the synthetic preparation of fischer-tropsch base oil.The fischer-tropsch condensation process is in the presence of suitable catalyzer and typically (for example 125-300 ℃ of high temperature, preferred 175-250 ℃) and/or high pressure (for example 5-100 crust, preferred 12-50 crust) under carbon monoxide and hydrogen are converted into the reaction of long chain hydrocarbon (normally paraffinic hydrocarbons).

Described fischer-tropsch process can be used for preparing multiple hydrocarbon fuel, comprises LPG, petroleum naphtha, kerosene and gas oil fraction.This wherein has been used for gas oil midbarrel fuel composition (as automobile diesel oil fuel particularly), typically with the gas oil blend of petroleum derivation.After hydrotreatment and vacuum distilling, (typically be C than heavy ends ₂₃-C ₄₀) a series of base oils that can obtain having different distillating properties and viscosity, these base oils can be used as for example lubricating base oil raw material.

For example WO-A-02070627 and WO-A-02070629 have described the method that is prepared the isomerization alkanes base oil by the wax of fischer-tropsch process preparation.This Fisher-Tropsch derived base oil tends to have excellent cryogenic properties, low pour point for example, and since with by the similar oil phase of mineral crude oil source preparation than relative simply preparation method and attractive.

Depend on the application of expection, base oil often need meet strict requirement aspect its viscosity, flash-point, distillating property, oxidative stability and the flowing property (particularly its low-temperature performance).For example high flash point is for planning as particularly important the base oil formulations of electric insulating oil, particularly when being used for hot environment or be used to relate to following time of situation of high peak temperature.If be intended to base oil is used for low temperature environment, then low pour point is important.Some character may be for example needed for the technical requirements of observing statutory requirement or user.

Base oil is divided into several classes according to their character.The method (often being the processed degree of described oil) that these character are subject to processing described oil again influences.So-called " I class " base oil must comprise the saturated hydrocarbon component that is lower than 90wt%, and/or greater than the sulphur of 0.03wt%, and must have minimum 80 and less than 120 viscosity index.It typically comprises the aromatic component of 10wt% or more, for example 15-35wt% and the about saturates of 65-85wt%, and experienced gentle relatively treatment condition, as solvent dewaxing and the solvent extraction that other undesirable component such as aromatic substance and naphthenic hydrocarbon are carried out.

" II class " base oil has higher quality: it must comprise the saturates of 90wt% at least and be no more than the sulphur of 0.03wt% and have minimum 80 and less than 120 viscosity index equally.These character are by the stricter processing of described oil experience is realized, carry out hydrotreatment typically to transform not desired components but not be removed, and therefore, the production of described oil is expensive more.Typical II class base oil comprises the saturates of about 93wt% and is lower than the aromatic substance of about 7wt%.

Have higher-quality " III class " base oil and still must satisfy saturates and the sulphur content requirement identical, but also must have viscosity index greater than 120 with II class base oil.In addition, these character are to realize by strict relatively hydrotreatment and catalytic dewaxing step.Typical III class base oil comprises the saturates and the aromatic substance that is lower than 5wt% of 95wt% at least.The Fisher-Tropsch derived base oil of the above-mentioned type is classified as III class base oil usually.

Usually hope can be produced and be had the base oil that is used for improving under the particular case performance, and/or can produce one group of character with expectation but the base oil that is to use so time-consuming and not expensive production technology to produce.

Known from US-B-7144497, mineral derived base oil and low viscous Fisher-Tropsch derived base oil blend are produced the base oil blend that viscosity index is higher generally.One of purpose of this blend of being claimed is with the upgrading of more low viscous fischer-tropsch oil, so that it is suitable as lubricating base oil.

But find surprisingly now, with the base oil blend of some type together the time, the blend that obtains can have than the better character of being predicted by each constitutive property (particularly surveying aspect stick nature and the oxidative stability at it), but still have acceptable, often be the volatility that is lower than prediction.Can allow to prepare higher-quality base oil blend like this, perhaps can allow to prepare the blend of one group of character, and use and thought necessary quality lower (and being to pass through less processing thus) base oil in the past with expectation.This may be beneficial to the technical requirements (typically under lower production cost) that base oil formulations meets expectation again, and/or expansion is than the Application Areas of the base oil of inferior quality (but typically more cheap).

Summary of the invention

According to a first aspect of the invention, the oily preparaton that provides the foundation comprises the blend of mineral derived base oil and Fisher-Tropsch derived lighter body.

The existence of Fisher-Tropsch derived lighter body can improve the character of whole blend in many ways.Generally speaking, it can improve the viscosity index of blend and improve oxidative stability and cold flow character (particularly pour point).Also finding increases in that it is produced the volatility that is lower than expection during with more full-bodied mineral derived base oil blend, although the Fisher-Tropsch derived base oil of in fact more low viscous lightweight typically has than the volatility higher with the mineral base oil of its blend.This also may be favourable, because low volatility often is that base oil formulations is needed.

In addition, find that also Fisher-Tropsch derived lighter body can reduce the cold cranking simulator of base oil blend (CCS) dynamic viscosity, this also is that base oil formulations is desired, particularly for expection is used as those base oils of engine oil.

This means and to make low-qualityer mineral derived base oil " upgrading " (being that its character is improved) effectively by adding Fisher-Tropsch derived base oil, in addition, improved degree may be predicted greater than theory, and can excessively not damage other character such as volatility.This can expand low-qualityer, as to pass through the mineral base oil of less processing potential application again, and/or allows to reduce the degree of treatment of given base oil and still guarantee its needed in use character.Any reduction of degree of treatment all can reduce the base oil production cost naturally and improve its efficient, and can cause the improvement of yield, possibility of pollution and other actual process benefit of reduction.

In base oil formulations of the present invention, mineral derived base oil is petroleum derivation typically, for example obtains by the petroleum refinement process.It can be I class, II class or III class base oil, typically I class or II class base oil.It can be 4-12.5 centistoke or 5 or 6 to 10 centistokes 100 ℃ kinematic viscosity (VK100) (ASTM D-445).

Especially, described mineral derived base oil can be the base oil of " undertreatment ", and this meaning is meant that the degree of treatment of this base oil experience before using is lower than in order to realize its required character and degree of treatment that should carry out under the expection applicable cases.The undertreatment of mineral derived base oil did not indicate in US-B-7144497.

In this case, " processing " be meant in the preparation process of base oil (particularly mineral derived base oil) in order to remove the processing type that desired components is not carried out.This component typically comprises aromatics (particularly many aromatics) component and/or condensed polycyoalkane component (the two can reduce oil oxidation stability and viscosity index), and/or waxy component (tending to the material of separating out at low temperature crystallization, mainly is straight-chain paraffin).Described processing for example can comprise carries out solvent extraction to desired components not, as is used to produce the typical I class base oil.As an alternative or in addition, it can comprise hydrotreatment and/or catalytic dewaxing, they are the stricter processing form that typically are used to produce higher-quality II class and III class base oil.

Therefore, for example according to the present invention, the I class base oil logistics of undertreatment (promptly experienced compare not with typical I class base oil so base oil of strict processing) can by with Fisher-Tropsch derived base oil blend by " upgrading " for being suitable for the I class base oil of purpose.Alternatively, the logistics of II class base oil may be a undertreatment, but still to make its performance upgrading be the standard that meets some expectation (for example otherwise the standard that the stricter processing of needs use realizes, typically as the II class base oil that is suitable for purpose) by adding fischer-tropsch oil.

The mineral derived base oil logistics of using in preparaton of the present invention can for example have and is lower than 95 viscosity index (ASTM D-2270) (the high viscosity index (HVI) mineral base oil that typically is suitable for purpose is processed at present and is equal to or greater than 95 viscosity index).It can have and is lower than 94 or 93, for example is the viscosity index of 90-93.Its pour point can be lower 1 or 2 or 3 ℃ or low more than the mineral base oil that typically is suitable for purpose, and is perhaps low 6 ℃ or low more, or low 12 ℃ or low more.For example its pour point (ASTM D-5950) can be-9 ℃ or higher, or-6 ℃ or higher, or be-3 ℃ or higher in some cases.

