Method for improving engine performance using renewable lubricant oil composition

Abstract

To provide a method of sustaining fuel economy while lowering LSPI.SOLUTION: There is provided according to the present patent specification, a lubricant composition comprising renewable base oil as embodied by hydrocarbon mixtures with controlled structure characteristics in combination with lubricant additives that address performance requirements and stricter environmental and fuel economy regulations. The lubricant composition provides performance in the cold crank simulated viscosity (CCS) vs Noack volatility relationship, which allows the formulation of lower viscosity engine oils with improved fuel economy, improved fuel economy retention, and retained LSPI prevention, additionally conferring improved characteristics to other devices or apparatus requiring lubrication.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] A method for improving engine performance with a lubricating oil composition containing a renewable base oil with a hydrocarbon blend and lubricating oil additives has been developed, which has unique compositional properties and exhibits excellent fuel economy improving capabilities and fuel economy retention over the life of the lubricating oil when used to lubricate various types of internal combustion engines. [Background technology]

[0002] The industry trend in engine oil formulations is moving toward a lower viscosity regime (0W-X) to enhance fuel economy benefits while also maintaining current or better levels of performance. However, as the industry moves toward lower viscosity and maintains low oil consumption, the durability of fuel economy becomes a challenge or becomes unachievable with available technology. Lowering oil viscosity increases volatility, which leads to increased engine oil evaporation and increases oil viscosity. Furthermore, fuel economy can be improved by reducing the oil's high-temperature, high-shear (HTHS) viscosity. Because HTHS is highly sensitive to viscosity modifiers, which also adjust low- and high-temperature viscosity, high viscosity index (VI) oils are desirable. While some ultra-low viscosity oils are commercially available, they cannot meet the most stringent volatility requirements.

[0003] Base stocks are commonly used to manufacture a variety of lubricants, including those for internal combustion engines, turbines, compressors, and hydraulic systems. They are also used as process oils, white oils, and heat transfer fluids. Finished lubricants generally consist of two components: base oil and additives. Base oils, either a single base stock or a mixture of base stocks, are the primary components of these finished lubricants and contribute significantly to performance characteristics such as viscosity and viscosity index, volatility, stability, and low-temperature performance. Generally, several base stocks are used to manufacture a wide variety of finished lubricants by varying the mixture of individual base stocks and individual additives.

[0004] A method for improving engine fuel efficiency using lubricating oil compositions containing fatty acid esters is described in US Pat. No. 9,885,004.

[0005] The American Petroleum Institute (API) classifies basestocks into five groups based on saturated hydrocarbon content, sulfur level, and viscosity index (Table 1 below). Group I, II, and III basestocks are mostly derived from crude oil through extensive processing, including solvent refining for Group I and hydrotreating for Group II and III. Certain Group III basestocks can also be produced from synthetic hydrocarbon liquids via gas-to-liquids (GTL) processes, obtained from natural gas, coal, or other fossil resources. Group IV basestocks, polyolefins (PAOs), are produced by the oligomerization of alpha-olefins such as 1-decene. Group V basestocks include all basestocks not included in Groups I-IV, including naphthenic basestocks, polyalkylene glycols (PAGs), and esters. Most feedstocks for large-scale basestock production are non-renewable. [Table 1]

[0006] Automotive engine oils are by far the largest market for base stocks. The automotive industry is imposing increasingly stringent performance specifications on engine oils due to demands for reduced emissions, extended drain intervals, and improved fuel economy. Specifically, automotive OEMs (original equipment manufacturers) are driving the adoption of lower viscosity engine oils, such as 0W-20, 0W-8, and even 0W-4, to reduce friction losses and achieve improved fuel economy. The use of Noack low-volatility base oils in engine oils allows formulations to maintain their designed viscosity for longer operating times, resulting in improved fuel economy and longer drain intervals, as described in U.S. Pat. No. 6,300,291. The use of Group I and Group II base stocks in engine oils with viscosity grades below 0W-20 is severely limited because blended formulations cannot meet the performance specifications of engine oils below 0W-20, leading to increased demand for Group III and Group IV base stocks.

[0007] Group III basestocks are mostly produced from vacuum gas oil (VGO) through hydrocracking and catalytic dewaxing (e.g., hydroisomerization). Group III basestocks can also be produced by catalytic dewaxing of slack wax derived from solvent refining or from Fischer-Tropsch synthesis of wax from natural gas or coal-based feedstocks, also known as gas-to-liquids (GTL) base oils.

[0008] Processes for producing Group III basestocks from VGO are described in U.S. Patent Nos. 5,993,644 and 6,974,535. Their boiling point distributions are typically higher than PAOs of the same viscosity, making them more volatile than PAOs. Furthermore, Group III basestocks typically have higher cold-crank viscosities (i.e., dynamic viscosities according to ASTM D5293, CCS) than Group IV basestocks of comparable viscosity.

[0009] GTL basestock processing is described in U.S. Patent Nos. 6,420,618 and 7,282,134, and U.S. Patent Application Publication No. 2008 / 0156697. For example, the latter publication describes a process for preparing basestocks from a Fischer-Tropsch synthesis product, a fraction of which having the appropriate boiling range is subjected to hydroisomerization to produce GTL basestock.

[0010] Such structures and properties of GTL base stocks are described, for example, in U.S. Patent Nos. 6,090,989 and 7,083,713, and U.S. Patent Application Publication No. 2005 / 0077208. U.S. Patent Application Publication No. 2005 / 0077208 describes lubricating oil base stocks with optimized branching, with the branched alkyl groups concentrated toward the center of the molecule to improve the cold flow properties of the base stock. Nevertheless, the pour points of GTL base stocks are typically inferior to those of PAO or other synthetic hydrocarbon base stocks.

[0011] An additional concern regarding GTL basestocks is that commercial supply is severely limited as a result of prohibitively large capital requirements for new GTL production facilities. Profitably producing GTL basestocks also requires access to low-cost natural gas. Furthermore, because GTL basestocks are typically distilled from isomerized oils with broad boiling point distributions, the process results in relatively low yields of basestocks with the desired viscosity when compared to typical PAO processes. These financial and yield constraints mean that there is currently only one Group III+ GTL basestock manufacturing plant, exposing formulations using GTL to supply chain and price volatility risks.

[0012] Polyalphaolefins (PAOs), or Group IV base oils, are produced by the polymerization of alphaolefins in the presence of Friedel-Crafts catalysts such as AlCl, BF, or BF complexes. For example, 1-octene, 1-decene, and 1-dodecene have been used to produce PAOs with a wide range of viscosities, from low molecular weights and low viscosities of about 2 cSt at 100°C to high molecular weights and viscous materials with viscosities exceeding 100 cSt at 100°C. The polymerization reaction is typically carried out in the absence of hydrogen, and the lube range product is then refined or hydrogenated to reduce residual unsaturation. Processes for producing PAO-based lubricants are disclosed, for example, in U.S. Patent Nos. 3,382,291, 4,172,855, 3,742,082, 3,780,128, 3,149178, 4,956,122, 5,082,986, 7,456,329, 7,544,850, and U.S. Patent Application Publication No. 2014 / 0323665. Previous efforts to prepare various PAOs capable of meeting the increasingly stringent performance requirements of modern lubricants and automotive engine oils have favored low-viscosity polyalphaolefin base stocks derived, in particular, from 1-decene alone or blends with other mineral oils. However, polyolefins derived from 1-decene can be very expensive due to limited supply. In an attempt to overcome the limitations of 1-decene availability, PAOs have been produced from mixed C8-C12 alpha-olefin feedstocks, reducing the amount of 1-decene required to impart properties. However, performance concerns have not allowed for the complete elimination of the need to provide 1-decene as the primary olefin feedstock.

[0013] Similarly, previous efforts using linear alpha olefins in the C14-C20 range have produced polyalphaolefins with unacceptably high pour points, making them unsuitable for use in a variety of lubricants, including 0W engine oils.

[0014] Thus, there remains a need for lubricating oil compositions having properties for use in, for example, automotive and other applications, within commercially acceptable ranges, such properties including one of viscosity, Noack volatility, and low temperature cold cranking viscosity. Additionally, there remains a need for lubricating oil compositions having improved properties, and methods for their manufacture, in which base stock compositions can reduce the amount of 1-decene incorporated therein, and more preferably, eliminate the use of 1-decene in their manufacture.

[0015] In addition to technological demands on the automotive industry, environmental awareness and regulations are driving manufacturers to use renewable feedstocks and raw materials in the production of base stocks and lubricants. Renewable, biologically derived esters and some Group III hydrocarbon base stocks (U.S. Patent No. 9,862,906 B2) are known to be used in applications such as refrigeration compressor lubricants, hydraulic oils, metal working fluids, and more recently in automotive and industrial lubricants (U.S. Patent No. 20170240832 A1). Common biological sources of hydrocarbons are natural oils, which can be obtained from plant sources such as canola oil, castor oil, sunflower seed oil, rapeseed oil, peanut oil, soybean oil, tall oil, or palm oil. Other commercial sources of hydrocarbons include engineered microorganisms such as algae and yeast.

[0016] Due to the increasing demand for high performance lubricant base stocks, there is a continuing need for improved hydrocarbon blends, and the industry is demanding that these hydrocarbon blends have excellent Noack volatility and low temperature viscometric properties, be able to meet more stringent engine oil requirements, and preferably be from renewable sources.

[0017] The automotive industry is moving toward downsized gasoline engines that combine turbocharging with gasoline direct injection to meet current and future CO2 regulations. To maximize fuel economy, these engines are typically tuned to operate at low speeds and high engine loads. Many of these downsized, turbocharged engines have experienced uncontrolled combustion events when the engine operates under low-speed, high-load conditions, commonly known as Low Speed ​​Pre-ignition (LSPI). LSPI is random in nature and can result in a sudden increase in in-cylinder pressure, potentially leading to catastrophic engine failure.

