EP1497397A2 - Oil composition and method of detecting a marker in an oil composition - Google Patents

Oil composition and method of detecting a marker in an oil composition

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Publication number
EP1497397A2
EP1497397A2 EP03717214A EP03717214A EP1497397A2 EP 1497397 A2 EP1497397 A2 EP 1497397A2 EP 03717214 A EP03717214 A EP 03717214A EP 03717214 A EP03717214 A EP 03717214A EP 1497397 A2 EP1497397 A2 EP 1497397A2
Authority
EP
European Patent Office
Prior art keywords
oil composition
acid
alkyl
oil
hydrogen
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Withdrawn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
EP03717214A
Other languages
German (de)
English (en)
French (fr)
Inventor
Nigel Edmund Lunt
Mark Clift Southby
Robert John Wetton
Emma Jayne Woollaston
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 EP03717214A priority Critical patent/EP1497397A2/en
Publication of EP1497397A2 publication Critical patent/EP1497397A2/en
Withdrawn legal-status Critical Current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
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/003—Marking, e.g. coloration by addition of pigments
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/226—Organic compounds containing nitrogen containing at least one nitrogen-to-nitrogen bond, e.g. azo compounds, azides, hydrazines
    • 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
    • C10M171/007—Coloured or dyes-containing lubricant compositions
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/26—Oils; Viscous liquids; Paints; Inks
    • G01N33/28—Oils, i.e. hydrocarbon liquids
    • G01N33/2835—Specific substances contained in the oils or fuels
    • G01N33/2882—Markers

Definitions

  • the present invention relates to an oil composition and a method of detecting a marker in an oil composition.
  • a dye or marker allows the authenticity of an oil composition to be assessed. This has many benefits for the oil composition manufacturer, including protection of brand name, increased customer confidence and tracking of product at any stage in the production and distribution chain.
  • a so-called silent marker that is to say, a marker which imparts substantially no colour to an oil composition at the level at which it is used, but which can be easily detected, qualitatively or quantitatively, in the tagged oil composition by performing chemical and/or physical tests thereon. It is often preferable that such testing can be conducted in the field and markers are therefore usually detected by a reactive extraction method.
  • US-A-5490872 discloses markers which are detectable by extraction from petroleum fuel with a dilute acidic solution such as a 10% hydrochloric acid 'or formic acid solution.
  • US-A-5560855 describes a method for tagging and identifying refrigeration lubricants using silent markers. Identification relies upon a reactive extraction method.
  • Rl and R20 a re the same or different and independently denote hydrogen or C -Cg alkyl optionally substituted by hydroxy and optionally interrupted by one or two oxygen atoms
  • R- ⁇ -5 and R!8 are the same or different and independently denote hydrogen, C j _-C4 alkyl or the radical NR13R14 ⁇ j_ n which R-L3 anc i R14 have the above meanings, R ⁇ °, R ⁇ and
  • R!9 are the same or different and independently denote hydrogen or C -C4 alkyl.
  • Markers of formula (I) have dye characteristics and additionally undergo a bathochro ic shift of their absorption maximum and an increase in absorbance when there is added thereto a protogenic acid.
  • the marked mineral oil of US-A-5145573 is tested by shaking a sample of the oil with a detector reagent comprising a protogenic acid, separating the two phases and comparing colorimetrically the coloured phase with a solution of known concentration, so that the dye content can be assessed quantitatively.
  • US-A-5182372 discloses mineral oils containing one or more azo dyes of formula (II) ,
  • R ⁇ , R2 and R ⁇ are the same or different and independently denote hydrogen, C1-C4 alkyl or C1-C4 alkoxy, -R ⁇ denotes C]_-Cg alkyl and R ⁇ denotes C2-Cg alkyl whiph is substituted by hydroxy and may be interrupted by 1, 2 or 3 oxygen atoms, provided that the total number of carbon atoms in the radicals R ⁇ and R ⁇ is at least 5.
  • the indication of the dyes of formula (II) in said mineral oils is achieved by testing the oil with aqueous acid to obtain a colour reaction.
