EP1752514A1 - Schmiermittelzusammensetzung - Google Patents

Schmiermittelzusammensetzung Download PDF

Info

Publication number
EP1752514A1
EP1752514A1 EP05017221A EP05017221A EP1752514A1 EP 1752514 A1 EP1752514 A1 EP 1752514A1 EP 05017221 A EP05017221 A EP 05017221A EP 05017221 A EP05017221 A EP 05017221A EP 1752514 A1 EP1752514 A1 EP 1752514A1
Authority
EP
European Patent Office
Prior art keywords
oil
asphalted
base
bright stock
range
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP05017221A
Other languages
English (en)
French (fr)
Inventor
Peter Busse
Steven Allen Holmes
Carsten Karl Puls
David John Wedlock
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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 BV filed Critical Shell Internationale Research Maatschappij BV
Priority to EP05017221A priority Critical patent/EP1752514A1/de
Publication of EP1752514A1 publication Critical patent/EP1752514A1/de
Withdrawn legal-status Critical Current

Links

Images

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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/02—Specified values of viscosity or viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil
    • 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
    • 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
    • C10M2203/108—Residual fractions, e.g. bright stocks
    • C10M2203/1085—Residual fractions, e.g. bright stocks used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the present invention relates to a base oil blend, a process to prepare a base oil blend and a lubricating oil composition comprising said base oil blend.
  • GB-A-1496045 describes a process to prepare high viscosity base oils wherein a vacuum residue of a crude petroleum source is first subjected to a propane de-asphalting step to obtain a de-asphalted oil (DAO). The DAO is further subjected to a furfural extraction process in order to extract de-asphalted cylinder oil (DACO) therefrom as the polycyclic compounds therein are undesirable because of their low viscosity index and oxidative stability.
  • the bright stock waxy raffinate obtained after furfural extraction is then subjected to a solvent de-waxing step and hydrofinishing in order to produce bright stock oil.
  • US-A-4592832 discloses a process to prepare a bright stock oil having a kinematic viscosity at 100 °C of 37 MM 2 /sec and a viscosity index of 95 as prepared from a light Arabian Vacuum Resid.
  • the light Arabian Vacuum Resid is subjected to a propane de-asphalting step to prepare a DAO.
  • the DAO is subjected to a N-methylpyrrolidone (NMP) solvent extraction step followed by de-waxing to obtain the bright stock oil.
  • NMP N-methylpyrrolidone
  • Bright stock oil is commonly used as a base oil in lubricating oil compositions, in particular in lubricating oil compositions for marine and stationary low-speed crosshead diesel engines burning residual fuels with sulphur contents of up to 4.0 wt. % and for trunk piston, medium-speed diesel engines operating on residual fuel in industrial and marine applications.
  • marine does not restrict such engines to those used in water-borne vessels. That is to say, in addition said term also includes engines used for power generation applications. These highly rated, fuel efficient, slow-speed marine and stationary diesel engines operate at high pressures, high temperatures and long strokes.
  • a base oil blend comprising (A) bright stock oil, (B) de-asphalted cylinder oil (DACO) and, optionally, (C) one or more medium to high viscosity distillate base oils, wherein said de-asphalted cylinder oil is present in an amount in the range of from 5 to 40 wt. %, based on the total amount of said base oil blend.
  • DACO de-asphalted cylinder oil
  • C medium to high viscosity distillate base oils
  • the present invention also provides a lubricating oil composition
  • a lubricating oil composition comprising said base oil blend and one or more additives selected from dispersants, detergents, antiwear agents, friction reducing agents, viscosity thickeners, metal passivators, acid sequestering agents, pour point depressants, corrosion inhibitors, defoaming agents, seal fix or seal compatibility agents and antioxidants.
