JP2010538116A - Method for producing two-cycle gasoline engine lubricant - Google Patents

Abstract

  A method for preparing a lubricating oil that satisfies the requirements of JASO M345: 2003: a step of hydroisomerizing and dewaxing raw materials to produce a base oil, and adding less than 5% by weight of solvent and detergent / dispersant to the base oil The above method comprising the step of blending with an agent package. A method of producing a lubricating oil comprising a base oil blend having a reduced pour point in a detergent / dispersant additive package, a smoke suppressant, optionally a pour point depressant, and optionally less than about 5% by weight hydrocarbon solvent. Blending together to produce a two-cycle gasoline engine lubricant. A method for producing a two-cycle gasoline engine lubricating oil comprising the step of preparing a pour point reducing blend component by feed isomerization, which is blended with a light distillate base oil to produce a pour point reducing base oil blend. And blending the reduced pour point base oil blend with a detergent / dispersant additive package and less than 5 wt% solvent. Lubricating oil produced by the method described herein.

Description

  The present invention is directed to a process for producing an improved two-cycle gasoline engine lubricating oil composition that requires less hydrocarbon solvent.

A two-cycle engine has three important advantages over a four-cycle engine:
-A two-cycle engine has no valves, simplifying its structure and reducing its weight.
• A 2-cycle engine burns once for every cycle, but a 4-cycle engine burns once every other cycle. This gives the 2-cycle engine a fairly high output.
The two-cycle engine can operate in any geometry, which can be important in things like chainsaws. Standard four-cycle engines may have problems with oil flow unless upright, and solving this problem may add complexity to the engine.

There are at least three potential disadvantages of a two-cycle engine:
• 2-cycle engines do not last as long as 4-cycle engines. The lack of a dedicated lubrication system means that the components of a two-cycle engine wear out fairly quickly.
• Two-cycle gasoline engine lubricants are expensive and require about 4 ounces per gallon of gasoline. If a two-cycle engine is used in an automobile, about 1 gallon of lubricating oil is consumed every 1,000 miles.
• Two-cycle engines cause a lot of pollution, including smoke from consumption of two-cycle gasoline engine lubricants and leakage of two-cycle gasoline engine lubricants through the exhaust port.

  Most two-cycle gasoline engine lubricants are formulated with low boiling hydrocarbon solvents and SAE 40 mineral base oil. Others use ester base oils that do not contain low-boiling solvents, reducing the potential for danger and minimizing smoke emissions, but these lubricating oils have less good oxidative stability. Absent. Others use polyalphaolefin base oils with improved low temperature properties. Polyalphaolefins and ester base oils are limited in stock and are very expensive. An improved two-cycle gasoline engine lubricating oil composition that includes a less expensive base oil and meets the requirements set by the standards setting agency is desirable. It is also desirable that these lubricating oil compositions have reduced levels of hydrocarbon solvents, reduced engine wear, and reduced contamination. Also, it is desirable for a two-cycle gasoline engine lubricating oil composition to have good low temperature performance, good gasoline miscibility, and high oxidative stability. Also, it is desirable for a two-cycle gasoline engine lubricating oil composition to have a higher flash point and reduced flammability. Also, the two-cycle gasoline engine lubricating oil composition can be manufactured using polyethylene plastic, and it is desirable to reduce environmental pollution due to waste plastic.

The present invention is a method for preparing a lubricating oil comprising:
a. Hydroisomerizing and dewaxing a substantially paraffinic wax feed, thereby producing a lubricating base oil; and b. One or more fractions of the lubricating base oil:
i. A hydrocarbon solvent having a maximum boiling point of less than about 250 ° C., less than about 5% by weight, based on the total lubricating oil composition, and ii. Blending with a detergent / dispersant additive package provides a method for lubricating oils to meet the requirements of JASO M345: 2003.

The present invention is also a method for producing a lubricating oil comprising:
a. together:
i. One or more fractions of a base oil having a kinematic viscosity between about 1.5 and about 3.5 mm ² / s at 100 ° C., and ii. Blending a pour point reducing blend component to produce a base oil blend having a reduced pour point; and b. For base oil blends with reduced pour points:
i. Detergent / dispersant additive package;
ii. Smoke suppressant;
iii. Optionally a pour point depressant; and iv. There is also provided the above method of optionally adding less than about 5% by weight of a hydrocarbon solvent having a maximum boiling point of less than 250 ° C., thereby producing a two-cycle gasoline engine lubricating oil.

The present invention is also a method for producing a two-cycle gasoline engine lubricant that meets the requirements of JASO M345: 2003:
a. Preparing a pour point reducing blend component by isomerizing the feed;
b. The pour point lowering blend component
i. Blending with a distillate base oil having a kinematic viscosity between about 1.5 and about 3.5 mm ² / s at 100 ° C. to produce a base oil blend having a reduced pour point;
c. Base oil blend with reduced pour point:
i. A detergent / dispersant additive package; and ii. The above process comprising blending in an appropriate proportion with a hydrocarbon solvent having a maximum boiling point of less than 5O <0> C and less than 5O <0> C, based on total 2-cycle gasoline engine lubricant, to obtain a 2-cycle gasoline engine lubricant Also provide.

The present invention also provides
a. Hydroisomerizing and dewaxing a substantially paraffinic wax feed to produce a base oil; and b. One or more fractions of the lubricating base oil:
i. A hydrocarbon solvent having a maximum boiling point of less than about 250 ° C., less than about 5% by weight, based on the total lubricating oil composition; and ii. There is also provided a lubricating oil produced by a process wherein the lubricating oil meets the requirements of JASO M345: 2003, including blending with a detergent / dispersant additive package.

A plot of kinematic viscosity at 100 ° C. vs. Noack volatility is given in weight percent, giving a formula for the upper limit of weight percent Noack volatility: Noack volatility factor (1) = 160-40 (kinematic viscosity at 100 ° C.), and Noack volatility factor (2) = 900 × (kinematic viscosity at 100 ° C.) ^−2.8 −15, where the kinematic viscosity at 100 ° C. rises to the power of −2.8 in the second equation.

  In order to operate a two-cycle gasoline engine, the crankcase holds a mixture of two-cycle gasoline engine lubricant and fuel. In a two-cycle engine, the crankcase functions as a pressurizing chamber and feeds air / fuel into the cylinder, so it cannot hold high viscosity oil that can be used in a four-cycle engine. Instead, a special two-cycle gasoline engine lubricant is mixed into the fuel and supplied to the crankshaft, connecting rod and cylinder wall.

  The recommended mixing ratio for two-cycle gasoline engine lubricants and fuels is specified by the engine manufacturer. Fuels useful in two-cycle gasoline engines are well known to those skilled in the art and, as a major component, fuels that are normally liquid, such as hydrocarbon-based petroleum distillate fuels, such as sparks defined by ASTM D4814-07. It mostly includes ignition engine fuel or motor gasoline as defined by ASTM D439-89. Such fuels can also include non-hydrocarbon materials such as alcohols, ethers, organic nitrogen compounds, and the like. For example, methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane and such fuels when the liquid fuel is a liquid derived from plants and mineral sources such as corn, switch glass, alpha shale and coal. Are within the scope of the present invention. Examples of such fuel mixtures are gasoline and ethanol, diesel fuel and ether, a combination of gasoline and nitromethane, and the like. In one embodiment, the fuel is unleaded gasoline.

  Two-cycle gasoline engine lubricating oil is mixed with fuel in an amount of about 20 to 250 parts by weight of fuel per part by weight of lubricating oil, and more typically in an amount of about 30 to 100 parts by weight of fuel per part by weight of lubricating oil. Used.

Two-cycle gasoline engine lubricants must meet the requirements set by standard setting agencies including the Japanese automobile standard JASO M345: 2003 and the international standard ISO 13738: 2000 (E). The requirements for these two standards are summarized in the following table.
Table I

  The index in the above requirement table is determined by assuming that the JATRE-1 oil has a value of 100. Category C applies to so-called low smoke type oil having excellent exhaust smoke performance and exhaust system shut-off tendency. Category D applies to oils that have better cleanliness than Category C oils when the engine is hot. According to ISO standards, the oils of categories B, C and D all have a sulfated ash content of up to 0.18% by weight. Sulfated ash may be measured according to ISO 3987 or ASTM D874-00.

