WO2012017023A1 - Composition lubrifiante - Google Patents

Composition lubrifiante Download PDF

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Publication number
WO2012017023A1
WO2012017023A1 PCT/EP2011/063397 EP2011063397W WO2012017023A1 WO 2012017023 A1 WO2012017023 A1 WO 2012017023A1 EP 2011063397 W EP2011063397 W EP 2011063397W WO 2012017023 A1 WO2012017023 A1 WO 2012017023A1
Authority
WO
WIPO (PCT)
Prior art keywords
lubricating composition
base oil
astm
cst
lubricating
Prior art date
Application number
PCT/EP2011/063397
Other languages
English (en)
Inventor
Gilbert Robert Bernard Germaine
David John Wedlock
Original Assignee
Shell Internationale Research Maatschappij B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to JP2013522245A priority Critical patent/JP5865907B2/ja
Publication of WO2012017023A1 publication Critical patent/WO2012017023A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • 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
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—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 type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • 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
    • C10N2030/68—Shear stability
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/74—Noack Volatility
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines

Definitions

  • the present invention relates to a lubricating composition
  • a lubricating composition comprising a base oil and one or more
  • a formulator typically has the choice of using mineral bright stock or heavy poly-alpha olefins (heavy PAOs; heavy PAOs typically have a kinematic viscosity at 100°C of above 20 cSt) .
  • a problem of the use of mineral bright stock, a residual mineral base oil, is the inherently lower quality thereof, resulting in e.g. limited oxidation stability.
  • a problem of the use of heavy PAOs is the inherent high cost thereof. Attempts have been made in the past to solve this problem by combining the desirable cost-effectiveness of lighter distillate GTL base oils with a minimal amount of heavy PAO.
  • SAE xW-50 and SAE xW-60 or even heavier formulations, more in particular SAE 20W-50 and SAE 20W-60 and heavier formulations.
  • a lubricating composition comprising a base oil and one or more additives, wherein the base oil comprises a residual Fischer-Tropsch derived base oil and wherein the
  • lubricating composition has a kinematic viscosity at 100°C (according to ASTM D 445) of above 16.3 cSt .
  • suitable lubricating compositions in particular engine oils
  • suitable lubricating compositions having a high kinematic viscosity at 100°C (such as SAE xW-50 and xW-60
  • formulations can be formulated, without the need of using mineral bright stock or heavy poly-alpha olefins (PAOs) .
  • PAOs poly-alpha olefins
  • An advantage of the present invention is that the lubricating compositions have surprisingly low Noack volatility values (according to ASTM D 5800), in some embodiments as low as below 3.5 wt . % .
  • the base oil used in lubricating composition according to the present invention comprises at least a residual Fischer-Tropsch derived base oil and provided that the requirements in respect of the
  • the base oil used in the present invention may - in addition to the residual Fischer-Tropsch derived base oil - conveniently comprise mixtures of one or more mineral oils and/or one or more synthetic oils; thus, according to the present invention, the term "base oil” may refer to a mixture containing more than one base oil, including at least one residual Fischer-Tropsch derived base oil.
  • Mineral oils include liquid petroleum oils and solvent- treated or acid-treated mineral lubricating oil of the paraffinic, naphthenic, or mixed paraffinic/naphthenic type which may be further refined by hydrofinishing processes and/or dewaxing.
  • Suitable base oils for use in the lubricating oil composition of the present invention are Group I-III mineral base oils (preferably Group III), Group IV poly- alpha olefins (PAOs), Group II-III Fischer-Tropsch derived base oils (preferably Group III) and mixtures thereof .
  • Group I lubricating oil base oils according to the definitions of American Petroleum Institute (API) for categories I, II, III and IV. These API categories are defined in API Publication 1509, 15th Edition, Appendix E, April 2002.
  • API American Petroleum Institute
  • Fischer-Tropsch derived base oils are known in the art.
  • Fischer-Tropsch derived is meant that a base oil is, or is derived from, a synthesis product of a Fischer-Tropsch process.
  • a Fischer-Tropsch derived base oil may also be referred to as a GTL (Gas-To-Liquids) base oil.
  • GTL Gas-To-Liquids
