CN109879925A - A kind of preparation method of phytosterin ester - Google Patents
A kind of preparation method of phytosterin ester Download PDFInfo
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- CN109879925A CN109879925A CN201910259656.8A CN201910259656A CN109879925A CN 109879925 A CN109879925 A CN 109879925A CN 201910259656 A CN201910259656 A CN 201910259656A CN 109879925 A CN109879925 A CN 109879925A
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- phytosterol
- phytosterin ester
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Abstract
The invention discloses a kind of preparation methods of phytosterin ester, specific preparation process is as follows: according to molar ratio being 1:(8~20 by phytosterol and small molecular organic acid) mixing, it is dissolved at a temperature of 70~82 DEG C, catalyst is added, it controls temperature to mix within progress esterification 8~12 hours at 70~82 DEG C, phytosterin ester crude product is obtained after esterification；Phytosterin ester crude product will be obtained to isolate and purify to obtain phytosterin ester.The preparation method had both solved problem of solvent residual in chemical catalysis synthetic method, while overcoming the problems, such as that biocatalysis synthetic method conversion ratio is not high, further, this preparation method green, it is environmentally friendly and efficient, energy consumption and external discharge are reduced, large-scale preparation is convenient for produce.
Description
Technical field
The present invention relates to cryochem processes in a kind of preparation method of phytosterin ester more particularly to a kind of solvent-free system
The preparation method of synthesizing phytosterol ester belongs to the technical fields such as food, medicine and cosmetics.
Background technique
Phytosterol, also known as phytosterol are that one kind is widely present in all plants and has steroidal compounds structure special
The substance of sign has very powerful physiological function, can promote the growth and development of animal, biological oxidation and improvement in anti-body
Meat quality, effect is very definite, the label of " good for health " can be used by the food that FDA approval is added to phytosterol, together
When " key of life " is described as by living nature.But phytosterol is slightly soluble in water, is also slightly soluble in organic solvent, inhales in animal body
Yield is lower, about 0.4-4%, thus greatly limits its application in animal-breeding.How the absorption of sterol is improved
It is a difficult problem put in face of whole world researcher.Therefore, phytosterol is modified, mention its absorptivity significantly
Height, it is moderate, it is applied to animal-breeding and produces, this there will be very far-reaching influence.
Currently, the synthetic method of phytosterin ester has been carried out extensive research, mainly there is chemical catalysis synthetic method (chemistry
Method) and biocatalysis synthetic method (enzyme process).And improves the mainly emulsion process of sterol oil-soluble method and repaired by phytosterol
Two class of sterol organic acid esters that decorations technology obtains.Emulsion process is although simple and easy, but actual transfer amount is lower, and generating product mouthfeel has
Chalk taste, while the phytosterol stability generated is bad, so being of limited application.
Summary of the invention
It is an object of the invention in place of overcome the deficiencies in the prior art, provide cryochem process in a kind of solvent-free system
The method of synthesizing phytosterol rouge.The present invention uses following reaction dissolvent system: using small molecular organic acid while former as reaction
Material and reaction dissolvent, this method had both solved problem of solvent residual in chemical catalysis synthetic method, while overcoming biocatalysis synthetic method
The not high problem of conversion ratio.Green of the invention, it is environmentally friendly and efficient, energy consumption and external discharge are reduced, large-scale preparation is convenient for
Production.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of preparation method of phytosterin ester, specific preparation process is as follows:
(1) it is 1:(8~20 according to molar ratio by phytosterol and small molecular organic acid) mixing, at a temperature of 70~82 DEG C
Dissolution, is added catalyst, and control temperature is mixed at 70~82 DEG C, obtained after esterification for progress esterification 8~12 hours
Phytosterin ester crude product；
(2) it will obtain removing filter residue, molecular distillation equipment being utilized to return after phytosterin ester crude product filters while hot in step (1)
Remaining acetic acid in filtrate is received, is decolourized with active carbon to heavy phase component, is filtered, gained filtrate is phytosterin ester.
Further, the small molecular organic acid is formic acid, acetic acid, minimum one kind in lactic acid.
Further, the small molecular organic acid is acetic acid.
Further, the acetic acid is glacial acetic acid.
Further, the phytosterol is minimum one in sitosterol, stigmasterol, campesterol and brassicasterol
Kind.
Further, phytosterol is mixed with the molar ratio of small molecular organic acid for 1: 10 in the step (1), control temperature
Degree 80 DEG C progress esterification 10 hours.
Further, phytosterol is mixed with the molar ratio of small molecular organic acid for 1: 8 in the step (1).
