WO2010033201A1 - Procédé destiné à améliorer la stabilité à l’oxydation du biodiesel, telle que mesurée par le test rancimat - Google Patents

Procédé destiné à améliorer la stabilité à l’oxydation du biodiesel, telle que mesurée par le test rancimat Download PDF

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Publication number
WO2010033201A1
WO2010033201A1 PCT/US2009/005185 US2009005185W WO2010033201A1 WO 2010033201 A1 WO2010033201 A1 WO 2010033201A1 US 2009005185 W US2009005185 W US 2009005185W WO 2010033201 A1 WO2010033201 A1 WO 2010033201A1
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WO
WIPO (PCT)
Prior art keywords
fuel
biodiesel
stability
biodiesel fuel
additive
Prior art date
Application number
PCT/US2009/005185
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English (en)
Inventor
Marc-Andre Poirier
Alex S. Lang
Original Assignee
Exxonmobil Research And Engineering Company
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 Exxonmobil Research And Engineering Company filed Critical Exxonmobil Research And Engineering Company
Priority to JP2011526874A priority Critical patent/JP2012503040A/ja
Priority to CA2734958A priority patent/CA2734958A1/fr
Priority to AU2009292637A priority patent/AU2009292637A1/en
Priority to US13/061,761 priority patent/US20110146139A1/en
Priority to EP09814893.5A priority patent/EP2342311B1/fr
Publication of WO2010033201A1 publication Critical patent/WO2010033201A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • 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

