CN110294784B - Method for extracting oryzanol by taking rice bran oil refined soapstock as raw material - Google Patents
Method for extracting oryzanol by taking rice bran oil refined soapstock as raw material Download PDFInfo
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- CN110294784B CN110294784B CN201910529378.3A CN201910529378A CN110294784B CN 110294784 B CN110294784 B CN 110294784B CN 201910529378 A CN201910529378 A CN 201910529378A CN 110294784 B CN110294784 B CN 110294784B
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- C07J53/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by condensation with a carbocyclic rings or by formation of an additional ring by means of a direct link between two ring carbon atoms, including carboxyclic rings fused to the cyclopenta(a)hydrophenanthrene skeleton are included in this class
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Abstract
A method for extracting oryzanol by taking rice bran oil refined soapstock as a raw material comprises the following steps: (1) alcohol extraction; (2) solid-liquid separation; (3) deacidifying, degreasing, decoloring and washing; (4) refining; (5) crystallizing; (6) filtering and washing; (7) and (5) drying. The finished product of the oryzanol prepared by the method is white powder which is pure natural oryzanol from rice bran, the purity of the obtained oryzanol can reach 99 percent, the impurity content is low, and the final yield of the oryzanol is more than 70 percent; the method does not use solvents with high toxicity, such as methanol and the like, removes solvent residues in the process, and uses edible ethanol in the final process link of product molding to ensure that the oryzanol product meets the export requirement; the production process is simple and easy to operate and realize; because the byproduct of rice bran oil refining soapstock produced in the oil industry is used as the raw material, the production cost is low, and the method is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of plant extraction and separation, relates to a method for extracting oryzanol, and particularly relates to a method for extracting oryzanol by taking rice bran oil refined soapstock as a raw material.
Background
Oryzanol (Oryzanol) exists in rice bran oil, and is a mixture of ferulic acid ester mainly comprising triterpene (alkene) alcohol. Mainly acts on autonomic nervous system and endocrine center of diencephalon, and can regulate autonomic nervous function, reduce endocrine balance disorder, and improve mental disorder symptoms. Also has various physiological functions of reducing blood fat, reducing liver lipid, preventing lipid oxidation, resisting oxidation, etc. In addition, it has effect in resisting arrhythmia, and can reduce myocardial excitability by regulating autonomic nerve function. The blood lipid lowering effect of oryzanol can also improve myocardial blood supply, and improve sleep.
Name: oryzanol gamma-Oryzanol
The molecular formula is as follows: c40H58O4
Molecular weight: 602.89
CAS number: 11042-64-1
Melting point: 135-137 DEG C
Structural formula (xvi):
solubility: can be dissolved in organic solvent such as methanol, ethanol, acetone, diethyl ether, chloroform and benzene, can be dissolved in vegetable oil and its mixture with petroleum ether, is slightly soluble in alkaline water, is insoluble in water, is soluble in alkaline methanol and ethanol solution, and is insoluble in acidic methanol or ethanol.
At present, manufacturers for producing rice bran oil and oryzanol are mainly grease factories for refining rice bran oil, and the oryzanol sold in the market mainly has three problems: 1. overproof solvent residues and use of illegal solvents: mainly remains organic solvents such as methanol, hexane and the like, so that oryzanol products cannot be exported from Europe, America and Japan, and the export products specified by the green export standard cannot use toxic solvents such as methanol and the like in the production process; 2. the actual content of most oryzanol products does not reach the standard: some commercial products have white color but the content is only about 95 percent, and analysis shows that the products generate some new degradation substances in the production process, and the oryzanol content is reduced although the products are also white, which is related to the production process; 3. the color of some oryzanol products does not meet the standard: the color of the product is off-white or off-white, yellowish white, but the content also reaches 98 percent.
The domestic patent and technical reports about oryzanol are more:
1. the following were classified according to the solvent used:
patent applications with application numbers of CN201710073967.6, CN201510769436.1, CN201310659297.8, CN201310099264.2, CN201010542976.3, CN201010224081.5, CN200810231528.8, and CN02135610.6 all use methanol as an extraction solvent, and are refined in a series to obtain oryzanol, which is easy to remain methanol and does not meet the regulations of export products.
The patent applications with application numbers of CN201510769436.1 and CN201010542976.3, etc. use hexane to refine or crystallize, and then go through some process steps to obtain oryzanol products, which are easy to remain hexane and cause the residual to exceed the standard.