[0018] Many studies have evaluated the effect of calcium treatability and concluded that increasing calcium content increases the incidence of LSPI.[12-14] Some researchers have proposed alternative lubricant formulation strategies to reduce the incidence of LSPI.[12-14] Generally, these lubricants were formulated by reducing the amount of LSPI accelerators (calcium-containing detergents) and increasing the amount of LSPI inhibitors (ZDDP, MoDTC, Mg-containing detergents, etc.). However, reducing the calcium content beyond certain limits can increase piston deposits, increase varnish, increase acid concentrations, and shorten oil drain intervals. Therefore, many studies limit the amount of calcium-containing detergents to 0.1% by weight.

[0019] Therefore, lubricating oil compositions that can reduce LSPI while improving fuel economy retention are desirable. Summary of the Invention

[0020] The present invention relates to a method for improving engine performance by supplying an internal combustion engine with a lubricating oil composition containing a saturated hydrocarbon mixture and lubricating oil additives having well-controlled structural characteristics that address performance requirements driven by more stringent environmental and fuel economy regulations for automotive engine oils. The branching characteristics of the hydrocarbon molecules in the base oil portion are controlled to consistently provide compositions with surprising CCS viscosity (ASTM D5329) and Noack volatility (ASTM D5800) relationships at -35°C.

[0021] One embodiment of the present invention is a method of supplying a lubricating oil composition to an internal combustion engine, and operating the engine at elevated operating temperatures results in a fuel economy improvement (FEI) that is at least 0.3% better than a conventional lubricating oil of equivalent viscosity. In a preferred embodiment, the FEI is at least 0.5% better than a conventional lubricating oil of equivalent viscosity.

[0022] A further embodiment of the present invention is a method of supplying a lubricating oil composition to an internal combustion engine, and operating the engine over an extended period of time benefits from a fuel economy retention (FER) that is at least 0.5% better than a conventional lubricating oil of equivalent viscosity. In a preferred embodiment, the FER is at least 1.0% better than a conventional lubricating oil of equivalent viscosity.

[0023] A further embodiment is a method of providing the lubricating oil composition to an internal combustion engine and operating the engine for extended periods at elevated operating temperatures to provide an LSPI prevention retention advantage by limiting the increase in added metal concentrations, in a preferred embodiment, the calcium concentration increase is limited to 15% or less.

[0024] An important aspect of the present invention relates to lubricating oil compositions having a renewable base oil, a saturated hydrocarbon mixture of greater than 80% of molecules with even carbon numbers by FIMS, a mixture exhibiting a branching characteristic of BP / BI ≥ -0.6037 (internal alkyl branches per molecule) + 2.0, and an average of at least 0.3 to 1.5 5+ methyl branches per molecule when the hydrocarbon mixture as a whole is analyzed by carbon NMR.

[0025] One method for synthesizing the hydrocarbon mixtures disclosed herein is by oligomerization of C14-C20 alpha or internal olefins followed by hydroisomerization of the oligomers. The use of C14-C20 olefins alleviates the demand for high-priced 1-decene and other crude oil- or syngas-based olefins as feedstocks, enabling alternative sources of olefin feedstocks, such as those derived from C14-C20 alcohols. The hydrocarbon composition is derived from one or more olefin comonomers, which are oligomerized to dimers, trimers, and higher oligomers. The oligomers are then subjected to hydroisomerization. The resulting hydrocarbon mixtures have excellent pour point, volatility, and viscosity characteristics, as well as additive solubility properties. [Brief explanation of the drawings]

[0026] [Figure 1] The plot shows the relationship between BP / BI per molecule and internal alkyl branching for various hydrocarbons, including low-viscosity PAOs made from 1-decene and 1-dodecene, GTL base oils, and hydroisomerized hexadecene oligomers. The straight line in the plot represents the equation BP / BI = -0.6037(internal alkyl branching per molecule) + 2.0. [Figure 2] The relationship between BP / BI and 5+ methyl branches per molecule for various hydrocarbons, including low-viscosity PAOs made from 1-decene and 1-dodecene, GTL base oils, and hydroisomerized hexadecene oligomers, is shown. This indicates that the 5+ methyl branches per molecule for the hydrocarbon mixtures disclosed in this patent are in the specific range of 0.3 to 1.5. [Figure 3]This figure shows the relationship between Noack volatility and CCS at -35°C for various hydrocarbons, including low-viscosity PAOs made from 1-decene and 1-dodecene, GTL base oils, Group III base oils, and hydroisomerized hexadecene oligomers. The solid and dotted lines represent the upper and lower limits of Noack vs. CCS at -35°C, respectively, indicated by Noack = 2,750(CCS at -35°C)(-0.8)+2 and Noack = 2,750(CCS at -35°C)(-0.8)-2, which are unique hydrocarbon blends of the present invention. [Figure 4] This is an expanded view of Figure 3 in the range of 800 to 2,800 cP for CCS at -35°C. [Figure 5] 1 is a graph of fuel economy benefits measured in a modified sequence VIF test using three different lubricating oil compositions. [Figure 6] 1 is a graph of the calcium content of three different oils measured in long-term testing. DETAILED DESCRIPTION OF THE INVENTION

[0027] All numerical values ​​within the detailed description and claims herein are "about" or "approximately" modified by the stated value and take into account experimental error and variations that would be expected by one of ordinary skill in the art.

[0028] Disclosed herein is a method for improving engine performance, specifically providing a lubricating oil composition that provides improved fuel economy, improved fuel economy retention, and improved LSPI prevention retention. The lubricating oil composition contains a renewable base oil stock containing a saturated hydrocarbon mixture with a unique branched structure characterized by NMR, which makes it suitable for use as a high-quality synthetic base stock and lubricating oil additive. The hydrocarbon mixture possesses excellent properties, such as very low volatility and good low-temperature properties, which are important performance attributes of high-quality base stocks. Specifically, the mixture comprises 80% or more molecules with even carbon numbers by FIMS. The branched characteristics of the hydrocarbon mixture by NMR include a BP / BI ratio within the range of ≥ -0.6037 (internal alkyl branches per molecule) + 2.0. Furthermore, on average, at least 0.3 to 1.5 of the internal methyl branches are located four or more carbons away from the terminal carbon. Saturated hydrocarbons with this unique branched structure exhibit a surprising cold-crank simulated viscosity (CCS) vs. Noack volatility relationship, which is beneficial for blending low-viscosity automotive engine oils.

[0029] In one embodiment, the hydrocarbon mixture described herein is the product of olefin oligomerization and subsequent hydroisomerization. C14-C20 olefins are oligomerized to form an oligomer distribution consisting of unreacted monomers, dimers (C28-C40), and trimers, as well as higher oligomers (≧C42). The unreacted monomers are distilled for reuse in subsequent oligomerization. The remaining oligomers are then hydroisomerized to achieve the final branched structure described herein, which consistently impacts the surprising cold crank simulated viscosity (CCS) vs. Noack volatility relationship.

[0030] definition As used herein, renewable refers to any biologically derived composition containing fatty alcohols, olefins, or oligomers. Such compositions may be made from biological organisms engineered to produce specific oils, as discussed in WO 2012 / 141784, but do not contain petroleum distillate or process oils, such as mineral oil. A suitable method for assessing materials derived from renewable resources is via the "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis" (ASTM D6866-12 or ASTM D6866-11). The carbon counts in a sample can be compared to SRM4990C directly or via a secondary standard. A reading of 0% carbon against an appropriate standard indicates that the carbon is entirely fossil-derived (e.g., petroleum-based). A 14C measurement of 100% indicates carbon derived entirely from modern sources (see, for example, WO2012 / 141784, incorporated herein by reference).

[0031] Viscosity is a physical property that measures the fluidity of a base stock. Viscosity is a strong function of temperature. Two commonly used viscosity measurements are dynamic viscosity and kinematic viscosity. Viscosity measures the internal resistance to flow of a fluid. The cold cranking simulator (CCS) viscosity of engine oil at -35°C is an example of a viscosity measurement. The SI unit of viscosity is Pa·s. The traditional unit used is centipoise (cP), which is equivalent to 0.001 Pa·s (or 1 mPa·s). The industry is gradually moving to the SI system of units. Kinematic viscosity is the ratio of viscosity to density. The SI unit of kinematic viscosity is mm² / s. Other units commonly used in industry are centistokes (cSt) at 40°C (KV40) and 100°C (KV100) and Saybolt Universal Second (SUS) at 100°F and 210°F. Conveniently, 1 mm2 / s is equal to 1 cSt. ASTM D5293 and D445 are methods for measuring CCS and kinematic viscosity, respectively. As used herein, "viscosity grade" refers to a lubricating oil composition containing renewable base oils formulated to meet the SAE XW-YY lubricant specifications (where X can be 0 or 5, and YY can be 4, 8, 12, 16, or 20). The properties of various viscosity grades are further defined in the SAE J300 industry standard.

[0032] Viscosity index (VI) is an empirical number used to measure the change in kinematic viscosity of a base stock as a function of temperature. The higher the VI, the less the relative change in viscosity with temperature. High VI base stocks are desirable for most lubricant applications, especially in multigrade automotive engine oils and other automotive lubricant applications with large operating temperature fluctuations. ASTM D2270 is a generally accepted method for determining VI.

[0033] Pour point is the lowest temperature at which movement of a test specimen is observed. Since most lubricants are designed to operate in the liquid phase, this is one of the most important properties for a base stock. A low pour point is usually desirable, especially for cold weather lubrication. ASTM D97 is the standard manual method for measuring pour point. It is gradually being replaced by automated methods such as ASTM D5950 and ASTM D6749. In the examples in this patent, ASTM D5950 with a 1°C test interval is used to measure pour point.

