CN1034367A - The technology of separating VE from foots of refining vegetable oil - Google Patents
The technology of separating VE from foots of refining vegetable oil Download PDFInfo
- Publication number
- CN1034367A CN1034367A CN 87106187 CN87106187A CN1034367A CN 1034367 A CN1034367 A CN 1034367A CN 87106187 CN87106187 CN 87106187 CN 87106187 A CN87106187 A CN 87106187A CN 1034367 A CN1034367 A CN 1034367A
- Authority
- CN
- China
- Prior art keywords
- vitamin
- esterification
- out under
- technical process
- carried out
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000007670 refining Methods 0.000 title claims abstract description 23
- 235000015112 vegetable and seed oil Nutrition 0.000 title claims abstract description 16
- 239000008158 vegetable oil Substances 0.000 title claims abstract description 16
- 210000002683 foot Anatomy 0.000 title claims abstract description 8
- 238000005516 engineering process Methods 0.000 title description 5
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims abstract description 157
- 229930003427 Vitamin E Natural products 0.000 claims abstract description 75
- 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 claims abstract description 75
- 239000011709 vitamin E Substances 0.000 claims abstract description 75
- 235000019165 vitamin E Nutrition 0.000 claims abstract description 75
- 229940046009 vitamin E Drugs 0.000 claims abstract description 75
- 230000032050 esterification Effects 0.000 claims abstract description 49
- 238000005886 esterification reaction Methods 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 26
- 238000000605 extraction Methods 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000004458 analytical method Methods 0.000 claims abstract description 20
- 238000010521 absorption reaction Methods 0.000 claims abstract description 10
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000741 silica gel Substances 0.000 claims abstract description 7
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 15
- 239000012043 crude product Substances 0.000 claims description 10
- 150000002632 lipids Chemical class 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003957 anion exchange resin Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000010773 plant oil Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- 230000035622 drinking Effects 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 13
- 235000019198 oils Nutrition 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 6
- 235000013311 vegetables Nutrition 0.000 abstract description 6
- 235000013305 food Nutrition 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- 229930003799 tocopherol Natural products 0.000 description 9
- 239000011732 tocopherol Substances 0.000 description 9
- 229960001295 tocopherol Drugs 0.000 description 7
- 235000010384 tocopherol Nutrition 0.000 description 7
- 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 description 7
- 229960004756 ethanol Drugs 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 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 5
- 239000006227 byproduct Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 229940088594 vitamin Drugs 0.000 description 4
- 229930003231 vitamin Natural products 0.000 description 4
- 235000013343 vitamin Nutrition 0.000 description 4
- 239000011782 vitamin Substances 0.000 description 4
- 150000003722 vitamin derivatives Chemical class 0.000 description 4
- 238000005349 anion exchange Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000002255 enzymatic effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 optionally shift Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000011731 tocotrienol Substances 0.000 description 3
- 229930003802 tocotrienol Natural products 0.000 description 3
- 229940068778 tocotrienols Drugs 0.000 description 3
- 235000019148 tocotrienols Nutrition 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 125000002640 tocopherol group Chemical class 0.000 description 2
- 235000019149 tocopherols Nutrition 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PZZKGQBMBVYPGR-UHFFFAOYSA-N η-tocopherol Chemical compound OC1=C(C)C=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 PZZKGQBMBVYPGR-UHFFFAOYSA-N 0.000 description 2
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 240000006891 Artemisia vulgaris Species 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 235000003228 Lactuca sativa Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 244000300264 Spinacia oleracea Species 0.000 description 1
- 235000009337 Spinacia oleracea Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical compound C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000000287 crude extract Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 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
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 230000003863 physical function Effects 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003611 tocopherol derivatives Chemical class 0.000 description 1
- 239000010497 wheat germ oil Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of technical process of separating VE from the low foots of refining vegetable oil of content of vitamin E belongs to the comprehensive utilization field of vegetable oil material crop.Technical process of the present invention is by slightly carrying and making with extra care and form, thick bag is drawn together esterification, washing, vacuum distilling, secondary esterification, secondary water washing, secondary vacuum distillation, extraction and cold analysis, and handle refining comprising with silica gel adsorption column absorption with anionite-exchange resin.The present invention can obtain concentration from the vegetables oil dregs of fat be 50～60% vitamin-E, and the vitamin-E of this kind concentration can be widely used in medicine, food and the fodder industry.Technical process of the present invention is simple, and economic benefit is obvious.
