CN113045422A - 高度不饱和脂肪酸或高度不饱和脂肪酸乙酯、药品、添加剂或食品 - Google Patents
高度不饱和脂肪酸或高度不饱和脂肪酸乙酯、药品、添加剂或食品 Download PDFInfo
- Publication number
- CN113045422A CN113045422A CN202110295239.6A CN202110295239A CN113045422A CN 113045422 A CN113045422 A CN 113045422A CN 202110295239 A CN202110295239 A CN 202110295239A CN 113045422 A CN113045422 A CN 113045422A
- Authority
- CN
- China
- Prior art keywords
- fatty acid
- unsaturated fatty
- highly unsaturated
- less
- acid
- 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.)
- Pending
Links
- 235000021122 unsaturated fatty acids Nutrition 0.000 title claims abstract description 90
- 150000004670 unsaturated fatty acids Chemical class 0.000 title claims abstract description 86
- 235000013305 food Nutrition 0.000 title claims abstract description 13
- 230000000996 additive effect Effects 0.000 title claims abstract description 9
- 239000000825 pharmaceutical preparation Substances 0.000 title description 3
- 229940127557 pharmaceutical product Drugs 0.000 title description 3
- 239000000546 pharmaceutical excipient Substances 0.000 title description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims abstract description 38
- 239000000194 fatty acid Substances 0.000 claims abstract description 34
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 33
- 229930195729 fatty acid Natural products 0.000 claims abstract description 33
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 32
- 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 claims abstract description 23
- 235000021323 fish oil Nutrition 0.000 claims abstract description 19
- 235000020673 eicosapentaenoic acid Nutrition 0.000 claims abstract description 18
- 235000020669 docosahexaenoic acid Nutrition 0.000 claims abstract description 16
- XYBSIYMGXVUVGY-UHFFFAOYSA-N 2,2',4,4'-Tetrabromodiphenyl ether Chemical compound BrC1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1Br XYBSIYMGXVUVGY-UHFFFAOYSA-N 0.000 claims abstract description 11
- QWVDUBDYUPHNHY-UHFFFAOYSA-N 2,2',4,5'-Tetrabromodiphenyl ether Chemical compound BrC1=CC(Br)=CC=C1OC1=CC(Br)=CC=C1Br QWVDUBDYUPHNHY-UHFFFAOYSA-N 0.000 claims abstract description 11
- WHPVYXDFIXRKLN-UHFFFAOYSA-N 2,4-dibromophenyl 2,4,5-tribromophenyl ether Chemical compound BrC1=CC(Br)=CC=C1OC1=CC(Br)=C(Br)C=C1Br WHPVYXDFIXRKLN-UHFFFAOYSA-N 0.000 claims abstract description 11
- NSKIRYMHNFTRLR-UHFFFAOYSA-N 2,4-dibromophenyl 2,4,6-tribromophenyl ether Chemical compound BrC1=CC(Br)=CC=C1OC1=C(Br)C=C(Br)C=C1Br NSKIRYMHNFTRLR-UHFFFAOYSA-N 0.000 claims abstract description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 9
- 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 claims abstract description 9
- 150000003071 polychlorinated biphenyls Chemical group 0.000 claims abstract description 9
- 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 claims abstract description 8
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229960005135 eicosapentaenoic acid Drugs 0.000 claims abstract description 7
- YUFFSWGQGVEMMI-JLNKQSITSA-N (7Z,10Z,13Z,16Z,19Z)-docosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCCCC(O)=O YUFFSWGQGVEMMI-JLNKQSITSA-N 0.000 claims abstract description 6
- 229940090949 docosahexaenoic acid Drugs 0.000 claims abstract description 6
- 235000021294 Docosapentaenoic acid Nutrition 0.000 claims abstract description 5
- 150000004826 dibenzofurans Chemical class 0.000 claims abstract description 5
- 235000021342 arachidonic acid Nutrition 0.000 claims abstract description 4
- 229940114079 arachidonic acid Drugs 0.000 claims abstract description 4
- HOBAELRKJCKHQD-UHFFFAOYSA-N (8Z,11Z,14Z)-8,11,14-eicosatrienoic acid Natural products CCCCCC=CCC=CCC=CCCCCCCC(O)=O HOBAELRKJCKHQD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000021298 Dihomo-γ-linolenic acid Nutrition 0.000 claims abstract description 3
- HOBAELRKJCKHQD-QNEBEIHSSA-N dihomo-γ-linolenic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/CCCCCCC(O)=O HOBAELRKJCKHQD-QNEBEIHSSA-N 0.000 claims abstract description 3
- 235000019198 oils Nutrition 0.000 claims description 66
- 239000003344 environmental pollutant Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 13
- 235000019512 sardine Nutrition 0.000 claims description 10
- -1 PCDF Chemical class 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- FOIBFBMSLDGNHL-UHFFFAOYSA-N 1,2,3,4,6,7,8,9-Octachlorodibenzo-p-dioxin Chemical compound ClC1=C(Cl)C(Cl)=C2OC3=C(Cl)C(Cl)=C(Cl)C(Cl)=C3OC2=C1Cl FOIBFBMSLDGNHL-UHFFFAOYSA-N 0.000 claims 1
- OGBQILNBLMPPDP-UHFFFAOYSA-N 2,3,4,7,8-Pentachlorodibenzofuran Chemical compound O1C2=C(Cl)C(Cl)=C(Cl)C=C2C2=C1C=C(Cl)C(Cl)=C2 OGBQILNBLMPPDP-UHFFFAOYSA-N 0.000 claims 1
- 241001125046 Sardina pilchardus Species 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 241000894007 species Species 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 66
- 238000000034 method Methods 0.000 description 44
- 238000004821 distillation Methods 0.000 description 38
- 238000000526 short-path distillation Methods 0.000 description 24
