EP2864456B1 - Schmierölzusammensetzungen enthaltend schwere fischer-tropsch basisöle und alkyliertes aromaten basisöl - Google Patents

Schmierölzusammensetzungen enthaltend schwere fischer-tropsch basisöle und alkyliertes aromaten basisöl Download PDF

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Publication number
EP2864456B1
EP2864456B1 EP13729949.1A EP13729949A EP2864456B1 EP 2864456 B1 EP2864456 B1 EP 2864456B1 EP 13729949 A EP13729949 A EP 13729949A EP 2864456 B1 EP2864456 B1 EP 2864456B1
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Prior art keywords
base oil
extra heavy
alkylated aromatic
heavy base
lubricating composition
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French (fr)
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EP2864456A1 (de
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David John Wedlock
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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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
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/02—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a non-macromolecular organic compound
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • 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
    • 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
    • C10M2203/104—Aromatic fractions
    • C10M2203/1045—Aromatic fractions 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/22—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts
    • C10M2205/223—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts 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
    • 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
    • C10N2020/02—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
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/70—Soluble oils
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • 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
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

  • the invention relates to lubricating compositions comprising Fischer-Tropsch extra heavy base oil.
  • the invention relates to lubricating compositions comprising a Fischer-Tropsch derived base oil with waxy haze components, which nevertheless have a clear and bright appearance.
  • waxy hydrocarbon feeds including those synthesized from gaseous components such as CO and H 2 , especially Fischer-Tropsch waxes, are suitable for conversion/treatment into lubricating base oils by subjecting such waxy feeds to hydrodewaxing or hydroisomerization/catalytic (and/or solvent) dewaxing whereby long chain normal-paraffins and slightly branched paraffins are removed and/or rearranged/isomerized into more heavily branched iso-paraffins of reduced pour and cloud point.
  • Lubricating base oils produced by the conversion/treatment of waxy hydrocarbon feeds of the type synthesized from gaseous components i.e.
  • Fischer-Tropsch derived base oils or simply FT base oils.
  • US 2008/0300157 A1 relates to lubricating oils of improved low temperature properties, especially viscometrics, and low pour points, and to a method for improving the low temperature properties, especially viscometrics, and reducing the pour points of Gas-to-Liquid (GTL) lubricating oils.
  • the viscosity of FT base oils may vary considerably. They may have a kinematic viscosity at 100°C according to ASTM D445 (VK 100) of at least about 3 mm 2 /s (cSt), e.g.
  • FT residual base oils with a VK 100 of at least 15 mm 2 /s are often referred to in the art as FT extra heavy base oils.
  • Some FT extra heavy base oils may even have a VK 100 of at least 17 mm 2 /s, or at least 20 mm 2 /s or at least 25 mm 2 /s.
  • FT residual base oils are often FT extra heavy base oils and are obtained from a residual (or bottoms) fraction resulting from distillation of an at least partly isomerised Fischer-Tropsch feedstock.
  • the at least partly isomerised Fischer-Tropsch feedstock may itself have been subjected to processing, such as dewaxing, before distillation.
  • the residual base oil may be obtained directly from the residual fraction, or indirectly by processing, such as dewaxing.
  • a residual base oil may be free from distillate, i.e. from side stream product recovered either from an atmospheric fractionation column or from a vacuum column.
  • WO 02/070627 , WO2009/080681 and WO2005/047439 describe exemplary processes for making Fischer-Tropsch derived residual base oils.
  • FT extra heavy base oils particularly FT residual extra heavy base oils
  • base oils can suffer from an undesirable appearance in the form of a waxy haze at ambient temperature.
  • Waxy haze may be inferred or measured in a number of ways.
  • the presence of waxy haze may for instance be measured according to ASTM D4176-04 which determines whether or not a fuel or lubricant conforms with a "clear and bright" standard. Whilst ASTM D4176-04 is written for fuels, it functions too for base oils.
  • the presence or extent of waxy haze may also be quantified as turbidity using nephelometric turbidity units (NTU), measured for example as described in US2011/0083995 .
  • NTU nephelometric turbidity units
  • Waxy haze in FT residual base oils which can also adversely affect the filterability of the oils, results from the presence of long carbon chain length paraffins, which have not been sufficiently isomerised (or cracked).
  • the content of long carbon chain length paraffins which stem from the waxy hydrocarbon feed, is particularly high in residual fractions from which residual base oils are derived. Since the presence of long carbon chain length paraffins also causes pour point and cloud point to be relatively high, residual fractions are typically subjected to one or more catalytic and/or solvent dewaxing steps. Such dewaxing steps are highly effective in lowering the pour point and cloud point in the resulting FT residual base oils, and under some conditions can also help to mitigate or eliminate haze, especially when combined with filtering.
  • US 2009/0186786 A1 relates to GTL base stocks and to GTL base stocks of reduced/mitigated haze formation.
  • the invention resides in a lubricating composition
  • a lubricating composition comprising 15 to 35 wt% FT extra heavy base oil and 65 to 85 wt% alkylated aromatic blendstock based on the total weight of FT extra heavy base oil and alkylated aromatic blendstock, wherein the FT extra heavy base oil has a kinematic viscosity at 100°C according to ASTM D445 in the range of from 19 to 35 mm2/s and a lower boiling point (T5) of at least 420°C and a higher boiling point (T80) of at least 600°C according to ASTM D-7169.
  • the FT extra heavy base oil and the alkylated aromatic blendstock act in synergy to provide a lubricating composition with good lubricating properties and stability in which waxy haze formation is mitigated.
  • the alkylated aromatic blendstock has been found to solubilise waxy haze in FT extra heavy base oil, including in FT residual extra heavy base oils made from heavy waxy hydrocarbon feeds.
  • the FT extra heavy base oil greatly enhances the lubricating properties of the composition.
  • the invention embraces a method of making a lubricating composition, the method comprising blending a FT extra heavy base oil and an alkylated aromatic blendstock consisting of one or more alkylated aromatic compounds.
  • the invention resides in the use of an alkylated aromatic blendstock consisting of one or more alkylated aromatic compounds for the purpose of reducing waxy haze in a FT extra heavy base oil, or in a precursor composition comprising a FT extra heavy base oil.
  • the use may comprise blending the alkylated aromatic blendstock with the FT extra heavy base oil or the precursor composition to form a lubricating composition.
  • the invention resides in a method of reducing waxy haze in a FT extra heavy base oil, or in a precursor composition comprising a FT extra heavy base oil, the method comprising blending an alkylated aromatic blendstock consisting of one or more alkylated aromatic compounds with the FT extra heavy base oil or the precursor composition to form a lubricating composition.
  • the invention resides in use of a lubricating composition
  • a lubricating composition comprising a FT extra heavy base oil and an alkylated aromatic blendstock consisting of one or more alkylated aromatic compounds for lubricating one or more of: an engine, e.g. compression ignition engine, an industrial machine such as a compressor, hydraulic pump, industrial turbine, or a gear box, and a power transmission system.
