EP1100764A1 - Concentration et purification d'esters d'acides gras polyinsatures par couplage distillation transesterification enzymatique - Google Patents
Concentration et purification d'esters d'acides gras polyinsatures par couplage distillation transesterification enzymatiqueInfo
- Publication number
- EP1100764A1 EP1100764A1 EP00938359A EP00938359A EP1100764A1 EP 1100764 A1 EP1100764 A1 EP 1100764A1 EP 00938359 A EP00938359 A EP 00938359A EP 00938359 A EP00938359 A EP 00938359A EP 1100764 A1 EP1100764 A1 EP 1100764A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- esters
- alcohol
- fatty acid
- fatty acids
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 title claims abstract description 30
- 238000000746 purification Methods 0.000 title description 14
- 238000000034 method Methods 0.000 claims abstract description 50
- 230000008569 process Effects 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 24
- -1 alkoxy alcohol Chemical compound 0.000 claims abstract description 19
- 150000002148 esters Chemical class 0.000 claims abstract description 19
- 108090001060 Lipase Proteins 0.000 claims abstract description 11
- 102000004882 Lipase Human genes 0.000 claims abstract description 11
- 125000005233 alkylalcohol group Chemical group 0.000 claims abstract description 9
- 239000004367 Lipase Substances 0.000 claims abstract description 7
- 235000019421 lipase Nutrition 0.000 claims abstract description 7
- 150000003626 triacylglycerols Chemical class 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 53
- 229930195729 fatty acid Natural products 0.000 claims description 53
- 239000000194 fatty acid Substances 0.000 claims description 53
- 235000019198 oils Nutrition 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 235000019441 ethanol Nutrition 0.000 claims description 27
- 238000000526 short-path distillation Methods 0.000 claims description 25
- 150000004665 fatty acids Chemical class 0.000 claims description 22
- 125000004494 ethyl ester group Chemical group 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 108090000790 Enzymes Proteins 0.000 claims description 15
- 102000004190 Enzymes Human genes 0.000 claims description 15
- 235000020664 gamma-linolenic acid Nutrition 0.000 claims description 12
- 108010048733 Lipozyme Proteins 0.000 claims description 11
- VZCCETWTMQHEPK-QNEBEIHSSA-N gamma-linolenic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/CCCCC(O)=O VZCCETWTMQHEPK-QNEBEIHSSA-N 0.000 claims description 11
- FCCDDURTIIUXBY-UHFFFAOYSA-N lipoamide Chemical compound NC(=O)CCCCC1CCSS1 FCCDDURTIIUXBY-UHFFFAOYSA-N 0.000 claims description 11
- VZCCETWTMQHEPK-UHFFFAOYSA-N gamma-Linolensaeure Natural products CCCCCC=CCC=CCC=CCCCCC(O)=O VZCCETWTMQHEPK-UHFFFAOYSA-N 0.000 claims description 10
- 229960002733 gamolenic acid Drugs 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 235000021281 monounsaturated fatty acids Nutrition 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 241000235403 Rhizomucor miehei Species 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 235000021324 borage oil Nutrition 0.000 claims description 4
- 108090000371 Esterases Proteins 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 241000303962 Rhizopus delemar Species 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims 6
- 125000000217 alkyl group Chemical group 0.000 claims 5
- 125000003118 aryl group Chemical group 0.000 claims 2
- 150000004668 long chain fatty acids Chemical class 0.000 claims 1
- 150000003138 primary alcohols Chemical class 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- MBMBGCFOFBJSGT-KUBAVDMBSA-N all-cis-docosa-4,7,10,13,16,19-hexaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 abstract description 42
- 235000020673 eicosapentaenoic acid Nutrition 0.000 abstract description 42
- 235000020669 docosahexaenoic acid Nutrition 0.000 abstract description 39
- 239000003921 oil Substances 0.000 abstract description 29
- 239000002253 acid Substances 0.000 abstract description 8
- 150000007513 acids Chemical class 0.000 abstract description 6
- 230000002255 enzymatic effect Effects 0.000 abstract description 5
- 229940013317 fish oils Drugs 0.000 abstract description 5
- 238000000199 molecular distillation Methods 0.000 abstract description 5
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 abstract description 3
- 229960005135 eicosapentaenoic acid Drugs 0.000 abstract description 3
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 abstract description 3
- 229940090949 docosahexaenoic acid Drugs 0.000 abstract description 2
- 238000002955 isolation Methods 0.000 abstract 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 238000004821 distillation Methods 0.000 description 15
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 7
