CN1603321A - Method for fixed bed transfer of natural vitamin E - Google Patents
Method for fixed bed transfer of natural vitamin E Download PDFInfo
- Publication number
- CN1603321A CN1603321A CN 200410053241 CN200410053241A CN1603321A CN 1603321 A CN1603321 A CN 1603321A CN 200410053241 CN200410053241 CN 200410053241 CN 200410053241 A CN200410053241 A CN 200410053241A CN 1603321 A CN1603321 A CN 1603321A
- Authority
- CN
- China
- Prior art keywords
- vitamin
- fixed
- natural
- catalyst
- tocopherol
- 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.)
- Granted
Links
Landscapes
- Pyrane Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
This invention relates to a fixed bed modification method of natural vitamin E. formalin is carboxymethyl catalyst that used in the reaction, benzene sulfonic acid is acid catalyst, and hydrogenation catalyst is granular palladium carbon catalyst and palladium carbon catalyst is filled in the bed reactor. Different content vitamin E being materials, d-beta, d-gamma-, d-delta vitamin E are transferred to d-alpha-vitamin E through fixed bed modification reaction, and yield of d-alpha-vitamin E is above 90%. The hydrogenation catalyst can be used continuously and the separation and recovery process of the catalyst is omitted. The advantage is that technical process is simple and it can be operated continuously.
Description
Affiliated technical field
The present invention relates to a kind of mixing vitamin E with different content is raw material, through fixed bed transition reaction, with the d-β in the raw material-, d-γ-, the d-delta-tocopherol is converted into the method for d-alpha-tocopherol, belongs to technical field of chemical engineering.
Background technology
Natural VE is a kind of mixture, four kinds of vitamin-E homologues of mainly being derived by tocol (Tocol) and coming are formed, comprising: and the d-alpha-tocopherol (d-α-tocopherol), d-β-vitamin-E (d-β-tocopherol), d-γ-vitamin-E (d-γ-tocopherol) and d-delta-tocopherol (d-δ-tocopherol).They all have saturated C
16Side chain, only on phenyl ring the position of methyl with quantitatively exist difference.
Alpha-tocopherol β-vitamin-E
γ-vitamin-E delta-tocopherol
The biologic activity of various natural VE homologues exists very big-difference: d-alpha-tocopherol (activity is 100)＞d-β-vitamin-E (activity is 10～50)＞d-γ-vitamin-E (activity is 10)＞d-delta-tocopherol (activity is 1).The function that the type of natural VE contained vitamin E and content have determined it, the high more then biological activity of d-alpha-tocopherol content is high more in the natural VE.
By reaction transition, it is the key that improves its biologic activity that the d-β-vitamin-E in the natural VE, d-γ-vitamin-E and d-delta-tocopherol are converted into the d-alpha-tocopherol.The method of vitamin-E reaction transition has a variety of, mainly comprises halomethylation method, formylation reduction method, amine-methylated method, methylolation method and permethylated method.In the middle of five kinds of methods, though the methylolation method need be reacted under high temperature, condition of high voltage, d-alpha-tocopherol yield is the highest, is a kind of method that makes the transition efficiently, is widely used.
So-called methylolation method is in the presence of protonic acid, non-d-alpha-tocopherol and formaldehyde reaction generate the methylol compound of non-d-alpha-tocopherol, under the hydrogenation catalyst effect, combine then methylol is reduced to methyl, thereby change into the d-alpha-tocopherol with hydrogen.With d-γ-vitamin-E is example, and the primitive reaction formula of methylolation method is:
Reaction transition of traditional methylolation is generally carried out in high temperature, highly compressed tank reactor, though technical maturity, the ubiquity reaction times is longer, side reaction complexity, product and hydrogenation catalyst separation difficulty, problem such as technological process is discontinuous.
Summary of the invention
The object of the present invention is to provide a kind of fixed bed transition method of vitamin-E, use fixed-bed reactor to carry out methylolation reaction transition, reaction can be carried out continuously, operates simple than tank reactor; Material and hydrogenation catalyst contact gear ratio tank reactor are abundant, can improve utilization ratio, the shortening reaction times of catalyzer; The separation problem that does not have product and catalyzer, catalyzer can life-time service.
