WO2010106536A1 - Carburant diesel provenant d'huiles végétale et animale mélangées à des lévulinates d'alkyle - Google Patents

Carburant diesel provenant d'huiles végétale et animale mélangées à des lévulinates d'alkyle Download PDF

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Publication number
WO2010106536A1
WO2010106536A1 PCT/IL2010/000213 IL2010000213W WO2010106536A1 WO 2010106536 A1 WO2010106536 A1 WO 2010106536A1 IL 2010000213 W IL2010000213 W IL 2010000213W WO 2010106536 A1 WO2010106536 A1 WO 2010106536A1
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WO
WIPO (PCT)
Prior art keywords
fuel composition
blend
levulinate
oil
weight
Prior art date
Application number
PCT/IL2010/000213
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English (en)
Inventor
Mordehai Herskowitz
Miron Landau
Yehudit Reizner
Original Assignee
Ben-Gurion University Of The Negev Research And Development Authority
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Filing date
Publication date
Application filed by Ben-Gurion University Of The Negev Research And Development Authority filed Critical Ben-Gurion University Of The Negev Research And Development Authority
Publication of WO2010106536A1 publication Critical patent/WO2010106536A1/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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • 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
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation

Definitions

  • the present disclosure relates to the production of liquid fuels, particularly diesel fuel, by blending renewable diesel produced from vegetable and/or animal oil(s) with alkyl levulinates.
  • crude oil is in limited supply, includes a high content of aromatics, and contains sulfur and nitrogen-containing compounds that can adversely affect the environment. Accordingly, there is increasing interest in producing liquid fuels from biological raw materials for use as fuel by themselves or in mixture with the petroleum-derived fuels in use today.
  • Diesel characteristics important for potential applications can include: (i) Cetane Number, which rates the ignition quality of diesel fuels; (ii) density, normally expressed as specific gravity, which is defined as the ratio of the mass of a volume of the fuel to the mass of the same volume of water; (iii) viscosity, which measures the fluid resistance to flow; (iv) lower heating value, which is a measure of available energy in the fuel; (v) carbon residue, which correlates with the amount of carbonaceous deposits in the combustion chamber; (vi) ash, which refers to extraneous solids that reside after combustion; (vii) sulfur; (viii) lubricity, which affects the wear of pumps and injection systems; (ix) Iodine Value, which measures the number of double bonds; (x) Distillation Curve, which is characterized by the initial temperature at which the first drop of liquid leaves the condenser and subsequent temperatures at each 10% of the liquid; (xi) flash point, which is the lowest temperature at which a combustible mixture can be formed above
  • a method for improving at least one property of a fuel composition comprising deriving a fuel composition from oil selected from the group consisting of vegetable oil, animal oil, and mixtures thereof; and blending the fuel composition with one or more alkyl levulinates to provide a fuel composition blend.
  • the alkyl levulinates are selected and blended in an amount sufficient to have the fuel composition blend exhibit improvement relative to the fuel composition in at least one property.
  • a fuel composition blend comprising a fuel composition derived from oil selected from the group consisting of vegetable oil, animal oil, and mixtures thereof; and one or more alkyl levulinates.
  • the alkyl levulinates are selected and blended in an amount sufficient to have the fuel composition blend exhibit improvement relative to the fuel composition in at least one property.
  • high quality (diesel) fuels can be obtained by blending renewable diesel fuel derived from vegetable oil(s) with alkyl levulinates. More particularly, it has been surprisingly discovered that properties of a fuel composition derived from vegetable oil and/or animal oil can be improved by blending the fuel composition with alkyl levulinates.
  • a method for improving at least one property of a fuel composition comprising deriving a fuel composition from vegetable oil and/or animal oil and blending the fuel composition with alkyl levulinates to provide a fuel composition blend.
  • the alkyl levulinates are selected and blended in an amount sufficient to have the fuel composition blend exhibit improvement relative to the fuel composition in at least one property.
  • alkyl levulinate refers to functional alkyl derivative esters of levulinic acid (4-oxopentanoic acid).