  Furthermore, it is desirable that these lubricating oils have good low temperature fluidity when used in conditions where low temperatures are encountered. Low temperature fluidity is measured by determining the Brookfield viscosity as measured by ASTM D2983-04a at specified temperatures of -10 ° C, -25 ° C, and -40 ° C. “Good low temperature fluidity” at one of the temperatures measured is about 7500 mPa.s for the oil being tested. It is defined in this disclosure that it has a Brookfield viscosity of s or less. For example, good low temperature fluidity at −10 ° C. means that the oil is about 7500 mPa.s at −10 ° C. s or less; good low temperature fluidity at -25 ° C means that the oil is about 7500 mPa.s at -25 ° C. s or less; and good low temperature fluidity at -40 ° C means that the oil is about 7500 mPa.s at -40 ° C. It means having a Brookfield viscosity of s or less.

  Furthermore, it is desirable that these lubricating oils have a passing result in a miscibility test according to ASTM D4682-87 (Reapproved 2002) at a temperature of −10 ° C. and / or −25 ° C.

  Two-cycle gasoline engine lubricating oil compositions may be used as injector oils, i.e. by evaporation, including outboard motors, snowmobiles, motorcycles, moppets, ATVs, golf carts, lawnmowers, chainsaws, string trimmers, etc. It is particularly suitable at fuel to lubricant mixing ratios of up to 150: 1 with suitable fuels such as gasoline in electronic fuel injection and direct fuel injection two-cycle engines.

Base oil :
The lubricating base oil used in the two-cycle gasoline engine lubricating oil composition is derived from a substantially paraffinic wax feed. The term “substantially paraffinic” is meant to contain high levels of n-paraffin, generally greater than 40% by weight. Some substantially paraffinic wax feeds can have, for example, greater than 50 wt%, or greater than 75 wt% n-paraffins. An example of a substantially paraffinic wax feed is a wax produced in a Fischer-Tropsch process. Another example is highly refined slack wax.

  Fischer-Tropsch wax is a well-known process such as industrial SASOL® slurry phase Fischer-Tropsch technology, industrial SHELL® middle distillate synthesis (SMDS) process, or non-industrial EXXON®. ) It can be obtained by an improved gas conversion (AGC-21) process. These processes and other details are described, for example, in EP-A-776959, EP-A-668342; U.S. Pat. Nos. 4,943,672, 5,059,299, 5,733,839, And RE 39073; and US Patent Publication No. 2005/0227866, WO-A-9934917, WO-A-9920720 and WO-A-05107935. Fischer-Tropsch synthesis products usually include hydrocarbons having 1 to 100, or even more than 100 carbon atoms, and typically include paraffins, olefins and oxidation products. Fischer-Tropsch is a viable process for producing clean alternative hydrocarbon products including Fischer-Tropsch wax.

  Slack wax can be obtained from conventional petroleum-derived feedstocks either by hydrocracking or solvent refining of the lube oil fraction. Typically, slack wax is recovered from the solvent dewaxing feedstock prepared by one of these processes. Hydrocracking is usually preferred because the nitrogen content can also be reduced to low values. Slack wax is derived from solvent refined oil and can be deoiled to reduce nitrogen content and increase viscosity index. Hydrogen treatment of slack wax can be used to reduce the nitrogen and sulfur content. Slack waxes have a very high viscosity index, usually in the range of about 140 to 200, depending on the oil and starting material from which the slack wax was prepared. Accordingly, slack wax is suitable for the preparation of base oils used in 2-cycle gasoline engine lubricating oils.

  In one embodiment, the wax feed has a combined nitrogen and sulfur with a total of less than 25 ppm. Nitrogen is measured by melting the wax feed prior to oxidative combustion and chemiluminescence detection according to ASTM D4629-02. The test method is further described in US Pat. No. 6,503,956, incorporated herein. Sulfur is measured by melting the wax feed prior to UV fluorescence according to ASTM D5453-00. The test method is further described in US Pat. No. 6,503,956, incorporated herein.

  For the determination of normal paraffins (n-paraffins) in wax-containing samples, a method should be used that can determine the content of individual C7-C110 n-paraffins with a detection limit of 0.1% by weight. . The method used is described later in this disclosure.

  Wax supplies are expected to be abundant and relatively cost competitive in the near future when large scale Fischer-Tropsch synthesis processes are added to production. Fischer-Tropsch derived base oils made from these wax feeds, and thus two-cycle gasoline engine lubricating oils containing them, are as expensive as lubricating oils made with other synthetic oils such as polyalphaolefins or esters. Not. The term “Fischer-Tropsch derived” or “FT derived” means that the product, fraction, or feed is produced or produced at any stage by the Fischer-Tropsch process. Fischer-Tropsch process feedstock may come from a wide variety of hydrocarbon-based sources including biomass, natural gas, coal, shale oil, petroleum, municipal waste, derivatives thereof, and combinations thereof . Synthetic feedstocks prepared from the Fischer-Tropsch process include a mixture of various solid, liquid, and gaseous hydrocarbons. These Fischer-Tropsch products boiling within the lube base oil contain a high proportion of wax, making them ideal candidates for processing into base oils. Thus, Fischer-Tropsch wax presents an excellent supply for preparing high quality base oils. Fischer-Tropsch wax is usually solid at room temperature and therefore exhibits poor low temperature properties such as pour point and cloud point. However, following hydroisomerization of the wax, a Fischer-Tropsch derived base oil with excellent low temperature properties can be prepared. A general description of examples of suitable hydroisomerization dewaxing processes can be found in US Pat. Nos. 5,135,638 and 5,282,958, incorporated herein, and US Patent Application No. 200501333409. Can be found in

  Hydroisomerization is accomplished by contacting the wax feed with a hydroisomerization catalyst in the isomerization zone under hydroisomerization conditions. The hydroisomerization catalyst preferably comprises a shape selective intermediate pore size molecular sieve, a noble metal hydrogenation component, and a refractory oxide support. Shape selective intermediate pore size molecular sieves are SAPO-11, SAPO-31, SAPO-41, SM-3, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ-32, offretite, It is preferably selected from the group consisting of ferrierite and combinations thereof. In one embodiment, SAPO-11, SM-3, SSZ-32, ZSM-23, ZSM-48, and combinations thereof are used. In one embodiment, the noble metal hydrogenation component is platinum, palladium, or a combination thereof.

The hydroisomerization conditions depend on the wax feed used, the hydroisomerization catalyst used, whether the catalyst is sulfided, the desired yield of the base oil and the desired properties. Examples of hydroisomerization conditions in one embodiment include a temperature of 260 ° C. to about 413 ° C. (500 to about 775 ° F.); a total pressure of 15 to 3000 psig, or 50 to 1000 psig; and about 2 to 30 MSCF / bbl, about 4~20MSCF / bbl (about 712.4～ about 3,562 liters _{H 2} / liter oil), and about 4.5 or 5 to about 10 MSCF / bbl, or hydrogen to feed ratio of from about 5 to about 8MSCF / bbl . In general, hydrogen may be separated from the product and recycled to the isomerization zone. Note that a feed rate of 10 MSCF / bbl is equal to a 1781 liter H ₂ / liter feed. In general, hydrogen may be separated from the product and recycled to the isomerization zone.

  Optionally, the base oil produced by hydroisomerization dewaxing may be hydrofinished. Hydrofinishing can occur in one or more steps, either before or after fractionating the base oil into one or more fractions. The hydrofinishing is intended to improve the oxidative stability, UV stability, and appearance of the product by removing aromatics, olefins, colored objects, and solvents. A general description of hydrofinishing can be found in US Pat. Nos. 3,852,207 and 4,673,487, incorporated herein. The hydrofinishing process may need to reduce the olefin weight percent in the base oil to less than 10, less than 5 or 2, less than 1, less than 0.5, and less than 0.05 or 0.01. . The hydrofinishing step may also reduce the weight percent of aromatics to less than 0.3 or 0.1, less than 0.05, less than 0.02, and in some embodiments further less than 0.01. May be necessary.

