CN1583780A - Method for preparing high-content beta-sitosterin products by catalytic hydrogenation - Google Patents
Method for preparing high-content beta-sitosterin products by catalytic hydrogenation Download PDFInfo
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- CN1583780A CN1583780A CN 200410024698 CN200410024698A CN1583780A CN 1583780 A CN1583780 A CN 1583780A CN 200410024698 CN200410024698 CN 200410024698 CN 200410024698 A CN200410024698 A CN 200410024698A CN 1583780 A CN1583780 A CN 1583780A
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Abstract
A catalytic hydrogenation preparation of high content beta - (citrostadienol ) sitosterol used in food, cosmetic and steroid drugs etc. is carried out by: mixing plant sterol materials, dissolving in organic solvent, catalytic hydrogenating with hydrogenated catalysts under normal temperature and pressure or at certain pressure, hydrogenising stigmasterol in mixed plant sterol to get beta -sitosterol, finally, obtaining liquid phase product with 60% - 75% content of beta -sitosterol and higher yields. The loss of sterol is bellow 10%. Its advantages include: operating simply and safely with simple equipment, low production cost, clean environment.
Description
Technical field
The present invention relates to the preparation method of plant sterols goods, specifically is the method that a kind of catalytic hydrogenation prepares high-content β-Gu Zaichun goods.Be used for food, field of medicine and chemical technology.
Background of invention:
Plant sterol is a big class tetracyclic triterpenes natural product that is widespread in nature, and because of it has the effect that reduces cholesterol levels in the human serum, and becomes the research focus of current hypolipemic function food.Occurring in nature plant sterol of a great variety, but in the middle of the plant sterol product development in general common source, relate generally to four plant sterols, they are: brassicasterol, campesterol, Stigmasterol and β-Gu Zaichun.
About the research of high-content β-Gu Zaichun, mainly contain two kinds of methods now.First kind is that the solvent recrystallization method (is permitted galaxy of literary talent, Huang Yibo, Qian Junhong etc.β-Gu Zaichun and Stigmasterol in the crystallization process separation and purification mixed phytosterin. process engineering journal .2003, vol.3 (1) .).This method as solvent, through three recrystallizations, brings up to 87% to the β-Gu Zaichun in the mixed phytosterin from 62% with pimelinketone.Second method is that high-speed countercurrent chromatography separates β-Gu Zaichun monomer (Zhou Yujie, Dai Lingmei, Chen Fuming etc.High-speed countercurrent chromatography separates the research of β-Gu Zaichun and campesterol.Fine chemistry industry .2002, vol.19 (3) .) raw material that adopts of these two kinds of methods all has singularity, contain four kinds of main plant sterols in the general commercially available mixed phytosterin, and the mass percent example of β-Gu Zaichun is below 50%.The raw material that first method is used is that total sterol content is 95% mixed phytosterin raw material, and wherein β-Gu Zaichun accounts for 62%, and Stigmasterol accounts for 28%, and the plant sterol content of other kinds is considerably less.Through three recrystallizations, must reduce the yield of β-Gu Zaichun.The raw material that second method is used is the standard substance of SIGMA, and the purity of total plant sterol is 98.1%, wherein β-Gu Zaichun 56.2% (mass percent).Can obtain 97% β-Gu Zaichun by chromatographic separation technology, yield is 56%.Because yield is lower, general suitable preparation separation method as the β-Gu Zaichun standard substance, and be difficult to industrial applications.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, provide a kind of catalytic hydrogenation to prepare the method for high-content β-Gu Zaichun goods, make it prepare high-load β-Gu Zaichun product, the yield that can guarantee β-Gu Zaichun again simultaneously has industrial prospect more than 90%.By adopting the synthetic method of selective catalytic hydrogenation, make to obtain high-load β-Gu Zaichun product, and have following advantage: method is easy and simple to handle, safety; Equipment requirements is simple, less investment, and production cost is low; The whole process of production cleanliness without any pollution, solvent can reclaim use.
The present invention is achieved by the following technical solutions, with the mixed phytosterin raw material, be dissolved in the middle of the organic solvent, under the condition of normal temperature and pressure or pressurization, make spent hydroprocessing catalyst carry out optionally catalytic hydrogenation, Stigmasterol hydrogenation in the mixed phytosterin is generated β-Gu Zaichun, finally obtain high-load β-Gu Zaichun goods, the content range of β-Gu Zaichun (according to the difference of material condition) is 60%-75%.In the middle of product, Stigmasterol is owing to be converted to β-Gu Zaichun, so its content almost can't detect.Brassicasterol also is hydrogenated to campesterol simultaneously, and the content range of campesterol is about 20%-30% in the middle of the product.
