JP6535923B2 - Plant tissue processing method for promoting degradation of plant tissue, main ingredient thereof, raw material composition extracted by the plant tissue processing method, and method for reducing bulk of plant tissue - Google Patents
Plant tissue processing method for promoting degradation of plant tissue, main ingredient thereof, raw material composition extracted by the plant tissue processing method, and method for reducing bulk of plant tissue Download PDFInfo
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- JP6535923B2 JP6535923B2 JP2018515739A JP2018515739A JP6535923B2 JP 6535923 B2 JP6535923 B2 JP 6535923B2 JP 2018515739 A JP2018515739 A JP 2018515739A JP 2018515739 A JP2018515739 A JP 2018515739A JP 6535923 B2 JP6535923 B2 JP 6535923B2
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 249
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
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- 150000007513 acids Chemical class 0.000 description 2
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- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
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- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 244000309146 drought grass Species 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- WHXSMMKQMYFTQS-IGMARMGPSA-N lithium-7 atom Chemical compound [7Li] WHXSMMKQMYFTQS-IGMARMGPSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/20—Compounds of alkali metals or ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paper (AREA)
- Processing Of Solid Wastes (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compounds Of Unknown Constitution (AREA)
Description
本発明は、木材片、草本片またはそれら由来の加工製品などの植物組織に添加することによって、その植物組織の分解を促進し、植物由来物質を抽出する植物組織処理方法、その主剤、その植物組織処理方法で抽出した原料組成物、および植物組織の嵩低減方法に関する。特に、大掛かりな処理装置を用いたり過剰なエネルギーを投入したりすることなく植物組織を簡単に分解し、植物組織から植物組織由来物質を容易に抽出することができるものに関する。 The present invention is a plant tissue processing method for promoting degradation of plant tissue and extracting a plant-derived substance by adding to plant tissue such as wood pieces, herb pieces or processed products derived therefrom, the main agent, the plant, and the plant The present invention relates to a raw material composition extracted by a tissue processing method and a method for reducing the bulk of plant tissue. In particular, the present invention relates to an apparatus capable of easily decomposing plant tissue and easily extracting a plant tissue-derived substance from plant tissue without using a large-scale processing apparatus or inputting excessive energy.
木材は、古くから多く利用されており、建築材料、燃料、紙パルプ材料など、その用途は多様である。このように伝統的には構造物としての木材そのものや、ほぐした木質繊維の利用が中心であった。
近年は、木材や草本類に含まれる植物組織由来物質を取り出して化合物としての素材利用が注目されている。近年、木材や草本等の植物組織から抽出される植物組織由来物質はそれぞれ産業上の利用価値があり、それら抽出物を多様な用途で積極的に利用する試みが進んでいる。Wood has been widely used since ancient times, and its applications are diverse, such as building materials, fuels, and pulp and paper materials. Thus, traditionally, the use of wood itself as a structure and loosened wood fiber has mainly been used.
In recent years, attention has been focused on utilization of materials as compounds by taking out plant tissue-derived substances contained in wood and herbs. In recent years, plant tissue-derived substances extracted from plant tissues such as wood and grass each have industrial application value, and attempts are being made to actively use these extracts for various applications.
地球上で最も豊富な有用素材とされるセルロースであるが、未だその活用は十分なものとは言えない。その大きな理由の一つとして、樹木や草本類の細胞の一部を構成するセルロースを取り出す方法に、物理的、化学的なコストの問題があげられる。
木材や草本等の植物組織は、化学構造が異なる多種多様な物質が含まれている複合体である。植物組織を構成する物質としては、セルロース、ヘミセルロース、リグニン、タンニン、スベリンなどが含まれている。植物組織の構成は、構造の中心にセルロースがあり、その周りをヘミセルロースが覆い、さらにリグニンが強固に存在している。セルロース抽出には、まず強固なリグニンを弛緩、あるいは除去する必要がある。つまり、これら植物組織由来物質を利用する際には、利用目的とする植物組織由来物質を植物組織から抽出し、それ以外の物質を除去しなければならない場合もあり得る。ここで、物理的・化学的コストが問題となってくる。Cellulose is considered to be the most abundant useful material on earth, but its utilization is not yet sufficient. One of the major reasons is the problem of physical and chemical costs in the method of removing cellulose that constitutes a part of tree and herbaceous cells.
Plant tissues such as wood and grass are composites containing various substances having different chemical structures. Substances constituting plant tissue include cellulose, hemicellulose, lignin, tannin, suberin and the like. In the structure of plant tissue, cellulose is at the center of the structure, hemicellulose covers it, and lignin is strongly present. For cellulose extraction, it is first necessary to relax or remove strong lignin. That is, when using these plant tissue-derived substances, it may be necessary to extract the plant tissue-derived substance to be used from the plant tissue and remove the other substances. Here, physical and chemical costs become a problem.
セルロースは、例えば、衣料用繊維、合成樹脂の原料として利用が進んでいる。セルロースから得られるグルコースは、バイオエタノールの原料になる等バイオマス関連において特に重要な物質である。
ヘミセルロースは、例えば、製紙のほか、他の抽出成分と合わせることにより化学製品の製造等に用いられ、工業原材料として広く用いられている。
リグニンは、例えば、セルロースなどと結合して細胞間を接着・固化する性質を利用した接着剤、医薬、消毒剤等の原材料として広く利用されている。
タンニンは、例えば、皮革の鞣し（いわゆるタンニン鞣し）に必要不可欠の物質であり、皮革工業に広く利用されている。
スベリンは、例えば、スベリン酸として、アルキド樹脂、ポリアミド等の製造原料となる物質であり、工業原材料として広く用いられている。
このように、植物組織由来物質には、多様な利用用途があり、産業上の利用価値は高く、工業原材料としての潜在的重要が大きいものである。Cellulose is being used, for example, as a raw material for clothing fibers and synthetic resins. Glucose obtained from cellulose is a substance which is particularly important in biomass related to be a raw material of bioethanol.
Hemicellulose is used, for example, in the production of chemical products by combining it with other extraction components besides papermaking, and is widely used as an industrial raw material.
Lignin is widely used, for example, as a raw material for adhesives, medicines, disinfectants and the like, which utilizes the property of bonding with cellulose etc. to adhere and solidify between cells.
Tannin is, for example, an essential substance for tanning (so-called tanning) of leather and is widely used in the leather industry.
For example, suberin is a substance serving as a raw material for producing alkyd resin, polyamide and the like as suberic acid, and is widely used as an industrial raw material.
Thus, plant tissue-derived substances have various uses, have high industrial application value, and are of great potential importance as industrial raw materials.
従来技術において、これら植物組織由来物質を得るための植物組織処理方法としては、高温高圧下で濃硫酸など強酸または強アルカリ（特に水酸化ナトリウム）を用いるアルカリ加水分解法（特許文献１）、環状炭酸類と酸を用いた加水分解法（特許文献２）などが知られている。触媒を併用することもある。また、爆砕処理という爆発的な圧力変化により木質繊維などを物理的に破壊・破砕する処理方法も知られている。このように、木材を出発原料として素材利用する際には高温高圧下での処理や爆砕処理など多大なエネルギー投入が必須である。 In the prior art, as a plant tissue processing method for obtaining these plant tissue-derived substances, alkaline hydrolysis using a strong acid such as concentrated sulfuric acid or a strong alkali (especially sodium hydroxide) under high temperature and pressure (especially patent document 1), cyclic The hydrolysis method (patent document 2) etc. which used carbonic acid and an acid are known. A catalyst may be used in combination. In addition, there is also known a processing method of physically destroying and breaking wood fibers and the like by explosive pressure change called explosion processing. As described above, when using wood as a starting material, it is necessary to use a large amount of energy, such as treatment under high temperature and pressure and explosion treatment.
また、近年バイオマス利用が進み、様々なバイオマス利用装置が稼働しているが、その炭素源であるバイオマスの安定供給、保存性の向上、輸送コストの低減などが課題となっている。バイオマスは、一般には、木材のみならず、稲わら、麦わら、ササ、ススキ、スイッチグラス、ジャイアントミスカンサスなどの草木や、木材間伐材の樹皮などが利用されている。木材の場合は塊のままでは運搬や保存に不便である。また、草木は嵩密度が低く体積が大きくやはり運搬や保存に不便である。いずれも植物組織の分解を促進して粉体化することが好ましい。 Further, in recent years, biomass utilization has been advanced, and various biomass utilization devices have been operated, but the stable supply of biomass which is a carbon source, improvement of storability, reduction of transportation cost, and the like have become issues. Biomass is generally used not only for wood but also for plants such as rice straw, straw, sasa, susuki, switchgrass, giant miscanthus, and bark of wood thinning. In the case of wood, lumps are inconvenient for transportation and storage. In addition, plants and plants have a low bulk density and a large volume, which is also inconvenient for transportation and storage. In any case, it is preferable to promote decomposition of plant tissue for powderization.
上記従来の植物組織処理方法のうち、アルカリ加水分解法は、植物組織を分解することができるものの、得られるものはアルカリセルロース（繊維素）と呼ばれるものである。このアルカリセルロースは、それ自体は工業原料となるもので、ビスコースレーヨンを作るビスコースやメチルセルロース、カルボキシメチルセルロースとして抽出される。これらは、それぞれ用途に応じた使い方をされる。
ここで、自然界におけるセルロースの結晶型はＩ型であり、その多形として、II型、III型、IV型が存在する。その中で自然界に存在するセルロースＩ型が夫々の多形の出発点である。Among the above-mentioned conventional plant tissue processing methods, although the alkaline hydrolysis method can decompose plant tissue, what is obtained is called alkaline cellulose (fibrin). The alkali cellulose itself is an industrial raw material, and is extracted as viscose, methyl cellulose and carboxymethyl cellulose which make viscose rayon. Each of these is used according to the application.
Here, the crystal form of cellulose in nature is Form I, and as polymorphs thereof, Form II, Form III and Form IV exist. Among them, the naturally occurring cellulose type I is the starting point of each polymorph.
しかし、上記従来技術のアルカリ加水分解法は、アルカリセルロースを得る方法として知られているが、セルロースＩ型成分を得る知見が知られていなかった。
また、上記従来技術の爆砕を伴う物理的手段はセルロースＩ型成分を得ることができるものの、いずれも高温高圧下において耐酸性または耐アルカリ性を持つ頑丈で大掛かりな高価な装置類や、爆砕処理という強烈な圧力変化に耐える頑丈で大掛かりな高価な装置類が必要となってしまうという問題がある。また、処理の過程で投入する酸、アルカリ、環状炭酸類、芳香族系グリコールエーテルなどの施用物を除去する後処理工程などが必要となり、コスト増加の一因になっていた。また、触媒を必要とする場合は触媒にコストが掛かってしまう。However, although the above-mentioned prior art alkaline hydrolysis method is known as a method for obtaining alkali cellulose, no knowledge for obtaining a cellulose type I component has been known.
In addition, although the physical means accompanied by explosion in the above-mentioned prior art can obtain a cellulose type I component, all are heavy-duty and large-scale expensive devices having acid resistance or alkali resistance under high temperature and pressure, and explosion treatment. There is a problem that a strong, large-scale and expensive apparatus that can withstand intense pressure changes is required. In addition, a post-treatment step for removing the applied substances such as acids, alkalis, cyclic carbonic acids and aromatic glycol ethers introduced in the process of treatment is required, which has contributed to the cost increase. In addition, when the catalyst is required, the cost of the catalyst is increased.
また、一方、植物由来物質を抽出した植物組織残渣の有効利用を考えた場合、バイオマスの炭素源とすることができるが、木材や草木などから炭素源を製作する場合、木材の場合であれば塊のままでは運搬や保存に不便である。また、草木であれば嵩密度が低く体積が大きくやはり運搬や保存に不便である。いずれも植物組織の分解を促進して粉体化することが好ましい。 In addition, on the other hand, considering the effective utilization of plant tissue residues from which plant-derived substances are extracted, it can be used as a carbon source of biomass, but in the case of wood, when carbon sources are produced from wood or plants It is inconvenient for transportation and storage if it is a lump. In the case of plants and trees, the bulk density is low and the volume is large, which is also inconvenient for transportation and storage. In any case, it is preferable to promote decomposition of plant tissue for powderization.
