EP2118250A1 - Fabrication de biodiesel - Google Patents

Fabrication de biodiesel

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Publication number
EP2118250A1
EP2118250A1 EP08700408A EP08700408A EP2118250A1 EP 2118250 A1 EP2118250 A1 EP 2118250A1 EP 08700408 A EP08700408 A EP 08700408A EP 08700408 A EP08700408 A EP 08700408A EP 2118250 A1 EP2118250 A1 EP 2118250A1
Authority
EP
European Patent Office
Prior art keywords
process according
fatty acid
lipase
ester mixture
mixture
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP08700408A
Other languages
German (de)
English (en)
Inventor
Walter Oschmanns
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalriada Meat Pty Ltd
Original Assignee
Dalriada Meat Pty Ltd
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
Priority claimed from AU2007900488A external-priority patent/AU2007900488A0/en
Application filed by Dalriada Meat Pty Ltd filed Critical Dalriada Meat Pty Ltd
Publication of EP2118250A1 publication Critical patent/EP2118250A1/fr
Withdrawn legal-status Critical Current

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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
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/62—Carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • 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
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • 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
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides
    • C12P7/6458—Glycerides by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/649—Biodiesel, i.e. fatty acid alkyl esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to processes for the production of alkyl fatty acid ester mixtures that are suitable for use as fuels, such as biodiesel, fuel additives and lubricants.
  • the present invention also relates to fuels, such as biodiesel, produced using the processes, and to systems for producing the fuels.
  • Biofuels are an alternative to fossil fuels that do not have the same negative environmental impacts as fossil fuels because they are derived from atmospheric carbon dioxide, and thus do not increase the net amount of carbon dioxide in the atmosphere. Furthermore, the use of biofuels may not require substantive changes to existing infrastructure and machinery as may be required form some other alternative energy sources.
  • Biodiesel is a biodegradable transportation fuel for use in diesel engines that is produced from plant- or animal-derived oils or fats. Biodiesel is used as a component of diesel fuel or as a replacement for diesel fuel. Biodiesel can be readily used in diesel-engine vehicles, which distinguishes biodiesel from the straight vegetable oils (SVO) or waste vegetable oils (WVO) used as fuels in some modified diesel vehicles. Biodiesel is biodegradable and non-toxic, and has significantly fewer emissions than petroleum-based diesel when burned and, therefore, its use can result in substantial environmental benefits.
  • SVO straight vegetable oils
  • WVO waste vegetable oils
  • Biodiesel manufactured from animal-derived fats show greater lubricity indexes than mineral- or plant-derived diesel/biodiesel fuels or mixtures, having a significant influence on engine maintenance by reducing engine component wear (for example see “Diesel Fuel Lubricity Reviewed", Paul Lacey, Sowthwest Research Institute, Steve Howell, MARC-IV Consulting, Inc., SAE paper 982567, International Fall Fuels and Lubricants Congress and Exposition, Oct. 19-22, 1998, San Francisco, California.)
  • biodiesel manufactured from animal-derived fats and high saturated plant fats have Cetane Index levels in excess of the ASTM D6751-07B Biodiesel
  • Biodiesel as an alternative to petroleum diesel is widely welcomed by environmental groups and the community.
  • Biodiesel is Europe's dominant renewable fuel and, as part of a range of measures to reduce greenhouse gas emissions, the European Union is encouraging the use of biofuels.
  • the 2003 EU Biofuels Directive requires 5.75% of the energy for transport to come from renewable sources by the end of 2010, rising to 20% by 2020.
  • Biodiesel is comprised of a mix of mono-alkyl esters of long chain fatty acids, and is typically produced by transesterification of vegetable oil or animal fat with methanol using acid or basic catalysts.
  • International patent application WO03/022961 describes a method for producing biofuel from waste oil or oil byproducts by transeterification with methanol in the presence of sulfuric acid.
  • International patent application WO2006/128881 describes a method for producing biodiesel from rapeseed oil or sunflower oil by transesterification with methanol in the presence of sodium hydroxide.
  • biodiesel can be produced from vegetable oils by an enzyme ⁇ Candida cylindracea) catalysed transesterification reaction (for example see published United States patent application 2005/0084941 ).
  • biodiesel Whilst the integration of biodiesel as a transport fuel has generally been successful, there remain some problems with its use. For example, one of the physical properties of biodiesel that can lead to problems in use is the temperature at which the fuel starts to gel (the 'gel temperature'). The viscosity of biodiesel increases as it is cooled and the solution eventually crystallizes. Eventually, the crystals formed become large enough to block the pores of a fuel filter.
