FORM 2
THE PATENT ACT 1970 & THE PATENTS RULES, 2003
COMPLETE SPECIFICATION (See section 10 and rule 13)
1. TITLE OF THE INVENTION
PROCESS FOR THE PREPARATION OF TOCOPHEROLS
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 oil from the seeds of soybean, sunflower, safflower, cotton and other like seeds. During the refining of these oils most 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 and 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 th& 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, the 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.
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] having free fatty acids and tocopherols with sterols, glycerides and squalene; subjecting said distillate to first molecular distillation at desired conditions forming a first distillate stream and a first residue stream; subjecting said first residue stream to a second molecular distillation at desired conditions forming a second distillate stream and a second residue stream; subjecting said second distillate stream to a third molecular distillation at desired conditions forming a third distillate stream and a third residue stream; and subjecting said third residue stream to solvent precipitation forming a enriched tocopherols fraction.
Present invention facilitates efficient process to enrich tocopherols comprising four steps namely: 1] first molecular distillation, 2] second molecular distillation of first residue stream, 3] third molecular distillation of second distillate stream and followed by, 4] solvent precipitation. 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 1; FIRST MOLECULAR DJSTJLLATJON OF DEODORIZER DISTILLATE Deodorizer distillate contained tocopherols 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 1 mTorr to 200 mTorr 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 free fatty acids. A first residue stream comprised about 4% to about 9% 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: SECOND MOLECULAR DISTILLATION OF FIRST RESIDUE STREAM In this step, said residue obtained of step 1 is subjected to a second molecular distillation step at the temperature between about 220 °C to about 250 °C in vacuum between about 1 mTorr to 200 mTorr at a feed flow rate between about 13 kg/h to about 22 kg/h and agitation rate of about 280 RPM. A second distillate stream comprised about 6% to about 14% tocopherols and second residue stream comprised about 50% to about 70% free fatty acids by weight. Said distillate stream is processed further to enrich tocopherols to desired purity and quality in step 3. The second

molecular distillation step is performed to distill most of the tocopherols in distillate and to remove high boiler in the first residue stream.
STEP 3: THIRD MOLECULAR DISTILLATION OF SECOND DISTILLATE STREAM The second distillate stream obtained in step 2 is further subjected to a third molecular distillation step at a temperature between about 170 °C to about 190 °C in vacuum between about 1 mTorr to about 200 mTorr at a feed flow rate of between about 25 kg/h to about 45 kg/h and agitation rate of about 280 RPM for removing remaining FFA form the distillate. Said distillation gives a third distillate stream and a third residue stream. The third residue stream comprised about 13% to about 18% tocopherols and third distillate stream comprised about 20% to about 40% free fatty acids by weight.
STEP 4: SOLVENT PRECIPITATION
The third residue stream obtained in step 3 is further subjected to a solvent precipitation at a temperature between about 8 °C to about 35 °C for about 10 minute to about 120 minutes to remove residual sterols and other impurities to get a final enriched tocopherols stream. Said stream is further centrifuged to separate filtrate from the residue. The said filtrate contains most of the tocopherols. Next, said filtrate is subjected to a distillation using methanol or acetone of hexane, to get final 20% to 25% tocopherols containing stream, while said residue is vacuum dried in an oven at about 60 °C to get crude sterols.

In another embodiment of the invention, process of preparation of tocopherols is initiated with first step of molecular distillation to remove about 50% to about 70% free fatty acids by weight. Second molecular distillation step is used to remove high boilers through residue. Then third molecular distillation is used to remove remaining free fatty acids in the distillate stream and to concentrate tocopherols in the residue.
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 like:
1. The Three steps molecular distillation route is a simple and cost effective process.
2. The disclosed process significantly reduces the chemical reaction cost leading to savings of utility cost and solvents;
3. Free fatty acids are a major by-product which is having better applications.
4. Solvent is recycled in the process after simple pretreatment.
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 58.13 67.00 68.28
2 Free tocopherols 5.24 2.48 3.40
3 Glycerides 6.54 3.95 5.09
4 Free sterols 4.17 3.81 1.1A
5 Total sterols 6.07 5.07 3.38
6 Squalene 0.25 1.71 0.32
EXAMPLE 1
About 100 kg of soya bean DOD [containing about 5.24% tocopherols, about 6.07% total sterols and 52% free fatty acids] was subjected to a first molecular distillation step (short path distillation) at temperature of about 170 °C under vacuum at 0.1 mm Hg, at a flow rate about 40 kg/h and.at