  • an engine e.g. compression ignition engine
  • an industrial machine such as a compressor, hydraulic pump, industrial turbine, or a gear box
  • a power transmission system e.g. compression ignition engine
  • a first essential component of the invention is the FT extra heavy base oil component.
  • the "FT extra heavy base oil” is a Fischer-Tropsch derived hydrocarbons base oil product comprising saturated paraffin molecules. On account of being an extra heavy oil, it is typically prone to the formation of waxy haze.
  • the FT extra heavy base oil may be characterised by one or more of the features described herein below, with no additional limiting technical meaning being attributed to the label "extra heavy”.
  • the FT extra heavy base oil may typically comprise at least 95 wt% saturated hydrocarbon molecules.
  • the FT extra heavy base oil is prepared from a Fischer-Tropsch wax and comprises more than 98 wt% of saturated hydrocarbons.
  • at least 85 wt%, more preferably at least 90 wt%, yet more preferably at least 95 wt%, and most preferably at least 98 wt% of these saturated hydrocarbon molecules are isoparaffinic.
  • at least 85 wt% of the saturated, paraffinic hydrocarbons are non-cyclic hydrocarbons. Naphthenic compounds (paraffinic cyclic hydrocarbons) are preferably present in an amount of no more than 15 wt%, more preferably less than 10 wt%.
  • the FT extra heavy base oil suitably contains hydrocarbon molecules having consecutive numbers of carbon atoms, such that it comprises a continuous series of consecutive iso-paraffins, i.e. iso-paraffins having n, n+1, n+2, n+3 and n+4 carbon atoms.
  • This series is a consequence of the Fischer-Tropsch hydrocarbon synthesis reaction from which the extra heavy base oil derives, following isomerisation of the wax feed.
  • the FT extra heavy base oil is typically a liquid at the temperature and pressure conditions of use and typically, although not always, under standard ambient temperature and pressure.
  • FT extra heavy base oils in which waxy haze formation is pronounced and/or persistent benefit particularly from the invention and are hence preferred as effective but economical components for use in the invention.
  • the kinematic viscosity at 100 °C according to ASTM D445 (VK 100) of the FT extra heavy base oil may typically be at least 15 mm 2 /s.
  • its VK 100 may be at least 17 mm 2 /s, more preferably at least 18 mm 2 /s, yet more preferably at least 19 mm 2 /s, again more preferably at least 22 mm 2 /s, and yet again more preferably at least 24 mm 2 /s.
  • the VK100 may be at most 100 mm 2 /s, or even at most 80 mm 2 /s or at most 50 mm 2 /s, or even at most 35 mm 2 /s.
  • the kinematic viscosity at 40 °C according to ASTM D445 (VK 40) of the alkylated aromatic blendstock may optionally be in the range of from 20 mm 2 /s to 300 mm 2 /s, preferably in the range of from 100 mm 2 /s to 250 mm 2 /s.
  • the viscosity index of the FT extra heavy base oil is preferably greater than 140, and preferably below 170.
  • the FT extra heavy base oil may have a lower boiling point (T5 or 5% off) of at least 420°C. More preferably, its lower boiling point (T5 or 5% off) may be at least 450°C, yet more preferably at least 470°C.
  • An upper boiling point (T80 or 80% off) of the FT extra heavy base oil may be at least 600°C. More preferably, its upper boiling point (T80) may be at least 620 °C, yet more preferably at least 640 °C.
  • the lower and upper boiling point values referred to herein are nominal and refer to the T5 and T80 boiling temperatures obtained by gas chromatograph simulated distillation (GCD) according to ASTM D-7169.
  • the lubricating composition according to the present invention comprises a FT extra heavy base oil having a lower boiling point (T5) of at least 420°C and a higher boiling point (T80) of at least 600°C according to ASTM D-7169.
  • any boiling range distributions of samples are measured herein according to ASTM D-7169. Since Fischer-Tropsch derived hydrocarbons comprise a mixture of varying molecular weight components having a wide boiling range, this disclosure refers to recovery points of boiling ranges. For example, a 10 wt% recovery point refers to that temperature at which 10 wt% of the hydrocarbons present within that cut will vaporise at atmospheric pressure, and could thus be recovered. Similarly, a 90 wt% recovery point refers to the temperature at which 90 wt% of the hydrocarbons present will vaporise at atmospheric pressure. Unless otherwise specified, when referring to a boiling range distribution, the boiling range between the 10 wt% and 90 wt% recovery boiling points is referred to in this specification.
  • the FT extra heavy base oil may preferably contain at least 95 wt% C30+ hydrocarbon molecules. More preferably, the FT extra heavy base oil may contain at least 75 wt% of C35+ hydrocarbon molecules.
  • Cloud point refers to the temperature at which a sample begins to develop a haze, as determined according to ASTM D-5773.
  • the FT extra heavy base oil may have a cloud point in the range of from +60°C to +5°C.
  • the FT extra heavy base oil has a cloud point in the range of from +50°C and +10°C, more preferably in the range of from +45°C and +15°C, more preferably in the range of from +40°C and +20°C and most preferably in the range of from +31°C and +20°C.
  • the FT extra heavy base oil may have a pour point of -9°C or lower, preferably of -12°C or -15°C or -21°C or -24°C or -27°C or even -30°C or -36°C or -39°C or -45°C or lower. It may thus be a base oil of the type which has been subjected to relatively severe (i.e. high temperature catalytic) dewaxing, such as can result in a pour point of -30°C or below, for example from -30 to -45 °C.
  • Such base oils may still comprise residual waxy haze and accordingly benefit from the invention.
  • the FT extra heavy base oil may have been subjected to relatively mild dewaxing to result in a pour point higher than -30°C, e.g. at least -15°C, such as in the range of from -12°C to 0°C.
  • the FT extra heavy base oil can further be characterised by its content of different carbon species. More particularly, the FT extra heavy base oil can be characterised by the percentage of its epsilon methylene carbon atoms, i.e. the percentage of recurring methylene carbons which are four or more carbons removed from the nearest end group and also from the nearest branch (further referred to as CH2>4) as compared to the percentage of its isopropyl carbon atoms. In the following text, the ratio of the percentage of epsilon methylene carbon atoms to the percentage of isopropyl carbon atoms (i.e.
  • isomerised FT residual base oils as disclosed in US-A-7053254 differ from Fischer-Tropsch derived paraffinic base oil components obtained at a higher dewaxing severity in that the latter compounds have an epsilon: isopropyl ratio of 8.2 or below.
  • FT extra heavy base oils of both these types are of use in the invention. Mildly dewaxed extra heavy base oils having an isopropyl ratio of above 8.2 may often comprise more pronounced waxy haze. However, it has been found that severely dewaxed extra heavy base oils having an epsilon: isopropyl ratio of 8.2 or below may also suffer from persistent haze and hence surprisingly benefit from the invention.