  • the gel temperature of pure biodiesel varies depending on the glyceride composition from which it is formed and, therefore, the feedstock oil used to produce the biodiesel. Generally, the higher the saturated fatty acid content of the glyceride composition, the higher the gel temperature of the biodiesel formed from that material. For example, biodiesel produced from tallow, palm oil or coconut oil using the prior art methods tends to gel at around +15 to 16 0 C. Many of these biodiesel fuels also have poor long term stability.
  • the present invention provides a process for producing alkyl fatty acid esters suitable for use as a fuel and/or lubricant, the process including treating a feedstock containing glycerides and/or free fatty acids with a lipase, a lower alkyl alcohol and an acid catalyst under conditions to produce said alkyl fatty acid esters.
  • the feedstock containing glycerides and/or free fatty acids may be initially treated with the lipase in the presence of the lower alkyl alcohol to produce a first alkyl fatty acid ester mixture which is subsequently reacted with the lower alkyl alcohol in the presence of the acid catalyst to produce a second alkyl fatty acid ester mixture which is suitable for use as a fuel and/or lubricant.
  • the present invention also provides an alkyl fatty acid ester mixture prepared according to the process of the invention.
  • the present invention further provides a biodiesel fuel prepared according to the process of the invention.
  • the present invention also provides a system for use in the process for producing alkyl fatty acid esters suitable for use as a fuel and/or lubricant according to the invention.
  • the feedstock containing glycerides and/or free fatty acids may be an animal fat or plant oil. Indeed, the process of the present invention is particularly suitable for producing biodiesel from beef tallow.
  • the lipase may be a latex lipase and/or a plant lipase from a high lipid content grain, legume or seed.
  • the latex lipase from the papaya plant is suitable in combination with a plant lipase from rice bran.
  • the active latex lipase may be a papain lipase, such as Carica papaya latex lipase, and the plant lipase may be rice bran lipase.
  • the latex lipase and/or the plant lipase may not be a single lipase and may indeed be a mixture of lipases.
  • the active lipases may be partially or wholly purified and used in the process of the present invention. Latex lipases and plant lipases from a number of other plant species may also be used in the process of the present invention.
  • the lipase may also be a suitable lipase of microbial origin.
  • the lipase may display some selectivity for smaller chain length fatty acids in the feedstock.
  • the lipase may also catalyse the transesterification of the naturally occurring glycerides in the plant oil or animal fat.
  • the effect of the acid catalyst is to further assist in the transesterification reaction.
  • the effect of the lipase and acid catalyst is to provide a biodiesel fuel product that is stable and which has a lower gel temperature than an equivalent product that is formed without the use of the lipase and acid catalyst combination.
  • the lipase may be immobilized on a substrate.
  • the latex lipase may be immobilised on a substrate formed from a saccharide and lignite.
  • the substrate is a pyrolised mixture of a saccharide and an acid precipitate of an alkaline lignite extract.
  • the lower alkyl alcohol may be selected from one or more of the group consisting of: methanol, ethanol, n-propanol, i-propranol, n-butanol, s-butanol, and t-butanol.
  • the lower alkyl alcohol is ethanol.
  • the acid catalyst may be a mineral acid, such as sulphuric acid.
  • the reaction of the first alkyl fatty acid ester mixture with the lower alkyl alcohol and the acid catalyst may be carried out under continuous reactive distillation conditions whereby any unreacted lower alkyl alcohol that is distilled from the reaction is returned to the reaction mixture and the second alkyl fatty acid ester mixture is distilled from the reaction mixture.
  • the distilled second alkyl fatty acid ester mixture may be treated, such as by gravity separation, to remove unreacted glycerine and soap.
  • the purified second alkyl fatty acid ester mixture thus obtained may be used as a biofuel.
  • the rice bran oil ester mixture may be prepared by reacting rice bran oil with a lower alkyl alcohol in the presence of methane sulphonic acid.
  • the lower alkyl alcohol may be n-butanol.
  • the n-butanol may be formed by enzymatic hydrolysis of the glycerine and soap mixture that is separated from the distilled second alkyl fatty acid mixture.
  • Figure 1 is a flow diagram showing details of a process for producing biodiesel in accordance with an embodiment of the present invention.
  • Figure 2(a) is a first part of a flow diagram showing details of an early part of a process for producing biodiesel in accordance with an embodiment of the present invention.
  • the present invention provides a process for producing alkyl fatty acid esters suitable for use as a fuel and/or lubricant.
  • the process is particularly useful for the production of high quality biodiesel from relatively low grade feedstocks.
  • the feedstock 12 containing glycerides and/or free fatty acids is treated with the lipase 14, the lower alkyl alcohol 16 and the acid catalyst 18 sequentially.