2. The method comprises the following steps:
patent application No. CN201710073967.6 discloses a oryzanol extraction process, which comprises degumming crude rice oil to obtain degummed oil; alkali refining the degummed oil to obtain soapstock; after the soapstock is supplemented and saponified, adding methanol, water and sodium carbonate for alkali dissolution to obtain supernatant liquor; adding hydrochloric acid and citric acid into the supernatant in sequence to adjust the pH value to obtain a crude oryzanol product; cleaning and drying to obtain the refined oryzanol. The method adopts alkaline methanol extraction, and the solvent is toxic; and sodium carbonate is weak alkali, cannot be combined with phenolic hydroxyl in oryzanol molecules in practice, and cannot promote the dissolution of the oryzanol.
Patent application No. CN201510769436.1 discloses a method for producing gamma-oryzanol, wherein filter residue is poured into a dissolving tank; adding methanol, mixing, adding hexane, and stirring; adding acetic acid for neutralization, stirring and refluxing; heating in water bath to 50 deg.C, heating, stirring, and refluxing; adding water, continuously stirring and standing for one hour; separating out the gamma-oryzanol of the crude product; the solution is automatically layered, and the upper layer is hexane solution; the lower layer is a crude product gamma-oryzanol educt and a methanol dissolving layer; the upper and lower methanol-dissolved layers are divided; heating the lower layer in water bath; decompressing and filtering the coarse product gamma-oryzanol precipitate heated in the water bath and a methanol dissolving layer, wherein the upper layer of the filter paper is coarse gamma-oryzanol; adding hexane into the precipitated particles of the crude gamma-oryzanol to wash out impurities which can be dissolved in the hexane; collecting the gamma-oryzanol precipitated particles and drying at low temperature. Under heating condition, oryzanol is easily dissolved in hexane, has high solubility in methanol, and has high toxicity. Since oryzanol is dissolved in both solvents, the separation cannot be achieved by this method.
Application number CN201310659297.8 discloses a method for extracting oryzanol from waste oil of bran meal, which comprises the following steps: 1) adding high temperature resistant enzyme into the waste oil of the bran meal, wherein the addition amount is 0.5-5% of the mass of the waste oil of the bran meal, stirring and digesting for 60-120min at 70-95 ℃, and filtering to obtain oil clear liquid; 2) alkali dissolution: mixing an alkaline methanol solution with the grease clear liquid obtained in the step 1) according to the mass ratio of 1: 5-1: 8, heating to 60 ℃, stirring, standing until two phases are separated, and extracting; 3) acid precipitation: heating the extract liquid in the step 2) to 40-60 ℃, adding acid to adjust the pH value to 3.0-6.0, standing overnight, and performing centrifugal separation to obtain a crude product of oryzanol; 4) refining oryzanol: washing the crude oryzanol obtained in the step 3) with distilled water, and then drying to obtain the refined oryzanol. The chemical nature of the enzyme is protein, most of the enzyme is inactivated at the temperature of more than 70 ℃, and the method scientificity needs to be researched; methanol is a toxic reagent; oryzanol is a water-insoluble substance, wherein impurities come from oil and are also strong lipophilic substances, and the aim of refining cannot be fulfilled by drying after simple distilled water washing, and the refining method needs to be further researched.
Application number CN201310099264.2 discloses a method for extracting oryzanol from crude rice bran oil, which comprises the following steps: (1) preparing four-grade rice bran oil, namely hydrating, degumming and dewaxing rice bran crude oil; ② dewaxing the rice bran oil for decolorization; physical refining of the decolorized rice bran oil; (2) extracting coarse oryzanol, namely preparing a soap base; alkali dissolving operation; ③ carrying out acid precipitation; (3) refining coarse oryzanol, namely, re-dissolving the coarse oryzanol and washing the coarse oryzanol with solvent oil liquid; acid precipitation and acid soaking; and thirdly, drying and crushing the oryzanol. The method uses toxic methanol, and the product has no crystallization step, and the content is further proved.
Application No. CN201010542976.3 discloses a process for extracting oryzanol from rice bran, which comprises adding methanol into crude bran oil, adjusting pH with sodium hydroxide, heating, keeping temperature, stirring, cooling, standing for layering, and discharging lower oil phase; adding citric acid into the methanol solution at the upper layer to adjust the pH value to 7, standing, filtering and taking precipitate to obtain a crude product; recrystallizing with hexane, washing, and drying to obtain refined product. This method uses toxic methanol, and methanol is added directly to the oil, and safety is to be evaluated.
