[go: up one dir, main page]

EP1080165B1 - Formulation liquide d'hydrocarbures - Google Patents

Formulation liquide d'hydrocarbures Download PDF

Info

Publication number
EP1080165B1
EP1080165B1 EP99922304A EP99922304A EP1080165B1 EP 1080165 B1 EP1080165 B1 EP 1080165B1 EP 99922304 A EP99922304 A EP 99922304A EP 99922304 A EP99922304 A EP 99922304A EP 1080165 B1 EP1080165 B1 EP 1080165B1
Authority
EP
European Patent Office
Prior art keywords
liquid
stabiliser
doping medium
apolar
aliphatic hydrocarbon
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 - Lifetime
Application number
EP99922304A
Other languages
German (de)
English (en)
Other versions
EP1080165A1 (fr
Inventor
Bernd Renner
Ulrich Schmidt
Philip Gerald Taylor
Cameron James Smith
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.)
Macfarlan Smith Ltd
Original Assignee
Macfarlan Smith Ltd
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 Macfarlan Smith Ltd filed Critical Macfarlan Smith Ltd
Publication of EP1080165A1 publication Critical patent/EP1080165A1/fr
Application granted granted Critical
Publication of EP1080165B1 publication Critical patent/EP1080165B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • 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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • 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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1857—Aldehydes; Ketones
    • 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
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic 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
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • 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
    • C10L1/224—Amides; Imides carboxylic acid amides, imides

Definitions

  • This invention relates to a denaturant formulation suitable for discouraging the ingestion of hydrocarbon liquids particularly paraffinic liquids such as lamp oil, white spirit, kerosene and other hydrocarbon solvents.
  • Liquid hydrocarbons are widely used for various technical purposes and are often available for household purposes, where unguarded use or storage may present risks to children and domestic animals who may confuse them with potable liquids. This is especially so in third world countries where near starving children will consume virtually any liquid in their desperation to quench a thirst.
  • the inadvertent consumption of such liquids by vulnerable individuals is also a high risk because they are available as essentially colourless transparent liquids which are visually indistinguishable from water.
  • the physiological damage arising from deliberate or inadvertent consumption of these liquids is serious and may be fatal.
  • Aversive agents are known which impart a highly bitter taste to substances when mixed therewith. These cause such a bitter taste if an attempt is made to swallow the substance that the substance is rejected immediately, which usually avoids absorption or ingestion of amounts having any lasting harmful effect.
  • Denatonium benzoate otherwise known as lignocaine benzyl benzoate is cited in the Guinness Book of Records as the most bitter substance known to man, and its preparation and properties are described in GB-A-955 309. It is available commercially under the Registered Trade Mark "BITREX”.
  • Other denatonium salts are known in the literature.
  • Denatonium saccharide is a bittering agent analogous to denatonium benzoate and is described in US-A-4 652 577.
  • Liquid hydrocarbons of the type of concern here are predominantly organic liquids of an aliphatic character (alkanes) and mainly recognisable as of the liquid paraffin type but the invention is not restricted to a particular petroleum distillate fraction commonly called paraffin oil.
  • the problem may be explained more generally by an understanding that aliphatic liquids are useful because of their relative chemical inertness. This, for example, makes white spirit useful as a diluent in enamel paints or as a cleaning liquid for removal of certain paints from surfaces without chemically attacking the surface.
  • This predictable non-reactive character and stability whilst providing desirable properties for marketing products based on such liquids, also presents a problem when seeking to include a denaturant or aversive agent therein.
  • denatonium benzoate is extremely insoluble in apolar liquids. Therefore even though that denaturant would exhibit an acceptable level of aversive activity at concentrations as low as 10 ppm it has not proved possible to introduce it directly to liquid hydrocarbons and maintain a satisfactory level of concentration therein for a sufficient period of time even to satisfy a typical shelf life before eventual use. As cited in GB-B-2 212 814, the denaturant does not form a stable solution in kerosine or the like liquids and tends to migrate rapidly to the container walls.
  • a stabiliser in the form of a co-solvent which is at least miscible with the target hydrocarbon and has sufficient affinity with the selected aversion agent which is a denatonium salt, (preferably denatonium benzoate) to permit introduction of effective amounts thereof to the target hydrocarbon with satisfactory stability of the final formulation.
  • a denatonium salt preferably denatonium benzoate
  • Suitable co-solvents for the purposes of the invention are C 6 -C 20 aliphatic or alicyclic alkanols, including diols and diol mono-ethers, esters, and mixtures thereof having at least one available, i.e. underivatised, hydroxyl group.
  • a preliminary screening test to confirm or determine suitability of a co-solvent from amongst these classes of solvents would include determining if the solvent under consideration is miscible with the hydrocarbon to be denatured and if it is also capable of dissolving the desired denaturant at a satisfactory level, say 0.1%. Preliminary work suggests that substituted alkanols would be acceptable.
  • a method for rendering a liquid hydrocarbon unpalatable with an aversive agent having poor solubility in said liquid hydrocarbon comprising selecting a stabiliser in the form of a co-solvent from C 6 -C 20 aliphatic or alicyclic alkanols and diols, optionally substituted with ester, ether, ketonic, alicyclic and/or aromatic groups, and having at least one available, i.e.
  • Preferred stabilisers include diols and diol mono-ethers, esters, and mixtures thereof particularly branched chain lower secondary alkanol esters of lower fatty acids, especially those formed using a secondary diol.
  • An especially suitable co-solvent is 2,2,4-trimethylpentan-1,3-diol-monoisobutanoate (CAS-Nr. : 25265-77-4, C 12 H 24 O 3 ), which proved to be uniquely suitable for the purpose of the invention.
  • Alkanols which have not been derivatised have also been observed to be useful for the purposes of the invention with varying degrees of stability.
  • aliphatic or alicyclic alkanols i.e. C 2 -C 20 and above such as 1-butanol and isopropanol
  • C 6 -C 20 alkanols such as 1-octanol, 1-hexadecanol, and mixtures thereof with esters such as 1-octanol/ethyl acetate 1:1 w/w which are now found to be effective in enabling introduction of the preferred aversive agent "BITREX®" at the desired level.
  • a base oil to be denatured is selected, a preferred denaturant such as the aversive agent denatonium benzoate is provided, a stabilising co-solvent therefor is selected from amongst alkanols and aliphatic esters of the aforesaid type, the denaturant is introduced to the co-solvent and dissolved therein e.g. by stirring or similar agitation, to provide a doping medium and thereafter an amount of said doping medium sufficient to have an aversive organoleptic effect is added to the base oil to denature same.
  • a preferred denaturant such as the aversive agent denatonium benzoate
  • a stabilising co-solvent therefor is selected from amongst alkanols and aliphatic esters of the aforesaid type

