FORM2
THE PATENT ACT 1970 & THE PATENTS RULES, 2003
COMPLETE SPECIFICATION (See section 10 and rule 13)
l. TITLE OF THE INVENTION
PROCESS FOR THE PREPARATION OF TOCOPHEROLS USING
ESTERIFICATION .
2. APPLICANT
(a) NAME: PRAJ Industries Limited
(b) NATIONALITY: Indian Company ' (b) ADDRESS: 274-275, PRAJ Tower, Bhumkar Chowk-
Hinjewadi Road, Hinjewadi, Pune - 411057, INDIA
3. PREAMBLE TO THE DESCRIPTION
The following specification describes the invention and the manner in
which it is to be performed.

4. DESCRIPTION FIELD OF INVENTION
The invention relates to a process for the preparation of tocopherols from vegetable oil industry by-products like deodorizer distillates. It particularly relates to the preparation of tocopherols from the deodorizer distillates obtained during processing of oils from seeds of soybean, sunflower, safflower and cotton.
BACKGROUND
The tocopherols [vitamin E derivatives] of plant origin are widely used for different consumer and industrial applications. Tocopherols are used as vitamin supplements in various food and cosmetics products. These tocopherols are isolated from different plant seed oils. They are also used in many nutraceutical and cosmetic products. Besides, they are used as raw materials for the preparation of several intermediate chemicals or derivatives of unique properties for the preparation of several medicinal molecules.
The deodorizer distillate (DOD) is a by-product of the deodorization step in the refining of oils from the seeds of soybean, sunflower, safflower, cotton and other similar seeds. During the refining of these oils most of the bioactive compounds such as free phytosterols, fatty

acid steryl esters, tocopherols and squalenes are concentrated in DOD. Furthermore, DOD also contains free fatty acids, polycyclic hydrocarbons besides the bioactive compounds making it is a good natural source of phytosterols, tocopherols and squalenes. A few methods have been developed to recover and purify the tocopherols from the deodorizer distillates of vegetable oils.
Tocopherols are an important group of organic molecules widely used in pharmaceutical, nutraceutical and cosmetic products. Many vegetative plant materials like roots, stems, leaves or seeds produce and store the tocopherols. The natural tocopherols have been widely used in the preparations like cosmetic products, animal and human healthcare products. Of the natural tocopherols, alpha and gamma derivatives are more important as active ingredients in the above mentioned products.
The tocopherols are present in large amounts in oil seeds of several types. During extraction and refining of oils, tocopherols containing fractions are separated and further processed to isolate the tocopherols as by-products of higher values. Several methods have been known that separate these components. However, tne quality of the final tocopherol . preparations largely depends on the physical and chemical processes used to isolate it.

The major issues with the recovery of tocopherols from materials like DOD are the yield and quality of the final compositions. They form raw materials for the preparation of many tocopherol derivatives used in pharmaceutical preparations. Thus, there is still a need for a process to produce tocopherols from plant materials using green, non-toxic and economic methods with higher quality of the final preparations for use in high-end applications like pharmaceutical and nutritional products.
DESCRIPTION OF DRAWINGS
The features, aspects, and advantages of the present invention will become better understood when the following detailed description is read with reference to the accompanying drawing, wherein:
FIGURE 1 depicts a process flow diagram for the preparation of tocopherols from a deodorizer distillate (DOD). Different elements of the process are identified and directional movements of different streams and components formed are shown to describe the features of an embodiment of the present invention.
FIGURE 2 depicts a process flow diagram for the preparation of tocopherols from a deodorizer distillate (DOD) using a silica column chromatography step. Different elements of the process are identified

and directional movements of different streams and components formed are shown to describe the features of an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
In one embodiment of the invention, the process comprises providing a deodorizer distillate [obtained from soybean oil deodorizer distillate, sunflower oil deodorizer distillate, cotton seed oil deodorizer distillate and like sources] having free fatty acids and tocopherols with other compounds; subjecting said distillate to first molecular distillation at desired conditions forming a first distillate stream and a first residue stream; the said first residue stream is subjected to esterification with an alcohol like methanol in the presence of acid catalyst at desired temperature and pressure for desired time, and allowed to form crude crystals of sterols in cooled reaction mixture by addition of water for an extended time. Said crude crystals are recovered from the liquid fraction by solid liquid separation. Said liquid fraction separated from sterols crystals contain the most of tocopherols, which is subjected to three molecular distillation steps forming an enriched tocopherols fraction. Said tocopherols fraction is subjected to crystallization and/ or chromatographic separation to get final tocopherols preparation of higher yield and purity. Said crude crystals which are recovered, then