Description
The present invention is the technology of separating VE from foots of refining vegetable oil, belongs to the comprehensive utilization field of vegetable oil material crop.
Vitamin-E is the general name of seven kinds of tocopherol compounds, comprises that α, β, δ, ε, τ, η tocopherol and α, β, four kinds of tocopherols of γ, δ take off H
2The derivative tocotrienols.In the vegetables oil (as cotton oil, soybean oil, Semen Maydis oil) particularly in the wheat germ oil, the content of vitamin-E is the abundantest.Vitamin-E (having another name called tocopherol) has many important physical functions.They all are chroman alcohol derivate, in being present in vegetables oil, also be present in widely on (as spinach, wormwood artemisia lettuce leaf etc.) in the green plants.But the content of vitamin-E is lower in general animality and the plant food source.Therefore wish to develop an effective way of from vegetables oil, extracting vitamin-E, to satisfy the demand in market.
Vegetables oil such as soybean oil, peanut oil, cottonseed wet goods will be at the pressure of 2～5mmHg through after depickling, the decolouring, and temperature is used the steam distillation deodorization down for 230 ℃, and cat head distilled low boiler cut-dregs of fat are the good sources of extracting vitamin-E.This in the past dregs of fat are at most its saponification to be handled make thick soap generally as waste disposal, it are not developed and utilized.
The clear 59-5179 of day disclosure special permission communique has described the overhead product based on lipid acid that obtains from the deodorization tower in the refining engineering of plam oil, its composition also comprises the bigger carbohydrate of stearic acid equimolecular quantity, stearic class and neutral lipid, and the concentration of tocopherol in the overhead product and tocotrienols class is 0.2～0.4%(weight).Utilize underpressure distillation, remove lipid acid, system pressure 2～20mmHg, about 200 ℃ of temperature, the lipid acid in the residue is fully distillated.Adopt lower alcohol earlier if give, for example the aforementioned overhead products of esterification such as methyl alcohol, ethanol, propyl alcohol remove lipid acid easily.Enzymatic synthesis condition is in the presence of the catalyst vitriolic, carries out under the temperature about 100 ℃.To add polar organic solvent through the resulting residue of underpressure distillation, and make the tocopherol and the tocotrienols class that contain in the distillation residue in polar organic solvent, optionally shift, concentrate, reach the purpose of extraction.And to the separation of vitamin-E in the vegetable oil refining by product, existing patent report adopts the saponification route more.Report vegetable oil residue that vegetable oil refining process deodorization procedures produces among the clear 59-212486 of day disclosure special permission communique through depickling, the combination of taking off extraction steps such as steroide and molecular distillation, obtained tocopherol content and be 30～80% product.And then adopt the ion exchange column of chlorine-based strong alkali anionite-exchange resin filling, utilize above-mentioned resin to the special adsorptivity of tocopherols to reach isolating purpose.And can utilize its difference to the tocopherol homologues adsorptive power, obtain the separation of vitamin-E homologue and refining.Above-mentioned patent has suitability separately, and all can not be used for handling the vegetables oil dregs of fat of low vitamin e content, the whole process that they neither the separation and Extraction vitamin-E.
The objective of the invention is to develop from the lower vegetable oil refining oil dregs of fat of content of vitamin E, the whole process of separation and Extraction vitamin-E is determined the processing condition that it is concrete, so that be used for handling the lower vegetable oil refining oil dregs of fat of content of vitamin E.
