WO2008016484A2 - Compositions lubrifiantes possédant des propriétés améliorées à basse température - Google Patents

Compositions lubrifiantes possédant des propriétés améliorées à basse température Download PDF

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WO2008016484A2
WO2008016484A2 PCT/US2007/016168 US2007016168W WO2008016484A2 WO 2008016484 A2 WO2008016484 A2 WO 2008016484A2 US 2007016168 W US2007016168 W US 2007016168W WO 2008016484 A2 WO2008016484 A2 WO 2008016484A2
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composition
earth metal
alkylated
alkaline earth
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WO2008016484A3 (fr
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Marc-Andre Poirier
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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Priority to EP07810518.6A priority Critical patent/EP2057256B1/fr
Priority to CA002658762A priority patent/CA2658762A1/fr
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Publication of WO2008016484A3 publication Critical patent/WO2008016484A3/fr
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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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • 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
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • 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
    • C10M2205/17—Fisher Tropsch reaction products
    • C10M2205/173—Fisher Tropsch reaction products used as base material
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10N2030/52—Base number [TBN]

Definitions

  • the invention relates to lubricant compositions exhibiting good low temperature properties. More particularly, the invention relates to lubricant compositions having good pour points.
  • Finished high performance and industrial lubricants consist of two main components.
  • the first major component is the lubricating base oil.
  • the second is the performance enhancing additives.
  • the additive component is required to assure that the finished composition meets specifications set by government agencies, equipment manufacturers and other organizations. For example, many commercial lubricating compositions have specifications for pour point which is a measure of the temperature at which a sample of the lubricating composition will begin to flow under carefully controlled test conditions such as specified by the American Society for Testing Materials (ASTM).
  • Pour point depressants are additives known in the art and typically include polymethacrylates, polyacrylates, polyacrylamides, alkylated fumarate vinyl acetate copolymers, vinylcarboxylate polymers, terpolymers of dialkylfumarates, vinyl esters of fatty acids and ethylene-vinyl acetate copolymers to mention a few. Because of their polymeric nature, these pour point depressants are subject to shearing during their use, thereby impacting the useful life of the lubricating compositions containing them. [0004] Experience has taught that the overall effect of additives may depend not only on the nature and concentration of the additives, but also on the nature of the oil as well. The invention disclosed herein lends support to the observation that the base oil of a lubricant formulation may have an influence on additive performance, especially on pour point depressant performance.
  • U.S. Patent Publication No. U.S. 2006/01 16302 describes a detergent additive for lubricating oil compositions that comprises at least two of low, high and medium TBN (total base number) detergents, preferably calcium salicylate detergents. No reference is made to the pour points of lubricants formulated with the mixed detergents. Indeed, the claimed benefits of the mixed detergents related to piston cleanliness, film forming tendency and frictional properties.
  • TBN total base number
  • Detergents are generally considered to be chemical compounds that chemically neutralize deposit precursors that form under high temperature conditions or as a result of burning fuels with high sulfur content or other materials that form acidic combustion by-products. Detergents have some ability to disperse and suspend contaminants. Detergents used in lubricant oil compositions are organic soaps and salts of alkaline earth metals such as barium, calcium and magnesium. Alkylated calcium and magnesium sulfonates, phenates and salicylates are widely used. The sulfonates, phenates and salicylates maybe neutral or over based which means that they may contain more of the alkaline metal than is required to neutralize the acidic components formed from the combustion of high sulfur fuels.
  • pour point depressants are lubricant additives designed to keep base oil flowing in cold weather.
  • pour point depressants are viscous or solid high molecular weight polymers that are delivered in oils or solvents.
  • PPDs are very effective in modifying the pour point of base oils with treat rates generally less than 0.5 wt%.
  • the amount of pour point depressant used varies according to the type of base oil and the concentration of the polymer in the oil. Because of their polymeric nature, PPDs can shear during lubricant life.
  • pour point depressants include poly(methacrylates) known as Viscoplex® series 1,9, 10, Viscoplex® 1-31, Viscoplex® 1-330 and Viscoplex® 5-557, Lubrizol® Lz 7749B 3 Lz® 7742, Lz® 7748, Texaco TC 5301 and TC 10314, C8-C18 dialkyl fumarate or maleate vinyl acetate copolymers such as Infineum® V385, Inf ⁇ neum® V387, Inf ⁇ neum® V390, styrene maleate copolymers such as Lz® 6662 and the like.
  • a method for improving the pour point of a lubricating composition comprising a major amount of a lubricating base oil and one or more detergents, the method comprising using a alkylated alkaline earth metal detergents as a pour point depressant.
  • a lubricating composition comprising a major amount of an oil of lubricating viscosity chosen from the group consisting of Group III, GTL and any combination thereof, an alkylated alkaline earth metal as a pour point depressant wherein the alkylated alkaline earth metal is greater than 0.4 and less than 10 weight percent, and a minor amount of at least one lubricant additives, the composition having a saturates content greater than 98%, a viscosity index (VI) greater than 120 and a sulfur content less than 0.03 wt%.
  • an oil of lubricating viscosity chosen from the group consisting of Group III, GTL and any combination thereof
  • an alkylated alkaline earth metal as a pour point depressant wherein the alkylated alkaline earth metal is greater than 0.4 and less than 10 weight percent
  • a minor amount of at least one lubricant additives the composition having a saturates content greater than 98%, a viscosity index (VI
  • pour point of lubricating oil compositions can be enhanced by formulating the composition with one or more alkylated alkaline earth metal detergents. More specifically, alkylated alkaline earth metal salicylates including calcium salicylate detergents were found to be effective in reducing then pout points of base oils.
  • the alkylated alkaline earth metal detergents are particularly effective in base oils or lubricant compositions having a saturates content greater than 98%, a viscosity index (VI) greater than 120 and a sulfur content less than 0.03 wt%.
