WO1993016149A1 - Sels metalliques utilises comme agents de marquage pour des bitumes combustibles - Google Patents

Sels metalliques utilises comme agents de marquage pour des bitumes combustibles Download PDF

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Publication number
WO1993016149A1
WO1993016149A1 PCT/EP1993/000241 EP9300241W WO9316149A1 WO 1993016149 A1 WO1993016149 A1 WO 1993016149A1 EP 9300241 W EP9300241 W EP 9300241W WO 9316149 A1 WO9316149 A1 WO 9316149A1
Authority
WO
WIPO (PCT)
Prior art keywords
bitumen
metal salts
alkyl
marking
optionally substituted
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.)
Ceased
Application number
PCT/EP1993/000241
Other languages
German (de)
English (en)
Inventor
Silvana Rabacchi
Alberto Osti
Virginio Sarto
Franco Piscitelli
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.)
BASF Italia SpA
Original Assignee
BASF Italia SpA
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 BASF Italia SpA filed Critical BASF Italia SpA
Priority to EP93917381A priority Critical patent/EP0626992B1/fr
Priority to DE59300463T priority patent/DE59300463D1/de
Publication of WO1993016149A1 publication Critical patent/WO1993016149A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • 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
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom

Definitions

  • the present invention relates to the use of metal salts of the formula
  • X® is a monovalent inorganic anion
  • n is the sum of m and y, which may be 2 or 3,
  • fuel bitumen is understood to mean those combustible products from the distillation of crude oil which have a boiling temperature which is higher than 200 ° C.
  • the object of the present invention was to provide suitable means for marking fuel bitumen. Since fuel bitumen is generally a mixture of petroleum derivatives, the properties (eg color or consistency) of which are generally very different from those of other petroleum fuels (eg mineral oils), it is possible to use the substances usually used as markers (eg azo dyes) do not apply.
  • fuel bitumen is generally a mixture of petroleum derivatives, the properties (eg color or consistency) of which are generally very different from those of other petroleum fuels (eg mineral oils), it is possible to use the substances usually used as markers (eg azo dyes) do not apply.
  • Suitable alkenyl groups generally have 1 to 3 double bonds. If Q denotes a phenyl, naphthyl, pyridyl or quinolinyl residue which is substituted by C 1 -C 2 alkyl, this residue generally has 1 or 2 substituents.
  • Suitable residues Q are e.g. Butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 2-methylhexyl, octyl, 2-ethylhexyl, 2,4, -trimethylpentyl, isooctyl, nonyl, isononyl , Decyl, isodecyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl (the above terms isooctyl, isononyl, isodecyl and isotridecyl are tricial names and come from the alcohols obtained after the oxo synthesis - see also Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 7, pages 215 to 217
  • Suitable monovalent inorganic anions are e.g. Halide ions, such as fluoride, chloride, bromide or iodide, or nitrate.
  • Metal salts of the abovementioned formula, in which Q is Cg -C 3 -alkyl, are particularly preferably used for marking fuel bitumen.
  • the metal salt of the formula is very particularly suitable as a marking agent for fuel bitumen
  • metal salts of the abovementioned formula, in which L denotes carbonyl are generally those salts which are known under the term "metal soaps".
  • the other salts are also known per se or can be obtained from the corresponding acids by methods of salt formation known per se.
  • the amount of metal salts to be used as a marking agent can vary within wide limits, the minimum value depending on the detection method.
  • the minimum content of marking agent is generally 60 ppm.
  • marking agents 60 to 600 ppm, preferably 250 to 400 ppm, of marking agents are generally used.
  • the metal salts are used either in bulk or preferably in solution by adding to the bitumen.
  • Suitable solvents are high-boiling organic solvents compatible with heating bitumen, e.g. aromatic solvents such as xylene or aliphatic solvents such as white spirit.
  • Aromatic solvents are preferably used, in particular those derived from petroleum distillation and one
  • a particularly favorable aromatic solvent is the product known under the trade name Shellsol® AB (Shell).
  • the solutions When using the metal salts in solution, the solutions generally have a solvent content of 30 to 80% by weight, based on the weight of the solution.
  • the marking means can be detected in the bitumen using two different methods, a simple qualitative detection method or a quantitative detection method.
  • the qualitative detection method for example, one proceeds by labeling labeled bitumen in an organic solvent, e.g. Chloroform, and this solution, which generally contains 30 to 70% by weight, preferably about 50% by weight, of fuel bitumen, in each case based on the weight of the solution, with a saturated solution of ammonium rhodanide in acetone / water in the presence of small amounts of silica. After a short time, usually about 5 minutes, the upper aqueous phase shows a characteristic color reaction. It is colored blue when cobalt salts are present and red when iron salts are present.
  • an organic solvent e.g. Chloroform
  • the quantitative detection method one proceeds, for example, by first "digesting" the labeled fuel bitumen by, for example, a sample with a mixture of 96% by weight sulfuric acid, 65% by weight nitric acid and 70 wt .-% perchloric acid treated with heating. If a colorless solution has formed, dilute with water to a known volume and measure the resulting solution using an atomic absorption spectrophotometer using known methods. If a device for atomic absorption analysis is not available, the marker can also be determined quantitatively as follows:
  • the lower aqueous phase is drained off and the colored organic phase is washed with a mixture of 5 ml of aqueous ammonium rhodanide solution and 6 ml of aqueous sodium pyrophosphate solution.
  • the phases are separated, the lower aqueous phase is discharged, the upper organic phase is transferred to a 5 ml flask and the flask is filled up with methyl isobutyl ketone.
  • the spectrophotometric measurement is carried out in a 1 cm cell at a wavelength of approximately 662 nm (cobalt salt) or approximately 475 nm (iron salt).
  • the content of the marking agent is determined by comparison with a previously determined calibration curve.
  • the metal salts to be used according to the invention are advantageously suitable for marking fuel bitumen. They are simple and can also be detected in low concentrations and have the parameters required at the outset.
  • Example 3 The procedure was analogous to Example 1.
  • the marking agent was stirred directly, i.e. without the help of a solvent, mixed with bitumen.
  • the upper phase was only pale yellow (almost colorless).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Paints Or Removers (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

