WO2011014424A1 - Biodiesel et carburants mélangés au biodiesel - Google Patents

Biodiesel et carburants mélangés au biodiesel Download PDF

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WO2011014424A1
WO2011014424A1 PCT/US2010/043039 US2010043039W WO2011014424A1 WO 2011014424 A1 WO2011014424 A1 WO 2011014424A1 US 2010043039 W US2010043039 W US 2010043039W WO 2011014424 A1 WO2011014424 A1 WO 2011014424A1
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nitrate
tert
butyl
biodiesel
butylphenol
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PCT/US2010/043039
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English (en)
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Marc-Andre Poirier
Paul P. Wells
Paul Bessonette
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Exxonmobil Research And Engineering Company
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Priority to JP2012522917A priority Critical patent/JP2013501090A/ja
Priority to CA2767928A priority patent/CA2767928A1/fr
Priority to SG2012002754A priority patent/SG177658A1/en
Priority to EP10804912.3A priority patent/EP2459687A4/fr
Publication of WO2011014424A1 publication Critical patent/WO2011014424A1/fr

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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
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—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
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • 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
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—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
    • 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
    • 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
    • C10L2230/08—Inhibitors
    • C10L2230/081—Anti-oxidants

Definitions

  • the invention provides fuel compositions comprising synergistic combinations of a biodiesel or biodiesel blend, an antioxidant comprising a mixture of at least one diphenol and at least one sterically hindered phenol, and a cetane improver.
  • Biodiesel is the name for a variety of ester-based oxygenated fuels made from vegetable oils, fats, greases, or other sources of triglycerides.
  • Biodiesel is a nontoxic and biodegradable blendstock which may be blended with petroleum diesel provided relevant specifications are met. Blends of biodiesel with petroleum diesel can substantially reduce the emission levels and toxicity of diesel exhaust. Biodiesel has been designated as an alternative fuel by the United States Department of Energy and the United States Department of Transportation, and is registered with the United States Environmental
  • Biodiesel fuels typically contain unsaturated fatty acid esters that can easily oxidize in the presence of oxygen, especially if UV light, and/or trace metals are also present. The products formed from this oxidation give rise to sediment and gum formation within the fuel that can lead to corrosion and plugging of filters, pumps and fuel injectors which utilize fuel containing biodiesel.
  • the fuel compositions comprise: (1) between about 0.01% to about 1% by volume of a cetane improver; (2) either (a) a biodiesel, or (b) a biodiesel blend comprising about 2% to about 98% by volume of a biodiesel and about 2% to about 98% by volume of a petroleum distillate; and (3) an antioxidant comprising a mixture of at least one diphenol and at least one sterically hindered phenol, wherein (a) the amount of the antioxidant is (i) between about 20 milligrams per kilogram of the biodiesel or biodiesel blend to about 10,000 milligrams per kilogram of the biodiesel or biodiesel blend, or (ii) is between about 16 milligrams per liter of the biodiesel or biodiesel blend to about 8,000 milligrams per liter of the biodiesel or biodiesel blend, and (b) wherein the volumetric ratio of the diphenol(s) to the sterically hindered
