EP0709447A1 - Polycyclische aromatische Verbindungen für verbessertes Niederschlagskontroll - Google Patents
Polycyclische aromatische Verbindungen für verbessertes Niederschlagskontroll Download PDFInfo
- Publication number
- EP0709447A1 EP0709447A1 EP95307523A EP95307523A EP0709447A1 EP 0709447 A1 EP0709447 A1 EP 0709447A1 EP 95307523 A EP95307523 A EP 95307523A EP 95307523 A EP95307523 A EP 95307523A EP 0709447 A1 EP0709447 A1 EP 0709447A1
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- EP
- European Patent Office
- Prior art keywords
- oil
- multiring
- composition
- antioxidant
- synthetic
- 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.)
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/067—Polyaryl amine alkanes
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/068—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings having amino groups bound to polycyclic aromatic ring systems, i.e. systems with three or more condensed rings
Definitions
- the present invention relates to novel deposit control additives for lube oils.
- Copper antioxidants are common additives, however they degrade and form deposits at higher temperatures. It would be desirable to provide additives and formulations that address the need to retard deposit formation and extend the life of copper antioxidants.
- the present invention provides for lubricating oil compositions, comprising a synergistic combination of a synthetic base stock, a copper containing antioxidant and a deposit control enhancing amount of an oil soluble or oil dispersible multiring aromatic compound.
- the present invention also provides for a method of controlling deposit formation in an engine lubricating system, comprising adding a deposit control enhancing amount of an oil soluble or oil dispersible multiring aromatic compound to a synthetic base stock of lubricating viscosity formulated with a copper containing antioxidant.
- the present invention may suitably comprise, consist or consist essentially of the elements disclosed herein and may be practiced in the absence of any element not specifically disclosed herein as required.
- multiring aromatic compounds when added to a synthetic base stock, such as a polymerized alpha olefin (PAO), a hydrocracked base stock or an isomerized base stock formulated with copper containing antioxidants can provide enhanced deposit control.
- PAO polymerized alpha olefin
- the present invention provides for novel lube oil compositions containing a synthetic base stock formulated with copper containing antioxidants in synergistic combination with a deposit controlling amount of multiring aromatics and the method of using them to provide enhanced enhanced antioxidancy.
- the starting materials disclosed herein may be obtained from commercial sources or formulated using art recognized procedures.
- oils containing copper containing antioxidants these compounds are generally present in a hydrocarbon, preferably oil, soluble or dispersible form.
- a hydrocarbon preferably oil, soluble or dispersible form.
- Representative examples include copper naphthenates, oleates, stearates, and polyisobutylene succinic anhydride ("PIBSA") compounds, although other known copper containing antioxidants also may be used.
- the base stock optionally may be formulated to contain a cobalt containing compound as an antioxidant. These are also commercially available.
- the cobalt containing compounds also are typically present in a hydrocarbon, preferably oil, soluble or dispersible form. Representative examples include cobalt naphthenates, stearates and acetyl acetonates. Such antioxidants are also commercially available.
- the base oil is required to be a synthetic base stock, preferably of lubricating viscosity.
- Wax isomerates, PAOs and hydrocracked base stocks are representative examples.
- Preferred are isomerized base stocks.
- Isomerized base stocks are the fraction remaining following dewaxing the isomerate formed from isomerizing wax in the presence of a suitable catalyst under isomerization conditions.
- the wax which is isomerized may originate from any number of sources. Synthetic waxes from Fischer-Tropsch processes may be used, as may be waxes recovered from the solvent or autorefrigerative dewaxing of conventional hydrocarbon oils, or mixtures of these waxes.
- Waxes from dewaxing conventional hydrocarbon oils are commonly called slack waxes and usually contain an appreciable amount of oil.
- the oil content of these slack waxes can range from 0 to 45% or more, but usually from 5 to 30% oil.
- the isomerization process is known in the art. Typically, by way of example, isomerization is conducted over a catalyst containing a hydrogenating metal component, typically one from Group VI, or Group VIII, or mixtures thereof, preferably Group VIII, more preferably noble Group VIII, and most preferably platinum on a halogenated refractory metal oxide support.
- a hydrogenating metal component typically one from Group VI, or Group VIII, or mixtures thereof, preferably Group VIII, more preferably noble Group VIII, and most preferably platinum on a halogenated refractory metal oxide support.
