EP0616636A1 - Reduction des degagements de matieres particulaires par les moteurs diesel - Google Patents
Reduction des degagements de matieres particulaires par les moteurs dieselInfo
- Publication number
- EP0616636A1 EP0616636A1 EP92916215A EP92916215A EP0616636A1 EP 0616636 A1 EP0616636 A1 EP 0616636A1 EP 92916215 A EP92916215 A EP 92916215A EP 92916215 A EP92916215 A EP 92916215A EP 0616636 A1 EP0616636 A1 EP 0616636A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- base oil
- lubricating composition
- measured
- oil
- mass
- 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- Withdrawn
Links
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- 150000002009 diols Chemical class 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 1
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- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
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- 150000003873 salicylate salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
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- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
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- 230000000153 supplemental effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
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Classifications
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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
- 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
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- C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
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- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
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- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
- C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
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- C10M129/42—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms polycarboxylic
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- C10M133/38—Heterocyclic nitrogen compounds
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- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
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- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/02—Sulfurised compounds
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- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M135/20—Thiols; Sulfides; Polysulfides
- C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
- C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives thereof
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- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
- C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
-
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
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- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
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- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
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- C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
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- 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
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/06—Well-defined aromatic compounds
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- 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
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- 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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/02—Unspecified siloxanes; Silicones
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
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- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
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- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- 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
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- 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
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- 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
- C10N2040/251—Alcohol fueled engines
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- 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
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- 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
- C10N2040/253—Small diesel engines
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- 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
- C10N2040/255—Gasoline engines
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- 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
- C10N2040/255—Gasoline engines
- C10N2040/28—Rotary engines
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
Definitions
- lubricant typically 0.0025 parts by mass of lubricant for 1 part by mass of fuel
- "breathable" gases nitrogen, water, carbon dioxide, and oxygen
- gaseous pollutants primarily carbon monoxide, unburnt hydrocarbons, nitrogen oxides and sulphur oxides
- particulate pollutants primarily unburnt oil, carbon, unburnt fuel and inorganic materials
- crankcase lubricating oils can be formulated to give reduced emission of particulate materials by diesel engines.
- the invention also provides the use of a lubricating composition having at least two, advantageously more than two, and preferably all, of characteristics or components (a) to (e) above, for reducing the amount of particulate material emitted by a diesel engine.
- the invention also provides a crankcase lubricating composition suitable for use in diesel engines which has at least two, advantageously more than two, and preferably all, of characteristics or components (a)' to (e) above.
- Solvent 130 Neutral Mineral Oil is an oil which is derived by the vacuum distillation of crude oil followed by solvent extraction, dewaxing, and finishing, and has a viscosity index, measured by ASTM D2270, of 100 or more, a pour point, measured by ASTM D97, of -15°C or .lower, and a kinematic viscosity at 40°C of 4.4 to 4.8 cSt (4.4 to 4.8 x 10 ⁇ 6 m 2 /s) .
- a lubricating composition for use in accordance with the first aspect of the invention or used in a process of the first aspect of the invention preferably has a high shear viscosity of less than 4.5 cP (4.5 mPas) . In some cases a high shear viscosity of less than 4 is desirable.
- the high shear viscosity is measured by Test Method CEC-L-36-T-8 . This method uses a Ravenfield viscometer in which the lubricating composition is fed to the gap between a small angle conical rotor and a correspondingly-shaped outer stator. The viscosity is measured at a shear rate of 10 ⁇ 6 seconds and a temperature of 150°C. v
- the lubricating composition of the first aspect of the invention advantageously also has a low shear viscosity which is relatively high.
- the low shear viscosity (measured at 100°C by ASTM D445) is advantageously at least 10 cSt (10 ⁇ 5 m 2 /s) .
- the invention also provides the use, for reducing the amount of particulate material emitted by a diesel engine, of an XW40 viscosity grade lubricating composition having a high shear viscosity (measured by Test Method CEC-L-36-T-84) of less than 4.5 cP (4.5 mPas) and a volatility (measured by Test Method CEC-L-40-T-87) of less than 15%, and further provides a process for lubricating a diesel engine with such a lubricating composition.
