WO2015128963A1 - Method for extracting and purifying polysaccharide from organism containing polysaccharides - Google Patents
Method for extracting and purifying polysaccharide from organism containing polysaccharides Download PDFInfo
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- WO2015128963A1 WO2015128963A1 PCT/JP2014/054689 JP2014054689W WO2015128963A1 WO 2015128963 A1 WO2015128963 A1 WO 2015128963A1 JP 2014054689 W JP2014054689 W JP 2014054689W WO 2015128963 A1 WO2015128963 A1 WO 2015128963A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/04—Alginic acid; Derivatives thereof
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- the present invention relates to the provision of a method for extracting and purifying polysaccharides such as alginic acid from organisms containing polysaccharides such as seaweed.
- seaweed that is the main object of the present invention is also an important biomass resource, and is also an extremely important biomass resource in that it does not compete with terrestrial plants for survival and contains substances different from terrestrial plants.
- seaweed contains a specific polysaccharide, many kinds of polysaccharides are produced and used as a raw material.
- brown algae such as kombu and seaweed are used as raw materials, and then alkaline water is added to the mixture and heated to solubilize alginic acid in the seaweed body.
- Example 4 50 kg of tap water and 200 g of sodium carbonate were added to 1 kg of raw comb and stirred for 1 hour, 200 ml of hydrogen peroxide (30% strength solution) was added, and the mixture was further stirred for 2 hours and mixed. The viscosity of the mixed solution was 95,000 Pa ⁇ s. Then, it left still at room temperature for 12 hours, centrifuged and removed solid content, and the supernatant liquid was obtained. This solution was filtered to remove insoluble substances by adding 70 ml of hydrochloric acid (30% strength solution) to the filtrate, collected by filtration, immersed in hydrochloric acid adjusted to pH 2.0, and heated to 80 ° C. (temperature reached). After warming, the solid was collected by filtration. The solid content thus obtained was washed twice with 10 liters of 2-propanol (isopropanol) and then dried at room temperature to obtain 50 g of dry alginic acid.
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Abstract
[Problem] To reduce the amount of water needed for the extraction and purification of polysaccharides from an organism containing polysaccharides, such as seaweed, to 1/3 - 1/4 the original amount, and also reduce the volume of the water tank, and thereby simplify the filtration process and the like, and achieve a lower cost. [Solution] When a polysaccharide is extracted from an organism containing polysaccharides using alkaline water containing an alkali metal, hydrogen peroxide is added and treatments such as filtration are performed. For instance, alginic acid is obtained from seaweed by a method characterized in comprising: a first step for obtaining an alginic acid extract liquid by immersing seaweed in an alkaline solution containing an alkali metal to which hydrogen peroxide has been added, extracting the alginic acid in the seaweed, and then removing the solid content; a second step for producing a solid by adding an acid or Ca compound aqueous solution to the alginic acid extract liquid obtained in the first step; and a third step for obtaining alginic acid by dehydrating the solid produced in the second step.
Description
本発明は、海草等の多糖体を含有する生物体からアルギン酸などの多糖体を抽出・精製する方法の提供に関するものである。
The present invention relates to the provision of a method for extracting and purifying polysaccharides such as alginic acid from organisms containing polysaccharides such as seaweed.
昨今において、バイオマスは再生可能な重要な資源であり、これを有効に利用することは、地球環境を保全しつつ人類が生存し続けられる唯一の手段である。
本発明の主たる対象となる海藻も重要なバイオマス資源で、陸生の植物と生存で競合しない上に陸生植物とは異なる物質を含有している点でも極めて重要なバイオマス資源である。そして、海藻は特有の多糖体を含むので、多くの種類の多糖体が海藻を原料に生産され、利用されている。
海藻からの「アルギン酸」の製造法においては、コンブ、ワカメ等の褐藻類を原料にして、まずそれにアルカリ水を加えて加熱し、海藻体中のアルギン酸を可溶化する。
次いで、その可溶化されたアルギン酸を含む海藻にナトリウム塩を添加してアルギン酸を水溶性にして海藻体外に溶出させ、アルギン酸含有の抽出液とする。
その後、前記抽出液から濾過などによって不溶物を除去し、アルギン酸の単離母液とする。この不純物除去作業を容易に行う際には、前記抽出液の粘度を下げる必要があり、大量の水が使用される。
因に、従来の海藻を原料とする方法では、アルギン酸の製造には、得られるアルギン酸の５００～１，０００倍（重量比で）以上の水が使用され、環境負荷が極めて大きい。
アルギン酸は、繊維工業、製紙工業、食品工業、鉄鋼業、水産業、電子工業、など多くの工業生産、さらには医療分野でも使用され経済的に重要な物質である。
したがって、アルギン酸の生産の環境負荷の低減（生産のためのエネルギーと水の消費量の低減）は経済的あるのみでなく、環境保全の面からも産業上極めて意義深いものである。 In recent years, biomass is an important renewable resource, and its effective use is the only way for human beings to survive while preserving the global environment.
The seaweed that is the main object of the present invention is also an important biomass resource, and is also an extremely important biomass resource in that it does not compete with terrestrial plants for survival and contains substances different from terrestrial plants. And since seaweed contains a specific polysaccharide, many kinds of polysaccharides are produced and used as a raw material.
In the method for producing “alginic acid” from seaweed, brown algae such as kombu and seaweed are used as raw materials, and then alkaline water is added to the mixture and heated to solubilize alginic acid in the seaweed body.
Next, a sodium salt is added to the solubilized seaweed containing alginic acid to make the alginic acid water-soluble and eluted out of the seaweed body to obtain an alginate-containing extract.
Thereafter, insoluble matters are removed from the extract by filtration or the like to obtain an alginic acid isolated mother liquor. When performing this impurity removal operation easily, it is necessary to lower the viscosity of the extract, and a large amount of water is used.
Incidentally, in the conventional method using seaweed as a raw material, the production of alginic acid uses 500 to 1,000 times (by weight) or more of the obtained alginic acid, and the environmental load is extremely large.
Alginic acid is an economically important substance that is used in many industrial productions such as textile industry, paper industry, food industry, steel industry, water industry, and electronics industry, and also in the medical field.
Therefore, reduction of the environmental load of production of alginic acid (reduction of energy and water consumption for production) is not only economical, but also extremely significant in industry from the viewpoint of environmental conservation.
本発明の主たる対象となる海藻も重要なバイオマス資源で、陸生の植物と生存で競合しない上に陸生植物とは異なる物質を含有している点でも極めて重要なバイオマス資源である。そして、海藻は特有の多糖体を含むので、多くの種類の多糖体が海藻を原料に生産され、利用されている。
海藻からの「アルギン酸」の製造法においては、コンブ、ワカメ等の褐藻類を原料にして、まずそれにアルカリ水を加えて加熱し、海藻体中のアルギン酸を可溶化する。
次いで、その可溶化されたアルギン酸を含む海藻にナトリウム塩を添加してアルギン酸を水溶性にして海藻体外に溶出させ、アルギン酸含有の抽出液とする。
その後、前記抽出液から濾過などによって不溶物を除去し、アルギン酸の単離母液とする。この不純物除去作業を容易に行う際には、前記抽出液の粘度を下げる必要があり、大量の水が使用される。
因に、従来の海藻を原料とする方法では、アルギン酸の製造には、得られるアルギン酸の５００～１，０００倍（重量比で）以上の水が使用され、環境負荷が極めて大きい。
アルギン酸は、繊維工業、製紙工業、食品工業、鉄鋼業、水産業、電子工業、など多くの工業生産、さらには医療分野でも使用され経済的に重要な物質である。
したがって、アルギン酸の生産の環境負荷の低減（生産のためのエネルギーと水の消費量の低減）は経済的あるのみでなく、環境保全の面からも産業上極めて意義深いものである。 In recent years, biomass is an important renewable resource, and its effective use is the only way for human beings to survive while preserving the global environment.
The seaweed that is the main object of the present invention is also an important biomass resource, and is also an extremely important biomass resource in that it does not compete with terrestrial plants for survival and contains substances different from terrestrial plants. And since seaweed contains a specific polysaccharide, many kinds of polysaccharides are produced and used as a raw material.
In the method for producing “alginic acid” from seaweed, brown algae such as kombu and seaweed are used as raw materials, and then alkaline water is added to the mixture and heated to solubilize alginic acid in the seaweed body.
