CN102144035A - Biodiesel production via enzymatic hydrolysis followed by chemical/enzymatic esterification - Google Patents
Biodiesel production via enzymatic hydrolysis followed by chemical/enzymatic esterification Download PDFInfo
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- CN102144035A CN102144035A CN2008801309674A CN200880130967A CN102144035A CN 102144035 A CN102144035 A CN 102144035A CN 2008801309674 A CN2008801309674 A CN 2008801309674A CN 200880130967 A CN200880130967 A CN 200880130967A CN 102144035 A CN102144035 A CN 102144035A
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- Prior art keywords
- lipase
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- esterification
- acid
- lipid acid
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- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- NCYCYZXNIZJOKI-UHFFFAOYSA-N vitamin A aldehyde Natural products O=CC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-UHFFFAOYSA-N 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
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- 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
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/02—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils
- C11C1/04—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by hydrolysis
- C11C1/045—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by hydrolysis using enzymes or microorganisms, living or dead
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- 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
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- 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
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- 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
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Abstract
A method for biodiesel production via enzymatic hydrolysis of oils or fats followed by chemical/enzymatic esterification of free fatty acids produced in a hydrolysis step. The process comprises enzymatically hydrolyzing a triglyceride to form a fatty acid and glycerol; and esterifying a lower alcohol with the fatty acid to form biodiesel.
Description
Background of invention
Biofuel (alkyl ester of longer chain fatty acid) is to carry out transesterify and the synthetic environment-friendly fuel by natural glycerin three esters (as vegetables oil, Tallow, beef) and the low-molecular-weight alcohol that is generally methyl alcohol.Biofuel industrial be by use highly basic as the chemical catalysis of catalyzer produce (referring to Connemann J and Krallmann A., Process for the continuous production of lower alkyl esters of higher fatty acid (method of the lower alkyl esters of continuous production higher fatty acid)., United States Patent (USP) 5,354, No. 878; Hanna MA, Transesterification process for production of Biodiesel (ester exchange method of production biofuel), U.S. Patent Publication 2003/0032826 A1; Lee JH, One-stage process for feed and Biodiesel and Lubricant oil (single stage method that is used for feed and biofuel and lubricating oil), U.S. Patent Publication 2004/0022929 A1).Yet strong alkali method has some shortcomings, for example is difficult to reclaim glycerine, need remove alkaline catalysts and handle alkaline waste water from product.In addition, raw material must meet strict specification (referring to Lotero E.et al., Ind.Eng.Chem.Res.Rev, 44:5353-5363 (2005)).For example, raw material must be anhydrous basically and FFA content can not surpass 0.5wt%.The existence of impurity can make the alkali method produce soap, thereby increases viscosity.High viscosity can cause the difficulty in downstream separation, thereby seriously hinders the production of fuel-grade biofuel.In order to satisfy above-mentioned raw material specification requirement, need to use height purified vegetables oil, its price can account for the 60-75% (referring to Lotero E.et al., Ind.Eng.Chem.Res.Rev, 44:5353-5363 (2005)) of biofuel final cost.In addition, refining process (250 ℃ and 1-3mmHg) has destroyed antioxidant (vitamin-E and carotene), thereby has reduced the oxidative stability of biofuel.
The above-mentioned shortcoming of alkali method makes the investigator seek to reduce difficulty and reduces the catalysis of cost and the alternative of processing.Method based on acid catalyzed reaction has the potentiality that realize this purpose, because acid catalyst is more insensitive to FFA, and catalytic esterification and transesterify simultaneously.Yet the catalytic ester exchange method of liquid acid is on commercial applications and universal unlike its corresponding base catalyzed reactions.The liquid acid catalyzed reaction is one of the main reasons (referring to Srivastava A and Prasad R., Renewable Sustainable Energy Rev., 4:111-133 (2000)) than slow this a lot of fact of liquid base catalyzed reaction.Though speed of reaction can increase by improving temperature, and the side reaction such as pure etherificate may take place under high temperature and high pressure.In addition, liquid catalyst causes serious pollution problem, and this makes must carry out good separation and purifying products flow process.In order to reduce the problem of separation and purifying, reported solid acid catalyst, but this method still needs high reaction temperature and pressure.For example, activatory montmorillonite KSF transformation efficiency of showing under 220 ℃ and 52 crust is 100% (referring to Lotero E.et al., Ind.Eng.Chem.Res.Rev, 44:5353-5363 (2005)).The esterification and the transesterification reaction of use macroporous resin 15 (Amberlyst 15) have been studied.Though macroporous resin has very high activity for the esterification of carboxylic acid, its activity for oily or fatty transesterify is very low, and needs gentle reaction conditions to avoid the degraded of catalyzer.Under relatively low temperature (60 ℃), when reaction is under atmospheric pressure carried out and the initial mol ratio of methyl alcohol and oil when being 6: 1, the transformation efficiency of sunflower seed oil it is reported only be 0.7% (referring to Vicente G et al., Ind.Crops Products, 8:29-35 (1998)).
Utilize the enzymatic transesterification of lipase to produce more attractive,, and be easy to finish the purifying of fatty acid methyl ester because can easily reclaim the glycerine that produces as by product for biodiesel fuel.Confirmed the methanolysis of utilizing enzyme (as fixed antarctic candida (Candida Antarctica) lipase) to carry out vegetables oil can be used for the production biofuel (referring to United States Patent (USP) 5,713, No. 965; 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).Yet lower alcohol (as methyl alcohol) makes poisoning by enzyme easily, thereby causes enzymic activity to reduce; Perhaps by product is adsorbed on the enzyme surface and the avtive spot of blocking-up substrate arrival enzyme, thus inhibitory enzyme activity.
Because previous reasons, need the effective and economically viable method of exploitation, use low-cost raw material to produce thing diesel oil next life such as the thick plam oil (CPO) that contains big water gaging and FFA.This method should provide make catalyzer (chemical catalyst or enzyme) but recirculation, and to the more insensitive system of water, FFA and methyl alcohol.The present invention has satisfied these and other demands.