- the polymer used in preparing an additive of the above- mentioned type advantageously has a shear stability index (percentage polymer breakdown as defined in IP procedure 294) of at least 25, preferably at least 30.
- the shear stability index of the polymer is advantageously in the range of from 30 to 50, and is preferably in the range of from 30 to 40.
- the use in the invention of a polymer having a specified minimum shear stability index is in contrast to the generally accepted view in the industry that the shear stability index of polymeric additives for lubricating oils should be as low as possible.
- Suitable polymers typically have number average molecular weights of from 30,000 to 80,000, preferably 40,000 to 60,000, as determined by gel permeation chromatograph .
- the polymers may, if desired, contain groups to impart characteristics to them in addition to their viscosity modifying properties.
- the polymers may have dispersant as well as viscosity modifying properties.
- a viscosity modifier suitable for the first aspect of the invention is in general dictated largely by handling considerations, and can be determined by routine experiment.
- a viscosity modifier comprising an olefin copolymer dissolved in a poly- ⁇ -olefin may comprise 5 to 15 mass % polymer and 95 to 85 mass % poly- ⁇ -olefin.
- a additive comprising about 7.5 mass % polymer and about 92.5 mass % poly- ⁇ -olefin was found to be advantageous.
- the base oil in which the viscosity modifier additive (polymer plus a base oil) is dissolved may be any oil of lubricating viscosity.
- the oil will conveniently have a viscosity of about 2.5 to about 12 cSt (about 2.5 x 10 -6 to about
- oils are those such that the final lubricating composition has a viscosity in the range of from 3 to 7 cSt (3 x 10 ⁇ 6 to
- Substances to be tested in this case base oils for lubricating compositions, are introduced into the engine, while it is running under the above conditions, via the air inlet system, the amount of the substance introduced being controlled using a valve.
- substantially equal masses of the substances should be introduced into the engine.
- base oils for the second aspect of the invention are base oils comprising synthetic oils of lubricating viscosity, for example, poly- ⁇ -olefins and poly-internal-ole ins.
- suitable poly- ⁇ -olefins are polyisobutene and poly-n-butene (poly-1-butene) .
- Poly- ⁇ -olefins having viscosities of about 4 to 8 cSt (4 x 10 -6 to 8 x 10 -6 m 2 /s) at 100°C are particularly suitable.
- a lubricating composition contains low or zero amounts of zinc compounds, for example, ZDDPs
- ZDDPs zinc compounds
- additives which may be used for this purpose in lubricating compositions which contain low or zero levels of zinc and/or phosphorus may be found in European Patent Specifications No. 280 579 A and 280 580 A, the disclosures of which are incorporated herein by reference.
- additives which may be incorporated in lubricating compositions to impart adequate antioxidant performance when ZDDPs are absent or present at only low levels are oil-soluble copper compounds, the compositions preferably containing 5 to 500 parts per million by mass (ppm) of added copper in oil- soluble form.
- the proportion of added copper in the compositions will generally be within the range of 10 to 400 ppm, typically 10 to 300 ppm, preferably 10 to 200 ppm, for example, 60 to 200 ppm. Copper compounds may if desired be used as supplementary antioxidants even when ZDDPs are present.
- carboxylic acids examples include CQ to Ci ⁇ fatty acids, for example, stearic or palmitic acid; unsaturated acids, for example, oleic acid; branched carboxylic acids, for example, naphthenic acids of molecular weight of from 200 to 500, neodecanoic acid or 2-ethylhexanoic acid; and alkyl or alkenyl-substituted dicarboxylic acids, for example, polyalkene-substituted succinic acids, for example, octadecenyl succinic acids, dodecenyl succinic acids and polyisobutenyl succinic acids.
