CN102224225A

CN102224225A - Process for making a two-cycle gasoline engine lubricant

Info

Publication number: CN102224225A
Application number: CN200880109624.XA
Authority: CN
Inventors: J·泰玛; N·J·伯特兰德; J·M·罗森鲍姆; J·帕德拉克; S·J·米勒
Original assignee: Chevron USA Inc
Current assignee: Chevron USA Inc
Priority date: 2007-08-27
Filing date: 2008-08-15
Publication date: 2011-10-19
Also published as: GB2491288B; WO2009029427A1; GB201003143D0; US20090062168A1; GB2465119B; AU2008293800A1; GB2465119A; GB2491288A; GB201214274D0; JP2010538116A

Abstract

A process to prepare a lubricating oil meeting JASO M345:2003 requirements, comprising: hydroisomerization dewaxing a feed to produce a base oil and blending the base oil with less than 5 wt% solvent and a detergent/dispersant additive package. A process for making lubricating oil, comprising blending together a pour point reduced base oil blend with a detergent/dispersant additive package, a smoke-suppression agent, optionally a pour point depressant, and optionally less than about 5 wt% hydrocarbon solvent, whereby a two-cycle gasoline engine lubricant is produced. A process to make a two-cycle gasoline engine lubricant, comprising preparing a pour point reducing blend component by isomerizing a feed, blending it with a light distillate base oil to produce a pour point reduced base oil blend, and blending the pour point reduced base oil blend with a detergent/dispersant additive package and less than 5 wt% solvent. A lubricating oil made by the process described herein.

Description

The preparation method of two-cycle gasoline engine lubricant

Invention field

Need to the present invention relates to the improved two-cycle gasoline engine lubricant preparation of compositions method of the hydrocarbon solvent of reduction.

Background of invention

Two-stroke engine is compared with Otto cycle engine has three important advantages:

● two-stroke engine does not have valve, and this has simplified their structure and has alleviated their weight.

● two-stroke engine circulates (revolution) igniting once at every turn, and Otto cycle engine is every once circulating igniting once.This has given the significant power of two-stroke engine and has excited.

● two-stroke engine can be worked in any direction, and this is extremely important in the thing as chain saw and so on.The Otto cycle engine of standard may have the problem of stream oil, unless it is axial, and addresses this problem the complicacy that can increase engine.

Two-stroke engine has at least three kinds of potential inferior positions:

● two-stroke engine hardly can be long-time lasting as Otto cycle engine.Lacking special oiling system, to mean that the component wear of two-stroke engine gets faster.

● two-cycle gasoline engine lubricant is expensive, and per gallon gasoline needs about 4 ounces of lubricants.If use two-stroke engine in automobile, per 1000 miles will consume about 1 gallon of lubricant.

● two-stroke engine produces a large amount of the pollution, comprises the two-cycle gasoline engine lubricant of the leakage of discharging from the incendiary cigarette of two-cycle gasoline engine lubricant with by exhaust outlet.

Most of two-cycle gasoline engine lubricants are formulated by low-boiling hydrocarbon solvent and SAE 40 mineral base oils.Other use ester base oil and do not use low boiling point solvent dangerous and cigarette shape discharge is minimized to reduce potential, however these lubricants do not have very good oxidative stability.Other use has the polyalphaolefin base of improved cryogenic properties.Polyalphaolefin and ester base oil supply are limited and very expensive.Comprising inexpensive base oil and satisfying sets up the improved two-cycle gasoline engine lubricant composition of the requirement of organization establishment to wish by standard.Wish that also these lubricant compositions have the engine scuffing of the hydrocarbon solvent content of minimizing, minimizing and the pollution of minimizing.Wish that also the two-cycle gasoline engine lubricant composition has good low-temperature performance, good gasoline compatibility and high oxidation stability.Wish that also the two-cycle gasoline engine lubricant composition has the higher flash-point and the combustibility of reduction.Wish that also the two-cycle gasoline engine lubricant composition can use vinyon manufacturing, to reduce the plastic waste environmental pollution.

Summary of the invention

The invention provides the method for preparing lubricating oil, comprising:

A. the wax stock that alkane is basically belonged to carries out the hydroisomerization dewaxing, thereby produces lubricating base oil; With

B. one or more cuts and the following material with described lubricating base oil is in harmonious proportion:

I. based on whole lubricating oil compositions less than the maximum boiling point of about 5wt% hydrocarbon solvent less than 250 ℃;

Ii. purification agent/dispersant additives bag; Wherein said lubricating oil satisfies the requirement of JASOM345:2003.

The present invention also provides the method for preparing lubricating oil, comprising:

A. the base oil blends that following material has been in harmonious proportion together with the production depression of pour point:

I.100 ℃ the kinematic viscosity under is about 1.5 and about 3.5mm ²One or more base oil fractions between the/s; With

Ii. pour point depressing blend component;

B. to described depression of pour point base oil blends in add following material:

I. purification agent/dispersant additives bag;

Ii. press down fumicants;

Iii. Ren Xuan pour point reducer; With

Iv. optional maximum boiling point less than about 5wt% is less than 250 ℃ hydrocarbon solvent;

Thereby production two-cycle gasoline engine lubricant.

The present invention also provides the preparation method of the two-cycle gasoline engine lubricant that satisfies JASO M345:2003 requirement, comprising:

A. by being carried out isomerization, raw material prepares the pour point depressing blend component;

B. the base oil blends that described pour point depressing blend component and following material has been in harmonious proportion with the production depression of pour point:

I. 100 ℃ of following kinematic viscosity about 1.5 and about 3.5mm ²Distillment base oil between the/s;

C. with described depression of pour point base oil blends and following material be in harmonious proportion in the proper ratio to obtain described two-cycle gasoline engine lubricant:

I. purification agent/dispersant additives bag; With

Ii. based on whole two-cycle gasoline engine lubricants less than the maximum boiling point of 5wt% hydrocarbon solvent less than 250 ℃.

The present invention also provides the lubricating oil of making by the method that may further comprise the steps:

A. the wax stock that alkane is basically belonged to carries out the hydroisomerization dewaxing, produces lubricating base oil thus; With

I. based on whole lubricating oil compositions less than the maximum boiling point of about 5wt% hydrocarbon solvent less than 250 ℃; With

Ii. purification agent/dispersant additives bag; Thereby make described lubricating oil satisfy the requirement of JASOM345:2003.

The accompanying drawing summary

Kinematic viscosity under Fig. 1 has shown 100 ℃ provides the formula that is used to calculate the wt%Noack volatility upper limit to the curve in the Noack volatility of wt%:

The Noack volatility factor (1)=160-40 * (kinematic viscosity under 100 ℃) and

The Noack volatility factor (2)=900 * (kinematic viscosity under 100 ℃) ^-2.8-15, wherein in second formula, the kinematic viscosity under 100 ℃ raises with-2.8 power exponent.

Detailed Description Of The Invention

In order to move two-cycle gasoline engine, fill the mixture of two-cycle gasoline engine lubricant and fuel in the crankcase. In two stroke engine, crankcase is used as the pumping chamber to force air/fuel to enter cylinder, so it can not fill the heavy oil that is similar to the heavy oil that uses in four-stroke engine. On the contrary, special two-cycle gasoline engine lubricant is blended in the fuel with lubricated crank axle, connecting rod and cylinder wall.

The recommendation mixed proportion of two-cycle gasoline engine lubricant and fuel is stipulated by manufacturers of engines. The fuel that is used for two-cycle gasoline engine is to well known to a person skilled in the art and the fuel that is generally liquid that usually contains major part hydrocarbon petroleum distillation fuel for example, for example by the fuels for spark ignition engines of ASTM D4814-07 definition, or by the motor gasoline of ASTM D439-89 definition. These fuel also can contain the non-hydrocarbons material, such as alcohol, ether, organic nitro-compound etc. For example, methyl alcohol, ethanol, ether, ethyl methyl ether, nitromethane, and these fuel within the scope of the present invention are derived from plant source and the mineral source liquid fuel of corn, switch grass, α shale and coal for example. The example of such fuel mixture is the combination etc. of combination, gasoline and nitromethane of combination, diesel fuel and the ether of gasoline and ethanol. In one embodiment, described fuel is unleaded gas.

Two-cycle gasoline engine lubricant uses with amount and the fuel mix of the per 1 weight portion lubricating oil of about 20-250 weight portion fuel, the per 1 weight portion lubricant of more generally about 30-100 weight portion fuel.

Two-cycle gasoline engine lubricant must satisfy the requirement of being set up organization establishment by standard, comprises Japanese car standard JASO M 345:2003 and international standard ISO 13738:2000 (E). The requirement of these two kinds of standards is summarized in the following table.