The technical solution adopted for the present invention to solve the technical problems is: with the natural mixing vitamin E of total content of vitamin E 50～100% raw material as reaction transition, react continuously in fixed-bed reactor, the process of fixed bed reaction transition is as follows:
1) be vitamin-E with natural mixing vitamin E, methylolation agent, acid catalyst and methyl alcohol according to mass volume ratio: methyl alcohol=1: 40～1: 10, methylolation agent: methyl alcohol=1: 40～1: 10, acid catalyst: methyl alcohol=1: 400～add in stirring tank at 1: 80, temperature is normal temperature～70 ℃, with the air in the nitrogen replacement stirring tank, use hydrogen exchange nitrogen again, and, mix with pressurized with hydrogen to 3.0～8.0MPa;
2) hydrogenation catalyst is seated in the fixed-bed reactor, the temperature of control fixed-bed reactor is 160～230 ℃, and pressure is 3.0～8.0MPa;
3) with 1) mixed reaction mass feeds the reaction that makes the transition in the fixed-bed reactor continuously in the step, and the residence time of material in fixed bed is controlled at 1～8h;
4) effluent liquid of collection fixed-bed reactor, steaming desolventizes normal hexane and obtains natural vitamin E product behind n-hexane extraction, washing, anhydrous sodium sulfate drying, wherein the d-alpha-tocopherol accounts for more than 97% of total vitamin-E, and d-alpha-tocopherol yield is higher than 90%.
Described methylolation agent is a formalin, formaldehyde content 37～40%.
Described acid catalyst is Phenylsulfonic acid, tosic acid, boric acid, acetate.
Described hydrogenation catalyst is the particulate state palladium-carbon catalyst.
Fixed bed makes the transition to be reflected under high temperature, the condition of high voltage and carries out.The temperature of fixed bed can be controlled with thermal oil or electrically heated.Before reaction transition, also must hunt leak to reaction system, guarantee that device has good stopping property.
Filling hydrogenation catalyst in the fixed-bed reactor.The filling situation has a significant impact the effect of transition reaction, must guarantee catalyzer in fixed bed, load closely, even.Concrete filling method is: the fixed bed bottom is a small amount of quartz sand of filling earlier, begin to add catalyzer then, the limit adds the catalyzer limit and knocks fixed bed, guarantee that filling evenly, filling finishes back nitrogen compacting, the gap is used catalyst make-up again, and till not having the space to produce substantially behind the logical nitrogen, a small amount of quartz sand at last recharges at the top.The purpose of filling quartz sand is to prevent that catalyzer from being taken out of.
Will note controlled temperature and pressure in the reaction process transition, and it is constant that feed rate keeps, and guarantees the sufficiently long contact reacts time.Because hydrogenation catalyst is seated in the fixed bed, do not mix with product solution after transition, can omit the Separation and Recovery process of catalyzer.
The useful effect that the present invention has is:
Natural mixing vitamin E with different content is a raw material, through fixed bed transition reaction, with the d-β in the raw material-, d-γ-, the d-delta-tocopherol is converted into the d-alpha-tocopherol, and the d-alpha-tocopherol accounts for more than 97% of total vitamin-E in the product, and d-alpha-tocopherol yield is higher than 90%.This method hydrogenation catalyst can use for a long time continuously, has omitted the Separation and Recovery process of catalyzer, and it is simple to have a technical process, but the advantage of operate continuously.