Next, a sodium salt is added to the solubilized seaweed containing alginic acid to make the alginic acid water-soluble and eluted out of the seaweed body to obtain an alginate-containing extract.
Thereafter, insoluble matters are removed from the extract by filtration or the like to obtain an alginic acid isolated mother liquor. When performing this impurity removal operation easily, it is necessary to lower the viscosity of the extract, and a large amount of water is used.
Incidentally, in the conventional method using seaweed as a raw material, the production of alginic acid uses 500 to 1,000 times (by weight) or more of the obtained alginic acid, and the environmental load is extremely large.
Alginic acid is an economically important substance that is used in many industrial productions such as textile industry, paper industry, food industry, steel industry, water industry, and electronics industry, and also in the medical field.
Therefore, reduction of the environmental load of production of alginic acid (reduction of energy and water consumption for production) is not only economical, but also extremely significant in industry from the viewpoint of environmental conservation.
アルギン酸は、褐藻類を原料にして、基本的に図１－（ａ）に示す様な抽出、濾過、析出、乾燥など複雑な工程を経て製造されている。（非特許文献１参照）。
しかし、この方法では、抽出液は極めて粘度が高く濾過は困難を極めるので、抽出液を濾過が可能になる程度に水で希釈する。この段階で多くの水が消費される。
次に、濾液に酸を加えてｐＨを下げ、不溶性のアルギン酸として析出させる。酸の代わりにカルシウム塩を用いると、不溶性のアルギン酸カルシウムとして析出させることもできる。
こうして得たアルギン酸を脱水・乾燥してアルギン酸が製造されている。
この製造工程の中で、最も重要な点は、藻類体抽出液中の不溶物を除去する操作にある。
大量の水を使用すること無く抽出液から不溶物を除去する技術の開発が最も重要な課題になっている。（非特許文献２参照） Alginic acid is basically produced from brown algae through complicated processes such as extraction, filtration, precipitation, and drying as shown in FIG. 1- (a). (Refer nonpatent literature 1).
However, in this method, since the extract is extremely viscous and difficult to filter, the extract is diluted with water to such an extent that it can be filtered. A lot of water is consumed at this stage.
Next, an acid is added to the filtrate to lower the pH and precipitate as insoluble alginic acid. If calcium salt is used instead of acid, it can be precipitated as insoluble calcium alginate.
Alginic acid thus obtained is produced by dehydration and drying.
The most important point in this production process is the operation of removing insoluble substances in the algal extract.
The most important issue is the development of technology for removing insoluble substances from the extract without using a large amount of water. (See Non-Patent Document 2)
しかし、この方法では、抽出液は極めて粘度が高く濾過は困難を極めるので、抽出液を濾過が可能になる程度に水で希釈する。この段階で多くの水が消費される。
次に、濾液に酸を加えてｐＨを下げ、不溶性のアルギン酸として析出させる。酸の代わりにカルシウム塩を用いると、不溶性のアルギン酸カルシウムとして析出させることもできる。
こうして得たアルギン酸を脱水・乾燥してアルギン酸が製造されている。
この製造工程の中で、最も重要な点は、藻類体抽出液中の不溶物を除去する操作にある。
大量の水を使用すること無く抽出液から不溶物を除去する技術の開発が最も重要な課題になっている。（非特許文献２参照） Alginic acid is basically produced from brown algae through complicated processes such as extraction, filtration, precipitation, and drying as shown in FIG. 1- (a). (Refer nonpatent literature 1).
However, in this method, since the extract is extremely viscous and difficult to filter, the extract is diluted with water to such an extent that it can be filtered. A lot of water is consumed at this stage.
Next, an acid is added to the filtrate to lower the pH and precipitate as insoluble alginic acid. If calcium salt is used instead of acid, it can be precipitated as insoluble calcium alginate.
Alginic acid thus obtained is produced by dehydration and drying.
The most important point in this production process is the operation of removing insoluble substances in the algal extract.
The most important issue is the development of technology for removing insoluble substances from the extract without using a large amount of water. (See Non-Patent Document 2)
藻類を原料にして多糖体を製造する場合には、（１）藻体の表皮を破砕して多糖体を藻体から遊離させ、（２）次いで混在する藻体成分と分離して単離する操作が必要である。工業的に多糖体を製造する際には、（１）の反応を効率よく行う目的でアルカリ性の条件下で加熱処理を施す、また、（２）のスッテップでは、多糖体の分離を容易にするために抽出した液に大量の水を加えて粘度を低下させることが必要である。さらに、この溶液からアルギン酸を単離するには、濾過を繰り返して混在する微細な粒子状の不純物を除去する操作、場合によっては活性炭などによる脱色が必要である。このように、海藻から多糖体を製造する工業は、大量の水と大量のエネルギーを消費することによって環境に大きな負荷をかける工業である。
本発明者らは、海藻から多糖体を製造する工程での熱エネルギーと水の消費量を低減させ、より環境負荷の小さい工程に改良することが産業上で重要であると考えた。 When manufacturing polysaccharides using algae as a raw material, (1) crushing the epidermis of the algae to release the polysaccharides from the algae, and (2) separating and isolating the mixed algae components. Operation is required. When producing polysaccharides industrially, heat treatment is performed under alkaline conditions for the purpose of efficiently performing the reaction of (1), and the step (2) facilitates the separation of the polysaccharides. Therefore, it is necessary to add a large amount of water to the extracted liquid to reduce the viscosity. Further, in order to isolate alginic acid from this solution, it is necessary to remove fine particulate impurities mixed by repeated filtration, and in some cases, decolorization with activated carbon or the like is necessary. Thus, the industry which manufactures a polysaccharide from a seaweed is an industry which places a heavy load on the environment by consuming a large amount of water and a large amount of energy.
The present inventors thought that it is industrially important to reduce the consumption of heat energy and water in the process of producing a polysaccharide from seaweed and to improve the process to a smaller environmental load.
本発明者らは、海藻から多糖体を製造する工程での熱エネルギーと水の消費量を低減させ、より環境負荷の小さい工程に改良することが産業上で重要であると考えた。 When manufacturing polysaccharides using algae as a raw material, (1) crushing the epidermis of the algae to release the polysaccharides from the algae, and (2) separating and isolating the mixed algae components. Operation is required. When producing polysaccharides industrially, heat treatment is performed under alkaline conditions for the purpose of efficiently performing the reaction of (1), and the step (2) facilitates the separation of the polysaccharides. Therefore, it is necessary to add a large amount of water to the extracted liquid to reduce the viscosity. Further, in order to isolate alginic acid from this solution, it is necessary to remove fine particulate impurities mixed by repeated filtration, and in some cases, decolorization with activated carbon or the like is necessary. Thus, the industry which manufactures a polysaccharide from a seaweed is an industry which places a heavy load on the environment by consuming a large amount of water and a large amount of energy.
The present inventors thought that it is industrially important to reduce the consumption of heat energy and water in the process of producing a polysaccharide from seaweed and to improve the process to a smaller environmental load.
本発明者らは、海藻体の表層の分解を促進すれば、海藻内部に存在する藻体組織との結合が破壊されて多糖体の体外への溶出が促進されると同時に抽出液の粘度も低くなるもの考えて研究を重ねた。
この研究の基礎となるアイデアは、海藻表層の生理的機能と構造を考察する過程で発想した。
すなわち、褐藻類の藻体を形成する細胞の細胞膜は内層部と外層部で性質が異なり、内層はセルロース、外層はペクチン質で、ここに大量のアルギン酸がカルシウム塩として不溶性の形で藻体表層の組織と結合することによって葉緑素など光合成や呼吸に関与する成分を包含する細胞を形成して藻体形を維持しているものと考えられている。[非特許文献３参照]。
このアルギン酸は水酸化ナトリウムなどアルカリで処理すると細胞膜が破壊されて細胞組織の一部と結合した形で細胞外に漏出する。 By promoting the decomposition of the surface layer of the seaweed body, the present inventors break the bond with the algal body tissue present in the seaweed and promote the elution of the polysaccharide outside the body, and at the same time the viscosity of the extract is also increased. I researched the idea of lowering.
The idea that forms the basis of this research came up in the process of considering the physiological function and structure of the seaweed surface layer.