agitation of about 280 rpm. This step afforded about 54.3 kg of first residue stream containing about 9.39% tocopherols by weight; and first distillate ■- stream containing about 0.84% tocopherols by weight. Next, said 54.3 kg of first residue stream was further subjected to a second molecular distillation step at temperature of about 232 °C and 0.038 mmHg of vacuum, at a flow rate about 17 kg/h of said residue and at agitation of about 280 RPM to enriched the tocopherols in distillate. This step afforded about 32.03 Kg of second distillate stream containing about 14.23% tocopherols by weight and second residue stream containing about 2.58 % tocopherols by weight. Next, said 32.32 kg of second distillate stream was again passed through the third step of molecular distillation at temperature of about 140 °C to about 175 °C and 0.065 mm Hg of vacuum, at a flow rate about 30.05 kg/hour of said residue and at agitation of about 280 rpm. This final distillation steps produced about 18.4 kg of third residue stream with about 17.8% tocopherols in it by weight and third distillate stream containing about 1.53% tocopherols by weight. Said third residue was further taken for methanol precipitation to remove residual sterol and other impurities from final tocopherols stream. Said 18.4 kg of residue was precipitated using 92 kg of 100% methanol at 25°C for 15 minutes. Said mixture was then centrifuged to get filtrate and residue. Here filtrate contained tocopherols and residue sterols. Final residue was dried in a vacuum oven at 60 °C to get 3.7 kg of crude sterol and said filtrate was subjected to distillation of methanol to produce enriched tocopherols. This process afforded about 14.7 kg of mass having about 20 % tocopherols in it by weight. The individual

tocopherol forms were as: about 3.88% alpha, about 1.65% beta, about 9.59% gamma and about 5.28% delta.
EXAMPLE 2
About 100 kg of sunflower oil deodorizer distillate [containing about 2.48% ' tocopherols, about 5.07% total sterols and 67% free fatty acids] was subjected to a first molecular distillation step (short path distillation) at a temperature of about 180 °C under vacuum at 0.01 mmHg, at a flow rate about 30 kg/h and at agitation of about 280 RPM. This step afforded about 45.9 kg of first residue stream containing about 4.73% tocopherols by weight; and first distillate stream containing about 0.34% tocopherols by weight. Next, said 45.9 kg of first residue stream was further subjected to a second molecular distillation step at a temperature of about 240 °C and 0.001 mmHg of vacuum, at a flow rate about 22 kg/h of said residue and at agitation of about 280 RPM to enriched the tocopherols in distillate. This step afforded about 33.88 kg of second distillate stream containing about 6.4% tocopherols by weight and second residue stream containing about 2.51% tocopherols by weight. Next, said 33.88 kg of second distillate stream was again passed through the third step of molecular distillation at a temperature of about 140°C to about 175 °C and 0,035 mmHg of vacuum, at a flow rate about 30 kg/h of said residue and at agitation of about 280 RPM. This final distillation steps produced about 12.84 kg of third resjdue stream with 13.98% tocopherols in it by weight and third distillate stream containing about 1.58% tocopherols by weight. Said third residue was used

further for methanol precipitation to remove residual sterols and other impurities from final tocopherol stream. Said 12.84 kg of residue was precipitated using 38.52 kg of 95% methanol at 25 °C for 15 minutes. Said mixture was then centrifuged to get filtrate and residue. Here filtrate contained tocopherols and residue sterols. Final residue was dried in a vacuum oven at 60 °C to get 3.3 kg of crude sterol and said filtrate was subjected to distillation of methanol to produce enriched tocopherols. This, process afforded about 8.8 kg of mass having 19 % tocopherols in it by weight. The individual tocopherol forms were as: about 15.66% alpha, about 0.82% beta, about 1.52% gamma and about 0.94% delta.
EXAMPLE 3
About 100 kg of sunflower oil deodorizer distillate [containing about 4.38% tocopherols, about 5.07% total sterols and 59% free fatty acids] was subjected to a first molecular distillation step [short path distillation] at a temperature of about 170 °C under vacuum at 0.001 mmHg, at a flow rate about 40 kg/h and at agitation of about 280 RPM. This step afforded about 51.8 kg of first residue stream containing about 8% tocopherols by weight; and first distillate stream containing about 0.40 % tocopherols by weight. Next, said 51.8 kg of first residue stream was further subjected to a second molecular distillation step at temperature of about 225 °C and 0.036 mmHg of vacuum, at a flow rate about 15 kg/h of said residue and at agitation of... about 280 RPM to enriched the tocopherols in distillate. This step afforded about 39 kg of second distillate stream containing about 8.46% tocopherols