  Optionally, the base oil produced by hydroisomerization dewaxing can be treated with an adsorbent such as bauxite or clay to remove impurities and improve color and biodegradability.

  Since the base oil is made from a wax feed, it has a continuous number of carbon atoms. By “consecutive number of carbon atoms” we mean that the wax feed also has a continuous number of carbon atoms, so that the hydrocarbon molecules of the base oil differ from each other by a continuous number of carbon atoms. is doing. For example, in a Fischer-Tropsch hydrocarbon synthesis reaction, the source of carbon atoms is CO, and the hydrocarbon molecules are built at one carbon atom at a time. Petroleum-derived wax feeds also have a sequential carbon number. In contrast to oils based on PAO, the base oil molecules have a more linear structure, short branches and relatively long skeletons. The PAO classic textbook description is a star molecule, especially tridecane, illustrated as three decane molecules attached to a central point. Although star-shaped molecules are theoretical, nevertheless, PAO molecules have fewer and longer molecular chains, like the hydrocarbon molecules that make up the base oil used in this disclosure. In another embodiment, the base oil having a consecutive number of carbon atoms also has less than 10 wt% naphthalene carbon by ndM.

In one embodiment, the lubricating base oil is separated into fractions, whereby one or more fractions are less than 0 ° C, less than -9 ° C, less than -15 ° C, less than -20 ° C, less than -30 ° C. Or may have a pour point of less than -35 ° C. The pour point is measured by ASTM D5950-02. Base oils are optionally separated into base oils of different viscosity grades. In the context of this disclosure, “base oils of different viscosity grades” are defined as two or more base oils having kinematic viscosities at 100 ° C. that differ from each other by at least 0.5 mm ² / s. Kinematic viscosity is measured using ASTM D445-06. Fractionation is performed using a vacuum distillation unit to obtain a cut fraction having a preselected boiling range. One of the fractions may be a bottoms product.

  In one embodiment, the base oil fraction has less than 0.01 wt% aromatic carbon and greater than about 90 wt% paraffinic carbon. The balance of carbon weight percent is naphthalene carbon. Aromatic carbon weight percent, paraffin carbon weight percent and naphthalene carbon weight percent are determined by ndM analysis according to ASTM D3238-95 (2005). In one embodiment, the paraffin carbon weight percent is between about 90 weight percent and about 97 weight percent, and the naphthalene carbon weight percent is between about 3 weight percent and about 10 weight percent.

In one embodiment, the viscosity index of the lubricating base oil fraction may be high. They can often have a viscosity index greater than 28 × Ln (kinematic viscosity at 100 ° C.) + 80. In one embodiment, they may have a viscosity index greater than 28 × Ln (kinematic viscosity at 100 ° C.) + 95. For example, an oil of 2.5 mm ² / s may have a viscosity index greater than 106, optionally greater than 121; an oil of 12 mm ² / s will have a viscosity index greater than 150, optionally greater than 165 obtain.

In another embodiment, the base oil is calculated by the pour point below −8 ° C .; the kinematic viscosity at 100 ° C. of at least 1.5 mm ² / s; and the formula: 22 × Ln (kinematic viscosity at 100 ° C.) + 132 A viscosity index greater than In this embodiment, for example, an oil having a kinematic viscosity of 2.5 mm ² / s at 100 ° C. may have a viscosity index greater than 152. Base oils having these characteristics are described in US Patent Publication No. 20050077208. In connection with the equations in this disclosure, the term “Ln” refers to the natural logarithm with a base “e”. The test method used to measure the viscosity index is ASTM D2270-04.

The base oil fraction has a kinematic viscosity between 100 and 25 mm ² / s at 100 ° C. In one embodiment, the base oil fraction has a kinematic viscosity at 100 ° C. of between about 1.5 and about 3.5 mm ² / s. In another embodiment, the base oil fraction has a kinematic viscosity between about 1.8 and about 3.2 mm ² / s.

  In one embodiment, the base oil fraction provides excellent oxidative stability, low Noack volatility, and the desired additive and elastomer compatibility. The base oil fraction has less than 10, less than 5, less than 1, less than 0.5, or less than 0.05 or less than 0.01 olefins by weight percent. The base oil fraction has less than 0.1, less than 0.05, or less than 0.02 aromatics by weight.

“Traction coefficient” is an index of inherent lubricating oil characteristics expressed as a dimensionless ratio of frictional force F and normal force N, where friction is the distance between sliding or rolling surfaces. It is a mechanical force that resists or obstructs movement. The traction coefficient is an MTM traction measurement made by PCS Instruments, comprising a 19 mm diameter abrasive ball (SAE AISI 52100 steel) inclined at 220 degrees against a 46 mm diameter flat abrasive disc (SAE AISI 52100 steel). It can be measured using the system. Steel balls and discs are independently measured at an average rolling speed of 3 m / s, a slide to roll ratio of 40%, and a load of 20N. The rolling ratio is the difference in sliding speed between the ball and disk divided by the average speed of the ball and disk, ie rolling ratio = (speed 1−speed 2) / ((speed 1 + speed 2). / 2). In some embodiments, the base oil fraction is less than 0.023, 0.021 or less, or 0.019 or less when measured with a kinematic viscosity of 15 mm ² / s and a sliding to rolling ratio of 40%. With a traction coefficient of In one embodiment, these are traction coefficients that are less than the amount defined by the formula: traction coefficient = 0.009 x Ln (kinematic viscosity)-0.001, where the kinematic viscosity during the traction coefficient measurement is 2 Between ˜50 mm ² / s; the traction coefficient is measured at an average rolling speed of 3 m / s, a sliding to rolling ratio of 40% and a load of 20 N.

In one embodiment, the base oil fraction has a traction coefficient of less than 0.015 or less than 0.011, as measured by a kinematic viscosity of 15 mm ² / s and a sliding to rolling ratio of 40%. Examples of these base oil fractions having a low traction coefficient include U.S. Patent No. 7,045,055 and U.S. Patent Application Nos. 11/400570 and 11/399773 (both on April 7, 2006). Application). In one embodiment, the base oil has a traction coefficient less than 0.015 and a 50 wt% boiling point greater than 565 ° C (1050 ° F). In another embodiment, the base oil has a traction coefficient of less than 0.011 and a 50 wt% boiling point by ASTM D6352-04 greater than 582 ° C (1080 ° F).

  In some embodiments, an isomerized base oil having a low traction coefficient also has a branching index of 23.4 or less, a branching proximity of 22.0 or more, and 9-30. The unique branching characteristics by NMR including the free carbon index between are shown. According to nd-M analysis according to ASTM D3238-95 (Reapproved 2005), in one embodiment, the base oil has at least 4 wt% naphthalene carbon, and in another embodiment, at least 5 wt%. Has naphthalene carbon. A two-cycle gasoline engine lubricant comprising a base oil fraction having a low traction coefficient provides reduced engine wear.

In some embodiments, the olefin and aromatic content in the lubricating base oil fraction of the lubricating oil is fairly low and the selected base oil fraction oxydata BN (Oxidator BN) is greater than 25 hours, for example, It can be over 35 hours, or even over 40 hours. The oxydata BN of the selected base oil fraction can typically be less than 70 hours. Oxydata BN is a conventional means for measuring the oxidative stability of base oils. The Oxydata BN test is described in US Pat. No. 3,852,207 by Stangeland et al. The oxydata BN test measures oxidation resistance with a Dornte oxygen absorber. R. W. See Dorte "Oxidation of White Oils" Industrial and Engineering Chemistry, 28, 26, 1936. Typically, the conditions are 340 ° F. and 1 atmosphere of pure oxygen. Results are reported in the time required for 100 g of oil to absorb 1000 ml of O ₂ . In the Oxydata BN test, 0.8 ml of catalyst is used per 100 grams of oil and the additive package is included in the oil. The catalyst is a mixture of kerosene soluble metal naphthenates. The mixture of soluble metal naphthenates simulates the average metal analysis of the crankcase oil used. The metal levels in the catalyst are as follows: copper = 6,927 ppm; iron = 4,083 ppm; lead = 80,208 ppm; manganese = 350 ppm; tin = 3565 ppm. The additive package is 80 millimoles of bispolypropylene phenyldithio-zinc phosphate per 100 grams of oil, or about 1.1 grams of OLOA ™ 260. The Oxydata BN test measures the lube base oil response in the simulated application. High values for absorbing 1 liter of oxygen, i.e. long times, indicate good oxidative stability. A two-cycle gasoline engine lubricating oil that includes a base oil fraction that has good oxidative stability may also have improved oxidative stability.