- CQ to Ci ⁇ fatty acids for example, stearic or palmitic acid
- unsaturated acids for example, oleic acid
- branched carboxylic acids for example, naphthenic acids of molecular weight of from 200 to 500, neodecanoic acid or 2-ethylhexa
- the copper may be introduced into the oil in an oil-insoluble form provided that in the finished lubricant composition the copper is in the form of an oil-soluble compound.
- the term "added copper” is intended to exclude copper present in the oil as a result of accumulation of copper in the oil during use, for example, by wear or corrosion of copper-containing components.
- antioxidants examples include phenolic antioxidants and, especially, amine-containing antioxidants, for example, aromatic amines, especially aromatic amines which contain at least one aryl or arylene group directly attached to at least one nitrogen atom.
- aromatic amines are N-aryl amines and N,N'— rylene diamines, and diphenylamines and phenylene diamines are especially preferred.
- Such antioxidants may be used in place of the copper-containing antioxidants or in conjunction with copper-containing antioxidants.
- the proportion of a sulphur-containing compound used in accordance with the present invention may be, for example, 0.5 to 1 mass % of active ingredient based on the fully formulated oil.
- a bearing corrosion inhibitor to inhibit corrosion effects on bearings such as Cu/Pb bearings, where, for example, copper staining and/or high weight loss can be a problem.
- Such additives have been found to enhance the antiwear performance of the oil.
- Preferred corrosion inhibitors for use in accordance with the invention are borate esters and thiadiazole mercaptans, for example, the borate esters and thiadiazole mercaptans (including derivatives thereof) described in European Specifications Nos. 280 579 A and 280 580 A.
- a lubricating composition having a total sulphated ash (SASH) level, as measured by ASTM D874, of zero or, if one or more ash-producing additives are present, having a SASH level of not more than 0.8 mass % and a ratio of Total Base Number (TBN) , measured by ASTM D 2896, to SASH level, as measured by
- SASH total sulphated ash
- the invention also provides the use, for reducing the amount of particulate material emitted by a diesel engine, of a lubricating, composition which comprises a base oil and one or more lubricating oil additives, the composition having a total sulphated ash (SASH) level, as measured by ASTM D874, of zero or, if one or more ash-producing additives are present, having a SASH level of not more than 0.8 mass % and a ratio of Total Base Number (TBN) , measured by ASTM D2896, to SASH level, as measured by ASTM D874, of less than 8.5.
- SASH total sulphated ash
- Lubricating compositions used in diesel engines typically have a TBN of the order of 10, whereas the TBN to SASH ratio indicated above will normally require the use of compositions of lower TBN.
- a lubricating composition of low TBN it may be desirable in some cases to use a fuel with a relatively low sulphur content, for example, a sulphur content of not more than 0.5 mass %, based on the fuel.
- the TBN of a lubricating composition for this aspect of the invention is in the range of from 1 to 8, preferably in the range of 3 to 6.
- a TBN of this order of magnitude may, for example, be obtained by the incorporation in the composition of approximately 0.3 to 0.8 mass %, preferably 0.45 to 0.65 mass %, of a metal-containing detergent having a TBN in the range of from 250 to 500, the percentages being given on an active ingredient basis.
- metal-containing detergents which may be used in this aspect of the invention include the metal-containing detergents (including magnesium-containing detergents) mentioned in accordance with aspect (e) .
- the European specification indicates that the lubricating oils disclosed therein are particularly useful in the crankcase of diesel engines having cylinders wherein the distance between the piston's top land and the cylinder wall liner is made small to minimize the amount of particulates generated in the cylinder's firing chamber.
- the lubricating compositions according to this aspect of the present invention are useful both in such engines and in conventional engines.
- the metal-containing detergents with which the invention is concerned are salts of an acidic organic compound, the salts • having a hydrophilic portion and a hydrophobic portion such that they are capable of acting as a surfactant.
- the salts contain a polar head (the salt-forming group) and one or more organophilic groups which together have sufficiently high molecular weight to form a hydrophobic tail to give the salts detergent (surfactant) properties.
- Such detergents may be neutral or basic (overbased) .
