EP1612257A2 - Composition de combustible - Google Patents

Composition de combustible Download PDF

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Publication number
EP1612257A2
EP1612257A2 EP05019565A EP05019565A EP1612257A2 EP 1612257 A2 EP1612257 A2 EP 1612257A2 EP 05019565 A EP05019565 A EP 05019565A EP 05019565 A EP05019565 A EP 05019565A EP 1612257 A2 EP1612257 A2 EP 1612257A2
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EP
European Patent Office
Prior art keywords
groups
gasoline
additive
fuel composition
mono
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.)
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Application number
EP05019565A
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German (de)
English (en)
Inventor
Harald Schwahn
Dietmar Posselt
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BASF SE
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BASF SE
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Publication of EP1612257A2 publication Critical patent/EP1612257A2/fr
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/08Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
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    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/143Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/19Esters ester radical containing compounds; ester ethers; carbonic acid esters
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    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/192Macromolecular compounds
    • C10L1/195Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1966Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
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    • C10L1/192Macromolecular compounds
    • C10L1/198Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
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    • C10L1/192Macromolecular compounds
    • C10L1/198Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/23Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
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    • C10L1/22Organic compounds containing nitrogen
    • C10L1/234Macromolecular compounds
    • C10L1/236Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
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    • C10L1/238Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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    • C10L1/234Macromolecular compounds
    • C10L1/238Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
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    • C10L1/00Liquid carbonaceous fuels
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    • C10L1/14Organic compounds
    • C10L1/24Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
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    • C10L1/14Organic compounds
    • C10L1/16Hydrocarbons
    • C10L1/1616Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
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    • C10L1/16Hydrocarbons
    • C10L1/1625Hydrocarbons macromolecular compounds
    • C10L1/1633Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
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    • C10L1/188Carboxylic acids; metal salts thereof
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    • C10L1/188Carboxylic acids; metal salts thereof
    • C10L1/1881Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
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    • C10L1/19Esters ester radical containing compounds; ester ethers; carbonic acid esters
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    • C10L1/224Amides; Imides carboxylic acid amides, imides

