CN105801552A - Preparation method of high-purity natural d-alpha-tocopheryl acetate - Google Patents
Preparation method of high-purity natural d-alpha-tocopheryl acetate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
- C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
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Abstract
The invention provides a preparation method of high-purity natural d-alpha-tocopheryl acetate.The preparation method includes the following steps of a, conducting of a d-alpha-tocopheryl acetate esterification reaction, wherein d-alpha-tocopheryl acetate and acetic anhydride are subjected to the esterification reaction under the condition of a catalyst to generate a d-alpha-tocopheryl acetate target object, the reaction temperature ranges from 50 DEG C to 55 DEG C, petroleum ether is adopted as a reaction solvent, and acetic anhydride is added dropwise; b, silica gel adsorption separation and purification, wherein a primary d-alpha-tocopheryl acetate concentrated solution is used as a raw material, silica gel is adopted as a stationary phase, normal hexane is used as eluant for elution, column feeding and elution are conducted, and meanwhile a secondary d-alpha-tocopheryl acetate concentrated solution is obtained; c, molecular distillation to increase the content and improve quality, wherein low-boiling-point substances of the secondary d-alpha-tocopheryl acetate concentrated solution are removed through a film evaporator at a high vacuum degree and certain temperature.The content of natural d-alpha-tocopheryl acetate can reach 98% or above, and industrialization is achieved.
Description
Technical field
The present invention relates to food additive natural d-α-tocopheryl acetate production technical field, tool
Body relates to the preparation method of a kind of high-purity natural d-α-tocopheryl acetate.
Background technology
Vitamin E (Vitamin E) is a kind of fatsoluble vitamin, also known as tocopherol, is
One of topmost antioxidant, is divided into chemosynthesis and the big class of natural extract vitamin E two,
Wherein chemosynthesis vitamin E yield accounts for more than 80%, is mainly used in feed additive.And
The vitamin E application of natural extract is more extensive, safer.
The vitamin E of natural extract is dextrorotation chemical isomer (d-configuration), has optical activity,
Physiologically active is better than the vitamin E of chemosynthesis.The physiologically active of natural Vitamin E is synthesis
3-8 times of vitamin E.The vitamin E of chemosynthesis is by left-handed and dextrorotation chemical isomer
The racemic modification (dl-alpha-tocopherol) constituted, without optical activity.
Natural Vitamin E presses number of methyl groups difference and unsaturated double-bond on aliphatic chain on phenyl ring, can
It is divided into α, β, γ, Delta-Tocopherol and α, β, γ, δ-tocotrienol 8 kinds with dividing
Isomer, their physiologically active is different, and natural d-alpha-tocopherol has heretofore known maximum
Physiologically active.
Natural d-a-tocopheryl acetate is natural Vitamin E one esterification derivative, frequently as
The supply form of business, is widely used in the row such as medicine, health product, food and feed additive
Industry, it has a extensive future.
The preparation of current natural d-a-tocopheryl acetate typically with d-alpha-tocopherol as raw material,
Carry out esterification with acetic anhydride under catalysts conditions to obtain.Used catalyst has acidic catalyst
Agent, base catalyst and lipase etc.；There are solvent method and solventless method；Reaction temperature has height to have
Low.The comparison that natural d-a-tocopheryl acetate is studied in terms of synthesis is many, and subsequent purification is studied
Less.Existing literature procedure is as follows:
1, the Study on Preparation (Zhejiang University, 2005) of natural Vitamin E ester.This conjunction
One-tenth technique is: the response time is 2 hours, and reaction temperature is room temperature, and acetic anhydride/alpha-tocopherol is
2 (mol/mol), catalyst selection concentrated hydrochloric acid/zinc oxide system, concentrated hydrochloric acid/alpha-tocopherol is
0.0056 (ml/g), zinc oxide dosage is the 0.56% of alpha-tocopherol, and normal hexane selected by solvent,
Normal hexane/alpha-tocopherol is 2.5 (ml/g).The conversion ratio of alpha-tocopherol and alpha-tocopherol
The yield of acetate is all more than 98%.
2, preparation (the modern food section of natural Vitamin E acetate
Skill, 2005,21 (2): 85-87).These process conditions are with 62.31% natural VE for raw material 50
Gram, acetic anhydride consumption be 9.0ml, the response time be 5.5 hours, Triethylamine catalyst uses
Amount is 60 DEG C for 5.0ml, reaction temperature.VE esterification yield is 94.93%.