That is, the cell membranes of the cells forming the algal bodies of brown algae have different properties in the inner layer and the outer layer, the inner layer is cellulose, the outer layer is pectic, and a large amount of alginic acid is insoluble in the form of calcium salt here. It is thought that cells that contain components involved in photosynthesis and respiration, such as chlorophyll, form a cell body that maintains the algal body shape. [See Non-Patent Document 3].
When this alginic acid is treated with an alkali such as sodium hydroxide, the cell membrane is destroyed and leaks out of the cell in a form bound to a part of the cell tissue.
この研究の基礎となるアイデアは、海藻表層の生理的機能と構造を考察する過程で発想した。
すなわち、褐藻類の藻体を形成する細胞の細胞膜は内層部と外層部で性質が異なり、内層はセルロース、外層はペクチン質で、ここに大量のアルギン酸がカルシウム塩として不溶性の形で藻体表層の組織と結合することによって葉緑素など光合成や呼吸に関与する成分を包含する細胞を形成して藻体形を維持しているものと考えられている。[非特許文献３参照]。
このアルギン酸は水酸化ナトリウムなどアルカリで処理すると細胞膜が破壊されて細胞組織の一部と結合した形で細胞外に漏出する。 By promoting the decomposition of the surface layer of the seaweed body, the present inventors break the bond with the algal body tissue present in the seaweed and promote the elution of the polysaccharide outside the body, and at the same time the viscosity of the extract is also increased. I researched the idea of lowering.
The idea that forms the basis of this research came up in the process of considering the physiological function and structure of the seaweed surface layer.
That is, the cell membranes of the cells forming the algal bodies of brown algae have different properties in the inner layer and the outer layer, the inner layer is cellulose, the outer layer is pectic, and a large amount of alginic acid is insoluble in the form of calcium salt here. It is thought that cells that contain components involved in photosynthesis and respiration, such as chlorophyll, form a cell body that maintains the algal body shape. [See Non-Patent Document 3].
When this alginic acid is treated with an alkali such as sodium hydroxide, the cell membrane is destroyed and leaks out of the cell in a form bound to a part of the cell tissue.
ところで、近年、ヒドロキシラジカル反応によって糖鎖が分解されることが発見されている。[非特許文献４参照]
本発明者らは、アルギン酸を含む海藻細胞表層の組織でヒドロキシラジカルを局所的に発生させることができれば、アルギン酸を細胞組織から切り離して効率よく抽出できるものと考えて研究を重ね、本発明を完成させた。
ヒドロキシラジカル（OH*）は、次に掲げる[反応式１]の化学反応（フェントン反応）によって作り出される酸化力が非常に強い活性酸素種であるが、此れをアルギン酸の分解を伴うこと無く局所で発生させることが必須である。本発明者らは、（１）褐藻体表層の組織中に鉄イオンやマグネシウムイオンなど２価の金属イオンが存在するが、（２）アルギン酸はＣａイオンとキレート結合物を形成しており、鉄イオンなど他の金属イオンが配位する余地は存在し得ないと推測して検討を重ねた。
H2O2 + Fe2+ → OH* （ヒドロキシラジカル）+ OH- + Fe3+ [反応式１]
こうした推論に基いて、褐藻類を水に懸濁し、これに過酸化水素水とアルカリ薬剤（水酸化ナトリウム、炭酸ナトリウムなど）を添加して処理することによって高濃度のアルギン酸溶液を得る本願発明に係る新規な方法を開発した。 Incidentally, in recent years, it has been discovered that sugar chains are decomposed by a hydroxyl radical reaction. [See Non-Patent Document 4]
The inventors of the present invention have completed the present invention by considering that alginic acid can be efficiently extracted by separating it from the cell tissue if hydroxy radicals can be locally generated in the seaweed cell surface tissue containing alginic acid. I let you.
Hydroxyl radical (OH * ) is a reactive oxygen species with very strong oxidizing power produced by the following chemical reaction (Fenton reaction) of [Reaction formula 1], but this is not locally accompanied by decomposition of alginic acid. It is essential to generate in. The present inventors have (1) divalent metal ions such as iron ions and magnesium ions in the structure of the brown alga body surface layer, but (2) alginic acid forms a chelate bond with Ca ions, and iron The investigation was repeated on the assumption that there is no room for coordination of other metal ions such as ions.
H 2 O 2 + Fe 2+ → OH * (Hydroxy radical) + OH − + Fe 3+ [Scheme 1]
Based on these inferences, the present invention obtains a high-concentration alginic acid solution by suspending brown algae in water and adding hydrogen peroxide and an alkaline agent (sodium hydroxide, sodium carbonate, etc.) to the suspension. Such a new method has been developed.
本発明者らは、アルギン酸を含む海藻細胞表層の組織でヒドロキシラジカルを局所的に発生させることができれば、アルギン酸を細胞組織から切り離して効率よく抽出できるものと考えて研究を重ね、本発明を完成させた。
ヒドロキシラジカル（OH*）は、次に掲げる[反応式１]の化学反応（フェントン反応）によって作り出される酸化力が非常に強い活性酸素種であるが、此れをアルギン酸の分解を伴うこと無く局所で発生させることが必須である。本発明者らは、（１）褐藻体表層の組織中に鉄イオンやマグネシウムイオンなど２価の金属イオンが存在するが、（２）アルギン酸はＣａイオンとキレート結合物を形成しており、鉄イオンなど他の金属イオンが配位する余地は存在し得ないと推測して検討を重ねた。
H2O2 + Fe2+ → OH* （ヒドロキシラジカル）+ OH- + Fe3+ [反応式１]
こうした推論に基いて、褐藻類を水に懸濁し、これに過酸化水素水とアルカリ薬剤（水酸化ナトリウム、炭酸ナトリウムなど）を添加して処理することによって高濃度のアルギン酸溶液を得る本願発明に係る新規な方法を開発した。 Incidentally, in recent years, it has been discovered that sugar chains are decomposed by a hydroxyl radical reaction. [See Non-Patent Document 4]
The inventors of the present invention have completed the present invention by considering that alginic acid can be efficiently extracted by separating it from the cell tissue if hydroxy radicals can be locally generated in the seaweed cell surface tissue containing alginic acid. I let you.
Hydroxyl radical (OH * ) is a reactive oxygen species with very strong oxidizing power produced by the following chemical reaction (Fenton reaction) of [Reaction formula 1], but this is not locally accompanied by decomposition of alginic acid. It is essential to generate in. The present inventors have (1) divalent metal ions such as iron ions and magnesium ions in the structure of the brown alga body surface layer, but (2) alginic acid forms a chelate bond with Ca ions, and iron The investigation was repeated on the assumption that there is no room for coordination of other metal ions such as ions.
H 2 O 2 + Fe 2+ → OH * (Hydroxy radical) + OH − + Fe 3+ [Scheme 1]
Based on these inferences, the present invention obtains a high-concentration alginic acid solution by suspending brown algae in water and adding hydrogen peroxide and an alkaline agent (sodium hydroxide, sodium carbonate, etc.) to the suspension. Such a new method has been developed.
すなわち、本発明の要旨は下記のとおりである。
[１] 多糖体を含有する生物体からアルカリ金属含有アルカリ水で多糖体を抽出する際に、過酸化水素を添加して行うことを特徴とする多糖体を含有する生物体から多糖体を抽出する方法。
[２] 多糖体を含有する生物体からアルカリ金属含有アルカリ水で多糖体を抽出・精製する際に、抽出された多糖体を含むアルカリ水懸濁液に過酸化水素を添加して、濾過処理することを特徴とする多糖体を含有する生物体から多糖体を抽出・精製する方法。
[３] 生物体が海藻であることを特徴とする上記[１]又は[２]記載の方法。
[４] 海藻を、過酸化水素が添加されたアルカリ金属含有アルカリ水に浸漬して海藻中のアルギン酸を抽出した後、固形分を除去してアルギン酸抽出液を得る第１工程と、
第１工程で得られたアルギン酸抽出液に酸又はＣａ化合物水溶液を添加して固形物を生成せしめる第２工程と、
第２工程で生成して固形物を脱水して、アルギン酸を取得する第３工程とからなることを特徴とする海藻からアルギン酸を取得する方法。
[５] 上記[１]又は[２]に記載の方法で製造された多糖体。
[６] 上記[３]又は[４]に記載の方法で製造されたアルギン酸。 That is, the gist of the present invention is as follows.