  OLOA (TM) is an acronym for Oronite Lubricating Oil Additive, a registered trademark of Chevron Oronite.

  In some embodiments, one or more lube base stock fractions can have excellent biodegradability. For suitable hydro-processing and / or adsorbent treatment, they are readily biodegradable by the OECD 301B shake flask test (Modified Storm Test). When the readily biodegradable base oil fraction is blended with a suitable biodegradable additive, such as a selected low ash or ashless additive, the lubricating oil has a sensitive area with minimal non-biodegradable residues. Provides rapid biodegradability of the effluent and prevents costly environmental cleanup.

  In some embodiments, the one or more lube base oil fractions have a low Noack volatility. Noack volatility is typically tested according to ASTM D5800-05, Procedure B. In one embodiment, the one or more lubricant base oil fractions have a Noack volatility of less than 100 wt%. The Noack volatility of the base oil generally increases as the kinematic viscosity decreases. As the Noack volatility decreases, the volatility of base oil and refined oil during use decreases.

The “Noack Volatility Factor” of the base oil is an empirical number derived from the kinematic viscosity of the base oil. The Noack volatility of base oils derived from highly paraffinic wax is very low and, in one embodiment, less than the amount calculated by the formula: Noack volatility factor (1) = 160-40 (kinematic viscosity at 100 ° C.) It is. Equation (1) given in US 2006/0201852 A1 gives a Noack volatility factor between 0 and 100 for kinematic viscosities between 1.5 and 4.0 mm ² / s. FIG. 1 is a graph of Noack volatility factors according to equation (1). In the second embodiment, the Noack volatility of one or more lube base oil fractions is given by the formula: Noack volatility factor (2) = (900 × (kinematic viscosity at 100 ° C.) ^−2.8 ) − Is less than the amount calculated by 15. Equation (2) given in US patent application Ser. No. 11 / 613,936 gives a Noack volatility factor between 0 and 100 for kinematic viscosities between 2.09 and 4.3 mm ² / s. FIG. 1 also includes a Noack volatility factor according to equation (2). For kinematic viscosities in the range of 2.4 to 3.8 mm ² / s, equation (2) gives a lower Noack volatility factor than equation (1) gives. Lower Noack Volatility Factors within the range of base oils having a kinematic viscosity of 2.4 to 3.8 mm ² / s are blended with other oils, especially where the base oil may have higher Noack volatility Sometimes desirable.

  Additional base oil may be included in the lubricating oil composition in an amount from about 1.0% to about 20% by weight. Examples of these additional base oils include esters, mixtures of esters, and complex esters described in US Pat. No. 6,197,731; polyalphaolefins, polyinternal olefins, polyisobutenes, alkylated naphthalenes, and the like Examples include alkylated aromatics, and conventional petroleum-derived API Group II and Group III mineral oils.

Pour point lowering blend component :
The two-cycle gasoline engine lubricant may include a pour point reducing blend component. As used herein, “pour point reducing blend component” refers to an isomerized wax product having a relatively high molecular weight and a specific degree of alkyl branching in the molecule, and a lubricating base oil containing that component. Reduce the pour point of the blend. Examples of pour point reducing blend components are disclosed in US Pat. Nos. 6,150,577 and 7,053,254, and US Patent Publication No. 2005050247600A1. The pour point reducing blend component is 1) an isomerized Fischer-Tropsch derived bottom product; 2) a bottom product prepared from isomerized high waxy mineral oil, or 3) a kinematic viscosity at 100 ° C. of at least about 8 mm ² / s. It may be an isomerized oil made from polyethylene plastic having

  In one embodiment, the pour point reducing blend component has an average molecular weight between 600-1100 and an isomerization having an average degree of branching of 6.5-10 alkyl branches per 100 carbon atoms in the molecule. Fischer-Tropsch derived vacuum distillation bottom product. In general, higher molecular weight hydrocarbons are more effective as pour point reducing blend components than lower molecular weight hydrocarbons. In one embodiment, the pour point reducing blend component is prepared using a higher cut point in a vacuum distillation unit that results in a higher boiling bottom material. A higher cut point also has the advantage of yielding a higher yield of the distillate base oil fraction. In one embodiment, the pour point reducing blend component is an isomerized Fischer-Tropsch derived vacuum distillation bottom product having a pour point that is at least 3 ° C. higher than the pour point of the distillate base oil to be blended.

  In one embodiment, the 10 percent point of the boiling point range of the pour point reducing blend component that is the vacuum distillation bottom product is between about 850 ° F to 1050 ° F (454 to 565 ° C). In another embodiment, the pour point reducing blend component is derived from either a Fischer-Tropsch product or a petroleum product having a boiling range greater than 950 ° F. (510 ° C.) and contains at least 50 weight percent paraffin. To do. In yet another embodiment, the pour point reducing blend component has a boiling range greater than 1050 ° F. (565 ° C.).

  In another embodiment, the pour point reducing blend component is an isomerized petroleum derived base oil containing materials having a boiling range greater than about 1050 ° F. In one embodiment, the isomerization bottoms material is solvent dewaxed before being used as a pour point reducing blend component. It was found that the wax product further separated from the pour point lowering blend component during solvent dewaxing exhibits superior improved pour point depressing properties compared to the oil product recovered after solvent dewaxing. .

In another embodiment, the pour point reducing blend component is an isomerized oil made from polyethylene plastic having a kinematic viscosity at 100 ° C. of at least about 8 mm ² / s. In one embodiment, the pour point reducing blend component is made from waste plastic. In another embodiment, the pour point reducing blend component is at least about at about 100 ° C. at pyrolysis of the polyethylene plastic, separation of the heavy portion, hydrotreatment of the heavy portion, catalytic isomerization of the hydrotreated heavy portion, and Produced from a process involving collection of pour point reducing blend components having a kinematic viscosity of 8 mm ² / s. In a third embodiment, it is derived from polyethylene plastic and has a boiling range greater than 1050 ° F. (565 ° C.), or even greater than 1200 ° F. (649 ° C.).

In one embodiment, the pour point reducing blend component has an average intramolecular branching in the range of 6.5 to 10 alkyl branches per 100 carbon atoms. In another embodiment, the pour point reducing blend component has an average molecular weight between 600-1100. In a third embodiment, it has an average molecular weight between 700-1100. In one embodiment, the pour point reducing blend component has a kinematic viscosity of 8-30 mm ² / s at 100 ° C. and the 10% point of the boiling range drops between about 850-1050 ° F. In yet another embodiment, the pour point reducing blend component has a kinematic viscosity of 15-20 mm ² / s and a pour point of −8 to −12 ° C. at 100 ° C.

In one embodiment, the pour point reducing blend component is an isomerized oil having a kinematic viscosity at 100 ° C. of at least about 8 mm ² / s and made from polyethylene plastic. In one embodiment, the pour point reducing blend component is made from waste plastic. In another embodiment, the pour point reducing blend component is at least about at about 100 ° C. at pyrolysis of the polyethylene plastic, separation of the heavy portion, hydrotreatment of the heavy portion, catalytic isomerization of the hydrotreated heavy portion, and Produced from a process involving collection of pour point reducing blend components having a kinematic viscosity of 8 mm ² / s. In a third embodiment, the pour point reducing blend component derived from polyethylene plastic has a boiling range greater than 1050 ° F. (565 ° C.), or even a boiling range greater than 1200 ° F. (649 ° C.).