[0034] Volatility is a measure of oil loss due to evaporation at high temperatures. This is a very important specification, especially for light-grade base stocks, due to concerns about emissions and operating life. Volatility depends on the molecular composition of the oil, especially at the front end of the boiling curve. Noack (ASTM D5800) is a generally accepted method for measuring the volatility of automotive lubricants. The Noack test method itself simulates evaporation loss in high-temperature service, such as in a running internal combustion engine.

[0035] Fuel Economy Improvement: The reduction in fuel consumption of an engine operating with a candidate oil compared to that observed when the same engine is operated under the same test conditions with a reference oil.

[0036] Fuel Economy Retention: The ability of a lubricant to maintain fuel consumption levels over the period of time the lubricant is exposed to aging conditions in an internal combustion engine. Fuel economy retention can also be expressed as the ability of a lubricant to maintain improved fuel economy over the period of time the lubricant is exposed to aging conditions in an internal combustion engine. Fuel economy retention can also be expressed as the lack of fuel economy loss over the period of time the lubricant is exposed to aging conditions in an internal combustion engine.

[0037] The boiling point distribution is the boiling point range defined by the true boiling point (TBP) at which 5% and 95% of the material evaporates. Herein, it is measured by ASTM D2887.

[0038] NMR branching analysis branching parameters measured by NMR spectroscopy for hydrocarbon characterization include:

[0039] Branching Index (BI): The percentage of methyl hydrogens appearing in the chemical shift range 0.5-1.05 ppm out of all hydrogens appearing in the 1H NMR chemical range 0.5-2.1 ppm for isoparaffinic hydrocarbons.

[0040] Branch Proximity (BP): The percentage of repeating methylene carbons that are four or more carbon atoms removed from an end group or branch that appears at the 13C NMR chemical shift of 29.8 ppm.

[0041] Internal alkyl carbons: The number of methyl, ethyl, or propyl carbons that are three or more carbons removed from the terminal methyl carbon, including 3-methyl, 4-methyl, 5+methyl, adjacent methyl, internal ethyl, n-propyl, and unknown methyls appearing between 13C NMR chemical shifts of 0.5 ppm and 22.0 ppm, excluding the terminal methyl carbon appearing at 13.8 ppm.

[0042] 5+ methyl carbons: The number of methyl carbons attached to the methine carbon that are more than four carbons away from the terminal carbon that appears at a 13C NMR chemical shift of 19.6 ppm for an average isoparaffinic molecule.

[0043] NMR spectra were acquired using a Bruker AVANCE500 spectrometer with a 5 mm BBI probe. Each sample was mixed 1:1 (wt:wt) with CDCl3. 1H NMR was recorded at 500.11 MHz with 9.0 μs (30°C) pulses applied at 4-second intervals, adding 64 scans to each spectrum. 13C NMR was recorded at 125.75 MHz with 7.0 μs pulses applied at 6-second intervals, using inverse gated decoupling, adding 4096 scans to each spectrum. A small amount of 0.1 M Cr(acac)3 was added as a relaxation agent, and TMS was used as an internal standard.

[0044] The branching properties of the lubricant base stock samples of the present invention are determined according to the following six-step process. The procedure is provided in detail in U.S. Patent No. 20050077208A1, which is incorporated herein in its entirety. The following procedure has been slightly modified to characterize the current sample set.

[0045] 1) Use the DEPT pulse sequence (Doddrell, DT; DT Pegg; MR Bendall, Journal of Magnetic Resonance 1982, 48, 323ff) to identify the CH branch centers and CH3 branch end points.

[0046] 2) Use an APT pulse sequence to verify the absence of carbons initiating multiple branches (quaternary carbons) (Patt, SL; JN Shoolery, Journal of Magnetic Resonance 1982, 46, 535ff).

[0047] 3) Using tabulated and calculated values, the various branched carbon resonances are assigned to specific branch positions and lengths (Lindeman, LP, Journal of Qualitative Analytical Chemistry 43, 1971 1245ff.; Netzel, DA, et. al., Fuel, 60, 1981, 307ff.). Branching NMR chemical shifts (ppm) [Table 2]

[0048] 4) Quantify the relative frequency of branching at various carbon positions by comparing the integrated intensity of the terminal methyl carbon with the intensity of the single carbon (total integral / number of carbons per molecule in the mixture). For example, the number of 5+ methyl branches per molecule is calculated from the signal intensity at a chemical shift of 19.6 ppm relative to the intensity of the single carbon.

[0049] For the unique case of the 2-methyl branch, where both the terminal and branch methyls occur at the same resonance position, the intensity was divided by 2 before calculating the frequency of branch occurrence.

[0050] When calculating and summing the fraction of the 4-methyl branch, the contribution to the 5+ methyl must be subtracted to avoid double counting.

[0051] The contribution of unknown methyl branches is calculated from the signal contributions appearing between 5.0 ppm and 22.5 ppm, but the branches reported in Table 2 are not included.

[0052] 5) Calculate the branching index (BI) and branching proximity (BP) using the calculations described in US Pat. No. 6,090,989, which is incorporated herein by reference in its entirety.

[0053] 6) Calculate the total internal alkyl branches per molecule by summing the branches found in steps 3 and 4, excluding the 2-methyl branch. These branches include 3-methyl, 4-methyl, 5+methyl, internal ethyl, n-propyl, adjacent methyl, and unknown methyl.

[0054] FIMS Analysis: The hydrocarbon distribution of the present invention was determined by FIMS (Field Ion Mass Spectrometry). FIMS spectra were acquired using a Waters GCT-TOF mass spectrometer. Samples were introduced via a solid probe heated from approximately 40°C to 500°C at a rate of 50°C per minute. The mass spectrometer was scanned from m / z 40 to m / z 1000 at a rate of 5 seconds per decade. The acquired mass spectra were summed to produce a single average spectrum that provided the carbon number distribution of paraffins and cycloparaffins containing up to six rings.

[0055] Hydrocarbon Structure and Properties The structure of the hydrocarbon mixture disclosed herein has been characterized by FIMS and NMR. FIMS analysis demonstrates that more than 80% of the molecules in the hydrocarbon mixture have even carbon numbers.

[0056] The unique branched structure of the hydrocarbon mixtures disclosed herein is characterized by NMR parameters such as BP, BI, internal alkyl branching, and 5+ methyls. The BP / BI of the hydrocarbon mixtures is in the range of ≥ -0.6037 (internal alkyl branching per molecule) + 2.0. The 5+ methyls of the hydrocarbon mixtures average 0.3-1.5 per molecule.

[0057] Based on the carbon number distribution, hydrocarbon mixtures can be classified into two carbon ranges: C28-C40 carbons and C42 and above. Generally, about 95%, or more than about 95%, of the molecules present in each hydrocarbon mixture have carbon numbers within the specified range. Representative molecular structures within the C28-C40 range can be proposed based on NMR and FIMS analysis. While not wishing to be bound by any particular theory, it is believed that structures formed by olefin oligomerization and hydroisomerization have methyl, ethyl, and butyl branches distributed throughout the structure, and that the branching index and branching proximity contribute to the surprisingly good low-temperature properties of the product. An exemplary structure for a hydrocarbon mixture of the present invention is as follows: [ka]

[0058] The unique branched structure and narrow carbon distribution of the hydrocarbon mixture make it suitable for use as a high-quality synthetic base oil, especially for low viscosity engine oil applications. KV100 in the range of 3.0~10.0cSt Pour point in the range of -20 to -55°C Noack 2750 (CCS at -35°C) (-0.8) The relationship between Noack and CCS at -35°C is between ±2

[0059] The relationship between Noack and CCS for hydrocarbon mixtures is shown in Figures 3 and 4. In each figure, the upper line represents Noack = 2750(CCS at -35°C)(-0.8)+2, and the lower line represents Noack = 2750(CCS at -35°C)(-0.8)-2. More preferably, the hydrocarbon mixture has a relationship between Noack and CCS at -35°C that is between Noack = 2750(CCS at -35°C)(-0.8)+0.5 and Noack = 2750(CCS at -35°C)(-0.8)-2. Hydrocarbon mixtures closer to the origin in Figures 3 and 4 have been found to be more advantageous for low-viscosity engine oils due to their lower volatility and reduced viscosity at -35°C.

[0060] In hydrocarbon mixtures according to the invention having a carbon number in the range of C28 to C40, and in other embodiments having a carbon number in the range of C28 to C36, or molecules having a carbon number of C32, the hydrocarbon mixtures according to the invention generally exhibit the following properties in addition to the BP / BI, internal alkyl branches per molecule, 5+ methyl branches per molecule, and Noack / CCS relationship properties described above: KV100 in the range of 3.0~6.0cSt VI in the range of 11 ln(BP / BI)+135 to 11 ln(BP / BI)+145 Pour point in the range of 33 ln(BP / BI)-45 to 33 ln(BP / BI)-35

[0061] In one embodiment, the KV100 of the C28 to C40 hydrocarbon mixture is in the range of 3.2 to 5.5 cSt, in another embodiment, the KV100 is in the range of 4.0 to 5.2 cSt, and in another embodiment, 4.1 to 4.5 cSt.

[0062] The VI of the C28 to C40 hydrocarbon mixture is in the range of 125 to 155 in one embodiment, and in the range of 135 to 145 in another embodiment.

[0063] In one embodiment, the pour point of the hydrocarbon mixture is in the range of 25 to -55°C, and in another embodiment in the range of 35 to -45°C.

[0064] In one embodiment, the boiling point range of the C28 to C40 hydrocarbon mixture, as measured by ASTM D2887, is 125° C. or less (95% TBP - 5% TBP), in another embodiment 100° C. or less, in one embodiment 75° C. or less, in another embodiment 50° C. or less, and in one embodiment 30° C. or less. In preferred embodiments, boiling point ranges of 50° C. or less, and even more preferably 30° C. or less, result in surprisingly low Noack volatility (ASTM D5800) for a given KV100.

