FR2617501A1 - Enzymatic process carried out in an organic solvent - Google Patents
Enzymatic process carried out in an organic solvent Download PDFInfo
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- FR2617501A1 FR2617501A1 FR8709366A FR8709366A FR2617501A1 FR 2617501 A1 FR2617501 A1 FR 2617501A1 FR 8709366 A FR8709366 A FR 8709366A FR 8709366 A FR8709366 A FR 8709366A FR 2617501 A1 FR2617501 A1 FR 2617501A1
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- 230000008569 process Effects 0.000 title claims abstract description 16
- 239000003960 organic solvent Substances 0.000 title claims abstract description 10
- 230000002255 enzymatic effect Effects 0.000 title description 2
- 150000003509 tertiary alcohols Chemical class 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 12
- 239000000194 fatty acid Substances 0.000 claims abstract description 12
- 229930195729 fatty acid Natural products 0.000 claims abstract description 12
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 11
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 10
- 238000006911 enzymatic reaction Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 8
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
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- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 108090000604 Hydrolases Proteins 0.000 description 2
- 102000004157 Hydrolases Human genes 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000012432 intermediate storage Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 1
- GSSDZVRLQDXOPL-UHFFFAOYSA-N 2,2-dimethylhexan-1-ol Chemical compound CCCCC(C)(C)CO GSSDZVRLQDXOPL-UHFFFAOYSA-N 0.000 description 1
- PMRPAQPKUQJWLD-UHFFFAOYSA-N 2-fluoroheptane Chemical compound CCCCCC(C)F PMRPAQPKUQJWLD-UHFFFAOYSA-N 0.000 description 1
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 108090000371 Esterases Proteins 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 description 1
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229940022682 acetone Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229940074076 glycerol formal Drugs 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 235000019626 lipase activity Nutrition 0.000 description 1
- 229940032007 methylethyl ketone Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 229940117972 triolein Drugs 0.000 description 1
Classifications
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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
- C12P7/62—Carboxylic acid esters
- C12P7/625—Polyesters of hydroxy carboxylic acids
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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
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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
- C12P1/00—Preparation of compounds or compositions, not provided for in groups C12P3/00 - C12P39/00, by using microorganisms or enzymes
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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
- C12P7/62—Carboxylic acid esters
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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
- C12P7/6436—Fatty acid esters
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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
- C12P7/6436—Fatty acid esters
- C12P7/6445—Glycerides
- C12P7/6454—Glycerides by esterification
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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
- C12P7/6436—Fatty acid esters
- C12P7/6445—Glycerides
- C12P7/6458—Glycerides by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis
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Abstract
Description
L'invention concerne un procédé permettant la réalisation de réactions enzymatiques entre des matières prises en solution dans un solvant organique. Elle est particulièrement utile dans le domaine des corps gras, où la transfor- mation est effectuée au moyen d'une hydrolase. The invention relates to a method for performing enzymatic reactions between materials taken in solution in an organic solvent. It is particularly useful in the field of fatty substances, where the transformation is carried out by means of a hydrolase.
Alors qu'à l'origine les réactions enzymatiques avaient toujours lieu en milieu aqueux, depuis quelques années on cherche à les effectuer dans des solvants organiques, éventuellement additionnés d'eau, afin de solubiliser, et. While the enzymatic reactions were always carried out in an aqueous medium, in recent years we have tried to carry them out in organic solvents, possibly with the addition of water, in order to solubilize, and.