  • the alkylated alkaline earth metal detergents were found very effective in hydroisomerized or isodewaxed Fischer-Tropsch wax derived base oils (GTL). Therefore, the lubricating oil compositions of the invention comprise a major amount of a lubricating base oil which consists essentially of a Group III base stock and/or a GTL base stock.
  • This invention is suitable for lubricating oil compositions used for internal combustion engines, natural gas engines, turbine engines, automatic and manual transmissions, marine diesel engines, greases, gear boxes, hydraulic systems that require low temperature properties such as MRV, kinematic and Brookfield viscosities when formulated with highly saturated, Group III, base oils preferably hydroisomerized or isodewaxed Fischer-Tropsch wax derived base oils (GTL).
  • Groups I, II, III, IV and V are broad categories of base oil stocks defined by the American Petroleum Institute (API Publication 1509; www.API.org) to create guidelines for lubricant base oils. Table A summarizes properties of each of these five groups.
  • the base oil preferably is
  • Group III base stocks derived from gases, i.e., Gas-to-Liquid (GTL) base stocks are most preferred.
  • GTL Gas-to-Liquid
  • wax hydrocarbonaceous material having a high pour point, typically existing as a solid at room temperature, i.e., at a temperature in the range from about 15°C to 25°C, and consisting predominantly of paraffinic materials;
  • paraffinic material any saturated hydrocarbons, such as alkanes. Paraffinic materials may include linear alkanes, branched alkanes (iso-paraffins), cycloalkanes (cycloparaffins; mono-ring and/or multi-ring), and branched cycloalkanes;
  • hydroprocessing a refining process in which a feedstock is heated with hydrogen at high temperature and under pressure, commonly in the presence of a catalyst, to remove and/or convert less desirable components and to produce an improved product;
  • hydrotreating a catalytic hydrogenation process that converts sulfur- and/or nitrogen-containing hydrocarbons into hydrocarbon products with reduced sulfur and/or nitrogen content, and which generates hydrogen sulfide and/or ammonia (respectively) as byproducts; similarly, oxygen containing hydrocarbons can also be reduced to hydrocarbons and water;
  • hydrodewaxing (or catalytic dewaxing): a catalytic process in which normal paraffins (wax) and/or waxy hydrocarbons are converted by cracking/fragmentation into lower molecular weight species, and by rearrangement/isomerization into more branched iso-paraffins;
  • hydroisomerization (or isomerization or isodewaxing): a catalytic process in which normal paraffins (wax) and/or slightly branched iso- paraffins are converted by rearrangement/isomerization into more branched iso- paraffins;
  • hydrocracking a catalytic process in which hydrogenation accompanies the cracking/fragmentation of hydrocarbons, e.g., converting heavier hydrocarbons into lighter hydrocarbons, or converting aromatics and/or cycloparaffms (naphthenes) into non-cyclic branched paraffins.
  • hydroisomerization/hydrodewaxing is used to refer to one or more catalytic processes which have the combined effect of converting normal paraffins and/or waxy hydrocarbons by cracking/fragmentation into lower molecular weight species and, by rearrangement/isomerization, into more branched iso-paraffins. Such combined processes are sometimes described as “catalytic dewaxing” or “selective hydrocracking".
  • GTL materials are materials that are derived via one or more synthesis, combination, transformation, rearrangement, and/or degradation/deconstructive processes from gaseous carbon-containing compounds, hydrogen-containing compounds, and/or elements as feedstocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes, and butynes.
  • GTL base stocks and base oils are GTL materials of lubricating viscosity that are generally derived from hydrocarbons, for example waxy synthesized hydrocarbons, that are themselves derived from simpler gaseous carbon-containing compounds, hydrogen-containing compounds and/or elements as feedstocks.
  • GTL base stock(s) include oils boiling in the lube oil boiling range separated/fractionated from GTL materials such as by, for example, distillation or thermal diffusion, and subsequently subjected to well-known catalytic or solvent dewaxing processes to produce lube oils of reduced/low pour point; wax isomerates, comprising, for example, hydroisomerized or isodewaxed synthesized hydrocarbons; hydroisomerized or isodewaxed Fischer-Tropsch (F- T) material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possible analogous oxygenates); preferably hydroisomerized or isodewaxed F-T hydrocarbons or hydroisomerized or isodewaxed F-T waxes, hydroisomerized or isodewaxed synthesized waxes, or mixtures thereof.
  • F- T Fischer-Tropsch
  • GTL base stock(s) derived from GTL materials especially, hydroisomerized/isodewaxed F-T material derived base stock(s), and other hydroisomerized/isodewaxed wax derived base stock(s) are characterized typically as having kinematic viscosities at 100 0 C of from about 2 mm /s to about 50 mm 2 /s, preferably from about 3 mm 2 /s to about 50 mm 2 /s, more preferably from about 3.5 mm 2 /s to about 30 mm 2 /s, as exemplified by a GTL base stock derived by the isodewaxing of F-T wax, which has a kinematic viscosity of about 4 mm 2 /s at 100 0 C and a viscosity index of about 130 or greater.
  • Kinematic viscosity refers to a measurement made by ASTM method D445.
  • GTL base stocks and base oils derived from GTL materials are further characterized typically as having pour points of about -5°C or lower, preferably about -10 0 C or lower, more preferably about -15°C or lower, still more preferably about -20 0 C or lower, and under some conditions may have advantageous pour points of about -25°C or lower, with useful pour points of about -30 0 C to about -40 0 C or lower. If necessary, a separate dewaxing step may be practiced to achieve the desired pour point.
  • pour point refer to measurement made by ASTM D97 and similar automated versions.
