JP4863532B1 - Method for separating and producing sesamin - Google Patents
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- PEYUIKBAABKQKQ-AFHBHXEDSA-N (+)-sesamin Chemical compound C1=C2OCOC2=CC([C@H]2OC[C@H]3[C@@H]2CO[C@@H]3C2=CC=C3OCOC3=C2)=C1 PEYUIKBAABKQKQ-AFHBHXEDSA-N 0.000 title claims abstract description 110
- PEYUIKBAABKQKQ-UHFFFAOYSA-N epiasarinin Natural products C1=C2OCOC2=CC(C2OCC3C2COC3C2=CC=C3OCOC3=C2)=C1 PEYUIKBAABKQKQ-UHFFFAOYSA-N 0.000 title claims abstract description 110
- VRMHCMWQHAXTOR-CMOCDZPBSA-N sesamin Natural products C1=C2OCOC2=CC([C@@H]2OC[C@@]3(C)[C@H](C=4C=C5OCOC5=CC=4)OC[C@]32C)=C1 VRMHCMWQHAXTOR-CMOCDZPBSA-N 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000007787 solid Substances 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 239000008159 sesame oil Substances 0.000 claims abstract description 32
- 235000011803 sesame oil Nutrition 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000000746 purification Methods 0.000 claims abstract description 27
- 238000011282 treatment Methods 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 230000001877 deodorizing effect Effects 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 116
- 239000013078 crystal Substances 0.000 claims description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 21
- 238000004090 dissolution Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- 238000001953 recrystallisation Methods 0.000 claims description 11
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- 241000207961 Sesamum Species 0.000 description 9
- 235000003434 Sesamum indicum Nutrition 0.000 description 9
- 238000001256 steam distillation Methods 0.000 description 9
- 238000004332 deodorization Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 238000007796 conventional method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 229930182558 Sterol Natural products 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 235000003702 sterols Nutrition 0.000 description 5
- 150000003432 sterols Chemical class 0.000 description 5
- 238000004042 decolorization Methods 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000199 molecular distillation Methods 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229930013686 lignan Natural products 0.000 description 2
- 150000005692 lignans Chemical class 0.000 description 2
- 235000009408 lignans Nutrition 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- -1 sesamorin Chemical compound 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- UIOFUWFRIANQPC-JKIFEVAISA-N Floxacillin Chemical compound N([C@@H]1C(N2[C@H](C(C)(C)S[C@@H]21)C(O)=O)=O)C(=O)C1=C(C)ON=C1C1=C(F)C=CC=C1Cl UIOFUWFRIANQPC-JKIFEVAISA-N 0.000 description 1
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 description 1
- LUSZGTFNYDARNI-UHFFFAOYSA-N Sesamol Natural products OC1=CC=C2OCOC2=C1 LUSZGTFNYDARNI-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 235000013402 health food Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000003908 liver function Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000010517 refined sesame oil Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- KQRXQIPRDKVZPW-ISZNXKAUSA-N sesaminol Chemical compound C1=C2OCOC2=CC([C@H]2OC[C@H]3[C@@H]2CO[C@@H]3C2=CC=3OCOC=3C=C2O)=C1 KQRXQIPRDKVZPW-ISZNXKAUSA-N 0.000 description 1
- KQRXQIPRDKVZPW-UHFFFAOYSA-N sesaminol Natural products C1=C2OCOC2=CC(C2OCC3C2COC3C2=CC=3OCOC=3C=C2O)=C1 KQRXQIPRDKVZPW-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000002328 sterol group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Abstract
【課題】脱臭スカムという廃棄物から、高純度で効率的に、かつ簡単、安価にセサミン類を分離製造すること。
【解決手段】セサミン類を分離製造する方法において、ゴマ油製造の脱臭工程で生じる脱臭スカムを静置し、その上層の液状部分を除いて得た固形部分を原料とし、原料に一種類の溶剤による温度の異なる二回以上の処理だけからなる洗浄・精製工程を施してセサミン類を分離製造することを特徴とする方法。
【選択図】 図１[PROBLEMS] To separate and manufacture sesamins from waste called deodorized scum at high purity, efficiently, simply and inexpensively.
In a method for separating and producing sesamins, a deodorized scum produced in a deodorizing step of sesame oil production is allowed to stand, and a solid part obtained by removing a liquid part in an upper layer is used as a raw material, and the raw material is obtained by using one kind of solvent. A method comprising separating and producing sesamin by performing a washing / purification process consisting of only two or more treatments at different temperatures.
[Selection] Figure 1
Description
本発明は、セサミン類の分離製造方法に関する。より具体的には、ゴマ油を減圧下に水蒸気蒸留して得られるセサミン類を含有する留出物から、一種類の溶剤による処理温度の異なる複数の処理だけで、セサミン類を高純度で効率的に、かつ容易、安価に分離製造する方法に関する。
ここで、本発明において、セサミン類は、セサミンおよび／またはエピセサミンを指す。
The present invention relates to a method for separating and producing sesamin. More specifically, sesamin can be purified with high purity and efficiency from a distillate containing sesamin obtained by steam-distilling sesame oil under reduced pressure only by multiple treatments with different treatment temperatures using a single solvent. Further, the present invention relates to a method for separating and manufacturing easily and inexpensively.
Here, in the present invention, sesamin refers to sesamin and / or episesamin.
ゴマ種子には様々な種類のゴマリグナンが存在しており、通常、セサミンが０．１〜０．５重量％程度含まれる他、セサモール、セサモリン、セサミノール等が含有されていることが知られている。また、ゴマ種子から搾油した未精製ゴマ油にはゴマリグナンとしてセサミンが０．５〜１．０重量％程度含有されている。
さらに、ゴマ油を活性白土等で処理を行うと、セサミンの他にセサミンの光学的転位生成物で、本来のゴマ種子には存在していないエピセサミンが生成されることも知られている（特許文献１）。
There are various types of sesame seeds in sesame seeds, and it is usually known that sesamin is contained in an amount of about 0.1 to 0.5% by weight, and that sesamol, sesamorin, sesaminol and the like are contained. Yes. In addition, unrefined sesame oil extracted from sesame seeds contains about 0.5 to 1.0% by weight of sesamin as sesame lignan.
Furthermore, when sesame oil is treated with activated clay or the like, it is also known that episesamin, which is not present in the original sesame seeds, is produced in addition to sesamin, an optical rearrangement product of sesamin (patent document) 1).
