WO2010059694A1 - Biocarburant et procédé de fabrication du biocarburant - Google Patents

Biocarburant et procédé de fabrication du biocarburant Download PDF

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Publication number
WO2010059694A1
WO2010059694A1 PCT/US2009/064946 US2009064946W WO2010059694A1 WO 2010059694 A1 WO2010059694 A1 WO 2010059694A1 US 2009064946 W US2009064946 W US 2009064946W WO 2010059694 A1 WO2010059694 A1 WO 2010059694A1
Authority
WO
WIPO (PCT)
Prior art keywords
blended
oil
alcohol
alcohol composition
fatty acid
Prior art date
Application number
PCT/US2009/064946
Other languages
English (en)
Inventor
Martin Allan Morris
Original Assignee
Bio-Alternative, 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 Bio-Alternative, LLC filed Critical Bio-Alternative, LLC
Priority to BRPI0921106A priority Critical patent/BRPI0921106A2/pt
Priority to EP09828150A priority patent/EP2367913A1/fr
Publication of WO2010059694A1 publication Critical patent/WO2010059694A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present invention relates to an improved process for making bio-diesel and a blended alcohol reaction composition for use in the process.
  • Bio-diesel is the name given to a variety of ester-based oxygenated fuels made from vegetable oils, fats, greases and other sources of triglycerides.
  • Bio-diesel is a clean-burning diesel replacement fuel that can be used in compression ignition (Cl) engines and is manufactured from renewable non-petroleum-based sources, including but not limited to, organic fats and oils such as virgin vegetable oil, recycled oil, such as used fryer oil and grease trap materials, and animal fats, such as lard and beef tallow.
  • Non-limiting examples of these feedstocks include soybean oil, peanut oil, coconut oil, palm oil, canola or rapeseed oil, algae oil, jatropha oil, animal fat tallow, waste vegetable grease, and other similar sources.
  • the basic biodiesel reaction involves a transesterification process to convert triglycerides in the feed stock to methyl esters.
  • the transesterification process typically involves the reaction of a raw oil (source of triglycerides) with methanol or ethanol and an alkaline catalyst such as sodium hydroxide or potassium hydroxide. Excess methanol is typically used to ensure that the process is driven to completion.
  • the alcohol and catalyst are mixed first and then the alcohol/catalyst mixture is mixed with the raw oil and allowed to react. Once the reactants are thoroughly mixed, the reaction begins and the raw oil begins to separate into methyl ester and glycerin (otherwise known as glycerol). Because the methyl ester is less dense than the glycerin, it floats to the top of the glycerin and may be separated from the glycerin by pumping it off the top or by draining the glycerin off the bottom. A centrifuge or other separation means may also be used to separate the methyl ester from the glycerin byproduct. Thereafter, the methyl ester is purified to produce the bio-diesel product. Bio-diesel is produced in pure form (100% biodiesel or "B100"), but is typically blended with conventional diesel at low levels between about 2% (B2) and about 20%
  • B20 in the U.S. and may be blended at higher levels in other parts of the world. While B2 biodiesels fuels may be used in conventional diesel engines without modification, higher level blends above approximately B5 (and up to B100) may require special handling and fuel management as well as vehicle modifications such as the use of heaters (especially in colder climates) and different seals/gaskets that come into contact with the fuel. The level of care needed depends on a variety of factors, including, but not limited to the engine, manufacturer, climate conditions, among others.
  • Bio-diesel has been designated an alternative fuel by the U.S. Department of
  • Environmental Protection Agency as a fuel and fuel additive. It can be used in any diesel engine (when blended with conventional diesel) and is compatible with existing petroleum distribution infrastructure.
  • biodiesel has been implemented in various countries around the world. In the U.S., the specifications have been implemented through the American Society of Testing and Materials (ASTM).
  • ASTM American Society of Testing and Materials
  • the ASTM specification for diesel is ASTM D975
  • ASTM standard for biodiesel is ASTM D6751. It is noted that the standard for biodiesel is as a blendstock for blending into conventional diesel and is not meant to be a specification for B100 alone. It is noted that both No. 1 and No. 2 petroleum diesel fuel (i.e., D1 and D2) may be blended with biodiesel for various reasons, including the need for lower temperature operation.
  • the present invention relates generally to an improved method of producing biodiesel comprising the steps of: a) providing a source of triglycerides; b) mixing a blended alcohol composition with a catalyst; c) reacting the source of triglycerides with the blended alcohol composition and catalyst to form a mixture of at least one fatty acid alcohol ester and glycerin; d) separating the at least one fatty acid alcohol ester from the glycerin; and e) optionally, purifying the at least one fatty acid alcohol ester to produce a bio-fuel.
  • the present invention also relates generally to an improved blended alcohol composition for use in the process of the invention.
  • the improved blended alcohol composition typically comprises: a) about 96 to about 98% of at least one lower alcohol; b) about 1 to about 3% of a ketone; and c) about 1 to about 3% ethyl acetate.
  • the present invention involves an improved chemical process for producing a bio-fuel (biodiesel) and for an improved blended alcohol composition for use in the process.
  • the inventors have surprisingly discovered that the use of the blended alcohol composition of the invention reduces the amount of glycerin produced as a by-product in the process by approximately 50% or more. In some embodiments, it is possible to reduce the amount of glycerin produced to less than 1%.
  • the process still undergoes a transesterification reaction but can be performed at production speeds without the use of chemical reactors and at room temperature within about 10-15 minutes.
  • the process of the invention does not need any additional pressure, cavitation or ultrasonic devices that are typically needed by other reactor devices to proceed at these speeds.
