JP2015029463A - Method for producing monosaccharide concentrate - Google Patents
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本発明は、バイオマスを分解して得られる糖化処理液を濃縮して単糖類濃縮液を製造する方法に関する。 The present invention relates to a method for producing a monosaccharide concentrate by concentrating a saccharification treatment solution obtained by decomposing biomass.
近年、バイオマスの有効活用に向けた様々な取り組みがなされており、例えば、バイオマスから有用化合物を生成する試みがなされている。バイオマスを分解処理して得られる有用化合物としてはエタノールや乳酸がよく知られており、エタノールはガソリン代替燃料としての利用が、乳酸はポリ乳酸に変換することによりバイオプラスチックとしての利用が既に一部始まっている。 In recent years, various efforts have been made for effective utilization of biomass. For example, attempts have been made to produce useful compounds from biomass. Ethanol and lactic acid are well known as useful compounds obtained by decomposing biomass, and ethanol is already used as an alternative fuel for gasoline, and lactic acid is converted to polylactic acid to partially use it as a bioplastic. It has begun.
バイオマスからエタノールや乳酸を生成する方法としては、バイオマスを物理化学的または生物学的に分解して糖化処理液を得て、これをエタノール発酵や乳酸発酵する方法が一般的である。ところで、糖化処理液をエタノール発酵や乳酸発酵させて効率的にエタノールや乳酸を生成させるためには、糖化処理液に十分な濃度の単糖類が含まれることが好ましい。しかし、バイオマスを分解して得られる糖化処理液には必ずしも十分な濃度の単糖類が含まれるとは限らない。バイオマスから糖化処理液を得て濃縮する方法として、例えば特許文献１には、バイオマスを生物処理して糖化処理液を得て、これを逆浸透処理することにより濃縮する方法が開示され、特許文献２には、バイオマスを物理化学処理して糖化処理液を得て、これを逆浸透処理することにより濃縮する方法が開示されている。 As a method for producing ethanol and lactic acid from biomass, a method is generally used in which biomass is physicochemically or biologically decomposed to obtain a saccharification treatment solution, and this is subjected to ethanol fermentation or lactic acid fermentation. By the way, in order to efficiently produce ethanol or lactic acid by subjecting the saccharification treatment liquid to ethanol fermentation or lactic acid fermentation, it is preferable that the saccharification treatment liquid contains a sufficient concentration of monosaccharides. However, a saccharification treatment solution obtained by decomposing biomass does not necessarily contain a sufficient concentration of monosaccharides. As a method for obtaining and concentrating a saccharification treatment liquid from biomass, for example, Patent Document 1 discloses a method of biologically treating biomass to obtain a saccharification treatment liquid and concentrating it by reverse osmosis treatment. No. 2 discloses a method of concentrating a biomass by physicochemical treatment to obtain a saccharification treatment solution and subjecting this to reverse osmosis treatment.
しかし本発明者らが検討したところ、糖化処理液の濃縮方法として逆浸透処理を採用した場合、糖化処理液に含まれる単糖類をある程度濃縮できるものの、濃縮の程度には限界があることが明らかになった。そして、糖化処理液から効率的にエタノールや乳酸を製造することを考慮すると、より効率的かつ高度な糖化処理液の濃縮を実現することが好ましい。 However, as a result of studies by the present inventors, when reverse osmosis treatment is employed as a concentration method for a saccharification treatment solution, it is clear that although monosaccharides contained in the saccharification treatment solution can be concentrated to some extent, the degree of concentration is limited. Became. In consideration of efficiently producing ethanol or lactic acid from the saccharification treatment solution, it is preferable to realize more efficient and advanced concentration of the saccharification treatment solution.
本発明は前記事情に鑑みてなされたものであり、その目的は、バイオマスを分解して得られる糖化処理液から効率的かつ高度に濃縮された単糖類濃縮液を製造する方法を提供することにある。 This invention is made | formed in view of the said situation, The objective is to provide the method of manufacturing the monosaccharide concentrate efficiently and highly concentrated from the saccharification processing liquid obtained by decomposing | disassembling biomass. is there.
前記課題を解決することができた本発明の単糖類濃縮液の製造方法とは、バイオマスを分解処理して単糖類を含有する糖化処理液を得る工程と、糖化処理液を正浸透処理して単糖類濃縮液を得る工程とを有するところに特徴を有する。本発明によれば、バイオマスを分解処理して得られた糖化処理液を濃縮するのに正浸透処理を採用することにより、例えば逆浸透処理する場合と比較して、糖化処理液を格段に効率的かつ高度に濃縮することができる。 The method for producing a monosaccharide concentrate of the present invention that has solved the above problems includes a step of decomposing biomass to obtain a saccharification treatment liquid containing monosaccharides, and forward osmosis treatment of the saccharification treatment liquid. And a step of obtaining a monosaccharide concentrate. According to the present invention, by adopting forward osmosis treatment to concentrate the saccharification treatment liquid obtained by decomposing biomass, for example, compared to the case of reverse osmosis treatment, the saccharification treatment liquid is much more efficient. And highly concentrated.