Definitions

  • the present invention relates to a fuel composition
  • a fuel composition comprising in a larger amount a specific gasoline fuel and in a smaller amount selected gasoline additives, in particular detergent additives having at least one polar grouping selected from the groups (a), (b), (c), (g ), (h) and (i).
  • Carburettors and intake systems of gasoline engines, as well as injection systems for fuel metering, are increasingly burdened by contaminants caused by dust particles from the air, unburned hydrocarbon residues from the combustion chamber and the crankcase vent gases directed into the gasifier.
  • valve seat wear-inhibiting additives based on alkali metal or alkaline earth metal compounds have been developed.
  • Modern gasoline engines require for a trouble-free use fuels with a complex property profile, which can be guaranteed only in combination with appropriate gasoline additives.
  • Such gasoline fuels usually consist of a complex mixture of chemical compounds and are characterized by physical quantities.
  • the interaction between gasoline fuels and corresponding additives is still in need of improvement in the case of the known fuel compositions with regard to the cleaning and / or retention effect and the valve seat wear-inhibiting effect.
  • the object of the present invention was therefore to find a more effective gasoline-petrol fuel additive composition.
  • the aromatic content of the gasoline is preferably not more than 40% by volume, in particular not more than 38% by volume. Preferred ranges for the aromatic content are from 20 to 42% by volume, in particular from 25 to 40% by volume.
  • the sulfur content of the gasoline is preferably not more than 100 ppm by weight, in particular not more than 50 ppm by weight. Preferred ranges for the sulfur content are from 0.5 to 150 ppm by weight, in particular from 1 to 100 ppm by weight.
  • the gasoline has an olefin content of not more than 21% by volume, preferably not more than 18% by volume, in particular not more than 10% by volume. Preferred ranges for the olefin content are from 6 to 21% by volume, in particular from 7 to 18% by volume.
  • the gasoline has a benzene content of not more than 1.0% by volume, in particular not more than 0.9% by volume.
  • Preferred ranges for the benzene content are from 0.5 to 1.0% by volume, in particular from 0.6 to 0.9% by volume.
  • the gasoline has an oxygen content of at most 2.7 wt .-%, preferably from 0.1 to 2.7 wt .-%, especially from 1.0 to 2.7 wt .-%, in particular from 1.2 to 2.0 wt .-%, on.
  • a gasoline fuel which simultaneously has an aromatics content of not more than 38% by volume, an olefin content of not more than 21% by volume, a sulfur content of not more than 50 ppm by weight, a benzene content of not more than 1.0% by volume and a Having oxygen content of 1.0 to 2.7 wt .-%.
  • the content of alcohols and ethers in gasoline is usually relatively low. Typical maximum contents for methanol are 3% by volume, for ethanol 5% by volume, for isopropanol 10% by volume, for tert-butanol 7% by volume, for isobutanol 10% by volume and for ethers 5 or more C atoms in the molecule 15 vol .-%.
  • the summer vapor pressure of the gasoline is usually not more than 70 kPa, in particular 60 kPa (each at 37 ° C).
  • the research octane number ("RON") of the gasoline is typically 90 to 100.
  • a common range for the corresponding engine octane number (“MOZ”) is 80 to 90.
  • the specified specifications are determined by conventional methods (DIN EN 228).
  • the hydrophobic hydrocarbon radical in the gasoline additives which provides sufficient solubility in the fuel, has a number average molecular weight (M N ) of from 85 to 20,000, especially from 113 to 10,000, especially from 300 to 5,000.
  • M N number average molecular weight
  • monoamino groups (a) containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A 196 20 262.
  • These reaction products typically are mixtures of pure nitropolyisobutanes (e.g., ⁇ , ⁇ -dinitropolyisobutane) and mixed hydroxynitropolyisobutanes (e.g., ⁇ -nitro- ⁇ -hydroxy polyisobutane).
  • Carboxyl groups or their alkali metal or alkaline earth metal salts (d) containing additives are preferably copolymers of C 2 -C 4O- olefins with maleic anhydride having a total molecular weight of 500 to 20,000, the carboxyl groups wholly or partly to the alkali metal or alkaline earth metal salts and a remaining Rest of the carboxyl groups are reacted with alcohols or amines.
  • Such additives are known in particular from EP-A 307 815. Such additives are primarily used to prevent valve seat wear and, as described in WO-A 87/01126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
  • Sulfonic acid groups or their alkali metal or alkaline earth metal salts (e) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobernsteinklakylesters, as described in particular in EP-A 639 632.
  • Such additives are primarily for preventing valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
  • Polyoxy-C 2 - to C 4 -alkylene (f) additives are preferably polyethers or polyetheramines which are obtainable by reaction of C 2 - to C 60 alkanols, C 6 - to C 30 alkanediols, mono- or di-C 2 C 30 -alkylamines, C 1 -C 30 -alkylcyclohexanols or C 1 -C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available.
  • Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416.
  • polyethers such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.
  • Carboxylic ester groups (g) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm 2 / s at 100 ° C, as described in particular in DE-A 38 38 918 are.
  • mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable long-chain representatives having, for example, 6 to 24 carbon atoms as ester alcohols or polyols.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also meet carrier oil properties.
  • Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings (i) containing additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine.
  • the polyisobutenyl-substituted Phenols may stem from conventional or highly reactive polyisobutene having an M N of from 300 to 5000th Such "polyisobutene-Mannich bases" are described in particular in EP-A 831 141.
  • the fuel composition of the invention may further contain other conventional components and additives.
  • Suitable solvents or diluents are aliphatic and aromatic hydrocarbons, e.g. Solvent naphtha, into consideration.