  • the present invention further provides for the use of said lubricating oil composition as a cylinder oil lubricant for cross-head engines or a trunk piston engine oil. Additionally, the lubricating oil composition of the present invention may be used in medium-speed industrial or marine propulsion and auxiliary engines burning residual fuel oils.
  • the base oil blend of the present invention preferably comprises an amount in the range of from 5 to 30 wt. %, more preferably in the range of from 5 to 21 wt. % of de-asphalted cylinder oil, based on the total amount of said base oil blend.
  • the base oil blend of the present invention preferably has a kinematic viscosity at 100 °C of at least 10 mm 2 /s, more preferably at least 13 mm 2 /s.
  • the kinematic viscosity at 100 °C of said base oil blend is no more than 16 mm 2 /s.
  • said base oil blend has a kinematic viscosity at 100 °C in the range of from 10 mm 2 /s to 16 mm 2 /s, more preferably.in the range of from 13 mm 2 /s to 16 mm 2 /s .
  • the viscosity index of the base oil blend of the present invention is preferably at least 71, more preferably in the range of from 80 to 120 and most preferably in the range of from 83 to 100.
  • the de-asphalted oil (DAO) used in the process of the present invention is defined as the product of a de-asphalting process step wherein asphalt is removed from a reduced crude petroleum feed or from the residue, bottom fraction, of a vacuum distillation of a crude petroleum feed (hereinafter referred to as "mineral-derived vacuum residues").
  • the de-asphalting process utilises a light hydrocarbon liquid solvent, for example propane, for asphalt compounds.
  • step (i) of the process of the present invention the de-asphalted oil undergoes solvent extraction, wherein aromatic extract known as de-asphalted cylinder oil (DACO) is removed therefrom.
  • DACO de-asphalted cylinder oil
  • the de-asphalted solvent-extracted oil is known as bright stock waxy raffinate.
  • solvent extraction process examples include furfural or NMP solvent extraction processes or other solvent extraction processes, for example, as described in Chapter 5 of "Lubricant base oil and wax processing", Avilino Sequeira, Jr., Marcel Dekker, Inc, New York, 1994, ISBN 0-8247-9256-4 .
  • step (i) of the process of the present invention the bright stock waxy raffinate subsequently undergoes a de-waxing process.
  • the de-waxing process is for example a solvent dewaxing process.
  • the de-waxed product is known as bright stock oil and preferably has a pour point of below -5 °C.
  • Said bright stock oil may be optionally hydro-finished prior to blending with a de-asphalted cylinder oil in step (ii) of the process of the present invention.
  • Hydrofinishing is typically carried out, for example, if the bright stock oil contains olefins or when the bright stock oil is sensitive to oxygenation.
  • Hydrofinishing may be conveniently carried out at a temperature between 180 and 380 °C, a total pressure of between 10 to 250 bar, preferably above 100 bar and more preferably between 120 and 250 bar.
  • the WHSV Weight hourly space velocity
  • the WHSV may range from 0.3 to 2 kg of oil per litre of catalyst per hour (kg/l.h).
  • the hydrogenation catalyst for hydrofinishing may suitably be a supported catalyst comprising a dispersed Group VIII metal.
  • Possible Group VIII metals are cobalt, nickel, palladium and platinum.
  • Cobalt and nickel containing catalysts may also comprise a Group VIB metal, suitably molybdenum and tungsten.
  • Suitable carrier or support materials include low acidity amorphous refractory oxides. Examples of suitable amorphous refractory oxides include inorganic oxides, such as alumina, silica, titania, zirconia, boria, silica-alumina, fluorided alumina, fluorided silica-alumina and mixtures of two or more of these.
