CN104130233B - One-step method prepares the method for natural alpha tocopherol and mixed tocopherol - Google Patents
One-step method prepares the method for natural alpha tocopherol and mixed tocopherol Download PDFInfo
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- CN104130233B CN104130233B CN201410315256.1A CN201410315256A CN104130233B CN 104130233 B CN104130233 B CN 104130233B CN 201410315256 A CN201410315256 A CN 201410315256A CN 104130233 B CN104130233 B CN 104130233B
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- 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 title claims abstract description 233
- 239000011732 tocopherol Substances 0.000 title claims abstract description 108
- 229930003799 tocopherols Natural products 0.000 title claims abstract description 108
- 229960001295 Tocopherol Drugs 0.000 title claims abstract description 106
- 235000010384 tocopherol Nutrition 0.000 title claims abstract description 106
- 229940087168 alpha Tocopherol Drugs 0.000 title claims abstract description 64
- 229960000984 tocofersolan Drugs 0.000 title claims abstract description 64
- 235000004835 α-tocopherol Nutrition 0.000 title claims abstract description 64
- 239000002076 α-tocopherol Substances 0.000 title claims abstract description 64
- 239000011347 resin Substances 0.000 claims abstract description 111
- 229920005989 resin Polymers 0.000 claims abstract description 111
- 238000005406 washing Methods 0.000 claims abstract description 50
- 238000010521 absorption reaction Methods 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000002699 waste material Substances 0.000 claims abstract description 24
- 238000004090 dissolution Methods 0.000 claims abstract description 9
- 230000001877 deodorizing Effects 0.000 claims abstract description 8
- 239000010773 plant oil Substances 0.000 claims abstract description 8
- 238000003795 desorption Methods 0.000 claims abstract description 7
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 102
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000003480 eluent Substances 0.000 claims description 20
- 239000006166 lysate Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 13
- 235000019198 oils Nutrition 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000000526 short-path distillation Methods 0.000 claims description 7
- 210000000582 Semen Anatomy 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 230000035558 fertility Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000004006 olive oil Substances 0.000 claims description 3
- 235000008390 olive oil Nutrition 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 2
- -1 Oleum Glycines Chemical class 0.000 claims description 2
- 238000007792 addition Methods 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 4
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract 1
- 238000000199 molecular distillation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 65
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- 238000002242 deionisation method Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000006073 displacement reaction Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- 239000003925 fat Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- GZIFEOYASATJEH-VHFRWLAGSA-N δ-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-VHFRWLAGSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 238000005349 anion exchange Methods 0.000 description 4
- 239000003957 anion exchange resin Substances 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 235000013373 food additive Nutrition 0.000 description 4
- 239000002778 food additive Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000011068 load Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000010583 slow cooling Methods 0.000 description 4
- WGVKWNUPNGFDFJ-DQCZWYHMSA-N β-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C WGVKWNUPNGFDFJ-DQCZWYHMSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 241000209140 Triticum Species 0.000 description 3
- 229940088594 Vitamin Drugs 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 235000010389 delta-tocopherol Nutrition 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000002640 tocopherol group Chemical group 0.000 description 3
- 230000001131 transforming Effects 0.000 description 3
- 235000013343 vitamin Nutrition 0.000 description 3
- 239000011782 vitamin Substances 0.000 description 3
- 150000003722 vitamin derivatives Chemical class 0.000 description 3
- 229930003231 vitamins Natural products 0.000 description 3
- 235000021307 wheat Nutrition 0.000 description 3
- 239000002446 δ-tocopherol Substances 0.000 description 3
- HVYWMOMLDIMFJA-DPAQBDIFSA-N (3β)-Cholest-5-en-3-ol 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 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- 230000003064 anti-oxidating Effects 0.000 description 2
- 229940066595 beta tocopherol Drugs 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- QUEDXNHFTDJVIY-WENCSYSZSA-N gamma-Tocopherol Natural products OC1=C(C)C(C)=C2O[C@](CCC[C@@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-WENCSYSZSA-N 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000000194 supercritical-fluid extraction Methods 0.000 description 2
- 235000019149 tocopherols Nutrition 0.000 description 2
- 230000002588 toxic Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 235000019165 vitamin E Nutrition 0.000 description 2
- 239000011709 vitamin E Substances 0.000 description 2
- 235000007680 β-tocopherol Nutrition 0.000 description 2
- 239000011590 β-tocopherol Substances 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 compound OC1=CC=C2OC(CC/C=C(C)/CC/C=C(C)/CCC=C(C)C)(C)CCC2=C1 GJJVAFUKOBZPCB-ZGRPYONQSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N Benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940107161 Cholesterol Drugs 0.000 description 1
- VZWXIQHBIQLMPN-UHFFFAOYSA-N Chromane Chemical compound C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 description 1