  • Suitable Fischer-Tropsch derived base oils that may be conveniently used as the base oil in the lubricating composition of the present invention are those as for example disclosed in EP 0 776 959, EP 0 668 342, WO
  • Synthetic oils include hydrocarbon oils such as olefin oligomers (including polyalphaolefin base oils; PAOs), dibasic acid esters, polyol esters, polyalkylene glycols
  • PAOs Poly-alpha olefin base oils
  • Preferred poly- alpha olefin base oils that may be used in the lubricating compositions of the present invention may be derived from linear C 2 to C32, preferably C6 to Ci 6 , alpha olefins.
  • Particularly preferred feedstocks for said poly-alpha olefins are 1-octene, 1-decene, 1-dodecene and 1- tetradecene .
  • the base oil contains more than 50 wt.%, preferably more than 60 wt.%, more preferably more than 70 wt.%, even more preferably more than 80 wt.%.
  • Fischer-Tropsch derived base oil preferably more than 90 wt.% Fischer-Tropsch derived base oil. In an especially preferred embodiment less than 10 wt.%, preferably less than 5 wt.%, more preferably not more than 2 wt.%, of the base oil is not a Fischer-Tropsch derived base oil.
  • the lubricating composition according to the present invention contains less than 20 wt.%, preferably less than 10 wt.%, more preferably less than 5 wt.%, of a PAO base oil, based on the total weight of the composition.
  • 100 wt% of the base oil is based on one or more Fischer-Tropsch derived base oils.
  • the total amount of base oil incorporated in the lubricating composition of the present invention is preferably present in an amount in the range of from 60 to
  • compositions of the present invention comprise a residual Fischer-Tropsch base oil.
  • residual base oil means a base oil where the initial boiling point can be fixed in a high vacuum column, at the heavy end or bottom end, but where the final boiling point is a resultant of the feedstock being distilled. Such final boiling point would exceed the thermal cracking temperature of the feedstock even under vacuum conditions.
  • a residual Fischer-Tropsch base oil gives a viscosity grade in the same range as mineral brightstock, yet while being residual, does not suffer from the compositional/ performance limitations of mineral brightstocks .
  • a residual Fischer-Tropsch base oil is highly paraffinic with low aromatics content, high inhibited oxidational stability and of the same order of viscosity as a heavy PAO.
  • the lubricating composition according to the present invention comprises a residual Fischer-Tropsch derived base oil having a kinematic viscosity at 100°C (according to ASTM D445) of at least 15 cSt and preferably above 18 cSt; preferably, this residual Fischer-Tropsch derived base oil has a kinematic viscosity at 100°C of below 30 cSt.
  • the lubricating composition according to the present invention may contain one or more further Fischer-Tropsch derived base oils having a lower kinematic viscosity at 100°C, such as about 3, 5 and 8 cSt .
  • the lubricating composition according to the present invention has a kinematic viscosity at 100°C of above 16.3 cSt .
  • the lubricating composition according to the present invention has a kinematic viscosity at 100°C of above 21.9 cSt, more preferably above 23.0 cSt .
  • composition according to the present invention is below 30.0 cSt, such as below 26.1 cSt .
  • the dynamic viscosity at -15°C of the lubricating composition is above 5000 cP, preferably above 6000 cP .
  • the dynamic viscosity at -20°C of the lubricating composition is below 15000 cP, preferably below 14000 cP .
  • the high temperature, high shear viscosity ("HTHS"; according to ASTM D 4683) of the lubricating composition according to the present invention is above 3.7 cP, preferably above 4.5 cP, more preferably above 5.0 cP, or even as high as above 5.5 or 6.0 cP .
  • the HTHS is below 8.0 cP .
  • the Noack volatility (according to ASTM D 5800) of the lubricating composition according to the present invention is between 1 and 15 wt.%, preferably below 14 wt.% and more preferably below 10.0 wt.%.
  • the Noack volatility is below 6.0 wt.%, more preferably below 5.0 wt . % or even as low as below 4.0 or below 3.5 wt.%.
  • the lubricating composition according to the present invention further comprises one or more additives such as anti-oxidants , anti-wear additives, dispersants,
  • the lubricating composition according to the present invention contains less than 1.0 wt.% of a Viscosity Index improver concentrate, based on the total weight of the composition.
  • a Viscosity Index improver concentrate based on the total weight of the composition.
  • composition is free of Viscosity Index improver
  • the lubricating composition contains at least 0.1 wt.% of a pour point depressant.
  • a pour point depressant As an
