US20070077635A1 - Obtaining fatty acid esters from native oils and fats - Google Patents

Obtaining fatty acid esters from native oils and fats Download PDF

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US20070077635A1
US20070077635A1 US10/531,658 US53165802A US2007077635A1 US 20070077635 A1 US20070077635 A1 US 20070077635A1 US 53165802 A US53165802 A US 53165802A US 2007077635 A1 US2007077635 A1 US 2007077635A1
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hydrolysis
centrifuge
organic phase
fatty acids
esterification
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Karlheinz Brunner
Rainer Frische
Rainer Ricker
Corinna Kaske
Dirk Kilian
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    • 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
    • C12P7/6409—Fatty acids
    • C12P7/6418—Fatty acids by hydrolysis of fatty acid esters
    • 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
    • C11C1/007—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids using organic solvents
    • 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
    • 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
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/18—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic polyhydric
    • C12P7/20—Glycerol
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/62—Carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides

Definitions

  • the invention concerns a process and a device for obtaining fatty acids or fatty acid esters from native oils and fats by their enzymatic hydrolysis and optional simultaneous esterification using alcohols, especially n- and iso-alcohols.
  • n- and iso-alcohols are of high economic importance in numerous applications, especially in the lubricant field.
  • esters of these alcohols with unsaturated fatty acids especially oleic acid esters
  • classical chemical routes such as acidic esterification.
  • Enzymatic preparation of these esters from fatty acids and alcohols has not been carried out in the past because of the high enzyme requirement.
  • the objective of this invention is to provide an economically feasible enzymatic process for producing fatty acids and fatty acid esters from native oils and fats, and a corresponding device.
  • the inventors have developed an economically efficient enzymatic process for hydrolyzing fats or oils, and a corresponding device to accomplish the process. They have also found that this process and device together constitute an outstanding solution to the previous problems of enzymatic hydrolysis and enzymatic production of the esters of interest in one operation.
  • the process of the present invention for the enzymatic preparation of fatty acid esters is characterized by the fact that lipases, as biocatalysts for the hydrolysis of oils or fats and for esterification, are caused to act on a mixture of an oil or fat, water, and a fat- or oil-soluble alcohol, especially n- and/or iso-alcohols.
  • the resulting reaction mixture is transferred to a self-discharging centrifuge in order to separate the glycerol-containing aqueous phase formed in the combined hydrolysis-esterification process from the organic phase which contains the fatty acid esters.
  • the centrifuge is adjusted so that an intermediate layer enriched in lipase (enzyme) that forms between the aqueous and organic phase collects in the centrifuge drum.
  • the centrifuge drum is emptied at specified times and the discharged contents are returned to the combined hydrolysis and esterification process.
  • the contents of the drum are also available to be used in another, separate hydrolysis and esterification process, in which is incorporated into the present process or just made available for a later process.
  • the above-mentioned intermediate layer is enriched in the plate pack of self-desludging separators, which are suitable as self-discharging centrifuges.
  • self-desludging separators which are suitable as self-discharging centrifuges.
  • principal ribbed inserts or other internal structures such as blades and the like may be used in an equivalent manner in place of the plate pack. It is important that the centrifuge be self-discharging, making it possible for the intermediate layer that collects in the centrifuge to be discharged from time to time by emptying the centrifuge drum.
  • the above-mentioned intermediate layer forms during the enzymatic fat hydrolysis even when alcohol is not added, along with the separation of the two phases that form: the glycerol-containing aqueous phase and the organic phase that contains the free fatty acids formed in the hydrolysis.
  • the problem of this emulsion-like intermediate layer is known from “Continuous Uses of Lipases in Fat Hydrolysis,” M. Bühler and Chr. Wandrey, Fat Science Technology 89, December 1987, pages 598 to 605; “Enzymische Fettspaltung” [Enzymatic Fat Hydrolysis], M. Bühler and Chr. Wandrey, Fettmaschine Technologie [Fat Science and Technology] 89, No. 4, 1987, pages 156 to 164; and “Oleochemicals by Biochemical Reactions?” M. Bühler and Chr. Wandrey, Fat Science Technology 94, No. 3, 1992, pages 82 to 94.