Definitions

  • the present invention relates to biodiesel fuels or mixtures of biodiesel fuel and conventional diesel fuel and to the improvement of the oxidation stability of such fuels by the use of additives.
  • Biodiesel fuels which constitute the short chain alkyl esters of vegetable or animal oils or fats, while having been identified in the art as useful for combustion in diesel engines or as blending stock for mixtures with conventional diesel fuels are characterized as being less stable than conventional diesel fuels.
  • Biodiesel fuels are mixtures of short chain alkyl esters of saturated and unsaturated vegetable oils or animal oils or fats and as such contain olefinic double bonds as well as the ester moiety.
  • Such functionalities are susceptible to oxidative degradation leading to the degradation of the biodiesel and its consequential unsuitability for use due to its lack of long-term stability caused by the presence therein of acids, alcohols, aldehydes, ketones, etc.
  • WO 2008/056203 teaches stabilizer compositions for blends of petroleum and renewable fuels.
  • Mixtures of renewable fuels such as biodiesel, ethanol and biomass mixed with conventional petroleum fuel are stabilized by the addition thereto of a multifunctional additive package which is a combination of one or more additives selected from the group consisting of a free radical chain terminating agent, a peroxide decomposition agent, an acid scavenger, a photochemical stabilizer, a gum dispersant and a metal sequestering agent.
  • Peroxide decomposition agents are selected from the group containing sulfur, nitrogen and phosphorus compounds. Suitable nitrogen-containing compounds are of the general formula:
  • R, R' and R" can be alkyl linear, branched, saturated or unsaturated Ci-C 30 , aromatic, cyclic, poly alkoxy, polycyclic. Identified as a useful nitrogen containing compound is N,N-dimethylcyclohexylamine. While
  • N,N-dimethylcyclohexylamine is taught as a useful peroxide decomposition agent, in the examples it is never employed by itself but always in combination with a phenolic anti-oxidant.
  • Reference to Figure 2 of WO 2008/056203 reveals that whereas the use of the combination of 75% phenol and 25% NjN-dimethylcyclohexylamine (at a treat level of 200 mg/1) resulted in an improvement in the relative stability of the fuel as compared to using 100% phenol over all time periods tested, an increase in the amount of N,N-dimethylcyclohexylamine in the additive mixture to 50% significantly reduced the beneficial effect of the additive mixture (still at a treat level of 200 mg/1) in terms of relative stability over all time periods tested as compared to the 75% phenol/25% N,N-dimethylcyclohexylamine mixture with the most significant reduction in benefit being observed over the long term; i.e., at the six hour time period.
  • US2004/0152930 teaches stable blended diesel fuel comprising an olefinic diesel fuel blending stock containing olefins in an amount of 2 to 80 wt%, non-olefms in an amount of 20 to 98 wt% wherein the non-olefms are substantially comprised of paraffins, oxygenates in an amount of at least 0.012 wt% and sulfur in an amount of less than 1 ppm, the blend diesel being stabilized by an effective amount of a sulfur-free antioxidant.
  • An effective amount of sulfur-free antioxidant is identified as 5 to 500 ppm, preferably 8 to 200 ppm of additive.
  • the sulfur-free antioxidant is selected from the group consisting of phenols, cyclic amines and combinations thereof.
  • the phenols contain one hydroxyl group and are hindered phenols.
  • the cyclic amine antioxidants are amines of the formula:
  • A is a six-membered cycloalkyl or aryl ring
  • R 1 , R 2 , R 3 and R 4 are independently H or alkyl and X is 1 or 2.
  • An example of a sulfur-free antioxidant is given as di-methylcyclohexylamine. See also U.S. Patent 7,179,311.
  • U.S. 2008/0127550 discloses stabilized biodiesel fuel composition wherein the stabilizing agent is a combination of: i) one or more compounds selected from the group consisting of sterically-hindered phenolic anti-oxidants; and ii) one or more compounds selected from the group consisting of triazole metal deactivators.
  • U.S. 2007/0289203 discloses a stabilized biodiesel wherein the stabilizing additive is a mixture of at least one aromatic diamine and at least one sterically-hindered phenol.
  • U.S. 2007/0151143 discloses a stabilized biodiesel wherein the stabilizing additive is selected from one or more of the group consisting of the 3-arylbenzofuranones and the hindered amine light stabilizers and, optionally, one or more hindered phenolic anti-oxidants.
  • U.S. 2007/0248740 discloses an additive composition comprising 2,5-di-tert-butyl hydroquinone (BHQ), NjN'-disalicylidenepropylenediamine.
  • BHQ 2,5-di-tert-butyl hydroquinone
  • NjN'-disalicylidenepropylenediamine The additive is used to stabilize fuel containing at least 2% by weight of an oil derived from plant or animal material.
  • U.S. 2007/0113467 discloses a biodiesel fuel composition having improved oxidation stability.
  • the fuel contains at least one anti-oxidant that increases the oxidative stability of the fuel selected from the group recited in paragraphs [0006] to [0012] of said published application.
  • U.S. Patent 3,336,124 discloses stabilized distillate fuel oils and additive compositions for such fuel oils.
  • One additive composition comprises a mixture of: (a) an oil soluble dispersant terpolymer of a particular type; (b) from 0.2 to about 3 parts by weight per part of said oil soluble dispersant tripolymer of N,N-dimethylcyclohexylamine; and (c) a normally liquid inert hydrocarbon carrier solvent in an amount to constitute from about 20% to 80% by weight of the additive composition. See also GB 1,036,384.
