EP0211689B1 - Détermination de l'origine d'un métal dans une huile usée - Google Patents

Détermination de l'origine d'un métal dans une huile usée Download PDF

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Publication number
EP0211689B1
EP0211689B1 EP19860306424 EP86306424A EP0211689B1 EP 0211689 B1 EP0211689 B1 EP 0211689B1 EP 19860306424 EP19860306424 EP 19860306424 EP 86306424 A EP86306424 A EP 86306424A EP 0211689 B1 EP0211689 B1 EP 0211689B1
Authority
EP
European Patent Office
Prior art keywords
oil
metal
copper
barium
wear
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.)
Expired
Application number
EP19860306424
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German (de)
English (en)
Other versions
EP0211689A2 (fr
EP0211689A3 (en
Inventor
Monroe Wallwork Munsell
Richard Francil Finn
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.)
ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Filing date
Publication date
Priority claimed from US06/767,744 external-priority patent/US4683070A/en
Application filed by Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
Priority claimed from PCT/US1987/000211 external-priority patent/WO1988005811A1/fr
Publication of EP0211689A2 publication Critical patent/EP0211689A2/fr
Publication of EP0211689A3 publication Critical patent/EP0211689A3/en
Application granted granted Critical
Publication of EP0211689B1 publication Critical patent/EP0211689B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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