  • the transesterification process of the invention can proceed quickly at room temperature and under normal (i.e., ambient) pressure.
  • the present invention relates generally to a method of producing biodiesel fuel comprising the steps of: a) providing a source of triglycerides; b) mixing a blended alcohol composition with a catalyst; c) reacting the source of triglycerides with the blended alcohol reaction composition and catalyst to form a mixture of at least one fatty acid alcohol ester and glycerin; d) separating the at least one fatty acid alcohol ester from the glycerin; and e) optionally, purifying the at least one fatty acid alcohol ester to produce a bio-fuel.
  • a batch system may typically comprise a simple mixing tank with a mixer and preferably a heater and upper and lower extraction ports.
  • a continuous system may be used which would typically comprise a closed reactor with a mixer, heating means and a centrifuge.
  • the source of triglycerides may be any of the conventionally used sources of triglycerides, including but not limited to soybean oil, peanut oil, coconut oil, palm oil, canola oil, rapeseed oil, algae oil, jatropha oil, animal fat tallow, waste vegetable oil and combinations of one or more of the foregoing.
  • the source of triglycerides comprises virgin soybean oil.
  • a purification step is not required, and in most instances, once the biodiesel reaction has occurred the biodiesel can simply be separated from the by-product.
  • this step of purifying the fatty acid alcohol ester typically comprises water washing the fatty acid alcohol ester one or more times.
  • any conventional methods of purifying the fatty acid alcohol ester known to those skilled in the art may also be used, including, but not limited to the use of Magnasol®, ion exchange, and distillation.
  • the catalyst is typically selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methylate, potassium methylate and combinations of one or more of the foregoing.
  • the catalyst comprises potassium hydroxide.
  • the step of separating the fatty acid alcohol ester from the glycerin may be accomplished by centrifuging the mixture for a period of time sufficient to separate the fatty acid alcohol ester and the glycerin.
  • Other conventional separation means may also be used as would generally be known to those skilled in the art and include, for example, settling.
  • the reaction (or transesterification) step is beneficially accomplished at a temperature within the range of about 40 and about 13O 0 F, and more preferably within the range of about 65 and about 85 0 F. However, it is most desirable to carry out the step of transesterifying the mixture at ambient temperature and pressure. At the ambient temperature and pressure conditions described herein, the reaction step typically proceeds to completion within a reaction time of about 15 to about 20 minutes. The inventors have found that if the temperature used is too high (above about 13O 0 F), then the reaction proceeds too rapidly and poorer results are achieved. Thus, it is generally preferably to select a suitable temperature and pressure so that a desired reaction rate of about 10 to 20 minutes is achieved.
  • the novel blended alcohol composition of the invention typically comprises: a) about 96 to about 98% of at least one lower alcohol; b) about 1 to about 3% of a ketone; and c) about 1 to about 3% ethyl acetate.
  • the at least one lower alcohol comprises a mixture of methanol and ethanol and in some embodiments, the mixture of methanol and ethanol comprises about 3 to about 5% methanol and about 95 to about 97% ethanol.
  • mixtures of other lower alcohols may be used in the practice of the present invention.
  • lower alcohols refer to alcohols with carbon chains (straight or branched) of less than 4 carbons.
  • a non-limiting list of lower alcohols usable in the practice of the invention includes methanol, ethanol, butanol and propyl alcohols.
  • the ketone be one of methyl isobutyl ketone and methyl ethyl ketone, and combinations thereof, other similar ketones would also be usable in the practice of the invention, including but not limited to acetone and acetoacetate.
  • the ketone is methyl isobutyl ketone.
  • the inventors have found that the use of the novel blended alcohol composition in the transesterification process of the invention (in place of the methanol or other lower alcohol used in the prior art) allows the reaction to proceed under more beneficial conditions, i.e., ambient temperature and pressure, and proceeds at a faster rate and produces a bio-diesel product with less glycerin produced as a byproduct.
  • the inventors have found that the use of the blended alcohol composition of the invention reduces by half the amount of glycerin produced in the process.
  • ethyl acetate keeps the reaction at room temperature and that the use of the ketone as a chemical mediator prevents glycerin from forming, i.e., the ketone does not allow carbon to form the necessary bonds to produce glycerin so the result is that less glycerin is produced.
  • the transesterification process proceeds as follows:
  • soybean oil was reacted with 275 milliliters of the blended alcohol composition with 14 grams of potassium hydroxide dissolved in it and stirred vigorously until the desired color change was apparent. The mixture was then allowed to sit at room temperature for approximately 10 minutes without agitation. Upon reaching the maximum cloud point, the mixture is placed in a separation container and allowed to separate into the biodiesel and the byproduct. If faster separation rates are desired, the mixture may be centrifugally separated once maximum cloud point has been reached.
  • Cloud point is significant in the U.S. because biodiesels produced from different feedstocks may perform differently in different geographic regions and climates. Cloud point is performed as part of ASTM 6751 testing to characterize the low temperature operability of diesel fuel. It defines the temperature at which a cloud or haze appears in the fuel under prescribed test conditions. The cloud point for biodiesel blends is generally higher than it is for petroleum diesel fuel.
  • a one gallon sample of this material was subjected to ASTM D6751 testing and passed.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Fats And Perfumes (AREA)

