WO2011104528A2 - Compositions de biodiesel - Google Patents

Compositions de biodiesel Download PDF

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Publication number
WO2011104528A2
WO2011104528A2 PCT/GB2011/050324 GB2011050324W WO2011104528A2 WO 2011104528 A2 WO2011104528 A2 WO 2011104528A2 GB 2011050324 W GB2011050324 W GB 2011050324W WO 2011104528 A2 WO2011104528 A2 WO 2011104528A2
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composition
esters
ester
composition according
iii
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PCT/GB2011/050324
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English (en)
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WO2011104528A3 (fr
Inventor
Raymond Mccague
Brian Michael Adger
Stephen John Clifford Taylor
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Hycagen Limited
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Publication of WO2011104528A3 publication Critical patent/WO2011104528A3/fr

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    • 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
    • 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
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • 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
    • 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
    • C10G2300/1014—Biomass of vegetal origin
    • 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 novel biodiesel compositions, their use as fuels, and processes for their manufacture from interesterification reactions between triglycerides such as vegetable oils, and an ester, or mixture of esters.
  • Biodiesel is a term that is understood in the literature to refer to a fuel composition useful in diesel engines produced from processing of triglyceride oils.
  • the triglyceride oils are typically vegetable oils obtainable from various plant species, but might also be obtained from other sources such as from algae or by microbial fermentation. They principally comprise triesters of glycerol with fatty acids of between 10 and 24 carbon atoms.
  • fatty acids include, for example, capric, lauric, myristic, palmitic, stearic, arachidic, oleic, myristoleic, palmitoleic, sapienic, linoleic, linolenic, arachidonic and erucic acids.
  • triglyceride oils themselves are not well suited for use as fuels because their viscosities are too high.
  • the triglyceride is made to undergo a transesterification process with a lower alcohol, most usually methanol, and the biodiesel comprises the methyl esters of the fatty acid components from the triglycerides.
  • a lower alcohol most usually methanol
  • the biodiesel comprises the methyl esters of the fatty acid components from the triglycerides.
  • These methyl esters have approximately one eighth the viscosity of the parent triglycerides and consequently are much more suited for use as a fuel.
  • disadvantages associated with these fatty acid methyl esters and the processes to them are several disadvantages associated with these fatty acid methyl esters and the processes to them:
  • the process generates a waste stream of glycerol, which either must be disposed of, or some other use found for it.
  • the glycerol is immiscible with the fatty acid ester so it cannot be combined in with the fuel as such. Handling of the waste glycerol is also hampered by its containing methanol and catalyst (typically alkali) from the transesterification reaction.
  • the glycerol component of the triglyceride represents about 5% of the available combustion energy, which is not passed on to the fuel with the conventional biodiesel .
  • the catalyst used for the transesterification is typically sodium hydroxide or sodium methoxide, and this must be completely removed from the biodiesel before it can be used, else presumably incombustible sodium salts will otherwise remain and build up in the engine. Consequently an additional wash step (or steps) is needed for the biodiesel, which complicates the processing and makes the process more expensive to operate.
  • glycerol mono-fatty acid esters are liable to crystallise out from the biodiesel once it is cooled, clogging fuel lines and so making the composition unsuitable.
  • Use of an excess of methanol (or other alcohol) means that the excess has to be removed before the biodiesel can be used. If methanol is left in the biodiesel, being highly volatile and flammable, it can result in the biodiesel having an unacceptable flash point. Removal of the excess methanol will typically require an extra processing step incurring additional expense, such a step would involve for example evaporation of the methanol by heating the biodiesel product under a partial vacuum.
  • the conventional biodiesel compositions are prone to freeze at low ambient temperatures, and this may limit their use in cold climates.
  • a typical biodiesel composition might start to freeze around -5°C.
  • An alternative processing method to convert triglyceride oils into a biodiesel composition involves an interesterification reaction with a low molecular weight ester.
  • interesterification is used to describe a reaction in which the alkoxy and acyl groups are interchanged between two or more reactants that have ester functionality.
  • the interesterification reaction between a triglyceride and another ester molecule R 1 C(0)-0R 2 is illustrated by Scheme 1 below.
