JPH08500598A - トコフェロールおよびステロールの回収 - Google Patents
トコフェロールおよびステロールの回収Info
- Publication number
- JPH08500598A JPH08500598A JP6506799A JP50679994A JPH08500598A JP H08500598 A JPH08500598 A JP H08500598A JP 6506799 A JP6506799 A JP 6506799A JP 50679994 A JP50679994 A JP 50679994A JP H08500598 A JPH08500598 A JP H08500598A
- Authority
- JP
- Japan
- Prior art keywords
- mixture
- transesterification
- lower alcohol
- tocopherol
- 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.)
- Granted
Links
- 229930003799 tocopherol Natural products 0.000 title claims abstract description 55
- 239000011732 tocopherol Substances 0.000 title claims abstract description 55
- 229930182558 Sterol Natural products 0.000 title claims abstract description 51
- 235000003702 sterols Nutrition 0.000 title claims abstract description 51
- 150000003432 sterols Chemical class 0.000 title claims abstract description 44
- 235000019149 tocopherols Nutrition 0.000 title claims abstract description 23
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 title claims abstract 4
- 238000011084 recovery Methods 0.000 title description 5
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 39
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 32
- 235000010384 tocopherol Nutrition 0.000 claims abstract description 32
- 229960001295 tocopherol Drugs 0.000 claims abstract description 32
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 20
- 229930195729 fatty acid Natural products 0.000 claims abstract description 20
- 239000000194 fatty acid Substances 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003925 fat Substances 0.000 claims abstract description 11
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 11
- 235000021588 free fatty acids Nutrition 0.000 claims abstract description 11
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 10
- 239000011541 reaction mixture Substances 0.000 claims abstract description 6
- 239000007858 starting material Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 239000003549 soybean oil Substances 0.000 claims description 9
- 235000012424 soybean oil Nutrition 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000003784 tall oil Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 235000019198 oils Nutrition 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 125000002640 tocopherol group Chemical class 0.000 description 19
- 229930003427 Vitamin E Natural products 0.000 description 9
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 9
- -1 steroid alcohols Chemical group 0.000 description 9
- 235000019165 vitamin E Nutrition 0.000 description 9
- 239000011709 vitamin E Substances 0.000 description 9
- 229940046009 vitamin E Drugs 0.000 description 9
- 125000005456 glyceride group Chemical group 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 244000068988 Glycine max Species 0.000 description 5
- 235000010469 Glycine max Nutrition 0.000 description 5
- 235000019484 Rapeseed oil Nutrition 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 235000019197 fats Nutrition 0.000 description 5
- 150000003626 triacylglycerols Chemical class 0.000 description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 description 5
- 239000008158 vegetable oil Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 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
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OILXMJHPFNGGTO-UHFFFAOYSA-N (22E)-(24xi)-24-methylcholesta-5,22-dien-3beta-ol Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(C)C(C)C)C1(C)CC2 OILXMJHPFNGGTO-UHFFFAOYSA-N 0.000 description 3
