EP2780435A1 - Tert-butyl hydroperoxide (tbhp) as a diesel additive - Google Patents

Tert-butyl hydroperoxide (tbhp) as a diesel additive

Info

Publication number
EP2780435A1
EP2780435A1 EP12784622.8A EP12784622A EP2780435A1 EP 2780435 A1 EP2780435 A1 EP 2780435A1 EP 12784622 A EP12784622 A EP 12784622A EP 2780435 A1 EP2780435 A1 EP 2780435A1
Authority
EP
European Patent Office
Prior art keywords
tbhp
fuel
additive
diesel
weight
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.)
Granted
Application number
EP12784622.8A
Other languages
German (de)
French (fr)
Other versions
EP2780435B1 (en
Inventor
Sven Gutewort
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.)
United Initiators GmbH and Co KG
Original Assignee
United Initiators GmbH and Co KG
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 United Initiators GmbH and Co KG filed Critical United Initiators GmbH and Co KG
Priority to EP12784622.8A priority Critical patent/EP2780435B1/en
Publication of EP2780435A1 publication Critical patent/EP2780435A1/en
Application granted granted Critical
Publication of EP2780435B1 publication Critical patent/EP2780435B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • 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
    • 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
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
    • 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 tert-butyl hydroperoxide (TBHP) and blends thereof as a fuel additive and, in particular, as an additive to diesel fuels.
  • TBHP tert-butyl hydroperoxide
  • 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.
  • An object of the present invention was to provide an improved fuel additive, in particular with regard to pollutant emissions, effectiveness, manageability and costs.
  • the invention therefore relates to a fuel comprising tert-butyl hydroperoxide (TBHP) as an additive.
  • the invention relates to a fuel comprising tert-butyl hydroperoxide (TBHP) as an additive component in a mixture of TBHP with other organic peroxides, in particular other organic anhydrous peroxides such as di-tert-butyl peroxide (DTBP).
  • TBHP tert-butyl hydroperoxide
  • DTBP di-tert-butyl peroxide
  • tert-butyl hydroperoxide in particular in anhydrous form, is suitable as a fuel additive.
  • TBHP 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 emissions in particular the hydrocarbon emission and / or the carbon monoxide emission, are significantly reduced, at the same time the NOx emission is not significantly increased.
  • TBHP especially anhydrous TBHP and blends thereof as a fuel additive thus reduce pollutant emissions, especially the emission of hydrocarbons and carbon monoxide, regardless of the spread of catalytic converters.
  • 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 TBHP, especially anhydrous TBHP as an additive, is particularly high. This is the desired effect, especially for short-distance traffic.
  • the pollutant emissions of, for example, hydrocarbons and carbon monoxide are higher in the combustion of low-grade fuel qualities than in higher-grade fuel qualities.
  • TBHP as an additive reduces the pollutant emissions of e.g. Hydrocarbons and carbon monoxide when using higher quality diesel grades, e.g. a commercial Euro4 diesel, more reduced than using lower grade diesel such as e.g. a commercial US diesel.
  • TBHP is suitable, e.g. also especially as a fuel additive for regions in which typically higher quality fuel grades are used.
  • Anhydrous TBHP is preferably used according to the invention as a fuel additive.
  • 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 which is miscible with fuel and in particular with diesel fuel, avoids the formation of an undesirable second aqueous phase.
  • TBHP is preferably used as an additive in an anhydrous organic solvent.
  • Polar and non-polar solvents can be used.
  • suitable non-polar solvents are alkyls and in particular aliphatic hydrocarbons, in particular isododecane, isooctane, decane, nonane and / or n-octane 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.
  • 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.
  • the amount of TBHP in the additive is preferably at least 10 wt%, more preferably at least 30 wt%, even more preferably at least 40 wt%, and most preferably at least 50 wt%. Pure TBHP is not preferred for safety reasons.
  • the amount of TBHP in the additive is therefore preferably up to 90% by weight, more preferably up to 75% by weight, and most preferably up to 60% by weight.
  • the proportion of anhydrous organic solvents is correspondingly at least 10% 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.
  • an additive which contains 30 to 70% by weight of TBHP in 70 to 30% by weight of tert-butanol. Even more preferred is an additive containing 50 to 60 wt.% TBHP in 50 to 40 wt.% Tert-butanol. Most preferred is an additive containing 55 wt% TBHP and 45 wt% TBA.
  • an oxygen-containing solvent preferably in an alcohol and in particular in tert-butanol
  • Further particularly preferred solvents are ethers and polyethers, particularly preferably aliphatic or cyclic ethers and / or polyethers.
  • the oxygen content of the additive is also increased to reduce pollutants in the exhaust gas.
  • an oxygen content of about 29.3 wt.% Oxygen, of which about 9.8 wt.% Active oxygen is contained.
  • the fuel according to the invention may contain fuels or fuels known as the basic fuel, such as gasoline fuels, in particular gasoline, super etc., diesel fuels such as diesel, biodiesel or similar, but also very low diesel qualities, e.g.
  • the fuel in particular a diesel fuel or kerosene, may e.g. for diesel engines in e.g. Be provided for motor vehicles, ships or for stationary diesel engines for power generation or for aircraft or rocket engines.
  • the fuel according to the invention as a basic fuel particularly preferably comprises a high-quality diesel which meets the Euro 4 diesel requirements.
  • the TBHP used according to the invention as an additive is also significantly safer in terms of safety compared to the additives commonly used, such as 2-EHN, for example.
  • the use of TBHP in anhydrous form, especially in an anhydrous organic solvent, avoids the formation of two separate phases, thereby allowing the use of TBHP as fuel additive.
  • TBHP as an additive (especially lower hydrocarbon, carbon monoxide and soot emissions). Furthermore, TBHP contains no nitrogen, so that the associated problems and in particular the problem of the formation of nitrogen oxides are inventively reduced. Furthermore, TBHP 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.
  • TBHP advantageously has a higher flash point of 21 ° C.
  • the flashpoint of DTBP is significantly lower than that of TBHP and below room temperature at ⁇ 0 ° C.
  • the conductance of DTBP at ⁇ 3 pS / m is extremely low, so DTBP replenishment processes are very critical in terms of safety because of 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 polar TBHP is conductive (> 1000 pS / m) and thus, such charge separations do not occur, so TBHP can be handled much more safely than DTBP.
  • the fuel is preferably 0.001 wt% to 10 wt%, more preferably 0.005 wt% to 5 wt%, and most preferably 0.01 wt% to 2 wt% TBHP.
  • the fuel according to the invention particularly preferably has up to 0.5% by weight TBHP, more preferably up to 0.25% by weight TBHP and most preferably up to 0.15% by weight.
  • TBHP-containing additive according to the invention with other additives.
  • Preferred is, for example, the combination with other peroxides, in particular with other organic peroxides and preferably with other anhydrous organic peroxides, and in particular with di-tert-butyl peroxide (DTBP).
  • DTBP di-tert-butyl peroxide
  • an additive comprising TBHP and DTPB.
  • an additive comprising TBHP, DTPB and TBA.
  • the weight ratio of TBHP and DTPB is preferably from 10:90 to 90:10, in particular from 20:80 to 80:20 and even more preferably from 30:70 to 70:30.
  • the amount of TBHP and DTPB in the additive is preferably preferably at least 10% by weight, more preferably at least 30% by weight, even more preferably at least 40% by weight, and most preferably at least 50% by weight. Further, the amount of TBHP and DTPB in the additive is preferably up to 90% by weight, more preferably up to 75% by weight, and most preferably up to 60% by weight.
  • the proportion of anhydrous organic solvents, in particular of alcohols and preferably of tert-butanol, is correspondingly at least 10% 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 production of TBHP can be carried out according to known production methods.
  • the fuel additive according to the invention contains in particular anhydrous TBHP and preferably TBHP in an organic solvent.
  • the organic solvent is preferably an alcohol, especially tert-butanol.
  • an additive comprising 30 to 70 wt.% TBHP in 70 to 30 wt.% Organic solvent, especially TBA, more preferably 50 to 60 wt.% TBHP in 50 to 40 wt.% Organic solvent, especially TBA.
  • a fuel additive which, in addition to TBHP, comprises a further organic peroxide, in particular a further anhydrous organic peroxide.
  • an additive comprising TBHP and DTBP.
  • the peroxides in the additive are present in an alcohol, in particular in TBA.
  • a fuel additive is also referred to, which in addition to TBHP contains another known fuel additive, such as 2-EHN.
  • the TBHP is present in an alcohol, in particular in TBA.
  • TBHP optionally further organic peroxide such as e.g. DTBP as well as organic solvent, especially TBA, are as previously described herein.
  • the emission of pollutants can be reduced by using the fuel additive according to the invention or a fuel comprising the fuel additive according to the invention.
  • the invention therefore also relates to the use of TBHP for pollutant reduction, in particular for the reduction of the hydrocarbon emission and / or the carbon monoxide emission.
  • the invention relates to the use of TBHP for pollutant emissions in vehicles with catalyst.
  • an additive comprising TBHP, DTBP and TBA for pollutant reduction.
  • the invention further relates to a fuel additive comprising TBHP, in particular as described hereinbefore, and to the use of TBHP or the cetane increasing fuel additives described herein.
  • the invention further relates to a fuel additive comprising TBHP, in particular as described hereinbefore, and the use of TBHP or the fuel additive described herein for pollutant reduction, in particular for reducing the emission of hydrocarbons and / or carbon monoxide.
  • Fuel comprising TBHP as additive A conventional US base diesel fuel has a cetane number of 45.2. This fuel is an additive consisting of 55 wt.% TBHP and 45 wt.% Tert-butanol in a concentration based on TBHP of 0.026 wt.% Additive amount and in a concentration of 0.1 1 wt.% Added.
  • the CETAN number increases from 45.2 to 47.4. With a further addition of a total of 0.1 1 wt.% TBHP, the CETAN number is increased to 50.0. Comparative emission and fuel consumption measurements were made with a conventional US base diesel fuel (cetane number 45.2) and a conventional EU4 base diesel fuel (cetane number 54.6) with and without TBHP 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 emissions were determined in multiple measurements before and after the catalyst.
  • the ⁇ emissions increase below the measurement tolerance.
  • phase 1 (cycle 1 - 4 NEDC) a very strong reduction of emissions downstream of the catalytic converter was measured, as this does not yet have the required operating temperature:
  • Fuel comprising TBHP and DTBP 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.
  • Blend 1 contains 0.013 wt% TBHP and 0.024 wt% DTBP.
  • Mixture 2 contains 0.052% by weight of TBHP and 0.094% by weight of DTBP.
  • 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.