ainsi mieux soumettre à l'action de l'enzyme, les substrats non hydrosolubles à traiter. C'est, notamment, le cas des différentes opérations sur les corps gras qui, étant insolubles dans l'eau, devaient être traités en milieu hétérogène, dont on connaît les inconvénients. Cependant, la recherche en ce domaine comporte beaucoup de difficultés, surtout à cause de la désactivation des enzymes par la plupart des solvants usuels. Un certain progrès fut réalisé par l'emploi de CO2 supercritique comme milieu de la réaction enzymatique, mais cela complique le travail ne serait-ce que par l'obliga- tion d'opérer sous pression.Un perfectionnement marqué a été obtenu par l'utilisation d'un solvant organique, notamment pour des matières grasses à hydrolyser, accompagné d'un tiers solvant ou d'un agent tensioactif,de façon à homogénéiser l'eau avec ce solvant organique tenant en solution la matière grasse ; ce procédé, décrit dans FR 2 585 365, a donné d'excellents résultats dans l'hydrolyse de différents glycérides en vue de l'obtention des acides gras correspondants. I1 exige, cependant, l'emploi d'un solvant tiers ou d'un agent tensioactif, en plus du solvant organique de la matière grasse ; il est, en outre, quelque peu limité à l'hydrolyse.thus better subject to the action of the enzyme, non-water-soluble substrates to be treated. This is particularly the case of the various operations on fatty substances which, being insoluble in water, should be treated in a heterogeneous medium, the disadvantages of which are known. However, research in this area is fraught with difficulty, especially because of the deactivation of enzymes by most of the usual solvents. Some progress has been made by the use of supercritical CO2 as the medium of the enzymatic reaction, but this complicates the work if only by the obligation to operate under pressure. A marked improvement has been obtained by the use of an organic solvent, especially for fat to be hydrolysed, accompanied by a third solvent or a surfactant, so as to homogenize the water with the organic solvent in solution the fat; this process, described in FR 2,585,365, has given excellent results in the hydrolysis of different glycerides in order to obtain the corresponding fatty acids. It requires, however, the use of a third solvent or a surfactant, in addition to the organic solvent of the fat; it is, in addition, somewhat limited to hydrolysis.
Un autre procédé récent, objet de FR 86 04352 apporte des nouvelles possibilités, fort intéressantes pour la chimie enzymatique, par l'utilisation d'hydrocarbures .fluorés comme solvants des matières à traiter ; il permet les opérations telles qu'estérification, thioestérification, transestérification, amidation, etc. avec bons rendements diverses matières grasses peuvent ainsi être traitées en solution organique, en discontinu ou en continu. En particulier, l'estérification d'acides gras se fait rapidement, avec différents alcools, à des taux très élevés ; cependant l'estérification avec du glycérol est assez lente et conduit à un mélange de mono- et di-glycéride en proportions du même ordre, ne permettant pas l'obtention sélective de monoglycéride. Another recent process, which is the subject of FR 86 04352, provides new and very interesting possibilities for enzymatic chemistry by the use of fluorinated hydrocarbons as solvents of the materials to be treated; it allows operations such as esterification, thioesterification, transesterification, amidation, etc. with good yields various fats can thus be treated in organic solution, batchwise or continuously. In particular, the esterification of fatty acids is carried out rapidly, with different alcohols, at very high levels; however, the esterification with glycerol is rather slow and leads to a mixture of mono- and di-glyceride in proportions of the same order, not allowing the selective production of monoglyceride.
Or, dans.le cadre de la présente invention, on a trouvé qu'en travaillant avec certains solvants organiques spéciaux, il devient possible d'obtenir des résultats que ne donnent pas les procédés précités. En effet, l'invention permet-elle de travailler plus aisément en continu. Dans le cas des estérifications aux polyols, en particulier au glycérol, elle rend possible l'obtention sélective de monoester, fait tout à fait nouveau. Ce résultat est sans doute lié à ce que cette invention comporte la solubilisation si- multanée de l'acide gras et du polyol dans le milieu réactionnel. However, in the context of the present invention, it has been found that by working with certain special organic solvents, it becomes possible to obtain results which are not provided by the aforementioned methods. Indeed, the invention allows it to work more easily continuously. In the case of esterifications with polyols, in particular glycerol, it makes possible the selective production of monoester, quite new. This result is undoubtedly related to the fact that this invention involves the simultaneous solubilization of the fatty acid and the polyol in the reaction medium.
Le procédé suivant l'invention, qui consiste à effectuer une réaction enzymatique au sein d'un solvant organique du substrat à traiter, est caractérisé en ce que le solvant comprend ou est constitué par un ou plusieurs alcools tertiaires. The process according to the invention, which consists in carrying out an enzymatic reaction in an organic solvent of the substrate to be treated, is characterized in that the solvent comprises or consists of one or more tertiary alcohols.
