WO2011009056A1 - Carburants obtenus à partir de bio-huiles miscibles et leur production - Google Patents

Carburants obtenus à partir de bio-huiles miscibles et leur production Download PDF

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Publication number
WO2011009056A1
WO2011009056A1 PCT/US2010/042294 US2010042294W WO2011009056A1 WO 2011009056 A1 WO2011009056 A1 WO 2011009056A1 US 2010042294 W US2010042294 W US 2010042294W WO 2011009056 A1 WO2011009056 A1 WO 2011009056A1
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WO
WIPO (PCT)
Prior art keywords
oil
bio
fuel
fluid
mixture
Prior art date
Application number
PCT/US2010/042294
Other languages
English (en)
Inventor
Christopher Churchill
William Kolker
Original Assignee
Tolero Energy, Llc
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 Tolero Energy, Llc filed Critical Tolero Energy, Llc
Publication of WO2011009056A1 publication Critical patent/WO2011009056A1/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
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/001—Purifying combustible gases containing carbon monoxide working-up the condensates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials

Definitions

  • bio-oil derived from the pyrolysis of biomass that may be miscible in petroleum diesel and distillates.
  • a pyrolysis system is used to create bio-oil products after biomass conversion in a condensation process.
  • Biodiesel is used and defined as a mono alkyl ester of fatty acid.
  • a bio-oil/biodiesel mixture is then treated (fractionated and dewatered) prior to being mixed with petroleum-based diesel fuel to produce a miscible, multi-component diesel fuel.
  • the high acidity of the bio-oil component that is mixed with the biodiesel renders compliance with biodiesel test methods very problematic if not improbable.
  • High acidity e.g., low pH
  • ASTM 6751 oxidative reactivity measured by ASTM 6751
  • the high acidity of bio-oil provided by WO 2008/066950 means the fuel that is formed must be tested under ASTM 6751.
  • Fuel that is formed by WO 2008/066950 is not suitable for metal components (e.g., engines, engine gaskets) because it is excessively corrosive to metal components.
  • Biodiesel is considerably more expensive than petroleum diesel and miscible bio-oil. Biodiesel is also not as readily available as petroleum diesel in locations that bio-oil is being produced. The use of biodiesel as a condensate to render bio-oil miscible is not only problematic, it may be economically unfeasible.
  • An improved miscible bio-oil fuel described herein includes a first fluid as an agent when obtaining the bio- oil.
  • the first fluid may include petroleum diesel (petrodiesel), a petroleum product and/or its distillate and may also include but is not limited to one or more of No. 2 fuel oil, No. 4 fuel oil, No. 6 fuel oil, kerosene, jet fuel and the like as well as one or more of algal bio fuel, ethanol (produced from cellulose or other means), non-ester renewable diesel (produced from cellulose or other means), butanol, biobutanol, oils from plants such as palm oil, jatropha oil, and the like, including plants such as switchgrass and the like.
  • the ratio of first fluid to bio-oil in a fuel mixture may range from 95:05 to 05:95.
  • the improved miscible bio-oil fuel described herein may not be highly acidic.
  • improved miscible bio-oil fuels described herein will comply with ASTM D975 (or various other tests required for use or for application of the improved fuel).
  • a fuel described herein, such as one complying with ASTM D975 does not contain biodiesel; thus, testing under ASTM 6751 is not necessary or required.
  • an improved miscible bio-oil fuel comprising a mixture of bio-oil, a first fluid and optionally a second fluid, wherein the mixture is formed after the first fluid is provided as a quenching agent when obtaining a bio-oil vapor via biomass pyro lysis.
  • an improved miscible bio-oil fuel comprising a mixture of bio-oil, a first fluid and optionally a second fluid, wherein the mixture obtained with the use of the first fluid has a final ratio of first fluid to bio-oil from 95:05 to 05:95.
  • an improved miscible bio-oil fuel comprising a mixture of bio-oil, a first fluid and optionally a second fluid, wherein the mixture obtained with use of the first fluid is filtered using an acid esterification reaction that raises pH of the mixture and provides oxidative stability.
  • One or more embodiments further include an improved miscible bio-oil fuel comprising a bio-oil, a first fluid and optionally a second fluid, wherein diesel fuel is less than about 5% by total volume.
  • Additional embodiments include an improved miscible bio-oil fuel wherein the fuel is in compliance with ASTM D975 or an equivalent test for use of the improved fuel.
  • Still further embodiments include an improved miscible bio-oil fuel wherein the fuel does not contain biodiesel.
  • Yet further embodiments include an improved miscible bio-oil fuel wherein the fuel does not require testing under ASTM 6751.
  • a first fluid is heated to an elevated temperature, such as about 60 degrees C or greater and used as a condensate for bio-oil vapors.
  • Methanol or a chemical component of similar activity and/or structure is a downstream by-product of biomass pyrolysis. As described herein, this downstream by-product may be added as a second fluid to the first fluid (at an amount generally up to about 5% mass weight; however, in some forms the amount may be greater than 5%).
