JP2011115147A - METHOD FOR PRODUCING RICE BRAN OIL ENRICHED WITH gamma-ORYZANOL, AND FOOD OR FEED PRODUCT ADDED WITH DEFATTED RICE BRAN OR RICE BRAN OIL OBTAINED BY THE METHOD - Google Patents

Abstract

A method of producing rice bran oil that can obtain defatted rice bran containing no harmful components as a by-product without using hexane as an extraction solvent for rice bran oil, and that further contains γ-oryzanol. provide.
[MEANS FOR SOLVING PROBLEMS] Ethanol (biomass ethanol) is added to rice bran instead of hexane, and polar substances such as γ-oryzanol, which is a functional component contained in rice bran, are extracted together with rice bran oil. After that, ethanol is distilled off to separate into oil and saccharide containing a functional component such as γ-oryzanol, and further by adding water-ethanol to the oil, γ-oryzanol, etc. Can be separated into an ethanol layer (alcohol-dissolving layer) containing a large amount of polar components and rice bran oil not containing the polar components. Thereafter, the rice bran oil (crude rice bran oil) enriched with functional components such as γ-oryzanol can be obtained by distilling off the solvent in the ethanol layer.
[Selection] Figure 1

Description

  The present invention relates to a method for producing rice bran oil that efficiently concentrates functional components, particularly γ-oryzanol, in extracting fats and oils from rice bran. The present invention also relates to a method for producing rice bran oil that can effectively use defatted rice bran, which is a by-product after extracting rice bran oil from rice bran, for livestock feed and food.

  Conventionally, functional components consisting of ferulic acid esters such as γ-oryzanol, ferulic acid, and tocotrienol contained in rice bran oil have been used as natural antioxidants for their oxidative stability and strong in vivo antioxidant activity. It has various physiological activities and is known to be used as a raw material for cosmetics and functional ingredients in foods and pharmaceuticals.

  For example, as an application field of γ-oryzanol to pharmaceuticals, an improvement effect on menopause is known (Patent Document 1). Moreover, the improvement effect with respect to a skin disease is known as an example of use of (gamma)-oryzanol for cosmetics (patent document 2). For use in foods, it is known that γ-oryzanol functions as an antioxidant (Patent Document 3).

  Further, various methods for producing rice bran oil for increasing the content of γ-oryzanol are also known. For example, a method for producing a rice bran oil using a special apparatus such as a vacuum steam distillation apparatus as in Patent Document 4, and Patent Document A production method using a weak alkaline aqueous solution as in No. 5, and a production method for extracting rice bran oil using hexane (solvent) as in Patent Document 6 are known.

  On the other hand, defatted rice bran, which is a by-product after extracting rice bran oil from rice bran, has been effectively used for livestock feed. For example, as in Patent Document 7, when effectively utilizing the defatted cocoon after hexane extraction as livestock feed, the defatted cocoon is subjected to superheated steam treatment (superheat treatment) in order to remove hexane (hazardous substance) remaining in the defatted cocoon. ) Is known to do.

JP-A-6-48940 JP-A-5-255037 JP 2002-142673 A JP-A-6-340889 JP 2000-119682 A JP 2002-238455 A JP 2008-54586 A

However, in the production method of Patent Document 4, the content of γ-oryzanol concentrated in rice bran oil is 2.0%. Also in the production method according to Patent Document 5, γ- concentrated in rice bran oil. Since the content of oryzanol is 2.0% or less, it has been desired to develop a production method capable of containing γ-oryzanol at a higher concentration. Furthermore, in the production method according to Patent Document 6, hexane (solvent) used as an extraction solvent during the production process is flammable and is concerned with safety, and is not preferable as a work environment. In addition, regarding the conversion of defatted culm after hexane extraction in Patent Document 7 above to a livestock feed, superheated steam treatment (superheat treatment) for removing hexane (hazardous substances) remaining in the defatted culm is performed, so that the manufacturing equipment is extra. It was necessary.
Therefore, in view of the above problems, the present invention can produce defatted rice bran containing no harmful components as a by-product without using hexane, and produces rice bran oil containing a higher concentration of γ-oryzanol. It is a technical problem to provide a method.