further subjected to re-crystallization using an organic solvent like acetone to get the final sterol preparations of higher purity and yield useful for the preparation of pharmaceutical, nutraceutical or cosmetic products. It may be appreciate that the steps disclosed herein are equally applicable to a deodorizer distillate other than the DODs herein described as primary components of different distillates are similar. In another embodiment of the invention, the process to enrich tocopherols comprises eight steps namely: 1] first molecular distillation of deodorizer distillate, 2] esterification of first residue and crystallization, 3]solid-liquid separation, 4] washing and drying, 5) second molecular distillation of liquid stream, 6] third molecular distillation of second residue, 7] final molecular distillation of third residue, and 8] crystallization or chromatographic separation of final distillate stream. Each step has one or more elements for performing specific or optional functions as required for removing about 85% to about 95% free fatty acids and achieving enrichment of tocopherols from the raw material. A person skilled in the art may appreciate different variations and/ or combinations of these elements that may be used to perform the objects of the invention disclosed herein.

STEP l: FIRST MOLECULAR DISTILLATION
A deodorizer distillate contained tocopherols of about 2.5% to 5% by weight along with free fatty acids, sterols, glycerides and squalene. Said distillate is subjected to a first molecular distillation unit with a surface area of about 0.5 m3, at temperature between about 150 °C to about 190 °C in vacuum between about 0.01 mmHg to about 0.20 mmHg at a feed flow rate of about 25 kg/h to about 45 kg/h and agitation rate of about 280 RPM for the removal of free fatty acids. A first residue stream comprised about 4% to about 10% tocopherols and about 30% to about 50% free fatty acids by weight. Said residue stream is further processed to enrich tocopherols to desired purity and quality.
STEP 2: ESTERIFICATION OF FIRST RESIDUE AND CRYSTALLIZATION
The first residue stream obtained at the end of first molecular distillation step is subjected to esterification in the presence of an acid catalyst of about 0.5% to about 4% with an alcohol like methanol or ethanol at a temperature of about 6o°C to about 130°C, under nitrogen pressure of about 2 kg/cm2 for about 4 h. Then desired quantity of water is added to the esterified mixture to accelerate the crystallization of sterol. During this process the free fatty acids are converted into esters helping easy removal of said fatty acids from the crystallizing

sterols. Then said reaction mass is cooled gradually to room temperature where crystallization is continued under mild stirring.
STEP 3: SOLID - LIQUID SEPARATION AND RECRYSTALLIZATION OF STEROL
Said crude crystals are recovered from the liquid fraction by solid liquid separation using bag centrifuge or nutch filter. Said liquid fraction separated from sterols crystals contains the most of tocopherols. Said crude crystals which are recovered from the liquid fraction and further subjected to re-crystallization using an organic solvent like acetone to get the final sterol preparations of higher purity and yield useful for use in the preparation of pharmaceutical or cosmetic products. This process afforded about 58% sterol by weight and about 5% to 10% tocopherol by weight in liquid fraction depending upon tocopherols present in the feedstock.
STEP 4: WASHING AND DRYING
The liquid fraction which is obtained during solid -liquid fraction contained tocopherol along with fatty acid methyl ester, unreacted methanol and water. Next, said liquid fraction was decanted to get upper layer of fatty acid methyl esters and tocopherols layer. Methanol and water mixture was settled at the bottom from which methanol was

recovered by distillation. Obtained fatty acid methyl esters and tocopherols mixture was further washed with water to remove the catalyst. Then the mixture was dried to remove any stresses of moisture in it.
STEP 5: SECOND MOLECULAR DISTILLATION OF MIXTURE In this step, said mixture obtained of step 4 is subjected to a second molecular distillation step at the temperature between about 150 °C to about 190 °C in vacuum between about 0.10 mmHg to about 0.40 mmHg at a feed flow rate between about 25 kg/h to about 35 kg/h and agitation rate of about 280 RPM for removing remaining fatty acid methyl ester and to enrich tocopherol in it. A second residue stream comprised about 12% to about 30% tocopherols by weight.
STEP 6: THIRD MOLECULAR DISTILLATION OF SECOND RESIDUE
STREAM
The second residue stream obtained in step 5 is further subjected to a
third molecular distillation step at a temperature between about 140 °C
to about 180 °C in vacuum between about 0.20mmHg to about 0.40
*
mmHg at a feed flow rate of between about 25 kg/h to about 35 kg/h and agitation rate of about 280 RPM for removing final traces of fatty acid methyl ester from the distillate. Said distillation gives a third