3, synthesis (" China's oil of natural Vitamin E acetate
Fat ", 2010,35 (5): 58-60).This synthesis condition, with natural VE as raw material, reacts
Time 60min, reaction temperature 110 DEG C, acetic anhydride consumption 45%, catalyst amount 4.0%.VE
Acetate conversion ratio reaches 99.4%.
4, alpha-tocopherol acetate preparation (" Chemical Engineering Technology with open
Send out ", 2011,40 (8): 28-30).This preparation method is with 95% alpha-tocopherol and acetic acid
Acid anhydride is raw material, and p-methyl benzenesulfonic acid is prepared by catalyst, and reaction raw materials is than n (alpha-tocopherol): n is (right
Toluenesulfonic acid): n (acetic anhydride)=1:0.007:2, the response time is 1h, and reaction temperature is
100 DEG C, alpha-tocopherol acetate yield is 95%.
5, vitamin e acetate preparation method and spectral characterization (Hengshui student burnout engineering college；Journey
Great waves).New catalyst solid super-strong acid SO42-/TiO2 is utilized to synthesize VE acetas, synthesis
Technique: temperature 40 DEG C, time 3h, acetic anhydride and VE mol ratio 1.2, solid super-strong acid
SO42-/TiO2 catalyst amount 1.0g, reaction esterification yield is 96.6%.
6, (University Of Xiangtan master learns in the preparation of natural alpha-tocofecol and alpha-tocopherol acetate
Degree thesis whole-length；On May 1st, 2007).This synthetic method is homemade 93.60% with content
Alpha-tocopherol is raw material, and acetic anhydride is 1.8～2:1 with the mol ratio of alpha-tocopherol, catalyst
Selecting p-methyl benzenesulfonic acid, p-methyl benzenesulfonic acid consumption is the 0.3% of alpha-tocopherol, and reaction temperature is
95 DEG C, the acetylization reaction time is 1h, and the conversion ratio of alpha-tocopherol can reach 99.48%, reaction
Selectivity is 98.81%, and the yield of alpha-tocopherol acetate can reach 98.30%.
7, with natural tocopherol, the synthetic tocopherol tocopherol acetas that has been raw material comparative study
Preparation technology (Wuhan University of Technology's master thesis；On June 1st, 2008).This conjunction
One-tenth condition is 4 hours response time, reaction temperature 55 DEG C, Triethylamine catalyst consumption 6ml,
Acetic anhydride/tocopherol mol ratio is 2, natural tocopherol conversion ratio 92.78%.
8, research (Gong Xue soldier's master's degree of lipase-catalyzed synthesis natural Vitamin E ester
Paper).Develop laboratory self-control immobilized candida sp.lipase sp99-125 catalysis herein
The process route of synthesis of natural vitamin-e ester.Alpha-tocopherol 0.6g, the consumption of anhydride is 4mL,
Reaction temperature 70 DEG C, immobilized enzyme consumption 0.6g, in reaction system, add water absorbing agent 13X divide
Son sieve, the conversion ratio of reaction is 95%.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of natural d-α-tocopheryl acetate content
Can reach more than more than 98% and realize the high-purity natural d-α-tocopheryl acetate of industrialization
Preparation method.
For reaching above-mentioned purpose, the present invention is realized by the following technical scheme.
1, d-alpha-tocopherol esterification reaction: use the d-alpha-tocopherol that our factory produces at goods
For raw material, content about 93%, first under catalysts conditions, carry out esterification with acetic anhydride
Generating d-α-tocopheryl acetate object, catalyst uses lewis acid anhydrous zinc chloride, instead
Answering temperature 50-55 DEG C, reaction dissolvent uses petroleum ether (boiling range 30-60 DEG C), and acetic anhydride is to drip
The form added adds, time for adding 1.5-2.5 hour, 2-3 hour response time, and esterification is anti-
After should terminating reaction mass wash with water three times may insure that removing water-solubility impurity (zinc chloride,
Acetic acid etc.), then by vaporizer concentration and recovery solvent, obtain d-α-tocopherol acetate simultaneously
Phenol concentrated solution.
2, silica gel adsorption is isolated and purified: with d-α-tocopheryl acetate concentrated solution as raw material, adopt
With silica gel as fixing phase, normal hexane is that eluent carries out eluting, first d-α-tocopherol acetate
Phenol concentrated solution and normal hexane are configured to upper prop liquid by the mass ratio of 1:0.5-1, then press
The flow of 295-505L/h carries out upper prop, and the upper column quantity of each d-α-tocopheryl acetate is silica gel
The 6-10% of quality.Upper prop carries out eluting with normal hexane by the flow of 495-805L/h after terminating,
Operation temperature is room temperature, collects d-α-tocopheryl acetate eluent fraction, then evaporation and concentration
Recycling design, obtains d-α-tocopheryl acetate concentrated solution simultaneously.