The present invention is a kind of technical process of separating VE from the low foots of refining vegetable oil of content of vitamin E, slightly carry and refining two portions are formed by vitamin-E, when the content of vitamin-E in the foots of refining vegetable oil less than 1% the time, thick bag is drawn together esterification, washing, vacuum distilling, the secondary esterification, washing, secondary vacuum distillation, extraction and cold analysis; Then the crude extract that contains vitamin e1 about 0% is made with extra care, this process comprises with silica gel adsorption column and adsorbs and use anion exchange process, also can only use anion exchange process in refining.This technical process as shown in Figure 1.Each unit is respectively in the accompanying drawing 1: 1. esterification; 2. washing; 3. vacuum distilling; 4. secondary esterification; 5. washing; 6. vacuum distilling; 7. solvent extraction; 8. cold analysis; 9. silica gel adsorption column; 10. ion exchange column.Entering 1 logistics is the material plant dregs of fat; The logistics of coming out from Unit 3,6 is a by product mixed fatty acid fat; From 8 come out discard for precipitate; From 10 come out for the vitamin-E product.
1 pair of this technical process is elaborated in conjunction with the accompanying drawings now.
(1) esterification: the refined plant oil dregs of fat at first will carry out esterification, esterification can be adopted methyl alcohol or ethanol, and the amount that adds ethanol or methyl alcohol is for calculating 4～5 times of corresponding fatty acid content, 60～80 ℃ of esterification temperatures according to acid number, esterification time 4 hours carries out in the mode of reflux.
(2) washing: will repeatedly wash with 60～70 ℃ warm water through the esterification products that esterification obtained, be washed till washing water and be till the neutrality.Attention water will be tried one's best from oil phase and be separated totally.
(3) vacuum distilling: will under 1～5mmHg, carry out vacuum distilling through the esterification products after the washing, and take fractionated way.Cut below 190 ℃ is as by product mixed fatty acid fat, and the cut of getting 190～230 ℃ is as the vitamin-E crude product.
(4) secondary esterification vitamin-E crude product, enzymatic synthesis condition is with an esterification.
(5) product of secondary water washing secondary esterification, condition with once wash identical.
(6) esterification products after the secondary vacuum distillation secondary water washing, condition is got 190 ℃ of following fractions as the vitamin-E crude product with a vacuum distilling.
(7) solvent extraction: make extraction agent with methyl alcohol or methyl alcohol-acetone, the vitamin-E in the crude product is extracted.
(8) cold analysis: extraction liquid is placed on cold analysis under the refrigerator (10 ℃～-20 ℃), precipitate is filtered remove, obtain the spissated clear liquid of vitamin-E.
(9) absorption:, reach concentrating and making with extra care to vitamin-E with silicagel column hanging column, drip washing, enrichment under the flow velocity that 1～2ml/ divides.Through condition experiment, eluent is that the volume ratio of normal hexane/dehydrated alcohol is 10: 2 a solvent.
(10) ion-exchange: spissated vitamin-E is further carried dense and refining with strongly basic anion exchange resin.The operation of ion exchange column will be passed through steps such as transition, regeneration, hanging column, wash-out.
In above-mentioned technical process, also can save absorption, promptly in treating process, only adopt anion exchange process, all the other technical process are all identical with above-mentioned flow process with processing condition.
Can remove secondary esterification, washing and secondary vacuum distillation procedure to the dregs of fat of content of vitamin E about 1%.Reduce its corresponding art breading link, content of vitamin E still can reach about 10% after extraction and cold analysis.Can directly handle after cold analysis is handled in this technology, can reach the requirement of product concentration equally through ion exchange resin column.Its technical process as shown in Figure 2.Each unit is respectively in the accompanying drawing 2: 1. esterification; 2. washing; 3. vacuum distilling; 4. solvent extraction; 5. cold analysis; 6. ion exchange column.Entering 1 logistics is the material plant dregs of fat; The logistics of coming out from Unit 3 is a by product mixed fatty acid fat; From 5 come out discard for precipitate; From 6 come out for the vitamin-E product.Listed processing condition are identical in the detailed description of the processing condition of each step and accompanying drawing 1.
