CN103509076B - The method of fatty acid phytosterin ester is prepared in a kind of silicon-dioxide catalysis - Google Patents
The method of fatty acid phytosterin ester is prepared in a kind of silicon-dioxide catalysis Download PDFInfo
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Abstract
The invention provides a kind of method that fatty acid phytosterin ester is prepared in silicon-dioxide catalysis, the method adopts silicon-dioxide as the catalyzer of lipid acid and plant sterol esterification, fatty acid phytosterin ester prepared after adopting this catalyzer has lighter color, without advantages such as metal or silicon ion remain, can be applicable to prepare fatty acid phytosterin ester on a large scale.
Description
Technical field
The present invention relates to a kind of method that fatty acid phytosterin ester is prepared in silicon-dioxide catalysis.
Background technology
Plant sterol, is that one obtains through physical purification from the grain such as corn, soybean, has features such as being of high nutritive value, physiology plant sterol activity is strong.Plant sterol reduces the risk of cardiovascular diseases by reducing cholesterol.It is widely used in the fields such as food, medicine, makeup, growth of animal agent and sheet processing, printing, weaving, particularly very general as foodstuff additive in Europe, is widely used in food to reduce body's cholesterol.Because the solvability of plant sterol is bad, need to be prepared into the solvability that corresponding fatty acid sterols ester is used for improving product, thus improve human body to the absorption of plant sterol.Therefore, the focus be prepared into as people pay close attention to of fatty acid phytosterin ester, this preparation method also has many relevant reports, but more or less there are some problems.Such as:
US0015347 discloses a kind of method utilizing rape-oil methyl ester and plant sterol to prepare plant sterol ester, and reaction process take sodium methylate as catalyzer, and the by-product carbinol in the severe corrosive of sodium methylate and preparation process, makes it not be used for foodstuff additive.
US0068425 discloses a kind of manufacture method being rich in the plant sterol ester of oleic acid, but its thionyl chloride being applied to pollution in the fabrication process larger makees catalyzer, and its operational condition is harsh, is difficult to suitability for industrialized production.
EP195311 describes the method for lipase-catalyzed lipid acid, plant sterol direct esterification synthesis sterol ester, and its reaction system is moisture organic solvent.Direct esterification advantage to obtain single fat acid sterol ester, adjusts the characteristics such as product fusing point easily, and the synergistic function of practical function polyunsaturated fatty acid and sterol.
US0020098536 discloses with soybean oil deodorization thing for raw material, and lipase-catalyzed plant sterol, triglyceride level transesterification generate the method for mixed fatty acid sterol ester.This method can produced in situ (deodorization thing can not need pure sterol directly as reaction raw materials without the need to being separated, lipid acid do raw material), and cost is low.Generally speaking, biological catalyst specificity is strong, and reaction conditions is gentle, and product property is good, environmental friendliness.But catalytic activity is not high, easy inactivation, cost is higher, still can not meet industrialization needs.
AU769543 describes the method for lipid acid, plant sterol direct esterification synthesis sterol ester, select calcium oxide as catalyzer in its reaction system, calcium oxide is not removed by filtering, calcium oxide and lipid acid react and form a large amount of soaps on the contrary, first the loss of raw material is caused, the a large amount of soaps simultaneously generated are difficult to remove in subsequent process, cause the complexity of follow-up work.
CN101235067 discloses with the method for lipid acid, plant sterol direct esterification synthesis sterol ester, and catalyzer described in it is calcium oxide, magnesium oxide, lanthanum trioxide etc., and calcium oxide wherein and magnesium oxide and lipid acid react formation soap, cause follow-up work complexity.
It is that zinc oxide or Lewis acid are (as BeCl that US6184397 discloses catalyzer
2, CO
2, CO, Hg (NO
3)
2), with the method for lipid acid and plant sterol lactate synthesis sterol ester.But catalyzer needs water to assist, its temperature of reaction is at 100-220 DEG C, and the reaction times is 8-15h, and optimum is 12-13h, and the reaction times is longer; Decolouring is needed, the 0.05%-1% of discoloring agent to be carclazyte addition be gross weight after having reacted.Final purification process purity is more than 90%, and optimum is 95%.