Application No. CN201010224081.5 discloses a method for extracting oryzanol by a nonpolar solvent extraction method, which comprises the steps of selecting rice bran oil alkali refining soapstock, adding methanol and ether alkaline solution, fully stirring, standing for layering, adjusting the pH value by using a hydrochloric acid solution, wherein the upper layer is a neutral substance, the lower layer is an alkaline substance containing the oryzanol, and the oryzanol is crystallized and separated out. Then washing and vacuum drying to obtain the finished product of the oryzanol. The method uses poisonous methanol and ether, and the ether is a controlled reagent; the content of oryzanol precipitated by adjusting the acid is further verified.
Application No. CN200810231528.8 discloses a production method for extracting oryzanol from rice bran oil soapstock, which comprises the steps of heating and dissolving rice bran oil soapstock rich in oryzanol, diluting with methanol, adding alkali for supplementary saponification, then carrying out alkali dissolution filtration to obtain filtrate of saponified solution, carrying out acid dilution filtration on the saponified filtrate, washing with water, carrying out acid leaching, purifying, granulating, and then drying. The method uses toxic methanol, the main process is alkaline alcohol dissolution and acid precipitation, and the content of oryzanol after simple purification needs to be further verified.
Application No. CN200810244052.8 discloses a method for extracting oryzanol, which comprises the steps of taking crude rice bran oil as a raw material, performing pre-deacidification on mixed oil of the rice bran oil and n-hexane by using ethanolamine, enriching the oryzanol into nigre by using NaOH solution, extracting oryzanol sodium salt in the nigre by using methanol, adjusting the pH value by using acid solution to separate out the oryzanol crystals contained in the nigre, and separating to obtain the oryzanol. The method uses toxic methanol, the main process is alkaline alcohol dissolution and acidification, and the obtained product is low-content oryzanol.
Application No. CN02135610.6 discloses a method for extracting oryzanol by a solvent extraction method, which comprises the steps of pretreating rice bran crude oil, physically refining the pretreated rice bran oil to remove free fatty acid in the oil, adding alkaline methanol into the refined rice bran oil to perform continuous countercurrent extraction, adding acid into extracted methanol mother liquor to crystallize and separate out the oryzanol contained in the extracted methanol mother liquor, and separating to obtain the oryzanol. The method uses toxic methanol, and the main process is alkaline alcohol dissolution and acid precipitation, and the obtained product is low-content oryzanol.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a method for extracting the oryzanol by taking rice bran oil refined soapstock as a raw material, wherein the actual content of the prepared oryzanol is more than 98%, the color of the prepared oryzanol is white, the purity and the color of the product are up to the standard, and the solvent residue used in the production process of the product meet the export standard.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for extracting oryzanol by taking rice bran oil refined soapstock as a raw material comprises the following steps:
(1) alcohol extraction: heating refined rice bran oil soapstock for softening, adding edible ethanol, mixing, adjusting pH, heating for extraction, and filtering to obtain extractive solution;
(2) solid-liquid separation: adjusting pH, precipitating completely, filtering, collecting filtrate and precipitate respectively, wherein the filtrate is used for preparing byproduct rice bran oil fatty acid, and the precipitate is used for preparing oryzanol;
(3) deacidifying, degreasing, decoloring and washing: adding isopropanol into the precipitate, heating, stirring, mixing, filtering, removing residual fatty acid, most lipid impurities and pigment to obtain deacidified, degreased and decolored precipitate; adding purified water into the deacidification, degreasing and decoloration precipitate, stirring and uniformly mixing, filtering and washing to remove residual isopropanol;
(4) refining: adding No. 6 solvent oil or petroleum ether into the deacidified, degreased and decolored precipitate, heating, stirring, mixing uniformly, filtering, and removing residual lipid impurities and pigments to obtain a white-like refined precipitate;
(5) and (3) crystallization: adding edible ethanol into the refined precipitate, heating, stirring for dissolving, cooling to room temperature, and crystallizing to obtain white precipitate;
(6) filtering and washing: after the crystal is completely separated out, filtering, and washing the precipitate with purified water to obtain a crystal precipitate;
(7) and (3) drying: drying the crystallized precipitate to obtain the finished product of oryzanol.
Preferably, in the step (1), the temperature for heating and softening the rice bran oil refining soapstock is 35-65 ℃. If the heating temperature is low, the soapstock keeps a solid hardening state and can be softened only by heating for a long time; if the heating temperature is high, the soapstock is alkaline, so that the oryzanol is obviously damaged.