Further, phytosterol is mixed with the molar ratio of small molecular organic acid for 1: 20 in the step (1).
Further, the quality of the catalyst accounts for the 0.5-2% of phytosterol Yu small molecular organic acid gross mass.
Further, the catalyst is minimum one kind in calcium oxide, magnesia and zinc oxide.
Further, the catalyst be calcium oxide, magnesia, zinc oxide mixture, the calcium oxide, magnesia,
The molar ratio of zinc oxide is 3: 3: 4；The mixture gross mass of the calcium oxide, magnesia and zinc oxide is phytosterol and small point
The 0.5% of sub- organic acid gross mass.
Degree of esterification is using measurement sterol surplus indirect measure in the present invention.
The present invention compared with the existing technology it is advantageous that:
(1) entire reaction carries out at lower than 85 DEG C, and by-product is few (phytosterol is oxidizable when being higher than 85 DEG C), simultaneously
Certain temperature is kept, Lai Tigao reaction speed shortens the time for reaching balance, to improve esterification speed.
(2) principle that chemically balances it is found that in esterification system reactant concentration increase be conducive to mentioning for conversion ratio
It is high.Acetic acid had not only made reactant but also had made solvent in this reaction system, and proportion of acetic acid improves, and promoted the generation of sterol ester, while without volume
The sterol ester of outer solvent, generation is safer, health and green.
(3) used catalyst calcium oxide, magnesia and zinc oxide do not dissolve in solvent, and filtering can be removed, will not be to production
Product impact, and technical process is short, easy to operate, are suitble to industrialized production.
(4) technique applicability is wide, and raw material is general chemical raw material, easily purchases, process flow is short, at low cost, Yi Shixian
Industrialization.
Detailed description of the invention
Fig. 1 is the result that reaction process mid and far infrared detects in embodiment 13.
Specific embodiment
Further to illustrate technological means and its effect adopted by the present invention, below in conjunction with preferred implementation of the invention
Example to further illustrate the technical scheme of the present invention, but the present invention is not limited in scope of embodiments.
The present invention will be further described combined with specific embodiments below, but the scope of protection of the present invention is not limited thereto.
The synthesis of embodiment 1-12 stigmasterol ester.
Before experiment, stigmasterol is placed in baking oven, 60 DEG C are dried overnight.The stigmasterol for weighing certain mass is burnt in 250ml
In bottle, the glacial acetic acid of corresponding ratio is added, then is warming up to desired temperature, is kept the temperature.Then addition proper catalyst (press by catalyst
Molar ratio according to calcium oxide, magnesia, zinc oxide is 3: 3: 4 configurations), stirring is reacted 2~12 hours.Pilot process is every two
Hour sampling is primary, and final product measures esterification degree using LC.The amount and sterol enzymatic synthesis condition and esterification yield of each reactant
It is as shown in table 1:
The influence of 1 differential responses time of table and acid alcohol molar ratio to esterification yield
It is clear that increasing glacial acetic acid ratio, extend the reaction time conducive to the esterification yield of sterol is improved.But in actual production
The indexs such as source and price, the purposes of product and quality requirement, production efficiency, utilization rate of equipment and installations of raw material need to be comprehensively considered, really
Synthetic method used by fixed and process route.
Embodiment 13
Take 100g stigmasterol (sterol content 95%), glacial acetic acid 150ml, add catalyst (catalyst according to calcium oxide,
Magnesia, zinc oxide molar ratio be 3: 3: 4 configuration) 1.3g, at 82 DEG C carry out esterification 10h.After reaction terminating, while hot
Filtering, filtrate is transferred in molecular still, vacuum pressure 3mmHg, 120 DEG C of distillations, recycles light phase 120ml, and 110 grams of heavy phase, face
Color depth brown adds 1 gram of activated carbon in heavy phase, and 90 DEG C, 100r/min stirs 1h, and it is saturating that heat filtering obtains 109 grams of faint yellow clarifications
Bright stigmasterol ester product.Reach 90.3% through LC measurement stigmasterol ester purity
Fig. 1 is that stigmasterol is before unreacted in implementation 13,3400cm-1There is a vibration peak at place, this is hydroxyl in stigmasterol
Peak, after esterification is complete, 3400cm-1The peak at place disappears, and in 1700cm-1Place and 1250cm-1Place increases C=0 respectively
With the stretching vibration peak of C-O-C, this is to generate ester structure after showing reaction.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of preparation method of phytosterin ester, which is characterized in that specific preparation process is as follows:
(1) it is 1:(8~20 according to molar ratio by phytosterol and small molecular organic acid) mixing, it is molten at a temperature of 70~82 DEG C
Solution, is added catalyst, and control temperature is mixed at 70~82 DEG C, planted after esterification for progress esterification 8~12 hours
Object sterol ester crude product；
(2) it will obtain removing filter residue, utilizing molecular distillation equipment recycling filter after phytosterin ester crude product filters while hot in step (1)
Remaining acetic acid in liquid decolourizes to heavy phase component with active carbon, and filtering, gained filtrate is phytosterin ester.