  In order to solve the above-mentioned problems, the production method of the present invention is characterized in that rice bran or defatted rice bran after squeezing the rice bran by a mechanical pressing method is added with ethanol instead of hexane, and the functionality contained in the rice bran or defatted porridge. Extracting polar substances such as γ-oryzanol, which is a component, with rice bran oil, and then distilling off ethanol to separate into oils and carbohydrates containing functional components such as γ-oryzanol, and further to the oil By adding water-ethanol, an ethanol layer (alcohol-dissolving layer) containing a large amount of polar components such as defatting acid and γ-oryzanol generated by hydrolysis from rice bran oil, and rice bran oil not containing the polar component, Can be separated. Thereafter, by removing the solvent in the ethanol layer, crude rice bran oil (rice bran oil) enriched with functional components such as γ-oryzanol can be obtained. Further, the rice bran oil containing γ-oryzanol at a high concentration and purified by subjecting the crude rice bran oil to a physical deoxidation to remove fatty acids and then performing a purification treatment such as a deodorizing treatment and a decoloring treatment. Can be obtained. In the above solution, the addition of the water-alcohol is a useful means that has a high effect of containing γ-oryzanol, which is a polar component, in rice bran oil at a high concentration.

  According to the method for producing rice bran oil of the present invention, rice bran oil containing a high concentration of γ-oryzanol can be obtained, and useful carbohydrates such as inositol contained in rice bran can also be obtained by separation at the same time. .

  In addition, the production method of the present invention is a method of using ethanol without using hexane as an extraction solvent, and defatted soot as a by-product is a component that is not harmful even if ethanol remains a little. It can be used as livestock feed and edible, and there is no need to provide a processing device for removing the solvent. Moreover, the rice bran oil containing high concentration of γ-oryzanol obtained by the production method of the present invention can be added to food materials and used for health foods.

  Furthermore, since the manufacturing method of the present invention does not use hexane in terms of work environment, there is no concern about ignition and the like, and safety is ensured. In addition, the use of hexane is derived from petroleum, leading to an increase in carbon dioxide gas and exhaustion of petroleum resources. However, the use of ethanol in the present invention is a resource that ethanol can be recycled, and carbon dioxide is generated. However, it is preferable in terms of the global environment because it can be absorbed by plants and recovered again as alcohol.

  In the present invention, the extraction solvent is biomass ethanol produced from raw materials (such as rice bran, sharpened soup, crushed rice, etc.) made of starch produced in the rice mill, so that the by-products in the rice mill are useful. can do.

The flow of the manufacturing method of this invention is shown.

  In practicing the present invention, rice bran need not be specially treated, but can be pretreated. In order to inactivate the lipase that causes fatty acid generation, it may be heated to 70 ° C. or higher. The rice bran that is brought in is immersed in alcohol, so the lipase is deactivated. It is preferable to treat rice bran as much as possible from brown rice as early as possible. When ordinary rice bran is left at room temperature, the rice bran oil is decomposed into fatty acids, leading to a decrease in the yield of rice bran oil. Most preferably, it is extracted at a rice mill.

  Ethanol used for extraction of rice bran oil may be one produced by a synthetic method, but it is preferable to use biomass ethanol produced by a fermentation method. In particular, it is preferable to use high-concentration biomass ethanol obtained by purifying and concentrating biomass ethanol water obtained by fermentation using crushed rice or sugar contained in rice bran. The purity of biomass ethanol is preferably 99.5% to 95%. In the biomass ethanol, when the water content increases, the yield of rice bran oil decreases. Therefore, when extracting oil from rice bran, it is preferable to use 95% or more.