- OQMZNAMGEHIHNN-UHFFFAOYSA-N 7-Dehydrostigmasterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CC(CC)C(C)C)CCC33)C)C3=CC=C21 OQMZNAMGEHIHNN-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- LGJMUZUPVCAVPU-UHFFFAOYSA-N beta-Sitostanol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(CC)C(C)C)C1(C)CC2 LGJMUZUPVCAVPU-UHFFFAOYSA-N 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 238000000199 molecular distillation Methods 0.000 description 3
- 238000001256 steam distillation Methods 0.000 description 3
- 229930193551 sterin Natural products 0.000 description 3
- 150000003611 tocopherol derivatives Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DFUSDJMZWQVQSF-XLGIIRLISA-N (2r)-2-methyl-2-[(4r,8r)-4,8,12-trimethyltridecyl]-3,4-dihydrochromen-6-ol Chemical class OC1=CC=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 DFUSDJMZWQVQSF-XLGIIRLISA-N 0.000 description 2
- GJJVAFUKOBZPCB-ZGRPYONQSA-N (r)-3,4-dihydro-2-methyl-2-(4,8,12-trimethyl-3,7,11-tridecatrienyl)-2h-1-benzopyran-6-ol Chemical class OC1=CC=C2OC(CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1 GJJVAFUKOBZPCB-ZGRPYONQSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- RJKFOVLPORLFTN-LEKSSAKUSA-N Progesterone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 RJKFOVLPORLFTN-LEKSSAKUSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- HZYXFRGVBOPPNZ-UHFFFAOYSA-N UNPD88870 Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)=CCC(CC)C(C)C)C1(C)CC2 HZYXFRGVBOPPNZ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 235000012000 cholesterol Nutrition 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- UACIBCPNAKBWHX-CTBOZYAPSA-N gonane Chemical group C1CCC[C@@H]2[C@H]3CC[C@@H]4CCC[C@H]4[C@@H]3CCC21 UACIBCPNAKBWHX-CTBOZYAPSA-N 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 239000010773 plant oil Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- HCXVJBMSMIARIN-PHZDYDNGSA-N stigmasterol 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)/C=C/[C@@H](CC)C(C)C)[C@@]1(C)CC2 HCXVJBMSMIARIN-PHZDYDNGSA-N 0.000 description 2
- 235000016831 stigmasterol Nutrition 0.000 description 2
- 229940032091 stigmasterol Drugs 0.000 description 2
- BFDNMXAIBMJLBB-UHFFFAOYSA-N stigmasterol Natural products CCC(C=CC(C)C1CCCC2C3CC=C4CC(O)CCC4(C)C3CCC12C)C(C)C BFDNMXAIBMJLBB-UHFFFAOYSA-N 0.000 description 2
- 235000004835 α-tocopherol Nutrition 0.000 description 2
- KZJWDPNRJALLNS-VPUBHVLGSA-N (-)-beta-Sitosterol Natural products O[C@@H]1CC=2[C@@](C)([C@@H]3[C@H]([C@H]4[C@@](C)([C@H]([C@H](CC[C@@H](C(C)C)CC)C)CC4)CC3)CC=2)CC1 KZJWDPNRJALLNS-VPUBHVLGSA-N 0.000 description 1
- CSVWWLUMXNHWSU-UHFFFAOYSA-N (22E)-(24xi)-24-ethyl-5alpha-cholest-22-en-3beta-ol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(CC)C(C)C)C1(C)CC2 CSVWWLUMXNHWSU-UHFFFAOYSA-N 0.000 description 1
- RQOCXCFLRBRBCS-UHFFFAOYSA-N (22E)-cholesta-5,7,22-trien-3beta-ol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CCC(C)C)CCC33)C)C3=CC=C21 RQOCXCFLRBRBCS-UHFFFAOYSA-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
- KLEXDBGYSOIREE-UHFFFAOYSA-N 24xi-n-propylcholesterol Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(CCC)C(C)C)C1(C)CC2 KLEXDBGYSOIREE-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- 235000019737 Animal fat Nutrition 0.000 description 1
- SGNBVLSWZMBQTH-FGAXOLDCSA-N Campesterol Natural products O[C@@H]1CC=2[C@@](C)([C@@H]3[C@H]([C@H]4[C@@](C)([C@H]([C@H](CC[C@H](C(C)C)C)C)CC4)CC3)CC=2)CC1 SGNBVLSWZMBQTH-FGAXOLDCSA-N 0.000 description 1
- LPZCCMIISIBREI-MTFRKTCUSA-N Citrostadienol Natural products CC=C(CC[C@@H](C)[C@H]1CC[C@H]2C3=CC[C@H]4[C@H](C)[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C)C(C)C LPZCCMIISIBREI-MTFRKTCUSA-N 0.000 description 1