  • the feedstock 12 is reacted in a first step with the lipase 14 in the presence of the lower alkyl alcohol 16 to produce a first alkyl fatty acid ester mixture 20 which is then reacted with the lower alkyl alcohol 16 in the presence of the acid catalyst 18 to produce a second alkyl fatty acid ester mixture 46.
  • Glyceride containing plant oils or animal fats are particularly suitable as the feedstock 12.
  • the term "glyceride containing plant oil or animal fat” means any oil or fat product of plant or animal origin that contains esters formed from glycerol and fatty acids (i.e. glycerides).
  • Glycerol has three hydroxyl functional groups which can be esterified with one, two or three fatty acids to form monoglycerides, diglycerides, and triglycerides, respectively.
  • Plant oils and animal fats contain mostly triglycerides, although they typically also contain some monoglycerides and diglycerides.
  • the glyceride containing plant oil or animal fat may be selected from the group consisting of: animal tallow, vegetable oils, used cooking oils and fats, seeds, seed residue feedstocks, and grease trap oils.
  • Animal fats are fats obtained from animal sources. Suitable animal fats that may be used in the production of biodiesel include: tallow (beef fat), lard (pork fat), schmaltz (chicken fat), blubber, cod liver oil, yellow grease, and the by-products of the production of omega-3 fatty acids from fish oil. For example, we have found that the process of the present invention is particularly suitable for converting tallow to biodiesel fuel.
  • Suitable vegetable oils that may be used in the production of biodiesel include: rapeseed oil, soybean oil, palm oil, mustard oil, castor oil, coconut oil (copra oil), corn oil, cottonseed oil, false flax oil, hemp oil, peanut oil, radish oil, ramtil oil, rice bran oil, safflower oil, sunflower oil, tung oil, algae oil, copaiba oil, honge oil, jatropha oil, jojoba oil, milk bush oil, petroleum nut oil, walnut oil, sunflower oil, dammar oil, linseed oil, poppyseed oil, stillingia oil, vernonia oil, amur cork tree fruit oil, apple seed oil, balanos oil, bladderpod oil, brucea javanica oil, burdock oil (bur oil), candlenut oil (kukui nut oil), carrot seed oil, chaulmoogra oil, crambe oil, cuphea oil, lemon oil, orange oil, mango oil, mowrah butter, neem oil
  • the lower alkyl alcohol 16 may be a CrC 6 alcohol.
  • the lower alkyl alcohol 16 is selected from one or more of the group consisting of: methanol, ethanol, n-propanol, i-propranol, n-butanol, s-butanol, and t-butanol.
  • Methanol is an alcohol that is commonly used in biodiesel production but we have found ethanol to be particularly suitable for use in the process of the present invention.
  • the ratio of lower alkyl alcohol 16 to glyceride containing plant oils or animal fats 12 in the combined stream 28 is about 1 :1 mol ratio.
  • a feedstock supply stream 22 of the feedstock 12 containing glycerides and/or free fatty acids is fed through a flow control device 24 and is combined with a regulated stream 26 of the lower alkyl alcohol 16, which is fed from an injection pump.
  • the combined stream 28 is mixed via a static mixer 30.
  • the combined stream 28 containing lower alkyl alcohol 16 and plant oil or animal fat 12 is reacted in the presence of the lipase 14 in a suitable reaction vessel 32.
  • the reaction vessel 32 may be temperature controlled.
  • the lipase 14 may be a latex lipase and/or a plant lipase from a high lipid content grain, legume or seed.
  • the lipase 14 is a combination of a latex lipase and a plant lipase from a high lipid content grain, legume or seed.
  • lipase means an enzyme that catalyzes the hydrolysis of triglycerides.
  • latex lipase means a lipase found naturally in the latex of a plant. Many plant species have a latex that contains a lipase.
  • the latex lipase may be used as a crude mixture, a semi- purified mixture, or the lipase maybe purified.
  • the latex can be collected from plants using standard methods, such as tapping the fruits of the plant and collecting the exudate latex.
  • the latex may be frozen for storage and/or it may be freeze dried to obtain a crude solid latex lipase preparation suitable for use.
  • the latex lipase may be purified using known protein purification techniques, such as chromatography.
  • the latex lipase from the papaya plant is used.
  • Latex from papaya is used in the food and beverage industries in the form of a protease preparation, papain.
  • Papain EC 3.4.22.2
  • papaya latex (CAS Number: 9001-73-4) is commercially available in crude form or in a lypophylised form from Sigma-Aldrich (for example under Catolog No. P4762).
  • the active latex lipase may be a papain lipase, such as Carica papaya latex lipase.
  • plant lipase from a high lipid content grain, legume or seed means a lipase found naturally in any grain, legume or seed having a relatively high lipid content.
  • grains, legumes or seeds include, without limitation, castor beans, rice bran, wheat bran, oat bran, rye, oily legumes, and oily seeds (such as canola).