これらセサミン等を主成分とするゴマリグナンには、ピレスリン系殺虫剤に対して強い共力効果（特許文献１）、Δ５―不飽和化酵素阻害（特許文献２）、肝機能改善（特許文献３）、片頭痛の抑制ないし予防治療（特許文献５）、アルコール代謝の促進、血中過酸化脂質の生成抑制、発癌の抑制など、多くの生理活性機能をもつ重要な物質（特許文献６）であり、これらの生理活性機能に基づく健康食品としての有用性が期待され、その重要性が増している。 These sesame lignans mainly composed of sesamin and the like have a strong synergistic effect on pyrethrin insecticides (Patent Document 1), Δ 5 -desaturase inhibition (Patent Document 2), liver function improvement (Patent Document 3) ), Mitigation or prevention treatment (Patent Document 5), promotion of alcohol metabolism, suppression of lipid peroxide formation in blood, suppression of carcinogenesis, etc. Therefore, it is expected to be useful as a health food based on these physiologically active functions, and its importance is increasing.
ゴマ油、ゴマ種子やゴマ粕からセサミン類を分離する方法としては、例えば、ゴマ油とは実質的に非混和性であり、かつセサミン類を抽出、溶解することができる種々の有機溶剤（アセトン、メチルエチルケトン、ジエチルケトン、メタノール、エタノール等）を用いて、抽出、濃縮し、溶剤画分から溶剤を蒸発除去してセサミン類を得る方法（抽出分離法）などが知られている（特許文献２、３）。 Examples of methods for separating sesamin from sesame oil, sesame seeds and sesame seeds include various organic solvents (acetone, methyl ethyl ketone) that are substantially immiscible with sesame oil and that can extract and dissolve sesamin. , Diethyl ketone, methanol, ethanol, etc.) are used to extract and concentrate and evaporate and remove the solvent from the solvent fraction (extraction separation method) (Patent Documents 2 and 3). .
また、ゴマ油を減圧下に水蒸気蒸留して得られるセサミン類を含有する留出物、例えばゴマ油の精製（脱臭）工程で生じる脱臭留出物である脱臭スカムなどからセサミン等を分離する方法も種々知られており、例えば、（１）ゴマ油脱臭留出物をエタノール濃度５５％以上のエタノール−水混合溶液と混合して、その混合系から溶液画分を分離し、分離した該溶液画分を吸着剤で吸着処理した後、該吸着剤から脱着溶出させ、セサミン、セサモリンを得る方法（特許文献４）、（２）ゴマ油を減圧下に水蒸気蒸留し、その留出物をさらに分子蒸留するか、または、（３）該留出物をエステル化反応及び／またはエステル交換反応させた後、その反応処理物をさらに分子蒸留して、セサミン、エピセサミンを得る方法（特許文献１、５）、（４）ゴマ油を減圧下に水蒸気蒸留し、その留出物を水、水性溶媒またはこれらの混合溶媒と混合した後、その混合系中にてアルカリ存在下にセサミン類を析出させる方法（特許文献５、６）、さらに、（５）ゴマ油を減圧下に水蒸気蒸留し、その留出物を４０重量％以上のエタノールを含有するエタノール水溶液と混合して、その混合系から溶液区分を分離した後、該溶液区分にアルカリを添加してセサミン類を析出させる方法（特許文献５）などが知られている。 There are also various methods for separating sesamin and the like from a distillate containing sesamin obtained by steam distillation of sesame oil under reduced pressure, such as deodorized scum, which is a deodorized distillate produced in the purification (deodorization) step of sesame oil. For example, (1) a sesame oil deodorized distillate is mixed with an ethanol-water mixed solution having an ethanol concentration of 55% or more, a solution fraction is separated from the mixed system, and the separated solution fraction is After adsorbing with adsorbent, desorbing and eluting from the adsorbent to obtain sesamin and sesamorin (Patent Document 4), (2) Whether sesame oil is steam distilled under reduced pressure, and the distillate is further molecularly distilled. Or (3) A method of obtaining sesamin and episesamin by subjecting the distillate to esterification and / or transesterification, and then subjecting the reaction product to molecular distillation to obtain sesamin and episesamin (Patent Documents 1 and 5), 4 Sesame oil is subjected to steam distillation under reduced pressure, the distillate is mixed with water, an aqueous solvent or a mixed solvent thereof, and then sesamins are precipitated in the mixed system in the presence of alkali (Patent Documents 5 and 6). ) And (5) steam-distilled sesame oil under reduced pressure, mix the distillate with an aqueous ethanol solution containing 40% by weight or more of ethanol, separate the solution section from the mixed system, There is known a method (Patent Document 5) in which sesamin is precipitated by adding an alkali to the section.
また、抽出分離、分子蒸留、析出または脱着溶出後に、更に再結晶処理を施すことによって、セサミン類の濃度を高めることができることも知られているところである（特許文献１〜６参照）。 It is also known that the concentration of sesamins can be increased by further performing a recrystallization treatment after extraction separation, molecular distillation, precipitation or desorption elution (see Patent Documents 1 to 6).
しかしながら、特許文献１には、従来のゴマ油等から溶剤によるセサミン類の抽出分離法について、従来、各種の有機溶媒を用いて、セサミン類をゴマ油から直接抽出する方法が提案されているとして、有機溶媒として、メタノールを用いる例、アセトン／水を用いる例、冷却した石油エーテルを用いる例、アセトニトリルを用いる例、γ−ブチロラクトンを用いる例等を例示して、「これらの従来法には、１）得られる抽出物がセサミン類の他にセサモリンやグリセライド等を相当量含有しているため、該抽出物におけるセサミン類の濃度が低い、２）ゴマ油のセサミン類含有率は多くても１重量％程度であるため、有機溶媒の使用量が多い、３）使用した有機溶媒を留去するためのエネルギーコストが膨大である、４）ゴマ油中に有機溶媒の残留が避けられないため、特に上記のような有機溶媒を使用する場合には、食品衛生上の面で実際上、該ゴマ油を食用に供することができなくなってしまう、という課題がある。」と記載している。 However, in Patent Document 1, as a conventional method for extracting and separating sesamin from a sesame oil using a solvent, a method for directly extracting sesamin from sesame oil using various organic solvents has been proposed. Examples of using methanol, an example using acetone / water, an example using cooled petroleum ether, an example using acetonitrile, an example using γ-butyrolactone, etc. Since the obtained extract contains a considerable amount of sesamin, glyceride, etc. in addition to sesamin, the concentration of sesamin in the extract is low. 2) The content of sesamin in sesame oil is at most about 1% by weight. Therefore, the amount of organic solvent used is large. 3) The energy cost for distilling off the used organic solvent is enormous. 4) Organic solvent is dissolved in sesame oil. In particular, when using an organic solvent as described above, there is a problem that the sesame oil cannot actually be used for food in terms of food hygiene. It is described.