  • oil is hydrolyzed continuously in a first stirred reactor.
  • the reaction product which in addition to free fatty acids contains water, glycerol, and mono- and diglycerides, unhydrolyzed oil and enzyme, is transferred to a solid wall plate centrifuge which is adjusted so that the intermediate layer between the aqueous glycerol phase and the organic phase is discharged with the organic phase.
  • the organic phase containing the intermediate layer is delivered to a second stirred reactor, to which a fresh water/enzyme mixture is also added.
  • the reaction product from the second reactor is again transferred to a solid wall plate centrifuge, which in this case is adjusted so that the intermediate layer is discharged with the glycerol-containing aqueous phase, so that the free fatty acids produced will be discharged without any intermediate emulsion layer.
  • the aqueous phase is returned to the first reaction, so that the enzyme portion contained in the emulsion intermediate layer is resupplied to that process.
  • the solids that deposit on the drum wall are discharged discontinuously when the drum is emptied.
  • An emulsion-like intermediate layer also forms during the phase separation in the hydrolysis carried out according to the present invention, with or without simultaneous esterification.
  • This intermediate layer contains substantial quantities of enzyme, along with the organic phase that contains the free fatty acids or their esters which are formed, and with the glycerol- containing aqueous phase.
  • the objective is accomplished successfully with a centrifuge having exceptionally high capability, and an efficient and nearly loss-free recycling of the enzyme is achieved. This makes it possible to perform the fat hydrolysis with a high cleavage rate and the esterification in high yield, at high enzyme concentration and consequently short reaction time, without significant loss of enzyme.
  • a self-discharging centrifuge is used, preferably a self-discharging separator with a plate pack.
  • the centrifuge is adjusted so that significant amounts of the enzyme-containing interfacial emulsion are not included in the ester-containing organic phase, nor in the aqueous phase. Instead, this emulsion accumulates in the centrifuge, preferably in the region of the separation zone in the plate pack of a separator. This is an unusual operating configuration to the extent that generally the accumulation of large quantities of an intermediate layer in the plate package during liquid/liquid phase separation is specifically avoided with the known self-discharging separators or self-desludging separators.
  • adjustment of the centrifuge according to the present invention means applying the measures known to the art for adjusting the weir and/or adjusting the back pressure at the exit port to insure that both the organic phase and the aqueous glycerol-containing phase discharge as clear and free of emulsion as possible.
  • the presence of alcohols does not result in either significantly higher enzyme consumption or substantially extended reaction time.
  • the recovery of the esters from the reaction mixture in a simple manner is also possible.
  • the alcohols are added in the stoichiometrically required proportion for ester formation, but it is advantageous to use an excess of 2% to 100%, preferably 5% to 20%, based on the stoichiometric requirement for the corresponding oils or fats.
  • An excess of alcohol accelerates the fat hydrolysis and unexpectedly causes complete hydrolysis of all glycerides in a short time.
  • the glycerol formed in the reaction moves into the water phase because of its extremely high solubility in water and very low solubility in the hydrophobic organic phase. Since the medium-chain to long-chain alcohols are very poorly soluble in water but quite soluble in the organic phase, while water on the other hand is very poorly soluble in the organic phase, these alcohols are converted enzymatically to fatty acid esters according to the chemical equilibrium. This occurs either by esterification of the fatty acid derived from the fat hydrolysis with the loss of water, where this latter product migrates to the aqueous phase, or by transesterification of the oils or fats with loss of glycerol, where this latter product likewise moves into the aqueous phase. Thus, the chemical equilibrium in the organic phase lies completely-on the side of the ester.
  • the addition of more than the stoichiometric amount of alcohol will shift the equilibrium further toward the ester side, and the rate of reaction will be increased significantly.
  • the enzymatic fat hydrolysis of the present invention is nearly complete even with the addition of a slight excess of 5% over the stoichiometric amount of alcohol.
  • the hydrophobic organic phase contains no mono-, di- or triglycerides. It consists solely of the fatty acid esters of the added alcohol, a small amount of the free fatty acids along with the corresponding amount of alcohol, and the excess alcohol. It is possible to remove the excess alcohol, including the unreacted alcohol portion, and the free fatty acids from the organic phase, in order to obtain the pure esters.
