WO2013072479A1 - Préparation de peroxyde de di-tert-butyle (dtbp) conductrice utilisée comme additif pour diesel - Google Patents

Préparation de peroxyde de di-tert-butyle (dtbp) conductrice utilisée comme additif pour diesel Download PDF

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Publication number
WO2013072479A1
WO2013072479A1 PCT/EP2012/072878 EP2012072878W WO2013072479A1 WO 2013072479 A1 WO2013072479 A1 WO 2013072479A1 EP 2012072878 W EP2012072878 W EP 2012072878W WO 2013072479 A1 WO2013072479 A1 WO 2013072479A1
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dtbp
fuel
conductive
preparation
tert
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PCT/EP2012/072878
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German (de)
English (en)
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Sven Gutewort
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United Initiators Gmbh & Co. Kg
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    • 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
    • C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1811—Organic compounds containing oxygen peroxides; ozonides
    • 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
    • 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
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • 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
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/20—Function and purpose of a components of a fuel or the composition as a whole for improving conductivity
    • 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
    • C10L2300/00—Mixture of two or more additives covered by the same group of C10L1/00 - C10L1/308
    • C10L2300/20—Mixture of two components

Definitions

  • the present invention relates to the use of safely-handled conductive di-tert-butyl peroxide (DTBP) formulations as a fuel additive, and more particularly as an additive to diesel fuel.
  • DTBP conductive di-tert-butyl peroxide
  • the cetane number is a characteristic parameter for the combustion quality of diesel fuel.
  • the cetane number is a measure of the ignition or the ignition delay, ie the time between the start of the fuel injection and the beginning of the combustion.
  • a rapid ignition followed by a uniform and complete combustion as possible.
  • the higher the cetane number the shorter the ignition delay and the better the combustion quality.
  • Cetane number increasing additives are also described, for example, in US 2,763,537, including acyl nitrates, nitrites, nitroso compounds, diazo compounds and organic peroxides.
  • Organic peroxides are currently not commercially used as diesel additives with the exception of small amounts of DTBP (di-tert-butyl peroxide). This for cost, security and compatibility reasons.
  • commercially available peroxide preparations often contain substantial amounts of water as phlegmatizers, are thermally or chemically unstable, can not be used commercially as fuel additives because of the raw materials or production processes used, or contain aromatic radicals which negatively influence pollutant emissions.
  • Water-stabilized peroxides are unsuitable as a fuel additive, since water does not mix with the fuel, but forms a two-phase system.
  • Organic peroxides are thermally labile compounds that decompose exothermically with cleavage of the peroxide oxygen-oxygen bond. Therefore, for safety reasons, organic peroxides often have to be phlegmatized for safe handling or safe transport or are already produced technically in dilution.
  • DTBP has an extremely low conductivity of ⁇ 3 pS / m. Safety aspects limit the use of DTBP in larger quantities as a fuel additive.
  • An object of the present invention was to provide an improved fuel additive, particularly in terms of manageability and safety aspects.
  • the invention therefore relates to a fuel comprising a conductive di-tert-butyl peroxide (DTBP) preparation as an additive.
  • DTBP conductive di-tert-butyl peroxide
  • the invention also relates to a fuel additive comprising a conductive di-tert-butyl peroxide (DTBP) preparation.
  • DTBP conductive di-tert-butyl peroxide
  • DTBP since it is thermally stable, can be prepared as a pure substance, in particular with a purity of> 98% by weight, more preferably> 99% by weight and even more preferably> 99.3% by weight.
  • DTBP with a lower content can also be used specifically for combustion processes if this DTBP quality can be produced at lower costs and it is ensured that this DTBP quality has no adverse effects on the fuel, such as increased water or acid content.
  • a conductive DTBP preparation in which a conductivity-improving additive is added to the DTBP.
  • the amount of added conductivity-improving additive is at most 10% by weight, in particular at most 5% by weight, preferably at most 1% by weight, more preferably up to 0.5% by weight and even more preferably up to 0.1% by weight %, based on the total weight of the DTBP preparation.
