CN110294784A - A method of oryzanol is extracted by raw material of refining of crude rice bran oil soap stock - Google Patents
A method of oryzanol is extracted by raw material of refining of crude rice bran oil soap stock Download PDFInfo
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Abstract
A method of oryzanol is extracted by raw material of refining of crude rice bran oil soap stock, comprising the following steps: (1) alcohol extracting；(2) it is separated by solid-liquid separation；(3) depickling degreasing decoloring and washing；(4) it refines；(5) it crystallizes；(6) filtering and washing；(7) dry.It is white powder using oryzanol finished product produced by the present invention, is the pure natural oryzanol in rice bran source, the purity of gained oryzanol may be up to 99%, and impurity content is few, the ultimate yield > 70% of oryzanol；The present invention eliminates the dissolvent residual in technical process without using big solvents of toxicity such as methanol, using edible ethanol in the last process link of formed product, product oryzanol is made to meet export requirement；Simple production process, it is easy to operate and realize；It is raw material due to being using the byproduct refining of crude rice bran oil soap stock of oils industry production rice bran oil, so production cost is low, is suitble to industrialized production.
Description
Technical field
The invention belongs to plant extract separation technology fields, are related to a kind of method for extracting oryzanol, and in particular to a kind of
The method for extracting oryzanol as raw material using refining of crude rice bran oil soap stock.
Background technique
Oryzanol (Oryzanol) is present in rice bran oil, is the mixing of the ferulic acid ester based on triterpene (alkene) alcohol
Object.The autonomic nerves system and endocrine maincenter for mainly acting on diencephalon, can adjust autonomic nervous function, reduce incretion balance
Obstacle improves spiritual nervous disorder symptom.Also having simultaneously reduces blood lipid, reduces liver lipids, prevent lipid oxidation, is anti-oxidant
Etc. different physiological roles.In addition, cardiac muscle can be kept emerging by adjusting vegetative nerve function there are also antiarrhythmic effect is supported
Putting forth energy property reduces.The effect for reducing fat of oryzanol can also improve the blood supply of cardiac muscle, play the role of improving sleep.
Title: oryzanol gamma-Oryzanol
Molecular formula: C40H58O4
Molecular weight: 602.89
No. CAS: 11042-64-1
Fusing point: 135~137 °C
Structural formula:
Dissolubility: can be dissolved in the organic solvents such as methanol, ethyl alcohol, acetone, ether, chloroform and benzene, can be dissolved in vegetable oil and its and stone
The mixture of oily ether is slightly soluble in buck, not soluble in water, dissolves in the methanol and ethanol solution of alkalinity, insoluble in acid methanol
Or in ethyl alcohol.
The producer of production rice bran oil oryzanol is mainly the grease factory of refined rice bran oil at present, and commercially available oryzanol is primarily present
Three aspect problems: 1, dissolvent residual is exceeded and uses violation solvent: the mainly organic solvent residuals such as methanol, hexane cause
Oryzanol product can not export American-European and Japan, and green export standard regulation exported product must not use methanol in process of production
Equal toxic solvents；2, the actual content of most oryzanol products is below standard: although some commercial product white colors, content only have
95% or so, know that these products produce some new degradation materials in process of production through analysis, although being similarly white,
Oryzanol content is reduced, this is related with production technology；3, the color of some oryzanol products is below standard: the color of this kind of product
For off-white color or canescence, yellowish white, but content has also reached 98%.
The domestic patented technology report in relation to oryzanol also compares more:
1, by be described below using solvent:
Application No. is CN201710073967.6, CN201510769436.1, CN201310659297.8,
CN201310099264.2、CN201010542976.3、CN201010224081.5、CN200810231528.8、
The patent applications such as CN02135610.6 are to be refining to obtain oryzanol using a series of using methanol as Extraction solvent, are easy remaining
Methanol and do not meet exported product regulation.
Application No. is the patent applications such as CN201510769436.1, CN201010542976.3 to be refined or be crystallized with hexane,
Oryzanol product is obtained using some processing steps, remaining hexane is easy, causes to remain exceeded.