3, molecular distillation improves content and quality: condition of high vacuum degree and certain at a temperature of, d-
α-tocopheryl acetate concentrated solution removes low-boiling-point substance through membrane evaporator；One-level short-path distillation removes
Remove front-end volatiles；Two grades of short-path distillations remove high-boiling components, obtain high-quality high-purity natural simultaneously
D-α-tocopherol acetate phenolic product, content is more than more than 98%；Three grades of short-path distillations reclaim residue
D-α-tocopheryl acetate.
Concrete scheme is as follows:
One, d-alpha-tocopherol esterification reaction
1, the d-alpha-tocopherol using our factory to produce is raw material at goods, content about 93%,
This is the technical merit that my company reaches at present.
2, feed intake: by d-α-tocopheryl acetate in goods, reaction dissolvent petroleum ether, catalysis
Agent anhydrous powder zinc chloride puts in esterifying kettle.D-α-tocopheryl acetate is at goods: petroleum ether
Mass ratio 1:0.5-1, catalyst anhydrous zinc chloride is that d-α-tocopheryl acetate is at quality of item
3-5%.
3, dropping: heating is warmed up to 50 DEG C material, drips vinegar in 1.5-2.5 hour
Anhydride, continue esterification 2-3 hour, control reaction temperature between 50-55 DEG C, d-α
-tocopherol: the mol ratio of acetic anhydride is 1:1.1-1.3.
4, sampling detection: esterification terminates, d-alpha-tocopherol in sampling detection esterifying liquid
Content less than 0.5%, can reach 0.5/93=99.5% through the conversion ratio of measuring and calculating d-alpha-tocopherol
Above.
5, washing: with a certain amount of distilled water wash, esterifying liquid may insure that removing is water-soluble for three times
Property impurity (zinc chloride, acetic acid etc.), each slurry is that d-alpha-tocopherol is in goods matter
The 60-80% of amount.Washing process such as occurring, emulsion can add the second of washings quality 5%
Alcohol carries out breakdown of emulsion.
6, evaporation: the esterifying liquid washed is through membrane evaporator recycling design petroleum ether, same
Time obtain d-α-tocopheryl acetate concentrated solution, d-α-tocopheryl acetate concentrated solution contains after testing
Amount can reach about 94%.
Two, silica gel adsorption is isolated and purified
7, with d-α-tocopheryl acetate concentrated solution as raw material, rustless steel silicagel column φ 600 ×
12000, use silochrom (80-100 mesh) as fixing phase.
8, wet method dress post: silochrom is put into baking oven, activates 2-3 at a temperature of 150 DEG C
Hour.Then the ratio with normal hexane 1:0.5-1 by weight mixes in mixing kettle, uses
In nitrogen press-in rustless steel silicagel column, the rustless steel silicagel column dress silicon of specification φ 600 × 12000
Glue amount is about about 1500kg.
9, the preparation of upper prop liquid: by d-α-tocopheryl acetate concentrated solution with normal hexane by weight
The ratio of 1:1-3 mixes in mixing kettle, is configured to upper prop liquid, and d-α in upper prop liquid-
Tocopheryl acetate mass percent is 25-50%.
10, upper prop: the upper prop liquid prepared is carried out upper prop by the flow velocity of 295-505L/h,
Column temperature is room temperature, divides and carries out upper prop for 4-5 time, and the upper column quantity of each d-α-tocopheryl acetate is
The 6-10% of silica gel quality.
11, normal hexane eluting: with flowing phase normal hexane by 495-805ml/h every time after upper prop terminates
Flow carry out eluting, collect impure eluent simultaneously；Use tlc analysis fast detection method
For process control, when eluent has detected that d-α-tocopheryl acetate starts when flowing out to collect
D-α-tocopheryl acetate eluent, until terminating when flowing out without d-α-tocopheryl acetate.
12, evaporation: d-α-tocopheryl acetate eluent membrane evaporator is evaporated reclaiming
Normal hexane, obtains d-α-tocopheryl acetate concentrated solution, after testing d-α-tocopherol acetate simultaneously
Phenol concentrated solution content can reach about 97%.
Three, molecular distillation improves content and quality
13, thin film evaporation: d-α-tocopheryl acetate secondary concentration liquid is pressed 200-250L/h and (risen
/ hour) flow velocity entrance membrane evaporator.Membrane evaporator area is 4-6, uses 0.3MPa
The steam heating of left and right, about vacuum degree control 3KPa.Removing normal hexane is residual with this understanding
Stay solvent and low-boiling-point substance.