  • Branching in the FT extra heavy base oil may also be expressed as an average degree of branching.
  • Such an average degree of branching of the FT extra heavy base oil may in some embodiments be in the range of from 6.5 to about 10 alkyl branches per 100 carbon atoms, as disclosed in US 7,053,254 . In other embodiments, the average degree of branching in the molecules may be above 10 alkyl branches per 100 carbon atoms, as determined in line with the method disclosed in US-A-7053254 .
  • the branching properties as well as the carbon composition of a Fischer-Tropsch derived base oil blending component can conveniently be determined by analysing a sample of the oil using 13 C-NMR, vapour pressure osmometry (VPO) and field ionisation mass spectrometry (FIMS), as described in US 8,152,869 .
  • VPO vapour pressure osmometry
  • FIMS field ionisation mass spectrometry
  • the FT extra heavy base oil may typically have a viscosity index (ASTM D-2270) of between 120 and 180. It will preferably contain no or very little sulphur and nitrogen containing compounds. This is typical for a product derived from a Fischer-Tropsch reaction, which uses synthesis gas containing almost no heteroatom impurities.
  • the FT extra heavy base oil comprises sulphur, nitrogen and metals in the form of hydrocarbon compounds containing them, in amounts of less than 50 ppmw (parts per million by weight), more preferably less than 20 ppmw, yet more preferably less than 10 ppmw.
  • sulphur and nitrogen at levels generally below the detection limits, which are currently 5 ppmw for sulphur and 1 ppmw for nitrogen, when using, for instance, X-ray or 'Antek' Nitrogen tests for determination.
  • the FT extra heavy base oil is preferably a FT residual base oil, i.e. obtained from a residual or high vacuum bottoms fraction from the hydrocarbons produced during a Fischer-Tropsch synthesis reaction.
  • this fraction is a distillation residue comprising the highest molecular weight compounds still present in the product after a hydroisomerisation step.
  • the 10 wt% recovery boiling point of said fraction is preferably above 370°C, more preferably above 400°C and most preferably above 480°C for certain embodiments of the present invention.
  • the density of the FT extra heavy base oil component is suitably from about 700 to 1100 kg/m 3 , preferably from about 834 to 841 kg/m 3 .
  • the present invention embraces the use of a paraffinic heavy base oil component having one or more of the above described properties, whether or not the component is Fischer-Tropsch derived.
  • the FT extra heavy base oil component may contain a mixture of two or more FT extra heavy base oils.
  • a Fischer-Tropsch derived residual fraction or bottoms product is suitably subjected to an isomerisation process.
  • This converts n-to iso-paraffins, thus increasing the degree of branching in the hydrocarbon molecules and improving cold flow properties.
  • it can result in long chain hydrocarbon molecules having relatively highly branched end regions. Such molecules tend to exhibit relatively good cold flow performance.
  • the isomerised bottoms product may undergo further downstream processes, for example hydrocracking, hydrotreating and/or hydrofinishing.
  • a dewaxing step either by solvent or more preferably by catalytic dewaxing, as described below, which serves further to reduce its pour point.
  • a dewaxing step either by solvent or more preferably by catalytic dewaxing, as described below, which serves further to reduce its pour point.
  • a FT residual extra heavy base oil will still have a residual wax haze due to the extremely high molecular weight molecules which the dewaxing process cannot completely remove.
  • a FT extra heavy base oil for use in the present invention may be prepared by any suitable Fischer-Tropsch process.
  • the FT extra heavy base oil component (b) is a heavy bottom fraction obtained from a Fischer-Tropsch derived wax or waxy raffinate feed by: a) hydrocracking/hydroisomerising a Fischer-Tropsch derived feed, wherein at least 20 wt% of compounds in the Fischer-Tropsch derived feed have at least 30 carbon atoms, b) separating the product of step (a) into one or more distillate fraction (s) and a residual heavy fraction, preferably comprising at least 10 wt% of compounds boiling above 540°C; (c) subjecting the residual fraction to a catalytic pour point reducing step; and (d) isolating from the effluent of step (c), preferably as a residual heavy fraction, the Fischer-Tropsch derived paraffinic heavy base oil component.
  • the Fischer-Tropsch derived product fractions may undergo various other operations, such as hydrocracking, hydrotreating and/or hydrofinishing.
  • the feed from step (a) is a Fischer-Tropsch derived product.
  • the initial boiling point of the Fischer-Tropsch product may be up to 400°C.
  • any compounds having 4 or fewer carbon atoms and any compounds having a boiling point in that range are separated from a Fischer-Tropsch synthesis product before the Fischer-Tropsch synthesis product is used in said hydroisomerisation step.
  • Fischer-Tropsch process An example of a suitable Fischer-Tropsch process is described in WO-A-99/34917 and in AU-A-698391 .
  • the disclosed processes yield a Fischer-Tropsch product as described above.
  • the Fischer-Tropsch product can be obtained by well-known processes, for example the so-called Sasol process, the Shell Middle Distillate Synthesis process or the ExxonMobil "AGC-21" process. These and other processes are for example described in more detail in EP-A-0776959 , EP-A-0668342 , US-A-4943672 , US-A-5059299 , WO-A-99/34917 and WO-A-99/20720 .
  • the Fischer-Tropsch process will generally comprise a Fischer-Tropsch synthesis and a hydroisomerisation step, as described in these publications.
  • the Fischer-Tropsch synthesis can be performed on synthesis gas prepared from any sort of hydrocarbonaceous material such as coal, natural gas or biological matter such as wood or hay.
  • the Fischer-Tropsch product directly obtained from a Fischer-Tropsch process contains a waxy fraction that is normally a solid at room temperature.
  • the feed to the hydroisomerisation step (a) is preferably a Fischer-Tropsch product which has at least 30 wt%, preferably at least 50 wt%, and more preferably at least - 55 wt% of compounds having at least 30 carbon atoms. Furthermore the weight ratio, in this feed, of compounds having at least 60 carbon atoms to those having at least 30 but fewer than 60 carbon atoms is preferably at least 0.2, more preferably at least 0.4 and most preferably at least 0.55. If the feed has a 10 wt% recovery boiling point of above 500°C, the wax content will suitably be greater than 50 wt%.
  • the Fischer-Tropsch product comprises a C20+ fraction having an ASF-alpha value (Anderson-Schulz- Flory chain growth factor) of at least 0.925, preferably at least 0.935, more preferably at least 0.945, even more preferably at least 0.955.
  • ASF-alpha value Anderson-Schulz- Flory chain growth factor
  • the hydrocracking/hydroisomerisation reaction of step (a) is preferably performed in the presence of hydrogen and a catalyst, which catalyst can be chosen from those known to one skilled in the art as being suitable for this reaction.
  • Catalysts for use in the hydroisomerisation typically comprise an acidic functionality and a hydrogenation-dehydrogenation functionality.
