WO2021098680A1 - 一种以含谷维素的皂脚为原料制备谷维素的方法 - Google Patents

一种以含谷维素的皂脚为原料制备谷维素的方法 Download PDF

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WO2021098680A1
WO2021098680A1 PCT/CN2020/129370 CN2020129370W WO2021098680A1 WO 2021098680 A1 WO2021098680 A1 WO 2021098680A1 CN 2020129370 W CN2020129370 W CN 2020129370W WO 2021098680 A1 WO2021098680 A1 WO 2021098680A1
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oryzanol
ethanol
temperature
membrane
washing
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PCT/CN2020/129370
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English (en)
French (fr)
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黄华学
刘庚贵
何安乐
曾润清
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湖南华诚生物资源股份有限公司
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Priority to US17/310,122 priority Critical patent/US20220041646A1/en
Priority to JP2021544705A priority patent/JP7093595B2/ja
Priority to EP20878033.8A priority patent/EP3858848B1/en
Publication of WO2021098680A1 publication Critical patent/WO2021098680A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • 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
    • C07J53/002—Carbocyclic rings fused
    • C07J53/004—3 membered carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes

Definitions

  • the invention belongs to the technical field of plant extraction and separation, and relates to a method for preparing oryzanol, in particular to a method for preparing oryzanol by using soap stock containing oryzanol as a raw material.
  • Oryzanol exists in rice bran oil and is a mixture of ferulic acid esters with triterpene alcohol as the main body. It mainly acts on the autonomic nervous system and endocrine center of the diencephalon, can adjust the autonomic nerve function, reduce endocrine balance disorders, and improve the symptoms of mental nerve disorders. It also has a variety of physiological functions such as lowering blood lipids, lowering liver lipids, preventing lipid oxidation, and anti-oxidation. In addition, some people have recently used oryzanol as a raw material for skin care products and food antioxidants. Generally, soapstocks such as rice bran oil rich in oryzanol are used as raw materials to extract oryzanol, but the general product purity and yield are not satisfactory.
  • CN201710073967, CN201510769436, CN201310659297, CN201310099264, CN201010542976, CN201010224081, CN200810231528, CN02135610 and other patents all use methanol as the extraction solvent, and then undergo a series of refining to obtain oryzanol, which easily retains methanol and does not meet the export product regulations.
  • CN201510769436, CN201010542976 and other patents use hexane to refine or crystallize, and then go through some process steps to obtain oryzanol products, which are likely to remain hexane, resulting in excessive residues.
  • the patent application with application number CN201710073967.6 discloses an oryzanol extraction process.
  • the crude rice oil is first degummed to obtain degummed oil; the degummed oil is alkali-refined to obtain soapstock; after soapstock is supplemented and saponified, methanol and water are added.
  • Alkali dissolve with sodium carbonate to obtain the supernatant; add hydrochloric acid and citric acid to adjust the pH of the supernatant to obtain crude oryzanol; wash and dry to obtain refined oryzanol.
  • This method uses alkaline methanol extraction, the solvent is toxic, and the product has residues; and sodium carbonate is a weak base, which cannot be combined with the phenolic hydroxyl group in the oryzanol molecule in practice, and cannot promote the dissolution of oryzanol.
  • the patent application with the application number CN201510769436.1 discloses a production method of ⁇ -oryzanol.
  • the filter residue is poured into a dissolving tank; methanol is added and mixed and then stirred with hexane; acetic acid is added for neutralization and stirred and refluxed; the water bath is heated to 50°C and added Warm stirring and reflux; add water and continue to stir and let stand for one hour; the crude product ⁇ -oryzanol is precipitated; the solution is automatically layered, the upper layer is hexane solution; the lower layer is the crude product ⁇ -oryzanol precipitate and methanol dissolving layer; the upper and lower layers are dissolved in methanol Layer splitting; the lower layer is heated in a water bath; the crude ⁇ -oryzanol precipitates heated in the water bath and the methanol dissolved layer are filtered under reduced pressure, the upper layer of the filter paper is crude ⁇ -oryzanol; hexane is added to the
  • oryzanol Under heating conditions, oryzanol is easily soluble in hexane, and has greater solubility in methanol. Methanol is more toxic and easily remains in the product; since oryzanol is dissolved in the two-phase solvent, the method cannot achieve the purpose of separation. Further research is needed; hexane is extremely flammable and explosive, and production safety needs to be further improved.
  • the application number is CN201310659297.8 discloses a method for extracting oryzanol from the waste oil of bran meal, including the following steps: 1) Add heat-resistant enzyme to the waste oil of bran meal, and the addition amount is 0.5-5 of the mass of the waste oil of bran meal %, stirred and digested at 70-95°C for 60-120min, filtered to obtain the grease clear liquid; 2) Alkali dissolution: mix the alkaline methanol solution with the step 1) grease clear liquid in a mass ratio of 1:5 to 1:8 , Heat to 60°C, stir, leave it to stand until the two phases are separated, and extract; 3) Acid precipitation: heat the extract of step 2) to 40-60°C, add acid to adjust the pH to 3.0-6.0, and let it stand overnight.
  • the application number is CN201310099264.2 discloses a method for extracting oryzanol from rice bran crude oil.
  • the steps are as follows: (1) preparing four-level rice bran oil 1 hydration degumming and dewaxing of rice bran crude oil; 2 dewaxing rice bran oil; 3 decolorizing rice bran Oil physical refining; (2) Extraction of crude oryzanol 1Preparation of soap base; 2Alkali dissolving operation; 3Acid precipitation operation; (3) Refining crude oryzanol 1Redissolving crude oryzanol and solvent oil-liquid washing; 2Acid precipitation and acid Soaking; 3 Oryzanol drying and crushing.
  • Toxic methanol is used in this method, and there is residue in the product; the product has no crystallization step, and the content needs to be further confirmed; mineral spirits are extremely flammable and explosive, and the production safety needs to be further improved.
  • the application number is CN201010542976.3 discloses a process for extracting oryzanol from rice bran.
  • the crude bran oil is added with methanol, the pH is adjusted with sodium hydroxide, heated and kept agitated, cooled and left to stand for stratification, and the lower oil phase is released; the upper methanol liquid Add citric acid to adjust the pH to 7, stand still and filter the precipitate to obtain a crude product; recrystallize with hexane, wash and dry to obtain a refined product.
  • This method uses toxic methanol with residues in the product; hexane is extremely flammable and explosive, and production safety needs to be further improved.
  • the application number is CN201010224081.5 discloses a method for extracting oryzanol by non-polar solvent extraction.
  • the rice bran oil base is used to refine the soapstock, the methanol ether alkaline solution is added, and the mixture is fully stirred and then left to stand for layering.
  • the upper layer is a neutral substance.
  • the lower layer is the alkaline substance containing oryzanol, and the pH value is adjusted with hydrochloric acid solution, at this time the oryzanol crystallizes. Then, the finished product of oryzanol is obtained by washing and vacuum drying.
  • This method uses toxic methanol and ether, and there will be methanol residues in the product; ether is a controlled reagent, extremely flammable and explosive, and production safety needs to be further improved; whether the content of oryzanol precipitated by acid adjustment meets the standard needs to be further confirmed.
  • Application number CN200810231528.8 discloses a production method for extracting oryzanol from rice bran oil soapstock. After heating and melting the rice bran oil soapstock rich in oryzanol, it is diluted with methanol, and alkali is added to supplement the saponification. Alkali-soluble filtration is used to obtain the filtrate of the saponification liquid, and the saponification filtrate is filtered again, washed with water, and then subjected to acid leaching, purification, granulation, and then drying.
  • This method uses toxic methanol, and the product has residues; the main process is alkaline alcohol dissolution and acid precipitation. After simple purification, whether the content of oryzanol meets the standard needs to be further confirmed.
  • the application number CN200810244052.8 discloses an extraction method of oryzanol.
  • Using rice bran crude oil as raw material firstly ethanolamine is used to pre-deacidify the mixed oil of rice bran oil and n-hexane, and then the oryzanol is enriched into soapstock with NaOH solution. , And then extract the sodium salt of oryzanol in the soapstock with methanol, and finally adjust the pH value with an acid solution to crystallize the oryzanol contained therein, and obtain the oryzanol after separation.
  • This method uses toxic methanol, and the product has residues; the main process is alkali alcohol dissolution and acid precipitation, and the product obtained is low-content oryzanol.
  • Application number CN02135610.6 discloses a method for extracting oryzanol by solvent extraction method.
  • the refined bran oil Alkaline methanol is added for continuous countercurrent extraction, acid is added to the extracted methanol mother liquor to crystallize the oryzanol contained therein, and the oryzanol is obtained after separation.
