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EP1682639A1 - Procede d'encapsulation et de dispersion et capsule associee - Google Patents

Procede d'encapsulation et de dispersion et capsule associee

Info

Publication number
EP1682639A1
EP1682639A1 EP04791632A EP04791632A EP1682639A1 EP 1682639 A1 EP1682639 A1 EP 1682639A1 EP 04791632 A EP04791632 A EP 04791632A EP 04791632 A EP04791632 A EP 04791632A EP 1682639 A1 EP1682639 A1 EP 1682639A1
Authority
EP
European Patent Office
Prior art keywords
capsule
tablet
marker
liquid
compound
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Withdrawn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
EP04791632A
Other languages
German (de)
English (en)
Inventor
Darrell Green
Clive Antony Marchant
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.)
Johnson Matthey PLC
Original Assignee
Johnson Matthey PLC
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 Johnson Matthey PLC filed Critical Johnson Matthey PLC
Publication of EP1682639A1 publication Critical patent/EP1682639A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/42—Flashing oils or marking oils
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/12—Micro capsules

Definitions

  • the present invention relates to a method for dispersing a measured amount of a material into a liquid, and, in a particular embodiment, to a capsule adapted to contain the measured amount of material and disperse it on introduction into the liquid.
  • Dispersion of solid and liquid materials by encapsulation is known in e.g. laundry products, drugs and agrochemicals for example. It is known to incorporate marker compounds into commercially formulated products in order to identify the source of the product or to trace the flow of a particular chemical composition. Such marking or "tagging" of products may be used to counteract counterfeit products or simply to monitor the flow of chemicals through a process or supply chain. However, it is not known to supply a marking or tagging composition for a liquid product in the form of an encapsulated pre-measured amount of the marker compound in a package which enables dispersion of the marker in the liquid when the package is placed in contact with the liquid.
  • Petroleum products are often subject to taxes and regulations which require that the amount and composition of the products sold is monitored and recordable. In such situations any deviation from a regulated standard of purity may impact the amount of tax which is recoverable in the state in which it is sold.
  • Petroleum products such as automotive fuel gasoline may contain hydrocarbon solvents such as toluene, xylene or hexane but the amount of solvent permitted is normally strictly controlled to avoid potential damage to engines and to limit the amount of tax lost on the non- petroleum content of such fuels.
  • gasoline may contain a certain proportion of a non-hydrocarbon component such as ethanol. It is often difficult to separate and thus identify and measure solvents found in a petroleum mixture because the petroleum is itself a complex mixture of compounds.
  • markers compounds may be used, for example radioactive materials, dyes, fluorescent materials or other materials which are readily detectable by particular methods. However it is often relatively simple to counterfeit such a tagged material.
  • systems may be devised that employ two or more taggants that interact, for example as described in US 6312958 where two or more interacting fluorescent dyes are employed as markers for liquids such as petroleum products, e.g. gasoline and diesel fuels.
  • the taggants are generally powdery solids at room temperature and are either soluble in oil or the hydrocarbon-based petroleum products or in another constituent of the petroleum product, such as a permitted solvent, e.g. methanol or ethanol if present. In use they are required at very low concentrations, typically below 500 ppb by weight. Heretofore they have been added to petroleum products through the intermediary of a concentrated stock solution. Often it is desirable to employ a known concentration of taggant, especially where mixtures of taggants are employed. Heretofore this has necessitated measuring out relatively small amounts of the concentrated stock solutions.
  • marker composition we mean a composition which may contain one or more than one marker compound (or tag or taggant) and optionally one or more additional compounds such as a dispersing agent, surfactant, diluent etc.
  • a marker compound is an individual marker such as a chemical marker or dye which is used to mark or tag a liquid product, for example to enable the liquid product to be traced and/or identified in a supply chain or process.
  • a tablet or capsule containing a predetermined amount of a marker composition, said tablet or capsule being capable of dispersing said marker composition when the tablet or capsule is introduced into a bulk liquid medium.
  • the marker composition When the marker composition is a powder, it may simply be bound together to form a tablet, containing a known amount of the marker composition powder, with a binder. Alternatively, and preferably, the marker composition may be charged into a capsule so that the capsule contains a specified amount of the marker composition. In some cases it may be desirable to charge a marker composition which comprises a known mixture of marker compound materials to a single tablet or capsule. Alternatively it may be more preferable to charge known amounts of marker compounds or marker compositions singly to separate tablets or capsules and, where mixtures of marker compounds are required simply to add the appropriate number of different tablets or capsules to the bulk liquid to be tagged or marked. Typically each tablet or capsule contains 1 to 100 g of the marker composition.