  • suitable hydrogenation catalysts for hydrofinishing are nickel-molybdenum containing catalyst such as KF-847 and KF-8010 (AKZO Nobel) M-8-24 and M-8-25 (BASF), and C-424, DN-190, HDS-3 and HDS-4 (Criterion); nickel-tungsten containing catalysts such as NI-4342 and NI-4352 (Engelhard) and C-454 (Criterion); cobalt-molybdenum containing catalysts such as KF-330 (AKZO-Nobel), HDS-22 (Criterion) and HPC-601 (Engelhard).
  • platinum-containing and more preferably platinum- and palladium-containing catalysts are used.
  • Preferred supports for these palladium and/or platinum containing catalysts are amorphous silica-alumina.
  • suitable silica-alumina carriers are disclosed in WO-A-94/10263 .
  • a preferred catalyst comprises an alloy of palladium and platinum preferably supported on an amorphous silica-alumina carrier of which the commercially available catalyst C-624 of Criterion Catalyst Company (Houston, TX) is an example.
  • the kinematic viscosity at 100 °C of the bright stock oil is in the range of from 29 to 35 mm 2 /s.
  • the viscosity index of the bright stock oil is preferably in the range of from 92 to 98.
  • the de-asphalted cylinder oil preferably has a negative viscosity index or a viscosity index in the range of from -45 to 80.
  • the kinematic viscosity at 100 °C of the de-asphalted cylinder oil is preferably at least 40 mm 2 /s, more preferably at least 48 mm 2 /s.
  • the pour point of the de-asphalted cylinder oil is preferably below 50 °C, more preferably below 27 °C and most preferably below 21 °C.
  • the de-asphalted cylinder oil may be prepared by de-asphalting a mineral-derived vacuum residue to obtain a de-asphalted oil, solvent-extracting the de-asphalted oil and obtaining the de-asphalted cylinder oil (DACO) extract.
  • DACO de-asphalted cylinder oil
  • the de-asphalted cylinder oil (DACO) extract may be subjected to a solvent de-waxing step prior to being using in the present invention.
  • the de-asphalted cylinder oil extract is used as obtained in the solvent extraction process step without subjecting said de-asphalted cylinder oil to a de-waxing step.
  • the de-asphalted cylinder oil used in step (ii) of the process of the present invention may be conveniently obtained from a separate process or process run to that in which the bright stock oil is prepared.
  • This embodiment has particular utility in situations wherein the base oil blend is to be prepared in a separate location or at a different time from that in which the bright stock oil and/or de-asphalted cylinder oil are prepared.
  • the de-asphalted cylinder oil extracted in step (i) of the process of the present invention may be subsequently blended in step (ii) with the bright stock oil prepared in step (i) in an integrated process. That is to say, in said embodiment of the present invention, the preparation, isolation and subsequent blending of bright stock oil and de-asphalted cylinder oil are integral parts of the same process.
  • one or more medium to high viscosity distillate base oils may be blended with the bright stock oil and/or de-asphalted cylinder oil.
  • step (iii) may take place after blending together of the bright stock oil and de-asphalted cylinder oil in step (ii)
  • said optional step (iii) may take place by blending the one or more medium to high viscosity distillate base oils with the bright stock oil prior to blending with the de-asphalted cylinder oil in step (ii)
  • said optional step (iii) may take place by blending the one or more medium to high viscosity distillate base oils with the de-asphalted cylinder oil prior to blending with the bright stock oil in step (ii) or, alternatively, (d) the bright stock oil, de-asphalted cylinder oil and one or more medium to high viscosity distillate base oils may be conveniently blended together simultaneously in step (ii).
  • the one or more medium to high viscosity distillate base oils which may be optionally present in the base oil blend of the present invention may be conveniently prepared by vacuum distillation, solvent extraction, de-waxing, and hydrogenation and/or hydroisomerisation.