[0065] In one embodiment, the C28 to C40 hydrocarbon mixture has a branching proximity (BP) in the range of 14 to 30 with a branching index (BI) in the range of 15 to 25, and in another embodiment, a BP in the range of 15 to 28 and a BI in the range of 16 to 24.

[0066] The Noack volatility (ASTM D5800) of the C28 to C40 hydrocarbon mixture is, in one embodiment, less than 16 wt%, in one embodiment, less than 12 wt%, in one embodiment, less than 10 wt%, in one embodiment, less than 8 wt%, and in one embodiment, less than 7 wt%. The C28 to C40 hydrocarbon mixture in one embodiment also has a CCS viscosity at -35°C of less than 2700 cP, in another embodiment, less than 2000 cP, in one embodiment, less than 1700 cP, and in one embodiment, less than 1500 cP.

[0067] Hydrocarbon mixtures in the carbon number range of C42 and above generally exhibit the following properties in addition to the BP / BI, internal alkyl branches per molecule, 5+ methyl branches per molecule, and the Noack vs. CCS relationship at -35°C described above: KV100 in the range of 6.0~10.0cSt VI in the range of 11 ln(BP / BI)+145 to 11 ln(BP / BI)+160 Pour point in the range of 33 ln(BP / BI)-40 to 33 ln(BP / BI)-25

[0068] In one embodiment, the hydrocarbon mixture containing C42 or more carbon atoms has a KV100 in the range of 8.0 to 10.0 cSt, and in another embodiment, has a KV100 in the range of 8.5 to 9.5 cSt.

[0069] The VI of the hydrocarbon mixture having ≧42 carbons is 140-170 in one embodiment, and 150-160 in another embodiment.

[0070] The pour point is in the range of -15 to -50°C in one embodiment, and in the range of -20 to -40°C in another embodiment.

[0071] In one embodiment, the hydrocarbon mixture containing ≧42 carbons has a BP in the range of 18 to 28 with a BI in the range of 17 to 23. In another embodiment, the hydrocarbon mixture has a BP in the range of 18 to 28 and a BI in the range of 17 to 23.

[0072] Generally, both hydrocarbon mixtures disclosed above exhibit the following properties: At least 80% of the molecules have an even number of carbon atoms according to FIMS KV100 in the range of 3.0~10.0cSt Pour point in the range of -20 to -55°C Noack 2750 (CCS at -35°C) (-0.8) The relationship between Noack and CCS at -35°C is ±2. BP / BI in the range of ≥ -0.6037 (internal alkyl branching) + 2.0 per molecule Average of 0.3-1.5 5+ methyl branches per molecule

[0073] synthesis Possible processes or methods for producing the disclosed hydrocarbon mixtures are provided herein. The novel hydrocarbon mixtures disclosed herein can be synthesized by achieving the desired carbon chain length through olefin oligomerization, followed by fluid isomerization to improve their cold flow properties, such as pour point and CCS. In one embodiment, olefins ranging in length from C14 to C20 are oligomerized using an acid catalyst to form an oligomeric mixture. The olefins can be sourced from natural molecules, such as crude oil or gas-based olefins, or from ethylene polymerization. In some variations, approximately 100% of the carbon atoms in the olefin feedstocks described herein can be derived from renewable carbon sources. For example, alpha-olefin comonomers can be produced by the oligomerization of ethylene derived from the dehydration of ethanol produced from renewable carbon sources. In some variations, alpha-olefin comonomers can be produced by the dehydration of primary alcohols other than ethanol produced from renewable carbon sources. The aforementioned renewable alcohols can be dehydrated to olefins using gamma alumina or sulfuric acid. In some embodiments, the modified or partially hydrogenated terpene feedstock derived from renewable resources is combined with one or more olefins derived from renewable resources.

[0074] In one embodiment, C14-C20 olefin monomers are oligomerized in the presence of BF3 and / or BF3 promoted with a mixture of alcohols and / or esters, such as linear alcohols and alkyl acetates, using a continuous stirred tank reactor (CSTR) with an average residence time of 60 to 400 minutes. In another embodiment, C14-C20 olefin monomers are oligomerized in the presence of BF3 and / or promoted BF3 using a continuous stirred tank reactor with an average residence time of 90 to 300 minutes. In yet another embodiment, C14-C20 olefin monomers are oligomerized in the presence of BF3 and / or promoted BF3 using a continuous stirred tank reactor with an average residence time of 120 to 240 minutes. The temperature of the oligomerization reaction can range from 10°C to 90°C. However, in one preferred embodiment, the temperature is maintained in the range of 15 to 75°C, most preferably in the range of 20 to 40°C, during the reaction.

[0075] Lewis acid catalysts suitable for the oligomerization process include metalloid halides and metal halides commonly used as Friedel-Crafts catalysts, such as, for example, AlCl, BF, BF complexes, BCl, AlBr, TiCl, TiCl, SnCl, and SbCl. Either metalloid halide or metal halide catalysts can be used with or without a cocatalytic proton promoter (e.g., water, alcohol, acid, or ester). In one embodiment, the oligomerization catalyst is selected from the group consisting of zeolites, Friedel-Crafts catalysts, Bronsted acids, Lewis acids, acidic resins, acidic solid oxides, acidic silica aluminophosphates, Group IVB metal oxides, Group VB metal oxides, Group VIB metal oxides, hydroxides or free metal forms of Group VIII metals, and any combination thereof.

[0076] If the dimer portion is saturated without isomerization to a Br index (ASTM D2710) of less than 100 mgBr / 100 g, proper control of the oligomerization reaction temperature and residence time in the CSTR is required to ensure that the dimer portion (C28-C40) of the oligomerization product has a branching proximity (BP) between 25 and 35, preferably between 27 and 35, more preferably between 27 and 33, and most preferably between 28 and 32. A branching proximity that is too low before hydroisomerization results in an isomerized hydrocarbon mixture that falls below the solid line in Figure 1 and has an undesirably high CCS viscosity at -35°C for a given Noack volatility value within the range shown in Figures 3 and 4. Conversely, a branching proximity that is too high requires more isomerization to reach an acceptable pour point, which simultaneously increases the Noack volatility and CCS at -35°C. In one embodiment, the unsaturated oligomer product is distilled to remove unreacted monomer. For example, unreacted monomers can be separated from the oligomer product, such as by distillation, and recycled into the mixture of first and / or second feeds for oligomerization thereof.

[0077] The oligomer product is then hydroisomerized to provide the additional internal alkyl branching necessary to achieve the ideal branching profile. In one embodiment, the entire oligomer product, including both dimers (C28-C40) and heavier oligomers (≧C42), is hydroisomerized prior to separation by distillation. The hydroisomerized product is then separated into final hydrocarbon products by distillation. In another embodiment, the dimers and heavier oligomers are separately fractionated and hydroisomerized.

[0078] Hydroisomerization catalysts useful in the present invention typically contain a shape-selective molecular sieve, a metal or mixture of metals catalytically active for hydrogenation, and a refractory oxide support. The presence of the hydrogenation component leads to improved product performance, particularly VI and stability. Typical catalytically active hydrogenation metals include chromium, molybdenum, nickel, vanadium, cobalt, tungsten, zinc, platinum, and palladium. Platinum and palladium are particularly preferred, with platinum being most preferred. When platinum and / or palladium are used, the metal content is typically within the range of 0.1 to 5 weight percent of the total catalyst, usually 0.1 to 2 weight percent, and not exceeding 10 weight percent. Hydroisomerization catalysts are described, for example, in U.S. Patent Nos. 7,390,763 and 9,616,419, and U.S. Patent Application Publication Nos. 2011 / 0192766 and 2017 / 0183583.

[0079] The hydroisomerization conditions are adjusted to achieve an isomerized hydrocarbon mixture with specific branching characteristics, as described above, and therefore depend on the characteristics of the feedstock used. The reaction temperature is generally between about 200°C and 400°C, preferably between 260°C and 370°C, and most preferably between 288°C and 345°C, and the liquid hourly space velocity (LHSV) is generally about 0.5 h -1 ~approximately 20 hours -1 The pressure is typically between about 15 psig and about 2500 psig, preferably between about 50 psig and about 2000 psig, and more preferably between about 100 psig and about 1500 psig. Lower pressures increase isomerization selectivity, resulting in more isomerization, less cracking of the feedstock, and higher yields.

[0080] Hydrogen is present in the reaction zone during the hydroisomerization process, typically at a hydrogen-to-feed ratio of about 0.1 to 10 MSCF / bbl (thousand standard cubic feet per barrel), preferably about 0.3 to about 5 MSCF / bbl. The hydrogen is separated from the product and recycled to the reaction zone.

[0081] In one embodiment, an additional step of hydrogenation is added before hydroisomerization to protect the downstream hydroisomerization catalyst, and in another embodiment, an additional step of hydrogenation or hydrofinishing is added after hydroisomerization to further improve saturation and stability of the hydrocarbon mixture.

[0082] The hydroisomerized hydrocarbon mixtures are comprised of a mixture of dimers having carbon numbers ranging from C28 to C40 and trimers having carbon numbers of C42 and above. Each hydrocarbon mixture exhibits a BP / BI in the range of ≥ -0.6037 (internal alkyl branching) ± 2.0 per molecule, and exhibits, on average, 0.3 to 1.5 methyl branches at positions 5 and above per molecule. Importantly, at least 80% of the molecules in each composition also have a uniform carbon number as determined by FIMS. In another embodiment, each of the hydrocarbon compositions also has a Noack of 2750 (CCS at -35°C). (-0.8) The relationship between Noack and CCS at -35°C is also shown to be between ±2. These properties enable the formulation of low viscosity engine oils and many other high performance lubricant products.

[0083] In one embodiment, C16 olefins are used as feedstocks for oligomerization reactions. When C16 olefins are used as feedstocks, the hydroisomerized dimer product typically exhibits a KV100 of 4.3 cSt, a Noack loss of <8%, and a CCS of approximately 1,700 cP at -35°C. The very low Noack volatility is due to a high onset boiling point and narrow boiling point distribution compared to other 3.9-4.4 cSt synthetic basestocks. This makes it ideal for use in low-viscosity engine oils with stringent volatility requirements. The excellent CCS and pour point properties are due to the branching characteristics described above. In one embodiment, the material has a pour point of ≤ -40°C, which is necessary to pass critical engine oil formulation requirements for 0W formulations, including Mini-Rotary Viscosity (ASTM D4684) and Scanning Brookfield Viscosity (ASTM D2983) specifications.

[0084] Finished lubricant formulations for improved engine performance This specification describes improved fuel economy, fuel economy retention, and LSPI prevention for ultra-low viscosity engine oils formulated using renewable base oils compared to conventional base oils. Finished lubricant compositions containing the renewable base oils described herein not only reduce friction, resulting in improved fuel economy when fresh, but also unexpectedly maintain reduced friction upon aging compared to conventional base oil formulations. These advantages were utilized in the formulation of finished engine oils, and the fuel economy improvement and fuel economy retention benefits were demonstrated using a modified sequence VIF fuel economy engine test stand. Test results show that the use of renewable base oils in finished engine oil formulations results in unexpected and significant fresh oil fuel economy improvements that cannot be explained by viscosity measurements of the renewable base lubricant. Furthermore, aged oil fuel economy is significantly better maintained compared to conventional base oil engine oil formulations, resulting in unprecedented fuel economy improvement and retention over the life of the lubricant in the engine.

[0085] Also described herein is a reduction in calcium gain over extended periods of exposure to high temperatures in sequence VIF engines, thereby improving the ability of the lubricating oil composition to retain its LSPI prevention properties.

[0086] Lubricating oil compositions containing the renewable base oils described herein can be used in a variety of lubricant-related end uses, including lubricating oils or greases for devices or equipment requiring lubrication of moving and / or interacting mechanical parts, components, or surfaces. Useful equipment includes engines and machinery. More specific equipment includes, but is not limited to, gasoline-burning engines, diesel-burning engines, natural gas-burning engines, gearboxes, wind turbines, and cyclic hydraulic pumps. Lubricating oil compositions containing the base oils described herein can be used in the formulation of automotive crankcase lubricants, automotive gear oils, transmission oils, and many industrial lubricants, including cyclic lubricants, industrial gear lubricants, greases, compressor oils, pump oils, refrigeration lubricants, hydraulic lubricants, and metal working fluids.

[0087] These benefits were observed in a Sequence VIF Engine Test modified for longer time / duration and higher temperatures. The Sequence VIF Engine Test described in ASTM D8226, as known to those skilled in the art, involves a comparative fuel economy improvement (FEI) evaluation of the fuel saving potential of automotive engine oils under repeatable laboratory conditions for low viscosity oils.

[0088] The test parameters were as follows: (1) The test duration was 196 hours. (2) Fuel consumption was measured at six speed / load / temperature test conditions for the SAE 20W-30 baseline (BL) lubricant to ensure consistent engine response. (3) The candidate lubricant was introduced and aged for 16 hours at the aging condition, and then fuel consumption was measured at six test conditions for FEI 1. (4) The candidate lubricant was left in the engine and aged for 109 hours at the aging condition for FEI 2. (5) Fuel consumption at each of the six BL test conditions was repeated at the end of the test to further ensure consistent engine response throughout the test. (5) FEI 1, FEI 2, and FEI total (FEI 1 plus FEI 2) were calculated from a comparison of the candidate oil's fuel economy measurements with those of the baseline lubricant (BL).

[0089] Fuel consumption was measured at six speed / load / temperature test conditions for the SAE 20W-30 baseline (BL) lubricant to ensure consistent engine response. After introducing the candidate lubricant and aging it for 16 hours at the aging condition, fuel consumption was measured at the six test conditions (Table 3). Fuel consumption at each of the six BL test conditions was repeated at the end of the test to further ensure consistent engine response throughout the test period. [Table 3] Modifications to this sequence VIF engine test conditions are shown. [Table 4]

[0090] The lubricating oils of the present invention comprise renewable base oils used in base oil blends and further comprise one or more of the following additives: dispersants, inhibitors, antioxidants, detergents, friction modifiers, pour point depressants, viscosity modifiers, and the like.

[0091] In one embodiment, the amount of renewable base oil in the total amount of base oil is at least 20 wt. %. In another embodiment, the amount of renewable base oil in the total amount of base oil is from about 20 wt. % to about 100 wt. As is known in the art, the fuel economy of an internal combustion engine is determined in part by the viscosity of the lubricating oil and in part by the frictional properties. The frictional properties of a lubricating oil are determined by the chemistry of the additives, in the sense that surfactant additives, such as detergents, anti-wear additives, and friction modifiers, can form solid, friction-altering surface layers on the metal surfaces of lubricated contacts in the engine. It would not be expected by those skilled in the art that a base oil would play a role in altering engine friction unless the viscosity of the lubricating oil is altered.

[0092] One embodiment of the present invention describes a method for deriving improved fuel economy from a lubricant containing renewable base oil and having the same additives as a comparative lubricant of equal viscosity that does not contain renewable base oil.

[0093] In one embodiment, the fuel economy improvement when using a lubricating oil composition comprising 90 wt. % renewable base oil and 10 wt. % of a combination of additives including dispersants, detergents, inhibitors, friction modifiers, and pour point depressants is at least 0.3%, preferably 0.5%, better than a conventional lubricating oil of equal viscosity without the renewable base oil.

[0094] As is known in the art, fuel economy improvement measurements are made on fresh lubricants or lubricants that have been subjected to a small amount of aging under conditions that are representative of moderately severe driving conditions. It is also known that, in many cases, the driving conditions can be more severe when the lubricant is subjected to extended aging conditions, such as elevated ambient conditions or extended oil change intervals. However, there are no standardized tools for determining the fuel economy of lubricants that have been subjected to more severe aging conditions, see row 5 of Table 4, for severe aging conditions as described herein.

[0095] The present invention describes a method for deriving a fuel economy retention (FER) benefit from a lubricant containing renewable base oil and having the same viscosity and additives as a comparative lubricant containing no renewable base oil. The fuel economy retention (FER) is evaluated after an aging period representing a typical shorter oil change interval. Alternatively, the FER is evaluated after an aging period representing an extended oil change interval.

[0096] In one embodiment, fuel economy retention at conditions representing shorter oil change intervals is at least 1.0%, preferably 1.5%, better than a conventional lubricant of equal viscosity that does not contain renewable base oil when using a lubricant composition comprising 90 wt. % renewable base oil and 10 wt. % of a combination of additives including dispersants, detergents, inhibitors, friction modifiers, and pour point depressants.

[0097] In one embodiment, fuel economy retention at conditions representing shorter oil change intervals is at least 0.5%, preferably 1.0%, better than a conventional lubricant of equal viscosity without the renewable base oil when using a lubricant composition comprising 45 wt. % renewable base oil, 45 wt. % non-renewable base oil, and 10 wt. % additive combination including dispersants, detergents, inhibitors, friction modifiers, and pour point depressants.

[0098] In one embodiment, the fuel economy retention (FER) at conditions representing extended oil change intervals is at least 1.0%, preferably 1.5%, better than a conventional lubricant of equal viscosity without the renewable base oil when using a lubricant composition comprising 90 wt. % renewable base oil and 10 wt. % additive combination including dispersants, detergents, inhibitors, friction modifiers, and pour point depressants.

[0099] In one embodiment, the fuel economy retention (FER) at conditions representing extended oil change intervals is at least 0.5%, preferably 1.0%, better than a conventional lubricant of equal viscosity without the renewable base oil when using a lubricant composition comprising 45 wt. % renewable base oil, 45 wt. % non-renewable base oil, and 10 wt. % additive combination including dispersants, detergents, inhibitors, friction modifiers, and pour point depressants.

[0100] In one embodiment, fuel economy retention over the life of the lubricant is at least 0.5%, preferably 1.0%, better than a conventional lubricant of equal viscosity without the renewable base oil when using a lubricant composition comprising 45 wt. % renewable base oil, 45 wt. % non-renewable base oil, and 10 wt. % additive combination including dispersants, detergents, inhibitors, friction modifiers, and pour point depressants.

[0101] As used herein, "lubricant life" includes the period from when the lubricant is introduced into an engine until the condition of the lubricant deteriorates to a level where engine damage may occur if the lubricant is not replenished.

[0102] In one embodiment, fuel economy retention over the life of the lubricant is at least 1.0%, preferably 1.5%, better than a conventional lubricant of equal viscosity without the renewable base oil when using a lubricant composition comprising 90 wt. % renewable base oil and 10 wt. % additive combination including dispersants, detergents, inhibitors, friction modifiers, and pour point depressants.

[0103] A further embodiment of the present invention is a method for improving FER while retaining low speed pre-ignition (LSPI) prevention capabilities during extended internal combustion engine operation. Lubricant formulations were aged by exposure to high temperatures in a GM High Feature 3.6L LY7 V6 engine mounted on a dynamometer. The lubricant formulations were aged in two stages. In stage 1, the lubricant formulations were exposed to 120°C for 16 hours. In the next aging stage, the lubricant formulations were exposed to 140°C for 288 hours. During the aging stages, the lubricant was sampled every 25 hours for used oil analysis and chemical characterization to observe changes in the lubricant additives during the test.

[0104] As shown in Table 9 and Figure 6, the comparative oils (Examples 1, 2, and 3) all showed a significant increase in calcium content as they aged in the engine. The calcium content of the comparative oils increased by between 20% and 76% at the end of the test. In comparison, the inventive lubricating oil compositions described herein maintained calcium concentrations very close to the original value throughout the test period.