Additives and additive packages :
Various detergent / dispersant additive packages may be combined with the base oil in a two-cycle oil gasoline engine lubricant formulation. Ashless, low ash, or ash-containing additives may be used for this purpose.

  Suitable ashless additives include polyamides, alkenyl succinimides, boric acid modified alkenyl succinimides, phenolamines and succinate derivatives or combinations of any two or more such additives.

  Examples of low ash additive packages are: (i) polybutenyl (Mn 400-2500) succinimide present in an amount of 0.2-5% by weight in the lubricant, or another oil-soluble, acylated nitrogen A contained lubricating oil dispersant, and (ii) a metal phenolate, sulfate, or salicylate oil-soluble detergent additive. In one embodiment, the oil soluble detergent additive is a neutral base detergent or overbased metal detergent that has a total base number of 200 or less present in the lubricating oil in an amount of 0.1 to 2% by weight. It is an agent. In this embodiment, the metal is calcium, barium or magnesium. Neutral calcium salicylate is an example and may be present in the lubricating oil in an amount of about 0.5-1.5 wt%.

  Commonly used polyamide detergent / dispersant additives such as tetraethylenepentamine isostearate are incorporated by reference herein in their entirety as if fully set forth herein. As described in US Pat. No. 3,169,980, it may be prepared by reaction of a fatty acid with a polyalkylene polyamine. These polyamides may contain a measurable amount of cyclic imidazoline formed by internal condensation of linear polyamides upon continuous heating at elevated temperatures. Another useful class of polyamide additives includes polyalkylene polyamines and C19-C25 kofu acids, R.I. Prepared by the procedure of Hartle et al., JAOCS, 57 (5): 156-59 (1980).

  Alkenyl succinimides can be reacted with olefins such as polybutene (MV1200) with maleic anhydride to give polybutenyl succinic anhydride adducts, which are then reacted with amines such as alkylamines or polyamines to form the desired product. It is formed by a step-by-step procedure.

  Phenolamines are prepared by the well-known Mannich reaction (C. Mannich and W. Krosche, Arch. Pharm., 250: 674 (1912)) involving polyalkylene-substituted phenols, formaldehyde and polyalkylene polyamines.

  A succinic ester derivative is obtained by reacting an olefin (eg, polybutene) with maleic anhydride to give a polybutenyl succinic anhydride adduct, and further reacting with a polyol, eg, pentaerythritol, to give the desired product. Prepared.

  Suitable ash-containing detergent / dispersant additives include alkaline earth metals (eg, magnesium, calcium, barium), sulfates, phosphates or phenolates, or any combination of two or more such additives. Can be mentioned.

  The detergent / dispersant additive described above is present in the lubricating oil composition described herein in an amount of about 1 to about 25 wt%, and more preferably about 3 to about 20 wt%, based on the total weight of the composition. % May be included.

  A two-cycle gasoline engine lubricant, such as LUBRIZOL400, LUBRIZOL6827, LUBRIZOL6830, LUBRIZOL600, LUBRIZOL606, ORONITE OLOA® 9333, ORONITE, in combination with a base oil in a commercially available two-cycle lubricant detergent / dispersant additive package OLOA® 340A, ORONITE OLOA® 6721, and ORONITE OLOA® 9357 can be generated.

  Various other additives may be included in the two-cycle gasoline engine lubricant if desired. Examples of these are smoke suppressants such as polybutene or polyisobutene (PIB), extreme pressure additives such as dialkyldithiophosphates or esters, antifoaming agents such as silicone oils, pour point depressants, rust or corrosion inhibitors, Examples include triazole derivatives, propyl gallate or alkali metal phenolate or sulfate, oxidation inhibitors such as substituted diarylamines, phenothiazines, hindered phenols and the like. Some of these additives may be multifunctional, such as polymethacrylates that can function as antifoaming agents as well as pour point depressants. Pour point depressants, when used, are used in amounts between 0.005 and 0.1% by weight, based on total lubricating oil. Examples of pour point depressants are: polymethacrylates (PMA); polyacrylates; polyacrylamides; condensation products of haloparaffin waxes and aromatic compounds; vinyl carboxylate polymers; dialkyl fumarate esters, vinyl esters of fatty acids, and alkyl vinyl ethers As well as mixtures thereof.

  In one embodiment, the smoke suppressor is an olefinically unsaturated polymer selected from the group consisting of polybutene, polyisobutene, and mixtures of polybutene and polyisobutene, having a number average molecular weight of 400-2200 and a double bond in the polymer. It has a terminal vinylidene content of at least 60 mol%, based on the total number. These types of smoke suppressants are taught in EP 1743932 A2. A commercial example of these smoke suppressants is GLISSSOPAL® 1000 from BASF Corporation.

  Volatile, flammable, high flash hydrocarbon solvents such as kerosene, Exxsol D80, or Staudard solvents can also be used as additives. Exxsol D80 has a dearomatization with an initial boiling point of at least 200 ° C, a Kauri-Butanol value of about 28 (between 20 and 40), and an aniline point of 73.9-79.4 ° C. It is an aliphatic high flash solvent. Volatile, flammable high flash hydrocarbon solvent is added to the two-cycle engine lubricant in an amount of less than 5% by weight of the total lubricant to bring the smoke index to a value of at least 75 in the JASO M342-92 test, and / or Alternatively, the compatibility and / or solubility of other additives may be improved and low temperature properties such as viscosity and gasoline miscibility may be improved. In one embodiment, the two-cycle gasoline engine lubricant comprises a low level, eg, less than about 5%, less than about 2% by weight of the total lubricant, or even essentially free of less than 250 ° C. It is a hydrocarbon solvent with the highest boiling point. Low levels of solvent in two-cycle gasoline engine lubricants reduce pollution due to evaporation of volatile organics, improved compatibility with elastomers used in packaging and transportation, and improved transportation and storage safety. Provides for the reduction of flammable dangerous goods.

  Most of the above additives may be included in the lubricating oil composition in an amount of about 0.005% to about 15%, or about 0.005% to about 6%, based on the total weight of the lubricating oil composition. . In the case of polybutene or polyisobutene, the amount may vary from 1% to 50%. The amount of each additive or additive package selected within a particular range should not adversely affect the desired performance characteristics of the lubricating oil. The effects produced by such additives can be readily determined by routine testing.

Or the lubricant is:
a. One or more base oil fractions between 20 and 70% by weight, based on total lubricant, having:
i. A consecutive number of carbon atoms;
ii. A kinematic viscosity of between about 1.5 and about 3.5 mm ² / s at 100 ° C .;
iii. Between about 90% and about 97% by weight of paraffinic carbon;
iv. From about 3% to about 10% by weight naphthalene carbon; and v. Less than 0.01 wt% aromatic carbon;
b. 0.5 to 25 wt% pour point reducing blend component based on total lubricating oil;
c. A hydrocarbon solvent having a maximum boiling point of less than about 250 ° C., less than about 5% by weight, based on total lubricating oil;
d. About 1% to about 25% by weight of detergent / dispersant additive package based on total lubricant;
e. About 1% to about 50% by weight smoke suppressant, based on total lubricating oil; and f. A pour point depressant of less than 0.1% by weight based on the total lubricating oil;
Consisting of or consisting essentially of a blend kinematic viscosity of at least 6.5 mm ² / s at 100 ° C, good low temperature fluidity at -25 ° C, and an exhaust smoke index greater than 65 .

  Two-cycle gasoline engine lubricants have a high flash point due to the low level of solvents they contain. These flash points are in some embodiments greater than 120 ° C, or greater than 150 ° C.

Specific analytical test methods :
Normal paraffin weight% in wax-containing samples:
Quantitative analysis of normal paraffins in wax-containing samples is determined by gas chromatography (GC). GC (Agilent 6890 or 5890 with capillary split / splitless inlet and flame ionization detector) is equipped with a flame ionization detector and is sensitive to hydrocarbons. This method utilizes a methylsilicone capillary column and is routinely used to separate hydrocarbon mixtures by boiling point. The column is fused silica, 100% methyl silicone, 30 meters long, 0.25 mm inner diameter, 0.1 micron film thickness and is supplied by Agilent. Helium is a carrier gas (2 ml / min) and hydrogen and air are used as fuel for the flame.