  • R ⁇ is hydrogen or C]_-C 5 alkyl which may be interrupted by from 1 to 4 ether oxygen atoms
  • R2 is C -C]_5 alkyl which may be interrupted by from 1 to 4 ether oxygen atoms, or a radical of the formula L-N ⁇ l ⁇ , where L is C2-Cg alkylene and ⁇ l and ⁇ independently of one another are each C]_-Cg alkyl or, together with the nitrogen atom linking them, form a 5-membered or 6-membered saturated heterocyclic radical which may furthermore contain an oxygen atom in the ring, R ⁇ , R4, R5 ⁇ 6 ⁇ R7 independently of one another are each hydrogen, C]_-C]_5 alkyl or C -C ] _5 alkoxy and R ⁇ is hydrogen, C ] _-C ] _5 alkyl, C]_-C ] _5 alkoxy, cyano,
  • Testing of the tagged hydrocarbon is said to occur by extracting an amount thereof with an amount of aqueous alcoholic or alcoholic solution of the protic acid.
  • Reactive extraction methods present a number of problems . Said methods often give rise to handling difficulties in the field as they involve reagents which may leak or spill, and which are often highly concentrated acidic solutions. Furthermore, testing is wasteful as sampled oils are contaminated and cannot be returned to the bulk oil. Thus, such methods also present disposal problems for the reagents used and the samples tested. A further problem is that extractive testing methods require a clear, homogeneous phase separation, which can often be a slow process.
  • An alternative method that has been suggested in EP-A-0887644 is to draw a fuel composition comprising an acid- or base- extractable marker through an ion-exchange resin column which is acidic or basic, as the case may be.
  • a further difficulty in developing such a method that can be carried out by unskilled operators is that often oil compositions may have some inherent colouration due to the presence of certain additives and/or contaminants therein.
  • the aromatics content of a base oil may lead to a yellow-orange colouration thereof and thus compositions comprising said base oil therein may have an inherent colouration.
  • Such an inherent colouration may present difficulties in detecting a marker therein when said marker undergoes a colour change upon testing.
  • the colour change of a marker which generally changes to from colourless/yellow to red upon action of an acid may not be easily detected if there is a yellow- orange background colouration to the oil composition. Such a colour change may then only be presented as a deepening in the yellow-orange colouration.
  • the present invention provides an oil composition
  • an oil composition comprising a major amount of a natural and/or synthetic base oil and, as a marking substance, a detectable level of one or more compounds of formula IV,
  • the present invention further provides a method for detecting the presence of a marking substance in an oil composition which comprises a major amount of a natural and/or synthetic base oil and a detectable amount level of a marking substance, wherein the oil composition is contacted with a test strip comprising an acidic compound supported thereon, such that said marking substance gives a colour reaction upon contact with the test strip.
  • said colour reaction will be apparent by a colour change on the portion of the test strip which is contacted with said oil composition.
  • test strip comprising an acidic compound supported thereon.
  • conjugated group in the present invention is meant a group, R ⁇ , which is conjugated through the adjacent nitrogen atom to which R10 is also bonded, to the azo part of the molecule under action of an acidic compound, thereby shifting the value of ⁇ max for the marking substance as a whole to above 485 nm, preferably above 495 nm, provided that said group does not increase ⁇ max for the marking substance as a whole in its basic state to wavelengths of higher than 485 nm, preferably than 475 nm.
  • X is chosen from hydrogen, C]__s alkyl, alcohol, ether, acid, amine, aldehyde, nitro and halide, in particular -Cl
  • Y is hydrogen or an
  • RU may contain heteroatoms and in a preferred embodiment is selected from an optionally substituted conjugated olefinic group containing ' from 2 to 8 carbon atoms in the olefin backbone of the group, an optionally substituted aromatic group, an optionally substituted polyaromatic group, an optionally substituted aromatic heterocyclic group and an optionally substituted polyaromatic heterocyclic group.
  • optionally substituted aromatic groups and optionally substituted polyaromatic groups include phenyl, naphthyl, anthracenyl, phenanthracenyl.
  • optionally substituted aromatic heterocyclic groups and optionally substituted polyaromatic heterocyclic groups include 1-pyrrolyl, 2- pyrrolyl, 3-pyrrolyl, furyl, thienyl, indenyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, carbazolyl, thiazolyl, benzothiazolyl, thiadiazolyl, pyrimidinyl, pyridyl and pyridazinyl.
  • Said groups may be optionally substituted with one or more groups such as C]__g alkyl, alcohol, ether, acid, amine, aldehyde, nitro and halide, in particular -Cl.
  • non-conjugated group in the present invention is meant a group which does not shift the value of A TMax for the marking substance as a whole in its basic state to wavelengths of higher than 485 nm, preferably than 475 nm.