2, it is described below by technique class:
Application No. is the patent applications of CN201710073967.6 to disclose a kind of oryzanol extraction process, first to rice crude oil
Degumming is carried out, degummed oil is obtained；Alkali refining is carried out to degummed oil, obtains soap stock；Methanol, water and carbonic acid is added after supplement saponification in soap stock
Sodium carries out alkali soluble, obtains supernatant liquor；Supernatant liquor sequentially adds hydrochloric acid, lemon acid for adjusting pH, obtains oryzanol semifinished product；Cleaning,
It is dry, obtain purification oryzanol.This method is extracted using alkaline methanol, toxic solvent；And sodium carbonate is weak base, it in practice can not be with
Phenolic hydroxyl group in oryzanol molecule combines, and oryzanol can not be promoted to dissolve.
Application No. is the patent applications of CN201510769436.1 to disclose a kind of gamma oryzanol production method, by filter residue
Pour into dissolving tank；It is added after methanol mixing plus hexane stirs；Add acetic acid to neutralize, is stirred at reflux；Heating water bath to 50 DEG C, heating is stirred
Mix reflux；One hour is stood after adding water to continue stirring；Semifinished product gamma oryzanol is precipitated；Solution AUTOMATIC ZONING, upper layer are that hexane is molten
Liquid；Lower layer is semifinished product gamma oryzanol precipitate and methanol dissolving layer；Upper and lower level methanol dissolving layer is shunted；Under heating water bath
Layer gained；Semifinished product gamma oryzanol precipitate after heating water bath is filtered under diminished pressure with methanol dissolving layer, filter paper upper layer is thick
Gamma oryzanol；Hexane is added to thick gamma oryzanol, the impurity that wash-off in particle is dissolvable in water hexane is precipitated；Collect γ-Gu Wei
Particle low temperature drying is precipitated in element.Under heating condition, oryzanol is soluble in hexane, and solubility is larger in methyl alcohol, methanol
There is larger toxicity.Since being dissolved with oryzanol in two-phase solvent, method is unable to reach the purpose of separation.
Application No. is CN201310659297.8 to disclose a kind of method that oryzanol is extracted from chaff dregs of rice waste grease, packet
It including following steps: 1) high temperature resistant enzyme being added into chaff dregs of rice waste grease, additional amount is the 0.5-5% of chaff dregs of rice waste grease quality,
Stirring digestion 60-120min, filtering obtain grease clear liquid at 70-95 DEG C；2) alkali soluble: by basic methanol solution and step 1) oil
Rouge clear liquid example 1:5~1:8 in mass ratio is mixed, and is heated up to 60 DEG C, and stirring is stood to two-phase laminated flow, extraction；3) acid out:
Step 2 extract liquor is heated to 40-60 DEG C, it is 3.0-6.0 that acid, which is added, and adjusts to pH, stands overnight, is centrifugated, obtains paddy
Tie up plain crude product；4) refine oryzanol: the oryzanol crude product that step 3) is obtained is rinsed with distilled water, is then dried, obtained
Refine oryzanol.The chemical nature of enzyme is protein, can be inactivated in 70 DEG C or more most enzymes, methodological science requires study；First
Alcohol is toxic reagent；Oryzanol is water-insoluble matter, and wherein impurity also comes from oil, is similarly in strong lipophilic substance, simple to steam
Distilled water is dry after rinsing, it is impossible to realize the purpose of purification, which needs further to be studied.
Application No. is CN201310099264.2 to disclose a kind of method for extracting oryzanol from rice bran crude oil, and steps are as follows:
(1) level Four the rice bran oil 1. degumming of Rice bran crude oil aquation and dewaxing are produced；2. dewax rice bran oil decolorization；3. rice bran oil physics essence of decolourizing
Refining；(2) preparation of thick oryzanol 1. soap base is extracted；2. alkali soluble operates；3. acid out operates；(3) refining crude oryzanol 1. tie up by rough rice
Element weight molten and solvent oil liquid-liquid washing；2. acid out and acid soak；3. oryzanol drying and crushing.This law uses toxic first
Alcohol, and product nodeless mesh step, content need further to be confirmed.
Application No. is CN201010542976.3 to disclose a kind of technique that oryzanol is extracted from rice bran, and hair oil extracted from rice husks is added
Methanol adjusts pH, heating and thermal insulation stirring with sodium hydroxide, and lower layer's oil phase is released in cooling and standings layering；Add into upper layer methanol solution
Enter lemon acid for adjusting pH to 7, stands leaching precipitating, obtain crude product；It is recrystallized with hexane, washed, dry fine work.The method is used
Toxic methanol, and methanol is applied directly in oil, safety has to be assessed.
Application No. is CN201010224081.5 to disclose a kind of method of extracting oryzanol by non-polar solvent extraction method, choosing
With rice bran oil alkali refining soap stock, methanol ether alkaline solution is added, rear stratification is sufficiently stirred, upper layer is neutral substance, lower layer
It is the alkaline matter containing oryzanol, adjusts pH value with hydrochloric acid solution, has oryzanol crystallization to be precipitated at this time.It is washed out, vacuum
Dry oryzanol finished product.The method uses toxic methanol and ether, and ether is control reagent；The oryzanol for adjusting acid to be precipitated
Content needs further to be confirmed.
Application No. is CN200810231528.8 to disclose a kind of production method that oryzanol is extracted from rice bran oil soapstock,
Will be enriched in oryzanol rice bran oil soapstock heating, dissolve after, be diluted with methanol, then plus alkali supplement saponification, later, carry out alkali
Molten filtering obtains the filtrate of saponification liquor, carries out the dilute filtering of acid again to the filtrate of saponification, through acidleach, purification, granulation after washing, then
Drying.The method uses toxic methanol, and main technique is that alkali alcohol dissolves acid out, the simple content for purifying oryzanol later
Need further to be confirmed.
Application No. is CN200810244052.8 to disclose a kind of extracting method of oryzanol, using Rice bran crude oil as raw material,
Pre- depickling is carried out to rice bran oil and n-hexane miscella with ethanol amine first, oryzanol is then enriched to soap stock with NaOH solution
In, then with oryzanol sodium salt in methanol extraction soap stock, oryzanol crystallization contained therein finally is precipitated with acid solution tune pH value,
Oryzanol is obtained after separation.This law uses toxic methanol, and main technique is that alkali alcohol dissolves acid out, and products obtained therefrom is low content paddy dimension
Element.
Application No. is CN02135610.6 to disclose a kind of method that solvent extraction method extracts oryzanol, first to rice bran
Crude oil is pre-processed, and carries out chaff of the physical refining to remove free fatty acid in oil, after refining to pretreated oil extracted from rice husks
Alkaline methanol is added in oil and carries out continuous countercurrent extraction, acid adding makes oryzanol knot contained therein into methanol mother liquor extracted
Partial crystallization goes out, and oryzanol is obtained after separation.The method uses toxic methanol, and main technique is that alkali alcohol dissolves acid out, and products obtained therefrom is low
Content oryzanol.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide obtained by one kind
Oryzanol actual content is greater than the industrial products that 98%, color is white, i.e. purity and color is up to standard, and production mistake
The solvent and dissolvent residual that journey uses meet the method for extracting oryzanol as raw material using refining of crude rice bran oil soap stock of export standard,
This method is suitble to plant extracts factory to use, and production technology is relatively simple, and energy large-scale production goes out good oryzanol industry and produces
Product can reduce production cost, improve the economic and social benefit of enterprise.
The technical solution adopted by the present invention to solve the technical problems is: a kind of to extract by raw material of refining of crude rice bran oil soap stock
The method of oryzanol, comprising the following steps:
(1) alcohol extracting: refining of crude rice bran oil soap stock is heated and softened, and edible ethanol is added and is uniformly mixed, adjusting pH, heating extraction,
Filtering, obtains extracting solution；
(2) be separated by solid-liquid separation: adjusting pH, it is to be precipitated completely after, filtrate and precipitating are collected in filtering respectively, and filtrate is used to prepare by-product
Product rice bran oil fatty acid, precipitating are used to prepare oryzanol；
(3) depickling degreasing decoloring and washing: isopropanol being added into precipitating, and heating stirring is simultaneously uniformly mixed, filtering, removal remaining
Fatty acid and most of lipid impurities and pigment, obtain depickling degreasing decoloring precipitating；It is added again into depickling degreasing decoloring precipitating
Purified water is stirred and is uniformly mixed, and is filtered and is washed, and the isopropanol of remaining is removed；
(4) it refining: No. 6 solvent naphthas or petroleum ether being added into depickling degreasing decoloring precipitating, heating stirring mixing is equal, filtering,
Remaining lipid impurities and pigment are removed, the purification precipitating of off-white color is obtained；
(5) it crystallizes: edible ethanol being added into purification precipitating, heating stirring dissolution is let cool to room temperature, crystallization, obtains white sink
It forms sediment；
(6) filtering and washing: after crystal is precipitated completely, filtering, and with water washing precipitating is purified, obtain crystalline deposit；
(7) dry: by crystalline deposit it is dry finished product oryzanol.