14, one-level short-path distillation: enter one-level from membrane evaporator material gear pump out
Short-path distillation.One-level short-path distillation area 4, utilizes the deep fat of deep fat electric heater to add
Heat, short-path distillation import hot oil temperature controls 160-175 DEG C, and system vacuum controls 2-3Pa.
Remove front-end volatiles with this understanding.
15, two grades of short-path distillations: enter two from one-level short-path distillation material out gear pump
Level short-path distillation.Two grades of short-path distillation areas 4, utilize the deep fat of deep fat electric heater to carry out
Heating, short-path distillation import hot oil temperature controls 180-190 DEG C, and system vacuum controls
2-3Pa.Collecting d-α-tocopherol acetate phenolic product with this understanding, d-α-acetic acid is raw after testing
Educate phenolic product content more than more than 98%.
16, three grades of short-path distillations: enter three from two grades of short-path distillations material out gear pump
Level short-path distillation.Three grades of short-path distillation areas 4, utilize the deep fat of deep fat electric heater to carry out
Heating, short-path distillation import hot oil temperature controls 200-210 DEG C, and system vacuum controls
2-3Pa.Reclaim remaining d-α-tocopheryl acetate with this understanding.
The natural d-alpha-tocopherol that present invention our factory produces is raw material at goods, by esterification
Reaction, silica gel adsorption purification, the method for molecular distillation, obtain high-quality high-purity natural d-
α-tocopherol acetate phenolic product.Have an advantage in that: 1, utilize lewis acid anhydrous zinc chloride conduct
Catalyst, excellent catalytic effect, reaction gentleness, side reaction is few, and conversion ratio is high, removes and compares appearance
Easily.2, use petroleum ether (boiling range 30-60 DEG C) as reaction dissolvent, esterification can be made anti-
Should carry out under homogeneous phase condition, prevent reaction mass hot-spot, reduce the generation of side reaction.
The vaporization backflow of part low boiling petroleum ether can be made, it is simple to reaction temperature under the conditions of this reaction temperature
Control.3, acetic anhydride uses the mode of dropping to add, and makes reaction latent heat discharge uniformly,
It is easy to the control of reaction temperature and prevents reaction mass hot-spot.4, after esterification,
The boiling point making d-α-tocopheryl acetate and impurity there occurs change, can make by fractional distillation distill into
One step improves product content and is possibly realized.5, silica gel wet method dress post is used, in silicagel column can being made
Silica gel be mounted so as to evenly, reduce material generation channel, short circuit phenomenon, improve silicagel column
Isolated and purified effect.6, silica gel adsorption purification uses single solvent normal hexane to carry out dispensing and stream
The eluting of dynamic phase, it is simple to operation and the recovery of solvent.7, molecular distillation uses fine vacuum, company
Continuous operation, material heated time is short, is conducive to improving product color.8, silica gel adsorption is used
The mode that isolated and purified and molecular distillation combines, can obtain high-quality high-purity natural d-
α-tocopheryl acetate, 9, to use tlc analysis fast detection method to be used for collecting d-α-acetic acid raw
Educate phenol eluent, make process control simple, quick, practical.
Detailed description of the invention
Following instance is used for illustrating the present invention, but does not limits the scope of the invention.
Embodiment one:
One, d-alpha-tocopherol esterification reaction
1, the d-alpha-tocopherol using our factory to produce is raw material at goods, content 92.86%.
2, feed intake: by d-α-tocopheryl acetate at goods 500kg, reaction dissolvent petroleum ether
500kg, catalyst anhydrous powder zinc chloride 20kg put in esterifying kettle.
3, dropping: heating is warmed up to 50 DEG C material, is added drop-wise to esterification by 130kg acetic anhydride
In still, time for adding 2 hours, continue esterification 3 hours, reaction temperature 50-55 DEG C,
It is computed d-alpha-tocopherol: the mol ratio of acetic anhydride is 1:1.18.
4, sampling detection: esterification terminates, d-alpha-tocopherol in sampling detection esterifying liquid
Content 0.36%.
5, washing: the distilled water of esterifying liquid 350kg washs, altogether washing three times, water
Occur emulsion to add 15kg ethanol when washing and carry out breakdown of emulsion, respond well.
6, evaporation: the esterifying liquid washed is through membrane evaporator recycling design petroleum ether, same
Time obtain 544kg d-α-tocopheryl acetate concentrated solution, d-α-tocopheryl acetate is dense after testing
Contracting liquid hold-up can reach 93.92%.Esterification object d-α-tocopheryl acetate molecular weight ratio
Raw material d-alpha-tocopherol increase by 102, so the quantity of d-α-tocopheryl acetate concentrated solution and
Content all can increased compared with raw material.