  • Said one or more medium to high viscosity distillate base oils may conveniently be base oils having a kinematic viscosity at 100 °C in the range of from 5 to 13 mm 2 /s and a viscosity index in the range of from 80 to 120, preferably in the range of from 94 to 120.
  • Particularly preferred medium to high viscosity distillate base oils include Group I and Group II base oils.
  • Group I base oils and “Group II” base oils in the present invention are meant base oils according to the definitions of American Petroleum Institute (API) categories I and II. Such API categories are defined in API Publication 1509, 15th Edition, Appendix E, April 2002 .
  • API American Petroleum Institute
  • Group I base oils contain less than 90 % saturates (according to ASTM D2007) and/or greater than 0.03 % sulphur (according to ASTM D2622, D4294, D4927 or D3120) and have a viscosity index of greater than or equal to 80 and less than 120 (according to ASTM D2270).
  • Group II base oils contain greater than or equal to 90 % saturates and less than or equal to 0.03 % sulphur and have a viscosity index of greater than or equal to 80 and less than 120, according to the aforementioned ASTM methods.
  • the base oil blend of the present invention preferably comprises an amount in the range of from 40 to 80 wt. % of said one or more medium to high viscosity distillate base oils, based on the total amount of said base oil blend.
  • the bright stock oil (A), de-asphalted cylinder oil (B) and, optionally, one or more medium to high viscosity distillate base oils (C) may be conveniently blended together in a blending unit under elevated temperatures of not exceeding 80 °C.
  • the resulting de-asphalted oil (DAO) 5 is fed to a solvent extraction unit 6 wherein said material undergoes solvent extraction, for example with furfural or NMP, in order to extract de-asphalted cylinder oil (DACO) 7 therefrom.
  • solvent extraction for example with furfural or NMP
  • the resulting bright stock waxy raffinate 8 is then passed to a de-waxing unit 9 wherein said material undergoes de-waxing utilising, for example, methyl ethyl ketone (MEK)and/or toluene to remove bright stock slack wax 10 therefrom.
  • de-waxing utilising, for example, methyl ethyl ketone (MEK)and/or toluene to remove bright stock slack wax 10 therefrom.
  • MEK methyl ethyl ketone
  • the resulting bright stock oil 11 may undergo optional hydrofinishing (not shown in Figure 1) prior to being fed to blending unit 12.
  • the bright stock oil 11 is blended with de-asphalted cylinder oil 7 from the solvent extraction unit 6 in blending unit 12 in order to produce the base oil blend 13 as described herein.
  • the amount of de-asphalted cylinder oil (DACO) 7 required in the base oil blend 13 will depend on the desired resultant properties thereof. Any non-used de-asphalted cylinder oil (DACO) 7 may be conveniently discharged from the process as a separate product via a separate line (not shown in Figure 1).
  • the base oil blend of the present invention may conveniently find application in lubricating oil compositions, in particular in cylinder oil lubricants for cross-head engines or trunk piston engine oils.
  • Cylinder oil lubricants are preferably used on a once-through basis by means of injection devices that apply the cylinder oil lubricant to lubricators positioned around the cylinder liner of a slow speed diesel engine.
  • Diesel engines may generally be classified as slow-speed, medium-speed or high-speed engines, with the slow-speed variety being used for the largest, deep draft vessels and in industrial applications.
  • Slow-speed diesel engines are typically direct coupled, direct reversing, two-stroke cycle engines operating in the range of about 57 to 250 rpm and usually run on residual fuels. These engines are of crosshead construction with a diaphragm and stuffing boxes separating the power cylinders from the crankcase to prevent combustion products from entering the crankcase and mixing with the crankcase oil.
