CN103554211A - Method for extracting oryzanol from crude rice bran oil - Google Patents
Method for extracting oryzanol from crude rice bran oil Download PDFInfo
- Publication number
- CN103554211A CN103554211A CN201310571652.6A CN201310571652A CN103554211A CN 103554211 A CN103554211 A CN 103554211A CN 201310571652 A CN201310571652 A CN 201310571652A CN 103554211 A CN103554211 A CN 103554211A
- Authority
- CN
- China
- Prior art keywords
- thiaminogen
- reaction
- rice bran
- crude oil
- gained
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Fats And Perfumes (AREA)
Abstract
The invention provides a method for extracting oryzanol from crude rice bran oil. The method comprises the following steps: (1) decoloring the crude rice bran oil, centrifuging after decoloring and taking supernatant liquid; (2) carrying out a methyl esterification reaction on the supernatant liquid obtained in the step (1), removing a methyl esterification catalyst by water after the reaction, standing and layering to obtain the supernatant liquid; (3) carrying out molecular distillation on the supernatant liquid obtained in the step (2), so as to obtain a first light component and a first heavy component; (4) carrying out transesterification on the heavy component obtained in the step (3), so as to obtain an upper reaction liquid and a lower reaction liquid; (5) carrying out a neutral reaction on the lower reaction liquid obtained in the step (4), standing and layering, so as to obtain an upper layer and a lower layer; (6); carrying out molecular distillation on the upper layer obtained in the step (5), so as to obtain a second light component and a second heavy component; (7) carrying out a crystallization reaction on the second heavy component obtained in the step (6), so as to obtain oryzanol crystals. By adopting the method provided by the invention, use of an organic solvent is greatly reduced; the obtained oryzanol is high in purity; the produced by-product fatty acid methyl ester can be purified into biodiesel. Thus, the additional value is further increased.
Description
Technical field
The present invention relates to the method that rice bran crude oil extracts thiaminogen.
Background technology
In the rice bran crude oil being extracted by rice bran, contain the multiple biologically active substance with commercial value, as tocopherol, tocotrienols, thiaminogen, Yelkin TTS, carotenoid, octacosanol and squalene etc., the wherein about 0.9-2.9% of the content of thiaminogen in rice bran crude oil.
Thiaminogen is a kind of mixture of phytosterol ferulic acid ester, wherein take cycloartenyl ferulate, 24-methylene radical γ-oryzanol, β-sitosterol ferulic acid ester and campesterol ferulic acid ester as main, also comprise stigmasteryl ferulate, the less compositions of other content such as dihydro rape oil ferulic acid ester and γ-oryzanol.
Due to the different physiological roles of thiaminogen, be therefore widely used in medicine, healthcare products, makeup and foodstuff additive.Thiaminogen, for skin care product, can make skin moist delicate, also possesses sunscreen effect simultaneously.Thiaminogen, more can be accepted than synthetic antioxidant for food as a kind of natural antioxidant.Thiaminogen is as medicine, is used for the treatment of neurosis, climacteric syndrome and catatonic syndrome before menstrual period, has the effect of regulating plant maladjusted nervous system and incretion balance obstacle.In addition, thiaminogen also has reducing blood-fat, anti-inflammatory, the different physiological roles such as anti-oxidant.Current research shows that thiaminogen also has assisting therapy type ii diabetes, recovers impaired other effects such as liver function of long-term excessive drinking.Therefore, thiaminogen has wide commercial application prospect.
Industrial, from rice bran crude oil, to extract thiaminogen and mainly by solvent extration, obtain, this method need consume a large amount of organic solvents, and environmental pollution is serious.
Summary of the invention
The invention provides a kind of method that rice bran crude oil addressing the above problem extracts thiaminogen.
The invention provides a kind of method that rice bran crude oil extracts thiaminogen, comprise the steps:
(1) rice bran crude oil is decoloured, centrifugal after decolouring, get supernatant liquid;
(2) supernatant liquid of step (1) gained is carried out to esterification reaction of organic acid, after reaction, water is removed esterification reaction of organic acid catalyzer, and stratification is got supernatant liquor;
(3) supernatant liquor of step (2) gained is carried out to molecular distillation, obtain the first light constituent and the first heavy constituent;
(4) heavy constituent of step (3) gained is carried out to transesterification reaction, obtain upper strata reaction solution and lower floor's reaction solution;
(5) lower floor's reaction solution of step (4) gained is carried out to neutralization reaction, stratification obtains the upper and lower,
(6) molecular distillation is carried out in step (5) gained upper strata, obtain the second light constituent and the second heavy constituent;
(7) gained the second heavy constituent in step (6) is carried out to crystallization reaction and obtain thiaminogen crystal.
The method of extracting thiaminogen from rice bran crude oil provided by the invention, removes major impurity by esterification and transesterification reaction binding molecule distillation technique.Compared to used solvent extration to extract thiaminogen in the past, the present invention has greatly reduced the use of organic solvent, reduced thus the pollution of organic solvent to environment, and gained thiaminogen purity is high, and organic solvent residual is few.In addition, the present invention adopts molecular distillation technique to remove the light constituent impurity such as fatty acid methyl ester, and the separate vacuum degree of molecular distillation technique is high, distillation temperature is low, has effectively avoided the thiaminogen causing due to high temperature to decompose, and has greatly reduced the loss of thiaminogen.
According to the present invention, gained thiaminogen crystal two-story valley dimension cellulose content is 90-95%, and thiaminogen yield is not less than 55%.
Preferably, adopt in step (1) carclazyte to decolour to rice bran crude oil, carclazyte adding proportion is 6-10%, w/w (mass ratio), bleaching temperature is 90-110 ℃, bleaching time be 25-35min (minute).
Preferably, use methyl alcohol to carry out esterification reaction of organic acid in step (2), wherein after methyl alcohol and decolouring, rice bran crude oil ratio is 1.1-1.3, v/w (volume/mass), employing tosic acid is catalyzer, and temperature of reaction is 60-70 ℃, and the reaction times is 50-70min.
Preferably, in step (3) or (6), distillation temperature is 130-140 ℃.
Preferably, use methyl alcohol to carry out transesterification reaction in step (4), wherein methyl alcohol adding proportion is 35-45%, v/w (volume/mass), and employing potassium hydroxide is catalyzer, and temperature of reaction is 60-70 ℃, and the reaction times is 50-70min.
Preferably, in step (5), use Glacial acetic acid to carry out neutralization reaction.
Preferably, in step (7), crystallization reaction comprises: first use the mixed solution of ethanol and ethyl acetate at room temperature to stir 1-2 hour, again solution is placed to 20-24h at-30 ± 2 ℃, vacuum filtration is removed solid impurity, remove again the product that solvent in filtrate obtains enrichment thiaminogen, then, by the product of enrichment thiaminogen standing 1-2 days at 0-2 ℃, add 1.53 times of volume normal hexanes, continue standing 1-2 days, then under room temperature, filter to obtain white thiaminogen crystal.
Preferably, step (7) gained thiaminogen crystal can further be dried to obtain thiaminogen powder.Thiaminogen powder two-story valley dimension cellulose content is 90-95%, and thiaminogen yield is 55-65%.
Middle gained the first light constituent of step (3) and step (4) at the middle and upper levels reaction solution main component are fatty acid methyl ester, further, the first light constituent and upper strata reaction solution can be further purified to obtain to biofuel.
Therefore, according to method provided by the present invention, not only reduced the use of organic solvent, reduced the pollution to environment, gained thiaminogen purity is high, and can also obtain valuable byproduct biofuel.
Accompanying drawing explanation
Fig. 1 is the schema that rice bran crude oil of the present invention extracts thiaminogen.
Embodiment
Embodiment 1
From raw material rice bran crude oil, extract thiaminogen, wherein raw material rice bran crude oil contains thiaminogen approximately 2%, acid value 20, and proterties is the opaque grease of brown, and Fig. 1 has simply described extraction step, and concrete extracting method is as follows:
Step (1), decolouring, centrifugal
Specific as follows:
Rice bran crude oil is decoloured, centrifugal after decolouring, get supernatant liquid.Use carclazyte as discoloring agent.Decolorization condition is: carclazyte adding proportion 8% (mass ratio), 100 ℃ of bleaching temperatures, bleaching time 30 minutes, fully stir, centrifugal after decolouring, centrifugal condition is: centrifuge speed 7500r/min, centrifugation time 10 minutes, supernatant liquid is the rear rice bran crude oil of decolouring, lower floor is spent bleaching clay.After decolouring, rice bran crude oil acid value is 19 left and right, slightly reduces, and thiaminogen content is constant, almost not loss, and proterties is the transparent grease of light brown, absorbancy is 0.378.Decoloration process crude oil rate of loss is about 3.5%.
The impurity such as crude oil decolouring can be removed natural pigment, metal ion in rice bran crude oil, had sordes matter, chaff slag, colloid.Carclazyte low price, good decolorizing effect, unharmful substance discharge and convenient post-treatment.
Step (2), esterification reaction of organic acid
Specific as follows:
Supernatant liquid to step (1) gained carries out esterification reaction of organic acid, and after reaction, water is removed esterification reaction of organic acid catalyzer, and stratification is got supernatant liquor.Esterification condition: methyl alcohol: crude oil=1.2 (v/w) after decolouring; Catalyzer is tosic acid, and charging capacity is 2% (w/w); Temperature of reaction is 65 ℃; 1 hour reaction times.Reaction finishes rear reaction solution and removes tosic acid with warm water washing, and stratification, gets upper strata liquid.Through esterification reaction of organic acid, rice bran crude oil acid value is reduced to 0.5-0.8 by 19, thiaminogen free of losses.
Rice bran crude oil after decolouring is carried out to esterification reaction of organic acid, make free fatty acids wherein change into fatty acid methyl ester, reduce its boiling point, facilitate follow-up separation.
Step (3), molecular distillation
Specific as follows: the supernatant liquor of step (2) gained to be carried out to molecular distillation, obtain the first light constituent and the first heavy constituent.Molecular distillation condition: equipment is German UIC-5,80 ℃ of preheating temperatures; 140 ℃ of distillation temperatures; 40 ℃ of interior cold temperature; Blade applicator 450r/min; Feeding rate 4-6mL/min; Vacuum tightness 0.1Pa.Molecular distillation obtains the first light constituent and the first heavy constituent.Wherein the first light constituent is mainly fatty acid methyl ester, can be further purified and obtain biofuel.The first restructuring is divided into containing thiaminogen product.In rice bran crude oil after molecular distillation, fatty acid methyl ester clearance rate nearly 100%; Acid value is 0.1-0.2; Product yield is 8183%; Thiaminogen content is 2.4-2.5%, and thiaminogen is not loss almost.
The object of molecular distillation is fatty acid methyl ester and a small amount of nonesterified free fatty acids of removing in crude oil.
Step (4), transesterification reaction
Specific as follows:
The heavy constituent of step (3) gained is carried out to transesterification reaction, obtain upper strata reaction solution and lower floor's reaction solution.Transesterification reaction condition: catalyzer is KOH; Methyl alcohol adding proportion is 40% (v/w), catalyst ratio 1.0%, 65 ℃ of temperature of reaction; 1 hour reaction times.After transesterification reaction, reaction solution layering obtains upper strata reaction solution and lower floor's reaction solution, and the mass ratio of upper strata reaction solution and lower floor's reaction solution is about 3:1, upper strata reaction solution is containing thiaminogen 0.5-0.6%, all the other are mainly fatty acid methyl ester, and lower floor's reaction solution is containing thiaminogen 78%, and all the other are mainly glycerine etc.
Transesterification reaction is transformed into fatty acid methyl ester by glycerin fatty acid ester, reduces its boiling point, and the acid byproduct fatty methyl esters that separation obtains also can further be purified and make biofuel.
Step (5), neutralization reaction:
Specific as follows:
Lower floor's reaction solution of step (4) gained is added to appropriate acetic acid regulates PH to slightly acidic, standing rear layering obtains the upper and lower, and upper strata and lower floor's mass ratio are about 1:2, and upper strata two-story valley dimension cellulose content is 19-22%, lower floor is not containing thiaminogen, and main component is glycerine.
Step (6), molecular distillation
Specific as follows: molecular distillation to be carried out in step (5) gained upper strata, obtain the second light constituent and the second heavy constituent.Molecular distillation condition: equipment is German UIC-5,80 ℃ of preheating temperatures; 140 ℃ of distillation temperatures; 40 ℃ of interior cold temperature; Blade applicator 450r/min; Feeding rate 4-6mL/min; Vacuum tightness 0.1Pa.In the second light constituent, without thiaminogen, be mainly impurity.The second restructuring is divided into containing thiaminogen product, and thiaminogen content is 21-23%, and product yield is 90-92%.
Step (7): crystallization reaction.
Specific as follows:
Gained the second heavy constituent in step (6) is placed in to the solvent (ethanol/ethyl acetate (8:2, v/v)) of 10 times of volumes, the lower airtight stirring of room temperature (20.5 ± 1.5 ℃) 1 hour.Solution is placed 20h at-30 ± 2 ℃.Vacuum filtration is removed solid impurity, then revolves and steam the product that the solvent remove in filtrate obtains enrichment thiaminogen.Then by being rich in standing 1-2 angel thiaminogen crystal at product 0-2 ℃ of thiaminogen, fully increase.Add again 2 times of volume normal hexanes, and continue standing 1-2 days at 0-2 ℃, under room temperature, filter to obtain white thiaminogen crystal.Crystal two-story valley dimension cellulose content 92.4%, the rate of recovery 61.1%.
The present invention can also be dried the thiaminogen crystal of step (7) gained again, obtains thiaminogen powder.
Drying conditions is: 105 ℃ of drying temperatures, be 4h time of drying.After dry, the purity of the finished product thiaminogen powder is 92.6%, thiaminogen free of losses.
Claims (10)
1. rice bran crude oil extracts a method for thiaminogen, comprises the steps:
(1) rice bran crude oil is decoloured, centrifugal after decolouring, get supernatant liquid;
(2) supernatant liquid of step (1) gained is carried out to esterification reaction of organic acid, after reaction, water is removed esterification reaction of organic acid catalyzer, and stratification is got supernatant liquor;
(3) supernatant liquor of step (2) gained is carried out to molecular distillation, obtain the first light constituent and the first heavy constituent;
(4) the first heavy constituent of step (3) gained is carried out to transesterification reaction, obtain upper strata reaction solution and lower floor's reaction solution;
(5) lower floor's reaction solution of step (4) gained is carried out to neutralization reaction, stratification obtains the upper and lower,
(6) molecular distillation is carried out in step (5) gained upper strata, obtain the second light constituent and the second heavy constituent;
(7) gained the second heavy constituent in step (6) is carried out to crystallization reaction and obtain thiaminogen crystal.
2. rice bran crude oil according to claim 1 extracts the method for thiaminogen, it is characterized in that, in step (1), adopt in vain and above rice bran crude oil is decoloured, carclazyte adding proportion is 6-10% (w/w), bleaching temperature is 90-110 ℃, and bleaching time is 25-35min.
3. rice bran crude oil according to claim 1 extracts the method for thiaminogen, it is characterized in that, in step (2), use methyl alcohol to carry out esterification reaction of organic acid, wherein after methyl alcohol and decolouring, rice bran crude oil ratio is 1.1-1.3 (v/w), employing tosic acid is catalyzer, temperature of reaction is 60-70 ℃, and the reaction times is 50-70min.
4. rice bran crude oil according to claim 1 extracts the method for thiaminogen, it is characterized in that, in step (3) or (6), distillation temperature is 130-140 ℃.
5. according to the rice bran crude oil described in claim 1, extract the method for thiaminogen, it is characterized in that, in step (4), use methyl alcohol to carry out transesterification reaction, wherein methyl alcohol adding proportion is 35-45% (w/w), employing potassium hydroxide is catalyzer, temperature of reaction is 6070 ℃, and the reaction times is 50-70min.
6. according to the rice bran crude oil described in claim 1, extract the method for thiaminogen, it is characterized in that, in step (5), use Glacial acetic acid to carry out neutralization reaction.
7. according to the rice bran crude oil described in claim 1, extract the method for thiaminogen, it is characterized in that, in step (7), crystallization reaction comprises: first use the ethanol of 9-12 times of volume and the mixed solution of ethyl acetate at room temperature to feel and mix 1-2h, again solution is placed to 20-24h at-30 ± 2 ℃, vacuum filtration is removed solid impurity, remove again the product that solvent in filtrate obtains enrichment thiaminogen, then by the product of enrichment thiaminogen standing 1-2 days at 0-2 ℃, add again 1.5-3 times of volume normal hexane, continue standing 1-2 days, then filter to obtain white thiaminogen crystal.
8. rice bran crude oil according to claim 1 extracts the method for thiaminogen, and gained thiaminogen crystal two-story valley dimension cellulose content is 90-95%, and thiaminogen yield is 55-65%.
9. according to the rice bran crude oil described in claim 1, extract the method for thiaminogen, it is characterized in that, in step (3), in gained the first light constituent or step (4), gained upper strata reaction solution can be further purified to obtain biofuel.