- 239000003925 fat Substances 0.000 description 16
- 238000000199 molecular distillation Methods 0.000 description 16
- 235000019197 fats Nutrition 0.000 description 15
- 238000004440 column chromatography Methods 0.000 description 13
- 230000001988 toxicity Effects 0.000 description 13
- 231100000419 toxicity Toxicity 0.000 description 13
- 229920000064 Ethyl eicosapentaenoic acid Polymers 0.000 description 12
- SSQPWTVBQMWLSZ-AAQCHOMXSA-N ethyl (5Z,8Z,11Z,14Z,17Z)-icosapentaenoate Chemical compound CCOC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CC SSQPWTVBQMWLSZ-AAQCHOMXSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000010409 thin film Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 241001125048 Sardina Species 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000000470 constituent Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003814 drug Substances 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 230000032050 esterification Effects 0.000 description 6
- 235000021588 free fatty acids Nutrition 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 235000014593 oils and fats Nutrition 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000283153 Cetacea Species 0.000 description 3
- 241000208202 Linaceae Species 0.000 description 3
- 235000004431 Linum usitatissimum Nutrition 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229960002600 icosapent ethyl Drugs 0.000 description 3
- 229940106134 krill oil Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LVYBAQIVPKCOEE-UHFFFAOYSA-N 1,2,3,4,7,8-Hexachlorodibenzofuran Chemical compound O1C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C2C2=C1C=C(Cl)C(Cl)=C2 LVYBAQIVPKCOEE-UHFFFAOYSA-N 0.000 description 2
- SBMIVUVRFPGOEB-UHFFFAOYSA-N 1,2,3,7,8-Pentachlorodibenzofuran Chemical compound O1C2=CC(Cl)=C(Cl)C(Cl)=C2C2=C1C=C(Cl)C(Cl)=C2 SBMIVUVRFPGOEB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 240000002791 Brassica napus Species 0.000 description 2
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 2
- 241000273930 Brevoortia tyrannus Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000006399 behavior Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 235000012000 cholesterol Nutrition 0.000 description 2
- 239000003026 cod liver oil Substances 0.000 description 2
- 235000012716 cod liver oil Nutrition 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 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
- 239000012530 fluid Substances 0.000 description 2
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 229960002809 lindane Drugs 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 239000002207 metabolite Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- HOBAELRKJCKHQD-YHTMAJSVSA-N (8e,11e,14e)-icosa-8,11,14-trienoic acid Chemical compound CCCCC\C=C\C\C=C\C\C=C\CCCCCCC(O)=O HOBAELRKJCKHQD-YHTMAJSVSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- VHNPZYZQKWIWOD-UHFFFAOYSA-N 2,2',4,4',5,6'-Hexabromodiphenyl ether Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=CC(Br)=C(Br)C=C1Br VHNPZYZQKWIWOD-UHFFFAOYSA-N 0.000 description 1
- DHUMTYRHKMCVAG-UHFFFAOYSA-N 2,4-dibromophenyl 3,4-dibromophenyl ether Chemical compound BrC1=CC(Br)=CC=C1OC1=CC=C(Br)C(Br)=C1 DHUMTYRHKMCVAG-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- UPNBETHEXPIWQX-UHFFFAOYSA-N 4-bromophenyl 2,4-dibromophenyl ether Chemical compound C1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1Br UPNBETHEXPIWQX-UHFFFAOYSA-N 0.000 description 1
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- 241000252203 Clupea harengus Species 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 239000005506 Diclofop Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000239366 Euphausiacea Species 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 241001417902 Mallotus villosus Species 0.000 description 1
- JJWSNOOGIUMOEE-UHFFFAOYSA-N Monomethylmercury Chemical compound [Hg]C JJWSNOOGIUMOEE-UHFFFAOYSA-N 0.000 description 1
- 241000235575 Mortierella Species 0.000 description 1
- 241000228143 Penicillium Species 0.000 description 1
- 241000223252 Rhodotorula Species 0.000 description 1
- 241000269851 Sarda sarda Species 0.000 description 1
- CRPUJAZIXJMDBK-UHFFFAOYSA-N Toxaphene Natural products C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010932 ethanolysis reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019688 fish Nutrition 0.000 description 1
- 229940013317 fish oils Drugs 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- VZCCETWTMQHEPK-UHFFFAOYSA-N gamma-Linolensaeure Natural products CCCCCC=CCC=CCC=CCCCCC(O)=O VZCCETWTMQHEPK-UHFFFAOYSA-N 0.000 description 1
- 235000020664 gamma-linolenic acid Nutrition 0.000 description 1
- 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 description 1