Preferably, in step (1), the temperature that the refining of crude rice bran oil soap stock heats and softens is 35~65 DEG C.Ruo Jiarewen
Spend it is low, then soap stock keep solid hardening state, need long-time heating that could soften；If heating temperature is high, since soap stock is in alkali
Property, then there is significant destroy to oryzanol.
Preferably, in step (1), the volumetric concentration of the edible ethanol is 80%~95%, and the dosage of edible ethanol is soap
3~6 times of foot weight.There is reported in literature methanol before, present invention discover that can also be extracted oryzanol with edible ethanol
Come, and meets the use of exported product solvent and residue criterion.Technically in contrast, the oryzanol color that ethyl alcohol extracts
Shallowly, impurity is less, purity is high.If edible ethanol concentration is low, most of oryzanol can not be extracted, loss is big；If food
With concentration of alcohol height, then it is difficult to be recycled to high concentration edible ethanol in production.The dosage of edible ethanol is according to refining of crude rice bran oil soap
The content of oryzanol is fixed in foot raw material, and then times quantity increases general oryzanol content height, and the low then times quantity of content is reduced, and mainly examines
Consider economic benefit.
Preferably, in step (1), substance used in the adjusting pH be sodium hydrate aqueous solution, corrresponding quality concentration be 2~
10%, adjusting pH is 8~11.Sodium hydrate aqueous solution is the substance for adjusting alkaline solution most economical, and the low then dosage of concentration is big, concentration
Gao Ze is also easy to produce a large amount of heats of solution in process for preparation and influences labor safety.The final extracting solution pH that adjusts is excessively high, then can be significant
Oryzanol is destroyed, oryzanol low yield is caused；It is too low, it is unfavorable for oryzanol dissolution, it is few so as to cause yield.
Preferably, in step (1), the heating extraction temperature is 50~65 DEG C, and the time is 10~40min.If heating mentions
It takes temperature height or time long, then has significant destruction to oryzanol under alkaline condition；If heating extraction temperature is low or the time
It is short, then it is unfavorable for the dissolution of oryzanol.
Preferably, in step (1), the mode of the filtering is sedimentation centrifugation or disk centrifugal or tubular type centrifugation.Above three
Kind mode may be incorporated for the extracting solution containing oryzanol and extract the separation of slag, premised on obtaining clear filtrate.
Preferably, in step (2), substance used in the adjusting pH is hydrochloric acid or aqueous sulfuric acid, and corrresponding quality concentration is 5
~20%, adjusting pH is 6.5~7.5.Hydrochloric acid and aqueous sulfuric acid can be in production to adjust the pH of alkaline solution into
Property or acidity, have a wide range of application, and do not chemically react with major product.The low then dosage of concentration is big, concentration height then process for preparation
It generates a large amount of heats of solution and is unfavorable for labor safety.Final adjusting pH is too low, then abundant fatty acid is attached to major product oryzanol
In, it is unfavorable for oryzanol purifying；If pH is excessively high, major product is precipitated not exclusively, and yield is low.
Preferably, in step (2), the precipitating complete time is 2~12h.If the sedimentation time is short, oryzanol precipitating
Not exclusively, yield is reduced；If the sedimentation time is long, the production cycle is influenced, reduces production efficiency.
Preferably, in step (2), the mode of the filtering is to filter or settle centrifugation or tubular type centrifugation or disk centrifugal.
The mode filtered herein is fixed according to product characteristics, if precipitating is scattered, selects suction filtration；Or sealed Belt oil stick nature, then it selects
The filter type of sedimentation centrifugation or tubular type centrifugation or disk centrifugal.
Preferably, in step (3), the 1st purifying is that depickling degreasing decoloring solvent for use is isopropanol, and additional amount is precipitating
1~3 times of weight, heating temperature are 40~60 DEG C.It is found through testing a variety of organic solvents, isopropanol is resulting to the present invention
It adjusts acid precipitating that there is good depickling degreasing decoloring performance, remaining fatty acid can be removed, dissolve most grease ingredient and pigment,
Convenient for the operation of later period refining step.If quantity of isopropanol is excessive or heating temperature is high, have to oryzanol a degree of molten
It solves and yield is caused to decline, it is very few if additional amount or to remove fatty acid, lipid impurities and pigment effect if heating temperature is low poor, no
These most of substances can be effectively removed, the purpose of purifying is not achieved.