L'invention concerne l'utilisation de sels métalliques ayant la formule suivante (I) dans laquelle M + représente l'équivalent d'un ion cobalt ou fer, Q est un alkyle en C4-C22, alkényle en C4-C22, aryle ou hétaryle, L est un carbonyle ou un sulfonyle, X- est un anion anorganique monovalent, m est égal à 1, 2 ou 3, y est égal à 0, 1 ou 2, n est la somme de m et y, celle-ci pouvant être égale à 2 ou 3, pour le marquage de bitumes combustibles, ainsi que les bitumes combustibles renfermant un ou plusieurs des sels métalliques précités.
PCT/EP1993/000241 1992-02-14 1993-02-03 Sels metalliques utilises comme agents de marquage pour des bitumes combustibles Ceased WO1993016149A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP93917381A EP0626992B1 (fr) 1992-02-14 1993-02-03 Sels metalliques utilises comme agents de marquage pour des bitumes combustibles
DE59300463T DE59300463D1 (de) 1992-02-14 1993-02-03 Metallsalze als markierungsmittel für brennbitumen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI920320A IT1254456B (it) 1992-02-14 1992-02-14 Composizione marcante-denaturante particolarmente adatta per marcare edenaturare bitumi combustibili o prodotti affini.
ITMI92A000320 1992-02-14

Publications (1)

Publication Number Publication Date
WO1993016149A1 true WO1993016149A1 (fr) 1993-08-19

Family

ID=11361972

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/000241 Ceased WO1993016149A1 (fr) 1992-02-14 1993-02-03 Sels metalliques utilises comme agents de marquage pour des bitumes combustibles