  A flow of the manufacturing method of the present invention will be described (see FIG. 1). In the production method of the present invention, as a raw material, defatted rice bran (residual oil ratio: 10 to 8%) after squeezing rice bran by a rice bran or a mechanical pressing method (pressing type oil press), or oil by a mechanical pressing method It is preferable to use the residue after squeezing the rice seed (soybean, rapeseed, cotton, peanut, sunflower seed, sesame, etc.). Here, rice bran is used as a raw material. First, the biomass ethanol is added to the rice bran raw material and held for an arbitrary period of time, and then filtered to extract polar substances and functional components such as γ-oryzanol contained in the rice bran together with rice bran oil (lipid). (Extraction of lipid extract). By this extraction, a by-product defatted soot is obtained as a residue. Thereafter, by distilling off biomass ethanol contained in the lipid extract, it can be separated into an oil and a saccharide containing a functional component such as γ-oryzanol. Next, by adding water-biomass ethanol to the oil component, an ethanol layer (alcohol-dissolving layer <biomass ethanol>) containing a large amount of polar components such as defatting acid and functional component γ-oryzanol, and Rice bran oil that does not contain fatty acids can be separated. At the same time, a saccharide composed of inositol or the like can be separated as a precipitate layer. Subsequently, the rice bran oil containing the functional component γ-oryzanol and the like in a high concentration by distilling off the fatty acid by a solvent (ethanol) and vacuum distillation or the like of the ethanol layer (hereinafter, “crude rice bran” for convenience of explanation) Oil ”or“ functional component-enriched rice bran oil ”). In addition, since it is difficult to take out the said saccharide | sugar, it is good to add water and dissolve and take out.

  The water content in the water-biomass ethanol is preferably in the range of 2 to 30%. That is, when the water content of the water-biomass ethanol is less than 2% (low water content), rice bran oil containing almost no fatty acid and ethanol containing functional components such as fatty acid and γ-oryzanol as polar components Separation from the layer (hydroalcoholic layer) does not occur, and a concentrate such as γ-oryzanol cannot be obtained. Conversely, when the amount of water exceeds 30% (the amount of water is high), the amount of rice bran oil increases, and the rice bran oil to be extracted into the ethanol layer is hardly extracted. -Concentrated rice bran oil such as oryzanol cannot be obtained.

  The rice bran oil is an oil having a low fatty acid content, and a small amount of residual alcohol is distilled off by distillation, and it is easily converted to refined rice bran oil through degumming, omission, deoxidation, and decolorization treatments more easily than ordinary rice bran oil. be able to. In addition, for the crude rice bran oil (functional component-enriched rice bran oil), functions such as γ-oryzanol purified by removing the concentrated fatty acid by physical deoxidation such as vacuum distillation and then performing leakage and decoloring treatments. It can be made into a concentrated rice bran oil. In addition, carbohydrates can be purified by removing moisture.

  Functional rice-enriched rice bran oil such as rice bran oil and γ-oryzanol obtained by the present invention can be used as ordinary salad oil. Moreover, the obtained saccharide | sugar can be used for sweeteners and aquaculture as a normal functional component. The functional component-enriched rice bran oil can be used as a supplement by filling soft capsules for health foods, or as rice bran oil for mayonnaise. Furthermore, the defatted rice bran (degreased rice bran) after extracting the rice bran oil (lipid) from the rice bran is the one after ethanol extraction instead of hexane extraction, so safety is ensured and alcohol is removed by drying. It can be used later for food. As the use of the defatted rice, it can be mixed with bread or noodles or added to foods such as cookies. Moreover, a rice bran protein component is extracted from the defatted rice bran, and the rice bran protein component can be used as a material for various processed foods and the like, and is safe.

