EP1392801B1 - Procédé de Préparation d'un Additif de Carburant - Google Patents

Procédé de Préparation d'un Additif de Carburant Download PDF

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Publication number
EP1392801B1
EP1392801B1 EP02738197A EP02738197A EP1392801B1 EP 1392801 B1 EP1392801 B1 EP 1392801B1 EP 02738197 A EP02738197 A EP 02738197A EP 02738197 A EP02738197 A EP 02738197A EP 1392801 B1 EP1392801 B1 EP 1392801B1
Authority
EP
European Patent Office
Prior art keywords
fatty acids
mixture
acid
melting point
high melting
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.)
Revoked
Application number
EP02738197A
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German (de)
English (en)
Other versions
EP1392801A1 (fr
Inventor
Martti Fredrikson
Heikki Ahonen
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Forchem Oyj
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Forchem Oyj
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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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • 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
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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
    • C10L1/18—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, 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
    • C10L1/18—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, 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
    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained

Definitions

  • the present invention relates to a method for manufacturing a fuel additive and the additive.
  • the invention particularly relates to a lubricating additive, which is especially suitable for use as an additive used with diesel engines.
  • Fatty acids have proven to be good additives for fuel, particularly diesel fuel.
  • fatty acids have the well-known drawback that they crystallize or that substances such as stearic acid and arachid acid crystallize easily out of them, in other words, fatty acids as such are not suitable for very cold conditions.
  • the esters of these acids also easily crystallize out of, for instance, olive oil.
  • US patent 6,129,772 discloses a fuel additive, manufactured from saturated fatty acids and from oligomeric fatty acids, in which tertiary amines are used to prevent crystallization.
  • the patent emphasizes especially that mixtures of different saturated fatty acids are not used, but gives no reasons for this.
  • US patent 5,578,090 discloses a fuel and a fuel additive, which is characterized in that it is composed of the esters of fatty acids, some of which are glycerine esters and some are triglycerides.
  • WO 94/17160 discloses a fuel additive, comprising a fatty acid, which is esterified using alcohol containing one or several carbons.
  • EP 826765 discloses a corresponding diesel-fuel additive, which is a fatty acid and a partial ester of polyol, for example, glycerine and an ester of monocarboxylic acid, 75 - 200 ppm of which is added to middle distillates.
  • US patent 6,194,361 discloses that a usable lubricant can be obtained from the distilled fatty acids of tall oil by allowing the fatty acid of tall oil to react with diethanolamine and then allowing the fatty acid to react with aminoethylpiperazidine after the previous reaction.
  • This compound is used, among other things, for lubricating oil wells, both with oil and as a water emulsion.
  • US patent 6,197,731 discloses that a suitable lubricant for two-stroke engine fuel can be obtained by esterifying polyols with polycarboxylic acids.
  • JP 08092581 discloses how the -OH group of castor oil can be esterified with a saturated monovalent fatty acid to obtain a lubricant that will operate at very low temperatures.
  • US patent 6,086,645 discloses how a fuel additive can be advantageously obtained by manufacturing amides of carboxylic acids for this purpose from oleic acid and/or linolenic acid.
  • US patent 5,882,364 discloses a corresponding fuel additive comprising the esters of an unsaturated fatty acid and a polyvalent alcohol, two grades of which are mixed together in the same mixture.
  • US patent 6,203, 584 discloses a fuel additive comprising esters of polybasic carboxylic acid and polyoxyamine and a mixture of carboxylic acid and an ester of polyvalent alcohol, which acts with them.
  • US patent 5,997,593 discloses a fuel lubricant comprising the reaction product of carboxylic acid and an amine, in which the said amine is guanidine, amino guanidine, urea, or thiourea.
  • US patent 6,051,039 discloses a diesel fuel additive, which is obtained from an amine of dicarboxylic acid, which is an amine derivative of succinic acid or phtalic acid and their mixture, as well as of an NR 3 amine, in which R contains 6 - 24 carbons.
  • the mixture is added to diesel fuel in a concentration of at least 1000 ppm.