The mixed phytosterin raw material that is adopted is the soybean oil plant sterol, and preferred total purity is 92.6% soybean oil plant sterol, and wherein brassicasterol 5.68%, Stigmasterol 28.29%, campesterol 21.23%, β-Gu Zaichun 41.75% (mass percent).
According to the difference of the industrial scale size and the equipment of employing, the mass volume ratio scope of mixed phytosterin raw material and organic solvent is 1: 20 to 1: 50.Because the difference of each dissolution with solvents ability size according to selected solvent species, is adjusted this ratio to guarantee that plant sterol can fully dissolve.
Under pressurized conditions, pressure range is at 0.1-1.1MPa.
Described organic solvent is: alcohol, ketone, ester or ether, preferentially use the dissolving solvent of propyl carbinol as the plant sterol raw material.
Described hydrogenation catalyst is hydrogenation catalyst commonly used, such as platinum, palladium, rhodium, nickel etc., catalyst levels can be adjusted in the scope of 0.5%-20% according to other reaction conditionss, reaction times is about 1-10 hour, whole process is used magnetic agitation, as long as catalyzer is stirred in whole reaction system.Recyclable and the regeneration use of catalyzer.
The liquid high-content β-Gu Zaichun goods that obtain through concentrated, crystallization, refining, precipitation, finally obtain high-load β-Gu Zaichun crystalline powder (about 70%) again.High-load β-Gu Zaichun crystallization and derivative thereof (for example further with its esterification) can be used in fields such as steroid drugs industry at bread and cheese, functional foodstuff, makeup or as raw material.
Because more existing technology are difficult to obtain high-load β-Gu Zaichun from common commercially available mixed phytosterin raw material, but yield is extremely low perhaps to obtain high-load β-Gu Zaichun.Catalytic hydrogenation of the present invention prepares high-load β-Gu Zaichun, can keep higher sterol yield when obtaining 70% concentration β-Gu Zaichun, and the loss of sterol can be controlled in below 10%.Simultaneously, this method is easy and simple to handle, safety; Equipment requirements is simple, and production cost is low; The sanitation and hygiene compliance with environmental protection requirements.
Embodiment
The step of combining method provides embodiment:
1. the mixed phytosterin raw material of Cai Yonging is: the quality purity of total sterol is 92.6%, is a kind of plant sterol from soybean oil deodorizer distillate.Wherein brassicasterol 5.68%, Stigmasterol 28.29%, campesterol 21.23%, β-Gu Zaichun 41.75% (mass percent).
2. get above-mentioned mixed phytosterin 1g, place the glass hydrogenation triangular flask of 150ml, add the analytical pure propyl carbinol reagent of 50ml, plant sterol fully is dissolved in the solvent.
3. add the catalyzer of the Raney-Ni (nickel) of 4% (mass percent), install hydrogenation apparatus and magnetic stirring apparatus as hydrogenation.Reaction conditions is a normal temperature and pressure, and the reaction times is 6 hours, and reaction process is used magnetic agitation, and speed is 90 rev/mins.Be advisable catalyzer can be stirred in whole reaction system.
4. after reaction is finished, detaching device.Reaction product is filtered, and filter residue is a catalyzer, can reclaim use.Filtrate is concentrated into about 20ml, and (4 ℃ of refrigerators) makes its slow crystallization at low temperatures.The crystal that crystalline product obtains through suction filtration is the β-Gu Zaichun of 70% content.
5. further wash 70% β-Gu Zaichun with ethanol, precipitation.The 70% β-Gu Zaichun product that obtains can be applied to multi-form food, can be applied to protective foods or be applied to steroid drugs industry as raw material with forms such as capsule or tablets.