そこで、上記問題に鑑み、本発明は、大掛かりな処理装置を用いたり過剰なエネルギーを投入したりすることなく植物組織を簡単に分解しつつ、植物組織からセルロースＩ型成分を含む植物組織由来物質を容易に抽出することができる植物組織処理剤および植物組織処理方法を提供することを目的とする。 Therefore, in view of the above problems, the present invention is a plant tissue-derived substance containing cellulose I-type component from plant tissue while easily degrading plant tissue without using a large-scale processing apparatus or inputting excessive energy. It is an object of the present invention to provide a plant tissue treating agent and a plant tissue treating method which can be easily extracted.
本発明は、木材片または草本片の植物組織またはそれらを原料として加工した植物由来加工物に植物組織処理剤を添加することにより前記植物組織または前記植物由来加工物の分解を促進させ、内部のセルロースＩ型成分を抽出する方法であって、水酸化リチウムを主剤とする植物組織処理剤を前記植物組織または前記植物由来加工物に常温かつ常圧で添加して、組織内のセルロースミクロフィブリルまで直接浸透させるとともに、他の有効成分を施用させずに、前記セルロースミクロフィブリルの非結晶部分の少なくとも一部を穏やかに溶解して前記セルロースＩ型成分を溶出させる、セルロースＩ型成分の緩慢的な溶解抽出方法である。
植物組織は主に炭素で構成されているので、炭素原子より原子径の小さな金属化合物はリチウム化合物であり、水溶性を示すものとして、水酸化リチウムを挙げることができる。ここで、本発明は、従来技術のように他の有効成分を施用さたりエネルギーを投入せずに、水酸化リチウム水溶液への浸漬により水酸化リチウムを施用することにより、セルロースミクロフィブリルの非結晶部分の少なくとも一部を穏やかに溶解してセルロースＩ型成分を溶出させる方法である。本発明者らはセルロースＩ型成分の穏やかな溶解抽出方法を発明した。
本発明者らは、研究を通じて、水酸化リチウム水溶液は植物組織の破壊能力が大きく、工業用途に耐える程度の植物組織由来物質の植物組織処理剤として利用可能であることを初めて突き止めた。The present invention promotes degradation of the plant tissue or the plant-derived processed material by adding a plant tissue treating agent to plant tissue of wood pieces or herb pieces or plant-derived products processed using them as a raw material, A method for extracting a cellulose type I component, which comprises adding a plant tissue treating agent containing lithium hydroxide as a main ingredient to the plant tissue or the plant-derived processed product at normal temperature and normal pressure, to cellulose microfibrils in the tissue A slow type of cellulose I-type component, in which the cellulose I-type component is eluted by gently dissolving at least a part of the non-crystalline portion of the cellulose microfibrils, while directly infiltrating and without applying other active ingredients. It is a dissolution extraction method.
Since a plant tissue is mainly composed of carbon, a metal compound having an atomic diameter smaller than that of a carbon atom is a lithium compound, and lithium hydroxide can be mentioned as one showing water solubility. Here, the present invention is a non-crystalline form of cellulose microfibrils by applying lithium hydroxide by immersion in a lithium hydroxide aqueous solution without applying other active ingredients or inputting energy as in the prior art. At least a part of the portion is gently dissolved to elute the cellulose type I component. The inventors have invented a method for the mild dissolution and extraction of cellulose type I components.
The present inventors have found for the first time through research that lithium hydroxide aqueous solution has a large ability to destroy plant tissue and can be used as a plant tissue treating agent for plant tissue-derived substances that can withstand industrial use.
本発明の植物組織処理方法は、植物組織を簡単に分解しつつ、植物組織から植物組織由来物質を容易に抽出することができるものであり、従来技術のように高温高圧下で強酸や強アルカリによる加水分解処理や、爆砕処理などの高エネルギー処理を必要とするものではない。
図２は植物組織の構造を極めて簡単に示した図である。図２（ａ）に示すように、木材、草本類の基本構成である植物組織はセルロース、ヘミセルロース、リグニンであり、セルロースを中心にヘミセルロース、リグニンが強固に絡み合った組織構造をしており、それら基本構造の分解が難しい。特に、中央に位置するセルロースの基本形であるセルロースＩ型成分の抽出は難しい。従来技術では、木材資源を利用する際、爆砕処理等の物理処理や、高温高圧で強酸または強アルカリを用いた加水分解処理等の熱化学処理を行ってセルロースを抽出するという前処理工程が必須工程であったが、本発明は、従来技術における加水分解処理や爆砕処理等の前処理工程を一切用いずに、また、特段ほかの有効成分を施用させる必要なく、図２（ｂ）に示すように、水酸化リチウムの持つ高い極性と浸透性によって容易に植物組織の構造を弛緩させ、セルロースミクロフィブリルまで浸透してアクセスし、セルロースミクロフィブリルの非結晶部分に水酸化リチウムを施用させ、穏やかに溶解してセルロースＩ型成分を溶出させ、セルロースレベルまでの分解処理を実施できるというセルロースＩ型成分の緩慢的な溶解抽出方法の発見に基づくものである。ここで、植物組織を構成する原子径より小さな原子径を持つリチウムの水溶性化合物、特に水酸化リチウム主剤とする植物組織処理剤を植物組織に常温かつ常圧で添加すれば、組織内のセルロースミクロフィブリルまで直接浸透させることができる。水酸化リチウムは植物組織の内部への浸透性が大きく、内部のセルロースミクロフィブリルに作用しやすいと考えられる。セルロースミクロフィブリルの非結晶部分に水酸化リチウムを施用させ、ゆっくりと穏やかに非結晶部分の少なくとも一部を破壊・分解し、セルロースＩ型成分として溶脱させる。
本発明の植物組織処理方法を用いれば、植物組織からセルロースＩ型成分、さらには、ヘミセルロース、リグニン、タンニン、スベリンなどの植物由来物質が取り出しやすくなる。The plant tissue processing method of the present invention can easily extract a plant tissue-derived substance from plant tissue while easily degrading plant tissue, and as in the prior art, strong acids and strong alkalis under high temperature and high pressure conditions. It does not require high energy treatment such as hydrolysis treatment or explosion treatment.
FIG. 2 shows the structure of plant tissue very simply. As shown in FIG. 2 (a), the plant tissue which is the basic composition of wood and herbs is cellulose, hemicellulose and lignin, and it has a tissue structure in which hemicellulose and lignin are strongly intertwined with each other around cellulose It is difficult to disassemble the basic structure. In particular, it is difficult to extract the cellulose type I component, which is the basic form of centrally located cellulose. In the prior art, when utilizing wood resources, it is essential to carry out physical treatment such as explosion treatment and thermochemical treatment such as hydrolysis treatment using strong acid or strong alkali at high temperature and pressure to extract cellulose. Although this is a step, the present invention is shown in FIG. 2 (b) without using any pretreatment step such as hydrolysis treatment or explosion treatment in the prior art, and without particularly applying other active ingredients. Thus, the high polarity and permeability of lithium hydroxide easily relaxes the structure of plant tissue, penetrates and accesses cellulose microfibrils, and applies lithium hydroxide to the non-crystalline part of cellulose microfibrils to moderate. Slow dissolution and extraction method of cellulose I type component that can be dissolved in water to elute cellulose type I component and decomposition processing to cellulose level can be performed. It is based on the look. Here, if a water-soluble lithium compound having an atomic diameter smaller than that of the plant tissue, in particular a plant tissue treating agent containing lithium hydroxide as the main agent, is added to the plant tissue at normal temperature and pressure, cellulose in the tissue is obtained. Direct penetration into microfibrils is possible. Lithium hydroxide is considered to be highly permeable to the inside of plant tissue and to be likely to act on cellulose microfibrils inside. Lithium hydroxide is applied to the noncrystalline portion of the cellulose microfibrils, and at least a portion of the noncrystalline portion is slowly broken and decomposed gently and leached out as a cellulose type I component.
By using the plant tissue processing method of the present invention, it becomes easy to take out the cellulose type I component and further plant derived substances such as hemicellulose, lignin, tannin and suberin from plant tissue.
植物組織処理剤としては、水酸化リチウムを主剤とするものである。配合としては、濃度は１ｗ％から一水塩を構成する５０ｗ％台まであり得るが、３ｗ％から１０ｗ％、特に７ｗ％程度が好ましい。植物組織をこれら濃度範囲の植物組織処理剤の水溶液に常温常圧で浸漬させることにより、比較的短期間の処理時間によって植物組織から内部の植物組織由来物質を抽出することができる。
植物組織としては、竹類、稲わら、麦わら、ササ、ススキ、スイッチグラス、ジャイアントミスカンサス、木材木質、木材樹皮、製紙工程から排出されるパルプ液に含まれる植物片残渣のいずれかまたはそれらの組み合わせなどを利用することができる。The plant tissue treating agent is mainly composed of lithium hydroxide. As for the composition, the concentration may be in the range of 1 w% to 50 w% or so constituting the monohydrochloride, but 3 w% to 10 w%, particularly about 7 w% is preferable. By immersing a plant tissue in an aqueous solution of a plant tissue treating agent in the above concentration range at normal temperature and pressure, an internal plant tissue-derived substance can be extracted from the plant tissue with a relatively short treatment time.
Examples of plant tissue include bamboos, rice straw, straw, scorpion, persimmon, switchgrass, giant miscanthus, woody wood, wood bark, and plant debris left in pulp fluid discharged from the paper-making process, or Combinations and the like can be used.
本発明の植物組織処理方法において、植物由来物質を効率的に収集するため、上記の分解抽出処理工程の後、さらに、浸漬液に溶出している植物由来物質を抽出する浸漬液処理工程と、植物組織の残渣に残存している植物由来物質を抽出する残渣処理工程を後続させることができる。
本発明者らは実験を重ねた結果、分解抽出処理工程の結果、分解した植物由来物質は浸漬液側にも溶出するし、残渣側にも残存している。浸漬液側にはセルロースＩ型分子やヘミセルロース分子の形で溶出しており、残渣側には一部が植物組織として維持されている部分が残っている場合もあるが、内部では植物組織が破壊され、セルロースＩ型分子内の水素結合やヘミセルロース分子などの共有結合が断裂している割合が多くなっていると考えられる。In the plant tissue processing method of the present invention, in order to efficiently collect plant-derived substances, an immersion liquid processing step of extracting the plant-derived substances eluted in the immersion liquid after the above-mentioned decomposition extraction processing step; A residue treatment step may be followed to extract plant-derived material remaining in the residue of plant tissue.
As a result of repeated experiments, as a result of the decomposition and extraction treatment step, the inventors of the present invention dissolve the decomposed plant-derived material also on the immersion liquid side and remain on the residue side. Although it may elute in the form of cellulose I-type molecules or hemicellulose molecules on the immersion liquid side, there may be a portion where a part is maintained as a plant tissue on the residue side, but the plant tissue is broken inside It is considered that the percentage of covalent bonds such as hydrogen bonds and hemicellulose molecules in the cellulose type I molecule is increased.
また、植物組織処理剤は、主剤である水酸化リチウムのみで副剤を用いない構成も可能であるが、副剤として水酸化ナトリウムを用いることもできる。配合としては、主剤と副剤を合わせた濃度として、３ｗ％から１０ｗ％、特に７ｗ％程度が好ましい。植物組織をこれら濃度範囲の植物組織処理剤の水溶液に常温常圧で浸漬させることにより、比較的短期間の処理時間によって植物組織から内部の植物組織由来物質を抽出することができる。
植物組織処理剤の主剤である水酸化リチウム水溶液と前記副剤の水酸化ナトリウム水溶液の比率として１００：０〜７５：２５の範囲に調整することができる。
次に、主剤として使用したリチウムやナトリウムの回収に関しては、浸漬液および植物組織の残渣を水洗して得た液体に対して、二酸化炭素を反応させ、液分中に含まれている主剤中の金属元素を炭酸加工物として析出して回収する回収工程を備えることができる。In addition, the plant tissue treating agent may be configured to use only lithium hydroxide as the main agent and not using an auxiliary agent, but sodium hydroxide can also be used as an auxiliary agent. The composition is preferably 3 w% to 10 w%, particularly about 7 w%, as the concentration of the main agent and the auxiliary agent. By immersing a plant tissue in an aqueous solution of a plant tissue treating agent in the above concentration range at normal temperature and pressure, an internal plant tissue-derived substance can be extracted from the plant tissue with a relatively short treatment time.
The ratio of the lithium hydroxide aqueous solution, which is the main agent of the plant tissue treating agent, to the sodium hydroxide aqueous solution of the auxiliary agent can be adjusted in the range of 100: 0 to 75:25.
Next, with regard to the recovery of lithium and sodium used as the main ingredient, carbon dioxide is reacted with the liquid obtained by washing the immersion liquid and the residue of the plant tissue, and the main ingredient contained in the liquid is contained in the main ingredient. It is possible to include a recovery step of depositing and recovering the metal element as a carbonic acid processed product.
植物組織残渣側の処理としては、水洗工程での水洗処理後の植物組織残渣を乾燥させる乾燥工程と、乾燥工程での乾燥処理後の植物組織残渣を粉砕する粉末化工程を備えた製造工程により、効率的に植物組織の粉体を得ることができる。例えば、粉体化後、バイオマスの原料として使用することもできる。 The treatment process on the plant tissue residue side is a production process including a drying step of drying the plant tissue residue after the water washing treatment in the water washing step, and a powdering step of grinding the plant tissue residue after the drying treatment in the drying step The powder of plant tissue can be obtained efficiently. For example, it can also be used as a raw material of biomass after pulverization.
また、本発明は植物組織の嵩低減方法に応用することができる。つまり、本発明の植物組織処理方法を用いて植物組織の分解抽出処理工程を促進させれば、植物組織の嵩密度を増加せしめて体積を小さくすることができる。 In addition, the present invention can be applied to a method for reducing plant tissue bulk. That is, if the plant tissue processing method of the present invention is used to accelerate the process of decomposing and extracting plant tissue, the bulk density of plant tissue can be increased and the volume can be reduced.
竹類、稲わら、麦わら、ササ、ススキ、スイッチグラス、ジャイアントミスカンサス、木材間伐材樹皮などは比較的に体積が大きく保存に不利であるところ、本発明の嵩低減方法を用いればこれら植物組織の保存コストを低減させることができる。 Bamboos, rice straws, straws, scorpions, grasses, switchgrass, giant miscanthus, bark of lumber thinnings and the like are relatively large in volume and disadvantageous for preservation, but when using the method for reducing bulk according to the present invention, these plant tissues Storage costs can be reduced.
本発明の植物組織の分解を促進する植物組織処理方法によれば、木材や草本等の植物組織を常温常圧下で水酸化リチウム溶液の主剤に浸漬するという極めて簡単な工程により、植物組織からセルロースＩ型成分を含む植物組織由来物質を抽出することができる。 According to the plant tissue processing method for promoting the decomposition of plant tissue of the present invention, cellulose from plant tissue is obtained by an extremely simple process of immersing plant tissue such as wood or herb in the main agent of lithium hydroxide solution under normal temperature and normal pressure. A plant tissue-derived substance containing a type I component can be extracted.
以下、図面を参照しつつ、本発明の植物組織の分解を促進する植物組織処理方法および植物組織処理剤の実施形態を説明する。ただし、本発明の技術的範囲は以下の実施形態に示した具体的な用途や形状・寸法などには限定されない。 Hereinafter, with reference to the drawings, embodiments of a plant tissue processing method and a plant tissue processing agent for promoting degradation of a plant tissue of the present invention will be described. However, the technical scope of the present invention is not limited to the specific application, shape, dimensions, etc. shown in the following embodiments.
本発明の植物組織処理方法の工程について説明する。
図１は本発明の植物組織処理方法の工程を簡単に示すフロー図である。
本発明の植物組織処理方法の工程の概略は、原料となる木材や稲わらなどの植物組織に対して植物組織処理剤を添加し、植物組織の分解抽出処理工程を経て、セルロースＩ型成分を効率的に抽出する方法である。この本発明の植物組織処理方法によって製造したセルロースＩ型成分は、様々な工業用途に利用可能な原材料となり得る。
なお、本発明の植物組織処理方法の必須の工程は、分解抽出処理工程（１）であり、その他の分離工程（２）〜セルラーゼ反応工程（６）などは一例に過ぎず、用途や内容に応じてそれら工程の他にも多様な処理工程があり得る。
本実施例１では以下、分解抽出処理工程（１）について中心に述べる。The steps of the plant tissue processing method of the present invention will be described.
FIG. 1 is a flow chart briefly showing the steps of the plant tissue processing method of the present invention.
The outline of the process of the plant tissue processing method of the present invention is to add a plant tissue processing agent to plant tissue such as wood and rice straw as a raw material, and through the process of decomposition and extraction of plant tissue, It is a method to extract efficiently. The cellulose type I component produced by the plant tissue processing method of the present invention can be a raw material that can be used for various industrial applications.
The essential step of the plant tissue processing method of the present invention is the decomposition extraction step (1), and the other separation steps (2) to the cellulase reaction step (6) etc. are only an example, and it is possible to use and contents. Accordingly, there may be various processing steps in addition to these steps.
In the first embodiment, the decomposition extraction process step (1) will be mainly described below.
図１に示した分解抽出処理工程（１）において、投入される原材料となる植物組織としては、木材、草本の天然植物資源や、化学処理済みの植物資源などで良い。例えば、天然植物資源としては、竹類、稲わら、麦わら、ササ、ススキ、スイッチグラス、ジャイアントミスカンサス、木材間伐材樹皮のいずれかまたはそれらの組み合わせなどで良い。例えば、化学処理済みの植物資源としては、製紙工程から排出されるパルプ液に含まれる植物片残渣などなども利用可能である。 In the decomposition and extraction treatment step (1) shown in FIG. 1, as a plant tissue which is a raw material to be input, wood, natural plant resources of herbaceous material, chemically processed plant resources and the like may be used. For example, natural plant resources may be bamboos, rice straw, wheat straw, sasa, susuki, switchgrass, giant miscanthus, bark of lumber thinning timber, or a combination thereof. For example, as chemically treated plant resources, plant debris and the like contained in pulp liquid discharged from a papermaking process can also be used.
また、図１に示した分解抽出処理工程（１）において、投入される植物組織処理剤は、水酸化リチウムを主剤とするものである。
本発明は、図２に示すように、木材片または草本片の植物組織またはそれらを原料として加工した植物由来加工物に植物組織処理剤を添加することにより植物組織または植物由来加工物の分解を促進させ、内部のセルロースＩ型成分を抽出する方法である。本発明者らは、ここで、植物組織を構成する原子径より小さな原子径を持つ金属元素の化合物かつ水溶性を示す化合物を主剤とする植物組織処理剤を植物組織に常温かつ常圧で添加し、組織内のセルロースミクロフィブリルまで直接浸透させることを考えた。植物組織は主に炭素で構成されているので、炭素原子より原子径の小さな金属化合物はリチウム化合物であり、水溶性を示すものとして、水酸化リチウムを挙げることができる。水酸化リチウムはリチウムの原子径が植物組織を構成する炭素の原子径より小さいため植物組織の内部への浸透性が大きく、内部のセルロースミクロフィブリルに作用しやすいと考えられる。セルロースミクロフィブリルの非結晶部分に水酸化リチウムを施用させ、特段ほかに他の有効成分を施用させず、穏やかに溶解してセルロースＩ型成分を溶出させる、セルロースＩ型成分の緩慢的な溶解抽出方法を確立した。
なお、本発明の植物組織処理剤は、同じアルカリ金属水酸化物であっても、他のアルカリ金属水酸化物を主剤とするものを用いてもかならずしも本発明と同等の効果を得ることはできない。一般的に、アルカリ金属水酸化物としては、水酸化リチウム溶液、水酸化ナトリウム溶液、水酸化カリウム溶液、水酸化カルシウム溶液などが広く用いられているが、植物組織の破壊能力についてはアルカリ金属水酸化物すべてに広く見られる性質とまでは言えない。本発明者らの研究により、水酸化リチウムの持つ植物組織の破壊能力は、他のアルカリ金属水酸化物の持つ植物組織の破壊能力より明確に大きいことを初めて突き止めた。なお、水酸化ナトリウムは水酸化リチウムに比べて植物組織の破壊能力は劣るものの、水酸化リチウム水溶液を主剤としつつ、副剤として使用することも検討できる。In addition, in the decomposition and extraction treatment step (1) shown in FIG. 1, the plant tissue treating agent to be added is mainly composed of lithium hydroxide.
In the present invention, as shown in FIG. 2, degradation of a plant tissue or a plant-derived processed product is achieved by adding a plant tissue treating agent to a plant tissue of wood pieces or grass pieces or a plant-derived processed material processed using them. It is a method of promoting and extracting the cellulose type I component inside. Here, the present inventors added a plant tissue treating agent containing a compound of a metal element having an atomic diameter smaller than that of a plant tissue and a compound showing water solubility to a plant tissue at normal temperature and pressure. It was considered to directly penetrate cellulose microfibrils in the tissue. Since a plant tissue is mainly composed of carbon, a metal compound having an atomic diameter smaller than that of a carbon atom is a lithium compound, and lithium hydroxide can be mentioned as one showing water solubility. Lithium hydroxide has a large atomic diameter of lithium smaller than that of carbon constituting plant tissue, so it is considered that the permeability to the inside of plant tissue is large and it is likely to act on cellulose microfibrils inside. Slow dissolution and extraction of cellulose I-type component by applying lithium hydroxide to the non-crystalline part of cellulose microfibrils and gently dissolving it to elute the cellulose I-type component without applying other active ingredients. The method was established.
In addition, even if it is the same alkali metal hydroxide as the plant tissue processing agent of this invention, even if it uses another alkali metal hydroxide as a main agent, the effect equivalent to this invention can not be acquired necessarily. . Generally, lithium hydroxide solution, sodium hydroxide solution, potassium hydroxide solution, calcium hydroxide solution, etc. are widely used as alkali metal hydroxides, but alkali metal water is used for the ability to destroy plant tissue. It can not be said that it is a property widely seen in all oxides. The present inventors have found for the first time that the ability of lithium hydroxide to destroy plant tissue is clearly greater than that of other alkali metal hydroxides. Although sodium hydroxide is inferior to lithium hydroxide in its ability to destroy plant tissue, it can also be considered to use an aqueous solution of lithium hydroxide as a main agent and to use it as an auxiliary agent.
植物組織処理剤のｐＨは、ｐＨ１３以下の弱アルカリ性に調製した。
本発明はセルロースミクロフィブリルの非結晶部分に対して水酸化リチウムを施用させて緩慢に非結晶部分を破壊・溶解できるものであるので、温度および圧力は、常温常圧で施用させれば良いが、処理速度の一層の向上のため高温高圧下の処理環境とすることを排除はしない。例えば、温度は５℃から２００℃の範囲が好ましい。The pH of the plant tissue treating agent was adjusted to be weakly alkaline at pH 13 or less.
In the present invention, lithium hydroxide can be applied to the noncrystalline portion of cellulose microfibrils to slowly break and dissolve the noncrystalline portion, so the temperature and pressure may be applied at normal temperature and pressure. However, the processing environment under high temperature and high pressure is not excluded in order to further improve the processing speed. For example, the temperature is preferably in the range of 5 ° C to 200 ° C.
次に、植物組織処理方法の分解抽出処理工程の検証実験について述べる。
［試験片］
実験に用いる植物組織の試験片として孟宗竹材とスギ（辺材と心材混合）材を８０メッシュ以上３０メッシュ以下の大きさに調整したものを１００ｍｇずつ用意した。Next, verification experiments of the decomposition extraction processing step of the plant tissue processing method will be described.
[Test pieces]
As test pieces of plant tissue used in the experiment, 100 mg of each prepared with a size of 80 mesh or more and 30 mesh or less of a Shiso bamboo material and a cedar (sapwood and heartwood mixed) material was prepared.
［植物組織処理剤］
分解抽出工程（１）における植物組織処理剤として、水酸化リチウムを用いた試験区分と、比較対象として水酸化ナトリウムを用いた試験区分を用意した。
水酸化リチウム水溶液の濃度は、本発明の植物組織処理方法で想定する濃度範囲３ｗ％から１０ｗ％のうち代表的な濃度である７ｗｔ％のものを用いた。一方、比較対象である水酸化ナトリウム溶液は、水酸化リチウム溶液７ｗ％と同モル数に換算して、１１．８ｗｔ％の水酸化ナトリウム溶液を用いた。[Plant tissue treatment agent]
A test section using lithium hydroxide as a plant tissue treating agent in the decomposition extraction step (1) and a test section using sodium hydroxide as a comparison target were prepared.
The concentration of the lithium hydroxide aqueous solution was 7 wt% which is a typical concentration out of the concentration range of 3 w% to 10 w% assumed in the method for treating plant tissue of the present invention. On the other hand, as a sodium hydroxide solution to be compared, a 11.8 wt% sodium hydroxide solution was used in terms of the same number of moles as 7 w% of lithium hydroxide solution.
［植物組織処理方法］
植物組織処理方法は、用意した試験片をビーカーに入れ、試験片が十分に浸漬する程度、植物組織処理剤を投入し、浮かないようガラス栓により押さえ、そのまま、１時間の静置浸漬した。
その後、流水で約１時間水洗して中性にした。[Plant tissue processing method]
The plant tissue processing method put the prepared test piece in a beaker, added the plant tissue processing agent to the extent that the test piece was sufficiently immersed, pressed it with a glass plug so as not to float, and left it still for 1 hour.
Thereafter, it was washed with running water for about 1 hour to be neutral.
［評価方法］
評価は京都大学生存圏研究所にて行った。
それぞれの試験区分で得られたセルロースの結晶型を調べるため「Rigaku X-RAY PIFFRACTOMETER」を用いてエックス線回析を行い、回析結果を得て解析した。
図３、図４はエックス線回析の結果を示す図である。
図３は、スギ材の場合の試験結果、図４は、孟宗竹の場合の試験結果である。
図３（ａ）、図４（ａ）に示すように、エックス線回析グラフを解析した結果、水酸化リチウムを用いた試験区分では、２０度から２３度付近に高いピークがあり、１０度付近にセルロースＩＩ型の特有のピークが見られないためセルロースＩ型のみが抽出されたものと判定することができた。つまり、セルロースＩＩ型のアルカリセルロースは抽出されておらず、結晶型はすべてセルロースＩ型であった。
濃度範囲を変えて検証した結果、植物組織処理剤の主剤である水酸化リチウム溶液３ｗ％〜１０ｗ％の範囲においてエックス線回析結果を解析すると結晶型はすべてセルロースＩ型であった。[Evaluation method]
The evaluation was conducted at the Kyoto University Survival Zone Research Institute.
X-ray diffraction was performed using "Rigaku X-RAY PIFFRACTOMETER" in order to examine the crystal form of cellulose obtained in each test category, and the diffraction results were obtained and analyzed.
3 and 4 show the results of X-ray diffraction.
FIG. 3 shows the test results in the case of cedar wood, and FIG. 4 shows the test results in the case of moso bamboo.
As shown in FIGS. 3 (a) and 4 (a), as a result of analyzing the X-ray diffraction graph, in the test section using lithium hydroxide, there is a high peak near 20 degrees to 23 degrees and around 10 degrees Since no characteristic peak of cellulose type II was observed, it was determined that only cellulose type I was extracted. That is, alkali cellulose of cellulose type II was not extracted, and all crystal types were cellulose type I.
As a result of verification by changing the concentration range, when the X-ray diffraction results were analyzed in the range of 3 w% to 10 w% of lithium hydroxide solution which is the main agent of the plant tissue treating agent, all crystal forms were cellulose I type.
一方、水酸化ナトリウムを用いた試験区分では、エックス線回析結果において、１０度付近にセルロースＩＩ型の特有のピークが見られたため、セルロースＩＩ型が抽出されたものと判定することができた。水酸化ナトリウムを用いた試験区分ではセルロースＩＩ型のアルカリセルロースであると検証できた。
このように、本発明の植物組織処理剤の主剤として水酸化リチウムを用いたものは、爆砕などの物理的処理を伴うことなく、水酸化リチウムを常温常圧で浸透させるという緩慢な化学的処理だけで、セルロースＩ型の結晶型のセルロースを得ることができる。On the other hand, in the test section using sodium hydroxide, a characteristic peak of cellulose type II was observed in the vicinity of 10 degrees in the X-ray diffraction result, so that it could be judged that cellulose type II was extracted. In the test section using sodium hydroxide, it could be verified that it is an alkali cellulose of cellulose type II.
Thus, the one using lithium hydroxide as the main ingredient of the plant tissue treating agent of the present invention is a slow chemical treatment in which lithium hydroxide is infiltrated at normal temperature and pressure without physical treatment such as explosion. By itself, cellulose of crystalline form I can be obtained.
次に、それぞれの試験区分におけるセルロース抽出量を比較する実験も行った。
セルロースの抽出量の多寡は直接計測することが難しいため、セルロースをグルコースへと分解し、そのグルコース量を比較することで行った。
実験および評価は京都大学生存圏研究所にて行った。
試験方法の手順は以下とした。
試験片は、スギ材は１．０ｇを用いた。
植物組織処理剤は、上記と同じく、水酸化リチウム７ｗ％、水酸化ナトリウムは同モル数となるよう１１．８ｗ％の試験区分を用意した。
植物組織処理方法は、上記と同じく、１時間浸漬して抽出物を得た。
評価方法は、セルロース抽出量を直接測ることに代え、セルラーゼ反応工程によりグルコース変換してそのグルコース量の多寡を測定した。
それぞれの試験区分に対して、tricoderma由来のセルラーゼ４０ｍｌを施用させた。溶液温度をセルラーゼの酵素活性が高くなる５０〜５３℃付近に保ちつつ振盪して反応させた。
次に、セルラーゼ浸漬後、６０分、１２０分、２４０分にグルコース収量を測定した。グルコース収量測定にはＧＯＤ、比色法を用いた。Next, experiments were also conducted to compare the amount of extracted cellulose in each test category.
Since it is difficult to directly measure the amount of extracted cellulose, cellulose was decomposed into glucose and the amount of glucose was compared.
The experiments and evaluations were conducted at the Research Institute for Survival Zone, Kyoto University.
The procedure of the test method was as follows.
As a test piece, 1.0 g of cedar wood was used.
The plant tissue treating agent prepared 7 w% of lithium hydroxide and 11.8 w% of the test division so that sodium hydroxide became the same number of moles as above.
The plant tissue processing method was immersed for 1 hour as described above to obtain an extract.
As an evaluation method, instead of directly measuring the amount of extracted cellulose, glucose was converted by the cellulase reaction step, and the amount of glucose was measured.
For each test section, 40 ml of cellulase from tricoderma was applied. The solution was shaken and reacted while maintaining the solution temperature around 50 to 53 ° C. at which the enzyme activity of cellulase increases.
Next, the glucose yield was measured at 60 minutes, 120 minutes, and 240 minutes after the cellulase immersion. GOD, a colorimetric method was used for glucose yield measurement.
結果を図５に示す。
図５に示すように、グルコースの収量は、本発明の植物組織処理剤の主剤である水酸化リチウムの試験区分の方が、水酸化ナトリウムの試験区分よりも多いことが分かる。つまり、セルロースの抽出量においても水酸化リチウムの優位性が確認できる。
さらに、上記したエックス線回析結果を加味すれば、図５において、水酸化リチウムの試験区分は、セルロースＩ型成分から生成されたグルコース量であり、水酸化ナトリウムの試験区分は、セルロースＩＩ型のアルカリセルロースから生成されたグルコース量である。The results are shown in FIG.
As shown in FIG. 5, it can be seen that the yield of glucose is higher in the test section of lithium hydroxide which is the main ingredient of the plant tissue treating agent of the present invention than in the test section of sodium hydroxide. That is, the superiority of lithium hydroxide can be confirmed also in the amount of extraction of cellulose.
Furthermore, in consideration of the above-mentioned X-ray diffraction results, in FIG. 5, the test division of lithium hydroxide is the amount of glucose produced from the cellulose type I component, and the test division of sodium hydroxide is cellulose type II. It is the amount of glucose produced from alkaline cellulose.
次に、植物組織の破壊の進行の指標として、試験片の耐圧強度の変化を調べるべく圧縮試験にかけることで評価した。
評価は京都大学生存圏研究所にて行った。
試験片の初期状態はいわゆるコルク質、木質のもので硬くまとまっており崩れることはない。しかし、植物組織の破壊が進行するといわゆる脆くなり始め、進行が進むと粗い粉体のような破壊状態になってゆく。この物理的変化は試験片の圧縮耐圧変化を調べることで評価できる。
処理対象材はスギ材とした。また参考に処理対象材としてブナ材、稲わら材も用いて観察した。
植物組織処理剤は、上記と同じく、水酸化リチウム７ｗ％、水酸化ナトリウムは同モル数となるよう１１．８ｗ％の試験区分を用意した。
植物組織処理方法は、１時間浸漬、２時間浸漬、４時間浸漬、１２時間浸漬、２４時間浸漬したものをそれぞれ用意した。Next, as an indicator of the progress of destruction of plant tissue, evaluation was made by subjecting it to a compression test in order to investigate changes in the compressive strength of the test piece.
The evaluation was conducted at the Kyoto University Survival Zone Research Institute.
The initial state of the test pieces is so-called cork-like and woody ones, which are firmly assembled and do not collapse. However, when the destruction of plant tissue proceeds, it starts to become so-called brittle, and as the progress progresses, it becomes a broken state like coarse powder. This physical change can be evaluated by examining the change in compression resistance of the test piece.
The material to be treated was cedar. Moreover, it observed using a beech wood and rice straw wood as a processing object material for reference.
The plant tissue treating agent prepared 7 w% of lithium hydroxide and 11.8 w% of the test division so that sodium hydroxide became the same number of moles as above.
The plant tissue treatment method was prepared by soaking for 1 hour, 2 hours, 4 hours, 12 hours, and 24 hours.
水酸化リチウム溶液に浸漬した試験区分は、いずれも水酸化ナトリウム溶液に浸漬した試験区分よりも破壊が進行していることが確認できた。水酸化リチウム溶液に浸漬したスギ材についてはそれぞれ試験時間内では粉体までの破壊はなかったが脆くなっていることが触感により確認できた。なお、参考までにコルク材を用いた場合は、粗い粉体、いわゆる粉々になるまでの破壊が見られた。
一方、水酸化ナトリウム溶液に浸漬したスギ材についても試験時間内では木材の硬さの変化が小さいことが触感により確認できた。It was confirmed that the test sections immersed in the lithium hydroxide solution were more likely to be destroyed than the test sections immersed in the sodium hydroxide solution. About the cedar material which was immersed in the lithium hydroxide solution, it was able to be confirmed by the sense of touch that there was no destruction to the powder within the test time, but it became brittle. In addition, when a cork material was used for reference, the destruction to coarse powder, so-called shattering was seen.
On the other hand, it was confirmed by touch that the change in hardness of wood was small within the test time also for cedar wood soaked in sodium hydroxide solution.
スギ材の圧縮試験にかけた試験片の耐圧変化の結果を図５および図６に示す。図６は測定結果、図７はそれをグラフ化したものである。
図６および図７に示すように、水酸化リチウム溶液に浸漬したスギ材の試験区分は脆性が大きくなるよう変化していることが分かる。水酸化ナトリウム溶液に浸漬したスギ材の試験区分も同様、脆性が大きくなるよう変化していることが分かる。
また、ブナ材の圧縮試験にかけた試験片の耐圧変化の結果を図１３および図１４に示す。図８は測定結果、図８はそれをグラフ化したものである。
図８および図９に示すように、水酸化リチウム溶液に浸漬したブナ材の試験区分は脆性が大きくなるよう変化していることが分かる。水酸化ナトリウム溶液に浸漬したブナ材の試験区分も同様、脆性が大きくなるよう変化していることが分かる。The results of the change in pressure resistance of the test pieces subjected to the compression test of cedar wood are shown in FIGS. 5 and 6. FIG. 6 shows the measurement result, and FIG. 7 is a graph of it.
As shown in FIG. 6 and FIG. 7, it can be seen that the test section of cedar wood soaked in lithium hydroxide solution has changed so as to increase the brittleness. It can be seen that the test sections of cedar wood soaked in sodium hydroxide solution are also changed so as to increase the brittleness.
Moreover, the result of the pressure | voltage resistant change of the test piece which gave the compression test of the beech material is shown in FIG. 13 and FIG. FIG. 8 shows the measurement result, and FIG. 8 is a graph of it.
As shown in FIG. 8 and FIG. 9, it can be seen that the test section of beech wood soaked in lithium hydroxide solution has changed so as to increase the brittleness. It can be seen that the test section of beech wood soaked in sodium hydroxide solution is also changed so as to increase the brittleness.
以上から、本発明の植物組織処理方法によれば、爆砕などの物理的手段を伴うことなく、化学的処理のみで、従来では得ることが難しかったセルロースＩ型を抽出することができ、かつ、その収量が大きいものであると結論付けられる。 From the above, according to the plant tissue processing method of the present invention, it is possible to extract cellulose type I, which has been difficult to obtain conventionally, only by chemical processing without physical means such as explosion, and It can be concluded that the yield is large.
実施例として、主剤である水酸化リチウムに対して、副剤を混合して用いる例を述べる。
［植物組織処理剤の調製］
本発明の植物組織処理剤の主剤として、水酸化リチウム水溶液を主剤として用意した。植物組織処理剤の水酸化リチウム水溶液濃度は７ｗ％となるよう調製した。副剤として水酸化ナトリウムを添加する場合、水酸化リチウムの代替となるよう、水酸化ナトリウム水溶液濃度を７％に調整した。主剤の水酸化リチウムと副剤の水酸化ナトリウムの混合比率を変えて以下の５つの植物組織処理剤を用意した。
それぞれの植物組織処理剤の液量は１０ｍｌとし、ビーカーに入れた試験片が十分に浸漬される程度の量を用意した。ｐＨは１０から１２程度になるよう調製した。As an example, an example will be described in which an auxiliary agent is mixed with lithium hydroxide which is a main agent.
[Preparation of plant tissue treating agent]
Lithium hydroxide aqueous solution was prepared as a main ingredient as a main ingredient of a plant tissue treating agent of the present invention. The concentration of the aqueous solution of lithium hydroxide in the plant tissue treating agent was adjusted to 7 w%. When sodium hydroxide was added as an auxiliary agent, the aqueous sodium hydroxide solution concentration was adjusted to 7% so as to replace lithium hydroxide. The following five plant tissue treating agents were prepared by changing the mixing ratio of the main agent lithium hydroxide and the auxiliary agent sodium hydroxide.
The liquid volume of each plant tissue treating agent was 10 ml, and an amount was prepared such that the test piece placed in the beaker was sufficiently immersed. The pH was adjusted to about 10 to 12.
［試験片］
実験に用いる植物組織の試験片として、スギ材（Ｓ）、孟宗竹材（Ｔ）を用意した。
孟宗竹材とスギ（辺材と心材混合）材を８０メッシュ以上３０メッシュ以下の大きさに調整したものを１００ｍｇずつ用意した。[Test pieces]
As a test piece of a plant tissue used for an experiment, cedar wood (S) and moso bamboo wood (T) were prepared.
100 mg each was prepared by adjusting the size of bamboo mesh and cedar (sapwood and heartwood mixed) material to a size of 80 mesh or more and 30 mesh or less.
［植物組織処理方法］
植物組織処理方法は、上記５つの植物組織処理剤をそれぞれビーカーに入れ、用意した試験片が十分に植物組織処理剤に浸漬するようにし、浮かないようガラス栓により押さえ、そのまま、１時間の静置浸漬した。
その後、流水で約１時間水洗して中性にした。[Plant tissue processing method]
The plant tissue treatment method is to put each of the above five plant tissue treatment agents in a beaker so that the prepared test specimen is sufficiently immersed in the plant tissue treatment agent, hold it with a glass stopper so as not to float, and leave it for 1 hour. It was immersed in water.
Thereafter, it was washed with running water for about 1 hour to be neutral.
［効果検証］
以下、３つの試験（セルロースの結晶化度、抽出物生成の効率を評価するグルコース生成量試験、抽出物のエックス線回析試験）を行って効果の検証をした。
セルロースの結晶化度
結晶化度の測定は京都大学生存圏研究所にて行った。
上記した各混合比率の植物組織処理剤を用いて得た抽出結果物を十分乾燥後、「Rigaku X-RAY PIFFRACTOMETER」でエックス線回析をし、そのプロットしたグラフから面積質量法により、各試験結果の結晶化度を求めた。[Effect verification]
In the following, three tests (cellulose crystallinity, glucose production test for evaluating the efficiency of extract formation, X-ray diffraction test for the extract) were conducted to verify the effect.
Degree of Crystallization of Cellulose The degree of crystallinity was measured at the Research Institute for Survival Zone, Kyoto University.
After thoroughly drying the extraction result obtained using the plant tissue treating agent at each mixing ratio described above, X-ray diffraction was performed with "Rigaku X-RAY PIFFRACTOMETER", and each graph was obtained by area mass method from the plotted graph. Was determined.
図１０は、各混合比率の植物組織処理剤を用いて得た抽出結果物の結晶化度を示す図である。図１０においてＴは孟宗竹の場合、Ｓはスギ材の場合である。引数は各々の植物組織処理剤の項番である。例えば、Ｔ−１は孟宗竹を項番１の植物組織処理剤を用いて処理した抽出物の結晶化度を示すものである。
結晶化度とは、注目する分子が結晶化している度合いであり、結晶化度が高いほど高分子化して安定であり、結晶化度が低いほど分解が進み、抽出しやすい状態となっていることを示す。FIG. 10 is a view showing the crystallinity of the extraction result obtained using the plant tissue treating agent at each mixing ratio. In FIG. 10, T is a case of Zinso bamboo, and S is a case of cedar wood. The argument is the item number of each plant tissue treatment agent. For example, T-1 indicates the crystallinity of an extract obtained by treating moso bamboo with the No. 1 plant tissue treating agent.
The degree of crystallization is the degree to which the molecule of interest is crystallized, and the higher the degree of crystallization, the higher the degree of polymerization and stability, and the lower the degree of crystallization, the more advanced decomposition and the state of easy extraction Indicates that.
図１０に示すように、孟宗竹の試験結果を見れば、明らかにＴ−１の結晶化度は低い。Ｔ−１からＴ−２、・・Ｔ−５の順で結晶化度が高くなっていることが分かる。また、図１０に示すように、スギ材の試験結果を見れば、やはり、明らかにＴ−１の結晶化度は低い。Ｔ−１からＴ−２、・・Ｔ−５の順で結晶化度が高くなっている傾向が分かる。
このことから、やはり、水酸化リチウム１００％の植物組織処理剤がもっとも炭素源を分解していることが分かる。もし副剤を用いるとしても、Ｔ−１からＴ−２の間、Ｓ−１からＳ−２の間程度とするべきであると言える。つまり、水酸化リチウムと水酸化ナトリウムとの混合比率は、１００：０〜７５：２５の範囲とすることが好ましいと結論付けられる。As shown in FIG. 10, the crystallinity of T-1 is apparently low according to the test results of the moso bamboo. It can be seen that the degree of crystallinity increases in the order of T-1 to T-2,. Also, as shown in FIG. 10, the crystallinity of T-1 is obviously low according to the test results of cedar wood. It can be seen that the degree of crystallinity increases in the order of T-1 to T-2,.
From this, it can be seen that the plant tissue treating agent of 100% lithium hydroxide is the most decomposing carbon source. It can be said that even if an auxiliary agent is used, it should be between T-1 and T-2 and between S-1 and S-2. That is, it is concluded that the mixing ratio of lithium hydroxide and sodium hydroxide is preferably in the range of 100: 0 to 75:25.
抽出物生成の効率を評価するグルコース生成量試験
次に、上記した各混合比率の植物組織処理剤を用いて得た抽出結果物におけるセルロースの収量を検証する。セルロースの収量は直接計測するのが難しいため、セルラーゼ反応によりセルロースをグルコースへと分解し、そのグルコース量を比較することで行った。
試験方法の手順は以下とした。
試験片は孟宗竹を４００ｍｇ使用した。植物組織処理剤は、表１の項番１と項番５、つまり、水酸化リチウム７ｗ％水溶液と、水酸化ナトリウム７％を用いて比較した。植物組織処理方法は上記と同じとした。
抽出した抽出物に対して、tricoderma由来のセルラーゼ４０ｍｌを施用させた。溶液温度をセルラーゼの酵素活性が高くなる５０〜５３℃付近に保ちつつ振盪して反応させた。
次に、セルラーゼ浸漬後、６０分、１２０分、２４０分にグルコース収量を測定した。グルコース収量測定にはＧＯＤ、比色法を用いた。Glucose production test to evaluate the efficiency of extract formation Next, the yield of cellulose in the extraction result obtained using the plant tissue treating agent at each mixing ratio described above is verified. Since it is difficult to directly measure the yield of cellulose, the cellulase reaction was performed to decompose cellulose into glucose and compare the amount of glucose.
The procedure of the test method was as follows.
The test piece used 400 mg of moso bamboo. The plant tissue treating agents were compared using No. 1 and No. 5 of Table 1, that is, using a 7 w% aqueous solution of lithium hydroxide and 7% sodium hydroxide. The plant tissue processing method was the same as above.
40 ml of cellulase derived from tricoderma was applied to the extracted extract. The solution was shaken and reacted while maintaining the solution temperature around 50 to 53 ° C. at which the enzyme activity of cellulase increases.
Next, the glucose yield was measured at 60 minutes, 120 minutes, and 240 minutes after the cellulase immersion. GOD, a colorimetric method was used for glucose yield measurement.
結果を図１１に示す。
図１１に示すように、孟宗竹４００ｍｇから優れたグルコースの収量は、水酸化リチウムの方が多く得られたことが分かる。水酸化リチウムの試験区分と水酸化ナトリウムの試験区分を比較すると、グルコース変換した収量において、水酸化リチウムの試験区分の方が、水酸化ナトリウムの試験区分より、１．５倍も収量が多いことが分かった。The results are shown in FIG.
As shown in FIG. 11, it can be seen that, from 400 mg of moso bamboo, an excellent glucose yield was obtained more with lithium hydroxide. Comparing the test division of lithium hydroxide and the test division of sodium hydroxide, it is found that the test division of lithium hydroxide has 1.5 times higher yield than the test division of sodium hydroxide in the glucose conversion yield I understand.
抽出物のエックス線回析試験
上記試験結果より、主剤である水酸化リチウムは、副剤と混合することなく１００％で用いることが良く、副剤として水酸化リチウムを加える場合も主剤と副剤の割合が１００：０〜７５：２５の範囲に抑えることが良いという結論を得たが、上記試験に用いた項番１（主剤と副剤の割合が１００：０の場合）、項番２（主剤と副剤の割合が７５：２５の場合）について、Ｘ線回析結果を出し、両者がセルロースＩ型であることを確認した。
つまり、試験片として、孟宗竹、スギ材の２種類をそれぞれ１００ｍｇずつ使用し、植物組織処理剤は、表１の項番１と項番２のものを使用し、植物組織処理方法は、上記のように１時間浸漬する方法とし、水洗、乾燥させた後の抽出物を用いた。Ｘ線回析試験は、「Rigaku X-RAY PIFFRACTOMETER」を用いてエックス線回析を行い、回析結果を得て解析した。X-ray Diffraction Test of Extract From the above test results, it is recommended to use lithium hydroxide which is the main agent at 100% without mixing with the auxiliary agent, and even when lithium hydroxide is added as the auxiliary agent, the main agent and auxiliary agent It was concluded that the ratio should be kept within the range of 100: 0 to 75:25, but the item No. 1 used in the above test (when the ratio of main agent to auxiliary agent is 100: 0), item No. 2 When the ratio of the main agent to the auxiliary agent was 75:25), X-ray diffraction results were obtained, and it was confirmed that both were cellulose type I.
In other words, 100 mg each of the two types of bamboo grass and cedar wood are used as test pieces, the plant tissue treating agents used are those of No. 1 and No. 2 of Table 1, and the plant tissue treating method is the above Thus, the extract was used after being soaked for 1 hour, washed with water and dried. The X-ray diffraction test performed the X-ray diffraction using "Rigaku X-RAY PIFFRACTOMETER", obtained and analyzed the diffraction result.
このＸ線回析試験、解析結果の確認は、京都大学生存圏研究所内にて行った。
図１２はスギを処理対象とした場合の抽出物のエックス線回析結果を示すグラフ、図１３は孟宗竹を処理対象とした場合の抽出物のエックス線回析結果を示すグラフである。
図１２、図１３のエックス線回析グラフより、いずれも２０度から２３度付近に高いピークがあり、１０度付近にセルロースＩＩ型の特有のピークが見られないため、主剤と副剤の割合が１００：０の場合も、主剤と副剤の割合が７５：２５の場合も、セルロースＩ型が抽出されたものと判定することができた。また、セルロースＩＩ型は抽出されておらず、セルロースＩ型以外のセルロース型が混在しないことも分かった。The X-ray diffraction test and the confirmation of the analysis result were performed in the Research Institute for Survival Zone, Kyoto University.
FIG. 12 is a graph showing the results of X-ray diffraction of the extract when cedar is treated, and FIG. 13 is a graph showing the results of x-ray diffraction of the extract when treating moso bamboo.
According to the X-ray diffraction graphs in FIG. 12 and FIG. 13, since there is a high peak in the vicinity of 20 ° to 23 ° and no characteristic peak of cellulose type II is observed in the vicinity of 10 °, the ratio of main agent to auxiliary agent is It was possible to determine that cellulose type I was extracted also in the cases of 100: 0 and in the case of the ratio of main agent to auxiliary agent of 75:25. In addition, it was also found that cellulose type II was not extracted, and cellulose types other than cellulose type I were not mixed.
実施例３は、植物組織処理の分解抽出処理工程の結果得られた浸漬液側の利用と、残渣側の利用を説明する。
本実施例３は、実施例１の図１に示した植物組織の分解抽出処理工程（１）を経て得られた浸漬液または植物組織残渣に対する後処理を行い、バイオマスの炭素源等の有用物質を得るものである。Example 3 demonstrates utilization of the immersion liquid side obtained as a result of the decomposition extraction process process of a plant tissue process, and utilization of the residue side.
In this Example 3, the immersion liquid or the plant tissue residue obtained through the decomposition extraction process step (1) of the plant tissue shown in FIG. 1 of Example 1 is subjected to a post treatment, and useful substances such as a carbon source of biomass To get
［浸漬液の分離工程］
図１の浸漬液側の工程として、分離工程（２）について述べる。
本発明の植物組織処理剤を用いた分解抽出処理工程の後、浸漬液には植物由来構成物質の一部が溶出している。図１に示すように、分解抽出処理工程の後工程である分離工程により利用可能な形に分離することができる。分離・抽出の方法は様々あり得る。
植物由来物質の中には、いわゆる水溶性のものと油溶性のものがあるが、これらは油分と水分の分離によりそれぞれ分離抽出することができる。図１に示す分離工程により、分離抽出した水分層に溶存している水溶性成分は脱水処理により濃縮することができ、また、油分層に溶存している油溶性成分は脱油処理により濃縮することができる。[Separating process of immersion liquid]
The separation step (2) will be described as the step on the immersion liquid side of FIG.
After the decomposition and extraction treatment step using the plant tissue treatment agent of the present invention, a part of the plant-derived constituent material is eluted in the immersion liquid. As shown in FIG. 1, it can be separated into a usable form by a separation step which is a step after the decomposition extraction treatment step. There are various methods of separation and extraction.
Among plant-derived substances, there are so-called water-soluble substances and oil-soluble substances, which can be separated and extracted by separation of oil and water. According to the separation process shown in FIG. 1, the water-soluble components dissolved in the separated and extracted water layer can be concentrated by dehydration treatment, and the oil-soluble components dissolved in the oil separation layer are concentrated by deoiling treatment be able to.
次に、残渣側の処理として、図１の水洗工程（３）以降について述べる。
図１の水洗工程（３）は、分解抽出処理工程（１）の後、分解処理済の植物組織残渣を取り出して水洗する工程である。分解抽出処理工程（１）では植物組織処理剤に浸漬されているので植物組織内部には植物組織処理剤が多量に残存している。この植物組織処理剤の成分はバイオマスの炭素源生成には不要であるので、除去する必要がある。植物組織処理剤は実施例１で示したように水酸化リチウムなどのアルカリ金属化合物であるので水溶性を示すので、水洗することによりほぼ洗い流すことが可能である。
水洗工程（３）の後、植物組織残渣は乾燥工程（５）に移行し、水洗した水洗処理水はリチウム回収工程（４）に移行する。Next, as the treatment on the residue side, the steps after the washing step (3) in FIG. 1 will be described.
The water washing process (3) of FIG. 1 is a process of taking out and washing the decomposition-treated plant tissue residue after the decomposition extraction process (1). In the decomposition and extraction treatment step (1), since the plant tissue treatment agent is immersed, a large amount of the plant tissue treatment agent remains inside the plant tissue. The component of this plant tissue treating agent is unnecessary for carbon source production of biomass, so it needs to be removed. Since the plant tissue treating agent is an alkali metal compound such as lithium hydroxide as described in Example 1, it exhibits water solubility, so it can be washed out by washing with water.
After the washing step (3), the plant tissue residue is transferred to the drying step (5), and the washed water after washing is transferred to the lithium recovery step (4).
リチウム回収工程（４）は、水洗処理水に包含されているリチウムを回収する工程である。リチウムは素材として経済価値のあるものであり、分解抽出処理工程に使用した水酸化リチウムはそのまま廃棄するのは勿体なく、リチウムを回収して再利用することが好ましい。 The lithium recovery step (4) is a step of recovering lithium contained in the water-washed water. Lithium has economic value as a raw material, and it is preferable to discard lithium lithium used in the decomposition extraction process as it is, and it is preferable to recover and reuse lithium.
リチウム回収工程（４）では水洗処理水に対して二酸化炭素を投入する。
水酸化リチウムは、二酸化炭素を加えることにより、炭酸リチウムに変化させると溶解度が大きく変化して沈殿するため、リチウムは炭酸リチウムの形で容易に回収することができる。
2LiOH・H2O+CO2 → Li2CO3+3H2O
炭酸リチウムの形でも経済価値の大きな物質であり、そのまま炭酸リチウムとして利用も可能である。
また、炭酸リチウムに対して水酸化カルシウムを反応させることにより、水酸化リチウムを生成して再利用することも可能である。
Li2CO3＋Ca(OH)2 → 2LiOH+CaCO3In the lithium recovery step (4), carbon dioxide is introduced into the water-washed water.
Lithium hydroxide can be easily recovered in the form of lithium carbonate, since lithium hydroxide is precipitated by the addition of carbon dioxide, and its solubility changes greatly and precipitates when it is converted to lithium carbonate.
2LiOH · H2O + CO2 → Li2CO3 + 3H2O
Even in the form of lithium carbonate, it is a substance of great economic value, and can be used as it is as lithium carbonate.
Further, lithium hydroxide can be produced and reused by reacting calcium hydroxide with lithium carbonate.
Li2CO3 + Ca (OH) 2 → 2LiOH + CaCO3
セルラーゼ反応工程（５）は、水洗工程（３）の処理後の植物組織残渣中に残存しているセルロースに対して、（１→４）−β−グルコシド結合の加水分解酵素であるセルラーゼを施用してセルロース分解を行う工程である。
セルロース分解酵素であるセルラーゼには多様な菌がある。用いる菌種は限定されず、セルロース分解を行うものであれば良い。
セルラーゼ反応工程はセルロースを分解してグルコースを生成する反応である。In the cellulase reaction step (5), cellulase, which is a hydrolase of (1 → 4) -β-glucoside bond, is applied to cellulose remaining in the plant tissue residue after the treatment in the water washing step (3). And cellulose decomposition.
There are various bacteria in cellulase which is a cellulolytic enzyme. The bacterial species to be used is not limited, as long as it can degrade cellulose.
The cellulase reaction step is a reaction that decomposes cellulose to produce glucose.
次に、濾過工程（６）について述べる。残渣側の工程におけるセルラーゼ反応工程（５）により生成されたグルコースを濾過により取り出す工程である。
グルコースは糖化が進んだ物質であり、例えば、バイオエタノールを得るための基本原料となるものであり、バイオマス利用に適した物質である。
グルコースは液分に溶出しているので、濾過工程（６）によりグルコースと、残渣を簡単に分離することができる。Next, the filtration step (6) will be described. This is a step of removing the glucose produced by the cellulase reaction step (5) in the step on the residue side by filtration.
Glucose is a substance with advanced saccharification, for example, it is a basic raw material for obtaining bioethanol, and is a substance suitable for biomass utilization.
Since glucose is eluted in liquid, the filtration step (6) can easily separate glucose from the residue.
濾過工程（６）で残渣として回収されたものは、脆くなっており、特別な粉砕機でなくともボールミル等の汎用的な粉砕機を用いて粉砕することができ、それもバイオマス源として利用用途に応じた原料となる。
これらの工程で得られたセルロースに対してセルロース分解酵素であるセルラーゼを適温で反応させれば、セルロース分解反応によりグルコースを生成することができる。What was recovered as a residue in the filtration step (6) is fragile and can be crushed using a general-purpose grinder such as a ball mill, even if it is not a special grinder, which is also used as a biomass source It becomes the raw material according to
If cellulose obtained in these steps is reacted with cellulase, which is a cellulolytic enzyme, at an appropriate temperature, glucose can be produced by a cellulolytic reaction.
実施例４として、本発明の植物組織処理方法を適用し、植物組織の分解を促進させて植物組織の体積を小さくする嵩低減方法の実施例について述べる。
以下の検証実験では、植物組織として「稲わら」を用いた例として各工程の結果を検証する。
本発明の水酸化リチウムを主剤とした植物組織処理剤を用いた試験区分（以下、水酸化リチウム溶液試験区分と略記する。）と、比較実験として、水酸化ナトリウムを主剤とした植物組織処理剤を用いた試験区分（以下、水酸化ナトリウム溶液試験区分と略記する。）と、コントロールとして植物組織処理剤を用いずに単なる精製水を用いた試験区分（以下、精製水試験区分と略記する。）を用意して実験した。As Example 4, an example of a method for reducing the volume of plant tissue by promoting decomposition of the plant tissue by applying the method for treating plant tissue of the present invention will be described.
In the following verification experiments, the results of each process are verified as an example using "rice straw" as a plant tissue.
A test tissue treatment agent using a plant tissue treating agent containing lithium hydroxide as a main ingredient of the present invention (hereinafter abbreviated as a lithium hydroxide solution test segment) and, as a comparative experiment, a plant tissue treating agent containing sodium hydroxide as a main agent Test division (hereinafter abbreviated as sodium hydroxide solution test division) using the above, and test division simply using purified water without using a plant tissue treating agent as control (hereinafter abbreviated as purified water test division). ) Was prepared and experimented.
実験に用いる植物組織である稲わらは、あらかじめ自然乾燥し、約３０ｍｍの長さにカットしたものを用いた。カットした稲わらを０．５ｇずつ用意した。
各試験区分において、水酸化リチウム溶液の濃度は７ｗ％、ｐＨは１０から１２程度になるよう調製されており、水酸化ナトリウム溶液の濃度は１１．８ｗ％、ｐＨは１０から１２程度になるよう調製したものを用いた。
図１における分解抽出処理工程（１）は、各試験区分とも溶液に６時間浸漬することで行った。
なお、分解抽出処理工程（１）の結果得られた植物組織残渣は乾燥させて保存に適した形態とすることが好ましい。Rice straw, which is a plant tissue used in the experiment, was naturally dried in advance and cut into a length of about 30 mm. 0.5 g of cut rice straw was prepared.
In each test section, the concentration of lithium hydroxide solution is adjusted to 7 w%, the pH is adjusted to approximately 10 to 12, the concentration of sodium hydroxide solution is adjusted to 11.8 w%, and the pH is adjusted to approximately 10 to 12 What was prepared was used.
The decomposition extraction process step (1) in FIG. 1 was performed by immersing in each solution for 6 hours in each test section.
In addition, it is preferable to dry the plant tissue residue obtained as a result of a decomposition extraction process process (1), and to set it as the form suitable for storage.
図１４は、植物組織の分解抽出処理工程、その後取り出した植物組織残渣の水洗工程、さらに乾燥工程を模擬した結果を示す図である。
図１４（ａ）は、植物組織の分解抽出処理工程（１）の結果を示す図である。
図１４（ａ）に示すように、水酸化リチウム溶液試験区分では浸漬溶液の色が時間経過とともに透明色から茶系の濃色に変化しており、植物由来構造物が溶脱している様子が見られる。FIG. 14 is a diagram showing the results of simulating a plant tissue decomposition extraction process, a water washing process of a plant tissue residue taken out thereafter, and a drying process.
FIG. 14 (a) is a diagram showing the result of the decomposition extraction process step (1) of a plant tissue.
As shown in FIG. 14 (a), in the lithium hydroxide solution test section, the color of the immersion solution changes from transparent to dark brown with the passage of time, and the appearance of leaching out of the plant-derived structure is Seen.
一方、水酸化ナトリウム溶液試験区分では、溶液の色の変化が水酸化リチウム溶液試験区分の溶液の色の変化とは若干違っているが、時間経過とともに透明色から茶系の濃色に変化しており、植物由来構造物が溶脱している様子が見られる。
精製水試験区分では精製水は透明のままであり特段何も溶脱していないことが分かる。On the other hand, in the sodium hydroxide solution test section, the color change of the solution is slightly different from the color change of the solution in the lithium hydroxide solution test section, but changes from transparent color to dark brown color over time It can be seen that the plant-derived structure has leached out.
In the purified water test section, it can be seen that the purified water remains clear and in particular nothing has leached out.
図１４（ｂ）は、それぞれの試験区分から植物組織残渣を取り出した様子を示す図である。水酸化リチウム溶液試験区分ではかなり脆くなっていることが触感で感得された。水酸化ナトリウム溶液試験区分では全体に粘り気があり、若干植物組織が軟らかくなっているようであったが脆くなっているとまでは言えないことが触感で感得された。精製水試験区分は明らかに湿っているのみである。 FIG. 14 (b) is a diagram showing how plant tissue residue is taken out from each test section. In the lithium hydroxide solution test section, it was felt that it was considerably brittle by the touch. In the sodium hydroxide solution test section, it was felt that the whole was sticky and that the plant tissue appeared to be soft but not so fragile. The purified water test section is obviously only wet.
図１４（ｃ）は、水洗処理工程（３）を終えた状態の各試験区分の植物組織残渣の様子を示す図である。なお、ナイロン製ネット上で１８日間、風通しの良い屋内で室内風乾を行なった。
水酸化リチウム溶液試験区分では乾燥してさらに脆くなっていることが触感で感得された。水酸化ナトリウム溶液試験区分では乾燥により少し縮んだ感じであるが繊維がしっかりと残存しており脆くなっているとまでは言えないことが触感で感得された。精製水試験区分は原材料の稲わらの初期状態に戻った感じであった。FIG. 14 (c) is a view showing the state of plant tissue residue in each test section in a state where the water washing process (3) is finished. In addition, indoor air drying was performed on a nylon net for 18 days in a well-ventilated indoor area.
In the lithium hydroxide solution test section, it was felt that it became dry and more brittle. In the sodium hydroxide solution test section, although it felt a little shrunk due to drying, it was felt that the fibers remained firmly and it can not be said that it is fragile and that it feels tactilely. The purified water test category had a feeling of returning to the initial condition of rice straw as a raw material.
図１５は、植物組織残渣の粉砕し易さを示す図である。
図１５の上段は、植物組織残渣を簡単に指で擦った状態を示す図である。
水酸化リチウム溶液試験区分では、植物組織残渣が脆くなっており、指でも簡単にすり潰すことができ、繊維状に残るものは少なく、バラバラな小さな破砕片に砕けた。水酸化リチウム溶液試験区分では、浸漬時間を長くしたり撹拌を加えたりすることで繊維まで分解することができることが分かる。FIG. 15 is a view showing the easiness of crushing plant tissue residues.
The upper part of FIG. 15 is a diagram showing a state where the plant tissue residue is simply rubbed with a finger.
In the lithium hydroxide solution test section, the plant tissue residue was brittle and could be easily ground with a finger, few left in fibrous form and broken into small pieces. In the lithium hydroxide solution test section, it can be seen that the fibers can be degraded by prolonging the immersion time or adding agitation.
一方、水酸化ナトリウム溶液試験区分では、植物組織残渣が軟らかくなっており、指でも押し潰すことができたが、繊維に沿って裂ける程度であり、小さな破砕片に砕けることはなかった。
精製水試験区分では、稲わらが乾燥しただけであり割ること自体も容易とは言えないものであった。On the other hand, in the sodium hydroxide solution test section, the plant tissue residue became soft and could be crushed with a finger, but was only torn along the fiber and did not break into small fragments.
In the purified water test category, it was difficult to say that the rice straw was only dried and it was not easy to divide it.
次に、図１５の下段は、植物組織残渣を乳鉢ですり潰した状態を示す図である。
水酸化リチウム溶液試験区分では、植物組織残渣が脆くなっているので、乳鉢で軽く擦る程度でもすり潰すことができ、小さな粉体状になった。さらに力を込めて乳鉢ですり潰せばより粉末化が進んでいくことが分かった。つまり、植物組織残渣は容易に粉末化できるものであることが分かった。Next, the lower part of FIG. 15 is a view showing a state where the plant tissue residue is crushed with a mortar.
In the lithium hydroxide solution test section, since the plant tissue residue was brittle, it could be ground even with a slight rubbing with a mortar, resulting in a small powder. Further, it was found that if the mortar was crushed with force, powderization would be further progressed. That is, it turned out that a plant tissue residue can be easily powdered.
一方、水酸化ナトリウム溶液試験区分では、植物組織残渣が軟らかくなっており、繊維に沿って裂けて行くが、繊維がバラバラになるだけで小さな破砕片になることはなかった。つまり、植物組織残渣は容易に粉末化できるものでないことが分かった。 On the other hand, in the sodium hydroxide solution test section, the plant tissue residue was softened and was torn along the fibers, but the fibers were not broken apart without being broken apart. In other words, it was found that plant tissue residues can not be easily powdered.
なお、図１５に示した結果から、本発明の植物組織または植物由来加工物の処理方法によって植物組織残渣を効果的に粉末化することができる結果、嵩張っていた植物組織を粉末化することにより嵩密度を上げることができ、体積を小さくすることができることが分かる。
このように、植物組織または植物由来加工物をバイオマスの炭素源として利用する材料として体積を減らせることができれば、輸送、保存などのコストを低減することができる。From the results shown in FIG. 15, the plant tissue residue can be effectively powdered by the method for treating plant tissue or a plant-derived processed product according to the present invention, so that bulky plant tissue can be powdered. It can be seen that the bulk density can be increased and the volume can be reduced.
As described above, if the volume can be reduced as a material that uses plant tissue or a plant-derived processed material as a carbon source of biomass, costs such as transportation and storage can be reduced.
実施例５として、本発明の植物組織処理剤を、段ボールや紙製品などの植物由来加工物に適用し、その分解を促進させる実施例について述べる。
以下の検証実験では、植物由来加工物の例として「段ボール」と「紙片」を用いた場合を検証する。As Example 5, the plant tissue treating agent of the present invention is applied to a plant-derived processed material such as a cardboard or a paper product, and an example of promoting the degradation thereof is described.
In the following verification experiment, the case where "cardboard" and "paper piece" are used as an example of a plant origin processed material is verified.
まず、段ボールに対する本発明の植物組織処理剤の施用効果について検証した。
本発明の水酸化リチウムを主剤とした植物組織処理剤を用いた試験区分（以下、水酸化リチウム溶液試験区分と略記する。）と、比較実験として、水酸化ナトリウムを主剤とした植物組織処理剤を用いた試験区分（以下、水酸化ナトリウム溶液試験区分と略記する。）と、コントロールとして植物組織処理剤を用いずに単なる精製水を用いた試験区分（以下、精製水試験区分と略記する。）を用意して実験した。First, the application effect of the plant tissue treatment agent of the present invention on cardboard was verified.
A test tissue treatment agent using a plant tissue treating agent containing lithium hydroxide as a main ingredient of the present invention (hereinafter abbreviated as a lithium hydroxide solution test segment) and, as a comparative experiment, a plant tissue treating agent containing sodium hydroxide as a main agent Test division (hereinafter abbreviated as sodium hydroxide solution test division) using the above, and test division simply using purified water without using a plant tissue treating agent as control (hereinafter abbreviated as purified water test division). ) Was prepared and experimented.
実験に用いる段ボールは、あらかじめ自然乾燥したものを用いた。
各試験区分において、水酸化リチウム溶液の濃度は７ｗ％、ｐＨは１０から１２程度になるよう調製されており、水酸化ナトリウム溶液の濃度は１１．８ｗ％、ｐＨは１０から１２程度になるよう調製したものを用いた。
分解抽出処理工程は、各試験区分とも溶液を滴下して１時間施用させることで行った。１時間施用させた後の状態を観察した。The cardboard used for the experiment used what was dried naturally beforehand.
In each test section, the concentration of lithium hydroxide solution is adjusted to 7 w%, the pH is adjusted to approximately 10 to 12, the concentration of sodium hydroxide solution is adjusted to 11.8 w%, and the pH is adjusted to approximately 10 to 12 What was prepared was used.
The decomposition extraction process was carried out by applying the solution dropwise for 1 hour for each test section. The state after application for 1 hour was observed.
図１６は、段ボールの表面に各溶液を滴下して１時間経過した状態を観察した様子を示す図である。
図１６上段に示す水酸化リチウム溶液試験区分では、段ボールの表面から内部に向けて浸透しており、段ボールの表面が分解されてやや崩れ始めており、時間経過とともにやや変色してゆき、段ボールの植物由来構造物が溶脱している様子が見られる。FIG. 16 is a view showing a state in which each solution is dropped on the surface of a cardboard and one hour has elapsed.
In the lithium hydroxide solution test division shown in the upper part of FIG. 16, the surface of the cardboard penetrates from the surface of the cardboard toward the inside, and the surface of the cardboard is disintegrated and begins to collapse slightly. It can be seen that the derived structure is leaching out.
一方、図１６中段に示す水酸化ナトリウム溶液試験区分では、段ボールの表面から内部への浸透が水酸化リチウムほど大きくはなく、段ボールの表面がやや変色しているが崩れている様子までは観察されず、時間経過してもリチウム溶液試験区分の変化のような植物由来構造物の溶脱の度合いは大きくない。
一方、図１６下段に示す精製水試験区分では、段ボールの表面で撥かれて精製水が表面に溜まった状態で透明のままであり、特段何も溶脱していないことが分かる。On the other hand, in the sodium hydroxide solution test section shown in the middle of FIG. 16, the penetration from the surface of the cardboard into the interior is not as large as that of lithium hydroxide, and the surface of the cardboard is slightly discolored but discolored Also, the degree of leaching of plant-derived structures such as changes in the lithium solution test segment is not large even if time passes.
On the other hand, in the purified water test section shown in the lower part of FIG. 16, it can be seen that it remains transparent in a state where purified water is repelled by the surface of the cardboard and accumulated on the surface, and nothing is leached out.
次に、紙片に対する本発明の植物組織処理剤の施用効果について検証した。
本発明の水酸化リチウムを主剤とした植物組織処理剤を用いた試験区分（以下、水酸化リチウム溶液試験区分と略記する。）と、比較実験として、水酸化ナトリウムを主剤とした植物組織処理剤を用いた試験区分（以下、水酸化ナトリウム溶液試験区分と略記する。）と、コントロールとして植物組織処理剤を用いずに単なる精製水を用いた試験区分（以下、精製水試験区分と略記する。）を用意して実験した。Next, it verified about the application effect of the plant tissue processing agent of this invention with respect to a paper piece.
A test tissue treatment agent using a plant tissue treating agent containing lithium hydroxide as a main ingredient of the present invention (hereinafter abbreviated as a lithium hydroxide solution test segment) and, as a comparative experiment, a plant tissue treating agent containing sodium hydroxide as a main agent Test division (hereinafter abbreviated as sodium hydroxide solution test division) using the above, and test division simply using purified water without using a plant tissue treating agent as control (hereinafter abbreviated as purified water test division). ) Was prepared and experimented.
実験に用いる紙片は、あらかじめ自然乾燥したものを用いた。
各試験区分において、水酸化リチウム溶液の濃度は７ｗ％、ｐＨは１０から１２程度になるよう調製されており、水酸化ナトリウム溶液の濃度は１１．８ｗ％、ｐＨは１０から１２程度になるよう調製したものを用いた。
分解抽出処理工程は、各試験区分とも溶液を滴下して１時間施用させることで行った。１時間施用させた後の状態を観察した。The paper used for experiment used what was beforehand dried naturally.
In each test section, the concentration of lithium hydroxide solution is adjusted to 7 w%, the pH is adjusted to approximately 10 to 12, the concentration of sodium hydroxide solution is adjusted to 11.8 w%, and the pH is adjusted to approximately 10 to 12 What was prepared was used.
The decomposition extraction process was carried out by applying the solution dropwise for 1 hour for each test section. The state after application for 1 hour was observed.
図１７は、紙片の表面に各溶液を滴下して１時間経過した状態を観察した様子を示す図である。
図１７上段に示す水酸化リチウム溶液試験区分では、紙片の表面から内部に向けて浸透しており、紙片の表面が分解されて表面がやや崩れ始めており、時間経過とともにやや変色してゆき、植物由来構造物が溶脱している様子が見られる。FIG. 17 is a view showing a state in which each solution is dropped on the surface of the paper and one hour has elapsed.
In the lithium hydroxide solution test division shown in the upper part of FIG. 17, the surface of the paper is infiltrated from the surface of the paper to the inside, and the surface of the paper is disintegrated and the surface starts to break slightly. It can be seen that the derived structure is leaching out.
一方、図１７中段に示す水酸化ナトリウム溶液試験区分では、表面がやや変色しているが、崩れている様子までは観察されず、時間経過してもリチウム溶液試験区分の変化のような植物由来構造物の溶脱の度合いは大きくない。
一方、図１７下段に示す精製水試験区分では、紙片の表面で撥かれて精製水が表面に溜まった状態で透明のままであり、特段何も溶脱していないことが分かる。On the other hand, in the sodium hydroxide solution test division shown in the middle part of FIG. 17, the surface is slightly discolored, but it is not observed that the surface is broken, and plant origin such as a change in lithium solution test division over time The degree of leaching of the structure is not great.
On the other hand, in the purified water test section shown in the lower part of FIG. 17, it is clear that the purified water remains transparent in a state where it is squeezed on the surface of the paper piece and the purified water is accumulated on the surface.
木片や草本片の植物組織への本発明のセルロースＩ型成分の緩慢的な溶解効果や、植物組織の分解促進効果は、上記の実施例１から４で実証してきたが、この実証実験により、段ボールや紙片という植物由来加工物であっても同様に、本発明のセルロースＩ型成分の緩慢的な溶解効果や、植物組織の分解促進効果が得られることが分かる。もっとも、段ボールや紙片という植物由来の加工物は本質的には木片や草本片という植物組織を残した状態の加工物であるので、それら効果が得られることは当然といえる。 The slow dissolution effect of the cellulose type I component of the present invention in plant tissue of wood and grass pieces and the degradation promotion effect of plant tissue have been demonstrated in the above-mentioned Examples 1 to 4. Similarly, it is understood that the slow dissolution effect of the cellulose I-type component of the present invention and the decomposition promoting effect of plant tissue can be obtained even with a plant-derived processed product such as cardboard or paper. However, since the plant-derived processed products such as cardboard and paper are essentially processed products in which the plant tissue such as wood and grass remains, it is natural that these effects can be obtained.
以上、本発明の植物組織の分解を促進する植物組織または植物由来加工物の処理方法、その主剤、その植物組織または植物由来加工物の処理方法で抽出した原料組成物、および植物組織または植物由来加工物の嵩低減方法に関する実施例が示された。 As described above, the method for treating plant tissue or plant-derived processed matter that promotes degradation of plant tissue according to the present invention, its main agent, raw material composition extracted by the method for treating plant tissue or plant-derived processed matter, and plant tissue or plant-derived substance Examples have been presented regarding methods for reducing the bulk of a workpiece.
本発明によれば、植物組織をバイオマスの炭素源としての原材料へ生成する処理において、従来技術では必要とされていた、消費されてしまう処理剤（化学薬品）や、大掛かりな機械装置や、多量なエネルギーなどを不要とし、本発明の植物組織処理剤に対して浸漬するだけで緩慢に反応させるという、非常に簡易な方法で、かつ植物組織処理剤も消費せずに、木材、草本類の植物組織、段ボールや紙製品などの植物由来加工物からセルロースＩ型のセルロースを含む植物由来成分を抽出することができる。
また、草本系抽出後の植物組織残渣、例えば稲わらの場合では、容易にその体積を数分の一位に小さくすることが出来、生産地から消費地までのカーボンマイレイジ低減に大きく寄与するものである。貯蔵コストも低減できる。According to the present invention, in the process of producing plant tissue into raw material as a carbon source of biomass, the processing agent (chemical) which is consumed in the prior art, a large-scale mechanical device, a large amount of processing, etc. Of the wood and herbs in a very simple method, in which unnecessary energy and the like are not required, and the plant tissue treating agent of the present invention is made to react slowly only by immersion, in a very simple method and without consuming the plant tissue treating agent. A plant-derived component containing cellulose of type I cellulose can be extracted from plant-derived processed products such as plant tissue, cardboard and paper products.
In addition, in the case of plant tissue residues after herbaceous extraction, such as rice straw, the volume can be easily reduced to a fraction of a fraction, which greatly contributes to the reduction of carbon mileage from the production area to the consumption area. It is a thing. Storage costs can also be reduced.
本発明を用いれば、大きな土地も・大規模な装置も必要としないため、従来は農業の現場では活用が難しかった木材、草本類の植物組織から植物由来物質を簡易に抽出することおよびバイオマスの炭素源材料を得ることができ、農業地域での新しい雇用も生み出す可能性も持っている。 According to the present invention, it is possible to easily extract plant-derived substances from wood and herbaceous plant tissues which are conventionally difficult to use in agricultural fields because neither large land nor large-scale equipment is required, and biomass They can obtain carbon source materials and have the potential to create new jobs in agricultural areas.
リチウムはバッテリーなどの材料として工業的利用が進んでいるが、水酸化リチウムをこのような形態で植物組織処理に活用することは現在まで無かったところ、新たな活用を見出した意義もある。無機材料で塩基性の化合物としては水酸化ナトリウムが多用されてきたが、水酸化リチウムは同じ塩基性を示す化合物であるところ両者には植物組織に対する分解能力において大きな差があることを見出した。 Lithium has been industrially used as a material for batteries and the like. However, although lithium hydroxide has not been used in such a form for plant tissue processing up to the present, it is also significant to find new utilization. Although sodium hydroxide has been widely used as a basic compound in an inorganic material, it has been found that, although lithium hydroxide is a compound exhibiting the same basicity, there is a large difference in the decomposing ability to plant tissue.
今般、本発明にあたって、見出した水酸化リチウムの植物組織に対する分解能力、植物由来物質の抽出能力は今まで知られていなかった水酸化リチウムの効果であり、当該効果を本願の発明者である２名、つまり、当特許出願に際し参考文献とした「セルロースの事典」、朝倉出版の共同著書の一人である、京都大学生存圏研究所の吉村教授と共同開発者である堀井三郎２名の名前を取って「吉村・堀井効果」と称することとする。 In the present invention, the ability of lithium hydroxide to decompose to plant tissue and the ability to extract plant-derived substances found in the present invention is the effect of lithium hydroxide that has not been known until now, and the effect is the inventor of this application. Name: "Cellulose Encyclopedia" as reference for this patent application, name of two Saburo Horii, co-developer and professor Yoshimura of Kyoto Area Research Institute, who is one of the co-authors of Asakura Publishing Co., Ltd. We will call it "Yoshimura-Horii effect".
以上、本発明の植物組織処理剤および植物組織からの植物由来物質の製造方法の構成例における好ましい実施例を図示して説明してきたが、本発明の技術的範囲を逸脱することなく種々の変更が可能であることは理解されるであろう。 The preferred embodiments of the plant tissue treating agent of the present invention and the method for producing a plant-derived substance from plant tissue have been illustrated and described above, but various modifications can be made without departing from the technical scope of the present invention. It will be understood that is possible.
本発明は、現在低迷している国内林業の活性化と、それ程大規模ではないにしろ、地域振興の一翼を担えることが考えられる。 It is conceivable that the present invention can play a role in revitalizing domestic forestry, which is currently stagnating, and regional promotion, if not on such a large scale.
Claims (10)
前記植物組織処理剤が７ｗ％から１０ｗ％の濃度の水酸化リチウム水溶液を主剤とするものであり、前記植物組織または前記植物由来加工物に対して添加することにより前記セルロースＩ型成分を得ることを特徴とする植物組織または植物由来加工物処理方法。 Chemical decomposition means is added by adding a plant tissue treating agent to plant tissue of wood pieces or grass pieces or plant-derived processed products processed from them without using physical decomposition means of explosion method or ball milling method together used, the plant tissue or to promote the degradation of the plant-derived workpiece, a plant tissue or plant origin workpiece processing method for extracting internal cellulose I type components,
The plant tissue treating agent mainly comprises an aqueous solution of lithium hydroxide at a concentration of 7 w% to 10 w% , and the cellulose I-type component is obtained by adding it to the plant tissue or the plant-derived processed product. Plant tissue or a plant-derived processed product processing method characterized by
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