Abstract

L'invention porte sur un procédé de production de biocarburant à partir d'une source de triglycérides. La source de triglycérides est mise à réagir avec une composition d'alcool mélangé en présence d'un catalyseur pour former un mélange d'au moins un ester alcoolique d'acide gras et de glycérine. L'ester alcoolique d'acide gras est ensuite séparé de la glycérine et est purifié pour produire un biocarburant. La composition d'alcool mélangé comprend au moins un alcool inférieur, une cétone, et de l'acétate d'éthyle. L'utilisation de la composition d'alcool mélangé permet au procédé de transestérification de se dérouler dans des conditions de température ambiante et de pression ambiante en un temps de réaction relativement court.
PCT/US2009/064946 2008-11-21 2009-11-18 Biocarburant et procédé de fabrication du biocarburant WO2010059694A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
BRPI0921106A BRPI0921106A2 (pt) 2008-11-21 2009-11-18 biocombustível e processo para preparação de biocombustível
EP09828150A EP2367913A1 (fr) 2008-11-21 2009-11-18 Biocarburant et procédé de fabrication du biocarburant

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12/275,736 US8207362B2 (en) 2007-08-13 2008-11-21 Bio-fuel and process for making bio-fuel
US12/275,736 2008-11-21

Publications (1)

Publication Number Publication Date
WO2010059694A1 true WO2010059694A1 (fr) 2010-05-27

Family

ID=42198479

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2009/064946 WO2010059694A1 (fr) 2008-11-21 2009-11-18 Biocarburant et procédé de fabrication du biocarburant

Country Status (4)

Country Link
US (1) US8207362B2 (fr)
EP (1) EP2367913A1 (fr)
BR (1) BRPI0921106A2 (fr)
WO (1) WO2010059694A1 (fr)

Families Citing this family (19)

