WO2021028877A1 - Procédé pour améliorer les performances d'un moteur avec des compositions lubrifiantes renouvelables - Google Patents

Procédé pour améliorer les performances d'un moteur avec des compositions lubrifiantes renouvelables Download PDF

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Publication number
WO2021028877A1
WO2021028877A1 PCT/IB2020/057665 IB2020057665W WO2021028877A1 WO 2021028877 A1 WO2021028877 A1 WO 2021028877A1 IB 2020057665 W IB2020057665 W IB 2020057665W WO 2021028877 A1 WO2021028877 A1 WO 2021028877A1
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Prior art keywords
lubricant
viscosity
fuel economy
oil
lubricating
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PCT/IB2020/057665
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English (en)
Inventor
Willem Van Dam
Mihir K. Patel
David S. Lee
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Chevron U.S.A. Inc.
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Priority to CN202080062788.2A priority Critical patent/CN114423848A/zh
Priority to EP20760559.3A priority patent/EP4013839A1/fr
Priority to JP2022508799A priority patent/JP2022544282A/ja
Priority to KR1020227007627A priority patent/KR20220047299A/ko
Priority to CA3150741A priority patent/CA3150741A1/fr
Publication of WO2021028877A1 publication Critical patent/WO2021028877A1/fr
Priority to ZA2022/02382A priority patent/ZA202202382B/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/04—Well-defined hydrocarbons aliphatic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/02—Specified values of viscosity or viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/04—Specified molecular weight or molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/022—Well-defined aliphatic compounds saturated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/011—Cloud point
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/015—Distillation range
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/065—Saturated Compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/071—Branched chain compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/085—Non-volatile compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/72—Extended drain
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/74—Noack Volatility
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/02—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • Base stocks are commonly used to produce various lubricants, including lubricating oils for internal combustion engines, turbines, compressors, hydraulic systems, etc. They are also used as process oils, white oils, and heat transfer fluids. Finished lubricants generally consist of two components, base oils and additives. Base oil, which could be one or a mixture of base stocks, is the major constituent in these finished lubricants and contributes significantly to their performances, such as viscosity and viscosity index, volatility, stability, and low temperature performance. In general, a few base stocks are used to manufacture a wide variety of finished lubricants by varying the mixtures of individual base stocks and individual additives.
  • a method of improving engine fuel efficiency with a lubricant composition containing fatty acid esters is set forth in U.S. 9,885,004.
  • the American Petroleum Institute categorizes base stocks in five groups based on their saturated hydrocarbon content, sulfur level, and viscosity index (Table 1 below).
  • Group I, II, and III base stocks are mostly derived from crude oil via extensive processing, such as solvent refining for Group I, and hydroprocessing for Group II and Group III.
  • Certain Group III base stocks can also be produced from synthetic hydrocarbon liquids via a Gas-to-Liquids process (GTL), and are obtained from natural gas, coal or other fossil resources.
  • GTL Gas-to-Liquids process
  • Group IV base stocks the polyalphaolefins (PAO) are produced by oligomerization of alpha olefins, such as 1-decene.
  • Group V base stocks include everything that does not belong to Groups I - IV, such as naphthenic base stocks, polyalkylene glycols (PAG), and esters. Most of the feedstocks for large-scale base stock manufacturing are non renewable.
  • Automotive engine oils are by far the largest market for base stocks.
  • the automotive industry has been placing more stringent performance specifications on engine oils due to requirements for lower emissions, long drain intervals, and better fuel economy.
  • automotive OEMs original equipment manufacturer
  • Base Oils with a lower Noack Volatility in an engine oil allows the formulation to retain the designed viscosity for longer operation time allowing for increased fuel economy retention and longer drain intervals discussed in US6300291.
  • Group I and Group ITs usage in engine oils with viscosity grade below 0W-20 engine oils is highly limited because formulations blended with them cannot meet the performance specifications for lower than 0W-20 engine oils, leading to increased demands for Group III and Group IV base stocks.
  • Group III base stocks are mostly manufactured from vacuum gas oils (VGOs) through hydrocracking and catalytic dewaxing (e.g. hydroisomerization).
  • Group III base stocks can also be manufactured by catalytic dewaxing of slack waxes originating from solvent refining, or by catalytic dewaxing of waxes originating from Fischer-Tropsch synthesis from natural gas or coal based raw materials also known as Gas to Liquids base oils (GTL).
  • Group III base stocks from VGOs is discussed in U.S. Patent Nos. 5,993,644 and 6,974,535. Their boiling point distributions are typically higher when compared to PAOs of the same viscosity, causing them to have higher volatility than PAOs. Additionally, Group III base stocks typically have higher cold crank viscosity (i.e., dynamic viscosity according to ASTM D5293, CCS) than Group IV base stocks at equivalent viscosities.
  • GTL base stock processing is described in U.S. Patent Nos. 6,420,618 and 7,282,134, as well as U.S. Patent Application Publication 2008/0156697.
  • the latter publication describes a process for preparing base stocks from a Fischer-Tropsch synthesis product, the fractions of which with proper boiling ranges are subjected to hydroisomerization to produce GTL base stocks.
  • GTL base stocks Such structures and properties of GTL base stocks are described, for example, in U.S. Patent Nos. 6,090,989 and 7,083,713, as well as U.S. Patent Application Publication 2005/0077208.
  • lubricant base stocks with optimized branching are described, which have alkyl branches concentrated toward the center of the molecules to improve the base stocks’ cold flow properties. Nevertheless, pour points for GTL base stocks are typically worse than PAO or other synthetic hydrocarbon base stocks.
  • GTL base stocks are severely limited commercial supply, a result of the prohibitively large capital requirements for a new GTL manufacturing facility. Access to low cost natural gas is also required to profitably produce GTL base stocks. Furthermore, as GTL base stocks are typically distilled from an isomerized oil with a wide boiling point distribution, the process results in a relatively low yield to the base stock with a desired viscosity when compared to that of a typical PAO process. Due to these monetary and yield constraints there is currently only a single manufacturing plant of group III+ GTL base stocks, exposing formulations that use GTL to supply chain and price fluctuation risks.
  • Polyalphaolefms are produced by the polymerization of alphaolefms in the presence of a Friedel Crafts catalyst such as A1C13, BF3, or BF3 complexes.
  • a Friedel Crafts catalyst such as A1C13, BF3, or BF3 complexes.
  • 1-octene, 1-decene, and 1-dodecene have been used to manufacture PAOs that have a wide range of viscosities, varying from low molecular weight and low viscosity of about 2 cSt at 100°C, to high molecular weight, viscous materials with viscosities exceeding 100 cSt at 100°C.
  • the polymerization reaction is typically conducted in the absence of hydrogen; the lubricant range products are thereafter polished or hydrogenated to reduce the residual unsaturation.
  • Processes to produce 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 2014/0323665.
  • a lubricant composition having properties within commercially acceptable ranges, for example, for use in automotive and other applications, with such properties including one or more of viscosity, Noack volatility, and low temperature cold-cranking viscosity. Furthermore, there remains a need for lubricant compositions having improved properties and methods of manufacture thereof, where the base stock compositions have reduced amounts of 1-decene incorporated therein, and may even preferably eliminate the use of 1-decene in the manufacture thereof.
  • Group III hydrocarbon base stocks (US9862906B2) of renewable and biological origin have been used in applications such as refrigeration compressor lubricants, hydraulic oils and metal working fluids, and more recently in automotive and industrial lubricants (US20170240832A1).