  • the rice bran lipase may be used in the form of ground rice bran, or as a semi-purified or purified preparation. Methods for the extraction of lipases from rice bran are known (for example see Prabhu, A.V. et al., Biotechnol Prog. 1999; 15(6): 1083-9).
  • the lipase used may not be a single or homogenous lipase and may indeed be a mixture of different lipases.
  • the lipase may also contain some microbial lipases.
  • the active lipases may be partially or wholly purified and used in the process of the present invention.
  • the lipase 14 may be immobilised on a substrate.
  • An important factor for the economic efficiency of an enzymatic process is a suitable method for the immobilisation of the enzyme in order to allow ready recovery and multiple use of the enzyme as well as to achieve, if possible, an increase of its stability under the reaction conditions.
  • immobilisation of lipases see, for example F. X. Malcata et al., J. Am. Oil Chem. Soc. 1990, 67, 890-910.
  • the lipase 14 is introduced into the combined stream 28 via a static mixer 34 and fed into the reaction vessel 32.
  • the ratio of lipase to glycerol ester may be about 1 :10 w/w to about 1 :30 w/w.
  • the reactants are continuously mixed and the reaction is carried out at a temperature of from about 30 0 C to about 70 0 C.
  • the reaction may be carried out for a time period of from about 30 minutes to about 90 minutes.
  • the first alkyl fatty acid ester mixture 20 is pumped from the reaction vessel 32 through a flow control valve 38.
  • the first alkyl fatty acid ester mixture 20 may be separated from solid material, such as immobilised lipase 14. Separation of the first alkyl fatty acid ester mixture 20 from immobilised lipase 14 and/or other solid material may be accomplished using any suitable technique, including (but not limited to) mechanical separation, filtration, gravity separation, centrifugation, etc. In one embodiment of the invention the separation is achieved by centrifugation.
  • the first alkyl fatty acid ester mixture 20 may be pumped from the reaction vessel 32 through a flow control valve 38 to a centrifuge 40.
  • the purified first alkyl fatty acid ester mixture 20 may be drawn from the centrifuge in the usual manner.
  • the centrifuge reject 41 may be pumped to a stripping tank 43, where the immobilized lipases may be extracted and re-cycled back to the reaction vessel 32.
  • the purified first alkyl fatty acid ester mixture 20 that is obtained after centrifugation is then reacted with the lower alkyl alcohol 16 in the presence of the acid 18 to form a second alkyl fatty acid ester mixture 46.
  • the lower alkyl alcohol 16 may be any of the alcohols discussed previously herein and in one embodiment it is ethanol.
  • the acid catalyst 18 may be any suitable mineral acid, such as hydrochloric acid, sulphuric acid, etc. In one embodiment of the invention the mineral acid is sulphuric acid.
  • the reaction of the purified first alkyl fatty acid ester mixture 20 that is obtained after centrifugation with the lower alkyl alcohol 16 in the presence of a mineral acid 18 may be carried out under suitable conditions.
  • the lower alkyl alcohol and the mineral acid may be mixed in a ratio of about 1.5% mineral acid w/w of glycerol ester, in volume of lower alkyl alcohol that is calculated at a 12:1 molar ratio of the glycerol ester.
  • the reaction will require heating.
  • the reaction is carried out under reactive distillation conditions, such as continuous reactive distillation conditions.
  • the purified alkyl fatty acid ester mixture 20, lower alkyl alcohol 16, and the mineral acid 18 are fed through a heated static mixer 48 into a reactive distillation tower 50.
  • the heated static mixer 50 may be at a temperature of about 50 0 C to about 70 0 C. In one embodiment of the invention the heated static mixer is at a temperature of about 60°C.
  • Continuous reactive distillation is carried out in a tower and reboiler arrangement 50 with the reacting product flowing across a plate system via downcomers to the reboiler.
  • a plate system comprising plates formed from expanded mesh is particularly effective.
  • the expanded mesh maybe stainless steel mesh, zirconium coated steel mesh or nickel type steel mesh. Using this system we have been able to achieve 97% conversion.
  • the reaction is carried out a temperature of about 110 0 C to about 180 0 C. In one embodiment of the invention the reaction is carried out a temperature of about 125°C to about 165°C.
  • Unreacted lower alkyl alcohol is vaporised off and flows up and is condensed and recycled back into a heated static mixer 48 inflow. In this way unreacted lower alkyl alcohol that is distilled from the reaction is returned to the reaction mixture.
  • the second alkyl fatty acid ester mixture 46 is distilled from the reaction mixture.
  • the lipase 14 is a combination of a latex lipase 14a in combination with a plant lipase from a high lipid content grain, legume or seed 14b.