Two, silica gel adsorption is isolated and purified
7, with d-α-tocopheryl acetate concentrated solution as raw material, content 93.92%.Rustless steel silicon
Glue post specification φ 600 × 12000, uses silochrom (80-100 mesh) as fixing phase.
8, wet method dress post: 1500kg silochrom is put into baking oven, at a temperature of 150 DEG C
Activate 3 hours.Mix in the silica gel being baked and 1500kg normal hexane are put into mixing kettle,
With in nitrogen press-in rustless steel silicagel column.
9, the preparation of upper prop liquid: by 544kg d-α-tocopheryl acetate concentrated solution and 600kg
Normal hexane mixes in putting into mixing kettle, is configured to d-α-tocopheryl acetate upper prop liquid, its
Mass percent is 44.66%.
10, upper prop: the upper prop liquid prepared is carried out upper prop, column temperature by the flow velocity of 500L/h
For room temperature, carrying out upper prop in four times, the upper column quantity of each d-α-tocopheryl acetate is 136kg,
Through calculating upper column quantity is silica gel quality the 9.07% of each d-α-tocopheryl acetate.
11, normal hexane eluting: with flowing phase normal hexane by 800L/h's every time after upper prop terminates
Flow carries out eluting, collects impure eluent simultaneously.Tlc analysis fast detection method is used to use
In process control, when eluent has detected that d-α-tocopheryl acetate switches over when flowing out,
Start to collect d-α-tocopheryl acetate eluent, during until flowing out without d-α-tocopheryl acetate
Terminate.
12, evaporation: use membrane evaporator after being merged by four d-α-tocopheryl acetate eluents
It is evaporated reclaiming normal hexane, obtains d-α-tocopheryl acetate concentrated solution 497kg, warp simultaneously
Detection d-α-tocopheryl acetate concentrated solution content can reach 97.21%, and the response rate reaches 94.56%.
Three, molecular distillation improves content and quality
13, thin film evaporation: d-α-tocopheryl acetate concentrated solution is entered by 200 ls/h of flow velocitys
Membrane evaporator.Membrane evaporator area is 4, uses the steam heating of about 0.3MPa,
About vacuum degree control 3KPa.Removing normal hexane residual solvent and low-boiling-point substance with this understanding.
14, one-level short-path distillation: enter one-level from membrane evaporator material gear pump out
Short-path distillation.One-level short-path distillation area 4, utilizes the deep fat of deep fat electric heater to add
Heat, short-path distillation import hot oil temperature controls 170 DEG C, and system vacuum controls 2-3Pa.?
Front-end volatiles 36kg, after testing d-α-tocopheryl acetate product content is collected under the conditions of this
89.74%.Reclaim this d-α-tocopheryl acetate to can be used for allocating low specification d-α-tocopherol acetate
Phenolic product (such as 85% content d-α-tocopherol acetate phenolic product).
15, two grades of short-path distillations: enter two from one-level short-path distillation material out gear pump
Level short-path distillation.Two grades of short-path distillation areas 4, utilize the deep fat of deep fat electric heater to carry out
Heating, short-path distillation import hot oil temperature controls 185 DEG C, and system vacuum controls 2-3Pa.
Collecting d-α-tocopherol acetate phenolic product 386kg with this understanding, d-α-acetic acid is raw after testing
Educate phenolic product content 98.45%, reach 76.62% through measuring and calculating d-α-tocopheryl acetate recovery rate.
16, three grades of short-path distillations: enter three from two grades of short-path distillations material out gear pump
Level short-path distillation.Three grades of short-path distillation areas 4, utilize the deep fat of deep fat electric heater to carry out
Heating, short-path distillation import hot oil temperature controls 200 DEG C, and system vacuum controls 2-3Pa.
Reclaiming remaining d-α-tocopheryl acetate 73kg with this understanding, d-α-acetic acid is raw after testing
Educate phenolic product content 94.61%.Reclaim this d-α-tocopheryl acetate to can be used for allocating low specification
D-α-tocopherol acetate phenolic product (such as 90% content d-α-tocopherol acetate phenolic product).
Embodiment two:
One, d-alpha-tocopherol esterification reaction
1, the d-alpha-tocopherol using our factory to produce is raw material at goods, content 92.37%.
2, feed intake: by d-α-tocopheryl acetate at goods 540kg, reaction dissolvent petroleum ether
500kg, catalyst anhydrous powder zinc chloride 20kg put in esterifying kettle.