  • This method uses toxic methanol, and the product has residues; the main process is alkaline alcohol dissolution and acid precipitation, and the product obtained is low-content oryzanol.
  • the technical problem to be solved by the present invention is to overcome the above-mentioned shortcomings in the prior art and provide a preparation method of oryzanol.
  • the solvents and solvent residues used in the production process meet the export standards; the production safety is improved, and the toxic substances such as methanol are not used.
  • Solvents, as well as extremely flammable and explosive organic solvents such as ether, hexane, mineral spirits, etc.; establish a production process suitable for industrialization to produce high-quality oryzanol industrial products on a large scale; the actual content of oryzanol in the product is greater than 98%, and the yield is More than 73%, industrial products with white color, excellent purity and color performance; reduce production costs, and improve the economic and social benefits of the enterprise.
  • a method for preparing oryzanol using soapstock containing oryzanol as a raw material includes the following steps:
  • Alkaline alcohol hot melt add ethanol to the raw materials, heat to 50-60°C, adjust the system to weakly alkaline, dissolve the raw materials, and obtain a solution;
  • step 2) heat preservation and fine filtration: maintain the temperature in step 1), and use a precision filter to filter the dissolving liquid;
  • insulation ultrafiltration membrane separation under the condition of 50-60 °C, the filtrate is separated by high temperature ultrafiltration membrane, and the membrane separation liquid of 1000-5000 molecular weight section is collected;
  • Heat preservation and decolorization Add an inorganic decolorizer to the membrane separation solution, stir well, and filter to obtain a decolorization solution.
  • Acidification, neutralization and filtration neutralize the decolorizing liquid with dilute acid, cool it, and place it to make the precipitate completely separate out, centrifuge, and collect the centrifuged precipitate;
  • Washing Wash the centrifugal precipitation with ethyl acetate, high-concentration ethanol, and warm water in sequence. The washing is to add the washing solution of the above solvent or solution to the centrifugal precipitation, stir and mix thoroughly, and centrifuge to obtain the centrifugal precipitation. The next step of washing;
  • the temperature of the system is maintained at 50-60°C. Controlling the temperature within the above range and coordinating the process conditions and parameters of other steps can maximize the efficiency of extracting oryzanol, and ensure the purity of oryzanol in the product, which meets the requirements of industrial production for preparing high-quality oryzanol-containing products.
  • the ethanol refers to ethanol with a concentration greater than 80%, preferably ethanol with a concentration greater than 85%, more preferably, ethanol with a concentration greater than 85% is used; the amount of ethanol added is the weight of the grain soap base.
  • the heating refers to the heating temperature to 50-60°C; the adjustment to be weakly alkaline refers to the use of alkaline hydroxide, such as sodium hydroxide, and a hydroxide to adjust the pH to 8.5-9.5.
  • the method of adjusting pH with methanol was used to extract oryzanol.
  • the inventors found that using high-concentration edible ethanol and controlling the temperature at 50-60°C throughout the process can also extract oryzanol, and it meets the solvent usage and residue standards of export products.
  • the oryzanol extracted from ethanol is light in color, less impurity, and high in purity. If the concentration of edible ethanol is low, most of the oryzanol cannot be extracted and the loss is large; if the concentration of edible ethanol is high, it is difficult to recover high-concentration edible ethanol during production; the heating temperature is 50-60°C.
  • the heating temperature is high or the dissolution time is long, it will have a significant damaging effect on oryzanol under alkaline conditions and cause a serious decrease in the product yield; if the heating temperature is low or the dissolution time is short, it will not be conducive to the dissolution of oryzanol, and the insoluble matter will increase.
  • the filtration temperature is controlled at 50°C-60°C; the filtration adopts a precision filter with a folded filter element, wherein the filter element has a pore size of 0.45 ⁇ m and an operating pressure of 0.2-0.4 MPa.
  • the temperature is higher than 60°C, it will have a significant damaging effect on oryzanol under alkaline conditions and cause a serious decrease in the product yield; if the temperature is lower than 50°C, the dissolution of oryzanol will decrease and the insoluble matter will increase, which will reduce the product yield. At the same time, it also leads to a significant drop in the filtration speed of fine filtration, resulting in low production efficiency and easy clogging of the filter element.
  • the inventors have shown through many experiments that the selection of the above-mentioned pleated filter element has a good filtering effect on the highly ethanolic solution containing oryzanol, and the obtained filtrate is a clear and transparent solution; under the same conditions, filter materials such as microporous membranes are easily clogged. Cannot operate normally.
  • Choosing the proper pore size of the filter element is to match the clarity requirements of the ultrafiltration membrane separation. If the pore size is too large, more impurities will pass through, which will affect the service life of the ultrafiltration membrane; a small pore size will slow down the filtration rate and affect production. effectiveness.
  • the operating pressure of the precision filter is affected by the filter element. When the accumulation of impurities on the surface of the filter element increases, the corresponding operating pressure increases. When the pressure increases to a certain level, the filter element needs to be cleaned in time to ensure the filtering effect and speed.
  • ultrafiltration is performed at 50-60°C
  • the high-temperature-resistant ultrafiltration membrane used is made of polyethersulfone, such as the Duratherm series of GE (specific ions include NF 8040HF, NF RO8040, RO 8040HR, NF 8040HR, NF 3840HR, FLD-UF). It can withstand a temperature of 70°C.
  • Step 2) The heat preservation temperature of the filtrate is 50°C-60°C, and the heat preservation temperature of the ultrafiltration membrane separation operation is also the same temperature.
  • the ordinary ultrafiltration membrane can only withstand temperatures within 45°C. Therefore, the present invention has passed a lot of investigations and used high temperature resistant ultrafiltration membranes.
  • the filter membrane can withstand a temperature of 70°C, thus adapting to the separation conditions of the insulation membrane of the oryzanol solution.
  • Set the temperature of ultrafiltration at 50-60°C. If the temperature is higher than 60°C, it will have a significant damaging effect on oryzanol under alkaline conditions and cause a serious decrease in product yield; if the temperature is lower than 50°C, the oryzanol will be The reduction in the amount of dissolution and the increase in insoluble matter reduce the yield of the product, but also cause the operation speed of the ultrafiltration membrane to drop significantly, resulting in low production efficiency and easy clogging of the ultrafiltration membrane.
  • the molecular weight cut-off of the membrane is set to 1000-5000, and the membrane operating pressure is 1.0-2.0 MPa.
  • the membrane operating pressure is 1.0-2.0 MPa.
  • the order of membrane separation is to first pass an ultrafiltration membrane with a molecular weight of 5000, collect the downstream liquid of the membrane, that is, the permeate, and then pass the permeate through an ultrafiltration membrane with a molecular weight of 1000. Collect the upstream liquid of the membrane, that is, the retentate. Performing ultrafiltration in the above order can further improve the separation and purification effect.
  • the temperature is still maintained at 50-60°C during decolorization.
  • the temperature is higher than 60°C, it will have a significant damaging effect on oryzanol under alkaline conditions and cause a serious decrease in product yield; if the temperature is lower than 50°C , The dissolution of oryzanol is reduced, and the amount adsorbed by the inorganic decolorizing agent is increased. While reducing the product yield, it also causes difficulty in plate and frame filtration.
  • the decolorizing agent is at least one of activated clay and activated carbon, and the addition amount of the decolorizing agent is 3-6% by weight of the raw material of soap stock containing oryzanol; more preferably, the decolorizing agent It is a compound of activated clay and activated carbon according to the mass ratio of 1-2:1-2.
  • the present invention proves through experiments that activated clay has good degreasing and decolorization effects on fat-soluble components with grease, and can aid filtration; activated carbon also has good decolorization effects in polar solutions and can aid filtration. The two have a synergistic effect to remove grease and decolorization effects, and at the same time have the least impact on the final oryzanol yield.
  • the filtering method is plate and frame filtering with a canvas filter cloth as the filter material.
  • the plate and frame filtration can completely remove the fine activated clay and activated carbon particles, and the speed is fast. Therefore, under insulation conditions, through plate and frame filtration, a light yellow, clear and transparent decolorizing liquid can be obtained.
  • Other filtering methods can be used, but they cannot effectively remove inorganic decolorizing agents with smaller particles, or the filtering time is long, because the present invention needs to maintain the entire temperature control at 50-60°C.
  • the long-term filtering method is not conducive to reducing energy consumption and saving cost.
  • the dilute acid is dilute hydrochloric acid or dilute sulfuric acid aqueous solution, the corresponding concentration is 5-10 wt%, and the adjusted pH is 6.5-7.5.
  • Both hydrochloric acid and sulfuric acid aqueous solutions can be used in production to adjust the pH of the alkaline solution to neutral or weakly acidic, with a wide range of applications and no chemical reaction with the main product.