Embodiment
Embodiment 1:
With natural mixing vitamin E raw material 20.0g, formalin 20.0g, Phenylsulfonic acid 3.0g, methyl alcohol 400ml adds in the stirring tank.Total content of vitamin E 85.05% of raw material, d-alpha-tocopherol content 1.17% wherein, d-β-+d-γ-content of vitamin E 33.52%, d-delta-tocopherol content 50.36%.Fixed-bed reactor are of a size of φ 12 * 430, filling palladium-carbon catalyst 35g in the reactor, and be heated to 180 ℃.Air in the earlier logical nitrogen replacement system is used hydrogen exchange nitrogen then.Stirring tank is forced into 5.0MPa, begins to stir, reaction mass is mixed.Fixed-bed reactor are forced into 5.0MPa.Reaction mass fed in the fixed-bed reactor continuously react.The residence time of material in fixed bed is 4 hours.Collect the effluent liquid of fixed-bed reactor,, discard the methyl alcohol phase, use the distilled water wash normal hexane then three times mutually with n-hexane extraction three times, aqueous phase discarded, normal hexane steams to desolventize after with anhydrous sodium sulfate drying and obtains natural vitamin E product.Total content of vitamin E of product is 89.2%, and wherein the d-alpha-tocopherol accounts for 98% of total vitamin-E, and the yield of d-alpha-tocopherol is 90%.
Embodiment 2:
With natural mixing vitamin E raw material 25.0g, formalin 20.0g, tosic acid 4.0g, methyl alcohol 400ml adds in the stirring tank.Total content of vitamin E 56.21% of raw material, d-alpha-tocopherol content 1.12% wherein, d-β-+d-γ-content of vitamin E 25.86%, d-delta-tocopherol content 29.23%.Fixed-bed reactor are of a size of φ 12 * 430, filling palladium-carbon catalyst 35g in the reactor, and be heated to 185 ℃.Air in the earlier logical nitrogen replacement system is used hydrogen exchange nitrogen then.Stirring tank is forced into 5.0MPa, begins to stir, reaction mass is mixed.Fixed-bed reactor are forced into 5.0MPa.Reaction mass fed in the fixed-bed reactor continuously react.The residence time of material in fixed bed is 3 hours.Collect the effluent liquid of fixed-bed reactor,, discard the methyl alcohol phase, use the distilled water wash normal hexane then three times mutually with n-hexane extraction three times, aqueous phase discarded, normal hexane steams to desolventize after with anhydrous sodium sulfate drying and obtains natural vitamin E product.Total content of vitamin E of product is 60.4%, and wherein the d-alpha-tocopherol accounts for 97% of total vitamin-E, and the yield of d-alpha-tocopherol is 92%.
Embodiment 3:
With natural mixing vitamin E raw material 15.0g, formalin 20.0g, acetate 4.0g, methyl alcohol 400ml adds in the stirring tank.Total content of vitamin E 80.54% of raw material, d-alpha-tocopherol content 2.53% wherein, d-β-+d-γ-content of vitamin E 53.88%, d-delta-tocopherol content 24.13%.Fixed-bed reactor are of a size of φ 12 * 430, filling palladium-carbon catalyst 35g in the reactor, and be heated to 190 ℃.Air in the earlier logical nitrogen replacement system is used hydrogen exchange nitrogen then.Stirring tank is forced into 5.0MPa, begins to stir, reaction mass is mixed.Fixed-bed reactor are forced into 5.0MPa.Reaction mass fed in the fixed-bed reactor continuously react.The residence time of material in fixed bed is 3 hours.Collect the effluent liquid of fixed-bed reactor,, discard the methyl alcohol phase, use the distilled water wash normal hexane then three times mutually with n-hexane extraction three times, aqueous phase discarded, normal hexane steams to desolventize after with anhydrous sodium sulfate drying and obtains natural vitamin E product.Total content of vitamin E of product is 83.6%, and wherein the d-alpha-tocopherol accounts for 98% of total vitamin-E, and the yield of d-alpha-tocopherol is 92%.