  • Common biological sources for hydrocarbons are natural oils, which can be derived from plant sources such as canola oil, castor oil, sunflower seed oil, rapeseed oil, peanut oil, soy bean oil, and tall oil, or palm oil.
  • Other commercial sources of hydrocarbons include engineered microorganisms such as Algae or Yeast.
  • hydrocarbon mixtures Due to increasing demand for high performing lubricant base stocks there is a continuing need for improved hydrocarbon mixtures.
  • the industry requires these hydrocarbon mixtures to have superior Noack Volatility, and low temperature viscometric properties that can meet stricter engine oil requirements, preferably from renewable sources.
  • LSPI Low Speed Pre-ignition
  • the present invention relates to a method of improving engine performance by supplying an internal combustion engine with a lubricant composition, containing a saturated hydrocarbon mixture and lubricant additive with well-controlled structural characteristics that address the performance requirements driven by the stricter environmental and fuel economy regulations for automotive engine oils.
  • the branching characteristics of the hydrocarbon molecules of the base oil portion are controlled to consistently provide a composition that has a surprising CCS viscosity at -35°C (ASTM D5329) and Noack volatility (ASTM D5800) relationship.
  • An embodiment of the invention is a method where supplying the lubricant composition to an internal combustion engine and operation of the engine at elevated operating temperatures results in a Fuel Economy Improvement (FEI) that is at least 0.3% better than for a conventional lubricant of equal viscosity. In a preferred embodiment the FEI is at least 0.5% better than for a conventional lubricant of equal viscosity.
  • FEI Fuel Economy Improvement
  • a further embodiment of the invention is a method where supplying the lubricant composition to an internal combustion engine and operation of the engine over an extended period of time results in a Fuel Economy Retention (FER) benefit that is at least 0.5% better than for a conventional lubricant of equal viscosity.
  • FER Fuel Economy Retention
  • the FER is at least 1.0% better than for a conventional lubricant of equal viscosity.
  • a further embodiment is a method where supplying the lubricant composition to an internal combustion engine and operation of the engine at elevated operating temperature over an extended period of time results in an LSPI Prevention Retention benefit by limiting the additive metal concentration increase.
  • the Calcium concentration increase is limited to no more than 15%.
  • An important aspect of the present invention relates to a lubricant composition possessing a renewable base oil with a saturated hydrocarbon mixture having greater than 80% of the molecules with an even carbon number according to FIMS, with the mixture exhibiting a branching characteristic of BP/BI > -0.6037 (Internal alkyl branching per molecule) + 2.0, and when the hydrocarbon mixture is analyzed by carbon NMR as a whole, has on average at least 0.3 to 1.5 5+ methyl branches per molecule.
  • One way to synthesize the hydrocarbon mixture disclosed herein is through oligomerization of C14 -C20 alpha or internal -olefins, followed by hydroisomerization of the oligomers.
  • C14 -C20 olefins would ease the demand for high-price 1-decene and other crude oil or synthetic gas based olefins as feedstocks, and making available alternate sources of olefin feedstocks such as those derived from C14 - C20 alcohols.
  • the hydrocarbon compositions are derived from one or more olefin co-monomers, where said olefin comonomers 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 and additive solubility properties.
  • FIG. 1 illustrates the relationship between BP/BI and Internal Alkyl Branches per Molecule for various hydrocarbons, including low-viscosity PAO manufactured from 1- decene and 1-dodecene, GTL base oils, and hydroisomerized hexadecene oligomers.
  • FIG. 2 illustrates the relationship between BP/BI and 5+ Methyl Branches per Molecule for various hydrocarbons, including low-viscosity PAO manufactured from 1- decene and 1-dodecene, GTL base oils, and hydroisomerized hexadecene oligomers. It demonstrates that the 5+ Methyl Branches per Molecules for the hydrocarbon mixtures disclosed in this patent fall in a unique range of 0.3 - 1.5.
  • FIG. 3 illustrates the relationship between NOACK volatility and CCS at -35°C for various hydrocarbons, including low-viscosity PAO manufactured from 1-decene and 1- dodecene, GTL base oils, Group III base oils, and hydroisomerized hexadecene oligomers.
  • FIG. 4 is an enlarged view of FIG. 3 in the range of 800 - 2,800 cP of CCS at -35°C.
  • FIG. 5 is a graph of the fuel economy benefit as measured in a modified sequence VIF test using three different lubricant compositions.
  • FIG. 6 is a graph of the calcium content of three different oils as measured in an extended duration test.
  • the lubricant compositions contain a renewable base oil stock containing a saturated hydrocarbon mixture having a unique branching structure as characterized by NMR that makes it suitable to be used as a high-quality synthetic base stock and a lubricant additive.
  • the hydrocarbon mixture has outstanding properties including extremely low volatility, good low-temperature properties, etc., which are important performance attributes of high-quality base stocks.
  • the mixture comprises greater than 80% of the molecules with an even carbon number according to FIMS.
  • the branching characteristics of the hydrocarbon mixture by NMR comprises a BP/BI in the range > -0.6037 (Internal alkyl branching per molecule) + 2.0. Moreover, on average, at least 0.3 to 1.5 of the internal methyl branches are located more than four carbons away from the end carbon.
  • a saturated hydrocarbon with this unique branching structure exhibits a surprising cold crank simulated viscosity (CCS) vs. Noack volatility relationship that is beneficial for blending low-viscosity automotive engine oils.
  • the hydrocarbon mixtures described herein are the product of oligomerization of olefins and a subsequent hydroisomerization.
  • C14 to C20 olefins are oligomerized to form an oligomer distribution consisting of unreacted monomer, dimers (C28-C40), and trimers and higher oligomers (>C42).
  • the unreacted monomers are distilled off for possible re-use in a subsequent oligomerization.
  • the remaining oligomers are then hydroisomerized to achieve the final branching structures described herein which consistently impart a surprising cold crank simulated viscosity (CCS) vs. Noack volatility relationship.
  • CCS cold crank simulated viscosity
  • Renewable as used herein means any biologically derived composition, including fatty alcohols, olefins, or oligomers. Such compositions may be made, for nonlimiting example, from biological organisms designed to manufacture specific oils, as discussed in WO 2012/141784, but do not include petroleum distilled or processed oils such as, for non- limiting example, mineral oils.
  • a suitable method to assess materials derived from renewable resources is through "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis" (ASTM D6866-12 or ASTM D6866-11). Counts from 14C in a sample can be compared directly or through secondary standards to SRM 4990C.
  • a measurement of 0% 14C relative to the appropriate standard indicates carbon originating entirely from fossils (e.g., petroleum based).
  • a measurement of 100% 14C indicates carbon originating entirely from modem sources (See, e.g., WO 2012/141784, incorporated herein by reference).
  • Viscosity is the physical property that measures the fluidity of the base stock.
  • Viscosity is a strong function of temperature. Two commonly used viscosity measurements are dynamic viscosity and kinematic viscosity. Dynamic viscosity measures the fluid’s internal resistance to flow. Cold cranking simulator (CCS) viscosity at -35°C for engine oil is an example of dynamic viscosity measurements.
  • the SI unit of dynamic viscosity is Pa-s. The traditional unit used is centipoise (cP), which is equal to 0.001 Pa-s (or 1 m Pa-s). The industry is slowly moving to SI units.
  • Kinematic viscosity is the ratio of dynamic viscosity to density. The SI unit of kinematic viscosity is mm2/s.