  • the alkyl levulinates can include C 2-8 alkyl levulinates (e.g., ethyl levulinate, n-propyl levulinate, n-butyl levulinate, n-pentyl levulinate, 2-hexyl levulinate, 2-ethyl hexyl levulinate, heptyl levulinate, octyl levulinate, and mixtures thereof) and/or longer alkyl levulinates (e.g., decyl levulinate).
  • the alkyl levulinates are either pure butyl and higher carbon levulinates or a mixture of ethyl and higher carbon levulinates.
  • Alkyl levulinates can be prepared by a number of known methods.
  • alkyl levulinates can be produced by esterification of levulinic acid and (pure or mixtures of) aliphatic alcohols (e.g., bio-alcohols).
  • Levulinic acid can be manufactured from biomass by well-established commercial processes.
  • Ethanol and higher alcohols can also be produced from biomass by well-established commercial processes.
  • (mixtures of) higher alcohols can be produced by the Guerbet reaction from bio-ethanol.
  • Alkyl levulinates can also be produced by transesterification of ethyl levulinate with (mixtures of) higher (aliphatic) alcohols (e.g., bio-alcohols).
  • alkyl levulinates may contain several esters. As the length of the alkyl group in the alkyl levulinates increases, the miscibility of the alkyl levulinates in a fuel composition (e.g., diesel) increases. Thus, inclusion of higher alkyl levulinates (e.g., C 5-1O alkyl levulinates) in a fuel composition blend allows for a higher content of alkyl levulinates in the blend, which resultantly can provide greater improvements in one or more properties of the fuel composition.
  • a fuel composition e.g., diesel
  • alkyl levulinates for blending with a fuel composition is the CFPP of the fuel composition (e.g., diesel) blend.
  • the CFPP of the fuel composition blend should meet standards that may differ in various regions. Therefore, the alkyl levulinates (e.g., compositions and amounts of various alkyl levulinates in a mixture of alkyl levulinates) included in a fuel composition blend may be determined, among other considerations, by a required CFPP value.
  • the fuel composition can comprise a diesel fuel composition.
  • the fuel composition can be derived by hydrodeoxygenating and hydroisomerizing the oil in a single step, as described in U.S. Patent Application Publication No. 2006/0207166 Al, the content of which is hereby incorporated by reference in its entirety, which discloses a process for producing a fuel composition from vegetable and/or animal oil.
  • the fuel composition of U.S. Patent Application Publication No. 2006/0207166 Al comprises a mixture of C 14 to Qg paraffins having a ratio of iso to normal paraffins of 2 to 8 and less than 5 ppm sulfur.
  • Exemplary catalysts for the process described in U.S. Patent Application Publication No. 2006/0207166 Al are dual-functional catalysts comprising a metal component and an acidic component.
  • Exemplary metal components are platinum or palladium.
  • the acidic component comprises an acidic function in a porous solid support.
  • Exemplary acidic components include, for example, amorphous silica aluminas, fluorided alumina, ZSM-12, ZSM-21, ZSM-22, ZSM- 23, ZSM-35, ZSM-38, ZSM-48, ZSM-57, SSZ-32, ferrierite, SAPO-I l, SAPO-31, SAPO-41, MAPO-I l, MAPO-31, Y zeolite, L zeolite and Beta zeolite.
  • the catalyst is Pt/SAPO-11, specifically 1 wt % Pt/SAPO-11.
  • 2006/0207166 Al is carried out at relatively mild conditions, for example, at an LHSV in the range of 0.5-5 h "1 , for example, 0.6-3 h "1 , 0.7-1.2 h “1 , or 0.8-1.2 h "1 , at a temperature in the range of 300-450°C, for example, 350-420°C or 370-410 0 C, at a pressure of 10-60 atm, for example, 20-40 atm, and a H 2 /oil ratio of about 500-2000 NL/L, for example, 800-1200 NL/L.
  • suitable vegetable oils include soybean oil, palm oil, corn oil, sunflower oil, oils from desertic plants such as, for example, jatropha oil and balanites oil, rapeseed oil, colza oil, canola oil, tall oil, safflower oil, hempseed oil, olive oil, linseed oil, mustard oil, peanut oil, castor oil, coconut oil, or mixtures thereof.
  • the vegetable oil may be genetically modified oil, produced from transgenic crops.
  • the vegetable oil may be crude vegetable oil or refined or edible vegetable oil.
  • the vegetable oil is pretreated, for example, to separate or extract impurities from the crude vegetable oil.
  • Suitable animal oils include, for example, lard oil, tallow oil, train oil, fish oil, or mixtures thereof. Further, the vegetable and/or animal oil may be new oil, used oil, waste oil, or mixtures thereof.
  • the property that is improved can be, for example, initial boiling point, 90% boiling point, flash point, density, and/or viscosity.
  • the fuel composition blend can exhibit relative to the fuel composition an increased initial boiling point, decreased 90% boiling point, increased flash point, increased density, and/or decreased viscosity.