- 208000004981 Coronary Disease Diseases 0.000 description 1
- 240000007842 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N Martius yellow Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N P-Toluenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 208000006641 Skin Disease Diseases 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 229940046009 Vitamin E Drugs 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 201000004384 alopecia Diseases 0.000 description 1
- 230000003078 antioxidant Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000000975 bioactive Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 125000003016 chromanyl group Chemical group O1C(CCC2=CC=CC=C12)* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 201000008739 coronary artery disease Diseases 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drugs Drugs 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 235000019261 food antioxidant Nutrition 0.000 description 1
- 235000010382 gamma-tocopherol Nutrition 0.000 description 1
- 239000003163 gonadal steroid hormone Substances 0.000 description 1
- 230000003676 hair loss Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000037356 lipid metabolism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical group C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- UYVXZUTYZGILQG-UHFFFAOYSA-N methoxyboronic acid Chemical compound COB(O)O UYVXZUTYZGILQG-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004089 microcirculation Effects 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 230000003287 optical Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000001717 pathogenic Effects 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000069 prophylaxis Effects 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 231100000486 side effect Toxicity 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 230000001502 supplementation Effects 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 239000011731 tocotrienol Substances 0.000 description 1
- 229930003802 tocotrienols Natural products 0.000 description 1
- 235000019148 tocotrienols Nutrition 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003712 vitamin E derivatives Chemical class 0.000 description 1
- 239000002478 γ-tocopherol Substances 0.000 description 1
Abstract
The invention discloses a kind of method that one-step method prepares natural alpha tocopherol and mixed tocopherol, separation and extraction technology field in biological engineering, including: the esterification of plant oil deodorizing distillate；Washing；The dissolution filter of tocopherol；The resin fluidised bed adsorption to tocopherol solution；The resin dynamic adsorption to tocopherol absorption waste liquid；Desorption；Molecular distillation obtains alpha tocopherol and mixed tocopherol.The alpha tocopherol that the present invention produces uses organic solvent hardly, and more environmentally-friendly, safety is more green compared with alpha tocopherol prepared by traditional method, healthy；Simultaneously the present invention produce mixed tocopherol have high-quality, high yield, low cost, be prone to batch production feature.
Description
Technical field
The invention belongs to separation and extraction technology field in biological engineering, be specifically related to a kind of one-step method and prepare natural α fertility
Phenol and the method for mixed tocopherol.
Background technology
Natural Vitamin E also known as natural tocopherol, is one of vitamin the earliest of being found of the mankind.Tocopherol be by
Evans et al. nineteen twenty-two finds from wheat malt germ extract, and tocopherol is a kind of material that can affect animal reproduction ability,
So by its named " C antisterility vitamin ".1938, U.S. E.Fernholz elaborated have biological activity in paper
The molecular formula of natural tocopherol.In the same year, P.vonKarrer with H.Fritzsche et al. successfully synthesizes first by the most non-
What enantiomer formed has bioactive tocopherol.The eighties in last century, natural tocopherol started wind in the world
Waste, a lot of countries such as U.S., Germany, the high-purity natural tocopherol production line of the numerous and confused exploitation of Japan oneself.With in development
The raising of national economy level, Tocopherol natural phenolic product is more and more favored by people in recent years.The most natural life at present
There are ADM company of the U.S. and the Henkel company of Germany, annual production 1800 tons in the dominant company educating phenol.
Natural tocopherol is a kind of fatsoluble vitamin, for golden yellow or flaxen sticky oil thing, almost odorless, oxygen
After change, color gradually deepens to brownish red, with the presence of containing a small amount of crystal, its relative density is 0.947-0.950g/cm3。
Tocopherol is the most heat-resisting, the most stable, unstable in the basic conditions, has the metal ion such as ferrum, silver to deposit
Time oxidation accelerate.Tocopherol is dissolved in oils, ethanol, chloroform, acetone and other organic solvent, water insoluble.
The pharmacological action of natural tocopherol, antioxidation, avirulence, safety are obtained for the confirmation of associated mechanisms.
FAO (Food and Agriculture Organization of the United Nation)s (FAO) in 1962 and World Health Organization (WHO) (WHO) food additive committee propose report, it is believed that fertility
Phenol is the fatsoluble vitamin of not excess type, the most not yet finds the phenomenon being poisoned because of superfluous.Within 1985, FDA is to fertility
The edible safety of phenol is approved.Natural tocopherol purposes includes:
1, medicines and health protection aspect: promote people's sex hormone secretion in vivo；Prophylaxis of cancer, prevention of inflammation dermatoses, baldness；
Reduce cholesterol and improve microcirculation, improve lipid metabolism, prevent coronary heart disease；Pre-myopia prevention occurs and development.
2. field of food: tocopherol has higher biological activity and non-oxidizability, does not only have as food additive
Side effect, and the resistance of human body can be provided.
3, cosmetic field: reach the purpose of beauty care, slow down aging by supplementing suitable tocopherol, be in recent years
One fashion pathogenic wind pure and fresh, natural in trend of improving looks.
Tocopherol is widely present in nature, but can only be by phytosynthesis.Tocopherol be present in seed, leaf and
In the green portion of other higher plants.In nature, natural tocopherol mainly includes four kinds of lifes only containing dextrorotation optical isomer
Educate phenol and corresponding tocotrienol thereof.Four kinds of tocopherol monomers are all the derivants of chromane alcohol, according to contained on its phenyl ring
Methyl position sum purpose is different they are respectively designated as α-, β-,γ-, Delta-Tocopherol.Its molecular structural formula is as follows:
The content of each tocopherol, ratio with the kind of plant, the place of production is different and becomes.Such as, the fertility in the little wheat oil of the U.S.
Phenol be α-body be main component, European little wheat oil is then with β-body as main component, and soybean oil is then with δ-body as main component, beautiful
Miyou is then rich in γ-body.In 4 kinds of homologues of natural tocopherol, the biological activity of alpha-tocopherol is the highest and is easiest to absorb.
If the biological activity of alpha-tocopherol is in terms of 100, betatocopherol, the biological activity of gama tocopherol are 50 and 10 respectively, and δ-life
The biological activity educating phenol is only equivalent to 3.Therefore the tocopherol of other forms re-uses after often changing into alpha-tocopherol.Work as oils and fats
When middle tocopherol concentrations is higher (generally greater than 100ppm), the antioxidation order of tocopherol is: Delta-Tocopherol > Gamma-Tocopherol > β-
Tocopherol > alpha tocopherol, wherein Delta-Tocopherol does not affect its oxidation resistance at 180 DEG C, is to continue antioxygen in tocopherol homologues
The one that change ability is the strongest.Therefore, edible oil and fat, bake, the food such as fried use mixed tocopherol as antioxidant.
All there is tocopherol in oil crop such as Semen sojae atricolor, Fructus Tritici aestivi, Fructus Maydis, sunflower seed etc..At oil extraction processes
In, tocopherol is dissolved in oil and extracting together.But their tocopherol content is extremely low, typically less than one thousandth.Plant
In oil, major part tocopherol is retained in deodorization distillate.As far back as the forties in last century, people begin to from vegetable oil deodorized
Distillation extracts the mixed tocopherols of high level, since the eighties, along with people to high-quality healthy living
Pursuing, the market of natural tocopherol constantly expands.Numerous expert, scholar is attracted to be engaged in the preparation work of mixed tocopherols.
The preparation method of mixed tocopherol has at present: solvent extraction, urea complexation, the way of distillation, absorption and ion exchange, chromatography
Method and supercritical extraction.The open plant oil deodorizing distillate of patent CN1401644A, CN1440969A through over-churning, alcoholysis,
The method that freeze and separate, short-path distillation obtain mixed tocopherol finally by extraction or absorption.Patent CN1478776A,
CN1263096A is open uses organic solvent that high content mixed tocopherol is obtained by extraction with low content mixed tocopherol for raw material
Method.Patent CN1253951A, CN1314353A disclose use CO2The side of the method refine mixed tocopherol of supercritical extraction
Method.
Directly extracting the mixed tocopherol obtained from plant oil deodorizing distillate, its biological activity ratio is relatively low, 1mg
The biological activity of the mixed tocopherol concentrated solution of content 50% is 0.15IU, compared with 1mg natural alpha-tocofecol (1.49IU)
Biological activity has 10 times of gaps.The activity of natural tocopherol to be improved, it is important to the content of alpha-tocopherol in tocopherol to be increased.
Generally require on international market that the biological activity of natural tocopherol, at more than 1000IU/g, i.e. requires the sky containing more than 67.1%
So alpha-tocopherol, only high-load natural alpha-tocofecol just have wider application field.
In order to obtain high-load natural alpha-tocofecol, mixing can be made to close non-alpha-fertility in tocopherol by the method for transition
Phenol is converted into alpha-tocopherol.Its basic thought is to take corresponding synthesizing mean to introduce 1-on the chromane ring of non-alpha-tocopherol
2 methyl just can realize the conversion to alpha-tocopherol of the non-alpha-tocopherol.Industrial conventional transformation method includes following several: chlorine
Methylate-reducing process, methylolation-reducing process, formylated-reducing process and amine-methylated-reducing process.Patent CN1253447A is public
Having opened mixed tocopherol is the method that raw material is transformed into high-load alpha-tocopherol through fixed bed.Wherein methylol agent is formaldehyde
Aqueous solution, acid catalyst is benzenesulfonic acid, p-methyl benzenesulfonic acid, boric acid, acetic acid, and hydrogenation catalyst is palladium carbon.