  • the GTL base stock(s) derived from GTL materials, especially hydroisomerized/isodewaxed F-T material derived base stock(s), and other hydroisomerized/isodewaxed wax-derived base stock(s) which are base stock components which can be used in this invention are also characterized typically as having viscosity indices of 120 or greater in certain particular instances, viscosity index of these base stocks may be preferably 130 or greater, more preferably 135 or greater, and even more preferably 140 or greater.
  • GTL base stock(s) that derive from GTL materials preferably F-T materials especially F-T wax generally have a viscosity index of 130 or greater. References herein to viscosity index refer to ASTM method D2270.
  • GTL base stock(s) are typically highly paraffinic
  • GTL base stocks and base oils typically have very low sulfur and nitrogen content, generally containing less than about 10 ppm, and more typically less than about 5 ppm of each of these elements.
  • the sulfur and nitrogen content of GTL base stock and base oil obtained by the hydroisomerization/isodewaxing of F-T material, especially F-T wax is essentially nil.
  • the GTL base stock(s) comprises paraffinic materials that consist predominantly of non-cyclic isoparaffins and only minor amounts of cycloparaffins.
  • These GTL base stock(s) typically comprise paraffinic materials that consist of greater than 60 wt% non-cyclic isoparaffins, preferably greater than 80 wt% non-cyclic isoparaffins, more preferably greater than 85 wt% non-cyclic isoparaffins, and most preferably greater than 90 wt% non-cyclic isoparaffins.
  • compositions of GTL base stock(s), hydroisomerized or isodewaxed F-T material derived base stock(s), and wax-derived hydroisomerized/ isodewaxed base stock(s), such as wax isomerates/isodewaxates are recited in U.S. Pat. Nos. 6,080,301 ; 6,090,989, and 6,165,949 for example.
  • Isomerate/isodewaxate base stock(s), derived from waxy feeds which are also suitable for use in this invention, are paraffinic fluids of lubricating viscosity derived from hydroisomerized or isodewaxed waxy feedstocks of mineral oil, non-mineral oil, non-petroleum, or natural source origin, e.g., feedstocks such as one or more of gas oils, slack wax, waxy fuels hydrocracker bottoms, hydrocarbon raffinates, natural waxes, hyrocrackates, thermal crackates, foots oil, wax from coal liquefaction or from shale oil, or other suitable mineral oil, non-mineral oil, non-petroleum, or natural source derived waxy materials, linear or branched hydrocarbyl compounds with carbon number of about 20 or greater, preferably about 30 or greater, and mixtures of such isomerate/isodewaxate base stocks and base oils.
  • feedstocks such as one or more of gas
  • Slack wax is the wax recovered from petroleum oils by solvent or auto-refrigerative dewaxing.
  • Solvent dewaxing employs chilled solvent such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), mixtures of MEK/MIBK, mixtures of MEK and toluene, while autoref ⁇ gerative dewaxing employs pressurized, liquefied low boiling hydrocarbons such as propane or butane.
  • MEK methyl ethyl ketone
  • MIBK methyl isobutyl ketone
  • autoref ⁇ gerative dewaxing employs pressurized, liquefied low boiling hydrocarbons such as propane or butane.
  • Slack wax(es), being secured from petroleum oils, may contain sulfur and nitrogen containing compounds. Such heteroatom compounds must be removed by hydrotreating (and not hydrocracking), as for example by hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) so as to avoid subsequent poisoning/deactivation of the hydroisomerization catalyst.
  • hydrotreating and not hydrocracking
  • HDS hydrodesulfurization
  • HDN hydrodenitrogenation
  • GTL base oil/base stock and/or wax isomerate base oil/base stock as used herein and in the claims is to be understood as embracing individual fractions of GTL base stock/base oil or wax isomerate base stock/base oil as recovered in the production process, mixtures of two or more GTL base stocks/base oil fractions and/or wax isomerate base stocks/base oil fractions, as well as mixtures of one or two or more low viscosity GTL base stock(s)/base oil fraction(s) and/or wax isomerate base stock(s)/base oil fraction(s) with one, two or more high viscosity GTL base stock(s)/base oil fraction(s) and/or wax isomerate base stock(s)/base oil fraction(s) to produce a dumbbell blend wherein the blend exhibits a viscosity within the aforesaid recited range.
  • the GTL material, from which the GTL base stock(s) is/are derived is an F-T material (i.e., hydrocarbons, waxy hydro- carbons, wax).
  • F-T material i.e., hydrocarbons, waxy hydro- carbons, wax.
  • a slurry F-T synthesis process may be beneficially used for synthesizing the feed from CO and hydrogen and particularly one employing an F-T catalyst comprising a catalytic cobalt component to provide a high alpha for producing the more desirable higher molecular weight paraffins. This process is also well known to those skilled in the art.
  • a synthesis gas comprising a mixture of H 2 and CO is catalytically converted into hydrocarbons and preferably liquid hydrocarbons.
  • the mole ratio of the hydrogen to the carbon monoxide may broadly range from about 0.5 to 4, but which is more typically within the range of from about 0.7 to 2.75 and preferably from about 0.7 to 2.5.
  • F-T synthesis processes include processes in which the catalyst is in the form of a fixed bed, a fluidized bed or as a slurry of catalyst particles in a hydrocarbon slurry liquid.
  • the stoichiometric mole ratio for an F-T synthesis reaction is 2.0, but there are many reasons for using other than a stoichiometric ratio as those skilled in the art know.
  • the feed mole ratio of the H 2 to CO is typically about 2.1/1.
  • the synthesis gas comprising a mixture of H 2 and CO is bubbled up into the bottom of the slurry and reacts in the presence of the particulate F-T synthesis catalyst in the slurry liquid at conditions effective to form hydrocarbons, a portion of which are liquid at the reaction conditions and which comprise the hydrocarbon slurry liquid.
  • the synthesized hydrocarbon liquid is separated from the catalyst particles as filtrate by means such as filtration, although other separation means such as centrifugation can be used.