Use technical process provided by the invention, can be from the refined plant of the low levels vitamin-E oil dregs of fat, finally extract concentration and be 50～60% vitamin-E.The vitamin-E of this kind concentration can be widely used in medicine, food and the fodder industry.Why reach effect like this, be because in each step, fully taken into account vitamin-E with its difference of various other materials on physicochemical property of mixing mutually, taked effective processing condition.
The content of vitamin-E generally is lower than 1% in the refined vegetable oil slag, vacuum distillation method is to utilize vitamin-E to separate with the difference of the separation factor of other impurity (mainly being lipid acid), after esterification operation owing to the esterification of lipid acid, making impurity steam temperature reduces, not only lowered energy consumption, but also can obtain the mixed aliphatic ester that another kind has the essential industry using value, as by-product recovery.
Solvent extraction is to utilize methyl alcohol and the methyl alcohol-acetone mixed solution selected that the optionally different of vitamin-E and impurity solubleness are reached isolating.
Cold analysis is to utilize impurity such as hydrocarbon partial, the fatty acid ester solubleness in organic solvent when low temperature to reduce, thereby separates out.And the vitamin-E solubility change is very little, thereby reaches concentrated.Through above-mentioned steps, the concentration of vitamin-E in sample can reach more than 10%.
Silica gel adsorption column is based on the difference of vitamin-E and impurity composition adsorptive power and carries out the isolating of mixture.Be usually used in from big quantity of material, extracting some a spot of useful component.When moving phase moved, solute molecule reversibly was adsorbed onto on the activity site of stationary phase.Different molecules is because the strong and weak degree difference that they are adsorbed when drip washing, has produced difference on translational speed.Make the moving phase of resolving have different main ingredients, concentrate thereby realize separating at different sections.
Ion-exchange is to utilize strongly basic anion exchange resin (slightly acidic OH) has stronger exchange capacity of absorption and carries out isolating to the hydroxyl on tocopherol and the tocotrienols.Resin after washing, transition, the solvent exchange, carries out hanging column through alkali cleaning.The wash-out absorbed component vitamin-E of wash-out absorption more not is standby after the regenerating resin after cleaning post then.Wash-out not absorbed component adopts dehydrated alcohol, and the drip washing vitamin-E adopts the ethanol of 10: 1 volume ratios and the elutriant that mixes of acetate.
It is as follows to enumerate embodiment now:
Embodiment 1: 280g carries out esterification with foots of refining vegetable oil (content of vitamin E is 0.5%), 850 milliliters of methanol usage, 60～80 ℃ of esterification temperatures, esterification time 4 hours, get methyl esters sample 3Hg, acid number 9.37 is washed to PH=7, carries out vacuum distilling then, vacuum tightness is about the 1mmHg post, 190～230 ℃ of fractions are got in fractionation, and this section cut content of vitamin E is 4.14%, and acid number is 105.7.There this is had the valency cut carry out secondary esterification enzymatic synthesis condition to be the same, obtains esterification sample 43g, carries out the secondary vacuum distillation then, and vacuum tightness is 1mmHg, distillates the cut below 190 ℃.Residual fraction content of vitamin E 7.61%, heavy 29g.Vitamin-E sample to 7.61% extracts (on a small quantity repeatedly) with methyl alcohol, shared extraction agent 400ml.The solution that is dissolved in methyl alcohol partly places-10 ℃ refrigerator and cooled to analyse a night, and the elimination precipitate removes the solvent steaming.Obtain vitamin-E sample 14.5g, content of vitamin E 15.67% is used the strongly basic anion exchange resin hanging column, after the wash-out, obtains the sample 2.1g of content of vitamin E 59.4%.