Embodiment 4:
With natural mixing vitamin E raw material 200.0g, formalin 250.0g, Phenylsulfonic acid 50.0g, methyl alcohol 5000ml adds in the stirring tank.Total content of vitamin E 80.54% of raw material, d-alpha-tocopherol content 2.53% wherein, d-β-vitamin-E+d-γ-content of vitamin E 53.88%, d-delta-tocopherol content 24.13%.Fixed-bed reactor are of a size of φ 40 * 500, filling palladium-carbon catalyst 452g in the reactor, and be heated to 180 ℃.Air in the earlier logical nitrogen replacement system is used hydrogen exchange nitrogen then.Stirring tank is forced into 5.0MPa, begins to stir, reaction mass is mixed.Fixed-bed reactor are forced into 5.0MPa.Reaction mass fed in the fixed-bed reactor continuously react.The residence time of material in fixed bed is 3 hours.Collect the effluent liquid of fixed-bed reactor,, discard the methyl alcohol phase, use the distilled water wash normal hexane then three times mutually with n-hexane extraction three times, aqueous phase discarded, normal hexane steams to desolventize after with anhydrous sodium sulfate drying and obtains natural vitamin E product.Total content of vitamin E of product is 83.8%, and wherein the d-alpha-tocopherol accounts for 98% of total vitamin-E, and the yield of d-alpha-tocopherol is 93%.
Claims (4)
1. the fixed bed transition method of a natural VE is characterized in that reacting continuously in fixed-bed reactor with the natural mixing vitamin E of total content of vitamin E 50～100% raw material as reaction transition, and the process of fixed bed reaction transition is as follows:
1) be vitamin-E with natural mixing vitamin E, methylolation agent, acid catalyst and methyl alcohol according to mass volume ratio: methyl alcohol=1: 40～1: 10, methylolation agent: methyl alcohol=1: 40～1: 10, acid catalyst: methyl alcohol=1: 400～add in stirring tank at 1: 80, temperature is normal temperature～70 ℃, with the air in the nitrogen replacement stirring tank, use hydrogen exchange nitrogen again, and, mix with pressurized with hydrogen to 3.0～8.0MPa;
2) hydrogenation catalyst is seated in the fixed-bed reactor, the temperature of control fixed-bed reactor is 160～230 ℃, and pressure is 3.0～8.0MPa;
3) with 1) mixed reaction mass feeds the reaction that makes the transition in the fixed-bed reactor continuously in the step, and the residence time of material in fixed bed is controlled at 1～8h;
4) effluent liquid of collection fixed-bed reactor, steaming desolventizes normal hexane and obtains natural vitamin E product behind n-hexane extraction, washing, anhydrous sodium sulfate drying, wherein the d-alpha-tocopherol accounts for more than 97% of total vitamin-E, and d-alpha-tocopherol yield is higher than 90%.
2. the fixed bed transition method of a kind of natural VE according to claim 1, it is characterized in that: described methylolation agent is a formalin, formaldehyde content 37～40%.
3. the fixed bed transition method of a kind of natural VE according to claim 1, it is characterized in that: described acid catalyst is Phenylsulfonic acid, tosic acid, boric acid, acetate.
4. the fixed bed transition method of a kind of natural VE according to claim 1, it is characterized in that: described hydrogenation catalyst is the particulate state palladium-carbon catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410053241 CN1253447C (en) | 2004-07-23 | 2004-07-23 | Method for fixed bed transfer of natural vitamin E |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410053241 CN1253447C (en) | 2004-07-23 | 2004-07-23 | Method for fixed bed transfer of natural vitamin E |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1603321A true CN1603321A (en) | 2005-04-06 |
| CN1253447C CN1253447C (en) | 2006-04-26 |
Family
ID=34666093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410053241 Expired - Fee Related CN1253447C (en) | 2004-07-23 | 2004-07-23 | Method for fixed bed transfer of natural vitamin E |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1253447C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766266A (en) * | 2012-07-18 | 2012-11-07 | 浙江大学 | Method for extracting and separating vitamin E polyethylene glycol succinic acid monoester and diester |
| CN103342820A (en) * | 2013-06-27 | 2013-10-09 | 浙江大学 | Method for extracting and separating polyehtylne glycol fatty acid monoester and diester |