また、特許文献６には、ゴマ油を減圧下に水蒸気蒸留して得られるセサミン類を含有する留出物を原料とする従来の方法について、「特許文献１の従来法には、分子蒸留それ自体が厄介である上に、分子蒸留を効率良く行なうためには留出物の前処理が必要であり、しかも留出物からのセサミン類の回収率が低いという欠点がある。また特許文献４の従来法には、吸着処理で回収されるセサミン類の純度が低く、純度を高めようとすると、その精製が必要であり、結果的に留出物からのセサミン類の回収率も低くなってしまうという欠点がある。」と記載されている。 Patent Document 6 discloses a conventional method using a distillate containing sesamin obtained by steam-distilling sesame oil under reduced pressure as “the conventional method of Patent Document 1 includes molecular distillation itself. In addition, in order to efficiently perform molecular distillation, pretreatment of the distillate is required, and the recovery rate of sesamins from the distillate is low. In the conventional method, the purity of sesamin recovered by the adsorption treatment is low, and if it is attempted to increase the purity, the purification is necessary, and as a result, the recovery rate of sesamin from the distillate also decreases. ”Is described.”
本発明は上述の如き従来法の問題点を解決する新たなセサミン類の分離製造方法、すなわちセサミン類を高純度で効率的に、かつ簡単、安価に分離製造する方法を提供することを課題とするものである。 It is an object of the present invention to provide a new method for separating and producing sesamin that solves the problems of the conventional methods as described above, that is, a method for separating and producing sesamin in high purity, efficiently, simply and inexpensively. To do.
本発明者は、鋭意研究した結果、ゴマ油を減圧下に水蒸気蒸留して得られるセサミン類を含有する留出物、例えばゴマ油製造の脱臭工程で生じる脱臭スカムを静置し、その上層の液状部分を除いて得た固形部に、含水量の低いエタノールを作用させると、意外にも、その処理温度によっては、セサミン類を溶解させずに混在するオイルや高級脂肪酸やステロールなどの不純物だけを抽出除去する溶剤として使用できることを発見した。この知見は、従来法におけるセサミン類の分離が、有機溶剤（アセトン、メチルエチルケトン、ジエチルケトン、メタノール、エタノール等）、または有機溶剤−水混合溶液を用いて、セサミン類自体を抽出、溶解して行うものであったことからは予想外のことであった。そこで、この知見を基に多くの実験、検討を経て、ただ一種類の溶剤を用いて、処理温度の異なる複数の固液分離処理をするだけで、セサミン類を高純度で効率的に、かつ容易、安価に分離製造する方法を見出し、本発明を完成するに到った。 As a result of diligent research, the present inventor has left a distillate containing sesamin obtained by steam distillation of sesame oil under reduced pressure, for example, a deodorizing scum produced in a deodorizing step of sesame oil production, and a liquid portion of the upper layer. Surprisingly, when ethanol with low water content is allowed to act on the solid part obtained by removing only oil, impurities such as mixed oils, higher fatty acids and sterols are extracted without dissolving sesamin depending on the processing temperature. It was discovered that it can be used as a solvent to remove. This finding is that sesamin separation in the conventional method is performed by extracting and dissolving sesamin itself using an organic solvent (acetone, methyl ethyl ketone, diethyl ketone, methanol, ethanol, etc.) or an organic solvent-water mixed solution. It was unexpected from what was. Therefore, through many experiments and examinations based on this knowledge, sesamin can be obtained with high purity and efficiency simply by performing multiple solid-liquid separation treatments with different treatment temperatures using only one type of solvent. The inventors have found a method for separating and manufacturing easily and inexpensively, and have completed the present invention.
すなわち、本発明は下記１〜８のセサミンを分離製造する方法に関する。
１．セサミン類を分離製造する方法において、ゴマ油製造の脱臭工程で生じる脱臭スカムを静置し、その上層の液状部分を除いて得た固形部を原料とし、原料に一種類の溶剤による温度の異なる二回以上の処理だけからなる洗浄・精製工程を施してセサミン類を分離製造すること、温度の異なる二回以上の処理が、少なくとも常温で行う一回目の処理と、５０℃以上の温度で行う二回目の処理からなること、および上記溶剤は、エタノールが９０容量％以上のエタノールであることを特徴とする方法。
２．上記溶剤は、エタノールが９５容量％以上のエタノールである、上記１に記載のセサミン類を分離製造する方法。
３．洗浄・精製工程に続きさらに溶解・濾過、再結晶の各工程を施こすことを特徴とする上記１または２に記載のセサミン類を分離製造する方法。
４．溶解・濾過工程が、洗浄・精製工程と同一または異なる溶剤を用いて、沸点溶解し、温時濾過して濾液を得る工程である、上記３に記載のセサミン類を分離製造する方法。
５．洗浄・精製工程と異なる溶剤が、アセトンとエタノールの混合溶剤、またはアセトンと水の混合溶剤である、上記４に記載のセサミン類を分離製造する方法。
６．再結晶工程が、溶解・濾過工程で得た濾液の液温を下げて結晶を析出させ分離して溶剤除去前結晶（以後、「ウエット結晶」と略称する。）を得る工程である、上記３ないし５のいずれかに記載のセサミン類を分離製造する方法。
７．続いて、乾燥、粉砕、篩選別、混合の少なくとも一つの工程を施すことを特徴とする、上記１ないし６のいずれかに記載のセサミン類を分離製造する方法。
８．セサミン類がセサミンおよびエピセサミンである上記１ないし７のいずれかに記載のセサミン類を分離製造する方法。
That is, this invention relates to the method of isolate | separating and manufacturing the following 1-8 sesamin.
1. In the method for separating and producing sesamin, the deodorized scum generated in the deodorizing step of sesame oil production is left standing, and the solid part obtained by removing the liquid part of the upper layer is used as a raw material. Separating and producing sesamin by performing a washing / purifying process consisting of only one or more treatments, and two or more treatments at different temperatures are performed at least at the first treatment and at a temperature of 50 ° C. or more. The method is characterized in that it comprises a second treatment, and the solvent is ethanol containing 90% by volume or more of ethanol .
2 . 2. The method for separating and producing the sesamin according to 1 above, wherein the solvent is ethanol having an ethanol content of 95% by volume or more.
3 . 3. The method for separating and producing sesamins according to 1 or 2 above, wherein each step of dissolution, filtration and recrystallization is further performed after the washing and purification step.