  • a latex lipase 14a from the papaya plant in combination of a plant lipase 14b from rice bran is effective.
  • the latex lipase 14a may be immobilised on a substrate.
  • a substrate formed from a saccharide and lignite is particularly suitable.
  • the lignite may be an acid precipitate from an alkaline extract of lignite.
  • a micronised, pyrolised mixture of a saccharide and the lignite extract is particularly suitable as a substrate for the papaya latex lipase 14a.
  • the substrate may be formed as follows. Lignite is firstly micronised and the acid content of the lignite (e.g. humic acids, fulvic acids, etc) is then extracted under alkaline conditions. Suitable bases for the alkaline extraction include potassium hydroxide, magnesium hydroxide, and magnesium sulphate.
  • the pH of the resultant extract is then adjusted to about 3 to about 5.
  • a pH of about 4.0 to about 4.5 is particularly suitable.
  • the isolated precipitate is then mixed with a saccharide, such as (but not limited to) molasses, sucrose, etc, and the mixture is pyrolised at a temperature of between about 240 0 C and about 800 0 C.
  • the pyrolised mixture of saccharide and lignite extract thus formed is then used as a substrate for the papaya latex lipase.
  • the papaya latex lipase 14a and plant lipase from a high lipid content grain, legume or seed 14b are introduced into the combined stream 28 via a static mixer 30 and fed into the reaction vessel 32 containing the lower alkyl alcohol 16 and plant oil or animal fat 12.
  • the rice bran 19 may be a rice bran residue that is from the in-situ esterification of the rice bran oil in a process that is described later.
  • the ratio of papaya latex lipase 14a to plant oil or animal fat 12 may be about 1 :10 w/w to about 1 :30 w/w. In one embodiment of the invention the ratio of papaya latex lipase 14a to plant oil or animal fat 12 is about 1 :20 w/w.
  • the reactants are continuously mixed and the reaction is carried out at a temperature of from about 30 0 C to about 70 0 C. In one embodiment of the invention the reaction is carried out at a temperature of about 50 0 C. The reaction may be carried out for a time period of from about 30 minutes to about 90 minutes. In one embodiment of the invention the reaction is carried out for a time period of about 60 minutes.
  • the first alkyl fatty acid ester mixture 20 is separated from solid material, such as immobilised lipase 14a and rice bran 19, by centrifugation as described previously.
  • the purified first alkyl fatty acid ester mixture 20 that is obtained after centrifugation is then reacted with the lower alkyl alcohol 16 in the presence of the acid 18 to form a second alkyl fatty acid ester mixture 46 as described previously.
  • the second alkyl fatty acid ester mixture 46 is distilled from the reaction mixture and is continuously drawn from the reboiler 50 by a pump 52 through a flow control valve 54.
  • the second alkyl fatty acid ester mixture 46 may be used as is or purified for use as a biofuel, or it may be further treated.
  • the distilled second alkyl fatty acid ester mixture may be treated to remove unreacted glycerine.
  • the treatment may comprise gravity separation.
  • the second alkyl fatty acid ester mixture 46 may be drawn from the reboiler 50 by a pump 52 through a flow control valve 54 to a static glycerin/alkyl ester separator vessel 56.
  • the separator vessel 56 is used to separate raw glycerin and un-reacted glycerol esters 58 from alkyl fatty acid ester mixture 46, which are drawn off continuously from the top layers of the separator vessel 56.
  • the raw glycerin and un-reacted glycerol esters 58 may be recycled.
  • unreacted glycerol esters and unreacted ethanol may be separated from raw glycerin and soap based on the specific gravity of each component.
  • the raw glycerin and un-reacted glycerol esters 58 may be pumped from the separating vessel 58 to a centrifuge 60 where they are separated based on specific gravity.
  • the centrifuge extract 62 i.e. primarily unreacted glycerol esters and unreacted ethanol
  • the centrifuge reject 64 (i.e. primarily raw glycerin and soap) may be converted to butanol by fermentation. As illustrated in Figure 2(b), the centrifuge reject 64 may be mixed with an appropriate enzyme and pumped via flow control valve 66 to a multi compartmented rotating biological disc bioreactor 68 with immobilized specific bacteria and fermented to alcohols. Butanol is preferably produced using this method. Many microorganisms are known to produce butanol through fermentation. Several Clostridium spp (e.g. Clostridium acetobutylicum, Clostridium beijerinckii etc.) have been shown to catalyse the production of butanol may be used (see Jones, D. T.
  • Rice bran oil esters may be prepared using any suitable esterification or transesterification technique. However, we have found that it is advantageous to prepare rice bran oil esters using a sulphonic acid as the catalyst for the transesterification reaction. Suitable sulphonic acids include alkyl sulphonic acids, such as methane sulphonic acids. Thus, rice bran may be reacted with a lower alkyl alcohol in the presence of methane sulphonic acid to form a rice bran oil ester mixture.