  • Viscosity Grade refers to the lubricant composition containing a renewable base oil formulated to meet the definition of an SAE XW-YY lubricant (where X can be 0 or 5, and YY can be 4, 8, 12, 16, or 20). The properties for the various Viscosity Grades are further defined in the SAE J300 Industry Standard
  • Viscosity Index is an empirical number used to measure the change in the base stock’s kinematic viscosity as a function of temperature. The higher the VI, the less relative change is in viscosity with temperature. High VI base stocks are desired for most of the lubricant applications, especially in multigrade automotive engine oils and other automotive lubricants subject to large operating temperature variations. ASTM D2270 is a commonly accepted method to determine VI.
  • Pour point is the lowest temperature at which movement of the test specimen is observed. It is one of the most important properties for base stocks as most lubricants are designed to operate in the liquid phase. Low pour point is usually desirable, especially in cold weather lubrication. ASTM D97 is the standard manual method to measure pour point.
  • ASTM D5950 It is being gradually replaced by automatic methods, such as ASTM D5950 and ASTM D6749.
  • ASTM D5950 with 1°C testing interval is used for pour point measurement for the examples in this patent.
  • Volatility is a measurement of oil loss from evaporation at an elevated temperature. It has become a very important specification due to emission and operating life concerns, especially for lighter grade base stocks. Volatility is dependent on the oil’s molecular composition, especially at the front end of the boiling point curve.
  • Noack ASTM D5800
  • Noack test method is a commonly accepted method to measure volatility for automotive lubricants. The Noack test method itself simulates evaporative loss in high temperature service, such as an operating internal combustion engine.
  • Fuel Economy Improvement the reduction in fuel consumption for an engine running on the candidate oil relative to that observed with the same engine running at the same test conditions on a reference oil.
  • Fuel Economy Retention the capability of a lubricant to maintain its level of fuel consumption over a period of time where that lubricant is exposed to aging conditions in an internal combustion engine. Fuel economy Retention can also be expressed as the capability of a lubricant to retain its fuel economy improvement over a period of time where the lubricant is exposed to aging conditions in an internal combustion engine. Fuel economy Retention can also be expressed as a lack of fuel economy loss over a period of time where the lubricant is exposed to aging conditions in an internal combustion engine.
  • Boiling point distribution is the boiling point range that is defined by the True Boiling Points (TBP) at which 5% and 95% materials evaporates. It is measured by ASTM D2887 herein.
  • Branching Index the percentage of methyl hydrogens appearing in the chemical shift range of 0.5 to 1.05 ppm among all hydrogens appearing in the 1H NMR chemical range 0.5 to 2.1 ppm in an isoparaffinic hydrocarbon.
  • Branching Proximity the percentage of recurring methylene carbons which are four or more number of carbon atoms removed from an end group or branch appearing at 13C NMR chemical shift 29.8 ppm.
  • Internal Alkyl Carbons is the number of methyl, ethyl, or propyl carbons which are three or more carbons removed from end methyl carbons, that includes 3 -methyl, 4-methyl,
  • Methyl Carbons is the number of methyl carbons attached to a methine carbon which is more than four carbons away from an end carbon appearing at 13C NMR chemical shift 19.6 ppm in an average isoparaffinic molecule.
  • the NMR spectra were acquired using Bruker AVANCE 500 spectrometer using a 5 mm BBI probe. Each sample was mixed 1: 1 (wt:wt) with CDC13. The 1H NMR was recorded at 500.11 MHz and using a 9.0 ps (30o) pulse applied at 4 s intervals with 64 scans co-added for each spectrum. The 13C NMR was recorded at 125.75 MHz using a 7.0 ps pulse and with inverse gated decoupling, applied at 6 sec intervals with 4096 scans co-added for 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.
  • the branching properties of the lubricant base stock samples of the present invention are determined according to the following six-step process. Procedure is provided in detail in US 20050077208 Al, which is incorporated herein in its entirety. The following procedure is slightly modified to characterize the current set of samples:
  • FIMS Analysis The hydrocarbon distribution of the current invention is determined by FIMS (field ionization mass spectroscopy).
  • FIMS spectra were obtained on a Waters GCT-TOF mass spectrometer. The samples were introduced via a solid probe, which was heated from about 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 generate one averaged spectrum which provides carbon number distribution of paraffins and cycloparaffms containing up to six rings.
  • the structure of the hydrocarbon mixtures disclosed herein are characterized by FIMS and NMR. FIMS analysis demonstrate that more than 80% of the molecules in the hydrocarbon mixtures have an even carbon number.
  • the unique branching structure of the hydrocarbon mixtures disclosed herein are characterized by NMR parameters, such as BP, BI, internal alkyl branching, and 5+ methyls.
  • BP/BI of the hydrocarbon mixtures are in the range of > -0.6037 (Internal alkyl branching per molecule) + 2.0.
  • the 5+ methyls of the hydrocarbon mixtures average from 0.3 to 1.5 per molecule.
  • the hydrocarbon mixture can be classified into two carbon ranges based on the carbon number distribution, C28 to C40 carbons, and greater than or equal to C42.
  • each hydrocarbon mixture has carbon numbers within the specified range.
  • Representative molecular structures for the C28 to C40 range can be proposed based on the NMR and FIMS analysis. Without wishing to be bound to any one particular theory, it is believed that the structures made by oligomerization and hydroisomerization of olefins has methyl, ethyl, butyl branches distributed throughout the structure and the branch index and branch proximity contribute to the surprisingly good low temperature properties of the product.
  • Exemplary structures in the present hydrocarbon mixture are as follows:
  • the unique branching structure and narrow carbon distribution of the hydrocarbon mixtures makes them suitable to be used as high-quality synthetic base oils, especially for low-viscosity engine oil applications.
  • the hydrocarbon mixtures exhibit:
  • the Noack and CCS relationship for the hydrocarbon mixtures are shown in Figures 3 and 4.
  • Hydrocarbon mixtures that are closer to the origin in figure 3 and 4 have been found more advantageous for low viscosity engine oils due to the low volatility and decreased viscosity at -35 °C.
  • a hydrocarbon mixture in accordance with the present invention with carbon numbers in the range of C28 to C40, and in another embodiment carbon numbers in the range of from C28 to C36, or in another embodiment molecules with a carbon number of C32, will generally exhibit the following characteristics in addition to the characteristics of BP/BI, Internal alkyl branches per molecule, 5+ methyl branches per molecule, and Noack/CCS relationship described above:
  • the KV100 for the C28 - C40 hydrocarbon mixture ranges from 3.2 to 5.5 cSt; in another embodiment the KV100 ranges from 4.0 to 5.2 cSt; and from 4.1 to 4.5 c St in another embodiment.
  • the VI for the C28-C40 hydrocarbon mixture ranges from 125 to 155 in one embodiment and from 135 to 145 in another embodiment.
  • the Pour Point of the hydrocarbon mixture in one embodiment ranges from 25 to - 55°C and from 35 to -45°C in another embodiment.
  • the boiling point range of the C28-C40 hydrocarbon mixture in one embodiment is no greater than 125°C (TBP at 95% - TBP at 5%) as measured by ASTM D2887; no greater than 100°C in another embodiment; no greater than 75°C in one embodiment; no greater than 50°C in another embodiment; and no greater than 30°C in one embodiment.
  • those with a boiling point range no greater than 50 °C, and even more preferably no greater than 30°C give a surprisingly low Noack Volatility (ASTM D5800) for a given KV100.
  • the C28 - C40 hydrocarbon mixture in one embodiment has a Branching Proximity (BP) in the range of 14-30 with a Branching Index (BI) in the range of 15 - 25; and in another embodiment a BP in the range of 15 - 28 and a BI in the range of 16 - 24.