Preferably, in the step (1), the volume concentration of the edible ethanol is 80-95%, and the amount of the edible ethanol is 3-6 times of the weight of the soapstock. The invention discloses that oryzanol can be extracted by edible ethanol and meets the standards of solvent use and residue of an export product. Technically, the oryzanol extracted from the ethanol is light in color, less in impurities and high in purity. If the concentration of the edible ethanol is low, most oryzanol cannot be extracted, and the loss is large; if the concentration of edible ethanol is high, it is difficult to recover the edible ethanol to a high concentration during production. The dosage of the edible ethanol is determined according to the oryzanol content in the rice bran oil refined soapstock raw material, generally, the multiple quantity is increased when the oryzanol content is high, and the multiple quantity is reduced when the oryzanol content is low, and the economic benefit is mainly considered.
Preferably, in the step (1), the substance for adjusting the pH is a sodium hydroxide aqueous solution, the corresponding mass concentration is 2-10%, and the pH is adjusted to 8-11. The sodium hydroxide aqueous solution is the most economical substance for adjusting the alkalinity, the dosage is large when the concentration is low, and the labor safety is affected by a large amount of solution heat generated in the preparation process when the concentration is high. Finally, if the pH value of the extracting solution is adjusted to be too high, the oryzanol can be obviously damaged, so that the yield of the oryzanol is low; too low is not conducive to solubilization of oryzanol, resulting in low yields.
Preferably, in the step (1), the heating and extracting temperature is 50-65 ℃ and the time is 10-40 min. If the heating extraction temperature is high or the heating extraction time is long, the oryzanol is obviously damaged under the alkaline condition; if the temperature for extraction is low or the time is short, the dissolution of oryzanol is not favorable.
Preferably, in the step (1), the filtration mode is sedimentation centrifugation or disc centrifugation or tubular centrifugation. The above three modes can be used for separating the extract containing the oryzanol from the extraction residue on the premise of obtaining clear filtrate.
Preferably, in the step (2), the substance for adjusting the pH is a hydrochloric acid or sulfuric acid aqueous solution, the corresponding mass concentration is 5-20%, and the pH is adjusted to 6.5-7.5. The hydrochloric acid and the sulfuric acid aqueous solution can be used for adjusting the pH value of the alkaline solution to be neutral or acidic in production, have wide application range and do not generate chemical reaction with main products. The dosage is large when the concentration is low, and the preparation process generates a large amount of solution heat and is not beneficial to labor safety when the concentration is high. Finally, if the pH is adjusted to be too low, a large amount of fatty acid is attached to the oryzanol serving as a main product, so that the oryzanol is not purified; if the pH value is too high, the main product is not completely separated out, and the yield is low.
Preferably, in the step (2), the time for complete precipitation is 2-12 h. If the precipitation time is short, the oryzanol is incompletely precipitated, so that the yield is reduced; if the precipitation time is long, the production period is affected, and the production efficiency is reduced.
Preferably, in the step (2), the filtration mode is suction filtration or sedimentation centrifugation or tubular centrifugation or disc centrifugation. The filtration mode is determined according to the product properties, and if the precipitate is well dispersed, suction filtration is selected; or the sediment with oil viscosity is filtered by sedimentation centrifugation, tubular centrifugation or disc centrifugation.
Preferably, in the step (3), the solvent used in the 1 st purification, namely deacidification, degreasing and decoloration, is isopropanol, the adding amount of the isopropanol is 1-3 times of the weight of the precipitate, and the heating temperature is 40-60 ℃. Tests on various organic solvents show that the isopropanol has good deacidification, degreasing and decoloration performances on the acid-regulated precipitate obtained by the method, can remove residual fatty acid, dissolves most of oil components and pigments, and is convenient for the operation of a later refining process. If the addition amount of the isopropanol is too large or the heating temperature is high, the oryzanol is dissolved to a certain extent, so that the yield is reduced, and if the addition amount is too small or the heating temperature is low, the fatty acid, lipid impurities and pigments are removed poorly, most of the substances cannot be removed effectively, so that the aim of purification cannot be achieved.
Preferably, in the step (3), the filtration mode is suction filtration or sedimentation centrifugation or cloth bag centrifugation or tubular centrifugation or disc centrifugation. One of the above filtration modes can be selected according to the process requirements and the product performance characteristics.
Preferably, in the step (3), the amount of the added purified water is 2-6 times of the weight of the precipitate, the adding times are 1-3 times, the filtering mode is suction filtration or cloth bag centrifugation, and the washing mode is adding a small amount of purified water into the suction filtration precipitate or the cloth bag centrifugation precipitate in a fractional manner. The purpose of adding purified water is to completely dissolve residual isopropanol by water by utilizing the principle that isopropanol and water are mutually soluble so as to remove the residual isopropanol. The best filtration mode for removing the isopropanol residue by matching the process is suction filtration or cloth bag centrifugation.