In base oil formulations of the present invention, Fisher-Tropsch derived base oil is III class base oil typically, although can be II class base oil in some cases, this depends on its definite viscosity index.It is a lighter body, promptly has low viscous relatively base oil.It can for example have 4 centistokes or lower or 3.5 or 3 centistokes or lower as the VK 100 for 2-3.5 or 2-3 centistoke.Aptly, it is suitably 7.5-25 centistoke, for example 9-20 centistoke 40 ℃ kinematic viscosity (VK 40).This lighter body can for example have 320-430 ℃, more typically be total boiling spread of 350-400 ℃.

Fisher-Tropsch derived lighter body has passed through catalytic dewaxing aptly, is ideally to live through strict relatively dewaxing process.In that it mainly is a paraffinic hydrocarbons in nature, typically comprise 80wt% or more or 85 or 90wt% or more paraffinic components, this helps to improve its viscosity index and helps to be made into higher-quality base oil thus.It typically have 115 or bigger, for example be the viscosity index of 115-125 (ASTM D-2270).

Because be used to prepare the method for described oil, it typically comprises a high proportion of relatively isomerization alkanes but not normal paraffin; With molecular computing, it can for example comprise 90 or 95wt% or more isomerization alkanes.This tends to give fischer-tropsch oil again with improved flowability; Be used for Fisher-Tropsch derived base oil of the present invention for example can have-18 ℃ or lower, preferred-20 ℃ or-25 ℃ or-30 ℃ or lower, as pour point (ASTM D-5950) for-36 ℃ to-51 ℃.The isomerization alkanes content that increases also is used to reduce the volatility that Fisher-Tropsch derived base oil is compared with the mineral derived base oil with suitable kinematic viscosity; Be used for Fisher-Tropsch derived base oil of the present invention and have 35-60wt%, preferred 40-50wt%, the more preferably Noack volatility of 42-45wt% (CEC L-40-A-93) aptly.

This " lightweight " base oil self may have too low viscosity and can not be used as lubricating oil.Therefore, their application in base oil blend of the present invention can expand effectively derive from fischer-tropsch base oil production process otherwise by the application of the product logistics of less use.Therefore, the present invention can the two provides alternate application for Fisher-Tropsch derived lighter body and mineral derived base oil, and selects for the technician who wishes the preparation base oil product increases available.

In this article, term " Fisher-Tropsch derived " is meant as fischer-tropsch condensation process sintetics or derived from the material of described sintetics.Term " non-Fisher-Tropsch derived " can correspondingly be explained.Therefore, Fisher-Tropsch derived base oil is following hydrocarbon stream, and except the hydrogen that is added, its major portion all is directly or indirectly derived from the fischer-tropsch condensation process.

Fisher-Tropsch derived product also can be called the GTL product.

Hydrocarbon product can directly derive from Fischer-Tropsch reaction, perhaps for example by obtaining indirectly with fischer-tropsch synthesis product rectifying or by the fischer-tropsch synthesis product through hydrotreatment.Hydrotreatment can comprise the hydrocracking (referring to for example GB-B-2077289 and EP-A-0147873) that is used to adjust boiling spread and/or comprise and can improve the hydroisomerization of cold flow character by increasing the branched-chain hydrocarbon ratio.EP-A-0583836 has described two step hydroprocessing processs, wherein at first make fischer-tropsch synthesis product carry out hydrocracking, the condition of described hydrocracking makes it that isomerization or hydrocracking (this will make olefinic component and oxygen-containing component hydrogenation) not take place basically, make the products therefrom hydrocracking of at least a portion then, the condition of described hydrocracking makes hydrocracking and isomerization takes place, to obtain being essentially the product of paraffinic hydrocarbons.Can for example separate subsequently by the cut of distillation with expectation.

The character that can adopt such as other of polymerization, alkylation, distillation, cracking decarboxylation, isomerization and hydroforming processing after synthetic to regulate the fischer-tropsch condensation product is described in for example US-A-4125566 and US-A-4478955.

The fischer-tropsch synthetic typical catalyst that is used for paraffinic hydrocarbons comprises group VIII metal, particularly ruthenium, iron, cobalt or the nickel as the periodictable of catalytic active component.This catalyzer that is fit to for example is described among the EP-A-0 583 836 (the 3rd and 4 page).

Example of fischer-tropsch synthetic is a SMDS (shell middle runnings synthesis method, ShellMiddle Distillate Synthesis), be described in " The Shell MiddleDistillate Synthesis Process ", people such as van der Burgt, at 5thSynfuels Worldwide Symposium, Washington DC is among the November 1985; Also referring to from Shell International Petroleum Company Ltd, London, the publication in November, 1989 of the same title of UK.This method (being also referred to as Shell " Gas-To-Liquids " or " GTL " technology sometimes) produces the middle runnings range product by following process: Sweet natural gas (mainly being methane) deutero-synthesis gas is converted into heavy long chain hydrocarbon (paraffinic hydrocarbons) wax, then with its hydrocracking and rectifying, producing liquid transportation fuels, as can be used for the gas oil in the diesel fuel composition.Can also produce by this method and have certain limit viscosity and comprise lightweight simultaneously and the base oil of middle runnings and some heavy oils.

By fischer-tropsch process, Fisher-Tropsch derived product is substantially free of sulphur and nitrogen, perhaps comprise can not detection level sulphur and nitrogen.Comprise the poisonous substance that these heteroatomic compounds tend to become Fischer-Tropsch catalyst, and therefore from the synthesis gas charging, removed.This can bring additional advantage for base oil formulations of the present invention.

In addition, the fischer-tropsch process of operation does not produce or produces hardly aromatic component usually.The aromaticity content of the Fisher-Tropsch derived oil of measuring by ASTM D-4629 or IP-368 mode typically is lower than 1wt% aptly, preferably is lower than 0.5wt%, more preferably less than 0.1wt%.This can improve oil oxidation stability again.

Generally speaking, for example with the oil phase ratio of petroleum derivation, Fisher-Tropsch derived hydrocarbon product has low relatively polar compound content, particularly polar surfactant.This has and helps improve antifoam performance and fog removal performance.This polar compound for example can comprise oxygenate and comprise sulphur and nitrogen compound.Low low oxygenate and the nitrogenous compound content of sulphur content ordinary representation in Fisher-Tropsch derived oil is because they are all removed by identical treatment process.

Be preferred for Fisher-Tropsch derived lighter body in the preparaton of the present invention and be derived from the VK 100 of Fisher-Tropsch derived wax for about 2-4 centistoke or be the 2-3.5 centistoke or be the base oil of 2-3 centistoke.This oil tends to have good purity and high paraffinicity, and comprise have n, the continuous series of the isomerization alkanes of n+1, n+2, n+3 and n+4 carbon atom, as described below.Fisher-Tropsch derived base oil also tends to have excellent cryogenic properties, and to compare production relative simple with their mineral derived counterpart.

Be used for Fisher-Tropsch derived base oil of the present invention aptly by fischer-tropsch wax hydrocracking and the preferred waxy raffinate that obtains is dewaxed are obtained.This raffinate distillation can be comprised the multiple variant production of above-mentioned lighter body logistics with production.

Fisher-Tropsch derived lighter body can for example be that the full content of described document all is merged in this paper as a reference in the type described in WO-A-02070627, WO-A-02070629 or the WO-A-2006136594 and/or according to wherein said method preparation.

Because be used for lighter body of the present invention derived from fischer-tropsch wax, it mainly is a paraffinic hydrocarbons in nature, and typically comprises most isomerization alkanes as mentioned above.Aptly, it has the saturates content (measuring according to IP 386) greater than 98wt%, and wherein saturates content is (the total polarity thing of 100-content).Preferably, it comprises the isomerization alkanes of a series of n of having, n+1, n+2, a n+3 and n+4 carbon atom, and wherein n is 20-35.Preferably, the saturates content of base oil is greater than 99wt%, more preferably greater than 99.5wt%.

Preferred Fisher-Tropsch derived base oil has 0-15wt%, the cyclanes compound content of 4-9wt% more preferably.

The Fisher-Tropsch derived basic oil flash of measuring by ASTM D-92 is suitably 185 ℃ or higher.Usually find that compare with the base oil of mineral oil derived, Fisher-Tropsch derived basic oil flash can be advantageously high under given viscosity.