Landscapes

  • 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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

The invention relates to the use of TBHP as a fuel additive and in particular as an additive for diesel fuel.

Description

TER . - BUTYLHYDROPEROXID (TBHP) ALS DIESELADDITIV  TER. BUTYL HYDROPOXIDE (TBHP) AS DIESEL ADDITIVE
Beschreibung description
Die vorliegende Erfindung betrifft die Verwendung von tert.- Butylhydroperoxid (TBHP) und Abmischungen hiervon als Kraftstoffadditiv und insbesondere als Additiv zu Dieselkraftstoffen. Die Cetan-Zahl ist ein charakteristischer Parameter für die Verbrennungsqualität von Dieselkraftstoff. Die Cetan-Zahl ist ein Maß für die Zündwilligkeit bzw. die Zündverzögerung, also die Zeit zwischen dem Beginn der Kraftstoffeinspritzung und dem Beginn der Verbrennung. Günstig ist dabei eine rasche Zündung, gefolgt von einer gleichmäßigen und möglichst vollständigen Verbrennung. Je höher die Cetan-Zahl ist, desto kürzer die Zündverzögerung und desto besser die Verbrennungsqualität. The present invention relates to the use of tert-butyl hydroperoxide (TBHP) and blends thereof as a fuel additive and, in particular, as an additive to diesel fuels. 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. Favorable is 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.
Zur Erhöhung der Cetan-Zahl werden verschiedene Zusätze eingesetzt. Im kommerziellen Umfang wird derzeit nahezu ausschließlich 2-EHN (2- Ethylhexylnitrat) verwendet. Problematisch an diesem Zusatz sind seine hohe Giftigkeit, seine schlechte Lagerstabilität, sicherheitskritische Eigenschaften sowie beträchtliche Mehrkosten. Insbesondere aufgrund seiner Explosivität ist die Verwendung von 2-EHN problematisch. Weiterhin kann der Stickstoffgehalt zur erhöhten, unerwünschten NOX-Emissionen führen. To increase the cetane number, various additives are used. On a commercial scale, almost exclusively 2-EHN (2-ethylhexyl nitrate) is currently used. The problem with this additive is its high toxicity, its poor storage stability, safety-critical properties and considerable additional costs. In particular, due to its explosiveness, the use of 2-EHN is problematic. Furthermore, the nitrogen content can lead to increased, unwanted NOX emissions.
Cetan-Zahl-erhöhende Zusätze werden beispielsweise auch in US 2,763,537 beschrieben, darunter Akylnitrate, Nitrite, Nitrosoverbindungen, Diazoverbindungen und Organische Peroxide. Organische Peroxide werden derzeit mit Ausnahme von geringen Mengen an DTBP (Ditertbutylperoxid) kommerziell nicht als Dieseladditive eingesetzt. Dies aus Kosten-, Sicherheits- und Kompatibilitätsgründen. So enthalten kommerziell verfügbare Peroxidpreparationen oftmals als Phlegmatisierungsmittel beträchtliche Mengen an Wasser, sind thermisch oder chemisch zu instabil, aufgrund der verwendeten Rohstoffe bzw. Produktionsverfahren kommerziell als Kraftstoffadditiv nicht einsetzbar oder enthalten aromatische Reste, die den Schadstoffausstoß negativ beeinflussen. Mit Wasser phlegmatisierte Peroxide sind als Treibstoffzusatz aber ungeeignet, da sich Wasser nicht mit dem Treibstoff vermischt, sondern ein zweiphasiges System bildet. Organische Peroxide sind thermisch labile Verbindungen, die exotherm unter Spaltung der peroxidischen Sauerstoff-Sauerstoff-Bindung zerfallen. Daher müssen aus sicherheitstechnischen Überlegungen heraus Organische Peroxide zur sicheren Handhabung oder zum sicheren Transport oft phlegmatisiert werden bzw. werden bereits in Verdünnung technisch hergestellt. 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. For example, 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.
Insofern sind einige wasserfreie Peroxide nicht oder nur mit hohem technischen Aufwand erhältlich. Eine Aufgabe der vorliegenden Erfindung war es, ein verbessertes Kraftstoffadditiv bereitzustellen, insbesondere hinsichtlich Schadstoffausstoß, Wirksamkeit, Handhabbarkeit und Kosten. In this respect, some anhydrous peroxides are not available or only with great technical effort. An object of the present invention was to provide an improved fuel additive, in particular with regard to pollutant emissions, effectiveness, manageability and costs.
Die Erfindung betrifft deshalb einen Kraftstoff umfassend tert- Butylhydroperoxid (TBHP) als Additiv. In einer bevorzugten Ausführungsform betrifft die Erfindung einen Kraftstoff umfassend tert.-Butylhydroperoxid (TBHP) als Additivbestandteil in einer Mischung von TBHP mit anderen organischen Peroxiden, insbesondere anderen organischen wasserfreien Peroxiden wie zum Beispiel Di-tert.-butylperoxid (DTBP). The invention therefore relates to a fuel comprising tert-butyl hydroperoxide (TBHP) as an additive. In a preferred embodiment, the invention relates to a fuel comprising tert-butyl hydroperoxide (TBHP) as an additive component in a mixture of TBHP with other organic peroxides, in particular other organic anhydrous peroxides such as di-tert-butyl peroxide (DTBP).
Überraschenderweise wurde gefunden, dass tert.-Butylhydroperoxid, insbesondere in wasserfreier Form als Kraftstoffadditiv geeignet ist. Durch den Einsatz von TBHP als Additiv wird insbesondere die Cetan-Zahl des Kraftstoffs erhöht und bevorzugt gegenüber dem Basiskraftstoff um einen Wert von mindestens 2, mehr bevorzugt mindestens 3, noch mehr bevorzugt mindestens 4 und am meisten bevorzugt wenigstens 5 angehoben. Die Cetan-Zahl kann beispielsweise gemäß ASTM 0613 bestimmt werden. Eine Erhöhung der Cetan-Zahl ist ein Maß für die Verbesserung der Zündwilligkeit des Kraftstoffs. Surprisingly, it has been found that tert-butyl hydroperoxide, in particular in anhydrous form, is suitable as a fuel additive. By In particular, the use of TBHP 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.
Weiterhin wurde festgestellt, dass bei gleichem Verbrauch die Schadstoffemissionen, insbesondere die Kohlenwasserstoffemission und/oder die Kohlenmonoxidemission, signifikant abgesenkt werden, wobei gleichzeitig der NOx-Ausstoß nicht erheblich angehoben wird. Furthermore, it has been found that with the same consumption, the pollutant emissions, in particular the hydrocarbon emission and / or the carbon monoxide emission, are significantly reduced, at the same time the NOx emission is not significantly increased.
Diese Vorteile werden bei Fahrzeugen ohne Katalysator, überraschenderweise aber auch bei Fahrzeugen mit Katalysator erhalten. These advantages are obtained in vehicles without catalyst, but surprisingly also in vehicles with catalyst.