  • US patent 5,556,972 discloses how fats can be fractionated by crystallizing a stearin ester fraction from an oleic acid fraction in two stages and removing the said stearin fat fraction by filtration. This reduces the cloud point of the fat. The process is carried out by countercurrent crystallization, which thus reduces, for example, the congealing point of margarine.
  • US patent 5,952,518 discloses a method, by means of which fatty acids with a high melting point can be removed from other fatty acids. In this case, the assistance of an emulsifier is used, the mixture is cooled, and the saturated fatty acids are removed from the mixture by crystallization. Esters of a polyvalent alcohol and a fatty acid are used as the emulsifier. The fatty acids are hydrolyzed rapeseed or soya oils.
  • EP-A-0 635 558 discloses a lubricity improver derived from a mixture of saturated fatty acids, having a higher concentration of high M.Pt. saturated fatty acids which have been as verified.
  • the fatty acids of tall oil act well as fuel lubricants in combustion engines, as do their alcohol esters with alcohols, and the amines of fatty acids. However, the fatty acids as such would be the best lubricants.
  • Saturated fatty acids and their derivatives are stated to act particularly well as lubricants.
  • the present invention is intended to create a lubricant based on fatty acids and a method for manufacturing it for use as a fuel additive to improve lubrication. This is achieved in the manner stated to be characteristic in the accompanying Claims.
  • the question is how to very advantageously eliminate the said problems and drawbacks, when using compositions of tall oil and other fatty acids as an internal lubricant in fuel at low temperatures.
  • the fatty-acid composition is given a cold-treatment, preferably using such a heat exchanger, in which the fatty-acid composition is circulated, until a sufficient share of the amount of the fatty acids has crystallized on the heat-transfer surfaces of the heat exchanger being used and essentially only unsaturated fatty acids flow out of the composition.
  • saturated fatty acids crystallize out of a tall oil fatty-acid composition already at a temperature of 10° C, most of the stearic acid crystallizing already at a temperature of 5° C. The rest will also crystallize at the temperature range 5 - 0° C.
  • the crystallization process is slow and can take many days when the said fatty-acid mixtures stand in a vessel. This is due to the low diffusion coefficient and the high viscosity in cold conditions.
  • the composition is pumped through a heat-transfer surface, the low diffusivity is compensated by the mass transfer caused by the flow as such.
  • saturated fatty acids have been made to solidify on a heat-transfer surface, they can be removed from the surface by separately heating it.
  • a new fatty-acid composition is obtained, which has a substantially greater amount than before of saturated fatty acids, typically palmitinic acid, stearic acid, and arachinic acid. Typically these total, for example, 2 - 4 % by weight of a tall oil fatty-acid composition.
  • the melting point of unsaturated fatty acids is much lower than that of saturated fatty acids, but the lubricating properties of saturated fatty acids are, in turn, better, which is a generally known fact.
  • the separated saturated fatty acids are esterified, aminated, and permitted to react with enhancing cyclic compounds, such as lactams, oxazolidines, and similar.
  • enhancing cyclic compounds such as lactams, oxazolidines, and similar.
  • the melting point, solidifying point, or the pour point known in technology of each mixture occurs at a lower temperature, the more the mixture contains related but not identical compounds. Further, it is possible to envisage and claim that the more a mixture contains such compounds (in this case fatty-acid compounds), which form steric inhibitions to crystallization, branchings, branches, pendant groups, etc., then the lower will be the temperature at which the mixture will solidify, or at which crystals or a separate phase of some compound will precipitate from it.
  • the saturated fatty acids are separated from a fatty-acid composition by crystallization at a low temperature, and are made to react with an alcohol mixture, preferably with waste, i.e. fusel oil, obtained from the manufacture of alcohol, which contains many alcohols with a high boiling point, so that a mixture of many esters will be obtained directly.
  • Some of the saturated fatty acids are, in turn, made to react with amines, particularly with N,N-dimethyl or N,N-diethyl amines, when an excellent solvent and a low melting point for the said solvent will be obtained.
  • Part of the saturated fatty-acids separated from the composition can be advantageously made to react at an increased temperature and in the presence of an acid catalyst with lactams, preferably with capric lactam. This reaction must not include a large number of unsaturated fatty acids, because polymerization takes place easily and a solid phase with a high melting point will be obtained (+50°C) .