  • a low concentration means a large amount, and a high concentration generates a large amount of heat of dissolution during the configuration process and is not conducive to labor safety.
  • the time for the completion of the precipitation is 5-12h. If the precipitation time is short, the oryzanol precipitation will be incomplete and reduce the yield; if the precipitation time is long, the production cycle will be affected and the production efficiency will be reduced.
  • the centrifugal method is bag centrifugation.
  • the present invention compares sedimentation centrifugation, bag centrifugation, decanter centrifugation and disc centrifugation, and finds that bag centrifugation has the best effect, and can obtain centrifugal sedimentation that is drier, lighter in color and good in shape, and has advantages that other centrifugal methods cannot Dry humidity and purity, color and luster.
  • the high-concentration ethanol is edible ethanol with a concentration greater than 85%
  • the warm water refers to purified water with a temperature of 40-45° C., such as deionized water, distilled water, and ultrapure water.
  • the temperature exceeds 45°C, oryzanol absorbs water and swells significantly, but absorbs more impurities, and it is difficult to remove the water in this part of the swelling material, which is not conducive to removing residual ethanol; when the temperature is lower than 40°C, the effect of dissolving and removing ethanol is slightly worse. Control this temperature range to improve the effect of removing ethanol and impurities.
  • ethyl acetate has significant advantages: low toxicity, basically non-toxic; it is not a solvent prohibited by Europe, America and Japan, that is, it can be used in production; it has low solubility for oryzanol , Is basically insoluble, and has excellent solubility for lipophilic impurities and pigments, so oryzanol can be refined, and it has the dual advantages of purification and decolorization.
  • High-concentration edible ethanol and ethyl acetate are mutually soluble, and the remaining ethyl acetate can be removed by centrifugation; purified water and edible ethanol at a certain temperature are mutually soluble, and the remaining edible ethanol can be removed by centrifugation.
  • step 6 in the washing step using high-concentration ethanol and/or warm water, 50-70% high-concentration ethanol/or warm water is added to the centrifugal precipitation of the previous step, fully stirred and mixed, centrifuged, and then Add the remaining high-concentration ethanol/or warm water into the centrifuge in batches.
  • the number of divided additions is not particularly limited, and generally can be divided into 2-4 times to uniformly add the remaining washing liquid.
  • the quality of the centrifugal precipitation and the washing solution in step 6 is, the volume of ethyl acetate, high-concentration ethanol and warm water according to the mass-volume ratio (kg/L) is 1-2:2-5:2-5:3 -6, preferably 1-1.3:2-3:3-4:3.5-5.
  • the washing sequence is operated in sequence according to the above three solutions, and the centrifugation method is bag centrifugation. That is, first ethyl acetate, then high-concentration edible ethanol, and finally purified water at a certain temperature. Adjacent two kinds of solvents, through the bag centrifugation and the washing method of adding small amounts in batches, the latter solvent can remove the residue of the former solvent.
  • the present invention proves through experiments that firstly, the oryzanol is purified by using ethyl acetate, then dissolved by high-concentration edible ethanol, and the ethyl acetate is removed by cloth bag centrifugation, and finally dissolved by purified water at a certain temperature and the edible ethanol is removed by cloth bag centrifugation.
  • the drying method is not particularly limited, and examples that can be cited include blast drying, vacuum drying, or microwave vacuum drying, and the drying temperature is 55-65°C.
  • the physicochemical properties of oryzanol crystals are relatively stable at 55-65°C, and one or a combination of the above drying methods can be selected to improve production efficiency.
  • the oryzanol-containing soapstock that is, the byproduct of oryzanol-containing by alkali refining animal and vegetable oils, is used as a raw material to extract oryzanol, preferably rice bran oil soapstock.
  • the raw materials mainly contain oryzanol and fatty acids, Lipophilic impurities and fat-soluble pigments, etc., these ingredients can be fully dissolved by edible ethanol with a concentration of more than 85% at a pH of 8.5-9.5 and a temperature of 50-60°C, and oryzanol is relatively stable under this condition; Under the condition of -60°C, select the appropriate filtration method to separate the impurities insoluble in alkaline ethanol from the solution, and obtain a clear and transparent solution, thereby ensuring the normal progress of the refining operation and the clarity of the final product solution; According to the dissolution characteristics of oryzanol and impurities under these conditions, their molecular weight and molecular structure, and the temperature of the system, select a suitable ultrafiltration membrane for membrane separation.
  • oryzanol insoluble in acid ethanol by adjusting the pH of the solution to 6.5-7.5, the oryzanol is precipitated out, and most of the impurities are dissolved in acid ethanol, and the oryzanol and impurities are further separated by centrifugation. Separation to obtain relatively pure oryzanol; the oryzanol obtained by centrifugation still contains a small amount of lipophilic impurities and pigments.
  • the present invention adopts a specific order of washing steps, namely ethyl acetate, high-concentration ethanol, and warm water.
  • Ethyl acetate has significant advantages: low toxicity, basically non-toxic, not a solvent prohibited by Europe, America and Japan, and can be used in production. It has little solubility for oryzanol and is basically insoluble, and has excellent solubility for lipophilic impurities and pigments.
  • the invention provides an industrial product with an actual content of oryzanol greater than 99% and a white color, that is, the purity and color meet the standards, and the solvents and solvent residues used in the product production process meet the export standards.
  • the oryzanol obtained according to the method of the present invention is a white powder, and the purity of the obtained oryzanol can be as high as 98% or more by ultraviolet-visible spectroscopic absorption chromatography (UV) detection, with little impurity content, and a high-quality oryzanol product with white color.
  • UV ultraviolet-visible spectroscopic absorption chromatography
  • the final yield of oryzanol is >73%.
  • the preparation method of oryzanol provided by the present invention has the characteristics of high purity and yield.
  • the solvents and solvent residues used in the production process meet the export standards, and do not use toxic solvents such as methanol, and extremely flammable and explosive organic solvents such as ether, hexane, and mineral spirits; after testing, there is no solvent residue, which improves Improve product safety.
  • the present invention establishes an industrialized method suitable for the extraction and preparation of oryzanol, has simple extraction process, low production equipment requirements, can produce high-quality oryzanol industrial products on a large scale, and has low production cost and is suitable for industrialized large-scale production.
  • the raw material used in the examples of the present invention is soap stock containing oryzanol, purchased from Hunan Dongxiang Oil Co., Ltd., and the content of oryzanol is 13.65%.
  • the purity of the edible ethanol used in the embodiment of the present invention is 95%, and it is diluted with deionized water to the required concentration when necessary; the purity of ethyl acetate is 99.5% (food grade).
  • the chemical reagents and raw and auxiliary materials used in the embodiments of the present invention, unless otherwise specified, are all obtained through conventional commercial channels.
  • UV ultraviolet-visible spectroscopic absorption chromatography
  • Alkaline alcohol hot melt first add 2000L of 89% edible ethanol to a 6m 3 extraction tank, turn on the stirring, put 600kg of soap stock containing oryzanol into the extraction tank while continuously stirring, and then continue to add 2200L of 89% edible ethanol. Close the lid, continue to stir, turn on the cooling water, and heat it with steam. When heated to 54°C, a measured 4wt% aqueous sodium hydroxide solution was added to the extraction tank to adjust the pH of the system to 9.0. Take a sample to observe the dissolution of the solution. After 20 minutes, the raw materials are completely dissolved, leaving a small amount of oil residue, and 4500L of dissolving solution is obtained.
  • Insulation ultrafiltration membrane separation keep the temperature 54°C, the ultrafiltration membrane tube is pre-installed with polyethersulfone material and the highest temperature is 70°C high temperature resistant membrane (GE membrane Duratherm HWS UF series), set up 2 groups, respectively cut off the molecular weight For 5000 (FLD-UF001) and 1000 (FLD-UF005), maintain the membrane operating pressure at 1.5MPa, first pass the ultrafiltration membrane with a molecular weight of 5000, collect the downstream liquid of the membrane, and then add 100L of 89% edible ethanol to clean the membrane residue.
  • GE membrane Duratherm HWS UF series 70°C high temperature resistant membrane
  • Insulation and decolorization Keep the temperature at 54°C, add 32kg of activated clay and 32kg of activated carbon to the membrane separation solution and stir for 20min. Filter the frame with 1000 mesh canvas filter cloth to obtain a light yellow, clear and transparent decolorization solution.
  • Acidification, neutralization and filtration Under constant stirring, adjust the pH of the decolorizing solution to 7.0 with 6% dilute sulfuric acid, stop stirring, cool with tap water, and place for 8 hours to completely precipitate the precipitate; centrifuge in a three-legged cloth bag and collect and centrifuge Precipitate, get 204kg wet centrifugal sediment.