  • esters of C18 fatty acids and C18 alcohols are produced from corresponding oils or fats and alcohols, it is possible to remove the free C18 fatty acids along with the excess C18 alcohol from the end product of the hydrolysis/esterification reaction by distillation, because the fatty acid esters produced have a substantially lower vapor pressure than the free fatty acids and alcohols.
  • the free fatty acids and the resulting esters may have approximately the same vapor pressure. This occurs, for example, in the esters of C18 fatty acids with C 13 iso-alcohols. In these cases, it is possible to remove the excess amounts of C13 iso-alcohol by distillation and to separate the free C18 fatty acids from the ester/fatty acid mixture in the distillation pot by base extraction, followed by neutralization, so that these are available for recycling.
  • This method allows one to obtain the fatty acids or fatty acid esters for which this latter enzyme exhibits selective catalytic action in the hydrolysis and esterification process.
  • this latter enzyme exhibits selective catalytic action in the hydrolysis and esterification process.
  • the process of enzymatic fat hydrolysis starting from oils and fats of the present invention thus allows the targeted production of fatty acids and fatty acid esters which previously could be obtained only at substantially higher cost.
  • This process utilizes the known action of lipases as biocatalysts that establish a chemical equilibrium between esters, alcohols, water and acids. They act particularly on fats and oils.
  • the latter are glycerol esters, primarily triglycerides, of medium- to long-chain and generally unbranched fatty acids.
  • Lipases operate at the phase boundary of two-phase systems having oil or fatty acids as the hydrophobic phase and water as the hydrophilic phase, and establish a chemical equilibrium in both phases. The position of the chemical equilibrium is determined by the concentrations of the particular materials in the particular phases.
  • the water concentration is dominant in the water phase but very slight in the oil phase.
  • glycerol is very highly soluble in water, but hardly soluble at all in the hydrophobic phase of oil or hydrophobic fatty acids, the glycerol concentration at equilibrium must be substantially higher in the water phase than in the oil phase. Glycerol present or formed in the oil phase passes almost completely into the water phase. Native fatty acids with medium to long fatty acid chains are hydrophobic and almost insoluble in water. Their concentration in the water phase is consequently very low. On the other hand, they are quite soluble in the hydrophobic phase, and they themselves will occasionally constitute the hydrophobic phase.
  • K 1 ⁇ [triglyceride] ⁇ [H 2 O] ⁇ / ⁇ [diglyceride] ⁇ [fatty acid]
  • K 2 ⁇ [diglyceride] ⁇ [H 2 O] ⁇ / ⁇ [monoglyceride] ⁇ [fatty acid]
  • K 3 ⁇ [monoglyceride] ⁇ [H 2 O] ⁇ / ⁇ [glycerol] ⁇ [fatty acid] ⁇
  • lipases hydrolyze fats and oils almost completely to glycerol and fatty acids when the water concentration in the hydrophilic phase is high.
  • the glycerol that is formed thus dissolves in the water, and the fatty acids initially dissolve in oil, but later form a separate hydrophobic fatty acid phase.
  • the lipases will likewise produce a chemical equilibrium in the hydrophilic and hydrophobic phases. Exceptions to this are found for alcohols and alcohol concentrations that inhibit the activity of the enzyme, or which are incompatible with it and inactivate it. Even in this case, the position of the chemical equilibrium is determined by the distribution coefficients of the individual components between the hydrophilic and hydrophobic phases. The calculation or estimation of the chemical equilibrium distribution in two phases is naturally more complex than for simple fat or oil hydrolysis. That is particularly true for multifunctional alcohols which are water-soluble, for example trimethylolpropane and pentaerythritol.
  • Some lipases are unable to hydrolyze all the fatty acid ester glyceride bonds. In particular, it is not possible for certain lipases to hydrolyze the central fatty acid bonded to the glycerol C2. Such lipases are used to target the production of monoglycerides and fatty acids, for example. If the starting oils contain certain fatty acids that are not bound in the glyceride of the oil or fat randomly, but rather are systematically distributed, then it is possible to obtain fatty acids or their esters which do not correspond to the fatty acid pattern present in the triglyceride though the use of specifically acting lipases.
