WO2007055661A1 - Production enzymatique de biodiesels - Google Patents

Production enzymatique de biodiesels Download PDF

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Publication number
WO2007055661A1
WO2007055661A1 PCT/SG2006/000343 SG2006000343W WO2007055661A1 WO 2007055661 A1 WO2007055661 A1 WO 2007055661A1 SG 2006000343 W SG2006000343 W SG 2006000343W WO 2007055661 A1 WO2007055661 A1 WO 2007055661A1
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Prior art keywords
oil
mixture
group
alcohol
salt
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PCT/SG2006/000343
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English (en)
Inventor
Md. Mahabubur Rahman Talukder
Jinchuan Wu
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Agency For Science, Technology And Research
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Publication of WO2007055661A1 publication Critical patent/WO2007055661A1/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
    • C11C3/003—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
    • C12P7/649—Biodiesel, i.e. fatty acid alkyl esters
    • 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

  • Biodiesel fuel includes mono alkyl esters of long chain fatty acids derived from plant oils, animal oils or fats.
  • Biodiesel is a promising efficient alternative fuel source suitable as a diesel fuel, or diesel fuel lubricity additive because it is biodegradable, non-toxic and has low emission profiles.
  • the use of biodiesel has become increasingly important due to diminishing petroleum reserves and environmental regulations.
  • Biodiesels have been produced industrially via strong base-catalyzed transesterifications of vegetable oils and animal fats (see, U.S. Pat. No,, 5,354,878; U.S. Pat. Pub. No. 2003/0032826; and U.S. Pat. Pub. No. 2004/0022929).
  • Strong base-catalyzed -processes have drawbacks including difficulty in recovery of glycerol, the need for removal of the base catalyst from the product and the treatment of alkaline wastewater.
  • Enzymatic transesterification using lipase has become more attractive for biodiesel fuel production, since the glycerol produced as a by-product can easily be recovered and the purification of fatty methyl esters is simple to accomplish.
  • the utilization of enzymes e.g. immobilized Candida Antarctica lipase
  • methanolysis of vegetable oils has been shown to be useful in producing biodiesels (see, U.S. Pat. No. 5713965; Shimada, Y. et al. J. Am. Oil Chem. Soc. 1999, 76, 789; Nelson, L. A. et al. J. Am. Oil Chem. Soc. 1996, 73, 1191).
  • the enzyme is either easily poisoned by the alcohol resulting in low enzyme activity or inhibited by the by-product's adsorption on the surface of the enzyme, thereby blocking the substrate's access to the active site of the enzyme.
  • the method should provide a system having a high enzymatic activity with a minimized alcohol poison and substrate inhibition as well as an increased heat resistance for the production of biodiesels at elevated temperatures.
  • the method should also be economically feasible for large scale productions.
  • the present invention meets these and other needs.
  • a reaction mixture is prepared containing a substantially saturated or a saturated solution and a feedstock in contact with the solution, wherein the substantially saturated solution comprises an alcohol and a salt dissolved in a solvent.
  • the alcohol and the solvent have a predetermined volume ratio from about 1 :9 to about 9:1.
  • a reaction mixture contains a substantially saturated aqueous solution and an oil in contact with the solution, wherein the substantially saturated solution comprises methanol, water and a salt.
  • the methanol and water have a predetermined volume ratio from about 1:9 to about 9:1, preferably about 1:2 to about 2:1.
  • Suitable salts include, for example, LiCl, K 2 CO 3 , NaNO 3 , Mg(NO 3 ) 2 , NaBr 3 NaCl, KCl, MgCl 2 , potassium acetate or combinations thereof.
  • the oil is preferably soyabean oil, palm oil or olive oil.
  • the present invention provides a reaction mixture.
  • the reaction mixture is a substantially saturated solution, which contains methanol, water and a salt.
  • Suitable salts include, for example, LiCl 5 K 2 CO 3 , NaNO 3 , Mg(NO 3 ) 2 , NaBr, NaCl 5 KCl, MgCl 2 , potassium acetate or combinations thereof.
  • the volume ratio of methanol to water is from about 1 :9 to about 9:1, more preferably from about 1 :2 to about 2: 1.
  • the present invention provides a method for preparing a biodiesel from a feedstock.
  • the method includes admixing a substantially saturated or a saturated solution containing an alcohol and a salt dissolved in a solvent with the feedstock and an immobilized enzyme to produce a reaction mixture and heating the reaction mixture to prepare the biodiesel.
  • the method includes providing a substantially saturated solution containing an alcohol and a salt dissolved in a solvent, mixing the solution with the feedstock and an immobilized enzyme to produce a reaction mixture, and heating the reaction mixture to prepare the biodiesel.
  • the method includes heating a reaction blend, which comprises a substantially saturated solution containing an alcohol and a salt dissolved in a solvent; a feedstock; and an immobilized enzyme.
  • a reaction blend which comprises a substantially saturated solution containing an alcohol and a salt dissolved in a solvent; a feedstock; and an immobilized enzyme.
  • the present invention provides a method for the preparation of a biodiesel from an oil or a fat.