  • oleic acid - linoleic acid mixture Before the reaction with amines, preferably N,N- dimethyl or diethyl amines, a small amount of an oleic acid - linoleic acid mixture can be added to the mixture, thus providing an advantageous solvent for other reactions.
  • saturated fatty acids are separated from a fatty-acid mixture by crystallizing them, preferably on cold heat-transfer surfaces, the mixture of essentially saturated fatty acid being separated by heating the said heat-transfer surface and given an esterifying treatment in the presence of an acid catalyst, preferably using an alcohol mixture containing many different alcohols and/or a part of the said mixture of saturated fatty acids being allowed to react with amines, preferably with N,N-diammine and/or a part being permitted to react with lactams, preferably with capric lactam, at an increased temperature, and at least one of these reaction mixtures being re-mixed with the original mixture made from essentially unsaturated fatty acids.
  • the aforementioned method has advantages, including the fact that only part of the fatty acids, generally 2 - 5 %, must be treated and the best fatty acids, even though modified, can be used for lubrication. If the separate and modified fraction is multi-modified, the solidification point of this fraction will be at a lower temperature than if it had been esterified or aminated using only a single reagent.
  • the reaction product of capric lactam and fatty acids is like vaseline, provided the reaction of the product is stopped at a suitably early stage, for example, 30 min /150° C. If the product is kept hot, for example, for 2 hours, a relatively solid product will result, which will not longer optimally suit the purpose referred to here.
  • the catalyst used is an acid catalyst, para-toluenesulphonic acid, Lewis acid, or concentrated cation exchange resin or sulphuric acid, which must, however, be washed out. Normal Lewis acids, such as AlCl 3 are very suitable for this purpose.
  • N,N-dimethyl or ethyl fatty-acid amines When aminating fatty acids, there is reason to use advantageously N,N-dimethyl or ethyl fatty-acid amines, as they do not form hydrogen bridges with each other and thus remain liquid at room temperature.
  • esterifying fatty acids When esterifying fatty acids, one of the cheapest raw materials is an alcohol mixture, which in the alcohol industry goes by the name of fusel oil. If this is used in esterifying, many esters of fatty acids and acids will be obtained at one time, while a low solidification point for the reaction mixture will also be obtained.
  • the product thus obtained is typically mixed with diesel fuel to form a 0.01 - 0.04 % mixture.
  • a tall oil-fatty acid mixture which according to analysis contained palmitinic acid 0.4 % , stearic acid 1.1 %, and arachid acid 0.4%, was cooled to and kept cooled at a temperature of + 5.5° C, until no further sediment was deposited from it.
  • the solution was filtered, the filtration producing about 50 ml of mixture from a litre of the original composition.
  • the solidification point of the sediment was 35° C.
  • the composition of this mixture contained 8.3 % of stearic acid (1.1 % in the original mixture). It is obvious that filtration in a laboratory will not produce such good results as crystallization on cold heat-transfer surfaces, because a large amount of the other acids present in the mixture will remain between the crystals of the sedimented stearic acid.
  • Fusel oil traditionally contains salts that can be removed prior to use in esterification, for example, by distillation. However, in this case the salts were removed in another way; i.e. the fusel oil was cooled to a temperature of -18°C, when about one-fifth of the water precipitated as a salt phase, which was removed together with the salts, the remainder being used as follows.
  • stearic acid was esterified using an alcohol mixture, of so-called fusel oil, which was obtained from the waste of the distillation of ethanol.
  • the composition of the fusel oil was: propanol 3 w-%, isobutanol 24 w-%, 2-methyl-1-butanol 12 w-%, 3-methyl-1-butanol 37 w-%, ethanol 8 w-%, water 14 w-% ja solids in the form of salts 0.5 g/litre, which were removed according to the above procedure.
  • Example 2 The solution remaining in Example 2, which was a light brown liquid, with a viscosity clearly greater than that of fatty acids, was mixed with the filtrate of Example 1, in which there was thus a large amount of unsaturated fatty acids, together with the amine esters of stearic acid manufactured in Example 4, in which case the amount corresponded to the amount of the 'stearic-acid fraction' removed by crystallization.
  • the fatty-acid mixture thus created was allowed to stand for several days at a temperature of +2° C, during which time no sediment appeared in it, even though the same original product (Example 1 , +5° C) continued to crystallize significantly in the same conditions.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Lubricants (AREA)