  • BP Branching Proximity
  • BI Branching Index
  • the Noack volatility (ASTM D5800) of the C28 - C40 hydrocarbon mixture is 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.% in one embodiment and less than 7 wt.% in one embodiment.
  • the C28 - C40 hydrocarbon mixture in one embodiment also has a CCS viscosity at -35°C of less than 2700 cP; of less than 2000 cP in another embodiment; of less than 1700 cP in one embodiment; and less than 1500 cP in one embodiment.
  • the hydrocarbon mixture with the carbon number range of C42 and greater will generally exhibit the following characteristics, in addition to the characteristics of BP/BI, internal alkyl branches per molecule, 5+ methyl branches per molecule, and Noack and CCS at -35°C relationship described above:
  • the hydrocarbon mixture comprising C42 carbons or greater in one embodiment has a KV100 in the range of 8.0 to 10.0 cSt, and in another embodiment from 8.5 to 9.5 cSt.
  • the VI of the hydrocarbon mixture having > 42 carbons is 140 - 170 in one embodiment; and, from 150 - 160 in another embodiment.
  • the pour point in one embodiment ranges from -15 to -50°C; and, from -20 to -40°C in another embodiment.
  • the hydrocarbon mixture comprising > 42 carbons has a BP in the range of 18 - 28 with a BI in the range of 17 - 23. In another embodiment, the hydrocarbon mixture has a BP in the range of 18 - 28 and a BI in the range of 17 - 23.
  • novel hydrocarbon mixtures disclosed herein can be synthesized via olefin oligomerization to achieve the desired carbon chain length, followed by hydroisomerization to improve their cold-flow properties, such as pour point and CCS, etc.
  • olefins of C 14 to C20 in length are oligomerized using an acid catalyst to form an oligomer mixture.
  • the olefins can be sourced from natural occurring molecules, such as crude oil or gas based olefins, or from ethylene polymerizations. In some variations, about 100% of the carbon atoms in the olefin feedstocks described herein may originate from renewable carbon sources.
  • an alpha-olefin co-monomer may be produced by oligomerization of ethylene derived from dehydration of ethanol produced from a renewable carbon source.
  • an alpha-olefin co-monomer may be produced by dehydration of a primary alcohol other than ethanol that is produced from a renewable carbon source. Said renewable alcohols can be dehydrated into olefins, using gamma alumina or sulfuric acid.
  • modified or partially hydrogenated terpene feedstocks derived from renewable resources are coupled with one or more olefins that are derived from renewable resources.
  • an olefin monomer between C14 to C20 is oligomerized in the presence of BF3 and/or BF3 promoted with a mixture of an alcohol and/or an ester, such as a linear alcohol and an alkyl acetate ester, using a continuously stirred tank reactor (CSTR) with an average residence time of 60 to 400 minutes.
  • CSTR continuously stirred tank reactor
  • the C 14 to C20 olefin monomers are oligomerized in the presence of BF3 and/or promoted BF3 using a continuously stirred tank reactor with an average residence time of 90 to 300 minutes.
  • the C14 to C20 the olefin monomers are oligomerized in the presence of BF3 and/or promoted BF3 using a continuously stirred tank reactor with an average residence time of 120 to 240 minutes.
  • the temperature of the oligomerization reaction may be in a range of from 10 °C to 90 °C. However, in one preferred embodiment, the temperature is maintained in the range of from 15 to 75 °C, and most preferably 20 °C to 40 °C, for the duration of the reaction.
  • Suitable Lewis acids catalysts for the oligomerization process include metalloid halides and metal halides typically used as Friedel-Crafts catalysts, e.g., AlCb, BF3, BF3 complexes, BCb, AlBr 3 , TiCb, TiCL. SnCL. and SbCh. Any of the metalloid halide or metal halide catalysts can be used with or without a co-catalyst protic promoter (e.g., water, alcohol, acid, or ester).
  • a co-catalyst protic promoter e.g., water, alcohol, acid, or ester.
  • 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, hydroxide or free metal forms of Group VIII metals, and any combination thereof.
  • BP branching proximity
  • the unsaturated oligomer product is distilled to remove the unreacted monomer.
  • the unreacted monomer may be separated from the oligomer product, such as via distillation, and can be recycled back into the mixture of the first and/or second feedstocks for oligomerization thereof.
  • the oligomer product is then hydroisomerized to provide the additional internal alkyl branches required to achieve the ideal branching characteristics.
  • the whole oligomer product including both the dimers (C28 - C40) and heavier oligomers (>C42), are hydroisomerized prior to separation by distillation.
  • the hydroisomerized product is then separated into the final hydrocarbon products by distillation.
  • the dimers and heavier oligomers are fractionated and hydroisomerized separately.
  • Hydroisomerization catalysts useful in the present invention usually comprises a shape-selective molecular sieve, a metal or metal mixture that is catalytically active for hydrogenation, and a refractory oxide support.
  • Typical catalytically active hydrogenation metals include chromium, molybdenum, nickel, vanadium, cobalt, tungsten, zinc, platinum, and palladium. Platinum and palladium are especially preferred, with platinum mostly preferred. If platinum and/or palladium is used, the metal content is typically in the range of 0.1 to 5 weight percent of the total catalyst, usually from 0.1 to 2 weight percent, and not to exceed 10 weight percent.
  • Hydroisomerization catalysts are discussed, for example, in U.S. Patent Nos. 7,390,763 and 9,616,419, as well as U.S. Patent Application Publications 2011/0192766 and 2017/0183583.
  • the conditions for hydroisomerization are tailored to achieve an isomerized hydrocarbon mixture with specific branching properties, as described above, and thus will depend on the characteristics of feed used.
  • the reaction temperature is generally between about 200°C and 400°C, preferably between 260°C to 370°C, most preferably between 288°C to 345°C, at a liquid hourly space velocity (LHSV) generally between about 0.5 hr 1 and about 20 hr 1 .
  • the pressure is typically from about 15 psig to about 2500 psig, preferably from about 50 psig to about 2000 psig, more preferably from about 100 psig to about 1500 psig. Low pressure provides enhanced isomerization selectivity, which results in more isomerization and less cracking of the feed, thus leading to an increased yield.
  • Hydrogen is present in the reaction zone during the hydroisomerization process, typically in a hydrogen to feed ratio from about 0.1 to 10 MSCF/bbl (thousand standard cubic feet per barrel), preferably from about 0.3 to about 5 MSCF/bbl. Hydrogen may be separated from the product and recycled to the reaction zone.
  • an additional step of hydrogenation is added before the hydroisomerization to protect the downstream hydroisomerization catalyst.
  • an additional step of hydrogenation or hydrofmishing is added after the hydroisomerization to further improve the saturation and stability of the hydrocarbon mixture.
  • the hydroisomerized hydrocarbon mixtures are comprised of dimers having carbon numbers in the range of C28-C40, and a mixture of trimers+ having carbon numbers of C42 and greater.
  • Each of the hydrocarbon mixtures will exhibit a BP/BI in the range of > -0.6037 (internal alkyl branching) ⁇ 2.0 per molecule, and, on average, from 0.3 to 1.5 methyl branches on the fifth or greater position per molecule.
  • at least 80% of the molecules in each composition also have an even carbon number as determined by FIMS.
  • each of the hydrocarbon compositions will also exhibit a Noack and CCS at - 35 °C relationship such that the Noack is between 2750 (CCS at-35 °C) ( ° 8) ⁇ 2. These characteristics allow for the formulation of low-viscosity engine oils as well as many other high-performance lubricant products.
