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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/003—Marking, e.g. coloration by addition of pigments
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
  • C09B1/16—Amino-anthraquinones
  • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
  • C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
  • C09B5/24—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic rings being only condensed with an anthraquinone nucleus in 1-2 or 2-3 position
  • C09B5/44—Azines of the anthracene series
  • C09B5/46—Para-diazines
  • C09B5/48—Bis-anthraquinonediazines (indanthrone)
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
  • C10L1/2235—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom hydroxy containing
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/20—Organic compounds containing halogen
  • C10L1/202—Organic compounds containing halogen aromatic bond
• • 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
  • C10M2215/22—Heterocyclic nitrogen compounds
  • C10M2215/221—Six-membered rings containing nitrogen and carbon only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/20—Colour, e.g. dyes

Definitions

• This invention relates generally to a method for marking petroleum hydrocarbons with combinations of marker compounds for subsequent identification.
• U.S. Pat. No. 6,274,381 discloses a method for marking a petroleum hydrocarbon with at least two dyes having absorption maxima between 500 nm and 700 nm, thus allowing for creation of multiple absorption patterns which can be used to identify the hydrocarbon.
• This reference does not suggest a method for marking petroleum hydrocarbons with dyes absorbing in other wavelength ranges.
• Visible dyes having absorption maxima between 500 nm and 700 nm suffer from disadvantages as markers, including interference from other colored substances in the petroleum hydrocarbon, especially when the dyes are present at low levels.
• the problem addressed by this invention is to find an improved method for marking petroleum hydrocarbons with multiple markers.
• the present invention is directed to a method for marking a liquid petroleum hydrocarbon.
• the method comprises adding to the liquid petroleum hydrocarbon: (i) at least one anthraquinone dye having an absorption maximum in the range from 710 nm to 850 nm selected from the group consisting of 1,4,5,8-tetrasubstituted anthraquinones and anthraquinone dimers; and (ii) at least one visible dye having an absorption maximum in the range from 500 nm to 700 nm.
• ppm parts per million
• the term “petroleum hydrocarbons” refers to products having a predominantly hydrocarbon composition that are derived from petroleum, preferably lubricating oil, hydraulic fluid, brake fluid, gasoline, diesel fuel, kerosene, jet fuel and heating oil.
• An “alkyl” group is a hydrocarbyl group having from one to twenty carbon atoms in a linear, branched or cyclic arrangement. Alkyl groups optionally have one or more double or triple bonds.
• alkyl groups are substituted by one or more halo substituents.
• alkyl groups have no halo or alkoxy substituents.
• a “heteroalkyl” group is an alkyl group having at least one carbon which has been replaced by O, NR, or S, wherein R is hydrogen, alkyl, aryl or aralkyl.
• An “aryl” group is a substituent derived from an aromatic hydrocarbon compound. An aryl group has a total of from six to twenty ring atoms, and has one or more rings which are separate or fused.
• An “aralkyl” group is an “alkyl” group substituted by an “aryl” group.
• a “heterocyclic” group is a substituent derived from a heterocyclic compound having from five to twenty ring atoms, at least one of which is nitrogen, oxygen or sulfur. Preferably, heterocyclic groups do not contain sulfur. Substitution on aryl or heterocyclic groups of one or more halo, cyano, nitro, alkoxycarbonyl, dialkylamino, alkylamino, amino, hydroxy, alkyl, heteroalkyl, alkanoyl or alkoxy groups is permitted, with substitution by one or more halo groups being possible on alkyl, heteroalkyl, alkanoyl or alkoxy groups. Preferably, aryl and heterocyclic groups do not contain halogen atoms.
• An “aromatic heterocyclic” group is a heterocyclic group derived from an aromatic heterocyclic compound.
• a 1,4,5,8-tetrasubstituted anthraquinone dye having formula (I) is added to a petroleum hydrocarbon.