  • alkylated naphthalene and phenolic polymers, polymethacrylates , maleate/fumarate copolymer esters may be conveniently used as effective pour point depressants.
  • inventions may be conveniently prepared by admixing the one or more additives with the base oil(s) .
  • the above-mentioned additives are typically present in an amount in the range of from 0.01 to 35.0 wt.%, based on the total weight of the lubricating composition, preferably in an amount in the range of from 0.05 to 25.0 wt.%, more preferably from 1.0 to 20.0 wt.%, based on the total weight of the lubricating composition.
  • the composition contains at least 9.0 wt.%, preferably at least 10.0 wt.%, more preferably at least 11.0 wt% of an additive package comprising an anti- wear additive, a metal detergent, an ashless dispersant and an anti-oxidant .
  • PCMO Passenger Car Motor Oil
  • sulphated ash content (according to ASTM D 874) of up to 0.5 wt.%, up to 0.8 wt.% and up to 1.5 wt.%,
  • a phosphorus content (according to ASTM D 5185) of up to 0.05 wt.%, up to 0.08 wt.% and typically up to 0.1 wt.%, respectively;
  • sulphur content (according to ASTM D 5185) of up to 0.2 wt.%, up to 0.3 wt.% and typically up to 0.5 wt.%, respectively.
  • - a sulphated ash content (according to ASTM D 874) of up to 1 wt.%, up to 1 wt.% and up to 2 wt.%, respectively; - a phosphorus content (according to ASTM D 5185) of up to 0.08 wt.% (low SAPS) and up to 0.12 wt.% (mid SAPS), respectively; and
  • sulphur content (according to ASTM D 5185) of up to 0.3 wt.% (low SAPS) and up to 0.4 wt . % (mid SAPS),
  • Table 1 indicates the properties for the base oils used.
  • Table 2 indicates the composition and properties of the fully formulated SAE 20W-50, SAE 20W-60 and "20W- 70" engine oil formulations that were tested (SAE xW-70 grades do not exist yet; "XW-70” and “20W-70” are meant to refer to heavier grades than SAE xW-60 and SAE 20W-60, respectively) ; the amounts of the components are given in wt.%, based on the total weight of the fully formulated formulations .
  • Base oil 1 was a Fischer-Tropsch derived base oil
  • Base oil 2 was a Fischer-Tropsch derived base oil (“XHBO”) having a kinematic viscosity at 100°C (ASTM D445) of approx. 17 cSt (mm2s-l) .
  • Base oils 1 and 2 may be conveniently manufactured by the process described in e.g. US 7 354 508 B2, the teaching of which is hereby incorporated by reference.
  • Base oil 3 was a commercially available PAO base oil having a kinematic viscosity at 100°C (ASTM D445) of
  • Base oil 3 is commercially available from e.g. ExxonMobil Chemicals (Brussels, Belgium) under the trade designation "PAO 8".
  • Base oil 4" was a commercially available PAO base oil having a kinematic viscosity at 100°C (ASTM D445) of 40.33 cSt .
  • Base oil 4 is commercially available from e.g. ExxonMobil Chemicals (Brussels, Belgium) under the trade designation "PAO 40".
  • All tested engine oil formulations contained a combination of one more base oils, an additive package, a Viscosity Index improver concentrate and optionally a pour point depressant, which additive packages were the same in all tested compositions.
  • the additive package contained a combination of additives including anti-oxidants , a zinc-based anti-wear additive, an ashless dispersant, an overbased detergent mixture and about 10 ppm of an anti-foaming agent.
  • the Viscosity Index improver concentrate contained a conventional polymeric viscosity modifier (Infineum SV- 151 [a styrene-hydrogenated isoprene diblock polymer]; available from Infineum Additives (Milton Hill, Abingdon, UK) dissolved in a mixture of Shell XHVI base oil and an ester base stock) .
  • a conventional polymeric viscosity modifier Infineum SV- 151 [a styrene-hydrogenated isoprene diblock polymer]; available from Infineum Additives (Milton Hill, Abingdon, UK) dissolved in a mixture of Shell XHVI base oil and an ester base stock
  • the pour point depressant was a conventional
  • PAMA polyalkyl methacrylate
  • compositions of Example 1-7 were obtained by mixing the base oils with the additive packages and pour point depressant, using conventional lubricant blending procedures .
  • Base oil 1 Base oil 2
  • Base oil 3 Base oil 4 (XHBO 1) (XHBO 2) (PAO 8) (PAO 40)
  • the present invention surprisingly allows to formulate lubricating compositions such as engine oils having a high kinematic viscosity at 100°C (such as SAE xW-50, SAE xW-60 and "xW-70" grades), without the need of using mineral bright stock or heavy poly-alpha olefins (PAOs) .
  • lubricating compositions such as engine oils having a high kinematic viscosity at 100°C (such as SAE xW-50, SAE xW-60 and "xW-70” grades), without the need of using mineral bright stock or heavy poly-alpha olefins (PAOs) .
  • the lubricating composition according to the present invention have surprisingly low Noack volatility values, as low as below 3.5 wt . % .