Cyclanes compound content in the Fisher-Tropsch derived lighter body and the expectation the isomerization alkanes continuous series existence can (Field IonisationMass Spectrometry, FIMS) technology be measured by the field ion mass spectrum.According to this technology, at first by high performance liquid chromatography (HPLC) method IP 368/01 (but being to use pentane to replace hexane) as moving phase with oil sample be divided into polarity (aromatics) mutually with nonpolar (saturates) mutually.Use Finnigan MAT90 spectrometer analysis aromatic fraction and the saturates cut for example be equipped with the FD/FI interface then, FI (" soft " ionization techniques) is used for lacking to determine based on carbon number and hydrogen the type of hydrocarbon.

Also classify with " z " value usually by formed characteristic ion definite type of compounds in mass spectrum.This general formula CnH2n+z by all hydrocarbons provides.Because be that saturates is separated analysis mutually with aromatics, might measure the content of different isomerization paraffinic hydrocarbons with identical stoichiometry or n value.Can use commercially available software (for example to derive from Sierra Analytics LLC from mass spectrometric result, 3453 Dragoo Park Drive, Modesto, the Poly 32 of CaliforniaGA95350 USA) handle, to measure the relative proportion of various types of hydrocarbon.

The Fisher-Tropsch derived lighter body (continuous series that preferably comprises above-mentioned isomerization alkanes) that is used for preparaton of the present invention obtains by following process aptly: paraffin wax is carried out hydroisomerization, preferably carry out certain type dewaxing subsequently, as solvent dewaxing or catalytic dewaxing.Described paraffin wax can be loose paraffin wax.More preferably, described paraffin wax is Fisher-Tropsch derived wax, and this is because the product that its purity and high paraffinicity and this wax produce is included in the fact of the isomerization alkanes continuous series with n, n+1, n+2, n+3 and n+4 carbon atom in the molecular weight ranges of expectation.

The example that can be used for preparing the fischer-tropsch process of Fisher-Tropsch derived base oil is the so-called industrial slurries phase overhead product technology (commercial Slurry Phase Distillatetechnology) of Sasol, Shell Middle Distillate Synthesis method mentioned above and " AGC-21 " Exxon Mobil method.These and other method for example is described among EP-A-776959, EP-A-668342, US-A-4943672, US-A-5059299, WO-A-9934917 and the WO-A-9920720.Typically, these fischer-tropsch synthetic products comprise having 1-100 carbon atom or even surpass the hydrocarbon of 100 carbon atoms.This product can comprise normal paraffin, isomerization alkanes, oxidized component and unsaturated component.

When base oil is one of the isomerization alkanes product of expectation, maybe advantageously use the Fisher-Tropsch derived raw material of relative heavy.This raw material suitably comprises at least 30wt%, preferred 50wt% at least, the more preferably compound with at least 30 carbon atoms of 55wt% at least.In addition, the compound in raw material with at least 60 carbon atoms with have at least 30 but the weight ratio that is less than the compound of 60 carbon atoms preferably is at least 0.2, more preferably be at least 0.4 and most preferably be at least 0.55.

Preferably, Fisher-Tropsch derived raw material comprises that ASF-α value (the Anderson-Schulz-Flory chain growth factor) is at least 0.925, preferably is at least 0.935, more preferably is at least 0.945 even more preferably be at least 0.955 C ₂₀+ cut.This Fisher-Tropsch derived raw material can obtain by the above-mentioned any method that obtains suitable heavy product.The case description of the fischer-tropsch process that is fit to is in WO-A-9934917.

Fisher-Tropsch derived base oil does not comprise or comprises considerably less sulfur-bearing and nitrogen compound.This is typical for the product derived from the Fischer-Tropsch reaction that utilizes impure hardly synthesis gas.The content of sulphur and nitrogen is usually less than detectability, and the detectability of sulphur is 5mg/kg at present, and the detectability of nitrogen is 1mg/kg.

On wide significance, the present invention includes the application in the base oil formulations that comprises the second mineral derived base oil of the first paraffinic hydrocarbons lighter body with one or more above-mentioned character, no matter whether Fisher-Tropsch derived described first base oil is.

But the method that is used to prepare lighter body comprises aptly that fischer-tropsch is synthetic, the step of hydroisomerisation step and optional reduction pour point, wherein carries out described hydroisomerization and optional depression of pour point step according to the following procedure:

(a) with fischer-tropsch products hydrocracking/hydroisomerization and

(b) tell base oil or base oil middle runnings from the product of step (a).

If the basic oil viscosity and/or the pour point that obtain in step (b) meet the demands, then do not need further processing, described oil directly can be used in the preparaton of the present invention.But if desired, can be in step (c) by solvent dewaxing or more preferably catalytic dewaxing further reduce the pour point of base oil middle runnings.

Can be by from middle base oil fractions or pressed oil, separating the base oil viscosity that product that (by distillation) have suitable boiling spread and corresponding viscosity obtains to expect.Described distillation can be the vacuum distilling step.

The hydroconversion/hydroisomerisation of preferred steps (a) is reflected under the existence of hydrogen and catalyzer carries out, catalyzer can be selected from well known by persons skilled in the art those, the example is as detailed below.Can be knownly in this area to be suitable for making the isomerized any catalyzer of paraffin molecules on the catalyzer principle.In general, the hydroconversion/hydroisomerisation catalysts that is fit to is included in those of hydrogenation component of carrier band on the refractory oxide carrier, described refractory oxide carrier such as amorphous silicon oxide-aluminum oxide (ASA), aluminum oxide, fluorided alumina, molecular sieve (zeolite) or two or more the mixture in these.

The preferred catalyzer that is used for hydroconversion/hydroisomerisation step (a) comprises and comprises platinum and/or palladium as those of hydrogenation component.Hydroconversion/hydroisomerisation catalysts very preferably comprises platinum and the palladium of carrier band on amorphous silicon oxide-aluminum oxide (ASA) carrier.Described platinum and/or palladium calculate as element and based on the gross weight of carrier suitably with 0.1-5.0wt%, more suitably the amount with 0.2-2.0wt% exists.If there are described two kinds of elements simultaneously, the weight ratio of platinum and palladium changes in can wide region, but suitably at 0.05-10, more suitably in the scope at 0.1-5.The example of the precious metal that is fit on the ASA catalyzer for example is disclosed among WO-A-9410264 and the EP-A-0582347.Other noble metal-based catalysts that is fit to for example is disclosed among the US-A-5059299 and WO-A-9220759 as the platinum on fluorided alumina carrier.

Second type the hydroconversion/hydroisomerisation catalysts that is fit to comprises and comprises at least a group vib metal (preferred tungsten and/or molybdenum) and at least a non-noble metal group VIII metal (preferred nickel and/or cobalt) as those of hydrogenation component.Any metal or described two kinds of metals all can be used as oxide compound, sulfide or their array configuration and exist.Described group vib metal calculates as element and based on the gross weight of carrier suitably with 1-35wt%, more suitably the amount with 5-30wt% exists.Described non-noble metal group VIII metal calculates as element and based on the gross weight of carrier suitably with 1-25wt%, preferably the amount with 2-15wt% exists.Have been found that particularly suitable such hydrogenation conversion catalyst is included in the nickel of carrier band on fluorided alumina and the catalyzer of tungsten.

Above-mentioned non-noble metal-based catalysts is preferably used with their sulphided form.In order in use to keep the sulfur form of catalyzer, need in raw material, have some sulphur, for example 10mg/kg or the more preferably sulphur of 50-150mg/kg at least.

Can comprise that the non-noble metal group VIII metal (for example iron or nickel) of carrier band on acid carrier is in conjunction with I B-group metal (for example copper) with the preferred catalyzer that the unvulcanised form is used.Preferably having copper, is methane so that suppress hydrogenolysis of paraffins.Preferred catalyst has the pore volume by the 0.35-1.10ml/g of water absorption measurement, by the 200-500m of BET nitrogen determining adsorption ²The surface-area of/g and the bulk density of 0.4-1.0g/ml.Preferred described support of the catalyst is made by amorphous silicon oxide-aluminum oxide, and wherein aluminum oxide can 5-96wt%, the scope of preferred 20-85wt% exists.SiO in this carrier ₂The dioxide-containing silica of form is preferably 15-80wt%.Described carrier can also comprise the binding agent of (for example 20-30wt%) on a small quantity, as aluminum oxide, silicon oxide, IVA family metal oxide, clay, magnesium oxide etc., and preferred aluminum oxide or silicon oxide.