- 238000006911 enzymatic reaction Methods 0.000 description 7
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- 240000008791 Antiaris toxicaria Species 0.000 description 3
- 241001072256 Boraginaceae Species 0.000 description 3
- 235000007689 Borago officinalis Nutrition 0.000 description 3
- 241001125048 Sardina Species 0.000 description 3
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 3
- 235000021342 arachidonic acid Nutrition 0.000 description 3
- 229940114079 arachidonic acid Drugs 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- MJLYTDAIYLGSRZ-ORZIMQNZSA-N gamma-Linolenic acid ethyl ester Chemical compound CCCCC\C=C/C\C=C/C\C=C/CCCCC(=O)OCC MJLYTDAIYLGSRZ-ORZIMQNZSA-N 0.000 description 3
- 150000002632 lipids Chemical class 0.000 description 3
- 235000021313 oleic acid Nutrition 0.000 description 3
- 235000019512 sardine Nutrition 0.000 description 3
- 241000199912 Crypthecodinium cohnii Species 0.000 description 2
- 241000219925 Oenothera Species 0.000 description 2
- 235000004496 Oenothera biennis Nutrition 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 210000004556 brain Anatomy 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- ITNKVODZACVXDS-YNUSHXQLSA-N ethyl (4Z,7Z,10Z,13Z,16Z,19Z)-docosahexaenoate Chemical compound CCOC(=O)CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CC ITNKVODZACVXDS-YNUSHXQLSA-N 0.000 description 2
- 239000010475 evening primrose oil Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 235000020778 linoleic acid Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N linoleic acid group Chemical group C(CCCCCCC\C=C/C\C=C/CCCCC)(=O)O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002889 oleic acids Chemical class 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003180 prostaglandins Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000273930 Brevoortia tyrannus Species 0.000 description 1
- 241000238366 Cephalopoda Species 0.000 description 1
- 101001000747 Clarkia lewisii Glucose-6-phosphate isomerase, cytosolic 2A Proteins 0.000 description 1
- 101001000734 Clarkia lewisii Glucose-6-phosphate isomerase, cytosolic 2B Proteins 0.000 description 1
- 241001417105 Clupea pallasii Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000940612 Medina Species 0.000 description 1
- 241000180113 Monodus Species 0.000 description 1
- 241000235395 Mucor Species 0.000 description 1
- 241000195659 Neodesmus pupukensis Species 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- NCYSTSFUYSFMEO-OBLTVXDOSA-N PGI3 Chemical compound O1\C(=C/CCCC(O)=O)C[C@@H]2[C@@H](/C=C/[C@@H](O)C\C=C/CC)[C@H](O)C[C@@H]21 NCYSTSFUYSFMEO-OBLTVXDOSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- 235000013400 Quercus lobata Nutrition 0.000 description 1
- 240000001749 Quercus lobata Species 0.000 description 1
- 241000269821 Scombridae Species 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000828 canola oil Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 235000012716 cod liver oil Nutrition 0.000 description 1
- 239000003026 cod liver oil Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- DVSZKTAMJJTWFG-UHFFFAOYSA-N docosa-2,4,6,8,10,12-hexaenoic acid Chemical compound CCCCCCCCCC=CC=CC=CC=CC=CC=CC(O)=O DVSZKTAMJJTWFG-UHFFFAOYSA-N 0.000 description 1
- 235000004626 essential fatty acids Nutrition 0.000 description 1
- 235000008524 evening primrose extract Nutrition 0.000 description 1
- 229940089020 evening primrose oil Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 125000005481 linolenic acid group Chemical group 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 235000020640 mackerel Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 201000006417 multiple sclerosis Diseases 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940094443 oxytocics prostaglandins Drugs 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 210000001525 retina Anatomy 0.000 description 1
- 229940119224 salmon oil Drugs 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 208000010110 spontaneous platelet aggregation Diseases 0.000 description 1
- 125000005472 straight-chain saturated fatty acid group Chemical group 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 210000002182 synaptic membrane Anatomy 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/6445—Glycerides
- C12P7/6458—Glycerides by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- 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
- C12P7/6472—Glycerides containing polyunsaturated fatty acid [PUFA] residues, i.e. having two or more double bonds in their backbone
Definitions
- the present invention relates to a process for producing highly concentrated preparations of polyunsaturated fatty acids and their esters from oils from various sources, especially fish oils, vegetable oils and microalgae oils.