Existing natural alpha-tocofecol preparation technology is properly termed as two-step method.The first step, with plant oil deodorizing distillate be
The mixed tocopherol of high-load prepared by raw material, and second step is converted into highly purified with mixed tocopherol for raw material through chemical reaction
Alpha-tocopherol.The shortcoming of this technique is to use the organic solvent that a large amount of toxicity is higher, easy shadow in mixed tocopherol transformation process
Ring product quality, cause potential safety hazard；In mixed tocopherol, original alpha-tocopherol easily loses in transformation process simultaneously, causes
Unnecessary waste.When additional mixing tocopherol is as high temperature food antioxidant, alpha-tocopherol content height affects it on the contrary to be made
Use effect.It is very important so alpha-tocopherol in mixed tocopherol to be carried out in advance separation, and this part alpha-tocopherol is not
Need to process through transition, it is to avoid the use of toxic solvent, more green, healthy, preferably use as food additive.
Summary of the invention
The invention provides a kind of use hardly organic solvent, environmental protection, safety one-step method prepare natural alpha tocopherol and
The method of mixed tocopherol.
One-step method of the present invention prepares the method for natural alpha tocopherol and mixed tocopherol, comprises the following steps:
(1) esterification: plant oil deodorizing distillate is preheated to 35-40 DEG C, is slowly added to 0.5-1 times of volumes methanol examination
Agent, dropwise reaction liquor capacity 2%-6% concentrated sulphuric acid in stirring state downhill reaction thing, reaction temperature controls 60-70 DEG C, reaction
Time 2-3h；
(2) washing: add hot wash in above-mentioned reactant liquor, to aqueous pH values more than 5.0, stratification discards water
Phase；
(3) dissolution filter: add the low-alcohol solution of 0.2-1 times of volume in organic facies, be cooled to 5-25 DEG C, filter
Tocopherol lysate；
(4) absorption:
A the fluidised bed adsorption of () lysate: the tocopherol lysate of 5-12 times of column volume is placed in fluidised bed adsorption 2-6h, receives
Collection absorption waste liquid；
B () is containing the dynamic adsorption of alpha-tocopherol absorption waste liquid: the absorption waste liquid that step (a) is collected flows with 0.2-0.8BV/h
Speed enters post dynamic adsorption；
(5) desorption: be passed through low-alcohol solution respectively in the resin column of (a) and (b), control low-alcohol solution in resin column
0.2-0.8 times of column volume of volume, is passed through CO2Gas 1-2h, collects eluent in resin column, continues to be passed through low-alcohol solution eluting
To colourless, obtain eluent；
(6) distillation: the eluent thin film obtained (a) and (b) respectively distills, and obtains mixed tocopherol and α-fertility
The concentrated solution of phenol, then carries out short-path distillation, vacuum respectively to gained mixed tocopherol concentrated solution and alpha-tocopherol concentrated solution
For 1pa, vapo(u)rizing temperature is 180-230 DEG C, i.e. can get mixed tocopherol and alpha-tocopherol.
In described step (1), in plant oil deodorizing distillate, vegetable oil is Oleum Glycines, Semen Maydis oil, Semen Tritici aestivi germ oil, Oleum Brassicae campestris
Or the compositions of one or more in olive oil.
Described step (1) methanol addition is 0.6-0.8 times of volume, and reaction temperature is 66-68 DEG C.
In described step (3), tocopherol course of dissolution lower alcohol usage amount is 0.3-0.5 times of volume, and lysate is cooled to 8-
10℃。
Described lower alcohol is one or several the combination in methanol, ethanol or isopropanol.
In described step (5) in (a) during tocopherol lysate fluidised bed adsorption, lysate volume is 8-10 times of column volume,
The fluidised bed adsorption time is 3-4h；In described (b), absorption waste liquid dynamic adsorption flow velocity is 0.3-0.6BV/h.
In described step (5), in resin column, low-alcohol solution volume is 0.3-0.4 times of column volume.
Described step (6) medium or short range vapo(u)rizing temperature is 190-200 DEG C.
Compared with prior art, it is an advantage of the current invention that:
1, alpha-tocopherol prepared by the present invention is by extracting directly in absorption waste liquid, without isomerization, from all
On stopped the residual of toxic organic solvents, more green compared with traditional handicraft, healthy, with meeting new food additive
Requirement.
2, in mixed tocopherol prepared by the present invention, alpha-tocopherol content significantly reduces, and is more suitable for high temperature food antioxygen
Agent uses.
3, the alpha-tocopherol purity that prepared by the present invention can reach 90%, mixed tocopherol content more than 95%, production process
Short, product quality is high.