- metal-containing detergents suitable for use as additives in an oil-based composition are the neutral or overbased oil-soluble sulphonates, phenates, sulphurized phenates, thiophosphonates, salicylates, naphthenates and other carboxylates of the alkali or alkaline earth metals or magnesium, for example, sodium, lithium, calcium, barium and magnesium.
- the most commonly used metals are calcium and magnesium, mixtures of calcium and magnesium, and mixtures of calcium and/or magnesium with sodium.
- Overbased calcium and magnesium alkyl sulphonates and alkyl phenates are particularly widely used as detergents in oil-based compositions.
- Sulphonic acids for use in the preparation of oil soluble sulphonate detergents are typically obtained by sulphonation of alkyl-substituted aromatic hydrocarbons, for example, those obtained from the fractionation of petroleum by distillation and/or extraction, or by the alkylation of aromatic hydrocarbons, for example, benzene, toluene, xylene, naphthalene, or biphenyl.
- Alkylation of aromatic hydrocarbons may be carried out, in the presence of a catalyst, with alkylating agents having from 3 to more than 50 carbon atoms, such as, for example, haloparaffins, olefins that may be obtained by dehydrogenation of paraffins, and polyolefins, for example, polymers of ethylene, propylene, and/or butene.
- alkaryl sulphonates usually contain from 9 to 70 or more carbon atoms, preferably from 16 to 50 carbon atoms, per alkyl-substituted aromatic moiety.
- the metal compounds which may be used in neutralizing these alkaryl sulphonic acids to provide the sulphonates include the oxides, hydroxides and alkoxides, for example, calcium hydroxide or magnesium oxide. Hydrocarbon solvents and/or diluent oils may also be included, as well as promoters and viscosity control agents, for example, formates and halides.
- the highly basic metal sulphonates are usually produced by neutralizing an alkaryl sulphonic acid with a large excess of metal base over that required for complete neutralization and ⁇ thereafter forming a dispersed carbonate complex by reacting the excess metal base with carbon dioxide to provide the desired overbasing.
- Neutral or slightly basic metal sulphonates may be used in place of the alkaryl sulphonic acid.
- Highly basic metal sulphonates may have a TBN from 50 to 500, preferably 250 to 450, and contain about 10 to about 35 wt. % alkaryl sulphonate.
- TBN from 50 to 500, preferably 250 to 450, and contain about 10 to about 35 wt. % alkaryl sulphonate.
- sulphurized alkyl phenols which may be used for preparing sulphurized phenate detergents are phenols of the general structure:
- R is an alkyl radical
- n is an integer from 0 to 4
- x is an integer rom 1 to 4. All the R groups will normally be the same, but this is not essential.
- the average number of carbon atoms in all of the R groups is preferably at least about 9 in order to ensure adequate solubility in oil.
- the individual R groups may contain from 5 to 40, preferably 8 to 20 carbon atoms.
- Alkylation of phenol may be carried out with, for example, alkylating agents of the types used to alkylate aromatic hydrocarbons in the manufacture of alkaryl sulphonates. Dihydroxybenzenes may be used in place of phenol.
- Highly basic metal phenates may be made by methods similar to those used to prepare highly basic metal sulphonates. Highly basic metal phenates may have a TBN from, for example, 100 to 400, preferably about 200 to 350.
- the following patents provide illustrative examples of phenates and/or of processes for making them:
- Highly basic metal salicylates, naphthenates and thio- phosphonates may also be used in oil-based compositions and may be prepared by methods similar to those used to prepare highly basic sulphonates and phenates.
- metals with an ionization potential lower than that of magnesium are calcium, sodium, lithium and potassium.
- Detergents comprising any of these metals may be used in accordance with the invention. Because of their ready accessibility and other desirable properties, calcium- containing detergents are preferred. In accordance with this aspect of the invention, it is not essential that the lubricating compositions be completely free of magnesium-containing detergents.
- one or more detergents in which the metal has a lower ionization potential than magnesium may be used in admixture with a magnesium- containing detergent.
- magnesium- containing detergents are absent.