  • Non-conjugated groups that may be conveniently used include halide, hydroxy, ether, sulphonic acid, carboxylic acid or alkenyl groups wherein the double bond therein is not directly conjugated to the aryl ring.
  • R! - R ⁇ in (IV) are the same or different and are independently chosen from hydrogen, C]__g alkyl and other non-conjugated groups; and
  • R!0 is chosen from hydrogen and C ⁇ _g alkyl.
  • the marking substance is one or more compounds of formula V,
  • R-"- - R ⁇ are the same or different and are independently chosen from hydrogen, Ci- ⁇ s alkyl and other non-conjugated groups; R!0 is chosen from hydrogen and c l-15 alkyl; and R! - R!6 are the same or different and are independently chosen from hydrogen, Cj__]_5 alkyl and other non-conjugated groups.
  • R! - R ⁇ in (V) are the same or different and are independently chosen from . hydrogen, C]__g alkyl and other non-conjugated . groups; R 0 is independently chosen from hydrogen, C]__g alkyl; and R!2 - R S are the same or different and are independently chosen from hydrogen, C__g alkyl and other non-conjugated groups .
  • a particularly preferred marking substance according to the present invention is 4- (phenylazo) diphenylamine .
  • the general preparation of azo dyes by diazotization and coupling is well known in the art (see for example, Kirk-Othmer Encyclopaedia of Chemical Technology (3 rd Edition, New York, 1978), Volume 3, pp 387-392).
  • the marking substances of formulae (IV) and (V) may be conveniently prepared by methods described therein and also in GB-B-1311374, US-A-5182372, US-A-5827332, or by methods analogous thereto.
  • N-mono or di-substituted anilines which may be used in the preparation of said azo dyes are well known in the art and may conveniently be prepared by conventional methods, for example, by the reaction of aniline or N-monosubstituted aniline with alkyl halide (e.g. as described in Organic Chemistry, J. McMurry, Brooks/Cole Publishing Company, California, 1988, pp. 906-908 and J. Am. Chem. Soc. 82, 6163 (I960)); catalytic reduction of a Schiff' s base formed from aniline and an aldehyde (e.g. as described in Org. React.
  • alkyl halide e.g. as described in Organic Chemistry, J. McMurry, Brooks/Cole Publishing Company, California, 1988, pp. 906-908 and J. Am. Chem. Soc. 82, 6163 (I960)
  • the oil composition according to the present invention may conveniently comprise the marking substance in an amount in the range of from 1 to 400 ppmw, preferably in the range of from 5 to 100 ppmw and most preferably in the range of from 10 to 30 ppmw, based on the total weight of the oil composition.
  • the base oil used in the present invention is a natural or a synthetic base oil, or a mixture thereof. Said base oil may be conveniently used in fuel and/or lubricating oil compositions. The amount of base oil incorporated in the oil composition will depend upon the application in which it is intended to be used.
  • said base oil is preferably present in the oil composition in an amount in the range of from 60 to 99.95 % wt., more preferably in an amount in the range of from 65 to 99 % wt . , with respect to the total weight of the oil composition.
  • said base oil is preferably present in the oil composition in an amount in the range of from 60 to 99.95 % wt . , more preferably in an amount in the range of from 90 to 99.95 % wt., with respect to the total weight of the oil composition.
  • Liquid hydrocarbon fuel oils include gasolines, kerosines, jet fuels, diesel fuels, heating oils and heavy fuel oils. Such fuel oils may consist substantially of hydrocarbons or they may contain blending components, such as alcohols or ethers.
  • Liquid hydrocarbon fuel oils of the gasoline boiling range are typically mixtures of hydrocarbons boiling in the temperature range from about 25°C to about 232°C, • comprising mixtures of saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons.
  • the base fuel oil is derived from straight run gas-oline, polymer gasoline, natural gasoline, dimer and trimerized olefins, synthetically produced aromatic hydrocarbon mixtures, from thermally or catalytically reformed hydrocarbons, or from catalytically cracked or thermally cracked petroleum stocks, and mixtures of these.
  • the hydrocarbon composition and octane level of the base fuel are not critical.
  • the octane level, (R+M)/2 will generally be above about 85 (where R is Research Octane Number and M is Motor Octane Number) .
  • Liquid hydrocarbon fuel oils which are middle distillate fuel oils typically have a boiling range in the range 100°C to 500°C, e.g. 150°C to 400°C.
  • Petroleum-derived fuel oils may comprise atmospheric distillate or vacuum distillate, or cracked gas oil or a blend in any proportion of straight run and thermally and/or catalytically cracked distillates.