  • the interesterification reaction is an equilibrium between similar compounds, and in order to drive the reaction forward towards to the fatty acid methyl ester and triacetin (triacetylglycerol) in the case of using methyl acetate, a large excess amount of the low molecular weight ester is required. Thus a calculation would indicate that with 6 equivalents of methyl acetate, only two-thirds of the stoichiometric amount of fatty acid methyl ester might be formed.
  • methyl acetate which is volatile and flammable
  • the excess must be removed from the biodiesel before it is used, for example by an evaporation step, in order for the resulting biodiesel composition to be safe to use.
  • biodiesel compositions useful as a fuel can be obtained with much simpler processing than hitherto realised.
  • the only processing that may be required after the reaction is removal of the catalyst, although part of the excess ester can optionally be removed by evaporation.
  • the term "medium molecular weight ester” refers to an ester having a molecular weight of at least 126 grams per mole, which is the case if the ester has nine or more non-hydrogen atoms per molecule, to distinguish the esters used in this invention from the typically low molecular weight esters utilised in the prior art.
  • Advantages of biodiesel compositions encompassed by the present invention include, for example:
  • An enzyme catalyst may optionally be used, which enables very simple removal from the biodiesel composition at the end of the interesterification reaction.
  • the resulting biodiesel compositions have lower freezing point than the conventional biodiesel (fatty acid methyl esters) .
  • the present invention concerns a biodiesel composition made from an interesterification reaction using a medium molecular weight ester, where all or some of the excess/unreacted ester is retained within the composition, so that this ester remains at a proportion of at least 5 mol% of the resulting composition.
  • the obtained biodiesel compositions possess favourable properties for use as diesel engine fuels, for example for automotive use.
  • a particularly favourable property of the obtained composition is a low freezing point, lower than that of the corresponding fatty acid methyl ester, derived from the same triglyceride.
  • the present invention provides a composition comprising:
  • esters which may be the same or different, of formula E ⁇ -CiO) O-R 2 , wherein
  • R 1 is H or C 1 -C7 alkyl
  • R 2 is Ci-C 8 alkyl
  • R 1 -C(0)0-R 2 represents at least nine non-hydrogen atoms
  • R 1 is H or Ci-C 2 alkyl, then R 2 is C 5 -C 8 alkyl;
  • R 3 C(0) represents the acyl residue of a Ci 0 -C 2 4 fatty acid; and R 4 is Ci-Cs alkyl;
  • one or more carbon atoms may be replaced by oxygen atoms, or bear an oxo substituent; and components (i), (ii) and (iii) each represent a molar proportion of at least 5% of the mixture.
  • the one or more esters of component (i) represent 10 to 70 mole % of the composition. More preferably, the one or more esters of component (i) represent 15 to 50 mole % of the composition. Most preferably, the one or more esters of component (i) represent 20 to 45 mole % of the composition. Preferably, the one or more fatty acid esters of component (ii) represent 20 to 70 mole % of the composition. More preferably, the one or more fatty acid esters of component (ii) represent 25 to 60 mole % of the composition. Most preferably, the one or more fatty acid esters of component (ii) represent 30 to 50 mole % of the composition.
  • the one or more triesters of glycerol of component (iii) represent 20 to 70 mole % of the composition. More preferably, the one or more triesters of glycerol of component (iii) represent 25 to 60 mole % of the composition. Most preferably, the one or more triesters of glycerol of component (iii) represent 30 to 50 mole % of the composition .
  • a preferred composition comprises 10 to 70 mol% of the or more esters of component (i), 20 to 70 mol% of the one or more fatty acid esters of component (ii) , and 10 to 60 mol% of the one or more triesters of glycerol of component (iii) .
  • a more preferred composition comprises 15 to 50 mol% of the or more esters of component (i), 25 to 60 mol% of the one or more fatty acid esters of component (ii), and 15 to 50 mol% of the one or more triesters of glycerol of component (iii) .
  • the most preferred composition comprises 20 to 45 mol% of the or more esters of component (i) , 30 to 50 mol% of the one or more fatty acid esters of component (ii) , and 20 to 45 mol% of the one or more triesters of glycerol of component (iii) .