  • long-chain fatty acids with chain lengths >20 such as erucic acid
  • erucic acid long-chain fatty acids with chain lengths >20
  • erucic acid long-chain fatty acids with chain lengths >20
  • native oils and fats and not to the central hydroxyl group.
  • oils rich in erucic acid such as crambe oil, for instance, with more than 60% by weight erucic acid (and about 6% by weight of fatty acids >C22)
  • practically all the fatty acids having chain lengths >C20 are bound to the glycerol C1 and C3, while the remaining 33.33 mole-percent of C18 fatty acids are bound to the glycerol C2.
  • a specific lipase is used to target the cleavage of only the terminal acids and produce their esters. Then, the erucic acid esters are isolated by fractional crystallization, for example. In this case, the enzyme also acts at the phase boundary layer, and it is possible for it to be recycled efficiently according to the present invention.
  • the nonspecific lipase from Candida rugosa cleaves long-chain fatty acids such as erucic acid considerably more slowly than C16 and C18 fatty acids.
  • the enzymatic fat hydrolysis using Candida rugosa lipase yields the 1,3-diglyceride of erucic acid along with the fatty acids cleaved from the glycerol C2.
  • These latter are C 18 fatty acids, and these fatty acids and their esters are separated advantageously from the diglyceride as the distillate when short-path distillation is used. It is possible to realize similar results for many other fatty acids such as omega-3- and omega-6-fatty acids by using suitable enzymes.
  • the separation of the fatty acids from the reaction products of the hydrolysis reaction or, alternatively, the separation of the fatty acid esters from the reaction products of the hydrolysis/esterification reaction is preferably carried out by vacuum distillation, and especially by gentle short-path distillation. If the fatty acid esters produced have lower vapor pressure than the free fatty acids and alcohols, then the distillate contains the excess amount of n- or iso-alcohols, the unreacted alcohol, and the free fatty acids. The distillate is preferably recycled back to the hydrolysis/esterification process. It is possible to use adsorptive separation (such as column chromatography) as an alternative to the separation of the fatty acid esters or fatty acids by distillation.
  • adsorptive separation such as column chromatography
  • Vacuum thin-film evaporators such as falling film evaporators or short-path stills are gentler than batch distillation, and above all are operated continuously, and so their use is preferred. In any case, these distillation techniques also require a liquid residue of at least 5% to 10%, as otherwise the distillation film will break. This condition is satisfied in the present invention for both the hydrolysis and the combined hydrolysis/esterification processes.
  • the residue from the distillation in the combined hydrolysis/esterification process contains either the desired ester, or the ester and unreacted free fatty acids.
  • the distillate contains the hydrolyzed fatty acids.
  • the pot, or distillation residue contains the unreacted triglycerides, and is recycled back to the hydrolysis process.
  • the emulsion-like intermediate layer collected in the centrifuge according to the present invention, in the plate pack of a separator, according to the preferred embodiment, is discharged discontinuously by completely emptying the drum periodically, and the enzyme-containing intermediate layer obtained is reused.
  • the fact that both the aqueous and organic phases are also discharged when the drum is emptied fully is not disadvantageous because all the phases are reused by recycling them back into the reactor. It is also possible for the drum to be emptied partially instead of fully, and these procedures should be arranged so that the intermediate layer is discharged as completely as possible.
  • a technically interesting supplement to the invention for further reducing the enzyme loss in the separated organic phase consists of using an additional self-discharging polishing separator.
  • This additional separator is configured immediately after the separator for the single or last hydrolysis or hydrolysis/esterification step and receives the organic phase discharged from it.
  • This added separator is preferably a self-discharging centrifuge with a plate pack adjusted so that the solids undergoing sedimentation, the enzyme in this case, and the remnants of the aqueous phase which are still removable will separate at the drum wall. Then the quantities of enzyme centrifuged off in this manner are discharged discontinuously again and recycled back to the hydrolysis or hydrolysis/esterification process.