  • the amount of conductivity-improving additive is furthermore preferably at least 0.001% by weight, more preferably at least 0.005% by weight and in particular at least 0.01% by weight, based on the total weight of the DTBP preparation.
  • the additive is 0.1 to 100 ppm, more preferably 0.5 to 50 ppm, and most preferably 1 to 10 ppm. According to the invention, it is preferred to add so much conductivity-improving additive that the conductivity of the DTBP preparation is 50 pS / m, more preferably> 500 pS / m and even more preferably> 1000 pS / m.
  • Suitable conductivity-improving additives are, for example, organic acids and their salts, inorganic acids and salts thereof and mixtures thereof.
  • Suitable organic acids are, for example, polymeric compounds which contain one or more sulfuric acid groups, sulfonic acid groups, carboxylic acid groups, phosphoric acid groups or phosphonic acid groups.
  • Suitable organic acids are sulfuric acids, sulfonic acids, carboxylic acids, phosphoric acids or phosphonic acids or hydrates thereof, which have at least one Ci-C 30 hydrocarbon radical, in particular one or more Ci-C2 o alkyl radicals, C 2 -C 20 - alkenyl, C 6 -C 8 -aryl, C 7 -C 3 o-aralkyl or C 7 -C 3 O-alkaryl radicals.
  • the hydrocarbon radicals may include one or more hydroxy, alkoxy, carboxyamide or ester groups.
  • Conductivity-improving salts of organic acids are, for example, ammonium or quaternary ammonium sulfates, ammonium sulfonates, ammonium and quaternary ammonium carboxylates, ammonium and quaternary ammonium phosphates or ammonium and quaternary ammonium phosphonates which contain one or more C 1 -C 30 -hydrocarbon radicals in the anion or / and cation as defined above.
  • Suitable conductivity enhancing salts of inorganic acids are, for example, ammonium or quaternary ammonium halides, which may have one or more CiC 3 o-hydrocarbon radicals, as defined above.
  • Particularly preferred conductivity-improving additives are para-toluenesulfonic acid monohydrate, dodecylbenzenesulfonic acid, ethoxylated and phosphated nonylphenol, copper or chromium dialkyl salicylate, sodium (sec-C 3 -C 7 -alkyl) sulfonate, sodium or calcium dialkylsulfosuccinate, di (hydrogenated tallow) dimethylammonium methosulfate, didecyldimethylammonium chloride, polymeric compounds containing sulfonic acid groups, sulfonate groups and / or sulfone groups or polymeric compounds containing carboxylic acid groups and / or amide groups.
  • the conductive DTBP preparation used according to the invention comprises dodecylbenzenesulfonic acid for
  • the conductive DTBP preparation according to the invention comprises at least one quaternary ammonium compound for conductivity improvement.
  • the amount of dodecylbenzenesulfonic acid is preferably 0.1 to 100 ppm, more preferably 1 to 10 ppm, based on the amount of DTBP.
  • the amount of quaternary ammonium compound is preferably 0.1 to 100, more preferably 1 to 10 ppm, based on the amount of DTBP.
  • the conductive DTBP preparation used according to the invention is preferably anhydrous.
  • Anhydrous here means that the content of water in the composition is ⁇ 5% by weight, in particular less than 1% by weight and even more preferably ⁇ 0.3% by weight.
  • a conductive DTBP preparation is suitable as a fuel additive.
  • the use of DTBP as an additive increases the cetane number of the fuel, and preferably raises it above the base fuel by a value of at least 2, more preferably at least 3, even more preferably at least 4 and most preferably at least 5.
  • the cetane number can be determined, for example, according to ASTM 0613. Increasing the cetane number is a measure of improving the ignitability of the fuel.
  • the pollutant emission in particular the hydrocarbon emission and / or the carbon monoxide emission
  • the pollutant emission is significantly lowered, at the same time the NOx emission is not significantly increased.
  • reduced pollutant emissions were detected both before a downstream catalytic converter and after a downstream catalytic converter.
  • a reduction of pollutant emissions downstream of the catalytic converter was found especially in Phase 1 (Cycle 1 to 4) of the NEDC drive cycle, in which low speeds of up to 50 km / h are used and in which the catalytic converter has not yet reached the full operating temperature.
  • Conductive DTBP and blends thereof are also of great interest in regions where the catalyst density in the existing vehicle fleets is already very high, such as Europe, since there are a lot of trips with vehicles where the catalyst does not reach full operating temperature , Conductive DTBP and blends thereof as a fuel additive consequently reduce pollutant emissions, particularly hydrocarbon and carbon monoxide emissions, independently of the spread of catalytic converters.
  • phase 1 For vehicles operated without a catalytic converter, pollutant emission in phase 1 (cycle 1 to 4) of the NEDC driving cycle is higher than in phase 2 (cycle 5).