Table I

Each index in the above requirement table has value 100 and measures by JATRE-1 oil is taken as. The C class is applied to be called as the oil of low cigarette type oil, and this low cigarette type oil has excellent smoke evacuation performance and waste gas system stops up tendency. The D class is applied to the better oil of oil of detergency ratio classification C when engine thermal. The oil of the B in the iso standard, C and D class all has the sulfate ash content of maximum 0.18wt%. Sulfated ash can be measured according to ISO 3987 or ASTM D874-00.

In addition, wish that these lubricants have good low temperature flow when they are used to face in the condition of low temperature. Low temperature flow is measured by the brookfield viscosity that ASTM D2983-04a measures by determining under the set point of temperature of-10 ℃ ,-25 ℃ and-40 ℃. In this disclosure, when tested oil has about 7500mPa.s or lower brookfield viscosity, be defined as and measure at these that one of temperature are lower to have " good low temperature flow ". For example, mean that at-10 ℃ of lower good low temperature flows this oil has about 7500mPa.s or lower brookfield viscosity under-10 ℃. Mean that at-25 ℃ of lower good low temperature flows this oil has about 7500mPa.s or lower brookfield viscosity under-25 ℃; Mean that with good low temperature flows under-40 ℃ this oil has about 7500mPa.s or lower brookfield viscosity under-40 ℃.

In addition, wish the compatibility test by being undertaken by ASTMD4682-87 (2002 issue again) under the temperature of-10 ℃ and/or-25 ℃ of these lubricants.

Described two-cycle gasoline engine lubricant composition is particularly suitable as fuel oil injector or at 150: 1 fuel at the most: the gasoline in the two stroke engine (comprising outboard motor, sled motor, motorcycle, motor bike, ATV, golf load wagon, hay mover, chain saw, rope trimmer etc.) that sprays into direct fuel that sprays into such as fuel that cross in carburetion, electronic with suitable fuel under the mix lubricant ratio mixes.

Base oil

The wax stock that the lubricant base oil that uses in the two-cycle gasoline engine lubricant composition belongs to derived from alkane basically. Term " basically alkane belong to " means and contains high-load, usually greater than 40wt% normal paraffin hydrocarbons. Some basically the wax stock that belongs to of alkane for example can have greater than 50wt% or greater than the normal paraffin hydrocarbons of 75wt%. Basically an example of the wax stock of alkane genus is the wax that produces in Fischer-tropsch process. Another example is the slack wax of height refining.

Fischer-Tropsch wax can be obtained by known method, and is for example commercial

Slurry phase Fischer-tropsch process, commerce

Synthetic (SMDS) technology of middle distillation, or by non-commercial

Advanced gas transforms (AGC-21) technology and obtains. The details of these technologies and other content are stated in following patent, for example, and EP-A-776959, EP-A-668342, U.S. Patent number 4,943,672,5,059,299,5,733,839 and RE39073; With U.S. published application number 2005/0227866, WO-A-9934917, WO-A-9920720 and WO-A-05107935. Described Fischer-Tropsch synthetic usually comprise have 1-100 or even more than the hydrocarbon of 100 carbon atoms, and generally include alkane, alkene and OXO products. Fischer-Tropsch is the feasible method that generates the alternative hydrocarbon products of the cleaning that comprises Fischer-Tropsch wax.

Slack wax can obtain from the raw material of the petroleum derivation of routine by hydrocracking or the solvent refined of lube cut. Usually, carry out solvent dewaxing by the raw material to the preparation of one of these methods and reclaim slack wax. Usually preferred hydrocracking is because hydrocracking also can be down to low value with nitrogen content. With regard to regard to the slack wax of solvent refined oil, also available de-oiling reduces nitrogen content and improves viscosity index (VI). The hydrotreatment of slack wax can be used to reduce nitrogen and sulfur content. Slack wax has very high viscosity index (VI), depends on the raw material of oil content and preparation slack wax, is generally about 140-200. Therefore, slack wax is applicable to the base oil that preparation is used in two-cycle gasoline engine lubricant.

Described waxy feeds has the total amount less than nitrogen and the sulphur of 25ppm in one embodiment. Carry out oxidizing fire according to ASTM D4629-02 then and chemiluminescence detection is measured nitrogen by the described waxy feeds of melting. In the United States Patent (USP) 6503956 of incorporating this paper into, further described this method of testing. Carry out Ultraluminescence according to ASTM D5453-00 then by the described waxy feeds of melting and measure sulphur. In the United States Patent (USP) 6503956 of incorporating this paper into, further described this method of testing.

The mensuration of the normal paraffins in the content of wax sample (normal paraffin hydrocarbons) is carried out with the method that the detection that can measure independent C7-C110 normal paraffin hydrocarbons content is limited to 0.1wt%. Employed method is hereinafter stated at present disclosure.

In the near future, along with extensive fischer-tropsch synthesis process puts into production, the waxy feeds expection is a large amount of and relative cost competitiveness that has. The Fischer-tropsch derived base oil of being made by these waxy feeds and therefore comprise their described two-cycle gasoline engine lubricant will be than for example the lubricant made of polyalphaolefin or ester class is cheap with other artificial oil. Term " Fischer-tropsch derived " or " FT derives " refer to that described product, cut or raw material stem from certain one-phase of Fischer-tropsch process or at certain one-phase by Fischer-tropsch process production. The raw material of Fischer-tropsch process can from hydrocarbons matter resource, comprise living beings, natural gas, shale oil, oil, municipal garbage, these derivative and their combination. The mixture that is comprised multiple solid-state, liquid state and gaseous hydrocarbon by the synthetic crude of Fischer-tropsch process preparation. Those Fischer-Tropsch product of seething with excitement in the lubricating base oil scope contain a high proportion of wax, and this is so that they become the ideal candidates person of being processed into base oil. Therefore, Fischer-Tropsch wax has represented the excellent raw material for the preparation of high quality base oil. At room temperature Fischer-Tropsch wax is generally solid, and therefore represents the cryogenic properties of going on business, for example pour point and cloud point. Yet this wax can prepare the Fischer-tropsch derived base oil with excellent cryogenic properties through behind the hydroisomerization. U.S. Patent number 5,135,638 and 5,282,958 and U.S. Patent application 20050133409 that as seen the general description of suitable hydroisomerization process for dewaxing is incorporated herein.

Contact to implement hydroisomerization by making in described waxy feeds and the isomerization zone of hydroisomerisation catalysts under being in the hydroisomerization condition. Hydroisomerisation catalysts preferably comprises selects the medium hole dimension molecular sieve of shape, noble metal hydrogenation component and refractory oxide carrier. This is selected the medium hole dimension molecular sieve of shape and is preferably selected from SAPO-11, SAPO-31, SAPO-41, SM-3, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ-32, offretite, ferrierite and their combination. Use in one embodiment SAPO-11, SM-3, SSZ-32, ZSM-23, ZSM-48 and their combination. Described noble metal hydrogenation component is platinum, palladium or their combination in one embodiment.

The hydroisomerization condition depends on whether employed waxy feeds, employed hydroisomerisation catalysts, this catalyst cure, desirable yield and desirable basic oil properties. The example of the hydroisomerization condition of an embodiment comprises: temperature is about 413 ℃ of 260-(about 775 °F of 500-), and stagnation pressure is 15-3000psig, or 50-1000psig; The ratio of hydrogen and raw material is about 2-30MSCF/bbl, about 4-20MSCF/bbl (about 3562 liters of H of about 712.4-₂/ rise oil), about 4.5 or 5 to about 10MSCF/bbl, or the about 8MSCF/bbl of about 5-. Usually, hydrogen can separate with product and be recycled in this isomerization zone. The raw material ratio of noting 10MSCF/bbl is equivalent to 1781 liters of H₂/ rise raw material. Usually, hydrogen will separate with product and be recycled in this isomerization zone.

Randomly, but the base oil that hydrofinishing is produced by hydroisomerization dewaxing. This hydrofinishing can occur in one or more steps, this base oil fractionation can carried out for before or after one or more cuts. The hydrofinishing intention is improved oxidation stability, UV stability and the outward appearance of product by removing aromatic compounds, alkene, chromoplast and solvent. Can be referring to the U.S. Patent No. 3,852,207 and 4,673,487 that is incorporated herein to hydrorefined general introduction. May need the hydrofinishing step that the percentage by weight of the alkene in the base oil is reduced to less than 10, less than 5 or 2, less than 1, less than 0.5 with less than 0.05 or 0.01. Also may need the hydrofinishing step that the percentage by weight of aromatic compounds is reduced to less than 0.3 or 0.1, less than 0.05, less than 0.02 with in certain embodiments even less than 0.01.

Randomly, by hydroisomerization dewaxing the base oil that produces can for example bauxite or clay be processed to remove impurity and are improved color and biodegradability with adsorbent.

Because described base oil is made by waxy feeds, so described base oil has continuous carbon number. " continuous carbon number " refers to that the hydrocarbon molecule of this base oil differs from one another by continuous carbon number, and this is because waxy feeds also has continuous carbon number. For example, in the Fischer-Tropsch hydrocarbon synthetic reaction, the source of carbon atom is that CO consists of hydrocarbon molecule with each carbon atom of increase. The waxy feeds of petroleum derivation also has continuous carbon number. With the oil phase ratio based on PAO, the molecule of described base oil has more linear structure, comprises the relatively long main chain with short-chain branch. It is star-shaped molecule that the classical textbook of PAO is described, and tridecane (tridecane) particularly, and it is illustrated as three decane molecules that are connected on the central point. Although star-shaped molecule is theoretic, in any case the PAO molecule has than the hydrocarbon molecule that consists of the base oil that uses in the disclosure content still less and longer side chain. In another embodiment, the cycloalkanes that n-d-M records that passes through that also has less than 10wt% of this base oil with continuous carbon number belongs to carbon.

In one embodiment, described lubricating base oil is separated into cut, thereby one or more pour points that have in the described cut are less than 0 ℃, less than-9 ℃, less than-15 ℃, less than-20 ℃, less than-30 ℃, or less than-35 ℃. Measure pour point by ASTM D5950-02. Described lubricating base oil randomly is fractionated into the base oil of different viscosities grade. The kinematic viscosity that " base oil of different viscosities grade " is defined under 100 ℃ in the context of present disclosure differs at least 0.5mm each other²Two or more base oils of/s. Kinematic viscosity is measured with ASTM D445-06. Carry out fractionation to obtain having the cut of preliminary election boiling range with the decompression distillation unit. One of cut can be the distillation bottom product.

Described base oil fractions has less than the aromatics carbon of 0.01wt% with greater than the alkane of about 90wt% and belongs to carbon in one embodiment. Remaining wt% carbon is that cycloalkanes belongs to carbon. According to ASTM D3238-95 (2005) by n-d-M analyze to measure Wt% aromatics carbon, the wt% alkane belongs to carbon and wt% cycloalkanes belongs to carbon. In one embodiment, the wt% alkane belongs to carbon between about 90wt% and about 97wt%, and wt% cycloalkanes belongs to carbon between about 3wt% and about 10wt%.

In one embodiment, the viscosity index (VI) of described lubrication base oil distillate will be high. They will have the viscosity index (VI) greater than 28 * Ln (kinematic viscosity under 100 ℃)+80 usually. In one embodiment, they will have the viscosity index (VI) greater than 28 * Ln (kinematic viscosity under 100 ℃)+95. For example, 2.5mm²The oil of/s will have greater than 106, optional greater than 121 viscosity index (VI); And 12mm²The oil of/s will have greater than 150, optional greater than 165 viscosity index (VI).

In another embodiment, the pour point of described base oil is lower than-8 ℃, and the kinematic viscosity under 100 ℃ is at least 1.5mm²/ s and viscosity index (VI) are greater than the amount of being calculated by formula 22 * Ln (kinematic viscosity under 100 ℃)+132. In this embodiment, for example, be 2.5mm 100 ℃ of lower kinematic viscosity²The oil of/s will have the viscosity index (VI) greater than 152. Base oil with these character is described among the U.S. Patent Publication US20050077208. In the formula of present disclosure, term " Ln " refers to the natural logrithm take e the end of as. The method of testing that is used for measuring viscosity index (VI) is ASTMD2270-04.

The kinematic viscosity of described base oil fractions under 100 ℃ is about 1.3 and 25mm²Between/the s. In one embodiment, the kinematic viscosity of described base oil fractions under 100 ℃ is about 1.5 and about 3.5mm²Between/the s. In another embodiment, the kinematic viscosity of described base oil fractions is about 1.8 and about 3.2mm²Between/the s.

In one embodiment, described base oil fractions provides fabulous oxidative stability, low Noack volatility, and desirable additive solubleness and elastomer compatibility.The alkene wt% that described base oil fractions has is less than 10, less than 5, and less than 1, less than 0.5, or less than 0.05 or 0.01.The wt% of the aromatic substance that described base oil fractions has is less than 0.1, less than 0.05 or less than 0.02.

" drag coefficient " is an intrinsic lubricant properties index, nondimensional with frictional force F and normal force N than value representation, wherein frictional force be a kind of opposing or hinder slide or rolling surface between the mechanical force of motion.Drag coefficient can be measured with the MTM traction measuring system of PCS Instr Ltd., this system is furnished with the polishing ball (SAE AISI 52100 steel) of a diameter 19mm, and it becomes 220 degree angles with the smooth polishing disk (SAB AISI 52100 steel) of a diameter 46mm.Steel ball and disk are measured independently under the following conditions: the average rolling speed of 3 meter per seconds, slide with roll than be 40% and load be 20 newton.The rolling ratio is defined as between ball and the dish sliding velocity difference divided by the V-bar of ball and dish, ratio=(speed 1-speed 2)/((speed 1+ speed 2)/2) of promptly rolling.In some embodiments, when at 15mm ²When the ratio of the kinematic viscosity of/s and 40% slip and rolling was measured down, described base oil fractions had less than 0.023, be less than or equal to 0.021 or be less than or equal to 0.019 drag coefficient.In one embodiment, they have less than the drag coefficient by the defined amount of following formula: drag coefficient=0.009 * Ln (kinematic viscosity)-0.001, wherein said kinematic viscosity in the drag coefficient measuring process 2 and 50mm ²Between/the s; With wherein said drag coefficient is to measure under 40% and 20 newton's the load in the rolling speed of average 3m/s, the ratio with rolling of sliding.

In one embodiment, when at 15mm ²When the ratio of the kinematic viscosity of/s and 40% slip and rolling was measured down, described base oil fractions had less than 0.015 or less than 0.011 drag coefficient.Have the U.S. Patent number 7,045,055 that the example of these base oil fractions of low traction coefficient submits on April 7th, 2006 and all in the U.S. Patent application 11/400570 and 11/399773 of submission on April 7th, 2006, instruction is arranged.In one embodiment, the drag coefficient of described base oil less than 0.015 and the 50wt% boiling point be higher than 565 ℃ (1050 °F).In another embodiment, the drag coefficient of described base oil is less than 0.011 be higher than 582 ℃ (1080 °F) by the 50wt% boiling point that ASTM D6352-04 measures.

In some embodiments, the isomerized base oil with low traction coefficient has also shown unique branching character (being measured by NMR), comprises that branch index is less than or equal to 23.4, and the branching degree of approach is more than or equal to 22.0, and the uncombined carbon index is between 9 and 30.In one embodiment, the cycloalkanes of 4wt% belongs to carbon to use n-d-M assay determination, described base oil to have at least with ASTM D 3238-95 (2005 issue again), and in another embodiment, the cycloalkanes of 5wt% belongs to carbon at least.The two-cycle gasoline engine lubricant of preparation comprises the base oil fractions of low traction coefficient, thereby the engine scuffing that reduces is provided.

In some embodiments, when alkene and aromatic content in the lubricant base oil cut of described lubricating oil were significantly low, the oxidizer BN of selected base oil fractions will be greater than 25 hours, for example greater than 35 hours or even greater than 40 hours.The oxidizer BN of selected base oil fractions is generally less than 70 hours.Oxidizer BN is a short-cut method of measuring basic oil oxidation stability.People such as Stangeland have described described oxidizer BN test in United States Patent (USP) 3852207.Described oxidizer BN test is measured the oxidation tolerance with Dornte type oxygen adsorption unit.Referring to " oxidation of white oil " of R.W.Dornte, industry and engineering chemistry, the 28th volume, 26 pages, 1936.Usually, described condition is 1 an atmospheric purity oxygen under 340.The result absorbs 1000ml O with 100g oil ₂Hours report.In described oxidizer BN test, per 100 gram oil use in 0.8ml catalyzer and the described oil and have comprised additive-package.Described catalyzer is the mixture of soluble metal naphthenate in kerosene.The average metal analysis of described soluble metal naphthenate mixture simulation exhausted crankcase oils.Metal content in the described catalyzer is as follows: copper=6927ppm; Iron=4083ppm; Lead=80208ppm; Manganese=350ppm; Tin=3565ppm.Described additive-package is 80 mmole double focusing propylene phenyl zinc dithiophosphates/100 gram oil, or about 1.1 gram OLOA ^TM260.Described oxidizer BN measurements determination the response of the lubricating base oil in the simulation application.High value or the time that absorbs 1 liter of oxygen are grown and show that oxidative stability is good.The two-cycle gasoline engine lubricant that comprises the base oil fractions with good oxidation stability will also have improved oxidative stability.

OLOA ^TMBe the abbreviation of Ao Lunte lubricating oil additive (Oronite Lubricating OilAdditive), it is the registered trademark of Chevron Oronite.