  Here, the ethanol (extraction solvent) used when extracting the rice bran oil in the present invention will be described. The ethanol used in the present invention may be ethanol of any kind, such as one produced by a synthesis method (synthesized from petroleum or natural gas) or one produced by a fermentation method as described above, More preferably, biomass ethanol produced by fermentation is better. Biomass ethanol, for example, can be produced by fermentation and distillation using biomass such as sugar cane and corn as a raw material, and can be produced using a by-product consisting of starch produced in a rice mill. Examples of the by-products include polished rice, broken rice, rice bran, and washed rice drainage that are selected as defective due to partial coloring on the surface. Rice bran is a by-product that is produced when rice is milled in a rice mill, and the production of biomass ethanol using the by-product (rice bran) eliminates the need to purchase special raw materials from the outside, and by-products (rice bran) in the rice mill It is useful in that it can be used effectively. In addition, when the rice mill has a processing process for washing-free rice, the rice washing wastewater (rice sharpening juice) is produced. This rice washing wastewater can also be used as a raw material for producing biomass ethanol. This is also useful in terms of points.

  A specific description of the method for producing biomass ethanol from the by-product in the rice mill is not particularly given. For example, Japanese Patent Application Laid-Open No. 2007-325564 and Japanese Patent Application Laid-Open No. 2009-50195 by the present applicant. Refer to it.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these.

  In a 2 L four-necked flask equipped with a stir bar, thermometer, reflux tube and nitrogen blowing tube, 2000 g of rice bran is charged, 4000 ml of 99% ethanol is added, and the mixture is stirred at 60 ° C. for 2 hours. After stirring, suction filtration is performed using No2 filter paper, and the ethanol layer (lipid extract) is taken out. Again, the filtered rice bran is returned to the four-necked flask, 3200 ml of 99% ethanol is added, and the mixture is stirred at 60 ° C. for 2 hours. Thereafter, suction filtration is performed using No2 filter paper to obtain an ethanol layer (lipid extract). By this suction filtration, a by-product degreased residue is obtained as a residue.

  Next, the ethanol layer (lipid extract) is collected in a 2 L eggplant flask, and ethanol is repeatedly distilled off by a rotary evaporator to obtain 359.4 g of an oil layer (oil), which is transferred to a separating funnel. The oil layer and the white insoluble matter in the 2 L eggplant flask are separated, and 37.4 g of the white insoluble matter is washed with 200 ml of ethanol and collected by filtration. Add 600 ml of 10% water-ethanol solution to the separated oil layer. Fully penetrate the oil layer transferred to the separatory funnel and let stand. Next, the oil layer (A) separated at the bottom of the funnel is extracted to separate the ethanol layer. Ethanol in the oil layer (A) was distilled off to obtain 273.2 g of rice bran oil. Subsequently, ethanol is distilled off from the ethanol layer to obtain 52.4 g of an oil layer (B). The contents of γ-oryzanol in the oil layer (A) and the oil layer (B) were 1.6% and 1.7%, respectively. The acid value was 21.3 for crude rice bran oil, 2.1 for the oil layer (A), and 117.3 for the oil layer (B).

  Fatty acid was distilled while adding 52.4 g of the oil layer (B) to 100 ml of a flask equipped with a thermometer and heating with a vacuum pump. Vacuum distillation was carried out under heating at a vacuum degree of 2 mmHg and 200 ° C. The distillate was 27.3 g (acid value 181.2, γ-oryzanol 0.1%) and the residual oil was 23.6 g (acid value 13.8, γ-oryzanol 3.5%). As a result, rice bran oil enriched with γ-oryzanol was obtained.

Analysis of γ-oryzanol was carried out with HPLC column: ODS (150 mm × 4.6 mmφ) eluent: 30% water-methanol 1 ml / min detector: UV 315 nm.
In addition, the analysis of the acid value was performed using the standard fats and oils analysis test method edited by the Japan Oil Chemical Society.

