CN101323607B - Preparation of high content mixed tocopherols - Google Patents
Preparation of high content mixed tocopherols Download PDFInfo
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- CN101323607B CN101323607B CN2007100693005A CN200710069300A CN101323607B CN 101323607 B CN101323607 B CN 101323607B CN 2007100693005 A CN2007100693005 A CN 2007100693005A CN 200710069300 A CN200710069300 A CN 200710069300A CN 101323607 B CN101323607 B CN 101323607B
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Abstract
The invention discloses a method for extracting mixed tocopherols with high content form raw materials with low content of tocopherols. In the existing methods, the amount of some used solvents is too large, some methods have excessive requirements on equipment and some methods are too small in yield, thus being inapplicable to industrialized production. In the invention, deodorizing distillate of fatty acid oil is subjected to esterification and alcoholysis firstly and then freezing and crystallization are carried out to separate out phytosterol; then, after aliphatic ester in a filtrate is reclaimed by short-path distillation, a tocopherol concentrate is obtained and separated by silica gel column chromatography, and eluted with three organic solvents of different polarity so as to obtain the aliphatic ester, the mixed tocopherols with high content and phytosterol crude product. The method of the invention has low requirements on raw materials, is easy for large-scale industrialized production, and can obtain high content of mixed tocopherols and obtain fatty acid methyl ester and phytosterol.
Description
Technical field
The present invention relates to the preparation of tocopherol, specifically a kind of industrial method that from the raw material of low birthrate phenol content, extracts high content mixed tocopherol.
Background technology
Natural VE (Vitamin E) is most important liposoluble vitamin, and it can only synthesize in plant materials, is the very important dietary supplements of human and animal, sometimes also as medicine.Natural VE can be divided into tocopherol and tocotrienols according to two having or not of key on its side switch group, tocopherol generally is present in (as soybean oil, sunflower seed oil, Fructus Maydis oil and vegetable seed wet goods) in the common Vegetable oil lipoprotein, tocotrienols then in cereal seed (as oat, barley, rye and rice bran) content higher, its content is the highest in plam oil.Tocopherol and tocotrienols all are a kind of mixtures, and it contains α, β, four kinds of active isomers of γ, δ.Because the content of natural VE only is 0.04-0.1% in the vegetables oil, directly extracts tocopherol as raw material and does not still have industrial application value.
Vitamin-E is fat-soluble, and it is got at oil plant, and it is extracted out with oil in the oily process.Deodorization is one important operation in the oil and fat refining process, and it is a principle of utilizing wet distillation, the stripping process that carries out under high temperature, high vacuum state.The main purpose of deodorization is to remove the malodor components that influences oil quality in the grease, and to produce the light high quality oils of local flavor, overhead product is the byproduct of deodorization procedures.Vitamin-E is a low-molecular-weight component, can be distilled to come out and concentrated with one of deodorization distillate in deodorising process.Therefore, the plant oil deodorizing distillate of rich in vitamin E is to extract the important source material of vitamin-E and receive much attention always.
The content of tocopherol can reach 8% in the deodorization distillate, except tocopherol, also contains free fatty acids, neutral oil, plant sterol, pigment and other impurity etc. in the deodorization distillate.In order from deodorization distillate, to isolate vitamin-E, various methods are arranged, as solvent extration, molecular distillation method, vacuum distillation method, absorption method, ion exchange method, supercritical extraction and supercritical chromatography etc.And since the eighties in 20th century, expansion along with the tocopherol purposes, the enthusiasm that people study tocopherol greatly improves, relevant report and patent of separating the high-content tocopherol from deodorization distillate is a lot, and these methods respectively have its favourable one side, but also exist many defectives, the quantity of solvent that uses that has is too big, have to equipment require too highly, the then yield that has is on the low side, is unsuitable for suitability for industrialized production.
CN1,401,644A discloses a kind of method that obtains natural mixed tocopherol by steps such as fixed bed esterification, fractionation by adsorption, subzero fractionation, solvent extractions.Operation steps is comparatively loaded down with trivial details in this method, uses multiple organic solvent, and to the requirement height of raw material, fixed bed esterification effect neither be very good.
CN1,234, the 703C disclosed method then is after repeatedly esterification is removed free fatty acids, and resaponifying is after twice freezing and crystallizing removed sterol, and after absorption method obtains mixed tocopherol, this method steps is many, and quantity of solvent is big, and the product yield that obtains is low.