  • Preferred acidic functionalities are refractory metal oxide carriers.
  • Suitable carrier materials include silica, alumina, silica-alumina, zirconia, titania and mixtures thereof.
  • Preferred carrier materials for inclusion in the catalyst are silica, alumina and silica-alumina.
  • a particularly preferred catalyst comprises platinum supported on a silica-alumina carrier.
  • the catalyst does not contain a halogen compound, such as for example fluorine, because the use of such catalysts can require special operating conditions and can involve environmental problems.
  • a halogen compound such as for example fluorine
  • suitable hydrocracking/hydroisomerisation processes and catalysts are described in WO-A-00/14179 , EP-A-0532118 , EP-A-0666894 and EP-A-0776959 .
  • Preferred hydrogenation-dehydrogenation functionalities are Group VIII metals, for example cobalt, nickel, palladium and platinum, more preferably platinum.
  • the catalyst may comprise the hydrogenation-dehydrogenation active component in an amount of from 0,005 to 5 parts by weight, preferably from 0.02 to 2 parts by weight, per 100 parts by weight of carrier material.
  • nickel is used, a higher content will typically be present, and optionally the nickel is used in combination with copper.
  • a particularly preferred catalyst for use in the hydroconversion stage comprises platinum in an amount in the range of from 0.05 to 2 parts by weight, more preferably from 0.1 to 1 parts by weight, per 100 parts by weight of carrier material.
  • the catalyst may also comprise a binder to enhance the strength of the catalyst.
  • the binder can be non-acidic. Examples are clays and other binders known to one skilled in the art.
  • the feed is contacted with hydrogen in the presence of the catalyst at elevated temperature and pressure.
  • the temperatures typically will be in the range of from 175 to 380°C, preferably higher than 250°C and more preferably from 300 to 370 °C.
  • the pressure will typically be in the range of from 10 to 250 bar and preferably from 20 to 80 bar.
  • Hydrogen may be supplied at a gas hourly space velocity of from 100 to 10000 Nl/l/hr, preferably from 500 to 5000 Nl/l/hr.
  • the hydrocarbon feed may be provided at a weight hourly space velocity of from 0.1 to 5 kg/l/hr, preferably higher than 0.5 kg/l/hr and more preferably lower than 2 kg/l/hr.
  • the ratio of the hydrogen to the hydrocarbon feed may range from 100 to 5000 Nl/kg and is preferably from 250 to 2500 Nl/kg.
  • the conversion in the hydroisomerisation defined as the weight percentage of the feed boiling above 370°C which reacts per pass to a fraction boiling below 370°C, is suitably at least 20 wt%, preferably at least 25 wt%, but preferably not more than 80 wt%, more preferably not more than 70 wt%.
  • the feed as used above in the definition is the total hydrocarbon feed fed to the hydroisomerisation step, thus also any optional recycle to step (a).
  • the resulting product of the hydroisomerisation process preferably contains at least 50 wt% of iso-paraffins, more preferably at least 60 wt%, yet more preferably at least 70 wt%, the remainder being composed of n-paraffins naphthenic and aromatic compounds.
  • step (b) the product of step (a) is separated into one or more distillate fraction (s) and a residual heavy fraction, preferably comprising at least 10 wt% of compounds boiling above 540°C. This is conveniently done by performing one or more distillate separations on the effluent of the hydroisomerisation step to obtain at least one middle distillate fuel fraction and a residual fraction which is to be used in step (c).
  • the effluent from step (a) is first subjected to an atmospheric distillation.
  • the 10 wt% recovery boiling point of the residue may preferably vary between 350 and 550°C.
  • This atmospheric bottom product or residue preferably boils for at least 95 wt% above 370°C.
  • the residue as obtained in such a distillation may in certain preferred embodiments be subjected to a further distillation performed at near vacuum conditions to arrive at a fraction having a higher 10 wt% recovery boiling point.
  • This fraction may be directly used in step (c) or may be subjected to an additional vacuum distillation suitably performed at a pressure of between 0.001 and 0.1 bar.
  • the feed for step (c) is preferably obtained as the bottom product of such a vacuum distillation.
  • step (c) the heavy residual fraction obtained in step (b) is subjected to a catalytic pour point reducing step.
  • Step (c) may be performed using any hydroconversion process, which is capable of reducing the wax content to below 50 wt% of its original value.
  • the wax content in the intermediate product is preferably below 35 wt% and more preferably between 5 and 35 wt%, and even more preferably between 10 and 35 wt%.
  • the product as obtained in step (c) preferably has a congealing point of below 80°C.
  • more than 50 wt% and more preferably more than 70 wt% of the intermediate product boils above the 10 wt% recovery point of the wax feed used in step (a).
  • Wax contents may be measured according to the following procedure: 1 weight part of the oil fraction under analysis is diluted with 4 parts of a (50/50 vol/vol) mixture of methyl ethyl ketone and toluene, which is subsequently cooled to -20°C in a refrigerator. The mixture is subsequently filtered at -20°C. The wax is thoroughly washed with cold solvent, removed from the filter, dried and weighed. Where reference is made to oil content, a wt% value is meant which is 100 wt% minus the wax content in wt%.
  • step (c) is the hydroisomerisation process as described above for step (a). It has been found that wax levels may be reduced to the desired level using such catalysts. By varying the severity of the process conditions as described above, a skilled person will easily determine the required operating conditions to arrive at the desired wax conversion. However a temperature of between 300 and 330°C and a weight hourly space velocity of between 0.1 and 5, more preferably between 0.1 and 3, kg of oil per litre of catalyst per hour (kg/l/hr) are especially preferred for optimising the oil yield.
  • a more preferred class of catalyst, which may be applied in step (c), is the class of dewaxing catalysts. The process conditions applied when using such catalysts should be such that a wax content remains in the oil.
  • the dewaxing catalyst which may be applied in step (c) suitably comprises a molecular sieve, optionally in combination with a metal having a hydrogenation function, such as the Group VIII metals.
  • Molecular sieves and more suitably molecular sieves having a pore diameter of between 0.35 and 0.8 nm, have shown a good catalytic ability to reduce the wax content of the wax feed.
  • Suitable zeolites are mordenite, beta, ZSM-5, ZSM-12, ZSM-22, ZSM-23, SSZ-32, ZSM-35, ZSM-48, EU-2 and combinations of said zeolites, of which ZSM-12, ZSM-48 and EU-2 are most preferred.
  • the reference to ZSM-48 and EU-2 is used to indicate that all zeolites can be used that belong to the ZSM-48 family of disordered structures also referred to as the *MRE family and described in the Catalog of Disorder in Zeolite Frameworks published in 2000 on behalf of the Structure Commission of the International Zeolite Assocation. Even if EU-2 would be considered to be different from ZSM-48, both ZSM-48 and EU-2 can be used in the present invention. Zeolites ZBM-30 and EU-11 resemble ZSM-48 closely and also are considered to be members of the zeolites whose structure belongs to the ZSM-48 family.