  • the method includes mixing a substantially saturated aqueous solution containing methanol and a salt selected from the group consisting of LiCl, K 2 CO 3 , NaNO 3 , Mg(NO 3 ) 2 , NaBr, NaCl, KCl, MgCl 2 , potassium acetate or combinations thereof, with the oil or the fat to generate a reaction mixture and heating the reaction mixture to about 70 0 C to about 80 0 C, more preferably from about 40 0 C to about 60 0 C, to prepare the biodiesel.
  • a salt selected from the group consisting of LiCl, K 2 CO 3 , NaNO 3 , Mg(NO 3 ) 2 , NaBr, NaCl, KCl, MgCl 2 , potassium acetate or combinations thereof
  • the method includes providing a substantially saturated aqueous solution containing methanol and a salt, mixing the solution with the oil or the fat to generate a reaction mixture, and heating the reaction mixture to about 70 0 C to about 80 0 C, more preferably from about 40 0 C to about 60 0 C, to prepare the biodiesel.
  • a method for the preparation of a biodiesel from an oil or fat includes heating a reaction blend, which comprises a substantially saturated aqueous solution containing methanol and a salt, an oil or a fat, and an immobilized enzyme.
  • the present invention provides a use of a reaction mixture as described herein for the preparation of a biodiesel.
  • BRIEF DESCRIPTION OF THE DRAWINGS [0015]
  • Figure 1 illustrates a schematic showing a process of the present invention.
  • Figure 2 illustrates an effect of the methanol-palm oil ratio on the yield of biodiesel after 30 hours of reaction: (O) present invention, ( ⁇ ) comparative example (without MgCl 2 saturated water).
  • Experimental conditions were palm oil 1Og, lipase 0.4g, reaction temperature 40 0 C, methanol-MgC.2 saturated water ratio (3:1, v/v).
  • Figure 3 illustrates an effect of the palm oil-lipase ratio on the lipase specific activity: (O) present invention, ( ⁇ ) comparative example.
  • Experimental conditions were lipase 0.4g, reaction temperature 40 0 C, methanol-LiCl 2 saturated water ratio 2.33:1 (v/v), methanol-palm oil ratio 3:1 for the present invention and 3 :2 for the comparative example.
  • Figure 4 illustrates an effect of reaction temperature on lipase specific activity: (O) present invention, ( ⁇ ) comparative example. Experimental conditions were palm oil 1Og, lipase 0.4g, methanol-LiCl 2 saturated water ratio 2.33:1 (v/v), methanol-palm oil ratio 3:1 for the present invention and 3:2 for the comparative example.
  • Figure 5 illustrates a time course production of biodiesel: (O) present invention, ( ⁇ ) comparative example wherein methanolysis was conducted by two successive additions of methanol: 1/2 of the stoichiometric amount of methanol was added at the beginning of the reaction and the other 1/2 was added after 5 hours.
  • lower alkyl includes a saturated straight, branched, or cyclic hydrocarbon of Ci to C 6 , and specifically includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, cyclopentyl, isopentyl, neopentyl, hexyl, isohexyl, cyclohexyl, 3-methylpentyl, 2,2-dimethylbutyl, and 2,3-dimethylbutyl.
  • alkyl includes both straight chain and branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, and the like.
  • the alkyl group may optionally be substituted by one or more groups selected from alkyl, cycloalkyl, alkenyl, alkynyl, halo, haloalkyl, haloalkynyl, hydroxy, alkoxy, alkenyloxy, haloalkoxy, haloalkenyloxy, nitro, amino, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroheterocyclyl, alkylamino, dialkylamino, alkenylamine, alkynylamino, acyl, alkenoyl, .
  • alknoyl acylamino, diacylamino, acyloxy, alkylsulfonyloxy, heterocyclyl, heterocycloxy, heterocyclamino, haloheterocyclyl, alkylsulfenyl, alkylcarbonyloxy, alkylthio, acylthio, and phosphorus-containing groups such as phosphono and phosphinyl.
  • alcohol includes a hydrocarbon compound containing one or more hydroxy groups, and includes alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, pentanol, cyclopentanol, isopentanol, neopentanol, hexanol, isohexanol, cyclohexanol, 3-methylpentanol, 2,2-dimethylbutanol, and 2,3-dimethylbutanol.
  • lower alcohol refers to alcohols containing 1-6 carbon atoms.
  • oil or “oils” includes plant oils or fats, animal oils or fats, marine oils or fats, oils or fats from microbial origin, waste oils or greases, rendered product, or any mixture thereof.
  • the term "rendered product” includes a fat that has been treated, usually with heat, to remove water, solids, and other impurities.
  • biodiesel includes processed fuel derived from biological sources, as a transportation and power generation fuel or additives.
  • exemplary biodiesel includes fatty acid alkyl esters prepared from oils or fats.
  • feedstock includes any oils or fats from any source of plant oils or fats, animal oils or fats, marine oils or fats, oils of microbial origin, and artificial or synthetic glycerides, as well as wastes, effluents and residues from the processing of such materials.
  • plant oil includes fats, oils, or lipids derived from plant sources, such as agricultural crops and forest products, as well as wastes, effluents and residues from the processing of such materials, such as soap stock.
  • animal oil includes fats, oils or lipids derived from animal sources, as well as wastes, effluents and residues from the processing of such materials.
  • marine oils includes fats, oils or lipids derived from marine sources in water streams, as well as wastes, effluents and residues from the processing of such materials.