  • Drying Dry the precipitate in a microwave vacuum and control the drying temperature to 62°C to obtain 63.26kg of oryzanol finished product.
  • the content of the finished oryzanol is 99.12%, and the product yield is 76.56%.
  • Alkaline alcohol hot melt first add 1000L of 92% edible ethanol into the 3m 3 extraction tank, turn on the stirring, put 250kg of soap stock containing oryzanol into the extraction tank while continuously stirring, and then continue to add 1000L of 92% edible ethanol. Close the lid, continue to stir, turn on the cooling water, and heat it with steam. When heated to 52°C, a measured 6% sodium hydroxide aqueous solution is added to the extraction tank to adjust the pH of the system to 9.3. Take a sample to observe the dissolution of the solution. After 15 minutes, the raw materials are completely dissolved and a small amount of oil residue is left to obtain 2100L of dissolving liquid.
  • Insulation ultrafiltration membrane separation maintain the temperature at 52°C, the ultrafiltration membrane tube is pre-installed with imported high-temperature resistant membrane made of polyethersulfone and the highest temperature is 70°C. There are 2 groups, with molecular weight cutoffs of 5000 and 1000 respectively, to maintain the membrane The operating pressure is 1.7MPa, the ultrafiltration membrane with a molecular weight of 5000 is first collected, the downstream liquid of the membrane is collected, and then 100L of 92% edible ethanol is added to clean the membrane residue, and the feed permeate and cleaning permeate are combined to obtain the permeate; Then pass the permeate through an ultrafiltration membrane with a molecular weight of 1000, and collect the upstream liquid of the membrane to obtain 2150L of retentate, which is the membrane separation liquid.
  • Inorganic decolorant heat preservation and decolorization Keep the temperature at 52°C, add 20kg of activated clay and 10kg of activated carbon to the membrane separation liquid and stir well for 20min, and filter with 1000 mesh canvas filter cloth to obtain a light yellow, clear and transparent decolorizing liquid.
  • Acidification, neutralization and filtration Under constant stirring, adjust the pH of the decolorizing solution to 7.2 with 9% dilute hydrochloric acid, stop stirring, cool with tap water, and leave for 10 hours to completely precipitate the precipitate; centrifuge in a three-legged cloth bag, collect and centrifuge Precipitate, get 83kg wet centrifugal sediment.
  • Drying Dry the precipitate by blowing air, and control the drying temperature to 65°C to obtain 25.70 kg of oryzanol finished product, which is a white powder.
  • Example 2 The other steps are the same as in Example 1, the difference is that the temperature of the system is controlled to 50°C throughout the process in step 1) to step 4). Finally, 60.81 kg of oryzanol was obtained. After testing, the content of oryzanol in the finished product was 99.04%, and the product yield was 73.53%.
  • Example 2 The other steps are the same as in Example 1, the difference is that the temperature of the whole control system in step 1) to step 4) is. 56°C. Finally, 62.11kg of oryzanol was obtained. After testing, the content of oryzanol in the finished product was 99.26%, and the product yield was 75.28%.
  • Example 2 The other steps are the same as in Example 1, the difference is that the temperature of the system is controlled to 60°C in the whole process in step 1) to step 4). Finally, 61.53kg of oryzanol was obtained. After testing, the content of oryzanol in the finished product was 99.18%, and the product yield was 74.51%.
  • step 4 only 64kg of activated clay is used as the decolorizing agent, and finally 61.18kg of oryzanol is obtained. After testing, the content of oryzanol in the finished product is 98.67%, and the product yield is 73.71%.
  • step 4 only 64kg of activated carbon is used as the decolorizing agent, and finally 61.90kg of oryzanol is obtained. After testing, the content of oryzanol in the finished product is 98.25%, and the product yield is 74.26%.
  • step 3 the ultrafiltration membrane with a molecular weight of 1000 is first collected, the downstream liquid of the membrane is collected, and then 100L of 92% edible ethanol is added to clean the membrane residue, and the feed permeate is combined and cleaned.
  • the permeate is obtained by passing the permeate through an ultrafiltration membrane with a molecular weight of 5000, and finally 61.09 kg of oryzanol is obtained. After testing, the content of oryzanol in the finished product is 98.14%, and the product yield is 73.20%.
  • Example 2 The other steps are the same as in Example 1, the difference is that the temperature of the system is controlled to 46°C in the whole process in step 1) to step 4). Finally, 57.79kg of oryzanol was obtained. After testing, the content of oryzanol in the finished product was 95.38%, and the product yield was 67.30%.
  • step 3 when the insulation ultrafiltration membrane is separated, the clogging of the membrane occurs, and effective production cannot be achieved.
  • step 1 The other steps are the same as in Example 1, the difference is that the temperature of the system is controlled at 65°C in the whole process in step 1) to step 4). Finally, 54.46 kg of oryzanol was obtained. After testing, the content of oryzanol in the finished product was 96.72%, and the product yield was 64.31%.
  • step 6 washing, the ethyl acetate is replaced with isoamyl alcohol, and finally 61.94 kg of oryzanol is obtained. After testing, the content of oryzanol in the finished product is 95.84%, and the product yield is 72.48%.
  • step 6 the order of washing is to add 500L of ethyl acetate to the centrifugal sediment, stir and mix thoroughly, centrifuge through a three-legged cloth bag, and collect the centrifugal sediment; Add 600L of purified water at a temperature of 40°C to the precipitation, stir and mix thoroughly, centrifuge in a three-foot bag, and divide into the centrifuge 3 times, add 50L of purified water at a temperature of 40°C each time, fully permeate the precipitate, and collect the centrifuged sediment ; Then add 600L of edible ethanol with a concentration of 89% to the precipitate, stir and mix thoroughly, centrifuge through a three-legged cloth bag, and divide into the centrifuge twice, add 50L of edible ethanol with a concentration of 89% each time, fully permeate the precipitate, Collect the centrifugal pellet. Finally, 61.75kg of oryzanol was obtained. After
  • Example 2 The other steps are the same as in Example 1, the difference is that in the washing of step 6), the washing with ethyl acetate is omitted, and the washing with ethanol and warm water is directly carried out. Finally, 64.75kg of oryzanol was obtained. After testing, the content of oryzanol in the finished product was 91.36%, and the product yield was 72.23%.