residue stream which comprises about 14% to about 40% tocopherols by weight.
STEP 7: FINAL MOLECULAR DISTILLATION OF THIRD RESIDUE STREAM
The third residue stream obtained in step 6 is further subjected to a final molecular distillation step at a temperature between about 200 °C to about 250 °C in vacuum between about 0.01 mmHg to about 0.20 mmHg at a feed flow rate of between about 10 kg/h to about 20 kg/h and agitation rate of about 280 RPM. The final molecular distillation step is performed to distil most of the tocopherols in distillate and to remove high boiler in the fourth residue stream. Said distillation gives a final distillate stream which comprises about 19% to 45% by weight. Said distillate stream is processed further to enrich tocopherols to desired purity and quality in final step either by crystallization or by chromatography. The second molecular distillation step is performed to distil most of the tocopherols in distillate and to remove high boiler in the first residue stream.
STEP 8: POST CRYSTALLIZATION OR CHROMATOGRAPHIC SEPARATION OF FINAL DISTILLATE STREAM

The final distillate stream obtained in step 6 is further subjected to crystallization using about 94 % of acetone at about 5 °C to about -15 °C for about 4 hours. Next, the crystallized mass is separated from the liquid fraction using solid liquid separation. Residue obtained is again washed with acetone (100%). Next, obtained filtrate with acetone washed filtrate is then subjected to evaporation of solvent to get tocopherol fraction containing about 35% to 50% tocopherols by weight. After crystallization, said obtained residue is dried in vacuum oven at about 60 °C to get about 35% crude sterols by weight. In another embodiment, crystallization is carried out using acetone or ethanol.
In yet another embodiment, Instead of using crystallization, chromatographic separation technique is used to separate tocopherol from crude sterol fraction. The final distillate stream obtained in step 6 is loaded to the silica column having a mesh size of 60-120 mesh for about 55 minutes. Next, the column is eluted with a mixture of hexane & ethyl acetate. The amount of ethyl acetate in the solution varies from 0% to 100%. First about 2% ethyl acetate containing hexane is passed ,next about 5% ethyl acetate containing hexane is passed, then about 10% ethyl acetate containing hexane is passed, followed by about 100% ethyl acetate to remove all the polar impurities. At last column is regenerated by using hexane. First fraction of solvent is collected & solvent is

distilled off so that first fraction which majorly contains fatty acid methyl esters is separated. The second cut of solvent which consist of tocopherol fraction is further collected and solvent is distilled off to collect second fraction containing 90% tocopherol. And further final fraction of solvent which mainly contain highly polar impurities such as FFA is obtained after evaporation of solvent which also contain less fraction of tocopherol in it.
In yet another embodiment, for chromatography the feed and solvent ratio used for elution is about 1:60 for the first column and about 1:55 for the subsequent columns. The bulk density of silica used for chromatography is between about 0.50 to 0.66 g/cm3 for getting up to 90% tocopherol purity.
In another embodiment of the invention, process of preparation of tocopherols is initiated with first step of molecular distillation to remove about 30% to about 50% free fatty acids by weight. The esterification is used to convert free fatty acids into esters and crystallization used to remove them from the residue stream. Second and third molecular distillation steps are used to remove remaining fatty acid methyl esters and final molecular distillation step is used to remove high boilers and to concentrating tocopherols in the residue. Crystallization or column chromatography step is used to concentrate and purify the tocopherols.

Where crystallization is used the process afforded 25% to 50% tocopherols by weight and when column chromatography is used the process afforded 50% to 90% tocopherols by weight.
This invention discloses a process for the preparation of tocopherols from a deodorizer distillate as value added by-products of oil refining industry. The process having several advantages over the known methods as:
1. The four part molecular distillation route is a simple and cost effective process.
2. The final concentration of tocopherol obtained is about 25% to 50% by weight post crystallization irrespective of feed composition.
3. The disclosed process significantly reduces chemicals used, significantly saving in the utilities and solvents.
4. Free fatty acids (about 40 to 60% by weight) are a major by-product having good market demands.
5. Fatty acid methyl esters (about 30 to 50% by weight) are other byproduct of commercial value.
6. Solvents are recycled in the process after recovery without loss.
7. Column chromatography step gives up to 90% tocopherol purity by weight along with up to 90% recovery of the product.