The preparation of amorphous silicon oxide-aluminum oxide micro-sphere body is by Ryland, Lloyd B., Tamele, M.W. and Wilson, J.N. is at " Cracking Catalysts ", Catalysis:Volume VII, Ed.Paul H.Emmett, Reinhold Publishing Corporation, New York, 1960, describe to some extent among the pp.5-9.

Described catalyzer can by solution metal is impregnated into altogether on the carrier, 100-150 ℃ of drying and 200-550 ℃ in air calcination prepare.Described group VIII metal can exist with about 15wt% or amount still less, and be preferably 1-12wt%, and I B-group metal exists with lower amount usually: for example the weight ratio of I B-group metal and group VIII metal can be about 1: 2 to about 1: 20.

Typical catalyzer such as following defined:

Ni，wt％??????????2.5-3.5

Cu，wt％??????????0.25-0.35

Al ₂O ₃-SiO ₂wt％????65-75

Al ₂O ₃(tackiness agent) wt% 25-30

Surface-area 290-325m ²/ g

Pore volume (Hg) 0.35-0.45ml/g

Bulk density 0.58-0.68g/ml.

Another kind of suitable hydroconversion/hydroisomerisation catalysts comprises based on the molecular sieve type material, suitably comprise at least a metal component of group VIII (preferred Pt and/or Pd) as those of hydrogenation component.Zeolite and other aluminosilicate material of being fit to then comprise zeolite beta, zeolite Y, super steady Y, ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-48, MCM-68, ZSM-35, SSZ-32, ferrierite, mordenite and silicon oxide-aluminate or phosphate such as SAPO-I1 and SAPO-31.The example of the hydrocracking hydroisomerisation catalysts that is fit to for example is described among the WO-A-9201657.The combination of these catalyzer also is possible.

The hydroconversion/hydroisomerisation method that is fit to is to comprise those of the first step and second step, in first step, use catalyzer, and in second step, use catalyzer based on ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-48, MCM-68, ZSM-35, SSZ-32, ferrierite or mordenite based on zeolite beta or ZSM-48.In back one group, preferred ZSM-23, ZSM-22 and ZSM-48.The case description of this method wherein discloses and has used first step catalyzer that comprises platinum and zeolite beta and the second step catalyzer that comprises platinum and ZSM-48 in US-A-20040065581.

Can determine that following integrated processes is used for the preferred method of base oil of the present invention for preparation, first hydroisomerisation step that the amorphous catalyst that fischer-tropsch products experience is used comprise aforesaid silica-alumina carrier carries out, second hydroisomerisation step of using the catalyzer that comprises molecular sieve to carry out subsequently.Preferably, described first and second hydroisomerisation step are carried out in the crossfire mode.More preferably, described two steps are carried out in the single reactor of the bed that comprises above-mentioned amorphous catalyst and/or crystalline-state catalyst.

In step (a), the fischer-tropsch raw material is contacted in the presence of catalyzer under high temperature and high pressure with hydrogen.Described temperature typically is 175-380 ℃, preferably is higher than 250 ℃, more preferably 300-370 ℃.Described pressure typically is the 10-250 crust, is preferably the 20-80 crust.Hydrogen can be with the gas hourly space velocity supply of 100-10000Nl/l/hr, preferred 500-5000Nl/l/hr.Hydrocarbon feed can be with 0.1-5kg/l/hr, preferably be higher than 0.5kg/l/hr and provide more preferably less than the weight hourly space velocity of 2kg/l/hr.Hydrogen can be 100-5000Nl/kg with the ratio of hydrocarbon feed, is preferably 250-2500Nl/kg.

Transformation efficiency in the step (a) be defined as at every turn by the time reaction boiling point that is lower than 370 ℃ cut for boiling point be higher than the weight percent of 370 ℃ raw material, it suitably is 20wt% at least, preferred 25wt% at least, but preferably be no more than 80wt% and more preferably no more than 65wt%.Therefore the raw material that is used for above-mentioned definition is the total hydrocarbon feed that enters step (a), comprises the circulation of any optional high boiling fraction that may obtain in step (b).

In step (b), preferably the product with step (a) is separated into one or more distillate fuel cuts and base oil or base oil precursor fraction with desired viscosity.If the pour point of described base oil or precursor not in the scope of expectation, can further reduce pour point by dewaxing step (c), preferred catalytic dewaxing.In this embodiment, another possible advantage is that the more wide-boiling cut in the product of step (a) is dewaxed.Can separate base oil and other optional oil that required common light-weight has desired viscosity by for example distilling then from the dewaxed product that obtains.Dewaxing is preferably undertaken by catalytic dewaxing, as for example described in the WO-A-02070627, this publication at this by with reference to introducing (about the dewaxing condition that is fit to and the example of catalyzer, especially referring to the 8th page of the 27th row to the 11st page of the 6th row).If desired, the full boiling point of raw material of dewaxing step (c) can be the full boiling point of product of step (a) or lower.Typically, the raw material of catalytic dewaxing unit comprises C ₁₈-C ₄₀Hydrocarbon or C ₂₃-C ₄₀Hydrocarbon.

Before using preparaton of the present invention, for example in dewaxing step (c) afterwards, can carry out one or more other processing to base oil, as hydrofining, as for example at the 11st page of the 7th row of WO-A-02070627 to described in the 12nd page of the 12nd row.

According to the present invention, described base oil formulations can comprise the mixture of two or more Fisher-Tropsch derived base oils.It can comprise the mixture of two or more mineral derived base oils.

In preparaton of the present invention, the concentration of Fisher-Tropsch derived lighter body can be 2-50wt% or 2-45wt%, for example is 10-45wt% or 15 or 20-45wt%.

Usually the concentration of Fisher-Tropsch derived base oil is selected, with the viscosity that guarantees overall preparaton, viscosity index, volatility, pour point and/or other relevant character in the scope of expectation, for example in the technical requirements scope of industry or management.

The concentration of the mineral derived base oil in the preparaton can correspondingly be 50-98wt% or 55-98wt%, for example is 55-90wt% or 55 to 85 or 80wt%.

Fisher-Tropsch derived base oil and mineral derived base oil can be only base oil components in the preparaton.Alternatively, can with they and they and one or more additional base oil components be used in combination.This additional base oil component can be Fisher-Tropsch derived or non-Fisher-Tropsch derived.Total preparaton comprises aptly and is lower than 20wt%, preferably is lower than this additional base oil component of 10wt%.

The example of additional base oil component comprises based on the paraffinic hydrocarbons of mineral and naphthenic type base oil and synthetic base oil for example ester, poly-alpha olefins, polyalkylene glycol etc.This wherein, in order to improve the biodegradability of base oil formulations, ester may be favourable.If exist, the content of additional ester base oil can be 1-30wt%, more preferably 5-25wt% based on total preparaton.The ester that is fit to be can by make aliphatic series single, two and/or poly carboxylic acid react those that obtain with different tridecyl alcohol at enzymatic synthesis condition.This examples for compounds is an octane-1,8-diacid, 2-ethyl hexane-1,6-diacid and dodecane-1, the isotridecyl ester of 12-diacid.Preferably, described ester is so-called tetramethylolmethane four (lipid acid) ester (PET ester), as lipid acid (the preferred C by tetramethylolmethane (PET) and side chain or straight chain ₆-C ₁₀Acid) esterification is prepared.This ester can comprise two-PET as impurity.

Base oil formulations of the present invention can have the VK 100 (ASTMD-445) of 3.8-5 centistoke.It can have the VK 40 (40 ℃ kinematic viscosity, measuring according to ASTM D-445) of 18-27 centistoke.Be scheduled to be used for regulating viscosity according to it aptly.