  • the fuel compositions described herein facilitate a wider use of biodiesels and biodiesel blends. Further, the fuel compositions described herein should avoid the corrosion, plugging, and sediment and gum formation associated with known biodiesels and biodiesel blends.
  • FIGURE 1 and FIGURE 2 illustrate that the addition of a cetane improver to biodiesel fuels reduced their oxidation stability measured by the Rancimat test method (prEN 15751), as determined in the experiment of
  • Example 1 As described in Examples 1-4 hereinafter, the fuels tested were Fuel 1 (5% by volume of soybean methyl ester plus 95% by volume of petroleum diesel fuel), Fuel 2 (99.7% by volume of Fuel 1 + 0.3% by volume of 2- ethylhexyl nitrate), and variants of Fuel 2.
  • FIGURE 3 illustrates the oxidation-stabilizing effect of adding a diphenol and a sterically hindered phenol to biodiesel fuels containing a cetane improver, as determined in the experiment of Example 2.
  • FIGURE 4 illustrates that the presence of a diphenol and a sterically hindered phenol did not significantly affect the ignition quality of biodiesel fuels containing a cetane improver, as determined in the experiment of Example 3.
  • FIGURE 5 illustrates that a benzoquinone proved ineffective as an oxidation-stabilizing substitute for a diphenol, as determined in the experiment of Example 4.
  • Biodiesel means a composition that can be used as a fuel for diesel engines and that contains at least about 50% by weight of esters of saturated and unsaturated fatty acids, including fatty acid methyl esters (FAME's), fatty acid ethyl esters (FAEE' s), propyl esters of fatty acids, or combinations of two or more methyl, ethyl, and propyl esters.
  • FAME's fatty acid methyl esters
  • FEE's fatty acid ethyl esters
  • propyl esters of fatty acids or combinations of two or more methyl, ethyl, and propyl esters.
  • a biodiesel comprises between about 50% to about 99% by weight of methyl esters of saturated and unsaturated fatty acids, where the methyl esters of saturated and unsaturated fatty acids include C 8 -C 24 fatty acid methyl esters, where C 8 -C 24 indicates the number of carbons in the original fatty acid.
  • Biodiesels can be made by transesterification of one or more vegetable oils, animal fats, or mixtures thereof (e.g. soybean oil, rapeseed oil, palm oil, canola oil, sunflower oil, olive oil, corn oil, tallow oil, coconut oil, jatropha oil, yellow grease, animal fats, used cooking oil, and mixtures thereof) with an alcohol such as methanol or ethanol.
  • the fatty acid esters are largely unsaturated and comprise a rapeseed methyl ester, a canola methyl ester, a soybean methyl ester, a corn oil methyl ester, or a mixture thereof.
  • a 100% biodiesel (B lOO) should meet ASTM D6751 and/or EN 14214 specifications.
  • Biodiesel blends biodiesel blended with a petroleum distillate such as diesel fuel
  • Bx a petroleum distillate such as diesel fuel
  • Petroleum distillate includes naphtha or middle distillates including kerosene and diesel.
  • a non-limiting example of a “diesel fuel” or "a diesel” is composed of a mixture Of C 9 -C 24 hydrocarbons that comprise about 50% to about 95% by volume of aliphatic hydrocarbons, of which about 0% to about 50% by volume are cycloparaffins, about 0% to about 5% by volume of olefinic hydrocarbons, and about 5% to about 50% by volume of aromatic hydrocarbons, and which boil at between about 280 0 F (138°C) and 75O 0 F (399 0 C).
  • a non-limiting example of a "kerosene” comprises about 5% to about 50% by volume of an aromatic fraction, about 0% to about 50% by volume of a cycloparaffin fraction, and about 0% to about 5% by volume of an olefinic fraction, with the rest comprising aliphatic hydrocarbons.
  • An aromatics fraction can contain methyl aromatics and non-methyl alkyl aromatics.
  • Non-limiting examples of non-methyl alkyl aromatics include molecules such as,alkyl benzenes, dialkylbenzenes, alkylnaphthalenes, alkyl biphenyls, and alkyl phenanthrenes, and the like, in which one or more linear or branched alkyl groups containing two or more carbons is bonded to the aromatic ring.