  • the present invention relates to a method for improving the oxidation stability of biodiesel fuel(s) or mixtures or biodiesel fuel(s) and conventional diesel fuel(s) by the addition thereto of stability additive selected from the group consisting of one or a mixture of N,N-di(CrC 5 -alkyl)cyclohexylamine, preferably one or a mixture of N,N-di(Ci-C 2 -alkyl)cyclohexylamine, most preferably N,N-dimethylcyclohexylamine so as to increase the oxidation stability of said additized fuel as measured by the Rancimat Test by at least about 50%, preferably by at least about 60%, more preferably by at least about 65%, most preferably by 100% or more as compared to the oxidation stability of the fuel without the stability additive, said method comprising adding to the biodiesel fuel or mixture of biodiesel fuel and conventional diesel fuel at least 250 mg, preferably at least 500 mg, more preferably
  • Biodiesel fuels are mixtures of lower, short chain esters of mixed saturated and unsaturated straight chain fatty acids derived from vegetable and/or animal fats and oils.
  • the straight chain fatty acids are, typically, C 10 to C 26 fatty acids, preferably C 12 to C 22 fatty acids.
  • the fatty acids are made into biodiesel by transesterification using short chain alcohols; e.g., Ci to C 5 alcohols, in the presence of a catalyst such as a strong base.
  • Vegetable and/or animal oils and fats are natural triglycerides and are renewable sources of starting material.
  • Typical vegetable oils are soybean oil, rapeseed oil, corn oil, jojoba oil, safflower oil, sunflower seed oil, hemp oil, coconut oil, cottonseed oil, sunflower oil, palm oil, canola oil, peanut oil, mustard seed oil, olive oil, spent cooking oil, etc., without limitation.
  • Animal fats and oils include beef, pork, chicken fat, fish oil and oil recovered by the rendering of animal tissue.
  • the biodiesel is made by esterifying one or a mixture of such oils and fats using one or a mixture of short chain; e.g., C 1 to C 5 , alcohols, preferably methanol.
  • Transesterification is effected by the base catalyzed reaction of the fat and/or oil with the alcohol, direct acid catalyzed esterification of the oil and/or fat with the alcohol, conversion of the oil and/or fat to fatty acids and then to alkyl esters with as acid catalyst.
  • base catalyzed transesterification the oil and/or fat is reacted with a short chain (such as methanol or ethanol) alcohol in the presence of a catalyst such as sodium hydroxide or potassium hydroxide to produce glycerin and short chain alkyl esters.
  • the glycerin is separated from the product mixture and biodiesel is recovered. Any unreacted alcohol is removed by distillation. The recovered biodiesel is washed to remove residual catalyst or soap and dried.
  • the fuel is either 100% biodiesel, typically identified in the art as BlOO, or it is a mixture of biodiesel with conventional diesel fuel; i.e., X% conventional diesel fuel and Y% biodiesel which would be identified as BY; for example, 80% conventional diesel and 20% biodiesel fuel would be described as B20.
  • the biodiesel fuel has its stability against oxidation increased by at least 50%, preferably by at least 60%, more preferably by at least 65%, most preferably by 100% or more, as measured by the Rancimat Test by the addition thereto of the above-described stability additive in the amount indicated.
  • Biodiesel fuels or mixtures of biodiesel fuel and conventional fuels exhibiting oxidation stabilities of less than six hours can have their oxidation stabilities increased to an extent sufficient to meet the six hour induction time specification established in EN 14214 for biodiesel fuels as measured by the Rancimat Test (ISO 6886).
  • the biodiesel can be combined with N,N-dimethylcyclohexylamine (DMCHA) in an amount of at least 250 mg, preferably at least 500 mg, more preferably at least 1000 mg of DMCHA per liter of biodiesel fuel (B 100) or per liter of the biodiesel fuel component in the mixture of biodiesel fuel and conventional diesel fuel.
  • DMCHA N,N-dimethylcyclohexylamine
  • the determination whether the fuel when additized has its oxidation stability increased by at least 50%, preferably by at least 60%, more preferably by at least 65%, most preferably by 100% or more as compared to the fuel without the additive, or, alternatively, meets the minimum six hours induction time is made by subjecting the fuel to the Rancimat Test (ISO 6886, per EN 14112).
  • Rancimat Test samples of liquid are aged at a constant temperature (HO 0 C) while air is passed through the liquid at a rate of 10 liters/hour.
  • the exhaust airflow passes through a measuring cell filled with distilled water. The conductivity of the measuring cell is determined continuously and recorded automatically.
  • the biodiesel fuels can contain other performance additives commonly used in conventional diesel fuels such as dispersants, detergents, cetane improvers (such as 2-ethyl hexyl nitrate), demulsifiers, biocides, antifoaming agents, lubricity additives, dyes.
  • performance additives commonly used in conventional diesel fuels such as dispersants, detergents, cetane improvers (such as 2-ethyl hexyl nitrate), demulsifiers, biocides, antifoaming agents, lubricity additives, dyes.
  • the 2-ethylhexyl-3,4-epoxycyclohexane carboxylate acid scavenger was acquired from ATOFINA.
  • Fuel 1 Base Biodiesel Fuel, BlOO Canola Methyl Ester (unsaturated fatty acid methyl ester)
  • Fuel 2 Fuel 1 + 500 mg/L N,N-dimethylyclohexyamine (DMCHA)
  • Fuel 3 Fuel 1 + 1000 mg/L N,N-dimethylcyclohexylamine (DMCHA)
  • Fuel 4 Fuel 1 + 500 mg/L Additin RC 8500 acid scavenger
  • Fuel 5 Fuel 1 + 1000 mg/L Additin RC 8500 acid scavenger
  • Fuel 6 Fuel 1 + 500 mg/L 2-ethylhexyl-3,4-epoxycyclohexane carboxylate acid scavenger (EHEC)
  • Fuel 7 Fuel 1 + 1000 mg/L 2-ethylhexyl-3,4-epoxycyclohexane carboxylate acid scavenger (EHEC)