[1] Extracting polysaccharides from a polysaccharide-containing organism characterized by adding hydrogen peroxide when extracting polysaccharides from a polysaccharide-containing organism with alkali metal-containing alkaline water how to.
[2] When extracting and purifying a polysaccharide from a polysaccharide-containing organism with alkali metal-containing alkaline water, hydrogen peroxide is added to the alkaline water suspension containing the extracted polysaccharide, followed by filtration. A method for extracting and purifying a polysaccharide from an organism containing the polysaccharide.
[3] The method according to [1] or [2] above, wherein the organism is a seaweed.
[4] a first step of immersing seaweed in alkali metal-containing alkaline water to which hydrogen peroxide has been added to extract alginic acid in seaweed and then removing solids to obtain an alginic acid extract;
A second step of adding an acid or Ca compound aqueous solution to the alginic acid extract obtained in the first step to generate a solid,
A method of obtaining alginic acid from seaweed, comprising: a third step of obtaining alginic acid by dehydrating solids produced in the second step.
[5] A polysaccharide produced by the method according to [1] or [2] above.
[6] Alginic acid produced by the method according to [3] or [4] above.
[１] 多糖体を含有する生物体からアルカリ金属含有アルカリ水で多糖体を抽出する際に、過酸化水素を添加して行うことを特徴とする多糖体を含有する生物体から多糖体を抽出する方法。
[２] 多糖体を含有する生物体からアルカリ金属含有アルカリ水で多糖体を抽出・精製する際に、抽出された多糖体を含むアルカリ水懸濁液に過酸化水素を添加して、濾過処理することを特徴とする多糖体を含有する生物体から多糖体を抽出・精製する方法。
[３] 生物体が海藻であることを特徴とする上記[１]又は[２]記載の方法。
[４] 海藻を、過酸化水素が添加されたアルカリ金属含有アルカリ水に浸漬して海藻中のアルギン酸を抽出した後、固形分を除去してアルギン酸抽出液を得る第１工程と、
第１工程で得られたアルギン酸抽出液に酸又はＣａ化合物水溶液を添加して固形物を生成せしめる第２工程と、
第２工程で生成して固形物を脱水して、アルギン酸を取得する第３工程とからなることを特徴とする海藻からアルギン酸を取得する方法。
[５] 上記[１]又は[２]に記載の方法で製造された多糖体。
[６] 上記[３]又は[４]に記載の方法で製造されたアルギン酸。 That is, the gist of the present invention is as follows.
[1] Extracting polysaccharides from a polysaccharide-containing organism characterized by adding hydrogen peroxide when extracting polysaccharides from a polysaccharide-containing organism with alkali metal-containing alkaline water how to.
[2] When extracting and purifying a polysaccharide from a polysaccharide-containing organism with alkali metal-containing alkaline water, hydrogen peroxide is added to the alkaline water suspension containing the extracted polysaccharide, followed by filtration. A method for extracting and purifying a polysaccharide from an organism containing the polysaccharide.
[3] The method according to [1] or [2] above, wherein the organism is a seaweed.
[4] a first step of immersing seaweed in alkali metal-containing alkaline water to which hydrogen peroxide has been added to extract alginic acid in seaweed and then removing solids to obtain an alginic acid extract;
A second step of adding an acid or Ca compound aqueous solution to the alginic acid extract obtained in the first step to generate a solid,
A method of obtaining alginic acid from seaweed, comprising: a third step of obtaining alginic acid by dehydrating solids produced in the second step.
[5] A polysaccharide produced by the method according to [1] or [2] above.
[6] Alginic acid produced by the method according to [3] or [4] above.
本発明によれば、海藻から多糖体を抽出・精製するのに要する水の使用量を従来法の１／３～１／４に減量することができる。すなわち、過酸化水素の添加により、多糖体含有抽出液の粘度を低下することができ、不純物又は析出物の濾過が容易となる。
よって、大量の使用水を削減でき、かつ水槽の容量も縮小できて、濾過作業等の容易化、コストの低減化がはかれる。 According to the present invention, the amount of water used for extracting and purifying polysaccharides from seaweed can be reduced to 1/3 to 1/4 of the conventional method. That is, the addition of hydrogen peroxide can reduce the viscosity of the polysaccharide-containing extract and facilitates filtration of impurities or precipitates.
Therefore, a large amount of water used can be reduced, and the capacity of the water tank can be reduced, facilitating filtration work and reducing costs.
よって、大量の使用水を削減でき、かつ水槽の容量も縮小できて、濾過作業等の容易化、コストの低減化がはかれる。 According to the present invention, the amount of water used for extracting and purifying polysaccharides from seaweed can be reduced to 1/3 to 1/4 of the conventional method. That is, the addition of hydrogen peroxide can reduce the viscosity of the polysaccharide-containing extract and facilitates filtration of impurities or precipitates.
Therefore, a large amount of water used can be reduced, and the capacity of the water tank can be reduced, facilitating filtration work and reducing costs.
以下、図面を参照しながら本願発明の実施形態を説明する。
本願発明に係るアルギン酸製造の原料：
本願発明に係るアルギン酸製造の原料は、褐藻類に分類される藻類でアルギン酸を含む植物体であれば、海水性、淡水性、乾燥物、未処理物を問わず原料として用いられる。また、褐藻類が他の物質と混合された状態でも、原料として用いられる。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
Raw material for producing alginic acid according to the present invention:
The raw material for producing alginic acid according to the present invention is an algae classified as brown algae and is a plant containing alginic acid, and it is used as a raw material regardless of whether it is seawater, freshwater, dried or untreated. Moreover, it is used as a raw material even in a state where brown algae are mixed with other substances.
本願発明に係るアルギン酸製造の原料：
本願発明に係るアルギン酸製造の原料は、褐藻類に分類される藻類でアルギン酸を含む植物体であれば、海水性、淡水性、乾燥物、未処理物を問わず原料として用いられる。また、褐藻類が他の物質と混合された状態でも、原料として用いられる。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
Raw material for producing alginic acid according to the present invention:
The raw material for producing alginic acid according to the present invention is an algae classified as brown algae and is a plant containing alginic acid, and it is used as a raw material regardless of whether it is seawater, freshwater, dried or untreated. Moreover, it is used as a raw material even in a state where brown algae are mixed with other substances.
本願発明に係るアルカリ薬剤：
本願発明に係るアルカリ水を調製するためのアルカリ薬剤としては、有機、無機を問わずアルカリ性を示す薬剤であれば用いることができるが、実用的には、ナトリウム、カリウムなどのアルカリ金属を含有する化合物、例えば水酸化ナトリウム、水酸化カリウム、炭酸水素ナトリウム、炭酸ナトリウム、などが用いられる。アルカリ水中のこれらの薬剤の濃度は、０．０１～１０％程度で経済的に好ましくは、０．１～０．５％程度である。本発明に係る過酸化水素の濃度：
本発明において、過酸化水素が添加されたアルギン酸含有水溶液中の過酸化水素の濃度は、０．０１％以上の濃度であれば、上限は特に限定されないが、原料の仕込み濃度などによって、適宜決定される。実用的には０．０５～０．５％である。 Alkaline agent according to the present invention:
As an alkaline agent for preparing the alkaline water according to the present invention, any agent that exhibits alkalinity can be used regardless of whether it is organic or inorganic, but practically contains an alkali metal such as sodium or potassium. Compounds such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate and the like are used. The concentration of these agents in alkaline water is about 0.01 to 10%, and preferably about 0.1 to 0.5% economically. Concentration of hydrogen peroxide according to the present invention:
In the present invention, the upper limit of the concentration of hydrogen peroxide in the alginate-containing aqueous solution to which hydrogen peroxide has been added is not particularly limited as long as the concentration is 0.01% or more, but is appropriately determined depending on the concentration of raw materials charged. Is done. Practically, it is 0.05 to 0.5%.