  • substantially saturated solution includes a concentrated solution that is at least 50% saturated by a solute (i.e., a salt), more preferably between 60- 80% saturated, even more preferably between 70-90% saturated, still even more preferably between 90-98% saturated.
  • a solute i.e., a salt
  • substantially saturated solution also include those solution that is 200% saturated.
  • R, R', R" and the fatty acid groups on a given glyceride can be the same or different.
  • the acid groups R, R 1 and R" can be obtained from any of the free fatty acids described herein.
  • Glycerides for the present invention include triglycerides in which R, R 1 and R" are all fatty acid groups, diglycerides in which two of R, R' and R" are fatty acid groups and one alcohol functionality is present; monoglycerides in which one of R, R 1 and R" is a fatty acid group and two alcohol functionalities are present; and glycerol in which each of R, R' and R" is an alcohol group.
  • Glycerides useful as starting materials of the invention include natural, processed, refined and artificial or synthetic fats and oils.
  • R' in the "fatty acid groups” or “acid groups” attached to the glycerides or to other esters used as substrates in the present invention. That is, a substrate of the present invention may comprise fats, oils or other esters having fatty acid groups formed from the free fatty acids or fatty acids discussed herein. II. Genera]
  • the present invention provides a novel reaction mixture and a method for the efficient production of biodiesels.
  • the mixture can be a substantially saturated solution with a predetermined ratio of alcohol and solvent or a substantially saturated solution in contact with a feedstock having predetermined ratios of both alcohol to solvent and alcohol to feedstock.
  • the substantially saturated solution generally contains an alcohol and a salt dissolved in a solvent.
  • the method provides admixing a substantially saturated solution with a feedstock and an enzyme under conditions sufficient to prepare biodiesels.
  • Figure 1 illustrates the general concept of the present invention for the preparation of biodiesels.
  • an alcohol 110 and a salt 120 are dissolved in a solvent 130 to form a substantially saturated solution 140.
  • the substantially saturated solution 140 is admixed with a feedstock 150 to generate a reaction mixture 160.
  • an enzyme 170 under reaction conditions produces a biodiesel 180.
  • the enzyme is an immobilized enzyme and the mixture is heated in the presence of the enzyme for the preparation of biodiesels.
  • the processes of the present invention have the advantages of enhancing the activity of the enzyme, reducing the poison of alcohol and substrate inhibition of the enzyme, increasing the heat resistance and thermal stability of the enzyme, and lowering the production cost. III. Mixtures
  • the present invention provides a reaction mixture containing a substantially saturated solution and a feedstock, which is in contact with the solution.
  • the substantially saturated solution contains an alcohol and a salt dissolved in a solvent, wherein the volume ratio of the alcohol to solvent varies from about 1:9 to about 9:1.
  • the ratio is from about 1 :2 to about 2:1, such as 1:2, 1:1, 2:1 and fractional numbers in between.
  • the present invention provides a reaction mixture containing a substantially saturated aqueous solution and an oil in contact with the solution, wherein the substantially saturated solution contains methanol, water and a salt, and wherein the ratio of methanol to water is from about 9:1 to about 1:9, such as 8:1, 7:1, 6:1, 5:1: 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1 :4, 1 :5, 1 :6, 1 :7, 1 :8, 1:9 and fractional numbers in between.
  • Suitable salts include, but are not limited to, LiCl, K 2 CO 3 , NaNO 3 , Mg(NO 3 ) 2 , NaBr, NaCl, KCl, MgCl 2 , potassium acetate, sodium acetate and combinations thereof.
  • Preferred oils include soy bean oil, palm oil, olive oil or mixtures thereof.
  • the present invention provides a reaction mixture containing methanol, water and a salt selected from the group consisting of LiCl, K2CO 3 , NaNO 3 , Mg(NO 3 ) 2 , NaBr, NaCl, KCl, MgCl 2 , potassium acetate and combinations thereof.
  • the salt dissolves in the water to form a substantially saturated solution, wherein the methanol dissolves in the substantially saturated solution.
  • the methanol and water have a volume ratio from about 1:9 to about 9:1.
  • the substantially saturated solution used in the present invention is prepared by dissolving a salt or a mixture of salts and an alcohol or mixtures of alcohols in a solvent at ambient temperature or an elevated temperature.
  • the temperature can range from about 20 0 C to about 80 0 C.
  • the salt used can be any salt that has solubility in the solvent and is suitable for the preparation of biodiesels.
  • the salts used can be inorganic salts, organic salts, hydrates or solvates thereof.
  • the salts can be metal halide, metal sulfate, metal nitrate, metal carbonate, metal carboxylate, amino acid carboxylate, ammonium salt, metal phosphate and combinations thereof.
  • the salt is selected from the group consisting of metal halide, metal sulfate, metal nitrate and a combination thereof.
  • the metal used can be a main group metal selected from groups I to group V elements (such as group I, II, III, IV or V) or a transition metal selected from groups 3 to group 12 elements (such as group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12).
  • the salt is selected from the group consisting of alkali metal halide, alkali metal sulfate, alkali metal nitrate, alkaline metal halide, alkaline metal sulfate, alkaline metal nitrate, and a combination thereof.