[0105] Previous studies have concluded that higher viscosity base stocks increase LSPI, while lubricant volatility has only a minor effect on LSPI occurrence. In the current work, all lubricants were formulated with base stocks of similar kinematic viscosity. Based on the conclusions from previous studies, all four oils are predicted to exhibit the same behavior with respect to LSPI occurrence. However, previous studies have concluded that increasing calcium concentrations increase LSPI rates. Comparative Oils 1, 2, and 3 exhibit a significant increase in calcium content because these lubricants were exposed to higher temperatures and extended aging. Based on the conclusions from previous studies and the results presented in Table 9, all three comparative oils are predicted to exhibit increasing LSPI occurrence with aging. In contrast, the lubricant compositions described herein will retain their LSPI prevention performance throughout the test.

[0106] In certain variations, the base stocks prepared according to the methods described herein are blended with one or more additional base stocks, such as one or more commercially available PAOs, gas-to-liquid (GTL) base stocks, one or more mineral base stocks, vegetable oil base stocks, algae-derived base stocks, a second base stock described herein, or any other type of renewable base stock. Any effective amount of additional base stock can be added to achieve a blended base oil having desired properties. For example, the blended base oil can include a ratio of a first base oil described herein to a second base oil (e.g., a commercially available PAO base oil, GTL base oil, one or more mineral base oils, vegetable oil base oils, algae-derived base stocks, a second base stock described herein) in a ratio of about 1 to 99%, about 1 to 80%, about 1 to 70%, about 1 to 60%, about 1 to 50%, about 1 to 40%, about 1 to 30%, about 1 to 20%, or about 1 to 10%, based on the total weight of the resulting composition.

[0107] Also disclosed herein are lubricating oil compositions comprising the hydrocarbon mixtures described herein. In some variations, the lubricating oil compositions comprise a base oil comprising at least a portion of the hydrocarbon mixtures produced by any of the methods described herein, and one or more additives selected from the group consisting of antioxidants, viscosity modifiers, pour point depressants, antifoam agents, detergents, dispersants, dyes, markers, rust or other corrosion inhibitors, emulsifiers, demulsifiers, antiwear agents, friction modifiers, thermal stability improvers, multi-function additives (e.g., additives that function as both antioxidants and dispersants), or any combination thereof. The lubricating oil compositions may comprise the hydrocarbon mixtures described herein and any lubricating oil additive, combination of lubricating oil additives, or available additive packages.

[0108] Any of the compositions described herein used as a base stock may be present in an amount greater than about 1%, based on the total weight of the finished lubricating oil composition. In certain embodiments, the amount of base stock in the formulation is greater than about 2, 5, 15, or 20 wt. %, based on the total weight of the formulation. In some embodiments, the amount of base oil in the composition is about 1-99%, about 1-80%, about 1-70%, about 1-60%, about 1-50%, about 1-40%, about 1-30%, about 1-20%, or about 1-10%, based on the total weight of the composition. In certain embodiments, the amount of base stock in the formulations provided herein is about 1%, 5%, 7%, 10%, 13%, 15%, 20%, 30%, 40%, or 5%. As is known in the art, the type and amount of lubricating oil additives are selected in combination with the base oil so that the finished lubricating oil composition meets specific industry standards or specifications for a particular application. Generally, the concentration of each additive in the composition, if used, can range from about 0.001% to about 20%, about 0.01% to about 10%, about 0.1% to about 5%, or about 0.1% to about 2.5% by weight, based on the total weight of the composition. Furthermore, the total amount of additives in the composition can range from about 0.001% to about 50%, about 0.01% to about 40%, about 0.01% to about 30%, about 0.01% to about 20%, about 0.1% to about 10%, or about 0.1% to about 5% by weight, based on the total weight of the composition, and can be 0%, 60%, 70%, 80%, 90%, or 99% based on the total weight of the formulation.

[0109] In some variations, the base oils described herein are formulated into lubricating oil compositions for use as two-stroke engine oils, transmission oils, hydraulic fluids, compressor oils, turbine oils and greases, automotive engine oils, gear oils, marine lubricants, and process oils, including, but not limited to, rolling mill oils, coning oils, plasticizers, spindle oils, polymer processing, release agents, coatings, adhesives, sealants, blends for polishes and waxes, drawing oils, stamping oils, rubber compounding, pharmaceutical processing aids, personal care products, and inks.

[0110] In yet another variation, the base oils described herein are formulated into industrial oil or grease formulations and contain at least one additive selected from antioxidants, antiwear agents, extreme pressure agents, defoamers, detergents / dispersants, rust and corrosion inhibitors, thickeners, tackifiers, and demulsifiers. It is also contemplated that the base stocks of the present invention may be formulated as dielectric heat transfer fluids composed of relatively pure blends of compounds selected from aromatic hydrocarbons, polyalphaolefins, polyol esters, and natural vegetable oils, plus additives to improve pour point, increase stability, and reduce oxidation rates.

[0111] The present invention is further illustrated by the following examples, which are not intended to be limiting. [Example]

[0112] Examples 1 to 6 (C28 to C40 hydrocarbon mixture) Example 1 1-Hexadecene, containing less than 8% branched and internal olefins, was oligomerized under BF3 using a cocatalyst composition of butanol and butyl acetate. The reaction was held at 20°C during semi-continuous addition of the olefin and cocatalyst. The residence time was 90 minutes. Unreacted monomer was then distilled off, leaving a distillation residue of less than 0.1% monomer. A subsequent distillation was performed to separate the dimer from the trimer, with less than 5% trimer remaining in the dimer fraction.

[0113] The dimer was then hydroisomerized over an alumina-bound MRE structural type catalyst, a noble metal-impregnated aluminosilicate. The reaction was carried out in a fixed-bed reactor at 500 psig and 307°C. The cracked molecules were separated from the hydroisomerized C16 dimer using an online stripper.

[0114] Example 2 The oligomerization and subsequent distillation were carried out as in Example 1. The dimer was then hydroisomerized using a noble metal-impregnated aluminosilicate catalyst, an MRE structural type catalyst bound to alumina. The reaction was carried out in a fixed-bed reactor at 500 psig and 313°C. The cracked molecules were separated from the hydroisomerized C16 dimer using an online stripper.

[0115] Example 3 The oligomerization and subsequent distillation were carried out as in Example 1. The dimer was then hydroisomerized using a noble metal-impregnated aluminosilicate, an MRE structural type catalyst bound to alumina. The reaction was carried out in a fixed-bed reactor at 500 psig and 324°C. The cracked molecules were separated from the hydroisomerized C16 dimer using an online stripper.

[0116] Example 4 The oligomerization and subsequent distillation were carried out as in Example 1. The dimer was then hydroisomerized using a noble metal-impregnated aluminosilicate catalyst, an MTT structural type catalyst bound to alumina. The reaction was carried out in a fixed-bed reactor at 500 psig and 316°C. The cracked molecules were separated from the hydroisomerized C16 dimer using an online stripper.

[0117] Example 5 The oligomerization and subsequent distillation were carried out as in Example 1. The dimer was then hydroisomerized using a noble metal-impregnated aluminosilicate catalyst, an MTT structural type catalyst bound to alumina. The reaction was carried out in a fixed-bed reactor at 500 psig and 321°C. The cracked molecules were separated from the hydroisomerized C16 dimer using an online stripper.

[0118] Example 6 The oligomerization and subsequent distillation were carried out as in Example 1. The dimer was then hydroisomerized using a noble metal-impregnated aluminosilicate catalyst, an MTT structural type catalyst bound to alumina. The reaction was carried out in a fixed-bed reactor at 500 psig and 332°C. The cracked molecules were separated from the hydroisomerized C16 dimer using an online stripper.

[0119] Examples 7 to 12 (C≧42 Hydrocarbon Mixture) Example 7 1-Hexadecene, containing less than 8% branched and internal olefins, was oligomerized under BF3 using a cocatalyst composition of butanol and butyl acetate. The reaction was held at 20°C during semi-continuous addition of the olefin and cocatalyst. The residence time was 90 minutes. Unreacted monomer was then distilled off, leaving a distillation residue of less than 0.1% monomer. A subsequent distillation was performed to separate the dimer from the trimer and higher oligomers, and the resulting dimer had less than 5% trimer.

[0120] The trimer and higher oligomer (trimer+) fraction was then hydroisomerized over an alumina-bound MRE structural type catalyst, a noble metal-impregnated aluminosilicate. The reaction was carried out in a fixed-bed reactor at 500 psig and 313°C. The cracked molecules were separated from the hydroisomerized C16 trimer+ using an online stripper.

[0121] Example 8 Oligomerization and subsequent distillation were carried out as in Example 7. The trimer+ fraction was then hydroisomerized using a noble metal-impregnated aluminosilicate, an MRE structural type catalyst bound to alumina. The reaction was carried out in a fixed-bed reactor at 500 psig and 318°C. The cracked molecules were separated from the hydroisomerized C16 trimer+ using an online stripper.

[0122] Example 9 Oligomerization and subsequent distillation were carried out as in Example 7. The trimer+ fraction was then hydroisomerized using a noble metal-impregnated aluminosilicate, an MRE structural type catalyst bound to alumina. The reaction was carried out in a fixed-bed reactor at 500 psig and 324°C. The cracked molecules were separated from the hydroisomerized C16 trimer+ using an online stripper.

[0123] Example 10 Oligomerization and subsequent distillation were carried out as in Example 7. The trimer+ fraction was then hydroisomerized using a noble metal-impregnated aluminosilicate catalyst, an MTT structural type catalyst bound to alumina. The reaction was carried out in a fixed-bed reactor at 500 psig and 321°C. The cracked molecules were separated from the hydroisomerized C16 trimer+ using an online stripper.

[0124] Example 11 Oligomerization and subsequent distillation were carried out as in Example 7. The trimer+ fraction was then hydroisomerized using a noble metal-impregnated aluminosilicate catalyst, an MTT structural type catalyst bound to alumina. The reaction was carried out in a fixed-bed reactor at 500 psig and 327°C. The cracked molecules were separated from the hydroisomerized C16 trimer+ using an online stripper.