  • Medium-speed engines typically operate in the range of 250 to about 1100 rpm and may operate on the four-stroke or two-stroke cycle. These engines are trunk piston design, and many also operate on residual fuel containing in excess of 2.5 wt. % of sulphur. They may also operate on distillate fuel containing little or no residua. On deep-sea vessels these engines may be used for propulsion, ancillary applications or both.
  • Each type of diesel engine employs lubricating oils to lubricate piston rings, cylinder liners, bearings for crank shafts and connecting rods, valve train mechanisms including cams and valve lifters, among other moving members.
  • the lubricant prevents component wear, removes heat, neutralizes and disperses combustion products, prevents rust and corrosion, and prevents sludge formation or deposits.
  • the cylinders and crankcase are lubricated separately, with cylinder lubrication being provided on a once-through basis by means of injection devices that apply cylinder oil to lubricators positioned around the cylinder liner.
  • This is known as an "all-loss" lubrication system.
  • the cylinder oil is typically formulated to provide for good oxidation and thermal stability, water demulsability, corrosion protection and good antifoam performance.
  • Alkaline detergent additives are also present to neutralize acids formed during the combustion process. Dispersant, antioxidant, antifoam, antiwear and extreme pressure (EP) performance may also be provided by the use of suitable additives.
  • the lubricating oil composition according to the present invention comprises a base oil blend as hereinbefore described, which base oil blend comprises
  • the base oil blend as hereinbefore described is present in said lubricating oil composition in an amount in the range of from 72 to 90 wt. %, more preferably in an amount in the range of from 74 to 87 wt. %, based on the total amount of said lubricating oil composition.
  • Detergents that may be conveniently used in the lubricating oil composition of the present invention, include one or more detergents selected from phenate detergents, salicylate detergents and sulphonate detergents.
  • Alkali metal and alkaline earth metal salicylate, phenate and sulphonate detergents are preferred in the lubricating oil compositions of the present invention.
  • Calcium and magnesium salicylates, phenates and sulphonates are particularly preferred detergents therein.
  • Detergents used in the lubricating oil composition of the present invention may each, independently, have a TBN (total base number) value in the range of from 30 to 350 mg KOH/g, preferably about 70 mg KOH/g, as measured by ISO 3771 and are preferably present in a total amount in the range of from 0.5 to 18 wt. %, based on the total weight of said lubricating oil composition.
  • TBN total base number
  • Antioxidants which may be conveniently used in the lubricating oil composition of the present invention, include one or more antioxidants selected from the group of aminic antioxidants and/or phenolic antioxidants.
  • Said antioxidants may be generally present in a total amount in the range of from 0 to 2 wt. %, based on the total weight of said lubricating oil composition.
  • aminic antioxidants which may be conveniently used include alkylated diphenylamines, phenyl- ⁇ -naphthylamines, phenyl- ⁇ -naphthylamines and alkylated ⁇ -naphthylamines.
  • Preferred aminic antioxidants include dialkyldiphenylamines such as p,p'-dioctyl-diphenylamine, p,p'-di- ⁇ -methylbenzyl-diphenylamine and N-p-butylphenyl-N-p'-octylphenylamine, monoalkyldiphenylamines such as mono-t-butyldiphenylamine and mono-octyldiphenylamine, bis(dialkylphenyl)amines such as di-(2,4-diethylphenyl)amine and di(2-ethyl-4-nonylphenyl)amine, alkylphenyl-1-naphthylamines such as octylphenyl-1-naphthylamine and n-t-dodecylphenyl-1-naphthylamine, 1-naphthylamine, arylnaph
  • Preferred aminic antioxidants include those available under the following trade designations:
  • phenolic antioxidants which may be conveniently used include C7-C9 branched alkyl esters of 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-benzenepropanoic acid, 2-t-butylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-5-methylphenol, 2,4-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-4-alkylphenols such as 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol and 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-alkoxyphenols such as 2,6-di-t-butyl
  • Preferred phenolic antioxidants include those available under the following trade designations:
  • the lubricating oil composition of the present invention may comprise one or more zinc dithiophosphates as antiwear additives, the or each zinc dithiophosphate being selected from zinc dialkyl-, diaryl- or alkylaryl-dithiophosphates. Zinc dialkyl dithiophosphates are particularly preferred.
  • suitable zinc dithiophosphates which are commercially available include those available ex. Lubrizol Corporation under the trade designations “Lz 1097” and “Lz 1395", those available ex. Chevron Oronite under the trade designations “OLOA 26,7” and “OLOA 269R”, and that available ex. Ethyl under the trade designation “HITEC 7197”; zinc dithiophosphates such as those available ex. Lubrizol Corporation under the trade designations “Lz 677A”, “Lz 1095” and “Lz 1371", that available ex. Chevron Oronite under the trade designation “OLOA 262” and that available ex. Ethyl under the trade designation "HITEC 7169”; and zinc dithiophosphates such as those available ex. Lubrizol Corporation under the trade designations “Lz 1370” and “Lz 1373” and that available ex. Chevron Oronite under the trade designation "OLOA 260".
  • the lubricating oil composition according to the present invention may generally comprise in the range of from 0.1 to 1.5 wt. % of zinc dithiophosphate, preferably in the range of from 0.4 to 0.9 wt. % and most preferably in the range of from 0.45 to 0.8 wt. %, based on total weight of the lubricating oil composition.
  • antiwear additives that may be conveniently used include molybdenum-containing compounds and boron-containing compounds.
  • molybdenum-containing compounds may conveniently include molybdenum dithiocarbamates, trinuclear molybdenum compounds, for example as described in WO-A-98/26030 , sulphides of molybdenum and molybdenum dithiophosphate.
  • Said molybdenum-containing antiwear additives may be conveniently added to the lubricating oil composition of the present invention in an amount in the range of from 0.1 to 3.0 wt. %, based on the total weight of lubricating oil composition.
  • Boron-containing compounds that may be conveniently used include borate esters, borated fatty amines, borated epoxides, alkali metal (or mixed alkali metal or alkaline earth metal) borates and borated overbased metal salts.
  • Said boron-containing anti-wear additives may be conveniently added to the lubricating oil composition of the present invention in an amount in the range of from 0.1 to 3.0 wt. %, based on the total weight of lubricating oil composition.
  • the lubricating oil compositions of the present invention may additionally contain one or more dispersants which may be preferably admixed in an .amount in the range of from 5 to 15 wt. %, based on the total weight of the lubricating oil composition.
  • dispersants examples include the polyalkenyl succinimides and polyalkenyl succininic acid esters disclosed in Japanese Patent Nos. 1367796 , 1667140 , 1302811 and 1743435 .
  • Preferred dispersants include borated succinimides.
  • Preferred friction reducing agents that may be conveniently used include fatty acid amides, more preferably unsaturated fatty acid amides.
  • the total amount of friction reducing agents that may be added to the lubricating oil composition of the present invention is conveniently in the range of from 0.05 to 1.2 wt. %, based on the total weight of the lubricating oil composition.
  • Polymethacrylates such as those as disclosed in Japanese Patent Nos. 1195542 and 1264056 may be conveniently employed in the lubricating oil compositions of the present invention as effective pour point depressants.