  • the metals include, but are not limited to Li, Na, K, Cs, Mg, Ca, Ba, Fe, Cu, Zn, Ag, Al, Sn, In, Mn, Cr, Ni, Au and combinations thereof.
  • the salts are soluble or partially soluble in a solvent to form a substantially saturated solution.
  • the salts are soluble in water.
  • the salts used include group I, group II, group III and group IV metal halides.
  • the salts used are group I and group II metal halides.
  • the salts are LiX, NaX, KX, RbX, CsX, K 2 X 2 and MgX 2 , where X is a halide, nitrate or acetate. More preferably, the salts in the mixture are selected from the group consisting of LiCl, K 2 CO 3 , NaNO 3 , Mg(NO 3 ⁇ , NaBr, NaCl, KCl, MgCl 2 , sodium acetate potassium acetate, Na 2 SO 4 , K 2 SO 4 , MgSO 4 , Cs 2 SO 4 , Na 3 PO 4 , K 3 PO 4 , NaHSO 4 , KHSO 4 , MgSO 4 , CsHSO 4 , Na 2 HPO 4 , K 2 HPO 4 , NaH 2 PO 4 and KH 2 PO 4 and combinations thereof.
  • the salts used are compounds having the formula M a H b (ZO 0 ) ⁇ xH-O, wherein M is ammonium, Li 5 Na, K, Rb or Cs. Z is Cl, Br 5 S, Se 5 N, P, As, Si 5 C 5 Ge, B 5 V, Mn, Pd 5 Cr 5 Mo or a lanthanide element.
  • the subscripts a, b, c and d are rational numbers, such that the compound is charge balanced.
  • the subscript a is • an integer from 1-5, preferably from 1-4, even more preferably from 1-3 and most preferably from 1 -2; the subscript b is an integer from 0-3; the subscript c is an integer from 2-4; and the subscript d is 1 or 2.
  • x is a non-negative rational number.
  • Exemplary salts include, but are not limited to, M 2 SO 4 , MHSO 4 , M 3 H(SO 4 ) 2 , M 5 H 3 (SO 4 ) 4 -xH 2 O, M 3 PO 4 , M 2 HPO 4 , MH 2 PO 4 , M 2 SeO 4 , MHSeO 4 , M 3 H(Se0 4 ) 2 , M 5 H 3 (Se0 4 ) 4 , M 5 H 3 (SeO 4 VxH 2 O 5 M 4 SiO 4 , M 3 HSiO 4 , M 2 H 2 SiO 4 and M 3 HSiO 4 , where M is ammonium, Li, Na, K, Rb or Cs.
  • Any alcohol suitable for the preparation of the fatty acid alkyl esters that provides a biodiesel with the desired properties can be used.
  • Suitable alcohols for use in the present invention include, but are not limited to, saturated straight, branched, or cyclic alcohols of Cj to C 6 , and specifically include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, cyclopentanol, isopentanol, neopentanol, hexanol, isohexanol, cyclohexanol, 3-methylpentanol, 2,2-dimethylbutanol, 2,3-dimethylbutanol and combinations thereof.
  • the alcohol used in the present invention is preferably an aliphatic alcohol having 1 to 10 carbon atoms, though no particular limitation is imposed thereon.
  • Fatty acid esters used as diesel fuels or industrial raw materials are preferably lower alkyl esters.
  • the alcohol is more preferably a lower alkyl alcohol having about 1 to 6 carbon atoms such as methanol, ethanol, propanol, butanol, isobutanol, t-butanol, pentanol, cyclopentanol, isopentanol, neopentanol, hexanol, isohexanol, cyclohexanol, 3-methylpentanol, 2,2-dimethylbutanol, 2,3- dimethylbutanol and combinations thereof.
  • methanol or ethanol is even more preferable from the viewpoint of cost and easiness of recovery.
  • any solvents or mixtures of solvents that are substantially immiscible with the oils or the fats can be used.
  • the solvents used are miscible with lower alkyl alcohols.
  • the solvents used include, but are not limited to, water, dimethylsulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide, acetonitrile, ionic liquids and combinations thereof.
  • DMSO dimethylsulfoxide
  • DMF dimethylformamide
  • acetamide dimethylacetamide
  • acetonitrile ionic liquids and combinations thereof.
  • An example of such a solvent is water.
  • Water can be any one of tap water, well water, distilled water, deionized water and the like. In one embodiment, water is used. In another embodiment, a water-soluble substance such as glycerin, or a mixture thereof, with water can be used.
  • the solvent is selected from the group consisting of water, ionic liquid, a polar solvent substantially immiscible with oils and fats.
  • Various ratios of alcohol and solvent can be used in the present invention.
  • the present invention provides that the volume ratio of the alcohol and the solvent is from about 1:9 to about 9:1.
  • the ratio is from about 1 :2 to about 2:1.
  • the feedstock in the present invention can be any oil or fat from any source of glycerides, which can be used to prepare biodiesels or fuel additives with the desired properties.
  • the sources of glycerides include, but are not limited to, plants, animals, marines, microbe and artificial or synthetic glycerides.
  • the oil or fat can be refined and/or bleached, unrefined and/or unbleached.
  • Sources of glycerides for use in practicing the present invention include, but are not limited to, plant oils and fats, animal oils and fats, marine oils and fats, oils and fats of microbial origin, as well as artificial or synthetic glycerides.