Lorsque ce solvant n'est pas intégralement formé par un alcool tertiaire, il est généralement constitué par un mélange d'un ou de plusieurs de tels alcools avec de l'eau ou/et avec d'autres liquides, tels que par exemple les éthers d'alkyles en C1 à C6, compatibles avec l'enzyme utilisée. When this solvent is not entirely formed by a tertiary alcohol, it generally consists of a mixture of one or more of such alcohols with water and / or with other liquids, such as, for example, ethers. of C1 to C6 alkyls, compatible with the enzyme used.
Les alcools tertiaires, liquides aux températures inférieures à environ 60"C, c'est-à-dire à celles auxquelles ont lieu les réactions enzymatiques, sont peu nombreux ; pra tiquement comptent seulement les tertio-alcanols en C4 et
C5 fondant au-dessous de 260C, mais il peut néanmoins être avantageux d'en employer d'autres,de points de fusion plus élevés, à condition de les mélanger avec des solvants avec lesquels ils donnent du liquide ; c'est le cas des alcools tertiaires en C6 à C12 aliphatiques ou porteurs de groupes aryliques.Tertiary alcohols, which are liquid at temperatures below about 60 ° C, that is to say at those at which enzymatic reactions take place, are few in number, and only C4 tert-alkanols are practically counted.
C5 melting below 260C, but it may nevertheless be advantageous to use others, with higher melting points, provided they are mixed with solvents with which they give liquid; this is the case of aliphatic C 6 to C 12 tertiary alcohols or carriers of aryl groups.
Ainsi, les plus importants parmi les alcools ter tiares utiles selon l'invention. sont le méthyl-2
Thus, the most important among the tertiary alcohols useful according to the invention. are methyl-2
<tb> <SEP> OH
<tb> propanol-2 <SEP> CH3-C-CH3
<tb> tertio-butylique) <SEP> CH3
<tb> fondant à 250C (ou alcool bouillant à 82,90C entièrement miscible à l'eau et à l'éthanol le méthyl-2 butanol-2(ou alcool tertio-amylique)
fondant à -11,90C, bouillant à 1020C soluble dans l'eau à raison- de 14% à 300C
et intégralement dans l'éthanol.<tb><SEP> OH
<tb> propanol-2 <SEP> CH3-C-CH3
<tb> tert-butyl) <SEP> CH3
<tb> melting at 250C (or alcohol boiling at 82.90C fully miscible with water and ethanol) 2-methyl-2-butanol (or tertiary-amyl alcohol)
melting at -11.90C, boiling at 1020C soluble in water at a rate of 14% at 300C
and fully in ethanol.
Comme mentionné plus haut, ces alcools présentent l'intéressante propriété de dissoudre à la fois les matières grasses, acides et esters, comme les polyols, notamment le glycérol.As mentioned above, these alcohols have the interesting property of dissolving both fats, acids and esters, such as polyols, especially glycerol.
Toutefois, des alcools tertiaires plus lourds peuvent constituer des systèmes solvants fort utiles, lorsqu'ils sont pris en mélanges avec les deux précédents ou/et avec des composés tels comme par exemple diéthyl éther, di-isopropyl éther, méthyl t.butyl éther, di-isobutyl éther, di-n. However, heavier tertiary alcohols can be very useful solvent systems when they are taken in admixture with the two preceding ones and / or with compounds such as, for example, diethyl ether, di-isopropyl ether, methyl t-butyl ether, di-isobutyl ether, di-n.
butyl éther, di-méthoxypropane, phényl éthyl éther, di-éthoxy-1,2 éthane, diglyme, acétone, méthyl-éthyl cétone, glycérol-formal, etc., choisis - bien entendu - parmi ceux qui ne désactivent pas l'enzyme donnée.butyl ether, di-methoxypropane, phenyl ethyl ether, 1,2-di-ethoxyethane, diglyme, acetone, methyl-ethyl ketone, glycerol-formal, etc., chosen, of course, from those which do not deactivate the enzyme given.