  • C16 olefins are used as the feed for the oligomerization reaction.
  • the hydroisomerized dimer product When using C16 olefins as the feed, the hydroisomerized dimer product generally exhibits a KV100 of 4.3 cSt with ⁇ 8% Noack loss and a CCS at -35°C of approximately 1,700 cP.
  • the extremely low Noack volatility is due to the high starting boiling point and narrow boiling point distribution when compared other 3.9 to 4.4 cSt synthetic base stocks. This makes it ideal for use in low viscosity engine oils with strict volatility requirements.
  • the excellent CCS and pour point characteristics are due to the branching characteristics discussed above.
  • the material has a pour point of ⁇ -40 °C. This is required to pass critical engine oil formulation requirements for 0W formulations, including Mini-Rotary Viscosity (ASTM D4684) and Scanning Brookfield Viscosity (ASTM D2983) specifications.
  • Finished Lubricant Formulations for Improving Engine Performance Herein is described the improvement of fuel economy, and the retention of fuel economy and LSPI prevention of ultra-low viscosity engine oils formulated using renewable base oils compared to conventional base oils.
  • Finished lubricant compositions containing renewable base oils as herein described not only provide reduced friction and consequently improved fuel economy when fresh, but also unexpectedly maintain reduced friction when aged compared to conventional base oils formulations. These benefits were leveraged into finished engine oil formulations to demonstrate the fuel economy improvement and fuel economy retention benefits using a modified Sequence VIF fuel economy engine test stand.
  • test results indicate that the use of renewable base oils in finished engine oil formulations provides an unexpected and significant fresh oil fuel economy improvement which cannot be explained from the viscometrics of the renewable-based lubricant.
  • the aged oil fuel economy is remarkably well retained compared to conventional base oil engine oil formulations, amounting to an unprecedented fuel economy improvement and retention over the lifetime of the lubricant in the engine.
  • Lubricant compositions containing the renewable base oil herein described can be employed in a variety of lubricant-related end uses, such as a lubricant oil or grease for a device or apparatus requiring lubrication of moving and/or interacting mechanical parts, components, or surfaces.
  • Useful apparatuses include engines and machines. More specific equipment includes, but is not limited to, gasoline fired engines, diesel fired engines, natural gas fired engines, gear boxes, wind turbines and circulating hydraulic pumps.
  • Lubricant compositions containing the base oil as herein described may be use in the formulation of automotive crank case lubricants, automotive gear oils, transmission oils, many industrial lubricants including circulation lubricant, industrial gear lubricants, grease, compressor oil, pump oils, refrigeration lubricants, hydraulic lubricants, metal working fluids.
  • a Sequence VIF engine test as described in the ASTM D8226 comprises a comparative fuel economy improvement (FEI) assessment of the fuel-saving capabilities of automotive engine oils under repeatable laboratory conditions for low-viscosity oils.
  • FEI fuel economy improvement
  • the test parameters are (1) The test duration is 196 hours, (2) Fuel consumption is measured for six speed/load/temperature test conditions for an SAE 20W-30 baseline (BL) lubricant to ensure consistent engine response, (3) The candidate lubricant is introduced and aged for 16 hours at aging conditions and then fuel consumption is measured for six test conditions for FEI 1, (4) The candidate lubricant is left in the engine and aged for 109 hours at aging conditions for FEI 2, (5) Fuel consumption for each of the six test conditions for BL is repeated at the end of the test to further ensure consistent engine response over the duration of the test. (5) FEI 1, FEI 2 and FEI Sum (FEI 1 plus FEI 2) are calculated from the comparisons of the fuel economy measurements for the candidate oil with the fuel economy measurements on the baseline lubricant (BL).
  • Fuel consumption is measured for six speed/load/temperature test conditions for an SAE 20W-30 baseline (BL) lubricant to ensure consistent engine response.
  • the candidate lubricant is introduced and aged for 16 hours at aging conditions and then fuel consumption is measured for six test conditions (Table 3). Fuel consumption for each of the six test conditions for BL is repeated at the end of the test to further ensure consistent engine response over the duration of the test.
  • the lubricant of this invention comprises renewable base oil used in the base oil mixture and further comprises one or more of the following additives: dispersant, inhibitors, antioxidants, detergents, friction modifiers, pour point depressants, viscosity modifiers and the like.
  • 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.%.
  • the fuel economy of an internal combustion engine is in part determined by the viscosity and by the frictional characteristics of the lubricant.
  • the frictional characteristics of a lubricant are determined by the additive chemistry in a sense that the surface -active additives such as detergents anti-wear additives and friction modifiers can form a solid, friction-altering surface layer on the metal surfaces in the lubricated contacts in the engine.
  • Base oils are not expected, by those skilled in the art, to play a role in altering the friction in an engine as long as the viscosity of the lubricants is not changed.
  • An embodiment of the invention describes a method to derive a fuel economy improvement from a lubricant that comprises a renewable base oil and has equal viscosity and the same additives as a comparative lubricant that does not contain any of the renewable base oil.
  • the fuel economy improvement when employing a lubricating oil composition comprising 90 wt.% of the renewable base oil and 10 wt.% of an additive combination that includes dispersants, detergents, inhibitors, friction modifier, and pour point depressant, is at least 0.3 %, preferably 0.5% better than for a conventional lubricant of equal viscosity that does not comprise a renewable base oil.
  • This invention describes a method to derive a fuel economy retention (FER) benefit from a lubricant that comprises a renewable base oil and has equal viscosity and the same additives as a comparative lubricant that does not contain any of the renewable base oil.
  • the fuel economy retention (FER) is evaluated after a period of aging representative of a typical shorter oil change interval. Separately, FER is evaluated after a period of aging representative of an extended oil change interval.
  • the fuel economy retention at conditions representative of a shorter oil change interval when employing a lubricating oil composition comprising 90 wt.% of the renewable base oil and 10 wt.% of an additive combination that includes dispersants, detergents, inhibitors, friction modifier, and pour point depressant, is at least 1.0% better, preferably 1.5% better than for a conventional lubricant of equal viscosity that does not comprise a renewable base oil.
  • the fuel economy retention at conditions representative of a shorter oil change interval when employing a lubricating oil composition comprising 45 wt.% of the renewable base oil, 45% nonrenewable base oil and 10 wt.% of an additive combination that includes dispersants, detergents, inhibitors, friction modifier, and pour point depressant, is at least 0.5 % better, preferably 1.0% than a conventional lubricant of equal viscosity that does not comprise a renewable base oil.
  • the fuel economy retention (FER) at conditions representative of an extended oil change interval when employing a lubricating oil composition comprising 90 wt.% of the renewable base oil and 10 wt.% of an additive combination that includes dispersants, detergents, inhibitors, friction modifier, and pour point depressant, is at least 1.0% better, preferably 1.5% better than for a conventional lubricant of equal viscosity that does not comprise a renewable base oil.
  • the fuel economy retention (FER) at conditions representative of an extended oil change interval, when employing a lubricating oil composition comprising 45 wt.% of the renewable base oil, 45% non-renewable base oil and 10 wt.% of an additive combination that includes dispersants, detergents, inhibitors, friction modifier, and pour point depressant, is at least 0.5 % better, preferably 1.0% better than for a conventional lubricant of equal viscosity that does not comprise a renewable base oil.
  • the fuel economy retention over a life of a lubricant when employing a lubricating oil composition comprising 45 wt.% of the renewable base oil, 45% nonrenewable base oil and 10 wt.% of an additive combination that includes dispersants, detergents, inhibitors, friction modifier, and pour point depressant, is at least 0.5 % better, preferably 1.0% better than a conventional lubricant of equal viscosity that does not comprise a renewable base oil.