  • suitable plant oils and oils of microbial origin include, but are not limited to, crude or refined soybean oil, bamboo oil, bamboo fat, corn oil, coconut oil, palm oil, palm kernel oil, palm olein, palm stearin, palm kernel olein, palm kernel stearin, mango kernel oil, meadowfoam oil, neat's foot oil, sesame oil, rapeseed oil, cottonseed oil, linseed oil, groundnut oil, hazlenut oil, hempseed oil, jatropha oil, peanut oil, canola oil, olive oil, castor oil, safflower oil, rice germ oil, sasanqua oil, wheatgerm oil, tsubaki oil, rung oil and mixtures thereof.
  • suitable animal oils or fats include, but are not limited to, tallow, lard, butter fat, cocoa butter, cocoa butter substitutes, illipe fat, kokum butter, mowrah fat, phulwara butter, sal fat, bacon grease, yellow grease, fish oil, pig fat, poultry fat, milk fat, shea oil, beef tallow, mutton tallow, tallow, borneo tallow, lard, lanolin and mixtures thereof.
  • marine oils include, but are not limited to, fish oil, menhaden, candlefish oil, cod-liver oil, orange roughy oil, pile herd, sardine oil, whale and herring oils and mixtures thereof. Also, wastes of these fats and oils and wastes of these edible oils may also be used as the raw material.
  • the feedstock in the present invention is selected from the group consisting of animal fats, sunflower seed oil, soyabean oil, palm oil, coconut oil, linseed oil, rapeseed oil, corn oil, cottonseed oil, ground nut oil, canola oil, olive oil, castor oil and waste edible oils.
  • the feedstock is palm oil or olive oil.
  • glycerides include, but are not limited to, l,3-dipalmitoyl-2- monooleine (POP) 5 l(3)-palmitoyl-3(l)-stearoyl-2-monool- mecanic (POSt), l,3-distearoyl-2- monooleine (StOSt), triglyceride, diglyceride, monoglyceride, behenic acid triglyceride, trioleine, tripalmitine, tristearine, triglycerides of medium chain fatty acids and combinations thereof. Oils having both a higher boiling point and a lower boiling point can be used. A blend of at least two oils or fats selected from plant oils or fats, animal oils or fats, marine oils or fats, oils or fats of microbial origin and artificial or synthetic glycerides can also be used in the present invention.
  • POP l,3-dipalmitoyl-2- monooleine
  • POSt l,3-pal
  • Various molar ratios of alcohol to oil or fat can be used for the preparation of biodiesels.
  • the molar ratios of the alcohols to oils or fats range from 0.5 to 400, preferably from 0.5 to 100, even more preferably from 2 to 10.
  • the ratio of alcohol to oils or fats is from about 3 or about 5.
  • the present invention also provides a method for the preparation of a biodiesel from a feedstock.
  • the method includes mixing a substantially saturated or a saturated solution containing an alcohol and a salt dissolved in a solvent with the feedstock to produce a reaction mixture under conditions sufficient, for example, heating the reaction mixture in the presence of an immobilized enzyme to prepare the biodiesel.
  • the method includes providing a substantially saturated or a saturated solution containing an alcohol and a salt dissolved in a solvent, mixing the solution with the feedstock and an immobilized enzyme to produce a reaction mixture, and optionally heating the reaction mixture to prepare the biodiesel.
  • the method further comprises the step of separating the biodiesel from the mixture.
  • the method includes heating a reaction blend, which comprises a substantially saturated solution containing an alcohol and a salt dissolved in a solvent; a feedstock; and an immobilized enzyme.
  • the method includes mixing a saturated aqueous solution containing methanol and a salt with the oil or the fat to generate a reaction mixture and heating the reaction mixture to about 30 0 C to about 60 0 C to prepare the biodiesel.
  • the method includes providing a saturated aqueous solution containing methanol and a salt, mixing the solution with the oil or the fat to generate a reaction mixture, and heating the reaction mixture to about 30 0 C to about 60 0 C to prepare the biodiesel.
  • the method includes heating a reaction blend, which comprises a saturated aqueous solution containing methanol and a salt, an oil or a fat and an immobilized enzyme.
  • the salt is LiCl, NaCl, KCl, MgCl 2 , K 2 CO 3 , NaNO 3 , Mg(NO) 2 , NaBr, potassium acetate, or combinations thereof.
  • the reaction mixture in the present invention is obtained by either dissolving a salt and an alcohol in a solvent at a predetermined alcohol to solvent ratio or mixing a substantially saturated solution with an oil or a fat at a predetermined mixing ratio.
  • the ratios can be empirically chosen to achieve a desired degree of biodiesel formation. In general, however, it is preferred that the alcohol and the solvent have a volume ratio between about 1 :9 to about 9:1.
  • the solvent and the oil or the fat have a molar mixing ratio from about 2:3 to about 30:1.
  • the solvent is preferably water.
  • An immobilized enzyme can be added prior to mixing the solution and the oils or fats to form the reaction mixture or alternatively, an enzyme can be added to the reaction mixture after the formation of the reaction mixture.
  • Any enzyme can be used as an enzyme to be immobilized without any particular limitation insofar as it can catalyze the conversion of oils or fats to form biodiesels.