Überraschenderweise konnten verminderte Schadstoffemissionen sowohl vor einem nachgeschalteten Abgaskatalysator als auch nach einem nachgeschalteten Abgaskatalysator festgestellt werden. Eine Reduktion der Schadstoffemissionen nach dem Katalysator wurde speziell in der Phase 1 (Zyklus 1 bis 4) des NEFZ-Fahrzyklus gefunden, in dem niedrige Geschwindigkeiten bis 50 km/h gefahren werden und in dem der Katalysator noch nicht die vollständige Betriebstemperatur erreicht. Insofern sind TBHP, insbesondere wasserfreies TBHP, und Abmischungen hiervon auch in Regionen von sehr hohem Interesse, in welchen die Katalysatordichte in den bestehenden Fahrzeugflotten bereits sehr hoch ist, wie z.B. Europa, da eine Vielzahl von Fahrten mit Fahrzeugen erfolgen, bei welchen der Katalysator nicht die volle Betriebstemperatur erreicht. TBHP, insbesondere wasserfreies TBHP und Abmischungen hiervon als Kraftstoffadditiv vermindern folglich den Schadstoffausstoß, insbesondere den Ausstoß von Kohlenwasserstoffen und Kohlenmonoxid auch unabhängig von der Verbreitung von Abgaskatalysatoren. Auch bei Fahrzeugen, die ohne Katalysator betrieben werden ist Schadstoffemission in Phase 1 (Zyklus 1 bis 4) des NEFZ-Fahrzyklus höher als in Phase 2 (Zyklus 5). In Phase 1 ist die Reduktion der Kohlenwasserstoff- und Kohlenmonoxid-Emissionen mit Treibstoffen, die TBHP, insbesondere wasserfreies TBHP als Additiv enthalten, besonders hoch. Dies ist der gewünschte Effekt, speziell für den Kurzstreckenverkehr. Prinzipiell sind die Schadstoffemissionen von z.B. Kohlenwasserstoffen und Kohlenmonoxid bei der Verbrennung von niederwertigen Treibstoffqualitäten höher als bei höherwertigen Treibstoffqualitäten. Surprisingly, 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. Thus, TBHP, especially anhydrous TBHP, 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 is not reached the full operating temperature. TBHP, especially anhydrous TBHP and blends thereof as a fuel additive thus reduce pollutant emissions, especially the emission of hydrocarbons and carbon monoxide, regardless of the spread of catalytic converters. 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). In Phase 1, the reduction of hydrocarbon and carbon monoxide emissions with fuels containing TBHP, especially anhydrous TBHP as an additive, is particularly high. This is the desired effect, especially for short-distance traffic. In principle, the pollutant emissions of, for example, hydrocarbons and carbon monoxide are higher in the combustion of low-grade fuel qualities than in higher-grade fuel qualities.
Es wurde nun überraschenderweise gefunden, dass TBHP als Additiv die Schadstoffemissionen von z.B. Kohlenwasserstoffen und Kohlenmonoxid bei Verwendung von höherwertigen Dieselqualitäten, wie z.B. einem handelsüblichen Euro4 Diesel, stärker reduziert als bei Verwendung von niederwertigen Dieselqualitäten, wie z.B. einem handelsüblichen US Diesel. Insofern eignet sich TBHP z.B. auch speziell als Treibstoffadditiv für Regionen, in welchen typischerweise höherwertige Treibstoffqualitäten eingesetzt werden. It has now surprisingly been found that TBHP as an additive reduces the pollutant emissions of e.g. Hydrocarbons and carbon monoxide when using higher quality diesel grades, e.g. a commercial Euro4 diesel, more reduced than using lower grade diesel such as e.g. a commercial US diesel. In this respect, TBHP is suitable, e.g. also especially as a fuel additive for regions in which typically higher quality fuel grades are used.
Bevorzugt wird erfindungsgemäß wasserfreies TBHP als Kraftstoffadditiv eingesetzt. Wasserfrei bedeutet dabei, dass der Gehalt an Wasser in der TBHP-Zusammensetzung < 5 Gew.%, insbesondere < 1 Gew.%, noch mehr bevorzugt< 0,3 Gew.% ist. Anhydrous TBHP is preferably used according to the invention as a fuel additive. 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.
Durch den Einsatz von wasserfreiem TBHP, welches mit Kraftstoff und insbesondere mit Dieseltreibstoff mischbar ist, wird vermieden, dass sich eine unerwünschte, zweite wässrige Phase bildet. Bevorzugt wird TBHP als Additiv in einem wasserfreien organischen Lösungsmittel eingesetzt. Es können polare und unpolare Lösungsmittel verwendet werden. Beispiele für geeignete unpolare Lösungsmittel sind Alkyle und insbesondere aliphatische Kohlenwasserstoffe, insbesondere Isododecan, Isooktan, Decan, Nonan oder/und n-Oktan bzw. Mischungen verschiedener Aliphaten. Beispiele für polare Lösungsmittel sind insbesondere sauerstoffenthaltende Lösungsmittel, wie beispielsweise Alkohole oder/und Ether. Bevorzugt werden Alkylalkohole als Lösungsmittel eingesetzt, insbesondere C1 -C8-Alkylalkohole, mehr bevorzugt C2-C6-Alkylalkohole, noch mehr bevorzugt Butanol und am meisten bevorzugt tert.-Butanol. Durch Verwendung von Alkoholen und insbesondere von tert.-Butanol wird der Sauerstoffanteil in dem Kraftstoffadditiv weiter erhöht, was wünschenswert ist und zu einer durch die Sauerstoffanreicherung verbesserten Verbrennung und somit Reduzierung des Schadstoffausstoßes beiträgt. The use of anhydrous TBHP, which is miscible with fuel and in particular with diesel fuel, avoids the formation of an undesirable second aqueous phase. TBHP is preferably used 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, in particular isododecane, isooctane, decane, nonane and / or n-octane or mixtures of different aliphatics. Examples of 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. By using 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.
Gerade bei Einsatz eines Kraftstoffadditivs umfassend TBHP in tert.-Butanol (TBA) wurde eine signifikante Verringerung des Ruß- und Schadstoffausstoßes beobachtet. Die Menge an TBHP im Additiv beträgt vorzugsweise mindestens 10 Gew.%, mehr bevorzugt mindestens 30 Gew.%, noch mehr bevorzugt mindestens 40 Gew.-% und am meisten bevorzugt mindestens 50 Gew.%. Reines TBHP ist aus sicherheitstechnischen Überlegungen nicht bevorzugt. Die Menge an TBHP im Additiv beträgt deshalb vorzugsweise bis zu 90 Gew.%, mehr bevorzugt bis zu 75 Gew.% und am meisten bevorzugt bis zu 60 Gew.%. Der Anteil an wasserfreien organischen Lösungsmitteln, insbesondere an Alkoholen und bevorzugt an tert-Butanol, beträgt entsprechend mindestens 10 Gew.%, mehr bevorzugt mindestens 25 Gew. % und am meisten bevorzugt mindestens 40 Gew.% und bis zu 90 Gew.%, mehr bevorzugt bis zu 70 Gew.% und am meisten bevorzugt bis zu 50 Gew. %.  Especially when using a fuel additive comprising TBHP in tert-butanol (TBA), a significant reduction of soot and pollutant emissions was observed. The amount of TBHP in the additive is preferably at least 10 wt%, more preferably at least 30 wt%, even more preferably at least 40 wt%, and most preferably at least 50 wt%. Pure TBHP is not preferred for safety reasons. The amount of TBHP in the additive is therefore preferably up to 90% by weight, more preferably up to 75% by weight, and most preferably up to 60% by weight. The proportion of anhydrous organic solvents, in particular of alcohols and preferably of tert-butanol, is correspondingly at least 10% 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.
Als besonders geeignet und somit am meisten bevorzugt hat sich ein Additiv gezeigt, welches 30 bis 70 Gew.% TBHP in 70 bis 30 Gew.% tert-Butanol enthält. Noch mehr bevorzugt ist ein Additiv, welches 50 bis 60 Gew.-% TBHP in 50 bis 40 Gew.-% tert-Butanol enthält. Am meisten bevorzugt ist ein Additiv, welches 55 Gew.-% TBHP und 45 Gew.-% TBA enthält. Durch die Phlegmatisierung von TBHP in einem sauerstoffhaltigen Lösungsmittel, bevorzugt in einem Alkohol und insbesondere in tert.-Butanol, wird die Sicherheit während der technischen TBHP-Produktion, dem Transport und der weiteren Handhabung erhöht. Weitere besonders bevorzugte Lösungsmittel sind Ether und Polyether, besonders bevorzugt aliphatische oder cyclische Ether und/oder Polyether. Particularly suitable and thus most preferred is an additive which contains 30 to 70% by weight of TBHP in 70 to 30% by weight of tert-butanol. Even more preferred is an additive containing 50 to 60 wt.% TBHP in 50 to 40 wt.% Tert-butanol. Most preferred is an additive containing 55 wt% TBHP and 45 wt% TBA. By phlegmatizing TBHP in an oxygen-containing solvent, preferably in an alcohol and in particular in tert-butanol, the safety during the technical TBHP production, transport and further handling is increased. Further particularly preferred solvents are ethers and polyethers, particularly preferably aliphatic or cyclic ethers and / or polyethers.