  • Some of the synthesized hydrocarbons pass out the top of the hydrocarbon synthesis reactor as vapor, along with unreacted synthesis gas and other gaseous reaction products.
  • Some of these overhead hydrocarbon vapors are typically condensed to liquid and combined with the hydrocarbon liquid filtrate.
  • the initial boiling point of the filtrate may vary depending on whether or not some of the condensed hydrocarbon vapors have been combined with it.
  • Slurry hydrocarbon synthesis process conditions vary somewhat depending on the catalyst and desired products.
  • Typical conditions effective to form hydrocarbons comprising mostly C 5+ paraffins, (e.g., C 5+ -C 2 Oo) and preferably Ci 0+ paraffins, in a slurry hydrocarbon synthesis process employing a catalyst comprising a supported cobalt component include, for example, temperatures, pressures and hourly gas space velocities in the range of from about 320-850 0 F, 80-600 psi and 100-40,000 V/hr/V, expressed as standard volumes of the gaseous CO and H 2 mixture (0 0 C, 1 atm) per hour per volume of catalyst, respectively.
  • C 5+ is used herein to refer to hydrocarbons with a carbon number of greater than 4, but does not imply that material with carbon number 5 has to be present. Similarly other ranges quoted for carbon number do not imply that hydrocarbons having the limit values of the carbon number range have to be present, or that every carbon number in the quoted range is present. It is preferred that the hydrocarbon synthesis reaction be conducted under conditions in which limited or no water gas shift reaction occurs and more preferably with no water gas shift reaction occurring during the hydrocarbon synthesis. It is also preferred to conduct the reaction under conditions to achieve an alpha of at least 0.85, preferably at least 0.9 and more preferably at least 0.92, so as to synthesize more of the more desirable higher molecular weight hydrocarbons.
  • a catalyst containing a catalytic cobalt component This has been achieved in a slurry process using a catalyst containing a catalytic cobalt component.
  • suitable F-T reaction types of catalyst comprise, for example, one or more Group VIII catalytic metals such as Fe, Ni, Co, Ru and Re, it is preferred that the catalyst comprise a cobalt catalytic component.
  • the catalyst comprises catalytically effective amounts of Co and one or more of Re, Ru, Fe, Ni, Th, Zr, Hf, U, Mg and La on a suitable inorganic support material, preferably one which comprises one or more refractory metal oxides.
  • Preferred supports for Co containing catalysts comprise Titania, particularly.
  • the waxy feed from which the base stock(s) is/are derived is wax or waxy feed from mineral oil, non-mineral oil, non- petroleum, or other natural source, especially slack wax, or GTL material, preferably F-T material, referred to as F-T wax.
  • F-T wax preferably has an initial boiling point in the range of from 650-750 0 F and preferably continuously boils up to an end point of at least 1050 0 F.
  • a narrower cut waxy feed may also be used during the hydroisomerization.
  • a portion of the n-paraffin waxy feed is converted to lower boiling isoparaffinic material.
  • the waxy feed preferably comprises the entire 650-750°F+ fraction formed by the hydrocarbon synthesis process, having an initial cut point between 650 0 F and 750 0 F determined by the practitioner and an end point, preferably above 1050 0 F, determined by the catalyst and process variables employed by the practitioner for the synthesis.
  • Such fractions are referred to herein as "650-750°F+ fractions”.
  • 650-750°F " fractions" refers to a fraction with an unspecified initial cut point and an end point somewhere between 650 0 F and 750 0 F.
  • Waxy feeds may be processed as the entire fraction or as subsets of the entire fraction prepared by distillation or other separation techniques.
  • the waxy feed also typically comprises more than 90%, generally more than 95% and preferably more than 98 wt% paraffinic hydrocarbons, most of which are normal paraffins. It has negligible amounts of sulfur and nitrogen compounds (e.g., less than 1 wppm of each), with less than 2,000 wppm, preferably less than 1,000 wppm and more preferably less than 500 wppm of oxygen, in the form of oxygenates. Waxy feeds having these properties and useful in the process of the invention have been made using a slurry F-T process with a catalyst having a catalytic cobalt component, as previously indicated.
  • the process of making the lubricant oil base stocks from waxy stocks may be characterized as a hydrodewaxing process. If slack waxes are used as the feed, they may need to be subjected to a preliminary hydrotreating step under conditions already well known to those skilled in the art to reduce (to levels that would effectively avoid catalyst poisoning or deactivation) or to remove sulfur- and nitrogen-containing compounds which would otherwise deactivate the hydroisomerization/ hydrodewaxing catalyst used in subsequent steps.
  • F-T waxes are used, such preliminary treatment is not required because, as indicated above, such waxes have only trace amounts (less than about 10 ppm, or more typically less than about 5 ppm to nil) of sulfur or nitrogen compound content.
  • some hydrodewaxing catalyst fed F-T waxes may benefit from removal of oxygenates while others may benefit from oxygenates treatment.
  • the hydrodewaxing process may be conducted over a combination of catalysts, or over a single catalyst. Conversion temperatures range from about 150 0 C to about 500 0 C at pressures ranging from about 500 to 20,000 kPa. This process may be operated in the presence of hydrogen, and hydrogen partial pressures range from about 600 to 6000 kPa.
  • the ratio of hydrogen to the hydrocarbon feedstock typically range from about 10 to 3500 n.1.1. '1 (56 to 19,660 SCF/bbl) and the space velocity of the feedstock typically ranges from about 0.1 to 20 LHSV, preferably 0.1 to 10 LHSV.