Embodiment 2. carry out ethyl esterization with the dregs of fat (containing vitamin-E about 0.5%) 243g with 110ml ethanol, and 80 ℃ of esterification temperatures, esterification time are 4 hours, gets ethyl ester sample 310g, acid number 5.43.With 70 ° of water washings to PH=7.Carry out vacuum distilling then.Vacuum tightness is controlled in still-process in the scope of 1～5mmHg, and fractionation is steamed and got 195 ℃～230 ℃ cut, and this boiling range content of vitamin E is 3.13%, acid number 98.7.This there is the valency cut carry out secondary esterification (technology is the same) and vacuum distilling (processing condition are the same), steams the cut below 195 ℃.Get residual fraction 32g, content of vitamin E is 6.24%.Vitamin-E sample to 6.24% is made extraction agent with methyl alcohol and 3: 7 mixed solution of acetone, repeatedly extracts on a small quantity, and the extraction agent consumption is 450ml, then extraction phase is carried out cold analysis, the cold analysis temperature is-10 ℃, the elimination precipitate, steam solvent, obtain the sample that 9g contains vitamin e1 4.1%.After silicagel column is handled, obtain containing the sample 2.5g of vitamin-E 30.4%, use the strongly basic anion exchange resin hanging column, after the wash-out, obtain the sample of content of vitamin E 75%.
Embodiment 3. carry out ethyl esterization with the dregs of fat (containing about vitamin e1 .4%) 500g with 300ml ethanol, 80 ℃ of esterification temperatures, and esterification time is 4 hours, obtains ethyl ester sample 642g.Under vacuum tightness 1mmHg, carry out vacuum distilling, obtain 195～230 ℃ cut 62g, wherein content of vitamin E 12.3%, with 3: 7 acetone-methyl alcohol mixed liquors repeatedly extract, the extraction agent consumption is 600ml, cold analysis, (condition is with example 2) obtains the sample 26g of content of vitamin E 23.9%, uses the strongly basic anion exchange resin hanging column.After the wash-out, obtain content of vitamin E and be 55.6% product 10.3g.
Spectrophotometry is adopted in the process-monitor analysis of vitamin-E.Tocopherol and tocotrienols all have reductibility, can be quantitatively with Fe
3+Be reduced into Fe
2+Itself then is oxidized to quinones.
Above-mentioned reaction is quantitatively finished, and speed of response is very fast.The Fe that generates
2+Available α-α bipyridine complex colour developing, this complex compound has maximum absorption peak at the 522nm place, adopt visible spectrophotometer to measure its absorption value, obtains the total content of vitamin-E then with typical curve.Unreacted Fe
3+Use PO
≡ 4Its influence to measuring is eliminated in complexing.
The finished product generally adopt liquid-phase chromatographic analysis.The liquid-phase chromatographic analysis vitamin-E is quantitative according to the uv-absorbing of vitamin-E, and it can be separated the isomers of vitamin-E.At first use organic solvent (as alkane, alcohol), make it to form solution.Then solution is injected liquid-phase chromatographic column, under the wash-out of moving phase, absorption, desorb constantly realizes it and the separating of other component.Different according to vitamin-E and other component retention time are through flowing out after the regular hour outside the post, with its content of determination of uv absorption.
Claims (7)
1, a kind ofly is lower than the technical process of separating VE 1% the foots of refining vegetable oil from content of vitamin E, slightly carry and refining two portions are formed by vitamin-E, it is characterized in that thick bag draws together esterification, washing, vacuum distilling, secondary esterification, secondary water washing, secondary vacuum distillation, extraction and cold analysis; Handle refining comprising with silica gel adsorption column absorption with anionite-exchange resin.
2, according to the technical process of claim 1, it is characterized in that said esterification is to adopt methyl alcohol, methanol usage is 4～5 times of lipid acid in the dregs of fat, 60～80 ℃ of esterification temperatures, esterification time 4 hours, said vacuum distilling is carried out under 1～5mmHg, the fraction of getting 190 °～230 ℃ is as the vitamin-E crude product, said secondary vacuum distillation is carried out under 1～5mmHg, get fraction below 190 ℃ as the vitamin-E crude product, said extraction adopts methyl alcohol to make extraction agent, and said cold analysis is carried out under-10 ℃～-20 ℃.
