CN1993451B

CN1993451B - Multigrade engine oil prepared from fischer-tropsch distillate base oil

Info

Publication number: CN1993451B
Application number: CN2005800264418A
Authority: CN
Inventors: J·M·罗森鲍姆; S·J·米勒; S·M·阿伯内西
Original assignee: Chevron USA Inc
Current assignee: Chevron USA Inc
Priority date: 2004-08-05
Filing date: 2005-07-13
Publication date: 2011-09-28
Anticipated expiration: 2025-07-13
Also published as: ZA200700810B; CN1993451A

Abstract

The invention relates to a multigrade engine oil meeting the specifications for SAE J300 revised June 2001 requirements and a process for preparing it, said engine oil comprising (a) between 15 to 94.5 wt % of a hydroisomerized distillate Fischer-Tropsch base oil characterized by (i) a kinematic viscosity between 2.5 and 8 cSt at 100 DEG C, (ii) at least 3 wt % of the molecules having cycloparaffin functionality, and (iii) a ratio of weight percent molecules with monocycloparaffin functionality to weight percent of molecules with multicycloparaffin functionality greater than 15; (b) between 0.5 to 20 wt % of a pour point depressing base oil blending component prepared from an hydroisomerized bottoms material having an average degree of branching in the molecules between 5 and 9 alkyl-branches per 100 carbon atoms and wherein not more than 10 wt % boils below about 900 DEG F; and (c) between 5 to 30 wt % of an additive package designed to meet the specifications for ILSAC GF-3.

Description

Many grades machine oil by the preparation of fischer-tropsch distillate base oil

The cross reference of related application

The application requires the right of priority of the U.S. Provisional Application No.60/599665 of submission on August 5th, 2004.

The application also relates on November 7th, 2003 and submits to, title for submit in pendent U.S. Patent application Nos.10/704031 and on May 4th, 2004 of " use is derived from the method that the fischer-tropsch bottoms improves lubricating properties of base oils ", title for " using isomerized petroleum product to improve the method for lubricating properties of base oils " 10/839396, these two pieces of applications are incorporated herein by reference in full at this.

Invention field

The present invention relates to many grades machine oil by the preparation of fischer-tropsch distillate base oil, the SAE J300 requirement that it can satisfy the technical specification of ILSACGF-3 or GF-4 and revise June for MRV TP-12001, described MRV TP-1 is by blending fischer-tropsch base oil and depression of pour point base oil blending component and meet ILSAC GF-3 or the additive combination bag of GF-4 requirement prepares.

Background of invention

Machine oil be finished product crankcase with lubricator, be used for motor car engine and diesel motor, form by two kinds of basal components: lubricating base oil and additive.Lubricating base oil is the main component of finished lubricants, has determined the machine oil salient features.In general, by changing the mixture of each lubricating base oil and each additive, just can prepare miscellaneous machine oil with several lubricating base oils.

Many NGOs, wherein especially comprise Original Equipment Manufacturer (OEM), American Petroleum Institute (API) (API), ACEA (ACEA), U.S.'s test and materialogy meeting (ASTM), international lubricant levelization and the approval council (ILSAC), and SAE (SAE) waits other mechanisms, stipulated the technical specification of lubricating base oil and machine oil.Progressively requiring the machine oil technical specification is the product with good low-temperature performance, high oxidation stability and low volatility.At present, have only the base oil of the current production of sub-fraction can satisfy required technical specification.

Lubricating base oil be petroleum derivation or the synthetic hydrocarbon, have 100 ℃ of down about 2.5cSt or higher viscosity, preferably at 100 ℃ times about 4cSt or higher; About 9 ℃ or lower of pour point, preferred-15 ℃ or lower approximately; And VI (viscosity index) common about 90 or higher, preferred about 100 or higher.The VI of petroleum based oil is 120 at least.The Noack volatility that is used to prepare the lubricating base oil of finished lubricants should be not more than the I level or the II level lightweight neutral oil of present routine.

Term " base oil " is meant the hydrocarbon product that has above-mentioned performance before the additive adding.Usually reclaim base oil in the higher cut that from the vacuum distilling operation, reclaims.Can be by petroleum derivation or synthetic crude deutero-feedstock production base oil." additive " is to add in the finished lubricants to improve the chemical that specified property makes it to meet the minimum performance standards of finished lubricants grade.For example, the additive that adds machine oil can be used for improving lubricant stability, reduce its viscosity, rising viscosity index and control settling.Additive costs an arm and a leg, and can cause the compatibility problem of finished lubricants.Owing to these reasons, the additive level in the hope reduction machine oil is to the required minimum amount that meets the requirements usually.

The oil additives that two kinds of main types are arranged: DI additive combination bag (peace and quiet inhibitor additive combination bag and VI improving agent (viscosity index improver).DI additive combination bag plays suspension oil pollutent and combustion by-products and prevents the effect of oily oxidation, consequently forms varnish and slurry settling.The VI improving agent reduces thin speed and reduces the viscosity characteristics that thickening rate changes lubricant at low temperatures when heating up.VI improving agent thereby can under low temperature and high temperature, provide augmented performance.In the machine oil of many many grades was used, the VI improving agent must use with DI additive combination bag.Oil additives combination bag is available from additive supplier.Additive combination bag sky can be prepared, and when they were concocted with base oil with desired properties or base oil batching with box lunch, gained machine oil may satisfy specific machine oil and use kind.The specific machine oil of current use or exploitation uses kind to comprise ILSAC GF-3, ILSAC GF-4, APIC I-4 and API PC-10.

The SAE J300 standard of revision in June calendar year 2001 has been determined the minimum technical specification of the machine oil of various viscosity grades.Have following feature by machine oil by the F-T synthesis reaction product preparation, low-down sulphur content and advantages of excellent stability, thus make them become the high-quality alternative materials of blending high quality finished lubricants.Regrettably, be derived from fischer-tropsch machine oil and concoct low-temperature performance, especially the temperature pumping ability that the finished lubricants that forms has bad luck usually.Therefore, according to the SAE J300 of calendar year 2001 revision, the machine oil that is derived from fischer-tropsch is difficult to the viscosity specification requirements by minimum rotational viscosimeter (MRV) TP-1 of harshness.

ILSAC GF-3 is meant that the machine oil of automobile gasoline machine uses kind.This technical specification becomes statutory standards in July 1 calendar year 2001.ILSAC GF-4 was meant that the new oil at the motor vehicle gasoline machine of approval on January 8th, 2004 uses kind, and it becomes statutory standards on July 1st, 2004.This kind is introduced the new sulphur limit range of measuring by standard test methods ASTM D 1552.For 0W-XX and 5W-XX oil, the maximum upper limit of sulphur is 0.5wt%.For 10W-XX oil, the maximum upper limit of sulphur is 0.7wt%.Meet the machine oil that GF-4 requires and also meet the GF-3 requirement, may not meet requirement for GF-3 machine oil but meet machine oil that GF-3 requires.

Many grades machine oil is the machine oil with following feature: fall into the viscosity/temperature between the limit of two kinds of different SAE numbers in SAE J300.The present invention relates to following discovery: when the fischer-tropsch base oil with definite cycloalkanes functionality and depression of pour point batching and the blending of additive combination bag, the SAE J300 technical specification that can be met the calendar year 2001 revision by described fischer-tropsch base oil preparation is comprising many grades machine oil of MRV TP-1 viscosity technical specification.