本発明の製造方法では、糖化処理液を限外ろ過膜を用いて膜分離処理し、得られたろ液を正浸透処理することにより、単糖類濃縮液を得るようにすることが好ましい。糖化処理液を限外ろ過膜を用いて膜分離処理することにより、糖化処理液に含まれる高分子量の溶質を除去することができ、その結果、糖化処理液の浸透圧を下げて、正浸透処理における単糖類の濃縮をより好適に行えるようになる。 In the production method of the present invention, it is preferable to obtain a monosaccharide concentrated solution by subjecting the saccharification treatment solution to membrane separation treatment using an ultrafiltration membrane and subjecting the obtained filtrate to forward osmosis treatment. High-molecular-weight solute contained in the saccharification treatment liquid can be removed by subjecting the saccharification treatment liquid to membrane separation using an ultrafiltration membrane. As a result, the osmotic pressure of the saccharification treatment liquid is reduced and forward osmosis is performed. It becomes possible to more suitably concentrate monosaccharides in the treatment.
本発明では、糖化処理液を正浸透処理することにより、単糖類濃縮液のキシロースとグルコースの合計濃度を１２質量％以上とすることが好ましい。このような高濃度の単糖類濃縮液を得ることができれば、単糖類濃縮液を用いてエタノール発酵や乳酸発酵を効率的に行うことができる。 In the present invention, it is preferable that the total concentration of xylose and glucose in the monosaccharide concentrate is 12% by mass or more by subjecting the saccharification treatment solution to forward osmosis treatment. If such a high concentration monosaccharide concentrate can be obtained, ethanol fermentation and lactic acid fermentation can be efficiently performed using the monosaccharide concentrate.
バイオマスとしてはセルロース系バイオマスを用いることが好ましい。セルロース系バイオマスから得られた糖化処理液は単糖類濃度が低い場合が多く、セルロース系バイオマスから得られた糖化処理液を正浸透処理することによって、より効率的な濃縮が実現できる。 Cellulose biomass is preferably used as the biomass. The saccharification treatment liquid obtained from cellulosic biomass often has a low monosaccharide concentration, and more efficient concentration can be realized by forward osmosis treatment of the saccharification treatment liquid obtained from cellulosic biomass.
本発明の単糖類濃縮液の製造方法によれば、バイオマスを分解処理して得られた糖化処理液を濃縮するのに正浸透処理を採用することにより、糖化処理液を効率的かつ高度に濃縮することができる。 According to the method for producing a monosaccharide concentrate of the present invention, the saccharification treatment solution is efficiently and highly concentrated by adopting forward osmosis treatment to concentrate the saccharification treatment solution obtained by decomposing biomass. can do.
本発明は、バイオマスを分解（糖化）して得られる糖化処理液を濃縮して、単糖類濃縮液を製造する方法に関し、糖化処理液を正浸透処理することにより、糖化処理液に含まれる単糖類を効率的かつ高度に濃縮することを目指すものである。本発明の単糖類濃縮液の製造方法は、バイオマスを分解処理して、単糖類を含有する糖化処理液を得る工程（バイオマス分解工程）と、糖化処理液を正浸透処理して、単糖類濃縮液を得る工程（濃縮工程）とを有する。 The present invention relates to a method for producing a monosaccharide concentrate by concentrating a saccharification treatment solution obtained by decomposing (saccharifying) biomass, and by subjecting the saccharification treatment solution to forward osmosis treatment, The aim is to concentrate saccharides efficiently and highly. The method for producing a monosaccharide concentrate according to the present invention includes a step of decomposing biomass to obtain a saccharification treatment solution containing monosaccharides (biomass decomposition step), and forward osmosis treatment of the saccharification treatment solution to concentrate monosaccharides. A step of obtaining a liquid (concentration step).
本発明で原料として用いられるバイオマスは、分解することにより単糖類を生成するものであれば特に限定されないが、セルロース系バイオマスやデンプン系バイオマスが好ましく用いられる。セルロース系バイオマスとしては、間伐材、建設廃材、廃木材、枝葉、剪定草本、稲わら、麦わら、バガス、ヤシ殻、紙等が挙げられる。デンプン系バイオマスとしては、トウモロコシ、芋類、穀類等のデンプン系作物が挙げられる。なお、セルロース系バイオマスを分解処理した場合は、単糖類を高濃度に含む糖化処理液を得ることが難しいことから、セルロース系バイオマスを原料として用いた場合は、濃縮工程でより濃縮効率（濃縮倍率）を高めることが可能となる。従って、より高い濃縮効率を得る点からは、セルロース系バイオマスを原料として用いることが好ましい。 The biomass used as a raw material in the present invention is not particularly limited as long as it produces monosaccharides by decomposition, but cellulose-based biomass and starch-based biomass are preferably used. Examples of cellulosic biomass include thinned wood, construction waste, waste wood, branches and leaves, pruned herb, rice straw, straw, bagasse, coconut shell, and paper. Examples of starch-based biomass include starch-based crops such as corn, potatoes, and cereals. In addition, when cellulosic biomass is decomposed, it is difficult to obtain a saccharification solution containing monosaccharides at a high concentration. Therefore, when cellulosic biomass is used as a raw material, the concentration efficiency (concentration ratio) is higher in the concentration step. ) Can be increased. Therefore, it is preferable to use cellulosic biomass as a raw material from the viewpoint of obtaining higher concentration efficiency.