The wax feed is melted to obtain a 0.1 g homogeneous sample. The sample is immediately dissolved in carbon disulfide to give a 2 wt% solution. If necessary, heat the solution until it is visually clear and free of solids and then inject into the GC. The methylsilicone column is heated using the following temperature program:
Initial temperature: 150 ° C. (When C7 to C15 hydrocarbon is present, the initial temperature is 50 ° C.)
Lamp: 6 ° C / min Final temperature: 400 ° C
Final retention: 5 minutes or until peak no longer elutes

  The column then effectively separates normal paraffins from non-normal paraffins in order of increasing carbon number. Known reference standards are similarly analyzed to establish elution times for specific normal-paraffin peaks. The standard is the ASTM D2887 n-paraffin standard, purchased from a vendor (Agilent or Supelco) and mixed with 5 wt% polywax 500 polyethylene (purchased from Petrolite, Oklahoma). The standard is melted before injection. The historical data collected from the reference standard analysis also ensures the separation efficiency of the capillary column.

  When present in the sample, normal paraffin peaks are well separated and easily identifiable from other hydrocarbon peaks present in the sample. These peaks eluting outside the normal paraffin retention time are referred to as non-normal paraffins. All samples are integrated using a baseline hold from the start to the end of the run. n-paraffin is skimmed from all areas and integrated from valley to valley. All detected peaks are normalized to 100%. EZChrom is used for peak identification and calculation of results.

Olefin weight%:
The weight percent of olefin in the base oil is determined by proton NMR according to the following steps AD.
A. Prepare a deuterochloroform solution of 5-10% test hydrocarbons.
B. Acquire a normal proton spectrum with a spectral width of at least 12 ppm and accurately reference the chemical shift (ppm) axis. The device must have sufficient gain width to acquire the signal without overloading the receiver / ADC. If a 30 degree pulse is applied, the device must have a minimum signal digitization dynamic range of 65,000. Preferably, the dynamic range is 260,000 or more.
C. Measure the integrated intensity between:
6.0 to 4.5 ppm (olefin)
2.2 to 1.9 ppm (allyl)
1.9 to 0.5 ppm (saturated)
D. Using the molecular weight of the test substance as determined by ASTM D 2503:
1. 1. Average molecular formula of saturated hydrocarbon 2. Average molecular formula of olefin Total integrated intensity (= sum of all integrated intensities)
4). Integral intensity per sample hydrogen (= total integral / number of hydrogens in the equation)
5). Number of olefinic hydrogens (= olefin integral / integral per hydrogen)
6). Number of double bonds (= olefin hydrogen x hydrogen in olefin formula / 2)
7). Calculate% olefin weight by proton NMR = 100 × number of double bonds × number of hydrogen in typical olefin molecule / number of hydrogen in typical test substance molecule.

  The olefin weight percent by proton NMR calculation procedure D is most useful when the olefin percent result is low and less than about 15 weight percent. The olefin must be a dispersed mixture of “conventional” olefins, ie, olefin types having hydrogen bonded to double-bonded carbon, for example alpha, vinylidene, cis, trans, and trisubstituted olefin types. These olefin types have detectable allyl to olefin integral ratios of 1 to about 2.5. If this ratio exceeds 3, it indicates that there is a higher proportion of tri- or tetra-substituted olefin and that another assumption must be made to calculate the number of double bonds in the sample.

Aromatic measurement by HPLC-UV:
The method used to measure low levels of molecules having at least one aromatic functional group in a lubricant base oil is coupled to an HP 1050 Diode-Array UV-Vis detector connected to an HP Chem-station. A Hewlett Packard 1050 series four gradient high performance liquid chromatography (HPLC) system. Identification of individual aromatics in highly saturated base oils was based on their UV spectral patterns and their elution times. The amino column used for this analysis distinguishes aromatic molecules primarily based on their number of rings (or more precisely, the number of double bonds). Thus, monocyclic aromatic-containing molecules elute first, followed by polycyclic aromatics in order of increasing number of double bonds per molecule. For aromatics with similar double bond properties, aromatics with only alkyl substitution on the ring elute faster than aromatics with naphthenic substitution.

  The unambiguous identification of various base oil aromatic hydrocarbons from these UV absorption spectra indicates that these peak electronic transitions are pure model compound analogs to the extent that they depend on the amount of alkyl and naphthenic substitution of the ring system. It was done by recognizing that all were red-shifted. It is well known that these deep color shifts are caused by π-electron alkyl group delocalization of aromatic rings. Since some unsubstituted aromatics boil in the lube range, some red shift was expected and was observed for all of the major aromatic groups identified.

  Quantification of the eluting aromatic compound was done by integrating chromatograms made from wavelengths optimized for each general class of compound over the appropriate retention time frame for that aromatic. The retention time frame limits for each aromatic are manually assessed at different times for the individual absorption spectra of the eluting compounds and are based on their qualitative similarity to the model compound absorption spectra for the appropriate aromatics. Determined by assigning. With few exceptions, only five classes of aromatic compounds were observed in highly saturated API Group II and III lubricant base oils.

HPLC-UV calibration:
HPLC-UV is used to identify these classes of aromatic compounds even at very low levels. Polycyclic aromatics generally absorb 10 to 200 times more strongly than monocyclic aromatics. Alkyl substitution also affected absorption by about 20%. Therefore, it is important to use HPLC to separate and identify different classes of aromatics and to know how effectively they absorb.

  Five classes of aromatic compounds have been identified. With the exception of a slight overlap between the most retained alkyl-1-ring aromatic naphthene and the least retained alkylnaphthalene, all aromatic compounds were baseline separated. Integration limits for co-eluting 1-ring and 2-ring aromatics at 272 nm were established by the vertical drop method. The wavelength-dependent response factor for each common aromatic is first a Beer's Law plot from a pure model compound mixture relative to the spectral peak absorption closest to the substituted aromatic analog. It was determined by drawing.

  For example, alkyl-cyclohexylbenzene molecules in the base oil show a distinct peak absorption at 272 nm corresponding to the same (forbidden) transition that the unsubstituted tetralin model compound absorbs at 268 nm. The concentration of alkyl-1-ring aromatic naphthene in the base oil sample assumes that its molar absorptivity response factor at 272 nm is approximately equal to the molar absorptivity of tetralin at 268 nm, calculated from Beer's law plot. It was calculated. The weight percent concentration of aromatics was calculated assuming that the average molecular weight of each aromatic was approximately equal to the average molecular weight of the entire base oil sample.

  This calibration method was further improved by isolating the 1-ring aromatics directly from the lubricating base oil by elaborate HPLC chromatography. Direct calibration with these aromatics eliminated the assumptions and uncertainties associated with model compounds. As expected, the isolated aromatic sample had a lower response factor than the model compound because it was more highly substituted.

  More specifically, in order to accurately calibrate the HPLC-UV method, substituted benzene aromatics were separated from bulk lubricant base oils using a Waters semi-preparative HPLC apparatus. A 10 g sample was diluted 1: 1 in n-hexane and applied to an amino-bonded silica column from Rainin Instruments (Emeryville, Calif.), 5 cm × 22.4 mm ID guard, then 8-12 micron amino-bonded silica. The particles were injected into two 25 cm x 22.4 mm ID columns with mobile phase n-hexane at a flow rate of 18 ml / min. The column eluate was fractionated based on the detector response from a dual wavelength UV detector set at 265 nm and 295 nm. Saturated fractions were collected until the 265 nm absorption showed a change of 0.01 absorption units, which is the signal at the beginning of the elution of monocyclic aromatics. Monocyclic aromatic fractions were collected until the absorption ratio between 265 nm and 295 nm, indicating the onset of bicyclic aromatic elution, decreased to 2.0. Purification and separation of the monocyclic aromatic fraction was accomplished by re-chromatographing the monoaromatic fraction away from the “tailing” saturated fraction obtained from HPLC column overload.