  • the fuel composition blend can also exhibit relative to the fuel composition an improved CFPP (i.e., a decreased CFPP).
  • the fuel composition blend can have a density of about 0.80 g/cm 3 to about 0.88 g/cm 3 , for example, about 0.83 g/cm 3 to about 0.85 g/cm 3 or 0.820 g/cm 3 to 0.845 g/cm 3 (which values correspond to EN590).
  • the fuel composition blend can comprise about 5 weight% to about 40 weight% alkyl levulinates, for example, about 20 weight% to about 40 weight% alkyl levulinates.
  • the alkyl levulinates can be, for example, ethyl levulinate, butyl levulinate, hexyl levulinate, or mixtures thereof.
  • the fuel composition blend comprises about 30 weight% to about 40 weight% alkyl levulinates, and in particular, about 0-20 weight% C 2-4 alkyl levulinates (e.g., ethyl levulinate, propyl levulinate, and/or butyl levulinate) and about 10-40 weight% C 2-10 alkyl levulinates (e.g., ethyl levulinate, propyl levulinate, butyl levulinate, pentyl levulinate, hexyl levulinate, heptyl levulinate, octyl levulinate, and/or decyl levulinate).
  • the fuel composition blend can comprise about 5 weight% ethyl levulinate, about 5 weight% butyl levulinate, and about 20 weight% hexyl levulinate.
  • the fuel composition can have at least one property that does not meet desired specifications that is improved in the fuel composition blend relative to the fuel composition.
  • a property that does not meet desired specifications can be density.
  • the desired specifications can be, for example, EN590, ASTM D975, or ASTM D6751.
  • the alkyl levulinate and its amount is selected to improve the desired property.
  • a fuel composition blend comprising a fuel composition derived from vegetable oil and/or animal oil and alkyl levulinates.
  • the alkyl levulinates are selected and blended in an amount sufficient to have the fuel composition blend exhibit improvement relative to the fuel composition in at least one property.
  • a sample of renewable diesel (“1-1") was produced from tallow oil according to the process disclosed in U.S. Patent Application Publication No. 2006/0207166 Al.
  • the production of the renewable diesel included hydrodeoxygenation and hydroisomerization of the tallow oil in a single step, carried out in a fixed-bed reactor, specifically a trickle-bed reactor operated with gas and liquid running downflow at 30 bar and 375°C.
  • a mixture of the renewable diesel produced from tallow oil with 15 weight% butyl levulinate was prepared. Butyl levulinate content was limited by the phase separation temperature.
  • Table 1 lists characteristics of the renewable diesel ("1-1") and the mixture of the renewable diesel with butyl levulinate ("IB-2").
  • the initial boiling point (“IBP") of the mixture increased, as compared to the renewable diesel, while the 90% boiling point (“BP") of the mixture decreased, as compared to the renewable diesel.
  • the cloud point which actually represents the phase separation, of the mixture increased, as compared to the renewable diesel.
  • the flash point and density (specific gravity) of the mixture increased, as compared to the renewable diesel.
  • the viscosity of the mixture decreased, as compared to the renewable diesel.
  • the higher heating value of the mixture decreased slightly, as compared to the renewable diesel, due to the presence of oxygen in butyl levulinate.
  • Example 2 Blending of renewable diesel with hexyl levulinate As the length of the alkyl group in the alkyl levulinates increases, the miscibility of the alkyl levulinates in diesel increases. Therefore, the content of hexyl levulinate in the renewable diesel was considerably higher. In particular, two mixtures, one containing 30 weight% hexyl levulinate ("IH-I") and one containing 40 weight% hexyl levulinate (“IH-2”), were tested. Results are listed in Table 2. The mixtures exhibited improvements in boiling points (increase for IBP; decrease for 10% BP, 50% BP, and 90% BP), flash point (increase), and density (increase), as compared to the renewable diesel. Negligible effects on CFPP, copper corrosion, lubricity, and viscosity were recorded. As expected, the higher heating value of the blend decreased, as compared to the renewable diesel. Table 2
  • Example 3 Blending of renewable diesel with a mixture of alkyl levulinates
  • the renewable diesel (“1-1”) was blended with a mixture of alkyl levulinates.
  • the mixture (“MX-I”) contained 5 weight% ethyl levulinate, 5 weight% butyl levulinate, 20 weight% hexyl levulinate (total of 30 weight% alkyl levulinates), and balance renewable diesel. Results of testing are listed in Table 3. Negligible effect on the CFPP and cloud point were recorded. AU other properties of the mixture improved, as compared to the renewable diesel, specifically the 90% BP and the density (specific gravity).