- the process uses a combination of molecular distillation and selective enzymatic transesterification catalysed by upases which desirably can be immobilized.
- fatty acids mostly encountered, usually as their triglyceride esters but not exclusively, in fish oils and vegetable oils are oleic acid (C18:l), palmitoleic acid (C16:l), palmitic acid (C16:0) and gadolenic acid (C20:l), but other fatty acids possessing from 14 to 24 carbon atoms in their structure, with or without double bounds, can also be found.
- Polyunsaturated fatty acids possessing 3 double bonds or more are components of high economic value and have many applications in the pharmaceutical, nutrient and cosmetic fields.
- Two well-known families are the so-called ⁇ 3 and ⁇ 6 families, which include a single double bond located three and six carbon atoms respectively from the terminal methyl group.
- the two most important members of the ⁇ 3 family are eicosapentaenoic acid (EPA, C20:5) and docosahexenoic acid (DHA, C22:6) which play an important role in human physiology. They participate in the construction of cellular membranes and, as precursors of prostaglandins, in the formation of PGI3 and TxA3, which are extremely important factors for platelet aggregation prevention. Furthermore, DHA is the most important component of brain lipids and is believed to have a role in synaptic membrane functioning.
- the principal members of the ⁇ family are ⁇ -linolenic (GLA, C18:3) acid and arachidonic acid (AA, C20:4). The former is an essential fatty acid and used for certain therapeutic purposes such as the treatment of multiple sclerosis. The latter participates in prostaglandin metabolism and possesses specific functions in brain and retina.
- Fish oils are important sources for EPA and DHA.
- the weight percentages of EPA+DHA of the total fatty acids range from 7% (in Pacific herring oil) to 28% (in Pacific squid oil) .
- the most common source for EPA and DHA is sardine oil with a combined concentration of about 25%, comprising 18% EPA and 7% DHA.
- Other possible sources are salmon oil (19% EPA and DHA), menhaden oil (24%), cod liver oil (24%), and mackerel oil (15%) .
- the ratio of EPA to DHA in fish oils is usually about 2:1, but tuna oil contains about 5% EPA and about 18% DHA.
- EPA and DHA are also found in lipids produced by marine microalgae such as Monodus subterraneus UTEX 151 (34.2% EPA), Chlorella minutissima UTEX 2341 (31.3% EPA), Crypthecodinium cohnii UTEX L1649 (19.9% DHA) or Amphidini um carterae UTEX LB 1002 (17% DHA) .
- soybean and canola oils provide ⁇ linolenic acid (precursor of EPA and DHA) at 8-10% of the total fatty acids.
- the major sources for ⁇ -linolenic acid are borage, evening primrose and black current oils. The first is more important with 20% to 23% of ⁇ -linolenic acid, while the second contains only about 10% of ⁇ -linolenic acid and the last 14% to 20%.
- the composition of the reaction medium can be carefully controlled to purify selectively polyunsaturated fatty acids by the urea adduct formation method (Han, Daeseok; Shin, Hyun-Kyung; Yoon, Suk Hoo, ACS Symp. Ser. 1997, 674 (Flavor and Lipid Chemistry of Seafoods) ) .
- EPA and DHA have also been purified through silver salt complexation (EP 454 430, and EP 303 668), by chromatography (Robles Medina, .; Gimenez Gimenez,A.; Garcia Camacho, F.; Sanchez Perez, J.A.; Molina Grima, E . ; Contreras Gomez, A.; J.Am.Oil Chem. Soc. 1995 72(5) 575-83). These processes result in the preparation of highly purified polyunsaturated fatty acids, but only in very small quantities.
- the silver ion, Ag + can be immobilized on a clay mineral (Yamaguchi, Michihiro; Tanaka, Isao; Ohtsu, Yutaka; Yukagaku 1991 40(10), 959-64), which makes the method more practical.
- a clay mineral Yamauchi, Michihiro; Tanaka, Isao; Ohtsu, Yutaka; Yukagaku 1991 40(10), 959-64
- a very promising method currently used to obtain concentrates of polyunsaturated fatty acids is molecular distillation. This method makes use of high vacuum conditions to distil the thermolabile polyunsaturated fatty acids. This process, in some cases, results in very high concentrates of polyunsaturated fatty acids.