10. according to the rice bran crude oil described in claim 1, extract the method for thiaminogen, it is characterized in that, step (7) gained thiaminogen crystal can further be dried to obtain thiaminogen powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310571652.6A CN103554211A (en) | 2013-11-18 | 2013-11-18 | Method for extracting oryzanol from crude rice bran oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310571652.6A CN103554211A (en) | 2013-11-18 | 2013-11-18 | Method for extracting oryzanol from crude rice bran oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103554211A true CN103554211A (en) | 2014-02-05 |
Family
ID=50008603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310571652.6A Pending CN103554211A (en) | 2013-11-18 | 2013-11-18 | Method for extracting oryzanol from crude rice bran oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103554211A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348362A (en) * | 2015-11-12 | 2016-02-24 | 厦门理工学院 | Production method of gamma-oryzanol |
| CN111606965A (en) * | 2020-05-29 | 2020-09-01 | 宜春大海龟生命科学有限公司 | Method for extracting and purifying oryzanol from rice bran acidification oil |
| CN114652657A (en) * | 2022-03-07 | 2022-06-24 | 刘燕 | Skin care composition with anti-aging and anti-blue light effects and preparation method thereof |
-
2013
- 2013-11-18 CN CN201310571652.6A patent/CN103554211A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 刘军海: "米糠谷维素提取纯化方法研究进展", 《粮食与油脂》 * |
| 黄显慈: "从米糠油皂脚中提取脂肪酸甲酯、甘油、药物谷维素和不皂化物的方法", 《湖北化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348362A (en) * | 2015-11-12 | 2016-02-24 | 厦门理工学院 | Production method of gamma-oryzanol |
| CN105348362B (en) * | 2015-11-12 | 2017-04-26 | 厦门理工学院 | Production method of gamma-oryzanol |
| CN111606965A (en) * | 2020-05-29 | 2020-09-01 | 宜春大海龟生命科学有限公司 | Method for extracting and purifying oryzanol from rice bran acidification oil |
| CN114652657A (en) * | 2022-03-07 | 2022-06-24 | 刘燕 | Skin care composition with anti-aging and anti-blue light effects and preparation method thereof |
| CN114652657B (en) * | 2022-03-07 | 2024-02-09 | 科丽思化妆品（上海）有限公司 | Skin care composition with anti-aging and anti-blue light effects and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kartika et al. | Direct Calophyllum oil extraction and resin separation with a binary solvent of n-hexane and methanol mixture | |
| Vali et al. | A process for the preparation of food-grade rice bran wax and the determination of its composition | |
| CN105016956B (en) | A kind of method for extracting squalene | |
| CN101607977A (en) | Extract the method and the technology of purifying natural plant sterol in the oil deodorization distillate residual oil | |
| CN103554211A (en) | Method for extracting oryzanol from crude rice bran oil | |
| EP2528458B1 (en) | Solid/liquid extraction | |
| WO2015106186A2 (en) | Compositions of cosmetic, personal care and skin care products derived from lipid feedstocks and methods to produce the same | |
| Dikshit et al. | Advances in various techniques for isolation and purification of sterols | |
| CN106748615A (en) | A kind of method that squalene is extracted from grease | |
| US7833994B2 (en) | Ethanol extraction of phytosterols from corn fiber | |
| CN103432028A (en) | Paeonia ostii seed natural activity skin cream and preparation method thereof | |
| US11535583B1 (en) | Preparation method of eicosapentaenoic acid ethyl ester | |
| EP3586642A1 (en) | Ala enriched polyunsaturated fatty acid compositions | |
| CN101486951A (en) | Method for separating oleate, linolic acid, oleate and linoleate | |
| CN114574280B (en) | Preparation method of high-content polyunsaturated fatty acid grease | |
| CN101781216A (en) | Novel process for preparing propylgallate directly from gallnuts | |
| CN105452428A (en) | Processes for selective extraction of unsaponifiable materials from renewable raw materials by reactive trituration in the presence of a cosolvent | |
| CN113588485A (en) | Method for extracting total unsaponifiable matter from vegetable oil | |
| EP3052603B2 (en) | Enrichment of triterpene esters | |
| CN110642912B (en) | Method for refining perilla sterol | |
| CN105037313A (en) | Method for simply separating myricetrin and catechin in bark of waxberry tree | |
| EP3586640A1 (en) | Dha enriched polyunsaturated fatty acid compositions | |
| JPH03259049A (en) | Functional food material | |
| CN104164298B (en) | A kind of Oil of egg yolk preparation method containing Harman alkaloid | |
| EP3586641A1 (en) | Dha enriched polyunsaturated fatty acid compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140205 |