A titre d'exemples non limitatifs, voici quelques uns des alcools tertiaires fondant au-dessus de 45 cl, qui peuvent être employés dans les conditions sus indiquées
tertio-hexanols
méthyl éthyl isopropyl carbinol (tertio-heptanol) tertio-octanol diphényl-l,l éthanol fondant à 800C
Les alcools tertiaires suivant l'invention non seulement sont parfaitement compatibles avec le fonctionnement des lipases,estérases et protéases, dont ils n'affectent en rien l'activité, mais - de plus - ont un comportement inattendu : leur fonction alcool ne réagit pas avec des acides gras, en présence de l'enzyme, alors que les alcools primaires réagissent bien pour donner de l'ester.By way of nonlimiting examples, here are some of the tertiary alcohols melting above 45 cl, which can be used under the conditions indicated above.
tert-hexanol
methyl ethyl isopropyl carbinol (tertio-heptanol) tert-octanol diphenyl-l, 1 ethanol melting at 800 ° C
The tertiary alcohols according to the invention are not only perfectly compatible with the functioning of lipases, esterases and proteases, of which they do not affect the activity, but - moreover - have an unexpected behavior: their alcohol function does not react with fatty acids, in the presence of the enzyme, while the primary alcohols react well to give the ester.
Le solvant à base de tert.alcool, suivant l'invention, reste donc inaltéré et récupérable, tout au long des opérations portant sur les matières grasses.The solvent based on tert.alcohol, according to the invention, remains unaltered and recoverable throughout the operations on the fat.
Le procédé de l'invention peut en général être réalisé à des températures de 100 à 600C, et surtout entre 300 et 400C, la concentration du substrat à traiter par l'enzyme étant de 1 à 60% en poids dans le solvant employé. The process of the invention can generally be carried out at temperatures of from 100 to 600 ° C., and especially from 300 to 400 ° C., the concentration of the substrate to be treated by the enzyme being from 1 to 60% by weight in the solvent employed.
L'application de l'invention aux corps gras, particulièrement importante, peut être réalisée sous les différentes formes suivantes. The application of the invention to fatty substances, particularly important, can be carried out in the following different forms.
Le corps gras est hydrolysé après sa mise en solution dans le tert.alcool, accompagné de la quantité adéquate d'eau et de l'hydrolase appropriée. The fatty substance is hydrolysed after being dissolved in the tert.alcohol, accompanied by the appropriate amount of water and the appropriate hydrolase.
La synthèse directe d'un ester est effectuée par dissolution d'un acide gras et d'un polyol dans du tert.alcool, au contact de l'enzyme nécessaire. Cette opération peut avoir lieu en discontinu, auquel cas il est indiqué d'introduire dans le milieu réactionnel un adsorbant de l'eau,par exemple un tamis moléculaire, afin d'éliminer l'eau de la réaction. Pour conduire cette synthèse directe en continu, on fait passer la solution des réactifs à travers un lit catalytique supportant l'enzyme ;des éléments absorbant l'eau sont prévus sur le parcours de la solution. The direct synthesis of an ester is carried out by dissolving a fatty acid and a polyol in tert.alcohol, in contact with the necessary enzyme. This operation can take place batchwise, in which case it is advisable to introduce into the reaction medium an adsorbent of water, for example a molecular sieve, in order to remove the water from the reaction. To conduct this direct synthesis continuously, the reagent solution is passed through a catalyst bed supporting the enzyme and water-absorbing elements are provided along the solution pathway.
La synthèse a lieu suivant l'équation.
The synthesis takes place according to the equation.
<tb><Tb>
-OH <SEP> lipase <SEP> RCOO <SEP> HO
<tb> OH <SEP> + <SEP> R <SEP> COOH <SEP> W <SEP> <SEP> HO <SEP> <SEP> + <SEP> RCOO- <SEP>
<tb> tertio-alcool <SEP> HO <SEP> HO
<tb>
R étant en alkyle en C2 à C30.-OH <SEP> lipase <SEP> RCOO <SEP> HO
<tb> OH <SEP> + <SEP> R <SEP> COOH <SEP> W <SEP><SEP> HO <SEP><SEP> + <SEP> RCOO- <SEP>
<tb> tertio-alcohol <SEP> HO <SEP> HO
<Tb>
R being C2 to C30 alkyl.