- a British patent (GB 2 218 984) has claimed the process to be appropriate for industrial production of EPA and DHA. However multiple distillations are necessary to obtain a high concentration of polyunsaturated fatty acids and the distillation temperature used is very low (from 50 to 85°C) .
- Using a low temperature has an advantage of not altering the nature of the easily oxidized polyunsaturated fatty acids, but causes a major problem in industrial production since the throughput is proportional to the difference between the vapour pressure of the products to be distilled and the operating pressure, and the former is a function of temperature.
- molecular distillation Although very powerful, the concept of molecular distillation is close to that of batch distillation and thus has limitations. In particular, if the composition of the raw material is complex, molecular distillation does not allow an effective purification and for instance is inappropriate for the production of DHA free from EPA and vice versa. The same problem is encountered for the production of ⁇ -linolenic acid free from linoleic and oleic acids.
- Another way to obtain polyunsaturated fatty acids in high concentration is selective hydrolysis or selective synthesis using specific enzymes.
- Different upases known to have a selectivity for saturated fatty acids over polyunsaturated fatty acids are used.
- the most common way is to hydrolyse oils containing polyunsaturated fatty acid triglycerides followed by washing or extraction (JP 05095792, JP 03108489, and JP 07203979) .
- This invention seeks to provide an efficient economical process for the concentration and the purification of polyunsaturated fatty acids as onoesters of lower alcohols.
- the raw material for the process is either fish oil containing different concentrations of eicosapentaenoic acid (EPA C20:5) and docosahexaenoic acid (DHA C22:6), or vegetable oils like borage, evening primrose or black current oils, containing different concentrations of ⁇ -linolenic acid (GLA C18:3), or oils isolated from microalgae or other micro-organisms which contain fatty acids like DHA or arachidonic acid (AA C20:4).
- these desired acids are usually present in the natural oil as the triglyceride ester.
- the fatty acid triglyceride ester is first transesterified chemically.
- the esters are either submitted to fractionation concentration (EPA-DHA) prior to enzymatic transesterification catalysed by an appropriate enzyme, or directly enzymatically transesterified.
- the course of the reaction is followed by gas chromatography. It is stopped by the removal of the enzyme by filtration or centrifugation.
- the transesterified oil product is submitted, generally, to two molecular or so-called short path distillations.
- the excess of transesterification alcohol is removed as distillate, and the oil is also deodorized.
- a distillate is produced comprising the unsaturated fatty acid ester of interest as a generally clear, odorless compound.
- the residue of this distillation can also be used as a potential wax base, or split into its component fatty acids, or fatty acid esters of lower alcohols, which can also be purified by short path distillation.
- this invention comprises a multistep process which can be summarised as follows.
- Step 1 Oils containing polyunsaturated fatty acid triglycerides, such as sardine oil, borage oil and the like as described above, are first transesterified for three hours, with a primary lower alkyl alcohol at room temperature, using an alkali metal alcoholate of the same lower alkyl alcohol as catalyst. The esters obtained are separated from the glycerol formed during the reaction by decantation. The excess alcohol is removed under vacuum (15 bars) . The mixture is then treated according to its composition and to the polyunsaturated acids to be purified, using the following procedure.
- Step 2 The mixture of ethyl esters is subjected to a preliminary optional short path distillation at 160-190°C and a pressure of 10 "3 bar to remove impurities, which constitute the distillation residue.
- the distillate comprises the desired fatty acid ethyl esters.
- Step 3 The distillate from step 2, or the esters mixture from step 1 if step 2 is omitted, is subjected to short path distillation at 130-160°C and a pressure of 10 "3 mbar to separate the mixture into two ester fractions.
- the distillate is rich in esters of fatty acids possessing 18 carbons or less, and the distilland is rich in esters of fatty acids possessing 20 carbons or more.
- Step 4 The purified ethyl esters from Step 3 are transesterified with a mono- or poly-alkoxy alcohol using a reaction specific lipase, in the presence of sufficient water for the lipase enzyme to catalyse the transesterification reaction, to provide a mixture of fatty acid ethyl esters rich in polyunsaturated fatty acids and fatty acid alkoxyalkyl esters rich in saturated and monounsaturated fatty acids .