8. Stationary phase of column chromatography may be used up to 60 times without loss of efficiency.
EXAMPLES
Examples provided below" give wider utility of the invention without any limitations as to the variations that may be appreciated by a person skilled in the art. A non-limiting summary of various experimental results is given in the examples and tables, which demonstrate the advantageous and novel aspects of the process for preparation of tocopherols from a deodorizer distillate.
The characteristics of the suitable starting materials required for the above described process for producing the desired final tocopherol preparations are summarized in Table 1.
TABLE 1: Specifications of deodorizer distillates that may be used to prepare the tocopherols.

No. Composition [%] Soya DOD Sunflower DOD Cotton Seed DOD
1 Free fatty acids 5.8.13 67.OO 68.28
2 Tocopherols 5.24 2.48 340
3 Glycerides 6.54 3-95 5.09

4 Free sterols 4.17 3.8i 2.24
5 Total sterols 6.07 507 3.38
6 Squalene O.25 1.71 0.32
EXAMPLE 1
About 114 kg of soya bean oil deodorizer distillate [containing about 5.3% tocopherols, about 6% total sterols and 52% free fatty acids by weight] was subjected to molecular distillation step - 1 [short path distillation] for the removal of fatty acids at temperature of about 170 °C under vacuum of about 0.1 mmHg, at a flow rate about 40 kg/h and at agitation of about 280 RPM. This step afforded about 57 kg of first residue stream containing about 10% tocopherols by weight. Next, said first residue stream was reacted with about 16 kg of methanol in the presence of 1.15 kg of methane sulphonic acid [MSA] at temperature of about 100 °C, under nitrogen pressure of about 2 kg/cm2 for about 4 h. Then about 7.5 kg of water was added to this esterified mixture to accelerate the crystallization of sterols. Then said reaction mass was gradually cooled to room temperature where crystallization was continued under mild stirring. Next, the crystallized mass was separated from liquid by solid -liquid separation using a bag centrifuge or a nutsche filter. This process afforded about 7 kg of solid crude sterol fraction with about 58% sterols by weight; and about 10.5% tocopherols
*

in liquid fraction along with fatty acid methyl esters, unreacted methanol and water. Next, said liquid fraction was decanted to get upper layer of fatty acid methyl esters and tocopherols layer. Methanol and water mixture was settled at the bottom from which methanol was recovered by distillation. Obtained fatty acid methyl esters and tocopherols mixture was further washed with water to remove the catalyst. Then the mixture was dried to remove any stresses of moisture in it. Next, said mixture was subjected to molecular distillation step - 2 to remove fatty acid methyl esters from the mixture at temperature of about 170 °C and vacuum of about 0.3 mmHg, at a flow rate of about 30 kg/h and at agitation of about 280 RPM to enrich tocopherols in the residue. This step afforded about 17 kg of second residue stream containing about 27% tocopherols by weight. Next, said second residue stream was again passed through molecular distillation step -3 at temperature of between about 140 °C to about 180 °C, at vacuum of about 0.3 mmHg, at a flow rate about 32 kg/h and at agitation of about 280 RPM for removing any final traces of fatty acid methyl esters and to get about 15 kg of third residue stream with 30% tocopherols by weight. Said third residue stream was then subjected to molecular distillation step - 4' at temperature of about 235°C, at vacuum of about 0.1 mmHg, at a flow rate about 15 kg/h and at agitation of about 280 RPM. This final distillation step produced about 9.6 kg of fourth distillate stream

with about 43% tocopherols by weight. Said fourth distillate was crystallized further using about 33 kg of 94% acetone at about -15 °C for about 4 h. Next, the crystallized mass was separated from the liquid fraction using a basket centrifuge. Residue obtained was further washed with about 17 kg of pure acetone. This process afforded about 2.58 kg of solid crude sterol fraction with about 35% sterols by weight; filtrate and acetone washed filtrate obtained is then subjected to evaporation of solvent to get about 6.85 kg of tocopherol fraction containing about 50% tocopherols by weight.
EXAMPLE 2
The distillate of final molecular distillation was mixed with various solvents mixtures at about -15 °C for about 4 h, the results are shown in TABLE 2. TABLE 2:

EFFECT OF SOLVENT ON TOCOPHEROLS RECOVERY
Example Solvent in water (%) Tocopherol in Final MD distillate {%
W/W) Tocopherol Purity in liquid fraction (%
W/W) . Tocopherol Recovery
(%)
1 Acetone 99 43 50 90
2 Acetone 85 43 53 90
3 Acetone 95 - 43 52 94
4 Ethanol 95 43 48 78

EXAMPLE 3
Next, about 227 gm of distillate from molecular distillation step - 4 was
loaded to a column of 70 mm internal diameter and 770 mm height,
filled with about 1625 gm of silica having a mesh size of 60 - 120; the
time taken for loading was about 55 minutes. The column was eluted
with a mixture of hexane and ethyl acetate. Content of ethyl acetate in
the mixture varied from 0% to 100%. First, about 2500 ml of 2% ethyl
acetate in hexane was passed, followed by 5000 ml of 5% ethyl acetate
in hexane, then about 1200 ml of 10% ethyl acetate in hexane, and
finally about 1850 ml of 100% ethyl acetate to remove all the polar
impurities present in the distillate. At last the column was regenerated
by using 2500 ml of pure hexane. A first fraction of about 4600 ml
solvent was collected and solvent is distilled off to afford about 98 gm of
fatty acid methyl esters in the residue. The second cut of about 5850 ml
of solvent was collected and solvent was distilled off to afford about 91
gm of second fraction containing about 90% tocopherols by weight.
Finally about 2500 ml of final fraction of solvent mainly with highly
polar impurities such as FFA was obtained after evaporation of solvent.
Here about 38 gm of FFA was obtained with about 3.3% tocopherols by
weight, ,. J.

EXAMPLE 4
About 100 kg of sunflower oil deodorizer distillate [containing about
2.7% tocopherols, about 5% total sterols and 67% free fatty acids by weight] was subjected to molecular distillation step - 1 [short path distillation] for the removal of fatty acids at temperature of about 170 °C under vacuum of about 0.1 mmHg, at a flow rate about 40 kg/h and at agitation of about 280 RPM. This step afforded about 46 kg of first residue stream containing about 5.7% tocopherols by weight. Next, said first residue stream was reacted with about 13 kg of methanol in the presence of 0.92 kg of methane sulphonic acid [MSA] at temperature of about 100 °C, under nitrogen pressure of about 3 kg/cm2 for about 4 h. Then about 6.3kg of water was added to this esterified mixture to accelerate the crystallization of sterols. Then said reaction mass was gradually cooled to room temperature where crystallization was continued under mild stirring. Next, the crystallized mass was separated from liquid by solid -liquid separation using a basket centrifuge or a nutch filter. This process afforded about 3.46 kg of solid crude sterol fraction with about 60 % sterols by weight; and about 5.41% tocopherols in liquid fraction along with fatty acid methyl esters, unreacted methanol and water. Next, said liquid fraction was decanted to get upper layer of fatty acid methyl esters and tocopherols layer; Methanol and water mixture was settled at the bottom from which methanol was

recovered by distillation. Obtained fatty acid methyl esters and tocopherols mixture was further washed with water to remove the catalyst. The mixture was further dried to remove traces of'moisture. Further said mixture was subjected to molecular distillation step - 2 to remove fatty acid methyl esters from the mixture at temperature of about 170 °C and vacuum of about 0.3 mmHg, at a flow rate of about 30 kg/h and at agitation of about 280 RPM to enrich tocopherols in the residue. This step afforded about 14.39 kg of second residue stream containing about 15.99 % tocopherols by weight. Next, said second residue stream was subjected to molecular distillation step - 3 at temperature of between about 140 °C to about 180 °C, at vacuum of about 0.3 mmHg, at a flow rate about 32 kg/h and at agitation of about 280 RPM for removing any final traces of fatty acid methyl esters and to get about 10.69 kg of third residue stream with 18.41% tocopherols by weight. Said third residue stream was then subjected to molecular distillation step - 4 at temperature of about 235°C, at vacuum of about 0.1 mmHg, at a flow rate about 15 kg/h and at agitation of about 280 RPM. This final distillation step produced about 6.6 kg of fourth distillate stream with about 19.35% tocopherols by weight. Said fourth distillate was crystallized further using about 26.4 kg of 94% acetone at -15 °C for about 4 h. Next, the crystallized mass was separated from the liquid fraction using a basket centrifuge. Residue obtained was further