In some embodiments, described one or more lubrication base oil distillates will have fabulous biodegradable.Adopt suitable hydrotreatment and/or sorbent treatment, they are easy to by OECD 301B vibration beaker test (the Sturm test of modification) biological degradation.When the base oil fractions of readily biodegradable and suitable biodegradable additive (for example low ash or the ashless additive of Xuan Zeing) mediation, this lubricant will provide the fast degraded biologically of leakage in the sensitizing range, have minimum not biodegradable resistates, and the environment that will prevent to cost cleaning.

In some embodiments, described one or more lubrication base oil distillates have low Noack volatility.The Noack volatility is measured according to ASTM D5800-05 program B usually.In one embodiment, described one or more lubrication base oil distillates have the Noack volatility less than 100wt%.The Noack volatility of base oil reduces and increases along with kinematic viscosity usually.The Noack volatility is low more, and in use the evaporable tendency is just low more for the oil of base oil and preparation.

" the Noack volatility factor " of base oil is the empirical value by the kinematic viscosity derivation of described base oil.The Noack volatility of the base oil of the wax that belongs to derived from the height alkane is low-down, and in one embodiment less than the amount by following formula calculated: the Noack volatility factor (1)=160-40 (kinematic viscosity under 100 ℃).Formula (1) is as providing among the U.S. Patent Application Publication No. 2006/0201852A1, for 1.5 and 4.0mm ²Kinematic viscosity between the/s provides the factor of the Noack volatility between 0 and 100.Fig. 1 is the figure according to the Noack volatility factor of formula (1).In second embodiment, the Noack volatility of described one or more lubricant base oil cuts is less than the amount by following formula calculated: the Noack volatility factor (2)=(900 * (kinematic viscosity under 100 ℃) ^-2.8)-15.Formula (2) is as providing in the U.S. Patent Application Serial Number 11/613936, for 2.09 and 4.3mm ²Kinematic viscosity between the/s provides the factor of the Noack volatility between 0 and 100.Fig. 1 also comprises the Noack volatility factor according to formula (2).For at 2.4-3.8mm ²Kinematic viscosity in the/s scope, the Noack volatility factor that formula (2) provides than formula (1) provide low.In kinematic viscosity is 2.4-3.8mm ²In the scope of the base oil of/s, the lower Noack volatility factor is desirable, if when particularly this base oil will be in harmonious proportion with other oil that may have higher Noack volatility.

Can in described lubricant compositions, mix extra base oil with the amount of the about 20wt% of about 1.0wt%-.The example of the base oil that these are extra comprises the mixture of ester, ester and the API II class and the III class mineral oil of the petroleum derivation of the mixed ester of description in U.S. Patent number 6197731, polyalphaolefin, poly-internal olefin, polyisobutene, for example alkylating naphthalene of alkylating aromatic substance and routine.

The pour point depressing blend component

Described two-cycle gasoline engine lubricant can comprise pour point depressing temper component." pour point depressing blend component " used herein is meant isomerized content of wax product, and the alkyl-branched degree that it has high relatively molecular weight and have regulation in molecule is so that it reduces the pour point of the lubricating base oil temper that contains it.The example of pour point depressing blend component is disclosed in U.S. Patent number 6,150,577 and 7,053,254 and patent publication No. US20050247600A1 in.The pour point depressing blend component can be: 1) isomerized Fischer-tropsch derived bottoms; 2) by the bottoms of the mineral oil of isomerized height content of wax preparation, or 3) be at least about 8mm by the kinematic viscosity under 100 ℃ of vinyon preparation ²The isomerized oil of/s.

In one embodiment, the described pour point depressing blend component isomerized Fischer-tropsch derived underpressure distillation bottoms that is the average degree of branching of molecular-weight average between 600 and 1100 and in the molecule between per 100 carbon atoms 6.5 and 10 alkyl branches.Usually, more the high-molecular weight hydrocarbon more effectively is used as the pour point depressing blend component than more low-molecular-weight hydrocarbon, in one embodiment, in the underpressure distillation unit, use the higher cut point of the bottom material that causes higher to prepare described pour point depressing blend component.Higher cut point also has the advantage of the distillment base oil fractions that obtains high yield.In one embodiment, described pour point depressing blend component is isomerized Fischer-tropsch derived underpressure distillation bottoms, and it has than it and will go the pour point of the distillment base oil that is in harmonious proportion to exceed at least 3 ℃ pour point.

In one embodiment, for 10% of the boiling range of the described pour point depressing blend component of underpressure distillation bottoms between about 850 °F-1050 °F (454-565 ℃).In another embodiment, described pour point depressing blend component is higher than the Fischer-Tropsch product or the petroleum product of 950 (510 ℃) and contains the paraffinic hydrocarbons of 50wt% at least derived from boiling range.In another embodiment, the boiling range of described pour point depressing blend component is higher than 1050 °F (565 ℃).

In another embodiment, described pour point depressing blend component is the base oil of isomerized petroleum derivation, and it contains boiling range and is higher than about 1050 material.In one embodiment, described isomerized bottom material as before the pour point depressing blend component by solvent dewaxing.Compare with the oily product that reclaims after the solvent dewaxing, find that this content of wax product that further separates with described pour point depressing blend component has represented the character of fabulous improved inhibition pour point in the solvent dewaxing process.

In another embodiment, described pour point depressing blend component is that kinematic viscosity under 100 ℃ is at least about 8mm ²The isomerized oil of making by vinyon of/s.Described in one embodiment pour point depressing blend component is made by plastic waste.Described in another embodiment pour point depressing blend component is made by following steps, and described step comprises: the high temperature pyrolysis vinyon, isolate the last running of last running, this last running of hydrotreatment, this hydrotreatment of isoversion and be collected in kinematic viscosity under 100 ℃ at least about 8mm ²/ 8 described pour point depressing blend component.In the 3rd embodiment, described pour point depressing blend component is higher than 1050 °F (565 ℃) derived from vinyon and boiling range, or even boiling range be higher than 1200 °F (649 ℃).

In one embodiment, described pour point depressing blend component has the average degree of branching of 6.5-10 per 100 carbon atoms of alkyl branches at intramolecularly.In another embodiment, the molecular-weight average that has of described pour point depressing blend component is between 600-1100.In the 3rd embodiment, the molecular-weight average that it has is between 700-1000.In one embodiment, described pour point depressing blend component has at 100 ℃ of following 8-30mm of being ²The kinematic viscosity of/s, and drop on 10% point of the boiling range of the bottoms between about 850-1050.In another embodiment, it is down 15-20mm that described pour point depressing blend component has at 100 ℃ ²The pour point of the kinematic viscosity of/s and-8 to-12 ℃.

In one embodiment, described pour point depressing blend component is that kinematic viscosity under 100 ℃ is at least about 8mm ²The isomerized oil of making by vinyon of/s.Described in one embodiment pour point depressing blend component is made by plastic waste.Described in another embodiment pour point depressing blend component is made by following steps, and described step comprises: the high temperature pyrolysis vinyon, isolate the last running of last running, this last running of hydrotreatment, this hydrotreatment of isoversion and be collected in kinematic viscosity under 100 ℃ at least about 8mm ²The described pour point depressing blend component of/s.In the 3rd embodiment, be higher than 1050 °F (565 ℃) derived from the boiling range of the described pour point depressing blend component of vinyon, or even boiling range be higher than 1200 °F (649 ℃).

Additive and additive-package

In preparation two-stroke gasoline engine oil gasoline engine lubricant process, can use various purification agents/dispersant additives Bao Laiyu base oil to mix.Additive ashless, low ash or that contain ash can be used for this purpose.

Suitable ashless additive comprises any two or more the combination in polymeric amide, alkenyl succinimide, boric acid modified alkenyl succinimide, phenols amine and succinate derivative or these additives.

The example of low grey additive-package comprises: (i) be present in polyisobutenyl (Mn is 400-2500) succinimide or another kind of oil-soluble, acrylic acid modified, nitrogenous lubricating oil dispersant in the lubricating oil with the amount of 0.2-5wt%; The (ii) oil-soluble detergent additives of the phenates of metal, sulfonate or salicylate.In one embodiment, described oil-soluble detergent additives is that to be present in total basicnumber in the described lubricating oil be 200 or littler neutral metal detergent or overbased metal purification agent for amount with 0.1-2wt%.In this embodiment, described metal is calcium, barium or magnesium.The neutral calcium salicylate is an example, and can be present in the amount of about 0.5-1.5wt% in the described lubricating oil.