  This purified aromatic “standard” showed that alkyl substitution reduced the molar absorptivity response factor by about 20% with respect to unsubstituted tetralin.

Aromatic identification by NMR:
The weight percent of all molecules with at least one aromatic functional group in the purified monoaromatic standard was confirmed by long-term carbon-13 NMR analysis. NMR was easier to calibrate than HPLC-UV because it simply measured aromatic carbon and the response was not dependent on the type of aromatic being analyzed. The NMR results are consistent with% aromatic carbon to% aromatic molecules (HPLC-UV and D2007 by knowing that 95-99% of the aromatics in the highly saturated lubricating base oil are monocyclic aromatics. ).

  High power, long term, and good baseline analysis were required to accurately measure aromatics down to 0.2% aromatic molecules.

  More specifically, the standard D5292-99 method was modified to give a minimum carbon sensitivity of 500: 1 in order to accurately measure all low level molecules with at least one aromatic functional group by NMR. (According to ASTM standard procedure E386). A 15 hour duration run in 400-500 MHz NMR was used with a 10-12 mm Nalorac probe. Acorn PC integration software was used to define the baseline shape and consistently integrate. The carrier frequency was changed once during the run to avoid artifacts imaging the aliphatic peak into the aromatic region. By taking the spectrum on either side of the carrier spectrum, the resolution was significantly improved.

(Example 1)
A wax sample was prepared consisting of several batches of hydrotreated Fischer-Tropsch wax, all made using a Co-based Fischer-Tropsch catalyst. Various batches of wax making up the wax sample were analyzed and all found to have the properties shown in Table II.
Table II: Fischer-Tropsch wax

  Co-based Fischer-Tropsch wax was hydroisomerized with a Pt / SAPO-11 catalyst containing an alumina binder. The operating conditions were: temperature between 635 ° F. and 675 ° F. (335 ° C. to 358 ° C.), LHSV of 1.0 / hour, reactor pressure of about 500 psig, and flow-through hydrogen volume between 5 and 6 MSCF / bbl. Included. The reactor effluent directly passed to the second reactor containing the silica-alumina supported Pd hydrofinishing catalyst was also operated at 500 psig. The conditions in the second reactor included a temperature of about 350 ° F. (177 ° C.) and LHSV of 2.0 / hour.

Products boiling above 650 ° F. were fractionated by vacuum distillation to produce distillate fractions of different viscosity grades. Three Fischer-Tropsch derived lubricating base oils were obtained. Two were distillate side-cut fractions (XLFTBO and XXLFTBO) and one was a bottoms fraction (HFTBO) which was a distillate. Test data for three Fischer-Tropsch derived lubricant base oils is shown in Table III below.
Table III

  HFTBO is an example of a pour point reducing blend component having a low traction coefficient. XLFTBO is an example of a fraction of a lubricant base oil having a Noack volatility less than the Noack volatility factor according to Equation (1). XXLFTBO is an example of a lube base oil fraction having a Noack volatility less than a Noack volatility factor, both a Noack volatility factor according to Formula (1) and a Noack volatility factor according to Formula (2).

(Example 2)
Chevron MOTEX 2T-X is a two-cycle outboard engine oil formulated with a high quality mineral base oil, polyisobutene, a high performance low ash detergent / dispersant additive package, and a high flash solvent. Three different blends of the same high performance low ash detergent / dispersant additive package used in the Chevron Motex 2T-X and a two cycle gasoline engine lubricant using a polyisobutene synthetic base oil were combined with the Fischer-Tropsch described above. Prepared using derived base oils (Blend B, Blend C, and Blend F). A comparative blend (COMP blend A) using a conventional mineral base oil and high flash solvent was also prepared. The composition of the three blends is summarized in Table IV.
Table IV

The performance characteristics of these three two-cycle gasoline engine lubricant blends are shown in Table V.
Table V

  Flash point was measured by Cleveland Open Cup Tester using ASTM D92-05a. The aniline point was measured according to ASTM D611-04. Blend B, Blend C, and Blend F are essentially free of hydrocarbon solvents having a maximum boiling point of less than 250 ° C., and these are all COMP blends produced with conventional mineral oil base oils and high flash solvents. It had a lower exhaust smoke index value, lower pour point, and improved miscibility compared to A. Blend F with the highest level of HFTBO gave a particularly high lubricity index and still had excellent miscibility and a good exhaust smoke index.

(Example 3)
A blend of two-cycle gasoline engine lubricants using a detergent / dispersant additive package designed to meet the specifications for Tailand Domestic (TIS 1040-2541 [1998]) was previously described by Fischer-Tropsch. Prepared using derived base oil. A comparative blend using a conventional petroleum derived base oil and a high flash solvent was also prepared. The formulation of the three blends is summarized in the following VI.
Table VI

The performance characteristics of these two-cycle gasoline engine lubricant blends are shown in Table VII.
Table VII

  Blend E also contained a pour point reducing blend component, HFTBO, having a low traction coefficient. Note that this blend had a particularly low pour point and good cold flow at -25 ° C. Blend E has better low temperature flowability, lower pour point compared to COMP Blend D produced using a conventional mineral oil base oil and greater than 5 wt% hydrocarbon solvent with a maximum boiling point of less than 250 ° C. It had better gasoline miscibility, better cleanability, and better piston skirt deposition index. Blend E by addition of less than 5 wt.% Hydrocarbon solvent having a maximum boiling point less than 250 ° C. easily passed the requirements of both JASO M345: 2003 and ISO13738: 2000 (E), sections C and D.

  For purposes of this specification and the appended claims, all numbers and other numerical values representing amounts, percentages or proportions used in this specification and the appended claims, unless otherwise indicated, It should be understood that in all cases it is modified by the term “about”. In addition, all ranges disclosed in this specification include endpoints and can be combined independently.

  The publications, patents and patent applications cited in this application are hereby incorporated by reference in their entirety to the same extent as if each individual publication, patent and patent application was specifically and individually indicated to be incorporated by reference in its entirety. Is incorporated by reference.

  The description provided herein uses examples to disclose the invention, including the best mode, as well as examples to enable those skilled in the art to make and use the invention. Many modifications of the exemplary embodiments of the invention disclosed above will readily occur to those skilled in the art. Accordingly, the invention is to be construed as including all structure and methods that fall within the scope of the appended claims.

Claims (50)