Preferably, in step (3), the mode of the filtering be filter or sedimentation centrifugation or cloth bag centrifugation or tubular type centrifugation or
Disk centrifugal.According to the technological requirements and product property, one of above-mentioned filter type can be selected.
Preferably, in step (3), the amount that purified water is added is 2~6 times of Sediment weight, and it is 1~3 that number, which is added,
Secondary, filter type is suction filtration or cloth bag centrifugation, and mode of washing is to be added by several times on a small quantity to suction filtration precipitating or cloth bag centrifugation.This
The purpose that purified water is added in place is the principle dissolved each other using isopropyl alcohol and water, and the isopropanol of remaining is completely dissolved by moisture
Out, to remove isopropanol residual.This technique is cooperated to go the remaining optimum filtration mode of isopropanol for suction filtration or cloth bag centrifugation.
Preferably, in step (4), i.e. purification solvent for use is No. 6 solvent naphthas or petroleum ether, additional amount are for the 2nd purifying
1~3 times of Sediment weight, heating temperature are 45~60 DEG C.It is found through testing a variety of organic solvents, No. 6 solvent naphthas or petroleum
Ether has good further degreasing decoloring performance to the resulting depickling defatted preparations of the present invention, can remove remaining lubricant component and
Pigment is convenient for secondary crystallization process operations.If No. 6 solvent naphthas or petroleum ether additional amount excessively if cause that the production cost increases, add
It is poor to enter the excessively few then refining effect of amount.Heating temperature height then has a degree of dissolution to oryzanol and yield is caused to decline, and heats
Temperature is low, cannot be completely dissolved out as far as possible by remaining lipid impurities and pigment well, the purpose of purification is not achieved.
Preferably, in step (4), the filter type is to filter or settle centrifugation or cloth bag centrifugation or tubular type centrifugation, root
According to technique requirement and product property, one of above-mentioned filter type can be selected.
Preferably, in step (5), the i.e. crystallization solvent for use of the 3rd purifying is edible ethanol, and corresponding volumetric concentration is
85%~95%, the additional amount of edible ethanol is 15~25 times of the heavy amount of purification, and heating temperature is 55~80 DEG C.It is sent out through experiment
Existing, oryzanol controls enough ethyl alcohol and measures and be heated to again to dissolve to a certain degree in height ethanol solution, and lets cool
The characteristics of being substantially completely precipitated again afterwards, select height edible ethanol for recrystallisation solvent, using heating method.A large amount of heat simultaneously
Ethyl alcohol can be completely dissolved purification early period remaining No. 6 solvent naphthas of institute or a petroleum ether, it is to be crystallized completely after, can filter removal this
A little dissolvent residuals.
Preferably, in step (5), the mode that lets cool is to be placed at room temperature for natural cooling or the placement of logical cooling water or 0~4 DEG C
Refrigeration.Natural cooling analysis settling velocity is slower, and refrigeration analysis precipitating is slightly fast, is suitble to conditional factory.
Preferably, in step (6), the filter type is suction filtration or cloth bag centrifugation, and the amount of purified water is added as precipitating weight
2~6 times of amount, it is 1~3 time that number, which is added, and mode of washing is to be added by several times on a small quantity to suction filtration precipitating or cloth bag centrifugation.This
The purpose that purified water is added in place is the principle dissolved each other using edible ethanol and water, completely by moisture time by the edible ethanol of remaining
It is dissolved out, to remove ethyl alcohol residual.This technique is cooperated to go the remaining optimum filtration mode of ethyl alcohol for suction filtration or cloth bag centrifugation.
Preferably, in step (7), the drying mode of the crystalline deposit is that forced air drying or vacuum drying (can be micro-
Wave vacuum drying), drying temperature is 55~65 DEG C.The physicochemical property of oryzanol crystallization is more stable in general, Ke Yixuan
Select one or a combination set of above-mentioned drying mode.
The principle of the present invention:
The present invention extracts oryzanol by raw material of refining of crude rice bran oil soap stock.Oryzanol and fat are mainly contained in raw material soap stock
Acid, lipophilic contaminant and fat-soluble pigment, and the present invention is also secondary with other technique fractionation of fatty acid while extracting oryzanol
Product realizes the comprehensive utilization of raw material to reduce production cost.