4 . 4. The method for separating and producing sesamin according to 3 above, wherein the dissolution / filtration step is a step of dissolving at boiling point using the same or different solvent as the washing / purification step and obtaining a filtrate by warm filtration.
5 . 5. The method for separating and producing sesamins according to 4 above, wherein the solvent different from the cleaning / purification step is a mixed solvent of acetone and ethanol or a mixed solvent of acetone and water.
6 . Recrystallization step, dissolution and filtration step in resulting filtrate solution temperature was lowered to precipitate the crystals were separated solvent removed before crystallization (hereinafter. To be abbreviated as "wet crystals") to give compound, the 3 A method for separating and producing the sesamin according to any one of 5 to 5 .
7 . Subsequently, the method for separating and producing the sesamin according to any one of 1 to 6 above, wherein at least one step of drying, pulverization, sieving, and mixing is performed.
8 . 8. The method for separating and producing sesamin according to any one of 1 to 7 above, wherein the sesamin is sesamin and episesamin.
本発明により、ゴマ油を減圧下に水蒸気蒸留して得られるセサミン類を含有する留出物から簡単かつ安価にセサミン類を高純度かつ高収率で分離製造できる。また、原料として、通常廃棄されるゴマ油精製工程の脱臭工程で生じる脱臭留出物（脱臭スカム）を有効利用することができる。
より詳細には、原料としてゴマ油を減圧下に水蒸気蒸留して得られるセサミン類を含有する留出物、例えば精製ゴマ油製造の脱臭工程で生じる脱臭スカムを静置し、その上層の液状部分を除いて得た固形部を用いること、その原料に対して簡単かつ安価な手段を施すだけで、すなわち、ただ一種類の溶剤を用いて、処理温度を変えて複数の固液分離処理を施すだけで、セサミン類を高純度かつ高収率で分離製造できるのである。
According to the present invention, sesamins can be separated and produced with high purity and high yield from a distillate containing sesamins obtained by steam distillation of sesame oil under reduced pressure. Moreover, the deodorized distillate (deodorizing scum) produced in the deodorizing process of the sesame oil refining process normally discarded can be used effectively as a raw material.
More specifically, a distillate containing sesamin obtained by steam-distilling sesame oil as a raw material under reduced pressure, for example, deodorizing scum generated in the deodorizing process of refined sesame oil production, is allowed to stand, and the upper liquid portion is removed. Using the solid part obtained in this way, simply applying simple and inexpensive means to the raw material, that is, using only one type of solvent, changing the processing temperature and performing multiple solid-liquid separation processes Sesamin can be separated and produced with high purity and high yield.
［セサミン類］
本発明は、簡単かつ安価にセサミン類を高純度かつ高収率で分離製造できる。
本発明において、セサミン類は、セサミンおよび／またはエピセサミンを指す。セサミン類中のセサミンおよびエピセサミンのそれぞれの含有量は、用いる原料に由来する、すなわち、脱色の精製工程で採用する精製条件に依存する。例えば、脱色処理を軽度に行うか、または行わないと、セサミン類中のセサミンの含有量を高くすることができる。
実施例ではセサミン類中のセサミン含有量が９５％以上の純度のものが得られた。
また、本発明で分離製造されるセサミン類は、９０％以上の純度、特に９５％以上の純度であることが好ましい。
分離製造されるセサミン類の形態は、特に限定されないが、必要に応じて、定法により、固体、粉末とすることができる。
[Sesamin]
INDUSTRIAL APPLICABILITY According to the present invention, sesamins can be separated and produced with high purity and high yield simply and inexpensively.
In the present invention, sesamin refers to sesamin and / or episesamin. The contents of sesamin and episesamin in sesamin are dependent on the purification conditions derived from the raw material used, that is, employed in the decolorization purification step. For example, the content of sesamin in sesamins can be increased if the decolorization treatment is performed lightly or not.
In the examples, sesamin content in sesamin was obtained with a purity of 95% or more.
Further, the sesamin separated and produced in the present invention preferably has a purity of 90% or more, particularly 95% or more.
Although the form of sesamin produced separately is not specifically limited, If necessary, it can be made into a solid and a powder by a conventional method.
［原料としてのゴマ油製造の脱臭工程で生じる脱臭スカム］
本発明で用いる原料は、ゴマ油を減圧下に水蒸気蒸留時に留出するものである。水蒸気蒸留時の温度及び圧力条件により、様々な組成の留出物が得られるが、これらの留出物のうちで、セサミン類を含有する留出物、好ましくはセサミン類をできるだけ多く含有する留出物を用いる。公知の温度及び圧力条件を採用してかかる好ましい留出物を得ることができる。
[Deodorization scum produced in the deodorization process of sesame oil production]
The raw material used in the present invention is obtained by distilling sesame oil under reduced pressure during steam distillation. Depending on the temperature and pressure conditions during steam distillation, distillates having various compositions can be obtained. Among these distillates, distillates containing sesamins, preferably distillates containing as much sesamins as possible. Use a product. Such preferred distillates can be obtained by employing known temperature and pressure conditions.
また、ゴマ油の製造工場では、ゴマ種子を焙煎することなく、または焙煎した後、圧搾搾油または有機溶媒抽出して得たゴマ油から脱酸、脱色及び脱臭等の精製工程を経る場合がある。この場合の脱臭は、減圧下での水蒸気蒸留を利用しており、脱臭留出物（脱臭スカム）には比較的多くのセサミン類が含まれてくるので、本発明では、かかる留出物を用いることが有利である。具体的には、例えばTHINフィルム式の半連続式脱臭装置を用いた脱臭工程において、セサミン類の含有率は、真空ブースターに留出した留出物（所謂ブースタードレイン）では５〜３０重量％程度、真空排気系外に留出した留出物中では３〜２５重量％程度である。
このようなゴマ油精製工程の脱臭工程で生じる脱臭留出物（脱臭スカム）は、通常廃棄されるものであるので、この利用は、経済面のみならず環境面からも好ましいものである。
In addition, in a sesame oil manufacturing plant, sesame seeds may be subjected to purification steps such as deoxidation, decolorization and deodorization from sesame oil obtained by squeezing oil or organic solvent extraction after roasting or after roasting. . In this case, the deodorization uses steam distillation under reduced pressure, and the deodorized distillate (deodorized scum) contains a relatively large amount of sesamin. It is advantageous to use. Specifically, for example, in a deodorization process using a THIN film type semi-continuous deodorization apparatus, the content of sesamin is about 5 to 30% by weight in a distillate distilled in a vacuum booster (so-called booster drain). In the distillate distilled out of the vacuum exhaust system, it is about 3 to 25% by weight.