本願発明に係るアルカリ水を調製するためのアルカリ薬剤としては、有機、無機を問わずアルカリ性を示す薬剤であれば用いることができるが、実用的には、ナトリウム、カリウムなどのアルカリ金属を含有する化合物、例えば水酸化ナトリウム、水酸化カリウム、炭酸水素ナトリウム、炭酸ナトリウム、などが用いられる。アルカリ水中のこれらの薬剤の濃度は、０．０１～１０％程度で経済的に好ましくは、０．１～０．５％程度である。本発明に係る過酸化水素の濃度：
本発明において、過酸化水素が添加されたアルギン酸含有水溶液中の過酸化水素の濃度は、０．０１％以上の濃度であれば、上限は特に限定されないが、原料の仕込み濃度などによって、適宜決定される。実用的には０．０５～０．５％である。 Alkaline agent according to the present invention:
As an alkaline agent for preparing the alkaline water according to the present invention, any agent that exhibits alkalinity can be used regardless of whether it is organic or inorganic, but practically contains an alkali metal such as sodium or potassium. Compounds such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate and the like are used. The concentration of these agents in alkaline water is about 0.01 to 10%, and preferably about 0.1 to 0.5% economically. Concentration of hydrogen peroxide according to the present invention:
In the present invention, the upper limit of the concentration of hydrogen peroxide in the alginate-containing aqueous solution to which hydrogen peroxide has been added is not particularly limited as long as the concentration is 0.01% or more, but is appropriately determined depending on the concentration of raw materials charged. Is done. Practically, it is 0.05 to 0.5%.
本願発明に係る藻体からアルギン酸を製造する方法に関しては、以下の実施例で詳細に説明するが、本願発明に係るアルギン酸製造法の最も斬新的な点は、藻類からアルギン酸を抽出する際に、過酸化水素を添加することによって抽出液の粘度を低減させ、アルギン酸の精製・単離を容易にすることにある。これによって、アルギン酸製造に要する水量を従来法の１０％以下に低減させると共に、抽出液からのアルギン酸の製造工程を極度に単純化した点にある。
The method for producing alginic acid from the algal bodies according to the present invention will be described in detail in the following examples, but the most innovative point of the method for producing alginic acid according to the present invention is that when extracting alginic acid from algae, The purpose is to reduce the viscosity of the extract by adding hydrogen peroxide to facilitate the purification and isolation of alginic acid. As a result, the amount of water required for the production of alginic acid is reduced to 10% or less of the conventional method, and the production process of alginic acid from the extract is extremely simplified.
以下、実施例に基づき本発明を詳細に説明するが、本願発明はこれらの実施例によって何ら限定されるものではない。
実施例１：
乾燥したワカメ５０ｇに水道水１５００ｍｌを加え、１時間室温で浸漬させ、ワカメに十分含水させた後、炭酸ナトリウム３０ｇを加え１時間撹拌し、過酸化水素（濃度３０％溶液）を３０ｍｌ加え、さらに２時間撹拌して混合した。なお、この混合液の粘度は１５０，０００Ｐａ・ｓ以上であった。
その後、室温で１２時間静置した後、遠心分離（６，５００×ｇ、３０分間）して固形分を除去し、上清液を得た。この液を、濾過布を用いて濾過して混濁物質を除去した。この濾過液に塩酸（濃度３５％溶液）を５０ｍｌ加えて生じる不溶物を濾過で集め、ｐＨ２．０に調製した酸性水に浸し８０℃まで（達温）加温して洗浄し、濾過で固形物を集めた。こうして得られた固形物を、３００ｍｌの２－プロパノール（イソプロパノール）で２回洗浄した後、室温で乾燥させて１５ｇの乾燥物を得た（図１（ｂ）参照）。
この乾燥物を赤外吸収スペクトルで分析した結果、市販品のアルギン酸と一致した結果が得られた（図２参照）ので、この方法でワカメを原料にして、アルギン酸が製造できることが明らかである。また、得られたアルギン酸を加水解して構成ウロン酸を分析した結果、図３で見られるように、市販のアルギン酸と同様にグルロン酸とマンヌロン酸が検出された。
なお、図３の結果を得るために以下のとおりにして、分析を行った。
まず、アルギン酸標品２０ｍｇを０．２５ｍｌの濃度７５％硫酸溶液と混合し、２５℃で４０分間静置した後、２．７ｍｌの蒸留水を添加し、１００℃で２時間加熱した。この溶液に濃度２９％アンモニア水０．６４ｍｌを添加・混合した後、加水分解で生成した構成ウロン酸を陰イオンカラムクロマトグラフィーで分析した。
クロマトグラフィーは、Ｃａｒｂｏｐａｃ Ｐ×２５０（Ｄｉｏｎｅｘ社）を用い、分析カラム：ＣａｒｂｏｐａｃＰＡ１（４×２５０：Ｄｉｏｎｅｘ社）
、溶離液：５０ｍＭ ＮａＯＨと１５０ｍＭ酢酸ナトリウムの混合液、流速：１ｍｌ／ｍｉｎ、分析温度：３５℃で行った。
さらに、ゲルの形成能も市販のアルギン酸と同等以上の強いことが明らかになった(図４参照）ので、本願発明に係る方法がアルギン酸を製造する方法として利用できるこが証明された。
因に、この方法で１００ｇのアルギン酸を製造するのに要する水の量は、１２．５リットルであった。一方、従来法では、４０リットル以上の水を必要とする（比較例１参照）ので、本願発明のアルギン酸製造法は、優れた方法であることが明らかである。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited at all by these Examples.
Example 1:
Add 1500 ml of tap water to 50 g of dried seaweed, soak it at room temperature for 1 hour, fully hydrate the seaweed, add 30 g of sodium carbonate, stir for 1 hour, add 30 ml of hydrogen peroxide (30% strength solution), Stir for 2 hours to mix. In addition, the viscosity of this liquid mixture was 150,000 Pa.s or more.
Then, after leaving still at room temperature for 12 hours, it centrifuged (6,500 * g, 30 minutes), solid content was removed, and the supernatant liquid was obtained. This liquid was filtered using a filter cloth to remove turbid substances. 50 ml of hydrochloric acid (35% strength solution) is added to this filtrate, and the insoluble matter produced is collected by filtration, soaked in acidic water adjusted to pH 2.0, heated to 80 ° C. (temperature reached), washed, and filtered to solid Collected things. The solid thus obtained was washed twice with 300 ml of 2-propanol (isopropanol) and then dried at room temperature to obtain 15 g of a dried product (see FIG. 1B).
As a result of analyzing the dried product with an infrared absorption spectrum, a result consistent with commercially available alginic acid was obtained (see FIG. 2), and it is clear that algaic acid can be produced from wakame as a raw material by this method. Moreover, as a result of hydrolyzing the obtained alginic acid and analyzing the constituent uronic acid, as shown in FIG. 3, guluronic acid and mannuronic acid were detected in the same manner as commercially available alginic acid.
In addition, in order to obtain the result of FIG. 3, it analyzed as follows.
First, 20 mg of an alginate preparation was mixed with 0.25 ml of a 75% strength sulfuric acid solution, allowed to stand at 25 ° C. for 40 minutes, 2.7 ml of distilled water was added, and the mixture was heated at 100 ° C. for 2 hours. To this solution, 0.64 ml of 29% aqueous ammonia was added and mixed, and then the constituent uronic acid produced by hydrolysis was analyzed by anion column chromatography.
Chromatography uses Carbopac P × 250 (Dionex), analytical column: CarbopacPA1 (4 × 250: Dionex)
Eluent: a mixture of 50 mM NaOH and 150 mM sodium acetate, flow rate: 1 ml / min, analysis temperature: 35 ° C.
Furthermore, since it became clear that the gel-forming ability was equal to or higher than that of commercially available alginic acid (see FIG. 4), it was proved that the method according to the present invention can be used as a method for producing alginic acid.
Incidentally, the amount of water required to produce 100 g of alginic acid by this method was 12.5 liters. On the other hand, since the conventional method requires 40 liters or more of water (see Comparative Example 1), it is clear that the alginic acid production method of the present invention is an excellent method.