  • Non-limiting examples of methyl aromatics include aromatic molecules such as methylnaphthalene, dimethylnaphthalenes, and the like.
  • a cycloparaffin fraction consists of cycloalkanes or molecules containing at least one cycloalkane ring.
  • Non-limiting examples of components of the cycloparaffin fraction include alkylcyclohexanes and alkylcyclopentanes.
  • An olefinic fraction can contain linear, branched, and cyclo-olefins.
  • Non-limiting examples of components of the olefinic fraction include dodecenes and hexadecenes.
  • a "cetane improver” includes but is not limited to 2-ethylhexyl nitrate (EHN) (e.g. HITEC® 4103, Ethyl Corp., Richmond, VA), cyclohexyl nitrate, di- tert-butyl peroxide, methyl nitrate, ethyl nitrate, n-propyl nitrate, isopropyl nitrate, allyl nitrate, n-butyl nitrate, isobutyl nitrate, sec-butyl nitrate, tert-butyl nitrate, n-amyl nitrate, isoamyl nitrate, 2-amyl nitrate, 3-amyl nitrate, tert-amyl nitrate, n-hexyl nitrate, 2-ethylhexyl nitrate, n-hept
  • a "diphenol” includes but is not limited to hydroquinone (HQ), mono and dialkylated hydroquinones having one or two C 1 -C 8 alkyl groups (e.g. tert- butylhydroquinone (TBHQ), 2-tert-butyl- 1 ,4-hydroquinone, 2,5-di-tert-butyl- 1,4-hydroquinone, methylhydroquinone (toluhydroquinone or THQ), 2,5-di-tert.- octylhydroquinone (DOH)), and mixtures thereof.
  • HQ hydroquinone
  • TBHQ tert- butylhydroquinone
  • 2-tert-butyl- 1 ,4-hydroquinone 2,5-di-tert-butyl- 1,4-hydroquinone
  • methylhydroquinone toluhydroquinone or THQ
  • a "sterically hindered phenol” includes but is not limited to mono, di, and trialkylated phenols such as 2, 6-di-tert-butylphenol, 2, 4-di-tert- butylphenol, 2, 6-di-tert-butyl-4-methylphenol (BHT), 2-tert-butylphenol, 2, 4, 6-tri-tert-butylphenol, 2, 6-di-tert-butyl-4-dimethylaminomethylphenol, and mixtures thereof.
  • BHT 2, 6-di-tert-butylphenol
  • BHT 2, 6-di-tert-butyl-4-methylphenol
  • sterically hindered phenols that can be used in the fuel compositions described herein include Ethanox® 4703 and 4733 (Albermarle Corp., Baton Rouge, LA), Westco® AO-29 (Western Reserve Chemical, Stow, OH), Baynox® (Lanxess, Leverkusen, DE), and Ionol® BF 150 and BF 200 (Oxiris Chemicals S. A.., Barcelona, ES).
  • the diphenol and sterically hindered phenol are selected, respectively, from a compound of formula (I) and a compound of formula (II):
  • fuel compositions of the invention may also include an aromatic amine antioxidant (e.g. a phenylediamine- type antioxidant) such as N, N'-di-sec-butyl-p-phenylenediamine, 4-isopropylaminodiphenylamine, phenyl- naphthyl amine, and ring-alkylated diphenylamines.
  • aromatic amine antioxidant e.g. a phenylediamine- type antioxidant
  • aromatic amine antioxidant such as N, N'-di-sec-butyl-p-phenylenediamine, 4-isopropylaminodiphenylamine, phenyl- naphthyl amine, and ring-alkylated diphenylamines.
  • Fuel compositions of the invention may also include performance additives such as cold flow additives, cloud point depressants, biocides, conductivity improvers, corrosion inhibitors, metal deactivators, and engine cleaning agents.
  • performance additives such as cold flow additives, cloud point depressants, biocides, conductivity improvers, corrosion inhibitors, metal deactivators, and engine cleaning agents.
  • such additives are present in an amount which ranges from about 0.001 to about 2.0% by weight of the fuel composition.
  • the fuel compositions comprise: (1) between about 0.01% to about 1%, in some aspects between about 0.01% to about 0.75%, in some aspects between 0.01% to about 0.5%, and in some aspects between about 0.01% to about 0.35% by volume of a cetane improver; (2) either (a) a biodiesel comprising at least about 50% by weight, in some aspects at least about 60% by weight, in some aspects at least about 70% by weight, in some aspects at least about 80% by weight, in some aspects at least about 90% by weight, in some aspects at least about 95% by weight of esters of saturated and unsaturated fatty acids, or (b) a biodiesel blend comprising about 2% to about 98% by volume of a biodiesel as described herein and about 2% to about 98% by volume of a petroleum distillate, or in some aspects about 10% to about 90% by volume of a biodiesel and about 10% to about 90% by volume of a petroleum distillate, or in some aspects about 20% to about 80% by volume