• X is R 4 NH, NH 2 , OH or halo; and R 1 , R 2 , R 3 and R 4 independently are alkyl, aryl, aralkyl, heteroalkyl or heterocyclic. Preferably, at least two of R 1 , R 2 , and R 3 are aryl or aromatic heterocyclic. More preferably, X is R 4 NH, and at least three of R 1 , R 2 , R 3 and R 4 are aryl or aromatic heterocyclic, more preferably all four. Most preferably, all of R 1 , R 2 , R 3 and R 4 are aryl.
• an anthraquinone dye which is an anthraquinone dimer is added to a petroleum hydrocarbon.
• Anthraquinone dimers include: (i) substituted derivatives, having ⁇ max from 710 to 850 nm, of 6,15-dihydro-5,9,14,18-anthrazinetetrone, shown below,
• anthraquinone dimer is a substituted 6,15-dihydro-5,9,14,18-anthrazinetetrone of formula (II).
• R 1 , R 2 , R 3 , and R 4 independently are hydrogen, alkyl, heteroalkyl or alkylamino;
• R 5 is hydrogen, alkyl, heteroalkyl, alkylamino, arylamino or aromatic-heterocyclic-amino; and
• R is hydrogen, alkyl, arylamino or aromatic-heterocyclic-amino; provided that one of R and R 5 is arylamino or aromatic-heterocyclic-amino.
• R 1 , R 2 , R 3 , and R 4 are hydrogen.
• R 1 , R 2 , R 3 , R 4 and R 5 are hydrogen and R is arylamino.
• R is a hydrogen-bond donor arylamino group, e.g., phenylamino.
• R is phenylamino, such that the compound is of formula (III).
• This compound has a ⁇ max of 790 nm.
• R, R 1 , R 2 , R 3 , and R 4 are hydrogen; and R 5 is phenylamino, such that the compound is of formula (IV).
• This compound is 6,15-dihydro-8,17-bis(phenylamino)-5,9,14,18-anthrazinetetrone, and has been sold commercially under the trade names C.I. VAT GREEN 6 and CALEDON GREEN RC.
• each anthraquinone dye having an absorption maximum in the range from 710 nm to 850 nm which is added to the petroleum hydrocarbon is at least 0.01 ppm, more preferably at least 0.02 ppm, and most preferably at least 0.03 ppm.
• the amount of each dye is less than 10 ppm, more preferably less than 2 ppm, and most preferably less than 1 ppm.
• the marking is invisible, i.e., the dye cannot be detected by simple visual observation of the marked hydrocarbon.
• an anthraquinone dye having an absorption maximum in the range from 710 nm to 850 nm used in the method of this invention has an absorption maximum in the range from 720 nm to 850 nm, more preferably from 720 nm to 810 nm, and most preferably from 730 nm to 800 nm.
• at least two anthraquinone dyes having absorption maxima at differential wavelengths within one of the aforementioned ranges are added to the petroleum hydrocarbon.
• the anthraquinone dyes and the visible dyes are detected by exposing the marked hydrocarbon to electromagnetic radiation having wavelengths in the portion of the spectrum containing the absorption maxima of the dyes and detecting the absorption of light or fluorescent emissions. It is preferred that the detection equipment is capable of calculating dye concentrations and concentration ratios in a marked hydrocarbon. Typical spectrophotometers known in the art are capable of detecting the anthraquinone dyes used in the method of this invention which absorb in the 710 nm to 850 nm range when they are present at a level of at least 0.01 ppm. It is preferred to use the detectors described in U.S. Pat. No.
• the sample may be returned to its source after testing, eliminating the need for handling and disposal of hazardous chemicals. This is the case, for example, when the dyes are detected simply by measuring light absorption by a sample of the marked hydrocarbon.
• the dye is formulated in a solvent to facilitate its addition to the liquid hydrocarbon.
• the preferred solvents for tetra-substituted anthraquinones are N-methylpyrrolidinone, N,N-dimethyl propylene urea, nitrobenzene, toluene and N,N-dimethylformamide.
• the dye is present in the solvent at a concentration of from 0.1% to 10%.