  • enzymes include, but are not limited to, lipases and esterases. Lipases are typically obtained from prokaryotic or eukaryotic microorganisms and typically fall into one of three categories (see, Macrae, A. R. et al J. Am. Oil Chem. Soc. 1983, 60, 243A). A first category includes nonspecific lipases capable of releasing or binding any fatty acid from or to any glyceride position. These lipases are similar to chemical processes.
  • lipases have been obtained from Candida cylindracae, Corynebacterium acnes and Staphylococcus aureus.
  • a second category of lipases only adds or removes specific fatty acids to or from specific glycerides. Thus, these lipases generally tend to be useful for producing or modifying specific glycerides.
  • Such lipases have been obtained from Geotrichum candidium and Rhizopus Aspergilus, and Mucor genera.
  • a third category of Upases catalyze the removal or addition of fatty acids from the glyceride carbons on the end in the 1- and 3- positions.
  • the enzyme is preferably a lipase.
  • lipases derived from microorganisms such as those belonging to the genus of Rhizopus, the genus of Rhizomucor, the genus of Aspergillus, the genus of Chromobacterium., the genus of Mucor, the genus of Pseudomonas, the genus of Geotrichum, the genus of Penicilium, the genus of Humicola, the genus of Fusarium, and the genus of Candida; and animal lipases such as pancreatic lipase. Particularly preferred are lipases derived from bacteria belonging to the genus of Pseudomonas and the fungi belonging to the genus of Candida.
  • lipases examples include lipase of Rhizopus delemar, lipase of Rhizomucor miehei, lipase of Aspergillus niger, lipase of Humicola lanuginose, lipase of Mucor javanicus, lipase of Candida Antarctica, lipase of Candida cylindracea and lipase of Fusarium heterosporum. These lipases may be used in their native form, or in the form of lipase that has been immobilized on celite, ion exchange resin or a ceramic carrier.
  • the enzyme use in the method of the invention is a lipase selected from the group consisting of Candida Antartica, Candida Cylindracea, Pseudomonas Cepacia, Mucor Miehei, Mucor Javaicus, Aspergillus Niger, swine pancreas, Aspergillus Subtilis, Aspergillus Orayze, Rhyzopus Oryzae, Chromobacterium Visocosum.
  • the enzyme is a lipase from Candida Antartica.
  • Immobilization of the enzyme can be performed by any known method such as a carrier binding including an inorganic carrier covalent bond method and an organic carrier covalent bond method, cross-linking, entrapment and adsorption (see, U.S. Pat. Nos.
  • Carrier binding method is preferable in view of handling.
  • Carrier binding includes chemical adsorption by which the enzymes are adsorbed to an ion-exchange resin, or physical adsorption. In the present invention, physical adsorption using a porous carrier is preferable.
  • useful carriers have been described for enzyme immobilzation (see, U.S. Pat. Nos. 4,940,845 and 5,219,733).
  • Useful carriers are preferably microporous and have a hydrophobic porous surface.
  • the pores have an average radius of about 10 A to about 1,000 A, and a porosity from about 20% to about 80% by volume, more preferably, from about 40% to about 60% by volume.
  • the pores give the carrier an increased enzyme bonding area per particle of the carrier.
  • preferred inorganic carriers include, but are not limited to, porous glass, porous ceramics, celite, porous metallic particles such as titanium oxide, stainless steel or alumina, porous silica gel, molecular sieve, active carbon, clay, kaolinite, perlite, glass fibers, diatomaceous earth, bentonite, hydroxyapatite, calcium phosphate gel, alkylamine derivatives of inorganic carriers, and combinations thereof.
  • organic carriers examples include, but are not limited to, microporous Teflon, aliphatic olefinic polymer (e.g., polyethylene, polypropylene, a homo- or copolymer of styrene or a blend thereof or a pretreated inorganic support) nylon, polyamides, polycarbonates, nitrocellulose, acetylcellulose, and combinations thereof.
  • suitable organic carriers include, but are not limited to, hydrophillic polysaccharides such as agarose gel with an alkyl, phenyl, trityl or other similar hydrophobic group to provide a hydrophobic porous surface.
  • Microporous adsorbing resins include, but are not limited to, those made of styrene or alkylamine polymer, chelate resin, ion exchange resin such as weakly basic anion exchange resin having a tertiary amine as the exchange group, composed basically of polystyrene chains cross linked with divinylbenzene and hydrophilic cellulose resin such as one prepared by masking the hydrophilic group of a cellulosic carrier.
  • the immobilization of the enzyme can be conducted by immobilizing the enzyme on a suitable carrier.
  • a number of inorganic and organic carriers can be used to immobilize an enzyme.
  • carrier include, but are not limited to, celite, ion exchange resins, ceramics and the like.
  • an ion exchange resin is used.
  • the material, properties and ion-exchanging groups of the ion exchange resin can be chosen in view of the adsorbability and exhibiting rate of activity of the enzyme to be adsorbed.
  • an anion exchange resin is used.
  • anion exchange resin examples include phenol-formaldehyde-based anion exchange resins, polystyrene-based anion exchange resins, acrylamide-based anion exchange resins, and divinylbenzene-based anion exchange resins.
  • suitable carriers can be used to immobilized the enzyme used in the present invention.