- 229960002733 gamolenic acid Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 235000013402 health food Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 235000019514 herring Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 238000003987 high-resolution gas chromatography Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 235000020978 long-chain polyunsaturated fatty acids Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940119224 salmon oil Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OEJNXTAZZBRGDN-UHFFFAOYSA-N toxaphene Chemical compound ClC1C(Cl)C2(Cl)C(CCl)(CCl)C(=C)C1(Cl)C2(Cl)Cl OEJNXTAZZBRGDN-UHFFFAOYSA-N 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/587—Monocarboxylic acid esters having at least two carbon-to-carbon double bonds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/115—Fatty acids or derivatives thereof; Fats or oils
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/185—Acids; Anhydrides, halides or salts thereof, e.g. sulfur acids, imidic, hydrazonic or hydroximic acids
- A61K31/19—Carboxylic acids, e.g. valproic acid
- A61K31/20—Carboxylic acids, e.g. valproic acid having a carboxyl group bound to a chain of seven or more carbon atoms, e.g. stearic, palmitic, arachidic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/185—Acids; Anhydrides, halides or salts thereof, e.g. sulfur acids, imidic, hydrazonic or hydroximic acids
- A61K31/19—Carboxylic acids, e.g. valproic acid
- A61K31/20—Carboxylic acids, e.g. valproic acid having a carboxyl group bound to a chain of seven or more carbon atoms, e.g. stearic, palmitic, arachidic acids
- A61K31/202—Carboxylic acids, e.g. valproic acid having a carboxyl group bound to a chain of seven or more carbon atoms, e.g. stearic, palmitic, arachidic acids having three or more double bonds, e.g. linolenic
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/21—Esters, e.g. nitroglycerine, selenocyanates
- A61K31/215—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids
- A61K31/22—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids of acyclic acids, e.g. pravastatin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P3/00—Drugs for disorders of the metabolism
- A61P3/02—Nutrients, e.g. vitamins, minerals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/12—Straight chain carboxylic acids containing eighteen carbon atoms
-
- 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
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
-
- 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
-
- 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
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
- A23D9/02—Other edible oils or fats, e.g. shortenings, cooking oils characterised by the production or working-up
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/21—Esters, e.g. nitroglycerine, selenocyanates
- A61K31/215—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids
- A61K31/22—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids of acyclic acids, e.g. pravastatin
- A61K31/23—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids of acyclic acids, e.g. pravastatin of acids having a carboxyl group bound to a chain of seven or more carbon atoms
- A61K31/232—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids of acyclic acids, e.g. pravastatin of acids having a carboxyl group bound to a chain of seven or more carbon atoms having three or more double bonds, e.g. etretinate
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K35/00—Medicinal preparations containing materials or reaction products thereof with undetermined constitution
- A61K35/12—Materials from mammals; Compositions comprising non-specified tissues or cells; Compositions comprising non-embryonic stem cells; Genetically modified cells
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K35/00—Medicinal preparations containing materials or reaction products thereof with undetermined constitution
- A61K35/56—Materials from animals other than mammals
- A61K35/60—Fish, e.g. seahorses; Fish eggs
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K35/00—Medicinal preparations containing materials or reaction products thereof with undetermined constitution
- A61K35/56—Materials from animals other than mammals
- A61K35/612—Crustaceans, e.g. crabs, lobsters, shrimps, krill or crayfish; Barnacles
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K35/00—Medicinal preparations containing materials or reaction products thereof with undetermined constitution
- A61K35/66—Microorganisms or materials therefrom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/32—Bonded phase chromatography
- B01D15/325—Reversed phase
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/16—Refining fats or fatty oils by mechanical means
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Medicinal Chemistry (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Wood Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Food Science & Technology (AREA)
- Nutrition Science (AREA)
- Emergency Medicine (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Mycology (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Obesity (AREA)
- Hematology (AREA)