Described preparaton can have the viscosity index (ASTM D-2270) of 95-120.It can have the 1000-2000 centipoise at the CCS of-25 ℃ of measurements dynamic viscosity (ASTM D-5293).

Described preparaton can have the pour point (ASTMD-5950) of-30 to-6 ℃ or-25 ℃ to-10 ℃.It can have 180-210 ℃ D-93 flash-point (IP-34).It can have the Noack volatility (CEC L-40-A-93) of 16-25wt%.

For application in some cases, when for example being used for the engine of some type, possible preferred formulations is appropriate doctor negative preparaton or low-sulfur preparaton generally, for example comprises 100ppmw (1,000,000 umbers by weight) at the most, preferred 50ppmw at the most, more preferably at the most 10 or the sulphur of 5ppmw.

Described preparaton can comprise other component except that mineral derived base oil and Fisher-Tropsch derived base oil.For example it can be included in one or more base oil additives of normally used type in the base oil formulations.The character of any this additive all depends on the predetermined application of preparaton.They can for example be selected from pour point depressant, emulsifying agent, emulsion splitter, sanitas, sealed expander, anti-coloration additive, UV stablizer and the friction modifier of anti-wear additive, antioxidant, dispersion agent, purification agent, viscosity modifier, defoamer, pour point depressant such as hydro carbons or oxygenated hydrocarbon type.

The specific examples of this additive is described in for example Kirk-Othmer Encyclopediaof Chemical Technology, the third edition, and 14 volumes are in the 477-526 page or leaf.Aptly, dispersion agent is an ashless dispersant, for example polybutylene succinimide polyamine or Mannich bases dispersion agent.Aptly, purification agent is peralkaline metal detergent, and for example phosphonate, sulfonate, phenates or salicylate type are as described in the Encyclopedia mentioned above.Aptly, viscosity modifier is the polymkeric substance of regulating viscosity, for example polyisobutene, olefin copolymer, polymethacrylate, polyoxyethylene alkylphenyl ethene or hydrogenant polyisoprene star polymer (Shellvis).The example of the defoamer that is fit to is dimethione and polyglycol ether and ester.

In order to improve the gassing tendencies of base oil formulations, may preferably include aromatic substance, for example the aromatic substance of 0.05-10wt% or 0.1-5wt%.Preferred aromatic substance is the mixture of naphthane, diethylbenzene, diisopropyl benzene or alkylbenzene for example, as it is commercially available to can be used as " ShellOil 4697 " or " Shellsol A 150 " (all being " Shell " product that can derive from Shell Deutschland GmbH).Another kind of preferred mixture of aromatic compounds comprises 2,6 di t butyl phenol and 2, the mixture of 6-di-tertiary butyl methyl phenol.Base oil formulations can for example comprise 2 of the 2,6 di t butyl phenol of 0.1-3wt% and 0.1-2wt%, and the 6-di-tertiary butyl methyl phenol is suitably 1: 1-1: 1.5 weight ratio.

Base oil formulations can comprise copper passivator (being sometimes referred to as static discharge inhibitor or metal passivator), for example described in the 16-18 page or leaf of WO-A-2006136594.

Except as otherwise noted, the concentration of every kind of described annexing ingredient preferably is up to 50 in the base oil formulations, 000ppmw or 10, and 000ppmw or 1000ppmw for example are 5-1000ppmw.(except as otherwise noted, all additive concentrations of quoting from herein all are active material concentrations in mass.In addition, except as otherwise noted, all concentration is all quoted from as the per-cent of total base oil formulations.)

If desired, can be multifunctional additive for lubricating oils with listed those one or more binder component co-blended (preferably be fit to thinner) as mentioned, multifunctional additive for lubricating oils can be distributed to then in mineral derived base oil, the Fisher-Tropsch derived base oil or the blend of the two, so that prepare preparaton of the present invention.

The total additive level that comprises the additive thinning oil in base oil formulations can be suitably 0.5-20wt%, preferably is lower than 20 or 15wt%, or is lower than 10wt% in some cases.

Comprise one or more cold flow additives for example during pour point depressant at preparaton of the present invention, this additive can exist with the concentration that reduces owing to the existence of Fisher-Tropsch derived base oil.Therefore, for example the cold flow additive concentration of preparaton can than otherwise can be incorporated into wherein with the character that needing in predetermined the application to realize or expect and the cold flow additive concentration of performance and hang down maximum 20 or 30 or 40%.This reduction can with recognizing that the concentration that is present in the cold flow additive in the base oil formulations before can using fischer-tropsch deutero-base oil in mode provided by the invention compares, or with Fisher-Tropsch derived base oil is joined the similar base oil formulations that predetermined (for example selling) use under analogue in before the cold flow additive concentration that is present in the described similar preparaton compare.

Therefore, base oil formulations for example of the present invention can comprise and is lower than 3000ppmw, is suitably the cold flow additive (particularly pour point depressant) that is lower than 1500ppmw.

Similarly, when preparaton of the present invention comprised one or more viscosity adjustment additives, this additive can exist with the concentration that reduces owing to the existence of Fisher-Tropsch derived base oil.Therefore, for example the viscosity adjustment additive concentration of preparaton can than otherwise can be incorporated into wherein with the character that needing in predetermined the application to realize or expect and the viscosity adjustment additive concentration of performance and hang down maximum 30%.This reduction can with recognizing that the concentration that is present in the viscosity adjustment additive in the base oil formulations before can using fischer-tropsch deutero-base oil in mode provided by the invention compares, perhaps with Fisher-Tropsch derived base oil is joined the similar base oil formulations that predetermined (for example selling) use under analogue in before the viscosity adjustment additive concentration that is present in the described similar preparaton compare.

Therefore, preparaton for example of the present invention can comprise 10wt% or viscosity adjustment additive still less (typically being included as spissated polymers soln), is suitably 9 or 8 or 7 or 6 or 5wt% or still less.May not contain the viscosity adjustment additive fully in some cases.

When preparaton of the present invention comprised one or more antioxidants or other stabilization additives, described additive also can exist with the concentration that reduces owing to the existence of Fisher-Tropsch derived base oil.Therefore, for example the anti-oxidant additives concentration of preparaton can than otherwise can be incorporated into wherein with the character that needing in predetermined the application to realize or expect and the anti-oxidant additives concentration of performance and hang down maximum 20%.This reduction can with recognizing that the concentration that is present in the anti-oxidant additives in the base oil formulations before can using fischer-tropsch deutero-base oil in mode provided by the invention compares, perhaps with Fisher-Tropsch derived base oil is joined the similar base oil formulations that predetermined (for example selling) use under analogue in before the anti-oxidant additives concentration that is present in the described similar preparaton compare.

Therefore, preparaton for example of the present invention can comprise 5000ppmw or anti-oxidant additives still less, is suitably 4000 or 3000ppmw or still less.

Base oil formulations of the present invention can be suitable for multiple application.It can for example be fit to and/or be applicable to and/or expect as lubricant, for example as engine oil, as be used for oil engine or industrial lubricants.It can be fit to and/or be applicable to and/or expect as power transmitting fluids, particularly automatic power transmitting fluids, hydraulic efficiency oil, compressor oil, turbine oil (for example being used in gas, steam or the combined cycle turbine) or technical oil.

Described preparaton goes for and/or expects being used for using at colder weather and/or in colder season.When the system that is used for as for example vehicle motor, the cold flow performance of preparaton may influence the overall system performance under this condition.

Compare with their mineral derived counterpart, Fisher-Tropsch derived base oil has than higher biodegradability, this makes preparaton of the present invention be used for wherein considering particularly advantageous under the situation of biodegradability, for example as electric installation that moves such as the transformer oil in train, power truck or the mixed power car.Preparaton of the present invention can be applied to the equipment that uses similarly in the environment sensitive zone, as for example National parks, protective belt, water conservation district, tap water storage facilities etc.

Can be by comprising the biodegradability of further improving base oil formulations of the present invention based on the base oil of ester, for example as mentioned above.