Cette équation illustre le résultat inattendu de l'invention, mentionné plus haut : au sein d'un alcool tertiaire on obtient du mono-glycéride avec forte sélectivité, alors qué dans la technique antérieure les mono- et di-glycérides sont formés en proportions du même ordre.This equation illustrates the unexpected result of the invention, mentioned above: in a tertiary alcohol is obtained mono-glyceride with high selectivity, whereas in the prior art the mono- and di-glycerides are formed in proportions of same order.
La synthèse indirecte d'un ester s'obtient, suivant l'invention, par l'alcoolyse d'un ester donné, au sein d'une solution dans le tert.alcool, en présence de l'enzyme appropriée. On opère ainsi en milieu anhydre, et il est recommandable de déshydrater convenablement les matières en présence. C'est le cas notamment où l'on fait réagir du glycérol avec un triglycéride, en solution dans l'alcool tertiaire, en présence d'une lipase ; sous peine d'hydrolyse indésirable on doit déshydrater préalablement le milieu réactionnel ; de préférence il ne doit plus y rester que moins de 50 ppm d'eau. The indirect synthesis of an ester is obtained, according to the invention, by the alcoholysis of a given ester, in a solution in the tert.alcohol, in the presence of the appropriate enzyme. This is done in an anhydrous medium, and it is advisable to properly dehydrate the materials involved. This is particularly the case where glycerol is reacted with a triglyceride, in solution in the tertiary alcohol, in the presence of a lipase; under penalty of undesirable hydrolysis, the reaction medium must be dehydrated beforehand; preferably there should be less than 50 ppm water.
Dans les exemples non limitatifs, donnés plus loin, on relate différents essais effectués avec la lipase du champignon Rhizopus arrhizus (ATCC 24563) ; ce catalyseur était préparé selon FUKUMOTO et coll. (J. Gen. Appl. Microbiol. 10, 1964, 257-65), de la façon suivante. In the nonlimiting examples, given below, various trials carried out with the lipase of the fungus Rhizopus arrhizus (ATCC 24563); this catalyst was prepared according to FUKUMOTO et al. (J. Gen. Appl Microbiol 10, 1964, 257-65), as follows.
Le microorganisme est cultivé dans un fermenteur sur le milieu composé de
- huile de colza 20 g/l
- "Corn Steep Liquor" 50
KH2Po4 2
-KCl 0,5
-NaNO3 0,5
-MgSO4.7H2O 0,5
Le pH initial est de 4,6. La croissance a lieu pendant 3-5 jours à 25-300C. Le mycélium est alors essoré, lavé à l'eau distillée et séché soit à l'étuve sous vide à température modérée, soit par lyophilisation.The microorganism is cultured in a fermentor on the medium composed of
- rapeseed oil 20 g / l
- "Corn Steep Liquor" 50
KH2Po4 2
-KCl 0.5
-NaNO3 0.5
-MgSO4.7H2O 0.5
The initial pH is 4.6. Growth takes place for 3-5 days at 25-300C. The mycelium is then drained, washed with distilled water and dried either in a vacuum oven at a moderate temperature or by lyophilization.
Le mycélium sec est dégraissé par extraction, puis broyé, tamisé et conservé au sec.The dry mycelium is defatted by extraction, then crushed, sieved and kept dry.
L'activité lipasique du mycélium ainsi préparé se situe entre 0,9 et 4 unités/mg (sur trioléine en émulsion.The lipase activity of the mycelium thus prepared is between 0.9 and 4 units / mg (on triolein in emulsion.
EXEMPLE 1
Hydrolyse en discontinu
Le mélange réactionnel est constitué de 88,9g d'alcool tertio-amylique contenant 10g d'huile végétale raffinée et 1,5g d'eau. Chaque opération est réalisée sur 10 mu de ce mélange mis en contact avec 100 mg de mycélium de R.arrhizus préparé comme indiqué plus haut.EXAMPLE 1
Hydrolysis in batch
The reaction mixture consists of 88.9 g of tert-amyl alcohol containing 10 g of refined vegetable oil and 1.5 g of water. Each operation is carried out on 10 mu of this mixture brought into contact with 100 mg of R.arrhizus mycelium prepared as indicated above.