US3,122,565, US5,487,817 and US3,402,182 all use the content that strongly basic anion exchange resin improves mixed tocopherol, but with a distinct disadvantage of anionite-exchange resin are exactly: use a large amount of organic solvents, there is a pickling to take off and alkali regenerated process, the charge capacity of resin is low, and work-ing life is short, has so just limited its industrial applications.
US4,550,183 and EP0,171,009 considerations will be used a large amount of organic solvents with solvent extration refining mixed tocopherols in this method, will inevitably bring certain environmental pollution, and the yield of product is not high yet.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective that above-mentioned prior art exists, and a kind of easy and simple to handle, method of isolating high content mixed tocopherol from deodorization distillate of being easy to suitability for industrialized production is provided.
For this reason, the present invention adopts following technical scheme: 1) the fatty acid oil deodorization distillate and the methanol mixed of low birthrate phenol content are dissolved, be warming up to 60-70 ℃, the methanol solution that drips sodium methylate carries out the esterification alcoholysis reaction, be added dropwise to complete afterreaction 0.5-1.5 hour, make free fatty acids wherein become fatty acid methyl ester, neutral oil becomes fatty acid methyl ester and glycerine; 2) to 1) add deionized water in the reaction solution that obtains of step, standing demix, reclaim methyl alcohol in the water layer, with oil reservoir at-5～-10 ℃ of freezing and crystallizings, separate and obtain the plant sterol coarse crystallization, with behind the fatty acid methyl ester in the short-path distillation recovery filtrate, get the tocopherol concentrated solution again, wherein the content of tocopherol is about 40%; 3) separate going up silica gel column chromatography after described tocopherol concentrated solution and the non-polar organic solvent mixing, use non-polar organic solvent that sample uses respectively, go up non-polar organic solvent that sample uses and polar phase mixed solvent, the polar phase of stronger organic solvent carried out wash-out to stronger organic solvent, collect corresponding elutriant; 4) vacuum reclaims the organic solvent in the elutriant, obtains fatty acid methyl ester, high content mixed tocopherol, plant sterol crude product respectively.The present invention requires lowly to tocopherol content in the raw material, and the mixed tocopherol content height that obtains obtains high-quality fatty acid methyl ester and plant sterol simultaneously in the production process, and the yield height of product is easy to suitability for industrialized production.
The isolating concrete steps of silica gel column chromatography are as follows on the tocopherol concentrated solution: chromatography column on the mixed solution of above-mentioned tocopherol and non-polar organic solvent is separated, filling silica gel for chromatography in this chromatography column, the blade diameter length ratio of post is between the 1:3-1:15, the silica gel filling is finished before the sample, with the non-polar organic solvent balance that the last sample of column capacity 1-5 times volume is used, the non-polar organic solvent that last sample is used is any in normal hexane, normal heptane, octane, hexanaphthene, pentamethylene, ether, the sherwood oil.Applied sample amount is 0.01-1.5 a times of silica gel medium, and applied sample amount is relevant with eluent and the separate substance itself selected for use.Use the non-polar organic solvent continuation wash-out that sample is used behind the last sample, the eluent consumption is 1-12 a times of column capacity, collects elutriant I; Use the mixed solvent wash-out again, mixed solvent is made up of stronger organic solvent with non-polar solvent and polar phase last sample, the organic solvent that polarity is stronger is any one or two kinds of above mixed solutions in butanone, acetone, Virahol, the isopropylcarbinol, collect elutriant II, the eluent consumption is 1-12 a times of column capacity; With polar phase stronger organic solvent is continued the elution chromatography post at last, this organic solvent is any one or two kinds of above mixed solutions in butanone, acetone, Virahol, the isopropylcarbinol, collects elutriant III.
Vacuum concentration is collected the organic solvent in the elutriant, this organic solvent can be applied mechanically, the elutriant of different steps obtains different components, what mainly obtain among the elutriant I is fatty acid methyl ester, what mainly obtain among the elutriant II is high content mixed tocopherol, and what mainly obtain among the elutriant III is plant sterol.Must plant sterol after fully with the organic solvent evaporation among the elutriant III, this plant sterol can arrive after dehydrated alcohol is simply refining and obtain the off-white color crystallization, and wherein plant sterol content can reach more than 90%.