  • the hydroprocessing used for the production of base stocks from such waxy feeds may use an amorphous hydrocracking/hydroisomerization catalyst, such as a lube hydrocracking (LHDC) catalysts, for example catalysts containing Co, Mo, Ni, W, Mo, etc., on oxide supports, e.g., alumina, silica, silica/alumina, or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
  • LHDC lube hydrocracking
  • oxide supports e.g., alumina, silica, silica/alumina, or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
  • Hydrocarbon conversion catalysts useful in the conversion of the n-paraffin waxy feedstocks disclosed herein to form the isoparaffinic hydrocarbon base oil are zeolite catalysts, such as ZSM-5, ZSM-1 1, ZSM-23, ZSM-35, ZSM- 12, ZSM-38, ZSM-48, offretite, ferrierite, zeolite beta, zeolite theta, and zeolite alpha, as disclosed in USP 4,906,350. These catalysts are used in combination with Group VIII metals, in particular palladium or platinum. The Group VIII metals may be incorporated into the zeolite catalysts by conventional techniques, such as ion exchange.
  • conversion of the waxy feedstock may be conducted over a combination of Pt/zeolite beta and Pt/ZSM-23 catalysts in the presence of hydrogen.
  • the process of producing the lubricant oil base stocks comprises hydroisomerization and dewaxing over a single catalyst, such as Pt/ZSM-35.
  • the waxy feed can be fed over Group VIII metal loaded ZSM-48, preferably Group VIII noble metal loaded ZSM-48, more preferably Pt/ZSM-48 in either one stage or two stages. In any case, useful hydrocarbon base oil products may be obtained.
  • Catalyst ZSM-48 is described in USP 5,075,269. The use of the Group VIII metal loaded ZSM-48 family of catalysts, preferably platinum on ZSM-48, in the hydroisomerization of the waxy feedstock eliminates the need for any subsequent, separate dewaxing step, and is preferred.
  • a dewaxing step when needed, may be accomplished using either well known solvent or catalytic dewaxing processes and either the entire hydro- isomerate or the 650-750°F+ fraction may be dewaxed, depending on the intended use of the 650-750 0 F- material present, if it has not been separated from the higher boiling material prior to the dewaxing.
  • the hydroisomerate may be contacted with chilled solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), mixtures of MEK/MIBK, or mixtures of MEK/toluene and the like, and further chilled to precipitate out the higher pour point material as a waxy solid which is then separated from the solvent-containing lube oil fraction which is the raffinate.
  • the raffinate is typically further chilled in scraped surface chillers to remove more wax solids.
  • Low molecular weight hydrocarbons such as propane are also used for dewax- ing, in which the hydroisomerate is mixed with liquid propane, a least a portion of which is flashed off to chill down the hydroisomerate to precipitate out the wax.
  • the wax is separated from the raffinate by filtration, membrane separation or centrifugation.
  • the solvent is then stripped out of the raffinate, which is then fractionated to produce the preferred base stocks useful in the present invention.
  • catalytic dewaxing in which the hydroisomerate is reacted with hydrogen in the presence of a suitable dewaxing catalyst at conditions effective to lower the pour point of the hydroisomerate.
  • Catalytic dewaxing also converts a portion of the hydroisomerate to lower boiling materials, in the boiling range, for example, 650-750 0 F-, which are separated from the heavier 650-750°F+ base stock fraction and the base stock fraction fractionated into two or more base stocks. Separation of the lower boiling material may be accomplished either prior to or during fractionation of the 650-750°F+ material into the desired base stocks.
  • Any dewaxing catalyst which will reduce the pour point of the hydroisomerate and preferably those which provide a large yield of lube oil base stock from the hydroisomerate may be used.
  • These include shape selective molecular sieves which, when combined with at least one catalytic metal component, have been demonstrated as useful for dewaxing petroleum oil fractions and include, for example, ferrierite, mordenite, ZSM-5, ZSM-1 1 , ZSM-23, ZSM-35, ZSM-22 also known as theta one or TON, and the silicoaluminophosphates known as SAPO's.
  • a dewaxing catalyst which has been found to be unexpectedly particularly effective comprises a noble metal, preferably Pt, composited with H-mordenite.
  • the dewaxing may be accomplished with the catalyst in a fixed, fluid or slurry bed.
  • Typical dewaxing conditions include a temperature in the range of from about 400-600 0 F, a pressure of 500-900 psig, H 2 treat rate of 1500-3500 SCF/B for flow-through reactors and LHSV of 0.1 -10, preferably 0.2-2.0.
  • the dewaxing is typically conducted to convert no more than 40 wt% and preferably no more than 30 wt% of the hydroisomerate having an initial boiling point in the range of 650-750°F to material boiling below its initial boiling point.
  • GTL base stock(s), isomerized or isodewaxed wax-derived base stock(s), have a beneficial kinematic viscosity advantage over conventional Group II and Group III base stocks and base oils, and so may be very advantageously used with the instant invention.
  • Such GTL base stocks and base oils can have significantly higher kinematic viscosities, up to about 20-50 mm 2 /s at 100 0 C, whereas by comparison commercial Group II base oils can have kinematic viscosities, up to about 15 mm 2 /s at 100 0 C, and commercial Group III base oils can have kinematic viscosities, up to about 10 mm 2 /s at 100 0 C.
  • the higher kinematic viscosity range of GTL base stocks and base oils, compared to the more limited kinematic viscosity range of Group II and Group HI base stocks and base oils, in combination with the instant invention can provide additional beneficial advantages in formulating lubricant compositions.
  • the one or more isomerate/isodewaxate base stock(s), the GTL base stock(s), or mixtures thereof, preferably GTL base stock(s) can constitute all or part of the base oil.
  • GTL base stock(s) can constitute all or part of the base oil.
  • One or more of the wax isomerate/isodewaxate base stocks and base oils can be used as such or in combination with the GTL base stocks and base oils.
  • waxy feed derived base stocks and base oils derived from GTL materials and/or other waxy feed materials can similarly be used as such or further in combination with other base stocks and base oils of mineral oil origin, natural oils and/or with synthetic base oils.