  • the fuel compositions comprise: (1) between about 0.1% to about 0.35% by volume of a cetane improver; (2) a biodiesel blend comprising (a) about 5% to about 30% by volume of a biodiesel comprising a fatty acid ester selected from the group consisting of rapeseed methyl ester, a canola methyl ester, a soybean methyl ester, a corn oil methyl ester, or a mixture thereof, and (b) about 70 to about 95% by volume of a diesel; and (3) an antioxidant comprising (a) a diphenol selected from the group consisting of tert- butylhydroquinone, 2-tert-butyl- 1 ,4-hydroquinone, 2,5-di-tert-butyl- 1 ,4- hydroquinone, methylhydroquinone, and 2,5-di-tert.-octylhydroquinone, and (b) a sterically hindere
  • the fuel compositions comprise: (1) between about 0.1% to about 0.35% by volume of a cetane improver; (2) a biodiesel blend comprising (a) about 5% to about 15% by volume of a biodiesel comprising a fatty acid ester selected from the group consisting of rapeseed methyl ester, a canola methyl ester, a soybean methyl ester, a corn oil methyl ester, or a mixture thereof, and (b) about 85 to about 95% by volume of a diesel; and (3) an antioxidant comprising (a) a diphenol selected from the group consisting of tert- butylhydroquinone, 2-tert-butyl- 1 ,4-hydroquinone, 2,5-di-tert-butyl- 1 ,4- hydroquinone, methylhydroquinone, and 2,5-di-tert.-octylhydroquinone, and (b) a sterically hindere
  • the fuel compositions comprise: (1) between about 0.1% to about 0.35% by volume of a cetane improver; (2) a biodiesel blend comprising (a) about 5% to about 15% by volume of a biodiesel comprising between about 50% to about 99% by weight of methyl, ethyl, and propyl esters of saturated and unsaturated fatty acids, and (b) about 85 to about 95% by volume of a diesel; and (3) an antioxidant comprising (a) a diphenol selected from the group consisting of tert-butylhydroquinone, 2-tert-butyl-l,4- hydroquinone, 2,5-di-tert-butyl-l,4-hydroquinone, methylhydroquinone, and 2,5-di-tert-octylhydroquinone, and (b) a sterically hindered phenol selected from the group consisting of 2, 6-di-tert-butylphenol, 2, 4-
  • the fuel compositions comprise: (1) between about 0.1% to about 0.35% by volume of 2-ethylhexyl nitrate; (2) a biodiesel blend comprising (a) about 5% to about 10% by volume of a biodiesel comprising a fatty acid ester selected from the group consisting of rapeseed methyl ester, a canola methyl ester, a soybean methyl ester, a corn oil methyl ester, or a mixture thereof, and (b) about 90% to about 95% by volume of a diesel; and (3) an antioxidant comprising (a) a diphenol selected from the group consisting of tert- butylhydroquinone, 2-tert-butyl- 1 ,4-hydroquinone, 2,5-di-tert-butyl- 1 ,4- hydroquinone, methylhydroquinone, and 2,5-di-tert.-octylhydroquinone, and (b)
  • the fuel compositions comprise: (1) between about 0.1% to about 0.35% by volume of 2-ethylhexyl nitrate; (2) a biodiesel blend comprising (a) about 5% to about 10% by volume of a biodiesel comprising a fatty acid ester selected from the group consisting of rapeseed methyl ester, a canola methyl ester, a soybean methyl ester, a corn oil methyl ester, or a mixture thereof, and (b) about 90% to about 95% by volume of a diesel; and (3) a diphenol and a sterically hindered phenol selected, respectively, from a compound of formula (I) and a compound of formula (II):
  • R] and R 3 are H or a tert-butyl group, and R 2 is H, CH 3 , a tert-butyl group or - CH 2 -N(CH 3 ) 2 ;
  • the amount of the antioxidant is between about 100 milligrams per liter biodiesel blend to about 500 milligrams per liter of the biodiesel blend, and wherein (c) the volumetric ratio of the diphenol to the sterically hindered phenol is between about 0.5: 1 to about 1.5:1.