  • any reference to ZSM-48 zeolite also is a reference to ZBM-30 and EU-11 zeolite.
  • further zeolites can be present in the catalyst composition especially if it is desired to modify its catalytic properties. It has been found that it can be advantageous to have present zeolite ZSM-12 which zeolite has been defined in the Database of Zeolite Structures published in 2007/2008 on behalf of the Structure Commission of the International Zeolite Assocation.
  • SAPO silica-aluminaphosphate
  • SAPO-Il silica-aluminaphosphate
  • ZSM-5 may optionally be used in its HZSM-5 form in the absence of any Group VIII metal.
  • the other molecular sieves are preferably used in combination with an added Group VIII metal.
  • Suitable Group VIII metals are nickel, cobalt, platinum and palladium.
  • Examples of possible combinations are Pt/ZSM- 35, Ni/ZSM-5, Pt/ZSM-23, Pd/ZSM-23, Pt/ZSM-48 and Pt/SAPO" 11, or stacked configurations of Pt/zeolite beta and Pt/ZSM-23, Pt/zeolite beta and Pt/ZSM-48 or Pt/zeolite beta and Pt/ZSM-22.
  • Suitable molecular sieves and dewaxing conditions are for example described in WO-A-97/18278 , US-A-4343692 , US-A-5053373 , US-A-5252527 , US-A-2004/0065581 , US-A-4574043 and EP-A-1029029 .
  • Another preferred class of molecular sieves comprises those having a relatively low isomerisation selectivity and a high wax conversion selectivity, like ZSM-5 and ferrierite (ZSM-35).
  • the dewaxing catalyst suitably also comprises a binder.
  • the binder can be a synthetic or naturally occurring (inorganic) substance, for example clay, silica and/or a metal oxide. Natural occurring clays are for example of the montmorillonite and kaolin families.
  • the binder is preferably a porous binder material, for example a refractory oxide of which examples include alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia and silica-titania as well as ternary compositions, for example silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. More preferably, a low acidity refractory oxide binder material, which is essentially free of alumina, is used.
  • binder materials are silica, zirconia, titanium dioxide, germanium dioxide, boria and mixtures of two or more of these, of which examples are listed above.
  • the first preferred binder is silica.
  • the second preferred binder is titania.
  • a preferred class of dewaxing catalysts comprises intermediate zeolite crystallites as described above and a low acidity refractory oxide binder material which is essentially free of alumina as described above, wherein the surface of the aluminosilicate zeolite crystallites has been modified by subjecting the aluminosilicate zeolite crystallites to a surface dealumination treatment.
  • a preferred dealumination treatment involves contacting an extrudate of the binder and the zeolite with an aqueous solution of a fluorosilicate salt as described in for example US-A-5157191 or WO-A-00/29511 .
  • dewaxing catalysts as described above are silica bound and dealuminated Pt/ZSM- 5, or silica bound and dealuminated Pt/ZSM-35 as for example described in WO-A--00/29511 and EP-B-0832171 .
  • the conditions in step (c) when using a dewaxing catalyst typically involve operating temperatures in the range of from 200 to 500°C, suitably from 250 to 400°C. Preferably the temperature is between 300 and 330°C.
  • the hydrogen pressures may range from 10 to 200 bar, preferably from 40 to 70 bar.
  • Weight hourly space velocities (WHSV) may range from 0.1 to 10 kg of oil per litre of catalyst per hour (kg/l/hr), suitably from 0.1 to 5 kg/l/hr, more suitably from 0.1 to 3 kg/l/hr.
  • Hydrogen to oil ratios may range from 100 to 2000 litres of hydrogen per litre of oil.
  • step (d) the product of step (c) is usually sent to a vacuum column where various distillate base oil cuts are collected. These distillate base oil fractions may be used to prepare lubricating base oil blends, or they may be cracked into lower boiling products, such as diesel or naphtha.
  • the residual material collected from the vacuum column comprises a mixture of high boiling hydrocarbons, and can be used to prepare FT extra heavy base oil for use in the present invention.
  • the product obtained in step (c) may also be further treated, for example in a clay treating process or by contacting with active carbon, as for example described in US-A-4795546 and EP-A-0712922 , in order to remove unwanted components.
  • active carbon as for example described in US-A-4795546 and EP-A-0712922 .
  • Other suitable processes for the production of heavy and extra heavy Fischer-Tropsch derived base oils are described in WO-A-2004/033607 , US-A-7053254 , EP-A-1366134 , EP-A-1382639 , EP-A-1516038 , EP-A-1534801 , WO-A-2004/003113 and WO-A-2005/063941 .
  • the FT extra heavy base oil is defined and described herein as an added component. It may optionally represent the sole source of FT extra heavy base oil in the lubricating composition but this is not essential. Thus other FT extra heavy base oil may be present in the lubricating composition and amounts of FT extra heavy base oil indicated herein must be interpreted accordingly, unless context requires otherwise.
  • the FT extra heavy base oil may consist of or be synonymous with, any of the FT extra heavy base oils described or defined herein, or any combination thereof.
  • the FT extra heavy base oil may be prone to the formation of haze in the sense that it fails the 'clear and bright' standard (ASTM D4176-04) at standard conditions, and/or has a measurable turbitidy of at least 0.5 NTU (nephilometric turbidity units), preferably at least 1 NTU, more preferably at least 2 NTU, even more preferably at least 3 NTU and most preferably at least 4 NTU. Turbidity may be measured at 25°C according to the method described in US2011/0083995 .
  • the FT exta heavy base oil may be cloudy.
  • the amount of FT extra heavy base oil may be adjusted to achieve a desired waxy haze reduction and viscometric performance. Effective amounts of FT extra heavy base oil will depend to an extent on the nature of the FT extra heavy base oil, as well as the nature of the alkylated aromatic blendstock with which it is combined.
  • the amount of FT extra heavy base oil is in the range of from 5 to 50 wt%, preferably 10 to 40 wt%, more preferably 15 to 35 wt%, especially 20 to 25 wt % based on the total weight of FT extra heavy base oil and alkylated aromatic blendstock.
  • a second essential component of the invention is the alkylated aromatic blendstock.
  • the alkylated aromatic blendstock consists of one or more alkylated aromatic compounds (alkylated aromatics) consistent with achieving desired properties in the lubricating composition.
  • Alkylated aromatics have an aromatic head group and at least one alkyl chain.
  • the aromatic head group may be a substituted or unsubstituted mono- or polycyclic ring structure.
  • Aromatic head groups that contain one or more heteroatoms may also be suitable.
  • Preferred aromatic head groups in the context of the invention are benzene and naphthalene, with naphthalene being particularly preferred.
  • the one or more alkyl chains of the alkylated aromatics may each, individually, be a C 1 -C 30 , e.g. C 1 -C 20 linear alkyl group; or a C 3 -C 300 , e.g. C 3 -C 100 , or a C 3 -C 30 branched alkyl group. Longer alkyl chains can help to lower volatility and improve viscometric properties.