In specific implementation process, investigated of the influence of four important reaction parameters to reaction result, the setting of these parameters and hydrogenation result (mass percent) see the following form.
| The reaction parameter title | Parameter values is selected | β-Gu Zaichun in the product | Total plant sterol yield | Parameter selected in remarks |
| Temperature (℃) | ????4 | ????61.33％ | ????99.4％ | |
| ????30 | ????73.46％ | ????86.2％ | Selecting 25 ℃ is advisable | |
| ????90 | ????55.61％ | ????61.8％ | ||
| Pressure (MPa) | ????0.1 | ????70.04％ | ????90.6％ | Select synthesis under normal pressure |
| ????0.6 | ????59.22％ | ????77.8％ | ||
| ????1.1 | ????56.90％ | ????70.6％ |
| Reaction times (h) | ????1 | ????51.38％ | ????95.4％ | |
| ????6 | ????70.04％ | ????90.6％ | 6 hours the bests | |
| ????10 | ????72.36％ | ????83.4％ | ||
| Catalyst levels | ????0.5％ | ????50.63％ | ????98.9％ | |
| ????6％ | ????72.60％ | ????80.4％ | The 4%-6% consumption is advisable | |
| ????20％ | ????60.46％ | ????65.3％ |
Claims (8)
1. a catalytic hydrogenation prepares the method for high-content β-Gu Zaichun goods, it is characterized in that, with the mixed phytosterin raw material, be dissolved in the middle of the organic solvent in proportion, under the condition of normal temperature and pressure or pressurization, make spent hydroprocessing catalyst carry out catalytic hydrogenation, the Stigmasterol hydrogenation in the mixed phytosterin is generated β-Gu Zaichun, finally obtain liquid high-load β-Gu Zaichun goods, the content range of β-Gu Zaichun is 60%-75%.
2, catalytic hydrogenation according to claim 1 prepares the method for high-content β-Gu Zaichun goods, it is characterized in that, the mixed phytosterin raw material that is adopted is the soybean oil plant sterol, total purity is 92.6% soybean oil plant sterol, wherein brassicasterol 5.68%, Stigmasterol 28.29%, campesterol 21.23%, β-Gu Zaichun 41.75%.
3, catalytic hydrogenation according to claim 1 and 2 prepares the method for high-content β-Gu Zaichun goods, it is characterized in that, the mass volume ratio scope of mixed phytosterin raw material and organic solvent is 1: 20 to 1: 50.
4, catalytic hydrogenation according to claim 1 prepares the method for high-content β-Gu Zaichun goods, it is characterized in that, described organic solvent is: alcohol, ketone, ester or ether.
5, catalytic hydrogenation according to claim 4 prepares the method for high-content β-Gu Zaichun goods, it is characterized in that, described organic solvent: be further defined to propyl carbinol.
6, catalytic hydrogenation according to claim 1 prepares the method for high-content β-Gu Zaichun goods, it is characterized in that, described pressurization, and pressure range is at 0.1-1.1MPa.
7, catalytic hydrogenation according to claim 1 prepares the method for high-content β-Gu Zaichun goods, it is characterized in that, described hydrogenation catalyst consumption is in the scope of 0.5%-20%, reaction times is 1-10 hour, whole process is used magnetic agitation, catalyzer is stirred in whole reaction system, and the catalyzer use of reclaiming and regenerate.
8, catalytic hydrogenation according to claim 1 prepares the method for high-content β-Gu Zaichun goods, it is characterized in that, the liquid high-content β-Gu Zaichun goods that obtain through concentrated, crystallization, refining, precipitation, finally obtain high-load β-Gu Zaichun crystalline powder again.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410024698 CN1254480C (en) | 2004-05-27 | 2004-05-27 | Method for preparing high-content beta-sitosterin products by catalytic hydrogenation |
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| CN 200410024698 CN1254480C (en) | 2004-05-27 | 2004-05-27 | Method for preparing high-content beta-sitosterin products by catalytic hydrogenation |
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| CN1254480C CN1254480C (en) | 2006-05-03 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105311035A (en) * | 2015-11-09 | 2016-02-10 | 上海交通大学 | Application of phytosterol and/or phytosterol ester in uric acid control |
| CN112521438A (en) * | 2020-12-08 | 2021-03-19 | 苏利制药科技江阴有限公司 | Synthesis process of beta-sitosterol |
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2004
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105311035A (en) * | 2015-11-09 | 2016-02-10 | 上海交通大学 | Application of phytosterol and/or phytosterol ester in uric acid control |
| CN105311035B (en) * | 2015-11-09 | 2018-08-31 | 上海交通大学 | The application of phytosterol or/and phytosterin ester in uric acid control |
| CN112521438A (en) * | 2020-12-08 | 2021-03-19 | 苏利制药科技江阴有限公司 | Synthesis process of beta-sitosterol |
| CN112521438B (en) * | 2020-12-08 | 2021-11-23 | 苏利制药科技江阴有限公司 | Synthesis process of beta-sitosterol |
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