- ARVGMISWLZPBCH-UHFFFAOYSA-N Dehydro-beta-sitosterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)CCC(CC)C(C)C)CCC33)C)C3=CC=C21 ARVGMISWLZPBCH-UHFFFAOYSA-N 0.000 description 1
- DNVPQKQSNYMLRS-NXVQYWJNSA-N Ergosterol Natural products CC(C)[C@@H](C)C=C[C@H](C)[C@H]1CC[C@H]2C3=CC=C4C[C@@H](O)CC[C@]4(C)[C@@H]3CC[C@]12C DNVPQKQSNYMLRS-NXVQYWJNSA-N 0.000 description 1
- BTEISVKTSQLKST-UHFFFAOYSA-N Haliclonasterol Natural products CC(C=CC(C)C(C)(C)C)C1CCC2C3=CC=C4CC(O)CCC4(C)C3CCC12C BTEISVKTSQLKST-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 description 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical class [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 1
- GXCLVBGFBYZDAG-UHFFFAOYSA-N N-[2-(1H-indol-3-yl)ethyl]-N-methylprop-2-en-1-amine Chemical compound CN(CCC1=CNC2=C1C=CC=C2)CC=C GXCLVBGFBYZDAG-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 210000004100 adrenal gland Anatomy 0.000 description 1
- 229940087168 alpha tocopherol Drugs 0.000 description 1
- 210000001557 animal structure Anatomy 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- MJVXAPPOFPTTCA-UHFFFAOYSA-N beta-Sistosterol Natural products CCC(CCC(C)C1CCC2C3CC=C4C(C)C(O)CCC4(C)C3CCC12C)C(C)C MJVXAPPOFPTTCA-UHFFFAOYSA-N 0.000 description 1
- NJKOMDUNNDKEAI-UHFFFAOYSA-N beta-sitosterol Natural products CCC(CCC(C)C1CCC2(C)C3CC=C4CC(O)CCC4C3CCC12C)C(C)C NJKOMDUNNDKEAI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- SGNBVLSWZMBQTH-PODYLUTMSA-N campesterol 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)CC[C@@H](C)C(C)C)[C@@]1(C)CC2 SGNBVLSWZMBQTH-PODYLUTMSA-N 0.000 description 1
- 235000000431 campesterol Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- GZCJJOLJSBCUNR-UHFFFAOYSA-N chroman-6-ol Chemical class O1CCCC2=CC(O)=CC=C21 GZCJJOLJSBCUNR-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000039 congener Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 239000003246 corticosteroid Substances 0.000 description 1
- 229960001334 corticosteroids Drugs 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 235000010389 delta-tocopherol Nutrition 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- DNVPQKQSNYMLRS-SOWFXMKYSA-N ergosterol Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H](CC[C@]3([C@H]([C@H](C)/C=C/[C@@H](C)C(C)C)CC[C@H]33)C)C3=CC=C21 DNVPQKQSNYMLRS-SOWFXMKYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 235000010382 gamma-tocopherol Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940068065 phytosterols Drugs 0.000 description 1
- 235000002378 plant sterols Nutrition 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000186 progesterone Substances 0.000 description 1
- 229960003387 progesterone Drugs 0.000 description 1
- 239000000583 progesterone congener Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- KZJWDPNRJALLNS-VJSFXXLFSA-N sitosterol 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)CC[C@@H](CC)C(C)C)[C@@]1(C)CC2 KZJWDPNRJALLNS-VJSFXXLFSA-N 0.000 description 1
- 235000015500 sitosterol Nutrition 0.000 description 1
- NLQLSVXGSXCXFE-UHFFFAOYSA-N sitosterol Natural products CC=C(/CCC(C)C1CC2C3=CCC4C(C)C(O)CCC4(C)C3CCC2(C)C1)C(C)C NLQLSVXGSXCXFE-UHFFFAOYSA-N 0.000 description 1
- 229950005143 sitosterol Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 210000000278 spinal cord Anatomy 0.000 description 1
- 239000003270 steroid hormone Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical group 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 229930003802 tocotrienol Natural products 0.000 description 1
- 239000011731 tocotrienol Substances 0.000 description 1
- 229940068778 tocotrienols Drugs 0.000 description 1