バイオマス分解工程では、バイオマスを分解処理して、単糖類を含有する糖化処理液を得る。バイオマスを分解処理することにより、例えばセルロースやデンプンが単糖類まで分解（糖化）し、糖化処理液が得られる。 In the biomass decomposition step, the biomass is decomposed to obtain a saccharification treatment solution containing monosaccharides. By decomposing biomass, for example, cellulose and starch are decomposed (saccharified) to monosaccharides, and a saccharification treatment solution is obtained.
分解処理は、公知の物理化学処理や生物処理を採用すればよい。分解処理は、単一の処理であっても、異なる処理を組み合わせて行ってもよい。分解処理に用いられる物理化学処理としては、水熱処理、蒸煮爆砕処理、酸処理（例えば、濃硫酸や希硫酸による処理）、アルカリ処理、触媒加水分解処理等が挙げられる。生物処理としては、酵素や微生物を用いた処理が挙げられる。例えば、分解処理を、物理化学処理と生物処理を組み合わせて行うことにより、比較的穏和な条件で、単糖類の生成率を高めることができる。特に、セルロース系バイオマスを分解処理する場合は、セルロースの分解効率を高める点から、分解処理として少なくとも物理化学処理を採用することが好ましく、物理化学処理に引き続いて生物処理を行うことがより好ましい。 The decomposition process may be a known physicochemical process or biological process. The decomposition process may be a single process or a combination of different processes. Examples of the physicochemical treatment used for the decomposition treatment include hydrothermal treatment, steam explosion treatment, acid treatment (for example, treatment with concentrated sulfuric acid or dilute sulfuric acid), alkali treatment, catalytic hydrolysis treatment, and the like. Examples of biological treatment include treatment using enzymes and microorganisms. For example, by performing the decomposition treatment in combination with physicochemical treatment and biological treatment, the monosaccharide production rate can be increased under relatively mild conditions. In particular, when cellulosic biomass is decomposed, it is preferable to employ at least physicochemical treatment as the decomposition treatment from the viewpoint of increasing the decomposition efficiency of cellulose, and it is more preferable to perform biological treatment subsequent to physicochemical treatment.
糖化処理液は少なくとも単糖類を含有しており、さらに例えば多糖類を含有していてもよい。なお、バイオマスを分解処理することにより得られる単糖類としては、キシロースやグルコースがよく知られており、従って、糖化処理液は少なくともキシロースおよび／またはグルコースを含んでいることが好ましい。 The saccharification treatment liquid contains at least a monosaccharide, and may further contain, for example, a polysaccharide. In addition, xylose and glucose are well known as monosaccharides obtained by decomposing biomass, and therefore it is preferable that the saccharification treatment solution contains at least xylose and / or glucose.
糖化処理液は、原料となるバイオマスの種類に応じて、他に様々な物質（化合物）を含み得る。例えば、セルロース系バイオマスを原料として用いた場合は、糖化処理液は、リグニン等の難分解性物質や未分解の固形分を含み得る。 The saccharification treatment liquid may contain various other substances (compounds) depending on the type of biomass as a raw material. For example, when cellulosic biomass is used as a raw material, the saccharification treatment liquid may contain a hardly decomposable substance such as lignin and an undecomposed solid content.
糖化処理液に含まれる単糖類は、エタノールや乳酸等のより有用な化合物に変換させるための原料として使用できる。例えば、単糖類をエタノール発酵させることによりエタノールを生成することができ、このようにして得られたエタノールは燃料や水素原料への利用等様々な検討がなされている。また、単糖類を乳酸発酵させることにより乳酸を生成することができ、このようにして得られた乳酸は、ポリ乳酸に変換してバイオプラスチックへの利用等様々な検討がなされている。 The monosaccharide contained in the saccharification treatment solution can be used as a raw material for converting into a more useful compound such as ethanol or lactic acid. For example, ethanol can be produced by subjecting a monosaccharide to ethanol fermentation, and the ethanol thus obtained has been studied in various ways such as for use as a fuel or hydrogen raw material. Furthermore, lactic acid can be produced by lactic acid fermentation of monosaccharides, and various studies have been made such as conversion of lactic acid obtained in this way into polylactic acid for use in bioplastics.
ところで、糖化処理液のエタノール発酵や乳酸発酵等を効率的に行うためには、糖化処理液の単糖類濃度を高めることが好ましい。しかし、バイオマスを分解処理することにより得られる糖化処理液には必ずしも所望の濃度の単糖類が含まれるとは限らず、例えばセルロース系バイオマスを分解処理して得られた糖化処理液には、効率的なエタノール発酵や乳酸発酵を行うのに十分な濃度の単糖類が含まれない場合が多い。従って、糖化処理液に含まれる単糖類を効率的に有用な化合物に変換するためには、糖化処理液の単糖類濃度を高めることが好ましい。 By the way, in order to efficiently perform ethanol fermentation or lactic acid fermentation of the saccharification treatment liquid, it is preferable to increase the monosaccharide concentration of the saccharification treatment liquid. However, a saccharification treatment liquid obtained by decomposing biomass does not necessarily contain a monosaccharide having a desired concentration. For example, a saccharification treatment liquid obtained by decomposing cellulosic biomass has an efficiency. In many cases, monosaccharides at a concentration sufficient to perform typical ethanol fermentation and lactic acid fermentation are not included. Therefore, in order to efficiently convert the monosaccharide contained in the saccharification treatment liquid into a useful compound, it is preferable to increase the monosaccharide concentration of the saccharification treatment liquid.