  • the lower alkyl alcohol may be selected from one or more of the group consisting of methanol, ethanol, n-propanol, i-propranol, n-butanol, s-butanol, and t- butanol.
  • the lower alkyl alcohol is n-butanol.
  • the n-butanol may be formed by enzymatic hydrolysis of a glycerine and soap mixture that is formed during the production of the second alkyl fatty acid mixture, as described previously.
  • Rice bran 19 with an oil content of about 19 to about 23% w/w is continuously charged into a reactor vessel 74 and mixed with a regulated flow of butanol 76 mixed with methane sulphonic acid 78.
  • the butanol 76 and methane sulphonic acid 78 are pumped to a static mixer 80 prior to being injected into the reactor vessel 74.
  • the ratio of methane sulphonic acid to n-butanol that is injected into the reactor vessel 74 may be about 1 :40 w/w to about 1 :50 w/w. In one embodiment the ratio of methane sulphonic acid to n-butanol is about 1 :40 w/w to about 1 :50 w/w.
  • the reactor vessel 74 may be a continuously stirred temperature controlled jacketed bio-reactor.
  • the ratio of n-butanol to rice bran may be about 1 :3 w/w to about 1 :4 w/w. In one embodiment the ratio of n-butanol to rice bran in the starting reaction mixture is about 1 :3.5 w/w.
  • the rice bran oil ester mixture 82 may be separated from solid material prior to mixing with the second alkyl fatty acid mixture 46.
  • the rice bran oil ester mixture 82 may be separated from the solid material by centrifugation.
  • the rice bran oil ester mixture 82 may be drawn off and through a regulating flow control valve
  • the extract from the centrifuge i.e. rice bran oil ester mixture
  • 82 may be pumped to a mixing vessel 88 for mixing with the second alkyl fatty acid mixture 46.
  • Reject 90 from the centrifuge 86 may be reused in the reaction to produce alkyl fatty acid ester mixture 20.
  • the alkyl fatty acid ester mixture 46 which is drawn off continuously from the top layers of the separator vessel 56, may be mixed with the rice bran oil ester mixture 82 in a static mixer 92 and pumped into a continuously pump mixed vessel 94.
  • the pH of the mixture may be adjusted to about 6 to about 8. In one embodiment of the invention the pH of the mixture is adjusted to about 7.
  • the pH of the second alkyl fatty acid ester and rice bran oil ester mixture can be adjusted by adding an agent 95 selected from the group consisting of: potassium hydroxide, sodium hydroxide, magnesium hydroxide, ammonia, and calcium hydroxide.
  • an agent 95 selected from the group consisting of: potassium hydroxide, sodium hydroxide, magnesium hydroxide, ammonia, and calcium hydroxide.
  • the pH of the mixture is adjusted by adding magnesium hydroxide.
  • the second alkyl fatty acid ester and rice bran oil ester mixture may be treated with a filtering agent 96.
  • Suitable filtering agents 96 may be selected from the group consisting of diatomaceous earth, activated charcoal, and silicates.
  • the silicate may be an aluminosilicate or a magnesium silicate.
  • the filtering agent 96 is a magnesium silicate. Magnesium silicates are particularly beneficial as they not only act as filtering agent but they also extract residual water from the second alkyl fatty acid ester and rice bran oil ester mixture.
  • the filtering agent 96 may be separated from the second alkyl fatty acid ester and rice bran oil ester mixture by mechanical filtration.
  • the second alkyl fatty acid ester and rice bran oil ester mixture, filtering agent and reacted pH adjusting agent may be pumped through a continuous belt filter press 97.
  • Filtered alkyl esters are the finished product 98 and may be retained for storage.
  • the biodiesel produced has a gelling temperature somewhere between about 0 0 C and about 10 0 C depending on the starting feedstock material.
  • the starting feedstock is beef tallow (which is a readily available, inexpensive starting material) we are able to produce biodiesel having a gelling temperature in this range.
  • This is in contrast to prior art biodiesel fuels formed from beef tallow, which we have found have a gelling temperature of about 16°C.
  • using the processes of the present invention we are able to form a high grade biodiesel fuel from relatively low grade starting materials, such as tallow.
  • biodiesel produced using the processes of the present invention has excellent long term stability. For example, we have found that there is no evidence of oxidation of the sample after storage at room temperature in an open vessel for about
  • the process of the present invention may be operated in a continuous, zero-waste manner.
  • the finished product is suitable for use as biodiesel and may be used as is or in admixture with mineral diesel.
  • prior art biodiesel fuels are typically mixed with mineral diesel in a ratio of 9:1 mineral to biodiesel. This is primarily done because the high gelling point of the biodiesel limits the amount that can be used in the mixture.