  • Life of lubricant as described herein comprises the period from when the lubricant is put into the engine to the point where the condition of the lubricant has degraded to a level where engine damage may occur if the lubricant is not replenished.
  • the fuel economy retention over a life of a lubricant when employing a lubricating oil composition comprising 90 wt.% of the renewable base oil and 10 wt.% of an additive combination that includes dispersants, detergents, inhibitors, friction modifier, and pour point depressant, is at least 1.0% better, preferably 1.5% better than a conventional lubricant of equal viscosity that does not comprise a renewable base oil.
  • a further embodiment of the invention is a method of improving FER while retaining the low speed pre ignition (LSPI) prevention capability in the operation of an internal combustion engine over an extended period of time.
  • Lubricant formulations were aged by exposing them to the higher temperature in the GM High Feature 3.6L LY7 V6 engine attached to a dynamometer. Lubricant formulations were aged in 2 steps. In the aging stage 1, the lubricant formulation was subjected to 120°C for 16 hours. In the subsequent aging stage, lubricant formulation was subjected to 140°C for 288 hours. During the aging stages, the lubricant was sampled at every 25 hours for used oil analysis and chemical characterization to monitor changes in the lubricant additives during the test.
  • LSPI low speed pre ignition
  • Comparative Oils (Examples 1, 2 and 3) all demonstrated a significant increase in the calcium content as they aged in the engine.
  • the calcium content of Comparative Oils increased in the range of 20% to 76% at the end of the test.
  • the lubricant compositions of the invention, as described herein maintained a calcium concentration very close to the original value throughout the test duration.
  • Comparative Oils 1, 2 and 3 have shown a significant increase in the calcium content as these lubricants were exposed to higher temperature and extended duration aging. Based on the conclusion of previous studies and results shown in the table 9, we are predicting that all three Comparative Oils will show increasing LSPI occurrences with the aging. In contrast, the lubricant compositions as described herein will retain its LSPI prevention performance throughout the test.
  • a base stock prepared according to the methods described herein is blended with one or more additional base stocks, e.g., one or more commercially available PAOs, a Gas to Liquid (GTL) base stock, one or more mineral base stocks, a vegetable oil base stock, an algae-derived base stock, a second base stock as described herein, or any other type of renewable base stock. Any effective amount of additional base stock may be added to reach a blended base oil having desired properties.
  • additional base stocks e.g., one or more commercially available PAOs, a Gas to Liquid (GTL) base stock, one or more mineral base stocks, a vegetable oil base stock, an algae-derived base stock, a second base stock as described herein, or any other type of renewable base stock.
  • GTL Gas to Liquid
  • Any effective amount of additional base stock may be added to reach a blended base oil having desired properties.
  • blended base oils can comprise a ratio of a first base stock as described herein to a second base stock (e.g., a commercially available base oil PAO, a GTL base stock, one or more mineral base stocks, a vegetable oil base stock, an algae derived base stock, a second base stock as described herein) that is about is from about 1-99%, from about 1-80%, from about 1-70%, from about 1-60%, from about 1-50%, from about 1-40%, from about 1-30%, from about 1-20%, or from about 1-10%, based on the total weight of the composition may be made.
  • a second base stock e.g., a commercially available base oil PAO, a GTL base stock, one or more mineral base stocks, a vegetable oil base stock, an algae derived base stock, a second base stock as described herein
  • a ratio of a first base stock as described herein to a second base stock e.g., a commercially available base oil PAO, a GTL base stock, one or
  • lubricant compositions comprising a hydrocarbon mixture described herein.
  • the lubricant compositions comprise a base oil comprising at least a portion of a hydrocarbon mixture produced by any of the methods described herein, and one or more additives selected from the group of antioxidants, viscosity modifiers, pour point depressants, foam inhibitors, detergents, dispersants, dyes, markers, rust inhibitors or other corrosion inhibitors, emulsifiers, de-emulsifiers, antiwear agents, friction modifiers, thermal stability improvers, multifunctional additives (e.g., an additive that functions as both an antioxidant and a dispersant) or any combination thereof.
  • Lubricant compositions may comprise hydrocarbon mixtures described herein and any lubricant additive, combination of lubricant additives, or available additive package.
  • compositions described herein that are used as a base stock may be present at greater than about 1% based on the total weight of a finished lubricant composition.
  • amount of the base stock in the formulation is greater than about 2,
  • the amount of the base oil in the composition is from about 1-99%, from about 1-80%, from about 1-70%, from about 1-60%, from about 1-50%, from about 1-40%, from about 1-30%, from about 1-20%, or from about 1-10% based on the total weight of the composition.
  • the amount of base stock in formulations provided herein is about 1%, 5%, 7%, 10%, 13%, 15%, 20%, 30%, 40%, 5
  • types and amounts of lubricant additives are selected in combination with a base oil so that the finished lubricant composition meets certain industry standards or specifications for specific applications.
  • the concentration of each of the additives in the composition when used, may range from about 0.001 wt.% to about 20 wt.%, from about 0.01 wt.% to about 10 wt.%, from about 0.1 wt.% to about 5 wt.% or from about 0.1 wt.% to about 2.5 wt.%, based on the total weight of the composition.
  • the total amount of the additives in the composition may range from about 0.001 wt.% to about 50 wt.%, from about 0.01 wt.% to about 40 wt.%, from about 0.01 wt.% to about 30 wt.%, from about 0.01 wt.% to about 20 wt.%), from about 0.1 wt.% to about 10 wt.%, or from about 0.1 wt.% to about 5 wt.%, based on the total weight of the composition.0%, 60%, 70%, 80%, 90%, or 99% based on total weight of the formulation.
  • the base oils described herein are formulated in lubricant compositions for use as two cycle engine oils, as transmission oils, as hydraulic fluids, as compressor oils, as turbine oils and greases, as automotive engine oils, as gear oils, as marine lubricants, and as process oils.
  • Process oils applications include but are not limited to: rolling mill oils, coning oils, plasticizers, spindle oils, polymeric processing, release agents, coatings, adhesives, sealants, polish and wax blends, drawing oils, and stamping oils, rubber compounding, pharmaceutical process aids, personal care products, and inks.
  • the base oils described herein are formulated as industrial oil or grease formulations comprising at least one additive selected from antioxidants, anti-wear agents, extreme pressure agents, defoamants, detergent/dispersant, rust and corrosion inhibitors, thickeners, tackifiers, and demulsifiers. It is also contemplated that the base stocks of the 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, along with additives to improve pour point, increase stability and reduce oxidation rate.
  • Example 1 1-Hexadecene with less than 8% branched and internal olefins was oligomerized under BF3 with a co-catalyst composition of Butanol and Butyl Acetate. The reaction was held at 20 °C during semi-continuous addition of olefins and co-catalyst. The residence time was 90 minutes. The unreacted monomer was then distilled off, leaving behind less than 0.1% monomer distillation bottoms. A subsequent distillation was performed to separate the dimer from the trimer+ with less than 5% trimer remained in the dimer cut.
  • the dimers were then hydroisomerized with a noble-metal impregnated aluminoslicate of MRE structure type catalyst bound with alumina.
  • the reaction was carried out in a fixed bed reactor at 500 psig and 307°C. Cracked molecules were separated from the hydroisomerized C16 dimer using an online stripper.
  • Example 2 The oligomerization and subsequent distillation were performed identically to Example 1.