  • a self-discharging centrifuge When a self-discharging centrifuge is used to separate the organic phase containing the fatty acid esters, it is particularly advantageous to carry out the hydrolysis reaction in loop reactors, or in other words, intermittently or batchwise, not continuously in flow reactors.
  • a reactor is filled with oil, so that its loop is not active for circulating the oil or fat, water, alcohol and enzyme contained in the reactor.
  • a second reactor carries out the hydrolysis or hydrolysis/esterification reaction with an active loop.
  • a third reactor is being emptied through an self-discharging centrifuge, so that the reaction mixture is separated into the glycerol-containing aqueous phase, the organic phase containing the separated fatty acids or fatty acid esters, and the enzyme-containing emulsion boundary phase which forms as an intermediate layer.
  • the emulsion boundary phase is discharged discontinuously from the separator from time to time, replenished with fresh enzyme, and returned to the reactor.
  • An advantage of the present invention is that the amount of added water is low, both in the case involving only the hydrolysis process, as well as for the combined hydrolysis/esterification process. In the latter case, a minimum of 5% water by weight is added, based on the organic phase, including the oil or fat and alcohol used. It is possible to add more than 200% by weight water, but that just complicates the entire process unnecessarily.
  • the amount of added water should preferably be in the range of 20 to 30% by weight based on the organic phase used, and not over 50% by weight. Even in the process involving only hydrolysis, one works preferably in the range of 5 to 200% added water based on the organic phase used, preferably 20 to 30% and maximally 50% by weight.
  • the amount of lipase added to the reactor as an effective amount is generally at least 0.01 wt.%, based on the oil or fat used.
  • the present preferred range for the amount of lipase used in the working examples is between 0.1 and 0.5% by weight, based on the oil or fat used.
  • This high enzyme level greatly accelerates the hydrolysis as well as the hydrolysis/esterification process.
  • the actual enzyme consumption is very low because the enzyme is recycled, so that only fractions of the initial amounts need to be added later. In actual runs, the amounts of lipase added later were less than ten percent of the active amount placed in the reactor.
  • the optimal enzyme level is selected not only for the specific enzyme, but also depends on the activity of the particular enzyme preparation. Finally, one must consider that the process becomes steadily slower as the enzyme level in the process decreases. It is also known, and has previously been stated in the publications mentioned above, that increasing the enzyme level above certain values gives no advantage with respect to the process technology or economics. It is possible for one skilled in the art to determine the optimum enzyme level for the particular starting materials with a few experiments by considering these facts.
  • the hydrolysis or hydrolysis/esterification reaction it is possible for the hydrolysis or hydrolysis/esterification reaction to be carried out in just one stage in the presence of alcohol with complete release of the glycerol, with recycling of the enzyme in this stage.
  • the hydrolysis or hydrolysis/esterification reaction of the present invention is preferably carried out in multiple stages with circulating reactors, for example in two stages.
  • the aqueous glycerol phase obtained in the second stage is then recycled back to the first stage as the aqueous phase, and fresh water as the water aqueous phase as along with the organic phase obtained from the first stage are also cycled to the second stage.
  • Such a two-stage or multi-stage reaction is advantageous because the enzyme loss is further minimized.
  • the process of the present invention is also suitable for hydrolyzing the mono-, di-, and triglycerides from soap stock obtained from the alkali refining of feed oils, and converting them to fatty acid esters.
  • soap stock obtained from the alkali refining of feed oils
  • fatty acid esters it is preferable to release the fatty acids bound in the soaps by adding acid before the hydrolysis/esterification.
  • FIG. 1 a shows a schematic representation of an example of an industrial process of the present invention, designed for the case in which the resulting fatty acid esters are to be separated from the unreacted fatty acids and alcohol by distillation;
  • FIG. 1 b shows a corresponding schematic representation of a modified process for the case in which the fatty acid esters are only separated together with the free fatty acids by distillation
  • FIG. 2 shows a schematic representation of an example of an industrial hydrolysis process of the present invention, in which no esterification occurs and which is operated without addition of alcohol.