  • Preferred esters of formula R 1 -C(0)0-R 2 of the present invention are those wherein the acyl group R 1 -CO is selected from the group consisting of formyl, acetyl, propionyl, n-butyryl, isobutyryl, pentanoyl, hexanoyl, 2-ethylhexanoyl, octanoyl, crotonyl, sorbyl, levulinyl and 2-tetrahydrofuryl. More preferably, R 1 -CO- is n-butyryl, isobutyryl, or levulinyl.
  • esters of formula R 1 -C(0)0-R 2 wherein the alkyl group R 2 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, 2-ethylhexyl, cyclohexyl, cyclohexylmethyl , crotyl and 2-tetrahydrofurfuryl .
  • R 2 is selected from methyl, ethyl, n-butyl, and isobutyl.
  • esters of formula R 1 -C(0)0-R 2 for the purpose of this invention are ones that may be obtained from renewable resource materials.
  • n-butyric acid may be obtained by microbial fermentation and used to provide butyrate esters.
  • alcohols as ethanol, n-butanol and isobutanol may likewise be obtained through fermentation methods and used to provide corresponding esters .
  • n- Butanol can also be obtained by reduction of n-butyric acid obtained from fermentation methods, such as with hydrogen as described in US patent no. 199172, as can be the ester butyl butyrate directly, for example by the fermentation process with Clostridium acetobutylicum as described in US patent no. 4487832.
  • esters for the purpose of this invention are esters of n-butyric acid and levulinic acid and in particular n-butyl n-butyrate, isobutyl n-butyrate and methyl or ethyl levulinate. Most preferred are n-butyl n-butyrate and isobutyl n-butyrate.
  • R 4 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, 2-ethylhexyl, cyclohexyl, cyclohexylmethyl, crotyl and 2-tetrahydrofurfuryl.
  • R 2 is selected from methyl, ethyl, n-butyl, and isobutyl.
  • the triesters of glycerol of component (iii) comprise (a) esters of glycerol having three fatty acyl residues, (b) esters of glycerol having two fatty acyl residues and one shorter chain acyl residue, (c) esters or glycerol having one fatty acyl residue and two shorter chain acyl residues, and optionally (d) esters of glycerol having three shorter chain acyl residues.
  • the triglycerides used for the preparation of compositions of the present invetion may be obtained from any of the sources described herein and preferably, the triglyceride is or has been obtained from plant seeds or other parts of plants, algae, or a microbial fermentation .
  • other compounds may be added in addition to the ester either before or after the interesterification reaction.
  • examples of such other compounds that may be added are alcohols, for example, methanol, n-butanol, isobutanol or tetrahydrofurfuryl alcohol.
  • alcohols for example, methanol, n-butanol, isobutanol or tetrahydrofurfuryl alcohol.
  • no more than 0.5 equivalents relative to the triglyceride oil is used. That is to limit the extent of formation of mono- or di-glycerides (glycerol mono-esters or di-esters) which might crystallise from the product if it is cooled.
  • Other compounds added can include for example antioxidants or antimicrobial agents to improve stability, lubricants, or compounds to improve the low temperature flow properties .
  • compositions of the present invention may further comprise one or more components selected from (i) an alcohol having up to 8 carbon atoms in a molar amount that is not more than half of the amount of triglyceride used, (ii) an antioxidant, (iii) a lubricant, and (iv) a cold flow additive.
  • compositions of the invention may further comprise a catalyst for ester exchange reactions.
  • the catalyst is an enzyme.
  • Preferred compostions are fuel compositions for automotive, marine transport, machinery or electricity generation use.
  • the present invention provides a process for the manufacture of the compositions of the invention, wherein a mixture of a triglyceride oil composed of esters between glycerol and fatty acids of between 10 and 24 carbon atoms, and one or more esters of formula R 1 -C0(0)-R 2 , wherein R 1 is H or an alkyl group containing one to seven carbon atoms, and R 2 is an alkyl group containing one to eight carbon atoms, wherein the alkyl groups R 1 and R 2 may be linear, branched or cyclic, or a combination thereof, and optionally contain one or more double bonds; and optionally, one or more carbon atoms may be replaced by oxygen atoms or bear on oxo substituent; is made to undergo an ester exchange reaction by means of an added catalyst, then either (i) any excess ester R 1 -CO(0)-R 2 is not removed from the mixture, or (ii) some excess ester R 1 -CO(0)-R 2 is removed so
  • an option is to use a greater excess of the medium molecular weight ester, and to evaporate off some but not all of the excess ester after the interesterification, so that there remains at least 5 mol% of that ester in the mixture. In doing so, one can combine the benefits to the composition retaining some content of medium molecular weight ester with the benefits of a greater extent of cleavage of the triglyceride, such as lower viscosity .