- the TBN of a detergent to be used in accordance with this aspect of the invention is advantageously in the range of from 0 to 500, preferably 0 to 300. Calcium-containing detergents with TBNs of 0 to- 50 are particularly preferred for use in accordance with this aspect of the invention.
- a lubricating composition may if desired have two or more of characteristics or components (a) to (e) above.
- the characteristics or components, or combinations thereof, to be used in any particular case will depend on the performance required for the lubricating composition in question and, in particular, the level of the reduction in particulate emissions required.
- Additional additives may be incorporated in the compositions to enable them to meet particular requirements. Examples of additives which may be included in lubricating oil compositions are detergents and metal rust inhibitors, viscosity index improvers, corrosion inhibitors, oxidation inhibitors, friction modifiers, dispersants, anti-foaming agents, antiwear agents, and pour point depressants. Specific examples of these additives are given later in this specification.
- a lubricating composition typically comprises a lubricating oil (base oil), normally in a major proportion, and one or more additives, normally in a minor proportion.
- base oil normally in a major proportion
- additives normally in a minor proportion.
- the additive(s) is or are typically dissolved or dispersed in the base oil.
- the base oil is typically one suitable for use as a crankcase lubricating oil.
- compositions of the invention are suitable for use in any type of compression-ignited internal combustion engine, for example, automobile and truck diesel engines, and marine and railroad diesel engines.
- Synthetic base oils include alkyl esters of dicarboxylic acids, polyglycols and alcohols; poly- ⁇ -olefins, including polybutenes; alkyl benzenes; organic esters of phosphoric acids; and polysilicone oils.
- Natural base oils include mineral lubricating oils which may vary widely as to their crude source, for example, as to whether they are paraffinic, naphthenic, mixed, or paraffinic- naphthenic, as well as to features used in their production, for example, as to the distillation range chosen, and as to whether they are, for example, straight run or cracked, hydrofined or solvent extracted.
- natural lubricating oil base stocks which can be used may be straight mineral lubricating oil or distillates derived from paraffinic, naphthenic, asphaltic, or mixed base crude oils.
- various blended oils may be employed as well as residual oils, particularly those from which asphaltic constituents have been removed.
- the oils may be refined by any suitable method, for example, using acid, alkali, and/or clay or other agents such, for example, as aluminium chloride, or they may be extracted oils produced, for example, by solvent extraction with solvents, for example, phenol, sulphur dioxide, furfural, dichlorodiethyl ether, nitrobenzene, ' or crotonaldehyde.
- the lubricating oil basestock conveniently has a viscosity of about 2.5 to about 12 cSt (about 2.5 x 10 -6 to about 12 x 10 -6 m 2 /s) and preferably about 2.5 to about 9 cSt. (about 2.5 x 10 -6 to about 9 x 10" 6 m 2 /s) at 100°C. Mixtures of synthetic and natural base oils may be used if desired.
- Additives can be incorporated into a base oil in any convenient way. Thus, they can be added directly to the oil by dispersing or by dissolving them in the oil at the desired level of concentration. Such blending can occur at room temperature or at an elevated temperature.
- suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene, polymethacrylates, ethacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, interpolymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/ isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene.
- Phosphosulphurized hydrocarbons may be prepared by reacting a suitable hydrocarbon, for example, a terpene or a heavy petroleum fraction or a C 2 to C ⁇ olefin polymer such, for example, as polyisobutylene, with from 5 to 30 mass % of a sulphide of phosphorus for 1/2 to 15 hours, at a temperature in the range of about 65 to about 315°C.
- a suitable hydrocarbon for example, a terpene or a heavy petroleum fraction or a C 2 to C ⁇ olefin polymer such, for example, as polyisobutylene
- Neutralization of the phosphosulphurized hydrocarbon may be effected in any suitable manner, for example, in the manner taught in U.S. Patent No. 1,969,324.
- oxidation inhibitors or antioxidants which may be used in lubricating oil compositions comprise oil-soluble copper compounds.
- the copper may be blended into the oil as any suitable oil-soluble copper compound.