  • FIGS. 1 a and 1 b show a configuration of the present invention for a two-stage combined fat hydrolysis/fatty acid ester formation which is suitable for realizing the features noted on a production scale.
  • Two process stages 1 and 2 are provided, each of which comprises three circulation loop reactors. As already discussed above, the reactors are operated intermittently: filling, reaction phase, emptying phase.
  • the circulation loop for each of the three reactors in a stage is furnished with a centrifugal pump indicated in the drawing, and preceded by a heat exchanger.
  • the reactors are stainless steel vessels, for instance, and are equipped with stirrers. Also, a separator in the form of an self-discharging plate separator is provided for each stage.
  • the exit port of the separator for the second hydrolysis stage, from which the organic phase is discharged with the fatty acid esters, is connected to a vacuum short-path still, in which a short-path distillation is effected to separate the free fatty acids and the alcohols from the fatty acid esters formed, for the case presented above in which the latter have a lower vapor pressure than the former.
  • the residue from the distillation will contain the desired esters if the unreacted free fatty acids and the alcohol are more volatile than the desired fatty acid ester end product. This corresponds to the process shown in Figure 1 a.
  • the residue from the distillation contains both the esters and the free fatty acids.
  • the free fatty acids are neutralized in a separator by adding an alkaline solution such as sodium hydroxide, and then are separated from the fatty acid esters as the heavier soap phase by centrifugation.
  • the soap phase is cleaved to provide fatty acids and salts by a known method, e.g., in a second centrifuge after addition of an acid such as sulfuric acid, and the fatty acids are returned to the first stage of the reaction.
  • the reactor is charged with a buffer solution, the triglyceride to be hydrolyzed, the particular ester-forming alcohol, and the enzyme, i.e., lipase. More enzyme is obtained in each time the separator is emptied intermittently, and is returned to the reactor of the same stage that is being filled, with each particular separator routed to a particular reactor.
  • the enzyme remains in circulation in one stage, along with the discharged proportions of free fatty acids, unhydrolyzed triglycerides, etc. This prevents the partial mixing of starting materials of different quality from the two stages. This also reduces the risk of reverse reactions.
  • a glycerol solution is removed from the first-stage separator as the separated heavier liquid phase and is ready for further processing.
  • the glycerol solution from the second-stage separator is returned to the first-stage reactor that is being filled, as shown in the figures.
  • a slightly acidic standard solution selected and adjusted according to the conditions specified by the enzyme producer for use as the buffer solution is used as the buffer solution.
  • An aqueous solution with sodium acetate and acetic acid, adjusted to be slightly acidic, is used in the working examples.
  • the optimal pH of the buffer solution is adjusted for the particular enzyme.
  • Oleyl alcohol and stearyl alcohol were tested as the n-alcohols in the experimental series.
  • Experimental series were carried out with iso-C8, iso-C10, iso-C13, iso-C16, iso-C18, iso-C20 and iso-C24 as iso-alcohols.
  • esters were prepared from high-oleic sunflower oil. Depending on the application, it is possible to start with dewaxed and refined, or crude oil or fat.
  • An 80 liter stirrer vessel was charged with 20 kg of dewaxed and refined high-oleic sunflower oil 90plus®, and 22.3 kg (10% stoichiometric excess) of Isofol 20 (C20 alcohol from Fuchs Petrolub), 10.6 kg buffer solution (0.1 N sodium acetate/acetic acid, pH 4.6) and 40 g of OF Enzyme 360 (from the Meito Sangyo company) was blended in. This mixture was circulated with a centrifugal pump for 3 hours at about 40° C.
  • the combined phase mixture was moved directly by gravity feed at a rate of about 30 kg/hr to a plate centrifuge (SA 1-01, Westfalia Separator AG, Oelde) and separated continuously.
  • SA 1-01 Westfalia Separator AG, Oelde
  • the acid value of the discharged organic phase as determined by titration with 0.1 N KOH in alcoholic solution, according to DIN 53169 and DIN 53402, passed through a maximum of about 55, and decreased to about 15 at the end.
  • the enzyme was discharged from the centrifuge together with small amounts of the organic phase and glycerol-water. It showed hardly any loss of activity and could be reused.