  • the dimers were then hydroisomerized with a noble-metal impregnated aluminoslicate of MRE structure type catalyst bound with alumina.
  • the reaction was carried out in a fix bed reactor at 500 psig and 313°C. Cracked molecules were separated from the hydroisomerized C16 dimers using an online stripper.
  • Example 2 The oligomerization and subsequent distillation were performed identically to Example 1.
  • the dimers were then hydroisomerized with a noble-metal impregnated aluminoslicate of MRE structure type catalyst bound with alumina.
  • the reaction was carried out in a fix bed reactor at 500 psig and 324 °C. Cracked molecules were separated from the hydroisomerized C16 dimers using an online stripper.
  • Example 2 The oligomerization and subsequent distillation were performed identically to Example 1.
  • the dimers were then hydroisomerized with a noble-metal impregnated aluminoslicate of MTT structure type catalyst bound with alumina.
  • the reaction was carried out in a fix bed reactor at 500 psig and 316 °C. Cracked molecules were separated from the hydroisomerized C16 dimers using an online stripper.
  • Example 2 The oligomerization and subsequent distillation were performed identically to Example 1.
  • the dimers were then hydroisomerized with a noble-metal impregnated aluminoslicate of MTT structure type catalyst bound with alumina.
  • the reaction was carried out in a fix bed reactor at 500 psig and 321 °C. Cracked molecules were separated from the hydroisomerized C16 dimers using an online stripper.
  • Example 2 The oligomerization and subsequent distillation were performed identically to Example 1.
  • the dimers were then hydroisomerized with a noble-metal impregnated aluminoslicate of MTT structure type catalyst bound with alumina.
  • the reaction was carried out in a fix bed reactor at 500 psig and 332 °C. Cracked molecules were separated from the hydroisomerized C16 dimers using an online stripper.
  • 1-Hexadecene with less than 8% branched and internal olefins was oligomerized under BF3 with a co-catalyst composition of Butanol and Butyl Acetate.
  • the reaction was held at 20 °C during semi-continuous addition of olefins and co-catalyst. The residence time was 90 minutes.
  • the unreacted monomer was then distilled off, leaving behind less than 0.1% monomer distillation bottoms. A subsequent distillation was performed to separate the dimer from the trimer and higher oligomers, the resulting dimer has less than 5% trimer.
  • trimer and higher oligomers (trimer+) cut was then hydroisomerized with a noble- metal impregnated aluminoslicate of MRE structure type catalyst bound with alumina.
  • the reaction was carried out in a fixed bed reactor at 500 psig and 313 °C. Cracked molecules were separated from the hydroisomerized C16 trimer+ using an online stripper.
  • Example 7 The oligomerization and subsequent distillations were performed identically to Example 7.
  • the trimer+ cut was then hydroisomerized with a noble-metal impregnated aluminoslicate of MRE structure type catalyst bound with alumina.
  • the reaction was carried out in a fix bed reactor at 500 psig and 318 °C. Cracked molecules were separated from the hydroisomerized C16 trimer+ using an online stripper.
  • Example 7 The oligomerization and subsequent distillations were performed identically to Example 7.
  • the trimer+ cut was then hydroisomerized with a noble-metal impregnated aluminoslicate of MRE structure type catalyst bound with alumina.
  • the reaction was carried out in a fix bed reactor at 500 psig and 324 °C. Cracked molecules were separated from the hydroisomerized C16 trimer+ using an online stripper.
  • Example 7 The oligomerization and subsequent distillations were performed identically to Example 7.
  • the trimer+ cut was then hydroisomerized with a noble-metal impregnated aluminoslicate of MTT structure type catalyst bound with alumina.
  • the reaction was carried out in a fix bed reactor at 500 psig and 321 °C. Cracked molecules were separated from the hydroisomerized C16 trimer+ using an online stripper.
  • Example 11 The oligomerization and subsequent distillations were performed identically to
  • Example 7 The trimer+ cut was then hydroisomerized with a noble-metal impregnated aluminoslicate of MTT structure type catalyst bound with alumina. The reaction was carried out in a fix bed reactor at 500 psig and 327 °C. Cracked molecules were separated from the hydroisomerized C16 trimer+ using an online stripper.
  • Example 12
  • Example 7 The oligomerization and subsequent distillations were performed identically to Example 7.
  • the trimer+ cut was then hydroisomerized with a noble-metal impregnated aluminoslicate of MTT structure type catalyst bound with alumina.
  • the reaction was carried out in a fix bed reactor at 500 psig and 332 °C. Cracked molecules were separated from the hydroisomerized C16 trimer+ using an online stripper.
  • Figure 1 illustrates the relationship between BP/BI and Internal Alkyl Branches per Molecule for the various hydrocarbon mixtures.
  • the straight line in the plot depicts the equation of BP/BI -0.6037 (Internal alkyl branching per molecule) + 2.0. All of the hydrocarbon mixtures of the present invention are above the line. While a few of the prior art hydrocarbon mixtures are also above the line, they do not meet other important characteristics of the present hydrocarbon mixtures, as shown in Figures 2 - 4.
  • Figure 2 illustrates the relationship between BP/BI and 5+ Methyl Branches per Molecule for the various hydrocarbon mixtures. It demonstrates that the 5+ Methyl Branches per Molecules for the present hydrocarbon mixtures fall in a unique range of 0.3 - 1.5. All of the prior art mixtures fall outside the range.
  • Figures 3 and 4 illustrate the relationship between NOACK volatility and CCS at -35 °C for the various hydrocarbon mixtures.
  • Figure 4 is an enlarged view of Figure 3 in the range of 800 - 2,800 cP of CCS at -35 °C.
  • a preferable base stock will fall as close as possible to the origin of Figures 3 and 4, as a lower Noack volatility for a given CCS viscosity at -35 °C is ideal for modem engine oil formulations such as 0W-20 through 0W-8 formulations.
  • TABLE 7 shows a comparison of three lubricant compositions; conventional capability, high volatility and lubricant compositions of the invention as described herein when used in a modified sequence VIF test for fuel economy improvement benefit.
  • the lubricant of the invention which contained 90 wt.% renewable base oil and 10 wt.% of an additive package containing dispersants, detergents, inhibitors, friction modifier, and pour point depressant, was blended to meet the viscosity grade definition of an SAE 0W- 8 lubricant.
  • the kinematic viscosity of the lubricant at 100°C was 5.47 cSt
  • the CCS Viscosity at -35 °C was 2400 cP
  • the Noack volatility was 7%.
  • a comparative lubricant 1 was made with 90% of an API Group IV base oil and 10 wt.% of the same additive package containing dispersants, detergents, inhibitors, friction modifier, and pour point depressant. This comparative lubricant was also blended to meet the viscosity grade definition of an SAE 0W-8 lubricant.
  • the kinematic viscosity of the comparative lubricant at 100°C was 4.82 cSt
  • the CCS Viscosity at -35 °C was 2000 cP
  • the Noack volatility was 10.8%.
  • a third oil used for comparative purposes was purchased as it is a commercially available lubricating oil.
  • This lubricant also met the viscosity grade definition of an SAE 0W-8 lubricant.
  • the kinematic viscosity of the third commercially available lubricant at 100°C was 5.31cSt, the CCS Viscosity at -35 °C was 1236 cP, and the Noack volatility was 30.8%.
  • a 5900 ml sample of the lubricant of the invention and the two comparative lubricants were added to a GM 3.6 L V-6 engine following a triple flushing procedure to eliminate all the remnants of the reference lubricant that is evaluated before and after each test on a candidate lubricant.