Since the deodorized distillate (deodorized scum) generated in the deodorizing step of the sesame oil refining step is usually discarded, this use is preferable not only from the economic aspect but also from the environmental aspect.
［原料の選別：液部と固形部の分離］
初期段階で液部と固形部を分離する。原料として用いる留出物は、液温が高温時は全体として液状であるが、本発明では、上記留出物を固形部と液状部に分離するまで常温で静置した後、上層の液状部分を除いて得た固形部を原料とする。上層の液状部分はオイル部分を含むものである。液状部が混入している状態では、３０℃以上加温するとセサミン類が溶解してしまうので、液状部を分離した固形部を原料として用いることが必要である。オイルまたは油溶性不純物の除去により、固形部のセサミン類含量は２０ないし５０％程度になる。
この固形部に溶剤、例えばエタノールおよび／またはアセトンを用いて処理する。洗浄・精製工程における処理はエタノール、その後の溶解・濾過、再結晶の各工程における処理はエタノールおよび／またはアセトンを用いることが好ましい。
[Raw material selection: Separation of liquid and solid parts]
The liquid part and the solid part are separated in the initial stage. The distillate used as a raw material is liquid as a whole when the liquid temperature is high. In the present invention, the distillate is allowed to stand at room temperature until the distillate is separated into a solid part and a liquid part. The solid part obtained by removing is used as a raw material. The upper liquid portion includes an oil portion. In the state where the liquid part is mixed, sesamins are dissolved when heated at 30 ° C. or higher, so it is necessary to use the solid part from which the liquid part is separated as a raw material. By removing the oil or oil-soluble impurities, the sesamin content in the solid part is about 20 to 50%.
This solid part is treated with a solvent such as ethanol and / or acetone. It is preferable to use ethanol for the treatment in the washing / purification step, and use ethanol and / or acetone for the treatment in the subsequent dissolution / filtration and recrystallization steps.
［溶剤］
本発明において用いる溶剤のうちエタノールは、洗浄・精製工程でセサミン類に混在するオイル（スカム液部）や高級脂肪酸やステロール骨格をもつ物質などの不純物だけを効率的に抽出除去する。また、溶解・濾過工程、および再結晶工程で効率的に純度の高いセサミン類を回収するためにも用いる。
食品添加を考慮して、洗浄溶剤はエタノールを使用する。溶媒純度について、溶剤を回収する場合、水混入による純度低下が考えられる。よって、溶媒純度と洗浄力の関係について検討した。試料はスカム固体部（セサミン類純度２４．６重量％・揮発性物質０．６重量％）に、純度９９．５％、９５％、９０％、８０％のエタノールを用いて常温条件下で洗浄した（エタノール純度調整のため蒸留水を使用した）。表１の結果が得られた。
本発明では、この溶剤による処理温度の異なる複数の処理だけで、セサミン類を簡単かつ安価にセサミン類を高純度かつ高収率に分離製造するものである。
洗浄・精製工程の後の溶解・濾過、再結晶の各工程に用いる溶剤については、段落［００２２］で説明する。
[solvent]
Among the solvents used in the present invention, ethanol efficiently extracts and removes only impurities such as oil (scum liquid part) mixed with sesamin and substances having higher fatty acids and sterol skeletons in the washing and purification process. It is also used to efficiently collect highly pure sesamin in the dissolution / filtration step and the recrystallization step.
In consideration of food addition, ethanol is used as the cleaning solvent. About solvent purity, when recovering a solvent, the purity fall by water mixing can be considered. Therefore, the relationship between solvent purity and detergency was examined. The sample was washed at normal temperature using ethanol of purity 99.5%, 95%, 90%, 80% in the scum solid part (sesamin purity 24.6 wt%, volatile substance 0.6 wt%) (Distilled water was used to adjust ethanol purity). The results in Table 1 were obtained.
In the present invention, sesamin is separated and produced in high purity and high yield simply and inexpensively by only a plurality of treatments with different treatment temperatures using the solvent.
The solvent used in the dissolution / filtration and recrystallization steps after the washing / purification step will be described in paragraph [0022].
［洗浄・精製工程］
本発明の洗浄・精製工程は、残留しているオイルの除去とステロール系の不純物の除去を目的としている。洗浄・精製工程では、溶剤での処理温度を順次上げる洗浄・精製処理を複数回繰り返して、セサミン類を溶解せずに混在するオイルや高級脂肪酸やステロールなどの不純物だけを抽出除去し、固液分離して得られる固形部中のセサミン類の純度を順次上げてゆき、最終的にセサミン類のウエット結晶（セサミン類含有９２〜９９．９％）を得ることができる。
上述したように水蒸気蒸留留出物からの固形部のセサミン類含有量は一様ではないので、それに応じて、適用する処理温度、洗浄・精製の繰り返す回数は適宜選択できる。
すなわち、洗浄後の固液分離して得られる固形部のセサミン類の純度をHPLC分析により測定、チェックし、洗浄・精製の処理温度や繰り返す回数等を選択する。固形部のセサミン類含有が低い段階では残留オイルも含まれているので高い処理温度ではセサミン類の歩留まりが悪くなるため、エタノール洗浄は低い温度で行い、セサミン含有量が高くなった段階ではセサミン類はエタノールにより溶解しにくくなっているので、処理温度を上げて、残留しているステロール系の不純物の除去をしっかり行うようにする。
例えば、（１）固形部にエタノールを加え、常温（２０℃〜３５℃）で撹拌しながら保持後、液部を分離除去する。
（２）次いで、残存固形部にエタノールを加え、撹拌しながら、５０℃以上に加熱保持後、液部を分離除去する。液温は５０℃以上に保つことが必要である。また、この工程では、残留しているオイルもあるので、６０℃以上の加熱を行うとセサミン類の歩留まりが悪くなる。
（３）さらに、必要に応じ、残存固形部にエタノールを加え、撹拌しながら、（２）と同温度またはより高温度で加熱保持後、液部を分離除去し、固形部としてセサミンのウエット結晶を得ることを繰り返す例が挙げられる。仕込み時点でのセサミン類純度は９０％程度以上になっているので、エタノールに溶解しにくくなっており、加熱温度を７０℃に上げて、残留しているステロール系の不純物の除去をしっかり行う。処理後の固形部（ウエット結晶）セサミン類含量は、９２〜９９．９％になる。
[Washing and purification process]
The cleaning and refining process of the present invention aims to remove residual oil and sterol impurities. In the cleaning / purification process, the cleaning / purification process is repeated multiple times to raise the processing temperature with the solvent in order to extract and remove impurities such as mixed oils, higher fatty acids, and sterols without dissolving sesamin. The purity of sesamin in the solid part obtained by separation can be increased successively, and finally wet crystals of sesamin (containing sesamin 92 to 99.9%) can be obtained.