- Step 5 The unreacted alcohol remaining after the transesterification reaction in Step 4 is removed by short path distillation at 60-90°C under a pressure of 10 "3 mbar, or by washing with water followed by a suitable drying procedure.
- Step 6 The esters mixture from Step 5 is subjected to a final short path distillation at 100-180°C to separate the fatty acid ethyl esters distillate from fatty acid alkoxy alkyl esters (distilland) .
- steps 1 and 2 are not used in the purification of ⁇ -linolenic acid from borage oil as the principal constituents of this oil are linolenic, linoleic and oleic acids, which cannot be separated efficiently by distillation.
- Step 4 is omitted whenever a too high molecular weight alcohol such as polyethylene glycol methyl ether 350 is used.
- the primary lower alkyl alcohol preferably contains up to 7 carbon atoms, or can be benzyl alcohol. More preferably, the lower alkyl alcohol is ethyl alcohol.
- step 4 the amount of enzyme used is preferably from about 0.5% to about 5.0% by weight of the fatty acid esters present in the oil, and the amount of water present is from 1% to 10% by weight of the enzyme.
- the lipase enzyme is chosen from the group consisting of: Lipozyme IM from a Mucor miehei strain; Lipase D from a Rhizopus delemar strain; and Esterase 30000 from a Mucor miehei strain.
- the transesterification in step 4 is carried out at a temperature of 50 - 70°C, and a pressure of from about 0.1 - 20 mbars. More preferably, the transesterification in step 4 is carried out at a temperature of 60 - 70°C, and a pressure of about 15 mbars.
- the present invention provides a process to obtain polyunsaturated fatty acids on a large scale. It can be applied to different kinds of oils by coupling short path distillation and selective enzymatic transesterification.
- the two techniques can be used in a modular way in order to obtain products with a desirable composition. The combination makes it possible for the following to be obtained:
- thermolabile polyunsaturated fatty acid esters In any of the purification steps, whenever the product is subject to heating, for either a distillation step or in the enzymatic reaction, it is always under vacuum. This minimises any oxidation and the degradation of the thermolabile polyunsaturated fatty acid esters.
- the polyunsaturated fatty acids are purified as ethyl esters, whose vapour pressure is higher than that of the corresponding free acids. This makes it possible to obtain a high throughput in the short path distillation steps at 130- Steps 1 and 2 are used principally for the purification of EPA and DHA.
- the ethyl esters of these fatty acids have a much lower rate of distillation than that of lower fatty acids (C18, C16 and lower).
- a preliminary distillation makes it possible to obtain products containing up to 33% EPA and 22% DHA, and eliminates a high proportion of the lower fatty acids which are also present.
- the quantity of products to be treated enzymatically is therefore much smaller than the original material, usually from about 10% to about 20% of the starting material, according to its composition.
- the key step of the whole procedure is the transesterification of the fatty acid ethyl esters with a mono - or polyalkoxy alcohol, such as 2- (2-butoxyethoxy) ethanol and polyethylene glycol methyl ether 350, using a reaction specific lipase such as Lipozyme IM (Novo) under a vacuum of 10-20 mbars, and at appropriate temperature, such as 60-70°C for Lipozyme) .
- the reaction equilibrium is displaced by removing under vacuum the ethanol formed during the reaction.
- the rate at which the enzyme catalyses the transesterification reaction depends on the degree of unsaturation of the fatty acid in the ethyl ester; the reaction generally becomes slower as the degree of unsaturation increases.
- the fatty acid ethyl esters rich in polyunsaturated fatty acids are then separated from the products of the enzymatic reaction comprising the fatty acid alkoxyalkyl esters rich in saturated and monounsaturated fatty acids by a second short path distillation at 100-180°C under a pressure of 10 "3 mbars.
- the fatty acid ethyl esters rich in polyunsaturated fatty acids are recovered in the distillate while the fatty acid alkoxyalkyl esters rich in saturated and monounsaturated fatty acids, whose vapour pressure is practically nil, are recovered as the distilland.
- This short path distillation step is also used to remove the excess of alcohol if it has a zero vapour pressure, as in the case of polyethylene glycol.
- the distillate product obtained is highly rich in polyunsaturated fatty acid ethyl esters, and can contain more than 80% in most cases and can reach 90% or more.
- alkoxy alcohol is crucial for the purification.