Anhand der Phlegmatisierung mit einem sauerstoffhaltigen Lösungsmittel, bevorzugt einem Alkohol und insbesondere tert.-Butylalkohol, wird zur Reduktion von Schadstoffen im Abgas auch der Sauerstoffgehalt des Additivs erhöht. Beispielsweise ist in einem Gemisch aus 55 Gew.% TBHP und 45 Gew.% TBA ein Sauerstoffgehalt von etwa 29,3 Gew.% Sauerstoff, davon etwa 9,8 Gew.% Aktivsauerstoff enthalten. Der erfindungsgemäße Kraftstoff kann als Basiskraftstoff bekannte Kraftstoffe oder Treibstoffe enthalten, wie beispielsweise Ottokraftstoffe, insbesondere Benzin, Super etc., Dieselkraftstoffe wie beispielsweise Diesel, Biodiesel oder ähnliche, aber auch sehr niedrige Dieselqualitäten, wie z.B. verschiedene Schiffdieselqualitäten, Raps-Methylester, Oxymethylenether, Kerosin oder Raketentreibstoff. Der Kraftstoff, insbesondere ein Dieselkraftstoff oder Kerosin, kann z.B. für Dieselaggregate in z.B. Kraftfahrzeugen, Schiffen oder für stationäre Dieselmotoren zur Stromerzeugung oder auch für Flugzeuge oder Raketenmotoren vorgesehen sein. Based on the phlegmatization with an oxygen-containing solvent, preferably an alcohol and in particular tert-butyl alcohol, the oxygen content of the additive is also increased to reduce pollutants in the exhaust gas. For example, in a mixture of 55 wt.% TBHP and 45 wt.% TBA, an oxygen content of about 29.3 wt.% Oxygen, of which about 9.8 wt.% Active oxygen is contained. The fuel according to the invention may contain fuels or fuels known as the basic fuel, such as gasoline fuels, in particular gasoline, super etc., diesel fuels such as diesel, biodiesel or similar, but also very low diesel qualities, e.g. various types of ship diesel, rape methyl ester, oxymethylene ethers, kerosene or rocket fuel. The fuel, in particular a diesel fuel or kerosene, may e.g. for diesel engines in e.g. Be provided for motor vehicles, ships or for stationary diesel engines for power generation or for aircraft or rocket engines.
Durch das erfindungsgemäße Additiv wird insbesondere die Zündwilligkeit des Kraftstoffes erhöht. Weiterhin wird der Ausstoß an Ruß und Kohlenwasserstoffen und Kohlenmonoxid im Verbrennungsmotor deutlich reduziert, insbesondere bei gleichbleibendem oder nahezu gleichbleibendem NOx-Ausstoß. Besonders bevorzugt umfasst der erfindungsgemäße Kraftstoff als Basiskraftstoff einen hochwertigen Diesel, der die Euro4 Diesel- Anforderungen erfüllt. Das erfindungsgemäß als Additiv eingesetzte TBHP ist auch sicherheitstechnisch gegenüber den üblicherweise eingesetzten Additiven, wie z.B. 2-EHN, deutlich besser handhabbar. Durch den Einsatz von TBHP in wasserfreier Form, insbesondere in einem wasserfreien organischen Lösungsmittel, wird die Bildung von zwei separaten Phasen vermieden und dadurch erst der Einsatz von TBHP als Kraftstoffadditiv ermöglicht. By the additive according to the invention, in particular the ignitability of the fuel is increased. Furthermore, the emission of soot and hydrocarbons and carbon monoxide in the internal combustion engine is significantly reduced, in particular at constant or almost constant NOx emissions. The fuel according to the invention as a basic fuel particularly preferably comprises a high-quality diesel which meets the Euro 4 diesel requirements. The TBHP used according to the invention as an additive is also significantly safer in terms of safety compared to the additives commonly used, such as 2-EHN, for example. The use of TBHP in anhydrous form, especially in an anhydrous organic solvent, avoids the formation of two separate phases, thereby allowing the use of TBHP as fuel additive.
Im Vergleich zum herkömmlich eingesetzten 2-EHN wird durch den erfindungsgemäßen Einsatz von TBHP als Additiv die Verbrennung verbessert (insbesondere geringerer Kohlenwasserstoff-, Kohlenmonoxid- und Rußausstoß). Weiterhin enthält TBHP keinen Stickstoff, sodass die damit verbundenen Problematiken und insbesondere das Problem der Bildung von Stickoxiden erfindungsgemäß reduziert werden. TBHP ist weiterhin sicherheitstechnisch deutlich sicherer als 2-EHN, insbesondere in Bezug auf die Zersetzung. Compared to the conventionally used 2-EHN combustion is improved by the inventive use of TBHP as an additive (especially lower hydrocarbon, carbon monoxide and soot emissions). Furthermore, TBHP contains no nitrogen, so that the associated problems and in particular the problem of the formation of nitrogen oxides are inventively reduced. Furthermore, TBHP is significantly safer in terms of safety than 2-EHN, especially in terms of decomposition.
Ein Maß für die Zersetzungsgeschwindigkeit und den Druckaufbau bei der Zersetzung eines Produktes ist der Koenen-Test. Je größer der Koenen- Wert, desto heftiger erfolgt die Zersetzung. 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.
So ist der Koenen für 2-EHN = 1 ,0 während der Koenen für ein mit TBA phlegmatisiertes TBHP < 1 ist. Auch ist die bei der Zersetzung von 2-EHN freiwerdende Energie mit ΔΗ = 2210 J/g deutlich höher als die von einer TBHP-TBA Mischung mit ΔΗ = 729Thus, the Koenen for 2-EHN = 1, 0 while the Koenen for a TBA phlegmatized TBHP <1. Also, the energy released in the decomposition of 2-EHN with ΔΗ = 2210 J / g is significantly higher than that of a TBHP-TBA mixture with ΔΗ = 729
J/g. J / g.
Im Vergleich zum bereits als Kraftstoffadditiv eingesetzten di-tert.- Butylperoxid (DTBP) weist TBHP vorteilhafterweise einen höheren Flammpunkt von 21 °C auf. Der Flammpunkt von DTBP liegt z.B. deutlich niedriger als der von TBHP und unterhalb der Raumtemperatur bei < 0°C. Weiterhin ist die Leitfähigkeit von DTBP mit < 3 pS/m extrem niedrig, sodass Umfüllvorgänge von DTBP aufgrund von möglichen Ladungstrennungen sicherheitstechnisch sehr kritisch sind, da diese Ladungstrennungen eine ausreichende Zündenergie zum Zünden von DTBP erzeugen können, da DTBP nur eine sehr geringe Zündenergie von <0,1 mJ benötigt. Auch ist die bei der Zersetzung von DTBP freiwerdene Energie mit ΔΗ = 1370 J/g deutlich höher als die von dem mit TBA phlegmatisierten TBHP mit ΔΗ = 729In comparison with the di-tert-butyl peroxide (DTBP) already used as a fuel additive, TBHP advantageously has a higher flash point of 21 ° C. For example, the flashpoint of DTBP is significantly lower than that of TBHP and below room temperature at <0 ° C. Furthermore, the conductance of DTBP at <3 pS / m is extremely low, so DTBP replenishment processes are very critical in terms of safety because of 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. Also, the energy released by the decomposition of DTBP with ΔΗ = 1370 J / g is significantly higher than that of the TBA phlegmatized TBHP with ΔΗ = 729
J/g. Im Gegensatz zu dem unpolaren DTBP ist das polare TBHP leitfähig (> 1000 pS/m) und somit treten solche Ladungstrennungen nicht auf, sodass TBHP erheblich sicherer als DTBP gehandhabt werden kann. J / g. Unlike the nonpolar DTBP, the polar TBHP is conductive (> 1000 pS / m) and thus, such charge separations do not occur, so TBHP can be handled much more safely than DTBP.
Erfindungsgemäß weist der Kraftstoff vorzugsweise 0,001 Gew.% bis 10 Gew.%, mehr bevorzugt 0,005 Gew.% bis 5 Gew.% und am meisten bevorzugt 0,01 Gew.% bis 2 Gew.% TBHP auf. In the present invention, the fuel is preferably 0.001 wt% to 10 wt%, more preferably 0.005 wt% to 5 wt%, and most preferably 0.01 wt% to 2 wt% TBHP.