  • the preferred base stocks or base oils derived from GTL materials and/or from waxy feeds are characterized as having predominantly paraffinic compositions and are further characterized as having high saturates levels, low- to-nil sulfur, low-to-nil nitrogen, low-to-nil aromatics, and are essentially water- white in color.
  • the GTL base stock/base oil and/or wax hydroisomerate/isodewaxate preferably GTL base oils/base stocks obtained from F-T wax, more preferably GTL base oils/base stocks obtained by the hydroisomerization/isodewaxing of F-T wax, can constitute from 5 to 100 wt%, preferably 40 to 100 wt%, more preferably 70 to 100 wt% by weight of the total of the base oil, the amount employed being left to the practitioner in response to the requirements of the finished lubricant.
  • a preferred GTL liquid hydrocarbon composition is one comprising paraffinic hydrocarbon components in which the extent of branching, as measured by the percentage of methyl hydrogens (BI), and the proximity of branching, as measured by the percentage of recurring methylene carbons which are four or more carbons removed from an end group or branch (CH 2 > 4), are such that: (a) BI-O.5(CH 2 > 4) >15; and (b) BI+0.85(CH 2 > 4) ⁇ 45 as measured over said liquid hydrocarbon composition as a whole.
  • BI methyl hydrogens
  • the preferred GTL base oil can be further characterized, if necessary, as having less than 0.1 wt% aromatic hydrocarbons, less than 20 wppm nitrogen containing compounds, less than 20 wppm sulfur containing compounds, a pour point of less than -18°C, preferably less than -30 0 C, a preferred BI > 25.4 and (CH 2 > 4) ⁇ 22.5. They have a nominal boiling point of 370 0 C + , on average they average fewer than 10 hexyl or longer branches per 100 carbon atoms and on average have more than 16 methyl branches per 100 carbon atoms.
  • the preferred GTL base oil is also characterized as comprising a mixture of branched paraffins characterized in that the lubricant base oil contains at least 90% of a mixture of branched paraffins, wherein said branched paraffins are paraffins having a carbon chain length of about C 2 o to about C 40 , a molecular weight of about 280 to about 562, a boiling range of about 650 0 F to about 1050 0 F, and wherein said branched paraffins contain up to four alkyl branches and wherein the free carbon index of said branched paraffins is at least about 3.
  • FCI Free Carbon Index
  • the branching index (BI) is calculated as the ratio in percent of non-benzylic methyl hydrogens in the range of 0.5 to 1.05 ppm, to the total non- benzylic aliphatic hydrogens in the range of 0.5 to 2.1 ppm.
  • Enhancement by Polarization Transfer (DEPT) NMR spectra are obtained on a Brucker 360 MHzAMX spectrometer using 10% solutions in CDCL 3 .
  • TMS is the internal chemical shift reference.
  • CDCL 3 solvent gives a triplet located at 77.23 ppm in the 13 C spectrum.
  • All single pulse spectra are obtained under quantitative conditions using 45 degree pulses (6.3 ⁇ s), a pulse delay time of 60 s, which is at least five times the longest carbon spin-lattice relaxation time (Ti), to ensure complete relaxation of the sample, 200 scans to ensure good signal-to- noise ratios, and WALTZ- 16 proton decoupling.
  • FCI Free Carbon Index
  • step b divide the total carbon- 13 integral area (chart divisions or area counts) by the average carbon number from step a. to obtain the integral area per carbon in the sample;
  • step d. divide by the integral area per carbon from step b. to obtain FCI.
  • Branching measurements can be performed using any Fourier
  • Transform NMR spectrometer Preferably, the measurements are performed using a spectrometer having a magnet of 7.0T or greater. In all cases, after verification by Mass Spectrometry, UV or an NMR survey that aromatic carbons were absent, the spectral width was limited to the saturated carbon region, about 0-80 ppm vs. TMS (tetramethylsilane). Solutions of 15-25 percent by weight in chloroform-dl were excited by 45 degrees pulses followed by a 0.8 sec acquisition time. In order to minimize non-uniform intensity data, the proton decoupler was gated off during a 10 sec delay prior to the excitation pulse and on during acquisition. Total experiment times ranged from 11-80 minutes. The DEPT and APT sequences were carried out according to literature descriptions with minor deviations described in the Varian or Bruker operating manuals.
  • DEPT is Distortionless Enhancement by Polarization Transfer.
  • DEPT does not show quaternaries.
  • the DEPT 45 sequence gives a signal for all carbons bonded to protons.
  • DEPT 90 shows CH carbons only.
  • DEPT 135 shows CH and CH 3 up and CH 2 180 degrees out of phase (down).
  • APT is Attached Proton Test. It allows all carbons to be seen, but if CH and CH 3 are up, then quaternaries and CH 2 are down.
  • the sequences are useful in that every branch methyl should have a corresponding CH. And the methyls are clearly identified by chemical shift and phase.
  • the branching properties of each sample are determined by C- 13 NMR using the assumption in the calculations that the entire sample is isoparaff ⁇ nic. Corrections are not made for n-paraffins or cycloparaffins, which may be present in the oil samples in varying amounts.
  • the cycloparaffins content is measured using Field Ionization Mass Spectroscopy (FIMS).
  • GTL base oils and base oils derived from synthesized hydrocarbons are of low or zero sulfur and phosphorus content.
  • hydroisomerized or isodewaxed waxy synthesized hydrocarbon e.g., Fischer-Tropsch waxy hydrocarbon base oils
  • Fischer-Tropsch waxy hydrocarbon base oils are of low or zero sulfur and phosphorus content.
  • Such oils known as low SAP oils, would rely on the use of base oils which themselves, inherently, are of low or zero initial sulfur and phosphorus content.
  • Such oils when used as base oils can be formulated with the catalytic antioxidant additive disclosed herein replacing or used part of the heretofore additive such as ZDDP previously employed in stoichimetric or super stoichiometric amounts. Even if the remaining additive or additives included in the formulation contain sulfur and/or phosphorus the resulting formulated oils will be lower or low SAP.