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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)
  • Detergent Compositions (AREA)

Claims (22)

  1. Liquide à base d'hydrocarbures aliphatiques apolaire contenant, comme agent d'aversion, une quantité efficace du point de vue aversif d'un composé de la formule :
    Figure 00230001
       dans laquelle A est un anion, et un solvant miscible audit liquide, comme stabilisant pour favoriser la présence effective de l'agent d'aversion dans le liquide précité, ledit stabilisant étant choisi parmi les alcanols aliphatiques et alicycliques en C6-C20, notamment les diols et les monoéthers de diols, lesdits alcanols étant éventuellement substitués par des groupes ester, éther, cétoniques, alicycliques et/ou aromatiques, mais conservant au moins un groupe hydroxyle disponible, c'est-à-dire non substitué, la quantité dudit stabilisant étant suffisante pour maintenir une quantité efficace du point de vue aversif de l'agent aversif dans le liquide précité.
  2. Liquide apolaire suivant la revendication 1, dans lequel le stabilisant précité est choisi parmi le 1-octanol et le 1-hexadécanol.
  3. Liquide apolaire suivant la revendication 1, dans lequel le stabilisant précité est de l'éthyl-DL-2-hydroxyhexanoate.
  4. Liquide apolaire suivant la revendication 1, dans lequel le stabilisant précité est du monoisobutanoate de 2,2,4-triméthylpentane-1,3-diol.
  5. Liquide apolaire suivant la revendication 1, dans lequel le stabilisant précité est un mélange de 1-octanol et d'acétate d'éthyle (1/1 en poids/poids).
  6. Procédé pour rendre un liquide à base d'hydrocarbures aliphatiques apolaire d'un goût désagréable comprenant la sélection d'un agent aversif de la formule :
    Figure 00240001
       dans laquelle A- est un anion, et la présence d'un stabilisant liquide choisi parmi les alcanols aliphatiques et alicycliques en C6-C20, notamment les diols et monoéthers de diols, lesdits alcanols étant éventuellement substitués par des groupes ester, éther, cétoniques, alicycliques et/ou aromatiques, mais conservant au moins un groupe hydroxyle disponible, c'est-à-dire non substitué, comme stabilisant de solubilisation pour ledit agent aversif, l'amenée d'une quantité prédéterminée dudit agent audit stabilisant pour former ainsi un milieu dopant, et l'addition d'une quantité efficace de ce milieu dopant à un liquide à base d'hydrocarbures aliphatiques apolaires, de telle sorte que ledit liquide soit rendu d'un goût désagréable et qu'une quantité efficace du point de vue aversif dudit agent aversif soit maintenue dans le liquide précité.
  7. Procédé pour rendre un liquide à base d'hydrocarbures aliphatiques apolaire d'un goût désagréable suivant la revendication 6, comprenant la sélection d'un agent aversif de la formule :
    Figure 00250001
       dans laquelle A- est un anion, et la présence d'au moins un stabilisant de solubilisation pour ledit agent, choisi parmi le 1-octanol, le 1-hexadécanol, l'éthyl-DL-2-hydroxyhexanoate, le monoisobutanoate de 2,2,4-triméthylpentane-1,3-diol et un mélange (1/1 en poids/poids) de 1-octanol et d'acétate d'éthyle, l'amenée d'une quantité prédéterminée dudit agent audit stabilisant choisi pour former ainsi un milieu dopant, et l'addition d'une quantité efficace de ce milieu dopant à un liquide à base d'hydrocarbures aliphatiques apolaire, de telle sorte que ledit liquide soit rendu d'un goût désagréable et qu'une quantité efficace du point de vue aversif dudit agent aversif soit maintenue dans le liquide précité.
  8. Milieu dopant utilisable dans un procédé de traitement rendant un liquide hydrocarboné aliphatique apolaire d'un goût désagréable, ledit milieu se composant essentiellement d'au moins un stabilisant répondant à la formule générique :
    Figure 00250002
       dans laquelle R1, R2, R3, R4 et R5 sont choisis indépendamment dans le groupe comprenant l'hydrogène et les hydrocarbures aliphatiques à chaíne droite ou ramifiée, substitués ou non substitués, dans lequel chaque hydrocarbure comprend éventuellement un ou plusieurs substituants choisis dans le groupe comprenant les alcanols, les esters, les éthers, les cétones, les composantes alicycliques et les composantes aromatiques, dans laquelle le nombre d'atomes de carbone constitués par R1, R2 et R3 combinés n'est pas inférieur à quatre et n'excède pas dix-huit, et d'un agent aversif de la formule :
    Figure 00260001
       dans laquelle A- est un anion, en une quantité efficace pour être utilisé dans un procédé de traitement rendant un liquide hydrocarboné aliphatique apolaire d'un goût désagréable.