  • phase 1 the reduction of hydrocarbon and carbon monoxide emissions with fuels containing conductive DTBP as an additive is particularly high. This is the desired effect, especially for short-distance traffic.
  • conductive DTBP as an additive, the pollutant emissions of eg hydrocarbons and Carbon monoxide when using higher quality diesel, such as a commercial Euro4 diesel, more reduced than when using low-grade diesel, such as a commercial US diesel.
  • conductive DTBP is also particularly suitable, for example, as a fuel additive for regions in which typically higher quality fuel grades are used.
  • DTBP By using anhydrous DTBP, which is miscible with diesel fuel, it is avoided that forms an undesirable second aqueous phase. It is possible to use DTBP as an additive in an anhydrous organic solvent.
  • Polar and non-polar solvents can be used. Examples of suitable non-polar solvents are alkyls and in particular aliphatic hydrocarbons, preferably aliphatic hydrocarbons having 4 to 16 C atoms, even more preferably having 6 to 14 C atoms, most preferably having 7 to 12 C atoms and in particular isododecane, isooctane, Decane, nonane, n-octane and / or heptane or mixtures of different aliphatics.
  • polar solvents are, in particular, oxygen-containing solvents, such as, for example, alcohols or / and ethers.
  • Alkyl alcohols are preferably used as solvents, in particular C 1 -C 8 -alkyl alcohols, more preferably C 2 -C 6 -alkyl alcohols, even more preferably butanol and most preferably tert-butanol.
  • alcohols, and especially tertiary butanol the oxygen content in the fuel additive is further increased, which is desirable and contributes to combustion enhanced by oxygen enrichment and thus reduction of pollutant emissions.
  • Particularly preferred are C6-C14 aliphatic hydrocarbons.
  • Further particularly preferred solvents are ethers and polyethers, particularly preferably aliphatic or cyclic ethers and / or polyethers.
  • the amount of DTBP in the additive is preferably at least 10% by weight, preferably at least 30% by weight and in particular at least 50% by weight. More preferably, the amount of DTBP in the additive is at least 70 weight percent, more preferably at least 90 weight percent, and most preferably at least 99 weight percent. Pure DTBP is preferred, ie in particular a DTBP additive which does not comprise a solvent. However, the amount of DTBP in the additive can also be up to 90% by weight or up to 75% by weight or up to 60% by weight.
  • the proportion of anhydrous organic solvent is more preferably 0% by weight, but the proportion may also be corresponding to at least 0% by weight, more preferably at least 25% by weight and most preferably at least 40% by weight and up to 90% by weight. , more preferably up to 70% by weight, and most preferably up to 50% by weight.
  • the fuel according to the invention may contain as base fuel known fuels or fuels, such as gasoline, especially gasoline, super etc., diesel fuels such as diesel, biodiesel or similar, but also very low diesel qualities, such as various marine diesel, rapeseed methyl ester, oxymethylene ethers, kerosene or rocket fuels.
  • the base fuel is a diesel fuel.
  • the additive according to the invention in particular the ignitability of the fuel is increased. Furthermore, the emission of soot and hydrocarbons in the internal combustion engine is significantly reduced.
  • the conductive DTBP preparation used according to the invention as an additive is also significantly easier to handle in terms of safety than the additives usually used.
  • DTBP Compared with the conventionally used 2-EHN, the use of DTBP as additive according to the invention similarly improves the combustion. Further, DTBP contains no nitrogen, so that the associated problems and in particular the problem of the formation of nitrogen oxides are reduced according to the invention. Furthermore, DTBP is significantly safer in terms of safety than 2-EHN, especially in terms of decomposition.
  • a measure of the rate of decomposition and pressure build-up in the decomposition of a product is the Koenen test. The larger the Koenen value, the more violent the decomposition takes place.
  • the conductivity of pure DTBP is extremely low at ⁇ 3 pS / m, so that DTBP replenishment processes are very critical in terms of safety due to possible charge separations, since these charge separations can generate sufficient ignition energy to ignite DTBP since DTBP has only a very low ignition energy of ⁇ 0.1 mJ needed.
  • the use of conductive DTBP preparations eliminates this disadvantage.
  • the conductive DTBP preparations used according to the invention have a conductivity of> 50 pS / m, preferably> 500 pS / m and even more preferably> 1000 pS / m.
  • the fuel is preferably 0.001 wt% to 10 wt%, more preferably 0.05 wt% to 5 wt%, and most preferably 0.01 wt% to 2 wt% DTBP. According to the invention, it has been found that a reduction in pollutants can already be achieved with small amounts of additive. Accordingly, the fuel preferably has up to 0.5 wt% DTBP, more preferably up to 0.3 wt% DTBP and most preferably up to 0.2 wt% DTBP.