As described above, the sesamin content in the solid part from the steam distillation distillate is not uniform, and accordingly, the treatment temperature to be applied and the number of repetitions of washing and purification can be appropriately selected.
That is, the purity of sesamin in the solid part obtained by solid-liquid separation after washing is measured and checked by HPLC analysis, and the treatment temperature and the number of repetitions are selected. Residual oil is also included in the stage where the content of sesamin in the solid part is low, so the yield of sesamin deteriorates at high processing temperatures, so ethanol cleaning is performed at a low temperature, and sesamin in the stage where the sesamin content is high Since it is difficult to dissolve by ethanol, the processing temperature is raised so that the remaining sterol impurities are thoroughly removed.
For example, (1) ethanol is added to the solid part, and the liquid part is separated and removed after holding at room temperature (20 ° C. to 35 ° C.) while stirring.
(2) Next, ethanol is added to the remaining solid part, and the liquid part is separated and removed after being heated to 50 ° C. or higher while stirring. It is necessary to keep the liquid temperature at 50 ° C. or higher. In this step, some oil remains, so that heating at 60 ° C. or higher deteriorates the yield of sesamins.
(3) Further, if necessary, ethanol is added to the remaining solid part, and while stirring, the liquid part is separated and removed after heating and holding at the same temperature or higher temperature as in (2), and wet crystals of sesamin as the solid part An example of repeatedly obtaining is given. Since the purity of sesamin at the time of preparation is about 90% or more, it is difficult to dissolve in ethanol, and the heating temperature is raised to 70 ° C. to firmly remove the remaining sterol impurities. The solid part (wet crystal) sesamin content after the treatment is 92 to 99.9%.
洗浄・精製工程で使用するエタノールの量は特に限定されないが、あまり少量であると不純物の溶解が不十分であり、多すぎると固形部分の分離効率が悪くなる。例えば、固形部の重量の０．５〜１０倍量のエタノールが用いられる。温度の異なる二回以上の処理において、一回目は３〜１０倍量、二回目は１〜５倍量、必要に応じ三回目は０．５〜３倍量と、順次固形部に対するエタノール量を減らしてゆくことが好ましい。
洗浄・精製工程で、撹拌されながら保持されたスラリーから、固体部と液部を分離する方法は、特に限定されず、従来から用いられている固液分離器、例えば濾過器、遠心分離器を用いることができる。
分離された液部を蒸留して回収されたエタノールは、洗浄・精製工程で再使用することができる。
洗浄・精製工程に続き、必要に応じ、さらに溶解・濾過、再結晶の各工程を施こすことができる。溶解・濾過、再結晶の各工程を施こすことにより、セサミン類の純度アップおよび脱色ができる。
The amount of ethanol used in the washing / purification process is not particularly limited, but if it is too small, the impurities are not sufficiently dissolved, and if it is too large, the separation efficiency of the solid part is deteriorated. For example, 0.5 to 10 times the amount of ethanol by weight of the solid part is used. In two or more treatments at different temperatures, the amount of ethanol for the solid part is 3-10 times the amount for the first time, 1-5 times the amount for the second time, and 0.5-3 times the amount for the third time if necessary. It is preferable to reduce it.
The method of separating the solid part and the liquid part from the slurry held while stirring in the washing / purification step is not particularly limited, and a conventionally used solid-liquid separator, such as a filter or a centrifuge, is used. Can be used.
The ethanol recovered by distillation of the separated liquid part can be reused in the washing / purification process.
Subsequent to the washing / purification step, further steps of dissolution / filtration and recrystallization can be performed as necessary. By performing the steps of dissolution, filtration, and recrystallization, the purity of sesamins can be increased and the color can be removed.
［溶解・濾過工程］
本発明の、溶解・濾過工程は、洗浄・精製工程で得たウエット結晶に、エタノールを用いる場合は、エタノール（バージンエタノールが好ましい）を加え、沸点溶解する。加えるエタノール量は、セサミン類が十分溶解する量が用いられ、例えば、ウエット結晶の１５倍〜３０倍量が好ましく用いられる。
また、アセトン：エタノール混合溶剤（アセトン：エタノール、９：１〜６：４）を用いることも、アセトン：水混合溶剤（アセトン：水、８：２〜５：５）を用いることもできる。アセトン：水混合溶剤では、より脱色効果が大きい。
溶解を確認後、温時濾過により異物を除去し、その後さらに精密濾過を行う。濾過は、従来から用いられている濾過器が使用でき、例えば、フィルタープレス、スパクラフィルター濾過器、加圧濾過器、メンブランフィルター式精密濾過機、多段式加圧濾過機、加圧濾盤型濾過器、密閉式精密濾過器、リーフフィルター加圧濾過器、ハステロイ加圧濾過器などを適宜用いることができる。
[Dissolution / filtration process]
In the dissolution / filtration step of the present invention, when ethanol is used in the wet crystal obtained in the washing / purification step, ethanol (preferably virgin ethanol) is added and dissolved at the boiling point. The amount of ethanol to be added is such that sesamin is sufficiently dissolved, and for example, 15 to 30 times the amount of wet crystals is preferably used.
Further, an acetone: ethanol mixed solvent (acetone: ethanol, 9: 1 to 6: 4) can be used, or an acetone: water mixed solvent (acetone: water, 8: 2 to 5: 5) can be used. Acetone: water mixed solvent has a greater decolorization effect.
After confirming dissolution, the foreign matter is removed by hot filtration, and then further fine filtration is performed. For filtration, a conventionally used filter can be used, for example, a filter press, a spatula filter filter, a pressure filter, a membrane filter type microfilter, a multistage pressure filter, a pressure filter type filter. A filter, a closed microfilter, a leaf filter pressure filter, a Hastelloy pressure filter, or the like can be used as appropriate.