  After adding 400 ml of 99.5% ethanol to 200 g of rice bran, the mixture is stirred for 2 hours at 50 ° C. in a 1 L Erlenmeyer flask, and then filtered to remove the ethanol layer (lipid extract). The ethanol layer (filtrate) was placed in an eggplant flask and ethanol was removed by an evaporator to obtain 41.79 g (including saccharides) of an oil layer (oil). Further, rice bran is added to a 1 L Erlenmeyer flask, 400 ml of 99.5% ethanol is added, and the mixture is stirred at 50 ° C. for 2 hours. After this stirring, filtration is performed to obtain a lipid extract. By the filtration, a by-product defatted soot is obtained as a residue.

  Next, the lipid extract was added to the eggplant flask and allowed to flow out with an evaporator to obtain an oil layer (oil content). The oil layer weighed 49.71 g. Subsequently, 50 ml of 10% water-ethanol was added to this oil layer, whereby it was possible to separate into a sediment layer (carbohydrate), an oil layer (oil content), and an ethanol layer (alcohol-dissolving layer). The weight of each solution after evaporation of the solvent was 13.43 g of sediment layer (carbohydrate), 18.55 g of oil layer, 16.03 g of ethanol layer (alcohol-dissolving layer) (total 48.01 g: loss 1.70 g). ). Table 1 shows the contents of each weight and γ-oryzanol.

  500 ml of 99.5% ethanol was added to 200 g of rice bran, and the mixture was stirred in a 1 L Erlenmeyer flask at 50 ° C. for 2 hours and filtered. This filtrate (lipid extract) was placed in an eggplant flask and ethanol was distilled off by an evaporator to obtain an oil layer (oil) (including carbohydrates). Next, rice bran was further added to a 1 L Erlenmeyer flask, 500 ml of 99.5% ethanol was added, and the mixture was extracted at 50 ° C. for 2 hours and filtered to obtain a filtrate. These filtrates (lipid extracts) were added to the eggplant flask and allowed to flow out with an evaporator to obtain an oil layer (oil). The oil layer weighed 44.82 g. Next, 160 ml of 6.25% water-ethanol was added to the oil layer, and separated into a precipitate, an oil layer, and an ethanol layer (alcohol-dissolving layer). The weight of each liquid after evaporation of the solvent was 12.75 g of a sediment layer (saccharide), 13.05 g of an oil layer, and 33.3 g of an ethanol layer (alcohol-dissolving layer). Table 2 shows each weight and the amount of γ-oryzanol.

  The functional component-enriched rice bran oil obtained by the present invention can be used as a functional food for soft capsules, functional mayonnaise, and the like.

Claims (6)

A lipid extraction step of extracting lipids with ethanol from the defatted rice cake after squeezing the rice bran by a rice bran or mechanical pressing method,
An oil separation step in which ethanol is removed from the lipid extracted in the lipid extraction step and separated into an oil and a carbohydrate;
A rice bran oil separation step in which water-ethanol is mixed with the oil separated in the oil separation step and separated into an ethanol layer containing a polar component such as γ-oryzanol and rice bran oil,
Γ-oryzanol-enriched rice bran oil separation step for removing ethanol from the ethanol layer separated in the rice bran oil separation step and separating rice bran oil containing a polar component such as γ-oryzanol at a high concentration;
A method for producing rice bran oil enriched with γ-oryzanol, characterized by sequentially passing through the following steps.   The method for producing rice bran oil enriched in γ-oryzanol according to claim 1, wherein the water content in the water-ethanol is in the range of 2% to 30%.   The method for producing rice bran oil enriched in γ-oryzanol according to claim 1 or 2, wherein ethanol used in the lipid extraction step is biomass ethanol.   The rice bran oil enriched with γ-oryzanol according to claim 3, wherein the biomass ethanol is produced from a by-product made of starch such as rice bran, broken rice, and washed rice wastewater discharged from a rice mill. Manufacturing method.   A food or feed comprising the defatted rice bran obtained in the method for producing rice bran oil enriched with γ-oryzanol according to claim 1. A food comprising the rice bran oil enriched in γ-oryzanol obtained by the method for producing rice bran oil enriched in γ-oryzanol according to claim 1.

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