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Abstract

一种以含谷维素的皂脚为原料制备谷维素的方法，包括以下步骤：1)碱醇热溶；2)保温精滤；3)保温超滤膜分离；4)保温脱色；5)酸化中和与过滤；6)洗涤；7)干燥。其中步骤1)至步骤4)的温度控制在50-60℃。所述方法的特征在于在50-60℃下保温操作，配合膜分离、脱色和洗涤的工艺条件，最终制得产品为白色粉末，谷维素纯度高于98％，收率高于73％；该方法不使用甲醇、乙醚、已烷、溶剂油等有毒或易燃易爆的有机溶剂，提高了产品使用安全性；生产工艺简单，生产设备要求低，易于操作和实现；生产成本低，适合工业化生产。

Description

一种以含谷维素的皂脚为原料制备谷维素的方法 技术领域
本发明属于植物提取分离技术领域，涉及一种制备谷维素的方法，具体涉及一种以含谷维素的皂脚为原料制备谷维素的方法。
背景技术
谷维素(Oryzanol)存在于米糠油中，系以三萜(烯)醇为主体的阿魏酸酯的混合物。主要作用于间脑的自主神经系统与内分泌中枢，能调整自主神经功能，减少内分泌平衡障碍，改善精神神经失调症状。还同时具有降低血脂、降低肝脏脂质、防止脂质氧化、抗氧化等多种生理功能。此外，近来也有人利用谷维素作为护肤品和食品抗氧化剂的原料。一般采用富含谷维素的米糠油等的皂脚为原料提取制备谷维素，但普遍产品纯度和收率不能令人满意。
国内有关谷维素的专利技术报道也比较多，但各自存在一些缺陷，先分类详述如下。
1、按所使用溶剂类分述如下：
CN201710073967、CN201510769436、CN201310659297、CN201310099264、CN201010542976、CN201010224081、CN200810231528、CN02135610等专利均是以甲醇为提取溶剂，再经过一系列精制得谷维素，容易残存甲醇且不符合出口产品规定。CN201510769436、CN201010542976等专利以已烷精制或结晶，再经过一些工艺步骤得到谷维素产品，容易残存已烷，导致残留超标。现有技术大多使用甲醇，主要是因为甲醇对谷维素的提取效率高，但是后处理要求高，否则残存的甲醇导致超标。而且在生产工艺中大量使用甲醇，也对操作工人的健康有潜在的危险。
2、按工艺类分述如下：
申请号为CN201710073967.6的专利申请公开了一种谷维素提取工艺，首先对稻米原油进行脱胶，得脱胶油；对脱胶油进行碱炼，得皂脚；皂脚经补充皂化后，加入甲醇、水和碳酸钠进行碱溶，得上层清液；上层清液依次加入盐酸、柠檬酸调节pH，得谷维素粗制品；清洗、干燥，得精制谷维素。该方法使用碱性甲醇提取，溶剂有毒，产品有残留；且碳酸钠为弱碱，实际中无法与谷维素分子中的酚羟基结合，无法促进谷维素溶解。
申请号为CN201510769436.1的专利申请公开了一种γ-谷维素生产方法，将滤渣倒入溶解槽；加入甲醇混合后加己烷搅拌；加醋酸中和，搅拌回流；水浴加热至50℃、加温搅拌回流；加水继续搅拌后静置一小时；粗制品γ-谷维素析出；溶液自动分层，上层为己烷溶液；下层为粗制品γ-谷维素析出物与甲醇溶解层；将上下层甲醇溶解层分流；水浴加热下层所得；对水浴加热后的粗制品γ-谷维素析出物与甲醇溶解层减压过滤，滤纸上层为粗γ-谷维素；将己烷加入到粗γ-谷维素析出颗粒中洗出可溶解于己烷的杂质；收集γ-谷维素析出颗粒低温干燥即可。加热条件下，谷维素易溶于已烷，且在甲醇中溶解度较大，甲醇有较大毒性且易在产品中有残留；既然两相溶剂中均溶解有谷维素，其方法无法达到分离的目的，有待进一步研究；己烷极易燃易爆，生产安全性有待进一步提高。
申请号为CN201310659297.8公开了一种从糠粕废弃油脂中提取谷维素的方法，包括以下步骤：1)向糠粕废弃油脂中加入耐高温酶，加入量为糠粕废弃油脂质量的0.5-5％，在70-95℃下搅拌消化60-120min，过滤，得到油脂清液；2)碱溶：将碱性甲醇溶液与步骤1)油脂清液按质量比例1:5～1:8进行混合，加温至60℃，搅拌，静置待两相分离，萃取；3)酸析：将步骤2)萃取液加热至40-60℃，加入酸调节到pH为3.0-6.0，静置过夜，离心分离，得到谷维素粗品；4)精制谷维素：将步骤3)得到的谷维素粗品，用蒸馏水进行冲洗，然后干燥，得到精制谷维素。酶的化学本质是蛋白质，在70℃以上多数酶会失活，其方法的科学性有待研究；甲醇为有毒试剂；谷维素为水不溶物质，其中杂质亦来自油，同样为强亲脂性物质中，简单蒸馏水冲洗之后干燥，不可能实现精制的目的，该精制方法有待进一步研究。
申请号为CN201310099264.2公开了一种米糠毛油提取谷维素的方法，步骤如下：(1)制取四级米糠油①米糠毛油水化脱胶和脱蜡；②脱蜡米糠油脱色；③脱色米糠油物理精炼；(2)提取粗谷维素①皂基的制备；②碱溶操作；③酸析操作；(3)精制粗谷维素①粗谷维素重溶及溶剂油液—液洗涤；②酸析及酸浸泡；③谷维素烘干及粉碎。本法用到有毒的甲醇，产品中有残留；产品无结晶步骤，含量有待进一步证实；溶剂油极易燃易爆，生产安全性有待进一步提高。
申请号为CN201010542976.3公开了一种从米糠中提取谷维素的工艺，将毛糠油加甲醇，用氢氧化钠调节pH，加热保温搅拌，冷却静置分层，放出下层油相；向上层甲醇液中加入柠檬酸调节pH至7，静置滤取沉淀，得粗品；用己烷重结晶，经洗涤、干燥得精品。该法用到有毒的甲醇，产品中有残留；已烷极易燃易爆，生产安全性有待进 一步提高。
申请号为CN201010224081.5公开了一种非极性溶剂萃取法提取谷维素的方法，选用米糠油碱炼皂脚，加入甲醇乙醚碱性溶液，充分搅拌后静置分层，上层为中性物质，下层是含谷维素的碱性物质，用盐酸溶液调节pH值，此时即有谷维素结晶析出。然后洗涤、真空干燥得谷维素成品。该法用到有毒的甲醇和乙醚，产品中会有甲醇残留；乙醚是管制试剂，极易燃易爆，生产安全性有待进一步提高；调酸所析出的谷维素含量是否达标，有待进一步证实。
申请号为CN200810231528.8公开了一种从米糠油皂脚中提取谷维素的生产方法，将富含谷维素的米糠油皂脚加热、溶化后，用甲醇进行稀释，再加碱补充皂化，之后，进行碱溶过滤，得皂化液的滤液，对皂化的滤液再进行过滤，水洗后经酸浸、提纯、造粒，然后烘干，即可。该法用到有毒的甲醇，产品有残留；主要工艺为碱醇溶解酸析，简单提纯以后谷维素的含量是否达标，有待进一步证实。
申请号为CN200810244052.8公开了一种谷维素的提取方法，以米糠毛油为原料，首先用乙醇胺对米糠油与正己烷混合油进行预脱酸，接着用NaOH溶液把谷维素富集到皂脚中，然后用甲醇萃取皂脚中谷维素钠盐，最后用酸溶液调pH值使其中所含谷维素结晶析出，分离后得谷维素。该方法法用到有毒的甲醇，产品有残留；主要工艺为碱醇溶解酸析，所得产品为低含量谷维素。
申请号为CN02135610.6公开了一种溶剂法萃取法提取谷维素的方法，首先对米糠毛油进行预处理，对预处理后的糠油进行物理精炼以脱除油中游离脂肪酸，在精炼后的糠油中加入碱性甲醇进行连续逆流萃取，向萃取后的甲醇母液中加酸使其中所含的谷维素结晶析出，分离后得谷维素。该法用到有毒的甲醇，产品有残留；主要工艺为碱醇溶解酸析，所得产品为低含量谷维素。
可见，目前市售谷维素主要存在三方面问题：1、溶剂残留超标以及使用违规溶剂：主要是甲醇、乙醚、己烷烷等有机溶剂并有残留，导致谷维素产品无法出口欧美和日本，绿色出口标准规定出口产品不得在生产过程中使用甲醇等有毒溶剂；2、多数谷维素产品的实际含量未达标：一些市售产品虽然颜色白，但含量只有95％左右，经分析知这些产品在生产过程中产生了一些新的降解物质，虽然同样为白色，但降低了谷维素含量，这与生产工艺有关；3、一些谷维素产品的颜色未达标：虽然其产品含量达到了98％，但是往往没有经过脱色步骤，使得这类产品的颜色为类白色或灰白色、淡黄白色，此类产品在销往欧美等产地收到限制。因此，亟需提出一种谷维素生产工艺，使得产品收率 和纯度均能达到令人满意的程度，并且生产工艺绿色环保，不使用有毒或者易燃易爆的试剂。