3, according to the technical process of claim 1, it is characterized in that said esterification is to adopt ethanol, the ethanol consumption is 4～5 times of lipid acid in the dregs of fat, 60～80 ℃ of esterification temperatures, esterification time 4 hours, said vacuum distilling is carried out under 1-5mmHg, the fraction of getting 190 ℃～230 ℃ is as the vitamin-E crude product, said secondary vacuum distillation is carried out under 1～5mmHg, the following fraction of getting 190 ℃ is as the vitamin-E crude product, said extraction adopts methyl alcohol-acetone to make extraction agent, and said cold analysis is carried out under-10 ℃～-20 ℃.
4, a kind ofly be lower than the technical process of separating VE 1% the refined plant oil dregs of fat from content of vitamin E, slightly carry and refining two portions are formed by vitamin-E, it is characterized in that thick bag draw together esterification, washing, vacuum distilling, the prosperous セ of ⒍ drone plinth ⒍ hold the moon according to slender and delicate toad 5. leg " Tu an ancient drinking vessel wooden dipper ㄓ that falls into oblivion wastes the Guang of springing forth and chants and change emperor's bangs and write the rancour
5, a kind of is the technical process of separating VE about 1% the refined plant oil dregs of fat from content of vitamin E, slightly carry and refining two portions are formed by vitamin-E, it is characterized in that thick bag draws together esterification, washing, vacuum distilling, extraction and cold analysis, handle refining comprising with anion-exchange resin.
6, according to the technical process of claim 5, it is characterized in that said esterification employing methyl alcohol, its consumption is 4～5 times of lipid acid in the dregs of fat, 60～80 ℃ of esterification temperatures, esterification time 4 hours, said vacuum distilling is carried out under 1-5mmHg, and the fraction of getting 190 ℃～230 ℃ is as the vitamin-E crude product, the extraction agent of said extraction is a methyl alcohol, and said cold analysis is carried out under-10 ℃～-20 ℃.
7, according to the technical process of claim 5, it is characterized in that said esterification employing ethanol, its consumption is 4～5 times of ester fat acid in the dregs of fat, 60～80 ℃ of esterification temperatures, esterification time 4 hours, said vacuum distilling is carried out under 1-5mmHg, and the fraction of getting 190 ℃～230 ℃ is as the vitamin-E crude product, the extraction agent of said extraction is methyl alcohol-acetone, and said cold analysis is carried out under-10 ℃～-20 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87106187 CN1013197B (en) | 1987-09-17 | 1987-09-17 | Process for separating ve from foots of refining vegetable oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87106187 CN1013197B (en) | 1987-09-17 | 1987-09-17 | Process for separating ve from foots of refining vegetable oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1034367A true CN1034367A (en) | 1989-08-02 |
| CN1013197B CN1013197B (en) | 1991-07-17 |
Family
ID=4815614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87106187 Expired CN1013197B (en) | 1987-09-17 | 1987-09-17 | Process for separating ve from foots of refining vegetable oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1013197B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091107C (en) * | 1999-12-24 | 2002-09-18 | 上海交通大学 | Method for raising natural vitamin E concentrate transparency and fluidity |
| CN105693683A (en) * | 2014-11-28 | 2016-06-22 | 丰益(上海)生物技术研发中心有限公司 | A method of removing a plasticiser from vitamin E |
| CN112194647A (en) * | 2020-09-28 | 2021-01-08 | 福建福迩金生物科技有限公司 | Preparation method of natural vitamin E |
| CN112321555A (en) * | 2019-08-05 | 2021-02-05 | 浙江医药股份有限公司新昌制药厂 | Method for removing plasticizer from natural tocopherol |
| US11154795B2 (en) | 2016-10-21 | 2021-10-26 | Novasep Equipment Solutions | Use of compressed gas for moving eluent applied to chromatography |