  • the biodiesel produced according to the present invention may be mixed with mineral diesel in a ratio of about 7:3.
  • cetane index of a biodiesel product can be increased by adding butyl esters of rice bran oil to the product.
  • Biodiesel is produced using the procedures and apparatus as described previously. Specifically the following steps are carried out.
  • a feedstock supply stream 22 of tallow 12 is fed through a flow control device 24 and is combined with a regulated stream 26 of ethanol 16, which is fed from an injection pump.
  • the combined stream 28 is mixed via a static mixer 30.
  • the reaction mixture (containing the first alkyl fatty acid ester mixture 20) is then pumped from the reaction vessel 32 through a flow control valve 38 to a centrifuge 40 where it is separated from solid material, such as immobilised lipase 14.
  • the purified first alkyl fatty acid ester mixture 20 is drawn from the centrifuge in the usual manner.
  • the centrifuge reject 41 is pumped to a stripping tank 43, where the immobilized lipases are extracted and re-cycled back to the reaction vessel 32.
  • the purified first alkyl fatty acid ester mixture 20 that is obtained after centrifugation is then reacted with methanol 16 in the presence of sulphuric acid 18 to form a second alkyl fatty acid ester mixture 46.
  • the methanol 16 and sulphuric acid 18 are mixed in a ratio of about 1.5% sulphuric acid w/w, in a volume of methanol that is calculated at a 12:1 molar ratio.
  • the reaction is carried out under continuous reactive distillation conditions at a temperature of about 60°C.
  • the second alkyl fatty acid ester mixture 46 is distilled from the reaction mixture and is continuously drawn from the reboiler 50 by a pump 52 through a flow control valve 54.
  • the second alkyl fatty acid ester mixture 46 is passed in to a static glycerin/alkyl ester separator vessel 56 where raw glycerin and un-reacted glycerol esters 58 are separated from the alkyl fatty acid ester mixture 46 by gravity filtration.
  • the alkyl fatty acid ester mixture 46 is drawn off continuously from the top layers of the separator vessel 56.
  • the raw glycerin and un-reacted glycerol esters 58 are recycled by pumping from the separating vessel 58 to a centrifuge 60 where the unreacted glycerol esters and unreacted ethanol are separated from raw glycerin and soap based on the specific gravity of each component.
  • the centrifuge extract 62 i.e. primarily unreacted glycerol esters and unreacted ethanol is pumped back to the reboiler 50.
  • the centrifuge reject 64 (i.e. primarily raw glycerin and soap) is pumped via flow control valve 66 to a multi compartmented rotating biological disc bioreactor 68 containing immobilized Clostridium spp bacteria which ferment the material to butanol.
  • the butanol is distilled via a distillation apparatus 70 and used in the production of rice bran oil esters 82.
  • rice bran 74 with an oil content of about 19 to about 23% w/w is continuously charged into a reactor vessel 74 and mixed with a regulated flow of butanol 76 mixed with methanesulphonic acid.
  • the butanol 76 and methane sulphonic acid 78 are pumped to a static mixer 80 prior to being injected into the reactor vessel 74.
  • the ratio of methane sulphonic acid to n-butanol that is injected into the reactor vessel 74 is about 1 :40 w/w to about 1 :50 w/w.
  • the ratio of n- butanol to rice bran is 1 :3 w/w to 1 :4 w/w.
  • 110 Kg of rice bran per 1 Kl of alkyl ester is charged into the reactor vessel 74.
  • the reactor vessel 74 is continuously stirred and temperature controlled.
  • the rice bran oil ester mixture 82 is drawn off from the vessel 74 and through a regulating flow control valve 84 to a centrifuge 86.
  • the extract from the centrifuge i.e. rice bran oil ester mixture 82
  • the mixing vessel 88 for mixing with the second alkyl fatty acid mixture 46.
  • Reject 90 from the centrifuge 86 i.e. primarily rice bran is reused in the reaction to produce alkyl fatty acid ester mixture 20.
  • the alkyl fatty acid ester composition of the finished product 98 obtained from the reaction sequence described were analysed by gas chromatography (GC) essentially as described in British Standard Institution (BSI) reference method BS EN 14103:2003; " Fat and oil derivatives-Fatty Acid Methyl Esters (FAME) - Determination of ester and linolenic acid methyl ester contents".
  • GC gas chromatography
  • the present invention however relates to the formation of mixtures which are produced by way of transesterification reactions of animal fat and rice bran oil performed in the presence of ethanol and n-butanol, respectively, to produce fatty acyl ethyl esters and fatty alkyl butyl esters, respectively. Therefore in the spirit of the EN 14103:2003 Standard, the present invention reports all information necessary for the complete identification of the sample; the sampling method used; the test method used with reference to the European Standard; and the test results obtained.