3, dropping: heating is warmed up to 50 DEG C material, is added drop-wise to esterification by 145kg acetic anhydride
In still, time for adding 2 hours, continue esterification 3 hours, reaction temperature 50-55 DEG C,
It is computed d-alpha-tocopherol: the mol ratio of acetic anhydride is 1:1.23.
4, sampling detection: esterification terminates, d-alpha-tocopherol in sampling detection esterifying liquid
Content 0.31%.
5, washing: the distilled water of esterifying liquid 350kg washs, altogether washing three times.
6, evaporation: the esterifying liquid washed is through membrane evaporator recycling design petroleum ether, same
Time obtain 596kg d-α-tocopheryl acetate concentrated solution, d-α-tocopheryl acetate is dense after testing
Contracting liquid hold-up can reach 93.12%.Esterification object d-α-tocopheryl acetate molecular weight ratio
Raw material d-alpha-tocopherol increase by 102, so the quantity of d-α-tocopheryl acetate concentrated solution and
Content all can increased compared with raw material.
Two, silica gel adsorption is isolated and purified
7, with d-α-tocopheryl acetate concentrated solution as raw material, content 93.12%.Rustless steel silicon
Glue post specification φ 600 × 12000, uses silochrom (80-100 mesh) as fixing phase.
8, wet method dress post: 1500kg silochrom is put into baking oven, at a temperature of 150 DEG C
Activate 3 hours.Mix in the silica gel being baked and 1500kg normal hexane are put into mixing kettle,
With in nitrogen press-in rustless steel silicagel column.
9, the preparation of upper prop liquid: by 596kg d-α-tocopheryl acetate concentrated solution and 600kg
Normal hexane mixes in putting into mixing kettle, is configured to d-α-tocopheryl acetate upper prop liquid, its
Mass percent is 46.40%.
10, upper prop: the upper prop liquid prepared is carried out upper prop, column temperature by the flow velocity of 450L/h
For room temperature, carrying out upper prop in five times, the upper column quantity of each d-α-tocopheryl acetate is
119.2kg, is silica gel quality through calculating the upper column quantity of each d-α-tocopheryl acetate
7.95%.
11, normal hexane eluting: with flowing phase normal hexane by 700L/h's every time after upper prop terminates
Flow carries out eluting, collects impure eluent simultaneously.Tlc analysis fast detection method is used to use
In process control, when eluent has detected that d-α-tocopheryl acetate switches over when flowing out,
Start to collect d-α-tocopheryl acetate eluent, during until flowing out without d-α-tocopheryl acetate
Terminate.
12, evaporation: use membrane evaporator after being merged by five d-α-tocopheryl acetate eluents
It is evaporated reclaiming normal hexane, obtains d-α-tocopheryl acetate concentrated solution 562kg, warp simultaneously
Detection d-α-tocopheryl acetate concentrated solution content can reach 97.34%, and the response rate reaches 98.57%.
Three, molecular distillation improves content and quality
13, thin film evaporation: d-α-tocopheryl acetate concentrated solution is entered by 200 ls/h of flow velocitys
Membrane evaporator.Membrane evaporator area is 4, uses the steam heating of about 0.3MPa,
About vacuum degree control 3KPa.Removing normal hexane residual solvent and low-boiling-point substance with this understanding.
14, one-level short-path distillation: enter one-level from membrane evaporator material gear pump out
Short-path distillation.One-level short-path distillation area 4, utilizes the deep fat of deep fat electric heater to add
Heat, short-path distillation import hot oil temperature controls 175 DEG C, and system vacuum controls 2-3Pa.?
Front-end volatiles 45kg, after testing d-α-tocopheryl acetate product content is collected under the conditions of this
90.13%.Reclaim this d-α-tocopheryl acetate to can be used for allocating low specification d-α-tocopherol acetate
Phenolic product (such as 85% content d-α-tocopherol acetate phenolic product).
15, two grades of short-path distillations: enter two from one-level short-path distillation material out gear pump
Level short-path distillation.Two grades of short-path distillation areas 4, utilize the deep fat of deep fat electric heater to carry out
Heating, short-path distillation import hot oil temperature controls 185 DEG C, and system vacuum controls 2-3Pa.
Collecting d-α-tocopherol acetate phenolic product 463kg with this understanding, d-α-acetic acid is raw after testing
Educate phenolic product content 98.48%, reach 83.18% through measuring and calculating d-α-tocopheryl acetate recovery rate.