  • corrosion inhibitors for example those based on film-forming ammonium salts of organic carboxylic acids or heterocyclic aromatics in non-ferrous metal corrosion protection, antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or on phenols such as 2,4-diester .-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, demulsifiers, antistatic agents, metallocenes such as ferrocene or methylcyclopentadienyl manganese tricarbonyl, lubricity additives such as certain fatty acids, alkenyl succinic esters, bis (hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil as well as dyes (markers). Sometimes amines are also added to lower the pH of the fuel.
  • antioxidants or stabilizers for example based on amines such as p-phenyl
  • Typical mixtures of this type contain polyisobutene amines in combination with alkanol-initiated polyethers such as tridecanol or isotridecanol butoxylates or propoxylates, polyisobuteneamines in combination with alkanol-started polyetheramines such as tridecanol or isotridecanol butoxylate ammonia reaction products and alkanol-started polyetheramines such as tridecanol or isotridecaol butoxylate ammonia reaction products in combination with alkanol-started polyethers such as tridecanol or isotridecanol butoxylates or propoxylates, in each case together with the cited corrosion inhibitors or lubricity improvers.
  • alkanol-initiated polyethers such as tridecanol or isotridecanol butoxylates or propoxylates
  • alkanol-started polyetheramines such as tridecanol or
  • the aforementioned gasoline additives with the polar groups (a) to (i) and the other components mentioned are added to the gasoline and unfold their effect there.
  • the components or additives can be added to the gasoline fuel individually or as a previously prepared concentrate ("additive package").
  • gasoline additives with the polar groups (a) to (i) are added to the gasoline usually in an amount of 1 to 5000 ppm by weight, in particular 5 to 3000 ppm by weight, especially 10 to 1000 ppm by weight ,
  • the other components and additives mentioned are added, if desired, in customary amounts.
  • the same cleaning or valve seat wear-inhibiting effect can be obtained as in conventional fuel compositions of the prior art. Furthermore, when using the same amounts of detergent or valve seat wear-inhibiting agent in the inventive fuel composition over conventional fuel compositions surprisingly results in a significantly better cleansing or retaining or valve seat wear-inhibiting effect.
  • the fuel composition according to the invention additionally has the advantage that fewer deposits are formed in the combustion chamber of the gasoline engine and that less additive is added via the fuel dilution in the engine oil.
  • Example 2 Gasoline according to Example 1 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench tests with a Mercedes-Benz engine according to CEC F-05-A-93. As expected, the inlet valve deposits were significantly reduced compared to the non-additive base value according to Table 2 below.
  • Example 2 Gasoline according to Example 2 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below. Surprisingly, it has been found that in comparison to Example 13 with the same amount of fuel additive complete purification of the intake valves is achieved.
  • Example 3 Gasoline according to Example 3 was tested for its suitability for inlet system cleanliness. This was done with the help of engine tests in bench tests with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below.
  • Example 4 Gasoline according to Example 4 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below. Surprisingly, it has been found that in comparison with Example 15 with the same amount of fuel additive, a virtually complete purification of the intake valves is achieved.
  • Example 5 Gasoline according to Example 5 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below.
  • Example 6 Gasoline according to Example 6 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below. Surprisingly, it has been found that in comparison with Example 17 with the same amount of fuel additive, a virtually complete keeping clean of the intake valves is achieved.
  • Example 7 Gasoline according to Example 7 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were not compared to Additive basic value according to Table 2 below significantly reduced.
  • Example 8 Gasoline according to Example 8 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below. Surprisingly, it has been found that significantly less fuel additive compared to Example 19 is needed to the same order of magnitude cleanliness of the intake valves.
  • Example 9 Gasoline according to Example 9 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below.
  • Example 10 Gasoline according to Example 10 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below. Surprisingly, it was found that in comparison to Example 21 with the same amount of fuel additive significantly better cleanliness of the intake valves is achieved.
  • Gasoline according to Example 11 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were not compared to Additive basic value according to Table 2 below significantly reduced.
  • Example 12 Gasoline according to Example 12 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below. Surprisingly, it was found that in comparison to Example 23 with the same amount of fuel additive significantly better cleanliness of the intake valves is achieved.
  • Example 14 700 0 0 0 0 0 0 (239)
  • Example 15 600 19 60 86 34 50 (274)
  • Example 16 600 0 1 0 2 1 (239)
  • Example 17 400 0 75 17 182 69 (402)
  • Example 18 400 0 2 2 0 1 (239)
  • Example 19 750 31 120 111 30 73 (592)
  • Example 20 350 46 68 38 67 55 (239)
  • Example 21 500 181 95 26 68 93 (475)
  • Example 22 500 27 33 14 77 38 (239)
  • Example 23 700 123 12 98 55 72 (558)
  • Example 24 700 82 12 23 22 35 (239) (in brackets the basic value of the non-added fuel)

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NZ513306A (en) 2003-01-31
CZ20012854A3 (cs) 2002-05-15
KR20010111491A (ko) 2001-12-19
KR100663774B1 (ko) 2007-01-03
ZA200107409B (en) 2003-01-29
AR022534A1 (es) 2002-09-04
MY121511A (en) 2006-01-28
PL191309B1 (pl) 2006-04-28
BR0008087A (pt) 2001-11-06
IL144375A (en) 2004-08-31

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