  • additive containing DTBP according to the invention with other additives.
  • Preferred is e.g. the combination with other peroxides and especially with tert-butyl hydroperoxide (TBHP).
  • TBHP tert-butyl hydroperoxide
  • Particularly preferred is an additive comprising TBHP and DTPB.
  • the weight ratio of TBHP and DTPB is preferably from 10:90 to 90:10, in particular from 20:80 to 80:20 and particularly preferably from 30:70 to 70:30.
  • TBHP tert-butyl hydroperoxide
  • Anhydrous means that the content of water in the TBHP composition is ⁇ 5% by weight, in particular ⁇ 1% by weight, even more preferably ⁇ 0.3% by weight.
  • TBHP is preferably used as an additive in an anhydrous organic solvent.
  • Polar and non-polar solvents can be used.
  • suitable nonpolar Solvents are alkyls and in particular aliphatic hydrocarbons, in particular isododecane, isooctane, decane, nonane or / and n-octane or mixtures of various aliphatics.
  • polar solvents are, in particular, oxygen-containing solvents, such as, for example, alcohols and / or ethers and / or polyethers.
  • Alkyl alcohols are preferably used as solvents, in particular C 1 -C 8 -alkyl alcohols, more preferably butanol and most preferably tert-butanol.
  • solvents in particular C 1 -C 8 -alkyl alcohols, more preferably butanol and most preferably tert-butanol.
  • an additive has been found, which 10 to 90 wt.%, In particular 30 to 70 wt.% TBHP in 90 to 10 wt.%, In particular 70 to 30 Wt. Contains% tert-butanol.
  • the oxygen content of the additive is also increased to reduce pollutants in the exhaust gas.
  • a fuel additive is also referred to, which contains in addition to DTBP another known fuel additive, such as 2-EHN.
  • the invention further relates to a fuel additive comprising a conductive DTBP formulation as described herein and the use of a conductive DTBP preparation to increase the cetane number.
  • the invention furthermore relates to the use of a conductive DTBP preparation for pollutant reduction, in particular for reducing the emission of hydrocarbons or / and carbon monoxide.
  • dodecylbenzenesulfonic acid (1 ppm) and a quaternary ammonium compound (1 ppm).
  • the conductivity of the preparation obtained is> 1000 pS / m.
  • a fuel comprising a conductive DTBP formulation A conventional US base diesel fuel has a cetane number of 45.2. To this fuel is added a conductive DTBP formulation (DTBP-S-500 from United Initiators) at a concentration based on DTBP of 0.05% by weight of additive and at a concentration of 0.5% by weight.
  • DTBP-S-500 a conductive DTBP formulation from United Initiators
  • the addition of the additive significantly increases the cetane number.
  • the cetane number is significantly improved without significant increase in consumption at the same engine power in the presence of the additive DTBP and significantly reduces the emission of pollutants. In particular, there is a significant reduction in hydrocarbon emissions and carbon monoxide emissions.
  • the cetane number of the conventional US base diesel fuel of 45.2 is increased to 47.6 by addition of 0.047 wt% DTBP S-500 and a total of 0.157 wt% DTBP S-500 added to 55.4.
  • Comparative emission and fuel consumption measurements were taken on a conventional US base diesel fuel (cetane number 45.2) with and without DTBP S-500 additive on a chassis dynamometer according to the standard NEDC driving cycle.
  • the test vehicle was a Mercedes C 220 CDI, 4 cylinders, 1 10 KW power, built in 2005 with a 5-speed automatic transmission and a mileage of about 140,000 km used.
  • the vehicle is equipped with a particulate filter and catalytic converter.
  • the raw emissions were determined in multiple measurements before and after the catalyst.
  • the ⁇ emissions increase below the measurement tolerance.
  • a fuel comprising a conductive DTBP formulation and TBHP as an additive
  • a conventional US base diesel fuel is admixed with an additive consisting of 27.5 wt% TBHP, 22.5 wt% TBA and 50 wt% DTBP S-500.
  • Blend 1 contains 0.013 wt% TBHP and 0.024 wt% DTBP S-500.
  • Mixture 2 contains 0.052% by weight of TBHP and 0.094% by weight of DTBP S-500.
  • the CETAN number of the conventional base diesel fuel is 45.2, that of mixture 1 is 47.9 and that of mixture 2 is 56.7.
  • the cetane number is significantly increased by the addition of the additive and, according to the following table, the pollutant emissions are significantly reduced while the consumption remains constant, and even more significantly in phase 1.
  • the ⁇ emissions increase below the measurement tolerance.
  • the addition of the additive significantly increases the cetane number.
  • the cetane number is significantly improved without significant increase in consumption at the same engine power in the presence of the additive and at the same time Pollutant emission significantly reduced.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