  • the base oil of the compositions of the invention may also contain a Group IV base stock, i.e., a polyalphaolefin or PAO.
  • a Group IV base stock i.e., a polyalphaolefin or PAO.
  • PAOs are those prepared from Cg to C12 mono olefins.
  • the process of over basing a metal detergent means that a stoechiometric excess of the metal is present over what is required to neutralize the anion of the salt. It is the excess metal from over basing that has the effect of neutralizing acids which may build up.
  • the alkylated alkaline earth metal detergents useful in this invention may also be borated. Such process for borating alkylated alkaline earth metal detergents has been described in U.S. Patent 4,965,004.
  • the amount of alkylated alkaline earth metal detergent in the lubricating oil composition will be from about 0.4 wt% to about 10 wt%, preferably from about 0.5 wt% to about 5 wt% of the total weight of the lubricating oil composition.
  • the alkylated alkaline earth metal salicylate is the sole metal lubricating detergent present in the lubricating oil composition but other metal detergents such as metal sulfonates or phenates may also be present.
  • compositions of the invention may include one or more lubricant additives, such as, dispersants, detergents, antioxidants, antiwear agents, viscosity index improvers, friction modifiers and defoamants.
  • lubricant additives such as, dispersants, detergents, antioxidants, antiwear agents, viscosity index improvers, friction modifiers and defoamants.
  • Dispersants useful in this invention are borated and non-borated nitrogen-containing compounds that are oil soluble salts, amides, imides and esters made from high molecular weight mono and di-carboxylic acids and various amines.
  • Preferred dispersants are the reaction product of acid anhydrides of polyolefins having an average molecular weight in the range from about 800 to about 3000, such as isobutenyl succinic anhydride with an alkoxyl or alkylene polyamine, such as tetraethylenepentamine.
  • the borated dispersants contain boron in an amount from about 0.5 to 5.0 wt% based on dispersants.
  • Dispersants, borated and/or non-borated or mixture thereof are used generally in amounts from about 0.5 to about 10 wt% based on the total weight of the lubricating oil composition.
  • antioxidants examples include hindered phenols, such as
  • 2,6-di-tert-butylphenol 4,4'- methylene bis (2,6-di-tert-butylphenol) 2,6-di-tert- butyl-p-cresol and the like, amine antioxidants such as alkylated naphthylamines, alkylated diphenylamines and the like and mixtures thereof.
  • Antioxidants are used generally in amounts from about 0.01 to about 5 wt% based on the total weight of the lubricating oil composition.
  • Anti-wear agents generally are oil-soluble zinc dihydrocarbyl- dithiophosphates having at least a total of 5 carbon atoms, the alkyl group being preferably C 2 - Cg that is primary, secondary, branched or linear. There are typically present in amounts of from about 0.01 to 5 wt%, preferably 0.4 to 1.5 wt% based on total weight of the lubricating oil composition.
  • Suitable conventional viscosity index (VI) improvers are the olefin polymers such as polybutene, ethylene-propylene copolymers,hydrogenated polymers and copolymers and terpolymers of styrene with isoprene and/or butadiene, A-B block copolymer such as those made by polymerization of dienes such as butadiene and/or isoprene with vinyl aromatics such as styrene known as Shell Vis (star polymers), polymers of alkyl acrylates or alkyl methacrylates, copolymers of alky lmethacrylates with N- vinyl pyrrolidone or dimethylamino- alkyl methacrylate, post grafted polymers of ethylene-propylene with an active monomer such as maleic anhydride which may be further reacted with an alcohol or an alkylene polyamine, styrene-maleic anhydride polymers post- reacted with
  • Friction modifiers useful in this invention include polyol esters such as glycerol esters more specifically fatty acid esters mono, di and tri-esters and a combination therof. Examples include but are not limited to glycerol monostearate, monooleate and the like. Other friction modifiers useful in this invention comprise molybdenum dithiocarbamates, molybdenum amine complexes and molybdenum dithiophosphates.
  • molybdenum dithiocarbamates examples include C 6 -C t 8 dialkyl or diaryldithiocarbamates, or alkylaryldithiocarbamates such as dibutyl, diamyl, diamyl-di-(2-ethylhexyl), dilauryl, dioleyl and dicyclohexyl dithiocarbamate.
  • the amount of friction modifiers present in the oil ranges from about 0.05 to about 1 wt% based on total weight of lubricating oil composition.
  • the molybdenum content can range from about 20 to about 500 ppm, most preferably from about 50 to about 120 ppm.
  • Defoamants typically silicone compounds such as polydimethyl- siloxane polymers and polyacrylate esters are commercially available and may be used in conventional minor amounts along with other additives such as demulsifiers; usually the amount of these additives combined is less than 1 wt% and often less than 0.2 wt% based on total weight of lubricating composition.
  • compositions of the invention will also include a pour point depressant consisting of an alkylated alkaline earth metal detergent.
  • the alkylated alkaline earth metal detergents more preferably the alkylated calcium salicylates have been found to be particularly effective in the hydroisomerized or isodewaxed Fischer-Tropsch wax derived base oils having a kinematic viscosity in the range from about 2 mm 2 /s to about 4.5 mm 2 /s.
  • the effectiveness of the alkylated alkaline earth metal detergent to reduce the pour point of the base oil appears to depend on the amount and the chain length of the wax molecules.
  • the neutral and over based n-C )4 alkyl calcium salicylates were the most effective.
  • the over based alkylated calcium phenates and over based alkylated calcium sulfonates were not very effective in reducing the pour point of the 3-4 mm 2 /s GTL base oil. Accordingly, the alkylated alkaline earth metal detergents useful in this invention are neutral and over based.