- the alkoxy alcohol esters formed by the enzymatic reaction cannot be distilled in the range of temperature used for the distillation of fatty acid ethyl esters and thus the two ester types can be separated very efficiently by short path distillation.
- the enzyme selectivity is much higher with an alkoxy alcohol than with an aliphatic alcohol.
- oleyl alcohol for example, the enzymatic transesterification by Lipozyme IM is practically the same for all the fatty acids while with polyethylene glycol methyl ether 350, the reaction rate for saturated and monounsaturated fatty acids esters is at least 12 times greater than that for EPA (C20:5) ester and DHA ester.
- This characteristic allows not only the enrichment of polyunsaturated fatty acids but also the separation of DHA from EPA.
- the mixture of fatty acid ethyl esters enriched in EPA and DHA is subject to a transesterification with polyethylene glycol methyl ether by Lipozyme IM to convert EPA into its ester with polyethylene glycol methyl ether, which is then separated from DHA ethyl ester by short path distillation.
- EPA is recovered in its free form after a saponification or hydrolysis, or as an ester of a lower alcohol by a suitable transesterification reaction.
- ⁇ -linolenic acid which is one of the polyunsaturated fatty acids in borage and evening primrose oils, can also be isolated by the above procedure.
- 2- (2-butoxyethoxy) ethanol seems to be the best alcohol for the purification of ⁇ -linolenic acid ester, as ⁇ -linolenate ethyl ester with a concentration of up to 90% can be obtained at a yield of up to about 96%.
- the product is then submitted to short path distillation at 160 °C under a pressure of 10 3 mbars, and about 9.5 kg of clear, limpid ethyl esters is obtained as the distillate, containing 18% EPA and 7% DHA as their ethyl esters.
- the ethyl esters mixture is then submitted to short path distillation at 150 °C under a pressure of 10 ⁇ 3 mbars.
- the distilland representing 15 to 30% of the throughput is recovered.
- This product contains at least 28% to 40% EPA, and 20% to 35% DHA, as the ethyl esters. With more careful control, the process can produce 33% EPA and 22% DHA, as the ethyl esters.
- distilland from this first distillation is distilled again at 100-120°C and gives rise to an odourless distillate. Both distillations are carried out a pressure of 10 "3 mbars. Analysis by gas chromatography reveals that a concentration of AA ethyl ester higher than 95% can be reached.
- fatty acid ethyl esters containing 23% ⁇ -linolenic acid from borage oil
- borage oil 100 parts by weight of fatty acid ethyl esters containing 23% ⁇ -linolenic acid (from borage oil) is transesterified with 600 to 800 parts by weight of 2- (2-butoxy ethoxy) ethanol and 6 to 10 parts of Lipozyme IM or lipase D from Rhizopus delemar or esterase 30000 from Mucor mihei strains, in one presence of sufficient water for the enzymatic reaction to proceed, under a vacuum of 9 to 15 mbars and at a temperature of 50-60°C. The reaction is stopped by removing the enzyme by filtration. The resulting oil is submitted to two short path distillations. In the first one, performed between 50°C and 60°C, excess alcohol is removed as distillate.
- distilland residue thus obtained is subjected to a second distillation at 100-120°C. Both distillations are carried out at a pressure of 10 "3 mbar.
- the distillate is recovered and analysed by gas chromatography. A clear odourless oil is obtained, which contains no less than 50% ⁇ -linolenic acid ethyl ester. This concentration can reach 90%.
- a mixture of fatty acid ethyl esters from evening primrose oil is treated under the same conditions as in Example 4. After a few hours (between 2 and 4), the reaction is stopped and the oil treated as in Example .
- the product comprises a ⁇ -linolenic acid ethyl ester concentrate containing between 25% and 40%. This concentration can be dramatically increased when longer reaction times are applied.
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Abstract
L'invention se rapporte à un procédé de production de préparations fortement concentrées d'acides gras polyinsaturés et de leurs esters à partir d'huiles, notamment d'huiles de poisson, dans lesquelles ils sont présents principalement sous forme de leurs esters triglycérides. Ce procédé met en oeuvre la combinaison d'une transestérification des triglycérides avec un alcool d'alkyle inférieur ou un alcool de benzyle, d'une distillation moléculaire et d'une transestérification enzymatique sélective avec un alcoxy-alcool, catalysée par des lipases qui peuvent être immobilisées si nécessaire. Ce procédé permet la séparation du mélange d'acides habituellement rencontré dans les huiles, ainsi que l'extraction à rendement élevé des acides désirés. Les acides qu'il est typiquement possible d'extraire au moyen de ce procédé sont l'acide eicosapentanoïque (EPA, C20:5) et l'acide docosahexanoïque (DHA, C22:6).