糖化処理液には単糖類が溶解した状態で存在するため、糖化処理液の単糖類濃度を高めるためには、糖化処理液の水分を除去して濃縮させることが必要となる。糖化処理液の濃縮方法としては、例えば、熱処理により糖化処理液に含まれる水を蒸発除去する方法が考えられる。しかしこの場合、水分除去のために多大なエネルギーを要することとなり、バイオマスの有効利用技術としてコスト的に合わないものとなる。 Since the saccharification treatment liquid exists in a state in which monosaccharides are dissolved, in order to increase the monosaccharide concentration of the saccharification treatment liquid, it is necessary to remove the water from the saccharification treatment liquid and concentrate it. As a method for concentrating the saccharification treatment solution, for example, a method of evaporating and removing water contained in the saccharification treatment solution by heat treatment can be considered. However, in this case, a great deal of energy is required for removing water, which is not suitable as an effective biomass utilization technology.
糖化処理液の濃縮方法として逆浸透処理も考えられる。逆浸透処理では、糖化処理液を半透膜に接触させて加圧することにより、糖化処理液に含まれる水が半透膜を透過し、糖化処理液の単糖類濃度を高めることができる。逆浸透膜処理は、熱処理と比較して少ないエネルギーで糖化処理液から水分を除去することができる。しかし逆浸透処理では、半透膜の一方側の糖化処理液と他方側の透過液の浸透圧差（溶質濃度の差に基づく浸透圧差）に対抗して糖化処理液を加圧する必要があり、基本的に、糖化処理液の溶質濃度が高まるほど、糖化処理液をより加圧する必要が出てくる。そのため、高い単糖類濃度の糖化処理液を得ようとするほど、糖化処理液の加圧圧力を高める必要があり、その結果、設備を高圧対応仕様にするなど設備費がかさむこととなる。あるいは設備の仕様に応じて糖化処理液の溶質濃度の上限が定まるため、糖化処理液の単糖類濃度を高めるのには限界がある。さらに、糖化処理液の溶質濃度が高まるにつれて、単位時間当たりの膜の透過水量も減少するため、より高エネルギーの処理を長時間行う必要が出てくる。 Reverse osmosis treatment is also conceivable as a method for concentrating the saccharification treatment solution. In the reverse osmosis treatment, when the saccharification treatment liquid is brought into contact with the semipermeable membrane and pressurized, water contained in the saccharification treatment solution permeates the semipermeable membrane, and the monosaccharide concentration of the saccharification treatment solution can be increased. The reverse osmosis membrane treatment can remove moisture from the saccharification treatment liquid with less energy compared to the heat treatment. However, in reverse osmosis treatment, it is necessary to pressurize the saccharification treatment solution against the osmotic pressure difference (osmotic pressure difference based on the difference in solute concentration) between the saccharification treatment solution on one side and the other side of the semipermeable membrane. In particular, the higher the solute concentration of the saccharification treatment liquid, the more the saccharification treatment liquid needs to be pressurized. Therefore, as the saccharification treatment solution having a higher monosaccharide concentration is obtained, the pressurization pressure of the saccharification treatment solution needs to be increased. As a result, the equipment costs are increased, such as making the equipment compatible with high pressure. Or since the upper limit of the solute concentration of the saccharification treatment solution is determined according to the specifications of the equipment, there is a limit to increasing the monosaccharide concentration of the saccharification treatment solution. Further, as the solute concentration of the saccharification treatment liquid increases, the amount of permeated water per unit time also decreases, so that it is necessary to perform a higher energy treatment for a longer time.
これに対して本発明では、糖化処理液を正浸透処理して、糖化処理液の単糖類濃度を高め、単糖類濃縮液を得ている。正浸透処理は、糖化処理液を半透膜を介して濃厚溶液（糖化処理液よりも高い浸透圧を有する溶液）と接触させることにより、糖化処理液に含まれる水を、糖化処理液と濃厚溶液の浸透圧差に従って半透膜を介して濃厚溶液側に移行させて、糖化処理液から水分を除去するものである。正浸透処理では高圧設備を必要とせず、浸透圧に対抗した加圧操作も基本的に不要のため、逆浸透処理よりもさらに少ないエネルギーで、糖化処理液から水分を除去することを可能とする。 On the other hand, in the present invention, the saccharification treatment solution is forward osmosis treated to increase the monosaccharide concentration of the saccharification treatment solution to obtain a monosaccharide concentrate. In the forward osmosis treatment, water contained in the saccharification treatment solution is concentrated with the saccharification treatment solution by bringing the saccharification treatment solution into contact with a concentrated solution (solution having a higher osmotic pressure than the saccharification treatment solution) through the semipermeable membrane. According to the osmotic pressure difference of the solution, it is transferred to the concentrated solution side through the semipermeable membrane to remove moisture from the saccharification treatment solution. The forward osmosis treatment does not require high-pressure equipment and basically does not require a pressurization operation against the osmotic pressure, so it is possible to remove moisture from the saccharification treatment liquid with less energy than reverse osmosis treatment. .