According to second aspect, the invention provides the application of Fisher-Tropsch derived lighter body in the base oil formulations that comprises mineral derived base oil, be used to improve one or more character of preparaton, and excessively do not improve its volatility aptly and/or make the raising of volatility be lower than the caused of theoretical prediction owing to introducing Fisher-Tropsch derived lighter body.As mentioned above, have been found that Fisher-Tropsch derived lighter body is incorporated into to cause in the described preparation that the volatility that is lower than expection raises, and guaranteed the desirable improvement of other character simultaneously.Therefore, the volatility of preferred base oil formulations still is not higher than predetermined (for example selling) and is used for routine (mineral derived typically) base oil of identical purpose or the volatility of base oil formulations after introducing Fisher-Tropsch derived lighter body.

Fisher-Tropsch derived lighter body can be used to improve following character especially: cold flow character (particularly pour point), viscosity characteristics (particularly viscosity index and/or CCS dynamic viscosity) and oxidative stability.More particularly, it can be used to improve pour point, viscosity index and/or the oxidative stability of preparaton.In some cases, the improvement of oxidative stability may be a particularly important.

A third aspect of the present invention provides the method that is used to prepare mineral derived base oil, described method comprises the relevant nature of (i) Fundamentals of Measurement oil and (ii) with the amount blend with the relevant nature that is enough to improve total blend of described base oil and Fisher-Tropsch derived lighter body.Described relevant nature can for example be selected from top listed those, particularly viscosity index and CCS dynamic viscosity.Preferred described improvement is to realize the volatility that makes blend is compared the situation of raising within reason with independent mineral derived base oil under, as above-mentioned about as described in a second aspect of the present invention.

The volatility of base oil or base oil formulations can be estimated by measuring its Noack volatility aptly, and the Noack volatility has reflected under prescribed condition the oily per-cent that loses when oil or preparaton be heated to specified temperature.This value reduces to represent that volatility reduces, and this can be regarded as improvement under the situation of base oil formulations.Can use standard method of test CECL-40-A-93 or similar techniques to come measuring N oack volatility.

Can estimate its cold flow character by the pour point of Fundamentals of Measurement oil or base oil formulations aptly, pour point is to observe the minimum temperature that preparaton moves.The improvement of cold flow character is represented in the reduction of pour point, and this can enlarge the condition and range that can use described preparaton therein effectively conversely.Pour point can use standard method of test ASTM D-5950 or similar techniques to measure aptly.

Can also estimate cold flow character by measuring cloud point, for example use standard method of test ASTM D-5771 or similar techniques to measure.Equally, the improvement of cold flow character is represented in the reduction of cloud point.As an alternative or in addition, they can be estimated by for example using standard method of test ASTM D-2983 to measure brookfield viscosity, particularly are being used for automatic power transmitting fluids or as under the basic oil condition of automatic power transmitting fluids.The improvement of cold flow character is represented in the reduction of brookfield viscosity.

In general, the improvement of cold flow character can show as the minimum temperature that the system that uses described base oil formulations can move and be reduced to given standard.

The viscosity index of base oil or base oil formulations (this is measuring of the temperature variant degree of its kinematic viscosity) can use standard method of test ASTM D-2270 or similar techniques to estimate aptly.This exponential is increased under the situation of base oil formulations can think a kind of improvement.

The CCS dynamic viscosity of base oil or base oil formulations can use standard method of test ASTM D-5293 or similar techniques to estimate aptly.The reducing of this value can be thought a kind of improvement under the situation of base oil formulations, select because it can expand preparaton, helps the base oil blend is adjusted to the overall viscosity of expectation and helps to improve wear resisting property and volatility performance.

The oxidative stability of base oil or base oil formulations can use TOST or turbine oil stability test (ASTM D-943) or similar techniques to estimate aptly.The prolongation of the TOST time length of preparaton (for example in hour) can be thought a kind of improvement under the situation of base oil formulations.

Of the present invention second and the situation of the third aspect under, the character of " improvement " base oil formulations comprise with introduce Fisher-Tropsch derived lighter body before the improvement of any degree of comparing of preparaton performance.This can for example comprise the relevant nature of regulating preparaton by means of Fisher-Tropsch derived base oil, so that meet the desired target, and for example desired destination Noack volatility, pour point, viscosity index, CCS dynamic viscosity or oxidative stability.Similarly, the character of the base oil formulations that " raising " or " reduction " is measured comprises the raising or the reduction of any degree, according to circumstances can compare with the preparaton performance before introducing Fisher-Tropsch derived lighter body.

Under situation of the present invention, " application " of Fisher-Tropsch derived lighter body in base oil formulations be meant lighter body be incorporated in the preparaton, as introducing with the blend (being physical mixture) of one or more other base oil components (comprising mineral derived base oil) and optional one or more base oil additives.Fisher-Tropsch derived lighter body is introduced in preparaton being incorporated into system's (for example engine) that will use described preparaton operation aptly before.As an alternative or in addition, described application can be included in and wherein use the base oil formulations that comprises Fisher-Tropsch derived lighter body to move this system.

" application " of Fisher-Tropsch derived lighter body can also comprise according to the indication of in base oil formulations, using described base oil provide described base oil with realize of the present invention second, third, purpose aspect the 4th and/or the 5th, for example realize the desired destination volatility, and/or desired destination pour point, viscosity index, CCS dynamic viscosity or oxidative stability, and/or reduce the concentration of additive in the preparaton.

Fisher-Tropsch derived lighter body itself can be used as and is suitable for and/or expects that the component as the composition of base oil additive provides, in this case, can in this composition, comprise Fisher-Tropsch derived base oil, so that influence the relevant nature of base oil formulations as mentioned above.Therefore, Fisher-Tropsch derived lighter body can be incorporated in the compositions of additives or and pack with one or more other base oil additives.

According to a forth aspect of the invention, one or more character (for example being selected from top those listed character) of being used to improve the base oil formulations that comprises mineral derived base oil are provided, have still realized the method for the maximum volatility X of target of preparaton simultaneously, described method comprises the Fisher-Tropsch derived lighter body that adds concentration c to preparaton, wherein c is greater than c ', and described c ' is can adding in the preparaton of theoretical prediction and do not make the volatility of preparaton bring up to the peak concentration of the Fisher-Tropsch derived lighter body that is higher than target max X.

Zui Da fischer-tropsch base oil concentration c ' and use the linear blend rule to calculate aptly in theory based on the volatility of each component (promptly typically mineral derived base oil and Fisher-Tropsch derived lighter body) of preparaton with the relation of the volatility of preparaton.

It is the application of Fisher-Tropsch derived lighter body in the base oil formulations that comprises mineral derived base oil of c that a fifth aspect of the present invention provides concentration, be used to improve one or more character of preparaton, and the volatility that realizes preparaton simultaneously is lower than the attainable volatility when the Fisher-Tropsch derived lighter body of working concentration c of theoretical prediction.Equally, can use the linear blend rule to predict to comprise the two the theoretical volatility of preparaton of the mineral derived base oil of any given weight ratio and Fisher-Tropsch derived lighter body.

If as, then can calculate simply and be directed in the preparaton and volatility is brought up to be higher than the amount of the peaked Fisher-Tropsch derived base oil of desired destination for the desired utility theory of preparaton that comprises Fisher-Tropsch derived lighter body and mineral derived base oil simultaneously.But find now, with the mineral derived base oil blend of viscosity higher the time, if Fisher-Tropsch derived lighter body may make the raising of volatility improve less than being suitable for the theoretical volatility of being predicted.This permission is incorporated into more substantial Fisher-Tropsch derived base oil in the preparaton, this allow again with otherwise think that possible for example cold flow performance, viscosity characteristics and/or oxidative stability are improved and compare bigger improvement, be ideally in the presence of cold flow additive, viscosity modifier or the antioxidant of low concentration or do not have cold flow additive, viscosity modifier or antioxidant, as discussed above.

In order to make base oil formulations satisfy current health and safety technical requirements and/or to satisfy consumer demand, often expect certain maximum volatility.Similarly, the cold flow performance of certain level (for example maximum pour point) may wish for meeting corresponding base oil technical requirements, and the oxidative stability of certain minimal viscosity index, certain maximum CCS dynamic viscosity and/or certain minimum level may also be like this.According to the present invention, owing to comprised Fisher-Tropsch derived lighter body, these standards also can all realize when using the additive of reduction level through being everlasting or not having additive to exist simultaneously.