Main line of the present invention has three: first is that oryzanol content, second is that product colour, third is that dissolvent residual.Utilize major product paddy
Dimension element and acid byproduct fatty and most of impurity dissolve in the property of the alkaline ethanol of heat, by adjusting pH appropriate,
Major-minor product is extracted using height ethyl alcohol.Major product oryzanol is insoluble in acidic ethanol, and acid byproduct fatty is soluble in
Acidic ethanol can make that precipitating is precipitated in oryzanol and fatty acid is retained in acid ethanol solution by adjusting pH appropriate, then
The separation of major-minor product is realized by filter type appropriate.Mainly still contain a small amount of fatty acid in the tune acid precipitating containing oryzanol
And most of lipophilic contaminant and fat-soluble pigment, and these impurity and pigment can largely be dissolved by isopropanol, be led to
It crosses using isopropanol and uses heating method appropriate, remaining fatty acid and most of lipophilic contaminant and liposoluble can be removed
Property pigment and retain oryzanol, then the principle dissolved each other by filter type appropriate and isopropyl alcohol and water passes through purifying washing
It washs and removes isopropanol.The remaining lipophilic contaminant of isopropanol purifying institute and fat-soluble pigment are soluble in No. 6 solvent naphthas or petroleum
The lipophilic solvents such as ether are removed the lipophilic contaminant of remaining and fat-soluble pigment by these solvents, to be further purified
Oryzanol.Using oryzanol in cold and hot ethyl alcohol the big property of difference in solubility and remain in crystallization in a small amount of No. 6 it is molten
Agent oil or petroleum ether can obtain high-purity, color is white using filter type appropriate by the property that a large amount of height ethyl alcohol dissolve
Oryzanol fine work while, have also been removed lipophilic solvent residual.The principle and use finally dissolved each other using second alcohol and water are fitted
When filter type, obtain oryzanol fine work and eliminate ethyl alcohol residual.
Gained oryzanol actual content of the invention is greater than the industrial products that 98%, color is white, i.e. purity and color reaches
Mark, and the solvent that uses of process of producing product and dissolvent residual meet export standard.
Beneficial effects of the present invention are as follows:
(1) it is white powder according to oryzanol obtained by the present invention, absorbs chromatography (UV) detection, gained through UV-vis spectroscopy
The purity of oryzanol may be up to 99.25%, and impurity content is few, the ultimate yield > 70% of oryzanol；
(2) present invention is without using big solvents of toxicity such as methanol, and eliminates the dissolvent residual in technical process, uses edible second
Alcohol makes product oryzanol meet export requirement in the last process link of formed product；Simple production process, it is easily operated and real
It is existing；It is raw material due to being using the byproduct refining of crude rice bran oil soap stock of oils industry production rice bran oil, so production cost is low, fits
Close industrialized production.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Refining of crude rice bran oil soap stock raw material used in the embodiment of the present invention is purchased from Liaoning, and the content of oryzanol is 13.20%.
The purity of sodium hydroxide used in the embodiment of the present invention is 98%, and the mass concentration of sulfuric acid is 98%, and the mass concentration of hydrochloric acid is
35%.Chemical reagent and raw and auxiliary material used in the embodiment of the present invention are obtained by routine business approach unless otherwise specified
?.
In the embodiment of the present invention, the content of chromatography (UV) detection oryzanol is absorbed using UV-vis spectroscopy.
Embodiment 1
(1) the soap stock raw material 400kg of refining of crude rice bran oil alcohol extracting: is put into 3m3In extractor, steam is opened, controls temperature 45 C
It heats and softens, after softening, the edible ethanol 2000L that volumetric concentration 90% is added simultaneously is uniformly mixed, then with matter concentration 5%
The pH that sodium hydrate aqueous solution adjusts solution system is 10, extracts 20min in 55 DEG C of heating stirrings, was centrifuged while hot with sedimentation
Filter, centrifugation discard, and obtain extracting solution；
(2) it is separated by solid-liquid separation: being 7.2 with the pH that the aqueous hydrochloric acid solution of mass concentration 15% adjusts extracting solution, staticly settle 6h, to heavy
After forming sediment completely, centrifugal filtration is settled, collects precipitating and filtrate respectively, filtrate is used to prepare acid byproduct fatty, and precipitating is used to make
Standby oryzanol, obtains centrifugation 256kg；
(3) depickling degreasing decoloring and washing: 350L isopropanol being added into centrifugation, and 40 DEG C of heating stirrings are simultaneously uniformly mixed,
It filters, removes remaining fatty acid and most of lipid impurities and pigment, obtain depickling degreasing decoloring precipitating 204kg；Again to depickling
450L purified water is added in degreasing decoloring precipitating, stirring at normal temperature is simultaneously uniformly mixed, filter, backward nutsch filter in precipitating point less
Amount is repeatedly added purifying washing and filters, and 300L purified water is added altogether, removes the isopropanol of remaining, must precipitate 197kg；
(4) it refining: No. 6 solvent naphtha 300L being added into depickling degreasing decoloring precipitating, 50 DEG C of heating stirring mixing are equal, it filters,
Remaining lipid impurities and pigment are removed, the purification precipitating 128kg of off-white color is obtained；
(5) it crystallizes: 90% edible ethanol 2600L of volumetric concentration being added into purification precipitating, cooling is led in 75 DEG C of heating stirring dissolutions
Water, which is let cool, obtains white crystalline deposit to room temperature, crystallization；
(6) filtering and washing: after crystal is precipitated completely, filtering, backward nutsch filter in a small amount of repeatedly addition of precipitating point
Purifying washing filters, and 300L purified water is added altogether, removes the edible ethanol of remaining, obtains crystalline deposit 94kg；
(7) dry: crystalline deposit forced air drying is obtained into finished product oryzanol 38.1kg.