本発明によれば、糖化処理液の濃縮に正浸透処理を採用することにより、糖化処理液を極めて効率的かつ高度に濃縮できることが明らかになった。具体的には、濃縮に必要なエネルギーの点で非常に高い優位性を示し、得られる単糖類濃縮液の単糖類濃度や濃縮速度の点においても、逆浸透処理と比べて十分な濃縮性能を示すことが明らかになった。また、濃厚溶液の溶質濃度を高めることで半透膜を介した浸透圧差を高めることができるため、糖化処理液の溶質濃度が高くなっても、濃厚溶液の溶質濃度を調整することにより、単位時間当たりの膜の透過水量を高く維持することが可能となる。 According to the present invention, it has been clarified that the saccharification treatment solution can be concentrated very efficiently and highly by adopting forward osmosis treatment for concentration of the saccharification treatment solution. Specifically, it has a very high advantage in terms of energy required for concentration, and has sufficient concentration performance compared to reverse osmosis treatment in terms of monosaccharide concentration and concentration rate of the resulting monosaccharide concentrate. It became clear to show. In addition, since the osmotic pressure difference through the semipermeable membrane can be increased by increasing the solute concentration of the concentrated solution, even if the solute concentration of the saccharification treatment liquid increases, the solute concentration of the concentrated solution can be adjusted by adjusting the solute concentration of the concentrated solution. It is possible to maintain a high permeated water amount per hour.
正浸透処理において用いられる半透膜は、少なくとも水分子が透過し、水よりも単糖類の透過率が低い膜であれば特に限定されず、公知の半透膜を用いることができる。半透膜としては、逆浸透処理に一般に用いられる半透膜を使用してもよく、それより孔径の大きいいわゆるＮＦ膜を用いてもよい。 The semipermeable membrane used in the forward osmosis treatment is not particularly limited as long as it is a membrane that transmits at least water molecules and has a lower monosaccharide permeability than water, and a known semipermeable membrane can be used. As the semipermeable membrane, a semipermeable membrane generally used for reverse osmosis treatment may be used, or a so-called NF membrane having a larger pore diameter may be used.
膜を構成する材料や膜の形式等も特に限定されない。膜の構成材料としては、酢酸セルロース、芳香族ポリアミド、ポリビニルアルコール、ポリスルホン等が挙げられ、膜の形式としては、中空糸膜、スパイラル膜、チューブラ膜等が挙げられる。 There are no particular limitations on the material constituting the film, the form of the film, and the like. Examples of the constituent material of the membrane include cellulose acetate, aromatic polyamide, polyvinyl alcohol, polysulfone and the like, and examples of the membrane include a hollow fiber membrane, a spiral membrane and a tubular membrane.
正浸透処理において用いられる濃厚溶液（Ｄｒａｗ Ｓｏｌｕｔｉｏｎと一般に称される）は、溶質が溶解し、糖化処理液よりも高い浸透圧を示す溶液であれば特に限定されない。濃厚溶液の溶質としては、塩類、糖類、水溶性高分子等を用いることができる。また、濃厚溶液として、自然界に存在する高濃度塩水（例えば、海水、鹹水等）を用いてもよい。 The concentrated solution (generally referred to as “Draw Solution”) used in the forward osmosis treatment is not particularly limited as long as it is a solution in which the solute dissolves and shows a higher osmotic pressure than the saccharification treatment solution. As the solute of the concentrated solution, salts, saccharides, water-soluble polymers and the like can be used. Moreover, you may use the high concentration salt water (for example, seawater, brine etc.) which exists in nature as a concentrated solution.
本発明では、糖化処理液を正浸透処理することにより、例えば、単糖類濃縮液のキシロースとグルコースの合計濃度を１２質量％以上とすることができる。上記に説明したように、バイオマスを分解処理することにより単糖類としてキシロースやグルコースが主に生成するが、例えば、糖化処理液を逆浸透処理した場合は、単糖類濃縮液のキシロースとグルコースの合計濃度を１２質量％以上とすることは難しい。これに対して本発明によれば、キシロースとグルコースの合計濃度が１２質量％以上の単糖類濃縮液を得ることができ、前記合計濃度が１５質量％以上の単糖類濃縮液を得ることもできる。またこのように高濃度の単糖類濃縮液を得ることにより、単糖類を効率的に有用な化合物に変換することができるようになる。 In the present invention, by subjecting the saccharification treatment solution to forward osmosis treatment, for example, the total concentration of xylose and glucose in the monosaccharide concentrated solution can be set to 12% by mass or more. As explained above, by decomposing biomass, xylose and glucose are mainly produced as monosaccharides. For example, when reverse osmosis treatment is performed on the saccharification liquid, the total of xylose and glucose in the monosaccharide concentrate It is difficult to set the concentration to 12% by mass or more. On the other hand, according to the present invention, a monosaccharide concentrate having a total concentration of xylose and glucose of 12% by mass or more can be obtained, and a monosaccharide concentrate having a total concentration of 15% by mass or more can also be obtained. . Moreover, by obtaining a concentrated monosaccharide concentrate in this way, it becomes possible to efficiently convert monosaccharides into useful compounds.
本発明では、糖化処理液を正浸透処理するのに先立って、限外ろ過膜（ＵＦ膜）を用いて膜分離処理することが好ましい。すなわち、糖化処理液を、限外ろ過膜を用いて膜分離処理し、得られたろ液を正浸透処理することにより、単糖類濃縮液を得ることが好ましい。この場合、本発明の単糖類濃縮液の製造方法は、バイオマスを分解処理して、単糖類を含有する糖化処理液を得る工程と、糖化処理液を限外ろ過膜を用いて膜分離処理し、ろ液を得る工程と、前記ろ液を正浸透処理して、単糖類濃縮液を得る工程とを有することとなる。糖化処理液を限外ろ過膜を用いて膜分離処理することにより、糖化処理液に含まれる固形分を除去することができるとともに、高分子量の溶質も除去することが可能となる。特に、膜分離処理により糖化処理液の溶質の一部を除去することができれば、糖化処理液の浸透圧を下げることができ、引き続き行う正浸透処理において単糖類の濃縮をより好適に行いやすくなる。 In the present invention, prior to forward osmosis treatment of the saccharification treatment solution, it is preferable to perform membrane separation treatment using an ultrafiltration membrane (UF membrane). That is, it is preferable to obtain a monosaccharide concentrate by subjecting the saccharification treatment liquid to membrane separation treatment using an ultrafiltration membrane and subjecting the obtained filtrate to forward osmosis treatment. In this case, the method for producing a monosaccharide concentrate of the present invention includes a step of decomposing biomass to obtain a saccharification treatment liquid containing monosaccharides, and subjecting the saccharification treatment liquid to membrane separation treatment using an ultrafiltration membrane. And a step of obtaining a filtrate, and a step of subjecting the filtrate to forward osmosis treatment to obtain a monosaccharide concentrated solution. By subjecting the saccharification treatment liquid to membrane separation treatment using an ultrafiltration membrane, it is possible to remove solids contained in the saccharification treatment liquid and to remove high molecular weight solutes. In particular, if a part of the solute of the saccharification treatment solution can be removed by membrane separation treatment, the osmotic pressure of the saccharification treatment solution can be lowered, and the monosaccharide can be more easily concentrated in the subsequent forward osmosis treatment. .
膜分離処理に用いる限外ろ過膜としては、公知の限外ろ過膜を用いればよく、単糖類を透過させることができるものであればよい。限外ろ過膜の分画分子量は、例えば８００〜２００，０００程度であればよい。膜を構成する材料や膜の形式等は特に限定されない。膜の構成材料としては、酢酸セルロース、芳香族ポリアミド、ポリビニルアルコール、ポリスルホン、ポリフッ化ビニリデン、ポリエチレン、ポリアクリロニトリル、セラミック等が挙げられ、膜の形式としては、中空糸膜、スパイラル膜、チューブラ膜、平膜等が挙げられる。 As the ultrafiltration membrane used for the membrane separation treatment, a known ultrafiltration membrane may be used as long as it can permeate monosaccharides. The fractional molecular weight of the ultrafiltration membrane may be, for example, about 800 to 200,000. There are no particular limitations on the material constituting the film, the form of the film, or the like. Examples of the constituent material of the membrane include cellulose acetate, aromatic polyamide, polyvinyl alcohol, polysulfone, polyvinylidene fluoride, polyethylene, polyacrylonitrile, ceramic and the like. As the membrane type, hollow fiber membrane, spiral membrane, tubular membrane, Examples include flat membranes.
本発明ではまた、限外ろ過膜による膜分離処理に先立って、精密ろ過膜による膜分離処理を行ってもよい。糖化処理液の固形分濃度が高い場合などは、精密ろ過膜による膜分離処理を行うことにより、糖化処理液に含まれる固形分を高度に除去して、後段の限外ろ過膜による膜分離処理の処理負荷を下げ、また膜の目詰まりを起こりにくくすることができる。 In the present invention, the membrane separation treatment using a microfiltration membrane may be performed prior to the membrane separation treatment using an ultrafiltration membrane. When the saccharification treatment liquid has a high solid content concentration, etc., by performing membrane separation treatment with a microfiltration membrane, the solid content contained in the saccharification treatment solution is highly removed, and the membrane separation treatment with an ultrafiltration membrane in the subsequent stage The processing load can be reduced, and clogging of the film can be made difficult to occur.
以下に、実施例を示すことにより本発明を更に詳細に説明するが、本発明の範囲はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited thereto.
（１） 実験１
（１−１） 実験方法
バガスを水熱処理した後、酵素を用いてＣ５糖化処理することにより、糖化処理液を得た。糖化処理液には、単糖類としてキシロースが主に含まれ、グルコースも少量含まれていた。さらに糖化処理液には、高分子多糖類やリグニン由来物も含まれていた。この糖化処理液を、限外ろ過膜（Ｍｉｌｌｉｐｏｒｅ社製、再生セルロース膜）を用いて膜分離処理し、ろ液を得た。限外ろ過膜としては、分画分子量（ＭＷＣＯ）１，０００、３，０００、５，０００、１０，０００、１００，０００の５種類の膜を用い、それぞれの膜を用いた場合のキシロースの透過率を検討したが、いずれも８０％前後のキシロース透過率が得られた。次いで、膜分離処理により得られたろ液２．０Ｌを、ナノろ過膜（日東電工社製、ＰＶＡ膜、ＮＴＲ７２５０）を用いて、３ＭＰａの操作圧下、逆浸透処理を１５日間連続して行い、引き続き、正浸透膜（ＨＴＩ社製、ＯｓＭｅｍ（登録商標）ＣＴＡ−ＥＳ）を用いて正浸透処理を行った。正浸透処理は、濃厚溶液（Ｄｒａｗ Ｓｏｌｕｔｉｏｎ）として５Ｍ ＮａＣｌ水溶液を用いて室温で行い、正浸透膜は、活性層がろ液（糖化処理液）側に向くように配置し、ろ液（糖化処理液）を循環供給しながら行った。
(1) Experiment 1
(1-1) Experimental method After hydrothermally treating bagasse, a saccharification treatment solution was obtained by C5 saccharification treatment using an enzyme. The saccharification treatment liquid mainly contained xylose as a monosaccharide and contained a small amount of glucose. Further, the saccharification treatment liquid contained a high molecular polysaccharide and a lignin-derived material. This saccharification solution was subjected to membrane separation using an ultrafiltration membrane (reproduced cellulose membrane manufactured by Millipore) to obtain a filtrate. As the ultrafiltration membrane, five types of membranes having molecular weight cut-off (MWCO) of 1,000, 3,000, 5,000, 10,000, and 100,000 were used, and the xylose of each membrane was used. The transmittance was examined, and in all cases, a xylose transmittance of about 80% was obtained. Next, 2.0 L of the filtrate obtained by membrane separation treatment was continuously subjected to reverse osmosis treatment for 15 days under an operating pressure of 3 MPa using a nanofiltration membrane (manufactured by Nitto Denko Corporation, PVA membrane, NTR7250). Forward osmosis treatment was performed using a forward osmosis membrane (OsMem (registered trademark) CTA-ES, manufactured by HTI). The forward osmosis treatment is performed at room temperature using a 5M NaCl aqueous solution as a concentrated solution (Draw Solution), and the forward osmosis membrane is arranged so that the active layer faces the filtrate (saccharification treatment solution) side, and the filtrate (saccharification treatment) Liquid) was circulated and supplied.
（１−２） 分析方法
糖類の分析は、高速液体クロマトグラフシステム（島津製作所社製、Ｐｒｏｍｉｎｅｎｃｅ（登録商標））を用いて行った。カラムとして、Ｕｎｉｓｏｎ ＵＫ−Ａｍｉｎｏ（ＵＫＡ０６、４．６ｍｍ×２５ｃｍ）を用い、検出器として、蒸発光散乱検出器（ＥＬＳＤ−ＬＴ ＩＩ）を用いた。
(1-2) Analysis Method Analysis of saccharides was performed using a high performance liquid chromatograph system (Prominence (registered trademark) manufactured by Shimadzu Corporation). Unison UK-Amino (UKA06, 4.6 mm × 25 cm) was used as the column, and an evaporative light scattering detector (ELSD-LT II) was used as the detector.
（１−３） 実験結果
ろ液（糖化処理液）を逆浸透処理と正浸透処理により連続処理した結果を図１および図２に示す。図１は、逆浸透処理の結果を表したグラフであり、ろ液からの透過水量とろ液のキシロース濃度の経時変化を表す。図２は、逆浸透処理に引き続いて行った正浸透処理の結果を表したグラフであり、ろ液からの透過水量とろ液のキシロース濃度の経時変化を表す。
(1-3) Experimental results The results of continuous treatment of the filtrate (saccharification treatment solution) by reverse osmosis treatment and forward osmosis treatment are shown in FIGS. FIG. 1 is a graph showing the results of reverse osmosis treatment, and shows the change over time in the amount of permeated water from the filtrate and the xylose concentration in the filtrate. FIG. 2 is a graph showing the results of the forward osmosis treatment subsequent to the reverse osmosis treatment, and shows the change over time in the amount of permeated water from the filtrate and the xylose concentration in the filtrate.
逆浸透処理前のろ液は、キシロース濃度が１．８質量％、グルコース濃度が０．１２質量％であったが、逆浸透処理を１５日間連続して行うことにより、キシロース濃度が１０．９質量％、グルコース濃度が１．１８質量％まで濃縮された。しかし、図１からも分かるように、逆浸透処理の開始１０日目以降はＮＦ膜を水がほとんど透過せず、それ以上濃縮が進まなかった。そこで、逆浸透処理から正浸透処理に切り替えた。なおその際、正浸透膜装置に逆浸透処理液を導入するために、正浸透膜装置に導入する流路を水で満たしたため、逆浸透処理液は約１．２倍希釈される結果となった。逆浸透処理液を正浸透処理したところ、図２に示すように、１時間で約１．５倍濃縮され、キシロース濃度が１４．０質量％、グルコース濃度が１．２１質量％まで濃縮された。なお逆浸透処理では、処理の途中でＮＦ膜を新しいものに交換しても、透水速度の向上は認められなかった。以上の結果から、糖化処理液を正浸透処理することにより、効率的かつ高度に単糖類を濃縮できることが分かった。 The filtrate before the reverse osmosis treatment had a xylose concentration of 1.8% by mass and a glucose concentration of 0.12% by mass. However, by performing the reverse osmosis treatment continuously for 15 days, the xylose concentration was 10.9%. Mass%, glucose concentration was concentrated to 1.18 mass%. However, as can be seen from FIG. 1, water hardly permeated through the NF membrane after the 10th day from the start of the reverse osmosis treatment, and the concentration did not proceed further. Therefore, the reverse osmosis treatment was switched to the forward osmosis treatment. At that time, in order to introduce the reverse osmosis treatment liquid into the forward osmosis membrane device, the flow path to be introduced into the forward osmosis membrane device was filled with water, so that the reverse osmosis treatment liquid was diluted by about 1.2 times. It was. When the reverse osmosis treatment solution was subjected to forward osmosis treatment, as shown in FIG. 2, it was concentrated about 1.5 times in 1 hour, and the xylose concentration was concentrated to 14.0 mass% and the glucose concentration was 1.21 mass%. . In the reverse osmosis treatment, even if the NF membrane was replaced with a new one in the middle of the treatment, an improvement in the water transmission rate was not recognized. From the above results, it was found that monosaccharides can be concentrated efficiently and highly by subjecting the saccharification treatment solution to forward osmosis treatment.
（２） 実験２
（２−１） 実験方法
キシロース濃度２．１質量％の人工糖化液１６Ｌを調製し、正浸透膜（ＨＴＩ社製、ＯｓＭｅｍ（登録商標）ＣＴＡ−ＥＳ）を用いて正浸透処理を行った。正浸透処理は、濃厚溶液（Ｄｒａｗ Ｓｏｌｕｔｉｏｎ）として５Ｍ ＮａＣｌ水溶液を用い、２５℃の温度条件下で、人工糖化液を循環供給しながら約３日間連続して行った。
(2) Experiment 2
(2-1) Experimental Method An artificial saccharified solution 16L having a xylose concentration of 2.1% by mass was prepared, and forward osmosis treatment was performed using a forward osmosis membrane (OsMem (registered trademark) CTA-ES, manufactured by HTI). The forward osmosis treatment was carried out continuously for about 3 days using a 5M NaCl aqueous solution as a concentrated solution and circulating the artificial saccharified solution under a temperature condition of 25 ° C.
（２−２） 分析方法
糖類の分析は、実験１と同様にして行った。
(2-2) Analysis method The analysis of saccharides was performed in the same manner as in Experiment 1.
（２−３） 実験結果
図３に正浸透処理の結果を示す。図３は人工糖化液を正浸透処理した際のキシロース濃度と透過水量の経時変化を表す。人工糖化液を正浸透処理することにより、キシロース濃度が２．１質量％から３８．１質量％になるまで濃縮できた。また、濃厚溶液（Ｄｒａｗ Ｓｏｌｕｔｉｏｎ）にキシロースが漏洩していないことも確認された。比較的希薄な単糖類濃度の糖化処理液を、逆浸透処理を施さずに最初から正浸透処理を行っても、効率的かつ高度に単糖類を濃縮できることが分かった。
(2-3) Experimental results Fig. 3 shows the results of forward osmosis treatment. FIG. 3 shows changes with time in the xylose concentration and the amount of permeated water when the artificial saccharified solution is forward osmosis treated. By subjecting the artificial saccharified solution to forward osmosis treatment, the xylose concentration could be concentrated from 2.1 mass% to 38.1 mass%. It was also confirmed that no xylose leaked into the concentrated solution (Draw Solution). It was found that monosaccharides can be concentrated efficiently and highly even if a normal osmosis treatment is performed from the beginning without applying reverse osmosis treatment to a saccharification treatment solution having a relatively dilute monosaccharide concentration.
本発明によれば、バイオマスから単糖類濃縮液を効率的に得ることができ、このようにして得られた単糖類濃縮液は、エタノールや乳酸等の化合物に変換させるための原料として使用することができる。 According to the present invention, a monosaccharide concentrate can be efficiently obtained from biomass, and the monosaccharide concentrate thus obtained is used as a raw material for converting into a compound such as ethanol or lactic acid. Can do.
Claims (4)
前記糖化処理液を正浸透処理して、単糖類濃縮液を得る工程とを有することを特徴とする単糖類濃縮液の製造方法。 Decomposing biomass to obtain a saccharification treatment solution containing monosaccharides;
And a step of obtaining a monosaccharide concentrate by forward osmosis treatment of the saccharification treatment liquid.
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|---|---|---|---|---|
| WO2016152883A1 (en) * | 2015-03-24 | 2016-09-29 | 東レ株式会社 | Method for producing sugar solution |
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| WO2016152883A1 (en) * | 2015-03-24 | 2016-09-29 | 東レ株式会社 | Method for producing sugar solution |
| US10844444B2 (en) | 2015-03-24 | 2020-11-24 | Toray Industries, Inc. | Method of producing sugar solution |
| CN110574823A (en) * | 2019-09-27 | 2019-12-17 | 烟台双塔食品股份有限公司 | process method and device for extracting pea albumin from water |
| CN110574823B (en) * | 2019-09-27 | 2022-04-22 | 烟台双塔食品股份有限公司 | Process method and device for extracting pea albumin from water |
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