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002273570A CA2273570A1 (fr) | 1999-05-31 | 1999-05-31 | Concentration et purification d'ester d'acides gras polyinsatures par distillation-transesterification enzymatique |
CA2273570 | 1999-05-31 | ||
PCT/CA2000/000643 WO2000073254A1 (fr) | 1999-05-31 | 2000-05-31 | Concentration et purification d'esters d'acides gras polyinsatures par couplage distillation transesterification enzymatique |
Publications (1)
Publication Number | Publication Date |
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EP1100764A1 true EP1100764A1 (fr) | 2001-05-23 |
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ID=4163590
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Application Number | Title | Priority Date | Filing Date |
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EP00938359A Withdrawn EP1100764A1 (fr) | 1999-05-31 | 2000-05-31 | Concentration et purification d'esters d'acides gras polyinsatures par couplage distillation transesterification enzymatique |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1100764A1 (fr) |
JP (1) | JP2003500082A (fr) |
AU (1) | AU5377400A (fr) |
CA (1) | CA2273570A1 (fr) |
WO (1) | WO2000073254A1 (fr) |
Families Citing this family (30)
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SE0202188D0 (sv) | 2002-07-11 | 2002-07-11 | Pronova Biocare As | A process for decreasing environmental pollutants in an oil or a fat, a volatile fat or oil environmental pollutants decreasing working fluid, a health supplement, and an animal feed product |
EP2295529B2 (fr) | 2002-07-11 | 2022-05-18 | Basf As | Procédé de diminution des polluants environnementaux dans une huile ou une graisse et produit d'alimentation pour poissons |
NO319194B1 (no) * | 2002-11-14 | 2005-06-27 | Pronova Biocare As | Lipase-katalysert forestringsfremgangsmate av marine oljer |
EP2251429B1 (fr) | 2003-12-30 | 2017-03-01 | DSM IP Assets B.V. | Procédé de désaération |
US7473539B2 (en) * | 2004-09-20 | 2009-01-06 | Sunho Biodiesel Corporation | Methods for producing alkyl esters |
JP5828612B2 (ja) * | 2005-05-23 | 2015-12-09 | エパックス ホブデバイグダ エーエス | グリセロールを用いた酵素反応による脂肪酸アルキルエステルの濃縮方法 |
CA2605832C (fr) | 2005-06-16 | 2018-05-08 | Ocean Nutrition Canada Ltd. | Enzymes immobilisees et leurs procedes d'utilisation |
EP2046136A2 (fr) * | 2006-06-23 | 2009-04-15 | The Procter and Gamble Company | Acides gras oméga 3 concentrés et sans odeur |
WO2008004900A1 (fr) * | 2006-07-05 | 2008-01-10 | Photonz Corporation Limited | Production d'epa et de lipides polaires ultra purs au départ d'une culture largement hétérotrophe |
DE502008000886D1 (de) | 2007-04-02 | 2010-08-19 | Cognis Ip Man Gmbh | Ein Gemisch enthaltend Fettsäureglyceride |
EP1978101A1 (fr) | 2007-04-02 | 2008-10-08 | Cognis IP Management GmbH | Procédé d'enrichissement en acides gras polyinsaturés |
EP2173699A4 (fr) * | 2007-06-29 | 2014-04-16 | Dsm Ip Assets Bv | Production et purification d'esters d'acides gras polyinsaturés |
CL2008002020A1 (es) | 2007-07-12 | 2008-11-14 | Ocean Nutrition Canada Ltd | Metodo de modificacion de un aceite, que comprende hidrolizar gliceridos con una solucion de lipasa thermomyces lanuginosus, separar la fraccion de acido graso saturado de la fraccion de glicerido hidrolizado y esterificar los gliceridos hidrolizados en la presencia de candida antarctica lipasa b; y composicion de aceite. |