- oil-soluble it is meant that the compound is oil-soluble under normal blending conditions in the oil or additive package.
- the copper may be in the cuprous or cupric form.
- the copper may, for example, be in the form of a copper dihydrocarbyl thio- or dithio- phosphate.
- the copper may be added as the copper salt of a synthetic or natural carboxylic acid.
- suitable acids include CQ to Ci ⁇ fatty acids, such, for example, as stearic or palmitic acid, but unsaturated acids such, for example, as oleic acid or branched carboxylic acids such, for example, as naphthenic acids of molecular weights of from about 200 to 500, or synthetic carboxylic acids, are preferred, because of the improved handling and solubility properties of the resulting copper carboxylates .
- Examples of useful copper compounds are copper Cu 1 and/or Cu 11 salts derived from an alkenyl succinic acids or anhydride.
- the salts themselves may be basic, neutral or acidic. They may be formed by reacting (a) polyalkylene succinimides (having polymer groups of M n of 700 to 5,000) derived from polyalkylene-polyamines, which have at least one free carboxylic acid group, with (b) a reactive metal compound.
- Suitable reactive metal compounds include those such, for example, as cupric or cuprous hydroxides, oxides, acetates, borates, and carbonates or basic copper carbonate.
- Examples of these metal salts are Cu salts derived from polyisobutenyl succinic anhydride, and Cu salts of polyisobutenyl succinic acid.
- the copper is in its divalent form, Cu 11 .
- the preferred substrates are polyalkenyl succinic acids in which the alkenyl group has a molecular weight greater than about 700.
- the alkenyl group desirably has a M n from about 900 to 1,400, and up to 2,500, with a M n of about 950 being most preferred.
- polyisobutylene succinic anhydride or acid is especially preferred.
- Friction modifiers and fuel economy agents which are compatible with the other ingredients of the final oil may also be included.
- examples of such materials are glyceryl monoesters of higher fatty acids, for example, glyceryl mono- oleate, esters of long chain polycarboxylic acids with diols, for example, the butane diol ester of a dimerized unsaturated fatty acid, and oxazoline compounds.
- Dispersants maintain oil-insoluble substances, resulting from oxidation during use, in suspension in the fluid, thus preventing sludge flocculation and precipitation or deposition on metal parts.
- So-called ashless dispersants are organic materials which form substantially no ash on combustion, in contrast to the metal-containing (and thus ash-forming) detergents described above.
- Suitable dispersants include, for example, derivatives of long chain hydrocarbon-substituted carboxylic acids in which the hydrocarbon groups contain 50 to 400 carbon atoms, examples of such derivatives being derivatives of high molecular weight hydrocarbyl-substituted succinic acid.
- Pour point depressants otherwise known as lube oil flow improvers, lower the minimum temperature at which the fluid will flow or can be poured.
- Such additives are well known. Typical of those additives which improve the low temperature fluidity of the fluid are C to Ci ⁇ dialkyl fumarate/vinyl acetate copolymers, polymethacrylates, and wax naphthalene.
- Foam control can be provided by an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
- compositions when containing the above-mentioned additives are typically blended into the base oil in amounts which are effective to provide their normal function.
- Effective amounts of such additives are illustrated as follows: Additive Mass a.i.* Mass % a.i. (Broad) (Preferred)
- Detergents/Rust inhibitors 0.01-6 0.01-4 Viscosity Modifier 0.01- : 6 0.01-4 Corrosion Inhibitor 0.01-5 0.01-1.5 Oxidation Inhibitor 0.01-5 0.01-1.5 Dispersant 0.1-20 0.1-8
- additive concentrates comprising the additives (the concentrate being referred to herein as an additive package) whereby several additives can be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive concentrate into the lubricating oil may be facilitated, for example, by mixing accompanied with heating, but this is not essential.
- the concentrate or additive package will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final formulation when the additive package is combined with a predetermined amount of base lubricant.