- Diabetes (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
- Edible Oils And Fats (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Developmental Biology & Embryology (AREA)
- Marine Sciences & Fisheries (AREA)
- Biomedical Technology (AREA)
- Biotechnology (AREA)
- Cell Biology (AREA)
Abstract
Description
本申请是原申请的申请日为2013年5月14日,申请号为201380024834.X,发明名称为《减低了环境污染物质的高度不饱和脂肪酸或高度不饱和脂肪酸乙酯及其制造方法》的中国专利申请的分案申请。
技术领域
背景技术
今天,以二英类为代表的环境污染物质在地球上的几乎任一个地方都有发现。另外已知其对于生长栖息在受污染了的海域的鱼类也具有影响。可认为如果是微量则对健康没有直接影响,但是即使那样,也期望着人以食品、饲料的方式摄取的成分中所含的环境污染物质的量少。
在海产物油例如鱼油中包含有EPA(二十碳五烯酸、C20:5,n-3,全-顺式-5,8,11,14,17-二十碳五烯酸)以及DHA(二十二碳六烯酸、C22:6,n-3,全-顺式-4,7,10,13,16,19-二十二碳六烯酸)等高度不饱和脂肪酸。EPA、DHA已知有各种生理功能,用作药品、健康食品、食品、饲料等的成分。为了利用海产物油中的EPA和/或DHA,因而实施各种精制工序。
非专利文献1中记载了利用分子蒸馏从鱼油中去除杀虫剂DDT以及其代谢物。非专利文献2中记载了通过使用真空汽提或者薄膜蒸馏,可从脂肪或者油中去除氯化烃以及游离脂肪酸。非专利文献3中记载了为了从油组合物中去除游离脂肪酸等不期望的物质而使用物理性的精制以及分子蒸馏。
专利文献1、非专利文献4中记载了一种用于减低油脂中的环境污染物质的方法,其包含如下过程:将挥发性工作流体添加于该混合物的过程,以及与添加了该混合物的该挥发性工作流体一起输送至至少1次汽提处理过程的过程。
非专利文献5中记载了如果将鱼油在高温除臭,则使得高度不饱和脂肪酸发生热分解。
现有技术文献
专利文献
专利文献1:日本特许第3905538号(WO2004/007654)
非专利文献
非专利文献1:K.Julshamn,L.Karlsen and O.R.Braekkan,Removal of DDT andits metabolites from fish oils by molecular distillation,Fiskeridirektoratetsskrifter;Serie teknologiske undersokelser,Vol.5No.15(1973)
非专利文献2:Anthony P.Bimbo:Guidelines for characterization of food-grade fishoil.INFORM 9(5),473-483(1998)
非专利文献3:Jiri Cmolik,Jan Pokorny:Physical refining of edible oils,Eur.J.Lipid Sci.Technol.102(7),472-486(2000)
非专利文献4:Harald Breivik,Olav Thorstad:Removal of organicenvironmental pollutants from fish oil by short-path distillation,LipidTechnology,17(3),55-58(2005)
非专利文献5:Veronique Fournier,et al.;Thermal degradation of long-chain polyunsaturated fatty acids during deodorization of fish oil.,Eur.J.LipidSci.Technol.,108,33-42(2006)
非专利文献6:油脂,62(11),38-39,2009
发明内容
发明想要解决的课题
用于解决课题的方法
本发明通过发现如下事实从而完成:在含有容易发生氧化、异构化等改性的高度不饱和脂肪酸作为构成脂肪酸的油脂的精制中,通过在一定的条件下进行分子蒸馏或短程蒸馏,从而可一边抑制高度不饱和脂肪酸的改性,一边将环境污染物质减低为非常低的浓度。通过该方法,可将油脂中的环境污染物质量减低至二英类的总含量以毒性当量计小于0.2pg-TEQ/g。进一步以其为原料而获得乙酯。通过对该乙酯进行蒸馏以及柱层析处理,从而可进一步降低乙酯中的二英类。
本发明的要旨在于下述的高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯及其制造方法、以及含有它们的饲料、食品、药品等。
(1)一种高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯,其为以含有高度不饱和脂肪酸作为构成脂肪酸的油脂作为原料油而制造并且减低了环境污染物质的含量的高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯,所包含的二英类之中,多氯二苯并对二英(PCDD)以及多氯二苯并呋喃(PCDF)的含量小于0.05pg-TEQ/g,共面多氯联苯(Co-PCB)小于0.03pg-TEQ/g。
(2)(1)的高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯,进一步,将所包含的溴化阻燃剂的含量减低为:BDE-47的量小于0.18ng/g,BDE-100的量小于0.03ng/g,BDE-49的量小于0.05ng/g,或BDE-99的量小于0.05ng/g。
(3)(1)或(2)的高度不饱和脂肪酸的乙酯,高度不饱和脂肪酸在脂肪酸中所占的浓度为80面积%以上、85面积%以上、90面积%以上、95面积%以上、或者96面积%以上。
(4)(1)~(3)中任一项的高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯,含有高度不饱和脂肪酸作为构成脂肪酸的油脂为鱼油、磷虾油、海洋哺乳类油或微生物油。
(5)(1)~(4)中任一项的高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯,高度不饱和脂肪酸为二十碳五烯酸、二十二碳六烯酸、二十二碳五烯酸、二高-γ-亚麻酸、花生四烯酸中的任一者、或者它们的组合。
(6)一种药品、添加剂或食品,其含有(1)~(5)中任一项的高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯作为有效成分。
a)利用薄膜蒸馏从含有高度不饱和脂肪酸作为构成脂肪酸的原料油中去除游离脂肪酸以及环境污染物质,
b)将获得的含高度不饱和脂肪酸的油脂进行水解或乙酯化,
c)利用精馏以及柱层析进行精制。
(8)(7)的方法,进一步也降低溴化阻燃剂的含量。
(9)(7)或(8)的方法,高度不饱和脂肪酸在高度不饱和脂肪酸的脂肪酸中或高度不饱和脂肪酸的乙酯的脂肪酸中所占的浓度为80面积%以上、85面积%以上、90面积%以上、95面积%以上、或者96面积%以上。
(10)(7)~(9)中的任一种方法,含有高度不饱和脂肪酸作为构成脂肪酸的原料油为鱼油、磷虾油、海洋哺乳类油或微生物油。
(11)(7)~(10)中的任一种方法,前述薄膜蒸馏在200~270℃、220~260℃、或者220~250℃的温度实行。
(12)(7)~(11)中的任一种方法,前述薄膜蒸馏在5Pa以下、2Pa以下、或者1Pa以下的压力实行。
(13)(7)~(12)中的任一种方法,前述薄膜蒸馏以流速20~200(kg/h)/m2或者25~120(kg/h)/m2来实行。
(14)(7)~(13)中的任一种方法,前述薄膜蒸馏是分子蒸馏或短程蒸馏。
(15)(7)~(14)中的任一种方法,精馏通过利用3塔以上的蒸馏塔来进行。
(16)(7)~(15)中的任一种方法,在利用柱层析的精制中使用反相分配系的柱层析。
(18)(17)的高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯,进一步,将所包含的溴化阻燃剂的含量减低为:BDE-47的量小于0.18ng/g,BDE-100的量小于0.03ng/g,BDE-49的量小于0.05ng/g,或BDE-99的量小于0.05ng/g。
(19)(17)或(18)的高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯,高度不饱和脂肪酸在脂肪酸中所占的浓度为80面积%以上、85面积%以上、90面积%以上、95面积%以上、或者96面积%以上。
(20)一种药品、添加剂或食品,其含有(17)~(19)中任一项的高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯。
发明的效果
具体实施方式
以下,详细说明本发明。
在本发明中,高度不饱和脂肪酸是指碳原子数18以上、双键数3以上的脂肪酸,更优选为碳原子数20以上、双键数3以上或者4以上的脂肪酸,特别优选为碳原子数20以上、双键数5以上的脂肪酸。具体可例示:α-亚麻酸(18:3,n-3)、γ-亚麻酸(18:3,n-6)、二高-γ-亚麻酸(20:3、n-6)、花生四烯酸(20:4,n-6)、二十碳五烯酸(20:5,n-3)、二十二碳五烯酸(22:5,n-6)、二十二碳六烯酸(22:6,n-3)等。
已知它们在某种微生物油、植物油、海产动物油等中大量含有。具体可例示:沙丁鱼油、鲔鱼油、鲣鱼油、鲱鱼油(menhaden oil)、鱼肝油(cod liver oil)、鲕鱼油(herringoil)、毛鳞鱼油、以及鲑鱼油等鱼油、磷虾等甲壳类的海产动物油,胡麻、亚麻(flax)、大豆、菜籽(rapeseed)等的植物油,属于被孢霉属、青霉属、曲霉属、红酵母属、镰刀菌属中的微生物所产生的油脂等。
在本说明书中含有高度不饱和脂肪酸作为构成脂肪酸的油脂是指甘油三酯、或磷脂质。
使用这些油脂作为本发明的原料油的情况下,也可在输送至分子蒸馏或短程蒸馏之前进行前处理。作为这样的前处理,可例示:脱胶工序、使用了活性白土、活性炭的脱色工序、水洗工序等。
在本发明中,环境污染物质包含:多氯联苯(PCB)、DDT、多氯三联苯(PCT)、二苯并二英(PCDD)以及二苯并呋喃(PCDF)、氯苯酚以及六氯环己烷(HCH)、毒杀芬、二英、溴化阻燃剂、聚芳香族烃(PAH)、有机锡化合物(例如三丁基锡、三苯基锡)有机水银化合物(例如甲基水银)等。关于去除了它们的程度的基准,作为不易去除并且在哪里都存在的代表性的物质,将二英类的合计量以毒性当量(pg-TEQ/g)的单位表示。
在本发明中二英类是指表1所示的多氯二苯并对二英(PCDD)、多氯二苯并呋喃(PCDF)以及共面多氯联苯(Co-PCB)的合计,测定各成分的含量,将各自的实测值乘以毒性当量因子并进行合计而算出,以毒性当量(pg-TEQ/g)表示。
另外,也测定了溴化阻燃剂。溴化阻燃剂是指表9所示那样的化合物的总称。相对于环境中的二英类的污染开始降低,对于溴化阻燃剂还发现了增加倾向,是应当关注的物质。可将鱼油中比较多的包含的BDE-100、BDE-49、BDE-99、BDE-47等设为指标。
表1
表-1分析对象项目