実施例１：
乾燥したワカメ５０ｇに水道水１５００ｍｌを加え、１時間室温で浸漬させ、ワカメに十分含水させた後、炭酸ナトリウム３０ｇを加え１時間撹拌し、過酸化水素（濃度３０％溶液）を３０ｍｌ加え、さらに２時間撹拌して混合した。なお、この混合液の粘度は１５０，０００Ｐａ・ｓ以上であった。
その後、室温で１２時間静置した後、遠心分離（６，５００×ｇ、３０分間）して固形分を除去し、上清液を得た。この液を、濾過布を用いて濾過して混濁物質を除去した。この濾過液に塩酸（濃度３５％溶液）を５０ｍｌ加えて生じる不溶物を濾過で集め、ｐＨ２．０に調製した酸性水に浸し８０℃まで（達温）加温して洗浄し、濾過で固形物を集めた。こうして得られた固形物を、３００ｍｌの２－プロパノール（イソプロパノール）で２回洗浄した後、室温で乾燥させて１５ｇの乾燥物を得た（図１（ｂ）参照）。
この乾燥物を赤外吸収スペクトルで分析した結果、市販品のアルギン酸と一致した結果が得られた（図２参照）ので、この方法でワカメを原料にして、アルギン酸が製造できることが明らかである。また、得られたアルギン酸を加水解して構成ウロン酸を分析した結果、図３で見られるように、市販のアルギン酸と同様にグルロン酸とマンヌロン酸が検出された。
なお、図３の結果を得るために以下のとおりにして、分析を行った。
まず、アルギン酸標品２０ｍｇを０．２５ｍｌの濃度７５％硫酸溶液と混合し、２５℃で４０分間静置した後、２．７ｍｌの蒸留水を添加し、１００℃で２時間加熱した。この溶液に濃度２９％アンモニア水０．６４ｍｌを添加・混合した後、加水分解で生成した構成ウロン酸を陰イオンカラムクロマトグラフィーで分析した。
クロマトグラフィーは、Ｃａｒｂｏｐａｃ Ｐ×２５０（Ｄｉｏｎｅｘ社）を用い、分析カラム：ＣａｒｂｏｐａｃＰＡ１（４×２５０：Ｄｉｏｎｅｘ社）
、溶離液：５０ｍＭ ＮａＯＨと１５０ｍＭ酢酸ナトリウムの混合液、流速：１ｍｌ／ｍｉｎ、分析温度：３５℃で行った。
さらに、ゲルの形成能も市販のアルギン酸と同等以上の強いことが明らかになった(図４参照）ので、本願発明に係る方法がアルギン酸を製造する方法として利用できるこが証明された。
因に、この方法で１００ｇのアルギン酸を製造するのに要する水の量は、１２．５リットルであった。一方、従来法では、４０リットル以上の水を必要とする（比較例１参照）ので、本願発明のアルギン酸製造法は、優れた方法であることが明らかである。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited at all by these Examples.
Example 1:
Add 1500 ml of tap water to 50 g of dried seaweed, soak it at room temperature for 1 hour, fully hydrate the seaweed, add 30 g of sodium carbonate, stir for 1 hour, add 30 ml of hydrogen peroxide (30% strength solution), Stir for 2 hours to mix. In addition, the viscosity of this liquid mixture was 150,000 Pa.s or more.
Then, after leaving still at room temperature for 12 hours, it centrifuged (6,500 * g, 30 minutes), solid content was removed, and the supernatant liquid was obtained. This liquid was filtered using a filter cloth to remove turbid substances. 50 ml of hydrochloric acid (35% strength solution) is added to this filtrate, and the insoluble matter produced is collected by filtration, soaked in acidic water adjusted to pH 2.0, heated to 80 ° C. (temperature reached), washed, and filtered to solid Collected things. The solid thus obtained was washed twice with 300 ml of 2-propanol (isopropanol) and then dried at room temperature to obtain 15 g of a dried product (see FIG. 1B).
As a result of analyzing the dried product with an infrared absorption spectrum, a result consistent with commercially available alginic acid was obtained (see FIG. 2), and it is clear that algaic acid can be produced from wakame as a raw material by this method. Moreover, as a result of hydrolyzing the obtained alginic acid and analyzing the constituent uronic acid, as shown in FIG. 3, guluronic acid and mannuronic acid were detected in the same manner as commercially available alginic acid.
In addition, in order to obtain the result of FIG. 3, it analyzed as follows.
First, 20 mg of an alginate preparation was mixed with 0.25 ml of a 75% strength sulfuric acid solution, allowed to stand at 25 ° C. for 40 minutes, 2.7 ml of distilled water was added, and the mixture was heated at 100 ° C. for 2 hours. To this solution, 0.64 ml of 29% aqueous ammonia was added and mixed, and then the constituent uronic acid produced by hydrolysis was analyzed by anion column chromatography.
Chromatography uses Carbopac P × 250 (Dionex), analytical column: CarbopacPA1 (4 × 250: Dionex)
Eluent: a mixture of 50 mM NaOH and 150 mM sodium acetate, flow rate: 1 ml / min, analysis temperature: 35 ° C.
Furthermore, since it became clear that the gel-forming ability was equal to or higher than that of commercially available alginic acid (see FIG. 4), it was proved that the method according to the present invention can be used as a method for producing alginic acid.
Incidentally, the amount of water required to produce 100 g of alginic acid by this method was 12.5 liters. On the other hand, since the conventional method requires 40 liters or more of water (see Comparative Example 1), it is clear that the alginic acid production method of the present invention is an excellent method.
実施例２：
乾燥したコンブ５０ｇに水道水１，５００ｍｌを加え、１時間４０℃で浸漬させてコンブに十分含水させた後、炭酸ナトリウム３０ｇを加え１時間撹拌した後、過酸化水素水（濃度３０％溶液）３０ｍｌを加え、さらに２時間撹拌して混合した。なお、この混合液の粘度は４０，０００Ｐａ・ｓであった。
その後、室温で１２時間静置し、遠心分離で固形物を除去し、上清液（１，３００ｍｌ）を得た。この液を、濾布を用いて濾過して混濁物質を完全に除去した。この濾過液に塩酸（濃度３５％溶液）を５０ｍｌ加えて生じる不溶物を濾過で集め、ｐＨ２．０に調製した塩酸溶液に浸して８０℃まで加温（達温）して洗浄し、濾過で固形物を集めた。こうして得られた固形物を、３００ｍｌの２－プロパノール（イソプロパノール）で２回洗浄した後、室温で乾燥させて７ｇの乾燥物を得た。 Example 2:
Add 1,500 ml of tap water to 50 g of dried comb, soak it at 40 ° C. for 1 hour and thoroughly hydrate the kombu, add 30 g of sodium carbonate, stir for 1 hour, and then hydrogen peroxide (concentration 30% solution). 30 ml was added and stirred for another 2 hours to mix. The viscosity of this mixed solution was 40,000 Pa · s.
Then, it left still at room temperature for 12 hours, the solid substance was removed by centrifugation, and the supernatant liquid (1,300 ml) was obtained. This liquid was filtered using a filter cloth to completely remove turbid materials. 50 ml of hydrochloric acid (35% strength solution) was added to this filtrate, and the insoluble matter produced was collected by filtration, immersed in a hydrochloric acid solution adjusted to pH 2.0, heated to 80 ° C. (washed), washed, and filtered. The solid was collected. The solid thus obtained was washed twice with 300 ml of 2-propanol (isopropanol) and then dried at room temperature to obtain 7 g of a dried product.
乾燥したコンブ５０ｇに水道水１，５００ｍｌを加え、１時間４０℃で浸漬させてコンブに十分含水させた後、炭酸ナトリウム３０ｇを加え１時間撹拌した後、過酸化水素水（濃度３０％溶液）３０ｍｌを加え、さらに２時間撹拌して混合した。なお、この混合液の粘度は４０，０００Ｐａ・ｓであった。
その後、室温で１２時間静置し、遠心分離で固形物を除去し、上清液（１，３００ｍｌ）を得た。この液を、濾布を用いて濾過して混濁物質を完全に除去した。この濾過液に塩酸（濃度３５％溶液）を５０ｍｌ加えて生じる不溶物を濾過で集め、ｐＨ２．０に調製した塩酸溶液に浸して８０℃まで加温（達温）して洗浄し、濾過で固形物を集めた。こうして得られた固形物を、３００ｍｌの２－プロパノール（イソプロパノール）で２回洗浄した後、室温で乾燥させて７ｇの乾燥物を得た。 Example 2:
Add 1,500 ml of tap water to 50 g of dried comb, soak it at 40 ° C. for 1 hour and thoroughly hydrate the kombu, add 30 g of sodium carbonate, stir for 1 hour, and then hydrogen peroxide (
Then, it left still at room temperature for 12 hours, the solid substance was removed by centrifugation, and the supernatant liquid (1,300 ml) was obtained. This liquid was filtered using a filter cloth to completely remove turbid materials. 50 ml of hydrochloric acid (35% strength solution) was added to this filtrate, and the insoluble matter produced was collected by filtration, immersed in a hydrochloric acid solution adjusted to pH 2.0, heated to 80 ° C. (washed), washed, and filtered. The solid was collected. The solid thus obtained was washed twice with 300 ml of 2-propanol (isopropanol) and then dried at room temperature to obtain 7 g of a dried product.