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Publication number Priority date Publication date Assignee Title
US8889932B2 (en) 2008-11-26 2014-11-18 Elevance Renewable Sciences, Inc. Methods of producing jet fuel from natural oil feedstocks through oxygen-cleaved reactions
CN102227394B (zh) * 2008-11-26 2014-09-24 埃莱文斯可更新科学公司 由天然油原料通过复分解反应生产喷气燃料的方法
US9175231B2 (en) 2009-10-12 2015-11-03 Elevance Renewable Sciences, Inc. Methods of refining natural oils and methods of producing fuel compositions
US9169447B2 (en) 2009-10-12 2015-10-27 Elevance Renewable Sciences, Inc. Methods of refining natural oils, and methods of producing fuel compositions
PL2488474T3 (pl) 2009-10-12 2017-07-31 Elevance Renewable Sciences, Inc. Sposoby rafinacji i wytwarzania paliw z surowców na bazie olejów naturalnych
US8735640B2 (en) 2009-10-12 2014-05-27 Elevance Renewable Sciences, Inc. Methods of refining and producing fuel and specialty chemicals from natural oil feedstocks
US9365487B2 (en) 2009-10-12 2016-06-14 Elevance Renewable Sciences, Inc. Methods of refining and producing dibasic esters and acids from natural oil feedstocks
US9051519B2 (en) 2009-10-12 2015-06-09 Elevance Renewable Sciences, Inc. Diene-selective hydrogenation of metathesis derived olefins and unsaturated esters
US9000246B2 (en) 2009-10-12 2015-04-07 Elevance Renewable Sciences, Inc. Methods of refining and producing dibasic esters and acids from natural oil feedstocks
US9222056B2 (en) 2009-10-12 2015-12-29 Elevance Renewable Sciences, Inc. Methods of refining natural oils, and methods of producing fuel compositions
US9382502B2 (en) 2009-10-12 2016-07-05 Elevance Renewable Sciences, Inc. Methods of refining and producing isomerized fatty acid esters and fatty acids from natural oil feedstocks
CN102311883B (zh) 2011-08-10 2013-04-24 北京清研利华石油化学技术有限公司 一种制备高纯度生物柴油的方法
US9133416B2 (en) 2011-12-22 2015-09-15 Elevance Renewable Sciences, Inc. Methods for suppressing isomerization of olefin metathesis products
US9169174B2 (en) 2011-12-22 2015-10-27 Elevance Renewable Sciences, Inc. Methods for suppressing isomerization of olefin metathesis products
US9139493B2 (en) 2011-12-22 2015-09-22 Elevance Renewable Sciences, Inc. Methods for suppressing isomerization of olefin metathesis products
US9388098B2 (en) 2012-10-09 2016-07-12 Elevance Renewable Sciences, Inc. Methods of making high-weight esters, acids, and derivatives thereof
EP2862915B1 (fr) 2013-10-18 2015-12-09 Rigas Tehniska universitate Procédé de fabrication de biodiesel
US10221387B2 (en) 2013-11-01 2019-03-05 Rayeman Elements, Inc. Integrated ethanol and biodiesel facility
US8722924B1 (en) 2013-11-01 2014-05-13 WB Technologies LLC Integrated ethanol and biodiesel facility

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US20030167681A1 (en) * 2002-01-18 2003-09-11 Industrial Management, S.A. Procedure to obtain biodiesel fuel with improved properties at low temperature
US20070056213A1 (en) * 2005-03-11 2007-03-15 French William T Renewable fuel/lubricant mixture for use in a two-stroke internal combustion engine
US20070197412A1 (en) * 2006-02-03 2007-08-23 Thomas Edward Carter Antioxidant compositions useful in biodiesel and other fatty acid and acid ester compositions
US7321052B2 (en) * 2005-03-01 2008-01-22 Board Of Trustees Of Michigan State University Process for production of a composition useful as a fuel

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AU2003224942A1 (en) * 2002-04-12 2003-10-27 Alfred Center Continuous transesterification process
WO2005093015A1 (fr) * 2004-02-24 2005-10-06 Institut Francais Du Petrole Procédé de fabrication de biocarburants ; transformation de triglycérides en au moins deux familles de biocarburants monoesters d'acides gras et éthers et/ou acétals solubles du glycérol
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Publication number Priority date Publication date Assignee Title
US20030167681A1 (en) * 2002-01-18 2003-09-11 Industrial Management, S.A. Procedure to obtain biodiesel fuel with improved properties at low temperature
US7321052B2 (en) * 2005-03-01 2008-01-22 Board Of Trustees Of Michigan State University Process for production of a composition useful as a fuel
US20070056213A1 (en) * 2005-03-11 2007-03-15 French William T Renewable fuel/lubricant mixture for use in a two-stroke internal combustion engine
US20070197412A1 (en) * 2006-02-03 2007-08-23 Thomas Edward Carter Antioxidant compositions useful in biodiesel and other fatty acid and acid ester compositions

Also Published As

Publication number Publication date
EP2367913A1 (fr) 2011-09-28
US8207362B2 (en) 2012-06-26
US20100043280A1 (en) 2010-02-25
BRPI0921106A2 (pt) 2017-03-28

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