[0125] Example 12 Oligomerization and subsequent distillation were carried out as in Example 7. The trimer+ fraction was then hydroisomerized using a noble metal-impregnated aluminosilicate catalyst, an MTT structural type catalyst bound to alumina. The reaction was carried out in a fixed-bed reactor at 500 psig and 332°C. The cracked molecules were separated from the hydroisomerized C16 trimer+ using an online stripper.

[0126] The test results for the hydrocarbon mixtures obtained in Examples 1 to 12 are summarized in Table 3 below. [Table 5]

[0127] Comparative GTL and PAO basestocks The characterization results of the comparative GTL and PAO samples used in Figures 1-4 are summarized in Table 4. The comparative GTL samples are shown in the following publications: GTL#1 in WO2007068795, GTL#2 in WO2007068795, and GTL#3 in US2005007720. The comparative PAO samples were measured using the techniques described above for commercially available samples. [Table 6]

[0128] When the above data are graphically represented, the important structural and property differences are clearly evident when comparing the hydrocarbon mixtures of the present invention with the hydrocarbon mixtures of the prior art, demonstrating the surprising improvement in properties of the hydrocarbon mixtures of the present invention. Figures 1-4 graphically represent some of the above characterizations.

[0129] Figure 1 shows the relationship between BP / BI and internal alkyl branches per molecule for various hydrocarbon mixtures. The straight line used in the plot represents the equation BP / BI - 0.6037 (internal alkyl branches per molecule) + 2.0. All hydrocarbon mixtures of the present invention lie above the line. While some hydrocarbons from prior art hydrocarbon mixtures also lie above the line, they do not meet other important characteristics of the hydrocarbon mixtures of the present invention, as shown in Figures 2-4.

[0130] Figure 2 shows the relationship between BP / BI and 5+ methyl branches per molecule for various hydrocarbon blends. It shows that the 5+ methyl branches per molecule for the hydrocarbon blends of the present invention fall within the specific range of 0.3 to 1.5. All prior art blends fall outside this range.

[0131] Figures 3 and 4 show the relationship between Noack volatility and CCS at -35°C for various hydrocarbon blends. Some commercially available Group III base oils are included because they do not meet the FIMS requirement of 80% even carbon numbers. The solid and dotted lines represent the upper and lower limits of Noack vs. CCS at -35°C exhibited by the unique hydrocarbon blends of the present invention, where Noack = 2,750 (CCS at -35°C), respectively. (-0.8) +2 and Noack = 2,750 (CCS at -35°C) (-0.8)The range is -2. It can be seen that all hydrocarbon blends of the present invention fall within the range, while essentially all prior art samples fall outside the range, with the exception of the high viscosity PAOs that lack the desired branching seen in Figures 1 and 2. Figure 4 is an expanded view of Figure 3, covering the range of 800 to 2,800 cP CCS at -35°C. Generally, with regard to engine oil formulation, the preferred base stocks fall as close as possible to the starting points of Figures 3 and 4, since low Noack volatility for a given CCS viscosity at -35°C is ideal for modern engine oil formulations, such as 0W-20 to 0W-8 formulations.

[0132] The foregoing data and figures demonstrate the unique branching characteristics of the hydrocarbon blends of the present invention as characterized by NMR, and the resulting unique properties. The novel combination of structural features is shown to result in outstanding properties, including extremely low volatility and good low temperature properties, which are key performance attributes of high quality base stocks. Example 13

[0133] Table 7 shows a comparison of three lubricating oil compositions, showing the performance of conventional, high-volatility, and inventive lubricating oil compositions as described herein when used in a modified sequence VIF test for the benefit of improved fuel economy. As shown in Table 7, lubricating oils of the present invention containing 90 wt. % renewable base oil and 10 wt. % additive package including dispersants, detergents, inhibitors, friction modifiers, and pour point depressants were blended to meet the viscosity grade requirements of an SAE 0W-8 lubricant. The lubricant had a kinematic viscosity of 5.47 cSt at 100°C, a CCS viscosity of 2400 cP at -35°C, and a Noack volatility of 7%. Comparative Lubricant 1 was made with 90% API Group IV base oil and 10 wt. % of the same additive package including dispersants, detergents, inhibitors, friction modifiers, and pour point depressants. This comparative lubricant was also blended to meet the viscosity grade requirements of an SAE 0W-8 lubricant. The comparative lubricant had a kinematic viscosity of 4.82 cSt at 100°C, a CCS viscosity of 2000 cP at -35°C, and a Noack volatility of 10.8%. The third oil used for comparison was purchased because it was a commercially available lubricant. This lubricant also met the viscosity grade requirements for SAE 0W-8 lubricants. The third commercially available lubricant had a kinematic viscosity of 5.31 cSt at 100°C, a CCS viscosity of 1236 cP at -35°C, and a Noack volatility of 30.8%. [Table 7]

[0134] Following three flushing procedures to remove all residue from the reference lubricant (evaluated before and after each test against the candidate lubricant), a 5900 ml sample of the inventive lubricant and two comparative lubricants were added to a GM 3.6L V-6 engine. The fuel economy improvement (FEI) is expressed as a percentage increase or decrease in fuel consumption relative to the fuel consumed with the reference lubricant, an SAE 20W-30 viscosity grade oil. Table 7 shows that the comparative lubricant, with an SAE 0W-8 viscosity grade, exhibits a fuel economy advantage based on its low viscosity, ranging from 2.5 to 3.0% fuel economy improvement (FEI). The 3.7% FEI found with the inventive lubricant is quite surprising, as it represents a 1.2% improvement in FE compared to Comparative Example 1, a conventional lubricant that represents best-in-class results using a high-quality Group IV base oil. This result is particularly surprising given that the viscosities of these lubricants are nearly identical and the additive systems responsible for their frictional properties are identical.

[0135] Example 14 [Table 8]

[0136] Table 8 shows a comparison of four lubricating oil compositions, two demonstrating conventional performance and two demonstrating lubricating oil compositions of the present invention, when used in the modified sequence VIF test for fuel economy retention benefits as described herein. As shown in Table 8, inventive lubricating oil composition 1, containing 45 wt. % renewable base oil, 45 wt. % non-renewable base oil, and 10 wt. % additive package containing dispersants, detergents, inhibitors, friction modifiers, and pour point depressants, was blended to meet the SAE 0W-8 lubricating oil viscosity grade. The lubricating oil had a kinematic viscosity of 4.4 cSt at 100°C, a CCS viscosity of 1394 cP at -35°C, and a Noack volatility of 14%. Inventive lubricating oil composition 2, containing 90 wt. % renewable base oil and 10 wt. % additive package containing dispersants, detergents, inhibitors, friction modifiers, and pour point depressants, was blended to meet the SAE 0W-8 lubricating oil viscosity grade. The lubricant had a kinematic viscosity of 5.5 cSt at 100°C, a CCS viscosity of 2400 cP at -35°C, and a Noack volatility of 7%. Comparative Oil 1 was purchased for comparison because it was a commercially available lubricant. This lubricant also met the SAE 0W-8 lubricant viscosity grade requirements. A third commercially available lubricant had a kinematic viscosity of 5.31 cSt at 100°C, a CCS viscosity of 1236 cP at -35°C, and a Noack volatility of 30.8%. Comparative Lubricant 2 was made with 90% API Group IV base oil and 10 wt.% of the same additive package, including dispersants, detergents, inhibitors, friction modifiers, and pour point depressants. This comparative lubricant was also blended to meet the SAE 0W-8 lubricant viscosity grade requirements. The comparative lubricant had a kinematic viscosity of 4.82 cSt at 100°C, a CCS viscosity of 2000 cP at -35°C, and a Noack volatility of 10.8%.

[0137] Following three flushing procedures to remove all residue of the reference lubricant (evaluated before and after each test against the candidate lubricant), a 5900 ml sample of the lubricant of the present invention and two comparison lubricants were added to a GM 3.6L V-6 engine. Fuel economy improvement (FEI) is expressed as a percentage increase or decrease in fuel consumption relative to the fuel consumed with the reference lubricant, which was an SAE 20W-30 viscosity grade oil.

[0138] The GM3.6L engine was operated under conditions more precisely specified in the ASTM Sequence VIF engine test, except for the lubricant temperature, which increased from 120°C to 140°C during the extended aging period. A detailed description of the modified test conditions is summarized in Table 4. Each candidate test began with a fresh lubricant fuel economy measurement, followed by additional fuel economy measurements 172 hours after lubricant aging and again at 328 hours. After 172 hours of aging, the lubricant deteriorates similarly to normal drain interval conditions. Therefore, the fuel economy measurements performed after the 172-hour test period represent a deterioration in fuel economy under normal drain interval conditions. After 328 hours of aging, the lubricant deteriorates similarly to extended drain interval conditions. Therefore, the fuel economy measurements performed after the 328-hour test period represent a deterioration in fuel economy under extended drain interval conditions. The aging conditions are more precisely specified in the ASTM Sequence VIF engine test. Fuel economy ratings are based on six total fuel consumption measures, as specified in more detail in Table 3.

[0139] Table 8 also summarizes the percent change in fuel economy relative to the reference oil after the lubricant was aged under similar conditions as the normal extended drain interval. Additionally, Table 8 summarizes the average percent change in fuel economy over the life of the lubricant. The average change in fuel economy value was calculated by averaging the percent change in fuel economy values ​​over the normal extended drain interval.

[0140] As shown in Table 8, after aging in an engine at high temperatures, the comparative lubricants exhibit a rapidly increasing disadvantage compared to the lubricants of the present invention, without suffering a loss of fuel economy benefit and with excellent fuel economy retention over the life of the lubricant. For example, when Comparative Examples 1 and 2 were aged under similar conditions as normal drain intervals, they exhibited fuel economy improvements in the range of 1% to 2%, while the lubricants of the present invention retained a fuel economy improvement advantage in the range of 3% to 4%.