  • a capsule for dispersing a measured amount of a solid or liquid compound in a larger volume of bulk liquid said capsule comprising a compound-containing portion for containing the solid or liquid compound to be dispersed, a buoyancy portion to control the rate at which the capsule sinks within the bulk liquid and, optionally, a counterweight portion to ballast the capsule and maintain its orientation in the bulk liquid.
  • the compound-containing portion may comprise a matrix of soluble material in which the compound to be dispersed is incorporated or, alternatively and preferably, it comprises an enclosed chamber in which the solid or liquid compound to be dispersed is placed.
  • the capsule is formed from a material which is soluble in the liquid in which the solid or liquid compound it contains is to be dispersed.
  • the entire capsule is formed from the soluble material, however it is essential that at least a part of the material forming the enclosed chamber is the soluble material.
  • the container is capable of dissolving in the bulk liquid in such a way that no or minimal solid residues of the container remain which could foul the transfer lines in a subsequent transfer of the bulk liquid.
  • suitable soluble materials include hydrophilic, water-soluble polymers, starch, gelatin etc.
  • the soluble material is preferably a non-polar soluble polymer or a solid hydrocarbon, e.g. a hydrocarbonaceous material selected from paraffin wax or polystyrene, compounded with or encapsulating a soluble marker composition.
  • the hydrocarbonaceous material is preferably paraffin wax of melting point in the range 50 to 60°C. Paraffin wax is available in various grades according to its melting point, or set point. We have found that for dissolution in gasoline, a wax having a melting point of 50 - 60°C, preferably 50 - 56°C, especially 51 - 53°C is particularly suitable. Waxes of higher melting point only dissolve slowly in petroleum liquids, especially where the latter contains a significant proportion of non-hydrocarbon solvent such as ethanol, while waxes of lower melting point may soften in hot climates.
  • the material In order for the capsule to be sufficiently robust, normally the material is of a thickness which is completely soluble only after several minutes in contact with the bulk liquid. This is especially true in situations where access to the bulk liquid for mixing following contact with the capsule is difficult. Therefore in a preferred embodiment the material forming the enclosed chamber is of a non-uniform thickness. In this way one or more portions of the chamber walls may be of thinner material which can dissolve in the bulk liquid more quickly than the thicker portions of material to accelerate the release of the material within the chamber.
  • the invention also provides a method of tagging or marking a liquid petroleum product comprising adding one or more tablets or capsules as described above containing a marker composition to a known amount of a bulk liquid petroleum product.
  • the counterweight portion is preferably present but may be omitted. It is preferred to maintain a particular orientation of the capsule within the bulk liquid in order to ensure that certain parts of the capsule, particularly thinner parts of the wall of the chamber are maintained in contact with the bulk liquid so that they dissolve quickly. In this way the dissolution of the wall of the chamber and thus the release of its contents may be controlled.
  • the counterweight portion preferably comprises the same soluble material from which the remainder of the capsule is formed. Therefore the counterweight may be provided by a thicker portion of the chamber or a solid part of the capsule in the region of the base of the capsule.
  • the buoyancy portion is provided to control the rate at which the capsule sinks within the bulk liquid and to enable the capsule to float within the bulk liquid for at least some of the time taken to dissolve sufficient of the material to release a significant proportion of the compound which is to be dispersed. It will be appreciated that if the capsule sinks to the bottom of the bulk liquid before the compound has been dispersed from the capsule, then dispersion of the compound within the liquid is less easy and may require agitation.
  • the buoyancy portion may comprise a portion of the capsule formed from or containing a material which is less dense than the bulk liquid into which the material contained in the capsule is to be dispersed. Examples of such less-dense materials include gases and foams.
  • the buoyancy portion preferably comprises an air-filled chamber.
  • the capsule may optionally comprise fins or grooves to control its orientation within the bulk liquid medium. For example fins may be supplied which induce spinning of the capsule in order to assist in dispersion of the contents.
  • the tablet or capsule may be of various proportions but is preferably of suitable size and shape to be handled easily, e.g. from about 20mm to about 200 mm.
  • the tablet or capsule may incorporate a small amount of visible pigment or dye to identify different types or amounts of taggant material.
  • the capsule or tablet may be marked, e.g. by printing or embossing in order to identify the type of contents or a batch number etc.
  • marker compounds or tags may be used, for example radioactive materials, dyes, fluorescent materials or other materials which are readily detectable by particular methods, including chemical analysis and chromatography.
  • the marker composition may comprise one or more than one marker compound, each marker compound being detectable by similar or by different means.
  • a first group of particularly suitable marker compounds are fluorophores which absorb radiation at one or more wavelengths and re-emit the radiation at one or more characteristic, longer, wavelengths.
  • fluorophores are fluorescent dyes such as quinone-imine dyes, especially oxazine dyes, and xanthene dyes, particularly the Rhodamine dyes and coumarin dyes, 4-(butylamino)-N-butyl-1 ,8-naphthalimide, and Glowbug Invisible Red S- Organic Europium Complex, Glowbug Invisible Lemon S- Organic Non-longenic Oxazine Derivative, and Glowbug Invisible Cyan S -Organic Pyrazoline Derivative supplied by Capricorn Chemicals.