16, three grades of short-path distillations: enter three from two grades of short-path distillations material out gear pump
Level short-path distillation.Three grades of short-path distillation areas 4, utilize the deep fat of deep fat electric heater to carry out
Heating, short-path distillation import hot oil temperature controls 200 DEG C, and system vacuum controls 2-3Pa.
Reclaiming remaining d-α-tocopheryl acetate 53kg with this understanding, d-α-acetic acid is raw after testing
Educate phenolic product content 94.84%.Reclaim this d-α-tocopheryl acetate to can be used for allocating low specification
D-α-tocopherol acetate phenolic product (such as 90% content d-α-tocopherol acetate phenolic product).
Claims (5)
1. the preparation method of high-purity natural d-α-tocopheryl acetate, it is characterised in that bag
Include following steps: a), the esterification reaction of d-alpha-tocopherol: use d-α-life that our factory produces
Educating phenol at goods is raw material, and first content about 93% enter with acetic anhydride under catalysts conditions
Row esterification generates d-α-tocopheryl acetate object, and catalyst uses lewis acid anhydrous
Zinc chloride, reaction temperature 50-55 DEG C, reaction dissolvent uses petroleum ether, and acetic anhydride is with dropping
Form adds, time for adding 1.5-2.5 hour, 2-3 hour response time, and esterification is tied
After bundle, reaction mass washes with water three times, then by vaporizer concentration and recovery solvent, simultaneously
To d-α-tocopheryl acetate concentrated solution first；
B), silica gel adsorption isolated and purified: with the α of d-first-tocopheryl acetate concentrated solution as raw material,
Using silica gel as fixing phase, normal hexane is that eluent carries out eluting, and first d-α-acetic acid is raw
Educate phenol concentrated solution and be configured to upper prop liquid with normal hexane by the mass ratio of 1:0.5-1, then press
The flow of 295-505L/h carries out upper prop, and the upper column quantity of each d-α-tocopheryl acetate is silica gel
The 6-10% of quality；Upper prop carries out eluting with normal hexane by the flow of 495-805L/h after terminating,
Operation temperature is room temperature, collects d-α-tocopheryl acetate eluent fraction, then evaporation and concentration
Recycling design, obtains secondary d-α-tocopheryl acetate concentrated solution simultaneously；
C), molecular distillation improve content and quality: condition of high vacuum degree and certain at a temperature of, two
Secondary d-α-tocopheryl acetate concentrated solution removes low-boiling-point substance through membrane evaporator；One-level short distance is steamed
Evaporate removing front-end volatiles；Two grades of short-path distillations remove high-boiling components, obtain high-quality high-purity sky simultaneously
So d-α-tocopherol acetate phenolic product, content is more than more than 98%；Three grades of short-path distillations reclaim surplus
Remaining d-α-tocopheryl acetate.
2. the preparation method of high-purity natural d-α-tocopheryl acetate, it is characterised in that
Comprise the following steps: a), select materials: the d-alpha-tocopherol using our factory to produce is former at goods
Material, content about 93%；
B), feed intake: by d-α-tocopheryl acetate in goods, reaction dissolvent petroleum ether, catalysis
Agent anhydrous powder zinc chloride puts in esterifying kettle；D-α-tocopheryl acetate is at goods: petroleum ether
Mass ratio 1:0.5-1, catalyst anhydrous zinc chloride is that d-α-tocopheryl acetate is at quality of item
3-5%；
C), dropping: heating is warmed up to 50 DEG C material, drips in 1.5-2.5 hour
Acetic anhydride, continue esterification 2-3 hour, control reaction temperature between 50-55 DEG C, d-
Alpha-tocopherol: the mol ratio of acetic anhydride is 1:1.1-1.3；
D), sampling detection: esterification terminates, d-alpha-tocopherol in sampling detection esterifying liquid；
E), wash: a certain amount of distilled water wash of esterifying liquid three times, each slurry is
D-alpha-tocopherol is at the 60-80% of quality of item；
F), evaporation: the esterifying liquid washed is through membrane evaporator recycling design petroleum ether, same
Time obtain d-α-tocopheryl acetate concentrated solution first, detect d-α-tocopheryl acetate first dense
Contracting liquid hold-up；
G), fixing phase is selected: with d-α-tocopheryl acetate concentrated solution first as raw material, rustless steel
Silicagel column φ 600 × 12000, uses the silochrom of 80-100 mesh as fixing phase；
H), wet method dress post: silochrom is put into baking oven, activates 2-3 at a temperature of 150 DEG C
Hour；Then the ratio with normal hexane 1:0.5-1 by weight mixes in mixing kettle, uses