Country Status (4)

Country Link
EP (1) EP0626992B1 (fr)
DE (1) DE59300463D1 (fr)
IT (1) IT1254456B (fr)
WO (1) WO1993016149A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995021278A1 (fr) * 1994-02-03 1995-08-10 Henkel Kommanditgesellschaft Auf Aktien Procede au chromate ou au phosphate et materiaux appropries pour determiner le mode de traitement
WO1996000271A1 (fr) * 1994-06-24 1996-01-04 Basf Italia S.P.A. Utilisation de composes carbonyle pour marquer des hydrocarbures

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR698152A (fr) * 1930-06-17 1931-01-28 Patent Fuels & Color Corp Essence minérale colorée et stabilisée
US2074288A (en) * 1934-11-21 1937-03-16 Du Pont Fluorescent hydrocarbon oils
FR1070581A (fr) * 1952-11-13 1954-07-29 Nat Aluminate Corp Procédé pour la réduction de la formation et du dépot de carbone dans la combustion des huiles combustibles et produits en résultant
US3692503A (en) * 1969-02-26 1972-09-19 Apollo Chem Activated manganese containing additive for fuels
EP0077552A1 (fr) * 1981-10-19 1983-04-27 Matsushita Electric Industrial Co., Ltd. Huile colorée
EP0078249A1 (fr) * 1981-10-12 1983-05-04 Lang & Co., chemisch-technische Produkte Kommanditgesellschaft Additif améliorant la combustion et réduisant la formation de noir de fumée des huiles combustibles, carburant diesel et autres combustibles et carburants liquides ainsi que ce combustible et carburant liquide en soi
EP0388591A1 (fr) * 1989-03-23 1990-09-26 Hüls Aktiengesellschaft Procédé de marquage d'un matériau absorbant par un colorant thermiquement stable

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR698152A (fr) * 1930-06-17 1931-01-28 Patent Fuels & Color Corp Essence minérale colorée et stabilisée
US2074288A (en) * 1934-11-21 1937-03-16 Du Pont Fluorescent hydrocarbon oils
FR1070581A (fr) * 1952-11-13 1954-07-29 Nat Aluminate Corp Procédé pour la réduction de la formation et du dépot de carbone dans la combustion des huiles combustibles et produits en résultant
US3692503A (en) * 1969-02-26 1972-09-19 Apollo Chem Activated manganese containing additive for fuels
EP0078249A1 (fr) * 1981-10-12 1983-05-04 Lang & Co., chemisch-technische Produkte Kommanditgesellschaft Additif améliorant la combustion et réduisant la formation de noir de fumée des huiles combustibles, carburant diesel et autres combustibles et carburants liquides ainsi que ce combustible et carburant liquide en soi
EP0077552A1 (fr) * 1981-10-19 1983-04-27 Matsushita Electric Industrial Co., Ltd. Huile colorée
EP0388591A1 (fr) * 1989-03-23 1990-09-26 Hüls Aktiengesellschaft Procédé de marquage d'un matériau absorbant par un colorant thermiquement stable

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPIL Week 8604, Derwent Publications Ltd., London, GB; AN 86-026482 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995021278A1 (fr) * 1994-02-03 1995-08-10 Henkel Kommanditgesellschaft Auf Aktien Procede au chromate ou au phosphate et materiaux appropries pour determiner le mode de traitement
WO1996000271A1 (fr) * 1994-06-24 1996-01-04 Basf Italia S.P.A. Utilisation de composes carbonyle pour marquer des hydrocarbures

Also Published As

Publication number Publication date
EP0626992A1 (fr) 1994-12-07
IT1254456B (it) 1995-09-25
ITMI920320A1 (it) 1993-08-14
ITMI920320A0 (it) 1992-02-14
EP0626992B1 (fr) 1995-08-09
DE59300463D1 (de) 1995-09-14

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