  9. Milieu dopant suivant la revendication 8 utilisable dans un procédé de traitement rendant un liquide hydrocarboné aliphatique apolaire d'un goût désagréable et se composant essentiellement d'un stabilisant choisi parmi le monoisobutanoate de 2,2,4-triméthylpentane-1,3-diol, l'éthyl-DL-2-hydroxyhexanoate, le 1-octanol, le 1-hexadécanol et un mélange de 1-octanol/acétate d'éthyle (1/1 en poids/poids), et d'un agent aversif de la formule :
    Figure 00260002
       dans laquelle A- est un anion, en une quantité efficace pour rendre ledit liquide hydrocarboné aliphatique apolaire d'un goût désagréable, la présence du stabilisant précité permettant de maintenir une quantité efficace du point de vue aversif dudit agent aversif dans le liquide précité.
  10. Utilisation d'un milieu dopant dans un procédé de traitement rendant un liquide hydrocarboné aliphatique apolaire d'un goût désagréable, ledit milieu dopant comprenant un agent aversif de la formule :
    Figure 00270001
       dans laquelle A- est un anion, en une quantité efficace pour rendre ledit liquide hydrocarboné aliphatique apolaire d'un goût désagréable, et un solvant miscible audit liquide et comportant au moins un groupe hydroxyle disponible, c'est-à-dire non substitué, comme stabilisant de solvatation pour promouvoir la présence effective de l'agent d'aversion dans le liquide précité, ledit stabilisant étant choisi parmi les alcanols aliphatiques et alicycliques en C6-C20, notamment les diols et les monoéthers de diols, éventuellement substitués par des groupes ester, éther, cétoniques, alicycliques et/ou aromatiques, ladite quantité du stabilisant précité étant suffisante pour maintenir une quantité efficace du point de vue aversif dudit agent aversif dans le liquide hydrocarboné aliphatique apolaire précité.
  11. Utilisation d'un milieu dopant suivant la revendication 10, dans laquelle le milieu dopant est un milieu dopant suivant la revendication 8, ou suivant la revendication 9, et dans laquelle le liquide hydrocarboné contient moins de 0,1% de substances aromatiques avant traitement.
  12. Utilisation d'un milieu dopant suivant la revendication 10, dans laquelle le milieu dopant est un milieu dopant suivant la revendication 8, ou la revendication 9, et dans laquelle le liquide hydrocarboné est une huile blanche.
  13. Utilisation d'un milieu dopant suivant la revendication 10, dans laquelle le milieu dopant est un milieu dopant suivant la revendication 8, ou la revendication 9, et dans laquelle le liquide hydrocarboné est un mélange désaromatisé de n-paraffines.
  14. Utilisation d'un milieu dopant suivant la revendication 10, dans laquelle le stabilisant de solubilisation précité est du monoisobutanoate de 2,2,4-triméthylpentane-1,3-diol.
  15. Utilisation d'un milieu dopant suivant la revendication 10, dans laquelle le stabilisant de solubilisation précité est de l'éthyl-DL-2-hydroxyhexanoate.
  16. Utilisation d'un milieu dopant suivant la revendication 10, dans laquelle le stabilisant de solubilisation précité est un mélange de 1-octanol et d'acétate d'éthyle (1/1 en poids/poids).
  17. Utilisation d'un milieu dopant suivant la revendication 10, dans laquelle le liquide hydrocarboné contient moins de 0,1% de substances aromatiques avant traitement.
  18. Utilisation d'un milieu dopant suivant la revendication 10, dans laquelle le liquide hydrocarboné est une huile blanche.
  19. Utilisation d'un milieu dopant suivant la revendication 18, dans laquelle le liquide hydrocarboné est un mélange désaromatisé de n-paraffines.
  20. Utilisation suivant l'une quelconque des revendications 10 à 19, dans laquelle l'agent aversif est suffisamment stabilisé pour maintenir un niveau d'au moins 10 ppm de celui-ci dans le liquide traité.
  21. Utilisation suivant l'une quelconque des revendications 10 à 19, dans laquelle l'agent aversif est suffisamment stabilisé pour maintenir un niveau d'au moins 40 ppm de celui-ci dans le liquide traité.
  22. Liquide à base d'hydrocarbures aliphatiques apolaire suivant la revendication 1, contenant un composé de la formule :
    Figure 00290001
       dans laquelle A- est un anion, comme agent aversif, et du monoisobutanoate de 2,2,4-triméthylpentane-1,3-diol comme stabilisant présent à raison de 0,1 à 25% (poids/poids) et permettant de maintenir une quantité efficace du point de vue aversif de l'agent dans le liquide.
EP99922304A 1998-05-15 1999-05-13 Formulation liquide d'hydrocarbures Expired - Lifetime EP1080165B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9810408.6A GB9810408D0 (en) 1998-05-15 1998-05-15 Hydrocarbon liquid formulation
GB9810408 1998-05-15
PCT/GB1999/001523 WO1999060077A1 (fr) 1998-05-15 1999-05-13 Formulation liquide d'hydrocarbures