本発明での溶解・濾過工程に続く再結晶工程では、溶解・濾過工程で得た濾液の液温を下げ、１次結晶を析出させ分離して１次ウエット結晶を得た後、必要に応じ、分離した濾液の液温をさらに下げ、２次結晶を析出させ分離して２次ウエット結晶を得ることができる。
結晶の分離は、特に限定されず、従来から用いられている固液分離器、例えば濾過器、遠心分離器を用いることができるが、遠心分離器が好ましい。なお、溶剤としてエタノールを用いた場合、この工程で分離された濾液を蒸留して回収されたエタノールは、洗浄・精製工程で再使用してもよい。
また、さらに必要に応じて、乾燥工程、粉砕工程、篩選別工程、混合工程の少なくとも一つの工程を施すことができる。
In the recrystallization step subsequent to the dissolution / filtration step in the present invention, the liquid temperature of the filtrate obtained in the dissolution / filtration step is lowered to precipitate the primary crystals and separate them to obtain primary wet crystals. Then, the liquid temperature of the separated filtrate is further lowered, and secondary crystals can be precipitated and separated to obtain secondary wet crystals.
The separation of the crystal is not particularly limited, and a conventionally used solid-liquid separator such as a filter or a centrifuge can be used, but a centrifuge is preferable. When ethanol is used as the solvent, the ethanol recovered by distillation of the filtrate separated in this step may be reused in the washing / purification step.
Furthermore, at least one step of a drying step, a pulverizing step, a sieve selecting step, and a mixing step can be performed as necessary.
得られた１次ウエット結晶、２次ウエット結晶は必要に応じて、混合または混合しないで、乾燥することにより、精製されたセサミン類高含有組成物を得ることができる。
得られたウエット結晶を乾燥する場合、１次ウエット結晶と２次ウエット結晶は、その性状を分析し、結晶の状態が異なる場合は、別々に分けて乾燥したほうが、その後の使用に有利である。
乾燥方法は、特に限定されないが、例えば、風乾後、真空または減圧乾燥をすることができる。好ましくは減圧下（１〜１００ｍｍＨｇ程度）で、３０〜１００℃、好ましくは４０〜８０℃程度に加熱して行うことができ、特に真空乾燥で４０℃以下で行うのが好ましい。乾燥機は、従来から用いられている乾燥機使用でき、例えば棚式熱風乾燥機、棚式真空乾燥機、真空混合式乾燥機、箱形棚式乾燥機、コニカルドライヤー、振動流動乾燥機、箱形棚式熱風乾燥機、グラスライニングコニカルドライヤーなどを用いることができる。
The obtained primary wet crystal and secondary wet crystal can be obtained by drying without mixing or mixing, if necessary, to obtain a purified high composition containing sesamin.
When the obtained wet crystals are dried, the properties of the primary wet crystals and the secondary wet crystals are analyzed, and when the crystal states are different, it is advantageous to separate and dry them for subsequent use. .
Although the drying method is not particularly limited, for example, it can be vacuum dried or vacuum dried after air drying. Preferably, it can be carried out under reduced pressure (about 1 to 100 mmHg) by heating to 30 to 100 ° C., preferably about 40 to 80 ° C., and particularly preferably performed at 40 ° C. or less by vacuum drying. Conventional dryers can be used, such as shelf hot air dryers, shelf vacuum dryers, vacuum mixed dryers, box-type shelf dryers, conical dryers, vibratory fluid dryers, boxes A shelf-type hot air dryer, a glass-lined conical dryer, or the like can be used.
本発明において、最終的に粉末セサミン類を製造する場合では、上記の乾燥工程後、さらに、通常知られている、粉砕工程、篩選別工程、混合工程を施すことができる。例えば、パワーミル、ロールミル、スタンプミル、振動ボールミル、カッターミル、スルートミル、シュレダーミル、クラシックロールグラインダー、ディスクグラインダー、コーミル、ジェットミル粉砕機、エッジランナー、ハンマーミル、フェザーミルなどで粉砕し、除鉄後、振動篩選別により、所望の粒度範囲の粉末を得、次いで、例えば、Ｖブレンダー、Ｗブレンダー、パン型混合機、リボンブレンダー、ダブルコーンブレンダー、フラッシュブレンダー、ミクロブレンダーなどで混合し、均一な粉末を得ることができる。 In the present invention, in the case of finally producing powdered sesamins, after the above-described drying step, generally known pulverization step, sieve selection step, and mixing step can be further performed. For example, power mill, roll mill, stamp mill, vibration ball mill, cutter mill, slut mill, shredder mill, classic roll grinder, disc grinder, comb mill, jet mill grinder, edge runner, hammer mill, feather mill, etc. The powder in the desired particle size range is obtained by vibration sieve screening, and then mixed with, for example, a V blender, a W blender, a pan-type mixer, a ribbon blender, a double cone blender, a flash blender, a micro blender, and the like to obtain a uniform powder Can be obtained.
以下に本発明の詳細および効果を実施例で説明する。本発明はこれらの実施例によってなんら限定されるものではない。
分離製造されたセサミン類の純度は、高速液体クロマトグラフィー法である下記の条件下で測定した。
カラム ： Inertsil ODS-3（GL-SCIENCES社）
移動相 ： 水：メチルアルコール＝３：７（容積比）
流量 ： １．０ml/min
検出器 ： UV Detector
測定波長： ２９０nm
標準品のピーク面積と比較して算出したセサミン含量及びエピセサミン含量の合計値をセサミン類含量とし、純度を算出した。実施例におけるウエット結晶のセサミン類含量はこの分析法で求め、乾燥後のセサミン類の純度はこの手法で算出した。
The details and effects of the present invention will be described in the following examples. The present invention is not limited to these examples.
The purity of sesamin produced separately was measured under the following conditions, which are high performance liquid chromatography methods.
Column: Inertsil ODS-3 (GL-SCIENCES)
Mobile phase: water: methyl alcohol = 3: 7 (volume ratio)
Flow rate: 1.0ml / min
Detector: UV Detector
Measurement wavelength: 290nm
The total value of the sesamin content and the episesamin content calculated by comparison with the peak area of the standard product was taken as the sesamin content, and the purity was calculated. The sesamin content of the wet crystals in the examples was determined by this analysis method, and the purity of the sesamin after drying was calculated by this method.