According to technology of the present invention, wherein the post of silica gel column chromatography carries the capacity height, does not need other regenerative process, and the number of times of applying mechanically of chromatography media reaches more than 50 to hundred times.
The preparation method of described high content mixed tocopherol, the quality percentage composition of the non-polar organic solvent that last sample is used in the mixed solvent is 1-65%, adjust the ratio of two kinds of solvents according to different solvents, obtain the mixed tocopherol of different content, the purity of product can reach more than 70%-90% or 90% respectively according to need, reaching as high as more than 95%, specific rotation can reach+and 24.More than, and product color is transparent, and good fluidity can satisfy food or drug standard fully.
The preparation method of described high content mixed tocopherol, the consumption of sodium methylate is 0.05-0.2 a times of deodorization distillate quality, the consumption of methyl alcohol is 6-10 a times of deodorization distillate quality.
The present invention has following beneficial effect: use MIN organic solvent in the technology, step is simple, easy handling; To raw material require lowly, as long as tocopherol content can both be applied to produce greater than 1% in the raw material, the mixed tocopherol content height that obtains, and can also obtain high-quality fatty acid methyl ester and plant sterol in the production process, raw material is fully utilized fully; Organic solvent can effectively be reclaimed and be applied mechanically in the production process, greatly reduces production cost when reducing environmental pollution.These have all invested the present invention is a kind of very economical, be easy to the method for large-scale industrial production.
The present invention is further illustrated below in conjunction with embodiment, but the present invention is not limited to these embodiment.
Embodiment
Embodiment 1
With fatty acid oil deodorization distillate 3000g (wherein tocopherol content is 5.30%) and 9000ml methyl alcohol after fully mixing under 62 ℃, drip the methanol solution 255g of 37% sodium methylate, under this temperature, react 1.0hr, the deionized water that adds 3000ml, leave standstill layering behind the 20min after the gentle agitation, remove lower aqueous layer, reclaim under reduced pressure methyl alcohol wherein.With upper oil phase suction filtration behind-6 ℃ of following freezing and crystallizing 6hr, get thick sterol filter cake 176.7g, this thick sterol gets crystallization of sterols 106.5g behind the anhydrous alcohol solution freezing and crystallizing of 8 times of amounts, and sterol content is 89.4%; With the mother liquor behind the thick sterol filter cake of suction filtration with short-path distillation reclaim behind the fatty acid methyl ester tocopherol concentrated solution 413.9g, wherein the content of mixed tocopherol is 36.54%.
Embodiment 2
Get the tocopherol concentrated solution 135.0g that obtains among the embodiment 1, dissolve with 200ml hexanaphthene thorough mixing, advance silica gel column chromatography (glass column: 3cm*27cm) separate, will be after post installs with the hexanaphthene balance about 360ml to drive bubble wherein away, continue hexanaphthene wash-out behind the last sample, collect elutriant I with 400ml; Use again hexanaphthene and butanone (20:80, mixed solvent wash-out w/w), the consumption of mixed solvent are 600ml, collect elutriant II; Butanone wash-out with 600ml gets elutriant III at last.
Behind the organic solvent among reclaim under reduced pressure elutriant I, II, the III, obtain fatty acid methyl ester, mixed tocopherol, plant sterol crude product respectively, wherein the content of mixed tocopherol is 75.4%, quality is 60.4g, and transparent color and luster, good fluidity; Plant sterol crude product 48.5g gets elaboration 32.1g after the dehydrated alcohol freezing and crystallizing of 8 times of amounts is refining, plant sterol content is 92.1%.