Summary of the invention
The invention provides by enzymatic hydrolysis then esterification come from the oil or the especially high-efficiency method of fatty production biofuel.In certain embodiments, this method needs gentle reaction conditions, and uses low cost raw material, for example contains the thick plam oil (" CPO ") of big water gaging and free fatty acids.Method as herein described has reduced and the commercial used relevant problem of base-catalyzed method.
Therefore, in one embodiment, the invention provides the production method of bio-diesel oil, this method comprises:
With the triglyceride level enzymically hydrolyse to form lipid acid and glycerine; And
Thereby the lower alcohol esterification is formed biofuel with described lipid acid.
In some aspects, described esterif iotacation step is chemical catalysis or enzyme-catalyzed change.For example, in one embodiment, the chemical esterification of described lipid acid comprises:
Lipid acid is mixed with pure and mild acid catalyst; And
Mixture is hatched time enough to form biofuel under enough temperature.
In other respects, the enzymatic esterification of described lipid acid comprises:
Lipid acid is mixed with pure and mild lipase; And
Mixture is hatched time enough to form biofuel under enough temperature.
Compared with prior art, method of the present invention makes that output is higher, catalyst recovery is easier and product separation is simpler.By detailed Description Of The Invention and accompanying drawing hereinafter, above-mentioned and other purpose, aspect and embodiment can be more apparent.
Description of drawings
Fig. 1 illustrates embodiment of the present invention.
Fig. 2 illustrates embodiment of the present invention.
Fig. 3 A-B illustrates before the CPO hydrolysis of coming unstuck the UV spectrum of (B) sample behind (A) and hydrolysis.
Fig. 4 A-B illustrates before the PALM FATTY ACID esterification UV spectrum of (B) sample behind (A) and esterification.
Fig. 5 is illustrated in the CPO hydrolysis under the different lipase concentration in the damping fluid.Reaction conditions: CPO2g, lipase solution 2ml, hunting speed 250rpm, 40 ℃ of temperature.
Fig. 6 illustrates the hydrolysis reaction of CPO under differing temps that come unstuck.Reaction conditions: CPO 2g, lipase solution (1mg/ml) 2ml, hunting speed 250rpm.
Fig. 7 illustrates the hydrolysis reaction of CPO under different damping fluids and oil ratio example (v/v) that come unstuck.Reaction conditions: CPO 2g, lipase 2mg, hunting speed 250rpm, 40 ℃ of temperature.
Fig. 8 illustrates methyl and the ethyl esterification of macroporous resin 15 catalytic palm FFA in the octane-iso.Reaction conditions: the 10ml raw material (FA in the octane-iso, 0.32M), 1g macroporous resin 15,60 ℃ of temperature, 400% stoichiometric methyl alcohol or ethanol, 250rpm vibration.
Fig. 9 illustrates methyl and the ethyl esterification of Novozym 435 catalytic palm FFA.Reaction conditions: 10ml raw material (FFA in the octane-iso, 0.32M)), 0.04g Novozym 435[15? ], 40 ℃ of temperature, 120% stoichiometric methyl alcohol or ethanol, 250rpm vibration.
Figure 10 illustrates the comparison of Novozym 435 catalysis and macroporous resin 15 catalytic palm FFA methyl-esterified.
Figure 11 illustrates macroporous resin 15 (A) and the reusable result of Novozym435 (B) in one embodiment of the invention.
Figure 12 illustrates the enzymically hydrolyse of the CPO that comes unstuck in embodiment of the present invention and the result of macroporous resin 15 or Novozym 435 catalytic esterifications, and this provides good productive rate (98-99%).
Detailed Description Of The Invention
I. definition
Term used herein " low alkyl group " comprises C
1To C
6Saturated straight chain, side chain or cyclisation hydrocarbon, and comprise methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-especially,, the tertiary butyl, amyl group, cyclopentyl, isopentyl, neo-pentyl, hexyl, isohexyl, cyclohexyl, 3-methyl amyl, 2,2-dimethylbutyl and 2, the 3-dimethylbutyl.
Term used herein " alcohol " comprises the hydrocarbon compound that contains one or more hydroxyls, and comprise for example following alcohol: methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, isopropylcarbinol, the trimethyl carbinol, amylalcohol, cyclopentanol, primary isoamyl alcohol, neopentyl alcohol, hexanol, isohexyl alcohol, hexalin, 3-methyl amyl alcohol, 2,2-dimethyl butyrate alcohol, 2,3-dimethyl butyrate alcohol, and their isomer.
Term used herein " oil (oil) " or " oil (oils) " comprise vegetables oil or fat, animal oil or fat, marine oil or fat, microbe-derived oil or fat, abendoned oil or lubricating grease, refinement product (rendered product) or their any mixture.
Term used herein " refinement product " comprise usually remove by heat treated anhydrate, the fat of solid and other impurity.
Term used herein " biofuel " comprises the fatty acid alkyl ester as transportation and fuel used to generate electricity or additive.
Term used herein " raw material " comprises thick plam oil; Perhaps any oil or fat, it derives from any vegetables oil or fat, animal oil or fat, marine oil or fat, microbe-derived oil and artificial or synthetic glyceryl ester; And from waste, waste water and the residue of the course of processing of above-mentioned materials.
Term used herein " vegetables oil " comprises from fat, oil or lipid such as the plant origin of farm crop and Forest products, and from waste, waste water and residue such as the above-mentioned materials course of processing of soap stock.
Term used herein " animal oil " comprises fat, oil or the lipid from animal-origin, and from waste, waste water and the residue of the above-mentioned materials course of processing.
Term used herein " marine oil " comprises fat, oil or the lipid from marine products source in the current, and from waste, waste water and the residue of the above-mentioned materials course of processing.