发明内容
本发明所要解决的技术问题是，克服现有技术存在的上述缺陷，提供一种谷维素的制备方法，生产过程使用的溶剂以及溶剂残留符合出口标准；提高生产安全性，不使用甲醇等毒性大的溶剂，以及乙醚、己烷、溶剂油等极易燃易爆的有机溶剂；建立适合工业化推广的生产工艺，能规模生产出优质的谷维素工业产品；产品中谷维素实际含量大于98％、收率大于73％,颜色为白色的工业产品，纯度和颜色性能优异；降低生产成本，提高企业的经济和社会效益。
本发明解决其技术问题所采用的技术方案如下：
一种以含谷维素的皂脚为原料制备谷维素的方法，包括以下步骤：
1)、碱醇热溶：向原料加入乙醇，加热至50-60℃，调节体系至弱碱性，使原料溶解，得溶解液；
2)、保温精滤：保持步骤1)中的温度，使用精密过滤器将溶解液过滤；
3)、保温超滤膜分离：在50-60℃条件下，将滤液通过耐高温超滤膜进行膜分离，收集1000-5000分子量区段的膜分离液；
4)、保温脱色：向膜分离液中加入无机脱色剂，充分搅拌，过滤，得脱色液。
5)、酸化中和与过滤：用稀酸中和脱色液，冷却，放置，使沉淀完全析出，离心，收集离心沉淀；
6)、洗涤：向离心沉淀中依次进行乙酸乙酯、高浓度乙醇、温水的洗涤，所述洗涤是向离心沉淀加入上述溶剂或溶液的洗涤液，充分搅拌混匀，离心得到离心沉淀，进行下一步的洗涤；
7)、干燥。将沉淀干燥，得到谷维素成品。
优选地，本发明上述方法步骤1)至步骤4)中体系保持温度在50-60℃。将温度控制在上述范围内，配合其他步骤的工艺条件和参数，可以最大限度提高提取谷维素的效率，并且保证产品中谷维素的纯度，满足了工业化生产制备优质含有谷维素产品的要求。
优选地，步骤1)中，所述乙醇是指浓度大于80％的乙醇，优选浓度大于85％的乙醇，更为优选地，采用浓度大于85％的乙醇；乙醇加入量为含谷皂基重量的5-10倍； 所述加热是指加热温度至50-60℃；所述调节为弱碱性是指用碱性氢氧化物，比如氢氧化钠，氢氧化剂调节pH为8.5-9.5。
之前有文献报导用甲醇调pH的方法提取谷维素，发明人发现用高浓度食用乙醇，全程温度控制在50-60℃，亦可以将谷维素提取出来，且符合出口产品溶剂使用及残留标准。从技术上相对而言，乙醇提取出来的谷维素颜色浅，杂质更少，纯度高。若食用乙醇浓度低，则无法将大部分谷维素提取出来，损失大；若食用乙醇浓度高，则生产中难以回收至高浓度食用乙醇；加热温度至50-60℃。若加热温度高或溶解时间长，则在碱性条件下对谷维素有显著破坏作用，并导致产品收率严重下降；若加热温度低或溶解时间短，则不利于谷维素的溶出，不溶物增加，在降低产品收率的同时，也导致精滤的过滤速度慢；最终调节溶解液的pH过高，则会显著破坏谷维素，导致谷维素产率低；过低则不利于谷维素溶解，从而导致产量少；在合适的pH范围内，体系在后续的膜分离操作中对膜无影响，在膜所承受的pH范围内。
优选地，步骤2)中，过滤的温度控制在50℃-60℃；所述过滤采用带有折叠滤芯的精密过滤器，其中滤芯孔径为0.45μm，操作压力为0.2-0.4MPa。
若温度高于60℃，则在碱性条件下对谷维素有显著破坏作用，并导致产品收率严重下降；若温度低于50℃，则谷维素的溶出量减少，不溶物增加，在降低产品收率的同时，也导致精滤的过滤速度大幅度下降，从而导致生产效率低下，并容易堵塞滤芯。此外，发明人经多次实验表明，选择上述折叠滤芯对含谷维素的高度乙醇溶液具有良好的过滤效果，所得滤液为澄清透明的溶液；相同条件下，微孔滤膜等滤材极易堵塞，无法正常操作。选择合适的滤芯孔径，是为了与超滤膜分离对溶液的澄清度要求相匹配，孔径过大则透过的杂质多，影响超滤膜的使用寿命；孔径小则过滤速度较慢，影响生产效率。精密过滤器的操作压力受滤芯的影响，当滤芯表面积累杂质增加的时候，相应的操作压力增加，当压力增加到一定程度时，需要及时清理滤芯，以保证过滤的效果和速度。
优选地，步骤3)中，是在50-60℃下进行超滤，使用的耐高温超滤膜，材质为聚醚砜，比如GE公司的Duratherm系列(具体的离子包括NF 8040HF、NF RO8040、RO 8040HR、NF 8040HR、NF 3840HR、FLD-UF)。可承受温度为70℃。步骤2)滤液保温温度为50℃-60℃，且超滤膜分离操作的保温温度也是相同温度，普通超滤膜只能承受45℃以内温度，因此，本发明通过大量调研，使用耐高温超滤膜，可承受70℃温度，从而适应了谷维素溶液的保温膜分离条件。设置超滤时的温度在50-60℃，若温度高于60℃，则在碱性条 件下对谷维素有显著破坏作用，并导致产品收率严重下降；若温度低于50℃，则谷维素的溶出量减少，不溶物增加，在降低产品收率的同时，也导致超滤膜的运行速度大幅度下降，从而导致生产效率低下，并容易堵塞超滤膜。
更优选地，步骤3)中，所述膜的截留分子量设置为1000-5000，膜运行压力为1.0-2.0MPa。确定了膜的种类及性能符合要求以后，需要根据谷维素分子量、化学结构和杂质和种类，进一步选择超滤膜的截留分子量。本发明通过大量实验证明，溶液中95％的谷维素分布于膜截留分子量1000-5000范围内，并且溶液颜色由红褐色变成了黄色，即通过此分子量的膜分离，具有显著的脱色和提纯效果。超滤膜需要在适当的压力下运行，压力低则过膜速度慢，压力高则易造成谷维素的损失。
进一步优选地，步骤3)中，所述膜分离的顺序，先过分子量为5000的超滤膜，收集膜下游液，即透过液，再将透过液过分子量为1000的超滤膜，收集膜上游液，即截留液。按照上述顺序进行超滤，能进一步提高分离提纯的效果。步骤4)中，脱色时仍保持温度为50-60℃，若温度高于60℃，则在碱性条件下对谷维素有显著破坏作用，并导致产品收率严重下降；若温度低于50℃，则谷维素的溶出量减少，被无机脱色剂所吸附的量增加，在降低产品收率的同时，也导致板框过滤困难。
优选地，步骤4)中，所述脱色剂为活性白土和活性碳中的至少一种，脱色剂添加量为含谷维素的皂脚原料重量的3-6％；更优选地，所述脱色剂为活性白土和活性炭按照质量比1-2:1-2的复配。本发明通过实验证明，活性白土对具有油脂的脂溶性成分具有良好的除油和脱色效果，并可助滤；活性炭在极性溶液中也具有良好的脱色效果，并可助滤。二者协同作用，除油脂和脱色效果更好，同时对最终谷维素素的收率影响最小。
进一步优选地，步骤4)中，所述过滤方式为滤材为帆布型滤布的板框过滤。板框过滤能完全去除细小的活性白土和活性炭颗粒，并且速度快。因此，在保温条件下，经板框过滤，可以得到淡黄色、澄清透明的脱色液。使用其他过滤方式也可，但无法有效出去颗粒较小的无机脱色剂，或者过滤时间长，因为本发明要维持全程温度控制在50-60℃，长时间的过滤方式不利于降低能耗，节约成本。
步骤5)中，所述稀酸为稀盐酸或稀硫酸水溶液，相应浓度为5-10wt％，所调节pH为6.5-7.5。盐酸和硫酸水溶液均可以在生产中用以调节碱性溶液的pH至中性或弱酸性，应用范围广，且不与主产品发生化学反应。浓度低则用量大，浓度高则配置过程产生大量溶解热且不利于劳动安全。最终调节pH过低，则大量脂肪酸附着到主产品谷维素中，不利于谷维素纯化；若pH过高，则主产品析出不完全，收率低。
优选地，步骤5)中，所述沉淀完全的时间为5-12h。若沉淀时间短，则谷维素沉淀不完全，降低了收率；若沉淀时间长，则影响生产周期，降低了生产效率。
进一步优选地，步骤5)中，所述离心方式为布袋离心。本发明通过比较沉降离心、布袋离心、卧螺离心和碟式离心，发现布袋离心具有最优的效果，可以得到较干燥、颜色浅、性状好的离心沉淀，具有其他离心方式所达不到的干湿度和纯度、色泽。
步骤6)中，所述高浓度乙醇是浓度大于85％的食用乙醇，所述温水是指温度在40-45℃的纯化水，比如去离子水，蒸馏水，超纯水。温度超过45℃时，谷维素吸水膨胀明显，反而吸入更多杂质，并难以去除这部分膨胀物质中的水，不利于去除残留乙醇；温度低于40℃时，溶解并去除乙醇效果略差。控制此温度范围，以提高去除乙醇和杂质的效果。