  • a composition equivalent to those produced by the interesterification reactions disclosed herein may be generated by other means, such as by mixing together separately produced components being (i) one or more medium molecular weight ester, (ii) one or more fatty acid esters, and (iii) one or more glycerol triesters, or by mixing the third such component with a mixture that contains the other two.
  • a mixture of fatty acid esters and glycerol triesters produced by other means may be combined with a medium molecular weight ester such that the resulting composition contains at least 5 mol% of each of these three components.
  • a preferred embodiment is to carry out an interesterification between a triglyceride oil and a low molecular weight ester such as methyl acetate with a catalyst, to remove the catalyst, to evaporate off the excess low molecular weight ester, and then to add one or more medium molecular weight esters so there is at least 5 mol% of the medium molecular weight ester within the resulting composition.
  • a low molecular weight ester such as methyl acetate
  • catalysts known in the prior art for interesterification reactions may be used, for example a basic catalyst such as sodium methoxide or magnesium oxide, an acidic catalyst such as an acidic ion exchange resin or para-toluenesulfonic acid, or an enzyme catalyst.
  • a basic catalyst such as sodium methoxide or magnesium oxide
  • an acidic catalyst such as an acidic ion exchange resin or para-toluenesulfonic acid
  • an enzyme catalysts are enzymes because they can be easily removed at the end of the interesterification, do not leave metal ions in the resulting composition, and will not affect the olefinic linkages in the fatty acid chains.
  • Preferred enzymes for the purpose of this invention are either present in a microbial cell, isolated from the microbial cell, or immobilised on a support.
  • Preferred enzymes for the purpose of this invention are those from the class of enzymes known as lipases.
  • the interesterification is conducted so that a resulting composition can be obtained that has at least 5 mol% of a low or medium molecular weight ester, by means of any of the above embodiments of the invention.
  • a molar ratio of the low or medium molecular weight ester, to the triglyceride in the range of 1.0 to 12.0. More preferred is to use in the interesterification, a molar ratio of the low or medium molecular weight ester, to the triglyceride in the range of 1.5 to 6.0.
  • a molar ratio of the low or medium molecular weight ester, to the triglyceride in the range of 2.0 to 4.0.
  • the preferred molar ratio of the low or medium molecular weight ester, to the triglyceride will also depend upon the particular embodiment of this invention employed. Thus, when excess or unreacted ester is not removed after the interesterification reaction, it is preferred to use a molar ratio of less than or equal to 3.0.
  • any amount of ester is removed by evaporation after the interesterification it is preferred to use a molar ratio that is more than 3.0 in the interesterification, and then to remove excess ester to the extent that the resulting composition comprises a molar ratio of ester relative to the input triglyceride of less than or equal to 3.0.
  • the scope of this invention is limited by the requirement for a medium molecular weight ester R 1 -C(0)0-R 2 having a molecular weight of at least 126 grams per mole that represents at least nine non-hydrogen atoms; with the proviso that if R 1 is H or Ci-C 2 alkyl, then R 2 is C 5 -C 8 alkyl.
  • R 1 is H or Ci-C 2 alkyl
  • R 2 is C 5 -C 8 alkyl.
  • butyl propionate which is not encompassed by the scope of the present invention, was found to result in an inferior process because the reaction with the enzyme is slower than with esters of the present invention, for example butyl butyrate .
  • a slower reaction means that either (i) more enzyme must be used to achieve a given conversion, (ii) more time is needed to achieve a given conversion, or (iii) a lower conversion to products is obtained such that the product is less satisfactory.
  • Use of a longer reaction time or more enzyme results in a higher process cost.