  • FAEE fatty alkyl ethyl esters
  • FBE fatty alkyl butyl esters
  • FID flame ionization detector
  • HP-lnnowax capillary column (1909N-1 13; J & W Scientific; 30m x 320um x 0.25um) using high-purity Helium as carrier gas.
  • FAEE and FABE were analysed using identical temperature programming conditions of 140 0 C for Omin, then 5°C / min to 220 0 C for 3min, then 20 0 C / min to 260°C for 8 mins.
  • FAEEs were identified from their retention times against mixes of commercially obtained FAEE standards (Nu-Chek Prep, Inc., Elysian, MN, USA) which were aliquoted in heptane containing 0.005% (w/v) butylated hydroxy anisole as antioxidant.
  • FABEs were identified from their retention times against FABE mixes prepared from commercially available triacylglycerides (TAG) (Nu-Chek).
  • Fatty acids are designated by their carbon length followed by the number of unsaturated double bonds and expressed as wt (%) of the total fatty acids.
  • Other fatty acids represent fatty acids with retention times greater than C22:6 n-3ee or C22:6 n-3be.
  • Table 1 shows the fatty acid composition of the mixture derived from the esterification of animal fat in stage 1 of the biodiesel process in which this material is treated with an immobilised plant lipase in the presence of ethanol and later sulphuric acid.
  • the fatty alkyl esters identified in this mixture were only of the ethyl ester type as opposed to methyl esters described for other biodiesel mixtures.
  • Ethyl esters were primarily C16:0 (palmitate) 23.8%, C18:0 (stearate) 22.2%, and C18:1cis 9 (oleate) 37.9%, with an overall degree of saturation of 48.2% consistent with the fatty acids of the starting material being of animal origin.
  • Table 2 shows the fatty acid composition of the mixture derived from the esterification of rice bran oil in stage 2 of the biodiesel process in which this material is treated in the presence of n-butanol and methanesulphonic acid.
  • the fatty alkyl esters identified in this mixture were only of the butyl ester type as opposed to methyl esters described for other biodiesel mixtures and the ethyl esters described for stage 1 of the present invention.
  • Butyl esters were primarily C16:0 (palmitate) 19.1 %, C18:1 cis 9 (oleate) 32.7% and C18:2 (linoleate) 28.7%, with an overall degree of saturation of 23.6% consistent with the fatty acids of the starting material being of plant origin.
  • Several other fatty alkyl ethyl esters were detected but these were difficult to unequivocally identify with the butyl ester standards available, and together comprised about 14.5% of the total fatty acid esters in this sample.
  • Table 2 - Fatty acid analyses of biodiesel mixtures produced by esterification of rice bran oil Biodiesel sample # 3).
  • Table 3 shows the fatty acid composition of the combined mixture derived from both the esterification of animal fat in stage 1 of the biodiesel process in which this material is treated with an immobilised plant lipase in the presence of ethanol and later sulphuric acid, and the esterification of rice bran oil in stage 2 of the biodiesel process in which this material is treated with in the presence of n-butanol and methane sulphonic acid.
  • Both ethyl esters and butyl esters are identified in this mixture with the ethyl esters comprising approximately 91% and the butyl esters 9% of the total fatty alkyl esters.
  • the complete fatty alkyl ester composition of this biodiesel mixture is shown as both total % FAEE plus FABE (left hand column) and % FAEE or % FABE (right hand column).
  • the FAEE profile compares well with that shown in Table 1 , while for the butyl esters, the major species present, C 16:1 (18.0%), C 18:1 (30.1 %) and C 18:2 (30.0%), are also similar in proportion to that shown in Table 2 for the rice bran derived fatty alkyl butyl esters.
  • Fatty acid ethyl esters (FAEE)
  • Fatty acid butyl esters (FABE)

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Abstract

L'invention porte sur un procédé de fabrication d'esters alkyliques d'acides gras appropriés pour être utilisés comme carburant et/ou lubrifiant. Le procédé comprend le traitement d'une charge d'alimentation contenant des glycérides et/ou des acides gras libres avec une lipase, un alcool alkylique inférieur et un catalyseur acide dans des conditions permettant de produire lesdits esters alkyliques d'acides gras.
EP08700408A 2007-02-02 2008-02-01 Fabrication de biodiesel Withdrawn EP2118250A1 (fr)

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AU2007900488A AU2007900488A0 (en) 2007-02-02 Biodiesel production
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US8765425B2 (en) 2011-03-23 2014-07-01 Butamax Advanced Biofuels Llc In situ expression of lipase for enzymatic production of alcohol esters during fermentation
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