  • the fuel compositions comprise: (1) between about 0.1% to about 0.35% by volume of 2-ethylhexyl nitrate; (2) a biodiesel comprising about a fatty acid ester selected from the group consisting of rapeseed methyl ester, a canola methyl ester, a soybean methyl ester, a corn oil methyl ester, or a mixture thereof; and (3) a diphenol and a sterically hindered phenol selected, respectively, from a compound of formula (I) and a compound of formula (II):
  • Ri and R 3 are H or a tert-butyl group, and R 2 is H, CH 3 , a tert-butyl group or - CH 2 -N(CH 3 ) 2 ;
  • the amount of the antioxidant is between about 200 milligrams per liter of the biodiesel blend to about 400 milligrams per liter of the biodiesel blend, and wherein (c) the volumetric ratio of the diphenol to the sterically hindered phenol is between about 0.9: 1 to about 1 : 1.
  • oxidation is induced by passing a stream of purified air at the rate of 10 liters/hr through the biodiesel sample (approx. 7.5 g), kept at constant temperature.
  • the vapors released during the oxidation process, together with the air, are passed into the flask containing 60 ml of water which has been demineralized or distilled and contains an electrode for measuring the
  • the electrode is connected to a measuring and recording device.
  • the end of the induction period is indicated when the conductivity begins to increase rapidly. This accelerated increase in conductivity is caused by the dissociation of volatile carboxylic acids which are produced during the oxidation process and which are absorbed in the water.
  • an oxidation curve is obtained whose point of inflection indicates the induction period; which provides the characteristic value for the oxidation stability.
  • the EN 14214 Standard for the BlOO and ASTM D7467 Standard for the B6-B20 biodiesel fuels specify a Rancimat induction period of six hours minimum.
  • a cetane improver such as 2-ethylhexyl nitrate improves the ignition quality of, and degrades the Rancimat oxidation stability of, a biodiesel blend or a biodiesel.
  • Sterically hindered phenolic antioxidants improved the oxidation stability of the biodiesel or biodiesel blend fuels, but not to the same extent as a diphenol such as tert- butylhydroquinone antioxidant.
  • a combination of a sterically hindered phenolic antioxidant with a diphenol such as tert-butylhydroquinone provided similar, and in some cases even directionally better, oxidation stability when compared to the use of only a diphenol.
  • Fuel 1 5 vol% Soybean Methyl Ester + 95 vol% petroleum diesel fuel
  • Fuel 2 99.7 vol% Fuel 1 + 0.3 vol% 2-ethylhexyl nitrate
  • Fuel 3 Fuel 2 + 400 mg/L Ethanox 4733
  • Fuel 4 Fuel 2 + 400 mg/L Ethanox 4703
  • Fuel 5 Fuel 2 + 400 mg/L 2-tert-butyl- 1 ,4-hydroquinone
  • Fuel 6 Fuel 2 + 200 mg/L Ethanox 4703 + 200mg/L 2-tert-butyl- 1, 4- hydroquinone
  • Fuel 7 Fuel 2 + 200 mg/L Ethanox 4733 + 200 mg/L 2-tert-butyl- 1 , 4- hydroquinone
  • Fuel 8 Fuel 6 calculated Rancimat stability
  • Fuel 9 Fuel 7 calculated Rancimat stability Example 3
  • Fuel 1 5 vol% Soybean Methyl Ester + 95 vol% petroleum diesel fuel
  • Fuel 2 99.7 vol% Fuel 1 + 0.3 vol% 2-ethylhexyl nitrate
  • Fuel 3 Fuel 2 + 400 mg/L Ethanox 4733
  • Fuel 4 Fuel 2 + 400 mg/L Ethanox 4703
  • Fuel 5 Fuel 2 + 400 mg/L 2-tert-butyl-l, 4-hydroquinone
  • Fuel 6 Fuel 2 + 200 mg/L Ethanox 4703 + 200mg/L 2-tert-butyl-l, 4- hydroquinone
  • Fuel 7 Fuel 2 + 200 mg/L Ethanox 4733 + 200 mg/L 2-tert-butyl-l, 4- hydroquinone
  • Fuel 2 99.7 vol% Fuel 1 + 0.3 vol% 2-ethylhexyl nitrate Fuel 3 : Fuel 2 + 400 mg/L Ethanox 4733
  • Fuel 4 Fuel 2 + 400 mg/L Ethanox 4703
  • Fuel 10 Fuel 2 + 400 mg/L 2,6-di-tert-butylbenzoquinone
  • Fuel 11 Fuel 2 + 200 mg/L Ethanox 4733 + 200 mg/L 2,6-di-tert- butylbenzoquinone
  • Fuel 12 Fuel 2 + 200 mg/L Ethanox 4703 + 200 mg/L 2,6-di-tert- butylbenzoquinone
  • Fuels 2, 3, 4, 10, 11, and 12 were comprised of Fuels 1 or 2 (Example 1).