実施例３：
生ワカメ１ｋｇに水道水１０００ｍｌと炭酸ナトリウム４０ｇを加えて、１時間程撹拌し、過酸化水素（濃度３０％溶液）を４０ｍｌ加え、さらに２時間程撹拌して混合した。なお、この混合液の粘度は８１，０００Ｐａ・ｓであった。その後、室温で１２時間以上静置し、遠心分離して固形分を除去し、上清液を得た。この液を、精密濾過で濾過して混濁物質を除去した。この濾過液に塩酸（濃度３５％溶液）を７０ｍｌ加えて生じる不溶物を濾過で集め、ｐＨ２．０に調製した酸性水に浸し８０℃まで加温した（達温）後、濾過で固形物を集めた。こうして得られた固形物を、４００ｍｌの２－プロパノール（イソプロパノール）で２回洗浄した後、室温で乾燥させて１７ｇの乾燥物を得た。こうして得られたアルギン酸を実施例１に示した手法で分析して市販のアルギン酸と同等以上の性質を有することを確認した。 Example 3:
To 1 kg of raw seaweed, 1000 ml of tap water and 40 g of sodium carbonate were added and stirred for about 1 hour, 40 ml of hydrogen peroxide (30% strength solution) was added, and the mixture was further stirred for about 2 hours and mixed. The viscosity of the mixed solution was 81,000 Pa · s. Thereafter, the mixture was allowed to stand at room temperature for 12 hours or more, and centrifuged to remove solids, thereby obtaining a supernatant. This liquid was filtered by microfiltration to remove turbid substances. 70 ml of hydrochloric acid (35% strength solution) was added to this filtrate, and the resulting insoluble matter was collected by filtration, soaked in acidic water adjusted to pH 2.0 and heated to 80 ° C. (temperature reached), and then the solid matter was filtered. collected. The solid thus obtained was washed twice with 400 ml of 2-propanol (isopropanol) and then dried at room temperature to obtain 17 g of a dried product. The alginic acid thus obtained was analyzed by the method shown in Example 1, and it was confirmed that it had properties equivalent to or better than commercially available alginic acid.
生ワカメ１ｋｇに水道水１０００ｍｌと炭酸ナトリウム４０ｇを加えて、１時間程撹拌し、過酸化水素（濃度３０％溶液）を４０ｍｌ加え、さらに２時間程撹拌して混合した。なお、この混合液の粘度は８１，０００Ｐａ・ｓであった。その後、室温で１２時間以上静置し、遠心分離して固形分を除去し、上清液を得た。この液を、精密濾過で濾過して混濁物質を除去した。この濾過液に塩酸（濃度３５％溶液）を７０ｍｌ加えて生じる不溶物を濾過で集め、ｐＨ２．０に調製した酸性水に浸し８０℃まで加温した（達温）後、濾過で固形物を集めた。こうして得られた固形物を、４００ｍｌの２－プロパノール（イソプロパノール）で２回洗浄した後、室温で乾燥させて１７ｇの乾燥物を得た。こうして得られたアルギン酸を実施例１に示した手法で分析して市販のアルギン酸と同等以上の性質を有することを確認した。 Example 3:
To 1 kg of raw seaweed, 1000 ml of tap water and 40 g of sodium carbonate were added and stirred for about 1 hour, 40 ml of hydrogen peroxide (30% strength solution) was added, and the mixture was further stirred for about 2 hours and mixed. The viscosity of the mixed solution was 81,000 Pa · s. Thereafter, the mixture was allowed to stand at room temperature for 12 hours or more, and centrifuged to remove solids, thereby obtaining a supernatant. This liquid was filtered by microfiltration to remove turbid substances. 70 ml of hydrochloric acid (35% strength solution) was added to this filtrate, and the resulting insoluble matter was collected by filtration, soaked in acidic water adjusted to pH 2.0 and heated to 80 ° C. (temperature reached), and then the solid matter was filtered. collected. The solid thus obtained was washed twice with 400 ml of 2-propanol (isopropanol) and then dried at room temperature to obtain 17 g of a dried product. The alginic acid thus obtained was analyzed by the method shown in Example 1, and it was confirmed that it had properties equivalent to or better than commercially available alginic acid.
実施例４：
生コンブ１ｋｇに水道水５０リットルと炭酸ナトリウム２００ｇを加えて、１時間撹拌し、過酸化水素水（濃度３０％溶液）を２００ｍｌ加え、さらに２時間撹拌して混合した。なお、この混合液の粘度は９５，０００Ｐａ・ｓであった。その後、室温で１２時間静置し、遠心分離して固形分を除去し、上清液を得た。この液を、濾過で混濁物質を除去した濾過液に塩酸（濃度３０％溶液）７０ｍｌ加えて生じる不溶物を濾過で集め、ｐＨ２．０に調製した塩酸水に浸し８０℃（達温）まで加温した後、濾過で固形物を集めた。こうして得られた固形分を、１０リットルの２－プロパノール（イソプロパノール）で２回洗浄した後、室温で乾燥させて５０ｇの乾燥アルギン酸を得た。 Example 4:
50 kg of tap water and 200 g of sodium carbonate were added to 1 kg of raw comb and stirred for 1 hour, 200 ml of hydrogen peroxide (30% strength solution) was added, and the mixture was further stirred for 2 hours and mixed. The viscosity of the mixed solution was 95,000 Pa · s. Then, it left still at room temperature for 12 hours, centrifuged and removed solid content, and the supernatant liquid was obtained. This solution was filtered to remove insoluble substances by adding 70 ml of hydrochloric acid (30% strength solution) to the filtrate, collected by filtration, immersed in hydrochloric acid adjusted to pH 2.0, and heated to 80 ° C. (temperature reached). After warming, the solid was collected by filtration. The solid content thus obtained was washed twice with 10 liters of 2-propanol (isopropanol) and then dried at room temperature to obtain 50 g of dry alginic acid.
生コンブ１ｋｇに水道水５０リットルと炭酸ナトリウム２００ｇを加えて、１時間撹拌し、過酸化水素水（濃度３０％溶液）を２００ｍｌ加え、さらに２時間撹拌して混合した。なお、この混合液の粘度は９５，０００Ｐａ・ｓであった。その後、室温で１２時間静置し、遠心分離して固形分を除去し、上清液を得た。この液を、濾過で混濁物質を除去した濾過液に塩酸（濃度３０％溶液）７０ｍｌ加えて生じる不溶物を濾過で集め、ｐＨ２．０に調製した塩酸水に浸し８０℃（達温）まで加温した後、濾過で固形物を集めた。こうして得られた固形分を、１０リットルの２－プロパノール（イソプロパノール）で２回洗浄した後、室温で乾燥させて５０ｇの乾燥アルギン酸を得た。 Example 4:
50 kg of tap water and 200 g of sodium carbonate were added to 1 kg of raw comb and stirred for 1 hour, 200 ml of hydrogen peroxide (30% strength solution) was added, and the mixture was further stirred for 2 hours and mixed. The viscosity of the mixed solution was 95,000 Pa · s. Then, it left still at room temperature for 12 hours, centrifuged and removed solid content, and the supernatant liquid was obtained. This solution was filtered to remove insoluble substances by adding 70 ml of hydrochloric acid (30% strength solution) to the filtrate, collected by filtration, immersed in hydrochloric acid adjusted to pH 2.0, and heated to 80 ° C. (temperature reached). After warming, the solid was collected by filtration. The solid content thus obtained was washed twice with 10 liters of 2-propanol (isopropanol) and then dried at room temperature to obtain 50 g of dry alginic acid.