Publications (2)

Publication Number Publication Date
EP1080165A1 EP1080165A1 (fr) 2001-03-07
EP1080165B1 true EP1080165B1 (fr) 2004-01-21

Family

ID=10832084

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99922304A Expired - Lifetime EP1080165B1 (fr) 1998-05-15 1999-05-13 Formulation liquide d'hydrocarbures

Country Status (9)

Country Link
EP (1) EP1080165B1 (fr)
JP (1) JP2002515536A (fr)
AR (1) AR015299A1 (fr)
AU (1) AU745819B2 (fr)
DE (1) DE69914323T2 (fr)
ES (1) ES2213368T3 (fr)
GB (2) GB9810408D0 (fr)
WO (1) WO1999060077A1 (fr)
ZA (1) ZA200006574B (fr)

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB955309A (en) * 1959-11-20 1964-04-15 Edinburgh Pharmaceutical Ind L New quaternary salts and compositions containing them
GB866605A (en) * 1960-02-27 1961-04-26 T & H Smith Ltd Denaturing of potable alcoholic liquids
US4005038A (en) * 1974-04-15 1977-01-25 Peerless Paint And Varnish Corporation Paint composition containing denatonium benzoate or lignocaine benzyl octanoate with a latex resin binder for application over old paint films to prevent ingestion of poisons therefrom
US4084939A (en) * 1976-12-22 1978-04-18 Colgate-Palmolive Company Audibly burning gelled alcohol
GB8727504D0 (en) * 1987-11-24 1987-12-23 Glaxo Group Ltd Chemical compositions
JP2668420B2 (ja) * 1988-11-07 1997-10-27 新高化学工業株式会社 誤食防止性能を有する固形燃料
JP3724043B2 (ja) * 1995-03-30 2005-12-07 ぺんてる株式会社 描画材組成物
DE19605162C1 (de) * 1996-02-13 1997-09-18 Elf Oil Deutschland Gmbh Synthetisches Schmieröl und dessen Verwendung
CN1048751C (zh) * 1996-05-29 2000-01-26 鲜京工业股份有限公司 含有苦味剂的气体组合物
GB9624070D0 (en) * 1996-11-20 1997-01-08 Rolls Royce Plc Control system for a ducted fan gas turbine engine
PL187600B1 (pl) * 1997-06-09 2004-08-31 Shell Int Research Kompozycja płynnego gazu ziemnego