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne des compositions de carburants comprenant des combinaisons synergiques d'un biodiesel ou d'un mélange comprenant du biodiesel, d'un antioxydant comprenant un mélange d'au moins un diphénol et d'au moins un phénol stériquement encombré, et d'un amélioreur de cétane. Les compositions de carburants décrites ici présentent une combinaison unique d'une stabilité améliorée à l'oxydation et d'une meilleure qualité d'allumage.
PCT/US2010/043039 2009-07-31 2010-07-23 Biodiesel et carburants mélangés au biodiesel WO2011014424A1 (fr)

Priority Applications (4)

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JP2012522917A JP2013501090A (ja) 2009-07-31 2010-07-23 バイオディーゼルおよびバイオディーゼルブレンド燃料
CA2767928A CA2767928A1 (fr) 2009-07-31 2010-07-23 Biodiesel et carburants melanges au biodiesel
SG2012002754A SG177658A1 (en) 2009-07-31 2010-07-23 Biodiesel and biodiesel blend fuels
EP10804912.3A EP2459687A4 (fr) 2009-07-31 2010-07-23 Biodiesel et carburants mélangés au biodiesel

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US27318109P 2009-07-31 2009-07-31
US61/273,181 2009-07-31
US12/841,526 2010-07-22
US12/841,526 US20110023351A1 (en) 2009-07-31 2010-07-22 Biodiesel and biodiesel blend fuels

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CN111534337A (zh) * 2020-05-12 2020-08-14 开封泓盈化工发展有限公司 生产高闪点非硝酸酯柴油十六烷值抗磨抗静电复合剂的工艺

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CN104919028B (zh) 2012-11-19 2017-09-22 路博润公司 用于生物柴油发动机中的偶合苯酚
US11186789B2 (en) 2017-07-18 2021-11-30 Hull Partners, Llc Biodiesel fuel mixtures
US11306266B2 (en) * 2017-07-31 2022-04-19 Hull Partners Llc Biodiesel fuel mixtures
KR102343229B1 (ko) * 2019-06-10 2021-12-27 한국기계연구원 디젤 엔진용 바이오연료 조성물
FR3125298A1 (fr) * 2021-07-19 2023-01-20 Totalenergies Marketing Services Utilisation d’une composition d’additifs pour réduire les émissions des véhicules Diesel
FR3137105A1 (fr) * 2022-06-23 2023-12-29 Veryone Carburant pour moteur à compression à base d’ammoniac contenant un additif d’amélioration de la combustion.
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CN111534337A (zh) * 2020-05-12 2020-08-14 开封泓盈化工发展有限公司 生产高闪点非硝酸酯柴油十六烷值抗磨抗静电复合剂的工艺

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CA2767928A1 (fr) 2011-02-03
EP2459687A4 (fr) 2013-10-30
EP2459687A1 (fr) 2012-06-06
JP2013501090A (ja) 2013-01-10
SG177658A1 (en) 2012-02-28

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