- 235000019148 tocotrienols Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 150000003772 α-tocopherols Chemical class 0.000 description 1
- 235000007680 β-tocopherol Nutrition 0.000 description 1
- 150000003781 β-tocopherols Chemical class 0.000 description 1
- 150000003785 γ-tocopherols Chemical class 0.000 description 1
- 150000003789 δ-tocopherols Chemical class 0.000 description 1
Classifications
-
- 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
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3544—Organic compounds containing hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
- C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nutrition Science (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Microbiology (AREA)
- Pyrane Compounds (AREA)
- Fats And Perfumes (AREA)
- Steroid Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Description
Claims (1)
- 【特許請求の範囲】 1.トコフェロール、脂肪および/または脂肪誘導体(特に脂肪酸)並びにス テロールおよび/またはステロール誘導体を含有する混合物、とりわけ天然油お よび脂肪のスチーマー留出物から、トコフェロールおよびステロールを同時に回 収する方法であって、 1)混合物中の遊離脂肪酸を低級アルコール、好ましくはメタノールでエステ ル化し(混合物0.4〜1.6容量部、とりわけ1〜1.5容量部を低級アルコ ール1容量部によるエステル化に付し)、 2)次いで、混合物を、塩基性触媒の存在下に低級アルコールによるエステル 交換に付し、 3)エステル交換後の反応混合物から、過剰の低級アルコールを留去し、 4)エステル交換触媒および場合により存在するグリセロールを、とりわけ洗 浄によって除去し、 5)混合物から脂肪酸アルキルエステルを、とりわけエステル交換触媒の除去 後に留去し、 6)要すれば、トコフェロールおよびステロールを既知の方法で分離すること を含んで成る方法。 2.出発物質は大豆油スチーマー留出物である請求項1記載の方法。 3.出発物質はトール油である請求項1記載の方法。 4.脂肪酸のエステル化は、強酸性イオン交換体(とりわけ固定層反応器内に 存在する)の存在下、60〜100℃、とりわけ65〜70℃の温度で行う請求 項1〜3のいずれかに記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4228476.7 | 1992-08-27 | ||
DE4228476A DE4228476C2 (de) | 1992-08-27 | 1992-08-27 | Verfahren zum Gewinnen von Tocopherol und/oder Sterin |
PCT/EP1993/002207 WO1994005650A1 (de) | 1992-08-27 | 1993-08-18 | Gewinnung von tocopherol und sterol |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH08500598A true JPH08500598A (ja) | 1996-01-23 |
JP3746292B2 JP3746292B2 (ja) | 2006-02-15 |
Family
ID=6466542
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP50679994A Expired - Fee Related JP3746292B2 (ja) | 1992-08-27 | 1993-08-18 | トコフェロールおよびステロールの回収 |
Country Status (11)
Country | Link |
---|---|
US (1) | US5627289A (ja) |
EP (1) | EP0656894B2 (ja) |
JP (1) | JP3746292B2 (ja) |
AT (1) | ATE163416T1 (ja) |
BR (1) | BR9306967A (ja) |
CA (1) | CA2143441C (ja) |
DE (2) | DE4228476C2 (ja) |
DK (1) | DK0656894T4 (ja) |
ES (1) | ES2112427T5 (ja) |
MY (1) | MY111793A (ja) |
WO (1) | WO1994005650A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2002542161A (ja) * | 1999-04-09 | 2002-12-10 | コグニス・ドイチュラント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・ウント・コムパニー・コマンディットゲゼルシャフト | 植物ステロールを回収する方法 |
JP2011513578A (ja) * | 2008-03-10 | 2011-04-28 | サンパイン アーベー | 残留植物油ストリームからの植物性ステロールの再生 |
JP2014510823A (ja) * | 2011-04-14 | 2014-05-01 | アルファ−ラヴァル・コーポレート・アーベー | 脂肪酸の自己触媒エステル化のための方法 |
JP2016216456A (ja) * | 2015-05-18 | 2016-12-22 | 国立大学法人東北大学 | ビタミンe類の選択的な分離方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE289301T1 (de) * | 1993-08-06 | 2005-03-15 | Cognis Corp | Wiedergewinnung von tocopherolen |
US5703252A (en) * | 1995-12-13 | 1997-12-30 | Henkel Corporation | Recovery of Tocopherols |
FR2787714B1 (fr) | 1998-12-23 | 2003-01-31 | Pharmascience Lab | Utilisation d'insaponifiables d'huiles vegetales pour la preparation d'un medicament stimulant l'expression du tgf-beta ou l'expression de l'inhibiteur pai-1 de l'activateur du plasminogene |
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Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1170126A (fr) * | 1954-09-23 | 1959-01-09 | Eastman Kodak Co | Procédé d'obtention de concentrés de tocophérol à partir de boues de désodorisation et produits obtenus |