- the catalyst typically contains from 0.1 to 5.0 wt%, preferably 0.1 to 1.0 wt%, and most preferably from 0.2 to 0.8 wt% metal.
- the halogenated metal oxide support is typically an alumina (e.g. gamma or eta) containing chlorides (typically from 0.1 to 2 wt%, preferably 0.5 to 1.5 wt%) and fluorides (typically 0.1 to 10 wt%, preferably 0.3 to 0.8 wt%).
- Isomerization 270° to 400°C (preferably between 300° to 360°C), at pressures of from 500 to 3000 psi H2 (preferably 1000-1500 psi H2), at hydrogen gas rates of from 1000 to 10,000 SCF/bbl and at a space velocity in the range of from 0.1 to 10 v/v/hr., preferably from 1 to 2 v/v/hr.
- the isomerate may undergo hydrogenation to stabilize the oil and remove residual aromatics and are thus also known as "hydroisomerized" base stocks.
- the resulting product may then be fractionated into a lubes cut and fuels cut, the lubes cut being identified as that fraction boiling in the 330°C+ range, preferably the 370°C+ range, or even higher.
- This lubes fraction is then dewaxed to reduce the pour point typically to between about -15°C to about -24°C.
- the term "isomerized" base stocks is used herein to include "hydroisomerized” base stocks. It should be noted that the resulting base oil is essentially free of aromatics.
- PAOs are polymerized alpha olefins, i.e., polymerized oligomers of the types suitably used for lube applications. Suitable hydrocracked base stocks are also known in the art.
- the base stock is typically present in a major amount to a minor amount of each additive, and usually to a major amount in comparison to all additives in combination.
- minor amount is intended to mean an amount less than 50% by weight of the composition.
- major amount is intended to mean more than 50% by weight of the composition.
- the synergistic effect of addition of the multiring aromatics is to be expected over the range of weight percents at which copper containing antioxidant additives are typically added to the basestock.
- the multiring aromatics used to enhance the antioxidancy of the synthetic oils according to the present invention are hydrocarbon, preferably oil, soluble or dispersible.
- hydrocarbon or oil "soluble” and “dispersible” means that the material is soluble or stably dispersible in hydrocarbons, preferably oils of lubricating viscosity, that are liquid at temperatures found in the environments at which hydrocarbons or oils are typically used.
- stably dispersible means that the material is capable of being dispersed in the hydrocarbon or oil to an extent that allows it to function in its intended manner.
- a lube oil antioxidant is oil soluble or dispersible if it is capable of being dissolved, dispersed or otherwise suspended in a lubricating oil in a manner sufficient to allow the oil to function as a lubricant.
- the multiring aromatics should be present in an amount sufficient to enhance deposit control in the oil.
- the minor amount is less than about 25 wt% based on the total weight of the lubricant composition.
- the multiring aromatic additive is present in an amount from 0.5 to 25 wt%, preferably from 1.0 to 15 wt.%, more preferably from 2.0 to 10 wt.%. Most preferably the amount of the additive is at least 4.0 wt.%, for example 4.5 wt.%.
- the multiring aromatics are oil soluble or dispersible, preferably two, three and four ring multiring aromatics. Both unsubstituted and alkyl substituted multiring aromatics and mixtures thereof may be used. Representative examples include phenanthrene, naphthalenes, anthracenes, pyrenes; both unsubsituted and alkyl versions thereof are suitable.
- the present invention also permits the use of other additives and agents in the oil compositions.
- additives include such conventional additive types as viscosity modifiers, extreme pressure agents, corrosion-inhibiting agents, pour point depressants, color stabilizing agents, anti-foam agents, and other such additive materials known generally to those skilled in the art of formulating lubricants.
- a commercially available synthetic base stock may be formulated to contain a commercially available monofunctional viscosity index improver, a neutral and/or overbased blend of calcium sulfonated detergent, nonylphenyl sulfide, and borated PIBSA-PAM dispersant, in addition to a copper containing antioxidant such as copper PIBSA.
- the formulated oils containing the antioxidancy enhancing multiring aromatic additives are suitable for essentially any lube application in which oxidation protection is desired and in which the formulated oil without the multiring aromatics additives could be used. It is expected that similar benefits could be obtained in fuels.