在本发明中,通过薄膜蒸馏来进行二英类的去除。在薄膜蒸馏中也优选为分子蒸馏(Molecular Distillation)或短程蒸馏(SPD:Short Path Distillation)。在薄膜蒸馏中,存在有在相对于在高真空(<0.1Pa)下的一定压力下从加热面蒸发出的蒸气分子的平均自由行程而言短的距离内配置冷凝器来进行的蒸馏,将这样的蒸馏称为分子蒸馏。为了提高分子蒸馏的蒸馏能力而开发出的蒸馏是短程蒸馏。关于短程蒸馏,在高于0.1Pa的中真空区域的压力下进行,也将冷凝器在与蒸发分子的平均自由行程相等的距离前后进行配置,因此是蒸馏能力与分子蒸馏相比显著地改善而实用的方法。
关于分子蒸馏或短程蒸馏,由于被蒸馏物暴露于高温的时间非常短,因而适于从含有耐热性差的EPA、DHA等的甘油三酯中去除不需要成分。
关于本发明的分子蒸馏或短程蒸馏,在200~270℃、优选在220~260℃、特别优选在220~250℃的温度实行。另外,在压力低于5Pa、优选在低于2Pa、进一步优选在低于1Pa的压力实行。另外,利用在流速为20~200(kg/h)/m2、优选为25~120(kg/h)/m2的条件下实行的薄膜法来进行。如果流量过少,则生产率降低,因而优选一边确认去除二英类,一边在能够去除的范围以最大量流动。如果在这样的条件下进行蒸馏,则虽然是耐温度性差的高度不饱和脂肪酸,但是基本上不产生品质的劣化。
通过在这样的条件下进行蒸馏,从而可将二英类之中的PCDD以及PCDF控制为小于测定极限,即,实质上为0。此处关于0,例如,根据表6检测极限的数值来计算时,则可设为小于0.043pg-TEQ/g,即,小于0.05pg-TEQ/g。也可将共面多氯联苯降低至小于0.2pg-TEQ/g,进一步降低至小于0.1pg-TEQ/g,小于0.05pg-TEQ/g,小于0.02pg-TEQ/g,小于0.01pg-TEQ/g。
另外,在溴化阻燃剂中,如果以BDE-100、BDE-49、BDE-99、BDE-47等为指标,则可将它们降低为小于0.05μg/g,优选为小于0.03μg/g,进一步为小于0.02μg/g。
以下说明本发明的方法的实施方式。
原料油优选使用利用水洗等方法实施脱胶处理而得到的油。将水洗了的原料油直接在上述条件下输送至分子蒸馏或短程蒸馏,将胆固醇、游离脂肪酸、环境污染物质等作为馏分而去除,获得包含甘油三酯的残馏分。该残馏分也可直接使用,也可进一步进行利用活性炭、活性白土等的脱色处理、利用水蒸汽蒸馏等的除臭处理而使用。可将这样制造的精制油脂用作饲料、食品、添加剂的成分。
向残馏分中加入乙醇和催化剂或酶,进行反应,生成甘油三酯的构成脂肪酸与乙醇的酯。关于乙酯化,使用公知的任一种方法都没有关系。
在进行乙酯化后,也可根据需要进一步精制。为了提高EPA乙酯、DHA乙酯的纯度,可进一步使用分子蒸馏、精馏、柱层析等方法。具体而言,可通过日本特开平5-222392(同族专利EP0610506)、日本特开平4-41457(同族专利EP0460917)、日本特开平6-33088等中记载的方法进行精制。
精馏是在高真空下利用3塔以上的蒸馏塔来进行的,可通过将EPA乙酯和/或DHA乙酯作为主馏分,与挥发性更高的初馏分以及挥发性更低的残馏分分离从而获得。作为精馏的条件,温度为150~200℃,优选为160~190℃,进一步优选为170~190℃,压力为1~300Pa,优选为1~200Pa,进一步优选为1~133Pa。优选在1~133Pa的真空度下,获得160~190℃、优选为170~190℃的主馏分。
特别优选在精馏后进行柱层析的方法。本申请发明人等发现了,利用精馏将EPA、DHA浓缩时,则二英类的浓度相对升高,但是通过进行柱层析,从而可相对于精馏前的水平而言降低。在柱层析中可使用硅胶、离子交换树脂、活性白土、硝酸银等,但是特别优选反相分配系的柱层析。按照构成反相分配系的方式,例如可使用烷基键合二氧化硅填充剂(ODS柱等)等,另外,作为溶剂系,可使用水、醇、酮类。优选为甲醇。它们可单独使用,或者也可混合使用。
通过将上述的精馏、柱层析进行组合,可将高度不饱和脂肪酸进行浓缩,另一方面降低环境污染物质的浓度。可将高度不饱和脂肪酸,例如,EPA乙酯和/或DHA乙酯的浓度提高为80面积%以上、85面积%以上、90面积%以上、95面积%以上、进一步96面积%以上的纯度,且可使二英类之中的PCDD以及PCDF成为测定极限以下,即,实质上0(在根据检测极限的计算中小于0.043pg-TEQ/g),也可将共面多氯联苯降低至小于0.1pg-TEQ/g,进一步小于0.03pg-TEQ/g,小于0.01pg-TEQ/g。或者,对于溴化阻燃剂,可将BDE-47的量降低为小于0.18ng/g,可将BDE-100的量降低为小于0.03ng/g,可将BDE-49的量降低为小于0.05ng/g,或者可将BDE-99的量降低为小于0.05ng/g。可将BDE-100、BDE-49、BDE-99、BDE-47降低为小于0.05μg/g,优选为小于0.03μg/g,进一步为小于0.02μg/g。作为药品,EPA乙酯和/或DHA乙酯的浓度优选为96面积%以上的纯度。
它们这样的高度不饱和脂肪酸的浓度高并且环境污染物质的浓度低的游离脂肪酸、脂肪酸酯,适合用于以高度不饱和脂肪酸作为有效成分的药品、添加剂原料。
在药品以及食品添加剂等中使用的情况下,需要根据目的将脂肪酸中的EPA和/或DHA的含量进行浓缩。在该情况下,可通过利用脂肪酶反应将高度不饱和脂肪酸选择性浓缩的方法(WO2009/17102等)从而将甘油酯中的高度不饱和脂肪酸进行浓缩。对于进行了这样的处理的甘油酯,也可通过使用本发明的方法,从而提高高度不饱和脂肪酸的浓度,另一方面减低环境污染物质。
高度不饱和脂肪酸可通过将利用上述方法制造的高度不饱和脂肪酸的酯进行水解而获得。
以下记载本发明的实施例,但本发明不受它们的任何限定。
关于溴化阻燃剂的测定,委托作为食品等的分析公司的eurofins。测定方法根据高分辨率质谱分析法(HRGC/HRMS法)来进行。
酸值(AV)的测定
在本发明的实施例中,酸值(AV)的测定按照基准油脂分析试验法(2003年度版)(社团法人日本油化学会编)进行。
脂肪酸组成的测定
关于原料中使用的鱼油以及进行利用短程蒸馏的处理后的油的脂肪酸组成,将鱼油进行乙酯化并利用气相色谱法来测定。即,向鱼油40μL中加入1N乙醇钠/乙醇溶液1mL,搅拌约30秒。然后,加入1mL的1N盐酸并中和,加入己烷2mL、饱和硫酸氨水溶液3mL,进行搅拌,静置,然后利用气相色谱法来测定上层。
气相色谱法分析条件
机器种类:Agilent 6850GC system(Agilent公司)
柱:DB-WAX J&W 123-7032E
柱温度:200℃
进样温度:300℃
进样方法:分流
分流比:100:1
检测器温度:300℃
检测器:FID
载气:氦气
实施例1
使用酸值、二英类的含量不同的2种沙丁鱼原油,进行了在各种蒸馏条件下蒸馏并且去除二英类的试验。所使用的蒸馏装置是短程蒸馏装置(SPD)KD 10(UIC GmbH公司制,蒸馏表面积0.1m2)。将蒸馏的条件(温度、压力、流速)示于表2。将蒸馏温度固定于250℃,将压力在0.4~3.0Pa的范围内变动,将流速在25~121(kg/hr)/m2的范围内变动。
表2
实施例2
使用与实施例1相同的装置,将鲔鱼油(实施了脱胶、脱氧处理的精制油)在表3的蒸馏条件下进行了二英类的去除。如表3所示,即使是鲔鱼油,也可利用本发明的方法(蒸馏温度250℃、压力0.1Pa、流速48(kg/hr)/m2),从而将二英类的含量降低为0.1pg-TEQ/以下。
另外,使用其它的短程蒸馏装置(SPD)KD 6(UIC GmbH公司制,蒸馏表面积0.06m2)而从沙丁鱼粗油中去除了二英类。如表3所示,在该装置中也可利用本发明的方法(蒸馏温度270℃,压力0.6Pa,流速20(kg/hr)/m2)将二英类的含量降低为0.1pg-TEQ/以下。
表3
实施例3
使用离心式分子蒸馏装置MS380(日本车辆制造株式会社制,蒸馏表面积0.11m2),将沙丁鱼粗油在表4所示的蒸馏条件下进行了二英类的去除。如表4所示,即使利用分子蒸馏装置,也可与实施例1、2同样地将二英类的含量降低为0.2pg-TEQ/以下。
表4
实施例4
将沙丁鱼原油(酸值6,含有EPA19%、DHA8%)用85℃的温水(相对于原油为5%)进行水洗,然后使用短程蒸馏装置(SPD)KD1800(UIC GmbH公司制,蒸馏面积18m2),进行了短程蒸馏。条件为真空度0.7~1Pa、本体温度250℃、供给量约2000kg/H(流速110(kg/h)/m2)。
将原油和蒸馏后(SPD油)的油中的二英类的测定结果分别示于表5、6。可将二英类的总量以毒性当量计从3.0pg-TEQ/g降低为0.014pg-TEQ/g。另外,蒸馏后的油的酸值为0.2以下,在脂肪酸组成方面没有变化。
表5
注1.实测浓度小于检测下限的情况下由“N.D.”表示
2.毒性当量(TEQ)通过将小于检测下限的实测浓度设为“0”而算出
3.毒性等价系数(TEF)使用WHO(2006)
4. 1,2,3,7,8-PeCDF以及1,2,3,4,7,8-HxCDF无法通过SP-2331柱而分离出来,因而以合计值进行表示
表6
注1.实测浓度小于检测下限的情况下由“N.D.”表示
2.毒性当量(TEQ)通过将小于检测下限的实测浓度设为“0”而算出
3.毒性等价系数(TEF)使用WHO(2006)
4. 1,2,3,7,8-PeCDF以及1,2,3,4,7,8-HxCDF无法通过SP-2331柱而分离出来,因而以合计值进行表示
实施例5
将沙丁鱼粗油在与实施例4相同的条件下进行短程蒸馏,通过前述的方法测定出蒸馏前后的脂肪酸组成。将结果示于表7。示出了因加热而容易发生氧化、异构化等改性的碳原子数18以上、双键数3以上的脂肪酸在原料油和蒸馏后的脂肪酸整体中所占的比例及其增减。任一脂肪酸的增减都是轻微的,对于双键数多的脂肪酸,变动也不会特别大。由该结果确认了:本发明的方法对于在不使高度不饱和脂肪发生改性的状态下去除二英类而言是优异的方法。表7中,ARA是花生四烯酸,DPA是二十二碳五烯酸。
表7
实施例6
将由实施例4制造的蒸馏后的油作为原料,制造了EPA乙酯。
关于制造方法,将通过SPD进行了蒸馏处理的油在碱性催化剂下与乙醇进行乙醇分解反应,制成乙酯。利用温水进行水洗,然后进行脱水,通过精馏(真空度13Pa、主馏分的温度约176℃)而获得主馏分,进一步使用反相分配系(ODS)的柱层析来进行HPLC处理,将溶剂蒸馏去除,制造了EPA纯度97%的EPA乙酯。
与实施例4同样地测定该乙酯的二英类,将结果示于表8。利用乙酯化以及随后的精制行程从而不会使二英类发生浓缩,使用实施例4的进行了处理的原料从而可制造二英类的总量以毒性当量计为0.07pg-TEQ/g以下的EPA乙酯。表8示出使用3个不同的批次的原料而实施的结果。根据本发明的方法确认出,可稳定地制造二英类的总量以毒性当量计为0.006~0.021pg-TEQ/g的EPA乙酯。关于测定极限以下的ND,意味着即使通过***测定极限的数值来计算,数值也仅仅升高0.005,可制造0.011~0.026pg-TEQ/g的EPA乙酯。
表8
实施例7
对于乙酯化后的精制工序的精馏和柱层析处理对二英类的浓度造成的影响,进行了确认。作为原料油,使用了仅进行了脱氧、脱色处理而没有进行薄膜蒸馏的沙丁鱼原油。这是因为,使用了稍微多地包含二英类的油脂时,容易观察精制处理的影响。
利用碱性催化剂将原料油进行乙酯化。首先将乙酯施加于精馏工序,采集了包含碳原子数20的脂肪酸的乙酯的馏分。接着,利用ODS的柱层析,采集了二十碳五烯酸乙酯的馏分。
表9示出了变动大的4个成分(绝对量和毒性当量)和二英类的合计(毒性当量)。与酯化后相比,通过精馏工序,使得#105、#118的成分大幅浓缩了。另一方面,在#77方面不如说是降低了。在精馏方面可认为,二十碳五烯酸乙酯等与二英类显示出类似的行为,伴随着二十碳五烯酸乙酯等的浓缩而二英类发生了浓缩。