Claims (10)

  1. Procédé pour fabriquer des composants acides gras pour être utilisés comme additif lubrifiant pour carburant, caractérisé en ce que des acides gras saturés dotés d'un point de fusion élevé de 10 à 0 °C sont séparés d'un mélange d'acides gras par refroidissement, la fraction d'acides gras avec un point de fusion élevé est estérifiée et/ou aminée pour former une mixture de plus de trois esters et/ou amines et la mixture ainsi formée est mélangée de nouveau avec cette partie du mélange acide gras original, à partir de laquelle les acides gras avec un point de fusion élevé avaient été séparés, et mélangée avec une quantité nécessaire du mélange citée en dernier pour constituer un carburant lubrifiant.
  2. Procédé selon la revendication 1, caractérisé en ce que les acides gras avec un point de fusion élevé sont séparés du mélange d'acide gras en faisant passer le mélange à travers une surface refroidissent de transmission de chaleur et que les acides gras s'adhérant à la surface de refroidissement sont ensuite enlevés en augmentant la température de celle-ci.
  3. Procédé selon la revendication 1, caractérisé en ce que la fraction d'acides gras saturés avec un point de fusion élevé est estérifiée en utilisant un mélange de plusieurs alcools.
  4. Procédé selon la revendication 3, caractérisé en ce que l'estérification se fait en utilisant l'huile de fusel.
  5. Procédé selon la revendication 4, caractérisé en ce que l'estérification se fait en utilisant l'huile de fusel dans laquelle il y a de l'eau, les sels dissous en sont enlevés en refroidissant ladite huile de fusel à une température de moins de 0°C, particulièrement à une température de -10 à -25 °C et en enlevant la phase de l'eau séparée.
  6. Procédé selon la revendication 4, caractérisé en ce que l'huile de fusel est distillée avant le traitement par estérification.
  7. Procédé selon la revendication 1, caractérisé en ce que la fraction d'acides gras avec un point de fusion élevé est aminée, particulièrement en utilisant des diamines ou des amino-alcools et/ou des lactames.
  8. Procédé selon la revendication 7, caractérisé en ce que l'amination a lieu à une température de 130 à 150 °C et en présence d'un catalyseur acide pendant l'action de mélange d'une durée d'au moins 1 heure.
  9. Procédé selon la revendication 7, caractérisé en ce que l'amination a lieu en utilisant des N,N-dialkylamines.
  10. Procédé selon l'une quelconque des revendications ci-dessus, caractérisé en ce que les acides gras saturés sont traités par estérification et par amination, ensemble ou séparément, et que les produits obtenus sont mélangés avec des acides gras insaturés qui sont restés du mélange d'acides, duquel les acides gras saturés avaient été séparés.
EP02738197A 2001-06-08 2002-06-10 Procédé de Préparation d'un Additif de Carburant Revoked EP1392801B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI20011214A FI111380B (fi) 2001-06-08 2001-06-08 Menetelmä polttoaineen apuaineen valmistamiseksi ja apuaine
FI20011214 2001-06-08
PCT/FI2002/000501 WO2002100987A1 (fr) 2001-06-08 2002-06-10 Procede de preparation d'un additif de carburant et cet additif

Publications (2)

Publication Number Publication Date
EP1392801A1 EP1392801A1 (fr) 2004-03-03
EP1392801B1 true EP1392801B1 (fr) 2007-12-26

Family

ID=8561368

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02738197A Revoked EP1392801B1 (fr) 2001-06-08 2002-06-10 Procédé de Préparation d'un Additif de Carburant

Country Status (8)

Country Link
US (1) US20040187379A1 (fr)
EP (1) EP1392801B1 (fr)
JP (1) JP2004529263A (fr)
AT (1) ATE382078T1 (fr)
CA (1) CA2445904A1 (fr)
DE (1) DE60224268D1 (fr)
FI (1) FI111380B (fr)
WO (1) WO2002100987A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT504745B1 (de) * 2003-07-28 2010-07-15 Mittelbach Martin Schwefelarmer dieseltreibstoff sowie verwendung von fettsäuremonoalkylestern als schmierfähigkeitsverbesserer für schwefelarme dieseltreibstoffe
US20090077862A1 (en) * 2007-09-25 2009-03-26 Schwab Scott D Lubricity additives and methods of producing lubricity additives
CN101768480B (zh) * 2010-03-16 2013-06-05 王著 一种低酸高效柴油抗磨剂及其制备方法
CN102031178B (zh) * 2010-12-24 2013-07-03 淄博润博化工销售有限公司 低硫柴油润滑性添加剂及其制备方法
DE102011006362A1 (de) * 2011-03-29 2012-10-04 Evonik Goldschmidt Gmbh Isopentylester zur Verwendung in kosmetischen, dermatologischen oder pharmazeutischen Kompositionen

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1692784A (en) * 1925-01-23 1928-11-20 Boyce Ite Products Inc Fuel and fuel ingredients
US4364743A (en) * 1979-09-05 1982-12-21 Erner William E Synthetic liquid fuel and fuel mixtures for oil-burning devices
US4504280A (en) * 1983-08-17 1985-03-12 Phillips Petroleum Company Fuel additives from SO2 treated mixtures of amides and esters derived from vegetable oil, tall oil acid, or aralkyl acid
DE4040317A1 (de) * 1990-12-17 1992-06-25 Henkel Kgaa Mischungen von fettsaeureniedrigalkylestern mit verbesserter kaeltestabilitaet
IT1270954B (it) * 1993-07-21 1997-05-26 Euron Spa Composizione di gasolio
US6194361B1 (en) * 1998-05-14 2001-02-27 Larry W. Gatlin Lubricant composition

Also Published As

Publication number Publication date
FI20011214A0 (fi) 2001-06-08
DE60224268D1 (de) 2008-02-07
ATE382078T1 (de) 2008-01-15
FI111380B (fi) 2003-07-15
WO2002100987A1 (fr) 2002-12-19
JP2004529263A (ja) 2004-09-24
EP1392801A1 (fr) 2004-03-03
US20040187379A1 (en) 2004-09-30
CA2445904A1 (fr) 2002-12-19
FI20011214A (fi) 2002-12-09

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