  • the addition of the second fluid may occur prior to use of the first fluid as the bio-oil vapor condensate or may occur as a separate step, e.g., via addition as a spray at the time of vapor condensation, and provided as a co-condensate with the first fluid.
  • the resultant mixture will include a first fluid and bio-oil and optionally a downstream by-product of biomass pyrolysis, which is a second fluid such as methanol.
  • the first fluid may include petrodiesel, a petroleum product and/or its distillate and may also include but is not limited to one or more of No. 2 fuel oil, No. 4 fuel oil, No. 6 fuel oil, kerosene, jet fuel and the like as well as one or more of algal bio fuel, ethanol (produced from cellulose or other means), non-ester renewable diesel (produced from cellulose or other means), butanol, biobutanol, oils from plants such as palm oil, jatropha oil, and the like, including plants such as switchgrass and the like.
  • alkanes and aromatic hydrocarbons are heated to an elevated temperature, such as about 60 degrees C or greater and used as a condensate for bio-oil vapors.
  • Methanol or a chemical component of similar activity and/or structure is a downstream by-product of biomass pyrolysis.
  • This downstream by-product may be added in one or more embodiments to the petroleum diesel (at an amount generally up to about 5% mass weight). The addition may occur prior to petroleum diesel use as the bio-oil vapor condensate or may occur as a separate step, e.g., via addition as a spray at the time of vapor condensation, and provided as a co-condensate with the petroleum diesel.
  • the resultant mixture will include petrodiesel and bio-oil and optionally a downstream by-product of biomass pyrolysis, such as methanol.
  • the ratio of the first fluid to bio-oil in the fuel ranges from 95:05 to 05:95.
  • the mixing ratio of the first fluid to bio-oil is generally provided at a ratio from about 95:05 or from about 90:10 or from about 80:20 or from about 70:30 or from about 60:40 or from about 40:60 or from about 30:70 or from about 20:80 or from about 10:90 or from about 05:95.
  • Such mixing ratios may be met by taking advantage of the condensate reaction and quenching properties of the first fluid when the first fluid is used as the condensate for the bio-oil vapor.
  • the ratio of bio-oil may be increased as the temperature of the first fluid is raised, generally in a range from about 20 degrees Centigrade (C) to about 140 degrees C.
  • the first fluid Prior to exposure to the bio-oil vapor, the first fluid is heated to a preferred temperature in an inert vessel, where is can be stored until use.
  • the heat for the temperature gain may be obtained from the synthesis gas (syngas) produced by the pyrolysis reaction or by natural gas or by electricity.
  • the temperature is controlled by a thermostat that controls the amount of heat directed to the heating vessel containing the first fluid.
  • a bio-oil/first fluid mixture After a bio-oil/first fluid mixture is obtained, it is generally cooled or kept at a temperature that is at or about 120 to 140 degrees C. In addition or as an alternative, the mixture may then be dewatered. Some improved fuel mixtures may not require further processing. These products may be stored in one or more storage containers until use. Some forms may be stored in one or more storage containers until further processing. As an alternative, other improved fuel mixtures will be further processed before storage and/or use, such as those useful as transportation fuels. Further processing may include one or more steps to modify pH of the mixture. In addition or as an alternative, the improved fuel mixture may undergo filtering. In addition or as an alternative, the described mixture, following dewatering and filtering, is passed through a filter encasing.
  • An example of means for filtering as used herein is a polymer based catalyst and ion exchange resin, such as those prepared of functionalized styrene components, such as a divinylbenzene copolymer.
  • a polymer based catalyst and ion exchange resin such as those prepared of functionalized styrene components, such as a divinylbenzene copolymer.
  • Many standard grade resins or beads for alkylation reactions may be suitable, such as, for example, AmberlystTM 15 or AmberlystTM BD20 beads (AmberlystTM is a trademark of Rohm and Haas Company).
  • Catalytic filtration may be run online as the mixture is formed.
  • Suitable polymers beads provide a catalytic effect for acid esterification which, in addition to some second fluids (that improves stability and cetane number of a resulting mixture, such as methanol), raises the pH of the mixture and, therefore, provides oxidative stability.
  • a filtered mixture may be stored in one or more storage containers prior to further processing, shipping or use. After filtering, a filtered mixture may be tested for compliance with ASTM D975 or other suitable test for use.
  • ASTM D975 or other suitable test for use.
  • filtered mixtures provided herein may comprises about 5% or less diesel fuel by total volume. Accordingly, said fuels as described herein do not have a requirement for further labeling by the Federal Trade Commission as would be required for alternative fuels, such as transportation fuels having greater than 5% or less diesel fuel or other alternative fuel in the mixture.