Erfindungsgemäß wurde festgestellt, dass auch bereits mit geringen Mengen an Additiv eine Verringerung des Schadstoffausstoßes erreicht werden kann. Besonders bevorzugt weist der erfindungsgemäße Kraftstoff deshalb bis zu 0,5 Gew.-% TBHPnoch mehr bevorzugt bis zu 0,25 Gew.-% TBHP und am meisten bevorzugt bis 0,15 Gew.%auf. According to the invention, it has been found that even with small amounts of additive, a reduction of pollutant emissions can be achieved. Therefore, the fuel according to the invention particularly preferably has up to 0.5% by weight TBHP, more preferably up to 0.25% by weight TBHP and most preferably up to 0.15% by weight.
Es ist erfindungsgemäß auch möglich, das erfindungsgemäße TBHP- enthaltende Additiv mit anderen Additiven zu kombinieren. Bevorzugt ist z.B. die Kombination mit anderen Peroxiden, insbesondere mit anderen organischen Peroxiden und bevorzugt mit anderen wasserfreien organischen Peroxiden, und insbesondere mit di-tert.-Butylperoxid (DTBP). Besonders bevorzugt ist ein Additiv, welches TBHP und DTPB umfasst. Am meisten bevorzugt ist ein Additiv umfassend TBHP, DTPB und TBA. Für die Kombination von wasserfreiem TBHP mit DTBP als Additiv wurden überraschenderweise synergistische Effekte gefunden, so dass die erfindungsgemäße Kombination von wasserfreiem TBHP mit DTBP zu einer höheren Schadstoffreduktion führt, als dies durch vergleichbare Mengen von TBHP oder DTBP alleine erreicht werden kann. It is also possible according to the invention to combine the TBHP-containing additive according to the invention with other additives. Preferred is, for example, the combination with other peroxides, in particular with other organic peroxides and preferably with other anhydrous organic peroxides, and in particular with di-tert-butyl peroxide (DTBP). Particularly preferred is an additive comprising TBHP and DTPB. Most preferred is an additive comprising TBHP, DTPB and TBA. For the combination of anhydrous TBHP with DTBP as an additive synergistic effects were surprisingly found, so that the inventive combination of anhydrous TBHP with DTBP leads to a higher pollutant reduction than can be achieved by comparable amounts of TBHP or DTBP alone.
Das Gewichtsverhältnis von TBHP und DTPB beträgt dabei bevorzugt von 10 : 90 bis 90 : 10, insbesondere 20 : 80 bis 80 : 20 und noch mehr bevorzugt 30 : 70 bis 70 : 30. The weight ratio of TBHP and DTPB is preferably from 10:90 to 90:10, in particular from 20:80 to 80:20 and even more preferably from 30:70 to 70:30.
Die Menge an TBHP und DTPB im Additiv beträgt vorzugsweise vorzugsweise mindestens 10 Gew.%, mehr bevorzugt mindestens 30 Gew.%, noch mehr bevorzugt mindestens 40 Gew.-% und am meisten bevorzugt mindestens 50 Gew.%. Weiterhin beträgt die Menge von TBHP und DTPB im Additiv vorzugsweise bis zu 90 Gew.%, mehr bevorzugt bis zu 75 Gew.% und am meisten bevorzugt bis zu 60 Gew.%. Der Anteil an wasserfreien organischen Lösungsmitteln, insbesondere an Alkoholen und bevorzugt an tert-Butanol, beträgt entsprechend mindestens 10 Gew.%, mehr bevorzugt mindestens 25 Gew. % und am meisten bevorzugt mindestens 40 Gew.% und bis zu 90 Gew.%, mehr bevorzugt bis zu 70 Gew.% und am meisten bevorzugt bis zu 50 Gew. %. The amount of TBHP and DTPB in the additive is preferably preferably at least 10% by weight, more preferably at least 30% by weight, even more preferably at least 40% by weight, and most preferably at least 50% by weight. Further, the amount of TBHP and DTPB in the additive is preferably up to 90% by weight, more preferably up to 75% by weight, and most preferably up to 60% by weight. The proportion of anhydrous organic solvents, in particular of alcohols and preferably of tert-butanol, is correspondingly at least 10% 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.
Die Herstellung von TBHP kann nach bekannten Herstellungsverfahren erfolgen. The production of TBHP can be carried out according to known production methods.
Das erfindungsgemäße Kraftstoffadditiv enthält insbesondere wasserfreies TBHP und vorzugsweise TBHP in einem organischen Lösungsmittel. Das organische Lösungsmittel ist vorzugsweise ein Alkohol, insbesondere tert- Butanol. Besonders bevorzugt ist ein Additiv, umfassend 30 bis 70 Gew.-% TBHP in 70 bis 30 Gew.-% organischem Lösungsmittel, insbesondere TBA, mehr bevorzugt 50 bis 60 Gew.-% TBHP in 50 bis 40 Gew.-% organischem Lösungsmittel, insbesondere TBA. Weiterhin besonders bevorzugt ist ein Kraftstoffadditiv, welches zusätzlich zu TBHP ein weiteres organisches Peroxid, insbesondere ein weiteres wasserfreies organisches Peroxid umfasst. Am meisten bevorzugt ist ein Additiv umfassend TBHP und DTBP. In einer besondersbevorzugten Ausführungsform liegen die Peroxide im Additiv in einem Alkohol, insbesondere in TBA vor. The fuel additive according to the invention contains in particular anhydrous TBHP and preferably TBHP in an organic solvent. The organic solvent is preferably an alcohol, especially tert-butanol. Particularly preferred is an additive comprising 30 to 70 wt.% TBHP in 70 to 30 wt.% Organic solvent, especially TBA, more preferably 50 to 60 wt.% TBHP in 50 to 40 wt.% Organic solvent, especially TBA. Also particularly preferred is a fuel additive which, in addition to TBHP, comprises a further organic peroxide, in particular a further anhydrous organic peroxide. Most preferred is an additive comprising TBHP and DTBP. In a particularly preferred embodiment, the peroxides in the additive are present in an alcohol, in particular in TBA.
Weiterhin ist auch ein Kraftstoffadditiv bezugt, welches zusätzlich zu TBHP ein anderes bekanntes Kraftstoffadditiv, wie zum Beispiel 2-EHN enthält. In einer besonders bevorzugten Ausführungsform liegt dabei das TBHP in einem Alkohol, insbesondere in TBA vor. Furthermore, a fuel additive is also referred to, which in addition to TBHP contains another known fuel additive, such as 2-EHN. In a particularly preferred embodiment, the TBHP is present in an alcohol, in particular in TBA.
Die bevorzugten Mengenverhältnisse von TBHP, gegebenenfalls weiterem organischen Peroxid wie z.B. DTBP sowie organischem Lösungsmittel, insbesondere TBA, sind wie hierin zuvor beschrieben. The preferred proportions of TBHP, optionally further organic peroxide such as e.g. DTBP as well as organic solvent, especially TBA, are as previously described herein.
Weiterhin wurde erfindungsgemäß festgestellt, dass unter Verwendung des erfindungsgemäß Kraftstoff additivs bzw. eines das erfindungsgemäße Kraftstoffadditiv umfassenden Kraftstoffes der Schadstoffausstoß verringert werden kann. Die Erfindung betrifft deshalb auch die Verwendung von TBHP zur Schadstoffreduktion, insbesondere zur Reduktion der Kohlenwasserstoffemission und/oder der Kohlenmonoxidemission. Besonders bevorzugt betrifft die Erfindung die Verwendung von TBHP zur Schadstoffemission bei Fahrzeugen mit Katalysator. Am meisten bevorzugt ist die Verwendung eines Additivs umfassend TBHP, DTBP und TBA zur Schadstoffreduktion. Furthermore, it has been found according to the invention that the emission of pollutants can be reduced by using the fuel additive according to the invention or a fuel comprising the fuel additive according to the invention. The invention therefore also relates to the use of TBHP for pollutant reduction, in particular for the reduction of the hydrocarbon emission and / or the carbon monoxide emission. Particularly preferably, the invention relates to the use of TBHP for pollutant emissions in vehicles with catalyst. Most preferred is the use of an additive comprising TBHP, DTBP and TBA for pollutant reduction.