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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

La présente invention concerne une composition lubrifiante comprenant une huile de base et un ou plusieurs additifs. L'huile de base comprend une huile de base résiduelle dérivée de Fischer Tropsch. À 0°C selon ASTM D 445, la composition lubrifiante présente une viscosité cinématique supérieure à 16.3 cSt.
PCT/EP2011/063397 2010-08-03 2011-08-03 Composition lubrifiante WO2012017023A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2013522245A JP5865907B2 (ja) 2010-08-03 2011-08-03 潤滑組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10305858.2 2010-08-03
EP10305858 2010-08-03

Publications (1)

Publication Number Publication Date
WO2012017023A1 true WO2012017023A1 (fr) 2012-02-09

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JP (1) JP5865907B2 (fr)
WO (1) WO2012017023A1 (fr)

Cited By (4)

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WO2014020007A1 (fr) * 2012-08-01 2014-02-06 Shell Internationale Research Maatschappij B.V. Composition de remplissage de câbles
CN104762123A (zh) * 2014-01-02 2015-07-08 英菲诺姆国际有限公司 用于润滑油组合物的粘度指数改进剂浓缩物
US9304231B2 (en) 2014-02-04 2016-04-05 Kraton Polymers U.S. Llc Heat fusible oil gels
CN112342071A (zh) * 2020-10-26 2021-02-09 中国石油化工股份有限公司 一种高hths性能的基础油组合物及其制备方法

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EP0668342A1 (fr) 1994-02-08 1995-08-23 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'une huile lubrifiante de base
EP0776959A2 (fr) 1995-11-28 1997-06-04 Shell Internationale Researchmaatschappij B.V. Procédé pour la production d'huiles lubrifiantes
WO1997021788A1 (fr) 1995-12-08 1997-06-19 Exxon Research And Engineering Company Huiles de base hydrocarbonees biodegradables et extremement efficaces
EP1029029A1 (fr) 1997-10-20 2000-08-23 Mobil Oil Corporation Compositions d'huiles de base de lubrifiant isoparaffiniques
WO1999041332A1 (fr) 1998-02-13 1999-08-19 Exxon Research And Engineering Company Huile de base a faible viscosite pour lubrifiants
WO2000008115A1 (fr) 1998-08-04 2000-02-17 Exxon Research And Engineering Company Huile de base pour lubrifiant a stabilite amelioree vis-a-vis de l'oxydation
WO2000014187A2 (fr) 1998-09-04 2000-03-16 Exxon Research And Engineering Company Lubrifiants synthetiques de premiere qualite
WO2000014183A1 (fr) 1998-09-04 2000-03-16 Exxon Research And Engineering Company Production de lubrifiant synthetique et de matiere de base pour lubrifiant sans deparaffinage
WO2000014179A1 (fr) 1998-09-04 2000-03-16 Exxon Research And Engineering Company Base de lubrifiant synthetique de premiere qualite
WO2000014188A2 (fr) 1998-09-04 2000-03-16 Exxon Research And Engineering Company Lubrifiant de premiere qualite resistant a l'usure
WO2000015736A2 (fr) 1998-09-11 2000-03-23 Exxon Research And Engineering Company Huiles lubrifiantes isoparaffiniques synthetiques a large fraction de distillation
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