A sixth aspect of the present invention provides Fisher-Tropsch derived application or the application in preparation base oil formulations of lighter body in base oil formulations, is used for allowing using and the lower mineral derived base oil of the necessary specific mass mutually of one or more desired destination character of otherwise realizing preparaton at preparaton.

As discussed above, in this case, the mineral derived base oil of " than inferior quality " is typically through handling the base oil of (particularly hydrotreatment and/or dewaxing) than low degree." than the low degree " handled can comprise handles the short time period and/or under so not strict condition (for example use lower extraction severity in lower hydrotreatment temperature or in the upgrading step or do not use catalytic dewaxing and make solvent dewaxing or reduce the degree that wax removes or transforms respectively in solvent dewaxing or catalytic dewaxing step) and/or do not have treatment step fully.Low-qualityer mineral derived base oil typically has lower viscosity index and/or higher volatility.It can comprise higher concentration one or more be selected from the component of unsaturates (particularly aromatic substance), naphthenic hydrocarbon and wax.

One or more desired destination character of preparaton can for example be selected from volatility, cold flow character (particularly pour point), viscosity index, CCS dynamic viscosity and oxidative stability.

According to a seventh aspect of the invention, provide the method that is used to prepare base oil formulations (as the preparaton of first aspect), described method comprises mineral derived base oil and Fisher-Tropsch derived lighter body blend.Implement described blend can be used to realize above-mentioned about the one or more purposes described in second to the 6th aspect of the present invention, particularly at viscosity index, cold flow character, oxidative stability, CCS dynamic viscosity and/or the volatility of resulting base oil formulations.

Can implement this method at the quality of improving mineral derived base oil especially.It can for example be used for the base oil that the I class is mineral derived " upgrading " for the II class, perhaps be the III class with II class " upgrading ", or the improvement quality low relatively mineral derived basic oil properties of II class.

In a preferred embodiment of the invention, described method can comprise using than the preparaton that has been used to make base oil in advance or has comprised described base oil and realizes that the processing of one or more desirable propertieses compares lower degree of treatment and prepare mineral derived base oil.This can for example comprise the length that shortens the treatment step be used to prepare mineral derived base oil and/or reduce its severity, perhaps omit treatment step fully.Therefore, the method of seventh aspect present invention can comprise deliberately to be made mineral derived base oil and compares undertreatment in the processing of adopting in the past in preparation process, and uses fischer-tropsch deutero-lighter body to compensate at least in part because the change of the low caused mineral derived base oil character of the degree of treatment of experience now.Described method can for example comprise mineral base oil is treated to lower viscosity index.

A eighth aspect of the present invention provides system, for example engine or its parts, and described system comprises according to the base oil formulations of first aspect and/or according to the base oil formulations of second to the 7th either side preparation.

In specification sheets and claim, word " comprises " and " comprising " and variant thereof the meaning is " including but not limited to " and part, additive, component, integral body or the step of not planning to get rid of other.

In specification sheets and claim, unless context has requirement in addition, the object of singulative comprises its plural form.Especially, when using indefinite article, should be appreciated that specification sheets not only considered singulative but also considered plural form, unless context has the phase cross-demand.

The preferred feature of each aspect of the present invention can be described in conjunction with any others.

Can further feature of the present invention be become apparent by following examples.Generally speaking, the invention provides the combination of the disclosed any novel characteristics of this specification sheets (comprising claim and accompanying drawing) or any novel characteristics.Therefore, characteristics, integral body, feature, compound, chemical part or the group described in conjunction with particular aspects of the present invention, embodiment or embodiment are construed as and are applicable to described any others, embodiment or embodiment herein, unless it is incompatible with described any others, embodiment or embodiment.

In addition, except as otherwise noted, any feature disclosed herein can replace with the alternative features that plays identical or similar purpose.

Following examples illustrate the character and the performance of base oil formulations of the present invention, and estimate the influence of Fisher-Tropsch derived lighter body to the character of the preparaton that comprises mineral derived base oil.

Embodiment 1

Can be with the mineral derived I class base oil and Fisher-Tropsch derived lighter body (FTBO) blend of II/III class of " undertreatment ", to produce preparaton of the present invention.Described mineral oil can then for example only be handled about 93 or 92 viscosity index, and more typical I class base oil is to handle at least 95 viscosity index.

In this experiment, the I class mineral base oil of employed undertreatment has the VK 100 (ASTM D-445) of 5.341 centistokes, the VK 40 (ASTM D-445) of 33.02 centistokes and 92 viscosity index (ASTM D-2270).Total polar material content with estimation of 32.8wt%.The fischer-tropsch base oil has the VK 100 of 2.68 centistokes and 119 viscosity index.With of the weight ratio blend of two kinds of components, so that produce total VK 100 with about 4 centistokes with 71.0: 29.0.

The character of the measuring of this blend is illustrated in the following table 1.This table also show typical processed conventionally I class mineral base oil (in this case for HVI-55 available from ShellCAPSA, relevant nature Argentina), they can be regarded as " target " character of the blend of the present invention preparation.

Table 1

Character	Testing method	The mineral base oil of undertreatment	??FTBO	Blend	Target (processed conventionally mineral base oil)
						VK 40 (centistoke)	??ASTM?D-445	??33.02	??9.58	??20.95	?22.41
VK 100 (centistoke)	??ASTM?D-445	??5.34	??2.68	??4.20	?4.304
						Viscosity index	??ASTM?D-2270	??92	??119	??103	?95
Noack volatility (wt%)	??CEC??L-40-A-93	??14.6	??42.4	??21.3	?26.7
						The oxidative stability (TOST life-span, hour) that contains the preparaton * of additive	??ASTM?D-934	??1680	??＞3000	??＞2424	?＞2000

* at the included additive=OLOA4994S of the base oil that is used for stability test (available from Chevron-Oronite Additive Company), comprise wear resistant components and antioxidant ingredients; Additive treating ratio=0.75wt%.

Table 1 shows the viscosity index that can how to use fischer-tropsch deutero-lighter body to improve mineral oil, and improves its quality thus.Although increase, it is pointed out that described increase does not make total blend exceed the acceptable value that is used for the blend of crankcase oils preparaton owing to the higher volatility of fischer-tropsch oil inherent is compared to some extent the volatility of blend with independent mineral oil.

It can also be seen that fischer-tropsch oil has improved the mineral oil oxidation stability.

In fact, for shown in all parameters, the blend of the present invention preparation not only satisfies " target " character of processed conventionally I class base oil, and has in fact improved described " target " character.

Can change the fischer-tropsch oil concentration in the blend of the present invention so that regulate one or more described character, other base oil produced by different way with the technical requirements that meets expectation (for example realizing the minimal viscosity index of expectation) and/or simulation or the character of base oil formulations.

Embodiment 2

By with the Fisher-Tropsch derived lighter body (VK 100 is approximately 3 centistokes) of 22.7wt% and the commercially available standard I class mineral base oil (HVI-65 of 77.3wt%, available from Shell PernisRefinery, Rotterdam, The Netherlands, VK 100 is approximately 5 centistokes, and viscosity index is 100) blend prepares base oil formulations of the present invention together.

Fisher-Tropsch derived base oil (FTBO) is to use the method for above-mentioned general type to prepare, and comprises strict relatively hydrotreatment and catalytic dewaxing step.Its character is illustrated in the following table 2.