- one or more additives can be added to small amounts of base oil or other compatible solvents along with other desirable additives to form additive packages containing active ingredients in an amount, based on the additive package, of, for example, from about 2.5 to about 90 mass %, and preferably from about 5 to about 75 mass %, and most preferably from about 8 to about 50 mass % by weight, additives in the appropriate proportions with the remainder being base oil.
- the final formulations may employ typically about 10 to 15 mass % of the additive-package with the remainder being base oil.
- Two XW40 lubricating compositions, A and B, comprising a base oil, a detergent inhibitor formulation, and a viscosity modifier were prepared.
- Each composition comprised a total of 81 mass % base oil (61% poly- ⁇ -olefin and 20% synthetic diester) , 9.7 mass % detergent inhibitor, and 9.3 mass % viscosity modifier.
- the base oil and detergent inhibitor were the same in each case.
- composition A the viscosity modifier was a standard viscosity modifier as defined earlier in this specification, while in composition B a viscosity modifier (an olefin copolymer dissolved in a synthetic basestock) in accordance with the first aspect of the invention was used.
- a viscosity modifier an olefin copolymer dissolved in a synthetic basestock
- any effect that these may have had on the viscosity and volatility of the compositions was the same in each case.
- compositions A and B were as follows:
- compositions A and B were used in the crankcase of a 1988 Opel Kadett vehicle fitted with a 1.7 litre diesel engine running over the European ECE 15 emissions test cycle.
- the particulate and nitrogen oxide emissions are indicated below.
- Each of the figures given below is the average of the results obtained in four tests.
- composition A B Composition A B
- compositions Two lubricating compositions were prepared using the same viscosity modifier and detergent inhibitor but different base oils. The proportions by mass of the three components in each case were: viscosity modifier -16.0%, detergent inhibitor -11.5%, base oil -72.5%.
- the base oil was a 80:20 mix (by mass) of a poly- ⁇ -olefin and a diester, while in the other composition (D) , the diester was replaced by a base oil which gave a reduced ignition delay compared with that given by 150 solvent neutral: when the ignition delay given by 150 solvent neutral was 32 degrees of crankshaft rotation, that given by the diester was 32.2 degrees, while that given by the base oil used for composition D was 27.6 degrees.
- Two lubricating compositions each comprising a base oil of lubricating viscosity, a viscosity modifier, and a detergent inhibitor system, were blended. The proportions of the three above-mentioned components were the same in each case.
- One of the lubricating compositions (E) also contained ZDDP in an amount to give the proportion of zinc indicated below.
- the other composition (F) contained no ZDDP.
- composition F The slight rise in nitrogen oxide emissions found when using composition F was more than offset by the reduction in particulate emissions.
- Two lubricating compositions each comprising a mineral base oil of lubricating viscosity, a viscosity modifier, a pour point depressant, and a detergent inhibitor, were prepared.
- the proportions by mass of the four components in each case were: base oil -77.5%, viscosity modifier -10.5%, pour point depressant -0.2%, and detergent inhibitor -11.8%.
- the compositions differed primarily in the SASH level and the ratio of TBN to SASH level imparted by the detergent inhibitor.
- One oil (G) had a TBN to ash ratio of 8.95:1, while the other (H) had a much lower ratio of 7.67:1.
- the two lubricating compositions were tested using the U.S. Heavy Duty transient emissions cycle.
- the engine used was a Volvo TD 121/2 (1990 model year) modified to incorporate high pressure fuel injection.
- the emissions of particulate matter and nitrogen oxides are given below. In each case the average of six results is given.
- Two lubricating compositions each comprising a base oil, a viscosity modifier, a pour point depressant, and a detergent system, were prepared.
- the proportions by mass of the four components were: base oil -79.3%, viscosity modifier -9.0%, pour point depressant -0.2%, detergent system -11.5%.
- the base oil, viscosity modifier and ZDDP were the same for each of the compositions, as were the proportions of the base oil, the viscosity modifier, ZDDP, and the detergent system.