本发明通过对比多种有机溶剂，结合生产实际，表明乙酸乙酯具有显著优点：低毒，基本无毒；不属于欧美和日本所禁止使用的溶剂，即可以在生产中使用；对谷维素溶解度小，基本不溶，而对亲脂性杂质和色素具有优良的溶解性能，因此可以精制谷维素，兼具提纯和脱色的双重优点。高浓度食用乙醇和乙酸乙酯可以互溶，通过离心，可以去掉残存的乙酸乙酯；一定温度的纯化水与食用乙醇互溶，通过离心，可以去掉残存的食用乙醇。
优选地，步骤6)中，使用高浓度乙醇和/或温水的洗涤步骤中，是向上一步的离心沉淀中加入50-70％的高浓度乙醇/或温水，充分搅拌混匀，离心，再向离心机内分次加入剩余的高浓度乙醇/或温水。所述分次加入的次数没有特别的限定，一般可以为分为2-4次均匀加入剩余洗涤液即可。
优选地，步骤6)中离心沉淀的质量和洗涤液，即乙酸乙酯、高浓度乙醇和温水的体积按照质量体积比(kg/L)为1-2:2-5:2-5:3-6进行，优选地，为1-1.3:2-3:3-4:3.5-5。洗涤的顺序按照上述三种溶液依次操作，离心方式为布袋离心。即先乙酸乙酯，然后高浓度食用乙醇，最后是一定温度的纯化水。相邻2种溶剂，通过布袋离心与分次少量加入的洗涤方式，后一种溶剂可去除前一种溶剂残留。本发明通过实验证明，先利用乙酸乙酯提纯谷维素，再通过高浓度食用乙醇溶出并采用布袋离心去除乙酸乙酯，最后通过一定温度的纯化水溶出并采用布袋离心去除食用乙醇。通过以上三种溶剂的组合使用，结合布袋离心操作，在精制谷维素的同时，也去除了溶剂残留，提升了产品品质和安全性。
步骤7)中，所述干燥方式没有特别限定，可与举出的例子包括鼓风干燥或真空干燥或微波真空干燥，干燥温度为55-65℃。谷维素结晶的理化性质在55-65℃下较稳定， 可以选择上述干燥方式之一或其组合，以提高生产效率为准。
本发明的原理如下所述：是以含谷维素的皂脚，也即以碱炼动植物油脂时的含谷维素副产品，为原料提取谷维素，优选为米糠油皂脚，原料中主要含有谷维素以及脂肪酸、亲脂性杂质和脂溶性色素等，这些成分可以被浓度85％以上的食用乙醇在pH为8.5-9.5，温度50-60℃的条件下充分溶解，并且谷维素在此条件下比较稳定；在保温50-60℃的条件下，选择合适的过滤方式，可以将碱性乙醇所不溶解的杂质与溶液分离，并且可以得到澄清透明的溶液，从而保证了精制操作的正常进行以及最终产品溶液的澄清；根据谷维素和杂质在此条件下的溶解特点、各自的分子量和分子结构、体系的温度，选择合适的超滤膜进行膜分离，在脱色的同时，也提高了谷维素的纯度，选择分子量1000-5000的区段，可以得到颜色浅、含量高的谷维素；超滤膜分离后的溶液具有一定颜色，根据油脂的亲脂性特点，可以将无机脱色剂如活性白土和活性炭联用，在进一步去除脂溶性杂质和色素的同时，对谷维素进一步提纯，并且对谷维素的收率的影响降至最低，并通过板框过滤的方式，可以完全去除溶液中残存的无机脱色剂粉末；经过前述工艺分离提纯，谷维素和一些杂质仍然存在于溶液中，根据谷维素不溶于酸性乙醇的性质，通过调节溶液pH为6.5-7.5，使谷维素沉淀析出，而大部分杂质溶解于酸性乙醇中，并通过离心进一步将谷维素与杂质分离，以得到较纯的谷维素；离心所得谷维素尚含有少量亲脂性杂质和色素，本发明采用特定顺序的洗涤步骤，即乙酸乙酯、高浓度乙醇、温水。乙酸乙酯具有显著优点：低毒，基本无毒、不属于欧美和日本所禁止使用的溶剂，可以在生产中使用，对谷维素溶解度小，基本不溶，而对亲脂性杂质和色素具有优良的溶解性能，因此可以精制谷维素，兼具提纯和脱色的双重优点；高浓度食用乙醇和乙酸乙酯可以互溶，通过离心，可以去掉残存的乙酸乙酯；一定温度的纯化水与食用乙醇互溶，通过离心，可以去掉残存的食用乙醇；通过以上三种溶剂按照特定顺序的组合使用，结合布袋离心操作，在精制谷维素的同时，也去除了溶剂残留，提升了产品品质和安全性。
本发明提供了一种谷维素实际含量大于99％、颜色为白色的工业产品，即纯度和颜色均达标，并且产品生产过程使用的溶剂以及溶剂残留符合出口标准。
本发明方法的有益效果如下：
一、按照本发明方法所得谷维素为白色粉末，经紫外-可见分光吸收色谱(UV)检测，所得谷维素的纯度可高达98％以上，杂质含量少，颜色为白色的优质谷维素产品。
二、谷维素的最终收率＞73％，本发明提供谷维素制备方法兼具了纯度和收率都较高的特点。
三、本发明提取制备谷维素的生产过程中，全程控制温度在50-60℃，发明人发现，在该温度范围内，产品谷维素的含量和收率能够取得最佳的平衡。
四、产品生产过程使用的溶剂以及溶剂残留符合出口标准，不使用甲醇等毒性大的溶剂，以及乙醚、已烷、溶剂油等极易燃易爆的有机溶剂；经过检测，没有溶剂残留，提高了产品使用安全性。
五、本发明建立适合谷维素提取制备的工业化方法，提工艺简单，生产设备要求低，能规模生产出优质的谷维素工业产品；生产成本低，适合工业化的大规模生产。
具体实施方式
下面结合实施例对本发明的提取工艺的方法作进一步说明。
本发明实施例所使用的原料为含谷维素的皂脚，购于湖南东翔油脂有限公司，谷维素的含量为13.65％。本发明实施例所使用的食用乙醇纯度为95％，需要时用去离子水稀释至需要浓度；乙酸乙酯纯度为99.5％(食品级)。本发明实施例所使用的化学试剂和原辅材料，如无特殊说明，均通过常规商业途径获得。
产品中谷维素的含量采用紫外-可见分光吸收色谱(UV)检测。
实施例1
1、碱醇热溶：先向6m 3提取罐中加入浓度89％食用乙醇2000L，开启搅拌，在不断搅拌中将600kg含谷维素的皂脚投入提取罐，再继续加入2200L浓度89％食用乙醇。关盖，继续搅拌，开启冷却水，并通蒸汽加热。当加热至54℃时，向提取罐内加入计量好的4wt％氢氧化钠水溶液，调节体系的pH为9.0。取样观察溶液的溶解情况，20min后，原料完全溶解，余少量油渣，得4500L溶解液。
2、保温精滤：保持温度54℃，配置精密过滤器折叠滤芯孔径为0.45um，将溶解液通过精密过滤器过滤，保持运行压力0.3MPa，得到澄清的滤液。
3、保温超滤膜分离：保持温度54℃，超滤膜管预装聚醚砜材质且最高承受温度为70℃的耐高温膜(GE膜Duratherm HWS UF系列)，设2组，分别截留分子量为5000(FLD-UF001)和1000(FLD-UF005)，维持膜运行压力1.5MPa，先过分子量为5000的超滤膜，收集膜下游液，再加100L浓度89％的食用乙醇清洗膜残留，合并进料透过液和清洗透过液，得透过液；再将透过液过分子量为1000的超滤膜，收集膜上游液，得4550L截留液，即膜分离液。
4、保温脱色：保持温度54℃，向膜分离液中加入32kg活性白土和32kg活性碳充 分搅拌20min，板框配以1000目帆布滤布过滤，得微黄色澄清透明的脱色液。
5、酸化中和与过滤：在不断搅拌下，用浓度6％稀硫酸调节脱色液的pH至7.0，停止搅拌，通自来水冷却，放置8h，使沉淀完全析出；过三足布袋离心，收集离心沉淀，得204kg湿润的离心沉淀。
6、洗涤：向离心沉淀中加入500L乙酸乙酯，充分搅拌混匀，过三足布袋离心，收集离心沉淀；再向沉淀中加入600L浓度89％的食用乙醇，充分搅拌混匀，过三足布袋离心，并向离心机内分2次，每次加入50L浓度89％的食用乙醇，充分透过沉淀，收集离心沉淀；再向沉淀中加入600L，温度40℃的纯化水，充分搅拌混匀，过三足布袋离心，并向离心机内分3次，每次加入50L温度40℃纯化水，充分透过沉淀，收集离心沉淀。
7、干燥：将沉淀微波真空干燥，控制干燥温度为62℃，得到63.26kg谷维素成品。
经检测，成品谷维素含量99.12％，产品收率76.56％。
实施例2
1、碱醇热溶：先向3m 3提取罐中加入浓度92％食用乙醇1000L，开启搅拌，在不断搅拌中将250kg含谷维素的皂脚投入提取罐，再继续加入1000L浓度92％食用乙醇。关盖，继续搅拌，开启冷却水，并通蒸汽加热。当加热至52℃时，向提取罐内加入计量好的6％氢氧化钠水溶液，调节体系的pH为9.3。取样观察溶液的溶解情况，15min后，原料完全溶解，余少量油渣，得2100L溶解液。
2、保温精滤：保持温度52℃，配置精密过滤器折叠滤芯孔径为0.45um，将溶解液通过精密过滤器过滤，保持运行压力0.25MPa，得到澄清的滤液。