  • the immobilization temperature is determined depending on the properties of the enzyme. It is desired to conduct the immobilization at a temperature where the enzymatic activity is not lost. The immobilization can be conducted at about 0 0 C to about 60 0 C, preferably at about 5 0 C to about 40 0 C.
  • Enzymatic activity generally tends to be affected by factors such as temperature, light and moisture content.
  • Light can be kept out by using the various light blocking or filtering means known in the art.
  • Moisture content which includes ambient atmospheric moisture, can be controlled by operating the process as a closed system.
  • the closed system can be under a positive inert atmospheric pressure to expel moisture.
  • a bed of nitrogen gas can be placed on top of the substrate, purification bed or column, or packed lipase column.
  • the reaction can be carried out at any temperature that is suitable for the preparation of biodiesels.
  • the reaction can be conducted at a temperature ranging from about 0 0 C to about 150 0 C.
  • the reaction is performed between about 30 0 C to about 85 0 C.
  • the reaction mixture is heated to a temperature between about 70 0 C to about 80 0 C.
  • the reaction is carried out at a temperature of about 30 0 C to about 60 0 C.
  • the feedstock to enzyme weight ratio is from about 10: 1 to about 200: 1. In a preferred embodiment, the feedstock to enzyme weight ratio is from about 10:1 to about 80: 1. In another embodiment, the feedstock to enzyme weight ratio is from about 50: 1 to 60: 1. In one embodiment the feedstock is palm oil and the ratio of palm oil to enzyme is from about 10: 1 to about 80: 1.
  • the methods of the present invention include mixing a substantially saturated aqueous solution with the oils or the fats and heating the reaction mixture in the presence of an immobilized enzyme to about 70 0 C - 80 0 C, or to about 30 0 C to 60 0 C.
  • the methods of the present invention include providing a substantially saturated aqueous solution, mixing the solution with the oils or the fats, and heating the reaction mixture in the presence of an immobilized enzyme to about 70 0 C - 80 0 C, or to about 30 0 C to 60 °C.
  • the substantially saturated aqueous solution contains a salt and methanol.
  • the salt used can be NaX, KX, K 2 X 2 , LiX, MgX 2 or a mixture thereof, wherein X is a halide, nitrate or acetate.
  • the salt used is LiCl, K 2 CO 3 , NaNO 3 , Mg(NO 3 ) 2 , NaBr, NaCl, KCl, MgCl 2 , potassium acetate, or combinations thereof.
  • the methanol to water volume ratio is from about 1 :9 to about 9: 1, preferably about 1:2 to about 2:1.
  • the molar ratio of the methanol to oil or fat is from about 1:2 to about 5:1.
  • the method for the preparation of a biodiesel from an oil or fat comprising: a) providing a substantially saturated aqueous solution containing methanol and a salt selected from the group consisting of LiCl, K 2 CO 3 , NaNO 3 , Mg(NO 3 ) 2 , NaBr, NaCl, KCl, MgCl 2 , potassium acetate, and combinations thereof. b) mixing the solution with the oils or fats to generate a reaction mixture; and c) heating the reaction mixture in the presence of an immobilized enzyme to about 40 0 C to about 60 0 C to prepare the biodiesel.
  • a salt selected from the group consisting of LiCl, K 2 CO 3 , NaNO 3 , Mg(NO 3 ) 2 , NaBr, NaCl, KCl, MgCl 2 , potassium acetate, and combinations thereof.
  • Biodiesels produced can be separated by various means, such as filtration, centrifugation and distillation.
  • the insoluble impurities can be removed by a separation means, such as centrifugation or filtration.
  • the insoluble impurities are removed by centrifugation.
  • the alcohol and/or solvent can be removed, for example, by distillation.
  • the process can include distilling or evaporating the alcohol or solvent prior to the distilling to separate at least a portion of the unreactive oils or fats.
  • the process can further comprise subjecting the distillate to a subsequent distillation to form a second distillate and a second residue, thereby further purifying and/or separating the unreactive oils or fats.
  • Biodiesels prepared according to the methods of the present invention can be analyzed by various instrumentation well known to those of skill in the art.
  • analytical analysis can be performed using HPLC with a UV detector.
  • the detector is set at 210 nm and a prevail C18 5 ⁇ column (250 4.6 mm, Alltech Associates, Inc., USA) can be employed.
  • the mobile phase comprises for example, three different components: hexane, isopropanol and methanol.
  • Reservoir A contains methanol and reservoir B contains a mixture of isopropanol and hexane (5:4, v/v).
  • a gradient from 100% A to 50% A + 50% B linearly over 30 min is used.
  • the flow rate of the mobile phase can be 1 ml/min and the sample injection volume is 10 1.
  • This non-aqueous RP-HPLC method is a modification of the prior art method (see, Holcapek, M. et al. J Chromatogr A 1999, 858, 13).
  • the methods of the present invention have provided an effective means of reducing or overcoming the enzyme poisoning frequently encountered in the production of biodiesels.
  • Figure 2 illustrates the effect of varying methanol to oil ratios on the production of biodiesels. In the present invention, nearly quantitative production of the biodiesels is observed at a methanol-oil ratio of about 3:1 to about 5:1.
  • the yield of the biodiesels is, however, less satisfactory (e.g, ⁇ 20% after 30 hours of reaction).