Preferably, in the step (4), the solvent used for the 2 nd purification, i.e. refining, is No. 6 solvent oil or petroleum ether, the addition amount is 1-3 times of the weight of the precipitate, and the heating temperature is 45-60 ℃. Tests on various organic solvents show that the No. 6 solvent oil or petroleum ether has good further degreasing and decoloring performance on the deacidification degreasing sediment obtained by the invention, can remove residual oil components and pigments, and is convenient for the later crystallization process operation. If the addition amount of No. 6 solvent oil or petroleum ether is too large, the production cost is increased, and if the addition amount is too small, the refining effect is poor. When the heating temperature is high, oryzanol is dissolved to a certain degree to cause yield reduction, and when the heating temperature is low, residual lipid impurities and pigments cannot be well dissolved out as completely as possible, so that the aim of refining cannot be achieved.
Preferably, in the step (4), the filtration mode is suction filtration or sedimentation centrifugation or cloth bag centrifugation or tubular centrifugation, and one of the filtration modes can be selected according to the process requirements and the product performance characteristics.
Preferably, in the step (5), the solvent used for the 3 rd purification, i.e. crystallization, is edible ethanol, the corresponding volume concentration is 85-95%, the adding amount of the edible ethanol is 15-25 times of the refined weight, and the heating temperature is 55-80 ℃. Experiments show that oryzanol can be dissolved in high-alcohol solution by controlling the amount of ethanol which is enough and heating to a certain degree, and can be basically and completely separated out after cooling, high-alcohol is selected as a crystallization solvent, and a heating mode is adopted. Meanwhile, a large amount of hot ethanol can completely dissolve the residual No. 6 solvent oil or petroleum ether in the previous refining stage, and after the crystallization is completed, the solvent residues can be removed by filtration.
Preferably, in the step (5), the cooling mode is natural cooling at room temperature or cooling water introduction or refrigeration at 0-4 ℃. The precipitation speed is slow by natural cooling and precipitation is slightly fast by refrigeration, thus being suitable for conditional factories.
Preferably, in the step (6), the filtration mode is suction filtration or cloth bag centrifugation, the amount of the added purified water is 2-6 times of the weight of the precipitate, the adding time is 1-3 times, and the washing mode is that the purified water is added to the suction filtration precipitate or the cloth bag centrifugation precipitate in small amount in several times. The purpose of adding purified water is to completely dissolve residual edible ethanol by water by utilizing the principle that the edible ethanol and water are mutually soluble so as to remove ethanol residues. The best filtration mode for removing the ethanol residue by matching the process is suction filtration or cloth bag centrifugation.
Preferably, in the step (7), the drying manner of the crystalline precipitate is forced air drying or vacuum drying (which may be microwave vacuum drying), and the drying temperature is 55-65 ℃. The oryzanol crystal has stable physical and chemical properties in general, and one or a combination of the drying methods can be selected.
The principle of the invention is as follows:
the invention takes rice bran oil refined soapstock as a raw material to extract oryzanol. The raw material soapstock mainly contains oryzanol, fatty acid, lipophilic impurities and fat-soluble pigment, and the invention also separates fatty acid by-products by other processes while extracting the oryzanol, thereby reducing the production cost and realizing the comprehensive utilization of the raw materials.
The main lines of the invention are three: one is the oryzanol content, the other is the product color, and the other is the solvent residue. By utilizing the property that the oryzanol as a main product, the fatty acid as a byproduct and most of impurities can be dissolved in hot alkaline ethanol, the main and auxiliary products are extracted by utilizing high-degree ethanol through adjusting proper pH. The main product oryzanol is difficult to dissolve in the acidic ethanol, the by-product fatty acid is easy to dissolve in the acidic ethanol, the oryzanol can be precipitated and the fatty acid can be kept in the acidic ethanol solution by adjusting the proper pH value, and then the separation of the main product and the auxiliary product can be realized by a proper filtration mode. The acid regulating precipitate mainly containing oryzanol still contains a small amount of fatty acid, most of lipophilic impurities and fat-soluble pigments, and the impurities and pigments can be mostly dissolved by isopropanol, residual fatty acid, most of lipophilic impurities and fat-soluble pigments can be removed by using the isopropanol and adopting a proper heating mode, the oryzanol is retained, and the isopropanol is removed by washing with purified water by a proper filtering mode and a principle that the isopropanol and water are mutually dissolved. The lipophilic impurities and fat-soluble pigments remaining from the purification with isopropanol are easily dissolved in the lipophilic solvent such as No. 6 solvent oil or petroleum ether, and the remaining lipophilic impurities and fat-soluble pigments are removed by the solvent, thereby further purifying oryzanol. By utilizing the property that the solubility of the oryzanol in cold and hot ethanol is greatly different and the property that a small amount of No. 6 solvent oil or petroleum ether remained in crystals can be dissolved by a large amount of high ethanol, a proper filtration mode is adopted, so that the lipophilic solvent residue is removed while the high-purity and white-color oryzanol refined product is obtained. And finally, by utilizing the mutual solubility principle of ethanol and water and adopting a proper filtering mode, a refined oryzanol product is obtained and ethanol residues are removed.