Embodiment 3-5
Embodiment 3-5 separates mixed tocopherol for the tocopherol concentrated solution of getting among the embodiment 1 respectively by silica gel column chromatography, and its result and embodiment 2 experimental results see the following form 1:
Table 1 embodiment 2-5 experimental result
| Project | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Applied sample amount (the quality multiple of chromatography media) | 0.68 | 0.52 | 1.00 | 1.20 |
| Last sample solvent | Hexanaphthene | Sherwood oil | Normal heptane | Pentamethylene |
| Mixed solvent during wash-out and proportioning | Hexanaphthene: butanone=20:80 | Sherwood oil: Virahol=70:30 | Normal heptane: isopropylcarbinol=35:65 | Pentamethylene: acetone=25:75 |
| Mixed solvent quantity during wash-out (bed volume multiple) | 3 times | 3 times | 4 times | 3.5 doubly |
| Organic solvent kind during the wash-out sterol and quantity (bed volume multiple) | 3 times of butanone | 4 times of Virahols | 2.5 times of isopropylcarbinols | 4.2 times in acetone |
| Mixed tocopherol quality and content | 60.4g(75.4％) | 47.7g(96.8％) | 49.4g(94.3％) | 48.3g(95.3％) |
| Sterol elaboration quality and content | 32.1(92.1％) | 36.0(90.5％) | 30.4g(93.2％) | 34.5g(91.7％) |
| The mixed tocopherol yield | 91.3％ | 92.6％ | 93.5％ | 92.8％ |
Claims (5)
1. the preparation method of high content mixed tocopherol, its concrete steps are as follows: 1) with the fatty acid oil deodorization distillate and the methanol mixed dissolving of low birthrate phenol content, the methanol solution that drips sodium methylate carries out the esterification alcoholysis reaction; 2) to 1) add deionized water in the reaction solution that obtains of step, standing demix reclaims methyl alcohol in the water layer, with the oil reservoir freezing and crystallizing, separates obtaining the plant sterol coarse crystallization, reclaim in the filtrate behind the fatty acid methyl ester with short-path distillation again, the tocopherol concentrated solution; 3) separate going up silica gel column chromatography after described tocopherol concentrated solution and the non-polar organic solvent mixing, use non-polar organic solvent that sample uses respectively, go up non-polar organic solvent that sample uses and polar phase mixed solvent, the polar phase of stronger organic solvent carried out wash-out to stronger organic solvent, collect corresponding elutriant; 4) vacuum reclaims the organic solvent in the elutriant, obtains fatty acid methyl ester, high content mixed tocopherol, plant sterol crude product respectively; Described polar phase is any one or two kinds of above mixed solutions in butanone, acetone, Virahol, the isopropylcarbinol to stronger organic solvent.
2. the preparation method of high content mixed tocopherol according to claim 1, the quality percentage composition of going up the non-polar organic solvent that sample uses in the mixed solvent is 1-65%, adjusts the ratio of two kinds of solvents in the mixed solvent, obtains the mixed tocopherol of different content.
3. the preparation method of high content mixed tocopherol according to claim 1 and 2, the consumption of sodium methylate be the deodorization distillate quality 0.05-0.2 doubly, the consumption of methyl alcohol be the deodorization distillate quality 6-10 doubly.
4. the preparation method of high content mixed tocopherol according to claim 1 and 2, when last silica gel column chromatography separates, applied sample amount be the silica gel medium 0.01-1.5 doubly.
5. the preparation method of high content mixed tocopherol according to claim 1 and 2, the non-polar organic solvent that last sample is used is any in normal hexane, normal heptane, octane, hexanaphthene, pentamethylene, ether, the sherwood oil.
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| CN103965155B (en) * | 2014-04-15 | 2018-10-16 | 江苏玺鑫维生素有限公司 | A kind of preparation process of natural VE |
| WO2018073500A1 (en) | 2016-10-21 | 2018-04-26 | Novasep Process | Use of compressed gas for moving eluent applied to chromatography |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401644A (en) * | 2002-09-19 | 2003-03-12 | 浙江大学 | Process for extracting high content mixed tocopherol |
| CN1440969A (en) * | 2003-01-04 | 2003-09-10 | 华东中药工程集团有限公司 | Prepn process of high-purity mixed tocopherol |
| CN1683364A (en) * | 2005-03-04 | 2005-10-19 | 江西天海药业股份有限公司 | New extracting process for natural vitamin E |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401644A (en) * | 2002-09-19 | 2003-03-12 | 浙江大学 | Process for extracting high content mixed tocopherol |
| CN1440969A (en) * | 2003-01-04 | 2003-09-10 | 华东中药工程集团有限公司 | Prepn process of high-purity mixed tocopherol |
| CN1683364A (en) * | 2005-03-04 | 2005-10-19 | 江西天海药业股份有限公司 | New extracting process for natural vitamin E |
Non-Patent Citations (1)
| Title |
|---|
| 金君素.天然维生素E 的提取.河北化工.1999,(3),9-11. * |
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