The term that uses in this specification sheets " comprises " or " containing " work done in the manner of a certain author is open transition implication, comprising the composition of indication, but not necessarily gets rid of the composition that other is not pointed out.Term " basically by ... form " or " essentially consist is " intend referring to get rid of any other important in fact composition concerning said composition.Wording " by ... form " or " its composition is " intend referring to get rid of all the components beyond the element of being quoted, but the impurity of trace exception only.

The invention summary

The present invention relates to meet many grades machine oil of revising in the SAE in June calendar year 2001 J300 technical specification, described machine oil comprises the hydroisomerization fischer-tropsch distillate base oil of (a) about 15 to about 94.5wt%, it is characterized in that (i) 100 ℃ of following kinematic viscosity between about 2.5 to about 8cSt, the molecular wt percentage ratio that (ii) has the cycloalkanes functionality at least about the molecule of 3wt% and (iii) have a mononaphthene functionality and the ratio of the molecular wt percentage ratio with polynaphthene functionality are greater than about 15; (b) the depression of pour point base oil blending component between about 0.5 to about 20wt%, its by the average degree of branching of intramolecularly be per 100 carbon atoms about 5 to about 9 alkyl branches, wherein be no more than the tower bottom material preparation of 10wt% ebullient hydroisomerization when being lower than about 900 ℉; Be to meet the additive combination bag that the technical specification of I LSAC GF-3 designs (c) between about 5 to about 30wt%.Use the present invention can prepare many grades machine oil, described many grades machine oil meets the technical specification of SAE viscosity grade 0W-XX, 5W-XX or 10W-XX machine oil, and wherein XX represents integer 20,30 or 40.Many grades machine oil that can produced according to the present inventionly meet the SAE0W-20 technical specification.

The invention still further relates to the method for the many grades machine oil for preparing the SAE J300 technical specification that meets revision in June calendar year 2001, this method comprises that (a) is in isomerization zone, in the presence of catalyzer and hydrogen, under for the definite preselected condition of the fischer-tropsch base oil product that hydroisomerization is provided, hydroisomerized wax shape fischer-tropsch base oil; (b) reclaim the fischer-tropsch base oil product of hydroisomerization from isomerization zone; (c) under preselected distillation condition, the fischer-tropsch base oil product of the hydroisomerization that distillation is reclaimed from isomerization zone is to collect the fischer-tropsch distillate base oil, the fischer-tropsch base oil product of described hydroisomerization be characterised in that (i) kinematic viscosity under 100 ℃ between about 2.5 to about 8cSt, the molecular wt percentage ratio that (ii) has the cycloalkanes functionality at least about the molecule of 3wt% and (iii) have a mononaphthene functionality and the ratio of the molecular wt percentage ratio with polynaphthene functionality are greater than about 15; (d) with suitable ratio with the fischer-tropsch distillate base oil with (i) be that per 100 carbon atoms about 5 are to about 9 alkyl branches by the average degree of branching of intramolecularly, the depression of pour point base oil blending component of the hydroisomerization tower bottom material preparation that being lower than seethes with excitement under about 900 ℉ is no more than 10wt%, and, obtain meeting many grades machine oil of the SAE J300 technical specification of revising June calendar year 2001 (ii) for meeting the additive combination bag blending that I LSAC GF-3 technical specification sets.Preferably in blending step (c) before, the cut base oil fraction of hydrofining hydroisomerization is to reduce the existing to low-level of any aromatic hydrocarbons and alkene.

Can prepare depression of pour point base oil blending component by tower bottom distillate from petroleum derivation or Fisher-Tropsch derived product.If depression of pour point base oil blending component is isomerized petroleum derivation bottom product, then preferred its molecular-weight average is at least 600.If depression of pour point base oil blending component is the Fisher-Tropsch derived bottom product of hydroisomerization, then preferred its molecular-weight average is between about 600 to about 1100.

Detailed Description Of The Invention

The SAE J300 technical specification (revision in June calendar year 2001) of machine oil is described in detail in detail in the following table 1.

Table 1*

* remarks: 1cP=1 centipoise=1mPa.s.Can this dynamic viscosity of conversion as described below: dynamic viscosity=density * kinematic viscosity.

At 106s ^-1According to ASTM D4683, ASTM D4741 or ASTM D5481 measure high temperature high shear rates viscosity down.

Measure cold crank simulator viscosity (CCS Vis) according to ASTM D5293.

Measure minimum rotational viscosimeter (MRV) TP-1 viscosity according to ASTM D4684.

Measure kinematic viscosity according to ASTM D445.

Analytical procedure

Measure described in the present invention kinematic viscosity by ASTM D445-01.

Use cold crank simulator viscosity (CCS VIS) to measure the viscosity performance of lubricating base oil under low temperature and high-shear.The test method of measuring CCS VIS is ASTM D5293-02.The result is with centipoise, and cP is a unit.Find that CCS VIS is relevant with the cryogenic engine bent axle.For motor vehicle machine oil, define the technical specification of maximum CCS VIS by the SAE J300 that revises June calendar year 2001 of listing in the last table 1.

High temperature high shear rates viscosity (HTHS) is in the oil engine of igniting, under the shaft bearing condition of simulation high capacity, and usually at 150 ℃, 100 ten thousand seconds ^-1Down, the fluid resistance to flow measures.HTHS is that the motion low shearing speed viscosity during with 100 ℃ is compared, and adopts better index when specifying lubricant how to operate engine during high temperature.The HTHS value is directly related with the thickness of oil film in bearing.The SAEJ300 (referring to table 1) of revision in June calendar year 2001 comprises present technical specification for the HTHS that measures by ASTMD4683, ASTM D4741 or ASTM D5481.The machine oil of SAE20 viscosity grade, for example maximum HTHS value requires 2.6 centipoises (cP).

Minimum rotational viscosimeter (MRV TP-1) test relates to pumping mechanism and is measuring of the low shearing speed measured by standard test methods ASTM D4684.The sample speed of cooling is the key feature of this method slowly.Pretreatment sample to be to have specific thermal history, and that described specific thermal history comprises is warm, slowly cooling and infusion.MRV TP-1 measures apparent yielding stress, if it is greater than threshold value, then shows potential air sinuses pumping failure problem.Be higher than certain viscosity (the SAE J300 by revision in June calendar year 2001 is defined as 60000cP at present), oil may be easy to the pumping failure because of the mechanism that is called as " restriction is flowed " behavior.For example, the SAE10W oil require is not having under the situation of yielding stress, and the peak viscosity under-30 ℃ is 60000cP.This method is also measured at 1-50s ^-1Velocity of shear under apparent viscosity.

Except the requirement that meets SAE J300 (revision in June calendar year 2001), can prepare many grades machine oil of the present invention meeting the technical specification of ILSAC GF-3, and harsh more GF-4 technical specification.It is 15 that GF-3 and GF-4 require minimum Noa ck volatility.Yet the Noack volatility number of preferred finished lubricants is for being less than or equal to 10.The Noack volatility of stipulating in ILSAC GF-3 and GF-4 is used standard test methods ASTM D 5800.According to this method, Noack is defined as when in the test crucible of constant airflow through therefrom drawing in 60 minutes, at 250 ℃ and subatmospheric 20mmHg (2.67kPa; 26.7mbar) down during heated oil, the quality of the oil of the loss of expressing with weight percentage.The conventional more method of calculating Noack volatility and the method relevant well with ASTM D 5800 are to use the thermogravimetric analyzer test (TGA) by ASTM D 6375.

Pour point is meant the temperature when sample begins to flow under the condition of accurately control.In the disclosure of invention, the pour point that wherein provides except as otherwise noted, otherwise all is to measure pour point by standard method of analysis ASTM D5950 or the method suitable with it.Can measure VI by using ASTMD2270-93 (1998) or the method suitable with it.Can come determining molecular weight by ASTM D2502, ASTM D2503 or other suitable method.For the present invention, preferably by ASTM D2503-02 determining molecular weight.The analytical procedure of equal value of canonical reference method as used herein is meant any analytical procedure that provides basically with the standard method identical result.

According to the method in following 7 steps, by using C-13NMR, analyze oil samples, measure the branching performance of depression of pour point base oil blending component of the present invention.The reference of quoting in specification sheets of the present invention provides the details of processing step.Step 1 and 2 is only carried out on from the parent material of novel process.

1) uses DEPT pulse sequence, identify CH branching center and CH ₃Side chain terminating point (Doddre11, D.T.; D.T.Pegg; M.R.Bendall, Journal of MagneticResonance1982,48,323ff).

2) use APT pulse sequence, identify not have carbon (quaternary carbon) (Patt, the S.L. that causes higly branched chain; J.N.Shoolery, Journal of Magnetic Resonance1982,46,535ff).

3) use tabulation and calculated value, with the resonance of various branching carbon owing to specific branch position and length (Lindeman, L.P., Journal of Qualitative AnalyticalChemistry43,19711245ff; Netzel, people such as D.A., Fuel, 60,1981,307ff).

Example:

Side chain nmr chemical displacement (ppm)

2-methyl 22.5

3-methyl 19.1 or 11.4

4-methyl 14.0

4+ methyl 19.6

Interior ethyl 10.8

Propyl group 14.4

Adjacent methyl 16.7

4) intensity of integrated intensity with the single carbon by its terminal methyl carbon relatively (carbon number in=total integrated value/mixture in each molecule), quantification is in the relative frequency of different carbon locations place side chain appearance.At identical resonant position the Special Circumstances of 2-methyl branch appear for end group and branched chain methyl, before calculating the side chain frequency of occurrences, with intensity divided by 2.As if the 4-methyl branch partly being calculated and tabulating, then must deduct its contribution, to avoid twice calculating to the 4+ methyl.

5) calculate average carbon number.Can pass through to use the molecular weight of sample divided by 14 (CH ₂Molecular weight), be enough to accurately measure the average carbon number of lubricant.

6) the side chain number of each molecule is the side chain sum that obtains in the step 4.

7) (step 6) * 100/ average carbon number is calculated the alkyl branches number in per 100 carbon atoms according to the quantity of side chain in each molecule.

Measurement can use any fourier transform NMR spectrometer to carry out.The preferred spectrometer that has 7.0T or bigger magnet that uses is measured.In all cases, after not having aromatics carbon by mass spectrum, UV or NMR measurement proof, spectrum width is subjected to the restriction in saturated carbon zone, about 0-80ppm vs.TMS (tetramethylsilane).Chloroform-d1 solution by 45 degree pulse excitation 15-25wt% has 0.8 second detection time afterwards.For inhomogeneous intensity data is minimized, close and in capture process, open in 10 seconds deferring procedures of proton-decoupled device before excitation pulse.Total experimental period scope is 11-80 minute.DEPT and APT sequence are carried out according to document description, with description in Varian or the Bruker operational manual deviation are arranged slightly.

DEPT is by the undistorted enhancing of polarization transfer.DEPT does not show quaternary carbon.The DEPT45 sequence provides all carbon signals that are connected with proton.DEPT90 only shows CH carbon.DEPT135 demonstrates CH and CH ₃Upwards with 180 ° of CH ₂Outer (downwards) mutually.APT is that the proton test is related.As seen it can make whole carbon, but if CH and CH ₃Make progress, then quaternary carbon and CH ₂Downwards.Sequence can be used for each branched chain methyl that should have corresponding CH.Methyl can be by chemical shift and clearly affirmation mutually.More than the two all in reference to some extent the record.The whole samples of hypothesis are different alkanes in calculating, measure the branching characteristic of each sample by C-13NMR.Do not proofread and correct with positive paraffins or naphthalene that different content is present in the oil samples.Can use field ionization mass spectrum (FIMS) to measure the content of naphthalene.

By being placed, a small amount of (about 0.1mg) machine oil to be measured carries out the FIMS analysis in the glass capillary.Kapillary is placed mass spectrograph solid probe tip, and in the mass spectrograph of under about 10-6torr, operating, probe is heated to 600 ℃ from about 50 ℃ with 100 ℃/minute speed.Employed mass spectrograph is micro-time-of-flight mass spectrometer.Projector is the Carbotec 5um projector that designs for the FI operation.Will as lock mass five fluorochlorobenzene constant currents by thin kapillary input mass spectrograph.The response factors of supposing all types of compounds is 1.0, so that directly provide weight percentage by area percent.

Because petroleum derivation hydrocarbon and Fisher-Tropsch derived hydrocarbon comprise the mixture of the various molecular weight with broad boiling range, therefore, disclosure text is meant 10% boiling point of the boiling range of depression of pour point base oil blending component.10% boiling point is meant the temperature the when hydrocarbon that has 10wt% in the depression of pour point base oil blending component under atmospheric pressure evaporates.When mentioning depression of pour point base oil blending component, use only 10% boiling point, this is because it is derived from tower bottom distillate usually, described tower bottom distillate has constituted and the irrelevant boiling upper limit of the purpose that limits material.Be higher than the sample of 1000 ℉ for boiling range, disclosure text is to use standard method of analysis ASTM D 6352 or the method suitable with it to measure.Be lower than the sample of 1000 ℉ for boiling range, disclosure text is to use standard method of analysis ASTM D 2887 or the method suitable with it to measure.

Hydroisomerization

Hydroisomerization is meant by selectivity in molecular structure increases branching to improve the cold flow properties of fischer-tropsch base oil.Also use hydroisomerization to prepare depression of pour point base oil blending component.The ideal isomerization is that the high level of wax to the different alkane of non-waxy transformed, and it is minimum that cracking is transformed.Preferably, the condition of hydroisomerization among control the present invention changes into and is lower than that ebullient conversion of compounds rate maintains about 10wt% to 50wt% under about 700 ℉ so that be higher than under about 700 ℉ the ebullient compound in the paraffin, preferably 15wt% to 45wt%.

According to the present invention, use the shape selective mesoporous molecular sieve, carry out hydroisomerization.Can be used for the metallic hydrogenation component that hydroisomerisation catalysts of the present invention is included in the shape selective mesoporous molecular sieve on the refractory oxide carrier and chooses wantonly with catalytic activity.Wording as used herein " mesopore " is meant that when the porous inorganic oxide was calcined form, the effective pore radius was about 3.9-about 7.1 The shape selective mesoporous molecular sieve that uses in the present invention's practice is 1-D10-, 11-or 12-toroidal molecule sieve normally.Preferred molecular sieve of the present invention is a 1-D10-ring variant, wherein the atom (T-atom) of 10 (perhaps 11-or 12-) toroidal molecule sieve (perhaps 11 or 12) individual tetrahedral coordination that connects by Sauerstoffatom that has 10.In the 1-D molecular sieve, the hole of 10-ring (or bigger) is parallel to each other, not interconnection.Yet, be noted that the broad definition of satisfying mesoporous molecular sieve, but comprise that the 1-D10-toroidal molecule sieve of the intersection hole with 8 yuan of rings also can include in the definition of molecular sieve of the present invention.By R.M.Barrer at Zeolites, Science and Technology (F.R.Rodrigues, L.D.Rollman and C.Naccache, NATO ASI Series edits, 1984) listed the classification of the zeolite interior passageway that is categorized as 1-D, 2-D and 3-D in, this is sorted in this and introduces in full with reference to (especially referring to the 75th page).

The preferred shape selectivity mesoporous molecular sieve that uses in the hydroisomerization is with aluminum phosphate, and for example SAPO-11, SAPO-31 and SAPO-41 are the basis, wherein more preferably SAPO-11 and SAPO-31, most preferably SAPO-11.SM-3 is the preferred especially SAPO of particularly preferred shape selective mesopore, and its crystalline texture drops in the SAPO-11 molecular sieve.Preparation and the unique feature thereof of SM-3 are disclosed in United States Patent(USP) Nos. 4943424 and 5158665.Same preferred shape selectivity mesoporous molecular sieve is a zeolite in the hydroisomerization, for example ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ-32, offretite and ferrierite.More preferably SSZ-32 and ZSM-23.

Preferred mesoporous molecular sieve is characterised in that the free diameter of crystallography of the selection of passage, the grain-size of selection (corresponding to the passage length of selecting) and the acidity of selecting.The free diameter range of required crystallography of the passage of molecular sieve is about 3.9-about 7.1

Figure S05826441820070207D00010123303QIETU

, the free diameter of maximum crystallography be not more than 7.1 and the free diameter of smallest crystals be not less than 3.9

Figure S05826441820070207D00010123307QIETU

The free diameter of preferred maximum crystallography is not more than 7.1

Figure S05826441820070207D00010123312QIETU

Be not less than 4.0 with the free diameter of smallest crystals

Figure S05826441820070207D00010123317QIETU

The free diameter of most preferably maximum crystallography is not more than 6.5

Figure S05826441820070207D00010123320QIETU

Be not less than 4.0 with the free diameter of smallest crystals At Ch.Baerlocher, W.M.Meier and D.H.Olson, " the zeolite structure type complete works " of Elsevier, the 5th revised edition, 2001, publication discloses the free diameter of crystallography of the passage of molecular sieve among the pp.10-15, is incorporated herein by reference.

For example disclosing the particularly preferred mesoporous molecular sieve that is used for method of the present invention in the United States Patent(USP) Nos. 5135638 and 5282958, its content is introduced by reference in its entirety at this.In U.S. Patent No. 5282958, this mesoporous molecular sieve has and is not more than about 0.5 micron grain-size and minimum diameter is at least about 4.8

Figure S05826441820070207D00010123355QIETU

With maximum diameter be about 7.1

Figure S05826441820070207D00010123402QIETU

Hole.

Catalyzer has enough acidity, so that when placing tubular reactor, under 370 ℃, 1200psig pressure, 160ml/min hydrogen flowing quantity and 1ml/hr feeding speed, the 0.5g catalyzer can transform at least 50% n-Hexadecane.When being used to make n-hexadecane (n-C ₁₆) when the transformation efficiency that changes into other species is 96% situation, this catalyzer also demonstrate 40% or higher isomerization selectivity (isomerization optionally is defined as follows: 100 * (branching C in the product ₁₆Weight percentage)/(branching C in the product ₁₆Weight percentage+product in C ₁₃Weight percentage).

The further characteristics of this particularly preferred molecular sieve are that the free diameter range of crystallography is about 4.0

Figure S05826441820070207D00011123436QIETU

To about 7.1 And preferable range is 4.0-6.5 Hole or passage.At Ch.Baerlocher, W.M.Meier and D.H.Olson, " the zeolite structure type complete works " of Elsevier, the 5th revised edition, 2001, publication discloses the free diameter of crystallography of the passage of molecular sieve among the pp.10-15, is incorporated herein by reference.

If free diameter the unknown of crystallography of the passage of molecular sieve, then can use the hydrocarbon compound of standard absorption technology and known minimum movement diameter to measure the effective pore radius of molecular sieve.Referring to, Br eck, Zeolite " molecular sieve ", 1974 (particularly the 8th chapters); Anderson, J.Catalysis58,114 (1979); With U.S. Patent No. 4440871, its relevant portion is here cited reference.Using standard technique for measuring in the absorptiometry that carries out in the aperture.Consider the specific molecular of getting rid of when being lower than at least 95% (at the 25 ℃ of following p/p0=0.5) that do not reach its balance absorption value in about 10 minutes on the molecular sieve, this method is very easily.It is 5.3-6.5 that the molecular sieve of mesopore allows the motion diameter usually Molecule more successfully enter.

Can be used for hydroisomerisation catalysts of the present invention and comprise hydrogenation metal with catalytic activity.The existence of the hydrogenation metal of catalytic activity causes product improvement, particularly VI and stability.The hydrogenation metal of catalytic activity commonly used comprises chromium, molybdenum, nickel, vanadium, cobalt, tungsten, zinc, platinum and palladium.Special preferable alloy platinum and palladium, the most preferred platinum.If use platinum and/or palladium, then total weight range of active hydrogenation metal is generally the 0.1-5wt% of whole catalyzer, common 0.1-2wt%, and be no more than 10wt%.

Refractory oxide carrier is optional from those conventional oxide carriers that are used for catalyzer, comprising silicon oxide, aluminum oxide, silica-alumina, magnesium oxide, titanium oxide and composition thereof.

Regulate the condition of hydroisomerization, with the ratio that obtains comprising molecular wt percentage ratio that has the cycloalkanes functionality and have a mononaphthene functionality greater than 5wt% and molecular wt percentage ratio with many ring functionality greater than 15 Fisher-Tropsch derived lubricant base oil.

The condition of hydroisomerization depends on raw materials used performance, used catalyzer, and whether catalyzer cures, required productive rate and the required performance of lubricant base oil.The condition that hydroisomerisation process of the present invention can be carried out comprises the temperature of about 550 ℉-Yue 775 ℉ (288 ℃-Yue 413 ℃), preferred about 750 ℉ of 600-℉ (315 ℃ to about 399 ℃), more preferably from about 600 ℉-Yue 700 ℉ (315 ℃-Yue 371 ℃); With the pressure of about 15-3000psig, preferred 100-2500psig.Hydroisomerization dewaxing pressure is meant the hydrogen partial pressure in hydroisomerization reactor in this text, although the dividing potential drop of hydrogen substantially the same with stagnation pressure (perhaps much at one).The about usually 0.1-20hr of liquid hourly space velocity degree in the contact process ^-1, the about 5hr of preferably about 0.1- ^-1During hydroisomerization carried out, hydrogen was present in the reaction zone, and hydrogen is about 0.5-30MSCF/bbl (1000 with the ratio of raw material usually ³/ bucket), the about 10MSCF/bbl of preferably about 1-.Hydrogen can be separated with product and be recycled in the reaction zone.Disclose the suitable condition that carries out hydroisomerization in United States Patent(USP) Nos. 5282958 and 5135638, its content is introduced reference in full at this.

Hydrofining

The hydrofining operation can improve the UV stability and the color of product.Be sure of generally and can realize that this is saturated can also to reduce aromatic hydrocarbons and olefin(e) centent to lower level by the saturated two keys that are present in the hydrocarbon molecule.In the present invention, before the blending step, preferably the cut base oil with hydroisomerization is transported in the hydrofinisher.Can in United States Patent(USP) Nos. 3852207 and 4673487, find the general remark of hydrofining technology.Term as used in this specification, UV stability are meant when being exposed to UV-light and oxygen following time, the stability of lubricating base oil or other products.Be exposed in UV-light and the air and the precipitation that to see or obscure color just to occur, cause sending out turbid in the base oil or when flocculating, show it is unsettled.The lubricating base oil of Shi Yonging requires UV stable usually in the present invention, and they just can be applicable to and make commercial lubricating oil afterwards.

Total pressure among the present invention in the hydrofining district is more than the 500psig, more than the preferred 1000psig and most preferably more than the 1500psig.Maximum total pressure is not crucial concerning this technology, but because the limitation of equipment causes total pressure will be no more than 3000psig, and be no more than about 2500psig usually.Temperature range in hydrofining reactor usually in about 300 ℉ (150 ℃)-Yue 700 ℉ (370 ℃) scope, the temperature of wherein preferred about 400 ℉ (205 ℃)-Yue 500 ℉ (260 ℃).It is about 2.0 that the scope of LHSV is generally about 0.2-, preferred 0.2-1.5 and 0.7-1.0 most preferably from about.Usually the speed of hydrogen with the about 10000SCF/ bucket of about 1000-raw material is fed in the hydrofining reactor.Usually fill hydrogen with the speed of about 3000SCF/ bucket.

The Hydrobon catalyst that is suitable for contains VIII family noble metal component and oxide carrier usually.The metal or the compound that are used for Hydrobon catalyst comprise ruthenium, rhodium, iridium, palladium, platinum and osmium.Preferred one or more metals are platinum, palladium, or the mixture of platinum and palladium.Refractory oxide carrier is made up of silica-alumina, silica-alumina-zirconium white and analogue usually.Typical Hydrobon catalyst is disclosed in United States Patent(USP) Nos. 3852207,4157294 and 4673487.

The fischer-tropsch distillate base oil of hydroisomerization

Usually pass through or normal pressure or vacuum distilling, perhaps normal pressure carries out separating of fischer-tropsch products with the combination of vacuum distilling.Usually use the distillate cut that air distillation will be lighter, for example petroleum naphtha and medium distillate separate to the tower bottom distillate more than about 750 ℉ (about 370 ℃-Yue 400 ℃) with about 700 ℉ of initial boiling point.The thermo-cracking of hydrocarbon can take place under comparatively high temps, thereby causes equipment scaling and lower than the last running productive rate.Usually use the raw material of vacuum distilling separation higher, for example employed cut base oil fraction among the present invention.

Term used in the present invention " distillates cut " or " cut " is meant or from atmospheric fractional tower or the effluent product that reclaims from vacuum column, it is opposite with " bottom product ", and the residual high boiling fraction at the bottom of tower is reclaimed in described bottom product representative.

The fischer-tropsch distillate base oil of employed hydroisomerization contains low-down sulphur, high VI and good cold flow properties among the present invention.After hydroisomerisation step, the cut base oil of hydrofining hydroisomerization except the UV stability that can improve base oil, can also reduce aromatic hydrocarbons to lower aq usually; Preferred aromatic hydrocarbons comprises less than about 0.3wt%.After the hydrofining step, base oil also contains small amounts of olefins, and preferred content is lower than the detection level by the carbon-13NMR of long duration.

Usually, the minimum movement viscosity of fischer-tropsch base oil is down 2.5cSt at least at 100 ℃, preferably 3cSt and more preferably 4cSt at least at least, and on be limited to about 8cSt.The pour point of fischer-tropsch base oil is lower than 20 ℃, preferably is lower than-12 ℃ and VI usually greater than 90, is preferably greater than 100, even more preferably greater than 120.

The molecule number of fischer-tropsch distillate base oil with hydroisomerization of cycloalkanes functionality is 5wt% at least, and the molecule number that preferably has the cycloalkanes functionality is at least about 10wt%.The weight percentage of weight percentage and the molecule with polynaphthene functionality of molecule that has the mononaphthene functionality in the fischer-tropsch base oil of hydroisomerization is preferably greater than about 50 also greater than about 15.Can be by carefully selecting the operational condition of hydroisomerisation step, control whole cycloalkanes functionality simultaneously and be present in the ratio of mononaphthene functionality and polynaphthene functionality in the base oil.

The viscosity index of the fischer-tropsch distillate base oil of hydroisomerization preferably is equal to or greater than the numerical value that calculates by following equation:

VI=28 * Ln (kinematic viscosity under 100 ℃)+95

Wherein: VI represents viscosity index

Ln represents natural logarithm.

The cold bent axle simulator viscosity of the fischer-tropsch distillate base oil of hydroisomerization under-35 ℃ preferably is equal to or less than the numerical value that calculates by following equation:

CCS VIS (35 ℃)=38 * (kinematic viscosity under 100 ℃) ³

Wherein: the cold bent axle simulator viscosity of CCS VIS (35 ℃) representative under-35 ℃.

Even more preferably the cold bent axle simulator viscosity of fischer-tropsch distillate base oil under-35 ℃ of hydroisomerization preferably is equal to or less than the numerical value that calculates by following equation:

CCS VIS (35 ℃)=38 * (kinematic viscosity under 100 ℃) ^2.8

Depression of pour point base oil blending component

Usually distill after the more lower boiling base oil fraction, prepare depression of pour point base oil blending component by high boiling point bottoms residual in the vacuum column.Its molecular weight is at least 600.It can by or the preparation of the bottoms of Fisher-Tropsch derived or petroleum derivation.The hydroisomerization bottoms is that per 100 carbon atoms about 5 are between about 9 alkyl branches with the average degree of branching that realizes molecule.After hydroisomerization, the pour point of depression of pour point base oil blending component should be between about-20 ℃ to about 20 ℃, is generally approximately between-10 ℃ to about 20 ℃.For being suitable for actually operating of the present invention, molecular weight and particularly crucial in the intramolecular degree of branching.

With regard to the fischer-tropsch synthetic crude, prepare depression of pour point base oil blending component by being generally solid wax shape cut under the room temperature.Can perhaps can prepare wax shape cut by fischer-tropsch synthetic crude direct production wax shape cut by more lower boiling Fisher-Tropsch derived olefin oligomer.No matter the source of fischer-tropsch wax why, and it must contain the above ebullient hydrocarbon of 950 ℉ that have an appointment, so that be created in the bottoms that uses in the preparation depression of pour point base oil blending component.In order to improve pour point and VI, the hydroisomerizing fossil waxes is introduced intramolecularly with favourable side chain.The paraffin of hydroisomerization is transported in the vacuum column usually, collects various distillate base oil fraction at this.With regard to Fisher-Tropsch derived base oil, the distillate base oil fraction can be used for hydroisomerization fischer-tropsch distillate base oil.The bottoms of collecting from vacuum column comprises high boiling hydrocarbon mixture, and described mixture is used to prepare depression of pour point base oil blending component.Except hydroisomerization and rectifying, wax shape cut can experience various other operations, for example hydrocracking, hydrotreatment and hydrofining.Depression of pour point base oil blending component of the present invention is not the additive in the common purposes of this term in this area, and this is because its only actually is high boiling base oil fraction.

The pour point of depression of pour point base oil blending component is than at least 3 ℃ of the pour point height of the fischer-tropsch distillate base oil of hydroisomerization.When the bottoms of having found the hydroisomerization described in this specification sheets is used to reduce the pour point of concoction, the pour point of concoction will be lower than the two the pour point of fischer-tropsch distillate base oil of depression of pour point base oil blending component and hydroisomerization.Therefore, do not need to reduce the target pour point of the pour point of bottoms to machine oil.Therefore, actual hydroisomerization degree does not need with desired the same high in other cases, and can operate hydroisomerization reactor under the situation of less cracking and less loss of yield under low harsh degree.Find that oil foot should the excessive hydrogenation isomerization, perhaps sacrifices the ability that it serves as depression of pour point base oil blending component.Therefore, the intramolecular average degree of branching should drop in the scope of about 9 alkyl branches/100 carbon atoms of about 5-in the fischer-tropsch bottoms.

The molecular-weight average that is derived from the depression of pour point base oil blending component of fischer-tropsch raw material is about 600 to about 1100, preferred about 700 to about 1000.In the kinematic viscosity under 100 ℃ usually within the about 22cSt scope of about 8cSt-.The boiling point of bottoms 10% boiling range usually at about 850 ℉ between about 1050 ℉.Usually, the hydrocarbon of higher molecular weight is more effective as the more low-molecular-weight hydrocarbon of depression of pour point base oil blending component.Usually, the molecular weight of depression of pour point base oil blending component is more than or equal to 600.Therefore, when preparation depression of pour point base oil blending component, can produce the higher fraction point of higher bottoms raw material in the usually preferred fractional column.The advantage that higher fraction point also has is to produce the distillate base oil fraction of higher yields.

Find that also by usually-10 ℃ or lower at low temperatures, the bottoms raw material of solvent dewaxing hydroisomerization can improve the effectiveness of depression of pour point base oil blending component.Have been found that in the solvent dewaxing process isolating wax shape product has shown enhanced depression of pour point performance from bottoms, condition is that the branching performance still remains in the limit of the present invention.Reclaim the oily product after the solvent dewaxing operation, the depression of pour point performance that it demonstrates is effective not as wax shape product.

For the situation of petroleum derivation, basic preparation method is with above-described substantially the same.Depression of pour point base oil blending component for the preparation petroleum derivation particularly preferably is the bright stock that contains high paraffinicity.Bright stock is can be highly purified and the tower bottom distillate of dewaxing.Bright stock is full-bodied base oil, and it is named because of the SUS viscosity under 210 ℉.Usually, petroleum derivation light oil viscosity is more than 40 ℃ of following 180cSt, more than preferred 40 ℃ of following 250cSt and more preferably within 40 ℃ of following 500-1100cSt.Find that the bright stock that is derived from Daqing crude oil is particularly suitable for as depression of pour point base oil blending component of the present invention.Bright stock can hydroisomerization and randomly solvent dewaxing.Found that the bright stock that only prepares by solvent dewaxing is not very effective as depression of pour point base oil blending component.

The preferred alkane content of depression of pour point base oil blending component of petroleum derivation is at least about 30wt%, more preferably 40wt% and most preferably 50wt% at least at least.The boiling range of depression of pour point base oil blending component should be more than about 950 ℉ (510 ℃).10% boiling point should be greater than about 1050 ℉ (565 ℃), and wherein preferred 10% boiling point surpasses 1150 ℉ (620 ℃).The intramolecular average degree of branching of depression of pour point base oil blending component is about about 8 alkyl branches of about 6-at per 100 carbon atoms preferably.

The additive combination bag

The additive combination bag intends providing the finished lubricants extra performance, for example the additive of antifatigue, wear-resisting and ultimate pressure performance.Be blended into the technical specification that the interior additive combination bag of many grades machine oil must be set to meet ILSAC GF-3 or GF-4.The technical specification of GF-4 is similar to GF-3, but GF-4 requires to be difficult to more reach in some test.Therefore, any many grades machine oil that meets the GF-4 technical specification will meet GF-3 equally.Yet, be false on the contrary.That is to say that many grades machine oil of the not all GF-3 of meeting technical specification can reach GF-4.The commercial supplier that GF-3 and GF-4 additive combination bag much are provided is arranged on the market.LubrizolLZ20000 (The Lubrizol Corporation) and 0loa 55006A (ChevronOronite Company LLC) be can the commercial GF-3 additive combination bag of buying two typical case.Although commercially available additive combination bag is special-purpose, for the additive combination bag, United States Patent(USP) Nos. 6500786 and 6730638 discloses the prescription that can ILSAC GF-4 requires.

Zinc dialkyl dithiophosphate (ZDDP) is a kind of attrition resistant additive, and it is the common component that is present in the commercial additive combination bag.Yet ZDDP produces ash content, and ash content helps to form particulate matter in automobile emission, and the environmental emission of zinc is being attempted to reduce by administration.In addition, phosphorus, a kind of component among the ZDDP thinks that it has limited the work-ing life that is used in the catalytic converter that pollutes with reduction on the automobile.Because toxicity and environment reason are wished to be limited in particulate matter and the pollutent that forms in the engine use, but be it is also important that, keep the wear resisting property of lubricating oil not reduce.In view of the known shortcoming that contains the additive of zinc and phosphorus, be reduced in the zinc of existence in the additive combination bag and for a short time being fruitful of content of phosphorus.Preferably, the additive combination that uses in preparation many grades machine oil of the present invention includes the zinc less than about 1.00wt% of expressing with metal element.This additive combination bag also preferably contains the phosphorus less than about 0.90wt% of expressing with metal element.

Many grades machine oil

Commercial many grades machine oil is meant that viscosity/temperature profile drops between two kinds of different SAE numerical value utmost points of SAE J300 (referring to table 1) and also meets or ILSAC GF-3 or GF-4 requirement, add that API uses kind, for example machine oil of SL (for the vehicle of gasoline driven) or CI-4 (for the vehicle of diesel driven).There is the technical specification system of oneself in Europe, but they do not introduce the test of some North Americas.The North America system is used in all the other places, whole world great majority to a certain extent, but mainly adopts out of date API to use kind in developing country.Many grades machine oil within the scope of the present invention comprises about 15 to about 94.5wt% hydroisomerization fischer-tropsch distillate base oil, the about 0.5 additive combination bag to about 20wt% depression of pour point base oil blending component and about 5 to about 30wt%.Usually, many grades machine oil of the present invention contains enough depression of pour point base oil blending components, can reduce by 2 ℃ of the pour points of the fischer-tropsch distillate base oil of hydroisomerization at least.In addition, many grades machine oil can randomly also contain other component or additive.For example, many grades machine oil also can contain the about 70wt% of the 5wt%-that has an appointment and is selected from olefin polymerization at least a polyalphaolefin base oil, poly-internal olefin base oil or polyalphaolefin and the poly-internal olefin base oil mixture.Yet, usually must extra pour point depressant and/or viscosity index improver in the prescription of preparation according to the present invention.

When concocting many grades machine oil of the present invention, the order of various components blendings is inessential.For example, when mentioning enough depression of pour point base oil blending components be arranged, during with at least 2 ℃ of the pour points of the fischer-tropsch distillate base oil that reduces hydroisomerization, be not that depression of pour point base oil blending component and hydro-isomerised fraction base oil must at first mix, the mixed additive combination is wrapped in next step then.The meaning is meant in final concoction, if there is not the additive combination bag, with depression of pour point base oil blending component hydroisomerization fischer-tropsch distillate base oil blending together, the ratio of the two should make at least 2 ℃ of the depressions of pour point of fischer-tropsch distillate base oil of hydroisomerization.Irrelevant with the PS of each component of blend wherein.

Can prepare many grades machine oil within the scope of the present invention, to meet the technical specification of SAE viscosity grade 0W-XX, 5W-XX or 10W-XX machine oil, wherein XX represents integer 20,30 or 40.Use the present invention successfully to prepare the prescription of the technical specification that meets SAE viscosity grade 0W-20.The MRV TP-1 of this requirement prescription must have the result at-40 ℃ of following 60000cP, and does not have yielding stress.Equally, the result that can prepare respectively at MRV TP-1 under the temperature of-35 ℃ and-30 ℃ is the many grades machine oil within 60000 the scope of the invention.In the result of-40 ℃ of following MVR TP-1 is that 30000 and 15000 prescription also is possible.

In order to satisfy the requirement of ILSAC GF-3 and GF-4, must be by the Noack volatility numerical value 15 of standard test methods ASTMD5800 measurement.Because the volatility of the fischer-tropsch material that uses is low, therefore can realize 10 or lower Noack volatility in the present invention prescription.

Further set forth the present invention by following embodiment, yet, the invention is not restricted to the scope of described embodiment.

Embodiment

Two kinds of fischer-tropsch wax with iron-based or the preparation of cobalt-based Fischer-Tropsch catalyst.They have the performance shown in the table 2:

Table 2

Fischer-Tropsch catalyst	The Fe-base	The Co-base
			Total nitrogen and sulphur, ppm	Less than 10	Less than 25
By the oxygen of neutron activation, wt%	0.15	0.69
			Oil-contg, D721, wt%	<0.8	6.68
Total normal alkane is measured wt% by GC	92.15	83.72
			D6352S?IMDI?ST(wt％)，℉
T0.5	784	129
			T5	853	568
T10	875	625
			T20	914	674
T30	941	717
			T40	968	756
T50	995	792
			T60	1013	827
T70	1031	873
			T80	1051	914
T90	1081	965
			T95	1107	1005
T99.5	1133	1090

By being carried on the Pt/SAPO-11 of alumina supporter, the fischer-tropsch wax of hydroisomerization table 2 prepares four kinds of different Fisher-Tropsch derived products.By two kinds of products of iron-based fischer-tropsch wax preparation, by two kinds of products of cobalt-based fischer-tropsch wax preparation.Separate the omnidistance wide isomerization paraffin wax product of boiling by vacuum distilling subsequently.Summarized the performance of these four kinds of cuts in the table 3.FT-4.4 and FT-4.5 are that the Fisher-Tropsch derived lubricant base oil fraction of hydroisomerization and FT-8.0 and FT-9.8 are tower bottom distillates.Notice that 10% boiling point is greater than 900 ℉ in its boiling range for FT-9.8, and pour point is between-15 ℃ to about 20 ℃ approximately.

Table 3

Notice that FT-9.8 satisfies the performance of the employed depression of pour point base oil of preparation mixture of the present invention blending component.It has preferred methyl branch content, positive paraffins composition, CCS VIS, 10% boiling point and pour point.FT-8 does not satisfy the performance of depression of pour point base oil blending component of the present invention.It has 10% boiling point far below 900 ℉.

Use three kinds of different many grades machine oil prescriptions of above-described Fisher-Tropsch derived base oil preparation.The component of each machine oil prescription has been shown in the table 4.

Table 4

Component, wt%	Machine oil 1	Contrast machine oil 2	Contrast machine oil 3
				The SAE grade	0W-20	OW-20	5W-20
FT-4.4	0	53.74	15.34
				FT-4.5	79.83	0	0
FT-8	0	35.61	74.01
				FT-9.8	8.87	0	0
GF-3 additive #1	11.30	0	0
				GF-3 additive #2	0	10.35	10.35
PAMA?PPD	0	0.30	0.30
				Amount to	100.00	100.00	100.00

Contrast machine oil 2 and 3 contains poly-alkylmethacrylate (PAMA) pour point depressant, and machine oil 1 does not contain.None embodiment contains the extra viscosity index improver except the material that may attach the content existence in GF-3 additive combination bag.

Summarized the viscosity performance of three kinds of machine oil prescriptions in the table 5.

Table 5

Performance	Machine oil 1	Contrast machine oil 2	Contrast machine oil 3
				Viscosity under 100 ℃	6.67	7.09	8.89
Pour point, ℃	-43	-43	Not test
				MRV TP-1@-40 ℃ yielding stress	12400 do not have	71156 do not have	Not test
MRV TP-1@-35 ℃ yielding stress	Not test	Not test	17640080
				The Noack volatility, wt%	9.0	Not test	Not test

Note the extremely low MRV TP-1 viscosity of machine oil 1.Consider and use expection will not have the machine oil prescription of the high viscosity bottom product preparation of good low temperature properties, this result is wonderful.Consider and do not add pour point depressant or viscosity index improver in this prescription, this result is wonderful especially.Be sure of that these good low-temperature performancies relate to the high boiling point and the special branching performance of (a) depression of pour point base oil blending component and (b) are blended into the desired properties of the fischer-tropsch lubricant base oil of the hydroisomerization in the machine oil prescription.

Claims

1. satisfy many grades machine oil of the SAE J300 technical specification that revision requires in June calendar year 2001, described machine oil comprises:

(a) 15 to 94.5wt% hydroisomerization fischer-tropsch distillate base oil is characterized in that

(i) kinematic viscosity is 2.5 to 8cSt under 100 ℃, (ii) at least the molecule of the 3wt% ratio of weight percentage and the weight percentage of molecule of molecule that has the cycloalkanes functionality and (iii) have a mononaphthene functionality with polynaphthene functionality greater than 15;

(b) the depression of pour point base oil blending component between 0.5 to 20wt%, its by in the intramolecular average degree of branching between 5 to 9 alkyl branches/100 carbon atoms with wherein be not more than 10wt% and be lower than the bottoms material preparation of 900 following ebullient hydroisomerizations; With

(c) 5 to 30wt% for satisfying the additive combination bag that ILSAC GF-3 technical specification designs.

2. many grades of claim 1 machine oil, wherein the additive combination bag designs for meeting the ILSACGF-4 technical specification.

3. many grades of claim 1 machine oil, wherein additive combination includes with metal element and expresses zinc less than 1.00wt%.

4. many grades of claim 1 machine oil, wherein additive combination includes with element and expresses phosphorus less than 0.90wt%.

5. many grades of claim 1 machine oil, it satisfies the technical specification of SAE viscosity grade 0W-XX, 5W-XX or 10W-XX machine oil, and wherein XX represents integer 20,30 or 40.

6. many grades of claim 5 machine oil, it satisfies the technical specification of SAE viscosity grade 0W-20.

7. many grades of claim 1 machine oil, its MRV TP-1 result under-30 ℃ is less than 60000cP.

8. many grades of claim 7 machine oil, its MRV TP-1 result under-35 ℃ is less than 60000cP.

9. many grades of claim 8 machine oil, its MRV TP-1 result under-40 ℃ is less than 60000cP.

10. many grades of claim 9 machine oil, its MRV TP-1 result under-40 ℃ is less than 30000cP.

11. many grades of claim 10 machine oil, its MRV TP-1 result under-40 ℃ is less than 15000cP.

12. many grades of claim 1 machine oil, its Noack volatility number 15% or lower.

13. many grades of claim 12 machine oil, its Noack volatility number 10% or lower.

14. many grades of claim 1 machine oil, wherein the fischer-tropsch distillate base oil of hydroisomerization is characterised in that the molecule of 10wt% has ring-type alkane functionality at least.

15. many grades of claim 1 machine oil, wherein the fischer-tropsch distillate base oil of the hydroisomerization weight percentage that is characterised in that the molecule with mononaphthene functionality and the ratio of the weight percentage of the molecule with polynaphthene functionality are greater than 50.

16. many grades of claim 1 machine oil, wherein the fischer-tropsch distillate base oil of hydroisomerization contains the aromatic hydrocarbons less than 0.3wt%.

17. many grades of claim 1 machine oil, wherein the fischer-tropsch distillate base oil of hydroisomerization contain useful C-13NMR by long duration detect less than amount of alkene.

18. many grades of claim 1 machine oil, wherein depression of pour point base oil blending component derived from molecular weight between 600 to 1100 isomerized Fisher-Tropsch derived bottom product.

19. many grades of claim 1 machine oil, wherein depression of pour point base oil blending component is that molecular-weight average is the bottom product of at least 600 isomerized petroleum derivation.

20. many grades of claim 1 machine oil, wherein depression of pour point base oil blending component is between 6 to 8 alkyl branches/100 carbon atoms in the intramolecular average degree of branching.

21. many grades of claim 1 machine oil comprises that further 5wt%-70wt% is selected from least a olefin polymerization in polyalphaolefin base oil, poly-internal olefin base oil or polyalphaolefin base oil and the poly-internal olefin base oil mixture.

22. many grades of claim 1 machine oil, it does not contain extra depression of pour point additive or viscosity index improver.

23. the method for many grades machine oil of the SAE J300 technical specification that revision requires in June calendar year 2001 is satisfied in preparation, this method comprises:

(a) in isomerization zone, in the presence of hydroisomerisation catalysts and hydrogen, under for the definite preselected condition of the fischer-tropsch base oil product that hydroisomerization is provided, hydroisomerized wax shape fischer-tropsch base oil;

(b) reclaim the fischer-tropsch base oil product of hydroisomerization from isomerization zone;

(c) for collecting under the preselected distillation condition of fischer-tropsch distillate base oil, distillation is from the fischer-tropsch base oil product of the hydroisomerization of isomerization zone recovery, the fischer-tropsch base oil product of described hydroisomerization is characterised in that (i) kinematic viscosity is 2.5 to 8cSt under 100 ℃, (ii) at least the molecule of the 3wt% ratio of weight percentage and the weight percentage of molecule of molecule that has the cycloalkanes functionality and (iii) have a mononaphthene functionality with polynaphthene functionality greater than 15;

(d) with suitable ratio with the fischer-tropsch distillate base oil with (i) by in the intramolecular average degree of branching between 5 to 9 alkyl branches/100 carbon atoms with wherein be not more than the depression of pour point base oil blending component that 10wt% prepares at the bottoms material that is lower than 900 following ebullient hydroisomerizations, and, be met many grades machine oil of the SAE J300 technical specification of revision in June calendar year 2001 (ii) for satisfying the additive combination bag blending that ILSAC GF-3 technical specification designs.

24. the method for claim 23, it comprises the additional step of the cut base oil product of hydrofining hydroisomerization, in the cut base oil product of described hydroisomerization aromatic hydrocarbons account for hydroisomerization the fischer-tropsch base oil be not more than 0.3wt%, and the C-13NMR of olefin(e) centent by long duration detect less than.

25. the method for claim 23, wherein the viscosity index of fischer-tropsch distillate base oil is equal to or greater than the viscosity index of calculating by following equation:

VI=28 * Ln (kinematic viscosity under 100 ℃)+95

Wherein: VI represents viscosity index

Ln represents natural logarithm.

26. the method for claim 23, wherein the cold bent axle simulator viscosity of fischer-tropsch distillate base oil under-35 ℃ is equal to or less than the numerical value that calculates by following equation:

CCS VIS (35 ℃)=38 * (kinematic viscosity under 100 ℃) ³

27. the method for claim 26, wherein the cold bent axle simulator viscosity of fischer-tropsch distillate base oil under-35 ℃ is equal to or less than the numerical value that calculates by following equation:

CCS VIS (35 ℃)=38 * (kinematic viscosity under 100 ℃) ^2.8

28. the method for claim 23, wherein the molecular weight of depression of pour point base oil blending component is at least 600.

29. the method for claim 23, wherein depression of pour point base oil blending component in the intramolecular average degree of branching between 6 to 8 alkyl branches/100 carbon atoms.

30. the method for claim 23 wherein is blended into enough depression of pour point base oil blending components in many grades machine oil, with at least 2 ℃ of the pour points that reduce the fischer-tropsch distillate base oil.

31. the method for claim 23 wherein designs the additive combination bag, to satisfy the technical specification of ILSACGF-4.

32. the method for claim 23, wherein with suitable proportion with fischer-tropsch distillate base oil and depression of pour point base oil blending component and the blending of additive combination bag, to obtain the many grades machine oil less than 60000cP-30 ℃ of following MRV TP-1 results.

33. the method for claim 32, wherein with suitable proportion with fischer-tropsch distillate base oil and depression of pour point base oil blending component and the blending of additive combination bag, to obtain the many grades machine oil less than 60000cP-35 ℃ of following MRV TP-1 results.

34. the method for claim 33, wherein with suitable proportion with fischer-tropsch distillate base oil and depression of pour point base oil blending component and the blending of additive combination bag, to obtain the many grades machine oil less than 60000cP-40 ℃ of following MRV TP-1 results.

35. the method for claim 34, wherein with suitable proportion with fischer-tropsch distillate base oil and depression of pour point base oil blending component and the blending of additive combination bag, to obtain the many grades machine oil less than 30000cP-40 ℃ of following MRV TP-1 results.

36. the method for claim 35, wherein with suitable proportion with fischer-tropsch distillate base oil and depression of pour point base oil blending component and the blending of additive combination bag, to obtain the many grades machine oil less than 15000cP-40 ℃ of following MRV TP-1 results.