  • at least one linear or branched alkyl group of the alkylated aromatics may preferably comprise at least ten carbon atoms, more preferably at least 15 carbon atoms e.g.
  • the number of alkyl chains per aromatic head group may vary.
  • One or more alkyl chains e.g. one, two, three, four, five or six alkyl chains may be bonded directly to the aromatic system of the aromatic head group.
  • An alkyl chain may be bonded to the aromatic system at every available position on the aromatic head group.
  • the average number of carbon atoms in the alkylated aromatics may be at least 11, preferably at least 15, more preferably at least 25, or even at least 40.
  • the alkylated aromatics may have a number average molecular weight of at least about 150, preferably at least about 180, and more preferably at least about 300 or even at least about 480.
  • alkylated aromatics The preparation of alkylated aromatics is well known in the art. Although any method of preparation is suitable in the context of the invention, suitable alkylated aromatics may conveniently be formed by an alkylation reaction between an aromatic compound and an alkylating agent. Olefins are particularly common alkylating agents used in the art.
  • the alkylation reaction is generally performed over acidic catalysts, especially Friedel-Crafts catalysts such as AlCl 3 , BF 3 , FeCl 3 , acidic zeolites, amorphous aluminosilicates, acid clays or acidic metal oxides.
  • Alkylated aromatics obtained by alkylation generally include a mixture of compounds and isomers.
  • alkylated aromatics-containing feeds may be made from aromatisation of a suitable stream available from the FT process.
  • Alkylated aromatics obtained in this manner may be used directly in the invention, or as an alkylation feedstock, depending on desired properties.
  • Hydrogenated or partially hydrogenated analogues of the alkylated aromatics described herein may optionally also be used in or as the alkylated aromatic blendstock.
  • Alkylated naphthalenes are particularly preferred alkylated aromatics for use in or as the alkylated aromatic blendstock.
  • alkyl naphthalenes are mono-, di-, tri-, tetra-, or penta-C 3 alkyl naphthalene, -C 4 alkyl naphthalene, -C 5 alkyl naphthalene, -C 6 alkyl naphthalene, -C 8 alkyl naphthalene, -C 10 alkyl naphthalene, -C 12 alkyl naphthalene, -C 14 alkyl naphthalene, -C 16 alkyl naphthalene, -C 18 alkyl naphthalene, etc., C 10 -C 14 mixed alkyl naphthalene, C 6 -C 8 mixed alkyl naphthalene, or the mono-, di-, tri- , tetra-, or penta C 3 , C 4 , C 5 , C 6 , C 8 , C 10 , -
  • the alkyl group can also be a branched alkyl group with C 10 to C 300 , e.g., C 24 -C 56 branched alkyl naphthalene, C 24 -C 56 branched alkyl mono-, di-, tri-, tetra- or penta- C 1 -C 4 naphthalene.
  • C 24 -C 56 branched alkyl naphthalene C 24 -C 56 branched alkyl mono-, di-, tri-, tetra- or penta- C 1 -C 4 naphthalene.
  • These branched alkyl group substituted naphthalenes or branched alkyl group substituted mono-, di-, tri-, tetra- or penta C 1 -C 4 naphthalene can also be used as mixtures with the previously recited materials.
  • the branched alkyl group is very large (that is 8 to 300 carbons), usually only one or two of such alkyl groups are attached to the naphthalene head group.
  • the alkyl groups on the naphthalene ring can be mixtures of any of the above alkyl groups.
  • alkyl naphthalenes are prepared by alkylation of naphthalene or short chain alkyl naphthalene, such as methyl or di-methyl naphthalene, with olefins, alcohols or alkylchlorides over acidic catalysts inducing typical Friedel Crafts catalysts.
  • Methods for the production of alkyl naphthalenes suitable for use in the present invention are described in US 5,034,563 , US 5,516,954 , and US 6,436,882 , as well as in references cited in those patents and elsewhere in the literature. Because alkylated naphthalene synthesis techniques are well known in the art such techniques will not be further described herein.
  • Suitable alkylated naphthalenes are available commercially from ExxonMobil Chemical Company (TM) under the tradename Synesstic AN (TM).
  • Alkylated benzenes are also preferred alkylated aromatics for use in the invention.
  • the R can be linear C 10 -C 30 alkyl group or a C 10 -C 300 branched alkyl group preferably C 10 -C 100 branched alkyl group, more preferably C 15 -C 50 branched alkyl group.
  • up to C-1 of the alkyl groups can individually be a small alkyl group of C 1 to C 5 , preferably a C 1 -C 2 alkyl group, with the at least one remaining alkyl group being a linear C 10 -C 30 alkyl group or a C 10 -C 300 branched alkyl group preferably C 10 -C 100 branched alkyl group, more preferably C 15 -C 50 branched alkyl group.
  • Branched large alkyl radicals can be prepared from the oligomerization or polymerization of C 3 to C 20 internal or alpha-olefins or mixture of these olefins.
  • Alkylated benzenes may be prepared by alkylation of benzene or short chain alkyl benzene, such as methyl or di-methyl benzene, with olefins, alcohols or alkylchlorides over acidic catalysts inducing typical Friedel Crafts catalysts.
  • Preferred alkylated benzene fluids can be prepared according to US 6,071,864 or US 6,491,809 or EP 0,168,534 .
  • alkylated aromatic blendstock is defined and described herein as an added component. It may optionally represent the sole source of alkylated aromatics in the lubricating composition but this is not essential. Thus other alkylated aromatics may be present in the lubricating composition and amounts of alkylated aromatics indicated herein must be interpreted accordingly, unless context requires otherwise.
  • the alkylated aromatic blendstock may consist of or be synonymous with, any of the alkylated aromatics described or defined herein, or any combination thereof, e.g. alkylated naphthalenes and/or alkylated benzenes.
  • the kinematic viscosity at 100 °C according to ASTM D445 (VK 100) of the alkylated aromatic blendstock may be in the range of from 1 mm 2 /s to 50 mm 2 /s, preferably in the range of from 2 mm 2 /s to 30 mm 2 /s, more preferably in the range of from 3 mm 2 /s to 20 mm 2 /s, most preferably in the range of from 4 mm 2 /s to 15 mm 2 /s, e.g. 4 to 7 mm 2 /s or 11 to 15 mm 2 /s .
  • the kinematic viscosity at 40 °C according to ASTM D445 (VK 40) of the alkylated aromatic blendstock may be in the range of from 20 mm 2 /s to 150 mm 2 /s, preferably in the range of from 25 mm 2 /s to 120 mm 2 /s.
  • the alkylated aromatic blendstock may preferably have a pour point (ASTM D97) of 0° C or less, preferably -20° C, more preferably -30° C or less; and/or a viscosity index (ASTM D 2270) in the range of from about 0 to 200, preferably about 60 to 200, more preferably about 70 to about 160, e.g. about 75 to about 110; and/or a Noack Volatility (ASTM D5800) of less than 15 wt%, preferably 7 wt%, more preferably 5 wt%.