4, production process use equipment few, simple to operate, resin can Reusability, reduce production cost, easily produce in batches.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
One-step method prepares the method for natural alpha tocopherol and mixed tocopherol, comprises the following steps:
(1) esterification: take soybean deodorized sludge 1Kg and be preheated to 40 DEG C, is slowly added to 700ml methanol reagent, stirs feelings
Dripping 5% concentrated sulphuric acid in condition downhill reaction thing, reaction temperature controls at 66-68 DEG C, and the response time is 3h；
(2) washing: add 80-85 DEG C of hot water in above-mentioned reactant liquor, washs to aqueous pH values more than 5.0, stratification
Aqueous phase discarded；
(3) dissolution filter: add 500ml ethanol solution, stirring, slow cooling to 10 DEG C in organic facies, stand 2h, cloth
Family name's funnel sucking filtration obtains tocopherol lysate 1640ml；
(4) absorption:
The fluidised bed adsorption of (a) lysate: 1# resin column loads 200ml strong-base anion-exchange resin, configuration
600ml1mol/L sodium hydroxide solution is with 1BV/h flow velocity washing resin, and then deionized water rinsing resin is to resin effluent pH
Value 7-8；Configuration 600ml1mol/L hydrochloric acid solution is with 1BV/h flow velocity washing resin, and then deionization washing rinses resin to resin
Effluent pH value 4-5；Configuration 600ml1mol/L sodium hydroxide solution is with 1BV/h flow velocity washing resin, and then deionization washing is rushed
Wash resin to resin effluent pH value 7-8；In 95% ethanol solution displacement resin, water stops to resin effluent concentration of alcohol 92%
Only displacement, adsorption time 3.5h, collects absorption waste liquid 1750ml；
B () is containing the dynamic adsorption of alpha-tocopherol absorption waste liquid: 2# resin column loads 200ml strong alkalinity anion exchange tree
Fat, configuration 600ml1mol/L sodium hydroxide solution is with 1BV/h flow velocity washing resin, and then deionized water rinsing resin is to resin
Effluent pH value 7-8；Configuration 600ml1mol/L hydrochloric acid solution is with 1BV/h flow velocity washing resin, and then tree is rinsed in deionization washing
Fat is to resin effluent pH value 4-5；Configuration 600ml1mol/L sodium hydroxide solution with 1BV/h flow velocity washing resin, then go from
Son washing rinses resin to resin effluent pH value 7-8；In 95% ethanol solution displacement resin, water is dense to resin effluent ethanol
Degree 90% stopping displacement；Absorption waste liquid step (a) collected enters post dynamic adsorption with 0.4BV/h flow velocity；
(5) desorption: after having adsorbed, is passed through fresh ethanol solution respectively in 1#, 2# resin column, controls in resin column
Volumes of aqueous ethanol 60-80ml, is passed through CO2Gas 2h, collects eluent in resin column, continues to be passed through ethanol solution and is eluted to stream
The ethanol elution gone out is colourless, obtains eluent；
(6) distillation: the eluent thin film obtained (a) and (b) respectively distills, and obtains mixed tocopherol and α-fertility
The concentrated solution of phenol, then carries out short-path distillation, vacuum respectively to gained mixed tocopherol concentrated solution and alpha-tocopherol concentrated solution
For 1pa, vapo(u)rizing temperature is 190-200 DEG C, i.e. can get mixed tocopherol and alpha-tocopherol.
Product checking result is as follows:
HPLC detects alpha-tocopherol purity 92%, content 91%；Mixed tocopherol alpha-tocopherol purity 2.7%, content
96.4%；Total recovery 89.5%.