- IPDT Inclined Panel Deposit Test
- the IPDT is a bench test that simulates piston deposit formation during engine operation. 35 ml of oil was heated to 150°C and run down a metal panel heated to 308°C at a 2 degree angle. The oil was then pumped through a sump back onto the panel. The oil was exposed to a synthetic blow-by gas throughout the 2 hour duration of the test. The panel was then cooled, washed with heptane and rated. The rating figure (demerit) value indicates the amount of deposit on formation on the plate. A higher number (greater demerit) indicates a greater deposit formation, with 10 being the highest and zero the lowest.
- Table 1 indicates the IPDT results for a commercially available hydroisomerized base stock formulated with a copper antioxidant and a copper antioxidant in combination with a cobalt antioxidant as baselines. Runs 2 and 4 demonstrate the enhanced synergistic effect of adding phenanthrene as the multiring aromatic to copper and copper-cobalt antioxidant additive formulations.
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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)
- Engineering & Computer Science (AREA)
- Lubricants (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US32821494A | 1994-10-25 | 1994-10-25 | |
US328214 | 1994-10-25 |
Publications (1)
Publication Number | Publication Date |
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EP0709447A1 true EP0709447A1 (de) | 1996-05-01 |
Family
ID=23280021
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP95307523A Withdrawn EP0709447A1 (de) | 1994-10-25 | 1995-10-24 | Polycyclische aromatische Verbindungen für verbessertes Niederschlagskontroll |
Country Status (1)
Country | Link |
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EP (1) | EP0709447A1 (de) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0863965A1 (de) * | 1995-10-31 | 1998-09-16 | Exxon Research And Engineering Company | Antioxidationszusatze zur kontrolle von schlammbildung |
US6764983B1 (en) | 2001-06-29 | 2004-07-20 | Iowa State University Research Foundation | Antioxidant compositions and industrial fluids containing same |
WO2008102114A1 (en) * | 2007-02-21 | 2008-08-28 | Bp P.L.C. | Lubricant base oils and lubricant compositions and methods for making them |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB815802A (en) * | 1956-06-15 | 1959-07-01 | Exxon Research Engineering Co | Lubricant |
US3026263A (en) * | 1959-03-05 | 1962-03-20 | Du Pont | High temperature mechanical fluid compositions |
WO1989000186A1 (en) * | 1987-07-08 | 1989-01-12 | The Lubrizol Corporation | Aliphatic hydrocarbon substituted aromatic hydrocarbons to control black sludge in lubricants |
EP0330523A2 (de) * | 1988-02-26 | 1989-08-30 | Exxon Chemical Patents Inc. | Reibungsmodifizierte ölige Konzentrate mit verbesserter Stabilität |
EP0444830A1 (de) * | 1990-02-26 | 1991-09-04 | Ethyl Petroleum Additives Limited | Succinimid-Zusammensetzung |
-
1995
- 1995-10-24 EP EP95307523A patent/EP0709447A1/de not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB815802A (en) * | 1956-06-15 | 1959-07-01 | Exxon Research Engineering Co | Lubricant |
US3026263A (en) * | 1959-03-05 | 1962-03-20 | Du Pont | High temperature mechanical fluid compositions |
WO1989000186A1 (en) * | 1987-07-08 | 1989-01-12 | The Lubrizol Corporation | Aliphatic hydrocarbon substituted aromatic hydrocarbons to control black sludge in lubricants |
EP0330523A2 (de) * | 1988-02-26 | 1989-08-30 | Exxon Chemical Patents Inc. | Reibungsmodifizierte ölige Konzentrate mit verbesserter Stabilität |
EP0444830A1 (de) * | 1990-02-26 | 1991-09-04 | Ethyl Petroleum Additives Limited | Succinimid-Zusammensetzung |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0863965A1 (de) * | 1995-10-31 | 1998-09-16 | Exxon Research And Engineering Company | Antioxidationszusatze zur kontrolle von schlammbildung |
EP0863965A4 (de) * | 1995-10-31 | 1999-02-10 | Exxon Research Engineering Co | Antioxidationszusatze zur kontrolle von schlammbildung |
US6764983B1 (en) | 2001-06-29 | 2004-07-20 | Iowa State University Research Foundation | Antioxidant compositions and industrial fluids containing same |
WO2008102114A1 (en) * | 2007-02-21 | 2008-08-28 | Bp P.L.C. | Lubricant base oils and lubricant compositions and methods for making them |
EP1967571A1 (de) * | 2007-02-21 | 2008-09-10 | BP p.l.c. | Zusammensetzungen und Verfahren |
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