Polymeric amide purification agent/dispersant additives, Chang Yong tetren isostearate for example can react by lipid acid and polyalkylene polyamine and prepares, as described in U.S. Patent number 3169980, it is incorporated in this specification sheets in full for reference, it is introduced in full the same seemingly.These polymeric amide can contain measurable amount by straight polyamide through continuously heating and internal condensation and the ring-type tetrahydroglyoxaline that generates at elevated temperatures.The polymeric amide additive of another kind of useful kind by polyalkylene polyamine with C19-C25 Koch acid group according to people such as R Hartle at JAOCS, 57 (5): the program of description prepares among the 156-59 (1980).

Alkenyl succinimide generates by program progressively, alkene wherein, for example polybutene (MV 1200) and maleic anhydride reaction to be generating polybutylene-based succinyl oxide adducts, its then with the amine product wanted with generation of alkylamine or polyamines reaction for example.

Phenols amine prepares (C Mannich and W.Krosche, Arch.Pharm., 250:674 (1912)) by known mannich reaction, and this reaction relates to phenol, formaldehyde and the polyalkylene polyamine that polyalkylene replaces.

Succinate derivative is prepared as follows: by the reaction of alkene (for example polybutene class material (for example polybutene)) and maleic anhydride generating polybutylene-based succinyl oxide adducts, its further with for example tetramethylolmethane reaction of polyvalent alcohol, provide the product of wanting.

Suitable contain any two or more combination that grey purification agent/dispersant additives comprises sulfonate, phosphoric acid salt or the phenates of alkaline-earth metal (for example magnesium, calcium, barium) or examples of such additives.

Above-mentioned purification agent/dispersant additives can be with the amount based on the about 25wt% of the about 1-of the gross weight of lubricant compositions as herein described, and more preferably the amount with the about 20wt% of about 3-is incorporated in the lubricant compositions as herein described.

The double stroke lubricant purification agent/dispersant additives bag that is available commercially can be used in combination to produce described two-cycle gasoline engine lubricant with described base oil, LUBRIZOL400 for example, and LUBRIZOL 6827, LUBRIZOL 6830, LUBRIZOL 600, LUBRIZOL606, ORONITE 9333, ORONITE

340A, ORONITE 6721 and ORONITE

9357.

Can as required various other additives be incorporated in the described two-cycle gasoline engine lubricant.These comprise: press down fumicants, for example polybutene or polyisobutene (PIB); Extreme-pressure additive, for example dialkyl dithiophosphate or ester; Defoamer, for example silicone oil; Pour point reducer; Rust-preventive agent or anticorrosive agent, for example triazole derivative, do not have stone propyl propionate or alkali metal phenolate or sulfonate; Oxidation retarder, the diarylamine of Qu Daiing for example, thiodiphenylamine, hindered phenol etc.Some these additive can be multi-functional, polymethacrylate for example, and it can be used as defoamer and pour point reducer.When using pour point reducer, it is to use based on the amount between whole lubricating oil 0.005-0.1wt%.The example of pour point reducer is: polymethacrylate (PMA); Polyacrylic ester; Polyacrylamide; The condensation product of halogenated alkane chloroflo and aromatic substance; The carboxylic acid vinyl ester polymer; The trimer of dialkyl fumarate, fatty acid vinyl ester and alkyl vinyl ether; With their mixture.

In one embodiment, but described fumicants is the olefinic unsaturated polymer that is selected from the mixture of polybutene, polyisobutene or polybutene and polyisobutene, and its number-average molecular weight is at least 60 moles of % that 400-2200 and end position vinylidene content account for the two key sums in this polymkeric substance.The fumicants that presses down of these types has instruction in EP1743932A2.These business-like examples that press down fumicants are BASF AG

1000.

Volatile, combustible high flash point hydrocarbon solvent for example kerosene, Exxsol D80 or Stoddard solvent also can be used as additive.Exxsol D80 is the aliphatic high-flash solvent of the dearomatization of at least 200 ℃ of initial boiling points, and its kauri-butanol number is about 28 (between 20 and 40), and aniline point is 73.9-79.4 ℃.Volatile, combustible high flash point hydrocarbon solvent can be to join less than whole amounts of the 5wt% of lubricating oil in the described two-stroke engine profit lubricant so that in JASO M342-92 test smoke index at least 75 value and/or with improve to the consistency of other additive and or solvability, and improve cryogenic properties for example viscosity and gasoline compatibility.In one embodiment, described two-cycle gasoline engine lubricant comprises the solvent of low levels, for example less than about 5wt%, less than about 2wt% or even all do not have maximum boiling point in the lubricating oil basically less than 250 ℃ hydrocarbon solvent.Solvent in the described two-cycle gasoline engine lubricant is low to have reduced the pollution that is produced by the volatile organic matter volatilization, has improved with the elastomeric consistency of using in packing and transportation and has reduced flammable risk to strengthen transportation and storage security.

Most of above-mentioned additives can be incorporated in the described lubricant compositions with the amount of about 0.005%-about 15% or about 0.005%-6%, and wt% is based on the gross weight of described lubricant compositions.Under the situation of polybutene or polyisobutene, described amount can be 1%-50%.Each additive selected in stated limit or the amount of additive-package should not influence the character of wanting of described lubricant nocuously.Can easily determine by conventionally test by the influence that these additives produce.

Perhaps, described lubricating oil is by following material or the lubricating oil be made up of following material basically:

A. based on the 20wt% of whole lubricating oil and one or more base oil fractions between the 70wt%, this base oil fractions has:

I. successive carbonatoms;

Ii. about 1.5 and about 3.5mm ²Kinematic viscosity under 100 ℃ between the/s;

Iii. the alkane between about 90wt% and about 97wt% belongs to carbon;

Iv. the cycloalkanes between about 3wt% and about 10wt% belongs to carbon;

V. less than the aromatics carbon of 0.01wt%;

B. based on the pour point depressing blend component between 0.5 and the 25wt% of whole lubricating oil;

C. based on whole lubricating oil less than the maximum boiling point of about 5wt% hydrocarbon solvent less than 250 ℃;

D. based on purification agent/dispersant additives bag of the about 25wt% of about 1-of whole lubricating oil;

e。The fumicants that presses down based on the about 50wt% of about 1-of whole lubricating oil; With

f。Based on the pour point reducer of whole lubricating oil less than 0.1wt%;

The temper kinematic viscosity of wherein said lubricating oil under 100 ℃ is 6.5mm ²/ s or bigger, the low-temperature fluidity under-25 ℃ is good, and the smoke evacuation index is greater than 65.

The solvent that described two-cycle gasoline engine lubricant contains low levels owing to them has high flash point.Their flash-point is in some embodiments greater than 120 ℃ or greater than 150 ℃.

Concrete analysis test method

The wt% of the normal paraffin in the content of wax sample:

The quantitative analysis of the normal paraffin in the content of wax sample is determined by gas-chromatography (GC).GC (Agilent6890 or 5890 with kapillary shunting/overstepping one's bounds influx and flame ionization detector) is furnished with the super-sensitive flame ionization detector of hydrocarbon.Present method is used the methylsiloxane capillary column that is conventionally used for by boiling point separate hydrocarbons mixture.This post is the silicon-dioxide of consolidation, 100% methylsiloxane, and 30 meters are long, internal diameter 0.25mm, 0.1 micron thickness is provided by Agilent.Carrier gas is helium (2ml/ minute) and uses hydrogen and air as flame furl.

With described waxy feeds fusion to obtain the even sample of 0.1g.This sample is dissolved in the dithiocarbonic anhydride immediately to provide the solution of 2wt%.If desired, heat this solution, inject GC then until seeming the limpid solid that do not contain.Use following temperature program(me) to heat described methylsiloxane post:

● initial temperature: 150 ℃ (if there is the C7-C15 hydrocarbon, initial temperature is 50 ℃)

● slope: 6 ℃/minute

● warm eventually: 400 ℃

● the final maintenance: 5 minutes or until peak wash-out no longer

This post separates normal paraffin and non-normal paraffin effectively according to the order that carbon number increases then.Analyze known reference standard thing in the same way to set up the elution time at concrete normal paraffin peak.This standard substance is an ASTM D2887 n-paraffin standard substance, purchases in vendor (Agilent or Supelco), mixes Polywax 500 polyethylene (available from the Petrolite company of Oklahoma) of 5wt%.This standard substance of fusing before injection.From the analysis of described reference standard thing and the historical data of collecting has also been guaranteed the resolution efficient of this capillary column.

If exist in sample, the normal paraffin peak is to identify in other hydrocarbon types that well separate and that be easy to exist from sample.Those peaks of wash-out are known as non-normal paraffin beyond the retention time of normal paraffin.Use begins to come the integration entire sample to the baseline that finishes to continue from operation.N-paraffin omits from the total area, and carries out integration from paddy to paddy.All detected peaks are normalized to 100%.Use EZChrom to discern peak and calculation result.