  • a pour point ASTM D97
  • a viscosity index ASTM D 2270
  • ASTM D5800 Noack Volatility
  • the amount of alkylated aromatic blendstock may be adjusted to achieve a desired waxy haze reduction. Effective amounts of alkylated aromatic blendstock will depend to an extent on the nature of the blendstock, as well as the nature of the FT residual oil with which it is combined.
  • the lubricating composition according to the present invention comprises 15 to 35 wt% FT extra heavy base oil and an 65 to 85 wt% alkylated aromatic blendstock based on the total weight of FT extra heavy base oil and alkylated aromatic blendstock.
  • the amount of alkylated aromatic blendstock is in the range of from 50 to 95 wt%, preferably 60 to 90 wt%, more preferably 65 to 85 wt%, especially 75 to 80 wt%, based on the total weight of FT extra heavy base oil and alkylated aromatic blendstock.
  • the lubricating composition has a less hazy appearance than the FT extra heavy base oil used to formulate it.
  • the lubricating composition may pass the 'clear and bright' standard (ASTM D4176-04). It may preferably have a turbidity of at most 2 NTU, preferably at most 1 NTU, more preferably at most 0.5 NTU, even more preferably at most 0.2 NTU and ideally of 0 NTU, as measured according to the method of US2011/0083995 at 25° C.
  • the lubricating composition may conform with one or more of the above haziness measurements at least 14 days after blending.
  • the lubricating composition according to the present invention comprises a FT extra heavy base oil having a kinematic viscosity at 100°C according to ASTM D445 in the range of from 19 to 35 mm2/s.
  • the kinematic viscosity at 100 °C according to ASTM D445 (VK 100) of the lubricating composition may preferably be in the range of from 1 mm 2 /s to 30 mm 2 /s, preferably in the range of from 2 mm 2 /s to 25 mm 2 /s, more preferably in the range of from 3 mm 2 /s to 20 mm 2 /s, most preferably in the range of from 4 mm 2 /s to 18 mm 2 /s, e.g. 7 to 12 mm 2 /s or 14 to 17 mm 2 /s.
  • the kinematic viscosity at 40 °C according to ASTM D445 (VK 40) of the lubricating composition may preferably be in the range of from 30 mm 2 /s to 150 mm 2 /s, preferably in the range of from 35 mm 2 /s to 140 mm 2 /s.
  • the lubricating composition may have a viscosity index (ASTM D-2270) in the range of from 95 to 180, preferably from 110 to 130.
  • the pour point of the lubricating composition may be -10°C or lower, preferably of -15°C or lower, more preferably -20°C or lower, even more preferably -30°C or lower.
  • the lubricating composition has a surprisingly good oxidative stability and may preferably show the oxidative performance of a Group II base oil.
  • the lubricating composition comprising the FT extra heavy base oil and the alkylated aromatic blendstock may comprise:
  • the FT extra heavy base oil and the alkylated aromatic blendstock may make up the entirety of the lubricating composition, or preferably at least 95wt% or at least 98wt%, or at least 99wt% or at least 99.5wt% or at least 99.99wt% of the total composition.
  • the lubricating composition according to the present invention may further comprise one or more additives such as anti-oxidants, anti-wear additives, (preferably ashless) dispersants, detergents, extreme-pressure additives, friction modifiers, metal deactivators, corrosion inhibitors, demulsifiers, anti-foam agents, seal compatibility agents and additive diluent base oils, etc.
  • additives such as anti-oxidants, anti-wear additives, (preferably ashless) dispersants, detergents, extreme-pressure additives, friction modifiers, metal deactivators, corrosion inhibitors, demulsifiers, anti-foam agents, seal compatibility agents and additive diluent base oils, etc.
  • additives such as anti-oxidants, anti-wear additives, (preferably ashless) dispersants, detergents, extreme-pressure additives, friction modifiers, metal deactivators, corrosion inhibitors, demulsifiers, anti-foam agents, seal compatibility agents and additive diluent base oils, etc.
  • Such additives
  • the lubricating composition may be used as a lubricant blendstock, or in any suitable lubricating application. It may be of particular benefit as a base oil blend component where a relatively high VK100 is required such as in monograde gas engine oils (SAE 40 monogrades) where current low sulphur base oils such as API Group II or Group III are sometimes borderline in VK100 and hence have problems meeting SAE J-300 viscometric specifications for monogrades.
  • SAE 40 monogrades monograde gas engine oils
  • API Group II or Group III API Group II or Group III
  • the lubricating composition may be formed by simple blending of its components as is known in the art.
  • One preferred method of the invention comprises: blending a FT extra heavy base oil failing the 'clear and bright' standard (ASTM D4176) with an amount of an alkylated aromatic blendstock to provide a lubricating composition that passes the 'clear and bright' standard (ASTM D4176) and/or has any of the other properties defined hereinabove.
  • the invention also embraces use of the alkylated aromatic blendstock for the purpose of reducing waxy haze in a FT extra heavy base oil, or in a precursor composition comprising the FT extra heavy base oil.
  • This use may embrace supplying or offering a lubricating composition comprising FT extra heavy base oil and alkylated aromatic blendstock together with information or advertising relating to a clear and bright appearance or an appearance of absent or low turbidity.
  • a high pour point (high PPt) XHBO base stock was prepared substantially as described in Example 6 of US 8,152,869 .
  • a low pour point (low Ppt) XHBO base stock was prepared according to the same process, with the only difference being the temperature at which the dewaxing catalyst was operated. A higher temperature leads to more severe dewaxing and a lower pour point.
  • the resultant XHBO base stocks had the properties shown in Table 1.
  • Table 1 Properties of the XHBO base stocks XHBO (low PPt) XHBO (high PPt) Vk 100 19.00 25.22 Vk 40 132.0 228.9 VI 163 140 Pour Point °C -30 -6 Cloud point °C +31 +31 Clear and Bright No - hazy No - hazy
  • the alkylated aromatic basestocks were alkylated naphthalenes and were obtained commercially from ExxonMobil Chemical Company under the trade name SynessticTM AN 5 and SynessticTM AN 12. They had the measured properties shown in Table 3 and a clear and bright appearance: Table 3. Properties of the alkylated naphthalene fluids SynessticTM 5 SynessticTM 12 Vk 100 4.81 12.75 Vk 40 28.54 111.00 VI 82 108 Pour Point (PPt) -39 -39
  • the synergistic behaviour of the blend according to the invention is further demonstrated through improvements in pour point (PPt) over the unblended alkylated aromatic basestock and XHBO base oil components.
  • PPt pour point
  • the alkylated aromatic basestock can solubilise waxy haze in the FT extra heavy base oil and the FT extra heavy base oil can lower the pour point of the alkylated aromatic basestock in a blend to below that of either component.