表9
实施例8
以沙丁鱼粗油为原料,与实施例4同样地操作,获得用SPD进行了蒸馏的SPD油,进一步利用与实施例6相同的方法来进行乙酯化、精制,获得了EPA乙酯。测定出它们中的溴化阻燃剂的含量。测定委托作为分析机构的eurofins。将结果示于表10。原料沙丁鱼油中所含的溴化阻燃剂中的任一者都减低为检测极限以下。可确认,原料油中包含检测极限以上的BDE-100、BDE-49、BDE-99、BDE-47、BDE-28、BDE-66、BDE-154中的任一者都降低了,特别是BDE-100、BDE-49、BDE-99、BDE-47明确地减低。
表10
产业可利用性
Claims (9)
1.一种高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯,其为以鱼油作为原料油而制造并且减低了环境污染物质的含量的高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯,
所包含的溴化阻燃剂的含量:2,2’,4,4’-四溴二苯醚即BDE-47的量小于0.18ng/g,2,2’,4,4’,6-五溴二苯醚即BDE-100的量小于0.03ng/g,2,2’,4,5’-四溴二苯醚即BDE-49的量小于0.05ng/g,或2,2’,4,4’,5-五溴二苯醚即BDE-99的量小于0.05ng/g,
高度不饱和脂肪酸在脂肪酸中所占的浓度为80面积%以上,
高度不饱和脂肪酸是二十碳五烯酸、二十二碳六烯酸、二十二碳五烯酸、二高-γ-亚麻酸、花生四烯酸、或者它们的组合。
2.根据权利要求1所述的高度不饱和脂肪酸的乙酯,高度不饱和脂肪酸在脂肪酸中所占的浓度为85面积%以上。
3.根据权利要求1所述的高度不饱和脂肪酸的乙酯,高度不饱和脂肪酸在脂肪酸中所占的浓度为90面积%以上。
4.根据权利要求1所述的高度不饱和脂肪酸的乙酯,高度不饱和脂肪酸在脂肪酸中所占的浓度为95面积%以上。
5.根据权利要求1所述的高度不饱和脂肪酸的乙酯,高度不饱和脂肪酸在脂肪酸中所占的浓度为96面积%以上。
6.根据权利要求1所述的高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯,高度不饱和脂肪酸是二十碳五烯酸或二十二碳六烯酸。
7.根据权利要求6所述的高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯,高度不饱和脂肪酸是二十碳五烯酸。
8.根据权利要求1~7中任一项所述的高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯,原料油为沙丁鱼油或鲔鱼油。
9.一种药品、添加剂或食品,其含有权利要求1~8中任一项所述的高度不饱和脂肪酸或高度不饱和脂肪酸的乙酯作为有效成分。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012110809 | 2012-05-14 | ||
JP2012-110809 | 2012-05-14 | ||
CN201380024834.XA CN104302615B (zh) | 2012-05-14 | 2013-05-14 | 减低了环境污染物质的高度不饱和脂肪酸或高度不饱和脂肪酸乙酯及其制造方法 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201380024834.XA Division CN104302615B (zh) | 2012-05-14 | 2013-05-14 | 减低了环境污染物质的高度不饱和脂肪酸或高度不饱和脂肪酸乙酯及其制造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113045422A true CN113045422A (zh) | 2021-06-29 |
Family
ID=49583751
Family Applications (5)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110295239.6A Pending CN113045422A (zh) | 2012-05-14 | 2013-05-14 | 高度不饱和脂肪酸或高度不饱和脂肪酸乙酯、药品、添加剂或食品 |
CN201710031298.6A Pending CN106810446A (zh) | 2012-05-14 | 2013-05-14 | 高度不饱和脂肪酸或高度不饱和脂肪酸乙酯、含有它们的药品、添加剂或食品 |
CN201710701544.4A Active CN107602378B (zh) | 2012-05-14 | 2013-05-14 | 高度不饱和脂肪酸或高度不饱和脂肪酸乙酯及其制造方法、药品、添加剂或食品 |
CN201380024834.XA Active CN104302615B (zh) | 2012-05-14 | 2013-05-14 | 减低了环境污染物质的高度不饱和脂肪酸或高度不饱和脂肪酸乙酯及其制造方法 |
CN202110299534.9A Pending CN113025434A (zh) | 2012-05-14 | 2013-05-14 | 高度不饱和脂肪酸或高度不饱和脂肪酸乙酯及其制造方法、药品、添加剂或食品 |
Family Applications After (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710031298.6A Pending CN106810446A (zh) | 2012-05-14 | 2013-05-14 | 高度不饱和脂肪酸或高度不饱和脂肪酸乙酯、含有它们的药品、添加剂或食品 |
CN201710701544.4A Active CN107602378B (zh) | 2012-05-14 | 2013-05-14 | 高度不饱和脂肪酸或高度不饱和脂肪酸乙酯及其制造方法、药品、添加剂或食品 |
CN201380024834.XA Active CN104302615B (zh) | 2012-05-14 | 2013-05-14 | 减低了环境污染物质的高度不饱和脂肪酸或高度不饱和脂肪酸乙酯及其制造方法 |
CN202110299534.9A Pending CN113025434A (zh) | 2012-05-14 | 2013-05-14 | 高度不饱和脂肪酸或高度不饱和脂肪酸乙酯及其制造方法、药品、添加剂或食品 |
Country Status (13)
Country | Link |
---|---|
US (6) | US9540306B2 (zh) |
EP (2) | EP2851361B1 (zh) |
JP (8) | JP5592570B2 (zh) |
KR (7) | KR102381331B1 (zh) |
CN (5) | CN113045422A (zh) |
CA (2) | CA3225865A1 (zh) |
CL (1) | CL2014003053A1 (zh) |
DE (1) | DE202013012875U1 (zh) |
DK (1) | DK2851361T3 (zh) |
ES (1) | ES2900618T3 (zh) |
HU (1) | HUE057283T2 (zh) |
PE (2) | PE20142380A1 (zh) |
WO (1) | WO2013172346A1 (zh) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102381331B1 (ko) * | 2012-05-14 | 2022-04-01 | 닛폰 스이산 가부시키가이샤 | 환경 오염 물질을 저감시킨 고도 불포화 지방산 또는 고도 불포화 지방산 에틸에스테르 및 그 제조 방법 |
KR102091463B1 (ko) | 2012-11-02 | 2020-03-23 | 프로노바 바이오파마 노르지 에이에스 | 유지 조성물로부터 바람직하지 않은 구성 성분의 제거 방법 |
CN105814209B (zh) | 2013-12-04 | 2022-02-25 | 日本水产株式会社 | 含有二高-γ-亚麻酸的微生物油和含有二高-γ-亚麻酸的微生物生物质 |
WO2017038861A1 (ja) | 2015-08-31 | 2017-03-09 | 日本水産株式会社 | 遊離多価不飽和脂肪酸含有組成物及びその製造方法 |
ITUB20153877A1 (it) * | 2015-09-24 | 2017-03-24 | Tiberio Bruzzese | Metodo di purificazione di gliceridi di acidi grassi, composizioni che ne derivano, e loro uso |
CN106349070A (zh) * | 2016-08-31 | 2017-01-25 | 山东康曼生物科技有限公司 | 一种从低含量乙酯鱼油生产欧米加‑3‑酸乙酯90的工艺 |
WO2018056609A1 (ko) * | 2016-09-23 | 2018-03-29 | 씨제이제일제당 (주) | 지방산 에틸 에스테르의 제조방법 |
ES2928748T3 (es) * | 2017-07-07 | 2022-11-22 | Bunge Loders Croklaan B V | Proceso para la preparación de una composición de grasa hidrogenada |
CN109438220B (zh) * | 2018-10-31 | 2021-04-13 | 苏州赛分科技有限公司 | 一种从鱼油中纯化epa的方法 |
US20210395183A1 (en) | 2018-12-26 | 2021-12-23 | Nisshin Pharma Inc. | Eicosapentaenoic acid alkyl ester-containing composition and method for producing same |
CN111302940A (zh) * | 2020-04-08 | 2020-06-19 | 燕园泽龙(涿鹿)生物科技有限公司 | 高纯度α-亚麻酸乙酯的生产方法 |
KR20230156643A (ko) * | 2021-03-17 | 2023-11-14 | 가부시키가이샤 닛스이 | 정제 방법 및 정제된 제품 |
CN114057574A (zh) * | 2021-12-03 | 2022-02-18 | 浙江工商大学 | 一种制备高纯度epa乙酯的方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004007654A1 (en) * | 2002-07-11 | 2004-01-22 | Pronova Biocare As | A process for decreasing environmental pollutants in an oil or a fat, a volatile environmental pollutants decreasing working fluid, a health supplement, and an animal feed product |