  • less than 7% of the biodiesels is obtained under the similar methanol-oil molar ratios.
  • the methods of the present invention also have the advantage of significantly reduced substrate inhibition and lowered production cost associated with lipases.
  • the reaction rate of the biodiesel production increases with the increasing of the palm oil-lipase ratio as a result of reduced substrate inhibition.
  • the reaction rates become optimized and reach constant at a palm-oil lipase ratio of 50: 1.
  • the reaction rate of the biodiesel production starts to decrease when the palm oil-lipase ratio is 25: 1.
  • the reaction rate of the biodiesel production using the method of the present invention is about seven times faster than that of the prior art.
  • the methods of the present invention are capable of enhancing the high temperature activity and stability of the enzyme. As shown in Figure 4, the lipases used in the methods of the present invention are about three times as reactive as those in the prior art.
  • the overall biodiesel production rate according to the methods of the present invention is significantly faster than those in the prior art.
  • the overall methanolysis rate using the methods of the present invention is about four times faster than that in the prior art ( Figure 5).
  • the enhanced reaction rate can be attributed in part to the large interfacial area between oil and solution, in-situ separation of the glycerol produced and facile substrate diffusion to the active site of the enzyme.
  • palm oil 1Og, lipase 0.4g, methanol-LiCl 2 saturated water having a ratio of 2.33:1 (v/v), methanol-palm oil having a ratio of 3.2:1 (inventive) and 3:1 for the comparative example were used.
  • the temperatures for the present invention and the comparative example were 60 °C and 40 0 C, respectively.
  • Time course production of the biodiesels was conducted at optimal reaction conditions. The results are shown in Fig. 5 and compared with those obtained by a method where methanolysis was conducted by two successive additions of 1/2 molar equivalent of methanol.

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Abstract

L'invention porte sur un nouveau procédé de production de biodiesels à partir d'huiles et de graisses consistant à préparer un mélange réactif contenant une solution de sel saturée ou quasi saturée, des d'huiles ou graisses et une enzyme immobilisée, dans des conditions propres à la préparation de biodiesels. Ladite solution contient un sel et un alcool dissous dans un solvant, l'alcool et le solvant se trouvant dans un rapport prédéterminé. L'invention recourt également à des rapports prédéterminés alcool/huiles ou graisses, et huiles ou graisses/enzyme.
PCT/SG2006/000343 2005-11-14 2006-11-10 Production enzymatique de biodiesels WO2007055661A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2189535A1 (fr) 2008-11-21 2010-05-26 Centre National de la Recherche Scientifique Utilisation de liquides ioniques pour la mise en oeuvre d'un procédé pour la préparation de biocarburant
WO2013109136A1 (fr) * 2012-01-20 2013-07-25 Universiti Malaya (Um) Procédé pour la production de lipase à partir d'huile de palme
CN103920468A (zh) * 2014-05-06 2014-07-16 济南大学 一种离子液体负载型棕榈树皮吸附剂的制备方法
CN109666711A (zh) * 2019-02-14 2019-04-23 莱芜职业技术学院 一种生物柴油及其制备方法
CN110184313A (zh) * 2019-06-07 2019-08-30 河南师范大学 一种离子液体促使酶催化制备生物柴油的方法

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WO2006050589A1 (fr) * 2004-11-09 2006-05-18 Cognis Ip Management Gmbh Production de biodiesel a partir de soapstock
WO2006077023A2 (fr) * 2005-01-19 2006-07-27 Cognis Ip Management Gmbh Compositions pouvant être utilisées comme biocarburant

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WO2006050589A1 (fr) * 2004-11-09 2006-05-18 Cognis Ip Management Gmbh Production de biodiesel a partir de soapstock
WO2006077023A2 (fr) * 2005-01-19 2006-07-27 Cognis Ip Management Gmbh Compositions pouvant être utilisées comme biocarburant

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2189535A1 (fr) 2008-11-21 2010-05-26 Centre National de la Recherche Scientifique Utilisation de liquides ioniques pour la mise en oeuvre d'un procédé pour la préparation de biocarburant
US8470565B2 (en) 2008-11-21 2013-06-25 Centre National De La Recherche Scientifique Use of ionic liquids for implementing a process for the preparation of biodiesel
WO2013109136A1 (fr) * 2012-01-20 2013-07-25 Universiti Malaya (Um) Procédé pour la production de lipase à partir d'huile de palme
CN103920468A (zh) * 2014-05-06 2014-07-16 济南大学 一种离子液体负载型棕榈树皮吸附剂的制备方法
CN103920468B (zh) * 2014-05-06 2016-01-20 济南大学 一种离子液体负载型棕榈树皮吸附剂的制备方法
CN109666711A (zh) * 2019-02-14 2019-04-23 莱芜职业技术学院 一种生物柴油及其制备方法
CN109666711B (zh) * 2019-02-14 2021-02-12 莱芜职业技术学院 一种生物柴油及其制备方法
CN110184313A (zh) * 2019-06-07 2019-08-30 河南师范大学 一种离子液体促使酶催化制备生物柴油的方法
CN110184313B (zh) * 2019-06-07 2022-10-11 河南师范大学 一种离子液体促使酶催化制备生物柴油的方法

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