Also Published As

Publication number Publication date
ZA200006574B (en) 2001-10-15
EP1080165A1 (fr) 2001-03-07
DE69914323T2 (de) 2004-11-18
GB9810408D0 (en) 1998-07-15
AU3941199A (en) 1999-12-06
JP2002515536A (ja) 2002-05-28
GB2354255B (en) 2002-10-23
AR015299A1 (es) 2001-04-18
WO1999060077A1 (fr) 1999-11-25
AU745819B2 (en) 2002-04-11
GB2354255A8 (en) 2003-08-07
GB0030498D0 (en) 2001-01-31
GB2354255A (en) 2001-03-21
ES2213368T3 (es) 2004-08-16
DE69914323D1 (de) 2004-02-26

Similar Documents

Publication Publication Date Title
KR100250115B1 (ko) 아민과 에톡실화 알콜을 갖는 천연계면활성제
Baharuddin et al. Development, formulation and optimization of a novel biocompatible ionic liquids dispersant for the effective oil spill remediation
US4469603A (en) Surface-active compositions and method for dispersing oil slicks
RU2141996C1 (ru) Многофазная эмульсия и способ ее приготовления
JPH01236298A (ja) 組成物
US7868048B2 (en) Heavy oil emulsion stabilizers containing saccharide based emulsion stabilizer
US3998733A (en) Detergent composition for dispersing oil spills
DE3604521A1 (de) Verfahren zur hemmung von mikroorganismen in fluessigen kohlenwasserstoffen
US5814163A (en) Composition and process for cleaning inks form various surfaces including printing plates
JP4870905B2 (ja) ディーゼル燃料エマルジョン
US6645390B1 (en) Composition and method for treating hydrocarbon fires
US4661120A (en) Diesel fuel additive
US5945026A (en) Composition and methods for firefighting hydrocarbon fires
US4110213A (en) Compositions and processes for the dispersing of oil spillages
EP1080165B1 (fr) Formulation liquide d'hydrocarbures
DE69731547T2 (de) Zusammensetzungen und verfahren zum dispergieren und zum biologischen abbau von ausgelaufenem erdöl und treibstoffen
NO137482B (no) Preparat for dispergering av oljes¦l.
RU2777538C1 (ru) Диспергент для ликвидации разливов нефти
EP0398860B1 (fr) Compositions dispersantes pour le traitement des nappes d'huile sur l'eau froide
NO315548B1 (no) Fremgangsmåte for behandling av et vandig miljö som er forurenset av hydrokarboner, samt demulgerende og dispergerende blanding på basis avpolyglykolestere
US3431209A (en) Solvent degreasing,self-emulsifying cleaning composition
EP0155208B1 (fr) Compositions tensio-actives utilisables notamment pour disperser une nappe d'huile à la surface de l'eau
KR100283678B1 (ko) 수용성 기재의 알킬폴리글리코사이드를 포함하는 환경친화형유처리제
LU83961A1 (fr) Compositions et procede pour l'elimination de nappes d'huile a la surface des eaux
US8936728B2 (en) Chemicals for oil spill cleanup

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20001214

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES FR GB IT NL

17Q First examination report despatched

Effective date: 20020809

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RBV Designated contracting states (corrected)

Designated state(s): BE DE ES FR IT NL

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR IT NL

REF Corresponds to:

Ref document number: 69914323

Country of ref document: DE

Date of ref document: 20040226

Kind code of ref document: P

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2213368

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20041022

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20090527

Year of fee payment: 11

Ref country code: ES

Payment date: 20090521

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20090529

Year of fee payment: 11

Ref country code: FR

Payment date: 20090513

Year of fee payment: 11

Ref country code: DE

Payment date: 20090525

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20090622

Year of fee payment: 11

BERE Be: lapsed

Owner name: *MACFARLAN SMITH LTD

Effective date: 20100531

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20101201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20110131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100513

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101201

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100531

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20110718

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110706

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100514