Die Erfindung betrifft weiterhin ein Kraftstoffadditiv umfassend TBHP, insbesondere wie hierin zuvor beschrieben, sowie die Verwendung von TBHP oder der hierin beschriebenen Kraftstoffadditive zur Erhöhung der Cetan-Zahl. Die Erfindung betrifft weiterhin ein Kraftstoffadditiv umfassend TBHP, insbesondere wie hierin zuvor beschrieben, sowie die Verwendung von TBHP oder der hierin beschriebenen Kraftstoff additive zur Schadstoffreduktion, insbesondere zur Reduktion der Emission von Kohlenwasserstoffen oder/und Kohlenmonoxid. The invention further relates to a fuel additive comprising TBHP, in particular as described hereinbefore, and to the use of TBHP or the cetane increasing fuel additives described herein. The invention further relates to a fuel additive comprising TBHP, in particular as described hereinbefore, and the use of TBHP or the fuel additive described herein for pollutant reduction, in particular for reducing the emission of hydrocarbons and / or carbon monoxide.
Die Erfindung wird durch die folgenden Beispiele weiter erläutert. The invention is further illustrated by the following examples.
Beispiel 1 example 1
Kraftstoff, umfassend TBHP als Additiv Ein herkömmlicher US-Basisdieselkraftstoff weist eine Cetan-Zahl von 45,2 auf. Diesem Kraftstoff wird ein Additiv bestehend aus 55 Gew.% TBHP und 45 Gew.% tert-Butanol in einer Konzentration basierend auf TBHP von 0,026 Gew.% Additivmenge sowie in einer Konzentration von 0,1 1 Gew.% zugesetzt. Fuel comprising TBHP as additive A conventional US base diesel fuel has a cetane number of 45.2. This fuel is an additive consisting of 55 wt.% TBHP and 45 wt.% Tert-butanol in a concentration based on TBHP of 0.026 wt.% Additive amount and in a concentration of 0.1 1 wt.% Added.
Durch Zusatz von 0,026 Gew% TBHP steigt die CETAN-Zahl von 45,2 auf 47,4. Bei einer weiteren Zugabe von insgesamt 0,1 1 Gew. % TBHP wird die CETAN-Zahl auf 50,0 erhöht. Vergleichende Emissions- und Verbrauchsmessungen wurden mit einem herkömmlichen US Basisdieseltreibstoff (Cetan-Zahl 45,2) und einem herkömmlichen EU4-Basisdieseltreibstoff (Cetan-Zahl 54,6) mit und ohne TBHP-Zusatz auf einem Rollenprüfstand entsprechend dem genormten NEFZ-Fahrzyklus vorgenommen. By adding 0.026 wt% TBHP, the CETAN number increases from 45.2 to 47.4. With a further addition of a total of 0.1 1 wt.% TBHP, the CETAN number is increased to 50.0. Comparative emission and fuel consumption measurements were made with a conventional US base diesel fuel (cetane number 45.2) and a conventional EU4 base diesel fuel (cetane number 54.6) with and without TBHP additive on a chassis dynamometer according to the standard NEDC driving cycle.
Als Testfahrzeug wurde ein Mercedes C 220 CDI, 4 Zylinder, 1 10 KW Leistung, Baujahr 2005 mit einem 5-Gang-Automatikgetriebe und einer Laufleistung von etwa 140.000 km eingesetzt. Das Fahrzeug ist mit einem Partikelfilter und Katalysator ausgerüstet. Die Emissionen wurden in Mehrfachmessungen vor und nach dem Katalysator ermittelt. Durch einen Zusatz von 0,1 1 Gew % TBHP zu einem herkömmlichen EU_Basisdieseltreibstoff mit der CETAN Zahl von 54,6 konnten bei gleichbleibendem Durchschnittsverbrauch die Rohemissionen vor dem Katalysator wie folgt abgesenkt werden: 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 emissions were determined in multiple measurements before and after the catalyst. By adding 0.1 1% by weight TBHP to a conventional EU base diesel fuel with the CETAN number of 54.6, it was possible to lower the pre-catalyst raw emissions while maintaining average fuel consumption as follows:
EU4 Basisdiesel EU4 basic diesel
Die ΝΟχ-Emissionen steigen nur sehr geringfügig um 6,1 % in Phase 1 und 2,9 % in Phase 2 an. The ΝΟχ emissions increase only very slightly by 6.1% in phase 1 and 2.9% in phase 2.
Besonders wichtig und ausgeprägt ist der positive Einfluß der Emissionsreduzierung in der Phase 1 , der Kaltstartphase im NEFZ-Zyklus 1 bis 4. Particularly important and pronounced is the positive influence of emission reduction in phase 1, the cold start phase in NEDC cycle 1 to 4.
EU4 Basisdiesel EU4 basic diesel
Durch einen Zusatz von 0,1 1 Gew % TBHP zu einem herkömmlichen US_Basisdieseltreibstoff mit der Cetan-Zahl von 45,2 konnten bei einem gleichbleibenden Durchschnittsverbrauch folgende Rohemissionen vor dem Katalysator beobachtet werden: By adding 0.1 1% by weight of TBHP to a conventional US base diesel fuel with the cetane number of 45.2, it was possible to obtain a Consistent average consumption, the following raw emissions are observed before the catalyst:
US Basisdiesel  US base diesel
Die ΝΟχ-Emissionen steigen unterhalb der Messtoleranz an. The ΝΟχ emissions increase below the measurement tolerance.
Speziell in der Phase 1 (Zyklus 1 - 4 NEFZ) wurde eine sehr starke Reduktion der Emissionen nach dem Katalysator gemessen, da dieser noch nicht die erforderliche Betriebstemperatur aufweist: Especially in phase 1 (cycle 1 - 4 NEDC) a very strong reduction of emissions downstream of the catalytic converter was measured, as this does not yet have the required operating temperature:
US Basisdiesel US base diesel
Die Absolutwerte der Schadstoffemissionen bezogen auf Kohlenwasserstoffe und Kohlenmonoxid sind bei der handelsüblichen EU4-Dieselqualität in jedem Fall niedriger als bei der handelsüblichen US-Basisdieselqualität. Trotzdem konnte mit 0.1 1 % TBHP als Additiv bei der höherwertigen handelsüblichen EU4 Diesel Treibstoffqualität eine noch stärkere prozentuale Schadstoffemissionsminimierung erzielt werden als bei der US- Basisdieselqualität: The absolute values of the pollutant emissions relative to hydrocarbons and carbon monoxide are in any case lower than the commercial US base diesel quality with the commercially available EU4 diesel quality. Nevertheless, with 0.1 1% TBHP as an additive in the higher-grade commercial EU4 diesel fuel quality, an even greater percentage emission emission reduction could be achieved than with the US base diesel quality:
Beispiel 2 Example 2
Kraftstoff, umfassend TBHP und DTBP als Additiv Fuel comprising TBHP and DTBP as an additive
Einem herkömmlichen US-Basisdieselkraftstoff wird ein Additiv bestehen aus 27,5 Gew.% TBHP, 22,5 Gew.% TBA und 50 Gew.% DTBP zugemischt. Mischung 1 enthält 0,013 Gew % TBHP und 0,024 Gew % DTBP. 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. Blend 1 contains 0.013 wt% TBHP and 0.024 wt% DTBP.
Mischung 2 enthält 0,052 Gew. % TBHP und 0,094 Gew % DTBP. Mixture 2 contains 0.052% by weight of TBHP and 0.094% by weight of DTBP.
Die CETAN-Zahl des herkömmlichen Basisdieseltreibstoffes beträgt 45,2, die der Mischung 1 beträgt 47,9 und die der Mischung 2 beträgt 56,7. Im Vergleich zum Basiskraftstoff wird durch Zugabe des Additives die Cetan- Zahl signifikant erhöht und entsprechend der folgenden Tabelle die Schadstoffemissionen bei gleichbleibendem Verbrauch signifikant und speziell in Phase 1 noch signifikanter reduziert. 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. Compared to the basic fuel, 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.
US Basisdiesel US base diesel
Speziell in der Phase 1 (Zyklus 1 - 4 NEFZ) wurde auch eine sehr starke Reduktion der Emissionen nach dem Katalysator gemessen, da dieser noch nicht die erforderliche Betriebstemperatur aufweist: US Basisdiesel Especially in Phase 1 (Cycle 1 - 4 NEDC), a very strong reduction in emissions downstream of the catalyst was also measured, since this does not yet have the required operating temperature: US base diesel
ie ΝΟχ-Emissionen steigen unterhalb der Messtoleranz an. he ΝΟχ emissions rise below the measurement tolerance.