The actual content of the oryzanol obtained by the method is more than 98%, the product is a white industrial product, namely, the purity and the color of the product reach the standard, and the solvent residue used in the production process of the product meet the export standard.
The invention has the following beneficial effects:
(1) the oryzanol prepared by the method is white powder, and the purity of the obtained oryzanol can reach 99.25 percent through ultraviolet-visible light absorption chromatography (UV) detection, the impurity content is low, and the final yield of the oryzanol is more than 70 percent;
(2) the method does not use solvents with high toxicity, such as methanol and the like, removes solvent residues in the process, and uses edible ethanol in the final process link of product molding to ensure that the oryzanol product meets the export requirement; the production process is simple and easy to operate and realize; because the byproduct of rice bran oil refining soapstock produced in the oil industry is used as the raw material, the production cost is low, and the method is suitable for industrial production.
Detailed Description
The present invention will be further described with reference to the following examples.
The rice bran oil refined soapstock used in the embodiment of the invention is purchased from Liaoning, and the content of oryzanol is 13.20%. The purity of the sodium hydroxide used in the embodiment of the invention is 98%, the mass concentration of the sulfuric acid is 98%, and the mass concentration of the hydrochloric acid is 35%. The chemical reagents and raw and auxiliary materials used in the examples of the present invention are commercially available in a conventional manner unless otherwise specified.
In the embodiment of the invention, the content of the oryzanol is detected by adopting ultraviolet-visible light absorption chromatography (UV).
Example 1
(1) Alcohol extraction: adding 400kg of soapstock raw material refined from rice bran oil into 3m3In the extraction tank, steam is started, the temperature is controlled to be 45 ℃, heating softening is carried out, 2000L of edible ethanol with the volume concentration of 90 percent is added after softening, stirring and mixing are carried out evenly, and the mass concentration is 5 percentAdjusting pH of the solution system to 10 with sodium hydroxide aqueous solution, heating and stirring at 55 deg.C for 20min, centrifuging and filtering while hot, centrifuging and removing precipitate to obtain extractive solution;
(2) solid-liquid separation: regulating the pH of the extracting solution to 7.2 by using a hydrochloric acid aqueous solution with the mass concentration of 15%, standing and precipitating for 6h, precipitating and centrifugally filtering after complete precipitation, respectively collecting precipitate and filtrate, wherein the filtrate is used for preparing a byproduct fatty acid, and the precipitate is used for preparing oryzanol to obtain 256kg of centrifugal precipitate;
(3) deacidifying, degreasing, decoloring and washing: adding 350L of isopropanol into the centrifugal precipitate, heating and stirring at 40 ℃, uniformly mixing, performing suction filtration, and removing residual fatty acid, most lipid impurities and pigments to obtain 204kg of deacidification, degreasing and decoloration precipitate; adding 450L of purified water into the deacidification, degreasing and decoloration precipitate, stirring at normal temperature, uniformly mixing, performing suction filtration, adding the purified water into the precipitate in a suction filter for multiple times in small amount, washing and performing suction filtration, adding 300L of purified water in total, and removing residual isopropanol to obtain 197kg of precipitate;
(4) refining: adding 300L No. 6 solvent oil into the deacidification, degreasing and decoloration precipitate, heating at 50 ℃, stirring, mixing uniformly, filtering, removing residual lipid impurities and pigments to obtain 128kg of white-like refined precipitate;
(5) and (3) crystallization: adding 2600L of 90% edible ethanol into the refined precipitate, heating and stirring at 75 deg.C for dissolving, cooling to room temperature with cooling water, and crystallizing to obtain white crystal precipitate;
(6) filtering and washing: after the crystals are completely separated out, carrying out suction filtration, then adding purified water into the precipitate in the suction filter for multiple times in small amount, washing and carrying out suction filtration, adding 300L of purified water in total, and removing the residual edible ethanol to obtain 94kg of crystallized precipitate;
(7) and (3) drying: and blowing and drying the crystallized precipitate to obtain 38.1kg of finished product oryzanol.
The obtained oryzanol is pure white powder, and the content of the oryzanol is 99.25% and the final yield is 72% by ultraviolet-visible light absorption chromatography (UV) detection.
Example 2
(1) Alcohol extraction: adding 250kg of soapstock raw material refined from rice bran oil into 3m3In an extraction tank, starting steam, controlling the temperature to be 50 ℃, heating for softening, adding 1500L of edible ethanol with the volume concentration of 85% after softening, stirring and mixing uniformly, adjusting the pH of a solution system to be 9 by using a sodium hydroxide aqueous solution with the mass concentration of 5%, heating, stirring and extracting at 50 ℃ for 30min, settling, centrifuging and filtering while hot, and removing centrifugal precipitate to obtain an extracting solution;
(2) solid-liquid separation: adjusting the pH of the extracting solution to 7.4 by using a sulfuric acid aqueous solution with the mass concentration of 15%, standing and precipitating for 4h, precipitating and centrifugally filtering after complete precipitation, respectively collecting precipitate and filtrate, preparing a byproduct fatty acid from the filtrate, and preparing oryzanol from the precipitate to obtain 162kg of centrifugal precipitate;
(3) deacidifying, degreasing, decoloring and washing: adding 200L of isopropanol into the centrifugal precipitate, heating and stirring at 45 ℃, uniformly mixing, performing suction filtration, and removing residual fatty acid, most lipid impurities and pigments to obtain 122kg of deacidified, degreased and decolored precipitate; adding 260L of purified water into the deacidification, degreasing and decoloration precipitate, stirring at normal temperature, uniformly mixing, performing suction filtration, adding the purified water into the precipitate in a suction filter for multiple times in small amount, washing and performing suction filtration, adding 200L of purified water in total, and removing residual isopropanol to obtain 115kg of precipitate;
(4) refining: adding 150L of petroleum ether into the deacidification, degreasing and decoloration precipitate, heating and stirring at 55 ℃, uniformly mixing, performing suction filtration, and removing residual lipid impurities and pigments to obtain 82kg of white-like refined precipitate;
(5) and (3) crystallization: adding 1800L of edible ethanol with the volume concentration of 85% into the refined precipitate, heating and stirring at 70 ℃, dissolving, introducing cooling water, cooling to room temperature, and crystallizing to obtain white crystal precipitate;
(6) filtering and washing: after the crystals are completely separated out, carrying out suction filtration, then adding a small amount of purified water into the precipitate in the suction filter for washing and suction filtration, adding 250L of purified water in total, and removing the residual edible ethanol to obtain 65kg of crystal precipitate;
(7) and (3) drying: and (5) performing microwave vacuum drying on the crystallized precipitate to obtain 24.7kg of finished product oryzanol.
The obtained oryzanol is pure white powder, and the content of the oryzanol is 99.10% and the final yield is 75% by ultraviolet-visible light absorption chromatography (UV) detection.