  • Fuel Economy Improvements (FEI) are expressed as a percentage increase or reduction in the amount of fuel consumed relative to the fuel consumed on the reference lubricant which is an SAE 20W-30 Viscosity Grade oil.
  • Table 7 points out that comparative lubricants of an SAE 0W-8 Viscosity Grade exhibit a fuel economy benefit based on their low viscosity, in the range of 2.5 to 3.0% Fuel Economy Improvement (FEI).
  • the 3.7% FEI that was found on the lubricant of the invention is a highly surprising result as it improves the FE by 1.2% relative to the Conventional Capability Comparative Example 1, which represents a best-in-class result using high quality Group IV base oil.
  • the result is especially surprising considering that the viscosity of these lubricants is nearly identical and the additive system, which is responsible for the frictional characteristics, was completely identical.
  • TABLE 8 shows a comparison of four lubricant compositions, two showing conventional capability and two lubricant compositions of the invention as described herein when used in a modified Sequence VIF test for fuel economy retention benefit.
  • lubricating oil composition of the invention 1 which contained 45 wt.% renewable base oil, 45% non-renewable base oil and 10 wt.% of an additive package containing dispersants, detergents, inhibitors, friction modifier, and pour point depressant, was blended to meet the viscosity grade definition of an SAE 0W-8 lubricant.
  • the kinematic viscosity of the lubricant at 100°C was 4.4 cSt
  • the CCS Viscosity at -35 °C was 1394 cP
  • the Noack volatility was 14%.
  • a lubricating oil composition of the invention 2 which contained 90 wt.% renewable base oil and 10 wt.% of an additive package containing dispersants, detergents, inhibitors, friction modifier, and pour point depressant, was blended to meet the viscosity grade definition of an SAE 0W-8 lubricant.
  • the kinematic viscosity of the lubricant at 100°C was 5.5 cSt, the CCS Viscosity at -35 °C was 2400 cP, and the Noack volatility was 7%.
  • a comparative oil 1 used for comparative purposes was purchased as it is a commercially available lubricating oil. This lubricant also met the viscosity grade definition of an SAE 0W-8 lubricant.
  • the kinematic viscosity of the third commercially available lubricant at 100°C was 5.3 lcSt, the CCS Viscosity at -35 °C was 1236 cP, and the Noack volatility was 30.8%.
  • a comparative lubricant 2 was made with 90% of an API Group IV base oil and 10 wt.% of the same additive package containing dispersants, detergents, inhibitors, friction modifier, and pour point depressant. This comparative lubricant was also blended to meet the viscosity grade definition of an SAE 0W-8 lubricant.
  • the kinematic viscosity of the comparative lubricant at 100°C was 4.82 cSt
  • the CCS Viscosity at -35 °C was 2000 cP
  • the Noack volatility was 10.8%.
  • FEI Fuel Economy Improvements
  • the GM 3.6 L engine was operated at conditions that are defined in more detail in the ASTM Sequence VIF engine test, with the exception of the lubricant temperature which was increased from 120°C to 140°C during the extended aging period.
  • modified test conditions is summarized in table 4.
  • Each candidate test was started with a fuel economy measurement on the lubricant in its fresh state, followed by additional fuel economy measurements after 172 h of lubricant aging and again after 328 h of lubricant aging. After 172 hours of aging, the lubricant would experience degradation similar to typical drain interval conditions. Hence fuel economy measurement conducted after 172 hours test duration represents degradation in the fuel economy at typical drain interval conditions.
  • the aging conditions are defined in more detail in the ASTM Sequence VIF engine test.
  • the fuel economy evaluations were based on the total fuel consumption measurements of the 6 stages that are defined in more detail in the table 3.
  • Table 8 also summarizes fuel economy change (%) relative to the reference oil after lubricants were aged similar to typical and extended drain interval conditions. Furthermore, table 8 summarizes average change in the fuel economy (%) over the life of a lubricants. Average change in the fuel economy values were calculated by averaging the values of fuel economy change (%) at typical and extended drain intervals.
  • comparative lubricants after aging in the engine at elevated temperature show a quickly increasing disadvantage relative to the lubricant of the invention, which does not suffer at all from a loss of fuel economy benefit, in other words, it has superior fuel economy retention over the life of the lubricant.
  • comparative example 1 and 2 were aged similar to typical drain interval conditions, they exhibit fuel economy improvement in the range of 1% to 2%. While lubricants of the invention retain fuel economy improvement benefits in the range of 3% to 4%.
  • Comparative examples 1 when comparative examples 1 was aged similar to extended drain interval conditions, it lost all its fuel economy improvement benefits and showed higher fuel consumption than the reference oil. Comparative example 2 maintained its fuel economy benefits around 2% when it was aged similar to extended drain interval conditions. While lubricants of the invention retained fuel economy improvement benefits in the range of 3% to 4% when they were aged in the extended drain interval conditions.
  • lubricants of the invention 1 and 2 shows fuel economy retention benefits by about 1% to 2% better than comparative examples, which represents best-in-class results using high quality group IV base oil. These results are highly surprising. The improvement in the fuel economy retention benefits cannot be explained by differences in the NOACK volatility. For example, in the extended drain interval conditions, high volatility comparative examples 1 and best-in-class comparative 2 shows 20% NOACK volatility difference and about 2% fuel economy benefits. Based on this, one skilled in the art would expect the lubricant of the invention 2 would bring 0.4% fuel economy benefits based on 4% NOACK volatility difference between comparative example 2 and lubricant of the invention 2.
  • TABLE 9 shows a comparison of four lubricant compositions, two showing conventional capability and two lubricant compositions of the invention as described herein when used in a modified Sequence VIF test, showing the reduced level of Calcium concentration increase after exposure to elevated temperature in the engine over the duration of an extended drain interval.
  • Boese D. a. R. A. "Controlling low-speed pre-ignition in modem automotive equipment: Defining approaches to and methods for analyzing data in new studies of lubricant-and fuel-related effects," in

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Abstract

L'invention concerne des compositions lubrifiantes comprenant des huiles de base renouvelables telles que définies par des mélanges d'hydrocarbures ayant des caractéristiques de structure contrôlées en combinaison avec des additifs lubrifiants qui apportent une solution aux exigences de performances et aux règlementations d'économie de carburant et environnementales plus strictes. La composition lubrifiante fournit des performances dans la relation de viscosité simulée de démarrage à froid (CCS) par rapport à la volatilité Noack, ce qui permet la formulation d'huiles de moteur à viscosité inférieure avec une économie de carburant améliorée, une meilleure rétention d'économie de carburant, et une prévention de LSPI conservée conférant en outre des caractéristiques améliorées à d'autres dispositifs ou appareils nécessitant une lubrification.
PCT/IB2020/057665 2019-08-14 2020-08-14 Procédé pour améliorer les performances d'un moteur avec des compositions lubrifiantes renouvelables WO2021028877A1 (fr)

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CA3200102A1 (fr) * 2020-10-28 2022-05-05 Chevron U.S.A. Inc. Composition d'huile lubrifiante avec une huile de base renouvelable, ayant une faible teneur en soufre et en cendres sulfatees et contenant des composes de molybdene et de bore
AU2022386648A1 (en) * 2021-11-10 2024-05-23 Evolve Lubricants, Inc. Sustainable lubricants
WO2023122405A1 (fr) * 2021-12-21 2023-06-29 ExxonMobil Technology and Engineering Company Compositions lubrifiantes d'huile moteur et leurs procédés de fabrication ayant une consommation d'huile supérieure

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