  • compounds such as alkenyl succinic acid or ester moieties thereof, benzotriazole-based compounds and thiodiazole-based compounds may be conveniently used in the lubricating oil composition of the present invention as corrosion inhibitors.
  • seal fix or seal compatibility agents include, for example, commercially available aromatic esters.
  • the lubricating oil compositions of the present invention may be conveniently prepared by admixing the base oil blend and the one or more additives selected from dispersants, detergents, antiwear agents, friction reducing agents, viscosity thickeners, metal passivators, acid sequestering agents, pour point depressants, corrosion inhibitors, defoaming agents, seal fix or seal compatibility agents and antioxidants.
  • additives selected from dispersants, detergents, antiwear agents, friction reducing agents, viscosity thickeners, metal passivators, acid sequestering agents, pour point depressants, corrosion inhibitors, defoaming agents, seal fix or seal compatibility agents and antioxidants.
  • a method of lubricating a marine or stationary low-speed crosshead diesel engine or a trunk piston medium speed diesel engine comprising applying a lubricating oil composition as hereinbefore described thereto.
  • Oil blends A-F were made using base oils listed in Table 1. Two different de-asphalted cylinder oils are listed in Table 1.
  • DACO de-asphalted cylinder oils
  • the bright stock oil was prepared by dewaxing waxy raffinate from a furfuryl extraction unit.
  • the High Viscosity Oil 1 (Medium VI) and Medium Viscosity Oil 3 were prepared by furfuryl extraction, dewaxing and hydrotreatment of distillate streams from Vacuum Distillation.
  • the High Viscosity Oil 2 (High VI) and Medium Viscosity Oil 4 were prepared by hydroisomerisation using catalytic isomerisation, dewaxing, and hydrogenation processes to lower the sulphur and nitrogen contents, increase the amount of saturated components to greater than 90 wt. %, and decrease the pour point of the saturated components to less than -12 °C.
  • the base oil blends shown in Table 2 target a kinematic viscosity at 100 °C of 14.4 mm 2 /s.
  • the base oil blends range in viscosity index from 84 to 100.
  • Increasing the amount of DACO has the effect of lowering the VI.
  • a greater amount of DACO may be blended with medium viscosity oil. For example, blending the High Viscosity Oil 2 (high VI) with DACO raises the VI to 100.
  • Blend A is comparative in nature whilst blends B to F are according to the present invention.
  • TABLE 2 Base Oil Blends A B C D E F De-asphalted cylinder oil 1* (DACO) (wt. %) 0 8 0 34 10 39 De-asphalted cylinder oil 2** (DACO) (wt. %) 0 0 19 0 0 0 Bright Stock Oil (wt. %) 24 15 21.5 5 17 17.5 High Viscosity Oil 1 (wt. %) 76 77 0 0 0 0 High Viscosity Oil 2 (wt. %) 0 0 0 0 73 0 Medium Viscosity Oil 3 (wt.
  • Lubricating oil compositions were made by blending the base oil blends A-C with a 26.4 wt. % of a conventional fully formulated 70 mg KOH/g TBN detergent cylinder oil additive package containing highly overbased calcium phenate and sulphonate detergents, succinimide dispersant and zinc alkyl dithiophosphate in diluent oil (approximately 44 % of the total additive package).
  • the resulting lubricating oil compositions are denoted in Table 3 as A'-C', respectively.
  • Oxidation stability tendency was tested by using differential scanning calorimetry (DSC) at 210°C at 10 bar oxygen at continuous flow. Longer induction times inferred greater oxidation stability.
  • High temperature deposit forming tendency was tested by using a Micro Coker test. Test duration was 90 minutes. The temperature is recorded when deposits are observed to form.
  • blends A'-C' showed good to excellent test results compared with commercial products X and Y.
  • blends B' and C' (which contained DACO) showed comparable DSC and Wolf Strip data to blend A' (which did not contain DACO).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)
EP05017221A 2005-08-08 2005-08-08 Schmiermittelzusammensetzung Withdrawn EP1752514A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05017221A EP1752514A1 (de) 2005-08-08 2005-08-08 Schmiermittelzusammensetzung