The glyceryl ester that the present invention uses comprises that chemical formula is the molecule of (R) CH (R) CH (R ') (R ") CH (R "), wherein R, R ' and R " be selected from-H ,-OH or molecular formula-O (C=O) R " ' shown in fatty acid group, R wherein " ' be saturated, unsaturated or how unsaturated; straight or branched; have or the carbochain of unsubstituted, wherein glyceryl ester have at least one-O (C=O) R " '.R on the given glyceryl ester, R ', R " can be identical or different.R, R ' and R " can obtain from any free fatty acids as herein described.Glyceryl ester of the present invention comprises the triglyceride level with three fatty acid groups, has the triglyceride and the monoglyceride with a fatty acid group of two fatty acid groups.Comprise natural, processing, refining and artificial or synthetic is fatty and oily as the glyceryl ester of starting raw material of the present invention.
The term " fatty acid " group " or " acid groups " comprise molecular formula-O (C=O) R " ' shown in chemical group.These " fatty acid groups " or " acid groups " are by being connected with the rest part of glyceryl ester with the covalent linkage of the independent bonded Sauerstoffatom of carbonyl carbon.On the contrary, term " fatty acid " " or " free fatty acids " all refer to HO (C=O) R " ', and not with the glyceryl ester covalent attachment.As described herein, in " fatty acid group ", " acid groups ", " free fatty acids " and " lipid acid ", R " ' be saturated, unsaturated or how unsaturated, straight or branched has or the carbochain of unsubstituted.It should be recognized by those skilled in the art that the R of " free fatty acids " as herein described or " lipid acid " (be HO (C=O) R " ') " ' be connected with glyceryl ester or the present invention in be used as " fatty acid group " or the R in " acid groups " of other esters of substrate " ' effect is identical.Be that substrate of the present invention can comprise that fat, oil or other have the ester by free fatty acids as herein described or the formed fatty acid group of lipid acid.
II. embodiment
The invention provides the method thick or that refined plant is oily or Tallow, beef is produced biofuel (biological example diesel oil) of utilizing.On the one hand, the present invention relates to Tallow, beef, vegetables oil or their mixture that contains triglyceride level is that raw material is produced fatty acid ester.This method comprises by enzymically hydrolyse makes triglyceride feedstock produce free fatty acids.Then, introduce alcohol and with free fatty acids with described pure esterification, thereby form the product that contains fatty acid ester.
The invention provides the method for producing fatty acid ester economically by triglyceride feedstock hydrolysis and pure esterification subsequently.The method of this paper can be implemented continuously by the mode that output is higher than art methods.The fatty acid ester that is produced is of value to produces lubricant and such as the fuel of biofuel.
Fig. 1 illustrates an embodiment of production method of bio-diesel oil 100.On the one hand, will produce free fatty acids 115, G ﹠ W 120 such as the raw material enzymically hydrolyse that contains triglyceride level 112 of vegetables oil 110.Triglyceride level can derive from vegetables oil, Tallow, beef, tallow, lubricating grease or reclaim refine oily or fatty.Then, utilize catalyzer (for example acid or enzyme catalyst), lipid acid 115 can be used for the esterification of alcohol.Usually, described lipid acid is C
12To C
22Lipid acid.Esterification 122 produces biofuel 130 and water 132.Can randomly make with extra care G ﹠ W product, wherein water be distilled to produce purified glycerine 161, perhaps glycerine can be used for for example fermentation reaction of other chemical 141 from the crude vegetable oil hydrolysis.
Turn to Fig. 2 now, it shows the more detailed technical process 200 of the inventive method, wherein in the reactor 225 of moisture 212 (for example recirculation) and organic solvent 215 (for example recirculation), will contain the thick plam oil (CPO) of triglyceride level or vegetables oil or fat 202 and for example utilize that enzyme catalyst 210 (for example lipase) is hydrolyzed.The product that will contain free fatty acids, G ﹠ W is transferred to separation vessel 230 from reactor 225, wherein free fatty acids 233 can be transferred in second reactor 248 or 250 (for example is being used, and another is in regeneration) that contains such as the catalyzer of lipase or acid.The mixture 235 of glycerine, water and lipase can be transferred to hollow-fibre membrane 236, and make lipase 211 be circulated back to reactor 225.G ﹠ W 237 from film 236 can be used for fermentation and generate other chemical 240.In reactor 248 or 250, free fatty acids 233 is used for esterification such as lower alcohol (C for example
1-C
6Alcohol is as methyl alcohol or ethanol) alcohol.The esterification of lower alcohol 242 can utilize lipase (for example Novozym435) or acid catalyst (for example macroporous resin 15) catalysis.Catalyzer in the reaction vessel 248 or 250 can utilize such as the polar solvent of the trimethyl carbinol regenerates.After reaction finishes, come the ester of reaction mixture to separate, wherein with alcohol 238, solvent 258 and water 262 distillation and recirculation by distillation 271.Can use final biofuel product 260, or it is mixed with petroleum diesel.Suitable reactor is including, but not limited to fixed-bed reactor, fluidized-bed reactor and stirred-tank reactor.
In some cases, with raw material and enzyme (for example lipase) with water and the optional organic solvent reactor of packing into.Advantageously, the raw material that comprises triglyceride level can contain water.With raw material (the CPO for example comes unstuck) reactor of packing into, randomly be preheated to about 20-60 ℃, preferred about 25 ℃ to about 50 ℃ (for example 40 ℃), and add lytic enzyme (for example lipase).Lipase can derive from plant, bacterium, fungi and more high eukaryote.Lipase can derive from extracellular or the cell, perhaps is the form of full cell.The lipase that is suitable for hydrolysis reaction or esterification is including, but not limited to deriving from fold candida (Candida rugusa), cylinder candiyeast (Candida cylindracea), Rhizopus oryzae (Rhizopus oryzae), cement look bacillus (Chromobacterium viscosum), pseudomonas cepacia (Pseuodomonus cepacia), pig pancreas (Hog pancrease), Pseudomonas fluorescens (Pseudomonus fluorescent), the lipase of antarctic candida B (Candida antarctica B) and Novozym 435 (fixed antarctic candida lipase B).Lipase can be fixed on acrylic resin or any solid support.Those skilled in the art can know that other are applicable to lipase of the present invention.Randomly, lipase is regenerated by using polar solvent such as the trimethyl carbinol to wash.Other suitable polar solvents are including, but not limited to C
1-C
6Alkanol and other sterically hindered alkanols.
The fixing of enzyme can be undertaken by any currently known methods, the carrier that for example comprises inorganic carrier covalent linkage method and organic carrier covalent linkage method in conjunction with, crosslinked, catch and adsorb (referring to United States Patent (USP) 4,798, No. 793,5,166, No. 064,5,219, No. 733,5,292, No. 649 and 5,773, No. 266).Consider operation, the preferred vector combining method.Carrier is adsorbed onto any solid support (for example ion exchange resin) in conjunction with comprising by chemisorption or physical adsorption with enzyme.In the present invention, preferably utilize the physical adsorption of porous support.
Describe some and be used for the useful carrier of enzyme fixed (referring to United States Patent (USP) 4,940, No. 845 and 5,219, No. 733).Useful carrier is preferably micropore, and has hydrophobic porous surface.Usually, the mean radius in hole is for about
To about
Porosity is extremely about 80 volume % of about 20 volume %, and more preferably about 40 volume % are to about 60 volume %.The hole provides the enzyme bonded area of the every carrier granule that increases for carrier.The example of preferred inorganic carrier is including, but not limited to sintered glass, porous ceramics, celite (celite), such as the porous metal particle of titanium dioxide, stainless steel or aluminum oxide, porous silica gel, molecular sieve, gac, clay, kaolinite, perlite, glass fibre, diatomite, wilkinite, hydroxyapatite, calcium phosphate gel, the alkylamine derivative of inorganic carrier and their combination.The example of preferred organic carrier is including, but not limited to micropore teflon, aliphatic olefin hydrocarbon polymer (for example polyethylene, polypropylene, cinnamic homopolymer or multipolymer or their mixture or pretreated inorganic support) nylon, polymeric amide, polycarbonate, Nitrocellulose, rhodia and their combination.Other suitable organic carriers are including, but not limited to the hydrophilic polysaccharide such as sepharose, and it has alkyl, phenyl, trityl or other similar hydrophobic groupings so that the weep hole surface to be provided.Micropore polymeric adsorbent is including, but not limited to those micropore polymeric adsorbents of being made by vinylbenzene or alkylamine polymkeric substance; Resin; Ion exchange resin for example has the tertiary amine weak base anion-exchange resin of group in return; Basically the micropore polymeric adsorbent of forming by the crosslinked Vinylstyrene of polystyrene chain; And hydrophilic cellulose resin, for example the hydrophilic cellulose resin for preparing by the hydrophilic radical of covering cellulose carrier.
The fixing of enzyme can be undertaken by enzyme is fixed on the suitable carriers.Many inorganic and organic carriers can be used for fixing enzyme.The example of carrier is including, but not limited to celite, ion exchange resin, pottery etc.Make spent ion exchange resin in certain embodiments.The material of ion exchange resin, character and ion-exchange group can be selected according to the adsorptive power of the enzyme that will adsorb and the activity level that has.Use anionite-exchange resin in other embodiments.The example of anionite-exchange resin is including, but not limited to based on the anionite-exchange resin of phenol formaldehyde, based on the anionite-exchange resin of polystyrene, based on the anionite-exchange resin of acrylamide with based on the anionite-exchange resin of Vinylstyrene.It should be recognized by those skilled in the art that other suitable carriers can be used for fixing the used enzyme of the present invention.
The fixed temperature is determined according to the attribute of enzyme.Fixing need under the temperature that enzymic activity is not lost, carrying out.Fixing can carrying out under about 0 ℃ to about 60 ℃ preferably carries out under about 5 ℃ to about 40 ℃.
For the ratio of enzyme and immobilization carrier, for every weight part immobilization carrier, preferably use 0.05 to 10 weight part, the especially enzyme of 0.1 to 5 weight part.
Enzymatic activity can be subjected to the influence such as the factor of temperature, light and humidity usually.Light can be by using various light known in the art to block or filtering method is blocked.Humidity comprises the moisture in the ambient atmosphere, can control by operating procedure in closed system.Closed system can be under the positive inert atmosphere pressure to get rid of moisture.Perhaps, can place the nitrogen bed at substrate, purifying bed or post or above the lipase packed column.Also can use other rare gas elementes such as helium or argon.These technology have to make such as the added advantage of the oxidative compound in the atmosphere of oxygen away from substrate, product or enzyme.
In some cases, lipase for example is fixed on porous support or the powder.Enzymically hydrolyse reaction is preferably hatched being about under 20 ℃ to 50 ℃ the temperature.On the one hand, enzymically hydrolyse reaction incubation time is about 0.5 hour to about 24 hours, to realize by the conversion of triglyceride level to free fatty acids.The enzymically hydrolyse reaction is preferably carried out in the presence of water.In some aspects, enzymically hydrolyse is reflected in the buffered soln and carries out.On the one hand, the ratio of water and triglyceride level is about 1: 10 (v/v) to about 20: 1 (v/v).Lipase concentration can be about 0.125mg/ml to about 2mg/ml.In some aspects, the enzymically hydrolyse reaction also contains organic solvent, as C
5-C
12Alkane or sterically hindered alkanol.
In preferred embodiments, add enzyme (for example 1mg/ml), with the reaction mixture vibration with mixed preferably about 2 to 6 hours (for example 3 hours) 2 hours to about 10 hours with initial action.In some cases, hydrolysis reaction increases along with the raising of lipase concentration proportionally.
Though the temperature and pressure of hydrolysis reaction is particularly important not, can adjust these parameters to increase speed of reaction.In some cases, temperature can influence hydrolysis rate.For example, the hydrolysis of triglyceride level is carried out under about 20 ℃ to about 60 ℃, preferably carries out under about 30 ℃ to about 50 ℃, more preferably carries out under about 35 ℃ to about 45 ℃.In a preferred embodiment, be reflected under 45 ℃ and carry out.
In addition, in some aspects, buffer concentration can influence hydrolysis rate.Some preferred aspect, the ratio of buffer concentration and triglyceride level is about 0.5 (v/v) to about 2.0v/v (0.5: 2), preferably the ratio of buffer concentration and triglyceride level is about 1: 1 (v/v).Suitable damping fluid is including, but not limited to phosphoric acid salt, Citrate trianion, succinate etc.
After reaction finishes, add organic solvent (for example octane-iso or hexane) and separate with G ﹠ W with the lipid acid (FA) that will produce.Then can be randomly that mixture is centrifugal, the upper strata can directly be used as the raw material of esterification mutually.In some aspects, then raw material of fatty acid and catalyzer (for example acid or enzyme) are mixed with the beginning esterification with alcohol.
Though the temperature and pressure of esterification is particularly important not, can adjust these parameters to improve speed of reaction.Under the situation of chemical catalysis, randomly the FFA raw material preheating is arrived about 40 ℃ to about 80 ℃, preferred about 50 ℃ to about 70 ℃ (for example 60 ℃).Under enzymatic situation, randomly the FFA raw material preheating is arrived about 20 ℃ to about 60 ℃, preferred about 25 ℃ to about 50 ℃ (for example 40 ℃).Reaction begins by adding lower alcohol.Reaction removes catalyzer after finishing.
Be applicable to that alcohol in the esterification is including, but not limited to having a monobasic primary aliphatic alcohols and the secondary alcohol to eight carbon atoms.The preferred alcohols of using in the esterification process has methyl alcohol, ethanol, propyl alcohol, butanols and amylalcohol, and wherein methyl alcohol and ethanol are most preferred.For example, especially preferred alcohol is methyl alcohol, ethanol and their combination.
Suitable acid catalyst comprises inorganic acid catalyst, and (mineral acid for example is as HCl, H
2SO
4Deng) or organic acid catalyst (for example phenylformic acid).Acid catalyst can be liquid or solid.Acid can be taked the form of molecular sieve.In one case, acid catalyst is acid vinylbenzene-Vinylstyrene sulfonation ion exchange resin.Usually, esterification reaction mixture contains such as C
5-C
12The organic solvent of alkane or sterically hindered alkanol.In one embodiment, incubation temperature is about 20 ℃ to about 90 ℃.In some cases, incubation time is about 0.2 hour to about 24 hours.In addition, the ratio of solid acid catalyst and lipid acid is generally about 1: 10 to about 10: 1 (w/w).Randomly acid catalyst is regenerated by using polar solvent such as methyl alcohol to wash.Other suitable polar solvents comprise C
1-C
6Alkanol or sterically hindered alkanol.
In some cases, in the esterification process alcohol and the mol ratio of free fatty acids be about 6: 1 (mol: mol) to about 1: 1, more preferably from about 4: 1 to about 3: 1, or about 2: 1, or about 1.2: 1 or about 1: 1.For acid catalysis, alcohol can be about 6: 1 to about 3: 1 (for example 4: 1) with the mol ratio of triglyceride level.In one embodiment, when using macroporous resin 15, alcohol is 4: 1 with the FFA ratio.
For enzymatic esterification, suitable enzyme comprises the enzyme that lipase and other catalysis esters form.Usually, reaction contains such as C
5-C
12The organic solvent of alkane or sterically hindered alkanol.In some cases, be reflected under about 20 ℃ to about 70 ℃ of the temperature and carried out about 0.2 hour to about 24 hours.
For enzyme catalysis, alcohol is about 1: 1 to about 2: 1 (mol/mol) with the ratio of lipid acid.In other cases, described ratio is preferably about 1.2: 1 or 1.3: 1 or 1.4: 1 or about 1.5: 1.In one embodiment, when using Novozym 435, use the about 120% stoichiometric alcohol amount that is equivalent to.In one embodiment, the ratio of lipase and lipid acid is about 0.005: 1 to about 1: 1 (w/w).
After esterification finishes, with fatty acid ester and any reactants separate.Separation can realize by the known usually any method in this area, preferably by proportion separation and decant or centrifugal.Isolating fatty acid ester product can be dry then with the round-robin water washing.It is found that the triglyceride feedstock that method of the present invention reached is about 95% to about 97% to the total conversion rate of fatty acid ester.
Biofuel prepared according to the methods of the invention can be analyzed with various devices well known by persons skilled in the art.For example, analytical analysis can use the HPLC that has the UV detector to carry out.On the one hand, described detector be arranged on 210nm and can use C185u post commonly used (250 * 4.6mm, Alltech Associates, Inc., USA).Moving phase comprises for example three different componentss: hexane, Virahol and methyl alcohol.Reservoir A contains methyl alcohol, reservoir B contain Virahol and hexane mixture (5: 4, v/v).On the one hand, use the linear gradient of 100%A to 50%A+50%B to surpass 30min.The flow velocity of moving phase can be 1ml/min, and the sample feeding volume is 10l.This non-aqueous RP-HPLC method is the improvement of art methods (referring to Holcapek, M.et al.J Chromatogr A 1999,858,13).
III. embodiment
1. material and method
1.1 material
Come unstuck thick plam oil available from the Wawasan Tebran Sdn Bhd in state, Malaysian Johore, derive from the Meito Sangyo Co. of the lipase of fold candida available from Japan.Derive from the lipase of pseudomonas cepacia, cement look bacillus, cylinder candiyeast and Novozym 435 (being fixed on the antarctic candida lipase B on the acrylic resin) available from Sigma-Aldrich (USA (U.S.)).The lipase that derives from pig pancreas, pseudomonas cepacia and antarctic candida B (powder) is from Fluka (USA).(strongly acidic styrene-Vinylstyrene sulfonation ion exchange resin is 4.7mequiv/g) available from Sigma (USA) for macroporous resin 15.Octane-iso is available from the Fisher Chemical of N.J..
The thick palmitic hydrolysis 1.2 come unstuck
It is about 10 minutes that the 80ml blind nut vial that the CPO that comes unstuck (2g) will be housed is preheated to 40 ℃ of temperature of reaction.2ml lipase solution (1mg/ml) is joined among the CPO of preheating, with mixture under 250rpm, vibrate 3h (hour).After reaction finishes, with 20ml octane-iso or hexane with reaction mixture so that the lipid acid of generation is separated with G ﹠ W.Then with this mixture under 5000rpm centrifugal 5 minutes.Collect the raw material that the upper strata also directly is used as esterification mutually.
1.3 the esterification of free PALM FATTY ACID
To contain (the FA acid in the octane-iso of 10ml raw material, 0.32M) and the reaction mixture of 1g macroporous resin 15 or 0.04g Novozym 435 be preheated to 60 ℃ of temperature of reaction (for macroporous resin 15) and 40 ℃ (for Novozym 435), and hunting speed is 250rpm.Add respectively be equivalent to 400% stoichiometry of macroporous resin 15 be equivalent to the 120% stoichiometric methyl alcohol of Novozym 435 or ethanol with initial action.Reaction leaches Novozym435 and macroporous resin 15, and uses the trimethyl carbinol (HPLC level) and methanol wash respectively after finishing.Spend the night their freeze-drying standby.
1.4 analyze
Fatty acid content in the reaction mixture is by measuring with 0.2M NaOH titration.The conversion of triglyceride level is confirmed (referring to Fig. 3 A-B) by the HPLC that has 210nm UV detector.The C 18 5u posts that use is used always (250 * 4.6mm, Alltech Associates, Inc., USA).Moving phase comprises three different componentss: hexane, Virahol and methyl alcohol.Reservoir A contains methyl alcohol, reservoir B contain Virahol and hexane mixture (5: 4, v/v).The linear gradient of using 100%A to 50%A+50%B was above 30 minutes.The flow velocity of moving phase is 1ml/min, and the sample feeding amount is 10 μ l.This non-aqueous RP-HPLC is improved by reported method such as Holcapek (Holcapek M et al., J Chromatogr A, 858:13-31 (1999)).The lipid acid that consumes in the esterification is by monitoring with 0.2m NaOH titration.The output of methyl or ethyl ester (biofuel) is confirmed (referring to Fig. 4 A-B) by above-mentioned HPLC system.
2 results
The thick palmitic effect 2.1 different lipase hydrolysis are come unstuck
Table 1 shows different lipase are converted into CPO FFA under ankyrin concentration effect.Clearly, it is the most effective to derive from the lipase of fold candida and cement look bacillus.Though Novozym 435 (being fixed on the antarctic candida lipase B on the acrylic resin) is very high for esterification and transesterify activity, its hydrolytic activity is very low.Because fold candida lipase is than cheap 50 times of cement look bacillus lipase, so select it to be used for further research.
Table 1: the thick palmitic effect of different lipase hydrolysis
*
*Experiment condition: except that Novozym 435 (160mg), the protein concentration of all lipase in damping fluid is held constant at 0.5mg/ml, damping fluid 2ml, CPO 2g, 40 ℃ of temperature, hunting speed 250rpm, time 1h.
The hydrolysis of CPO 2.2 come unstuck under the different fold candida lipase concentration
Fig. 5 shows speed of reaction to be accelerated along with the increase of lipase concentration in the damping fluid.For any lipase concentration except that 0.125mg/ml, be reflected at FFA output and be at 99.0% o'clock and reach balance.Speed of reaction is slow under the low fat enzyme concn, and need be more than 20h to finish reaction under the concentration of 0.125mg/ml.
The hydrolysis of CPO 2.3 come unstuck under the differing temps
Fig. 6 shows the hydrolysis of CPO under the differential responses temperature.Speed of reaction under 40 ℃ and 55 ℃ much at one, yet lower under 30 ℃.Because lipase is stable more at a lower temperature and the CPO fusing point near 35 ℃, be temperature of reaction so select 40 ℃ for subsequent experimental.
2.4 different damping fluids and CPO ratio (v/v) be the hydrolysis of CPO down
Zui Jia damping fluid and CPO ratio are 1: 1 (v/v) as can be seen, and when being below or above this ratio, speed of reaction and FFA output all can reduce (Fig. 7).
2.5 the methyl of macroporous resin 15 catalytic palm FFA and ethyl esterification
Fig. 8 shows the comparison of macroporous resin 15 catalytic FFA methyl and ethyl esterification.Though in both cases, the output of biofuel all reaches 99%, and the methyl-esterified process is faster than ethyl esterification.The low cost of methyl alcohol makes it become the good selection of esterification.Yet ethanol can be used as the synthetic biological fully ideal candidates that generates fuel, because it derives from agricultural-food and lower than methyl alcohol toxicity.
2.6Novozym the methyl of 435 catalytic palm FFA and ethyl esterification
Clearly, though Novozym 435 catalytic methyl-esterified processes are faster than ethyl esterification, behind the 2h when BD output 99% two reactions all reach balance (Fig. 9).Because methyl alcohol is toxic to Novozym 435 under high density, so ethanol is the correct selection of Novozym 435 catalytic palm FFA esterifications.
2.7 the repeated use of macroporous resin 15 and Novozym 433
With the macroporous resin 15 of catalysis methyl and ethyl esterification and Novozym 435 respectively with reusing after solvent wash and the freeze-drying.The solvent that is used to wash macroporous resin 15 and Novozym 435 is respectively the methyl alcohol and the trimethyl carbinol.Figure 10 shows the BD output of reacting in each circulation behind 1.5h (for macroporous resin 15) and the 3h (for Novozym 435).Macroporous resin 15 and Novozym 435 can reuse respectively more than 100 circulations and 50 circulations (seeing Figure 11) as can be seen.
The inventive method and the comparison of public technology
By table 2 as seen, fold candida lipase catalytic hydrolysis then the method for macroporous resin 15 or Novozym 435 catalytic esterifications reasonably providing higher output (98-99%) in process period (4-5h).As the table shows, output relatively low (seeing Figure 12) in KOH-or the catalytic transesterify of NaOH-.
Table 2: the inventive method and the comparison of public technology
The come unstuck transesterify of thick plam oil (CPO)
The CPO transesterify that utilizes methyl alcohol is in 80mL blind nut vial, and 250rpm vibrates and carries out under 40 ℃ (for Novozym 435) or 60 ℃ (for macroporous resins 15).The standard reaction mixture comprises CPO, methyl alcohol and Novozym 435 (having and do not exist the 0.75ml LiCl saturated solution or the 10ml trimethyl carbinol respectively) or macroporous resin 15.The methyl alcohol that uses is equivalent to 400% stoichiometry of macroporous resin 15 and 120% stoichiometry of Novozym 435 respectively.The consumption of macroporous resin 15 is the every gram of 0.2g CPO, and the consumption of Novozym 435 is the every gram of 0.04g CPO.For the 435 catalytic methanolysis of Novozym in the solvent-free system, be 0,5 and add 40% stoichiometric methyl alcohol three times during 10h in the reaction times.
Whole public publications that this specification sheets is quoted and patent application mode are by reference incorporated this paper into, incorporate this paper especially and individually into as each public publication or patent application mode by reference.Although described aforementioned invention in detail so that be expressly understood by example and the mode of giving an example, but it will be apparent for a person skilled in the art that, according to instruction of the present invention, can under the prerequisite of the spirit or scope that do not depart from claims, carry out some variation and modification to it.
Claims (54)
1. production method of bio-diesel oil, described method comprises:
With the triglyceride level enzymically hydrolyse to form lipid acid and glycerine; And
With described fatty acid esterification lower alcohol to form described biofuel.
2. the method for claim 1 is wherein mixed described triglyceride level with lipase, and hatches time enough to form described lipid acid under enough temperature.
3. as each described method among the claim 1-2, wherein said triglyceride level is selected from the lard oil or the fat of vegetables oil, Tallow, beef, tallow, lubricating grease and recirculation.
4. as each described method among the claim 1-3, wherein said lipid acid is C
12To C
22Lipid acid.
5. as each described method among the claim 2-4, wherein said lipase derives from plant, bacterium, fungi and more high eukaryote.
6. method as claimed in claim 5, wherein said lipase derive from extracellular or the cell, perhaps are the form of full cell.
7. as each described method among the claim 2-6, wherein said lipase is fixed.
8. method as claimed in claim 7, wherein said being fixed on porous upholder or the powder realized.
9. method as claimed in claim 8, wherein said porous upholder is an acrylic resin.
10. method as claimed in claim 9, wherein said lipase are antarctic candida (Candida antarctica) lipase B.
11. as each described method among the claim 2-9, wherein said lipase derives from fold candida (Candida rugosa).
12. as each described method among the claim 1-11, wherein said enzymically hydrolyse is reflected at about 20 ℃ and hatches to about 50 ℃ temperature.
13. as each described method among the claim 1-12, wherein said enzymically hydrolyse reaction incubation time is about 0.5 hour to about 24 hours.
14. as each described method among the claim 1-13, wherein said enzymically hydrolyse is reflected under the existence of water and carries out.
15. as each described method among the claim 1-14, wherein said enzymically hydrolyse is reflected in the buffered soln and carries out.
16. method as claimed in claim 14, wherein the ratio of water and triglyceride level is about 1: 10 to about 20: 1 (v/v).
17. as each described method among the claim 2-16, wherein said lipase concentration is that about 0.125mg/ml is to about 2mg/ml.
18. as each described method among the claim 2-17, wherein said lipase can utilize hollow-fibre membrane or other strainers and recirculation.
19. method as claimed in claim 14, wherein said enzymically hydrolyse reaction also comprises organic solvent.
20. method as claimed in claim 19, wherein said organic solvent is selected from C
5-C
12Alkane and sterically hindered alkanol.
21. as each described method among the claim 1-20, wherein said esterif iotacation step is chemical catalysis or enzyme-catalyzed change.
22. method as claimed in claim 21, the described chemical esterification of wherein said lipid acid comprises:
Described lipid acid is mixed with described pure and mild acid catalyst; And
Mixture is hatched time enough to form biofuel under enough temperature.
23. method as claimed in claim 22, wherein said alcohol are C
1-C
5Alcohol.
24. method as claimed in claim 22, wherein said acid catalyst is selected from inorganic acid catalyst or organic acid catalyst.
25. method as claimed in claim 24, wherein said acid catalyst are liquid or solid.
26. as each described method among the claim 22-25, wherein said acid catalyst is acid vinylbenzene-Vinylstyrene sulfonation ion exchange resin.
27., wherein described acid catalyst is regenerated by washing with polar solvent as the described method of claim 22-26.
28. method as claimed in claim 27, wherein said polar solvent is selected from C
1-C
6Alkanol and sterically hindered alkanol.
29. as each described method among the claim 21-28, wherein said esterif iotacation step comprises organic solvent.
30. method as claimed in claim 29, wherein said organic solvent is selected from C
5-C
12Alkane and sterically hindered alkanol.
31. as each described method among the claim 21-30, wherein said esterif iotacation step comprises molecular sieve.
32. method as claimed in claim 31, wherein said incubation temperature are about 20 ℃ to about 90 ℃.
33. method as claimed in claim 32, wherein said incubation time are about 0.2 hour to about 24 hours.
34. method as claimed in claim 33, the ratio of wherein said alcohol and lipid acid are about 1: 1 to about 6: 1 (mol/mol).
35. as the described method of claim 21-34, wherein the ratio of solid acid catalyst and lipid acid is about 1: 10 to about 10: 1 (w/w).
36. method as claimed in claim 21, the described enzymatic esterification of wherein said lipid acid comprises:
Described lipid acid is mixed with described pure and mild lipase; And
Mixture is hatched time enough to form biofuel under enough temperature.
37. method as claimed in claim 36, wherein said lipase derive from plant, bacterium, fungi and more high eukaryote.
38. as the described method of claim 36-37, wherein said lipase derives from extracellular or the cell, perhaps is the form of full cell.
39. as the described method of claim 36-38, wherein said lipase is fixed.
40. method as claimed in claim 39, wherein said being fixed on porous upholder or the powder realized.
41. method as claimed in claim 40, wherein said porous upholder is an acrylic resin.
42. as the described method of claim 36-41, wherein said lipase is antarctic candida lipase B.
43. as each described method among the claim 36-42, wherein said lipase is by regenerating with the polar solvent washing.
44. method as claimed in claim 43, wherein said polar solvent is selected from C
1-C
6Alkanol and sterically hindered alkanol.
45. method as claimed in claim 36, wherein said esterification comprises organic solvent.
46. method as claimed in claim 45, wherein said organic solvent is selected from C
5-C
12Alkane and sterically hindered alkanol.
47. as each described method among the claim 36-46, wherein said esterification comprises molecular sieve.
48. method as claimed in claim 47, wherein said incubation temperature are about 20 ℃ to about 70 ℃.
49. as each described method among the claim 36-48, wherein said incubation time is about 0.2 hour to about 24 hours.
50. as each described method among the claim 36-49, the ratio of wherein said alcohol and described lipid acid is about 1: 1 to about 2: 1 (mol/mol).
51. as each described method among the claim 36-50, the ratio of wherein said lipase and described lipid acid is about 0.005: 1 to about 1: 1 (w/w).
52. as each described method among the claim 1-51, wherein said hydrolysis or esterification are carried out in reactor.
53. method as claimed in claim 52, wherein said reactor is selected from fixed-bed reactor, fluidized-bed reactor and stirred-tank reactor.
54., wherein described biofuel is mixed with petroleum diesel as each described method among the claim 1-53.
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|---|---|---|---|
| PCT/SG2008/000244 WO2010005391A1 (en) | 2008-07-08 | 2008-07-08 | Biodiesel production via enzymatic hydrolysis followed by chemical/enzymatic esterification |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102553658A (en) * | 2011-08-16 | 2012-07-11 | 中国海洋石油总公司 | Regeneration method of deacidification catalyst for refining biodiesel and refining of biodiesel |
| CN104080897A (en) * | 2011-09-30 | 2014-10-01 | 新加坡国立大学 | Method of converting grease containing high content of free fatty acids to fatty acid esters and catalysts for use in said method |
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Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2009333542A1 (en) | 2008-12-08 | 2011-07-28 | Initio Fuels Llc | Single step transesterification of feedstock using a gaseous catalyst |
| US9040263B2 (en) | 2010-07-28 | 2015-05-26 | Butamax Advanced Biofuels Llc | Production of alcohol esters and in situ product removal during alcohol fermentation |
| WO2011159967A1 (en) | 2010-06-18 | 2011-12-22 | Butamax(Tm) Advanced Biofuels Llc | Extraction solvents derived from oil for alcohol removal in extractive fermentation |
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| KR101769710B1 (en) | 2016-04-27 | 2017-08-30 | 씨에스 에너지 주식회사 | bio heavy fuel oil production system with temperature controller using dry air |
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| US10696923B2 (en) | 2018-02-07 | 2020-06-30 | Sartec Corporation | Methods and apparatus for producing alkyl esters from lipid feed stocks, alcohol feedstocks, and acids |
| US10544381B2 (en) | 2018-02-07 | 2020-01-28 | Sartec Corporation | Methods and apparatus for producing alkyl esters from a reaction mixture containing acidified soap stock, alcohol feedstock, and acid |
| CN112980828B (en) * | 2021-03-04 | 2023-09-05 | 扬州大学 | Catalyst for preparing biodiesel by two-dimensional polyamide immobilized lipase |
| WO2023043325A1 (en) * | 2021-09-15 | 2023-03-23 | Natural Extraction Technologies Limited | Solid phase lipid cleavage, and products therefrom |
| WO2024119202A1 (en) * | 2022-11-30 | 2024-06-06 | Vaal University Of Technology | Immobilised lipase and method of producing biodiesel using the same |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6982155B1 (en) * | 1999-11-26 | 2006-01-03 | Kansai Chemical Engineering Co., Ltd. | Process for producing fatty acid lower alcohol ester |
| US6398707B1 (en) * | 2001-05-31 | 2002-06-04 | Wen-Teng Wu | Method of preparing lower alkyl fatty acids esters and in particular biodiesel |
| JP4095392B2 (en) * | 2002-03-11 | 2008-06-04 | 水澤化学工業株式会社 | Biofuel production method |
| JP4426272B2 (en) * | 2003-12-11 | 2010-03-03 | 水澤化学工業株式会社 | Biofuel production method |
| CN1238469C (en) * | 2004-01-16 | 2006-01-25 | 清华大学 | Novel process for preparing biological diesel oil from grease catalyzed by lipase in the reaction system with organic substrate as medium |
| DE102005002700A1 (en) * | 2005-01-19 | 2006-07-27 | Cognis Deutschland Gmbh & Co. Kg | Compositions usable as biofuel |
| EP1876222A1 (en) * | 2006-07-06 | 2008-01-09 | Cognis IP Management GmbH | Process for production of fatty acids, fatty acid esters and sterolesters from soapstock |
-
2008
- 2008-07-08 WO PCT/SG2008/000244 patent/WO2010005391A1/en active Application Filing
- 2008-07-08 CN CN200880130967.4A patent/CN102144035B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| JIN G.等: "Producing biodiesel using whole-cell biocatalysts in separate hydrolysis and methanolysis reactions.", 《JOURNAL OF ENVIROMENTAL SCIENCE AND HEALTH PART A》 * |
| KUSDIANA D.等: "Two-step preparation for catalyst-free biodiesel fuel production.", 《APPLIED BIOCHEMISTRY AND BIOTECHNOLOGY》 * |
| MOJOVIC L.等: "Immobilization of lipase from Candida rugosa on a polymer support", 《APPL MICROBIOL BIOTECHNOL》 * |
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|---|---|
| CN102144035B (en) | 2014-10-08 |
| WO2010005391A1 (en) | 2010-01-14 |
| WO2010005391A8 (en) | 2010-03-04 |
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