JP5204776B2 (ja) | 2007-07-30 | 2013-06-05 | 日本水産株式会社 | Epa濃縮油およびdha濃縮油の製造方法 |
WO2009020406A1 (fr) * | 2007-08-07 | 2009-02-12 | Granate Seed Limited | Procédés de préparation de substances lipidiques, substances lipidiques ainsi produites et leurs utilisations |
JP5450954B2 (ja) * | 2007-12-10 | 2014-03-26 | 日本水産株式会社 | 脂肪酸低級アルコールエステルの製造方法 |
KR101357298B1 (ko) * | 2008-06-20 | 2014-01-28 | 에이케이 앤 엠엔 바이오팜 주식회사 | 오메가-3계 고도불포화 지방산의 고순도 정제방법 |
CL2009001343A1 (es) * | 2009-06-02 | 2009-07-10 | Golden Omega S A | Proceso de obtencion concentrado de esteres de epa y dha a partir de aceite marino, que comprende agregar al aceite alcali y agua a menos de 100 grados celsius, agregar solvente, separar fase de refinado, agregar acido, separar la fase no acuosa y agregar alcohol y un catalizador a menos de 150 grados celsius, desolventilizar y destilar. |
BR112012014253B1 (pt) * | 2009-12-17 | 2019-11-19 | Npc Industrias Quim Ltda | processos de modificação de óleos vegetais |
GB201001345D0 (en) | 2010-01-27 | 2010-03-17 | Equateq Ltd | Process for preparing and purifying fatty acids |
WO2012130961A1 (fr) * | 2011-03-30 | 2012-10-04 | Novozymes A/S | Procédé d'estérification |
FR2991337B1 (fr) * | 2012-05-29 | 2016-09-02 | Roquette Freres | Procede continu d'enrichissement en esters ethyliques de dha d'une huile produite par des microalgues |
JP6302310B2 (ja) * | 2013-08-30 | 2018-03-28 | 備前化成株式会社 | 高純度オメガ3系脂肪酸エチルエステルの生産方法 |
KR101815110B1 (ko) | 2015-10-16 | 2018-01-10 | 에이케이 앤 엠엔 바이오팜 주식회사 | 오메가-7계 불포화 지방산의 정제공정 |
CN107043794A (zh) * | 2017-06-12 | 2017-08-15 | 浙江工业大学 | 一种酶催化红花油醇解制备脂肪酸乙酯的方法 |
CN109053438A (zh) * | 2018-06-28 | 2018-12-21 | 菏泽中禾健元生物科技有限公司 | 一种提高共轭亚油酸甘油酯生产效率的方法 |
NO20181574A1 (en) * | 2018-12-06 | 2020-06-08 | Epax Norway As | Very long chain fatty acids |
JP2022531635A (ja) * | 2019-07-17 | 2022-07-07 | アークサーダ・アー・ゲー | 脱色したアセトアセチル化エチレングリコールを調製するための方法 |
FR3108622A1 (fr) * | 2020-03-27 | 2021-10-01 | Polaris | Procédé de fractionnement d’acides gras à deux carbones de différence par distillation moléculaire |
CN115976125B (zh) * | 2022-12-02 | 2023-11-07 | 河北康睿达脂质有限公司 | 结构脂质及其制备方法、结构脂肪乳以及结构脂肪乳制剂 |
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US4675132A (en) * | 1985-03-28 | 1987-06-23 | The United States Of America As Represented By The Secretary Of Commerce | Polyunsaturated fatty acids from fish oils |
FI95395C (fi) * | 1994-09-07 | 1996-01-25 | Raision Tehtaat Oy Ab | Entsymaattinen menetelmä synteettisen esterin valmistamiseksi kasviöljystä |
-
1999
- 1999-05-31 CA CA002273570A patent/CA2273570A1/fr not_active Abandoned
-
2000
- 2000-05-31 WO PCT/CA2000/000643 patent/WO2000073254A1/fr not_active Application Discontinuation
- 2000-05-31 JP JP2000621321A patent/JP2003500082A/ja active Pending
- 2000-05-31 AU AU53774/00A patent/AU5377400A/en not_active Abandoned
- 2000-05-31 EP EP00938359A patent/EP1100764A1/fr not_active Withdrawn
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See references of WO0073254A1 * |
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AU5377400A (en) | 2000-12-18 |
CA2273570A1 (fr) | 2000-11-30 |
WO2000073254A1 (fr) | 2000-12-07 |
JP2003500082A (ja) | 2003-01-07 |
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