Gained oryzanol is fine white powder, absorbs chromatography (UV) detection through UV-vis spectroscopy, the content of oryzanol is
99.25%, ultimate yield 72%.
Embodiment 2
(1) the soap stock raw material 250kg of refining of crude rice bran oil alcohol extracting: is put into 3m3In extractor, steam is opened, controls temperature 50 C
It heats and softens, after softening, the edible ethanol 1500L that volumetric concentration 85% is added simultaneously is uniformly mixed, then with mass concentration 5%
Sodium hydrate aqueous solution to adjust the pH of solution system be 9, extract 30min in 50 DEG C of heating stirrings, be centrifuged while hot with settling
Filter, centrifugation discard, and obtain extracting solution；
(2) it is separated by solid-liquid separation: being 7.4 with the pH that the aqueous sulfuric acid of mass concentration 15% adjusts extracting solution, staticly settle 4h, to heavy
After forming sediment completely, centrifugal filtration is settled, collects precipitating and filtrate respectively, filtrate is used to prepare acid byproduct fatty, and precipitating is used to make
Standby oryzanol, obtains centrifugation 162kg；
(3) depickling degreasing decoloring and washing: 200L isopropanol being added into centrifugation, and 45 DEG C of heating stirrings are simultaneously uniformly mixed,
It filters, removes remaining fatty acid and most of lipid impurities and pigment, obtain depickling degreasing decoloring precipitating 122kg；Again to depickling
260L purified water is added in degreasing decoloring precipitating, stirring at normal temperature is simultaneously uniformly mixed, filter, backward nutsch filter in precipitating point less
Amount is repeatedly added purifying washing and filters, and 200L purified water is added altogether, removes the isopropanol of remaining, must precipitate 115kg；
(4) it refines: petroleum ether 150L being added into depickling degreasing decoloring precipitating, 55 DEG C of heating stirring mixing are equal, filter, removal
Remaining lipid impurities and pigment obtain the purification precipitating 82kg of off-white color；
(5) it crystallizes: 85% edible ethanol 1800L of volumetric concentration being added into purification precipitating, cooling is led in 70 DEG C of heating stirring dissolutions
Water, which is let cool, obtains white crystalline deposit to room temperature, crystallization；
(6) filtering and washing: after crystal is precipitated completely, filtering, backward nutsch filter in a small amount of repeatedly addition of precipitating point
Purifying washing filters, and 250L purified water is added altogether, removes the edible ethanol of remaining, obtains crystalline deposit 65kg；
(7) dry: crystalline deposit micro-wave vacuum is obtained into finished product oryzanol 24.7kg.
Gained oryzanol is fine white powder, absorbs chromatography (UV) detection through UV-vis spectroscopy, the content of oryzanol is
99.10%, ultimate yield 75%.