Family Cites Families (52)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57149400A (en) | 1981-03-12 | 1982-09-14 | Kureha Chemical Ind Co Ltd | Manufacture of high purity long chain highly unsaturated fatty acid ester |
JPS5888339A (ja) | 1981-11-20 | 1983-05-26 | Kagakuhin Kensa Kyokai | エイコサペンタエン酸又はそのエステルとドコサヘキサエン酸又はそのエステルの分離精製方法 |
NL8200559A (nl) | 1982-02-15 | 1983-09-01 | Ir Jan Bart Le Poole Prof Dr | Bestralingsinrichting met bundelsplitsing. |
JPS60208940A (ja) | 1984-03-31 | 1985-10-21 | Nippon Zeon Co Ltd | 長鎮不飽和脂肪酸化合物の分離精製法 |
GB8819110D0 (en) | 1988-08-11 | 1988-09-14 | Norsk Hydro As | Antihypertensive drug & method for production |
JPH0633088B2 (ja) | 1990-02-20 | 1994-05-02 | 金沢樹脂工業株式会社 | 組立式フォークリフト用パレット |
CA2043615C (en) | 1990-06-04 | 2001-08-14 | Kazuhiko Hata | Method of producing eicosapentaenoic acid or the ester derivative thereof |
JP3290152B2 (ja) | 1990-06-04 | 2002-06-10 | 日本水産株式会社 | 高濃度エイコサペンタエン酸またはそのエステル |
JPH07105223B2 (ja) | 1991-03-11 | 1995-11-13 | 日本碍子株式会社 | 高温電池集合体 |
US5215630A (en) | 1991-06-04 | 1993-06-01 | Nippon Suisan Kaisha, Ltd. | Method of purifying eicosapentaenoic acid or the ester derivative thereof by fractional distillation |
JP2988754B2 (ja) | 1991-09-03 | 1999-12-13 | 日本水産株式会社 | 高真空連続蒸留装置 |
JP3400466B2 (ja) | 1991-10-28 | 2003-04-28 | 日本水産株式会社 | 高純度エイコサペンタエン酸またはそのエステルの製造方法 |
JP3614177B2 (ja) | 1992-07-21 | 2005-01-26 | 日本水産株式会社 | 高純度ドコサヘキサエン酸またはそのエステルの 製造方法 |
GB9404483D0 (en) * | 1994-03-08 | 1994-04-20 | Norsk Hydro As | Refining marine oil compositions |
JPH08100191A (ja) * | 1994-09-30 | 1996-04-16 | Nisshin Flour Milling Co Ltd | 高度不飽和脂肪酸またはそのエステルの精製方法 |
NO314788B1 (no) | 1994-11-15 | 2003-05-26 | K D Pharma Gmbh | Framgangsmåte for utvinning av en eller flere forbindelser fra en blanding |
JPH09302380A (ja) * | 1996-05-10 | 1997-11-25 | Nippon Wax Polymer Kaihatsu Kenkyusho:Kk | エイコサペンタエン酸又はそのエステルの精製方法 |
JPH1095744A (ja) * | 1996-09-20 | 1998-04-14 | Nof Corp | 高度不飽和脂肪酸又はそのアルキルエステルの製造方法 |
JPH10310551A (ja) * | 1997-05-12 | 1998-11-24 | Nippon Wax Polymer Kaihatsu Kenkyusho:Kk | エイコサペンタエン酸又はそのエステルの精製方法 |
CN1072711C (zh) * | 1998-01-05 | 2001-10-10 | 山东禹王制药有限公司 | 一种高度不饱和脂肪酸的工业化生产方法 |
JP2872986B1 (ja) | 1998-01-21 | 1999-03-24 | 池田食研株式会社 | 高純度高度不飽和脂肪酸の低級アルコールエステル精製方法 |
CA2334022C (en) * | 1998-06-05 | 2008-12-02 | Merck Patent Gesellschaft Mit Beschraenkter Haftung | Contaminant reduced marine oil |
DE19923558A1 (de) | 1999-05-21 | 2000-11-23 | K D Pharma Bexbach Gmbh | Verfahren zur Herstellung von geruchs- und geschmacksfreien ungesättigten Fettsäuren aus Naturölen und deren Verwendung |
ES2159257B1 (es) | 1999-11-19 | 2002-04-16 | Kd Iqa S L | Nuevo procedimiento de preparacion del ester etilico del acido eicosa pentaenoico. |
EP1125914A1 (en) | 2000-02-14 | 2001-08-22 | Nisshin Flour Milling Co., Ltd. | Process for separating and purifying eicosapentaenoic acid or its ester |
JP4752118B2 (ja) * | 2000-02-17 | 2011-08-17 | 住友化学株式会社 | 脂肪酸エステルの製造方法および脂肪酸エステルを含む燃料 |
CA2336513C (en) | 2000-02-17 | 2010-08-24 | Tatsuo Tateno | Process for producing fatty acid esters and fuels comprising fatty acid ester |
PT1303580E (pt) * | 2000-07-19 | 2006-09-29 | Lysi Hf | Processo para a producao de oleos marinhos com niveis reduzidos de contaminantes |
FR2894772B1 (fr) * | 2005-12-20 | 2008-03-14 | Pierre Fabre Medicament Sa | Procede d'enrichissement en dha |
DE102006012866B4 (de) | 2006-03-19 | 2009-04-09 | Uic Gmbh | Verfahren zur Abtrennung leichtflüchtiger Komponenten aus einem Stoffgemisch sowie Vorrichtung zur Durchführung dieses Verfahrens |
WO2008133573A1 (en) * | 2007-04-26 | 2008-11-06 | Patrick Adlercreutz | A polyunsaturated fatty acid (pufa) enriched marine oil comprising eicosapentaenoic acid (epa) and docosahexaenoic acid (dha), and a process of production thereof |
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 |
DK2062484T3 (da) | 2007-11-23 | 2011-07-18 | Reemtsma H F & Ph | Fremgangsmåde til fremstilling af røgfri tobaksvarer og røgfri tobaksvare til oral konsumption |
EP2548456B1 (en) | 2008-03-20 | 2015-07-08 | Virun, Inc. | Emulsions including a PEG-derivative of tocopherol |
MX2010012482A (es) | 2008-05-15 | 2010-12-01 | Pronova Biopharma Norge As | Proceso para aceite de kril. |
KR101357298B1 (ko) | 2008-06-20 | 2014-01-28 | 에이케이 앤 엠엔 바이오팜 주식회사 | 오메가-3계 고도불포화 지방산의 고순도 정제방법 |
JP2010118383A (ja) * | 2008-11-11 | 2010-05-27 | Nikon Corp | 照明装置、露光装置、及びデバイス製造方法 |
JP6176894B2 (ja) | 2009-03-09 | 2017-08-09 | プロノヴァ・バイオファーマ・ノルゲ・アーエス | 脂肪酸油混合物及び界面活性剤を含む組成物、並びにその方法及び使用 |
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. |
RU2014146265A (ru) * | 2009-12-30 | 2015-07-10 | Басф Фарма (Калланиш) Лимитед | Способ хроматографического разделения с псевдодвижущимся слоем |
WO2011119228A1 (en) | 2010-03-23 | 2011-09-29 | Virun, Inc. | Nanoemulsion including sucrose fatty acid ester |
EP2578691A4 (en) | 2010-05-28 | 2016-11-23 | Nippon Suisan Kaisha Ltd | PROCESS FOR PREPARING OIL OR FAT WITH A LIPASE-SUBSTANTIAL HIGH-UNSATURATED FATTY ACID |