3、保温超滤膜分离：保持温度52℃，超滤膜管预装聚醚砜材质且最高承受温度为70℃的进口耐高温膜，设2组，分别截留分子量为5000和1000，维持膜运行压力1.7MPa，先过分子量为5000的超滤膜，收集膜下游液，再加100L浓度92％的食用乙醇清洗膜残留，合并进料透过液和清洗透过液，得透过液；再将透过液过分子量为1000的超滤膜，收集膜上游液，得2150L截留液，即膜分离液。
4、无机脱色剂保温脱色：保持温度52℃，向膜分离液中加入20kg活性白土和10kg活性碳充分搅拌20min，板框配以1000目帆布滤布过滤，得微黄色澄清透明的脱色液。
5、酸化中和与过滤：在不断搅拌下，用浓度9％稀盐酸调节脱色液的pH至7.2，停止搅拌，通自来水冷却，放置10h，使沉淀完全析出；过三足布袋离心，收集离心沉淀，得83kg湿润的离心沉淀。
6、洗涤：向离心沉淀中加入250L乙酸乙酯，充分搅拌混匀，过三足布袋离心，收集离心沉淀；再向沉淀中加入230L浓度92％的食用乙醇，充分搅拌混匀，过三足布袋离心，并向离心机内分2次，每次加入50L浓度92％的食用乙醇，充分透过沉淀，收集离心沉淀；再向沉淀中加入250L，温度40℃的纯化水，充分搅拌混匀，过三足布袋离心，并向离心机内分3次，每次加入50L温度40℃纯化水，充分透过沉淀，收集离心沉淀。
7、干燥：将沉淀鼓风干燥，控制干燥温度为65℃，得到25.70kg谷维素成品，产品为白色粉末。
经检测，成品谷维素含量99.35％，产品收率74.82％。
实施例3
其他步骤和实施例1相同，区别在于步骤1)-步骤4)中全程控制体系温度为50℃。最终得到60.81kg谷维素成品，经检测，成品谷维素含量99.04％，产品收率73.53％。
实施例4
其他步骤和实施例1相同，区别在于步骤1)-步骤4)中全程控制体系温度为。56℃。最终得到62.11kg谷维素成品，经检测，成品谷维素含量99.26％，产品收率75.28％
实施例5
其他步骤和实施例1相同，区别在于步骤1)-步骤4)中全程控制体系温度为60℃。最终得到61.53kg谷维素成品，经检测，成品谷维素含量99.18％，产品收率74.51％。
实施例6
其他步骤和实施例1相同，区别在于步骤4)中脱色剂仅使用64kg的活性白土，最终得到61.18kg谷维素成品，经检测，成品谷维素含量98.67％，产品收率73.71％。
实施例7
其他步骤和实施例1相同，区别在于步骤4)中脱色剂仅使用64kg的活性碳，最终得到61.90kg谷维素成品，经检测，成品谷维素含量98.25％，产品收率74.26％。
实施例8
其他步骤和实施例1相同，区别在于步骤3)中先过分子量为1000的超滤膜，收集膜下游液，再加100L浓度92％的食用乙醇清洗膜残留，合并进料透过液和清洗透过液，得透过液；再将透过液过分子量为5000的超滤膜，最终得到61.09kg谷维素成品，经检测，成品谷维素含量98.14％，产品收率73.20％。
对比例1
其他步骤和实施例1相同，区别在于步骤1)-步骤4)中全程控制体系温度为46℃。最终得到57.79kg谷维素成品，经检测，成品谷维素含量95.38％，产品收率67.30％。
对比例2
其他步骤和实施例1相同，区别在于步骤1)-步骤4)中全程控制体系温度为43℃。在步骤3)保温超滤膜分离时，发生膜的堵塞，无法有效生产。
对比例3
其他步骤和实施例1相同，区别在于步骤1)-步骤4)中全程控制体系温度为65℃。最终得到54.46kg谷维素成品，经检测，成品谷维素含量96.72％，产品收率64.31％。
对比例4
其他步骤和实施例1相同，区别在于，步骤6)洗涤，将乙酸乙酯替换为异戊醇，最终得到61.94kg谷维素成品，经检测，成品谷维素含量95.84％，产品收率72.48％。
对比例5
其他步骤和实施例1相同，区别在于，步骤6)的洗涤中，洗涤的次序变为向离心沉淀中加入500L乙酸乙酯，充分搅拌混匀，过三足布袋离心，收集离心沉淀；再向沉淀中加入600L，温度40℃的纯化水，充分搅拌混匀，过三足布袋离心，并向离心机内分3次，每次加入50L温度40℃纯化水，充分透过沉淀，收集离心沉淀；再向沉淀中加入600L浓度89％的食用乙醇，充分搅拌混匀，过三足布袋离心，并向离心机内分2次，每次加入50L浓度89％的食用乙醇，充分透过沉淀，收集离心沉淀。最终得到61.75kg谷维素成品，经检测，成品谷维素含量96.38％，产品收率72.67％。
对比例6
其他步骤和实施例1相同，区别在于，步骤6)的洗涤中，省略乙酸乙酯的洗涤，直接进行乙醇和温水的洗涤。最终得到64.75kg谷维素成品，经检测，成品谷维素含量91.36％，产品收率72.23％。
上述详细说明是针对本发明其中之一可行实施例的具体说明，该实施例并非用以限制本发明的专利范围，凡未脱离本发明所为的等效实施或变更，均应包含于本发明技术方案的范围内。

Claims (10)

  1. 一种以含谷维素的皂脚为原料制备谷维素的方法，包括以下步骤：
    1)碱醇热溶：向原料加入乙醇，加热至50-60℃，调节体系至弱碱性，使原料溶解，得溶解液；
    2)保温精滤：保持步骤1)中的温度，使用精密过滤器将溶解液过滤；
    3)保温超滤膜分离：在50-60℃条件下，将滤液通过耐高温超滤膜进行膜分离，收集1000-5000分子量区段的膜分离液；
    4)保温脱色：向膜分离液中加入无机脱色剂，充分搅拌，过滤，得脱色液；
    5)酸化中和与过滤：用稀酸中和脱色液，冷却，放置，使沉淀完全析出，离心，收集离心沉淀；
    6)洗涤：向离心沉淀中依次加入乙酸乙酯、高浓度乙醇、温水进行洗涤，所述洗涤是向离心沉淀加入上述溶剂或溶液的洗涤液，充分搅拌混匀，离心得到离心沉淀，进行下一步的洗涤；
    7)干燥，将沉淀干燥，得到谷维素成品。
  2. 如权利要求1所述的方法，其特征在于，步骤1)至步骤4)中体系保持温度在50-60℃。
  3. 如权利要求1所述的方法，其特征在于，步骤1)所述乙醇是指浓度大于80％的乙醇，优选浓度大于85％的乙醇，更为优选地，采用浓度大于85％的乙醇；乙醇加入量为含谷皂基重量的5-10倍；所述加热是指加热温度至50-60℃；所述调节为弱碱性是指用碱性氢氧化物，比如氢氧化钠，氢氧化剂调节pH为8.5-9.5。
  4. 如权利要求1所述的方法，其特征在于，步骤2)中，过滤的温度控制在50℃-60℃；所述过滤采用带有折叠滤芯的精密过滤器，其中滤芯孔径为0.45μm，操作压力为0.2-0.4MPa。
  5. 如权利要求1所述的方法，其特征在于，步骤3)中，所述耐高温超滤膜材质为聚醚砜，可承受温度为80℃。
  6. 如权利要求1所述的方法，其特征在于，步骤3)中，所述膜的截留分子量设置为1000-5000，膜运行压力为1.0-2.0MPa。
  7. 如权利要求6所述的方法，其特征在于，所述膜分离的顺序是先过分子量为5000的超滤膜，收集膜下游液，即透过液，再将透过液过分子量为1000的超滤膜，收集膜 上游液，即截留液。
  8. 如权利要求1所述的方法，其特征在于，步骤4)中，所述脱色剂为活性白土和活性碳中的至少一种，脱色剂添加量为含谷维素的皂脚原料重量的3-6％；优选地，所述脱色剂为活性白土和活性炭按照质量比1-2:1-2的复配。
  9. 如权利要求1所述的方法，其特征在于，步骤6)中，使用高浓度乙醇和/或温水的洗涤步骤中，是向上一步的离心沉淀中加入50-70％的高浓度乙醇或温水，充分搅拌混匀，离心，再向离心机内分次加入剩余的高浓度乙醇或温水。
  10. 如权利要求1所述的方法，其特征在于，步骤6)中离心沉淀的质量和洗涤液，即乙酸乙酯、高浓度乙醇和温水的体积按照质量体积比(kg/L)为1-2:2-5:2-5:3-6进行，优选地，乙酸乙酯、高浓度乙醇和温水的体积按照质量体积比(kg/L)为1-1.3:2-3:3-4:3.5-5。
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