Claims (8)
1. a kind of method for extracting oryzanol as raw material using refining of crude rice bran oil soap stock, which comprises the following steps:
(1) alcohol extracting: refining of crude rice bran oil soap stock is heated and softened, and edible ethanol is added and is uniformly mixed, adjusting pH, heating extraction,
Filtering, obtains extracting solution；
(2) be separated by solid-liquid separation: adjusting pH, it is to be precipitated completely after, filtrate and precipitating are collected in filtering respectively, and filtrate is used to prepare by-product
Product rice bran oil fatty acid, precipitating are used to prepare oryzanol；
(3) depickling degreasing decoloring and washing: isopropanol being added into precipitating, and heating stirring is simultaneously uniformly mixed, filtering, removal remaining
Fatty acid and most of lipid impurities and pigment, obtain depickling degreasing decoloring precipitating；It is added again into depickling degreasing decoloring precipitating
Purified water is stirred and is uniformly mixed, and is filtered and is washed, and the isopropanol of remaining is removed；
(4) it refining: No. 6 solvent naphthas or petroleum ether being added into depickling degreasing decoloring precipitating, heating stirring mixing is equal, filtering,
Remaining lipid impurities and pigment are removed, the purification precipitating of off-white color is obtained；
(5) it crystallizes: edible ethanol being added into purification precipitating, heating stirring dissolution is let cool to room temperature, crystallization, obtains white sink
It forms sediment；
(6) filtering and washing: after crystal is precipitated completely, filtering, and with water washing precipitating is purified, obtain crystalline deposit；
(7) dry: by crystalline deposit it is dry finished product oryzanol.
2. the method according to claim 1 for extracting oryzanol as raw material using refining of crude rice bran oil soap stock, which is characterized in that step
Suddenly in (1), the temperature that the refining of crude rice bran oil soap stock heats and softens is 35~65 DEG C, and the volumetric concentration of the edible ethanol is
80%~95%, the dosage of edible ethanol is 3~6 times of soap stock weight, and adjusting substance used in pH is sodium hydrate aqueous solution, accordingly
Mass concentration is 2~10%, and adjusting pH is 8~11, and extracting heating temperature is 50~65 DEG C, and extraction time is 10~40min, mistake
Filter mode is sedimentation centrifugation or disk centrifugal or tubular type centrifugation.
3. the method according to claim 1 or 2 for extracting oryzanol as raw material using refining of crude rice bran oil soap stock, feature exist
In in step (2), substance used in the adjusting pH is hydrochloric acid or aqueous sulfuric acid, and corresponding matter concentration is 5~20%, adjusts pH and is
6.5~7.5, precipitating the complete time is 2~12h, and filter type is to filter or settle centrifugation or tubular type centrifugation or disk centrifugal.
4. the method according to claim 1 or 2 for extracting oryzanol as raw material using refining of crude rice bran oil soap stock, feature exist
In in step (3), the depickling degreasing decoloring solvent is isopropanol, and additional amount is 1~3 times of Sediment weight, and heating temperature is
40~60 DEG C, filter type is to filter or settle centrifugation or cloth bag centrifugation or tubular type centrifugation or disk centrifugal；Purified water is added
Measuring is 2~6 times of Sediment weight, and it is 1~3 time that number, which is added, and filter type is that suction filtration or cloth bag are centrifuged, and mode of washing is to pumping
Filter precipitating or cloth bag centrifugation are added by several times on a small quantity.
5. the method according to claim 1 or 2 for extracting oryzanol as raw material using refining of crude rice bran oil soap stock, feature exist
In in step (4), the refining solvent is No. 6 solvent naphthas or petroleum ether, and additional amount is 1~3 times of Sediment weight, heating temperature
Degree is 45~60 DEG C, and filter type is to filter or settle centrifugation or cloth bag centrifugation or tubular type centrifugation.
6. the method according to claim 1 or 2 for extracting oryzanol as raw material using refining of crude rice bran oil soap stock, feature exist
In in step (5), the recrystallisation solvent is edible ethanol, and corresponding volumetric concentration is 85%~95%, the additional amount of edible ethanol
For 15~25 times for refining heavy amount, heating temperature is 55~80 DEG C, and the mode that lets cool is to be placed at room temperature for natural cooling or logical cooling
Water is placed or 0~4 DEG C of refrigeration.
7. the method according to claim 1 or 2 for extracting oryzanol as raw material using refining of crude rice bran oil soap stock, feature exist
In in step (6), the filter type is suction filtration or cloth bag centrifugation, and the amount that purified water is added is 2~6 times of Sediment weight, is added
Indegree is 1~3 time, and mode of washing is to be added by several times on a small quantity to suction filtration precipitating or cloth bag centrifugation.
8. the method according to claim 1 or 2 for extracting oryzanol as raw material using refining of crude rice bran oil soap stock, feature exist
In in step (7), the drying mode of the crystalline deposit is forced air drying or vacuum drying, and drying temperature is 55~65 DEG C.
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