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP05017221A EP1752514A1 (de) 2005-08-08 2005-08-08 Schmiermittelzusammensetzung

Publications (1)

Publication Number Publication Date
EP1752514A1 true EP1752514A1 (de) 2007-02-14

Family

ID=35432505

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05017221A Withdrawn EP1752514A1 (de) 2005-08-08 2005-08-08 Schmiermittelzusammensetzung

Country Status (1)

Country Link
EP (1) EP1752514A1 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2470626A1 (de) * 2009-08-28 2012-07-04 Shell Internationale Research Maatschappij B.V. Prozessölzusammensetzung
US8702968B2 (en) 2011-04-05 2014-04-22 Chevron Oronite Technology B.V. Low viscosity marine cylinder lubricating oil compositions
WO2018001908A1 (en) 2016-06-28 2018-01-04 Shell Internationale Research Maatschappij B.V. Lubricating composition
CN110563288A (zh) * 2019-09-06 2019-12-13 湖南伟方环保技术股份有限公司 用于处理罐底油泥的除砂降粘剂及应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2721181A (en) * 1952-10-09 1955-10-18 Kendall Refining Company Lubricant
US2830952A (en) * 1955-03-01 1958-04-15 Pure Oil Co Gear oil compositions
US4513155A (en) * 1982-06-24 1985-04-23 Nippon Mining Co., Ltd. Lubricating oil for diesel engines
FR2685705A1 (fr) * 1991-12-30 1993-07-02 Bp France Huiles de procede.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2721181A (en) * 1952-10-09 1955-10-18 Kendall Refining Company Lubricant
US2830952A (en) * 1955-03-01 1958-04-15 Pure Oil Co Gear oil compositions
US4513155A (en) * 1982-06-24 1985-04-23 Nippon Mining Co., Ltd. Lubricating oil for diesel engines
FR2685705A1 (fr) * 1991-12-30 1993-07-02 Bp France Huiles de procede.

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2470626A1 (de) * 2009-08-28 2012-07-04 Shell Internationale Research Maatschappij B.V. Prozessölzusammensetzung
US8702968B2 (en) 2011-04-05 2014-04-22 Chevron Oronite Technology B.V. Low viscosity marine cylinder lubricating oil compositions
WO2018001908A1 (en) 2016-06-28 2018-01-04 Shell Internationale Research Maatschappij B.V. Lubricating composition
CN109415644A (zh) * 2016-06-28 2019-03-01 国际壳牌研究有限公司 润滑组合物
KR20190022532A (ko) * 2016-06-28 2019-03-06 쉘 인터내셔날 리써취 마트샤피지 비.브이. 윤활 조성물
US20190203141A1 (en) * 2016-06-28 2019-07-04 Shell Oil Company Lubricating composition
US10752857B2 (en) * 2016-06-28 2020-08-25 Shell Oil Company Lubricating composition
CN109415644B (zh) * 2016-06-28 2021-11-12 国际壳牌研究有限公司 润滑组合物
CN110563288A (zh) * 2019-09-06 2019-12-13 湖南伟方环保技术股份有限公司 用于处理罐底油泥的除砂降粘剂及应用

Similar Documents

Publication Publication Date Title
EP1789521B1 (de) Schmierölzusammensetzung
RU2394876C2 (ru) Композиция смазочных материалов
US20060009366A1 (en) Lubricating oil composition
EP1752514A1 (de) Schmiermittelzusammensetzung
EP3227414B1 (de) Verwendung zur verminderung von vorzündung mit niedriger geschwindigkeit
EP2964738B1 (de) Schmiermittelzusammensetzung
EP1788068B1 (de) Verwendung eines Magnesium Detergenz in einer Schmierölzusammensetzung
JP5659163B2 (ja) 潤滑組成物
JP2021515081A (ja) 低粘度で摩耗防止を提供する潤滑油組成物
US20190309237A1 (en) Ether-Based Lubricant Compositions, Methods and Uses
KR20230118992A (ko) 유기 아민 및 글리시돌의 반응 생성물 및 마찰 조정제로서의이의 용도
US20070129266A1 (en) Lubricating Oil Composition
WO2016184842A1 (en) Lubricating composition
US11492566B2 (en) Ether-based lubricant compositions, methods and uses
EP3197986B1 (de) Verwendung eines aschefreien reibungsmodifikators
JP7107938B2 (ja) エーテル系の潤滑剤組成物、方法および使用
WO2010066862A1 (en) Lubricating compositions
EP3555251A1 (de) Etherbasierte schmiermittelzusammensetzungen, verfahren und verwendungen
EP3336162A1 (de) Schmiermittelzusammensetzung
WO2016032782A1 (en) Methods for lubricating a diamond-like carbon coated surface, associated lubricating oil compositions and associated screening methods
JP2023509364A (ja) ポリアルファオレフィンを含む潤滑油組成物
US20140315770A1 (en) Lubricating composition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20070305