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

L'invention concerne un procédé pour améliorer au moins une propriété d'une composition de carburant, consistant à : dériver une composition de carburant à partir d'huile végétale et/ou d'huile animale et mélanger ladite composition de carburant avec un ou plusieurs lévulinates d'alkyle afin d'obtenir un mélange de composition de carburant. Le ou les lévulinates d'alkyle sont sélectionnés et mélangés en quantité suffisante pour obtenir un mélange de composition de carburant présentant une amélioration d'au moins une propriété de ladite composition de carburant.
PCT/IL2010/000213 2009-03-16 2010-03-11 Carburant diesel provenant d'huiles végétale et animale mélangées à des lévulinates d'alkyle WO2010106536A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US16038709P 2009-03-16 2009-03-16
US61/160,387 2009-03-16

Publications (1)

Publication Number Publication Date
WO2010106536A1 true WO2010106536A1 (fr) 2010-09-23

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Application Number Title Priority Date Filing Date
PCT/IL2010/000213 WO2010106536A1 (fr) 2009-03-16 2010-03-11 Carburant diesel provenant d'huiles végétale et animale mélangées à des lévulinates d'alkyle

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050144835A1 (en) * 2003-11-10 2005-07-07 Groves Adrian P. Fuel compositions
US20060047139A1 (en) * 2004-01-26 2006-03-02 Ayoub Paul M Process for the reactive extractive extraction of levulinic acid
US20060180786A1 (en) * 2005-02-02 2006-08-17 Richard Sapienza Method of using environmentally benign anti-icing or deicing fluids employing industrial streams comprising hydroxycarboxylic acid salts and/or other effective deicing/anti-icing agents
US20060207166A1 (en) * 2005-03-21 2006-09-21 Ben-Gurion University Of The Negev Research & Development Authority Production of diesel fuel from vegetable and animal oils

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050144835A1 (en) * 2003-11-10 2005-07-07 Groves Adrian P. Fuel compositions
US20060047139A1 (en) * 2004-01-26 2006-03-02 Ayoub Paul M Process for the reactive extractive extraction of levulinic acid
US20060180786A1 (en) * 2005-02-02 2006-08-17 Richard Sapienza Method of using environmentally benign anti-icing or deicing fluids employing industrial streams comprising hydroxycarboxylic acid salts and/or other effective deicing/anti-icing agents
US20060207166A1 (en) * 2005-03-21 2006-09-21 Ben-Gurion University Of The Negev Research & Development Authority Production of diesel fuel from vegetable and animal oils

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