US3335154A (en) * | 1963-06-04 | 1967-08-08 | Eastman Kodak Co | Separation of tocopherols and sterols from deodorizer sludge and the like |
DE3126110A1 (de) * | 1980-07-04 | 1982-04-01 | The Nisshin Oil Mills, Ltd., Tokyo | Verfahren zur gewinnung von tocopherol-konzentraten |
JPS6042495A (ja) * | 1983-08-17 | 1985-03-06 | 日清製油株式会社 | 油脂脱臭留出物のメチルエステル化法 |
GB8418274D0 (en) * | 1984-07-18 | 1984-08-22 | Inst Penyelidikan Minyak Kelap | Carboxylic acid esterification |
DE3582904D1 (de) * | 1984-08-02 | 1991-06-27 | Henkel Corp | Reinigung von tocopherolen durch extraktion. |
DE3501761A1 (de) * | 1985-01-21 | 1986-07-24 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur vorveresterung freier fettsaeuren in rohfetten und/oder -oelen |
DE3615029A1 (de) * | 1985-05-06 | 1986-11-06 | Henkel Corp., Minneapolis, Minn. | Methanol-extraktion von tocopherol |
GB8729232D0 (en) * | 1987-12-15 | 1988-01-27 | Palm Oil Research Inst Of Mala | Recovery of carotenoids tocopherols tocotrienols & sterols from esterified palm oil |
EP0333472B1 (en) * | 1988-03-16 | 1997-10-08 | PALM OIL RESEARCH & DEVELOPMENT BOARD | Production of high concentration tocopherols and tocotrienols from palm oil by-products |
-
1992
- 1992-08-27 DE DE4228476A patent/DE4228476C2/de not_active Expired - Fee Related
-
1993
- 1993-08-18 JP JP50679994A patent/JP3746292B2/ja not_active Expired - Fee Related
- 1993-08-18 CA CA002143441A patent/CA2143441C/en not_active Expired - Fee Related
- 1993-08-18 AT AT93919091T patent/ATE163416T1/de not_active IP Right Cessation
- 1993-08-18 US US08/387,933 patent/US5627289A/en not_active Expired - Lifetime
- 1993-08-18 ES ES93919091T patent/ES2112427T5/es not_active Expired - Lifetime
- 1993-08-18 DE DE59308185T patent/DE59308185D1/de not_active Expired - Fee Related
- 1993-08-18 WO PCT/EP1993/002207 patent/WO1994005650A1/de active IP Right Grant
- 1993-08-18 DK DK93919091T patent/DK0656894T4/da active
- 1993-08-18 BR BR9306967A patent/BR9306967A/pt not_active Application Discontinuation
- 1993-08-18 EP EP93919091A patent/EP0656894B2/de not_active Expired - Lifetime
- 1993-08-24 MY MYPI93001694A patent/MY111793A/en unknown
Cited By (7)
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JP2002542161A (ja) * | 1999-04-09 | 2002-12-10 | コグニス・ドイチュラント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・ウント・コムパニー・コマンディットゲゼルシャフト | 植物ステロールを回収する方法 |
JP4796695B2 (ja) * | 1999-04-09 | 2011-10-19 | コグニス・アイピー・マネージメント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | 植物ステロールを回収する方法 |
JP2011513578A (ja) * | 2008-03-10 | 2011-04-28 | サンパイン アーベー | 残留植物油ストリームからの植物性ステロールの再生 |
JP2016222926A (ja) * | 2008-03-10 | 2016-12-28 | サンパイン アーベーSunpine Ab | 残留植物油ストリームからの植物性ステロールの再生 |
JP2014510823A (ja) * | 2011-04-14 | 2014-05-01 | アルファ−ラヴァル・コーポレート・アーベー | 脂肪酸の自己触媒エステル化のための方法 |
US9085547B2 (en) | 2011-04-14 | 2015-07-21 | Alfa Laval Corporate Ab | Process for autocatalytic esterification of fatty acids |
JP2016216456A (ja) * | 2015-05-18 | 2016-12-22 | 国立大学法人東北大学 | ビタミンe類の選択的な分離方法 |
Also Published As
Publication number | Publication date |
---|---|
CA2143441C (en) | 2004-03-30 |
DK0656894T3 (da) | 1998-09-23 |
DK0656894T4 (da) | 2002-07-15 |
EP0656894A1 (de) | 1995-06-14 |
ATE163416T1 (de) | 1998-03-15 |
JP3746292B2 (ja) | 2006-02-15 |
ES2112427T5 (es) | 2003-01-01 |
EP0656894B1 (de) | 1998-02-25 |
ES2112427T3 (es) | 1998-04-01 |
CA2143441A1 (en) | 1994-03-17 |
DE4228476A1 (de) | 1994-03-03 |
US5627289A (en) | 1997-05-06 |
DE59308185D1 (de) | 1998-04-02 |
EP0656894B2 (de) | 2002-06-12 |
BR9306967A (pt) | 1999-01-12 |
WO1994005650A1 (de) | 1994-03-17 |
MY111793A (en) | 2001-01-31 |
DE4228476C2 (de) | 2002-05-02 |
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