• each visible dye i.e., a dye having an absorption maximum in the range from 500 nm to 700 nm, preferably from 550 nm to 700 nm, and most preferably from 550 nm to 680 nm; is added in an amount of at least 0.1 ppm, preferably at least 0.2 ppm, and most preferably at least 0.5 ppm.
• the amount of each visible dye is no more than 10 ppm, more preferably no more than 5 ppm, more preferably no more than 3 ppm, and most preferably no more than 2 ppm.
• the visible dyes are selected from the classes of anthraquinone dyes and azo dyes.
• Suitable anthraquinone dyes having an absorption maximum in this region include, for example, 1,4-disubstituted anthraquinones having alkylamino, arylamino or aromatic-heterocyclic-amino substituents.
• Suitable azo dyes having an absorption maximum in this region include the bisazo dyes, for example, those having the structure Ar—N ⁇ N—Ar—N ⁇ N—Ar, in which Ar is an aryl group, and each Ar may be different.
• Specific examples of suitable commercial anthraquinone and bisazo dyes having an absorption maximum in this region are listed in the Colour Index, including C.I. Solvent Blue 98, C.I. Solvent Blue 79, C.I. Solvent Blue 99 and C.I. Solvent Blue 100.
• incorporación of at least one anthraquinone dye having an absorption maximum in the region from 710 nm to 850 nm allows identification of the liquid hydrocarbon by spectrophotometric means in a spectral region relatively free of interference. Low levels of these dyes are detectable in this region, allowing for a cost-effective marking process. Use of higher levels of at least one visible dye having an absorption maximum in the region from 500 nm to 700 nm facilitates quantitative spectrophotometric determination in this region. Accurate determination of the dye levels allows the amounts and ratios of the dyes to serve as parts of a code identifying the hydrocarbon.
• the markers are “silent markers.”
• a mixture of 10.87 g of 1,4,5,8-tetrachloroanthraquinone, 50 g of aniline, 13.4 g of potassium acetate, 1.24 g of copper sulfate, and 3.41 g of benzyl alcohol was heated to 130° C. under nitrogen and maintained at this temperature for 6.5 hours, followed by another holding period at 170° C. for 6 hours.
• the reaction mixture was cooled to ambient temperature and the precipitate was filtered to give black solids.
• a mixture of 10.87 g of 1,4,5,8-tetrachloroanthraquinone and 95 g of 4-n-butylaniline was allowed to react at 190° C. for 12 hours.
• the reaction mixture was then cooled to 70° C. and diluted with an equal amount of ethanol. On standing and further cooling to ambient temperature, some precipitate was formed.
• the mixture was filtered, washed and recrystallized from xylenes/isopropanol to give 6.6 g of a dark green crystalline material (>95% purity) with the structure confirmed by proton NMR as the desired product of 1,4,5,8-tetra(4-n-butylphenylamino)anthraquinone.
• This material had a maximum absorption band ( ⁇ max ) at a wavelength of 762 nm in toluene.
• the molar extinction coefficient ( ⁇ ) was determined to be ⁇ 36,900.
• TPAAQ 1,4,5,8-tetra(phenylamino)anthraquinone

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Lubricants (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2003
  • 2003-11-12 US US10/706,198 patent/US20040106526A1/en not_active Abandoned
  • 2003-11-13 IN IN1183MU2003 patent/IN2003MU01183A/en unknown
  • 2003-11-18 EP EP03257254A patent/EP1426434A3/en not_active Withdrawn
  • 2003-11-20 TW TW092132562A patent/TWI247037B/zh not_active IP Right Cessation
  • 2003-11-21 BR BR0305751-8A patent/BR0305751A/pt not_active IP Right Cessation
  • 2003-11-27 CN CNB2003101186565A patent/CN1258083C/zh not_active Expired - Fee Related
  • 2003-12-02 KR KR1020030086981A patent/KR20040050715A/ko not_active Withdrawn
  • 2003-12-02 JP JP2003402771A patent/JP3806114B2/ja not_active Expired - Fee Related

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