A method for preparing a lubricating oil comprising:
a. Hydroisomerizing and dewaxing a substantially paraffinic wax feed, thereby producing a lubricating base oil; and
b. One or more fractions of the lubricating base oil:
i. A hydrocarbon solvent having a maximum boiling point of less than about 250 ° C., less than about 5% by weight, based on the total lubricating oil composition, and ii. The above method comprising blending with a detergent / dispersant additive package, wherein the lubricating oil meets the requirements of JASO M345: 2003.   The process according to claim 1, wherein the substantially paraffinic wax feed is derived from Fischer-Tropsch.   Raw materials for the Fischer-Tropsch process used to produce a substantially paraffinic wax feed include biomass, natural gas, coal, shale oil, petroleum, municipal waste, their derivatives, and their The process according to claim 2, which is a hydrocarbonaceous source selected from the group consisting of combinations.   The process of claim 1, wherein the hydroisomerization dewaxing uses a catalyst comprising a shape selective intermediate pore size molecular sieve, a noble metal hydrogenation component, and a refractory oxide support.   Shape selective intermediate pore size molecular sieves are SAPO-11, SAPO-31, SAPO-41, SM-3, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ-32, offretite, 5. The method of claim 4, wherein the method is selected from the group consisting of ferrierite and combinations thereof.   The method of claim 4, wherein the noble metal hydrogenation component is platinum, palladium, or a combination thereof.   Blending one or more fractions of the lubricating base oil with a hydrocarbon solvent having a maximum boiling point of less than about 2O <0> C, less than about 2 wt%, based on the total lubricating oil composition. The method according to 1.   8. The method of claim 7, comprising blending one or more fractions of the lubricating base oil with a solvent that is essentially free of hydrocarbons.   The method of claim 1, further comprising blending one or more fractions of the lubricating base oil with a smoke suppressant selected from polybutene, polyisobutylene and mixtures thereof.   The method of claim 1, further comprising blending one or more fractions of the lubricating base oil with a pour point depressant.   The method of claim 1, further comprising blending one or more fractions of the lubricating base oil with the pour point reducing blend component. The method of claim 1, wherein the one or more fractions of the lubricating base oil have a kinematic viscosity at 100 ° C. of between about 1.5 and about 3.5 mm ² / s.   The method of claim 1, wherein the one or more fractions of the lubricating base oil have a Noack volatility of less than 90% by weight. One or more fractions of the lubricating base oil have a kinematic viscosity between 1.5 and 4.0 mm ² / s and a Noack volatility factor (1) = 160− (kinematic viscosity at 40 × 100 ° C.) 14. The method of claim 13, having a Noack volatility of less than 14. One or more fractions of the lubricating base oil have a kinematic viscosity between 2.09 and 4.0 mm ² / s, and a Noack volatility factor (2) = (900 × (kinematic viscosity at 100 ° C.) ^{− 2.8} ) The method of claim 14, having a Noack volatility of less than -15.   The one or more fractions of the lubricating base oil have greater than about 90 wt% paraffinic carbon and less than 0.01 wt% aromatic carbon according to ASTM D3238-95 (2005). Method.   The method of claim 1, wherein the one or more fractions of the lubricating base oil have an oxydata BN greater than 35 hours.   The method of claim 1, wherein the lubricating oil has a flash point greater than 120 ° C. according to ASTM D92-05a.   The method of claim 1, wherein the lubricating base oil has a viscosity index greater than 28 × Ln (kinematic viscosity at 100 ° C.) + 95. A method for producing a lubricating oil comprising:
a. together:
i. One or more fractions of a base oil having a kinematic viscosity between about 1.5 and about 3.5 mm ² / s at 100 ° C., and ii. Blending the pour point reducing blend component to produce a base oil blend component having a reduced pour point; and b. For base oil blends with reduced pour points:
i. Detergent / dispersant additive package;
ii. Smoke suppressant;
iii. Optionally a pour point depressant; and iv. The above process, optionally comprising adding less than about 5% by weight of a hydrocarbon solvent having a maximum boiling point of less than 250 ° C., thereby producing a two-cycle gasoline engine lubricating oil. Two-cycle gasoline engine lubricant:
(A) Good low temperature fluidity at -25 ° C;
(B) Result of passing in a miscibility test according to ASTM D4682-87 (Reapproved 2002) at -25 ° C;
21. The method of claim 20, having (c) an exhaust smoke index greater than 65; and (d) a pour point of about -35 ° C or less.   21. The method of claim 20, wherein the one or more fractions of base oil are produced from a wax feed.   21. The method of claim 20, wherein the exhaust smoke index is 85 or greater.   21. The method of claim 20, wherein the pour point is about −40 ° C. or less.   21. The method of claim 20, wherein the smoke suppressant is polyisobutylene.   21. The method of claim 20, wherein the hydrocarbon solvent is a dearomatized aliphatic solvent.   21. A process according to claim 20, wherein a solvent essentially free of hydrocarbons is added. 21. The method of claim 20, wherein the pour point reducing blend component has a traction coefficient of less than 0.015 when measured at a kinematic viscosity of 15 mm < ² > / s and a sliding to rolling ratio of 40%. A method of producing a two-cycle gasoline engine lubricant that meets the requirements of JASO M345: 2003, comprising:
a. Preparing a pour point reducing blend component by isomerizing the feed;
b. The pour point lowering blend component
i. Blending with a distillate base oil having a kinematic viscosity between about 1.5 and about 3.5 mm ² / s at 100 ° C. to produce a base oil blend having a reduced pour point;
c. Base oil blend with reduced pour point:
i. A detergent / dispersant additive package; and ii. The above process comprising blending in an appropriate proportion with a hydrocarbon solvent having a maximum boiling point of less than 5O <0> C and less than 5O <0> C, based on total 2-cycle gasoline engine lubricant, to obtain a 2-cycle gasoline engine lubricant .   30. The method of claim 29, wherein the feed is selected from the group consisting of Fischer-Tropsch derived wax, petroleum derived wax, plastic, and mixtures thereof. The pour point lowering blend component is:
a. Isomerized Fischer-Tropsch derived bottom product;
b. Bottom product prepared from isomerized high waxy mineral oil;
c. An isomerized oil made from polyethylene plastic having a kinematic viscosity at 100 ° C. of at least about 8 mm ² / s; and d. 30. The method of claim 29, selected from the group consisting of these mixtures. Pour point lowering blend components:
i. Pyrolysis of polyethylene plastics;
ii. Separating heavy components from the pyrolysis process;
iii. Hydrotreating heavy components;
iv. Catalytic isomerization of the hydrotreated heavy fraction; and v. 30. The method of claim 29, prepared by selecting a fraction of an isomerized product having a kinematic viscosity of at least about 8 mm < ² > / s at 100 <0> C. Pour point reducing blend component, when measured at 15 mm ² / s and 40 percent of the sliding pair roll ratio in kinematic viscosity, it has a traction coefficient less than 0.015, the method according to claim 29.   30. The method of claim 29, wherein the two-cycle gasoline engine lubricant has good low temperature fluidity at -25 [deg.] C.   30. The method of claim 29, wherein the two-cycle gasoline engine lubricant has an exhaust smoke index greater than 65.   30. The method of claim 29, wherein the two-cycle gasoline engine lubricant has a weight percent sulfated ash content of 0.18 or less.   30. The method of claim 29, further comprising blending a pour point reducing blend component with a smoke suppressant.   30. The method of claim 29, wherein the distillate base oil is derived from Fischer-Tropsch. a. Producing a lubricating base oil by hydroisomerizing and dewaxing a substantially paraffinic wax feed: and b. One or more fractions of the lubricating base oil:
i. A hydrocarbon solvent having a maximum boiling point of less than about 250 ° C., less than about 5% by weight, based on the total lubricating oil composition, and ii. A lubricating oil produced by a process wherein the lubricating oil meets the requirements of JASO M345: 2003, including blending with a detergent / dispersant additive package.   40. A lubricating oil produced by the method of claim 39, wherein the substantially paraffinic wax feed is derived from Fischer-Tropsch.   40. A lubricating oil produced by the process of claim 39, wherein a catalyst comprising a shape selective intermediate pore size molecular sieve, a noble metal hydrogenation component, and a refractory oxide support is used in hydroisomerization dewaxing.   40. blending one or more fractions of a lubricating base oil with a hydrocarbon solvent having a maximum boiling point of less than about 2O <0> C, less than about 2 wt%, based on total lubricating oil. Lubricating oil produced by the described method.   40. A lubricating oil produced by the method of claim 39, comprising blending one or more fractions of the lubricating base oil with a solvent that is essentially free of hydrocarbons.   40. The method of claim 39, further comprising blending one or more fractions of the lubricating base oil with a smoke suppressant selected from the group consisting of polybutene, polyisobutylene, and mixtures thereof. Lubricating oil.   40. The lubricating oil produced by the method of claim 39, further comprising blending one or more fractions of the lubricating base oil with a pour point depressant.   40. The one or more fractions of the lubricating base oil have greater than about 90 wt.% Paraffinic carbon and less than 0.01 wt.% Aromatic carbon according to ASTM D3238-95 (2005). Lubricating oil produced by the method.   40. A lubricating oil produced by the method of claim 39 that meets the requirements of JASO M345: 2003, Section C or Section D.   40. A lubricating oil produced by the method of claim 39 that meets the requirements of ISO13738: 2000 (E).   40. A lubricating oil produced by the method of claim 39, having good low temperature fluidity at -25 [deg.] C.   40. A lubricating oil produced by the method of claim 39 having a passing result in a miscibility test according to ASTM D4682-87 (Reapproved 2002) at -10 <0> C or -25 <0> C.

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