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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)

Abstract

Selon l’invention, la stabilité à l’oxydation d’un carburant biodiesel ou d’un mélange de carburant biodiesel et de carburant diesel classique est améliorée d’au moins 50 % par l’addition à un tel carburant d’au moins 250 mg de N-M (C1-C5) alkyl-cyclohexyl-amine par litre de carburant biodiesel ou par litre de composant carburant biodiesel dans le mélange de carburant biodiesel et de carburant diesel classique, par rapport à la stabilité à l’oxydation dudit carburant sans un tel additif.
PCT/US2009/005185 2008-09-17 2009-09-17 Procédé destiné à améliorer la stabilité à l’oxydation du biodiesel, telle que mesurée par le test rancimat WO2010033201A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2011526874A JP2012503040A (ja) 2008-09-17 2009-09-17 ランシマ−ト試験によって測定されるバイオディーゼルの酸化安定性の向上方法
CA2734958A CA2734958A1 (fr) 2008-09-17 2009-09-17 Procede destine a ameliorer la stabilite a l'oxydation du biodiesel, telle que mesuree par le test rancimat
AU2009292637A AU2009292637A1 (en) 2008-09-17 2009-09-17 Method for improving the oxidation stability of biodiesel as measured by the Rancimat Test
US13/061,761 US20110146139A1 (en) 2008-09-17 2009-09-17 Method for improving the oxidation stability of biodiesel as measured by the rancimat test
EP09814893.5A EP2342311B1 (fr) 2008-09-17 2009-09-17 Procédé destiné à améliorer la stabilité à l oxydation du biodiesel, telle que mesurée par le test rancimat

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US19232908P 2008-09-17 2008-09-17
US61/192,329 2008-09-17

Publications (1)

Publication Number Publication Date
WO2010033201A1 true WO2010033201A1 (fr) 2010-03-25

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Country Status (6)

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US (1) US20110146139A1 (fr)
EP (1) EP2342311B1 (fr)
JP (1) JP2012503040A (fr)
AU (1) AU2009292637A1 (fr)
CA (1) CA2734958A1 (fr)
WO (1) WO2010033201A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7563905B2 (ja) 2020-06-25 2024-10-08 三菱自動車工業株式会社 バイオディーゼル燃料の析出物溶解剤

Citations (2)

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Publication number Priority date Publication date Assignee Title
GB1036384A (en) 1964-03-24 1966-07-20 Du Pont Stabilized petroleum distillate fuels boiling in the fuel oil range and additive compositions therefor
US3640692A (en) * 1969-10-29 1972-02-08 Cities Service Oil Co Stabilized distillate hydrocarbon fuel oil compositions and additives therefor

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US3490882A (en) * 1966-08-11 1970-01-20 Du Pont Stabilized distillate fuel oils and additive compositions therefor
CA2010183A1 (fr) * 1989-03-02 1990-09-02 John G. Bostick Distillat moyen a stabilite au stockage amelioree
ES2060058T3 (es) * 1990-09-20 1994-11-16 Ethyl Petroleum Additives Ltd Composiciones de combustible hidrocarbonado y aditivos para las mismas.
US6143702A (en) * 1998-10-09 2000-11-07 Exxon Research And Engineering Company Lubricating oils of enhanced oxidation stability containing n-phenyl-naphthyl amines, or substituted derivatives of n-phenyl naphthyl amine and carbodiimide acid scavengers
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Publication number Priority date Publication date Assignee Title
GB1036384A (en) 1964-03-24 1966-07-20 Du Pont Stabilized petroleum distillate fuels boiling in the fuel oil range and additive compositions therefor
US3640692A (en) * 1969-10-29 1972-02-08 Cities Service Oil Co Stabilized distillate hydrocarbon fuel oil compositions and additives therefor

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Also Published As

Publication number Publication date
EP2342311B1 (fr) 2016-03-09
EP2342311A1 (fr) 2011-07-13
US20110146139A1 (en) 2011-06-23
CA2734958A1 (fr) 2010-03-25
EP2342311A4 (fr) 2012-04-18
JP2012503040A (ja) 2012-02-02
AU2009292637A1 (en) 2010-03-25

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