Embodiment 2
One-step method prepares the method for natural alpha tocopherol and mixed tocopherol, comprises the following steps:
(1) esterification: take Semen Maydis oil deodorization distillate 1Kg and be preheated to 40 DEG C, be slowly added to 500ml methanol reagent, stirring
In the case of in reactant, drip 2% concentrated sulphuric acid, reaction temperature controls at 60-64 DEG C, and the response time is 3h；
(2) washing: add 80-85 DEG C of hot water in above-mentioned reactant liquor, washs to aqueous pH values more than 5.0, stratification
Aqueous phase discarded；
(3) dissolution filter: add 200ml ethanol solution, stirring, slow cooling to 5 DEG C in organic facies, stand 2h, cloth
Family name's funnel sucking filtration obtains tocopherol lysate 1240ml；
(4) absorption:
The fluidised bed adsorption of (a) lysate: 1# resin column loads 250ml strong-base anion-exchange resin, configuration
750ml1mol/L sodium hydroxide solution is with 1BV/h flow velocity washing resin, and then deionized water rinsing resin is to resin effluent pH
Value 7-8；Configuration 750ml1mol/L hydrochloric acid solution is with 1BV/h flow velocity washing resin, and then deionization washing rinses resin to resin
Effluent pH value 4-5；Configuration 750ml1mol/L sodium hydroxide solution is with 1BV/h flow velocity washing resin, and then deionization washing is rushed
Wash resin to resin effluent pH value 7-8；In 95% ethanol solution displacement resin, water stops to resin effluent concentration of alcohol 90%
Only displacement, adsorption time 2h, collects absorption waste liquid 1480ml；
B () is containing the dynamic adsorption of alpha-tocopherol absorption waste liquid: 2# resin column loads 200ml strong alkalinity anion exchange tree
Fat, configuration 600ml1mol/L sodium hydroxide solution is with 1BV/h flow velocity washing resin, and then deionization washing rinses resin to tree
Fat effluent pH value 7-8；Configuration 600ml1mol/L hydrochloric acid solution is with 1BV/h flow velocity washing resin, and then deionization washing is rinsed
Resin is to resin effluent pH value 4-5；Configuration 600ml1mol/L sodium hydroxide solution, with 1BV/h flow velocity washing resin, then goes
Ion washing rinses resin to resin effluent pH value 7-8；In 95% ethanol solution displacement resin, water is to resin effluent ethanol
Concentration 90% stops displacement；Absorption waste liquid step (a) collected enters post dynamic adsorption with 0.2BV/h flow velocity；
(5) desorption: after having adsorbed, is passed through methanol solution respectively in 1#, 2# resin column, and in controlling resin column, methanol is molten
Liquid amasss 20ml-40ml, is passed through CO2Gas 2h, collects eluent in resin column, continues to be passed through ethanol solution and is eluted to outflow
Ethanol elution is colourless, obtains eluent；
(6) distillation: the eluent thin film obtained (a) and (b) respectively distills, and obtains mixed tocopherol and α-fertility
The concentrated solution of phenol, then carries out short-path distillation, vacuum respectively to gained mixed tocopherol concentrated solution and alpha-tocopherol concentrated solution
For 1pa, vapo(u)rizing temperature is 180-190 DEG C, i.e. can get mixed tocopherol and alpha-tocopherol.
Product checking result is as follows:
HPLC detects alpha-tocopherol purity 91%, content 91.4%；Mixed tocopherol alpha-tocopherol purity 4%, content
92.6%；Total recovery 83.8%.
Embodiment 3
One-step method prepares the method for natural alpha tocopherol and mixed tocopherol, comprises the following steps:
(1) esterification: take rapeseed oil deodorized distillate 700g, olive oil deodorization distillate 300g is preheated to 35 DEG C, slowly
Adding 1000ml methanol reagent, drip 6% concentrated sulphuric acid in stirring state downhill reaction thing, reaction temperature controls at 68-70 DEG C, instead
It is 2h between Ying Shi；
(2) washing: add 80-85 DEG C of hot water in above-mentioned reactant liquor, washs to aqueous pH values more than 5.0, stratification
Aqueous phase discarded；
(3) dissolution filter: add 1000ml ethanol solution, stirring, slow cooling to 25 DEG C in organic facies, stand 2h,
Buchner funnel sucking filtration obtains tocopherol lysate 2404ml；
(4) absorption:
The fluidised bed adsorption of (a) lysate: 1# resin column loads 200ml strong-base anion-exchange resin, configuration
600ml1mol/L sodium hydroxide solution is with 1BV/h flow velocity washing resin, and then deionization washing rinses resin to resin effluent
PH value 7-8；Configuration 600ml1mol/L hydrochloric acid solution is with 1BV/h flow velocity washing resin, and then deionization washing rinses resin to tree
Fat effluent pH value 4-5；Configuration 600ml1mol/L sodium hydroxide solution is with 1BV/h flow velocity washing resin, and then deionization is washed
Rinse resin to resin effluent pH value 7-8；In 95% ethanol solution displacement resin, water is to resin effluent concentration of alcohol 90%
Stop displacement, adsorption time 6h, collect absorption waste liquid 2500ml；
B () is containing the dynamic adsorption of alpha-tocopherol absorption waste liquid: 2# resin column loads 200ml strong alkalinity anion exchange tree
Fat, configuration 600ml1mol/L sodium hydroxide solution is with 1BV/h flow velocity washing resin, and then deionization washing rinses resin to tree
Fat effluent pH value 7-8；Configuration 600ml1mol/L hydrochloric acid solution is with 1BV/h flow velocity washing resin, and then deionization washing is rinsed
Resin is to resin effluent pH value 4-5；Configuration 600ml1mol/L sodium hydroxide solution, with 1BV/h flow velocity washing resin, then goes
Ion washing rinses resin to resin effluent pH value 7-8；In 95% ethanol solution displacement resin, water is to resin effluent ethanol
Concentration 90% stops displacement；The absorption waste liquid that step (a) is collected enters post dynamic adsorption with 0.8BV/h flow velocity；
(5) desorption: after adsorb, be passed through fresh methanol respectively in 1#, 2# resin column: ethanol (1:1) solution, controls
Resin column inner volume processed, than for the methanol of 1:1 and the mixed liquor volume 160ml of ethanol, is passed through CO2Gas 1h, collects resin column
Interior eluent, continues to be passed through the ethanol elution that ethanol solution is eluted to flow out colourless, obtains eluent；
(6) distillation: the eluent thin film obtained (a) and (b) respectively distills, and obtains mixed tocopherol and α-fertility
The concentrated solution of phenol, then carries out short-path distillation, vacuum respectively to gained mixed tocopherol concentrated solution and alpha-tocopherol concentrated solution
For 1pa, vapo(u)rizing temperature is 190-200 DEG C, i.e. can get mixed tocopherol and alpha-tocopherol.