  • the alkylated alkaline earth metal detergents can also be sulfurized.
  • the process for sulfurizing alkaline earth metal detergent especially metal phenate detergents is well known to those skilled in the art.
  • the preparation of alkylated alkaline earth metal detergents is well known and has been documented e.g. in U.S. Patents 6,642,190, 6,599,867 and EP 1 ,233,053.
  • the alkyl group on the aromatic ring is linear with a carbon number from C 8 to C 30 but more preferably from C
  • the detergent will be a calcium and/or magnesium salicylate, neutral and over based, and will have a Total Base Number (TBN) from about 40 to about 700 but preferably from about 50 to about 350.
  • TBN Total Base Number
  • the alkylated alkaline earth metal detergents of this invention are particularly useful but not limited to finished lubricants such as piston engine oils, circulatory oils, automatic transmission fluids, gear oils, greases, hydraulic fluids, turbine oils, natural gas engine oils and metal working fluids that typically require pour point depressant to achieve low temperature properties.
  • the alkylated alkaline earth metal detergents particularly the alkylated alkaline earth metal salicylate detergents are more effective than the alkylated alkaline earth metal sulfonates and phenates in reducing the pour point of base oils.
  • the alkylated alkaline earth metal salicylate detergents were more effective in reducing the pour point of GTL and Group III base oils over the Group I and Group II base oils.
  • Finished engine oil lubricants apply to both straight and multigrade and include those of SAE Viscosity Grade of OW-10 OW-20, 0W-30, OW-40, 0W-50, OW-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30 or 15W-40.
  • the lubricating oil composition can contain from about 4 to about 10 wt% of a secondary API Group V base stock such as alkylated aromatic, trimethylol propane ester... etc. but base stock component is preferably a long chain alkylated aromatic, such as an alkylated naphthalenes.
  • the base oils contain other Group III base oils such as those from slack wax isomerization and hydrocracked processes and polyalphaolefins (PAOs).
  • Polyalphaolefins are prepared by polymerization of 1-alkenes using typically Lewis acid or Ziegler catalysts. Their preparation and properties are described by J. Brennan in lnd. Eng. Chem. Prod. Res. Dev., 19080, 19, pp 2-6.
  • the polyalphaolefins are prepared preferably from Cg to C )2 monoolef ⁇ ns.
  • the preferred base oils will have a saturates content of 99% minimum, a VI greater than 120 and a sulfur content less than 0.03 wt%.
  • This Example shows that metal detergent retains the favorable pour point improvement in a fully formulated oil of viscosity grade 0W-30.
  • the engine oil contains no pour point depressant other then the alkylated alkaline earth metal with a GTL base stock having a kinematic viscosity of 3.6 mm2/s at 100 0 C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

L'invention permet d'améliorer considérablement le point d'écoulement de compositions lubrifiantes, en en incluant des détergents à base de métaux alcalino-terreux alkylés dans la formulation des matières de base GTL et du groupe III. Dans un mode de réalisation préféré, l'invention fait appel à des détergents au salicylate d'alkyle de calcium.
PCT/US2007/016168 2006-07-28 2007-07-17 Compositions lubrifiantes possédant des propriétés améliorées à basse température Ceased WO2008016484A2 (fr)

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EP07810518.6A EP2057256B1 (fr) 2006-07-28 2007-07-17 Méthode pour améliorer le point d'écoulement d'une composition lubrifiante
CA002658762A CA2658762A1 (fr) 2006-07-28 2007-07-17 Compositions lubrifiantes possedant des proprietes ameliorees a basse temperature

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US8377859B2 (en) * 2007-07-25 2013-02-19 Exxonmobil Research And Engineering Company Hydrocarbon fluids with improved pour point
EP2365049B1 (fr) * 2009-08-24 2013-04-03 Infineum International Limited Utilisation d'additif lubrifiant
WO2012096864A1 (fr) * 2011-01-10 2012-07-19 The Lubrizol Corporation Compositions de lubrifiant ou de fluide fonctionnel contenant un améliorant d'indice de viscosité
GB2496732B (en) * 2011-11-17 2014-03-12 Infineum Int Ltd Marine engine lubrication
EP3122308B1 (fr) * 2014-03-27 2019-10-02 PaciniMedico ApS Dispositif pour le traitement de la douleur

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US4965004A (en) * 1989-04-21 1990-10-23 Texaco Inc. Process for a borated detergent additive
US6348438B1 (en) * 1999-06-03 2002-02-19 Chevron Oronite S.A. Production of high BN alkaline earth metal single-aromatic ring hydrocarbyl salicylate-carboxylate
EP1233052A1 (fr) * 2001-02-16 2002-08-21 Infineum International Limited Des additifs détergents surbasiques
EP1236791A1 (fr) * 2001-02-16 2002-09-04 Infineum International Limited Additifs surbasiques en tant que détergents
US6784143B2 (en) * 2001-05-11 2004-08-31 Infineum International Ltd. Lubricating oil composition
US20030191032A1 (en) * 2002-01-31 2003-10-09 Deckman Douglas E. Mixed TBN detergents and lubricating oil compositions containing such detergents
US20030171228A1 (en) * 2002-01-31 2003-09-11 Deckman Douglas Edward Mixed TBN detergents and lubricating oil compositions containing such detergents
US20040127371A1 (en) * 2002-09-13 2004-07-01 Stephen Arrowsmith Combination of a low ash lubricating oil composition and low sulfur fuel
SG128780A1 (en) * 2004-07-09 2007-02-26 Shell Int Research Lubricating oil composition
EP1632552A1 (fr) * 2004-09-06 2006-03-08 Infineum International Limited Composition d'huile lubrifiante
US8318002B2 (en) * 2005-12-15 2012-11-27 Exxonmobil Research And Engineering Company Lubricant composition with improved solvency

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EP2057256B1 (fr) 2018-05-09

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