2. the preparation method of phytosterin ester according to claim 1, which is characterized in that the small molecular organic acid is first
Minimum one kind in acid, acetic acid or lactic acid.
3. the preparation method of phytosterin ester according to claim 2, which is characterized in that the small molecular organic acid is second
Acid.
4. the preparation method of phytosterin ester according to claim 1, which is characterized in that the phytosterol is paddy steroid
Minimum one kind in alcohol, stigmasterol, campesterol and brassicasterol.
5. according to claim 1 to the preparation method of any one of 4 phytosterin esters, which is characterized in that the phytosterol
Be mix at 1: 10 with the molar ratio of small molecular organic acid, control temperature 80 DEG C progress esterification 10 hours.
6. according to claim 1 to the preparation method of any one of 4 phytosterin esters, which is characterized in that the phytosterol
It is mixed with the molar ratio of small molecular organic acid for 1: 8.
7. according to claim 1 to the preparation method of any one of 4 phytosterin esters, which is characterized in that the phytosterol
It is mixed with the molar ratio of small molecular organic acid for 1: 20.
8. the preparation method of phytosterin ester according to claim 1, which is characterized in that the quality of the catalyst accounts for plant
The 0.5-2% of sterol and small molecular organic acid gross mass.
9. the preparation method of phytosterin ester according to claim 1, which is characterized in that, the catalyst is calcium oxide, oxygen
Change minimum one kind in magnesium and zinc oxide.
10. the preparation method of phytosterin ester according to claim 8, which is characterized in that the catalyst is calcium oxide, oxygen
Change the mixture of magnesium and zinc oxide, the molar ratio of the calcium oxide, magnesia and zinc oxide is 3: 3: 4；The calcium oxide, oxidation
The mixture gross mass of magnesium and zinc oxide is the 0.5% of phytosterol and small molecular organic acid gross mass.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910259656.8A CN109879925A (en) | 2019-04-02 | 2019-04-02 | A kind of preparation method of phytosterin ester |
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| CN201910259656.8A CN109879925A (en) | 2019-04-02 | 2019-04-02 | A kind of preparation method of phytosterin ester |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848715A (en) * | 2020-09-07 | 2020-10-30 | 广州善合化工有限公司 | Preparation method and application of phytosterol isostearate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985460A (en) * | 2010-08-10 | 2011-03-16 | 江南大学 | Method for preparing phytosterol ester |
| CN102603846A (en) * | 2012-02-03 | 2012-07-25 | 江南大学 | Preparation method of phytosterol in ionic liquid |
| CN103113445A (en) * | 2013-02-27 | 2013-05-22 | 哈尔滨工业大学 | High-efficiency synthesis method of soyasterol ester under catalyst-free and solvent-free conditions |
-
2019
- 2019-04-02 CN CN201910259656.8A patent/CN109879925A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985460A (en) * | 2010-08-10 | 2011-03-16 | 江南大学 | Method for preparing phytosterol ester |
| CN102603846A (en) * | 2012-02-03 | 2012-07-25 | 江南大学 | Preparation method of phytosterol in ionic liquid |
| CN103113445A (en) * | 2013-02-27 | 2013-05-22 | 哈尔滨工业大学 | High-efficiency synthesis method of soyasterol ester under catalyst-free and solvent-free conditions |
Non-Patent Citations (3)
| Title |
|---|
| FUMING YANG, ET AL.,: "Novel Synthesis of Phytosterol Ester from Soybean Sterol and Acetic Anhydride", 《JOURNAL OF FOOD SCIENCE》 * |
| 潘秋月等: "植物甾醇酯的绿色合成技术研究", 《中国粮油学报》 * |
| 许文林等: "回流操作条件下植物甾醇与过量乙酸酯化反应动力学", 《高校化学工程学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848715A (en) * | 2020-09-07 | 2020-10-30 | 广州善合化工有限公司 | Preparation method and application of phytosterol isostearate |
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Application publication date: 20190614 |