WO2011155852A1 (en) * | 2010-06-09 | 2011-12-15 | Photonz Corporation Limited | Compositions comprising eicosapentaenoic acid suitable for high purification |
PE20140202A1 (es) | 2010-09-24 | 2014-03-15 | Pronova Biopharma Norge As | Proceso para concentrar acidos grasos omega-3 |
JP5650506B2 (ja) | 2010-11-22 | 2015-01-07 | 優章 荒井 | 電解水の製造装置 |
KR20140007430A (ko) * | 2011-02-11 | 2014-01-17 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 에이코사펜타엔산 농축물 |
GB201111591D0 (en) * | 2011-07-06 | 2011-08-24 | Equateq Ltd | Further new process |
ES2395320B1 (es) | 2011-07-14 | 2013-12-18 | Soluciones Extractivas Alimentarias, S.L. | Nuevo método para la reducción de contaminantes en grasas y aceites a partir de aceites y sus derivados. |
EP2776544A1 (en) * | 2011-11-09 | 2014-09-17 | Evonik Membrane Extraction Technology Limited | Membrane-based processes for reducing at least one impurity and making a concentrate comprising at least one natural component from a non-marine fatty acid oil mixture, and compositions resulting thereof |
US8258330B1 (en) | 2012-01-04 | 2012-09-04 | Naturalis, S.A. | Carrier fluid composition comprising fatty acids ethyl esters and process for reducing the concentration of persistent organic pollutants in fish oil |
KR102381331B1 (ko) * | 2012-05-14 | 2022-04-01 | 닛폰 스이산 가부시키가이샤 | 환경 오염 물질을 저감시킨 고도 불포화 지방산 또는 고도 불포화 지방산 에틸에스테르 및 그 제조 방법 |
CN105814209B (zh) | 2013-12-04 | 2022-02-25 | 日本水产株式会社 | 含有二高-γ-亚麻酸的微生物油和含有二高-γ-亚麻酸的微生物生物质 |
-
2013
- 2013-05-14 KR KR1020217007317A patent/KR102381331B1/ko active IP Right Grant
- 2013-05-14 CA CA3225865A patent/CA3225865A1/en active Pending
- 2013-05-14 CN CN202110295239.6A patent/CN113045422A/zh active Pending
- 2013-05-14 KR KR1020207005902A patent/KR102117806B1/ko active IP Right Grant
- 2013-05-14 PE PE2014002012A patent/PE20142380A1/es active IP Right Grant
- 2013-05-14 EP EP13790465.2A patent/EP2851361B1/en active Active
- 2013-05-14 JP JP2013546117A patent/JP5592570B2/ja active Active
- 2013-05-14 CN CN201710031298.6A patent/CN106810446A/zh active Pending
- 2013-05-14 ES ES13790465T patent/ES2900618T3/es active Active
- 2013-05-14 PE PE2019001187A patent/PE20190969A1/es unknown
- 2013-05-14 DK DK13790465.2T patent/DK2851361T3/da active
- 2013-05-14 DE DE202013012875.5U patent/DE202013012875U1/de not_active Expired - Lifetime
- 2013-05-14 WO PCT/JP2013/063425 patent/WO2013172346A1/ja active Application Filing
- 2013-05-14 CN CN201710701544.4A patent/CN107602378B/zh active Active
- 2013-05-14 US US14/400,652 patent/US9540306B2/en active Active
- 2013-05-14 KR KR1020227034817A patent/KR20220140655A/ko not_active Application Discontinuation
- 2013-05-14 CN CN201380024834.XA patent/CN104302615B/zh active Active
- 2013-05-14 KR KR1020147034425A patent/KR102117725B1/ko active IP Right Grant
- 2013-05-14 KR KR1020227010218A patent/KR102453616B1/ko active IP Right Grant
- 2013-05-14 KR KR1020247018724A patent/KR20240096704A/ko unknown
- 2013-05-14 CA CA2873160A patent/CA2873160C/en active Active
- 2013-05-14 EP EP21206640.1A patent/EP3971165A1/en active Pending
- 2013-05-14 HU HUE13790465A patent/HUE057283T2/hu unknown
- 2013-05-14 CN CN202110299534.9A patent/CN113025434A/zh active Pending
- 2013-05-14 KR KR1020207014617A patent/KR102229106B1/ko active Application Filing
-
2014
- 2014-06-03 JP JP2014114769A patent/JP6309828B2/ja active Active
- 2014-11-10 CL CL2014003053A patent/CL2014003053A1/es unknown
-
2016
- 2016-12-01 US US15/366,522 patent/US10399922B2/en active Active
-
2017
- 2017-07-04 JP JP2017130947A patent/JP6434573B2/ja active Active
-
2018
- 2018-04-03 JP JP2018071685A patent/JP6389579B2/ja active Active
- 2018-06-27 US US16/019,992 patent/US10399923B2/en active Active
- 2018-09-27 JP JP2018181274A patent/JP6774469B2/ja active Active
-
2019
- 2019-07-17 US US16/514,191 patent/US11034643B2/en active Active
-
2020
- 2020-10-02 JP JP2020167387A patent/JP2021004254A/ja active Pending
-
2021
- 2021-05-11 US US17/317,179 patent/US11603347B2/en active Active
-
2022
- 2022-07-01 JP JP2022106906A patent/JP2022132317A/ja not_active Withdrawn
-
2023
- 2023-02-06 US US18/164,765 patent/US20230183165A1/en active Pending
-
2024
- 2024-02-28 JP JP2024028104A patent/JP2024069262A/ja active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004007654A1 (en) * | 2002-07-11 | 2004-01-22 | Pronova Biocare As | A process for decreasing environmental pollutants in an oil or a fat, a volatile environmental pollutants decreasing working fluid, a health supplement, and an animal feed product |
Non-Patent Citations (2)
Title |
---|
""经过担负精细化工业务的核心的SPD处理方式大幅减少二噁英"" * |
铃木刚: ""有效利用海洋的恩惠为"生活"做贡献"" * |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107602378B (zh) | 高度不饱和脂肪酸或高度不饱和脂肪酸乙酯及其制造方法、药品、添加剂或食品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 40057853 Country of ref document: HK |
|
CB02 | Change of applicant information | ||
CB02 | Change of applicant information |
Address after: Tokyo, Japan Applicant after: Rishui, Ltd. Address before: Tokyo, Japan Applicant before: NIPPON SUISAN Kabushiki Kaisha Ltd. |