[0141] Furthermore, when Comparative Example 1 was aged under similar extended drain interval conditions, it lost all of its fuel economy improvement benefit and exhibited higher fuel consumption than the reference oil. Comparative Example 2 maintained approximately a 2% fuel economy benefit when aged under similar extended drain interval conditions. Meanwhile, the lubricating oils of the present invention retained a fuel economy improvement benefit in the range of 3% to 4% when aged under extended drain interval conditions.

[0142] Under typical extended drain interval conditions, inventive lubricants 1 and 2 demonstrated approximately 1% to 2% better fuel economy retention advantage than the comparative examples, representing best-in-class results using high-quality Group IV base oils. These results are quite surprising. The improvement in fuel economy retention advantage cannot be explained by differences in Noack volatility. For example, under extended drain interval conditions, the high-volatility Comparative Example 1 and best-in-class Example 2 demonstrated a 20% Noack volatility difference and approximately a 2% fuel economy advantage. Based on this, one skilled in the art would expect inventive lubricant 2 to provide a 0.4% fuel economy advantage based on the 4% Noack volatility difference between Comparative Example 2 and inventive lubricant 2. However, the results showed a >2% fuel economy advantage between Comparative Example 2 and inventive lubricant 2. Furthermore, inventive lubricant 1 demonstrated a 1.3% fuel economy improvement compared to best-in-class Comparative Example 2, despite its approximately 4% higher Noack volatility. [Table 9]

[0143] Table 9 shows a comparison of four lubricating oil compositions, two showing conventional performance and two showing two lubricating oil compositions of the present invention described herein, which, when used in a modified sequence VIF test, exhibit reduced calcium concentration increase levels after exposure to elevated temperatures in an engine over an extended discharge interval. References: 1. Amann, M., Alger, T., and Mehta, D., “The Effect of EGR on Low-Speed ​​Pre-Ignition in Boosted SI Engines”, SAE Int. J. Engines 4(1):235-245, 2011, doi:10.4271 / 2011-01-0339. 2. Amann, M., Alger, T., Westmoreland, B., and Rothmaier, A., “The Effects of Piston Crevices and Injection Strategy on Low-Speed ​​Pre-Ignition in Boosted SI Engines”, SAE Int.J.Engines 5(3):1216-1228,2012,doi:10.4271 / 2012-01-1148. 3. Ritchie, A., Boese, D., and Young, A., “Controlling Low-Speed ​​Pre-Ignition in Modern Automotive Equipment Part 3: Identification of Key Additive Component Types and Other Lubricant Composition Effects on Low-Speed ​​Pre-Ignition”, SAE Int.J.Engines 9(2):832-840,2016,doi:10.4271 / 2016-01-0717. 4.Takeuchi,K.,Fujimoto,K.,Hirano,S.,and Yamashita,M.,“Investigation of Engine Oil Effect on Abnormal Combustion in Turbocharged Direct Injection-Spark Ignition Engines”、SAE Int.J.Fuels Lubr.5(3):1017-1024,2012,doi:10.4271 / 2012-01-1615. 5.Takeuchi,K.,Fujimoto,K.,Hirano,S.,and Yamashita,M.,“Investigation of Engine Oil Effect on Abnormal Combustion in Turbocharged Direct Injection-Spark Ignition Engines”、SAE Int.J.Fuels Lubr.5(3):1017-1024,2012,doi:10.4271 / 2012-01-1615. 6.Boese D.a.R.A.,“Controlling low-speed pre-ignition in modern automotive equipment:Defining approaches to and methods for analyzing data in new studies of lubricant-and fuel-related effects”in 7.Presentation at 20th International Colloquium Tribology,Germany,January12-14,2016. 8.Onodera,K.,Kato,T.,Ogano,S.,Fujimoto,K.et al.,“Engine Oil Formulation Technology to Prevent Pre-ignition in Turbocharged Direct Injection Spark Ignition Engines”、SAE Technical Paper 2015-01-2027,2015,doi:10.4271 / 2015-01-2027. 9.Boese,D.,Ritchie,A.,and Young,A.,“Controlling Low-Speed Pre-Ignition in Modern Automotive Equipment:Defining Approaches to and Methods for Analyzing Data in New Studies of Lubricant and Fuel-Related Effects(Part 2)”、SAE Technical Paper 2016-01-0716,2016,doi:10.4271 / 2016-01-0716. 10.Dahnz,C.,Han,K.,Spicher,U.etal.,“Investigations on Pre-Ignition in Highly Supercharged SI Engines”、SAE Int.J.Engines 3(1):214-224,2010,doi:10.4271 / 2010-01-0355. 11.Takeuchi,K.,Fujimoto,K.,Hirano,S.,and Yamashita,M.,“Investigation of Engine Oil Effect on Abnormal Combustion in Turbocharged Direct Injection-Spark Ignition Engines”、SAE Int.J.Fuels Lubr.5(3):1017-1024,2012,doi:10.4271 / 2012-01-1615. 12.Kocsis,M.,Briggs,T.,and Anderson,G.,“The Impact of Lubricant Volatility,Viscosity and Detergent Chemistry on Low Speed Pre-Ignition Behavior”、SAE Int.J.Engines 10(3):2017,doi:10.4271 / 2017-01-0685. 13.Michlberger,A.,Sutton,M., and Dohner,B.,“Low Speed Pre-Ignition(LSPI) Durability-A Study of LSPI in Fresh and Aged Engine Oils”、SAE Technical Paper 2018-01-0934,2018,doi:10.4271 / 2018-01-0934. 14.Hirano,S.,Yamashita,M.,Fujimoto,K.,and Kato,K.,“Investigation of Engine Oil Effect on Abnormal Combustion in Turbocharged Direct Injection-Spark Ignition Engines (Part2)”、SAE Technical Paper 2013-01-2569,2013,doi:10.4271 / 2013-01-2569. 15.Andrews,A.,Burns,R.,Dougherty,R.,Deckman,D.et al., “Investigation of Engine Oil Base Stock Effects on Low Speed Pre-Ignition in a Turbocharged Direct Injection SI Engine”、SAE Int. J.Fuels Lubr.9(2):2016,doi:10.4271 / 2016-01-9071.

Claims

1. 1. A method for improving fuel economy, comprising lubricating an internal combustion engine with a lubricating oil; The lubricating oil a. (a) a blend of base oils having at least 25 wt.% renewable base oils, including a saturated hydrocarbon blend; The saturated hydrocarbon mixture i. the percentage of molecules with even carbon numbers is ≥ 80% by FIMS; ii. BP / BI≧−0.6037 (internal alkyl branches per molecule)+2.0; iii. A mixture of said base oils, wherein there are an average of 0.3 to 1.55+ methyls per molecule; b. i. a dispersant; ii. a detergent; iii. an inhibitor; iv. a friction modifier; v. a pour point depressant; vi. a viscosity modifier; and at least one additive selected from the group consisting of

2. 10. The method of claim 1, wherein the lubricating oil composition comprises from 5 to 30 wt. % of the total additive concentrate and from 70 to 95 wt. % of the base oil blend.

3. 10. The method of claim 1, wherein the composition has a lubricating high temperature high shear viscosity of less than 2.3 cP based on ASTM D5481.

4. 10. The method of claim 1, wherein the composition has a lubricating kinematic viscosity at 100°C of 7.1 cSt or less based on ASTM D445.

5. 10. The method of claim 1, wherein the composition has a lubricating low temperature cold cranking viscosity at −35° C. of 6200 mPa.s or less based on ASTM D5293.

6. 10. The method of claim 1, wherein the lubricating composition has a lubricating SAE viscosity grade of 0W to 12 or less, based on SAE J300.

7. 10. The method of claim 1, wherein the fuel economy is improved by at least 0.3%.

8. 1. A method for improving fuel economy retention, comprising lubricating an internal combustion engine with a lubricating oil; The lubricating oil a. a base oil blend having at least 25 wt.% renewable base oils, comprising a saturated hydrocarbon blend; The saturated hydrocarbon mixture i. the percentage of molecules with even carbon numbers is ≥ 80% by FIMS; ii. BP / BI≧−0.6037 (internal alkyl branches per molecule)+2.0; iii. the base oil mixture, wherein an average of 0.3 to 1.5 5+ methyls are present per molecule; b. i. a dispersant; ii. a detergent; iii. an inhibitor; iv. a friction modifier; v. a pour point depressant; vi. a viscosity modifier; and at least one additive selected from the group consisting of The method wherein the lubricating oil composition comprises 5 to 30 weight percent of the total additive concentrate and 70 to 95 weight percent of the base oil blend.

9. 8. The method of claim 7, wherein the composition has a lubricating high temperature high shear viscosity of less than 2.3 cP based on ASTM D5481.

10. 8. The method of claim 7, wherein the composition has a lubricating kinematic viscosity at 100°C of 7.1 cSt or less based on ASTM D445.

11. 8. The method of claim 7, wherein the composition has a lubricating low temperature cold cranking viscosity at -35°C of 6200 mPas or less based on ASTM D5293.

12. 8. The method of claim 7, wherein the composition has a lubricant SAE viscosity grade of 0W to 12 or less, based on SAE J300.

13. 8. The method of claim 7, wherein the fuel economy loss for a typical exhaust interval is less than 0.5%.

14. 8. The method of claim 7, wherein the fuel economy loss for the extended drain interval is less than 0.4%.

15. 8. The method of claim 7, wherein the average fuel economy loss is less than 0.5% over the life of the lubricant.

16. 8. The method of claim 7, wherein there is improved fuel economy retention and retention of low speed pre-ignition protection in an internal combustion engine operating in high temperature conditions where the lubricating oil is exposed to such conditions for extended periods of time.

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