  • the use of butyl butyrate gives a composition having an unexpectedly higher and superior flash point compared to the use of butyl propionate.
  • compositions obtained according to this invention may be used as the fuel for a diesel engine as such, or may be blended with another suitable fuel in any proportion, for example another biodiesel composition (e.g. comprised of methyl esters of fatty acids), or a petroleum derived diesel fuel .
  • Said diesel engine could be within a vehicle for transportation, which could be for land or sea transport, or could be used to drive machinery, or be used for electricity generation .
  • compositions of this invention have been found to be more resistant to microbial growth than conventional biodiesel compositions. Microbial growth causes sediments to appear in the fuel which may block fuel lines or filters, and is also known to promote corrosion. This benefit is of particular importance where the fuel composition is to be stored for an extended period of time, such as within fuel tanks or during distribution.
  • An advantage of the present process is that it simply involves combining a starting mixture of triglyceride vegetable oil and a medium molecular weight ester with an enzyme (or other) catalyst.
  • a feature of the invention is that it may be conducted in different ways dependent on such circumstances as the scale required or availability of equipment. It may be conducted in a batch process where the starting mixture is stirred with the catalyst, or conducted by means of passing the mixture through a column of the catalyst until a sufficient conversion is obtained, or conducted by a combination of such processes .
  • Example 1 Interesterification with 2 equivalents of butyl butyrate catalysed by an enzyme.
  • a mixture of rapeseed oil (food grade having a kinematic viscosity at 40°C of 39.5 CSt; 50 g, 56 mmol) and butyl butyrate (16.1 g, 112 mmol, 2 equivs) were mixed together and the kinematic viscosity at 40°C was measured as 11.5 CSt, and an open-cup flash point as 80°C, and a freezing point at -9°C.
  • Immobilised Candida antarctica lipase B (0.5g) was added, then the mixture was shaken in a closed bottle at 40°C.
  • a mixture of rapeseed oil (food grade; 147 g, 166 mmol) and butyl butyrate (47.9 g, 332 mmol, 2 equivs) was warmed and the mixture was shaken at intervals and portions of sodium methoxide totalling 1.06 g added during 4 hrs .
  • the mixture was shaken with an aqueous solution of potassium dihydrogen phosphate, the phases allowed to separate, and the organic phase dried over anhydrous sodium sulfate and filtered to yield 186 g of a biodiesel with a kinematic viscosity at 40°C of 9.6 CSt and an open-cup flash point of 115°C was measured.
  • Example 3 Interesterification with 1.5 equivalents of butyl butyrate.
  • a mixture of rapeseed oil (food grade; 50 g, 56 mmol), butyl butyrate (12.1 g, 84 mmol, 1.5 equivs) and immobilised Candida antarctica lipase B (0.5g) was shaken in a closed bottle at 40°C. After 120 hours a sample had a kinematic viscosity at 40°C of 12.1 CSt.
  • Example 4 Interesterification with 2.5 equivalents of butyl butyrate. Rapeseed oil (food grade; 50 g, 56 mmol) and butyl butyrate (20.1 g, 140 mmol, 2.5 equivs) were mixed together then immobilised Candida antarctica lipase B (0.5g) was added. The mixture was shaken in a closed bottle at 40°C. After 120 hours a sample had a kinematic viscosity at 40°C of 7.8 CSt.
  • Example 5 Interesterification with 3.0 equivalents of butyl butyrate. Rapeseed oil (food grade; 25 g, 28 mmol) and butyl butyrate (12.1 g, 84 mmol, 3 equivs) were mixed together then immobilised Candida antarctica lipase B (0.25g) was added. The mixture was shaken in a closed bottle at 40°C. After 44 hours a sample had a kinematic viscosity at 40°C of 6.9 CSt.
  • Example 6 Interesterification with 4.0 equivalents of butyl butyrate. Rapeseed oil (food grade; 25 g, 28 mmol) and butyl butyrate (16.1 g, 112 mmol, 4 equivs) were mixed together then immobilised Candida antarctica lipase B (0.25g) was added. The mixture was shaken in a closed bottle at 40°C. After 44 hours a sample had a kinematic viscosity at 40°C of 5.4 CSt.