Claims

Ansprüche claims
1. Kraftstoff, umfassend tert.-Butylhydroperoxid (TBHP) als Additiv. 1. A fuel comprising tertiary butyl hydroperoxide (TBHP) as an additive.
2. Kraftstoff, umfassend TBHP als Additiv nach Anspruch 1 , 2. A fuel comprising TBHP as an additive according to claim 1,
dadurch gekennzeichnet, dass  characterized in that
das Additiv wasserfreies TBHP enthält.  the additive contains anhydrous TBHP.
3. Kraftstoff, umfassend TBHP als Additiv nach Anspruch 1 oder 2, 3. A fuel comprising TBHP as additive according to claim 1 or 2,
dadurch gekennzeichnet, dass  characterized in that
das Additiv TBHP in einem organischen Lösungsmittel enthält.  contains the additive TBHP in an organic solvent.
4. Kraftstoff, umfassend TBHP als Additiv nach einem der vorhergehenden Ansprüche, 4. Fuel, comprising TBHP as additive according to one of the preceding claims,
dadurch gekennzeichnet, dass  characterized in that
das Additiv TBHP in tert-Butanol enthält.  contains the additive TBHP in tert-butanol.
5. Kraftstoff, umfassend TBHP als Additiv nach einem der vorhergehenden Ansprüche, 5. A fuel comprising TBHP as an additive according to any one of the preceding claims,
dadurch gekennzeichnet, dass  characterized in that
das Additiv aus 30 bis 70 Gew.% TBHP in 70 bis 30 Gew.% organischem Lösungsmittel besteht.  the additive consists of 30 to 70 wt.% TBHP in 70 to 30 wt.% Organic solvent.
6. Kraftstoff, umfassend TBHP als Additiv nach einem der 6. Fuel comprising TBHP as an additive according to one of
vorhergehenden Ansprüche,  previous claims,
dadurch gekennzeichnet, dass  characterized in that
das TBHP in einer Menge von 0,001 Gew.% bis 10 Gew.%, bezogen auf das Gesamtgewicht des Kraftstoffs, vorliegt.  the TBHP is present in an amount of from 0.001% to 10% by weight, based on the total weight of the fuel.
7. Kraftstoff, umfassend TBHP als Additiv nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass 7. A fuel comprising TBHP as an additive according to any one of the preceding claims, characterized in that
der Basiskraftstoff ausgewählt ist aus Dieselkraftstoff, Ottokraftstoff, Raps-Methylester, Kerosin und Raketentreibstoffen the basic fuel is selected from diesel fuel, petrol, rapeseed methyl ester, kerosene and rocket fuels
8. Kraftstoff, umfassend TBHP ais Additiv nach einem der vorhergehenden Ansprüche, 8. A fuel comprising TBHP as an additive according to any one of the preceding claims,
dadurch gekennzeichnet, dass  characterized in that
der Kraftstoff ausgewählt ist aus Dieselkraftstoff.  the fuel is selected from diesel fuel.
9. Kraftstoff, umfassend TBHP als Additiv nach einem der vorhergehenden Ansprüche, 9. A fuel comprising TBHP as an additive according to any one of the preceding claims,
dadurch gekennzeichnet, dass  characterized in that
der Kraftstoff ein weiteres Additiv, insbesondere Ditertbutylperoxid, umfasst.  the fuel comprises a further additive, in particular di-tert-butyl peroxide.
10. Kraftstoffadditiv, umfassend TBHP. 10. Fuel additive comprising TBHP.
1 1. Kraftstoffadditiv, umfassend TBHP nach Anspruch 10, 1 1. A fuel additive comprising TBHP according to claim 10,
dadurch gekennzeichnet, dass  characterized in that
es wasserfreies TBHP umfasst.  it includes anhydrous TBHP.
12. Kraftstoffadditiv nach Anspruch 10, umfassend TBHP, DTBP und TBA. 12. A fuel additive according to claim 10, comprising TBHP, DTBP and TBA.
13. Kraftstoffadditiv nach Anspruch 10, umfassend TBHP, TBA und 2-EHN 13. A fuel additive according to claim 10, comprising TBHP, TBA and 2-EHN
14. Verwendung von TBHP zur Erhöhung der Cetan-Zahl. 14. Using TBHP to increase the cetane number.
15. Verwendung von TBHP zur Reduzierung der Kohlenmonoxid- und/oder Kohlenwasserstoffemission. 15. Use of TBHP to reduce carbon monoxide and / or hydrocarbon emissions.
16. Verwendung von einer Mischung von TBHP und DTBP zur Erhöhung der Cetanzahl. 16. Use of a mixture of TBHP and DTBP to increase the cetane number.
17. Verwendung von einer Mischung von TBHP und DTBP zur Reduzierung der Kohlenmonoxid- und der Kohlenwasserstoff- Emissionen. 17. Use of a mixture of TBHP and DTBP to reduce carbon monoxide and hydrocarbon emissions.
EP12784622.8A 2011-11-16 2012-11-16 Tertiobutyl hydroperoxide (tbhp) as a diesel additive Active EP2780435B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12784622.8A EP2780435B1 (en) 2011-11-16 2012-11-16 Tertiobutyl hydroperoxide (tbhp) as a diesel additive

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11189416.8A EP2594623A1 (en) 2011-11-16 2011-11-16 Tertiobutyl hydroperoxide (TBHP) as a diesel additive
EP12784622.8A EP2780435B1 (en) 2011-11-16 2012-11-16 Tertiobutyl hydroperoxide (tbhp) as a diesel additive
PCT/EP2012/072877 WO2013072478A1 (en) 2011-11-16 2012-11-16 Tert-butyl hydroperoxide (tbhp) as a diesel additive

Publications (2)

Publication Number Publication Date
EP2780435A1 true EP2780435A1 (en) 2014-09-24
EP2780435B1 EP2780435B1 (en) 2021-03-24

Family

ID=47178043

Family Applications (2)

Application Number Title Priority Date Filing Date
EP11189416.8A Ceased EP2594623A1 (en) 2011-11-16 2011-11-16 Tertiobutyl hydroperoxide (TBHP) as a diesel additive
EP12784622.8A Active EP2780435B1 (en) 2011-11-16 2012-11-16 Tertiobutyl hydroperoxide (tbhp) as a diesel additive

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP11189416.8A Ceased EP2594623A1 (en) 2011-11-16 2011-11-16 Tertiobutyl hydroperoxide (TBHP) as a diesel additive

Country Status (8)

Country Link
US (1) US9303224B2 (en)
EP (2) EP2594623A1 (en)
CN (1) CN103998582B (en)
ES (1) ES2864214T3 (en)
IN (1) IN2014KN01024A (en)
MX (1) MX2014005821A (en)
WO (1) WO2013072478A1 (en)
ZA (1) ZA201403247B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3088495A1 (en) 2015-04-28 2016-11-02 United Initiators GmbH & Co. KG Use of a fuel additive in diesel fuel for removing deposits in a diesel engine
EP3088494A1 (en) 2015-04-28 2016-11-02 United Initiators GmbH & Co. KG Use of a fuel additive in diesel fuel for reducing fuel consumption in a diesel engine

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106701221B (en) * 2017-02-24 2018-09-04 马鞍山纽盟知识产权管理服务有限公司 A kind of high power diesel fuel additives and its manufacture craft
CN109868166B (en) * 2019-03-12 2020-11-03 南京科技职业学院 Composite diesel additive