- the metal present in the greatest proportion (by mass) in the detergent system was magnesium, while in the other composition (K) the predominant metal was calcium.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Engineering & Computer Science (AREA)
- Lubricants (AREA)
Abstract
On peut réduire les dégagements de matières particulaires par les moteurs Diesel à l'aide d'une composition lubrifiante pour carter présentant un(e) ou plusieurs des caractéristiques ou constituants (a)-(e): (a) une viscosité de cisaillement élevé et une volatilité relativement faibles; (b) une huile de base assurant une réduction du délai d'allumage par rapport à celui du solvant 150 neutre; (c) une teneur en zinc nulle ou ne dépassant pas 0,06 % en masse en ce qui concerne les ingrédients actifs; (d) une teneur globale en cendre sulfatée (SASH) nulle ou, au cas où un ou plusieurs additifs produisant les cendres seraient présents, ne dépassant pas 0,8 % en masse, ainsi qu'un rapport indice de base totale/SASH inférieur à 8,5; et (e) au moins un détergent contenant du métal dans lequel le métal présente un premier potentiel d'ionisation inférieur à celui du magnésium.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB919116527A GB9116527D0 (en) | 1991-07-31 | 1991-07-31 | Reduction of diesel emissions |
| GB91165274 | 1991-07-31 | ||
| PCT/EP1992/001712 WO1993003126A1 (fr) | 1991-07-31 | 1992-07-29 | Reduction des degagements de matieres particulaires par les moteurs diesel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0616636A1 true EP0616636A1 (fr) | 1994-09-28 |
Family
ID=10699282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92916215A Withdrawn EP0616636A1 (fr) | 1991-07-31 | 1992-07-29 | Reduction des degagements de matieres particulaires par les moteurs diesel |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0616636A1 (fr) |
| GB (1) | GB9116527D0 (fr) |
| WO (1) | WO1993003126A1 (fr) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9319648D0 (en) * | 1993-09-23 | 1993-11-10 | Bp Chemicals Additives | Lubricating oil compositions |
| GB9519668D0 (en) * | 1995-09-27 | 1995-11-29 | Exxon Chemical Patents Inc | Low chlorine low ash crankcase lubricant |
| GB9716283D0 (en) * | 1997-08-01 | 1997-10-08 | Exxon Chemical Patents Inc | Lubricating oil compositions |
| US6588393B2 (en) * | 2000-09-19 | 2003-07-08 | The Lubrizol Corporation | Low-sulfur consumable lubricating oil composition and a method of operating an internal combustion engine using the same |
| US6586374B1 (en) * | 2002-07-18 | 2003-07-01 | Primrose Oil Company | Engineered synthetic engine oil and method of use |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS515645B2 (fr) * | 1971-12-02 | 1976-02-21 | ||
| GB1372699A (en) * | 1971-12-22 | 1974-11-06 | Burmah Oil Trading Ltd | Lubricating compositions |
| CA1208196A (fr) * | 1982-03-10 | 1986-07-22 | Raymond F. Watts | Produit lubrifiant |
| US4776967A (en) * | 1987-02-27 | 1988-10-11 | Idemitsu Kosan Company Limited | Lubricating oil composition |
| GB8704683D0 (en) * | 1987-02-27 | 1987-04-01 | Exxon Chemical Patents Inc | Low phosphorus/zinc lubricants |
| US4922045A (en) * | 1987-08-03 | 1990-05-01 | Texaco Inc. | Diesel lubricating oil consumption control additives |
| CA1327350C (fr) * | 1987-10-02 | 1994-03-01 | Glen Paul Fetterman, Jr. | Compositions lubrifiantes sans cendre pour moteurs a combustion interne |
-
1991
- 1991-07-31 GB GB919116527A patent/GB9116527D0/en active Pending
-
1992
- 1992-07-29 EP EP92916215A patent/EP0616636A1/fr not_active Withdrawn
- 1992-07-29 WO PCT/EP1992/001712 patent/WO1993003126A1/fr not_active Application Discontinuation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9303126A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9116527D0 (en) | 1991-09-11 |
| WO1993003126A1 (fr) | 1993-02-18 |
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