-
1987
- 1987-09-17 CN CN 87106187 patent/CN1013197B/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091107C (en) * | 1999-12-24 | 2002-09-18 | 上海交通大学 | Method for raising natural vitamin E concentrate transparency and fluidity |
| CN105693683A (en) * | 2014-11-28 | 2016-06-22 | 丰益(上海)生物技术研发中心有限公司 | A method of removing a plasticiser from vitamin E |
| CN105693683B (en) * | 2014-11-28 | 2018-11-27 | 丰益(上海)生物技术研发中心有限公司 | The method of vitamin E removing plasticiser |
| US11154795B2 (en) | 2016-10-21 | 2021-10-26 | Novasep Equipment Solutions | Use of compressed gas for moving eluent applied to chromatography |
| CN112321555A (en) * | 2019-08-05 | 2021-02-05 | 浙江医药股份有限公司新昌制药厂 | Method for removing plasticizer from natural tocopherol |
| CN112321555B (en) * | 2019-08-05 | 2022-05-31 | 浙江医药股份有限公司新昌制药厂 | Method for removing plasticizer from natural tocopherol |
| CN112194647A (en) * | 2020-09-28 | 2021-01-08 | 福建福迩金生物科技有限公司 | Preparation method of natural vitamin E |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1013197B (en) | 1991-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Isolation and purification of dimeric and trimeric procyanidins from grape seeds | |
| Medina et al. | Concentration and purification of stearidonic, eicosapentaenoic, and docosahexaenoic acids from cod liver oil and the marine microalgaIsochrysis galbana | |
| Gaydou et al. | Composition of the essential oil of ylang-ylang (Cananga odorata Hook Fil. et Thomson forma genuina) from Madagascar | |
| Luo et al. | Preparative separation of grape skin polyphenols by high-speed counter-current chromatography | |
| CN103708992B (en) | A kind of level chromatography method extracts the method for squalene in plant oil deodorizing distillate | |
| CN105154478B (en) | A kind of method of high speed adverse current chromatogram and high performance liquid chromatography combination preparation high-purity hydroxytyrosol | |
| Kleiman et al. | Boron trifluoride as catalyst to prepare methyl esters from oils containing unusual acyl groups | |
| CN104529772B (en) | A kind of simulated moving bed chromatography prepares high-purity EPA ester and the method for DHA ester monomer | |
| CN103804337B (en) | The technique that multi-stage countercurrent liquid-liquid extraction method extracts vitamin E and Squalene | |
| GB2117381A (en) | Vitamin E extraction | |
| CN101445498A (en) | Production method of high purity natural vitamin E and separation method of tocopherol homologues | |
| Silk et al. | South African pilchard oil. 4. The isolation and structure of a hexadecatetraenoic acid from South African pilchard oil | |
| Philip et al. | Quantitative analyses of major carotenoid fatty acid esters in fruits by liquid chromatography: persimmon and papaya | |
| CN1034367A (en) | The technology of separating VE from foots of refining vegetable oil | |
| CN105218367A (en) | A kind of High Purity Ethyl Eicosapentaenoate enriched material | |
| CN103351298B (en) | A kind of purification process of 1,3-DAG | |
| GB2090836A (en) | Method for the preparation of tocotrienol concentrates from oleaginous materials | |
| JP3651935B2 (en) | How to recover carotene | |
| Isso et al. | Extraction of α‐tocopherolquinone from vegetable oil deodorizer distillate waste | |
| CN104262076B (en) | A kind of method utilizing Silver Nitrate silica gel chromatography purification plant origin squalene | |
| Indyk et al. | Powders and infant formulas by HPLC | |
| De Greyt et al. | Analysis of tocopherols by gas‐liquid and high‐performance liquid chromatography: a comparative study | |
| Plank et al. | Minor components in vegetable oil methyl esters I: sterols in rape seed oil methyl ester | |
| JPS6193178A (en) | Separation of tocotrienols | |
| CN1084880A (en) | Semen Coicis neutral grease and extracting method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |