CN101440115B - Method for extracting oryzanol - Google Patents

Abstract

The invention provides a method for extracting oryzanol, which belongs to the field of oryzanol preparation. The method comprises the following steps: crude rice bran oil is used as a raw material, the rice bran oil and normal hexane mixing oil are subjected to pre-deacidification by ethanol first, and then oryzanol is enriched to nigre by NaOH solution, and oryzanol sodium salt is extracted from the nigre by methanol, and finally by regulating the pH value by acid solution, the oryzanol contained in the oryzanol sodium salt is separated out; when ethanolamine deacidification is applied to the production method of the oryzanol, nearly 20 percent loss of the oryzanol caused by alkali refining in the prior method is avoided, and the oryzanol yield is improved from 30 to 35 percent in the prior method to 60 to 70 percent in the method of the invention; moreover, because ethanol can not saponify glyceride, the loss rate of the crude oil caused by deacidification is greatly reduced, from 15 to 25 percent in the prior method to 2 to 5 percent in the method of the invention. The nigre ethanolamine fatty acid generated in the method can be used for cosmetics manufacturing industry to further increase added values.

Description

A kind of extracting method of thiaminogen

Technical field

A kind of extracting method of thiaminogen belongs to thiaminogen and produces the field.

Background technology

Thiaminogen is the commercial title of ring jackfruit alcohols ferulic acid ester as medicine.It is a kind of natural mixture that main body and part sterols ferulic acid ester are formed by ring jackfruit alcohols ferulic acid ester.Rice pollard oil two-story valley dimension cellulose content is about 1.8%～2.5%.Thiaminogen is mainly used in pharmacy, and thiaminogen enters cosmetic field as the skin care raw material in recent years, also has a small amount of as the food oil antioxidant.China 1969 has formed the production method of thiaminogen: the acidifying distillation and separation method by analyze and research chamber joint study exploitation thiaminogen and trial-produceed successfully in 1971 of Shanghai grain and oil industrial grease research department, Food Science Inst., Zhejiang Province grease research department, Shanghai institute of Pharmaceutical Industry at that time.This method is divided into capture, concentrates, separates the purification three phases, and the Rice pollard oil that is about to acid number about 40 at first is enriched in the soap stock through the secondary alkali refining; Remove lipid acid through the acidifying distillation, and thiaminogen is stayed in the black pin, thereby reaching thiaminogen concentrates; Utilize thiaminogen dissolved character in alkaline methanol then, reach and the isolating effects of unsaponifiables such as chaff wax, Fatty Alcohol(C12-C14 and C12-C18), sterol.Decompose the thiaminogen sodium salt with the weak acid organic acid more at last, be reduced to thiaminogen and separate out, finally make thiaminogen.

Though made thiaminogen, still there is certain defective in this method: the production cycle is long, needs 10 days from soap stock to the thiaminogen work in-process; The thiaminogen yield is low, only is about 15%.

Therefore, 1973, by Food Science Inst., Zhejiang Province, Shanghai grain and oil industrial grease research department, oil factory in The Big Red Gate, Beijing forms novel process and improves group, carries out lab scale, goes into operation separately.This method is extracted thiaminogen and is divided into capture, separates two stages of purifying.This method generates the thiaminogen sodium salt from Rice pollard oil with thiaminogen and NaOH in the secondary alkali refining oil.Crude oil is through the secondary alkali refining, and 80%～90% thiaminogen is enriched in the secondary soap stock in the oil, reaches the capture purpose.Then soap stock is replenished saponification, then decompose the thiaminogen sodium salt, thiaminogen is separated out, only make through two steps with weak acid.Though have than much progress, the thiaminogen yield also has only 30%～35%, and because NaOH alkalescence is stronger, and two kinds of methods all cause a large amount of neutral oil saponification, refining Rice pollard oil yield only is 50%～55%.

Thereafter, emerged in large numbers many other thiaminogen preparation methods again: " three take off unification " purifying method, solvent pairs branch formulation etc. all run into and preceding two kinds of problems that method is identical: the thiaminogen yield is low, the neutral oil loss is big.

Summary of the invention

The object of the present invention is to provide the high production method of from Rice pollard oil, extracting thiaminogen of a kind of yield.

For achieving the above object, technical scheme of the present invention is as follows: a kind of extracting method of thiaminogen, with the rice bran crude oil is raw material, at first Rice pollard oil and normal hexane mixing oil are carried out pre-depickling with thanomin, then thiaminogen is enriched in the soap stock with NaOH solution, use thiaminogen sodium salt in the methanol extraction soap stock then, with the acid solution adjust pH wherein contained thiaminogen crystallization is separated out at last, get thiaminogen after the separation;

(1) formulated rice oil extracted from rice husks and normal hexane mixing oil: it is 1/3～1mL/g Rice pollard oil weight that normal hexane adds volume;

(2) the pre-depickling of ethanolamine solutions: earlier Rice pollard oil and normal hexane mixing oil raw material are surveyed acid number, the add-on of thanomin is the required theoretical alkali number of depickling, thanomin quality volumetric concentration is 5%～20%, and temperature of reaction is 35～70 ℃, and the reaction times is 30～120min; Thanomin is selected Monoethanolamine MEA BASF, diethanolamine or trolamine for use;

(3) NaOH solution enrichment thiaminogen: in the reaction solution of step (2) gained, add NaOH solution, the consumption of NaOH is for recording the required amount of contained thiaminogen in the displacement Rice pollard oil, used NaOH mass concentration is 2%～10%, temperature of reaction is 50～70 ℃, reaction times is 30～120min, gets soap stock;

(4) extraction: the volume that adds methyl alcohol is 2～10 times of soap stock amount, and extraction temperature is 30～60 ℃, and the time is 10～60min;

(5) acid out: transferring pH is 3～7, and hydrochloric acid, phosphoric acid, tartrate or citric acid are selected in added acid for use, and temperature is 30～55 ℃, and the time is 1～2h, and the precipitating thing is thick thiaminogen;

(6) aftertreatment: the thick thiaminogen of precipitating thing behind the acid out carried out successively the hot methanol aqueous solution is washed, sherwood oil is washed, vacuum-drying, the product thiaminogen.After isolating thiaminogen, it is carried out further the hot methanol aqueous solution is washed, sherwood oil is washed and negative pressure drying, can improve the purity of thiaminogen.

Beneficial effect of the present invention: the thanomin depickling is applied in the thiaminogen production method, has avoided the soap stock that alkali refining produces in the current methods to make thiaminogen loss about 20%, the thiaminogen yield has brought up to 60%～70% by 30%～35% of current methods; In addition, because thanomin can not saponification glyceryl ester, this makes crude oil because the rate of loss that depickling caused reduces greatly, has been reduced to 2%～5% by 15%～25% of current methods.The soap stock ethanolamine fatty acid that the present invention produces can be used for the makeup production, has further improved added value.

Embodiment

Embodiment 1: the foundation of the ultraviolet spectrophotometry quantitative analysis method of thiaminogen content

The mensuration of typical curve: accurately take by weighing thiaminogen standard substance 0.0219g in the 100mL beaker with ten thousand/electronic balance, add the 2mL trichloromethane and make it dissolving, use dehydrated alcohol constant volume (concentration 0.438 μ g/mL) in the volumetric flask of 50mL then, concussion shakes up, as standardized solution, accurately measure 0.5,1.0,1.5,2.0, this solution of 2.5mL is respectively in the brown volumetric flask of 50mL, be diluted to scale and shake up with dehydrated alcohol.Use the 1cm quartz colorimetric utensil, do with dehydrated alcohol blank, in that (327 ± 1nm) locate to measure light absorption value, and (μ g/mL) is X-coordinate with concentration C, and light absorption value is an ordinate zou drawing standard curve.Obtaining the typical curve regression equation is A=0.0327C-0.0045, R ²=0.9992.

Sample determination: take by weighing oil sample 2～3g in the 50mL volumetric flask, dissolve constant volume, draw (gamma oryzanol content is between 8-18 μ g/mL) in this solution 1mL to 100mL volumetric flask, with the dehydrated alcohol constant volume and shake up with chloroform.Use the 1cm quartz colorimetric utensil, make blank, measure light absorption value at the 327nm place with dehydrated alcohol.Obtain concentration and calculate content by typical curve.

C---by typical curve gained concentration, μ g/mL;

50 * 100---extension rate;

W---example weight, g;

10 ⁶---unit conversion.

Embodiment 2: the selection of thanomin concentration

In Rice pollard oil (m): the ratio of normal hexane (V)=2: 1, take by weighing 50g hair Rice pollard oil and 25mL normal hexane, add in the there-necked flask (establishing reflux), add the Different concentrations of alcohol amine aqueous solution again, stir, temperature of reaction is 70 ℃, reaction times 30min, investigate of the influence of thanomin concentration, the results are shown in Table 1 reaction.