比較例１：
実施例４と同様の方法で過酸化水素水の替わりに蒸留水を用いてコンブからアルギン酸の製造を行ったところ、抽出操作後の濾過に際して１５０リットルの水を添加し、希釈して粘度を下げる必要があった。また、こうして製造したアルギン酸は淡褐色を示し、イオン交換樹脂処理などの脱色操作が必要であることが確認された。
すなわち、生コンブ１ｋｇを水道水５０リットルに懸濁し、炭酸ナトリウム２００gを加えて、１時間撹拌し、過酸化水素の替わりに２００ｍｌの蒸留水を加え、さらに２１時間撹拌して混合した。なお、この混合液の粘度は極めて高く（１５７，０００Ｐａ・ｓ以上）、その後の処理が不可能であったので、さらに水を１５０リットル加えて混合し、粘度を低下させた後、遠心分離器で混濁物質を除去した上清に塩酸（濃度３０％溶液）２８０ｍｌを加えて生じる不溶物を濾過で集め、ｐＨ２に調整した塩酸水に浸し８０℃（達温）迄加温した後、濾過で固形物を集めた。
こうして得られた固形分を、１０リットルの２－プロパノール（イソプロパノール）で洗浄した後、室温で乾燥させて４６ｇのアルギン酸を得た。 Comparative Example 1:
When alginic acid was produced from the kombu using distilled water instead of hydrogen peroxide in the same manner as in Example 4, 150 liters of water was added during the filtration after the extraction operation, and diluted to lower the viscosity. There was a need. In addition, the alginic acid produced in this way showed a light brown color, and it was confirmed that a decoloring operation such as an ion exchange resin treatment was necessary.
That is, 1 kg of raw kumbu was suspended in 50 liters of tap water, 200 g of sodium carbonate was added and stirred for 1 hour, 200 ml of distilled water was added instead of hydrogen peroxide, and the mixture was further stirred for 21 hours and mixed. In addition, since the viscosity of this liquid mixture was extremely high (157,000 Pa.s or more) and the subsequent treatment was impossible, 150 liters of water was further added and mixed to reduce the viscosity, and then the centrifuge Add 280 ml of hydrochloric acid (concentration 30% solution) to the supernatant after removing the turbid material in, collect the insoluble matter by filtration, soak in hydrochloric acid adjusted to pH 2 and warm to 80 ° C. (temperature), then filter. The solid was collected.
The solid content thus obtained was washed with 10 liters of 2-propanol (isopropanol) and then dried at room temperature to obtain 46 g of alginic acid.
実施例４と同様の方法で過酸化水素水の替わりに蒸留水を用いてコンブからアルギン酸の製造を行ったところ、抽出操作後の濾過に際して１５０リットルの水を添加し、希釈して粘度を下げる必要があった。また、こうして製造したアルギン酸は淡褐色を示し、イオン交換樹脂処理などの脱色操作が必要であることが確認された。
すなわち、生コンブ１ｋｇを水道水５０リットルに懸濁し、炭酸ナトリウム２００gを加えて、１時間撹拌し、過酸化水素の替わりに２００ｍｌの蒸留水を加え、さらに２１時間撹拌して混合した。なお、この混合液の粘度は極めて高く（１５７，０００Ｐａ・ｓ以上）、その後の処理が不可能であったので、さらに水を１５０リットル加えて混合し、粘度を低下させた後、遠心分離器で混濁物質を除去した上清に塩酸（濃度３０％溶液）２８０ｍｌを加えて生じる不溶物を濾過で集め、ｐＨ２に調整した塩酸水に浸し８０℃（達温）迄加温した後、濾過で固形物を集めた。
こうして得られた固形分を、１０リットルの２－プロパノール（イソプロパノール）で洗浄した後、室温で乾燥させて４６ｇのアルギン酸を得た。 Comparative Example 1:
When alginic acid was produced from the kombu using distilled water instead of hydrogen peroxide in the same manner as in Example 4, 150 liters of water was added during the filtration after the extraction operation, and diluted to lower the viscosity. There was a need. In addition, the alginic acid produced in this way showed a light brown color, and it was confirmed that a decoloring operation such as an ion exchange resin treatment was necessary.
That is, 1 kg of raw kumbu was suspended in 50 liters of tap water, 200 g of sodium carbonate was added and stirred for 1 hour, 200 ml of distilled water was added instead of hydrogen peroxide, and the mixture was further stirred for 21 hours and mixed. In addition, since the viscosity of this liquid mixture was extremely high (157,000 Pa.s or more) and the subsequent treatment was impossible, 150 liters of water was further added and mixed to reduce the viscosity, and then the centrifuge Add 280 ml of hydrochloric acid (
The solid content thus obtained was washed with 10 liters of 2-propanol (isopropanol) and then dried at room temperature to obtain 46 g of alginic acid.
また、本発明の技術は、海藻からアルギン酸を製造するのみでなく、広く多糖体を含む生物体から多糖体を抽出・精製して多糖体を製造する際にも利用できるものである。
Further, the technology of the present invention can be used not only for producing alginic acid from seaweed but also for producing polysaccharides by extracting and purifying polysaccharides from organisms containing a wide variety of polysaccharides.
Claims (6)
- 多糖体を含有する生物体からアルカリ金属含有アルカリ水で多糖体を抽出する際に、過酸化水素を添加して行うことを特徴とする多糖体を含有する生物体から多糖体を抽出する方法。 A method for extracting a polysaccharide from a polysaccharide-containing organism, wherein hydrogen peroxide is added to extract the polysaccharide from the polysaccharide-containing organism with alkali metal-containing alkaline water.
- 多糖体を含有する生物体からアルカリ金属含有アルカリ水で多糖体を抽出・精製する際に、抽出された多糖体を含むアルカリ水懸濁液に過酸化水素を添加して、濾過処理することを特徴とする多糖体を含有する生物体から多糖体を抽出・精製する方法。 When extracting and purifying a polysaccharide from a polysaccharide-containing organism with alkali metal-containing alkaline water, adding hydrogen peroxide to the alkaline water suspension containing the extracted polysaccharide and filtering it. A method for extracting and purifying a polysaccharide from an organism containing the characteristic polysaccharide.
- 生物体が海藻であることを特徴とする請求項１又は２に記載の方法。 The method according to claim 1 or 2, wherein the organism is a seaweed.
- 海藻を、過酸化水素が添加されたアルカリ金属含有アルカリ水に浸漬して海藻中のアルギン酸を抽出した後、固形分を除去してアルギン酸抽出液を得る第１工程と、
第１工程で得られたアルギン酸抽出液に酸又はＣａ化合物水溶液を添加して固形物を生成せしめる第２工程と、
第２工程で生成して固形物を脱水して、アルギン酸を取得する第３工程とからなることを特徴とする海藻からアルギン酸を取得する方法。 A first step of immersing the seaweed in an alkali metal-containing alkaline water to which hydrogen peroxide has been added to extract alginic acid in the seaweed and then removing the solids to obtain an alginic acid extract;
A second step of adding an acid or Ca compound aqueous solution to the alginic acid extract obtained in the first step to generate a solid,
A method of obtaining alginic acid from seaweed, comprising: a third step of obtaining alginic acid by dehydrating solids produced in the second step. - 請求項１又は２項に記載の方法で製造された多糖体。 A polysaccharide produced by the method according to claim 1 or 2.
- 請求項３又は４項に記載の方法で製造されたアルギン酸。 Alginic acid produced by the method according to claim 3 or 4.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111848827A (en) * | 2020-06-10 | 2020-10-30 | 青岛海大生物集团有限公司 | Novel chlorella polysaccharide bactericide and preparation method thereof |
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| JPS5212200A (en) * | 1975-06-04 | 1977-01-29 | Nobuyasu Hasebe | Method of producing alginic acid |
| JPH0499491A (en) * | 1990-08-17 | 1992-03-31 | Japan Steel Works Ltd:The | Production of alginic acid |
| JP2009149734A (en) * | 2007-12-19 | 2009-07-09 | Kao Corp | Production method for alginic acid of low molecular weight or derivative thereof |
| CN103172761A (en) * | 2013-04-22 | 2013-06-26 | 青岛贝尔特生物科技有限公司 | Energy-saving and emission-reducing production method of high-quality sodium alginate |
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