Claims (7)
1. A method for extracting oryzanol by taking rice bran oil refined soapstock as a raw material is characterized by comprising the following steps:
(1) alcohol extraction: heating refined rice bran oil soapstock for softening, adding edible ethanol, mixing, adjusting pH, heating for extraction, and filtering to obtain extractive solution;
(2) solid-liquid separation: adjusting pH, precipitating completely, filtering, collecting filtrate and precipitate respectively, wherein the filtrate is used for preparing byproduct rice bran oil fatty acid, and the precipitate is used for preparing oryzanol;
(3) deacidifying, degreasing, decoloring and washing: adding isopropanol into the precipitate, heating, stirring, mixing, filtering, removing residual fatty acid, most lipid impurities and pigment to obtain deacidified, degreased and decolored precipitate; adding purified water into the deacidification, degreasing and decoloration precipitate, stirring and uniformly mixing, filtering and washing to remove residual isopropanol;
(4) refining: adding No. 6 solvent oil or petroleum ether into the deacidified, degreased and decolored precipitate, heating, stirring, mixing uniformly, filtering, and removing residual lipid impurities and pigments to obtain a white-like refined precipitate;
(5) and (3) crystallization: adding edible ethanol into the refined precipitate, heating, stirring for dissolving, cooling to room temperature, and crystallizing to obtain white precipitate;
(6) filtering and washing: after the crystal is completely separated out, filtering, and washing the precipitate with purified water to obtain a crystal precipitate;
(7) and (3) drying: drying the crystallized precipitate to obtain oryzanol product;
in the step (1), the volume concentration of the edible ethanol is 80-95%, the consumption of the edible ethanol is 3-6 times of the weight of the soapstock, the substance for adjusting the pH is a sodium hydroxide aqueous solution, the corresponding mass concentration is 2-10%, the pH is adjusted to 8-11, the extraction heating temperature is 50-65 ℃, and the extraction time is 10-40 min;
in the step (2), the substance for adjusting the pH is a hydrochloric acid or sulfuric acid aqueous solution, the concentration of the corresponding substance is 5-20%, and the pH is adjusted to 6.5-7.5;
in the step (3), the deacidification, degreasing and decoloration solvent is isopropanol, the addition amount of the isopropanol is 1-3 times of the weight of the precipitate, the heating temperature is 40-60 ℃, and the filtration mode is suction filtration or sedimentation centrifugation or cloth bag centrifugation or tubular centrifugation or disc centrifugation;
in the step (4), the refined solvent is No. 6 solvent oil or petroleum ether, the addition amount is 1-3 times of the weight of the precipitate, the heating temperature is 45-60 ℃, and the filtering mode is suction filtration or sedimentation centrifugation or cloth bag centrifugation or tubular centrifugation;
in the step (5), the crystallization solvent is edible ethanol, the corresponding volume concentration is 85-95%, the adding amount of the edible ethanol is 15-25 times of the weight of the refined precipitate, and the heating temperature is 55-80 ℃.
2. The method for extracting oryzanol from rice bran oil refining soapstock as the raw material as claimed in claim 1, wherein in the step (1), the temperature for heating and softening the rice bran oil refining soapstock is 35-65 ℃, and the filtration mode is sedimentation centrifugation, disc centrifugation or tubular centrifugation.
3. The method for extracting oryzanol from rice bran oil refining soapstock as a raw material according to claim 1 or 2, wherein in the step (2), the time for complete precipitation is 2-12 h, and the filtering mode is suction filtration or sedimentation centrifugation or tubular centrifugation or disc centrifugation.
4. The method for extracting oryzanol from rice bran oil refined soapstock as a raw material as claimed in claim 1 or 2, wherein in the step (3), the amount of the added purified water is 2-6 times of the weight of the precipitate, the adding times are 1-3 times, the filtering mode is suction filtration or cloth bag centrifugation, and the washing mode is adding a small amount of purified water into the suction filtration precipitate or the cloth bag centrifugation precipitate.
5. The method for extracting oryzanol from rice bran oil refined soapstock as the raw material as claimed in claim 1 or 2, wherein the cooling manner in step (5) is natural cooling at room temperature, or cooling with cooling water or refrigeration at 0-4 ℃.
6. The method for extracting oryzanol from rice bran oil refined soapstock as the raw material as claimed in claim 1 or 2, wherein in the step (6), the filtration mode is suction filtration or cloth bag centrifugation, the amount of the added purified water is 2-6 times of the weight of the precipitate, the adding time is 1-3 times, and the washing mode is adding a small amount of purified water into the suction filtration precipitate or cloth bag centrifugation precipitate in several times.
7. The method for extracting oryzanol from rice bran oil refining soapstock as a raw material as claimed in claim 1 or 2, wherein in the step (7), the drying manner of the crystallized precipitate is air drying or vacuum drying, and the drying temperature is 55-65 ℃.
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| CN111004302B (en) * | 2019-12-06 | 2021-03-19 | 湖南华诚生物资源股份有限公司 | A method for preparing 5 ferulic acid esters with soapstock containing oryzanol as raw material |
| CN111072449B (en) * | 2019-12-25 | 2021-09-14 | 湖南华诚生物资源股份有限公司 | A method for preparing natural ferulic acid from nigre containing oryzanol |
| CN111620922B (en) * | 2020-05-29 | 2021-10-26 | 宜春大海龟生命科学有限公司 | Method for extracting and purifying oryzanol from rice bran acidification oil |
| TWI715503B (en) * | 2020-06-04 | 2021-01-01 | 台灣中油股份有限公司 | Method for preparing oryzanol |
| CN112552368A (en) * | 2020-12-11 | 2021-03-26 | 桂林莱茵生物科技股份有限公司 | Method for refining oryzanol by using mixed solvent |
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