Après 2 heures de réaction, la conversion, c'est-à-dire la proportion des acides gras libérés par rapport au total des acides gras présents est de 12,8%.After 2 hours of reaction, the conversion, that is to say the proportion of fatty acids released relative to the total fatty acids present is 12.8%.
EXEMPLE 2
Hydrolyse en continu
On fait passer en continu, à travers un réacteur, le mélange constitué de la façon suivante, en g pour 100g de mélange
Huile végétale 12
Eau 1,8
Alcool t.amylique 86,2
La colonne du réacteur contient 5,5g de mycélium pour 1Oml de silice, soit un volume total d'environ 35 ml.EXAMPLE 2
Continuous hydrolysis
The mixture constituted as follows is passed continuously through a reactor, in g per 100 g of mixture
Vegetable oil 12
Water 1.8
Amyl alcohol 86.2
The reactor column contains 5.5 g of mycelium per 100 ml of silica, ie a total volume of approximately 35 ml.
Le volume mort est de l'ordre de 15 ml pour un débit de l'ordre de 12 ml/h, ce qui correspond à un temps de séjour de l'ordre de 75 mn.The dead volume is of the order of 15 ml for a flow rate of the order of 12 ml / h, which corresponds to a residence time of the order of 75 minutes.
La réaction a lieu en continu avec un taux de conversion de 39% (proportion d'acide gras libérés par rapport aux acides gras présents).The reaction takes place continuously with a conversion of 39% (proportion of fatty acids released relative to the fatty acids present).
EXEMPLES 3 à 5
Estérification en discontinu
Le mélange réactionnel est constitué par 9,2 g de glycérol (0,1 M) et de 14,1g d'acide oléique (0,05 M) pour 100 ml de solvant qui varie d'un exemple à l'autre.EXAMPLES 3 to 5
Batch esterification
The reaction mixture consists of 9.2 g of glycerol (0.1 M) and 14.1 g of oleic acid (0.05 M) per 100 ml of solvent which varies from one example to another.
Après ajout de 2g de mycélium de R-arrhizus et 10 g de tamis moléculaire, on laisse sous agitation à TOC pendant e h puis on procède à l'analyse des produits de la réaction par chromatographie en phase gazeuse des dérivés triméthylsilyl de l'acide gras libre, ainsi que de mono- et diglycéride présents.After addition of 2 g of R-arrhizus mycelium and 10 g of molecular sieve, the mixture is left stirring with TOC for 1 hour and then the reaction products are analyzed by gas chromatography of the trimethylsilyl derivatives of the fatty acid. free, as well as mono- and diglyceride present.
Les résultats sont réunis dans le tableau ci-après, où la composition du mélange obtenu est exprimée en moles %
Exemple NO 3 4 5
Solvant alcool tert. trichloro-tri- C02/77 bars
amylique fluoro-éthane
TOC 400C 400C 32 "C
Durée e h 18 18 5
Etat du milieu 1- phase plusieurs
homogène phases
Composition % mol
acide oléique 82,9 32,4 32,2
monoglycéride 17,9 37,1 -44,1
diglycéride 0 30,5 23,7
Bien que, dans l'exemple 3 correspondant à l'emploi d'un alcool tertiaire, l'estérification soit allée moins loin que dans les exemples comparatifs 4 et 5 représentant l'art antérieur, le résultant est néanmoins très intéressant, puisqu'il démontre la possibilité d'obtention de monoglycé ride seul.The results are summarized in the table below, where the composition of the mixture obtained is expressed in mole%
Example NO 3 4 5
Solvent alcohol tert. trichloro-tri- CO2 / 77 bar
amyl fluoroethane
TOC 400C 400C 32 "C
Duration 18 18 5
State of the middle 1- phase several
homogeneous phases
% Mol composition
oleic acid 82.9 32.4 32.2
monoglyceride 17.9 37.1 -44.1
diglyceride 0 30.5 23.7
Although, in Example 3 corresponding to the use of a tertiary alcohol, the esterification has gone less far than in Comparative Examples 4 and 5 representing the prior art, the result is nonetheless very interesting, since demonstrates the possibility of getting monoglyceride alone.