Definitions

  • the present invention relates to oil compositions, particularly motor oils, containing a tracer metal component to determine the source of another metal component, such as metal wear, corrosion, contamination, and/or an additive component of the motor oil.
  • copper additives are particularly useful in motor oil as antioxidants. Such use has been described in Canadian Patent 1,170,247 and European Patent 24146. There is generally little or no problem in formulating passenger car crankcase oils with copper additives. However, a problem has arisen in applying these copper additives to motor oils for diesel engines which are extensively used in trucks. It has become a common practice for many truck fleet operators to have samples of the engine oil periodically analyzed for metals in order to diagnose contamination, corrosion and particularly excessive wear and impending failure of engine parts. Such metal analysis will typically include: copper, which can indicate excessive wear of copper-lead bearings; iron, which can indicate excessive wear or rust of the engine; chromium, which can indicate excessive wear of chrome faced piston rings, etc.
  • Adding a copper additive to the motor oil interferes with the copper analysis as there was no way to tell from the used oil analysis whether a high level of copper found by the analysis is due to excessive wear of copper-containing engine parts, and/or whether the copper is a component of the motor oil being used. Even if the fleet operator knows that the crankcase was initially filled with oil of a known copper content, the operator still does not generally know from the analysis if wear is occurring, particularly if make-up oil was added. Thus, the make-up oil may be obtained from different suppliers, who may or may not have a copper additive in the oil. Furthermore, even if both the original oil and all make-up oil are from the same supplier, there may be an accumulation of metals, including copper, due to varying oil losses due to volatility of the base oil, which accumulation interferes with determining accurately the source of the copper.
  • the problem is to find a reliable method of determining whether any copper in the oil is due to a copper additive used by the oil manufacturer, or is due to other sources such as wear of copper-containing parts, or whether the copper is from both an oil additive and wear. It also becomes important to determine the relative amount of copper individually due to an oil additive and to wear to indicate whether the wear is excessive.
  • the amount of the tracer metal in the used oil and the known predetermined ratio of primary metal and tracer metal in the fresh oil can be determined.
  • the source of copper may be determined.
  • the technique may also be used, for example, for iron, lead and chromium.
  • a fixed predetermined ratio of copper to barium e.g.
  • the copper may be blended into the oil as any oil soluble copper compound, i.e., soluble under normal blending conditions in the oil or additive package.
  • the copper compound may be in the cuprous or cupric form.
  • the copper may be added as the copper salt of a synthetic or natural carboxylic acid.
  • a synthetic or natural carboxylic acid examples in- dude 0 10 to Cn 8 fatty acids such as stearic or palmitic, but unsaturated acids such as oleic or branched carboxylic acids such as naphthenic acids of molecular weight from 200 to 500 or synthetic carboxylic acids are preferred because of the improved handling and solubility properties of the resulting copper carboxylates.
  • the copper may be in the form of copper dihydrocarbyl thio- or dithio-phosphates wherein one mole of cuprous or cupric oxide may be reacted with one or two moles of the dithiophosphoric acid respectively.
  • Copper dihydrocarbyl dithiophosphates may be prepared in accordance with known techniques by first forming a dithiophosphoric acid, usually by reaction of an alcohol or a phenol with P 2 S 5 andthen neutralising the dithiophosphoric acid with a suitable copper compound.
  • the dithiophosphoric acids may be represented by the formula: wherein R and R' may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12 carbon atoms and including radicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R and R' groups are alkyl groups of 2 to 8 carbon atoms.
  • the radicals may, for example, be ethyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-heptyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl, etc.
  • the total number of carbon atoms (i.e. R and R') in the dithiophosphoric acid will generally be about 5 or greater.
  • RR'NCSS oil soluble copper dithiocarbamates of the general formula (RR'NCSS) n Cu where n is 1 or 2 and R and R' are the same or different as described above for the copper dihydrocarbyl dithiophosphate. Copper sulphonates, phenates, and acetyl acetonates, etc. may also be used.
  • the barium may be present in the form of oil soluble lubricating oil additives such as neutral or basic metal salts of sulphonic acids, alkyl phenols, sulphurised alkyl phenols, alkyl salicylates, naphthenates, and oil soluble mono- and di-carboxylic acids, etc.
  • oil soluble lubricating oil additives such as neutral or basic metal salts of sulphonic acids, alkyl phenols, sulphurised alkyl phenols, alkyl salicylates, naphthenates, and oil soluble mono- and di-carboxylic acids, etc.
  • the neutral or basic barium sulfonates are usually produced by heating a mixture comprising an oil-soluble alkaryl sulfonic acid with a barium base such as the oxide or hydroxide sufficient for neutralization of the sulfonic acid.
  • a barium base such as the oxide or hydroxide sufficient for neutralization of the sulfonic acid.
  • Excess barium base is used to prepare an overbased additive which contains a dispersed carbonate complex formed by reacting the excess metal base with carbon dioxide to provide the desired overbasing.
  • the sulfonic aicds are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum by distillation and/or extraction or by the alkylation of aromatic hydrocarbons as for example, those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl and the halogen derivatives such as chlorobenzene, chlo- rotoluene and chloronaphthalene with polyolefins as for example, polymer from ethylene, propylene, isobutylene, etc.
  • the resulting alkaryl sulfonates usually contain from about 9 to about 70 or more carbon atoms, preferably from about 16 to about 50 carbon atoms per alkyl substituted aromatic moiety.
  • Salicylate and naphthenate materials are known additives for lubricating oil compositions to improve their high temperature performance and to counteract deposition of carbonaceous matter on pistons (U.S. Patent 2,744,069).
  • Salicylate/naphthenate rust inhibitors are preferably the barium salts of aromatic acids having the general formula: where AR is an aryl radical of 1 to 6 rings, R 1 is an alkyl group having from about 8 to 50 carbon atoms, preferably 12 to 30 carbon atoms (optimally about 12), X is a sulfur (-S-) or methylene (-CH 2 -) bridge, y is a number from 0 to 4 and n is a number from 0 to 4.
  • the individual R groups may each contain from 5 to 40, preferably 8 to 20, carbon atoms.
  • the metal salt is prepared by reacting an alkyl phenol sulfide with a sufficient quantity of metal containing material to impart the desired alkalinity to the sulfurized metal phenate.
  • the amount of added copper compound used in the oil formulations will be such to give copper concentrations of about 5 to about 500 ppm to weight of copper in the lubricant composition and preferably about 10 to 300, e.g. 60 to about 200 ppm.
  • the amount of barium compound used is such as to give 5 to 500, e.g., 10 to 300, preferably 25 to 150, most preferably 40 to 100 ppm of barium.
  • the copper and barium can be used in any relative ratio, such as 0.1 to 10, preferably about 1 to 5, most preferably 2 to 1 parts by weight of copper per part by weight of barium.
  • Concentrates comprising about 5 to 90, e.g., 10 to 60 wt.%, copper and barium compounds in lubricating oil may be first formed in whatever ratio is desired and these may be included as components in various additive packages which will be used to blend finished lubricating oils. In this way, an accurate and constant cop- per/barium ratio can be maintained in the final oil formulations being produced.
  • the lubricants to which the products of this invention can be added include not only hydrocarbon oils derived from petroleum, but also include synthetic oils such as alkyl esters of dicarboxylic acids, poly- gylcols and alcohols; polyalphaolefins, alkyl benzene, organic esters of phosphoric acids, polysilicone oil, etc.
  • compositions or concentrates other conventional additives may also be present, including dyes, pour point depressants, antiwear agents such as tricresyl phosphate or zinc dialkyl dithiophosphates of 3 to 8 carbon atoms in each alkyl group, other antioxidants such as N-phenyl a-naphthylamine, t-octylphenol sulfide, 4,4'-methylene bis (2,6-ditertbutyl phenol), viscosity index improvers such as ethylene-propylene copolymers, polymethacrylates, polyisobutylene, alkyl fumarate-vinyl acetate copolymers, and the like, as well as ashless dispersants such as polyisobutylene succinic anhydride reacted with amines, hydroxy amines, polyols, etc., calcium and magnesium metal detergents such as carbon dioxide overbased alkylaryl sufonates, etc.
  • antiwear agents such as tric
  • Techniques for measuring metals in used oil include flame atomic-absorption spectroscopy, electrothermal atomic-absorption spectroscopy, optical emission spectroscopy, inductively coupled plasma emission spectroscopy, scanning electron microscopy-X-ray analysis and X-ray florescence spectroscopy (see P.K. Hon, O.W. Lau and C.S. Mok, "Direct Determination of Metals in Lubricating Oils and Aqueous Inorganic Standards", Analyst 1980, 105, pp. 919-921, and the references cited therein.
  • Other related articles on analysis of used oils for metals are Lubrication, vol. 70(2), pp. 13-24 (1984); Lubrica- ion Engineering, vol. 34, 11, pp.
  • a concentrate was prepared consisting of 76.6 wt.% mineral lubricating oil, 3.4 wt.% of the neutral barium salt of alkaryl sulfonic acid, said sulfonic acid having an average molecular weight of about 1000 land being prepared by alkylation of benzene sulfonic acid with tetrapropylene and 20.0 wt.% of cupric oleate.
  • the weight ratio of copper to barium in said concentrate was 1.6 to 1.0.
  • a finished 15W40 crankcase motor oil composition was prepared containing a major amount of mineral lubricating oil, zinc dialkyl dithiophosphate, ashless dispersant of the succinimide type, magnesium and calcium sulfonates and sufficient of the above-noted concentrate to give about 80 ppm and 50 ppm barium in said finished oil composition.
  • the analysis was carried out by atomic adsorption.
  • Table 1 shows that the initial copper to barium ratio was 1.6 to 1.0.
  • the copper due to wear in the used oil can be calculated as follows:
  • the invention can be applied to other primary metals other than copper such as chromium, iron, lead, using either barium as the secondary or tracer metal, or other tracer metals such as potassium, tungsten or lithium can be used.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (7)