In nitrogen press-in rustless steel silicagel column, the rustless steel silicagel column dress silicon of specification φ 600 × 12000
Glue amount is 1500kg；
I), the preparation of upper prop liquid: by d-α-tocopheryl acetate concentrated solution with normal hexane by weight
The ratio of 1:1-3 mixes in mixing kettle, is configured to upper prop liquid, and d-α in upper prop liquid-
Tocopheryl acetate mass percent is 25-50%；
J), upper prop: the upper prop liquid prepared is carried out upper prop by the flow velocity of 295-505L/h,
Column temperature is room temperature, divides and carries out upper prop for 4-5 time, and the upper column quantity of each d-α-tocopheryl acetate is
The 6-10% of silica gel quality；
K), normal hexane eluting: with flowing phase normal hexane by 495-805ml/h every time after upper prop terminates
Flow carry out eluting, collect impure eluent simultaneously；Use tlc analysis fast detection method
For process control, when eluent has detected that d-α-tocopheryl acetate starts when flowing out to collect
D-α-tocopheryl acetate eluent, until terminating when flowing out without d-α-tocopheryl acetate；
L), evaporation: d-α-tocopheryl acetate eluent membrane evaporator is evaporated reclaiming
Normal hexane, obtains d-α-tocopheryl acetate secondary concentration liquid simultaneously, and detection d-α-acetic acid is raw
Educate phenol secondary concentration liquid hold-up；
M), thin film evaporation: d-α-tocopheryl acetate secondary concentration liquid presses 200-250L/h flow velocity
Enter membrane evaporator；Membrane evaporator area is 4-6, uses the steaming of about 0.3MPa
Vapour heats, about vacuum degree control 3KPa；With this understanding removing normal hexane residual solvent and
Low-boiling-point substance；
N), one-level short-path distillation: enter one-level from membrane evaporator material gear pump out
Short-path distillation；One-level short-path distillation area 4, utilizes the deep fat of deep fat electric heater to add
Heat, short-path distillation import hot oil temperature controls 160-175 DEG C, and system vacuum controls 2-3Pa；
Remove front-end volatiles with this understanding；
O), two grades of short-path distillations: enter two from one-level short-path distillation material out gear pump
Level short-path distillation；Two grades of short-path distillation areas 4, utilize the deep fat of deep fat electric heater to carry out
Heating, short-path distillation import hot oil temperature controls 180-190 DEG C, and system vacuum controls
2-3Pa；Collect d-α-tocopherol acetate phenolic product with this understanding, detect d-α-tocopherol acetate
Phenolic product content；
P), three grades of short-path distillations: enter three from two grades of short-path distillations material out gear pump
Level short-path distillation；Three grades of short-path distillation areas 4, utilize the deep fat of deep fat electric heater to carry out
Heating, short-path distillation import hot oil temperature controls 200-210 DEG C, and system vacuum controls
2-3Pa, reclaims remaining d-α-tocopheryl acetate with this understanding.
A kind of high-purity natural d-α-tocopheryl acetate the most according to claim 1 and 2
Preparation method, it is characterised in that described petroleum ether boiling range is 30-60 DEG C.
The system of a kind of high-purity natural d-α-tocopheryl acetate the most according to claim 2
Preparation Method, it is characterised in that add the second of washings quality 5% in described e, washing process
Alcohol carries out breakdown of emulsion.
The system of a kind of high-purity natural d-α-tocopheryl acetate the most according to claim 2
Preparation Method, it is characterised in that described d, sampling detect: esterification terminates, sampling inspection
Survey the content of d-alpha-tocopherol in esterifying liquid and be less than 0.5%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432583A (en) * | 2011-10-25 | 2012-05-02 | 浙江华源制药科技开发有限公司 | Method for preparing low-benzopyrene high-purity d-alpha tocopherol acetate |
| CN103788052A (en) * | 2013-10-17 | 2014-05-14 | 安徽丰原发酵技术工程研究有限公司 | Preparation method of vitamin E acetate |
| CN104741057A (en) * | 2013-12-31 | 2015-07-01 | 中粮营养健康研究院有限公司 | Equipment and method for producing d-alpha-tocopheryl acetate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432583A (en) * | 2011-10-25 | 2012-05-02 | 浙江华源制药科技开发有限公司 | Method for preparing low-benzopyrene high-purity d-alpha tocopherol acetate |
| CN103788052A (en) * | 2013-10-17 | 2014-05-14 | 安徽丰原发酵技术工程研究有限公司 | Preparation method of vitamin E acetate |
| CN104741057A (en) * | 2013-12-31 | 2015-07-01 | 中粮营养健康研究院有限公司 | Equipment and method for producing d-alpha-tocopheryl acetate |
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