EXEMPLE 6
Estérification en continu dans un réacteur segmenté
Le réacteur proprement dit est constitué de une ou plusieurs colonnes en cascade avec stockage intermédiaire.EXAMPLE 6
Continuous esterification in a segmented reactor
The reactor itself consists of one or more columns in cascade with intermediate storage.
Chaque colonne (résistanteau milieu solvant) est thermostatée par double enveloppe, et alimentée par une pompe volumétrique à débit constant.Each column (resistant solvent medium) is thermostated by double jacket, and powered by a constant displacement volumetric pump.
Le garnissage de chaque segment est fait à sec avec un mélange de mycélium broyé sec et de silice de granulométrie 300 , à raison de.0,54 g de silice pour 1 g de mycélium (soit environ 0,4 volume de silice pour 1 volume de mycélium).The lining of each segment is made dry with a mixture of dry milled mycelium and silica of particle size 300, at the rate of 0.54 g of silica per 1 g of mycelium (ie about 0.4 volume of silica per 1 volume of mycelium).
Le mélange initial est préparé dans un premier bac de stockage. La teneur en eau du mélange est ajustée dans chaque stockage intermédiaire. Le temps de séjour sur chaque étape est de l'ordre de 75 mn pour un volume parcouru voisin de la moitié du volume total.The initial mixture is prepared in a first storage tank. The water content of the mixture is adjusted in each intermediate storage. The residence time on each stage is of the order of 75 minutes for a volume traveled close to half the total volume.
Le mélange réactionnel est constitué d'acide oléique (1 mole) et de glycérol (3 moles) pour 1000 ml d'alcool tertio-amylique. Le débit est choisi de façon à assurer en continu un temps de séjour de l'ordre d'une heure par élément. Chaque élément de réacteur est suivi d'un élément de tamis moléculaire où le temps de séjour est du même ordre.The reaction mixture consists of oleic acid (1 mole) and glycerol (3 moles) per 1000 ml of tertiary amyl alcohol. The flow rate is chosen so as to ensure a continuous residence time of the order of one hour per element. Each reactor element is followed by a molecular sieve element where the residence time is of the same order.
Résultats
Temps de séjour 1 heure Conversion du mélange
obtenu
(% molaires)
acide oléique monoglycéride diglycéride
libre 1er passage 72,39 27,1 0,0 2ème " 53,3 44,7 2,0
En rapprochant ces résultats de ceux de l'exemple 3, on constate qu'il est bien possible, avec le procédé de l'invention, de pousser la formation de monoglycéride assez loin (44,7%) en n'obtenant qu'une très faible proportion de diglycéride (2%). Cet exemple est donc à comparer avec les exemples 4 et 5.Results
Residence time 1 hour Conversion of the mixture
got
(mol%)
oleic acid monoglyceride diglyceride
free 1st pass 72.39 27.1 0.0 2nd "53.3 44.7 2.0
Comparing these results with those of Example 3, it is found that it is possible with the process of the invention to push the formation of monoglyceride far enough (44.7%) by obtaining only one very low proportion of diglyceride (2%). This example is therefore compared with Examples 4 and 5.
EXEMPLE 7
Glycérolyse du suif en continu dans l'alcool tertio-amylique
Le mélange réactionnel est constitué de 50g de glycérol (0,54 mole) et de 50g de suif (0,05 mole) pour 1000 ml d'alcool tertio-amylique.EXAMPLE 7
Glycerolysis of tallow continuously in tertiary amyl alcohol
The reaction mixture consists of 50 g of glycerol (0.54 mol) and 50 g of tallow (0.05 mol) per 1000 ml of tert-amyl alcohol.
Le mélange est passé sur colonne à un débit assurant un temps de séjour de l'ordre de 75 mn au contact du mycélium.The mixture is passed over a column at a rate ensuring a residence time of about 75 minutes in contact with the mycelium.
L'analyse est faite par chromatographie en phase gazeuse des dérivés triméthyl-silyl, et rendue quantitative par utilisation d'un étalon interne (acide laurique).The analysis is made by gas chromatography of the trimethylsilyl derivatives, and made quantitative by using an internal standard (lauric acid).
te rendement observé en monoglycérides par rapport au suif est de 17,2g de monoglycérides pour 100g de suif.the observed yield of monoglycerides relative to tallow is 17.2 g of monoglycerides per 100 g of tallow.