  • Such fuel oils include kerosine, jet fuels, diesel fuels, heating oils and heavy fuel oils.
  • the fuel oil is a diesel fuel.
  • Diesel fuels typically have initial distillation temperature about 160°C and final distillation temperature of 290-360°C, depending on fuel grade and use.
  • Preferred diesel fuels are low-sulphur diesel fu ⁇ ls.
  • the fuel oil composition according to the present invention can contain further additives usually present in fuel oils, such as anti-static agents, pipeline drag reducers, flow improvers (e.g. ethylene/vinyl acetate copolymers or acrylate/maleic anhydride copolymers) and wax anti-settling agents (e.g. those commercially available under the Trade Marks "PARAFLOW” (ex Infineum International Ltd.), "DODI AX” (ex Clariant GmbH).
  • anti-static agents e.g. ethylene/vinyl acetate copolymers or acrylate/maleic anhydride copolymers
  • flow improvers e.g. ethylene/vinyl acetate copolymers or acrylate/maleic anhydride copolymers
  • wax anti-settling agents e.g. those commercially available under the Trade Marks "PARAFLOW” (ex Infineum International Ltd.), "DODI AX” (ex Clariant GmbH).
  • Fuel oil compositions of the present invention may contain other additive components in addition to those already indicated.
  • a dispersant additive e.g. a polyolefin substituted succinimide or succinamide of a polyamine
  • Such dispersant additives are described for example in UK Patent 960,493, EP-A-147 240, EP-A-482 253, EP-A-613 938, EP-A-557 561 and O-A-98/42808.
  • Such dispersant additives are preferably present in amounts in the range of from 10 to 400 ppmw, more preferably 40 to 200 ppmw, active matter based on the fuel oil composition.
  • the fuel oil composition preferably additionally contains a lubricity enhancer in an amount in the range from 50 to 500 ppmw based on the fuel oil composition.
  • lubricity enhancers include those available as “EC 831” and “PARADYNE (trade mark) 655" ex Infineum, “HITEC” (trade mark) E 580 ex Ethyl Corporation and “VEKTRON” (trade mark) 6010 ex Infineum.
  • Further additive components which may be present include ignition improvers (cetane improvers) (e.g.
  • reodorants e.g. phenolics such as ⁇ 2, 6-di-tert-butylphenol, or phenylenediamines such as N,N' -di-sec-butyl-p-phenylenediamine
  • corrosion inhibitors e.g. phenolics such as ⁇ 2, 6-di-tert-butylphenol, or phenylenediamines such as N,N' -di-sec-butyl-p-phenylenediamine
  • corrosion inhibitors e.g. phenolics such as ⁇ 2, 6-di-tert-butylphenol, or phenylenediamines such as N,N' -di-sec-butyl-p-phenylenediamine
  • corrosion inhibitors e.g. phenolics such as ⁇ 2, 6-di-tert-butylphenol, or phenylenediamines such as N,N' -di-sec-butyl-p-phen
  • the concentration of the ignition improver in the fuel is preferably in the range 0 to 600 ppmw, e.g. 300 to 500 ppmw. Concentrations of other additives not yet specified are each preferably in the range 0 to 20 ppmw.
  • the lubricant base oils that may be used in the oil composition of the present invention can be any base fluid which is suitable for use in lubricating oils.
  • the base oil can. be a natural or a synthetic lubricant base oil, or a mixture thereof.
  • the natural oil can be an animal oil or vegetable oil, such as lard oil or castor oil, or a mineral oil such as liquid petroleum oils and solvent treated or acid treated mineral lubricating oil of the paraffinic, naphthenic, or mixed paraffinic/naphthenic type which may be further refined by hydrocracking and hydrofinishing processes and/or dewaxing.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerised and interpolymerised olefins.
  • a suitable ' base oil may contain poly-alpha-olefins, such as polydecene.
  • the base oil is a hydrocarbon base oil. More preferably, the base fluid is a mineral oil which contains less than 10 % wt. of aromatic compounds, preferably less than 5 % wt., measured according to DIN 51378. It is further preferred that the base oil contains less than 1.0 % wt. of sulphur, calculated as elemental sulphur, preferably less than 0.1 % wt . , measured according to ASTM D 4045.
  • Such mineral oils can be prepared by severe hydroprocessing.
  • the lubricating oil has a kinematic viscosity in the range of from 5 to 220 cSt at 40 °C, more preferably of from 10 to 200 cSt, most preferably of from 20 to 100 cSt.