  • Example 7 Interesterification with 6 equivalents of butyl butyrate catalysed by sodium methoxide and recovery of part of the butyl butyrate .
  • Soya bean oil (food grade; 25 g, 28 mmol) and butyl butyrate (8.06 g, 56 mmol, 2 equivs) were mixed together then immobilised Candida antarctica lipase B (0.25g) was added. The mixture was shaken in a closed bottle at 40°C. After 113.5 hours a sample had a kinematic viscosity at 40°C of 9.1 CSt.
  • Example 11 Interesterification of corn oil with 2 equivalents of butyl butyrate .
  • Corn oil (food grade; 25 g, 28 mmol) and butyl butyrate (8.06 g, 56 mmol, 2 equivs) were mixed together then immobilised Candida antarctica lipase B (0.25g) was added. The mixture was shaken in a closed bottle at 40°C. After 113 hours a sample had a kinematic viscosity at 40°C of 9.0 CSt.
  • Example 13 Interesterification with butyl butyrate and tetrahydrofurfuryl alcohol.
  • Rapeseed oil (food grade; 25 g, 28 raraol) , butyl butyrate (4.03 g, 28 raraol, 1 equiv) and tetrahydrofurfuryl alcohol (2.88g, 28 ramol, 1 equiv) were mixed together then immobilised Candida antarctica lipase B (0.25g) was added. The mixture was shaken in a closed bottle at 40°C. After 164 hours a sample was taken which was assayed and had a kinematic viscosity at 40°C of 9.6 CSt .
  • Example 14 Interesterification with butyl butyrate and methanol.
  • Rapeseed oil (food grade; 25 g, 28 mmol) , butyl butyrate (8.06 g, 56 mmol, 2 equivs) and methanol (0.43g, 14 mmol, 0.5 equiv) were mixed together then immobilised Candida antarctica lipase B (0.25g) was added. The mixture was shaken in a closed bottle at 40°C. After 22 hours a sample had a kinematic viscosity at 40°C of 9.0 CSt.
  • Example 15 Interesterification with butyl butyrate and tributyrin. Rapeseed oil (food grade; 25 g, 28 mmol), butyl butyrate (8.06 g, 56 mmol, 2 equivs) and tributyrin (4.23g, 14 mmol, 0.5 equiv) were mixed together then immobilised Candida antarctica lipase B (0.25g) was added. The mixture was shaken in a closed bottle at 40°C. After 22 hours a sample was had a kinematic viscosity at 40°C of 10.5 CSt.
  • Example 16 Interesterification with 2 equivalents butyl butyrate and 0.5 equivalents butanol .
  • Rapeseed oil (food grade; 25 g, 28 mmol), butyl butyrate (8.06 g, 56 mmol, 2 equivs) and n-butanol (1.04g, 14 mmol, 0.5 equiv) were mixed together then immobilised Candida antarctica lipase B (0.25g) was added. The mixture was shaken in a closed bottle at 40°C. After 93 hours a sample had a kinematic viscosity at 40°C of 8.2 CSt.
  • Example 17 Interesterification with 1.5 equivalents butyl butyrate and 0.5 equivalents butanol.
  • Rapeseed oil (food grade; 25 g, 28 mmol), butyl butyrate (6.05 g, 42 mmol, 1.5 equivs) and n-butanol (1.04g, 14 mmol, 0.5 equiv) was mixed together then immobilised Candida antarctica lipase B (0.25g) was added. The mixture was shaken in a closed bottle at 40°C. After 93 hours a sample had a kinematic viscosity at 40°C of 10.1 CSt.
  • Example 18 Interesterification with isobutyl isobutyrate.
  • Rapeseed oil (food grade; 25 g, 28 raraol) and isobutyl isobutyrate (8.06 g, 56 raraol, 2 equivs) were mixed together then immobilised Candida antarctica lipase B (0.25g) was added. The mixture was shaken in a closed bottle at 40°C. After 69 hours a sample had a kinematic viscosity at 40°C of 10.5 CSt .