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB628347A (en) 1946-08-31 1949-08-26 Standard Oil Dev Co An improved manufacture of hydrocarbon diesel fuels
US2618538A (en) 1949-02-03 1952-11-18 Standard Oil Dev Co Diesel fuel composition
US2763537A (en) 1949-05-24 1956-09-18 California Research Corp Diesel fuel oil
US2912313A (en) * 1956-03-30 1959-11-10 Ethyl Corp Diesel fuel
US4104036A (en) * 1976-03-08 1978-08-01 Atlantic Richfield Company Iron-containing motor fuel compositions and method for using same
US4289501A (en) * 1978-03-20 1981-09-15 Bwm Corporation Hydrocarbon fuel additive
ES469590A1 (en) * 1978-05-08 1978-12-16 Peroxidos Organicos S A Process of purification of organic peroxides with water content. (Machine-translation by Google Translate, not legally binding)
US4294999A (en) * 1979-06-04 1981-10-13 Atlantic Richfield Company Preparing oxygen-containing fuel wherein tertiary butyl alcohol is the major product of the process
US4873380A (en) 1987-01-20 1989-10-10 Texaco Inc. Catalyst for removing peroxide contaminants from tertiary butyl alcohol
US4800847A (en) * 1987-06-05 1989-01-31 Pritchard Huw O Anaerobic operation of an internal combustion engine
DE3904099C1 (en) * 1989-02-11 1990-07-12 Schuelke & Mayr Gmbh, 2000 Norderstedt, De
US5104493B1 (en) 1991-01-24 1995-08-15 Arco Chem Tech Tertiary butyl hydroperoxide concentration
WO1993024593A1 (en) * 1992-06-02 1993-12-09 Greenbranch Enterprises, Inc. A phase stabilized alcohol based diesel fuel containing ignition additives
DE4232500A1 (en) * 1992-09-28 1994-03-31 Peroxid Chemie Gmbh Process for the preparation of anhydrous or anhydrous solutions of alkyl hydroperoxides
US5669938A (en) * 1995-12-21 1997-09-23 Ethyl Corporation Emulsion diesel fuel composition with reduced emissions
AU1367099A (en) * 1997-10-29 1999-05-17 James Kenneth Sanders Combustion catalyst and catalyzed fuels with enhanced combustion efficien cy and mileage
JP2002530515A (en) 1998-11-23 2002-09-17 ピュア エナジー コーポレイション Diesel fuel composition
AU1420600A (en) * 1999-09-06 2001-04-10 Agrofuel Ab Motor fuel for diesel engines
CN100395317C (en) * 2006-07-19 2008-06-18 北京工业大学 Fuel additive of homogeneous premixed compression ignition engine
US20100088949A1 (en) * 2006-09-05 2010-04-15 Cerion Technology, Inc. Method of conditioning an internal combustion engine
CN101319147A (en) 2008-01-18 2008-12-10 孙昔铭 Biological diesel oil for diesel engine and preparation method thereof
US8920633B2 (en) * 2009-09-16 2014-12-30 Cetamax Ventures Ltd. Method and system for oxidatively increasing cetane number of hydrocarbon fuel
WO2011053833A1 (en) * 2009-10-30 2011-05-05 Bp Corporation North America Inc. Composition and method for reducing nox emissions from diesel engines at minimum fuel consumption

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013072478A1 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3088495A1 (en) 2015-04-28 2016-11-02 United Initiators GmbH & Co. KG Use of a fuel additive in diesel fuel for removing deposits in a diesel engine
EP3088494A1 (en) 2015-04-28 2016-11-02 United Initiators GmbH & Co. KG Use of a fuel additive in diesel fuel for reducing fuel consumption in a diesel engine
WO2016174178A1 (en) 2015-04-28 2016-11-03 United Initiators Gmbh & Co. Kg Use of a fuel additive in diesel fuel for removing deposits in a diesel engine
WO2016174176A1 (en) 2015-04-28 2016-11-03 United Initiators Gmbh & Co. Kg Use of a fuel additive in diesel fuel for reducing fuel consumption in a diesel engine

Also Published As

Publication number Publication date
ES2864214T3 (en) 2021-10-13
MX2014005821A (en) 2014-10-24
US9303224B2 (en) 2016-04-05
IN2014KN01024A (en) 2015-10-09
WO2013072478A1 (en) 2013-05-23
EP2594623A1 (en) 2013-05-22
CN103998582B (en) 2016-05-18
US20140311019A1 (en) 2014-10-23
EP2780435B1 (en) 2021-03-24
CN103998582A (en) 2014-08-20
ZA201403247B (en) 2015-09-30

Similar Documents

Publication Publication Date Title
DE60024474T2 (en) FUEL FOR DIESEL, GAS TURBO AND TURBO INJECTION ENGINES, COMPRISING AT LEAST FOUR DIFFERENT OXYGENING FUNCTIONAL GROUPS, SELECTED FROM ALCOHOL, ETHER, ALDEHYDE, KETONE, ESTER, ANORGANIC ESTER, AZETATE, EPOXY AND PEROXIDE
DE102008032254B4 (en) Low-carbon diesel fuels containing a fuel additive, their use and the use of the fuel additive for the production of low-carbon diesel fuels
DE60111018T2 (en) METHOD FOR REDUCING THE VAPOR PRESSURE OF ETHANOL-CONTAINING ENGINEERING FRIENDS FOR SPARKLING INTERNAL COMBUSTION ENGINES
DE2216880C2 (en) Fuel additive
DE102009005356A1 (en) Method and device for operating a diesel engine with a mixed fuel
EP2233552A1 (en) Diesel fuel on an ethanol basis
EP2780435B1 (en) Tertiobutyl hydroperoxide (tbhp) as a diesel additive
DE69931014T2 (en) Base oil for diesel fuel and compositions containing it
EP2907866B1 (en) Fuel for self-ignition engines based on polyoxymethylene dialkyl ethers
DE3025258A1 (en) FUEL COMPOSITION
EP2759588B1 (en) Fuel for self-ignition engines based on monooxymethylene dimethyl ether
DE4333418C1 (en) Fuel mixture
DE4135294C2 (en) Fuel mixture and its use
DE102007003344B3 (en) Diesel fuel mixture
EP0118805A2 (en) Motor fuel
EP2803846B1 (en) Driving device and method for operating the same using a partially oxidised diesel fuel
CH689981A5 (en) Low sulfur, additivated diesel fuel with improved lubricity and increased density.
DE202006019072U1 (en) Diesel fuel mixture, useful as fuel components in diesel engines, comprises a fossil diesel fuel and/or biodiesel, and a conventional additive containing oxalic acid diethyl ester
EP0166096B1 (en) Motor fuels
RU2309975C2 (en) Additive compound for the cetane number boost of the diesel fuel
WO2013072479A1 (en) Conductive di-tert-butyl peroxide (dtbp) preparation as a diesel additive
DE102007040636B3 (en) Bio-fuel, useful in combustion motors of motor vehicles, comprises vegetable oil and at least one (meth)acrylic acid ester
DE102016223056A1 (en) Fuel additive
DE1221488B (en) Fuels for internal combustion engines with spark ignition
WO2016016336A1 (en) Synthetic gasoline and use thereof

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140509

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20170213

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNITED INITIATORS GMBH

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C10L 10/02 20060101ALI20201006BHEP

Ipc: C10L 1/182 20060101ALI20201006BHEP

Ipc: C10L 10/12 20060101ALI20201006BHEP

Ipc: C10L 1/14 20060101ALI20201006BHEP

Ipc: C10L 1/18 20060101AFI20201006BHEP

Ipc: C10L 1/23 20060101ALI20201006BHEP

INTG Intention to grant announced

Effective date: 20201111

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502012016689

Country of ref document: DE

Ref country code: AT

Ref legal event code: REF

Ref document number: 1374518

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210415

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

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

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210625

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210624

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210624

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

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2864214

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20211013

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

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

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

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210724

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210726

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502012016689

Country of ref document: DE

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

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

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

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

26N No opposition filed

Effective date: 20220104

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

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210724

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

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: LU

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

Effective date: 20211116

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

Ref country code: LI

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

Effective date: 20211130

Ref country code: CH

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

Effective date: 20211130

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

Ref country code: IE

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

Effective date: 20211116

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1374518

Country of ref document: AT

Kind code of ref document: T

Effective date: 20211116

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

Ref country code: AT

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

Effective date: 20211116

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

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20121116

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230524

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

Ref country code: NL

Payment date: 20231120

Year of fee payment: 12

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

Ref country code: GB

Payment date: 20231123

Year of fee payment: 12

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

Ref country code: TR

Payment date: 20231114

Year of fee payment: 12

Ref country code: IT

Payment date: 20231124

Year of fee payment: 12

Ref country code: FR

Payment date: 20231120

Year of fee payment: 12

Ref country code: DE

Payment date: 20231031

Year of fee payment: 12

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

Ref country code: BE

Payment date: 20231120

Year of fee payment: 12

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

Ref country code: ES

Payment date: 20240126

Year of fee payment: 12

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

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210324