CN2010101227103 discloses the mixture of any one or more in alumina catalyst, aluminium hydroxide, aluminium salt, the oxide compound of III other element of A race, Vanadium Pentoxide in FLAKES, phosphoric acid, phosphoric acid salt, molecular sieve or silica gel: wherein molecular sieve or silica gel patent disclosure consumption are the 1%-15% of reactant total mass.
From the preparation method of above fatty acid phytosterin ester, because used catalyzer has certain defect, after the completion of reaction, certain problem is brought to the aftertreatment of fatty acid sterols ester, therefore a kind of green, environmental protection, pollution-free, efficient is badly in need of, and to the preparation method of human body without the sour plant sterol ester of lipid acid of harm.
Summary of the invention
The first object of the present invention is to overcome above-mentioned problem, thus obtain a kind of preparation method of silicon-dioxide catalyze fatty acid plant sterol ester, the method improves current technique, overcome the deficiency of current technique, under the catalysts conditions of low levels, carry out catalyzed reaction prepare plant sterol ester, owing to decreasing the consumption of catalyzer, but obtain identical catalytic effect unexpectedly, therefore the absorption of catalyzer to grease can be reduced on the one hand, the aftertreatment of grease can be reduced on the other hand, be specially adapted to the needs of the scale operation such as factory.
The second object of the present invention is to provide a kind of fatty acid phytosterin ester utilizing the method to obtain.
The third object of the present invention is to provide a kind of silicon-dioxide preparing the application in fatty acid phytosterin ester.
The fourth object of the present invention is to provide a kind of white carbon black preparing the application in fatty acid phytosterin ester.
In a first aspect of the present invention, provide a kind of preparation method of fatty acid phytosterin ester, lipid acid contacts with plant sterol under being included in the existence of the silicon-dioxide of catalytic amount by the method.Described catalytic amount is preferably 0.1% ~ 5%.Can certain pre-treatment being carried out before this reaction, as carried out miscible at a certain temperature by lipid acid and plant sterol, and then carrying out esterification.
In an embodiment, the consumption of described silicon-dioxide is 0.1% ~ 1% of whole reaction system weight, preferred 0.3-0.8%.
In a specific embodiment of the present invention, contriver finds, when the consumption of employing SiO 2 catalyst is 0.1% ~ 1% of reaction system total mass, the reactive behavior of this catalyzer is similar to reactive behavior during consumption 5%, and the fatty acid phytosterin of reaction preparation has good color and luster.
In a specific embodiment of the present invention, the lipid acid used and the mol ratio of plant sterol are 0.5 ~ 5:1, are preferably 1.1 ~ 1.4:1.Those skilled in the art according to circumstances can adjust the differential responses ratio of lipid acid and plant sterol.
In the present invention, the plant sterol of use can be arbitrary plant sterol, and preferred plant sterol comprises one or more any mixing in Sitosterol, Stigmasterol, campesterol, brassicasterol.
In a specific embodiment of the present invention, described fatty acid phytosterin has carried out purifying, and this purification step comprises fatty acid phytosterin ester filtration, vacuumizes in airtight container at 180 DEG C ~ 220 DEG C; Preferably, comprise by the fatty acid phytosterin ester that obtains after esterification at 60-150 DEG C, vacuum filtration at being preferably 90-120 DEG C, the fatty acid phytosterin ester filtrate after filtering vacuumized at 180 DEG C ~ 220 DEG C, the preferred pumpdown time is 0.5-6 hour.This purification step also can be other known at present known technique means, as by molecular distillation, obtained fatty acid phytosterin ester is carried out purifying, obtains the highly purified heavy phase containing fatty acid sterols ester accordingly.
In a specific embodiment of the present invention, the silicon-dioxide of use is white carbon black, and preferred white carbon black is the white carbon black prepared by rice hull ash.
In a specific embodiment of the present invention, described lipid acid and the temperature of reaction of plant sterol are 130 DEG C ~ 250 DEG C.Being understandable that, in order to prepare fatty acid phytosterin ester, is all the conventional means of those skilled in the art in suitable scope adjustment temperature of reaction.
In a specific embodiment of the present invention, the reaction of lipid acid and plant sterol is 4 ~ 12 hours, is preferably 6 ~ 10 hours.This reaction process can carry out tracing detection by corresponding analyzing and testing equipment, judges whether to react completely according to detected result.
In a specific embodiment of the present invention, described fatty acid phytosterin ester under vacuum or inert gas protection is lower prepares.Employing vacuum condition is a kind of routine operation in this area, and described vacuum is general vacuum condition, and common vacuum apparatus can be adopted to realize, and as vacuum pump, vacuum oil pump, preferred vacuum pressure is below 4mBar, more preferably below 2mBar.Inert gas comprises nitrogen, helium, neon, argon gas, Krypton, xenon, radon gas etc. and does not produce the inert gas of chemical reaction with reactant.
A second aspect of the present invention additionally provides a kind of fatty acid phytosterin ester, and this fatty acid phytosterin ester adopts above-mentioned method preparation.
Present invention also offers a kind of food, containing fatty acid phytosterin ester as above in this food, preferably, fatty acid phytosterin ester adds in edible oil.
Present invention also offers a kind of makeup, containing fatty acid phytosterin ester as above in these makeup,
Accordingly, present invention also offers silicon-dioxide and prepare the application of fatty acid phytosterin ester.
Present invention also offers white carbon black and prepare the application of fatty acid phytosterin ester.
Because silica source is wide, cost is low, therefore, goes for scale operation, particularly use in the factory.Due to prepare fatty acid phytosterin ester on a large scale working condition under, vacuum is higher, therefore, temperature of reaction has certain reduction, therefore, silicon-dioxide provided by the present invention is conducive to reducing energy consumption as the method preparing fatty acid phytosterin ester, saves the energy, highly beneficial for the large batch of fatty acid phytosterin ester of production.
The present inventor is through extensive and deep research, by improving preparation technology, remaining for easily producing metal ion in the preparation process preparing fatty acid phytosterin ester at present, and easily make the shortcoming that the fatty acid sterols ester obtained darkens, and the Catalyst Adsorption fatty acid sterols ester added causes the problem of product loss, proposes a solution.The present invention is intended to realization and prepares fatty acid phytosterin ester and deepen without color and luster, and the highly purified fatty acid phytosterin ester that the basis of Low grease loss obtains, this fatty acid phytosterin ester reaches certain standard, can be applied in various field of food and go.Contriver completes the present invention on this basis.
Technical conceive of the present invention is as follows:
Instant invention overcomes the defect of prior art, propose a kind of method preparing fatty acid phytosterin ester, the basis of the original various catalyzer used is improved, use highly purified silicon-dioxide as catalyzer, decrease the remnants in metal ion fatty acid phytosterin ester after the reaction on the one hand, decrease the consumption of catalyzer on the other hand, also reduce the absorption of catalyzer to grease accordingly, found the color and luster obtaining good fatty acid phytosterin ester unexpectedly simultaneously, its color and luster is substantially identical with the reaction of the catalyzer using convention amount.
In the present invention, term " contains " or " comprising " represents that various composition can be applied in mixture of the present invention or composition together.Therefore, term " primarily of ... composition " and " by ... form " be included in term and " contain " or in " comprising ".
Below describe in detail to various aspects of the present invention:
Raw material
In the present invention, plant sterol is all to extract from plant or by the plant sterol of synthetic, preferred plant sterol comprises the mixture of one or more arbitrary proportion in Sitosterol, Stigmasterol, campesterol, brassicasterol, preferred β-sitosterol
In a specific embodiment of the present invention, use the mixture of 43.48% β-sitosterol, 25.06% Stigmasterol, 25.90% dish sterol, 1.01% brassicasterol.
The lipid acid used in the present invention is all known fatty acid types.Can be the lipid acid of straight chain, also can be the lipid acid of side chain.Can be saturated lipid acid, also can be cholesterol or polyunsaturated lipid acid.This lipid acid can be short chain (containing 2 ~ 6 carbon atoms) lipid acid, medium chain (containing 8 ~ 14 carbon atoms) lipid acid, long-chain (containing 16 ~ 18 carbon atoms) lipid acid and overlength chain (containing 20 or more carbon atoms) lipid acid.The saturated line style lipid acid of lipid acid in the fatty acid sterols ester of preparation preferably containing 2-26 carbon atom, unsaturated line style lipid acid and organic acid, example includes but not limited to: caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, lauric acid, myristic acid, palmitinic acid, stearic acid, eicosanoic acid, behenic acid, oleic acid, linolic acid, Lignoceric acid, hexacosanoic acid, Zoomeric acid, oleic acid, elaidic acid, linolic acid, linolenic acid, timnodonic acid, docosahexenoic acid, arachidonic acid, erucic acid, hydroxy fatty acid, ricinolic acid, acetic acid, propionic acid, butyric acid, valeric acid and isopropylformic acid.In these acid, the lipid acid containing 6-24 carbon atom is preferred, the lipid acid more preferably containing 8-22 carbon atom, and most preferably containing 12-20 carbon atom is preferred.Lipid acid in fatty acid phytosterin ester prepared be in the present invention preferably caproic acid, sad, capric acid, lauric acid, myristic acid, palmitinic acid, stearic acid, oleic acid, linolic acid, eicosanoic acid and/or behenic acid one or combine arbitrarily.
The silicon-dioxide used in the present invention, its purity is more than 90%, and the gross weight of the various impurity contained is below 10%, the gross weight of preferred various impurity is less than 7.5%, preferred, and the gross weight of impurity is less than 1.25%, most preferred, the purity of silicon-dioxide is more than 99%.The silicon-dioxide used in the present invention is highly purified silica product, comprise precipitated silica, fumed silica, soft silica etc., its outward appearance can be particulate state, also can be Powdered, preferably, silicon-dioxide is not containing crystal water.Especially, the silicon-dioxide used in the present invention does not comprise silica gel.
Especially, the silicon-dioxide used in the present invention, can derive from silicon-dioxide (also referred to as white carbon black) prepared by rice hull ash.The silicon-dioxide in this source, its cost prepared is low, therefore, can further reduce corresponding production cost.
Aftertreatment
The invention also discloses a kind of step of fatty acid phytosterin ester being carried out to purifying, this step comprises: by the fatty acid phytosterin ester that obtains after esterification at 60-150 DEG C, vacuum filtration at being preferably 90-120 DEG C, then container is put into by filtering the croude fatty acids plant sterol ester obtained, at high temperature as at 160-220 DEG C, vacuumize, keep 2-6 hour under this condition, obtain the fatty acid phytosterin ester after purifying.
Aftertreatment of the present invention also can be other Conventional processing steps, as utilized molecular distillation equipment by prepared fatty acid phytosterin ester at 100 DEG C-200 DEG C, 10
-1-10
-3molecular distillation is carried out, to obtain the heavy phase containing highly purified fatty acid phytosterin ester under the pressure of mbar.
Advantage
Utilize method provided by the present invention to prepare fatty acid phytosterin ester, the method compared with the existing technology, has following advantage:
1. use a kind of novel catalyzer, make not introduce the disadvantageous metal ion of human body in the process of reaction, and obtained fatty acid phytosterin ester obtains good color and luster.Another aspect of the present invention employs the catalyzer of low consumption, but has higher catalytic performance equally, and does not all reduce in the purity etc. of the reaction product of preparation, unexpectedly obtains the identical technique effect of same high catalyst consumption.Meanwhile, because decrease the usage quantity of catalyzer, not only simplify the post-processing step of reaction, and reduce the absorption of catalyzer to grease.
2. containing a certain amount of crystal water in silica gel used in the prior art, need removing in the esterification reaction, and catalyzer of the present invention is not containing impurity or containing less impurity, do not need in the esterification reaction to remove extra impurity, only need the simple operations such as filtration to realize.And utilize silica gel etc. as catalyst preparing fatty acid phytosterin ester, its color is comparatively dark, and by contrast, the fatty acid phytosterin ester that silicon-dioxide of the present invention prepares has of light color, the advantage that purity is high.
3. catalyzer used in the present invention is not easy to cause metal ion or being mixed into of other foreign ion and damages HUMAN HEALTH.Although as used aluminum oxide have higher reactive behavior and react purity preferably, being easily mixed into harmful aluminium element in grease, forming the potential threat of HUMAN HEALTH.
Embodiment
As no specific instructions, various raw material of the present invention all can be obtained by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Other aspects of the present invention, due to disclosure herein, are apparent to those skilled in the art.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, measures according to national standard usually.If there is no corresponding national standard, then according to general international standard, normal condition or carry out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all numbers are weight part, and all per-cent is weight percentage.
Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Raw material and detection method: the purity being purchased from the paddy in spring of plant sterol is the plant sterol of 95.45%, and wherein the content of various component is: 43.48% β-sitosterol, 25.06% Stigmasterol, 25.90% dish sterol, 1.01% brassicasterol.
The lipid acid used in following embodiment is all purchased from Jia Li fine chemical industry (Shanghai) Co., Ltd..
The silicon-dioxide used in following embodiment is commercial, its purity is respectively 99%(AR level, purchased from Chemical Reagent Co., Ltd., Sinopharm Group) and 92.5%(white carbon black, purchased from benefit sea (Jiamusi) biomass power generation company limited, its raw materials is rice hull ash).
The silica gel used in following embodiment is the discolour silica gel purchased from Qingdao Mike's silica-gel drier company limited.
Detection method: acid value (AV) adopts the method described in GB 5530-98 to detect, and peroxidation price (PV) adopts the method described in GB/T5538-1995 to detect.
Embodiment 1: the preparation of fatty acid phytosterin ester
Preparation method is: lipid acid and plant sterol are put into totally and the there-necked flask of drying according to the ratio in table 1, be heated to 130 DEG C, until form homogeneous oily mater, then react under vacuum according to the condition shown in table 1, vacuum pressure is below 4mBar.
Lipid acid is oleic acid, sad, capric acid, behenic acid, plant sterol is 43.48%-Sitosterol, the mixture of 25.06% Stigmasterol, 25.90% dish sterol, 1.01% brassicasterol (this mixture purity is 95.45%), and catalyzer is aluminum oxide, silicon-dioxide, silica gel.The mol ratio of lipid acid and plant sterol, the consumption (weight percent in whole reaction system) of catalyzer, esterification temperature, reaction times is as shown in table 1, whole reaction process is carried out under vacuo, until reacted, reacting finisheding degree can be monitored by HPLC.
Table 1: different reaction conditionss prepares the parameter of fatty acid phytosterin ester
Note: the white carbon black that the silica source used in the reaction of wherein experimental example 13,14 is produced in Yi Hai (Jiamusi) biomass power generation company limited, silica purity is 92.5%, and its raw materials is rice hull ash; Other silica purity used is 99%.
From above-mentioned reaction result, in the reaction preparing fatty acid phytosterin ester, the amount of silicon-dioxide is reduced to 1% and following time, compare with the catalyzer of high dosage in the purity etc. of the reactant of reactive behavior, preparation, there is similar effect.
When utilizing silica gel as catalyzer, owing to containing certain crystal water in silica gel, therefore when carrying out aftertreatment, also need corresponding water removal operation.
When carrying out scale operation, use silicon-dioxide as catalyzer, the consumption reducing catalyzer is all highly beneficial for aspects such as reduction production cost, minimizing operation stepss.The method not only operationally reduces the difficulty of operation; on the other hand; because silicon-dioxide also has certain absorption as catalyzer to the fatty acid phytosterin ester that reaction generates; because this reducing the consumption of silicon-dioxide; also consequently reduce the loss of grease, also have extraordinary effect for the protection of environment, the discharge of minimizing waste water and dregs.
Embodiment 2: the detection of the constituent content of the fatty acid phytosterin ester prepared under differential responses condition
Table 2: the detection of content of element of the fatty acid phytosterin ester prepared under differential responses condition
| Experiment numbers | Detect metallic element | Detected value |
| 1－5 | Al | 251mg/kg-755mg/kg |
| 6－21 | Si | Do not detect |
The detection of this constituent content adopts ICP/AES method to detect.
From this detected result, when carrying out the esterification of plant sterol by the catalyzer containing metallic element, having a certain amount of metallic element remains in reaction system, if this fatty acid phytosterin ester is applied to field of food, then the residual meeting of this metallic element causes potential harm to human body, so it is residual to need to reduce or avoid metallic element to produce in the esterification reaction as far as possible.And the detected result of silicon-dioxide is known, silicon-dioxide is in esterification reaction process, without any residual, if therefore utilize silicon-dioxide as catalyst application in field of food or cosmetic field, then can not have side effects to human body, can be used as a kind of safe catalyst application in field of food or cosmetic field.
Embodiment 3: the color detection of the fatty acid phytosterin ester prepared under differential responses condition
Table 3: the color detection of the fatty acid phytosterin ester prepared under differential responses condition
| Experiment numbers | Color |
| 1-5 | 0.5R，5Y |
| 6 | 0.5R,5Y |
| 7 | 0.5R,5Y |
| 8 | 0.5R,5Y |
| 9 | 0.6R,5Y |
| 10 | 0.4R,4Y |
| 11 | 0.4R,4Y |
| 12 | 0.5R,5Y |
| 13 | 0.5R,5Y |
| 14 | 0.5R,5Y |
| 15 | 0.5R,5Y |
| 16 | 0.5R,5Y |
| 17 | 0.5R,5Y |
| 18 | 0.5R,5Y |
| 19 | 0.5R,5Y |
| 20 | 0.5R,5Y |
| 21 | 0.5R,5Y |
| 22 | 7R,10Y |
| 23 | 7R,10Y |
| 24 | 7R,10Y |
The detection of color with oil color adopts GB/T 22460-2008 method to detect, and R is red abbreviation, and Y is yellow abbreviation, and numeral is the color and luster value adopting the method to record, and color and luster value is higher, represents that color and luster is darker.
From above-mentioned color detection data, adopt silicon-dioxide to be that catalyst preparing fatty acid phytosterin ester obtains good grease color, compared with silica gel, the color and luster of its grease prepared improves significantly.And at use silicon-dioxide as catalyzer, reduce the not corresponding decolorizing effect reduced to color with oil color in its reaction process of its consumption, on the contrary, reduce it and obtain decolorizing effect more better than the color of the silicon-dioxide of high consumption to a certain extent with quantitative response.
Its color and luster of the fatty acid phytosterin ester utilizing silica gel to prepare has significant intensification, therefore, is not easy for the fatty acid phytosterin ester being further purified to prepare food grade.
Embodiment 4: the purifying of fatty acid phytosterin ester
Get each 400g of thick plant sterol ester prepared by experimental example 6-21, put in there-necked flask, pass into nitrogen and start to vacuumize, be warming up to 200 DEG C and start timing, after this condition keeps 4 hours, obtain pure plant sterol ester, its purity all reaches more than 99.5%.
The index contrast of the indices that table 3 new resource food is recommended and experimental example 6-21
From above data, the fatty acid phytosterin ester prepared through method of the present invention can be applied in food, makeup, preferably, is applied in edible oil.
The foregoing is only preferred embodiment of the present invention, and be not used to limit substantial technological context of the present invention, substantial technological content of the present invention is broadly defined in the right of application, any technology entities that other people complete or method, if with application right define identical, also or a kind of change of equivalence, be all covered by being regarded as among this right.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read foregoing of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (37)
1. prepare a method for fatty acid phytosterin, it is characterized in that, lipid acid and plant sterol react under the condition that there is catalyzer silicon-dioxide.
2. the method for claim 1, is characterized in that, not containing crystal water in described silicon-dioxide.
3. the method for claim 1, is characterized in that, the consumption of described silicon-dioxide is 0.1% ~ 1% of reaction system total mass.
4. the method for claim 1, is characterized in that, the consumption of described silicon-dioxide is the 0.3%-0.8% of reaction system total mass.
5. the method for claim 1, is characterized in that, described lipid acid and the mol ratio of plant sterol are 0.5 ~ 5:1.
6. the method for claim 1, is characterized in that, described lipid acid and the mol ratio of plant sterol are 1.1 ~ 1.4:1.
7. the method for claim 1, is characterized in that, described lipid acid is the lipid acid comprising 2-26 carbon atom.
8. the method for claim 1, is characterized in that, described lipid acid is the lipid acid comprising 6-24 carbon atom.
9. the method for claim 1, is characterized in that, described lipid acid is the lipid acid containing 8-22 carbon atom.
10. the method for claim 1, is characterized in that, described lipid acid is the lipid acid containing 12-20 carbon atom.
11. the method for claim 1, it is characterized in that, described lipid acid is one or more in caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, lauric acid, myristic acid, palmitinic acid, stearic acid, eicosanoic acid, behenic acid, Lignoceric acid, hexacosanoic acid, Zoomeric acid, oleic acid, elaidic acid, linolic acid, linolenic acid, timnodonic acid, docosahexenoic acid, arachidonic acid, erucic acid, hydroxy fatty acid, ricinolic acid, acetic acid, propionic acid, butyric acid, valeric acid and isopropylformic acid.
12. the method for claim 1, is characterized in that, described lipid acid is one or more in caproic acid, sad, capric acid, lauric acid, myristic acid, palmitinic acid, stearic acid, oleic acid, linolic acid, eicosanoic acid and behenic acid.
13. the method for claim 1, is characterized in that, described plant sterol comprise in Sitosterol, Stigmasterol, campesterol, brassicasterol one or more.
14. the method for claim 1, is characterized in that, carry out purifying, comprise and being filtered by fatty acid phytosterin ester, vacuumize in airtight container at 180 DEG C ~ 220 DEG C after described fatty acid phytosterin reaction terminates.
15. the method for claim 1, is characterized in that, in described silicon-dioxide, foreign matter content is lower than gross weight 10%.
16. the method for claim 1, is characterized in that, in described silicon-dioxide, foreign matter content is lower than gross weight 7.5%.
17. the method for claim 1, is characterized in that, in described silicon-dioxide, foreign matter content is lower than gross weight 1.25%.
18. the method for claim 1, is characterized in that, in described silicon-dioxide, foreign matter content is lower than gross weight 1%.
19. the method for claim 1, is characterized in that, described silicon-dioxide is white carbon black.
20. methods as claimed in claim 19, it is characterized in that, described white carbon black is prepared by rice hull ash.
21. the method for claim 1, is characterized in that, described lipid acid and the temperature of reaction of plant sterol are 130 DEG C ~ 250 DEG C.
22. the method for claim 1, is characterized in that, described lipid acid and the reaction times of plant sterol are 4 ~ 12 hours.
23. the method for claim 1, is characterized in that, described lipid acid and the reaction times of plant sterol are 6 ~ 10 hours.
24. the method for claim 1, is characterized in that, described fatty acid phytosterin ester is prepared under vacuum or under protection of inert gas.
25. methods as claimed in claim 24, is characterized in that, described vacuum is that vacuum pressure is less than 4mBar.
26. methods as claimed in claim 24, is characterized in that, described vacuum is that vacuum pressure is less than 2mBar.
27. methods as claimed in claim 24, it is characterized in that, described inert gas comprises nitrogen, helium, neon, argon gas, Krypton, xenon, radon gas.
28. the method for claim 1, is characterized in that, also comprise purification step, and described purification step comprises:
A) by the fatty acid phytosterin ester that obtains after esterification at 60-150 DEG C, vacuum filtration, collects filtrate;
B) filtrate step a) obtained, at 160-220 DEG C, vacuumizes.
29. methods as claimed in claim 28, is characterized in that, described step a) in, by the fatty acid phytosterin ester that obtains after esterification at 90-120 DEG C, vacuum filtration, collects filtrate.
30. methods as claimed in claim 28, is characterized in that, at described step b) in, filtrate step a) obtained, at 180 DEG C ~ 220 DEG C, vacuumizes.
31. methods as described in claim 28 or 30, is characterized in that, at described step b) in, the pumpdown time is 0.5-6 hour.
32. the method for claim 1, is characterized in that, obtained plant sterol ester is carried out molecular distillation.
33. methods as claimed in claim 32, is characterized in that, the temperature of described molecular distillation is 100 DEG C-200 DEG C.
34. methods as claimed in claim 32, is characterized in that, the pressure of described molecular distillation is 10
-1-10
-3mbar.
35. silicon-dioxide are preparing the application in fatty acid phytosterin ester.
The application in fatty acid phytosterin ester prepared by 36. white carbon blacks.
37. apply as claimed in claim 36, it is characterized in that, described white carbon black is prepared by rice hull ash.
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| CN201210216746.7A CN103509076B (en) | 2012-06-27 | 2012-06-27 | The method of fatty acid phytosterin ester is prepared in a kind of silicon-dioxide catalysis |
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| CN108060202B (en) * | 2017-12-12 | 2021-02-23 | 江南大学 | Synthesis method of behenic acid sterol ester antifrost agent and application of behenic acid sterol ester antifrost agent in chocolate |
| CN109439476A (en) * | 2018-11-27 | 2019-03-08 | 安徽省玉兔日用化学品有限公司 | A kind of liquid toliet soap and its processing technology containing glyceric acid/Pidolidone/palmitinic acid modified corn sterol |
| CN115286677B (en) * | 2022-10-10 | 2023-06-23 | 海南浙江大学研究院 | Preparation method of feeding phytosterol ester, phytosterol ester and application thereof |
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