  • Rapeseed oil (food grade; x 276 g, 312 mmol) and isobutyl butyrate (90 g, 624 mmol, 2 equivs) were mixed together then immobilised Candida antarctica lipase B (2.76 g) was added. The mixture was stirred at 40°C After 3 days, gas chromatography showed that 59% of the isobutyl butyrate had been consumed and a sample had a kinematic viscosity at 40°C of 11.6 CSt. In the freezer, the product remained mobile at -19°C
  • Example 20 Interesterification with 2-ethylhexyl butyrate.
  • Example 21 Interesterification with tetrahydrofurfuryl butyrate.
  • Rapeseed oil (food grade; 25 g, 28 mmol) and tetrahydrofurfuryl butyrate (9.63 g, 56 mmol, 2 equivs) were mixed together then immobilised Candida antarctica lipase B (0.25g) was added. The mixture was shaken in a closed bottle at 40°C. After 69 hours a sample had a kinematic viscosity at 40°C of 13.4 CSt.
  • Example 22 Interesterification with ethyl levulinate.
  • Example 23 Interesterification with hexyl acetate.
  • Rapeseed oil (food grade; 25 g, 28 mmol) and hexyl acetate (8.06 g, 56 raraol, 2 equivs) were mixed together then immobilised Candida antarctica lipase B (0.25g) was added. The mixture was shaken in a closed bottle at 40°C. After 114 hours a sample was taken which was assayed and had a kinematic viscosity at 40°C of 11.5 CSt.
  • Example 24 Interesterification with methyl 2 -ethylhexanoate .
  • Rapeseed oil (food grade; 25 g, 28 mmol) and methyl 2-ethylhexanoate (8.79 g, 56 mmol, 2 equivs) were mixed together then immobilised Candida antarctica lipase B (0.25g) was added. The mixture was shaken in a closed bottle at 40°C. After 114 hours a sample was taken which was assayed and had a kinematic viscosity at 40°C of 12.6 CSt.
  • Example 25 Recycling of enzyme in the interesterification with butyl butyrate .
  • Rapeseed oil (food grade; 50 g, 56 mmol) and butyl butyrate (16.1 g, 112 mmol, 2 equivs) were mixed together.
  • Immobilised Candida antarctica lipase B (0.5g) was added, then mixture was shaken in a closed bottle at 40°C. After 7 days a sample had a kinematic viscosity at 40°C of 10.1 CSt.
  • the product was decanted from the immobilised enzyme, then 20ml fresh substrate added (substrate stock solution contained 250g of rapeseed oil and 81g butyl butyrate), and the mixture shaken at 40°C for 24 hours.
  • Rapeseed oil (2412g) and butyl butyrate (772g, 2 equivalents) were mixed by overhead stirrer in a 51 vessel.
  • Immobilised Candida antarctica lipase (36g, Novozyme 435) was added, then the reaction stirred at ambient temperature for 4 days, whereupon the conversion reached 50%.
  • the enzyme was removed by filtration through a sintered funnel, then the resulting biodiesel treated and stabilised by the addition of 0.3% w/v Wintron XC40 and 0.2% w/v BaynoxPlus .
  • Reactions were set up with rapeseed oil (food grade; 30 g, 34 mmol)and (i) 2 equivalents butyl butyrate ( 9.78 g, 68 raraol) ; (ii) 2 equivalents butyl propionate (8.83 g, 68 raraol) ; and (iii) 1 equivalent butyl butyrate (4.89 g, 34 mmol) and 1 equivalent butyl propionate (4.42 g, 34 mmol) .
  • Immobilised Candida antarctica lipase B Novozyme 435; 0.3g

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Abstract

La présente invention concerne de nouvelles compositions de biodiesel, leur utilisation en tant que carburants, et des procédés pour leur fabrication à partir de réactions d'interestérification entre des triglycérides tels que des huiles végétales, et un ester, ou un mélange d'esters.
PCT/GB2011/050324 2010-02-25 2011-02-18 Compositions de biodiesel WO2011104528A2 (fr)

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WO2024119202A1 (fr) 2022-11-30 2024-06-06 Vaal University Of Technology Lipase immobilisée et procédé de production de biodiesel l'utilisant

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EP2862915B1 (fr) * 2013-10-18 2015-12-09 Rigas Tehniska universitate Procédé de fabrication de biodiesel

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