Table 1 thanomin concentration is to the influence of reservation of thiaminogen rate of loss and acid removal rate in the oil

As can be seen from Table 1, the thiaminogen rate of loss is minimum in the oil when the concentration of thanomin is 20%, and this moment, acid removal rate was also higher, and when removing most of lipid acid, thiaminogen has obtained great reservation, so thanomin concentration is 20% o'clock best results.

The selection of embodiment 3:pH value

After method is carried out pre-depickling among the embodiment 2, centrifugal, thiaminogen in the pre-depickling edible vegetable oil is carried out enrichment, 70 ℃ of temperature, time 30min with 2% NaOH solution subsequently.Reaction is got soap stock after finishing, and dissolves with methyl alcohol, removes by filter unsaponifiables, promptly obtains containing the methanol solution of thiaminogen sodium salt and fatty acid sodium salt.Regulate this pH value of solution with citric acid, to seek the best pH that thiaminogen is separated out, evaluation criteria is a final gained thiaminogen quality (g).According to said method selected best pH is 5.5～6.0.

Embodiment 4:

Add the normal hexane of 500mL in 1kg rice bran crude oil, add ethanolamine solutions, the mass/volume concentration of thanomin is 20% (w/v), temperature is 35～70 ℃, carry out the stirring and refluxing reaction, the time is 30～120min, and reaction finishes back centrifuging and taking oil and normal hexane mixing clear liquid.In above-mentioned clear liquid, add concentration then and be 2%～10% NaOH solution, 50～70 ℃ of following stirring and refluxing reaction 30～120min.Reaction solution is centrifugal, get the soap stock layer, add methyl alcohol and extract, methyl alcohol add-on by volume is 2～10 times of soap stock amount.Soap stock is fully dissolved after-filtration remove unsaponifiables.In above-mentioned methanol solution, add acid, the thiaminogen crystallization is separated out, get thick thiaminogen after the separation.Can add hydrochloric acid, phosphoric acid, citric acid or tartrate etc. in the acid out, pH is 3～7, and temperature is 30～55 ℃, and the time is 1～2h.The moisture hot methanol of thick thiaminogen process is washed, sherwood oil is washed, last vacuum-drying can obtain the finished product thiaminogen.Finished product thiaminogen total yield can be up to 60%～70%, and purity is more than 98%.Methyl alcohol is recyclable to be recycled.

Claims (1)

1. the extracting method of a thiaminogen, it is characterized in that, with the rice bran crude oil is raw material, at first Rice pollard oil and normal hexane mixing oil are carried out pre-depickling with thanomin, then thiaminogen is enriched in the soap stock with NaOH solution, use thiaminogen sodium salt in the methanol extraction soap stock then, with the acid solution adjust pH wherein contained thiaminogen crystallization is separated out at last, get thiaminogen after the separation;

(1) formulated rice oil extracted from rice husks and normal hexane mixing oil: it is 1/3～1mL/g Rice pollard oil weight that normal hexane adds volume;

(2) the pre-depickling of ethanolamine solutions: earlier Rice pollard oil and normal hexane mixing oil raw material are surveyed acid number, the add-on of thanomin is the required theoretical alkali number of depickling, thanomin quality volumetric concentration is 5%～20%, and temperature of reaction is 35～70 ℃, and the reaction times is 30～120min; Thanomin is selected Monoethanolamine MEA BASF, diethanolamine or trolamine for use;

(3) NaOH solution enrichment thiaminogen: in the reaction solution of step (2) gained, add NaOH solution, the consumption of NaOH is for recording the required amount of contained thiaminogen in the displacement Rice pollard oil, used NaOH mass concentration is 2%～10%, temperature of reaction is 50～70 ℃, reaction times is 30～120min, gets soap stock;

(4) extraction: the volume that adds methyl alcohol is 2～10 times of soap stock amount, and extraction temperature is 30～60 ℃, and the time is 10～60min;

(5) acid out: transferring pH is 3～7, and hydrochloric acid, phosphoric acid, tartrate or citric acid are selected in added acid for use, and temperature is 30～55 ℃, and the time is 1～2h, and the precipitating thing is thick thiaminogen;

(6) aftertreatment: the thick thiaminogen of precipitating thing behind the acid out carried out successively the hot methanol aqueous solution is washed, sherwood oil is washed, vacuum-drying, the product thiaminogen.