1. Procédé de détermination de l'origine d'un premier métal dans une huile moteur après utilisation, dans lequel le premier métal peut être présent à la fois comme constituant d'un additif présent dans une huile neuve et en résultat de l'usure du moteur, procédé qui consiste à ajouter à ladite huile un second métal, différent, dont la seule origine dans l'huile usagée est son utilisation comme constituant d'un additif dans l'huile neuve, et à déterminer, à partir de la quantité du second métal dans l'huile usagée et du rapport prédéterminé connu du premier métal au second métal dans l'huile neuve, la quantité du premier métal dans l'huile usagée due à une usure.
2. Procédé suivant la revendication 1, dans lequel le premier métal est le cuivre, le fer, le plomb ou le chrome.
3. Procédé suivant la revendication 2, dans lequel le premier métal est le cuivre.
4. Procédé suivant l'une quelconque des revendications 1 à 3, dans lequel le second métal est le baryum, le potassium, le lithium ou le tungstène.
5. Procédé suivant la revendication 4, dans lequel le second métal est le baryum.
6. Procédé suivant les revendications 3 et 5, dans lequel le premier métal est ajouté sous forme d'oléate de cuivre et le second métal est ajouté sous forme d'un alkarylsulfonate de baryum neutre.
7. Procédé suivant la revendication 6, dans lequel l'oléate de cuivre est ajouté à l'huile en une quantité correspondant à une quantité de 5 à 500 ppm de cuivre et le sulfonate de baryum est ajouté en une quantité correspondant à une quantité de 10 à 300 ppm de baryum.
EP19860306424 1985-08-21 1986-08-19 Détermination de l'origine d'un métal dans une huile usée Expired EP0211689B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US06/767,744 US4683070A (en) 1985-08-21 1985-08-21 Determination of metal source in used oil
US767744 1985-08-21
PCT/US1987/000211 WO1988005811A1 (fr) 1987-01-30 1987-01-30 Determination de l'origine des metaux se trouvant dans des huiles usees

Publications (3)

Publication Number Publication Date
EP0211689A2 EP0211689A2 (fr) 1987-02-25
EP0211689A3 EP0211689A3 (en) 1987-12-09
EP0211689B1 true EP0211689B1 (fr) 1990-06-27

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EP19860306424 Expired EP0211689B1 (fr) 1985-08-21 1986-08-19 Détermination de l'origine d'un métal dans une huile usée

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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02502382A (ja) * 1987-01-30 1990-08-02 エクソン　ケミカル　パテンツ，インコーポレイテッド 使用済み油中の金属源の測定
FR2674533B1 (fr) * 1991-03-29 1994-08-05 Bp Chemicals Snc Liquide de frein et procedes de differenciation et d'identification.
CN110988108A (zh) * 2019-12-03 2020-04-10 广州机械科学研究院有限公司 一种用于检测密封件磨损量的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2744069A (en) * 1952-04-29 1956-05-01 Shell Dev Compounded lubricating compositions
GB2056482A (en) * 1979-08-13 1981-03-18 Exxon Research Engineering Co Lubricating oil compositions

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Publication number Publication date
EP0211689A2 (fr) 1987-02-25
EP0211689A3 (en) 1987-12-09

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