washed with about 17 kg of pure acetone. This process afforded about 1.78 kg of solid crude sterol fraction with about 35% sterols by weight; filtrate and acetone washed filtrate obtained is then subjected to evaporation of solvent to get about 4.80 kg of tocopherol fraction containing about 24% tocopherols by weight.
While the invention has been particularly shown and described with reference to embodiments listed in examples, it will be appreciated that several of the above disclosed and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. Also that various presently unforeseen and unanticipated alternatives, modifications, variations, or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims. Although the invention has been described with reference to specific preferred embodiments* it is not intended to be limited thereto, rather those having ordinary skill in the art will recognize that variations and modifications may be made therein which are within the spirit of the invention and within the scope of the claims.

5- CLAIMS
WE CLAIM:
l. A process for preparation tocopherols comprising:
(a) providing a deodorizer distillate comprising tocopherols;
(b) subjecting said deodorizer distillate to a first molecular distillation at desired conditions forming a first distillate stream and a first residue stream;
(c) subjecting said first residue stream to esterification with methanol at desired conditions forming an esterified stream;
(d) subjecting said esterified stream to crystallisation in water and removing crystalline material forming a filtrate stream;
(e) subjecting said filtrate stream to decantation to remove a upper oily layer from an aqueous layer;
(f) subjecting said oily layer to a second molecular distillation at desired conditions forming a second distillate stream and a second residue stream;
(g) subjecting said second residue stream to a third molecular distillation at desired conditions forming a third distillate stream and a third residue stream;

(h) subjecting said third residue stream to a final molecular
distillation at desired conditions forming a final distillate
stream and a final residue stream; and (i) subjecting said final distillate stream to crystallisation in
acetone to get an enriched composition of tocopherols; or (j) subjecting said final distillate stream to chromatographic
separation to get a highly enriched composition of
tocopherols.
2. The process of claim i? wherein said:
(a) deodorizer distillate is one of soybean oil deodorizer distillate, sunflower oil deodorizer distillate or cotton seed oil deodorizer distillate;
(b) deodorizer distillate comprises up to about 5% tocopherols by weight;
(c) first molecular distillation is performed at temperature between about 150 °C to about 190 °C in vacuum between about 0.01 mmHg to 0.20 mmHg at a feed flow rate between about 25 kg/h to about 45 kg/h and
agitation rate of about 280 RPM;
*
(d) second molecular distillation is performed at
temperature between about 150 °C to about 190 °C in

vacuum between about 0.10 mmHg to 0.40 mmHg at a feed flow rate between about 25 kg/h to about 35 kg/h and agitation rate of about 280 RPM;
(e) third molecular distillation is performed at temperature between about 140 °C to about 180 °C in vacuum between about 0.20 mmHg to 0.40 mmHg at a feed flow rate between about 25 kg/h to about 35 kg/h and agitation rate of about 280 RPM;
(f) final molecular distillation is performed at temperature between about 200 °C to about 250 °C in vacuum between 0.01 mmHg to 0.20 mmHg at a feed flow rate between about 10 kg/h to about 20 kg/h and agitation rate of about 280 RPM; and
(g)The process of claim 1, wherein said solvent is removed by filtration or.centrifugation followed by distillation.
3. The process of claim 1, wherein said chromatographic separation is achieved using silica gel as a stationary phase.
4. The process of claim 1, wherein said first residue stream comprises about 4% to about 9% tocopherols by weight.
5. The process of claim 1, wherein said second residue stream comprises about 15% to about 30% tocopherols by weight.

6. The process of claim 1, wherein said third residue stream comprises about 17% to about 33% tocopherols by weight.
7. The process of claim 1, wherein said forth molecular distillate stream comprises about 19% to 45% tocopherols by weight.
8. The process of claim l, wherein said enriched composition of tocopherols after crystallization comprises 25% to 50% tocopherols by weight.
9. The process of claim 1, wherein said chromatographic separation afforded between about 50% to 90% tocopherols by weight.
10. A tocopherol prepared according to the process of claim 1.