Alkene wt%:

Measure alkene wt% in the base oil according to following steps A-D by proton-NMR:

A. the solution of the 5-10% of hydrocarbon in deuterochloroform is tested in preparation.

B. obtain the normal proton spectra of 12ppm spectrum width at least and accurately with reference to chemical shift (ppm) axle.This instrument must have enough gain margins do not have receptor/ADC with picked up signal overload.When applying the pulse of 30 degree, this instrument must have 65000 minimum signal digitizing dynamicrange.Preferably, this dynamicrange will be 260000 or more.

C. measure the integrated intensity between the following scope:

(6.0-4.5ppm alkene)

(2.2-1.9ppm allyl type)

(1.9-0.5ppm saturated)

D. use the molecular weight of the test substances of determining by ASTM D2503 to calculate:

1. the average mark minor of stable hydrocarbon

2. the average mark minor of alkene

3. total mark intensity (=all integrated intensities and)

4. the integrated intensity of each sample hydrogen (number of the hydrogen in=total mark/molecular formula)

5. the number of alkene hydrogen (integration of=alkene integration/each hydrogen)

6. the number of two keys (hydrogen/2 in=alkene hydrogen * olefin hydrocarbon molecules formula)

7. the number of the hydrogen in the number/typical test substances molecule of the hydrogen in the number of the alkene wt%=100 * two keys that obtain by proton N MR * typical olefin hydrocarbon molecules.

Work preferably by the resulting alkene wt% of proton N MR computation program D when alkene % result low (less than about 15wt%).Described alkene must be " routine " alkene, i.e. the distributed mixture of those alkene types of linking to each other with double key carbon of hydrogen, for example: α, vinylidene, cis, trans and trisubstituted.These alkene types generally have detectable allyl group and the alkene integration ratio between 1 and about 2.5.When this ratio surpasses approximately 3 the time, it shows three or quaternary alkene of the higher per-cent of existence, and must make different hypothesis with the double key number order in the calculation sample.

Measure aromatic substance by HPLC-UV:

The method that is used for measuring the molecule with at least one aromatic functional group of the low levels in the lubricant base oil is used Hewlett Packard 1050 serial four gradient high performance liquid chromatography (HPLC) systems, this system links to each other with HP1050 diode array ultraviolet-visible(light)detector, and the interface is the HP chem workstation.Based on their UV spectrum pattern and their elution time, differentiate each the aromatics kind in the HI SA highly saturated base oil.The nh 2 column that is used for this analysis is mainly distinguished aromatic molecules based on the number of the ring of aromatic molecules (or more accurately, double key number order).Therefore, the molecule that contains monocyclic aromatics will be at first by wash-out, is the polycyclic aromatic substance then according to the cumulative order of the double key number order of per molecule by wash-out.For the aromatic substance with similar two key features, those that only have on the ring that alkyl replaces will get faster than those wash-outs with cycloalkyl substituted.

Differentiate clearly that from the UV absorption spectrum of various base oil aromatic hydrocarbons they are that peak transition of electron by recognizing them realizes with respect to whole red shift degree of pure model compound analogue, this red shift degree depends on the alkyl on the member ring systems and the amount of cycloalkyl substituted.The alkyl delocalizationization that well-known these red shifts are the π-electronics in the aromatic ring causes.Owing to seldom have unsubstituted aromatic substance in the lubricant scope, to seethe with excitement, for certified all main aryl, red shift to a certain degree be among expecting and arriving of observing.

Come the aromatic substance of wash-out is carried out quantitatively by integral chromatogram, wherein this color atlas is made in appropriate retention time window by the wavelength to the compound optimization of each big class, compound by artificial evaluation wash-out is appropriate aromatic species in the absorption spectrum separately of different time and based on the qualitative resemblance of they and model compound absorption spectrum with their ownership, comes to determine the retention time window limits for each aromatic species thus.Few exception is only observed 5 class aromatic substance in HI SA highly saturated API II class and III series lubricant agent base oil.

HPLC-UV proofreaies and correct:

HPLC-UV is used to identify even the unusual aromatic substance of these classes of low levels.The absorption of polynuclear aromatic compound generally than the strong 10-200 of the absorption of monocyclic aromatics doubly.Alkyl replaces also, and influence absorbs about 20%.Therefore, use HPLC separates and identifies various aromatic substance and know that how they absorb effectively is important.

5 class aromatic substance have been identified.Between the alkylnaphthalene class that alkyl-1-cyclophane family's naphthenic hydrocarbon of keeping at topnotch and inferior height keep, have little overlapping, all aromatic substance kinds are that baseline is differentiated.Determine at the 272nm place for the 1-ring of co-elute and the integration boundaries of 2-cyclophane compounds of group by the vertical line dropping method.By setting up Beer law figure,, at first determine the response factor that depends on wavelength of the big class of each aromatic substance based on the spectrum peak absorbancy the most close with the aromatics analogue of described replacement from pure model compound mixture.

For example, the alkyl in the base oil-cyclohexylbenzene molecule demonstrates clearly peak value absorbancy at the 272nm place, identical (taboo) transition that this takes place at the 268nm place corresponding to unsubstituted 1,2,3,4-tetralin model compound.By supposing that alkyl-1-cyclophane family naphthenic hydrocarbon is at the molar absorptivity response factor at 272nm place and from 1 of Beer law figure calculating, 2,3, the 4-tetraline calculates the concentration of alkyl-1-cyclophane family naphthenic hydrocarbon in the base oil sample in the molar absorptivity approximately equal at 268nm place.Be approximately equal to the molecular-weight average of whole base oil sample by the molecular-weight average of supposing each aromatic substance class, calculate the weight percent concentration of aromatic substance.

Further improve described bearing calibration by directly from lubricant base oil, separating described 1-cyclophane compounds of group via the HPLC chromatogram of exhausting property.Directly proofread and correct and eliminated hypothesis relevant and uncertainty with model compound with these aromatic substance.As expected, isolating aromatics sample has the response factor lower than model compound, because it is more highly to replace.

More specifically, in order accurately to proofread and correct this HPLC-UV method, use Waters partly to prepare the HPLC device is isolated replacement from described lubricant base oil body benzene aromatic substance.With the dilution in 1: 1 in normal hexane of 10g sample; and be expelled in the silica column (5cm * 22.4mm ID guard column) of amino bonded; the post of the 25cm * 22.4mm internal diameter of the silica dioxide granule of the amino bonded by two 8-12 microns is (by Rainin Instruments then; Emeryville; California makes), adopting flow is that 18ml/ minute normal hexane is as moving phase.Based on detector response, with the classification of post elutriant from the dual wavelength UV detector that is set in 265nm and 295nm.Collect saturates level part and show the variation of 0.01 absorbance unit up to the 265nm absorbancy, this is the signal that monocyclic aromatics begins wash-out.Collect the absorbancy ratio of monocyclic aromatics level part between 265nm and 295nm and drop to 2.0, this shows that bicyclic-aromatic compound begins wash-out.By described monocyclic aromatics level part being carried out again chromatography is eliminated because " hangover " saturates level part that the HPLC column overload causes, the purification of carrying out described monocyclic aromatics level part with separate.

The aromatics of this purification " standard substance " shows that with respect to unsubstituted 1,2,3,4-tetralin, alkyl replaces makes the molar absorptivity response factor reduce about 20%.

Confirm aromatic substance by NMR:

The C of weight percent by long duration that has all molecules of at least one aromatic functional group in single aromatics standard substance of described purification ¹³NMR analyzes and confirms.NMR is than the easier correction of HPLC UV, because it measures aromatics carbon simply, so its response does not rely on the kind of analyzed aromatic substance.Aromatic substance by the 95-99% in the saturated lubricant base oil of known altitude is a monocyclic aromatics, and NMR result is converted into aromatic molecules % (for consistent with HPLC-UV and D2007) from aromatics carbon %.

The baseline analysis that needs superpower, long duration to become reconciled is accurately to measure the aromatic substance that is low to moderate 0.2% aromatic molecules.

More specifically, in order accurately to measure all molecules with at least one aromatic functional group of low levels by NMR, the D5292-99 method of revising standard is to provide 500: 1 minimum carbon sensitivity (by ASTM standard practices E386).The 15 hour time length operation of employing on 400-500MHzNMR with 10-12mmNalorac probe.Use Acorn PC integration software to define the shape of baseline and integration as one man.Being in operation changes the primary carrier frequency, with the non-natural sign of avoiding being caused at the aromatics regional imaging by aliphatic peak.By taking the photograph spectrum in the both sides of described carrier wave spectrum, resolving power is able to remarkable improvement.

Embodiment

Embodiment 1

Prepared the wax sample of forming by the Fischer-Tropsch wax (all using the preparation of Co base fischer-tropsch catalysts) of the hydrotreatment of several different batches.Wax to the different batches that constitutes described wax sample analyzes and finds all have the character shown in the Table II.

The Table II Fischer-Tropsch wax

Fischer-tropsch catalysts	The Co base
		Sulphur, ppm	＜10
Nitrogen, ppm	＜10
		Oxygen, wt%	＜0.50
N-paraffin wt% by GC mensuration	＞85
		D6352?SIMDIST?TBP(wt％)，°F T10 T90	550-700 1000-1080
T90-T10，℃	＞154

Has the described Co base of hydroisomerization Fischer-Tropsch wax on the Pt/SAPO-11 catalyzer of alumina binder.Operational condition comprise temperature between 635 and 675 °F (335 ℃ and 358 ℃), LHSV is 1.0hr ^-1, the about 500psig of reactor pressure and one way hydrogen flow 5 and 6MSCF/bbl between.Reactor effluent is second reactor that contains the Pd Hydrobon catalyst on the silica-alumina by also operating under 500psig directly.The condition of this second reactor comprises the temperature and the 2.0hr of about 350 (177 ℃) ^-1LHSV.

The product that is higher than 650 by underpressure distillation fractionation boiling point is to produce the distillment cut of different viscosity grade.Three kinds of Fischer-tropsch derived lubricant base oils have been obtained.Two kinds be the distillment side adopt cut (XLFTBO and XXLFTBO) and a kind of be distillment bottom fraction (HFTBO).The test data of three kinds of Fischer-tropsch derived lubricant base oils is shown in down Table III.

Table III

Properties of samples	HFTBO	XLFTBO	XXLFTBO
				Viscosity under 100 ℃, mm ²/s	16.01	2.926	2.409
Viscosity index	161	124	125
				Pour point, ℃	-10	-37	-42

D6352?SIMDIST?TBP(wt％)，°F 5 10/30 50 70/90 95	963 988/1040 1074 1113/1181 1213	683 692/717 737 755/777 785	625 640/673 696 716/738 746
				Aromatic substance wt%	0.0306	0.0131	0.0185
Alkene wt%	＜0.1	＜0.1	＜0.1
				N-d-M wt% alkane belongs to carbon wt% cycloalkanes and belongs to carbon wt% aromatics carbon	92.98 7.02 0.00	95.42 4.58 0.00	96.13 3.87 0.00
Oxidizer BN, hour	45.32	40.16	47.69
				X among formula VI=28 * Ln (VIS100)+X	83.4	93.9	100
The Noack volatility, wt%	0.95	32.37	54.1
				NVF(1)＝160-(40×KV100)		42.96	63.64
NVF(2)＝(900×(KV100) ^-2.8)-15		29.5	61.75
				The alkyl branches of per 100 carbon atoms	7.58	Not test	10.2
At 15mm ²/ s and the drag coefficient under 40% slides/rolls ratio	＜0.015	Not test	0.032

HFTBO is the example with pour point depressing blend component of low traction coefficient.XLFTBO is the example of Noack volatility less than the lubrication base oil fraction of the Noack volatility factor of being calculated by formula (1).XXLFTBO is the Noack volatility less than the Noack volatility factor of being calculated by formula (1) and less than the example of the lubrication base oil fraction of the Noack volatility factor of being calculated by formula (2).

Embodiment 2

Chevron MOTEX 2T-X is the double stroke outboard engine oil by high-quality mineral base oil, polyisobutene, the low ash content purification agent of high-performance/dispersant additives bag and high-flash solvent preparation.Use previously described Fischer-tropsch derived base oil, the identical high-performance that use is used in Chevron MOTEX 2T-X is hanged down ash content purification agent/dispersant additives bag and polyisobutene synthetic base oil, has prepared the temper (temper B, temper C and temper F) of three kinds of different two-cycle gasoline engine lubricants of usefulness.Use conventional mineral base oil and high-flash solvent also to prepare contrast temper (contrast temper A).The prescription of these tempers is summarized in the Table IV.

Table IV

Component, wt%	Contrast temper A	Temper B	Temper C	Temper F
					ExxonMobil?AP/E?Core?600N	18.50	0	0	0
BxxonMobil?AP/E?Core?150N	29.00	0	0	0
					Exxsol?D80	20.00	0	0	0
HFTBO	0	8.40	16.90	22.50
					XLFTBO	0	0	0
XXL?FTBO	0	59.10	50.60	44.70
					Double stroke lubricant purification agent/dispersant additives bag	5.50	5.50	5.50	5.50
PIB	27.00	27.00	27.00	27.00
					Pour point reducer	0	0	0	0.3

The performance characteristics of these two-cycle gasoline engine lubricant tempers is shown in the Table V.

Table V

Character	Contrast temper A	Temper B	Temper C	Temper F
					Flowability, mPa.s-10 ℃-25 ℃	?959?＞7500	539 2579	5230 not tests	Do not test 3489
Compatibility-10 ℃-25 ℃	By failure	By passing through	Test is not passed through	Test is not passed through
					Kinematic viscosity mm under 100 ℃ ²/s	?8.058	7.137	9.13	8.082
Viscosity index	?136	11660	156	153
					Pour point, ℃	?-18	-40	-35	-49
Flash-point, ℃	?100	Not test	Not test	11994
					Aniline point, ℃	?110	Not test	Not test	124

Sulfated ash, wt%	?＜0.15	＜0.15	＜0.15	＜0.15
					Detergency was estimated in 180 minutes	?152	1488	101	Not test
Piston shirt rim deposition index	?112	110	95	Not test
					Oilness by JASCO M340-92 mensuration	?95	86	1033	104
The smoke evacuation index	?99	88	76	70

Use ASTM D92-05a, drive a glass tstr by Cleveland and measured flash-point.Use ASTM D611-04 to measure aniline point.Temper B, temper C and temper F do not have maximum boiling point basically less than 250 ℃ hydrocarbon solvent, yet with compare by conventional mineral oil basis oil and contrast temper A that high-flash solvent is made, they all have low smoke evacuation index value, lower pour point and improved compatibility.Comprise that the temper F of the most high-load HFTBO has provided especially high lubricity index, yet still have fabulous compatibility and good smoke evacuation index.

Embodiment 3

Use previous described Fischer-tropsch derived base oil, use design to be used for satisfying the purification agent/dispersant additives bag of the domestic specification of Thailand (TIS 1040-2541[1998]), prepared the temper of two-cycle gasoline engine lubricant.Use the base oil and the high-flash solvent of conventional petroleum derivation also to prepare the contrast temper.The prescription of these tempers is summarized in the Table VI.

Table VI

Component, wt%	Contrast temper D	Temper E
			TPI?600N	30.95	0
Exxsol?D80	25.50	0
			HFTBO	0	1.58
XLFTBO	0	0
			XXLFTBO	0	54.87
Double stroke lubricant purification agent/dispersant additives bag	5.50	5.50
			PIB	38.00	38.00
The PMA pour point reducer	0.05	0.05

The performance characteristics of these two-cycle gasoline engine lubricant tempers is shown in the Table VII.

Table VII

Character	Contrast temper D	Temper E
			Flowability, mPa.s-10 ℃-25 ℃	?1460?＞7500	1160 4799
Compatibility-10 ℃-25 ℃	By failure	By passing through
			Kinematic viscosity under 100 ℃, mm ²/s	?10.51	9.724
Viscosity index	?133	148
			Pour point, ℃	?-32	-50
Flash-point, ℃	?92	182
			Aniline point, ℃	?116.4	122
Sulfated ash, wt%	?＜0.18	＜0.18
			Detergency was estimated in 180 minutes	?131	151
Piston shirt rim deposition index	110	112
			The smoke evacuation index	137	84

Temper E also comprises the pour point depressing blend component HFTBO with low traction coefficient.Notice that this temper has low especially pour point and have good low-temperature fluidity under-25 ℃.With by conventional mineral oil basis oil with compare greater than the maximum boiling point of 5wt% contrast temper D less than 250 ℃ hydrocarbon solvent preparation, temper E has better low-temperature fluidity, lower pour point, better gasoline compatibility, better detergency and better piston shirt rim deposition index.Added less than the maximum boiling point of 5wt% less than the temper E of 250 ℃ hydrocarbon solvent will be easily by the two the requirement of JASO M345:2003 and ISO 13738:2000 (E) C class and D class.

For the purpose of this specification sheets and claims, unless indicate in addition, other used number of all numbers of expression amount, per-cent or ratio and specification sheets and claim all is interpreted as doing modification with term " about " in all cases.In addition, all scopes disclosed herein are to comprise also can independently making up of end points.

All publications, patent and the patent application of quoting among the application, quote its full content as a reference at this, it is quoted degree and ad hoc and is individually pointed out as the disclosure of each independent publication, patent application or patent, and is for reference with the full content of introducing them.