La présente invention concerne l'utilisation d'une préparation de DTBP conductrice comme additif pour carburant et en particulier comme additif pour carburant diesel.
PCT/EP2012/072878 2011-11-16 2012-11-16 Préparation de peroxyde de di-tert-butyle (dtbp) conductrice utilisée comme additif pour diesel WO2013072479A1 (fr)

Applications Claiming Priority (2)

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DE102011086515.2 2011-11-16
DE102011086515A DE102011086515A1 (de) 2011-11-16 2011-11-16 Leitfähige DTBP-Zubereitung als Dieseladditiv

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WO2013072479A1 true WO2013072479A1 (fr) 2013-05-23

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2763537A (en) 1949-05-24 1956-09-18 California Research Corp Diesel fuel oil
US4045188A (en) * 1975-12-29 1977-08-30 Hirschey Kenneth A Fuel additives for internal combustion engines
DE3880047T2 (de) * 1987-08-27 1993-09-09 Wynn Oil Co Zusammensetzung eines zusatzes.

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2763537A (en) 1949-05-24 1956-09-18 California Research Corp Diesel fuel oil
US4045188A (en) * 1975-12-29 1977-08-30 Hirschey Kenneth A Fuel additives for internal combustion engines
DE3880047T2 (de) * 1987-08-27 1993-09-09 Wynn Oil Co Zusammensetzung eines zusatzes.

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"DTBP S-500 The future of peroxides", 14 July 2010 (2010-07-14), XP055048793, Retrieved from the Internet <URL:http://web.archive.org/web/20100714155955/http://www.united-initiators.com/asp/documents/441_Document.pdf> [retrieved on 20130108] *
NANDI M K: "The performance of di-tertiary-butyl peroxide as cetane improver in diesel fuels", 1 August 1996 (1996-08-01), pages 863 - 867, XP002621745, Retrieved from the Internet <URL:http://www.anl.gov/PCS/acsfuel/preprint%20archive/Files/41_3_ORLANDO_08-96_0863.pdf> [retrieved on 20110210] *

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