| CN107935980A (en) * | 2017-11-24 | 2018-04-20 | 宁波大红鹰生物工程股份有限公司 | A kind of production technology of D alpha tocopherols |
-
2004
- 2004-07-23 CN CN 200410053241 patent/CN1253447C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766266A (en) * | 2012-07-18 | 2012-11-07 | 浙江大学 | Method for extracting and separating vitamin E polyethylene glycol succinic acid monoester and diester |
| CN102766266B (en) * | 2012-07-18 | 2013-09-25 | 浙江大学 | Method for extracting and separating vitamin E polyethylene glycol succinic acid monoester and diester |
| CN103342820A (en) * | 2013-06-27 | 2013-10-09 | 浙江大学 | Method for extracting and separating polyehtylne glycol fatty acid monoester and diester |
| CN107935980A (en) * | 2017-11-24 | 2018-04-20 | 宁波大红鹰生物工程股份有限公司 | A kind of production technology of D alpha tocopherols |
| CN107935980B (en) * | 2017-11-24 | 2021-06-18 | 宁波大红鹰生物工程股份有限公司 | Production process of D-alpha-tocopherol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1253447C (en) | 2006-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1914148A (en) | Process for the reactive extraction of levulinic acid | |
| CN1253447C (en) | Method for fixed bed transfer of natural vitamin E | |
| CN111440133A (en) | Method for preparing D, L-pantoic acid lactone by normal pressure reduction | |
| CN111138388A (en) | Method for preparing 2,5-furandimethanol by fructose one-pot method under hydrogen supply of formic acid | |
| CN112961123B (en) | Method for preparing 3- (2-furyl) -2-methyl-2-acrolein by catalyzing oxidation condensation of furfural and n-propanol | |
| CN1177791C (en) | Process and the manufacture of alpha, alpha-branched carboxylic acids | |
| CN101475474B (en) | Method for preparing oxalate by CO conjugation | |
| CN1927800A (en) | Synthesis process of 2,4,6-trimethyl benzoic acid | |
| CN1166608C (en) | Three-phase phase-transfer catalytic synthesis process of 9,9-dimethoxyl methyl) fluorene | |
| CN1765862A (en) | Method for synthesizing alkynol by ketone and acetylene | |
| CN108636423A (en) | A kind of preparation method of load type nano gold catalyst and application | |
| CN1156418C (en) | External coupler of rectifying reaction for preparing cyclohexane by catalyst hydrogenation of benzene and its synthesizing process | |
| CN100467439C (en) | Process for synthesizing dialkyldiphenylamine | |
| CN103497130A (en) | Preparation method of D,L-2-hydroxy-4-methylthio butyric ester | |
| CN111689933A (en) | Synthetic method of 5- [ (phenylamino) methyl ] -2-furanmethanol | |
| CN1769254A (en) | Method for synthesizing alkynol by ketone and acetylene | |
| CN1246307C (en) | Method for producing sulfolane by hydrogenation of sulfolene | |
| CN1300080C (en) | Method for synthesizing 4-methoxy styrene | |
| CN101033196A (en) | Method of rectifying and synthesizing N,N-dimethacrylamide by DMDMAA reaction | |
| CN109985664A (en) | The fructose converting acidic solid catalyst for 2,5- dimethyl furan of one-step catalytic | |
| CN112517013B (en) | Cu-based catalyst and method for preparing gamma-valerolactone and delta-cyclopentalactone by using same | |
| CN101066966A (en) | Process of synthesizing trihydroxy methyl propane acetal | |
| CN101314567A (en) | Method for synthesizing chirality source compound n-pentyl ester tartaric with boric acid catalysis | |
| CN101314565A (en) | Method for synthesizing chirality source compound n-propyl tartaric with boric acid catalysis | |
| CN1401645A (en) | Process for preparing high-purity alpha type natural vitamin E from high content mixed tocopherol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Zhejiang Worldbest Pharmaceuticals Science Technic Development Co., Ltd. Assignor: Zhejiang University Contract fulfillment period: 2008.10.20 to 2024.7.23 Contract record no.: 2008330001713 Denomination of invention: Method for fixed bed transfer of natural vitamin E Granted publication date: 20060426 License type: Exclusive license Record date: 20081105 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.10.20 TO 2024.7.23; CHANGE OF CONTRACT Name of requester: ZHEJIANG PROVINCE HUAYUAN PHARMACEUTICAL SCIENCE A Effective date: 20081105 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060426 Termination date: 20200723 |