  • the lubricating oil composition according to the present invention can contain further additives that are usually present in lubricating oils, such as pour point depressants, anti-foam agents and demulsifier.
  • Pour point depressants generally are high molecular weight polymers such as alkylaromatic polymers and polymethacrylates .
  • anti-foam agents silicone polymers and/or polymethacrylates are generally used.
  • Demulsifiers which are generally applied are polyalkylene glycol ethers.
  • detergents such as sulphonates and phenates, metal deactivators, antioxidants such as phenolic compounds, diphenyl amines and phenyl naphthyl amines, ashless anti-wear agents and/or ashless dispersants, such as succinimides, can be present.
  • the oil compositions of the present invention may be conveniently prepared by dissolving the desired amount of the marking substance in a carrier fluid and then admixing the resulting solution with base oil.
  • the carrier fluid may then optionally be removed from the oil composition by conventional means such as distillation.
  • Carrier fluids tljat may be conveniently used include hydrocarbon, alcohol and ester solvents.
  • Compounds of formulae IV and V as described herein may be used as pH-dependent marking substances in the oil compositions of the present invention as they give a colour reaction under action of an acidic compound.
  • Said acidic compound may be a protic acid and/or a Lew-j j S Acid.
  • said acidic compound is a protic acid.
  • the choice of acidic compound depends upon the marking substance being tested and the method being used.
  • the pKa of the acidic compound is below 4.8.
  • Such acidic compounds include mineral and organic acids such as o- & p- bromoacetic acid, chloroacetic acid, chlorobenzoic acid, chlorobutyric acid, chloropropionic acid, chloropropinic acid, citric acid, cyano acetic acid, cyanobutyric acid, cyanophenylacetic acid, cyclopropane 1:1 dicarboxylic acid, dichloroacetyl acetic acid, dihydroxymalic acid, dihydroxytartaric acid, lutidinic acid, maleic acid, malonic acid, naphthalene sulphonic acid, o-, m- & p- nitrobenzoic acid, oxalic acid, quinolinic acid, trichloroacetic acid, 2,4,6- trihydroxybenzoic acid, 2, 4, 6-trinitrophenol, hydrochloric acid, sulphuric acid, 4-dodecylbenzene sulphonic acid (DBSA) , picric acid , benz
  • acidic compounds which may be conveniently used are those with a pKa of less than 3.
  • Preferred acidic compounds are those with a pKa value of less than 2, such as trichloroacetic acid, hydrochloric acid, sulphuric acid, 4-dodecylbenzene sulphonic acid (DBSA) , picric acid and benzene sulphonic acid.
  • Particularly preferred acidic compounds are 4- dodecylbenzene sulphonic acid (DBSA) , sulphuric acid and hydrochloric acid.
  • the acidic compounds may be conveniently used in aqueous solution at a concentration in the range of from 0.05 to 1.5 mol/dm ⁇ , preferably 0.15 to 0.6 mol/dm ⁇ and most preferably 0.25 to 0.4 mol/dit .
  • said acidic compound is supported on a test strip.
  • Said test strip may be made of any solid material that is capable of supporting said acidic compound.
  • As the test strip will undergo colour reaction in the presence of a pH-dependent marking substance it is particularly preferred that said test strip is made from a material which is white or lightly coloured and which is not adversely effected by the presence of said acidic compound.
  • Suitable materials are, for example, glass microfibre, sintered glass, cellulose, cellulose nitrate, cellulose acetate, finely woven fabrics or porous materials including cotton, polypropylene, nylon, wood, neutral or acidic minerals.
  • Basic materials ' (such as AI2O3) are not suitable.
  • Compounds such as silica gel are not sufficiently acidic to be used on the test strip as the acidic compound per se.
  • test strip Depending upon the acid to be used in testing, it is 'within the skill of the skilled person to select appropriate material for the test strip.
  • the acidic compound may be optionally adsorbed onto a carrier prior to being supported on the test strip.
  • Suitable carriers are non-basic, absorbent and light in colour, and may conveniently include silica gel, cellulose, cellulose nitrate, cellulose acetate.
  • Said acidic compounds may be conveniently supported on the test strip at a concentration in the range of from
  • the test strip may comprise a narrow rectangular piece of the acidic compound-impregnated material as described above.
  • a smaller piece of such a test strip may be conveniently attached to a plastic-laminated material printed with appropriate instructions for use. The plastic lamination would enable the test strip to be wiped clean.