（セサミン類の分離製造）
ごま油精製の脱臭工程（２１０〜２３０℃・２〜４ｍｍＨｇにて水蒸気蒸留）で生じた脱臭スカムを、固形部と液状部に分離するまで常温で静置した後、その上層の液状部分を除いて得た固形部を原料とした。この固形部に固形部の約３倍量の９９％エタノールを加え、常温で撹拌しながら２時間以上保持後、遠心分離し濾液を分離除去した。分離した濾液から蒸留により回収したエタノールは以降の洗浄・精製工程に再使用する。次いで、固形部の重量の約１倍量の９９％エタノールを加え、６０℃で撹拌しながら２時間以上保持後、遠心分離し濾液を分離除去し、ウエット結晶（セサミン類含量９１．２％、収率：対固形部重量３２．２％）を得た。
(Separation of sesamin)
After leaving the deodorized scum produced in the deodorization step of sesame oil purification (steam distillation at 210 to 230 ° C. and 2 to 4 mmHg) until it is separated into a solid part and a liquid part, the liquid part of the upper layer is removed. The obtained solid part was used as a raw material. About 3 times the amount of 99% ethanol of the solid part was added to this solid part, kept at room temperature for 2 hours or more, and then centrifuged to separate and remove the filtrate. Ethanol recovered from the separated filtrate by distillation is reused in subsequent washing and purification steps. Next, 99% ethanol, which is about 1 times the weight of the solid part, was added, kept at 60 ° C. with stirring for 2 hours or more, centrifuged, and the filtrate was separated and removed to obtain wet crystals (sesamin content 91.2%, Yield: solid part weight 32.2%).
実施例１で得たウエット結晶をさらに、固形部分の重量の約０．７倍量の９９％エタノールを加え、７０℃で撹拌しながら２時間以上保持し、遠心分離し濾液を分離除去し、ウエット結晶（セサミン類含量９６．４％、収率：対固形部重量２５．８％）を得た。 The wet crystal obtained in Example 1 was further added with 99% ethanol of about 0.7 times the weight of the solid part, kept at 70 ° C. with stirring for 2 hours or more, and centrifuged to separate and remove the filtrate. Wet crystals (sesamin content 96.4%, yield: solid part weight 25.8%) were obtained.
実施例２で得たウエット結晶を約２０倍量の９９％エタノール（バージンアルコール）を加え、沸点溶解し、温時濾過により異物除去し、次いで、精密濾過する。液温を下げ、１次結晶を析出させ遠心分離でウエット結晶を得、ついで、さらに液温を下げ２次結晶を析出させ遠心分離でウエット結晶を得た。これにより、セサミン類（乾燥後の純度９８．６％）が得られた。
この段階での収率は、脱臭スカムの固形部重量に対して１６．４％であった。
About 20-fold amount of 99% ethanol (virgin alcohol) is added to the wet crystals obtained in Example 2, dissolved at the boiling point, removed for foreign matter by hot filtration, and then microfiltered. The liquid temperature was lowered and primary crystals were precipitated and centrifuged to obtain wet crystals. Then, the liquid temperature was further lowered to precipitate secondary crystals and centrifuged to obtain wet crystals. Thereby, sesamin (purity after drying 98.6%) was obtained.
The yield at this stage was 16.4% based on the solid part weight of the deodorized scum.
実施例１と同様な原料に、９９％エタノールを用い常温で撹拌しながら２時間以上保持後、遠心分離し濾液を分離除去した。次いで９９％エタノールを加え５０℃で撹拌しながら２時間保持後、遠心分離し濾液を分離除去しウエット結晶を得、さらに同温度での処理を繰り返した以外は、実施例１と同様な方法でウエット結晶を得た。このセサミン類純度は９５．６％、収率は対固形部重量１４．７％であった。 99% ethanol was used in the same raw material as in Example 1, and the mixture was kept at room temperature for 2 hours or more and then centrifuged to separate and remove the filtrate. Next, 99% ethanol was added and held at 50 ° C. with stirring for 2 hours, followed by centrifugation to separate and remove the filtrate to obtain wet crystals. Wet crystals were obtained. The purity of this sesamin was 95.6%, and the yield was 14.7% of the solid part weight.
実施例１と同様な処理で得たウエット結晶に、アセトン：エタノール（７：３）混合溶剤を加え、５６℃で撹拌し、溶解後濾過した。次いで２０℃まで冷却結晶化し、可溶部を除去した。さらにエタノール、６０℃で洗浄後、ウエット結晶を乾燥した。このセサミン類純度は９６％、収率は対固形部重量１３．３％であった。 An acetone: ethanol (7: 3) mixed solvent was added to wet crystals obtained by the same treatment as in Example 1, stirred at 56 ° C., dissolved, and filtered. Subsequently, it was cooled and crystallized to 20 ° C., and the soluble part was removed. Further, after washing at 60 ° C. with ethanol, the wet crystals were dried. The purity of this sesamin was 96%, and the yield was 13.3% by weight with respect to the solid part.
実施例１と同様な処理で得たウエット結晶に、アセトン：水（７：３）混合溶剤を加え、５０℃で撹拌し、溶解後濾過した。次いで−１５℃で４時間静置処理（冷却結晶化）し、可溶部を除去後、ウエット結晶を乾燥した。このセサミン類純度は９９％、収率は対固形部重量１２％であった。 An acetone: water (7: 3) mixed solvent was added to wet crystals obtained by the same treatment as in Example 1, stirred at 50 ° C., dissolved, and filtered. Next, the mixture was allowed to stand at −15 ° C. for 4 hours (cooled crystallization), and after removing the soluble portion, the wet crystal was dried. The sesamin purity was 99%, and the yield was 12% by weight of the solid part.
（粉末セサミン類の製造）
実施例２と同様な方法で得たセサミン類に乾燥工程として、風乾または、真空乾燥を行った。次いで、粉砕工程で、粉砕機にて粉砕し、粉末化する。篩選別により、６０メッシュパスの粉末を得た。
(Manufacture of powdered sesamin)
As a drying step, the sesamin obtained by the same method as in Example 2 was air-dried or vacuum-dried. Next, in the pulverization step, the powder is pulverized by a pulverizer. A 60 mesh pass powder was obtained by sieving.
本発明は、原料として通常廃棄される、ゴマ油精製工程の脱臭工程で生じる脱臭留出物（脱臭スカム）が用いられるので、廃棄物の有効利用という産業上の効果も奏する。
脱臭スカムという廃棄物から、高純度で効率的に、かつ簡単、安価に分離製造したセサミン類は産業上の利用可能性が高いものと期待される。
Since the deodorized distillate (deodorized scum) generated in the deodorizing step of the sesame oil refining step, which is normally discarded as a raw material, is used in the present invention, there is also an industrial effect of effective use of waste.
Sesamins that are separated and manufactured from waste called deodorized scum with high purity, efficiency, simple, and low cost are expected to have high industrial applicability.
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| CN107793425A (en) * | 2017-11-01 | 2018-03-13 | 安徽龙津生物科技有限公司 | A kind of technique that the sesamin of content more than 90% is extracted from sesame |
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