  • Suitable dyes are well known, for example in the field of laser dyes or histopathology and characteristics of suitable dyes may be found in manufacturers literature, for example
  • the fluorophore absorbs in the ultra-violet and/or visible parts of the electromagnetic radiation spectrum and re-emit in the visible and/or near infra-red parts.
  • a second group of suitable marker compounds are chemical markers which are detectable by chemical analysis.
  • marker compounds may be conveniently detected by gas chromatography apparatus coupled with a suitable detector which is capable of distinguishing the marker compound from compounds forming the bulk liquid composition.
  • Alternative methods of identifying a chemical marker compound such as X-ray fluorescence spectroscopy (XRF), inductively-coupled plasma analysis (ICP) or gas chromatography-mass spectrometry (gc/MS) in addition to or instead of XRF and/or ICP analysis.
  • Suitable chemical marker compounds include a halogenated hydrocarbon, or other compound which is not a natural or usual component of the petroleum product to which the marker composition is to be added.
  • Suitable halogenated hydrocarbons include halogenated aliphatic or aromatic compounds, such as bromopropane, iodobenzene, bromobenzene, a dichlorobenzene, trichloro ethylene ,1 ,1 ,2- trichloro ethane, tetrachloroethylene, 1 ,1 ,2,2-tetrachloro ethane, pentachloro ethane, hexachloro ethane, 1 ,2,4-trichloro benzene, 1 ,2,4,5-tetrachloro benzene, pentachloro benzene, dichloro-1 ,2-dibromoethane, dichlorotribromethane, hexafluoro benzene, difluoro-1- chloroethane, trifluoro-1 ,1 ,2-trichloroethane, tetrabromoethylene , tribrom
  • marker compounds include octafluoronaphthalene, 2,3,4,5,6-petafluorobenzhydrol, 3,9-dibromocamphor, perfluoroindan, lindane, aldrin, 2-fluoro-3-(thfluoromethyl)benzophenone, or 1 ,4-diiodobenzene.
  • the marker compounds e.g. dyes are selected to be soluble in the polar solvent. This increases the range of marker compounds which may be used.
  • Preferred marker compounds for use in such petroleum products are polar, most preferred are dyes or other marker compounds which are capable of dissolving fully in ethanol at a concentration of up to 500 ppb at ambient temperatures and pressures.
  • the marker composition may be solid or liquid. Both solid and liquid forms of suitable marker compounds are known.
  • the marker compound(s) which comprise the marker composition are selected to be sufficiently soluble in the bulk liquid to be marked that they are dispersed homogeneously with no or only mild to moderate mixing.
  • the marker compound(s) should preferably be capable of dissolving to provide a homogeneous solution in the petroleum when the mixing action is provided by the movement of the liquid in a road or rail tanker, over a period of a few hours.
  • Fig 1 depicts a tablet 10 comprising particles 12 of a marker compound dispersed in a soluble matrix of a hydrocarbon wax 14.
  • the tablet is introduced into the liquid to be marked and, on dissolution of the wax matrix, the solid marker particles are released into the liquid.
  • Fig 2 shows a capsule 20 formed of a soluble paraffin wax material.
  • the capsule contains a measured amount of a marker compound 22 contained within an enclosed chamber 24 within the capsule.
  • the walls 26 of the chamber are of variable thickness, as shown in Fig 2a in which a transverse section along line A—A is shown. Portions 36 of the interior wall are fluted to provide thinner sections which dissolve on the liquid more quickly so that the marker • compound 22 may be released.
  • Chamber 28 is sealed by wall 30 and lid 32 and is filled with air to provide buoyancy to the capsule to enable it to float in the liquid.
  • the base portion 34 of the capsule 20 is relatively dense, being formed from thicker material.
  • the channels 38 adjust the density of the base portion so that the capsule is sufficiently buoyed by the buoyancy chamber and also provide for more rapid dissolution of the base portion than would be possible if the base were completely solid.
  • Fig 3 shows an alternative capsule 40, also formed from a solid wax material.
  • the marker compound 42 is contained within chamber 44 which extends into the base portion 46 of the capsule.
  • Chamber 44 has a chamfered section 48 to enable the marker powder to flow into the base portion.
  • region 50 of the base portion is relatively thin so that it may dissolve rapidly in the liquid and release the marker compound 42.
  • the buoyancy chamber 52 is separated from the marker-containing chamber 44 by separating wall 54.
  • the method of the invention is particularly useful for marking petroleum products so that they may be identified and/or traced through the supply chain from source to consumer.
  • the method of the invention may be used to mark a genuine product when there is a risk of adulteration or of substitution with a similar product, e.g. for the avoidance of tax or duty on petroleum fuels.
  • petroleum products in which the marker composition may be used include gasoline, diesel, and paraffin fuels such as kerosene etc.
  • the method may be used to add a marker composition to hydrocarbon solvents such as toluene, xylene or hexane, for example in order that dilution of petroleum products with such marked solvents may be detected and quantified.
  • the marker composition may be added to a petroleum product in order that it may be traced in the subsequent transport or refining processes, e.g. so that fuel removed (lawfully or unlawfully) from a pipeline containing the fuel may be identified and traced.
  • the marking of a petroleum product may, alternatively, be used to trace the source of a spillage or in process monitoring applications.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Preparation (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)