This printed instructions uses embodiment to come open the present invention, comprises best mode, and also is used for making any those skilled in the art can understand and use the present invention.Those skilled in the art are easy to top disclosed exemplary of the present invention is carried out many modifications.Therefore, the present invention is interpreted as comprising all structures and the method that falls within the claims scope.

Claims

1. prepare the method for lubricating oil, comprising:

Ii. purification agent/dispersant additives bag; Described thus lubricating oil satisfies the requirement of JASOM345:2003.

2. the process of claim 1 wherein that the wax stock that described alkane basically belongs to is Fischer-tropsch derived.

3. the method for claim 2, the raw material that wherein is used for producing the Fischer-tropsch process of the wax stock that described alkane basically belongs to is the hydrocarbon matter resource that is selected from biomass, Sweet natural gas, shale oil, oil, municipal garbage, these derivative and their combination.

4. the process of claim 1 wherein that the dewaxing of described hydroisomerization uses catalyzer, described catalyzer comprises selects the medium hole dimension molecular sieve of shape, noble metal hydrogenation component and refractory oxide carrier.

5. the method for claim 4, the wherein said medium hole dimension molecular screening of shape of selecting is from SAPO-11, SAPO-31, SAPO-41, SM-3, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ-32, offretite, ferrierite and their combination.

6. the method for claim 4, wherein said noble metal hydrogenation component is platinum, palladium or their combination.

7. the method for claim 1, comprise with one or more cuts of described lubricating base oil with based on whole lubricating oil compositions less than the hydrocarbon solvent mediation of the maximum boiling point of about 2wt% less than 250 ℃.

8. the method for claim 7 comprises that one or more cuts of described lubricating base oil are not in harmonious proportion with hydrocarbon solvent basically.

9. the method for claim 1 comprises that also one or more cuts with described lubricating base oil are in harmonious proportion with the fumicants that presses down that is selected from polybutene, polyisobutene and their mixture.

10. the method for claim 1 comprises that also one or more cuts and the pour point reducer with described lubricating base oil is in harmonious proportion.

11. the method for claim 1 comprises that also one or more cuts and the pour point depressing blend component with described lubricating base oil is in harmonious proportion.

12. the process of claim 1 wherein that the kinematic viscosity of one or more cuts under 100 ℃ of described lubricating base oil is about 1.5 and about 3.5mm ²Between/the s.

13. the process of claim 1 wherein that the Noack volatility of one or more cuts of described lubricating base oil is less than 90wt%.

14. the method for claim 13, the kinematic viscosity of one or more cuts of wherein said lubricating base oil is 1.5 and 4.0mm ²Between/the s and the Noack volatility less than the Noack volatility factor (1)=160-(kinematic viscosity under 40 * 100 ℃).

15. the method for claim 14, the kinematic viscosity of one or more cuts of wherein said lubricating base oil is 2.09 and 4.0mm ²Between/the s and the Noack volatility less than the Noack volatility factor (2)=(900 * (kinematic viscosity under 100 ℃) ^-2.8)-15.

16. the process of claim 1 wherein that one or more cuts of described lubricating base oil have that the alkane of being measured by ASTM D3238-95 (2005) greater than about 90wt% belongs to carbon and less than the aromatics carbon of 0.01wt%.

17. the process of claim 1 wherein that the oxidizer BN of one or more cuts of described lubricating base oil was greater than 35 hours.

18. the process of claim 1 wherein described lubricating oil have by ASTM D92-05a measure greater than 120 ℃ flash-point.

19. the process of claim 1 wherein that the viscosity index of described lubricating base oil is greater than 28 * Ln (kinematic viscosity under 100 ℃)+95.

20. prepare the method for lubricating oil, comprising:

A. following material is in harmonious proportion together with generate depression of pour point base oil blends:

Ii. pour point depressing blend component;

I. purification agent/dispersant additives bag;

Ii. press down fumicants;

Iii. Ren Xuan pour point reducer; With

Thereby production two-cycle gasoline engine lubricant.

21. the method for claim 20, wherein said two-cycle gasoline engine lubricant has:

(a) good low-temperature fluidity under-25 ℃;

In the compatibility test of (b) under-25 ℃, carrying out according to ASTM D4682-87 (2002 issue again) " by " result;

(c) greater than 65 smoke evacuation index;

(d) be less than or equal to-35 ℃ pour point approximately.

22. the method for claim 20, wherein said one or more base oil fractions are made by waxy feeds.

23. the method for claim 20, wherein said smoke evacuation index is more than or equal to 85.

24. the method for claim 20, wherein said pour point are less than or equal to-40 ℃ approximately.

25. the method for claim 20, but wherein said fumicants is a polyisobutene.

26. the method for claim 20, wherein said hydrocarbon solvent are the aliphatic solventss that takes off aromatization.

27. the method for claim 20 does not wherein add hydrocarbon solvent basically.

28. the method for claim 20, wherein said pour point depressing blend component is 15mm in kinematic viscosity ²/ s and slides/rolls are than being that the drag coefficient measured in 40% o'clock is less than 0.015.

29. satisfy the preparation method of the two-cycle gasoline engine lubricant of JASO M345:2003 requirement, comprising:

I. purification agent/dispersant additives bag; With

30. the wherein said raw material of the method for claim 29 is selected from wax, plastics and their mixture of Fischer-tropsch derived wax, petroleum derivation.

31. the method for claim 29, wherein said pour point depressing blend component is selected from:

A. isomerized Fischer-tropsch derived bottoms;

B. the mineral oil by the isomerized height content of wax prepares bottoms;

C. the kinematic viscosity under 100 ℃ by the vinyon preparation is at least about 8mm ²The isomerized oil of/s; With

D. their mixture.

32. the method for claim 29, wherein said pour point depressing blend component is prepared by following steps:

I. high temperature pyrolysis vinyon;

Ii. from described high temperature pyrolysis step, isolate last running;

Iii. this last running of hydrotreatment;

Iv. the last running of this hydrotreatment of isoversion; With

V. be chosen in 100 ℃ of following kinematic viscosity at least about 8mm ²The cut of the isomerized product of/s.

33. the method for claim 29, wherein said pour point depressing blend component is 15mm in kinematic viscosity ²/ s and slides/rolls are than being that the drag coefficient measured in 40% o'clock is less than 0.015.

34. the method for claim 29, wherein said two-cycle gasoline engine lubricant have good low-temperature fluidity under-25 ℃.

35. the method for claim 29, the smoke evacuation index of wherein said two-cycle gasoline engine lubricant is greater than 65.

36. the method for claim 29, wherein said two-cycle gasoline engine lubricant have 0.18wt% or sulfated ash still less.

37. the method for claim 29 also comprises described pour point depressing blend component and presses down fumicants being in harmonious proportion.

38. the method for claim 29, wherein said distillment base oil is Fischer-tropsch derived.

39. the lubricating oil of making by the method that may further comprise the steps:

40. the lubricating oil that passes through described method manufacturing of claim 39, the wax stock that wherein said alkane basically belongs to is Fischer-tropsch derived.

41. the lubricating oil that passes through described method manufacturing of claim 39, wherein said hydroisomerization dewaxing is used and is comprised the catalyzer of selecting the medium hole dimension molecular sieve of shape, noble metal hydrogenation component and refractory oxide carrier.

42. claim 39 pass through the lubricating oil that described method is made, comprise with one or more cuts of described lubricating base oil with based on whole lubricating oil less than the hydrocarbon solvent mediation of the maximum boiling point of about 2wt% less than 250 ℃.

43. the lubricating oil that passes through described method manufacturing of claim 39 comprises that one or more cuts of described lubricating base oil are not in harmonious proportion with hydrocarbon solvent basically.

44. the lubricating oil that passes through described method manufacturing of claim 39 comprises that also one or more cuts with described lubricating base oil are in harmonious proportion with the fumicants that presses down that is selected from polybutene, polyisobutene and their mixture.

45. the lubricating oil that passes through described method manufacturing of claim 39 comprises that also one or more cuts and the pour point reducer with described lubricating base oil is in harmonious proportion.

46. claim 39 pass through the lubricating oil that described method is made, one or more cuts of wherein said lubricating base oil have that the alkane of being measured by ASTM D3238-95 (2005) greater than 90wt% belongs to carbon and less than the aromatics carbon of 0.01wt%.

47. the lubricating oil that passes through described method manufacturing of claim 39, it satisfies the requirement of JASOM345:2003C class or D class.

48. the lubricating oil that passes through described method manufacturing of claim 39, it satisfies the requirement of ISO13738:2000 (E).

49. the lubricating oil that passes through described method manufacturing of claim 39, it has good low-temperature fluidity under-25 ℃.

50. the lubricating oil that passes through described method manufacturing of claim 39, its compatibility that has passed through to be undertaken by ASTM D4682-87 (2002 issue again) under-10 ℃ or-25 ℃ is tested.