  • a clear oil-ester phase and a clear glycerol solution as the aqueous phase were taken from the centrifuge.
  • the aqueous phase contained 17% by weight of glycerol as expected.
  • the distillate contained the excess amount and the residual unreacted portions of iso-alcohol and free fatty acids.
  • the process of the present invention is also applicable to synthetic fatty acid esters, such as synthetic triglycerides and other polyol esters.
  • FIG. 2 shows clearly that the process control for the process involving only fat hydrolysis without simultaneous esterification by addition of alcohol does not differ in the essential points from the foregoing, for example the process control presented above in Figures 1 a and 1 b .
  • Possible mass throughputs are reported for examples, but the process can be and has been also carried out successfully with other quantities. Therefore only the distinguishing part of the process is explained.
  • the statements above about possible temperature ranges and handling of the enzyme apply equally.
  • the exit port of the second hydrolysis stage separator from which the organic phase with the fatty acids (instead of the fatty acid ester) is discharged, is again connected to a vacuum short-path distillation system in which short-path distillation is used to separate the free fatty acids.
  • the residue from the distillation was sent to a stirred crystallizer in which the waxes crystallized.
  • the residual oil in which the waxes and other higher-boiling components had crystallized out as solids was pumped into a filter assembly, where it was freed of those concomitants.
  • the oil purified in that manner was then returned to the first stage for hydrolysis.
  • a hydrolysis of high-oleic sunflower oil was carried out. After a starting phase, 30.0 kg of a crude, unrefined high-oleic sunflower oil 90 plus (registered trademark) from the Dr. Frische GmbH company, having an acid value of 4 as determined by titration with alkaline potassium hydroxide according to DIN 53169 and DIN 53402, was charged to one of the first-stage reactors along with 7.0 kg of a buffer solution consisting of a 12% glycerol/water solution buffered with 3.0 g sodium acetate. The charged mixture of oil and buffer solution was circulated by means of a centrifugal pump with stirring and maintained at 35 - 40° C.
  • the discharge product from the drum was transferred to the particular first-stage reactor that was being filled.
  • the second-stage reactor to be filled received, along with the oleic acid-containing organic phase from the first stage separator, 7.0 kg of the above-described buffer solution, 2 kg of the discharge product from the second-stage separator from the start-up phase, and replenished with 5 g fresh lipase of the type noted above. Otherwise, this process was carried out as in the first-stage fat hydrolysis, with the result that the lighter phase discharged from the second-stage separator was a clear crude oleic acid phase with an acid value of 184, corresponding to a 93% conversion for the hydrolysis (calculated as the measured acid value divided by the theoretical acid value for this mixture).
  • the heavy phase separated by the centrifuge constituted a 12% by weight solution of glycerol in aqueous buffer solution.
  • the crude fatty acid thus obtained in the second stage was collected in a 200 liter vessel serving as an intermediate container.
  • This was subjected to short-path distillation in a short-path vacuum still, Type KD, from UIC Co., Alzenau-Hörstein, with an initial degassing stage to separate any traces of water.
  • a short-path vacuum still Type KD
  • a distillation at 191° C. and system pressure of 0.014 mbar about 8% by weight of the fatty acid used came out continuously under these conditions as a residue of non-boiling components.
  • the residual product was dewaxed, in which the higher fatty acids (chain lengths of C22 and higher), waxes, and other higher-boiling components contained in the oil crystallized out as solids and were separated by filtration.
  • the filtered residual product was returned to the hydrolysis process at the first stage by a pump as indicated in FIG. 1 .
  • Some other examples were run in the same manner, including some with higher proportions of enzyme and correspondingly shorter hydrolysis times; with beef tallow, and with crambe oil.
  • crambe oil which contains 60% erucic acid
  • a mixture of the non-specific enzyme OF 360 noted above and the 1,3-specific enzyme Novozym 388 was used. The latter specifically hydrolyzes off the fatty acids bound to the 1- and 3-positions of the triglyceride structure, erucic acid in this case.