Abstract

L'invention concerne une composition de marqueur pour milieu liquide renfermant une pastille ou une capsule qui contient une quantité prédéterminée dudit marqueur et qui peut disperser ledit marqueur, lors de l'introduction de la pastille ou de la capsule dans ledit milieu liquide. Cette invention a aussi trait à un procédé d'étiquetage d'un produit pétrolier liquide à l'aide de la composition d'étiquetage, ainsi qu'à une capsule de dispersion d'un solide ou d'un liquide dans un corps liquide plus important.
EP04791632A 2003-11-19 2004-10-29 Procede d'encapsulation et de dispersion et capsule associee Withdrawn EP1682639A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0326932.1A GB0326932D0 (en) 2003-11-19 2003-11-19 Encapsulation and dispersion method and capsule therefor
PCT/GB2004/004597 WO2005052096A1 (fr) 2003-11-19 2004-10-29 Procede d'encapsulation et de dispersion et capsule associee

Publications (1)

Publication Number Publication Date
EP1682639A1 true EP1682639A1 (fr) 2006-07-26

Family

ID=29764078

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04791632A Withdrawn EP1682639A1 (fr) 2003-11-19 2004-10-29 Procede d'encapsulation et de dispersion et capsule associee

Country Status (4)

Country Link
EP (1) EP1682639A1 (fr)
BR (1) BRPI0416688A (fr)
GB (1) GB0326932D0 (fr)
WO (1) WO2005052096A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201107870D0 (en) * 2011-05-11 2011-06-22 Johnson Matthey Plc Tracers and method of marking hydrocarbon liquids
JP6298076B2 (ja) 2012-12-27 2018-03-20 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイＳｈｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌｅ Ｒｅｓｅａｒｃｈ Ｍａａｔｓｃｈａｐｐｉｊ Ｂｅｓｌｏｔｅｎ Ｖｅｎｎｏｏｔｓｈａｐ 組成物
EP2938714A1 (fr) 2012-12-27 2015-11-04 Shell Internationale Research Maatschappij B.V. Compositions
FR3023180B1 (fr) * 2014-07-03 2016-08-12 Commissariat Energie Atomique Utilisation d’aluminosilicates a des fins de marquage

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19818176A1 (de) 1998-04-23 1999-10-28 Basf Ag Verfahren zur Markierung von Flüssigkeiten mit mindestens zwei Markierstoffen und Verfahren zu deren Detektion
US4639255A (en) 1980-01-15 1987-01-27 Phillips Petroleum Company Solid form additives and method of forming same
US4608345A (en) * 1984-11-05 1986-08-26 Exxon Research And Engineering Co. Colorimetric detection of alcohols in gasoline
AU4213900A (en) 1999-04-07 2000-10-23 Petramec, Inc. Methods of making and using microcapsules with controlled density
CN1653163A (zh) * 2002-03-22 2005-08-10 克林迪塞尔技术公司 催化的金属添加剂浓缩物及其制法和用途

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005052096A1 *

Also Published As

Publication number Publication date
BRPI0416688A (pt) 2007-01-30
GB0326932D0 (en) 2003-12-24
WO2005052096A1 (fr) 2005-06-09

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