  • the base oils/blends were formulated into an industrial turbine oil. This was chosen because of the associated low additive treat rate, but the results would be applicable to other industrial lubricants such as hydraulic fluids or a crankcase lubricant of a passenger car of a heavy duty diesel variety.
  • the additives employed were as follows:
  • aromatic head groups present in alkylated naphthalene fluids would be expected to lead to oxidative vulnerability of any blend in which it was incorporated.
  • formulations 1 and 2 which include the alkylated aromatic blendstock component surprisingly have comparable oxidative stability to that of a typical API Group II base oil (formulations 3 and 4). This provides further evidence of the unexpected beneficial synergistic effect of blending the XHBO with alkylated aromatick blendstock.

Claims (13)

  1. Schmiermittelzusammensetzung, die 15 bis 35 Gew.-% extra schweres FT-Grundöl und 65 bis 85 Gew.-% alkyliertes aromatisches Gemisch auf Grundlage des Gesamtgewichts von extra schwerem FT-Grundöl und alkyliertem aromatischen Gemisch umfasst, wobei das extra schwere FT-Grundöl eine kinematische Viskosität bei 100°C gemäß ASTM D445 im Bereich von 19 bis 35 mm2/s und einen niedrigeren Siedepunkt (T5) von mindestens 420°C und einen höheren Siedepunkt (T80) von mindestens 600°C gemäß ASTM D-7169 aufweist.
  2. Schmiermittelzusammensetzung nach Anspruch 1, wobei das extra schwere FT-Grundöl mindestens 95 Gew.-% C30+-Kohlenwasserstoffmoleküle und mindestens 75 Gew.-% C35+-Kohlenwasserstoffmoleküle enthält.
  3. Schmiermittelzusammensetzung nach Anspruch 1 oder 2, wobei das extra schwere FT-Grundöl einen Trübungspunkt im Bereich von +60°C bis +5°C und einen Stockpunkt von -6°C oder niedriger aufweist.
  4. Schmiermittelzusammensetzung nach einem der vorstehenden Ansprüche, wobei das extra schwere FT-Grundöl ein Restgrundöl ist.
  5. Schmiermittelzusammensetzung nach Anspruch 4, wobei das extra schwere FT-Grundöl von einem Fischer-Tropsch-Produkt abgeleitet ist, das mindestens 55 Gew.-% Verbindungen mit mindestens 30 Kohlenstoffatomen aufweist, und in dem das Gewichtsverhältnis von Verbindungen mit mindestens 60 Kohlenstoffatomen zu solchen mit mindestens 30, aber weniger als 60 Kohlenstoffatomen mindestens 0,4 beträgt.
  6. Schmiermittelzusammensetzung nach einem der vorstehenden Ansprüche, wobei das extra schwere FT-Grundöl in dem Sinne trüb ist, dass es die Norm 'klar und hell' (ASTM D4176-04) unter Standardbedingungen nicht erfüllt.
  7. Schmiermittelzusammensetzung nach einem der vorstehenden Ansprüche, wobei das alkylierte aromatische Gemisch alkyliertes aromatisches Naphthalin und/oder alkyliertes aromatisches Benzol umfasst.
  8. Schmiermittelzusammensetzung nach einem der vorstehenden Ansprüche, wobei das alkylierte aromatische Gemisch eine kinematische Viskosität bei 100° C (ASTM D445) im Bereich von 4 mm2/s bis 15 mm2/s aufweist.
  9. Schmiermittelzusammensetzung nach einem der vorstehenden Ansprüche, die der Norm 'klar und hell' (ASTM D4176-04) bei Standardumgebungsbedingungen entspricht.
  10. Schmiermittelzusammensetzung nach einem der vorstehenden Ansprüche,
    die umfasst:
    a. 5 bis 25 Gew.-%, bezogen auf das Gesamtgewicht von extra schwerem FT-Grundöl und alkyliertem aromatischen Gemisch, eines extra schweren FT-Grundöls mit einem VK 100 gemäß ASTM D445 im Bereich von 19 bis 35 mm2/s; und
    b. 75 bis 95 Gew.-%, bezogen auf das Gesamtgewicht von extra schwerem FT-Grundöl und alkyliertem aromatischen Gemisch, eines alkylierten aromatischen Gemisches, umfassend oder bestehend aus alkylierten Naphthalinen und mit einem VK 100 im Bereich von 4 mm2/s bis 15 mm2/s.
  11. Verwendung einer Schmiermittelzusammensetzung nach einem der vorstehenden Ansprüche zum Schmieren eines Motors, eines Kompressors, einer Hydraulikpumpe, einer Industrieturbine, eines Getriebes oder eines Kraftübertragungssystems, wobei die Schmiermittelzusammensetzung 15 bis 35 Gew.-% extra schweres FT-Grundöl und 65 bis 85 Gew.-% alkyliertes aromatisches Gemisch, bezogen auf das Gesamtgewicht von extra schwerem FT-Grundöl und alkyliertem aromatischen Gemisch umfasst.
  12. Verfahren zur Herstellung einer Schmiermittelzusammensetzung, wobei das Verfahren das Vermischen eines extra schweren FT-Grundöls, das den Standard 'klar und hell' (ASTM D4176) nicht erfüllt, mit einem alkylierten aromatischen Gemisch umfasst, um eine Schmiermittelzusammensetzung bereitzustellen, die den Standard 'klar und hell' erfüllt, wobei das extra schwere FT-Grundöl eine kinematische Viskosität bei 100°C gemäß ASTM D445 im Bereich von 19 bis 35 mm2/s und einen niedrigeren Siedepunkt (T5) von mindestens 420°C und einen höheren Siedepunkt (T80) von mindestens 600°C gemäß ASTM D-7169 aufweist.
  13. Verwendung eines alkylierten aromatischen Gemisches von 65 bis 85 Gew.-% zum Zweck der Reduzierung von wachsartiger Trübung in einem extra schweren FT-Grundöl von 15 bis 35 Gew.-%, bezogen auf das Gesamtgewicht von extra schwerem FT-Grundöl und alkyliertem aromatischen Gemisch, oder in einer Vorstufen-Zusammensetzung, die das extra schwere FT-Grundöl umfasst.
EP13729949.1A 2012-06-21 2013-06-18 Schmierölzusammensetzungen enthaltend schwere fischer-tropsch basisöle und alkyliertes aromaten basisöl Not-in-force EP2864456B1 (de)

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PCT/EP2013/062668 WO2013189953A1 (en) 2012-06-21 2013-06-18 Lubricating oil compositions comprising heavy fischer - tropsch derived and alkylated aromatic base oil

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RU2015101730A (ru) 2016-08-10
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JP6266606B2 (ja) 2018-01-24
CN104508095A (zh) 2015-04-08
RU2658914C2 (ru) 2018-06-26
WO2013189953A1 (en) 2013-12-27
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