Product checking result is as follows:
HPLC detects alpha-tocopherol purity 88%, content 89.1%；Mixed tocopherol alpha-tocopherol purity 2.9%, content
93.2%；Total recovery 86.1%.
Embodiment 4
One-step method prepares the method for natural alpha tocopherol and mixed tocopherol, comprises the following steps:
(1) esterification: take rapeseed oil deodorized distillate 1Kg and be preheated to 35 DEG C, is slowly added to 1000ml methanol reagent, stirring
In the case of in reactant, drip 4% concentrated sulphuric acid, reaction temperature controls at 68-70 DEG C, and the response time is 2h；
(2) washing: add 80-85 DEG C of hot water in above-mentioned reactant liquor, washs to aqueous pH values more than 5.0, stratification
Aqueous phase discarded；
(3) dissolution filter: add 1000ml ethanol solution, stirring, slow cooling to 25 DEG C in organic facies, stand 2h,
Buchner funnel sucking filtration obtains tocopherol lysate 2384ml；
(4) absorption:
The fluidised bed adsorption of (a) lysate: 1# resin column loads 200ml strong-base anion-exchange resin, configuration
600ml1mol/L sodium hydroxide solution is with 1BV/h flow velocity washing resin, and then deionization washing rinses resin to resin effluent
PH value 7-8；Configuration 600ml1mol/L hydrochloric acid solution is with 1BV/h flow velocity washing resin, and then deionization washing rinses resin to tree
Fat effluent pH value 4-5；Configuration 600ml1mol/L sodium hydroxide solution is with 1BV/h flow velocity washing resin, and then deionization is washed
Rinse resin to resin effluent pH value 7-8；In 95% ethanol solution displacement resin, water is to resin effluent concentration of alcohol 90%
Stop displacement, adsorption time 6h, collect absorption waste liquid 2500ml；
B () is containing the dynamic adsorption of alpha-tocopherol absorption waste liquid: 2# resin column loads 200ml strong alkalinity anion exchange tree
Fat, configuration 600ml1mol/L sodium hydroxide solution is with 1BV/h flow velocity washing resin, and then deionization washing rinses resin to tree
Fat effluent pH value 7-8；Configuration 600ml1mol/L hydrochloric acid solution is with 1BV/h flow velocity washing resin, and then deionization washing is rinsed
Resin is to resin effluent pH value 4-5；Configuration 600ml1mol/L sodium hydroxide solution, with 1BV/h flow velocity washing resin, then goes
Ion washing rinses resin to resin effluent pH value 7-8；In 95% ethanol solution displacement resin, water is to resin effluent ethanol
Concentration 90% stops displacement；The absorption waste liquid that step (a) is collected enters post dynamic adsorption with 0.8BV/h flow velocity；
(5) desorption: after having adsorbed, be passed through fresh methanol respectively in 1#, 2# resin column: isopropanol (volume ratio 1:
1) solution, controls resin column inner volume ratio for the methanol of 1:1 and the mixed liquor volume 140ml of ethanol, is passed through CO2Gas 1h,
Collect eluent in resin column, continue to be passed through the ethanol elution that ethanol solution is eluted to flow out colourless, obtain eluent；
(6) distillation: the eluent thin film obtained (a) and (b) respectively distills, and obtains mixed tocopherol and α-fertility
The concentrated solution of phenol, then carries out short-path distillation, vacuum respectively to gained mixed tocopherol concentrated solution and alpha-tocopherol concentrated solution
For 1pa, vapo(u)rizing temperature is 210-220 DEG C, i.e. can get mixed tocopherol and alpha-tocopherol.
Product checking result is as follows:
HPLC detects alpha-tocopherol purity 88%, content 89.4%；Mixed tocopherol alpha-tocopherol purity 3.4%, content
94.2%；Total recovery 86.1%.