  • the test strip may comprise a white plastic-laminated opaque window mask in order to shroud the acidic compound-impregnated test strip and to therefore enhance the appearance of the colour change upon contact with the marking substance.
  • test strip may be conveniently located in a holder made of a durable material, for example, polypropylene .
  • such a test strip holder could be specifically designed to enable dipping of the test strip into the sump of an engine, that is to say, said holder could conveniently be a very narrow unit containing therein the acidic compound impregnated test strip attached to a disposable or re-usable dip-stick.
  • the oil composition comprises a marking substance according to formula (e) IV and/or V as hereinbefore described.
  • Test strips were prepared by submerging the test strip material in a solution of DBSA in heptane for 2 seconds, draining for 2 seconds and drying at 60°C.
  • Plastic thin layer chromatography (TLC) plates coated with a medium such as Si ⁇ 2 appeared to be ideal as a polar substrate that could support coating with acid.
  • TLC plastic thin layer chromatography
  • a medium such as Si ⁇ 2
  • gentle scuffing of the test strip substrate easily removed the absorbant surface, causing a poor scuffy surface and little acidified media.
  • the process of cutting the TLC plate material also induced cracking and media loss.
  • "Whatman" chromatography paper was found to be a very suitable medium for a spot test. This medium was scuff resistant, and could be easily cut to size giving a good finish.
  • the paper was tested in a variety of thicknesses and porosity. Tests showed that "Grade 4 CHR" gave optimal performance. The particular grade of paper was found to work with a variety of acids.
  • hydrochloric acid was found to make the paper brittle. If desired to use a combination of hydrochloric acid with "Whatman” chromatography paper Grade "4 CHR", the impregnated paper may be conveniently supported on a solid material, such as wood or plastic, in order to overcome any fragility of the impregnated paper. "Whatman" chromatography paper Grade "4 CHR” supporting DBSA at a concentration of » 0.002 g/cm 2 performed very well.
  • Example 2 Effect of type of Acid on Colour change in the Spot Test A variety of acids that could be used to promote a colour change were tested in the presence of a 15W50 synthetic oil containing 4- (phenylazo) diphenylamine marker therein doped at 30 pp ..
  • Oil compositions were prepared containing a range of concentrations of from 0 to 30 ppm of 4- (phenylazo) diphenylamine marker in 15W50 synthetic oil.
  • Strips of "Whatman” chromatography paper (Grade “4 CHR") were impregnated with a solution of 10% DBSA in n- heptane and were allowed to dry as described in Example 1.
  • the trained eye may also be able to distinguish a partially diluted oil composition from an undiluted oil composition by using the testing method of the present invention.

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  • Chemical & Material Sciences (AREA)
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EP03717214A 2002-03-15 2003-03-14 Oil composition and method of detecting a marker in an oil composition Withdrawn EP1497397A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP03717214A EP1497397A2 (en) 2002-03-15 2003-03-14 Oil composition and method of detecting a marker in an oil composition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP02251890 2002-03-15
EP02251890 2002-03-15
PCT/EP2003/002823 WO2003078551A2 (en) 2002-03-15 2003-03-14 Oil composition and method of detecting a marker in an oil composition
EP03717214A EP1497397A2 (en) 2002-03-15 2003-03-14 Oil composition and method of detecting a marker in an oil composition

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EP1497397A2 true EP1497397A2 (en) 2005-01-19

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US (1) US20050170976A1 (pt)
EP (1) EP1497397A2 (pt)
CN (1) CN1307292C (pt)
AR (1) AR038945A1 (pt)
AU (1) AU2003221504A1 (pt)
BR (1) BR0308359A (pt)
EA (1) EA006804B1 (pt)
PE (1) PE20040006A1 (pt)
SA (1) SA03240090B1 (pt)
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ZA200406841B (en) 2006-06-28
WO2003078551A2 (en) 2003-09-25
AR038945A1 (es) 2005-02-02
CN1307292C (zh) 2007-03-28
PE20040006A1 (es) 2004-02-12
EA200401211A1 (ru) 2005-04-28
EA006804B1 (ru) 2006-04-28
WO2003078551A3 (en) 2004-01-15
AU2003221504A1 (en) 2003-09-29
CN1643114A (zh) 2005-07-20
SA03240090B1 (ar) 2008-03-29
US20050170976A1 (en) 2005-08-04
BR0308359A (pt) 2005-01-25

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