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EP01115081A EP1270734B1 (de) 2001-06-21 2001-06-21 Verfahren zur enzymatischen Spaltung von Ölen und Fetten
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DE10156584A DE10156584A1 (de) 2001-06-21 2001-11-20 Verfahren und Vorrichtung zur Herstellung von Fettsäureestern aus nativen Ölen und Fetten und Alkoholen, insbesondere n-und Iso-Alkoholen
PCT/EP2002/006077 WO2003010323A1 (de) 2001-06-21 2002-06-04 Verfahren und vorrichtung zur gewinnung von fettsäureestern aus nativen ölen und fetten durch deren enzymatische spaltung

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US20140335580A1 (en) * 2011-09-21 2014-11-13 Board Of Supervisors Of Lousiana State University And Agricultural And Mechanical College Method for Enrichment of Eicosapentaenoic Acid and Docosahexaenoic Acid in Source Oils
US9040263B2 (en) 2010-07-28 2015-05-26 Butamax Advanced Biofuels Llc Production of alcohol esters and in situ product removal during alcohol fermentation
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US11111203B2 (en) 2019-04-04 2021-09-07 Lg Chem, Ltd. System and method for manufacturing ester-based composition
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US8409834B2 (en) 2010-06-18 2013-04-02 Butamax(Tm) Advanced Biofuels Llc Extraction solvents derived from oil for alcohol removal in extractive fermentation
US8476047B2 (en) 2010-06-18 2013-07-02 Butamax Advanced Biofuels Llc Extraction solvents derived from oil for alcohol removal in extractive fermentation
US9371547B2 (en) 2010-06-18 2016-06-21 Butamax Advanced Biofuels Llc Extraction solvents derived from oil for alcohol removal in extractive fermentation
US9206448B2 (en) 2010-06-18 2015-12-08 Butamax Advanced Biofuels Llc Extraction solvents derived from oil for alcohol removal in extractive fermentation
US8865443B2 (en) 2010-06-18 2014-10-21 Butamax Advanced Biofuels Llc Extraction solvents derived from oil for alcohol removal in extractive fermentation
US9175315B2 (en) 2010-06-18 2015-11-03 Butamax Advanced Biofuels Llc Production of alcohol esters and in situ product removal during alcohol fermentation
US9040263B2 (en) 2010-07-28 2015-05-26 Butamax Advanced Biofuels Llc Production of alcohol esters and in situ product removal during alcohol fermentation
US20140335580A1 (en) * 2011-09-21 2014-11-13 Board Of Supervisors Of Lousiana State University And Agricultural And Mechanical College Method for Enrichment of Eicosapentaenoic Acid and Docosahexaenoic Acid in Source Oils
WO2014037006A1 (en) * 2012-09-07 2014-03-13 Aarhuskarlshamn Ab Method for processing a vegetable fat composition
US9499768B2 (en) 2012-09-07 2016-11-22 Aak Ab (Publ) Method for processing a vegetable fat composition
US9115327B2 (en) 2012-09-13 2015-08-25 Chevron U.S.A. Inc. Base oil upgrading by co-feeding a ketone or beta-keto-ester feedstock
WO2014042778A1 (en) * 2012-09-13 2014-03-20 Chevron U.S.A. Inc. Base oil upgrading by co-feeding a ketone or beta-keto-ester feedstock
US11643606B2 (en) 2018-12-31 2023-05-09 Neste Oyj Method for producing renewable base oil and renewable fuel components
WO2020204555A1 (ko) * 2019-04-04 2020-10-08 주식회사 엘지화학 에스터계 조성물의 제조 시스템 및 방법
US11111203B2 (en) 2019-04-04 2021-09-07 Lg Chem, Ltd. System and method for manufacturing ester-based composition

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US6933139B2 (en) 2005-08-23
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JP4222937B2 (ja) 2009-02-12
PT1270734E (pt) 2008-03-24
WO2003010323A1 (de) 2003-02-06
CA2451372A1 (en) 2003-02-06
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DK1270734T3 (da) 2008-05-05
JP4038398B2 (ja) 2008-01-23
CY1107234T1 (el) 2012-11-21
US20020197687A1 (en) 2002-12-26
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JP2003064394A (ja) 2003-03-05
DE50113375D1 (de) 2008-01-24

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