Claims (6)
1. the method that an one-step method prepares natural alpha tocopherol and mixed tocopherol, it is characterised in that comprise the following steps:
(1) esterification: plant oil deodorizing distillate is preheated to 35-40 DEG C, is slowly added to 0.5-1 times of volumes methanol reagent, stirs
In the case of mixing in reactant dropwise reaction liquor capacity 2%-6% concentrated sulphuric acid, reaction temperature control 60-70 DEG C, the response time
2-3h；
(2) washing: add hot wash in above-mentioned reactant liquor, to aqueous pH values more than 5.0, stratification aqueous phase discarded；
(3) dissolution filter: add the low-alcohol solution of 0.2-1 times of volume in organic facies, be cooled to 5-25 DEG C, filters to obtain fertility
Phenol lysate；
(4) absorption:
A the fluidised bed adsorption of () lysate: the tocopherol lysate of 5-12 times of column volume is placed in fluidised bed adsorption 2-6h, collects and inhales
Attached waste liquid；
B () is containing the dynamic adsorption of alpha-tocopherol absorption waste liquid: the absorption waste liquid that step (a) is collected enters with 0.2-0.8BV/h flow velocity
Post dynamic adsorption；
(5) desorption:
Being passed through low-alcohol solution in the fluid bed of (a), controlling low-alcohol solution volume is 0.2-0.8 times of fluid bed volume, logical
Enter CO2Gas 1-2h, collects eluent in fluid bed, continues to be passed through low-alcohol solution and be eluted to colourless, obtain eluent；
In (b) resin column, each lead into low-alcohol solution, control 0.2-0.8 times of column volume of low-alcohol solution volume, be passed through CO2
Gas 1-2h, collects eluent in resin column, continues to be passed through low-alcohol solution and be eluted to colourless, obtain eluent；
(6) distillation: the eluent obtained (a) and (b) respectively distills, and obtains the concentration of mixed tocopherol and alpha-tocopherol
Liquid, then carries out short-path distillation respectively to gained mixed tocopherol concentrated solution and alpha-tocopherol concentrated solution, and vacuum is 1Pa, steams
Evaporate temperature and be 180-230 DEG C, i.e. can get mixed tocopherol and alpha-tocopherol；
Low-alcohol solution described in above-mentioned steps is the one in methanol solution, ethanol solution or aqueous isopropanol or several
The combination planted.
One-step method the most according to claim 1 prepares the method for natural alpha tocopherol and mixed tocopherol, it is characterised in that
Described in step (1), in plant oil deodorizing distillate, vegetable oil is Oleum Glycines, Semen Maydis oil, Semen Tritici aestivi germ oil, Oleum Brassicae campestris or olive oil
In the compositions of one or more.
One-step method the most according to claim 1 prepares the method for natural alpha tocopherol and mixed tocopherol, it is characterised in that
Described step (1) methanol addition is 0.6-0.8 times of volume, and reaction temperature is 66-68 DEG C.
One-step method the most according to claim 1 prepares the method for natural alpha tocopherol and mixed tocopherol, it is characterised in that
In step (3), tocopherol course of dissolution low-alcohol solution usage amount is 0.3-0.5 times of volume, and lysate is cooled to 8-10 DEG C.
One-step method the most according to claim 1 prepares the method for natural alpha tocopherol and mixed tocopherol, it is characterised in that
Described in step (4) in (a) during tocopherol lysate fluidised bed adsorption, lysate volume is 8-10 times of column volume, and fluid bed is inhaled
The attached time is 3-4h；In described (b), absorption waste liquid dynamic adsorption flow velocity is 0.3-0.6BV/h.
One-step method the most according to claim 1 prepares the method for natural alpha tocopherol and mixed tocopherol, it is characterised in that
Step (6) medium or short range vapo(u)rizing temperature is 190-200 DEG C.
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| CN102432584A (en) * | 2011-10-27 | 2012-05-02 | 中粮天科生物工程(天津)有限公司 | Method for preparing high-purity natural vitamin E monomers by separating mixed tocopherol |
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| CN101475557A (en) * | 2009-02-10 | 2009-07-08 | 中粮集团有限公司 | Preparation of high purity and high optical rotation mixing vitamin E |
| CN101643467A (en) * | 2009-09-14 | 2010-02-10 | 天津大学 | Method for extracting vitamin E and phytosterin from cottonseed oil deodorizer distillate |
| CN102382095A (en) * | 2011-09-22 | 2012-03-21 | 浙江华源制药科技开发有限公司 | Method for separating and mixing d-alpha-tocopherol in tocopherol by utilizing resin adsorption method |
| CN102432584A (en) * | 2011-10-27 | 2012-05-02 | 中粮天科生物工程(天津)有限公司 | Method for preparing high-purity natural vitamin E monomers by separating mixed tocopherol |
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