Table 2

Character	Testing method	??FTBO
			VK 40 (centistoke)	??ASTM?D-445	??9.581
VK 100 (centistoke)	??ASTM?D-445	??2.68
			Viscosity index	??ASTM?D-2270	??119
-40 ℃ Bu Shi dynamic viscosity (centistoke)	??ASTM?D-2983	??3120/3220
			-25 ℃ Bu Shi dynamic viscosity (centistoke)	??ASTM?D-2983	??180/180
Total polar material content: aromatic substance (wt%) saturates (wt%) rate of recovery (wt%)	The IP-368 mode	???0.7??99.5??100.2
			Density (kg/m at 15 ℃ 3)	??IP-365/97	??806.6
Filterability (minute)	??TMS-371	??6
			Noack volatility (wt%)	??CEC?L-40-A-93	??42.4
Flash-point D-93 (℃)	??ASTM?D-93	??185.5
			Flash-point D-92 (℃)	??ASTM?D-92	??198.0
Pour point (℃)	??ASTM?D-5950	??-42
			Pour point response (the methacrylic ester pour point depressant of+0.15wt%) (℃)	??ASTM?D-5950	??-69
Cloud point (℃)	??ASTM?D-5771	??-29
			Saybolt color	??ASTM?D-156	??+30
Aniline point (℃)	??IP-2	??113.0
			Air release (minute)	??IP-313	??＜0.5

Character	Testing method	??FTBO
			The water separability: disengaging time (minute)	??ASTM?D-1401	??40-40-05
Simulation distil (℃): IBP 5% 10% 15% 20% 25% 30% 35% 40% 45% 50% 55% 60% 65% 70% 75% 80% 85% 90% 95% FBP	??ASTM?D-2887	???340.0??354.0??359.0??363.5??367.0??370.0??373.0??376.0??378.5??381.0??383.5??386.0??388.0??390.5??392.5??394.5??396.5??399.0??401.5??404.5??414.0

VK 100 is illustrated in the following table 3 for the character of the base oil blend of about 4 centistokes.Also show the required destination properties of blend in the table, these character are the character of the straight run 4 centistoke I class mineral base oils of standard.

Table 3

Character	Testing method	Blend	Target
				VK 40 (centistoke)	??ASTM?D-445	??21.82	??22.41
VK 100 (centistoke)	??ASTM?D-445	??4.329	??4.304
				Viscosity index	??ASTM?D-2270	??105	??95

Character	Testing method	Blend	Target
				In-25 ℃ cold cranking simulators (CCS) dynamic viscosities (centistoke)	??ASTM?D-5293	??1438	??2516
Pour point (℃)	??ASTM?D-5950	??-24	??-6
				Noack volatility (wt%)	??CEC?L-40-A-93	??18.7	??26.7

Equally, these data show, the character that mineral derived base oil and Fisher-Tropsch derived lighter body be can be used for regulating total blend with the suitable proportion blend is to realize the desired destination technical requirements.In this case, the viscosity index of blend is higher than target value, and Noack volatility and pour point are lower.The CCS dynamic viscosity is also much lower than target value.Therefore, can improve the total mass and the purpose matching thereof of blend, and excessively not damage its volatility; Although in fact have the fischer-tropsch component of high relatively volatility, the volatility of total blend is still well in the technical requirements of expectation.

Embodiment 3

By following material blend is prepared other base oil formulations of the present invention together:

The Fisher-Tropsch derived lighter body that in embodiment 1 and embodiment 2, uses of B-1:41wt%, (VK100 is approximately 6 centistokes with the mineral derived II class base oil of the commercially available standard of the MO-1 of 59wt%, Star 6 is available from Motiva LLC, Port Arthur, Texas, USA), so that produce the blend that total VK 100 is approximately 4 centistokes.

The Fisher-Tropsch derived lighter body that in embodiment 1 and embodiment 2, uses of B-2:44wt%, mineral derived II class base oil MO-2 (VK 1006.85 centistokes with the commercially available standard of 56wt%, Star 6 is available from Motiva LLC, Port Arthur, Texas, USA), be used to produce the blend that total VK 100 is approximately 4 centistokes equally.

Character and their components separately of two kinds of blend B-1 and B-2 are illustrated in the following table 4.Also show the needed destination properties of blend in this table, these character are the character that mineral derived base oil (being the 4 centistoke II class base oils that are applicable to purpose of standard) that commercially available VK 100 is approximately 4 centistokes measures.

It is identical among used testing method and the embodiment 2,

Table 4

Character	??MO-1	??MO-2	??FTBO	??B-1	??B-2	Target
							VK 40 (centistoke)	??43	??44.09	??9.58	??20.87	??20.30	??21.5
VK100 (centistoke)	??6.45	??6.85	??2.68	??4.296	??4.305	??4.24
							Viscosity index	??100	??111	??119	??112	??120	??100
-25 ℃ CCS dynamic viscosity (Vd ccs) (centipoise)	??5600	??5433	Too low and can't measure	??1123	??1008	??1441
							Measured Vd reduces	??-	??-	??-	??22.07	??30.05	??-

Character	??MO-1	??MO-2	??FTBO	??B-1	??B-2	Target
							The ccs that compares with target value (relative value %)
Brookfield viscosity-40 ℃, mPa.s (pour point depressant that comprises 0.15wt%, ASTM D-2983)	??-	??-	??-	??8275	??6725	??17690
							Pour point (℃)	??-15	??-18	??-42	??-18	??-24	??-15
Noack volatility (wt%)	??11	??12.9	??42	??24	??26	??26
							Oxidation stability test-induction time, minute *	??-	??-	??-	??25.4	??-	??22.5

* employed testing method is described in (isothermal pressure DSC@200psig is with 4,4 of 0.5wt% '-methylene-bis (2,6-two-tert.-butyl phenol suppresses)) among the US-6008164.

Table 4 shows can be by promoting the character of mineral base oil for meeting certain required standard with Fisher-Tropsch derived lighter body blend.In fact, in this case, the character of blend of the present invention is further improved with respect to the basic oil properties of " target " 4 centistokes.Under the situation of blend B-2, with II class mineral base oil MO-2 upgrading to the viscosity index that has in the III class scope.

This shows, any given mineral base oil can be handled lower degree (promptly handle and be lower than conventional quality), and subsequently by rising to primary standard (or actual standard that rises to another expectation) with the blend of fischer-tropsch lighter body.

Especially, the data presentation of table 4 is compared with independent mineral oil, and the viscosity index of total blend is significantly increased, and depression of pour point, all is improved with respect to target value in both cases.The Noack volatility of blend also is lower than target value fully, and the volatility increase that the existence of fischer-tropsch oil causes is lower than can foreseeable degree.

The cold cranking simulator viscosity of blend also significantly reduces, and in fact fully is lower than the value of target mineral base oil.

Claims (9)

1. base oil formulations comprises the blend of mineral derived base oil and Fisher-Tropsch derived lighter body.

2. the base oil formulations of claim 1, wherein mineral derived base oil have and are lower than 95 viscosity index (ASTM D-2270).

3. claim 1 or 2 base oil formulations, wherein Fisher-Tropsch derived lighter body have 115 or bigger viscosity index (ASTM D-2270).

4. each base oil formulations in the aforementioned claim, the concentration of wherein Fisher-Tropsch derived lighter body is 2-45wt%.

5. the application of Fisher-Tropsch derived lighter body in the base oil formulations that comprises mineral derived base oil, be used to improve the character that is selected from cold flow character, viscosity characteristics and oxidative stability of preparaton, and the volatility increase is lower than increasing owing to introducing the caused volatility of Fisher-Tropsch derived lighter body of theoretical prediction.

6. be used to improve the character of the base oil formulations that comprises mineral derived base oil, simultaneously still realize the method for the maximum volatility X of target of preparaton, described character is selected from cold flow character, viscosity characteristics and oxidative stability, described method comprises the Fisher-Tropsch derived lighter body that adds concentration c in preparaton, described c is greater than c ', and described c ' is can adding in the preparaton of theoretical prediction and do not make the volatility of preparaton bring up to the peak concentration of the Fisher-Tropsch derived lighter body that is higher than target max X.

7. application or the application in preparation base oil formulations of Fisher-Tropsch derived lighter body in base oil formulations is used for allowing using and the necessary low-qualityer mineral derived base oil of one or more desired destination character of otherwise realizing preparaton at preparaton.

8. be used to prepare the method for base oil formulations, described method comprises mineral derived base oil and Fisher-Tropsch derived lighter body blend, wherein implement described method in order to make mineral derived base oil upgrading, described method comprises that the preparaton that had been used to make base oil before using or had comprised described base oil realizes that the processing of one or more desirable propertieses low degree of treatment of comparing prepares mineral derived base oil.

9. the method for claim 8 comprises deliberately making mineral derived base oil undertreatment and using fischer-tropsch deutero-lighter body to compensate at least in part because the change of the low caused mineral derived base oil character of the degree of treatment of experience now.