by weight and second residue stream containing about 3.77% tocopherols by weight. Next; said 39 kg of second distillate stream was again passed through the third step of molecular distillation at a temperature of about 185 °C and vacuum of about 0.065 mmHg, at a flow rate about 30 kg/h of said residue and at agitation of about 280 RPM. This final distillation steps produced about 19 kg of third residue stream with about 14% tocopherols by weight and third distillate stream containing about 3% tocopherols by weight. Said third residue was further treated for methanol precipitation to remove residual sterols and other impurities from final tocopherol stream. Said 19 kg of residue was precipitated using 38 kg of 100% methanol at 25 °C for 1 h. Said mixture was then centrifuged to get filtrate and residue. Here filtrate contained tocopherols and residue sterols. Final residue was dried in a vacuum oven at 60 °C to get about 3.3 kg of crude sterols and said filtrate was subjected to distillation of methanol to produce enriched tocopherols. This process afforded about 10.3 kg of mass having about 18.45% tocopherols by weight. The individual tocopherol forms were as: about 15.39% alpha, about 0.81% beta, about 1.42% gamma and about 0.83% delta.
EXAMPLE 4
About 100 kg of cottonseed oil deodorizer distillate [containing about 2.97% tocopherols, about 3.38% total sterols and 68.28% free fatty acids] was subjected to a first molecular distillation step [short path distillation] at a temperature of about 190 °C under vacuum at 0.001 mmHg, at a flow rate

about 50 kg/h and at agitation of about 280 RPM. This step afforded about 45.5 kg of first residue stream containing about 5.39% tocopherols by weight; and first distillate stream containing about 0.34% tocopherols by weight. Next, said 45.5 kg of first residue stream was further subjected to a second molecular distillation step at temperature of about 232 °C and at about 0.03 mmHg of vacuum, at a flow rate about 30 kg/h of said residue and at agitation of about 280 RPM to enriched the tocopherols in distillate. This step afforded about 33.95 Kg of second distillate stream containing about 6.29% tocopherols by weight and second residue stream containing about 1.86% tocopherols by weight. Next, said 33.95 kg of second distillate stream was again passed through the third step of molecular distillation at temperature of about 180 °C and 0.06 mmHg of vacuum, at a flow rate about 35 kg/h of said residue and at agitation of about 280 RPM. This final distillation steps produced about 12.68 kg of third residue stream with about 14.66% tocopherols by weight and third distillate stream containing about 1.41 % tocopherol by weight. Said third residue was further treated for methanol precipitation to remove residual sterol and other impurities from final tocopherol stream. Said 12.68 kg of residue was precipitated using 66 kg of 100% methanol at 25 °C for 1 h. Said mixture was then centrifuged to get filtrate and residue. Here filtrate contained tocopherols and residue sterols. Final residue was dried in a vacuum oven at 60 °C to get 3.8 kg of crude sterols and said filtrate was subjected to distillation of methanol to produce enriched tocopherols. This process afforded about 8.8 kg of mass having about 16.61 % tocopherols by weight. The individual

tocopherol forms were as: about 9.74% alpha, about 0.63% beta, about 5.8% gamma and about 0.45% delta.
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:
1. A process for preparation tocopherols comprising:
(a) providing a deodorizer distillate comprising free and bound tocopherols;
(b) subjecting said deodorizer distillate to first molecular distillation at desired conditions forming a first distillate stream and a first residue stream;
(c) subjecting said first residue stream to a second molecular distillation at desired conditions forming a second distillate stream and a second residue stream;
(d) subjecting said second distillate stream to a third molecular distillation at desired conditions forming a third distillate stream and a third residue stream to get an enriched composition tocopherols;
(e) extracting said third residue stream with a solvent- to separate sterols to get a final stream; and
(f) removing residual solvent to get an enriched composition of tocopherols.

2. The process of claim 1, 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 7% tocopherols by weight;
(c) first molecular distillation is performed at temperature between about 150 °C to about 190 °C in vacuum between about 1 mTorr to 200 mTorr 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 220 °C to about 250 °C in vacuum between about 1 mTorr to 200 mTorr at a feed flow rate between about 13 kg/h to about 22 kg/h and agitation rate of about 280 RPM;
(e) third molecular distillation is performed at temperature between about 170 "C to about 190 °C in vacuum between about 1 mTorr to about 200 mTorr at a feed flow rate between about 25 kg/h to about 45 kg/h and agitation rate of about 280 RPM; and
(f) solvent is methanol, acetone or hexane.

3. The process of claim 1, wherein said solvent extraction is performed at temperature between about 8 °C to about 35 °C for about 10 minutes to about 120 minutes.
4. The process of claim 1, wherein said solvent is removed by distillation, filtration or centrifugation followed by distillation.
5. The process of claim 1, wherein said first residue stream comprises about 4% to about 9% tocopherols by weight.
6. The process of claim 1, wherein said second distillate stream comprises about 6% to about 14% tocopherols by weight.
7. The process of claim 1, wherein said third residue stream comprises about 13% to about 18% tocopherols by weight.
8. The process of claim 1, wherein said final stream comprises about 20% tocopherols by weight.
9. The process of claim 1, wherein said process afforded up to 60% recovery of tocopherols.
10.A tocopherol prepared from deodorizer distillate obtained according to the process of claim 1.