EXEMPLE 8
Glycérolyse suif en continu dans l'alcool tertio-butylique
Le mélange réactionnel est constitué de 10g de glycérol et de 10g de suif pour 100g d'alcool tertio-butylique. Le mélange est préalablement déshydraté sur tamis moléculaire puis passé sur colonne à un débit assurant un temps de séjour de l'ordre de 75 mn au contact du mycélium.EXAMPLE 8
Glycerolysis continuously tallow in tertiary butyl alcohol
The reaction mixture consists of 10 g of glycerol and 10 g of tallow per 100 g of tert-butyl alcohol. The mixture is previously dehydrated on molecular sieves and then passed over a column at a rate ensuring a residence time of about 75 minutes in contact with the mycelium.
L'analyse est faite comme dans l'exemple 7.The analysis is done as in Example 7.
Le rendement obtenu est de 38,8 g de monoglycérides pour 100g de suif.The yield obtained is 38.8 g of monoglycerides per 100 g of tallow.
EXEMPLE 9
Glycérolyse du suif hydrogéné en continu dans l'alcool tertioamylique
Le mélange réactionnel est constitué de 5g de suif hydrogéné et de 5g de glycérol pour 85g d'alcool tertio-amylique, et est laissé en contact de 10g de tamis moléculaire pendant 20 heures avant réaction.EXAMPLE 9
Glycerolysis of hydrogenated tallow continuously in tertiary amyl alcohol
The reaction mixture consists of 5 g of hydrogenated tallow and 5 g of glycerol per 85 g of tert-amyl alcohol, and is left in contact with 10 g of molecular sieve for 20 hours before reaction.
Le mélange est passé sur colonne à un débit correspondant à un temps de séjour de 75 mn au contact du mycélium.The mixture is passed over a column at a rate corresponding to a residence time of 75 minutes in contact with the mycelium.
L'analyse est faite par chromatographie en phase gazeuse comme en 5a. Le rendement observé est de 27,7g de monoglycérides pour 100g de suif hydrogéné. The analysis is done by gas chromatography as in 5a. The yield observed is 27.7 g of monoglycerides per 100 g of hydrogenated tallow.
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Cited By (14)
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EP0293001A3 (en) * | 1987-05-29 | 1990-05-30 | Lion Corporation | Method for continuous preparation of highly pure monoglyceride |
EP0293001A2 (en) * | 1987-05-29 | 1988-11-30 | Lion Corporation | Method for continuous preparation of highly pure monoglyceride |
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EP0390624A1 (en) * | 1989-02-27 | 1990-10-03 | Elf Sanofi | Microbiological process for the preparation of methyl ketones |
US5935828A (en) * | 1989-05-01 | 1999-08-10 | Opta Food Ingredients, Inc. | Enzymatic production of monoglycerides containing omega-3 unsaturated fatty acids |
FR2648147A1 (en) * | 1989-06-13 | 1990-12-14 | Gattefosse Ets Sa | Process for the preparation of beta-monoglycerides and products obtained |
EP0413307A1 (en) * | 1989-08-15 | 1991-02-20 | Lion Corporation | Process for producing saccharide fatty acid monoesters |
EP1637610A1 (en) * | 2004-09-20 | 2006-03-22 | Sunho Biodiesel Corporation | Methods for producing alkyl esters |
US7473539B2 (en) | 2004-09-20 | 2009-01-06 | Sunho Biodiesel Corporation | Methods for producing alkyl esters |
US7666666B2 (en) | 2004-09-20 | 2010-02-23 | Sunho Biodiesel Corporation | Fuel production |
AU2005200356B2 (en) * | 2004-09-20 | 2011-03-03 | Sunho Biodiesel Corporation | Methods for producing alkyl esters |
US8076110B2 (en) | 2004-09-20 | 2011-12-13 | Sunho Biodiesel Corporation | Methods for producing alkyl esters |
Also Published As
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FR2617501B1 (en) | 1990-03-16 |
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