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

Abstract

Cette invention concerne des carburants améliorés obtenus à partir de bio-huiles miscibles contenant un carburant à base de pétrole ou au moins un premier fluide utilisé comme agent au moment de l’obtention d’une bio-huile. Le rapport premier fluide sur bio-huile en tant que mélange dans le carburant est compris entre 95:05 et 05:95. Les carburants améliorés obtenus à partir de bio-huiles miscibles ne sont généralement pas très acides. Le procédé de production desdits carburants améliorés consiste à fournir un premier fluide comme agent d’extinction au moment de l’obtention d’une vapeur de bio-huile lors de la pyrolyse de biomasse. Les carburants améliorés obtenus à partir de bio-huiles miscibles comprennent un mélange qui peut encore être traité et/ou filtré avant stockage ou utilisation. Les carburants améliorés obtenus à partir de bio-huiles miscibles peuvent ainsi, sous certaines formes, subir une estérification acide qui augmente le pH du mélange et assure une résistance à l’oxydation. D’autres procédés visant à augmenter le pH du mélange et/ou à assurer une résistance à l’oxydation conviennent également. Sous une ou plusieurs formes, les carburants améliorés obtenus à partir de bio-huiles miscibles décrits satisfont au moins à la norme ASTM D975 et/ou à d’autres tests comparables. Les carburants de l’invention ne contiennent pas de biocarburant ou en une quantité nécessitant des analyses, ce qui élimine l’obligation ou la nécessité des tests ASTM 6751.
PCT/US2010/042294 2009-07-16 2010-07-16 Carburants obtenus à partir de bio-huiles miscibles et leur production WO2011009056A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US22604209P 2009-07-16 2009-07-16
US61/226,042 2009-07-16
US24346109P 2009-09-17 2009-09-17
US61/243,461 2009-09-17

Publications (1)

Publication Number Publication Date
WO2011009056A1 true WO2011009056A1 (fr) 2011-01-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130014431A1 (en) * 2011-07-11 2013-01-17 Phillips 66 Company Advanced, biomass-derived, low-sulfur bunker fuels

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2678332A (en) * 1949-12-23 1954-05-11 Standard Oil Dev Co Esterification of olefins using ion exchange resins catalysts
US20050112735A1 (en) * 2003-10-02 2005-05-26 Zappi Mark E. Production of biodiesel and other valuable chemicals from wastewater treatment plant sludges
US20070261296A1 (en) * 2006-05-15 2007-11-15 Thomas Adams Miscible, multi-component, diesel fuels and methods of bio-oil transformation
US20090227766A1 (en) * 2006-08-16 2009-09-10 Aston University Biomass pyrolysis

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2678332A (en) * 1949-12-23 1954-05-11 Standard Oil Dev Co Esterification of olefins using ion exchange resins catalysts
US20050112735A1 (en) * 2003-10-02 2005-05-26 Zappi Mark E. Production of biodiesel and other valuable chemicals from wastewater treatment plant sludges
US20070261296A1 (en) * 2006-05-15 2007-11-15 Thomas Adams Miscible, multi-component, diesel fuels and methods of bio-oil transformation
US20090227766A1 (en) * 2006-08-16 2009-09-10 Aston University Biomass pyrolysis

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130014431A1 (en) * 2011-07-11 2013-01-17 Phillips 66 Company Advanced, biomass-derived, low-sulfur bunker fuels

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